CN106634038B - A kind of reactive dark blue dyestuff and preparation method thereof - Google Patents
A kind of reactive dark blue dyestuff and preparation method thereof Download PDFInfo
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- CN106634038B CN106634038B CN201611104713.8A CN201611104713A CN106634038B CN 106634038 B CN106634038 B CN 106634038B CN 201611104713 A CN201611104713 A CN 201611104713A CN 106634038 B CN106634038 B CN 106634038B
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- 0 *C1=CC=CC(N=*)=CC1 Chemical compound *C1=CC=CC(N=*)=CC1 0.000 description 9
- OBHIZDLDFMBCSQ-UHFFFAOYSA-N Cc1nc([I]=C)nc([I]=C)n1 Chemical compound Cc1nc([I]=C)nc([I]=C)n1 OBHIZDLDFMBCSQ-UHFFFAOYSA-N 0.000 description 1
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
- C09B62/513—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
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
- C09B67/0046—Mixtures of two or more azo dyes
- C09B67/0055—Mixtures of two or more disazo dyes
- C09B67/0057—Mixtures of two or more reactive disazo dyes
- C09B67/0059—Mixtures of two or more reactive disazo dyes all the reactive groups are not directly attached to a heterocyclic system
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes
- D06P1/384—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes reactive group not directly attached to heterocyclic group
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/58—Material containing hydroxyl groups
- D06P3/60—Natural or regenerated cellulose
- D06P3/66—Natural or regenerated cellulose using reactive dyes
- D06P3/666—Natural or regenerated cellulose using reactive dyes reactive group not directly attached to heterocyclic group
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Coloring (AREA)
Abstract
The invention discloses a kind of reactive dark blue dyestuffs and preparation method thereof, wherein reactive dark blue dyestuff has structure shown in formula (I), compared with prior art, reactive dark blue dye monomer compound structure novel of the invention, it has excellent performance, with good color fastness, degree of fixation is high, dye stabilizer, washable, rub resistance sun-resistant is spent, good with fiber combination stability, finished product has excellent vividness, is suitable for large-scale promotion application.
Description
Technical field
The invention belongs to field of fine chemical, and in particular to a kind of reactive dye, more particularly to a kind of reactive dark blue dyestuff
And preparation method thereof and the application printed and dyed on cotton fiber.
Background technology
Reactive dye bright in color light, wet fastness is good, but its degree of fixation, alkali resistance, sunlight fastness are generally relatively low, especially
The reactive dye of the blue series such as deep blue M-2GE of activity, coloured light is not bright-coloured, poor solubility, and the exhaustion rate of dyeing is low.Its structural formula
It is as follows：
The reactive dye of multi-active base have higher exhaustion rate, better degree of fixation than single active group reactive dye, simultaneously
Dye molecule can form cross-linked network with fiber, and dyestuff is made preferably to be combined with fiber.Therefore, the work of multi-active base
The synthesis of property dyestuff has been a hot spot of research with exploitation.
Invention content
The object of the present invention is to provide a kind of structure novel, the reactive dark blue dyestuffs and preparation method thereof haveing excellent performance.It should
Dyestuff has good degree of fixation, color fastness, there is good stability after dyeing, bright in color light, can be widely used in cotton, fiber crops,
The dyeings such as the dip dyeings of the fibres such as synthetic cotton, pad dyeing, ink-jet printed, and production cost is low, it can be with large-scale promotion
Using.
It is a further object of the present invention to provide a kind of preparation methods of above-mentioned reactive dark blue dyestuff.
The third object of the present invention is to provide a kind of application of above-mentioned reactive dark blue dyestuff.
The purpose of the present invention can be achieved by the following measures：
The reactive dark blue dyestuff of structure shown in a kind of general formula (I),
Wherein,
A is monosubstituted or polysubstituted phenyl, naphthalene or ethyl Carbamoylphenyl with vinylsulfone group, is taken
Dai Ji is selected from hydrogen ,-SO3M or C1~3Alkyl；
D is monosubstituted or polysubstituted phenyl or ethyl Carbamoylphenyl with vinylsulfone group, substituent group
Selected from hydrogen ,-SO3M or C1~3Alkyl；
X is halogen；
R1For hydrogen, C1~4Alkyl or aryl；
R2For hydrogen, C1~4Alkyl, C1~4Alkoxy ,-SO3M or aryl；
M is H or alkali metal.
In a kind of scheme, A is selected from following group：
In a kind of scheme, D is selected from following group：
In a kind of scheme, R1For methyl, ethyl, n-propyl, normal-butyl or phenyl.
In a kind of scheme, R2For hydrogen or-SO3M。
In a kind of scheme, X is F or Cl.
In a kind of scheme, M H, Na or K.
Further, currently preferred general formula (I) compound structure is as follows：
The reactive dark blue dyestuff of formula (I) of the present invention, can be with free acid (i.e. M is H) or a preferably alkali metal salt (M
For Na, K) form prepare, produce need in the case of, routinely condition can carry out mutually converting for acid and salt formula,
The dyeability of dyestuff is not influenced.
The present invention provides a kind of preparation methods of reactive dark blue dyestuff comprising following steps：
(1), formula (II) diazol and formula (III) compound are coupled (IV) compound,
(2), formula (V) compound and formula (VI) compound obtain formula (VII) compound through condensation reaction；
(3), formula (VIII) compound and formula (Ⅸ) compound obtain formula (X) compound through reductive amination process；
(4), formula (VII) compound and formula (X) compound obtain formula (XI) compound through condensation reaction.
(6), formula (XI) diazotising is made diazol (XII) and is coupled to obtain formula (I ') compound with formula (IV) compound
(6), formula (I ') compound obtains formula (I) compound after basic hydrolysis
Wherein, A ' is monosubstituted or polysubstituted phenyl, naphthalene or ethyl carbamyl with beta-sulfuric ester ethyl sulfonyl
Phenyl, A are monosubstituted or polysubstituted phenyl, naphthalene or ethyl Carbamoylphenyl with vinylsulfone group, A ' and A's
Substituent group is selected from hydrogen ,-SO3M or C1~3Alkyl；D ' is monosubstituted or polysubstituted phenyl or second with beta-sulfuric ester ethyl sulfonyl
Base Carbamoylphenyl, D are monosubstituted or polysubstituted phenyl or ethyl Carbamoylphenyl with vinylsulfone group, D '
It is selected from hydrogen ,-SO with the substituent group of D3M or C1~3Alkyl；X is halogen；R1For hydrogen, C1~4Alkyl or aryl；R2For hydrogen, C1~4Alkyl,
C1~4Alkoxy ,-SO3M or aryl；M is H or alkali metal.
In step 1, formula (III) compound is added in formula (II) diazol, is coupled, is obtained at 5-10 DEG C of temperature
(IV) compound；Step (1) specifically carries out as follows：Formula (III) compound is added in formula (II) diazol, temperature
5-10 DEG C is coupled, and (IV) compound is obtained.
In step 2, formula (IV) compound carries out condensation reaction after being mixed with formula (V) compound, and pH=is adjusted in reaction
3-5 fully obtains formula (VII) compound after reaction；Step (2) specifically carries out as follows：Formula (VI) compound ice mill is beaten
Slurry, formula (V) compound is added in slurries, carries out condensation reaction, condensation liquid sodium bicarbonate adjusts pH=3-5, fully anti-
Ying Hou, pH stable, feed liquid become clear, obtain formula (VII) compound.
In step 3, formula (VIII) compound is mixed with formula (Ⅸ) compound, and catalytic hydrogenation is carried out at 40-80 DEG C of temperature
Reduction reaction obtains formula (X) compound；Step (3) specifically carries out as follows：Formula (VIII) compound and formula (Ⅸ) compound
It mixes in ethanol, 40-80 DEG C of temperature, catalytic hydrogenating reduction, filtering, solvent evaporated obtain formula (X) compound.
In step 4, formula (X) compound is added containing in formula (VI) chemical combination material liquid, carries out condensation reaction, is adjusted in reaction
Whole pH=3-5 fully obtains formula (XI) compound after reaction；Step (4) specifically carries out as follows：By formula (X) compound
In addition formula (VI) chemical combination material liquid, condensation reaction is carried out, condensation liquid sodium bicarbonate adjusts pH=3-5, fully after reaction, pH
Value stabilization, feed liquid become clear, obtain formula (XI) compound.
In steps of 5, ice water, hydrochloric acid and sodium nitrite is added in formula (XI) compound, and temperature is kept to be less than 10 DEG C, pH=
1.0 ± 0.2 progress diazotising obtain diazol XII；Diazol XII is added to containing in formula (IV) chemical combination material liquid, pH is adjusted
5-10 DEG C of=6-8, temperature progress coupling reaction, obtain formula (I ') compound；Step (5) specifically carries out as follows：Formula
(XI) ice water and hydrochloric acid is added in compound, and after mashing uniformly, sodium nitrite solution is added dropwise, temperature is kept to be less than 10 DEG C, pH=1.0
± 0.2 progress diazotising obtains diazol；The diazol is added in formula (IV) chemical combination material liquid, pH=6- is adjusted with sodium bicarbonate
8,5-10 DEG C of temperature is coupled, and obtains formula (I ') compound.
In step 6, formula (I ') compound is reacted at pH=9-10,40-70 DEG C of temperature, obtains formula (I) compound.
Step (6) specifically carries out as follows：Formula (I ') compound obtains formula (I) then at pH=9-10,40-70 DEG C of reaction of temperature
Finished product is dried to obtain in compound, premenstrual standardization processing, spraying.
Unless otherwise stated, " alkyl " used in the specification and in the claims indicates the saturation of 1-20 carbon atom
Aliphatic group, including (digital scope mentioned in this specification, such as " 1-20 " they refer to the group, at this time for straight chain and branched group
For alkyl, 1 carbon atom, 2 carbon atoms, 3 carbon atoms etc. can be contained, until including 20 carbon atoms).It is former containing 1-5 carbon
The alkyl of son is known as low alkyl group.When low alkyl group does not have substituent group, it is called unsubstituted low alkyl group.More preferably
It is that alkyl is the medium sized alkyl for having 1-10 carbon atom, such as methyl, ethyl, propyl, 2- propyl, normal-butyl, isobutyl
Base, tertiary butyl, amyl etc..Preferably, alkyl is the low alkyl group for having 1-5 carbon atom, such as methyl, ethyl, propyl, 2- third
Base, normal-butyl, isobutyl group or tertiary butyl etc..Alkyl can be substituted or unsubstituted.
Unless otherwise stated, " aryl " used in the specification and in the claims indicates any and derives from simple aromatic rings
The functional group gone out or substituent group, including but not limited to phenyl, o-tolyl, 1- naphthalenes (or Alpha-Naphthyl), 2- naphthalenes etc..
The invention discloses a kind of dye composites, it is aided with dyestuff using above-mentioned reactive dark blue dyestuff as active component
Auxiliary agent in field.
The invention discloses another dye composites, it is with the reactive dark blue dyestuff and general formula of structure shown in general formula (I)
(1) the active deep red dyestuff of structure shown in is main active, and mass ratio between the two is 55~95：5~45,
Wherein, A, D, X, R1、R2It is as defined above；A1To have-SO3M or-SO2C2H4OSO3M substituent groups singly take
Generation or polysubstituted phenyl or naphthyl；D1For substituted or non-substituted phenyl, substituent group is selected from hydrogen ,-SO3M or C1~3Alkyl；M
For H or alkali metal.
In a kind of preferred embodiment, the reactive dark blue dyestuff and general formula of structure shown in the dye composite formula of (I)
(1) mass ratio of the active deep red dyestuff of structure shown in is 60~90：10~40.
In a kind of preferred embodiment, A1Selected from following group：
In a kind of preferred embodiment, D1Selected from following group：
In a kind of preferred embodiment, M H, Na or K.
In another preferred embodiment, the active deep red dyestuff of structure shown in general formula (one) specifically can be selected from following
Compound：
It can be with solid particle, powder with the dyestuff finished product made by reactive dark blue dyestuff of the present invention and composition
Or solution exists, the electrolyte salt contained, as common in sodium chloride, potassium chloride, sodium sulphate, potassium sulfate and commercial dyes
Auxiliary agent.
Dyestuff finished product made by reactive dark blue dyestuff and composition provided by the present invention can be applicable to scrim
In printing and dyeing, the application in terms of the dip dyeing of fibre cotton, fiber crops or synthetic cotton, pad dyeing or ink-jet printed dyeing is especially applied.
The fibre can be the materials such as cotton, fiber crops, synthetic cotton.Compared with prior art, reactive dark blue dye monomer of the invention
Compound structure is novel, has excellent performance, and has good color fastness, and degree of fixation is high, dye stabilizer, washable, rub resistance, sun-resistant
It spends, good with fiber combination stability, finished product has excellent vividness, is suitable for large-scale promotion application.
Specific implementation mode
With reference to specific embodiment, the present invention is described further, and the scope of the present invention includes but is not limited only to
This embodiment：
Embodiment 1：The preparation of formula (I -1) compound
(1) diazonium, coupling reaction
In 250ml beakers, 20 parts of (mass parts) ice, 24.3 part of 30% hydrochloric acid, 28.1 parts of meta position esters, ice mill mashing is added
30min, 6.97 parts of sodium nitrites are slowly added to generate diazol, 1h are stirred for after sodium nitrite is added completely into, with amino sulphur
Acid eliminates micro- excessive sodium nitrite；31.9 parts of H acid are added in diazol, the reaction was continued after adding disappears completely to diazol
It loses, while it is 0-10 DEG C to keep system temperature.
(2) p-phenylenediamine and cyanuric fluoride primary condensation
In the flask of 1000ml, 10.8 parts of p-phenylenediamine, 50 parts of ice water is added, 13.5 parts of (folding hundred) cyanuric fluorides are added
Entering into p-phenylenediamine, adjusts pH=3.5-5.0 with sodium bicarbonate, keep 0-10 DEG C of temperature, react 4-6h, feed clarification is transparent,
Reaction end is detected with amino agents, keeps temperature to stablize, waits for secondary condensation.
(3) reduction amination of aldehyde and amine
In 1000ml flasks, 4.4 parts of n-butanals of addition and 28.1 parts of meta position esters, 50 parts of ethyl alcohol, 1 part of Raney nickel,
10Mpa、H2, 60-80 DEG C of reduction 12h, Filtration of catalyst, solvent evaporated obtains product secondary amine.
(4), secondary amine and a contracting component secondary condensation
Secondary amine is added in a contracting component, reaction solution is warming up to 30-40 DEG C, while adjusting pH=3.5- with sodium bicarbonate
5.0,30-40 DEG C of temperature is kept, 4-6h is reacted, feed clarification is transparent, and reaction end is detected with amino agents.
(5), two contracting component diazonium and coupling component are coupled
20 parts of ice, 24.3 part of 30% hydrochloric acid are added in secondary condensation component, and ice mill mashing 30min is slowly added to 6.97 parts of Asias
Sodium nitrate generates diazol, and 1h is stirred for after sodium nitrite is added completely into, and micro- excessive sodium nitrite is eliminated with sulfamic acid；
Diazol is added in an above-mentioned coupling component, rear sodium bicarbonate is added and adjusts pH=5.5-8.0, keep pH value, temperature
For 0-10 DEG C of the reaction was continued 2h, diazol completely disappears.
(6) two even component hydrolysis
Soda ash is added into above-mentioned solution, adjusts pH=9-10, is warming up to 40-70 DEG C, reacts 8-10h.It is normalized to add
Dyestuff finished product is dried to obtain in work, spraying.(after purification, MS：[M+H] +=982.07)
Embodiment 2：The preparation of formula (I -2) compound
(1) diazonium, coupling reaction
In 250ml beakers, 20 parts of ice are added, 24.3 part of 30% hydrochloric acid, 28.1 parts of para-esters, ice, which is ground, is beaten 30min, and 6.97
Part sodium nitrite is slowly added to generate diazol, and 1h is stirred for after sodium nitrite is added completely into, and micro- mistake is eliminated with sulfamic acid
The sodium nitrite of amount；31.9 parts of H slow acids are added drop-wise in diazol, the reaction was continued 2h after adding, diazol completely disappears, together
When keep system temperature be 0-10 DEG C.
(2) m-phenylene diamine (MPD) and cyanuric fluoride primary condensation
In the flask of 1000ml, 10.8 parts of m-phenylene diamine (MPD)s, 50 parts (mass parts) ice water is added, by 13.5 parts of (foldings hundred) three
Poly- fluorine cyanogen is added in m-phenylene diamine (MPD), is adjusted pH=3.5-5.0 with sodium bicarbonate, is kept 0-10 DEG C of temperature, react 4-6h, feed liquid is clear
It is clear bright, reaction end is detected with amino agents, keeps temperature to stablize, waits for secondary condensation.
(3) reduction amination of aldehyde and amine
In 1000ml flasks, 4.4 parts of n-butanals of addition and 28.1 parts of para-esters, 50 parts of ethyl alcohol, 1 part of Raney nickel,
10MPaH2, 60-80 DEG C restores 12h, Filtration of catalyst, and solvent evaporated obtains product secondary amine.
(4), secondary amine and a contracting component secondary condensation
Secondary amine is added in a contracting component, reaction solution is warming up to 30-40 DEG C, while adjusting pH=3.5- with sodium bicarbonate
5.0,30-40 DEG C of temperature is kept, 4-6h is reacted, feed clarification is transparent, and reaction end is detected with amino agents.
(5), two contracting component diazonium and the secondary coupling of coupling component
20 parts of ice, 24.3 part of 30% hydrochloric acid are added in secondary condensation component, and ice mill mashing 30min is slowly added to 6.97 parts of Asias
Sodium nitrate generates diazol, and 1h is stirred for after sodium nitrite is added completely into, and micro- excessive sodium nitrite is eliminated with sulfamic acid；
Diazol is added in an above-mentioned coupling component, rear sodium bicarbonate is added and adjusts pH=5.5-8.0, keep pH value, temperature
For 0-10 DEG C of the reaction was continued 2h, diazol completely disappears.
(6) coupling component hydrolysis
Soda ash is added into above-mentioned solution, adjusts pH=9-10, heats up 40-70 DEG C, reacts 8-10h, adjusts pH=6.5-
7.Dyestuff finished product is dried to obtain in normalized processing, spraying.(after purification, MS：[M+H] +=964.12)
Wherein, M Na.
Embodiment 3-5：
According to 1 the method for embodiment, the difference is that the condensation component of the diazo component being coupled with H acid and Cyanuric Chloride,
And the amine and aldehyde of reduction amination, it is reacted using the raw material compound of equimolar amounts in the following table 1, you can obtain institute of the present invention
Formula (I -3~I -5) the reactive dark blue dyestuff stated.
Wherein, M Na.
Embodiment 6：A kind of preparation of active deep red dye composition
(1) diazonium, a coupling reaction
In 250ml beakers, 20 parts of ice are added, 24.3 part of 30% hydrochloric acid, 36.1 parts of sulfonation para-esters, ice, which is ground, is beaten 30min,
It is slowly added to 6.97 parts of sodium nitrites and generates diazol, be stirred for 1h after sodium nitrite is added completely into, eliminated with sulfamic acid
Micro- excessive sodium nitrite；Diazol is slowly dropped in 23.9 parts of J acid, pH=3-5 is adjusted with sodium bicarbonate when being added dropwise, adds
The reaction was continued after adding 2h, while it is 0-10 DEG C to keep system temperature, diazol completely disappears.
(2) acyl chlorides is condensed with p-phenylenediamine
In the flask of 1000ml, 50 parts (mass parts) ice water is added, 10.8 parts of (folding hundred) p-phenylenediamine are beaten 1h, are added dropwise
23.2 parts of 4- (2- chloroethyls sulfuryl) butyl chlorides adjust pH=3.5-5.0 with sodium bicarbonate, keep 0-10 DEG C of temperature, react 4-6h,
Feed clarification is transparent, keeps temperature to stablize, waits for diazonium.
(3) secondary diazonium, coupling reaction
20 parts of ice are added in above-mentioned condensation liquid, 24.3 part of 30% hydrochloric acid is slowly added to 6.97 parts of sodium nitrites and generates weight
Nitrogen salt is stirred for 1h after sodium nitrite is added completely into, and micro- excessive sodium nitrite is eliminated with sulfamic acid；Diazol is slow
It is added drop-wise in a diazo coupling component, pH=5.5-8.0 is adjusted with sodium bicarbonate when being added dropwise, the reaction was continued 2h after adding,
Diazol completely disappears, while it is 0-10 DEG C to keep system temperature, and dyestuff finished product is dried to obtain in normalized processing, spraying.(purifying
Afterwards, MS：[M+H] +=968.96)
Embodiment 7：A kind of preparation of active deep red dye composition
(1) diazonium, a coupling reaction
In 250ml beakers, 20 parts of (mass parts) ice, 24.3 part of 30% hydrochloric acid, 28.1 parts of meta position esters, ice mill mashing is added
30min, 6.97 parts of sodium nitrites are slowly added to generate diazol, 1h are stirred for after sodium nitrite is added completely into, with amino sulphur
Acid eliminates micro- excessive sodium nitrite；Diazol is slowly dropped in 23.9 parts of J acid, pH=is adjusted with sodium bicarbonate when being added dropwise
The reaction was continued 2h after 3-5 is added, diazol completely disappear, while it is 0-10 DEG C to keep system temperature.
(2) acyl chlorides is condensed with m-phenylene diamine (MPD)
In the flask of 1000ml, 50 parts of ice water is added, 10.8 parts of (folding hundred) m-phenylene diamine (MPD)s are beaten 1h, 23.2 parts of 4- (2-
Chloroethyl sulfuryl) butyl chloride, pH=3.5-5.0 is adjusted with sodium bicarbonate, keeps 0-10 DEG C of temperature, reacts 4-6h, feed clarification is saturating
It is bright, it keeps temperature to stablize, waits for diazonium.
(3) secondary diazonium, coupling reaction
20 parts of ice are added in above-mentioned condensation liquid, 24.3 part of 30% hydrochloric acid is slowly added to 6.97 parts of sodium nitrites and generates weight
Nitrogen salt is stirred for 1h after sodium nitrite is added completely into, and micro- excessive sodium nitrite is eliminated with sulfamic acid；Diazol is slow
It is added drop-wise in a coupling component, pH=5.5-8.0 is adjusted with sodium bicarbonate when being added dropwise, the reaction was continued after adding 2h, diazonium
Salt completely disappears, while it is 0-10 DEG C to keep system temperature, and dyestuff finished product is dried to obtain in normalized processing, spraying.(after purification,
Its MS：[M+H] +=890.02)
Embodiment 8：A kind of preparation of active deep red dye composition
(1) diazonium, a coupling reaction
In 250ml beakers, 20 parts of ice, 24.3 part of 30% hydrochloric acid, 41 parts of 6- hydroxyethyl sulfuryl sulfuric ester -2- naphthylamines-are added
1- sulfonic acid ice mill mashing 50min, is slowly added to 6.97 parts of sodium nitrites and generates diazol, stirred again after sodium nitrite is added completely into
1h is mixed, micro- excessive sodium nitrite is eliminated with sulfamic acid；Diazol is slowly dropped in 23.9 parts of J acid, is used when being added dropwise
Sodium bicarbonate adjusts pH=3-5, and the reaction was continued 2h after adding, diazol completely disappears, while it is 0-10 DEG C to keep system temperature.
(2) acyl chlorides is condensed with p-phenylenediamine
In the flask of 1000ml, 50 parts (mass parts) ice water is added, 10.8 parts of (folding hundred) p-phenylenediamine are beaten 1h, are added dropwise
23.2 parts of 4- (2- chloroethyls sulfuryl) butyl chlorides adjust pH=3.5-5.0 with sodium bicarbonate, keep 0-10 DEG C of temperature, react 4-6h,
Feed clarification is transparent, keeps temperature to stablize, waits for diazo coupling.
(3) secondary diazonium, coupling reaction
20 parts of ice are added in above-mentioned condensation liquid, 24.3 part of 30% hydrochloric acid is slowly added to 6.97 parts of sodium nitrites and generates weight
Nitrogen salt is stirred for 1h after sodium nitrite is added completely into, and micro- excessive sodium nitrite is eliminated with sulfamic acid；Diazol is slow
It is added drop-wise in a diazo coupling component, pH=5.5-8.0 is adjusted with sodium bicarbonate when being added dropwise, the reaction was continued 2h after adding,
Diazol completely disappears, while it is 0-10 DEG C to keep system temperature, and dyestuff finished product is dried to obtain in normalized processing, spraying.(purifying
Afterwards, MS：[M+H] +=1041.97)
Embodiment 9：
Using 15 parts of active deep red dyestuff made from 85 parts of reactive dark blue dyestuff made from the embodiment of the present invention 4, embodiment 7
Carry out a kind of brownish black reactive dye that inclined blue streak is made in compounding.
Embodiment 10：
Using 20 parts of active deep red dyestuff made from 80 parts of reactive dark blue dyestuff made from the embodiment of the present invention 1, embodiment 6
Carry out a kind of brownish black reactive dye that inclined feux rouges is made in compounding.
Embodiment 11：
Using 30 parts of active deep red dyestuff made from 70 parts of reactive dark blue dyestuff made from the embodiment of the present invention 5, embodiment 8
Carry out a kind of brown active dye that inclined blue streak is made in compounding.
Embodiment 12：
Using 35 parts of active deep red dyestuff made from 65 parts of reactive dark blue dyestuff made from the embodiment of the present invention 1, embodiment 6
Carry out a kind of brown active dye that inclined feux rouges is made in compounding.
Embodiment 13：
Using 40 parts of active deep red dyestuff made from 60 parts of reactive dark blue dyestuff made from the embodiment of the present invention 4, embodiment 7
Carry out a kind of rufous reactive dye that inclined feux rouges is made in compounding.
Embodiment 14：
Using 40 parts of active deep red dyestuff made from 60 parts of reactive dark blue dyestuff made from the embodiment of the present invention 5, embodiment 8
Carry out a kind of rufous reactive dye that inclined feux rouges is made in compounding.
Dyeing Example 1：
It takes 2g to obtain reactive dark blue dyestuff according to embodiment 1-6 and is made into 330ml dye liquors with anhydrous sodium sulphate.At a constant temperature by cotton
After disseminating a period of time, a certain amount of soda ash fixation is added for a period of time, then washed, soaped, dried.GB/T is pressed respectively
Method in 3920-2008, GB/T 3922-1995 and GB/T 3921-2008 tests its colour fastness to rubbing, sun-resistant jail
It spends, washing fastness, while being compared with the M-2GE of same type orchids, Supra Navy Blue 3GF, as a result such as table 2, from knot
Fruit can be seen that reactive dark blue dyestuff provided by the invention, and every fastness ability is excellent, and dye exhausting rate degree of fixation is high, uses water
Salt dosage is few, dyeing temperature is not high energy saving, is suitable for production and promotes.
2 Dyeing Example performance of table compares
Dye level：3%
From the results, it was seen that the reactive dark blue dyeing temperature that the embodiment of the present invention 1,2 provides is 40 DEG C, dyeing
Bath raio is 1：5 than M-2GE orchids, the dye bath ratio 1 of Supra Navy Blue 3GF：20 is small by 75%, greatlys save dyeing water consumption
Up to 75%；Color fixing temperature declines 20 DEG C simultaneously, saves 30% or more energy consumption；
The reactive dark blue dyeing temperature that embodiment 3,4 provides is 60 DEG C, and the bath raio of dyeing is 1：8 more blue than M-2GE,
The dye bath ratio 1 of Supra Navy Blue 3GF：20 is small by 60%, greatlys save dyeing water consumption 60%；What embodiment 5 dyed
Bath raio is 1：5 than M-2GE orchids, the dye bath ratio 1 of Supra Navy Blue 3GF：20 is small by 75%, greatlys save dyeing water consumption
Up to 75%；
The exhaustion rate for the reactive dark blue dyeing that embodiment 1-5 is provided is 92-96% ratios M-2GE orchids, Supra Navy
Blue 3GF80-82% high 12-20%, reactive dark blue degree of fixation are 85-90% ratios M-2GE orchids, Supra Navy Blue 3GF
71% and 68% high 20-35%, greatly reduce dyeing waste-water 40%；
The reactive dark blue dyeing items fastness ability that embodiment 1-5 is provided is excellent, especially (dry) ratio of crock fastness
M-2GE is blue, Supra Navy Blue 3GF improve 1-2 grades, crock fastness (wet) blue, Supra Navy Blue than M-2GE
3GF improves 1-2 grades, and sunlight fastness ratio M-2GE is blue, Supra Navy Blue 3GF improve 2-3 grades, washing fastness ratio M-2GE
Blue, Supra Navy Blue 3GF improve 1-2 grades.
Dyeing Example 2：
Brownish black, rufous reactive dye and anhydrous sodium sulphate that 2g is obtained according to embodiment 9-14 is taken to be made into 330ml dye liquors.
After cotton is disseminated a period of time under constant temperature, a certain amount of soda ash fixation is added for a period of time, then washed, soaped, dried.
Respectively its rub resistance color jail is tested by the method in GB/T 3920-2008, GB/T 3922-1995 and GB/T 3921-2008
Degree, sunlight fastness, washing fastness, while being compared with the brownish black of same type, rufous reactive dye, as a result such as table 2,
From the results, it was seen that brownish black provided by the invention, rufous reactive dye, every fastness ability is excellent, and dyeing is used with water
Salt amount is few, solubility, exhaustion rate, degree of fixation are high, is suitable for promoting production.
3 Dyeing Example of table (brownish black reactive dye) performance compares
Dye level：3%
From the results, it was seen that the bath raio for the brownish black reactive dyeing that the embodiment of the present invention 9,10 provides is 1：5 ratios
The dye bath ratio 1 of active black M-2R, active ash M-4R：20 is small by 75%, greatlys save dyeing water consumption up to 75%；
The exhaustion rate for the brownish black reactive dyeing that embodiment 9,10 provides is the black M-2R of 92-94% specific activities, activity
Grey M-4R high 12-18%, degree of fixation are the 60% and 65% high 35-50% of the black M-2R of 88-90% specific activities, active ash M-4R,
Greatly reduce dyeing waste-water 35-50%；
The brownish black reactive dyeing items fastness ability that embodiment 9,10 provides is excellent, especially crock fastness (dry)
The black M-2R of specific activity, active ash M-4R improve 1-2 grades, and the black M-2R of crock fastness (wet) specific activity, active ash M-4R improve 1-2
Grade, the black M-2R of sunlight fastness specific activity, active ash M-4R improve 2 grades, and the black M-2R of washing fastness specific activity, activity ash M-4R are carried
It is 2 grades high.
4 Dyeing Example of table (brown, rufous reactive dye) performance compares
Dye level：3%
From the results, it was seen that brown, the bath raio of rufous reactive dyeing that 11-14 of the embodiment of the present invention is provided are
1：The dye bath ratio 1 of the reddish brown K-B3R of 5 specific activities, active palm fibre K-GR：20 is small by 75%, greatlys save dyeing water consumption up to 75%；
Brown, the exhaustion rate of rufous reactive dyeing of embodiment 11-14 offers are the reddish brown K- of 92-96% specific activities
The 80% high 15-20% of B3R, active palm fibre K-GR, degree of fixation is the reddish brown K-B3R of 82-90% specific activities, activity palm fibre K-GR 60%
With 54% high 35-67%, greatly reduce dyeing waste-water 35-67%；
The brown of embodiment 11-14 offers, rufous reactive dyeing items fastness ability are excellent, especially friction jail
Spend the reddish brown K-B3R of (dry) specific activity, active palm fibre K-GR improves 1-2 grades, the reddish brown K-B3R of crock fastness (wet) specific activity, activity palm fibre
K-GR improves 1-2 grades, and the reddish brown K-B3R of sunlight fastness specific activity, active palm fibre K-GR improve 2 grades, and washing fastness specific activity is reddish brown
K-B3R, active palm fibre K-GR improve 2 grades.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
Understanding without departing from the principles and spirit of the present invention can carry out these embodiments a variety of variations, modification, replace
And modification, the scope of the present invention is defined by the appended.
Claims (5)
1. a kind of reactive dark blue dyestuff, is selected from following compounds：
Wherein, M Na.
2. application of the reactive dark blue dyestuff described in claim 1 in scrim printing and dyeing.
3. reactive dark blue dyestuff described in claim 1 is in the dip dyeing of fibre cotton, fiber crops or synthetic cotton, pad dyeing or ink-jet printed
Application in terms of dyeing.
4. a kind of dye composite, it is with the activity of structure shown in reactive dark blue dyestuff described in claim 1 and general formula (one)
Crimson is main active, and mass ratio between the two is 55~95：5~45,
Wherein,
A1To have-SO3M or-SO2C2H4OSO3The monosubstituted or polysubstituted phenyl or naphthyl of M substituent groups；
D1For substituted or non-substituted phenyl, substituent group is selected from-SO3M or C1~3Alkyl,
M is Na.
5. dye composite according to claim 4, wherein reactive dark blue dyestuff described in claim 1 and general formula (one)
The mass ratio of the active deep red dyestuff of shown structure is 60~90：10~40；Wherein, A1Selected from following group：
D1Selected from following group：
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101817994A (en) * | 2009-11-16 | 2010-09-01 | 天津德凯化工股份有限公司 | Active dark blue dye |
| CN102504582A (en) * | 2011-09-28 | 2012-06-20 | 吴江桃源染料有限公司 | Reactive dark blue bisazo dye and preparation method thereof |
| CN103443073A (en) * | 2011-04-07 | 2013-12-11 | 亨斯迈先进材料（瑞士）有限公司 | Fibre-reactive dyes, their preparation and their use |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101817994A (en) * | 2009-11-16 | 2010-09-01 | 天津德凯化工股份有限公司 | Active dark blue dye |
| CN103443073A (en) * | 2011-04-07 | 2013-12-11 | 亨斯迈先进材料（瑞士）有限公司 | Fibre-reactive dyes, their preparation and their use |
| CN102504582A (en) * | 2011-09-28 | 2012-06-20 | 吴江桃源染料有限公司 | Reactive dark blue bisazo dye and preparation method thereof |
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