CN107936614A - A kind of emerald green pyrazolone reactive dye compound of high solarization and its preparation method and application - Google Patents
A kind of emerald green pyrazolone reactive dye compound of high solarization and its preparation method and application Download PDFInfo
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- CN107936614A CN107936614A CN201711138807.1A CN201711138807A CN107936614A CN 107936614 A CN107936614 A CN 107936614A CN 201711138807 A CN201711138807 A CN 201711138807A CN 107936614 A CN107936614 A CN 107936614A
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- pyrazolone
- reactive dye
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- 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
- C09B62/517—Porphines; Azaporphines
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- 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
- D06P1/382—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 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
- 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
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- 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
- D06P3/663—Natural or regenerated cellulose using reactive dyes reactive group directly attached to heterocyclic group
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- 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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Abstract
The invention discloses a kind of high emerald green pyrazolone reactive dye compound of solarization and its preparation method and application, which has a following general structure (I), a+b+c=3.5, wherein, CuPc, M, n, X, R1、R2、R3、R4、R5And R6Definition is as noted in the discussion.Present invention also offers a kind of preparation method of reactive dye compound.Using the emerald green pyrazolone reactive dye compound of high solarization made from the method for the present invention, its intramolecular contains yellow and the double chromogens of blueness, can be directly realized by intramolecular color matching, thoroughly solves a series of problems that dyestuff compounding can be run into；And sunlight fastness excellent performance, application effect is good, has preferable development prospect.
Description
Technical field
The invention belongs to dyestuff and its preparing technical field, is related to pair containing yellow and blueness that a kind of intramolecular is matched colors
Emerald green pyrazolone reactive dye compound of high solarization of chromogen and its preparation method and application.
Background technology
Can be obtained by the blending of reactive brilliant yellow and reactive turquoise blue it is bright-coloured emerald green, and through to cellulose fibres such as cottons
The bright color of dyed fabric is found after being dyed, tone is soft, deep to be favored by consumers in general.However, in reality
But occur many problems in production application.Since these green colouring materials are mostly by two or three of dyestuff blending, molten
Xie Xing, to the substantivity of fiber, the reactivity for meeting alkali fixation etc. there are many differences, be easy to cause form and aspect stability it is poor,
Uneven dyeing, the end to end poor quality problems such as big.For using copper phthalocyanine for the Turquoise blue reactive dye of parent, due to its molecule
Amount is big, and diffusion in the fibre is poor, from the problems such as compatibility is poor often occurs during different weld colorant match
(bibliography：Compatibility [J] that Yang Xiaohong reactive turquoise blues spell dye with active yellow prints and dyes, 2007,33 (14):18-21.)；
In stamp, its color and luster also can change (bibliography with the change of stamp mode, printing machine speed, drying and fixed condition：
Discussion [J] the dyestuffs of the emerald green color and luster colorant match compatibility of Hu Pingfan activity and dyeing, 1983 (1):58-61.).Therefore, green dye
The synthesis of material and application process still need to further inquire into.
The content of the invention
The present invention proposes a kind of high emerald green pyrazolone reactive dye of solarization to solve the above problem of the prior art
Compound and its preparation method and application.
The emerald green pyrazolone reactive dye compound of high solarization provided by the present invention, the Huang contained by its intramolecular
Color and the double chromogens of blueness, can be directly realized by intramolecular color matching, thoroughly solve a series of problems caused by dyestuff blending.Together
When, due to introducing the pyrazolone with high light fastness in molecule, the light fastness of dyestuff can be effectively improved, clothes and/
Or other textiles, there is good development potentiality especially in curtain, automotive interior material.
To achieve the above object, the present invention uses following technical scheme：
The first aspect of the invention is to provide a kind of emerald green pyrazolone reactive dye compound of high solarization, has such as
Lower structure leads to formula (I)：
Wherein：
Shown in structure such as formula (II) representated by CuPc；
A+b+c=3.5；
N is selected from 2,3 and 4 integer；
M is selected from H, Na and K；
R1Selected from-H ,-OCH3With-SO2Y；R2Selected from-SO2Y and-H；Wherein, Y is selected from-CH2CH2OSO3M ,-CH=CH2With-
CH2CH2OH；
R3Selected from-H ,-SO3M、-OCH3,-COOM and-OH；
X is selected from-Cl and-F；
R4Selected from-N=N-R7With-SO3M；R5Selected from-SO3M and-N=N-R7；Wherein, R7Selected from the knot shown in formula (III)
Structure；
R6Selected from H and-SO3M。
The second aspect of the invention is to provide a kind of preparation of the emerald green pyrazolone reactive dye compound of high solarization
Method, includes the following steps：
(a) chlorosulfonation
At 40 DEG C, copper phthalocyanine powder is added slowly in chlorosulfonic acid, is warming up to 135~140 DEG C after stirring 30min, dimension
Hold reaction 3h；80 DEG C are cooled to, and thionyl chloride is added dropwise in 2h, then is warming up to 90 DEG C, keeps the temperature 2h；Room is down to after reaction
Temperature, is poured into frozen water while stirring, separates out precipitation；Stand, filtering, filter cake is washed till neutrality with frozen water, obtains copper phthalocyanine sulphonyl
Chlorine filter cake, it is spare；
(b) primary condensation reaction
Diamino benzene sulfonic acid derivative is dissolved in water, it is 6 to adjust pH value, then carries out primary condensation with Striazine derivative
Reaction, controls temperature and pH value, obtains a contracting thing solution after reaction；
(c) diazo-reaction
The contracting thing solution for maintaining step (b) is 0~5 DEG C, and adds concentrated hydrochloric acid, and sodium nitrite in aqueous solution is then added dropwise,
Carry out diazo-reaction；After reaction, sulfamic acid is added, obtains diazonium salt solution；
(d) coupling reaction
Pyrazolone derivative is dissolved in water, and adjusts pH value as 7~8, then the diazonium salt solution dropwise addition by step (c)
Into the pyrazolone derivative of dissolving, it is 7~8 to keep pH value, and temperature control is reacted 1~2h, be coupled at 5~10 DEG C
Solution；
(e) consecutive condensation
Add water in aliphatic diamine, and be 6~7 with 10% dilute hydrochloric acid adjusting pH value, then the idol of a dropping step (d)
Close in solution, pH value keeps 6~7, and reaction temperature is 40~45 DEG C, reacts 1.5h, obtains two contracting things solution；
(f) condensation reaction three times
Add water to be beaten the copper phthalocyanine sulfonic acid chloride filter cake of step (a), and adjust pH value as 6~7, then addition β-sulphur thereto
The two contracting things solution of perester radical ethyl sulfone derivative and step (e), reaction temperature are 40~45 DEG C, and pH value keeps 6~7, reaction 7
~8h；After reaction, through saltouing, filter, filtration cakes torrefaction, finally obtain the Gao containing copper phthalocyanine and the double chromogens of pyrazolone
Shine emerald green pyrazolone reactive dye compound.
Further, the diamino benzene sulfonic acid derivative in step (b) be selected from 2,4- diamino benzene sulfonic acids, m-phenylene diamine (MPD)-
One kind in 4,6- disulfonic acids and 2,5- diamino benzene sulfonic acids.
Further, the one kind of the Striazine derivative in step (b) in Cyanuric Chloride and cyanuric fluoride.
It is further preferred that when the Striazine derivative in step (b) is Cyanuric Chloride, step (b) is specially：Trimerization
Chlorine cyanogen and trash ice are in 0 DEG C of mashing；Diamino benzene sulfonic acid derivative is dissolved in water, and it is 6 to adjust pH value, is cooled to 0~5 DEG C,
Then add in Cyanuric Chloride, it is 4~5 to keep pH value, reacts 2~3h, obtains one contracting thing solution of dichloro s-triazine type.
It is further preferred that when the Striazine derivative in step (b) is cyanuric fluoride, step (b) is specially：By two
Amino phenyl sulfonyl acid derivative is dissolved in water, and it is 6 to adjust pH value, is cooled to -5~0 DEG C, then cyanuric fluoride is added dropwise, and keeps pH value
For 4~5,30min is reacted, obtains one contracting thing solution of difluoro s-triazine type.
Further, the pyrazolone derivative in step (d) is selected from 1- (4 '-sulfonic group phenyl) -3- methyl -5- pyrazoles
Quinoline ketone, 1- (2 ', 5 '-two chloro- 4 '-sulfonic group phenyl) -3- methyl -5- pyrazolones, 1- (4 '-sulfonic group phenyl) -3- carboxyls -
One kind in 5- pyrazolones mono-sodium salt and 1- [4- (2- sulfate group ethyls sulfuryl) phenyl] -3- methyl -5- pyrazolones.
Further, the aliphatic diamine in step (e) is selected from ethylenediamine, 1,3- propane diamine and Putriscine
It is a kind of.
Further, the beta-sulfuric ester base ethyl sulfone derivative in step (f) is selected from 4- (beta-sulfuric ester base ethyl sulfuryl)
Aniline, 4- (beta-sulfuric ester base ethyl sulfuryl) aniline -2- sulfonic acid, 2- methoxyl groups -4- (beta-sulfuric ester base ethyl sulfuryl) aniline, 2,
5- dimethoxy-4 's-(beta-sulfuric ester base ethyl sulfuryl) aniline, 2- amino -5- (beta-sulfuric ester base ethyl sulfuryl) benzoic acid, 3-
(beta-sulfuric ester base ethyl sulfuryl) aniline, 3- (beta-sulfuric ester base ethyl sulfuryl) aniline -6- sulfonic acid, 2- methoxyl groups -5- (β-sulfuric acid
Ester group ethyl sulfuryl) one kind in aniline and 2- hydroxyls -5- (beta-sulfuric ester base ethyl sulfuryl) aniline.
The third aspect of the invention is to provide a kind of emerald green pyrazolone reactive dye compound of high solarization
Application in the working process of textile.
Further, the emerald green pyrazolone reactive dye compound of the high solarization passes through the technology hand such as dyeing, stamp
Working processes of the Duan Shixian to textile.
The present invention uses above-mentioned technical proposal, compared with prior art, has the following technical effect that：
Emerald green pyrazolone reactive dye compound of high solarization of the present invention and preparation method thereof, is contained by intramolecular
Yellow and the double chromogens of blueness, intramolecular color matching can be directly realized by, thoroughly solve that dyestuff compounding can run into a series of asks
Topic；Simultaneously as introduce the pyrazolone with high light fastness in molecule, sunlight fastness excellent performance, application effect is good
It is good, in clothes and/or other textiles, especially there is preferable development prospect in curtain, automotive interior material.
Brief description of the drawings
Fig. 1 is Fu of the emerald green pyrazolone reactive dye compound (I-6A) of high solarization prepared by the embodiment of the present invention 6
In leaf infrared spectrum spectrogram；
Fig. 2 is the purple of the emerald green pyrazolone reactive dye compound (I-6A) of high solarization prepared by the embodiment of the present invention 6
Outside-visible absorption spectra figure.
Embodiment
The present invention is described in more detail below by specific embodiment, for a better understanding of the present invention,
But following embodiments are not intended to limit the scope of the invention.
To more fully understand the present invention, the dye structure in embodiment is represented in the form of free acid, but its actual shape
Formula is probably alkali metal salt, such as sodium salt, sylvite；Sulfuryl structure division is described in the form of β-ethyl sulfonyl sulfate, but its
May also exist with β-vinyl sulfone(RemzaolHuo Xingranliaohuoxingjituan) or beta-hydroxyethyl sulfone form；Aliphatic diamine used in embodiment is ethylenediamine, but
Can also be 1,3- propane diamine and/or Putriscine, dye structure and so on.
Embodiment 1
Emerald green pyrazolone reactive dye compound of a kind of high solarization and preparation method thereof is present embodiments provided, specifically
Step is as follows：
(a) chlorosulfonation：At 40 DEG C, 0.100mol copper phthalocyanines powder is slowly added into 220mL (in half an hour)
In chlorosulfonic acid, 135~140 DEG C are warming up to after stirring 30min, maintains reaction 3h；80 DEG C are cooled to, and is added dropwise in 2h
0.504mol thionyl chlorides, then 90 DEG C are warming up to, keep the temperature 2h；Room temperature is down to after reaction, is poured into while stirring in frozen water,
Separate out precipitation；Stand, filtering, filter cake is washed till neutrality with frozen water, obtains copper phthalocyanine sulfonic acid chloride filter cake, spare；
(b) primary condensation reaction：0.101mol Cyanuric Chlorides and 60g trash ices are beaten 30min at 0 DEG C；0.100mol 2,4-
Diamino benzene sulfonic acid, adds 160mL water to dissolve, and it is 6 to adjust its pH value with 10% dilute hydrochloric acid, is then added in Cyanuric Chloride, is protected
It is 4~5 to hold pH value, reacts 2~3h, obtains one contracting thing solution of dichloro s-triazine type；
(c) diazo-reaction：The contracting thing solution for maintaining step (b) is 0~5 DEG C, and adds 13mL concentrated hydrochloric acids；Will
0.106mol sodium nitrites are configured to 40% aqueous solution, are slowly added into a contracting thing, with Congored test paper and starch iodate
Potassium test paper detects, and equal moment becomes blue.After reacting 1.5h, sulfamic acid is added to decompose excessive nitrous acid, it is molten to obtain diazol
Liquid；
(d) coupling reaction：0.100mol 1- (4 '-sulfonic group phenyl) -3- methyl -5- pyrazolones are dissolved in 150mL water
In, and it is 7~8 to adjust pH value with 20% sodium carbonate liquor；The diazonium salt solution of step (c) is added dropwise to the pyrazolone of dissolving
In, it is 7~8 to keep pH value, and temperature control reacts 1~2h, obtain Coupling Solution at 5~10 DEG C；
(e) consecutive condensation：Add 10mL water in 10mL ethylenediamines, and it is 6~7 to adjust pH value with 10% dilute hydrochloric acid；
The Coupling Solution of a dropping step (d) wherein, pH value keep 6~7, and reaction temperature is 40~45 DEG C, reacts 1.5h, obtains two contractings
Thing solution；
(f) condensation reaction three times：Add 200mL water into the copper phthalocyanine sulfonic acid chloride filter cake of step (a), be beaten 30min, be used in combination
It is 6~7 that 20% sodium carbonate liquor, which adjusts pH value, then adds 0.100mol 4- (beta-sulfuric ester base ethyl sulfuryl) aniline thereto
With the two contracting things solution of step (e), reaction temperature is 40~45 DEG C, and pH value maintains 6~7, reacts 7~8h；After reaction,
Through saltouing, filter, filtration cakes torrefaction, finally obtain the emerald green pyrazolone of high solarization containing copper phthalocyanine and the double chromogens of pyrazolone
Shown in formula (I-1A) in reactive dye compound, structure such as table 1.
Embodiment 2~9
Embodiment each provides emerald green pyrazolone reactive dye compound of a kind of high solarization and preparation method thereof, tool
Body step is similar to Example 1.Difference lies in：4- (beta-sulfuric ester base ethyl sulfuryl) aniline in step (f) is changed to respectively
4- (beta-sulfuric ester base ethyl sulfuryl) aniline -2- sulfonic acid, 2- methoxyl groups -4- (beta-sulfuric ester base ethyl sulfuryl) aniline, 2,5- bis-
Methoxyl group -4- (beta-sulfuric ester base ethyl sulfuryl) aniline, 2- amino -5- (beta-sulfuric ester base ethyl sulfuryl) benzoic acid, 3- (β-sulphur
Perester radical ethyl sulfuryl) aniline, 3- (beta-sulfuric ester base ethyl sulfuryl) aniline -6- sulfonic acid, 2- methoxyl groups -5- (beta-sulfuric ester bases
Ethyl sulfuryl) aniline and 2- hydroxyls -5- (beta-sulfuric ester base ethyl sulfuryl) aniline, dosage is 0.100mol；Through step (f),
The emerald green pyrazolone reactive dye compound of high solarization containing copper phthalocyanine and the double chromogens of pyrazolone is finally obtained, structure is such as
Shown in formula (I-2A)~formula (I-9A) in table 1.
The high solarization prepared using Fourier infrared spectrograph and uv-visible absorption spectra instrument to embodiment 6 is emerald green
Pyrazolone reactive dye compound (I-6A) carries out spectrum test, its result difference is as depicted in figs. 1 and 2.
Embodiment 10~18
Embodiment each provides emerald green pyrazolone reactive dye compound of a kind of high solarization and preparation method thereof, tool
Body step is similar with 1~embodiment of embodiment 9.Difference lies in：2,4- diamino benzene sulfonic acids in step (b) are changed to isophthalic two
Amine -4,6- disulfonic acid, dosage are 0.100mol；Through step (f), finally obtain containing copper phthalocyanine and the double chromogens of pyrazolone
The high emerald green pyrazolone reactive dye compound of solarization, shown in formula (I-10A)~formula (I-18A) in structure such as table 1.
Embodiment 19~27
Embodiment each provides emerald green pyrazolone reactive dye compound of a kind of high solarization and preparation method thereof, tool
Body step is similar with 1~embodiment of embodiment 9.Difference lies in：2,4- diamino benzene sulfonic acids in step (b) are changed to 2,5- diaminos
Base benzene sulfonic acid, dosage are 0.100mol；Through step (f), the Gao containing copper phthalocyanine and the double chromogens of pyrazolone is finally obtained
Emerald green pyrazolone reactive dye compound is shone, shown in formula (I-19A)~formula (I-27A) in structure such as table 1.
Embodiment 28~54
Embodiment each provides emerald green pyrazolone reactive dye compound of a kind of high solarization and preparation method thereof, tool
Body step is similar with 1~embodiment of embodiment 27.Difference lies in：1- (4 '-sulfonic group phenyl) -3- methyl -5- in step (d)
Pyrazolone is changed to 1- (2 ', 5 '-two chloro- 4 '-sulfonic group phenyl) -3- methyl -5- pyrazolones, and dosage is 0.100mol；
Through step (f), the emerald green pyrazolone reactive dye of high solarization containing copper phthalocyanine and the double chromogens of pyrazolone are finally obtained
Shown in formula (I-1B)~formula (I-27B) in compound, structure such as table 1.
Embodiment 55~81
Embodiment each provides emerald green pyrazolone reactive dye compound of a kind of high solarization and preparation method thereof, tool
Body step is similar with 1~embodiment of embodiment 27.Difference lies in：1- (4 '-sulfonic group phenyl) -3- methyl -5- in step (d)
Pyrazolone is changed to 1- (4 '-sulfonic group phenyl) -3- carboxyl -5- pyrazolone mono-sodium salts, and dosage is 0.100mol；Through step
(f), the emerald green pyrazolone reactive dye compound of high solarization containing copper phthalocyanine and the double chromogens of pyrazolone, knot are finally obtained
Shown in formula (I-1C)~formula (I-27C) in structure such as table 1.
Embodiment 82~108
Embodiment each provides emerald green pyrazolone reactive dye compound of a kind of high solarization and preparation method thereof, tool
Body step is similar with 1~embodiment of embodiment 27.Difference lies in：1- (4 '-sulfonic group phenyl) -3- methyl -5- in step (d)
Pyrazolone is changed to 1- [4- (2- sulfate group ethyls sulfuryl) phenyl] -3- methyl -5- pyrazolones, and dosage is
0.100mol；Through step (f), finally obtain the emerald green pyrazolone of high solarization containing copper phthalocyanine and the double chromogens of pyrazolone and live
Property dye composition, shown in formula (I-1D)~formula (I-27D) in structure such as table 1.
Embodiment 108~216
Embodiment each provides emerald green pyrazolone reactive dye compound of a kind of high solarization and preparation method thereof, tool
Body step is similar with 1~embodiment of embodiment 108.Difference lies in step (b) to be：Diamino benzene sulfonic acid derivative is added into 160mL
Water dissolves, and it is 6 to adjust pH value, is cooled to -5~0 DEG C, then 0.103mol cyanuric fluorides are added dropwise, and holding pH value is 4~5 scopes, instead
30min is answered, obtains one contracting thing solution of difluoro s-triazine type；The reaction temperature of step (d) is 0~5 DEG C；The reaction temperature of step (e)
Spend for 15~20 DEG C；Through step (f), the emerald green pyrazoline of high solarization containing copper phthalocyanine and the double chromogens of pyrazolone is finally obtained
Formula (I-1E)~formula (I-27E), formula (I-1F)~formula (I-27F) in ketone reactive dye compound, structure such as table 1, formula (I-
Shown in 1G)~formula (I-27G) and formula (I-1H)~formula (I-27H).
Table 1
Application examples
The emerald green pyrrole of high solarization respectively prepared by embodiment 1,9,29,37,57,85,113,141,169,197 and 216
Oxazoline ketone reactive dye compound be applied to cotton fabric dyeing in as application examples 1,9,29,37,57,85,113,141,
169th, 197 and 216, formula for dye liquor and dyeing are as follows：Fabric 2.5g, dyestuff 2% (o.m.f), sodium chloride 60g/L, soda ash
15g/L, bath raio 1: 20；During dyeing, fabric room temperature enters dye, and 60 DEG C are warming up in 20min, adds soda ash fixation after dyeing 20min, protects
Warm 40min；After the completion of dyeing, fabric is taken out with cold water flush, then soap (soaping agent 2g/L, 1: 20,98 DEG C of bath raio ×
10min), cold water wash, drying, finally obtain emerald green dyed fabric.
Carry out colour fastness to rubbing (ISO 105-X12), washing fastness (ISO 105-C06 respectively to dyed fabric
(C1S)) tested with sunlight fastness (ISO 105-B02 (Method 2)), the results are shown in Table 2 for every fastness.
Comparative example
By reactive turquoise blue G (Remazol Turquoise Blue G) and gorgeous Huang GL (the Remazol Brilliant of Remazol
Yellow GL) using mass ratio as 10: 3 carry out blendings, be then applied in the dyeing of cotton fabric, specific formula, technique and
Color fastness test is identical with Application Example, and the results are shown in Table 2 for every color fastness of combination dyeing fabric.
Table 2
From the color fastness test result of above-mentioned table 2, the high emerald green pyrazolone activity dye of solarization of the present invention
Expecting compound, not only colour fastness to rubbing and washing fastness are excellent, suitable with comparative example or better than comparative example, and its is sun-resistant
Fastness ability is substantially better than comparative example, while tinctorial yield is high, and cost-effective, application effect is good, in clothes and/or other weavings
Product, especially there is preferable development prospect in curtain, automotive interior material.
The specific embodiment of the present invention is described in detail above, but it is intended only as example, it is of the invention and unlimited
It is formed on particular embodiments described above.To those skilled in the art, it is any to the equivalent modifications that carry out of the present invention and
Substitute also all among scope of the invention.Therefore, the impartial conversion made without departing from the spirit and scope of the invention and
Modification, all should be contained within the scope of the invention.
Claims (10)
1. a kind of emerald green pyrazolone reactive dye compound of high solarization, has following general structure (I)：
Wherein：
Shown in structure such as formula (II) representated by CuPc；
A+b+c=3.5；
N is selected from 2,3 and 4 integer；
M is selected from H, Na and K；
R1Selected from-H ,-OCH3With-SO2Y；R2Selected from-SO2Y and-H；Wherein, Y is selected from-CH2CH2OSO3M ,-CH=CH2With-
CH2CH2OH；
R3Selected from-H ,-SO3M、-OCH3,-COOM and-OH；
X is selected from-Cl and-F；
R4Selected from-N=N-R7With-SO3M；R5Selected from-SO3M and-N=N-R7；Wherein, R7Selected from the structure shown in formula (III)；
R6Selected from H and-SO3M。
2. a kind of preparation method of the emerald green pyrazolone reactive dye compound of high solarization, it is characterised in that including following step
Suddenly：
(a) chlorosulfonation
At 40 DEG C, copper phthalocyanine powder is added slowly in chlorosulfonic acid, 135~140 DEG C are warming up to after stirring 30min, remains anti-
Answer 3h；80 DEG C are cooled to, and thionyl chloride is added dropwise in 2h, then is warming up to 90 DEG C, keeps the temperature 2h；Room temperature is down to after reaction,
It is poured into while stirring in frozen water, separates out precipitation；Stand, filtering, filter cake is washed till neutrality with frozen water, obtains the filter of copper phthalocyanine sulfonic acid chloride
Cake, it is spare；
(b) primary condensation reaction
Diamino benzene sulfonic acid derivative is dissolved in water, it is 6 to adjust pH value, then anti-with Striazine derivative progress primary condensation
Should, temperature and pH value are controlled, obtains a contracting thing solution after reaction；
(c) diazo-reaction
The contracting thing solution for maintaining step (b) is 0~5 DEG C, and adds concentrated hydrochloric acid, and sodium nitrite in aqueous solution is then added dropwise, and is carried out
Diazo-reaction；After reaction, sulfamic acid is added, obtains diazonium salt solution；
(d) coupling reaction
Pyrazolone derivative is dissolved in water, and adjusts pH value as 7~8, then the diazonium salt solution of step (c) is added dropwise to molten
In the pyrazolone derivative of solution, it is 7~8 to keep pH value, and temperature control reacts 1~2h, obtain Coupling Solution at 5~10 DEG C；
(e) consecutive condensation
Add water in aliphatic diamine, and it is 6~7 to adjust pH value with 10% dilute hydrochloric acid, then the coupling of a dropping step (d) is molten
In liquid, pH value keeps 6~7, and reaction temperature is 40~45 DEG C, reacts 1.5h, obtains two contracting things solution；
(f) condensation reaction three times
Water is added to be beaten the copper phthalocyanine sulfonic acid chloride filter cake of step (a), and it is 6~7 to adjust pH value, then beta-sulfuric ester is added thereto
The two contracting things solution of base ethyl sulfone derivative and step (e), reaction temperature are 40~45 DEG C, pH value holding 6~7, reaction 7~
8h；After reaction, through saltouing, filter, filtration cakes torrefaction, finally obtain the high solarization containing copper phthalocyanine and the double chromogens of pyrazolone
Emerald green pyrazolone reactive dye compound.
3. the preparation method of the emerald green pyrazolone reactive dye compound of high solarization according to claim 2, its feature
Be, the diamino benzene sulfonic acid derivative in step (b) be selected from 2,4- diamino benzene sulfonic acids, m-phenylene diamine (MPD) -4,6- disulfonic acid and
One kind in 2,5- diamino benzene sulfonic acids.
4. the preparation method of the emerald green pyrazolone reactive dye compound of high solarization according to claim 2, its feature
It is, the one kind of the Striazine derivative in step (b) in Cyanuric Chloride and cyanuric fluoride.
5. preparation method according to claim 4, it is characterised in that when the Striazine derivative in step (b) is trimerization
During chlorine cyanogen, step (b) is specially：Cyanuric Chloride and trash ice are in 0 DEG C of mashing；Diamino benzene sulfonic acid derivative is dissolved in water, and
It is 6 to adjust pH value, is cooled to 0~5 DEG C, then adds in Cyanuric Chloride, and it is 4~5 to keep pH value, reacts 2~3h, obtains dichloro
One contracting thing solution of s-triazine type.
6. preparation method according to claim 4, it is characterised in that when the Striazine derivative in step (b) is trimerization
During fluorine cyanogen, step (b) is specially：Diamino benzene sulfonic acid derivative is dissolved in water, and it is 6 to adjust pH value, is cooled to -5~0
DEG C, then cyanuric fluoride is added dropwise, it is 4~5 to keep pH value, reacts 30min, obtains one contracting thing solution of difluoro s-triazine type.
7. the preparation method of the emerald green pyrazolone reactive dye compound of high solarization according to claim 2, its feature
Be, the pyrazolone derivative in step (d) be selected from 1- (4 '-sulfonic group phenyl) -3- methyl -5- pyrazolones, 1- (2 ',
5 '-two chloro- 4 '-sulfonic group phenyl) -3- methyl -5- pyrazolones, 1- (4 '-sulfonic group phenyl) -3- carboxyl -5- pyrazolones
One kind in mono-sodium salt and 1- [4- (2- sulfate group ethyls sulfuryl) phenyl] -3- methyl -5- pyrazolones.
8. the preparation method of the emerald green pyrazolone reactive dye compound of high solarization according to claim 2, its feature
It is, the aliphatic diamine in step (e) is selected from one kind in ethylenediamine, 1,3- propane diamine and Putriscine.
9. the preparation method of the emerald green pyrazolone reactive dye compound of high solarization according to claim 2, its feature
It is, the beta-sulfuric ester base ethyl sulfone derivative in step (f) is selected from 4- (beta-sulfuric ester base ethyl sulfuryl) aniline, 4- (β-sulphur
Perester radical ethyl sulfuryl) aniline -2- sulfonic acid, 2- methoxyl groups -4- (beta-sulfuric ester base ethyl sulfuryl) aniline, 2,5- dimethoxys -
4- (beta-sulfuric ester base ethyl sulfuryl) aniline, 2- amino -5- (beta-sulfuric ester base ethyl sulfuryl) benzoic acid, 3- (beta-sulfuric ester bases
Ethyl sulfuryl) aniline, 3- (beta-sulfuric ester base ethyl sulfuryl) aniline -6- sulfonic acid, 2- methoxyl groups -5- (beta-sulfuric ester base ethyl sulfones
Base) one kind in aniline and 2- hydroxyls -5- (beta-sulfuric ester base ethyl sulfuryl) aniline.
10. a kind of high emerald green pyrazolone reactive dye compound of solarization as claimed in claim 1 is in the processing of textile
Application in processing.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1003786A (en) * | 1961-02-28 | 1965-09-08 | Ciba Ltd | Phthalocyanine dyestuffs and process for their manufacture |
| JPS5465729A (en) * | 1977-10-18 | 1979-05-26 | Cassella Farbwerke Mainkur Ag | Water soluble fiber reactive green phthalocyanineeazo dye |
| JPS6187759A (en) * | 1984-09-06 | 1986-05-06 | Nippon Kayaku Co Ltd | Water-soluble phthalocyanine compound and method for coloring surface film of substrate by using the same |
| TW213944B (en) * | 1990-08-15 | 1993-10-01 | Ici Plc | |
| CN101580646A (en) * | 2008-05-13 | 2009-11-18 | 珠海纳思达企业管理有限公司 | Weather-proof dye and application thereof |
-
2017
- 2017-11-16 CN CN201711138807.1A patent/CN107936614A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1003786A (en) * | 1961-02-28 | 1965-09-08 | Ciba Ltd | Phthalocyanine dyestuffs and process for their manufacture |
| JPS5465729A (en) * | 1977-10-18 | 1979-05-26 | Cassella Farbwerke Mainkur Ag | Water soluble fiber reactive green phthalocyanineeazo dye |
| JPS6187759A (en) * | 1984-09-06 | 1986-05-06 | Nippon Kayaku Co Ltd | Water-soluble phthalocyanine compound and method for coloring surface film of substrate by using the same |
| TW213944B (en) * | 1990-08-15 | 1993-10-01 | Ici Plc | |
| CN101580646A (en) * | 2008-05-13 | 2009-11-18 | 珠海纳思达企业管理有限公司 | Weather-proof dye and application thereof |
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