CN106893353A - A kind of application of monoazos - Google Patents
A kind of application of monoazos Download PDFInfo
- Publication number
- CN106893353A CN106893353A CN201510956444.7A CN201510956444A CN106893353A CN 106893353 A CN106893353 A CN 106893353A CN 201510956444 A CN201510956444 A CN 201510956444A CN 106893353 A CN106893353 A CN 106893353A
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- Prior art keywords
- compound
- application
- dyeing
- monoazos
- reaction
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- 150000001875 compounds Chemical class 0.000 claims abstract description 59
- 238000010016 exhaust dyeing Methods 0.000 claims abstract description 9
- 229920000742 Cotton Polymers 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 238000010014 continuous dyeing Methods 0.000 claims abstract description 6
- 239000000835 fiber Substances 0.000 claims abstract description 6
- 239000000985 reactive dye Substances 0.000 claims abstract description 5
- 229940125904 compound 1 Drugs 0.000 claims description 33
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 150000002367 halogens Chemical group 0.000 claims description 10
- 239000004744 fabric Substances 0.000 claims description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 8
- 239000000460 chlorine Substances 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 239000002585 base Substances 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229920000297 Rayon Polymers 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 239000000975 dye Substances 0.000 abstract description 31
- 238000004043 dyeing Methods 0.000 abstract description 16
- 150000003839 salts Chemical class 0.000 abstract description 9
- 230000002708 enhancing effect Effects 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 4
- 229920003043 Cellulose fiber Polymers 0.000 abstract description 3
- 230000004075 alteration Effects 0.000 abstract description 3
- 108090000623 proteins and genes Proteins 0.000 abstract description 3
- 102000004169 proteins and genes Human genes 0.000 abstract description 3
- 238000010923 batch production Methods 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 description 38
- 238000006243 chemical reaction Methods 0.000 description 29
- 238000006467 substitution reaction Methods 0.000 description 24
- 238000000034 method Methods 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 18
- 239000002253 acid Substances 0.000 description 15
- 229940125782 compound 2 Drugs 0.000 description 14
- -1 N-propyl Chemical group 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000012544 monitoring process Methods 0.000 description 12
- 235000017550 sodium carbonate Nutrition 0.000 description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 description 9
- 229940126214 compound 3 Drugs 0.000 description 8
- 238000005859 coupling reaction Methods 0.000 description 7
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 239000012752 auxiliary agent Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 238000000589 high-performance liquid chromatography-mass spectrometry Methods 0.000 description 5
- 238000007639 printing Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000004753 textile Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000033228 biological regulation Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 229940125898 compound 5 Drugs 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- FHIVAFMUCKRCQO-UHFFFAOYSA-N diazinon Chemical compound CCOP(=S)(OCC)OC1=CC(C)=NC(C(C)C)=N1 FHIVAFMUCKRCQO-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910017464 nitrogen compound Inorganic materials 0.000 description 4
- 150000002830 nitrogen compounds Chemical class 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 238000001694 spray drying Methods 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 229940125773 compound 10 Drugs 0.000 description 3
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 3
- 239000010446 mirabilite Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 101100493713 Caenorhabditis elegans bath-45 gene Proteins 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 0 *C1C=CC(N)=CC1 Chemical compound *C1C=CC(N)=CC1 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- 241001270131 Agaricus moelleri Species 0.000 description 1
- 241001614291 Anoplistes Species 0.000 description 1
- 206010034960 Photophobia Diseases 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 208000013469 light sensitivity Diseases 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000009725 powder blending Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 238000010998 test method Methods 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
- C09B62/51—Monoazo dyes
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
Abstract
The invention discloses a kind of application of monoazos.The invention provides a kind of monoazos as shown in Equation 1 as reactive dye application, wherein, the compound has beautiful amber yellow, very big solubility, moderate substantivity, dye uptake and degree of fixation very high, good enhancing, the stability of extraordinary Salt And Alkali Tolerance, excellent wet colour fastness and light fastness, it is suitable in cotton, the cellulose fibres such as fiber crops or hair, exhaust dyeing on the protein fibres such as silk, continuous dyeing and stamp, it is particularly suited for tie dyeing and cold-pad-batch process dyeing, without dyeing defect, aberration phenomenon, shortcoming without difference in poor end to end and side, it is once high into dye rate.
Description
Technical field
The present invention relates to a kind of application of monoazos.
Background technology
Reactive dye are very perfect till now, either in quality quantity, or in product
Level very high has been had evolved in matter, whole chromatogram has been covered, the requirement in market has been substantially met.
Existing bright-coloured light yellow color system, has saturate feux rouges yellow, or even have again in Yellow series dyestuff
It is very gorgeous with the light yellow of fluorescence, these can meet the different needs in market.But these product
It is exactly poor light sensitivity that kind has a feature, it is impossible to meet the specific demand in market.
Also there are some to study this both at home and abroad, several patents have been delivered, wherein relatively good patent is US
Re.37004.Its precursor structure is essentially identical (such as compound 3-21) with this patent, but it inhales color
Rate does not have the height of this patent structure with degree of fixation.
Also be refer in patent CN102898867 it is such as dyestuff (I), but its solubility is very small,
Substantially without use value.
Therefore, this area needs a kind of suction color direct, very high with big solubility, moderate badly
Rate and degree of fixation, good enhancing, the stability of extraordinary Salt And Alkali Tolerance, excellent wet colour fastness
With the monoazos of light fastness.
The content of the invention
The technical problems to be solved by the invention are to overcome existing monoazos dye uptake
The defect such as the stability of, solubility low low with degree of fixation, enhancing and Salt And Alkali Tolerance is poor, and provide one kind
The application of monoazos, the compound has beautiful amber yellow, very big solubility, fits
In dye uptake direct, very high and degree of fixation, good enhancing, extraordinary Salt And Alkali Tolerance
Stability, excellent wet colour fastness and light fastness, be suitable to the cellulose fibres such as cotton, fiber crops or hair,
Exhaust dyeing, continuous dyeing and stamp on the protein fibres such as silk, are particularly suited for tie dyeing and cold pad--batch
Dyeing, without dyeing defect, aberration phenomenon, the shortcoming without difference in poor end to end and side is once high into dye rate.
The invention provides a kind of monoazos as shown in Equation 1,
Wherein, X is halogen, R1It is C1~C4Alkyl, R2、R3And R4It independently is hydrogen or alkali gold
Category.
Described halogen is the conventional halogen in this area, preferably chlorine or fluorine.
Described C1~C4Alkyl be the conventional C in this area1~C4Alkyl, for example methyl, ethyl,
N-propyl, isopropyl, normal-butyl, isobutyl group or the tert-butyl group, preferably methyl or ethyl.
Described alkali metal is the conventional alkali metal in this area, such as lithium, sodium or potassium, preferably sodium.
Present invention also offers a kind of preparation method of above-mentioned compound 1, it comprises the steps：Will
Compound 2 and compound 3 carry out substitution reaction, obtain compound 1；
Wherein, X1It is halogen (such as chlorine).
The substitution reaction that described compound 2 and described compound 3 is carried out can be to prepare monoazo class
The conventional substitution reaction in compound field, following reaction conditions specifically preferred according to the invention：In water, in fat
In the presence of alcohol APEO, under mildly acidic conditions, by described compound 2 and described chemical combination
Thing 3 carries out substitution reaction, obtains described compound 1；
In the preparation method of described compound 1, described AEO can be single to prepare
The conventional AEO in azo compound field, such as paregal O 25.
In the preparation method of described compound 1, described solutions of weak acidity can be to prepare monoazo class
The conventional acid condition in compound field, such as pH=5.5~6.5.
In the preparation method of described compound 1, the temperature of described substitution reaction can be single even to prepare
The conventional temperature of such reaction of nitrogen compound field, such as 40~45 DEG C.
In the preparation method of described compound 1, the process of described substitution reaction can be using preparation
Routine monitoring method (such as TLC, HPLC or NMR) in monoazos field is carried out
Monitoring, as reaction end when typically being disappeared with compound 2, reaction time such as 10.0~12.0h.
It is preferred that the preparation method of described compound 1 also comprises the steps：By compound 4 and change
Compound 5 carries out coupling reaction, obtains described compound 2；
Wherein, A-To prepare the anion of the conventional diazol in monoazos field, such as chlorine from
Son or sulfate ion.
The coupling reaction that described compound 4 is carried out with described compound 5 can be to prepare monoazo class
The conventional coupling reaction in compound field, following reaction conditions specifically preferred according to the invention：In water, in weak acid
Property under the conditions of, described compound 4 and described compound 5 are carried out into coupling reaction, obtain described
Compound 2；
In the preparation method of described compound 2, described solutions of weak acidity can be to prepare monoazo class
The conventional acid condition in compound field, such as pH=4.5~6.5 (again such as 5.0,6.0).
In the preparation method of described compound 2, the temperature of described coupling reaction can be single even to prepare
The conventional temperature of such reaction of nitrogen compound field, such as 5~15 DEG C (such as 10 DEG C again).
In the preparation method of described compound 2, the process of described coupling reaction can be using preparation
Routine monitoring method (such as TLC, HPLC or NMR) in monoazos field is carried out
Monitoring, as reaction end when typically being disappeared with compound 4, reaction time such as 2.0~3.0h.
It is preferred that the preparation method of described compound 1 also comprises the steps：Compound 6 is carried out
Diazo-reaction, obtains described compound 4；
The diazo-reaction that described compound 4 is carried out can be to prepare monoazos field routine
Diazo-reaction, for example, execute diazo-reaction, following reaction conditions specifically preferred according to the invention：In water,
In the presence of acid, described compound 6 and alkali metal nitrites (such as natrium nitrosum) are carried out
Diazo-reaction, obtains described compound 4；
In the preparation method of described compound 4, described acid can be to prepare monoazos neck
The conventional acid in domain, such as hydrochloric acid, sulfuric acid.
In the preparation method of described compound 4, the temperature of described diazo-reaction can be single to prepare
The conventional temperature of such reaction of azo compound field, such as 0~20 DEG C (again such as 5 DEG C, 10 DEG C).
In the preparation method of described compound 4, the process of described diazo-reaction can be using system
Routine monitoring method (such as TLC, HPLC or NMR) in standby monoazos field is entered
Row monitoring, as reaction end when typically being disappeared with compound 6, reaction time such as 3.0~5.0h (examples again
Such as 4h).
It is preferred that the preparation method of described compound 1 also comprises the steps：By compound 8 and change
Compound 7 carries out substitution reaction, obtains described compound 3；
Wherein, X2It is halogen (such as chlorine).
The substitution reaction that described compound 8 and compound 7 is carried out is to prepare monoazos field
Conventional substitution reaction, following reaction conditions specifically preferred according to the invention：In water, in fatty alcohol polyoxy second
In the presence of alkene ether, in acid condition, compound 8 and compound 7 are carried out into substitution reaction, obtained
Compound 3；
In the preparation method of described compound 3, described AEO can be single to prepare
The conventional AEO in azo compound field, such as paregal O 25.
In the preparation method of described compound 3, described acid condition can be to prepare monoazo class
The conventional acid condition in compound field, such as pH=2.0~5.0.
In the preparation method of described compound 3, the temperature of described substitution reaction can be single even to prepare
The conventional temperature of such reaction of nitrogen compound field, such as 0~5 DEG C.
In the preparation method of described compound 3, the process of described substitution reaction can be using preparation
Routine monitoring method (such as TLC, HPLC or NMR) in monoazos field is carried out
Monitoring, as reaction end when typically being disappeared with compound 8, reaction time such as 1.5~2.0h.
It is preferred that the preparation method of described compound 1 is as follows：
Present invention also offers a kind of preparation method of above-mentioned compound 1, it comprises the steps：Will
Compound 8 and compound 9 carry out substitution reaction, obtain compound 1；
Wherein, X3It is halogen (such as chlorine).
The substitution reaction that described compound 8 and compound 9 is carried out can be to prepare monoazos neck
The conventional substitution reaction in domain, following reaction conditions specifically preferred according to the invention：In water, in fatty alcohol polyoxy
In the presence of vinethene, under faintly acid to neutrallty condition, by described compound 8 and described chemical combination
Thing 9 carries out substitution reaction, obtains described compound 1；
In the preparation method of described compound 1, described AEO can be single to prepare
The conventional AEO in azo compound field, such as paregal O 25.
In the preparation method of described compound 1, described faintly acid can be single to prepare to neutrallty condition
The conventional condition in azo compound field, such as pH=6.5~7.0.
In the preparation method of described compound 1, the temperature of described substitution reaction is to prepare monoazo
The conventional temperature of such reaction of class compound field, such as 40~45 DEG C.
In the preparation method of described compound 1, the process of described substitution reaction can be using preparation
Routine monitoring method (such as TLC, HPLC or NMR) in monoazos field is carried out
Monitoring, as reaction end when typically being disappeared with compound 9, reaction time such as 8.0~10.0h.
It is preferred that the preparation method of described compound 1 also comprises the steps：By compound 2 and change
Compound 10 carries out substitution reaction, obtains described compound 9；
Wherein, X4It is halogen (such as chlorine).
The substitution reaction that described compound 2 and described compound 10 is carried out can be to prepare monoazo class
The conventional substitution reaction in compound field, following reaction conditions specifically preferred according to the invention：In water, in fat
In the presence of fat alcohol APEO, under faintly acid to neutrallty condition, by described compound 2 and institute
The compound 10 stated carries out substitution reaction, obtains described compound 9；
In the preparation method of described compound 9, described AEO can be single to prepare
The conventional AEO in azo compound field, such as paregal O 25.
In the preparation method of described compound 9, described faintly acid can be single to prepare to neutrallty condition
The conventional condition in azo compound field, such as pH=5.5~7.0.
In the preparation method of described compound 9, the temperature of described substitution reaction can be single even to prepare
The conventional temperature of such reaction of nitrogen compound field, such as 0~5 DEG C.
In the preparation method of described compound 9, the process of described substitution reaction can be using preparation
Routine monitoring method (such as TLC, HPLC or NMR) in monoazos field is carried out
Monitoring, as reaction end when typically being disappeared with compound 2, reaction time such as 4.0~5.0h.
It is preferred that the preparation method of described compound 1 also comprises the steps：By compound 4 and change
Compound 5 carries out coupling reaction, obtains described compound 2；
Wherein, A-To prepare the anion of the conventional diazol in monoazos field；Its reaction bar
Part is as previously described.
It is preferred that the preparation method of described compound 1 also comprises the steps：Compound 6 is carried out
Diazo-reaction, obtains described compound 4；Its reaction condition is as previously described；
It is preferred that the preparation method of described compound 1 is as follows：
Present invention also offers above-mentioned compound 1 as reactive dye application.
Described compound 1 is amber yellow.
Described compound 1 can be used for the exhaust dyeing of the cellulosic material containing hydroxyl or amino, continuous
The field such as dyeing or stamp.
The described cellulosic material containing hydroxyl or amino can be field of printing and dyeing it is conventional containing hydroxyl or
The cellulosic material of amino, such as cotton, viscose glue, fiber crops, silk etc. and its blend fabric.
Described exhaust dyeing can be the conventional exhaust dyeing of field of printing and dyeing, for example, with described in appropriate
Compound 1, glauber salt, soda ash are made into dye liquor, and bath raio 1: 15, in 60 DEG C of dyeing, is then washed with clear water
And acid is neutralized, then soap, hot water wash, cold water are washed, the technique such as dry can obtain the product of function admirable.
Described continuous dyeing can be the conventional continuous dyeing of field of printing and dyeing, for example, with described in appropriate
Compound 1, addition levelling agent etc. form tie dyeing liquid, then caustic soda, soda ash, salt are made into fixation liquid, pass through
The techniques such as leaching gadolinium dye liquor, drying, leaching gadolinium fixation liquid, decatize, washing, drying are crossed, performance can be obtained
Excellent product.
Described stamp can be the conventional stamp of field of printing and dyeing, for example, the compound 1 described in will be appropriate
Being configured to printing paste with sodium bicarbonate, urea, reserve salt, sodium alginate carries out stamp, prebake, decatize,
Washing, then soaps, the product of technique the obtains function admirable such as hot water wash, cold water are washed, ironed dry again.
Present invention also offers a kind of dye composite, it includes above-mentioned compound 1 and auxiliary agent.It is described
Auxiliary agent can be the conventional auxiliary agent in dye composite field, such as glauber salt and/or Dispersant MF.
Described dye composite can be made up of described compound 1 and described auxiliary agent.
Present invention also offers a kind of preparation method of above-mentioned dye composite, it comprises the steps：
Described compound 1 and described auxiliary agent are mixed, you can.The method of described mixing can be dye set
The conventional mixed method in compound field, such as dry powder blending or wet blending, preferably wet blending.
Without prejudice to the field on the basis of common sense, above-mentioned each optimum condition, can be combined, and obtain final product this
Invent each preferred embodiment.
Agents useful for same of the present invention and raw material are commercially available.
Positive effect of the invention is：The compound has beautiful amber yellow, very big molten
It is Xie Du, moderate dye uptake direct, very high and degree of fixation, good enhancing, extraordinary
The stability of Salt And Alkali Tolerance, excellent wet colour fastness and light fastness, are suitable in cellulose fibers such as cotton, fiber crops
Exhaust dyeing, continuous dyeing and stamp on the protein fibre such as dimension or hair, silk, are particularly suited for tie dyeing
And cold-pad-batch process dyeing, without dyeing defect, aberration phenomenon, the shortcoming without difference in poor end to end and side, once into
Dye rate is high.
Specific embodiment
The present invention is further illustrated below by the mode of embodiment, but is not therefore limited the present invention to
Among described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example, according to normal
Rule method and condition, or selected according to catalogue.
Unless otherwise indicated, temperature for degree Celsius, part and percentage are weight portion and percentage by weight, weight
Amount part and parts by volume relation with kilogram and liter relationship consistency.
Embodiment 1
By 36.1 parts of sulfonation para-esters300.0 parts of water and 150.0
Part concentrated hydrochloric acid, is beaten 1.0~2.0h, under ice cooling, 4, when temperature is down to 0-5 DEG C, adds 6.9 parts of Asias
Sodium nitrate (is made into 10% solution), carries out diazotising, and it is in micro- blueness to be tested with potassium iodide starch test paper
Afterwards, 4.0h, as reaction end are reacted below 10~20 DEG C.It is standby.
Urea groups aniline between 15.1 partsPlus 200 parts of water, with 10% sodium hydroxide solution
PH=5.0 or so is adjusted, 1.0h is beaten, above-mentioned diazol is slowly added at 10~15 DEG C, sodium bicarbonate is used
PH is between 6.0~6.5 for regulation, pH is adjusted after adding and is reacted between 6.0~6.5, is coupled 2.0~3.0h
It is terminal that diazol disappears.Obtain color base (5) compoundTesting its molecular weight by HPLC-MS is
567, it is consistent with its structure.
Embodiment 2
18.8 parts of Cyanuric Chlorides and 70 parts of ice, 50 parts of water and 0.1 part of paregal O 25, beat in ice bath
45~60min of slurry, is subsequently adding 31.7 parts of N- ethyl meta esters
It is previously dissolved in 100 parts of water), a condensation is carried out, reacted at 0~5 DEG C, the sodium carbonate with 10% is molten
Liquid adjusts pH2.0~5.0, reacts 1.5~2.0h, and terminal is during without free N- ethyl meta esters.Again
Add the color base of the synthesis of embodiment 1 to be warming up to 40 DEG C, two condensations are carried out at 40~45 DEG C, with 10%
Sodium carbonate liquor regulation medium pH5.5~6.5, react 10.0~12.0h, terminal are during leuco base, directly
Spray drying is connect, dyestuff 1-1 compounds are obtained.It is 1009 to test its molecular weight by HPLC-MS, with it
Structure is consistent.
Embodiment 3
18.8 parts of Cyanuric Chlorides and 70 parts of ice, 50 parts of water and 0.1 part of paregal O 25, beat in ice bath
45~60min of slurry, be subsequently adding the color base synthesized in embodiment 1 carries out a condensation at 0~5 DEG C, uses
10% sodium carbonate liquor regulation pH5.5~7.0, react 4.0~5.0h, and terminal is during leuco base.Then
Add 31.7 parts of N- ethyl meta esters to be warming up to 40 DEG C, two condensations are carried out at 40~45 DEG C, with 10%
Sodium carbonate liquor regulation medium pH6.5~7.0, react 8.0~10.0h, be terminal during none contracting thing,
Direct spray drying, obtains dyestuff 1-1 compounds.It is 1009 to test its molecular weight by HPLC-MS, with
Its structure is consistent.
Comparative example 1
Para-ester is used in example 2Instead of N- ethyl meta esters,
Synthetic dyestuffs, direct spray drying obtains dyestuff (I) compound.Testing its molecular weight by HPLC-MS is
981, it is consistent with its structure.
Comparative example 2
N- ethyl metanilic acids are used in example 2Instead of between N- ethyls
Position ester, synthetic dyestuffs, direct spray drying obtains dyestuff (3-21) compound.Tested by HPLC-MS
Its molecular weight is 835, is consistent with its structure.
Comparative example 3
Although compound (2) is than one more active group of compound (1), its degree of fixation is all after tested
80% or so, therefore, the raising effect for introducing active group is limited.
Comparative example 4
Although compound (4) is than one more ethyl of compound (3), both solubility all very littles,
Water is practically insoluble in, therefore, the raising effect for introducing ethyl is limited.
Effect example
Take 5 parts of embodiments it is 2-in-1 into dyestuff 1-1 compounds, carried out with pure cotton fabric conventional exhaust dyeing,
Washing, drying, obtain yellow fabric (for example, dyestuff, glauber salt, soda ash add bathtub, bath raio 1: 15,
60 DEG C are warming up to, 60min is incubated, are then washed, neutralized, 98 DEG C of 10min that soap, clear water is washed, and is dried
It is dry, obtain yellow fabric).
Take dyestuff (I) compounds of 5 parts of comparative examples 1 synthesis, carried out with pure cotton fabric conventional exhaust dyeing,
Washing, drying, obtain yellow fabric (actual conditions is ibid).
Take 5 parts of comparative examples it is 2-in-1 into dyestuff (3-21) compound, carried out conventional contaminating dye with pure cotton fabric
Color, washing, drying, obtain yellow fabric (actual conditions is ibid).
After tested, the performance of two dyestuffs is as shown in the table：
After tested, the λ of dyestuff 1-1max(water)=432mn, is amber yellow；Its direct S is
0.78, dye uptake is 95.32%；Its salt of 200g/L, the caustic soda of 4g/L, the soda ash of 20g/L,
In the dye solution of 20g/L dyestuffs 1-1, stabilization more than 10min is kept.
The direct S of dyestuff (I) is 0.91；And it is in salt, the caustic soda of 4g/L, the 20g/L of 200g/L
Soda ash, the dye solution of 20g/L dyestuffs (I) in only adhered to several seconds, then moment separate out.
Each performance test methods are with reference to following standards in this effect example：The 875--2008 of GB/T 21 contaminate
Expect the measure of lifting force；The measure of GB/T 2391-2014 reactive dye degree of fixation；GB/T 21879-2015
The measuring point filter paper method of water-soluble dye solubility；The experiment of GB/T5713-2013 textile color stabilities is water-fast
Color fastness；GB/T8426-1998 textile color stabilities test color fastness to light：Daylight；GB/T
3920-2008 textile color stabilities test colour fastness to rubbing；GB/T 3922-1995 textile perspiration resistances
Color fastness test method；GB/T 250-2008 textile color stability test evaluation discoloration gray scales.
Claims (10)
1. a kind of monoazos as shown in Equation 1 as reactive dye application；
Wherein, X is halogen, R1It is C1~C4Alkyl, R2、R3And R4It independently is hydrogen or alkali gold
Category.
2. application as claimed in claim 1, it is characterised in that described halogen is fluorine or chlorine.
3. application as claimed in claim 1, it is characterised in that described halogen is chlorine.
4. application as claimed in claim 1, it is characterised in that described C1~C4Alkyl be first
Base, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group or the tert-butyl group.
5. application as claimed in claim 1, it is characterised in that described C1~C4Alkyl be first
Base or ethyl.
6. application as claimed in claim 1, it is characterised in that described alkali metal be lithium, sodium or
Potassium.
7. application as claimed in claim 1, it is characterised in that described R2, described R3And institute
The R for stating4It is hydrogen or alkali metal.
8. application as claimed in claim 1, it is characterised in that described compound 1 is followingization
Compound：
9. application as claimed in claim 1, it is characterised in that described compound 1 is used to contain
The exhaust dyeing of the cellulosic material of hydroxyl or amino, continuous dyeing or stamp field.
10. application as claimed in claim 9, it is characterised in that described containing hydroxyl or amino
Cellulosic material is cotton, viscose glue, fiber crops or silk, and its blend fabric.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0056975A2 (en) * | 1981-01-24 | 1982-08-04 | Hoechst Aktiengesellschaft | Water soluble monoazocompounds, process for their preparation and their use as dyestuffs |
| JPH069893A (en) * | 1992-06-24 | 1994-01-18 | Mitsubishi Kasei Hoechst Kk | Water-soluble monoazo dye |
| US5380827A (en) * | 1992-04-20 | 1995-01-10 | Hoeshst Mitsubishi Kasei Co., Ltd. | Water-soluble monoazodye containing a triazinyl or pyrimidinyl group and at least one vinyl sulfonyl type group in its structure |
| EP0693536A1 (en) * | 1994-07-20 | 1996-01-24 | Bayer Ag | Azo dyes with a chlorotriazine group |
| CN102898867A (en) * | 2012-10-31 | 2013-01-30 | 无锡润新染料有限公司 | Composite reactive yellow dye and preparation method thereof |
| WO2013186029A1 (en) * | 2012-06-15 | 2013-12-19 | Huntsman Advanced Materials (Switzerland) Gmbh | Fibre-reactive dyes, their preparation and their use |
-
2015
- 2015-12-17 CN CN201510956444.7A patent/CN106893353B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0056975A2 (en) * | 1981-01-24 | 1982-08-04 | Hoechst Aktiengesellschaft | Water soluble monoazocompounds, process for their preparation and their use as dyestuffs |
| US5380827A (en) * | 1992-04-20 | 1995-01-10 | Hoeshst Mitsubishi Kasei Co., Ltd. | Water-soluble monoazodye containing a triazinyl or pyrimidinyl group and at least one vinyl sulfonyl type group in its structure |
| JPH069893A (en) * | 1992-06-24 | 1994-01-18 | Mitsubishi Kasei Hoechst Kk | Water-soluble monoazo dye |
| EP0693536A1 (en) * | 1994-07-20 | 1996-01-24 | Bayer Ag | Azo dyes with a chlorotriazine group |
| WO2013186029A1 (en) * | 2012-06-15 | 2013-12-19 | Huntsman Advanced Materials (Switzerland) Gmbh | Fibre-reactive dyes, their preparation and their use |
| CN102898867A (en) * | 2012-10-31 | 2013-01-30 | 无锡润新染料有限公司 | Composite reactive yellow dye and preparation method thereof |
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