CN106893353B - A kind of application of monoazos - Google Patents
A kind of application of monoazos Download PDFInfo
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- CN106893353B CN106893353B CN201510956444.7A CN201510956444A CN106893353B CN 106893353 B CN106893353 B CN 106893353B CN 201510956444 A CN201510956444 A CN 201510956444A CN 106893353 B CN106893353 B CN 106893353B
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- dyeing
- monoazos
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- 150000001875 compounds Chemical class 0.000 claims abstract description 55
- 238000010016 exhaust dyeing Methods 0.000 claims abstract description 10
- 229920000742 Cotton Polymers 0.000 claims abstract description 8
- 238000010014 continuous dyeing Methods 0.000 claims abstract description 7
- 239000000835 fiber Substances 0.000 claims abstract description 7
- 239000003513 alkali 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 7
- 239000000460 chlorine Substances 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- -1 normal-butyl Chemical group 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 239000000975 dye Substances 0.000 abstract description 35
- 238000004043 dyeing Methods 0.000 abstract description 14
- 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
- 102000004169 proteins and genes Human genes 0.000 abstract description 3
- 108090000623 proteins and genes Proteins 0.000 abstract description 3
- 238000010923 batch production Methods 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 description 33
- 238000006243 chemical reaction Methods 0.000 description 27
- 238000006467 substitution reaction Methods 0.000 description 22
- 238000000034 method Methods 0.000 description 19
- 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
- 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 18
- 239000002253 acid Substances 0.000 description 14
- 229940125782 compound 2 Drugs 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 150000002191 fatty alcohols Chemical class 0.000 description 12
- 229940051841 polyoxyethylene ether Drugs 0.000 description 12
- 229920000056 polyoxyethylene ether Polymers 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
- 229940126214 compound 3 Drugs 0.000 description 9
- 235000017550 sodium carbonate Nutrition 0.000 description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 description 9
- 238000005406 washing Methods 0.000 description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005859 coupling reaction Methods 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 238000012544 monitoring process Methods 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 239000012752 auxiliary agent Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 238000000589 high-performance liquid chromatography-mass spectrometry Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000007639 printing Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000004753 textile Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229940125898 compound 5 Drugs 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 238000001694 spray drying Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229940125773 compound 10 Drugs 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 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
- 239000007788 liquid Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 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
- 0 CC1C=C(C)C(N=Nc2ccc(*)cc2*)=CC1 Chemical compound CC1C=C(C)C(N=Nc2ccc(*)cc2*)=CC1 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 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
- 241000370738 Chlorion Species 0.000 description 1
- 206010034960 Photophobia Diseases 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical class C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- FHIVAFMUCKRCQO-UHFFFAOYSA-N diazinon Chemical compound CCOP(=S)(OCC)OC1=CC(C)=NC(C(C)C)=N1 FHIVAFMUCKRCQO-UHFFFAOYSA-N 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
- 238000002474 experimental method Methods 0.000 description 1
- 235000000396 iron Nutrition 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000002386 leaching Methods 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
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002791 soaking Methods 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
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 238000013112 stability test 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 applications of monoazos.A kind of application the present invention provides monoazos as shown in Equation 1 as reactive dye, wherein, the compound has beautiful amber yellow, prodigious solubility, moderate substantivity, very high dye uptake and degree of fixation, good enhancing, the stability of extraordinary saline-alkali tolerant, excellent wet colour fastness and light fastness, 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 suitable for tie dyeing and cold-pad-batch process dyeing, without dyeing defect, aberration phenomenon, without disadvantage poor in poor end to end and side, it is once high at dye rate.
Description
Technical field
The present invention relates to a kind of applications of monoazos.
Background technology
Reactive dye are very perfect till now, either in quality quantity, or in quality
Very high level has been developed to, whole chromatogram has been covered, has substantially met the requirement in market.It is existing fresh in Yellow series dyestuff
Gorgeous light yellow color system, and have saturate feux rouges yellow, or even have very gorgeous light yellow with fluorescence, these can
Meet the different needs in market.But these kinds are exactly that light sensitivity is poor there are one feature, cannot meet the special of market
Demand.
To this, there are also researchs both at home and abroad, have delivered several patents, wherein relatively good patent is US Re.37004.
Its precursor structure and this patent are essentially identical (such as compound 3-21), but its dye uptake does not have this patent structure with degree of fixation
Height.
Also referred in patent CN102898867 it is such as dyestuff (I), but its solubility is very small, does not make substantially
With value.
Therefore, this field having big solubility, moderate direct, very high dye uptake and fixation there is an urgent need for a kind of
The monoazo class of rate, good enhancing, the stability of extraordinary saline-alkali tolerant, excellent wet colour fastness and light fastness
Close object.
Invention content
The technical problem to be solved by the present invention is in order to overcome existing monoazos dye uptake and degree of fixation
Low, the defects of solubility is low, the stability of enhancing and saline-alkali tolerant is poor, and a kind of application of monoazos is provided,
The compound have beautiful amber yellow, prodigious solubility, moderate direct, very high dye uptake and degree of fixation,
Good enhancing, the stability of extraordinary saline-alkali tolerant, excellent wet colour fastness and light fastness are suitable in cotton, fiber crops etc.
Exhaust dyeing, continuous dyeing and stamp on the protein fibres such as cellulose fibre or hair, silk, are particularly suitable for tie dyeing and cold rolling
Heap dyeing, no dyeing defect, aberration phenomenon are once high at dye rate without disadvantage poor in poor end to end and side.
The present invention provides a kind of monoazos as shown in Equation 1,
Wherein, X is halogen, R1For C1~C4Alkyl, R2、R3And R4It independently is hydrogen or alkali metal.
The halogen is the halogen of this field routine, preferably chlorine or fluorine.
The C1~C4Alkyl be this field routine C1~C4Alkyl, such as methyl, ethyl, n-propyl, isopropyl
Base, normal-butyl, isobutyl group or tertiary butyl, preferably methyl or ethyl.
The alkali metal is the alkali metal of this field routine, such as lithium, sodium or potassium, preferably sodium.
The present invention also provides a kind of preparation methods of above-mentioned compound 1 comprising following step：By 2 He of compound
Compound 3 carries out substitution reaction, obtains compound 1；
Wherein, X1For halogen (such as chlorine).
The substitution reaction that the compound 2 and the compound 3 carry out can be to prepare monoazos field
Conventional substitution reaction, following reaction conditions specifically preferred according to the invention：In water, in the presence of fatty alcohol polyoxyethylene ether,
Under mildly acidic conditions, the compound 2 and the compound 3 are subjected to substitution reaction, obtain the compound 1 i.e.
It can；
In the preparation method of the compound 1, the fatty alcohol polyoxyethylene ether can be to prepare monoazo class
Close the fatty alcohol polyoxyethylene ether of object field routine, such as paregal O 25.
In the preparation method of the compound 1, the solutions of weak acidity can be to prepare monoazos neck
The acid condition of domain routine, such as pH=5.5~6.5.
In the preparation method of the compound 1, the temperature of the substitution reaction can be to prepare monoazo class chemical combination
The conventional temperature of such reaction of object field, such as 40~45 DEG C.
In the preparation method of the compound 1, the process of the substitution reaction, which may be used, prepares monoazo class
Routine monitoring method (such as TLC, HPLC or NMR) in compound field is monitored, and is anti-when generally being disappeared with compound 2
Answer terminal, reaction time such as 10.0~12.0h.
Preferably, the preparation method of the compound 1 further includes following step：Compound 4 and compound 5 are subjected to idol
Connection reaction, obtains the compound 2；
Wherein, A-For prepare monoazos field routine diazol anion, such as chlorion or sulfuric acid
Radical ion.
The coupling reaction that the compound 4 is carried out with the compound 5 can be to prepare monoazos field
Conventional coupling reaction, following reaction conditions specifically preferred according to the invention：In water, under mildly acidic conditions, by the chemical combination
Object 4 carries out coupling reaction with the compound 5, obtains the compound 2；
In the preparation method of the compound 2, the solutions of weak acidity can be to prepare monoazos neck
The acid condition of domain routine, such as pH=4.5~6.5 (again such as 5.0,6.0).
In the preparation method of the compound 2, the temperature of the coupling reaction can be to prepare monoazo class chemical combination
The conventional temperature of such reaction of object field, such as 5~15 DEG C (such as 10 DEG C again).
In the preparation method of the compound 2, the process of the coupling reaction, which may be used, prepares monoazo class
Routine monitoring method (such as TLC, HPLC or NMR) in compound field is monitored, and is anti-when generally being disappeared with compound 4
Answer terminal, reaction time such as 2.0~3.0h.
Preferably, the preparation method of the compound 1 further includes following step：Compound 6 is subjected to diazo-reaction,
Obtain the compound 4；
The diazo-reaction that the compound 4 carries out can be prepare monoazos field routine diazotising it is anti-
It answers, such as executes diazo-reaction, following reaction conditions specifically preferred according to the invention：It in water, in the presence of acid, will be described
Compound 6 and alkali metal nitrites (such as sodium nitrite) carry out diazo-reaction, obtain the compound 4；
In the preparation method of the compound 4, the acid can be to prepare monoazos field routine
Acid, such as hydrochloric acid, sulfuric acid.
In the preparation method of the compound 4, the temperature of the diazo-reaction can be to prepare monoazo class
Close the conventional temperature of such reaction of object field, such as 0~20 DEG C (again such as 5 DEG C, 10 DEG C).
In the preparation method of the compound 4, the process of the diazo-reaction, which may be used, prepares monoazo
Routine monitoring method (such as TLC, HPLC or NMR) in class compound field is monitored, and is when generally being disappeared with compound 6
Reaction end, reaction time such as 3.0~5.0h (such as 4h again).
Preferably, the preparation method of the compound 1 further includes following step：Compound 8 and compound 7 are taken
Generation reaction, obtains the compound 3；
Wherein, X2For halogen (such as chlorine).
The substitution reaction that the compound 8 and compound 7 carry out is to prepare taking for monoazos field routine
Generation reaction, following reaction conditions specifically preferred according to the invention：In water, in the presence of fatty alcohol polyoxyethylene ether, in acid item
Under part, compound 8 and compound 7 are subjected to substitution reaction, obtain compound 3；
In the preparation method of the compound 3, the fatty alcohol polyoxyethylene ether can be to prepare monoazo class
Close the fatty alcohol polyoxyethylene ether of object field routine, such as paregal O 25.
In the preparation method of the compound 3, the acid condition can be to prepare monoazos field
Conventional acid condition, such as pH=2.0~5.0.
In the preparation method of the compound 3, the temperature of the substitution reaction can be to prepare monoazo class chemical combination
The conventional temperature of such reaction of object field, such as 0~5 DEG C.
In the preparation method of the compound 3, the process of the substitution reaction, which may be used, prepares monoazo class
Routine monitoring method (such as TLC, HPLC or NMR) in compound field is monitored, and is anti-when generally being disappeared with compound 8
Answer terminal, reaction time such as 1.5~2.0h.
Preferably, the preparation method of the compound 1 is as follows：
The present invention also provides a kind of preparation methods of above-mentioned compound 1 comprising following step：By 8 He of compound
Compound 9 carries out substitution reaction, obtains compound 1；
Wherein, X3For halogen (such as chlorine).
The substitution reaction that the compound 8 and compound 9 carry out can be to prepare monoazos field routine
Substitution reaction, following reaction conditions specifically preferred according to the invention：In water, in the presence of fatty alcohol polyoxyethylene ether, in weak acid
Property under neutrallty condition, the compound 8 and the compound 9 are subjected to substitution reaction, obtain the compound 1 i.e.
It can；
In the preparation method of the compound 1, the fatty alcohol polyoxyethylene ether can be to prepare monoazo class
Close the fatty alcohol polyoxyethylene ether of object field routine, such as paregal O 25.
In the preparation method of the compound 1, the faintly acid to neutrallty condition can be to prepare monoazo class
Close the condition of object field routine, such as pH=6.5~7.0.
In the preparation method of the compound 1, the temperature of the substitution reaction is to prepare monoazos
The conventional temperature of such reaction of field, such as 40~45 DEG C.
In the preparation method of the compound 1, the process of the substitution reaction, which may be used, prepares monoazo class
Routine monitoring method (such as TLC, HPLC or NMR) in compound field is monitored, and is anti-when generally being disappeared with compound 9
Answer terminal, reaction time such as 8.0~10.0h.
Preferably, the preparation method of the compound 1 further includes following step：Compound 2 and compound 10 are carried out
Substitution reaction obtains the compound 9；
Wherein, X4For halogen (such as chlorine).
The substitution reaction that the compound 2 and the compound 10 carry out can be to prepare monoazos field
Conventional substitution reaction, following reaction conditions specifically preferred according to the invention：In water, in the presence of fatty alcohol polyoxyethylene ether,
Under faintly acid to neutrallty condition, the compound 2 and the compound 10 are subjected to substitution reaction, obtain the change
Close object 9；
In the preparation method of the compound 9, the fatty alcohol polyoxyethylene ether can be to prepare monoazo class
Close the fatty alcohol polyoxyethylene ether of object field routine, such as paregal O 25.
In the preparation method of the compound 9, the faintly acid to neutrallty condition can be to prepare monoazo class
Close the condition of object field routine, such as pH=5.5~7.0.
In the preparation method of the compound 9, the temperature of the substitution reaction can be to prepare monoazo class chemical combination
The conventional temperature of such reaction of object field, such as 0~5 DEG C.
In the preparation method of the compound 9, the process of the substitution reaction, which may be used, prepares monoazo class
Routine monitoring method (such as TLC, HPLC or NMR) in compound field is monitored, and is anti-when generally being disappeared with compound 2
Answer terminal, reaction time such as 4.0~5.0h.
Preferably, the preparation method of the compound 1 further includes following step：Compound 4 and compound 5 are subjected to idol
Connection reaction, obtains the compound 2；
Wherein, A-For prepare monoazos field routine diazol anion；For example preceding institute of its reaction condition
It states.
Preferably, the preparation method of the compound 1 further includes following step：Compound 6 is subjected to diazo-reaction,
Obtain the compound 4；Its reaction condition is as previously described；
Preferably, the preparation method of the compound 1 is as follows：
Application the present invention also provides above-mentioned compound 1 as reactive dye.
The compound 1 is amber yellow.
The compound 1 can be used for exhaust dyeing, continuous dyeing or the print of the cellulosic material containing hydroxyl or amino
Spend equal fields.
The cellulosic material containing hydroxyl or amino can be the fibre containing hydroxyl or amino of field of printing and dyeing routine
Tie up cellulosic material, such as cotton, viscose glue, fiber crops, silk etc. and its blended fabric.
The exhaust dyeing can be field of printing and dyeing routine exhaust dyeing, for example, with suitable compound 1,
Anhydrous sodium sulphate, soda ash are made into dye liquor, bath raio 1: 15, are dyed at 60 DEG C, are then washed with clear water and acid neutralizes, then soaped, hot water wash, cold
Washing, the techniques such as dry can obtain the product of function admirable.
The continuous dyeing can be field of printing and dyeing routine continuous dyeing, for example, with suitable compound 1,
Levelling agent etc. is added and forms tie dyeing liquid, then caustic soda, soda ash, salt are made into fixation liquid, by soaking gadolinium dye liquor, drying, leaching gadolinium fixation
The techniques such as liquid, decatize, washing, drying can obtain the product of function admirable.
The stamp can be the stamp of field of printing and dyeing routine, for example, by suitable compound 1 and sodium bicarbonate,
Urea, reserve salt, sodium alginate be configured to printing paste carry out stamp, prebake, decatize, washing, then soap again, hot water wash,
Cold water the techniques such as washes, irons dry and obtaining the product of function admirable.
The present invention also provides a kind of dye composites comprising above-mentioned compound 1 and auxiliary agent.The auxiliary agent can be
The auxiliary agent of dye composite field routine, such as anhydrous sodium sulphate and/or Dispersant MF.
The dye composite can be made of the compound 1 and the auxiliary agent.
The present invention also provides a kind of preparation methods of above-mentioned dye composite comprising following step：It will be described
Compound 1 and auxiliary agent mixing, you can.The method of the mixing can be the mixing side of dye composite field routine
Method, 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 arbitrarily each preferably to get the present invention
Embodiment.
The reagents and materials used in the present invention are commercially available.
The positive effect of the present invention is that：The compound has beautiful amber yellow, prodigious solubility, moderate
Direct, very high dye uptake and degree of fixation, good enhancing, the stability of extraordinary saline-alkali tolerant, excellent wet
Fastness and light fastness are handled, is suitable for the exhaust dyeing on the protein fibres such as the cellulose fibres such as cotton, fiber crops or hair, silk, connects
Continuous dyeing and stamp are particularly suitable for tie dyeing and cold-pad-batch process dyeing, no dyeing defect, aberration phenomenon, without poor in poor end to end and side
The shortcomings that, it is once high at dye rate.
Specific implementation mode
It is further illustrated the present invention below by the mode of embodiment, but does not therefore limit the present invention to the reality
It applies among a range.In the following examples, the experimental methods for specific conditions are not specified, according to conventional methods and conditions, or according to quotient
Product specification selects.
Unless otherwise indicated, temperature be degree Celsius, part and percentage are weight proportion and weight percentage, parts by weight and volume
Part relationship with kilogram and liter relationship consistency.
Embodiment 1
By 36.1 parts of sulfonation para-esters300.0 parts of water and 150.0 parts it is dense
Hydrochloric acid is beaten 1.0~2.0h, under ice cooling, 4, when temperature is down to 0-5 DEG C, 6.9 parts of sodium nitrites is added and (are made into 10%
Solution), diazotising is carried out, is in the reaction 4.0h at 10~20 DEG C or less after micro- blue with potassium iodide starch test paper test, as instead
Answer terminal.It is spare.
Urea groups aniline between 15.1 partsAdd 200 parts of water, with 10% sodium hydroxide solution tune pH=5.0
Left and right is beaten 1.0h, is slowly added into above-mentioned diazol at 10~15 DEG C, adjusts pH between 6.0~6.5 with sodium bicarbonate, adds
Adjustment pH reacts between 6.0~6.5 after complete, and it is terminal that coupling 2.0~3.0h diazols, which disappear,.Obtain color base (5) compoundIt is 567 to test its molecular weight by HPLC-MS, with it
Structure is consistent.
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 are beaten 45~60min in ice bath,
Then 31.7 parts of N- ethyl meta position esters are addedIt is previously dissolved in 100 parts of water), it carries out
One condensation, reacts at 0~5 DEG C, adjusts pH2.0~5.0 with 10% sodium carbonate liquor, 1.5~2.0h is reacted, without what is dissociated
As terminal when N- ethyl meta position esters.The color base for adding the synthesis of embodiment 1 is warming up to 40 DEG C, and two contractings are carried out at 40~45 DEG C
It closes, medium pH5.5~6.5 is adjusted with 10% sodium carbonate liquor, react 10.0~12.0h, as terminal when leuco base, directly
Spray drying obtains dyestuff 1-1 compounds.It is 1009 to test its molecular weight by HPLC-MS, is consistent with its structure.
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 are beaten 45~60min in ice bath,
Then the color base that synthesizes in embodiment 1 is added and carries out a condensation at 0~5 DEG C, with 10% sodium carbonate liquor adjusting pH5.5~
7.0,4.0~5.0h is reacted, as terminal when leuco base.Then 31.7 parts of N- ethyl meta position esters are added and are warming up to 40 DEG C, 40
Two condensations are carried out at~45 DEG C, are adjusted medium pH6.5~7.0 with 10% sodium carbonate liquor, are reacted 8.0~10.0h, none contracting
As terminal, direct spray drying when object, obtain dyestuff 1-1 compounds.It is 1009 to test its molecular weight by HPLC-MS, is tied with it
Structure is consistent.
Comparative example 1
Para-ester is used in example 2Instead of N- ethyl meta position esters, synthesis dye
Material, direct spray drying obtain dyestuff (I) compound.It is 981 to test its molecular weight by HPLC-MS, is consistent with its structure.
Comparative example 2
N- ethyl metanilic acids are used in example 2Instead of N- ethyl meta position esters, synthesis
Dyestuff, direct spray drying obtain dyestuff (3-21) compound.It is 835 to test its molecular weight by HPLC-MS, is consistent with its structure.
Comparative example 3
Although compound (2) mostly active group than compound (1), its degree of fixation is all 80% or so after tested,
Therefore, the raising effect for introducing active group is limited.
Comparative example 4
Although compound (4) mostly ethyl than compound (3), solubility all very littles of the two are practically insoluble in
Water, therefore, the raising effect for introducing ethyl are limited.
Effect example
The dyestuff 1-1 compounds for taking 5 parts of embodiments 2 to synthesize carry out conventional exhaust dyeing, washing, drying with pure cotton fabric,
Obtaining yellow fabric, (for example, bathtub is added in dyestuff, anhydrous sodium sulphate, soda ash, bath raio 1: 15 is warming up to 60 DEG C, keeps the temperature 60min, then
Washing neutralizes, and 98 DEG C of 10min that soap, clear water is washed, and dries, obtains yellow fabric).
Dyestuff (I) compound for taking 5 parts of comparative examples 1 to synthesize carries out conventional exhaust dyeing, washing, drying with pure cotton fabric,
Obtain yellow fabric (actual conditions are same as above).
Dyestuff (3-21) compound for taking 5 parts of comparative examples 2 to synthesize carries out conventional exhaust dyeing, washing, baking with pure cotton fabric
It is dry, obtain yellow fabric (actual conditions are same as above).
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 substantivity S is 0.78, and dye uptake is
95.32%；Its salt of 200g/L, the caustic soda of 4g/L, the soda ash of 20g/L, 20g/L dyestuffs 1-1 dye solution in, keep
Stablize 10min or more.
The direct S of dyestuff (I) is 0.91；And it is in the salt of 200g/L, soda ash, the 20g/ of the caustic soda of 4g/L, 20g/L
Only adhere in the dye solution of L dyestuffs (I) several seconds, then moment precipitation.
Each performance test methods are with reference to following standards in this effect example：21 875--2008 dyestuff lifting forces of GB/T
Measurement；The measurement of GB/T 2391-2014 reactive dye degree of fixation；The survey of GB/T 21879-2015 water-soluble dye solubility
Pinpoint filter paper method；GB/T5713-2013 textile color stabilities test color fastness to water；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 colour fastness to perspiration test method；GB/T 250-2008 textile color stability test evaluation discoloration gray scales.
Claims (10)
1. a kind of application of monoazos as shown in Equation 1 as reactive dye；
Wherein, X is halogen, R1For C1~C4Alkyl, R2、R3And R4It independently is hydrogen or alkali metal.
2. application as described in claim 1, which is characterized in that the halogen is fluorine or chlorine.
3. application as described in claim 1, which is characterized in that the halogen is chlorine.
4. application as described in claim 1, which is characterized in that the C1~C4Alkyl be methyl, it is ethyl, n-propyl, different
Propyl, normal-butyl, isobutyl group or tertiary butyl.
5. application as described in claim 1, which is characterized in that the C1~C4Alkyl be methyl or ethyl.
6. application as described in claim 1, which is characterized in that the alkali metal is lithium, sodium or potassium.
7. application as described in claim 1, which is characterized in that the R2, described R3With the R4It is hydrogen or alkali gold
Belong to.
8. application as described in claim 1, which is characterized in that the compound 1 is following compound：
9. application as described in claim 1, which is characterized in that the compound 1 is used for the fiber containing hydroxyl or amino
Exhaust dyeing, continuous dyeing or the stamp field of cellulosic material.
10. application as claimed in claim 9, which is characterized in that the cellulosic material containing hydroxyl or amino be cotton,
Viscose glue, fiber crops or silk and its blended 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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