CN102618081B - Sun-proof black active dye mixture, and preparation and application thereof - Google Patents
Sun-proof black active dye mixture, and preparation and application thereof Download PDFInfo
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- CN102618081B CN102618081B CN 201210063330 CN201210063330A CN102618081B CN 102618081 B CN102618081 B CN 102618081B CN 201210063330 CN201210063330 CN 201210063330 CN 201210063330 A CN201210063330 A CN 201210063330A CN 102618081 B CN102618081 B CN 102618081B
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- 239000000203 mixture Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims description 21
- 239000000975 dye Substances 0.000 claims abstract description 78
- 238000004043 dyeing Methods 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 16
- 229920000742 Cotton Polymers 0.000 claims abstract description 11
- 239000001045 blue dye Substances 0.000 claims abstract description 8
- 229920002678 cellulose Polymers 0.000 claims abstract description 6
- 239000001913 cellulose Substances 0.000 claims abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 4
- 239000001048 orange dye Substances 0.000 claims abstract description 4
- 238000005859 coupling reaction Methods 0.000 claims description 28
- 230000008878 coupling Effects 0.000 claims description 24
- 238000010168 coupling process Methods 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 238000006193 diazotization reaction Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000000985 reactive dye Substances 0.000 claims description 10
- 239000000835 fiber Substances 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 239000012954 diazonium Substances 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 claims description 3
- -1 4Be hydrogen Chemical class 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- JHXVRRJXCDAINK-UHFFFAOYSA-N NC(=O)N.N#CC#N Chemical compound NC(=O)N.N#CC#N JHXVRRJXCDAINK-UHFFFAOYSA-N 0.000 claims 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims 2
- 238000007796 conventional method Methods 0.000 claims 2
- 150000004820 halides Chemical class 0.000 claims 2
- 230000002378 acidificating effect Effects 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 238000007639 printing Methods 0.000 abstract description 9
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002657 fibrous material Substances 0.000 abstract 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 28
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 26
- 150000001875 compounds Chemical class 0.000 description 22
- 150000002148 esters Chemical class 0.000 description 16
- 239000000047 product Substances 0.000 description 15
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 12
- 238000010009 beating Methods 0.000 description 10
- 235000010288 sodium nitrite Nutrition 0.000 description 10
- 241000219146 Gossypium Species 0.000 description 9
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 8
- 101100118680 Caenorhabditis elegans sec-61.G gene Proteins 0.000 description 5
- 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 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 238000006482 condensation reaction Methods 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- ZMCHBSMFKQYNKA-UHFFFAOYSA-N 2-aminobenzenesulfonic acid Chemical compound NC1=CC=CC=C1S(O)(=O)=O ZMCHBSMFKQYNKA-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 0 *C1C(*Nc(cc(cc2[N+]/N=C(\c3ccccc3)/[N-][N+]3c4c5ccc(S(O)(=O)=O)c4)S(O)(=O)=O)c2O*3OC5=O)C1* Chemical compound *C1C(*Nc(cc(cc2[N+]/N=C(\c3ccccc3)/[N-][N+]3c4c5ccc(S(O)(=O)=O)c4)S(O)(=O)=O)c2O*3OC5=O)C1* 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910052728 basic metal Inorganic materials 0.000 description 2
- 150000003818 basic metals Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 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
- HMNPDEGBVWDHAR-UHFFFAOYSA-N 8-aminonaphthalen-1-ol Chemical class C1=CC(O)=C2C(N)=CC=CC2=C1 HMNPDEGBVWDHAR-UHFFFAOYSA-N 0.000 description 1
- ONMOULMPIIOVTQ-UHFFFAOYSA-N 98-47-5 Chemical class OS(=O)(=O)C1=CC=CC([N+]([O-])=O)=C1 ONMOULMPIIOVTQ-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 240000006240 Linum usitatissimum Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-N ethanesulfonic acid Chemical compound CCS(O)(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000009980 pad dyeing Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000344 soap 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
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229940056729 sodium sulfate anhydrous Drugs 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000006886 vinylation reaction Methods 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
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- Coloring (AREA)
Abstract
The invention discloses a sun-proof black active dye mixture, which is characterized by being formed by mixing 40-60 parts by weight of blue dye shown as a general formula (1), 20-25 parts by weight of one or more orange dyes shown as general formulae (2), (3) and (4), and 20-35 parts by weight of blue dye shown as a general formula (5). The dye mixture provided by the invention is suitable for dyeing and printing cellulose materials such as hydroxyl or nitrogen-containing fiber materials, in particular for dyed cotton fiber materials; and a dyed product has high sun-proof firmness.
Description
Technical field
The present invention relates to black and active dye, particularly sun-proof black reactive dye mixture and preparation thereof and application.Background technology
The dyeing practice proposes requirements at the higher level to the dyeing quality, therefore need be new, and that obtain easily and dye mixture that have good character.
Existing black dye mixer is described in many data, and these black dye mixers are when dying light color or middle look, and ubiquitous defective is that light fastness is relatively poor, can not expire service requirements.Therefore press for dyestuff manufactory and can be provided to printing and dyeing black, when particularly printing and dyeing light/dark balance, middle black, its light permanency can better dye species.
The purpose of this invention is to provide a kind of high light-fast black reactive dye mixture and methods for making and using same thereof, it is specially adapted to dye with the stamp filamentary material and can reaches above-mentioned high quality, described dyestuff can also obtain to have the dyeing of good comprehensive colour fastness, for example sun-proof, moisture-proof.
The present invention realizes by following technical scheme.The present invention includes a kind of high light-fast black reactive dye mixture, it is characterized in that its blue dyes 40-60 part by general formula (1), one or more orange dyes 20-25 part in general formula (2), general formula (3), the general formula (4) (is in the general formula 2,3,4, during wherein a kind of of choosing, account for 20-25 part, during as wherein multiple of choosing, this is multiple to account for 20-25 part altogether) and blue dyes 20-35 part of general formula (5) mix: the blue active dye of general formula (1) is:
The orange active dye of general formula (2), (3), (4) is:
The blue active dye of general formula (5) is:
In the following formula: a
1, a
2, a
3, a
4Be hydrogen, ethanoyl, sulfonic group, b
1, b
2, b
3Be sulfonic group, vinyl sulfone(Remzaol sulfate group, d
1, d
2Be hydrogen, sulfonic group, m
1, m
2Can be hydrogen, sulfonic group, X be a halogen, can be fluorine and chlorine, and D can be one of following:
NH
2C
2H
4SO
2C
2H
4OSO
3H NH
2C
2H
4OC
2H
4SO
2C
2H
4OSO
3H
NH
2C
2H
4SO
2C
2H
4Cl NH
2C
2H
4OC
2H
4SO
2C
2H
4Cl
According to above definition, general formula (1) can be preferably the dyestuff of following formula
According to above definition, general formula (2) can be preferably the dyestuff of following formula
According to above definition, general formula (3) can be preferably the dyestuff of following formula
According to above definition, general formula (4) can be preferably the dyestuff of following formula
According to above definition, general formula (5) can be preferably the dyestuff of following formula
The present invention also comprises the preparation method of high light-fast black dye mixer, may further comprise the steps
The dyestuff preparation method of general formula (1):
The compound of following formula (6) was pulled an oar 1 hour at 0-10 ℃, add hydrochloric acid, inferior sodium diazotization then successively, then with the compound of following formula (7) at 0-10 ℃, coupling under the condition of pH=1-3, to add hydrochloric acid successively as shown in the formula the compound of (8) 0-10 ℃ of making beating 1 hour in frozen water again, Sodium Nitrite carries out diazotization, last and a conjugates are at 0-10 ℃, coupling under the condition of pH=4-7 can obtain the dyestuff of general molecular formula (1).
The dyestuff preparation process of general formula (2)
The compound of following formula (9) was pulled an oar 1 hour at 0-10 ℃, add hydrochloric acid then successively, inferior sodium diazotization, then with the compound of following formula (10) at 0-10 ℃, coupling under the condition of pH=1-3, to pull an oar 1 hour in frozen water at 0-10 ℃ as shown in the formula the compound of (11) again, add hydrochloric acid successively, Sodium Nitrite carries out diazotization, last and a conjugates are at 0-10 ℃, coupling under the condition of pH=4-7, then with the compound of following formula (12) at 0-10 ℃, carry out coupling for the third time with the secondary conjugates under the pH=4-7 condition, can obtain the dyestuff of general molecular formula (2).
The preparation process of the dyestuff of general formula (3)
To pull an oar 1 hour at 0-10 ℃ as shown in the formula the compound of (13), add hydrochloric acid, inferior sodium diazotization then successively, then with the compound of following formula (14) at 0-10 ℃, coupling under the condition of pH=1-3, to carry out diazotization at 0-10 ℃ as shown in the formula the compound of (15) again, then with a conjugates at 0-10 ℃, coupling under the condition of pH=4-7 can obtain the dyestuff of general molecular formula (3).
The dyestuff preparation process of general formula (4)
To pull an oar 1 hour at 0-10 ℃ as shown in the formula the compound of (16), add hydrochloric acid, inferior sodium diazotization then successively, then with the compound of following formula (17) at 0-10 ℃, coupling under the condition of pH=1-3, to carry out conventional diazotization at 0-10 ℃ as shown in the formula the compound of (18) again, then with a conjugates at 0-10 ℃, secondary coupling under the condition of pH=4-7 can obtain the dyestuff of general molecular formula (4).
The dyestuff preparation process of general formula (5)
Will be as shown in the formula making beating in the compound ice of (19) 40 minutes, to add as shown in the formula the neutral solution of the compound of (20) then, control T=0-10 ℃, reaction is 20-200 minute under the condition of pH=4-8, finish condensation for the first time, again will be as shown in the formula the compound of (21) at 10-50, reaction is 20-200 minute under the condition of pH=5-10, can obtain the dyestuff of general molecular formula (5).
Formula (6) arrives a in the formula (21)
1, a
2, a
3, a
4, b
1, b
2, b
3, d
1, d
2, m
1, m
2, X, D have the above definition that provides separately.
Because last operation steps can be carried out with different order, so two kinds of different operational variables are possible, final product is optional in addition can experience conversion reaction, and this conversion reaction can be by handling with diluted sodium hydroxide solution.But with the vinylation groups converted that exists is vinyl form, for example, is that this reaction of vinyl sulfonic acid base group is known with β-sulfate ethylsulfonic acid base groups converted.
According to the reactive dyestuffs of high light-fast black dye mixer of the present invention or for the form of free acid or be preferably the form of its salt, the salt of being considered can be basic metal, and basic metal and ammonium salt are with salt that can organic amino.
The black reactive dye mixture of high light-fast of the present invention, it is blue dyes 40-60 part by general formula (1), in general formula (2), (3), (4) any one or multiple orange dye 20-25 part, blue dyes 20-35 part of general formula (5) mixes, be applicable to as dyeing and printing the very material of wide region, the filamentary material of hydroxyl or nitrogenous base for example, the example of the nitrogenous fibre materials that can mention is silk, leather, wool, tynex and urethane.Reactive dyestuffs of the present invention are specially adapted to dye and print the cellulose filamentary material of all kinds.The filamentary material of this cellulose for example is a native cellulose fibre, as cotton, flax and hemp, and Mierocrystalline cellulose and regenerated cellulose, preferred cotton.High light-fast black and active dye of the present invention also is suitable for dyeing or printing cellulosic mixture, for example mixture of cotton and tynex, particularly cotton polyester blend fiber.Can be in every way, particularly the form with aqueous dye solutions and dyestuff print paste is applied to filamentary material with reactive dyestuffs of the present invention, and is fixed on the fiber.They are applicable to the dip-dye method and according to the dyeing of pad dyeing method, according to these methods aqueous dye solutions (optional saliferous) dipping articles, and in alkaline purification or after handling in the presence of the alkali, dyestuff fixing, adopt heat effect in the time of suitably or carry out in room temperature storage a few hours, after fixing, adopt cold-peace hot water dyeing or printed matter, optional adding has dissemination and promotes the not reagent of fixed dye diffusion.
Black reactive dye mixture of the present invention has good light fastness performance when dying the cotton fibre of light color, middle look, can reach the 4-5 level, and the black and active dye of developing in the market, all has only 3 grades light fastness when dying light color, middle look.
In sum, black reactive dye mixture of the present invention is applicable to dyeing and printing cellulosic material, and as hydroxyl or nitrogenous fibre materials, the cotton fibre material that dyes especially, dyeing have good light fastness performance.
Embodiment
The following example explanation the present invention, unless otherwise, temperature be degree centigrade, and part is a weight part, and per-cent is weight percentage.
Embodiment 1, the preparation of dyestuff
In 200 parts frozen water, add 28.1 parts to (β-ethene sulfuryl sulfuric ester) aniline making beating 60 minutes, control T≤10 ℃, the hydrochloric acid that adds 14 part 30%, the solution that 7.2 parts of Sodium Nitrites are made into added about 40 minutes then, added reaction 60 minutes, eliminated unnecessary nitrous acid, add 34.1 parts of 1-amino-8-naphthols 3, the 6-disulfonic acid, in T≤10 ℃, reaction is 300 minutes under the condition of pH=1-3.
The frozen water that in another reaction vessel, adds 200 parts, add 28.1 parts to (β-ethene sulfuryl sulfuric ester) aniline making beating 60 minutes, control T≤10 ℃ add 14 part 30% hydrochloric acid, and the solution that 7.2 parts of Sodium Nitrites are made into added about 40 minutes then, add reaction 60 minutes, eliminate unnecessary nitrous acid, be added to then in conjugates, regulate pH=5-7 with sodium bicarbonate dry powder, reacted 2 hours, and can obtain the dyestuff of formula (1-1).
Embodiment 2-15, the preparation of dyestuff
According to embodiment 1 described method, will to (β-ethene sulfuryl sulfuric ester) aniline and as shown in the formula the compound of (22), (23), (24) as diazo component, adopt with embodiment 1 same process condition and just can obtain the dyestuff of formula (1-2) to formula (1-15).
The structural formula of formula (1-2) to (1-15)
Embodiment 16, the preparation of dyestuff
In 200 parts frozen water, add 28.1 parts to (β-ethene sulfuryl sulfuric ester) aniline making beating 60 minutes, control T≤10 ℃, the hydrochloric acid that adds 14 part 30%, the solution that 7.2 parts of Sodium Nitrites are made into added about 40 minutes then, added reaction 60 minutes, eliminate unnecessary nitrous acid, add 15.2 part 3, the 5-diaminobenzoic acid is in T≤10 ℃, reaction is 200-300 minute under the condition of pH=2-4, finishes coupling for the first time.The same then frozen water that in another reaction vessel, adds 200 parts, add 28.1 parts to (β-ethene sulfuryl sulfuric ester) aniline making beating 60 minutes, control T≤10 ℃ add 14 part 30% hydrochloric acid, and the solution that 7.2 parts of Sodium Nitrites are made into added about 40 minutes then, add reaction 60 minutes, eliminate unnecessary nitrous acid, be added to then in conjugates, then at pH=4-7, carry out the coupling second time under the T=0-10 ℃ of condition, react and finished coupling for the second time in 150-200 minute.Again with 28.1 parts to (β-ethene sulfuryl sulfuric ester) aniline, carry out diazotization by above-mentioned diazonium method, then at T=0-10 ℃, carry out coupling for the third time with the secondary coupling product under the condition of P=5-7, react and finished coupling for the third time in 120-150 minute, get final product the product of formula (2-1).
Embodiment 17-22, the preparation of dyestuff
Synthetic method according to embodiment 16, with the compound of formula (25), (26), (27), (28) respectively as first, second, third diazotizing diazotization component, adopt the processing condition identical, can obtain the product of formula (2-2)-(2-7) with embodiment 16
The structural formula of formula (2-2)-(2-7)
Embodiment 23, the preparation of dyestuff
In 200 parts frozen water, add 28.1 parts to (β-ethene sulfuryl sulfuric ester) aniline making beating 60 minutes, control T≤10 ℃, the hydrochloric acid that adds 14 part 30%, the solution that 7.2 parts of Sodium Nitrites are made into added about 40 minutes then, added reaction 60 minutes, eliminated unnecessary nitrous acid, add 23.9 parts of 2-amino-5-naphthols-7 sulfonic acid, in T≤10 ℃, reaction is 200-300 minute under the condition of pH=1-3, finishes coupled reaction one time.
The frozen water that in another reaction vessel, adds 200 parts, add 36.1 parts to (β-ethene sulfuryl sulfuric ester) 2-sulfo aniline making beating 60 minutes, control T≤10 ℃, the hydrochloric acid that adds 14 part 30%, the solution that 7.2 parts of Sodium Nitrites are made into added about 40 minutes then, add reaction 60 minutes, eliminate unnecessary nitrous acid, be added to then in conjugates, in T≤10 ℃, pH=4-7 reacted 150-200 minute, finish coupled reaction for the second time, can obtain the dyestuff of formula (3-1).
Embodiment 24-26, the preparation of dyestuff
Method according to embodiment 23 descriptions, select for use respectively to (β-ethene sulfuryl sulfuric ester) aniline and to (β-ethene sulfuryl sulfuric ester) 2-sulfo aniline as diazo component for the first time and for the second time, according to the processing condition identical, can obtain the product of formula (3-2) to (3-4) with embodiment 23.
Embodiment 27, the preparation of dyestuff
In 200 parts frozen water, add 28.1 parts to (β-ethene sulfuryl sulfuric ester) aniline making beating 60 minutes, control T≤10 ℃, the hydrochloric acid that adds 14 part 30%, the solution that 7.2 parts of Sodium Nitrites are made into added about 40 minutes then, added reaction 60 minutes, eliminate unnecessary nitrous acid, add 21 part 2, the 4-diamino benzene sulfonic acid is in T≤10 ℃, reaction is 200-300 minute under the condition of pH=1-3, finishes coupled reaction one time.
The frozen water that adds 200 parts in another reaction vessel adds 28.1 parts to (β-ethene sulfuryl sulfuric ester) aniline making beating 60 minutes, controls T≤10 ℃, the hydrochloric acid that adds 14 part 30%, the solution that 7.2 parts of Sodium Nitrites are made into added about 40 minutes then, added reaction 60 minutes, eliminated unnecessary nitrous acid, be added to then in conjugates, in T≤10 ℃, pH=4-7 reacted 120-150 minute, finish coupled reaction for the second time, can obtain the dyestuff of formula (4-1).
Embodiment 28-30, the preparation of dyestuff
Method according to embodiment 27 descriptions, will to (β-ethene sulfuryl sulfuric ester) aniline and to (β-ethene sulfuryl sulfuric ester) 2-sulfo aniline as diazo component for the first time and for the second time, according to the processing condition identical, can obtain the product of formula (4-2) to (4-4) with embodiment 27.
Embodiment 31, the preparation of dyestuff
18.5 parts cyanuric chlorides were pulled an oar 40 minutes in 200 parts frozen water, neutral solution with the compound of 59.6 parts of formulas (20) adds then, at pH=4-8, primary condensation reaction was finished in reaction in 150-200 minute under T=0-10 ℃ the condition, add 28.1 parts then to (β-ethene sulfuryl sulfuric ester) aniline, at T=10-50 ℃, the conditioned response 20-200 of pH=5-10 minute, finish the secondary condensation reaction, can obtain the product of formula (5-1).
Embodiment 32-37
The method of describing according to embodiment 31 changes the raw material of secondary condensation the compound of formula (29), (30), (31), (32), (33), (34) into, according to the processing condition of embodiment 31, can obtain the product of formula (5-2)-(5-7)
The structural formula of formula (5-2), (5-7)
Embodiment 38, the preparation of dyestuff
14 parts cyanuric fluorides were pulled an oar 40 minutes in 200 parts frozen water, neutral solution with the compound of 59.6 parts of formulas (20) adds then, at pH=4-8, primary condensation reaction was finished in reaction in 20-200 minute under T=0-10 ℃ the condition, add 28.1 parts then to (β-ethene sulfuryl sulfuric ester) aniline, at T=10-50 ℃, the conditioned response 20-200 of pH=5-10 minute, finish the secondary condensation reaction, can obtain the product of formula (5-8).
Embodiment 39-45, the preparation of dyestuff
The method of describing according to embodiment 38 changes the raw material of secondary condensation the compound of into formula (29), (30), (31), (32), (33) (34) respectively, can obtain the product of formula (5-9) to (5-14) according to the processing condition of example 38
Embodiment 46: dyeing
Under 30 ℃ temperature, 100 fens cottons are joined in 1000 parts of water, contain 2.4 parts of formulas (1-1) dyestuff, 0.8 part of formula (2-1) dyestuff, 0.8 part of formula (5-1) dyestuff, and in the dye liquor of 30 parts of Sodium sulfate anhydrous.min(99), in 30 minutes, dye liquor temperature is increased to 60 ℃, and under this temperature, kept 45 minutes, add 15 parts of soda ash then, keep 60 ℃ of dyeing 30 minutes again, take out cotton subsequently, with non-ionic cleaning agent soap boiling 15 minutes, with clear water washing and oven dry, can obtain having the black-dyeing product of good light fastness again.
Embodiment 47-52: dyeing
Use the method for embodiment 46, but be not to use the dyestuff of 0.8 part of formula (2-1), and the black-dyeing product that are to use the dyestuff of the formula (2-2) to (2-7) of equal amts can obtain to have the high light-fast fastness equally.
Embodiment 53-65: dyeing
Use the method for embodiment 46, but be not to use the dyestuff of 0.8 part of formula (5-1), and be to use (5-2) of equal amts dyestuff, can obtain to have the black-dyeing product of high light-fast fastness equally to (5-14).
Embodiment 66-80
Use the method for embodiment 46, use the dyestuff of 2.4 parts of formulas (1-1) to (1-15), use the dyestuff of 0.2 part (2-1), 0.3 part (3-1), 0.3 part (4-1) and 0.8 part (5-14), the black-dyeing product that can obtain to have the high light-fast fastness equally.
Embodiment 81-94
Use the method for embodiment 46, use the dyestuff of 2.4 parts of formulas (1-1), use the dyestuff of 0.3 part (3-1), 0.5 part (4-1) and 0.8 part (5-1) to (5-14), the black-dyeing product that can obtain to have the high light-fast fastness equally.
Embodiment 95: stamp
By quick stirring the dyestuff of the dyestuff of 2.0 parts of formulas (1-1), the dyestuff of 1.0 parts of formulas (2-3), 1.0 parts (5-14) is joined in the sodium bicarbonate magma of 150 parts 5% sodium alginate thickening material, 109.5 parts of water, 30 parts of urea, 3 parts of m-nitrobenzene sulfonic acids and 7.5 parts.The printing paste that makes with this method is to cotton fabric printing, decatize 5 minutes in 100-102 ℃ saturated vapor then, and rinsing then can be soaped under boiling as needs, and post rinse is also dry.Can obtain to have the black printing product of high light-fast fastness.
The performance index that the black reactive dye mixture of high light-fast of the present invention is implemented dyeing or stamp to filamentary material are as follows:
Claims (4)
1. sun-proof black reactive dye mixture, it is characterized in that its blue dyes 40-60 weight part by general formula (1), one or more orange dyes 20-25 weight part in general formula (2), general formula (3), the general formula (4) and the blue dyes 20-25 weight part of general formula (5) mix:
Wherein: a
1, a
2, a
3, a
4Be hydrogen, ethanoyl, sulfonic group; b
1, b
2, b
3Be sulfonic group, vinyl sulfone(Remzaol sulfate group; d
1, d
2Be hydrogen, sulfonic group; m
1, m
2Be hydrogen, sulfonic group; X is the fluorine or chlorine in the halogen; D is one of following formula:
2. the preparation method of sun-proof black reactive dye mixture according to claim 1 is characterized in that:
Will
0-10 ℃ of diazonium method diazotization routinely, then with 1-naphthalene ammonia 8-hydroxyl 3, the coupling under acidic conditions of 6-disulfonic acid then will
Diazotization with conjugates coupling under alkaline condition, can obtain the dyestuff of general molecular formula (1);
Will
Routinely after the diazonium method diazotization with 3, the 5-diaminobenzoic acid is at pH=2-4, T=0-10 ℃ of coupling for the first time, after will
Diazotization and a conjugates carry out at pH=4-7, and T=0-10 ℃ of coupling for the second time at last will
Diazotization, with the secondary conjugates at pH=4-7, T=0-10 ℃ is carried out coupling for the third time, can obtain the dyestuff of general molecular formula (2);
Will
Diazotization according to a conventional method, then with 2-amino-5 naphthols-7-sulfonic acid at pH=1-3, coupling under T=0-10 ℃ the condition then will
Diazotization product and a conjugates are at pH=5-7, and coupling for the second time can obtain the dyestuff of general molecular formula (3) under T=0-10 ℃ the condition;
Will
Diazotization according to a conventional method, then with 2, the 4-diamino benzene sulfonic acid is at pH=1-3, and coupling under T=0-10 ℃ the condition then will
Diazotization product and a conjugates are at pH=5-7, and coupling for the second time can obtain the dyestuff of general molecular formula (4) under T=0-10 ℃ the condition;
Quantitative cyanogen urea carboxylic acid halides was pulled an oar in frozen water 30 minutes, then will
Neutral solution be added in the cyanogen urea carboxylic acid halides, at pH=4-8, under the T=0-10 ℃ of condition reaction 20-200 minute, finish primary condensation, then with D at pH=5-10, reaction is 60-200 minute under T=5-50 ℃ the condition, can obtain the dyestuff of general molecular formula (5).
3. the purposes of dye mixture according to claim 1 is characterized in that: be used for dyeing and print hydroxyl or cellulose filamentary material.
4. the purposes of dye mixture according to claim 3, it is characterized in that: described cellulose filamentary material is to contain cotton fibre material.
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| CN103773076A (en) * | 2012-10-18 | 2014-05-07 | 浙江龙盛化工研究有限公司 | Yellow reactive dye compound |
| CN103773071A (en) * | 2012-10-18 | 2014-05-07 | 浙江龙盛化工研究有限公司 | Yellow reactive dye compound |
| CN103773074A (en) * | 2012-10-18 | 2014-05-07 | 浙江龙盛化工研究有限公司 | Yellow reactive dye compound |
| CN103773073A (en) * | 2012-10-18 | 2014-05-07 | 浙江龙盛化工研究有限公司 | Yellow reactive dye compound |
| BR112015007457A2 (en) * | 2012-10-25 | 2017-07-04 | Dystar Colours Distrib Gmbh | mixtures of azores fibroreactive pigments, their preparation and their use |
| CN102964870B (en) * | 2012-10-25 | 2014-10-15 | 浙江龙盛集团股份有限公司 | Active black dye composition |
| CN104073024B (en) * | 2014-07-10 | 2016-07-06 | 浙江瑞华化工有限公司 | A kind of Black reactive dye composition and its purposes |
| CN104402781B (en) * | 2014-12-11 | 2016-06-29 | 吴江桃源染料有限公司 | A kind of half-finished preparation method of active soil yellow dye |
| CN105778563B (en) * | 2016-03-17 | 2017-08-08 | 浙江瑞华化工有限公司 | A kind of Black reactive dye composition and its production and use |
| CN108440994A (en) * | 2018-05-14 | 2018-08-24 | 吴江桃源染料有限公司 | A kind of preparation method of active dark blue dye |
| CN112679988B (en) * | 2020-12-26 | 2022-09-27 | 浙江科永化工有限公司 | Active navy blue to black dye composition and dye product |
| CN115304930A (en) * | 2022-06-30 | 2022-11-08 | 浙江科永化工有限公司 | Reactive dye composition and dye product |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030140432A1 (en) * | 2001-06-01 | 2003-07-31 | Joachim Eichhorn | Black dye mixtures of fiber-reactive AZO dyes and use thereof for dyeing material containing hydroxy- and/or carboxamido groups |
| CN101565561A (en) * | 2009-04-14 | 2009-10-28 | 丽源(湖北)科技有限公司 | Black reactive dye mixture and preparation and application thereof |
| CN102358803A (en) * | 2011-08-25 | 2012-02-22 | 浙江亿得化工有限公司 | Composite black active dye |
-
2012
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030140432A1 (en) * | 2001-06-01 | 2003-07-31 | Joachim Eichhorn | Black dye mixtures of fiber-reactive AZO dyes and use thereof for dyeing material containing hydroxy- and/or carboxamido groups |
| CN101565561A (en) * | 2009-04-14 | 2009-10-28 | 丽源(湖北)科技有限公司 | Black reactive dye mixture and preparation and application thereof |
| CN102358803A (en) * | 2011-08-25 | 2012-02-22 | 浙江亿得化工有限公司 | Composite black active dye |
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