CN104341795A - Reactive yellow dye with high washing fastness and preparation method thereof - Google Patents
Reactive yellow dye with high washing fastness and preparation method thereof Download PDFInfo
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- CN104341795A CN104341795A CN201410561532.2A CN201410561532A CN104341795A CN 104341795 A CN104341795 A CN 104341795A CN 201410561532 A CN201410561532 A CN 201410561532A CN 104341795 A CN104341795 A CN 104341795A
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- reactive yellow
- washing fastness
- yellow dyes
- condensation
- high washing
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- 238000005406 washing Methods 0.000 title claims abstract description 35
- 239000001043 yellow dye Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 title abstract 4
- 238000009833 condensation Methods 0.000 claims abstract description 51
- 230000005494 condensation Effects 0.000 claims abstract description 51
- 238000005859 coupling reaction Methods 0.000 claims abstract description 35
- 230000008878 coupling Effects 0.000 claims abstract description 29
- 238000010168 coupling process Methods 0.000 claims abstract description 29
- -1 2-[2-(4-aminobenzenesulfonamido) ethylsulfuryl] hydroxyethyl sulphate Chemical compound 0.000 claims abstract description 27
- FZERHIULMFGESH-UHFFFAOYSA-N N-phenylacetamide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000012954 diazonium Substances 0.000 claims abstract description 17
- 150000001989 diazonium salts Chemical class 0.000 claims abstract description 14
- 150000003568 thioethers Chemical class 0.000 claims abstract description 14
- ZVCDLGYNFYZZOK-UHFFFAOYSA-M sodium cyanate Chemical compound [Na]OC#N ZVCDLGYNFYZZOK-UHFFFAOYSA-M 0.000 claims abstract description 12
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims abstract description 11
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims abstract description 11
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229960001413 acetanilide Drugs 0.000 claims abstract description 10
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 9
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000706 filtrate Substances 0.000 claims abstract description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 47
- 239000000047 product Substances 0.000 claims description 31
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 229940124530 sulfonamide Drugs 0.000 claims description 25
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 24
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 24
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 18
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 235000017550 sodium carbonate Nutrition 0.000 claims description 15
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 15
- GRDXCFKBQWDAJH-UHFFFAOYSA-N 4-acetamidobenzenesulfonyl chloride Chemical compound CC(=O)NC1=CC=C(S(Cl)(=O)=O)C=C1 GRDXCFKBQWDAJH-UHFFFAOYSA-N 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 150000001875 compounds Chemical group 0.000 claims description 13
- WXNPWCHMNVKSPP-UHFFFAOYSA-N C(C)C(CSCC(CC)O)O.C(C)(=O)NC1=C(C=CC=C1)S(=O)(=O)N Chemical compound C(C)C(CSCC(CC)O)O.C(C)(=O)NC1=C(C=CC=C1)S(=O)(=O)N WXNPWCHMNVKSPP-UHFFFAOYSA-N 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 230000009466 transformation Effects 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 125000003368 amide group Chemical group 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 230000032050 esterification Effects 0.000 claims description 7
- 238000005886 esterification reaction Methods 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- OBQKGKVDZPZYCD-UHFFFAOYSA-N C(C)N.OCCSCCO Chemical compound C(C)N.OCCSCCO OBQKGKVDZPZYCD-UHFFFAOYSA-N 0.000 claims description 6
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 6
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 238000010790 dilution Methods 0.000 claims description 4
- 239000012895 dilution Substances 0.000 claims description 4
- 230000004044 response Effects 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 2
- VKPPFDPXZWFDFA-UHFFFAOYSA-N 2-chloroethanamine Chemical compound NCCCl VKPPFDPXZWFDFA-UHFFFAOYSA-N 0.000 claims 2
- 238000000926 separation method Methods 0.000 claims 1
- 239000000835 fiber Substances 0.000 abstract description 16
- 238000004043 dyeing Methods 0.000 abstract description 9
- ONRREFWJTRBDRA-UHFFFAOYSA-N 2-chloroethanamine;hydron;chloride Chemical compound [Cl-].[NH3+]CCCl ONRREFWJTRBDRA-UHFFFAOYSA-N 0.000 abstract description 6
- 229920000297 Rayon Polymers 0.000 abstract description 4
- 238000009980 pad dyeing Methods 0.000 abstract description 4
- 108090000623 proteins and genes Proteins 0.000 abstract description 4
- 102000004169 proteins and genes Human genes 0.000 abstract description 4
- 238000005917 acylation reaction Methods 0.000 abstract description 3
- 238000007639 printing Methods 0.000 abstract description 2
- 229910021653 sulphate ion Inorganic materials 0.000 abstract description 2
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 abstract 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 abstract 1
- 229920003043 Cellulose fiber Polymers 0.000 abstract 1
- 239000004952 Polyamide Substances 0.000 abstract 1
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 230000010933 acylation Effects 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 229940018564 m-phenylenediamine Drugs 0.000 abstract 1
- 229920002647 polyamide Polymers 0.000 abstract 1
- 239000011265 semifinished product Substances 0.000 abstract 1
- 238000001694 spray drying Methods 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 45
- 239000002585 base Substances 0.000 description 34
- 239000000543 intermediate Substances 0.000 description 29
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 22
- 239000007791 liquid phase Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- 235000010288 sodium nitrite Nutrition 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 238000006482 condensation reaction Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000004753 textile Substances 0.000 description 6
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 4
- 239000002932 luster Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000013112 stability test Methods 0.000 description 4
- 101100118680 Caenorhabditis elegans sec-61.G gene Proteins 0.000 description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 3
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 3
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- SKAQIIQASPJOPO-UHFFFAOYSA-N ethyl hydrogen sulfate;hydrate Chemical compound O.CCOS(O)(=O)=O SKAQIIQASPJOPO-UHFFFAOYSA-N 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000985 reactive dye Substances 0.000 description 3
- 238000010583 slow cooling Methods 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000013517 stratification Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010186 staining Methods 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- UIEBGVDTKLYGTN-UHFFFAOYSA-J tetrasodium;7-[[2-(carbamoylamino)-4-[[4-chloro-6-[3-(2-sulfonatooxyethylsulfonyl)anilino]-1,3,5-triazin-2-yl]amino]phenyl]diazenyl]naphthalene-1,3,6-trisulfonate Chemical compound [Na+].[Na+].[Na+].[Na+].C=1C=C(N=NC=2C(=CC3=CC(=CC(=C3C=2)S([O-])(=O)=O)S([O-])(=O)=O)S([O-])(=O)=O)C(NC(=O)N)=CC=1NC(N=1)=NC(Cl)=NC=1NC1=CC=CC(S(=O)(=O)CCOS([O-])(=O)=O)=C1 UIEBGVDTKLYGTN-UHFFFAOYSA-J 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 241000532370 Atla Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 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 1
- 238000002156 mixing Methods 0.000 description 1
- 150000005002 naphthylamines Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000005477 standard model Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a reactive yellow dye with high washing fastness and a preparation method thereof. The preparation method comprises the following steps of carrying out acylation on m-phenylenediamine and sodium cyanate under an acidic condition to generate m-uramidoacylaminoaniline; coupling with a diazonium salt of 3,6,8-trisulfonic acid-2-naphthylamine to obtain a color base; carrying out primary condensation on the color base and cyanuric chloride; carrying out condensation on para-acetamidobenzene sulfonyl chloride and a sulfide to obtain thioether, wherein para-acetamidobenzene sulfonyl chloride is generated by reacting acetanilide with chlorosulfonic acid and sulfoxide chloride and the sulfide is generated by reacting 2-chloroethylamine hydrochloride with mercaptoethanol; carrying out secondary condensation on 2-[2-(4-aminobenzenesulfonamido) ethylsulfuryl] hydroxyethyl sulphate intermediate prepared by reoxidizing and esterifying thioether; and filtering, collecting filtrate and directly carrying out spray drying to obtain the semi-finished product. The reactive yellow dye has the advantages of high substantivity, good compatibility, high lifting capability, high fixation ratio and excellent various fastness and is suitable for dyeing, printing and pad dyeing of cellulose fiber, protein fiber, viscose fiber and polyamide fiber and the washing fastness of the reactive yellow dye is 0.5-1 grade higher than that of general varieties.
Description
Technical field
The present invention relates to technical field of fine, particularly relate to reactive yellow dyes of a kind of high washing fastness and preparation method thereof.Reactive yellow dyes has lovely luster, solubleness is high, and substantivity is high, compatibleness is good, the features such as lifting force is high, degree of fixation is high, and every fastness is excellent.This dyestuff is applicable to the dyeing of cellulosic fibre, protein fibre, viscose fiber and tynex, stamp and pad dyeing, and washing fastness is higher than the 0.5-1 level of general kind.
Background technology
Yellow active dye consumption is inferior to black, a red large veriety, main products has C.I REACTIVE Yellow 145 (reactive yellow M-3RE), C.I reactive yellow 176 (active yellow 3 R S), C.I REACTIVE Yellow 160 (reactive yellow B-4GLN), reactive yellow S-3R etc., although this several yellow cultivars can dye and obtain the coloured light of different vividness on cellulosic fibre, but C.I REACTIVE Yellow 160 (reactive yellow B-4GLN), reactive yellow S-3R are faint yellow, pile-on properties is bad, degree of fixation 60%; C.I reactive yellow 176 (active yellow 3 R S) dyeing colo r light is partially dark, degree of fixation 62%-65%; The synthesis of C.I REACTIVE Yellow 145 (reactive yellow M-3RE), because using 4,6,8-trisulfonic acid and a position, causes that cost is higher, sexual valence ratio, and printing and dyeing user is difficult to accept.C.I reactive yellow 176 dyeing colo r light is not bright-coloured, and easily detergency difference causes washing fastness poor simultaneously.The commodity that this product is output in market, sales volume is maximum, its dye structure is the compound of following formula (1).
Recent patent and dyestuff commodity market release the composite mixture of dyestuff (1) and dyestuff (2), dyestuff (3) or dyestuff (4).Dyestuff (1) and the composite mixture obtained of dyestuff (2) dye, although improve vividness and the washing fastness of coloured light to a certain extent on fiber; But the color and luster that dyeing obtains is full not, when contaminating dark, washing fastness does not still reach satisfied effect.
Dyestuff (1) and the composite mixture obtained of dyestuff (3) dye on fiber, although depth is better, vividness, washing fastness and fastness to rubbing are poorer.
Dyestuff (1) and the composite mixture obtained of dyestuff (4) dye on fiber, although vividness is better, the inclined gold-tinted of coloured light, depth is poor, washing fastness is poor.
Above-mentioned composite dye species, because each component structurally exists larger difference, easily causes the consistency of dyestuff not work in coordination with, and produces the demand that washing fastness can not meet actual life and environmental protection.
Summary of the invention
The object of the invention is the deficiency in order to overcome currently available products certain applications performance, a kind of reactive yellow dyes compound of high washing fastness is provided.
Another object of the present invention is to provide a kind of preparation method of above-claimed cpd.
A further object of the invention provides above-claimed cpd as the purposes of reactive yellow dyes.
Object of the present invention can be reached by following measures: in reactive monoazo dyestuffs structure design; between being generated by mphenylenediamine and Zassol acidylate, urea amido aniline is as coupling component; with 3; 6; the diazonium salt coupling of 8-trisulfonic acid-2-naphthylamines obtains color base; color base and cyanuric chloride carry out primary condensation, then with new intermediate 2-[2-(4-aminobenzene sulfonamide base) ethyl sulfuryl] hydroxide ethylsulfuric acid ester secondary condensation, dyestuff directly sprays baking.Vinyl sulfone(RemzaolHuo Xingranliaohuoxingjituan) sulphate activity base is structurally modified, introduces sulfoamido, ethyl sulfuryl that volume is larger, carry high molecular hydrophobic and hydrophilic ratio of components, the coplanarity of its molecular structure is significantly declined, thus suitably improve the substantivity of dyestuff; Condensation course adopts sodium bicarbonate adjust ph, improves the transformation efficiency of reaction, the purity of product; Above-mentioned two kinds of results improved improve dye uptake, the degree of fixation of product, and washing fastness improves 0.5-1 level relatively.
New intermediate 2-[2-(4-aminobenzene sulfonamide base) ethyl sulfuryl] hydroxide ethylsulfuric acid ester is by Acetanilide and chlorsulfonic acid, sulfur oxychloride reaction generates p-acetaminobenzenesulfonyl chloride, react with 2-chloroethyl amine hydrochloride and mercaptoethanol the sulfide generated to carry out condensation and obtain thioether, thioether is reoxidised into sulfuryl, acetylaminobenzene sulfonamide ethyl sulfuryl-2-hydroxyethyl again with 100% sulphating, hydrolysis generates 2-[2-(4-aminobenzene sulfonamide base) ethyl sulfuryl] hydroxide ethylsulfuric acid ester or 2-[2-(4-aminobenzene sulfonamide base) ethyl sulfuryl] hydroxide ethylsulfuric acid ester-3-sulfonic acid.
The present invention relates to a series of can as the following compound of the general structure of reactive yellow dyes:
In formula: R
1=H, CH
3, OCH
3, Cl or SO
3h.
In general formula, R
1preferred H, the preferred compound of the present invention, its structure is as follows:
In general formula, R
1preferably-SO
3h.The preferred compound of the present invention, its structure is as follows:
When this compound is as reactive yellow dyes, has lovely luster, solubleness is high, substantivity is high, compatibleness is good, the features such as lifting force is high, degree of fixation is high, and every fastness is excellent.This dyestuff is applicable to the dyeing of cellulosic fibre, protein fibre, viscose fiber and tynex, stamp and pad dyeing, and washing fastness is higher than the 0.5-1 level of general kind.
A kind of preparation method of formula (I) compound is: between being generated by mphenylenediamine and Zassol acidylate, urea amido aniline is as coupling component; with 3; 6; the diazonium salt coupling of 8-trisulfonic acid-2-naphthylamines obtains color base; color base and cyanuric chloride carry out primary condensation, then with new intermediate 2-[2-(4-aminobenzene sulfonamide base) ethyl sulfuryl] hydroxide ethylsulfuric acid ester secondary condensation, filter; collect solution, directly work in-process dyestuff is dried to obtain in spray.
New intermediate 2-[2-(4-aminobenzene sulfonamide base) ethyl sulfuryl] hydroxide ethylsulfuric acid ester is reacted by Acetanilide and chlorsulfonic acid, sulfur oxychloride and generates p-acetaminobenzenesulfonyl chloride, react with 2-chloroethyl amine hydrochloride and mercaptoethanol the sulfide generated to carry out condensation and obtain thioether, thioether is reoxidised into sulfuryl, acetylaminobenzene sulfonamide ethyl sulfuryl-2-hydroxyethyl again with 100% sulphating, be hydrolyzed and make.
A kind of preparation method of formula (II) compound is: between being generated by mphenylenediamine and Zassol acidylate, urea amido aniline is as coupling component; with 3; 6; the diazonium salt coupling of 8-trisulfonic acid-2-naphthylamines obtains color base; color base and cyanuric chloride carry out primary condensation, then with new intermediate 2-[2-(4-aminobenzene sulfonamide base) ethyl sulfuryl] hydroxide ethylsulfuric acid ester-3-sulfonic acid secondary condensation, filter; collect solution, directly work in-process dyestuff is dried to obtain in spray.Wherein new intermediate 2-[2-(4-aminobenzene sulfonamide base) ethyl sulfuryl] hydroxide ethylsulfuric acid ester-3-sulfonic acid is made up with 25% fuming acid sulfonation of 2-[2-(4-aminobenzene sulfonamide base) ethyl sulfuryl] hydroxide ethylsulfuric acid ester again.
Directly add during new intermediate secondary condensation, use sodium bicarbonate adjust ph, improve concentration, the speed of reactant, thus improve the transformation efficiency of reaction, the purity of product, the temperature of condensation is 40 ~ 55 DEG C, and pH value is 4 ~ 6.
The concrete preparation method of one of formula (I) compound is as follows:
16.28g Acetanilide is joined control temperature 20-30 DEG C in 138g chlorsulfonic acid, add rear be slowly warmed up to 40-65 DEG C reaction 2 hours, drip 28.4g sulfur oxychloride and react 2 hours, lower the temperature 25 DEG C and filter to obtain the damp product p-acetaminobenzenesulfonyl chloride of 63.1g (40%) with frozen water dilution precipitation.
14.1g2-chloroethylamine hydrochloride is under agitation joined with 9.4g mercaptoethanol solution, regulate pH=4.8 with sodium bicarbonate simultaneously, within 4 hours, generate 13.8g beta-hydroxyethyl thioether ethylamine in 55 DEG C of reactions.Terminal is cooled to 0 DEG C after arriving, slowly add the damp product p-acetaminobenzenesulfonyl chloride of 63.1g (40%), add rear sodium bicarbonate and regulate pH=3.8, control temperature 0-2 DEG C is reacted 4 hours, and stratification is separated, washing secondary obtains 32.6g acetylaminobenzene sulfonamide ethyl-2-hydroxyethyl thioether.
In there-necked flask, add 3.3g sodium wolframate crystal and 6.3g water, drip the hydrochloric acid of 0.45g30%, adjust pH=5.8.Slowly add 32.6g acetylaminobenzene sulfonamide ethyl-beta-hydroxyethyl thioether, then the hydrogen peroxide dripping 11.6g30% in 1 hour is warmed up to 30-40 DEG C, use the soda ash water 45g adjust pH 6 of 10% simultaneously, the hydrogen peroxide dripping 12.6g30% after adding again in 1 hour is warmed up to 50 DEG C, use soda ash water 15.4 adjust pH 6 of 10% simultaneously, finally be warmed up to 85 DEG C, react and be oxidized to sulfuryl in 8 hours, acidifying pH=3.5, slow cooling to 20 DEG C is separated out, and filters to obtain 60.2g (damp product content is 58.2%) acetylaminobenzene sulfonamide ethyl sulfuryl-2-hydroxyethyl.
The sulfuric acid of 10.5g98% is added in esterifier, 60.2 parts of (damp product content is 58.2%) acetylaminobenzene sulfonamide ethyl sulfuryl-2-hydroxyethyls are added under stirring, pull an oar 15 minutes, open vacuum, slowly be warmed up to 132 DEG C, controlling vacuum tightness size is 0.2-0.3Mpa, react 8 hours terminals to arrive, cooling discharge, pulverize to obtain 43.6g (content is 96.6%) intermediate 2-[2-(4-aminobenzene sulfonamide base) ethyl sulfuryl] hydroxide ethylsulfuric acid ester.
In beaker, add 45g water, 11.25g mphenylenediamine stirs, be warming up to whole dissolving, hydrochloric acid to the congo-red test paper adding 15g30% is blue, adds 14.06g sodium-chlor, stirs 30 minutes, cooling 25-30 DEG C.2.5-3 hour, temperature 25-30 DEG C, congo-red test paper in blue condition under slowly add Zassol 9.3g, speed is first quick and back slow.Add rear insulation 25-30 DEG C reaction 1 hour, survey liquid phase purity and reach 99%.Regulate pH=7-7.5 with the caustic soda 33.8g of 10% before coupling, treat that coupling is used.
End water 10g, ice 30g is added in diazonium cup, 61.8g (content 62%) 3 is added under stirring, 6,8-trisulfonic acid-2-naphthylamines, ice grinds 2 hours, then from liquid level, add 7.11g (97%) industrial goods Sodium Nitrite (being mixed with the sodium nitrite solution of 30%), control temperature 3-8 DEG C, the micro-blue look of KI test paper, congo-red test paper avy blue, sodium nitrite solution adds rear maintenance temperature 3-8 DEG C, the micro-blue colour response of KI test paper 1 hour, eliminates micro-excessive nitrous acid before coupling with a small amount of thionamic acid.
Add the mphenylenediamine acylate treating coupling under being stirred by the diazonium salt prepared, the soda ash aqueous solution 58g with 10% regulates pH=5.5-5.8, and control temperature is 5-10 DEG C simultaneously, reacts and disappears for terminal arrives to diazonium salt, survey liquid phase purity and reach 90%.The soda ash aqueous solution 16g of coupling terminal again with 10% after arriving regulates pH=6.7-7, pending primary condensation.
Join in condensation cup in 5g water, 30g ice, 18.6g cyanuric chloride and pull an oar 1 hour, temperature is less than 0 DEG C; Then the coupling solution that pH value regulates directly is added, add rear stirring and treat that pH is down to 2-3 in 1 hour, slow 11.6g sodium bicarbonate regulates pH=3.5-4, temperature controls 5 ~ 12 DEG C, keep pH=3-4, temperature 5 ~ 12 DEG C reaction 1 hour, regulate pH=6-7 with 5.2g sodium bicarbonate again, temperature controls 5 ~ 12 DEG C.Keep pH=6-7, temperature 5 ~ 12 DEG C reaction 3 hours, survey liquid phase purity and reach 88%, prepare secondary condensation.
New intermediate 2-[2-(4-aminobenzene sulfonamide base) ethyl sulfuryl] hydroxide ethylsulfuric acid ester 43.6g (content is 96.6%) the industrial goods powder prepared is added in the secondary condensation liquid that terminal arrives, add rear stirring 20 minutes, then pH=6-6.5 is regulated with 17g sodium bicarbonate, slowly be warming up to 40-45 DEG C again, keep pH=6-6.5 with 6.5g sodium bicarbonate simultaneously, keep pH=6-6.5, temperature 40-45 DEG C of reaction 2-3 hour, then heat up 55 DEG C, keep pH=6-6.5 with 1.52g sodium bicarbonate simultaneously, temperature 55 DEG C reaction 6-8 arrives to condensation terminal, survey liquid phase purity simultaneously and reach 78-80%.
Suction filtration after condensation terminal arrives, collects filtrate, all concentrates to obtain work in-process 153g, is processed into commodity sample according to standard or customer requirement.
The present invention relates to the preparation technology of formula (I) reactive yellow dyes, comprise following reaction: sulfonation reaction, condensation reaction, oxidizing reaction, hydrolysis reaction, esterification, acylation reaction, draw nitrogen reaction, coupled reaction.
The present invention relates to the condensation reaction condition preparing intermediate 2-[2-(4-aminobenzene sulfonamide base) ethyl sulfuryl] hydroxide ethylsulfuric acid ester: first 2-chloroethyl amine hydrochloride is generated beta-hydroxyethyl thioether ethylamine with mercaptoethanol condensation, improve speed of reaction and transformation efficiency by the temperature, the pH value that change reaction, obtain the thioether that yield does not wait; Beta-hydroxyethyl thioether ethylamine and p-acetaminobenzenesulfonyl chloride condensation generate acetylaminobenzene sulfonamide ethyl-2-hydroxyethyl thioether, consider the stability of its p-acetaminobenzenesulfonyl chloride, speed of reaction and transformation efficiency, determine temperature of reaction 0-2 DEG C, pH=3.5-4, the reaction times, optimize optimum proportioning, technique.
The present invention relates to the oxidation reaction condition of intermediate: constant at sodium wolframate consumption, pH value in reaction 5.5-6.5, temperature 30-85 DEG C, change the proportioning of hydrogen peroxide and acetylaminobenzene sulfonamide ethyl-2-hydroxyethyl thioether, the degree of oxidation of Liquid Detection acetylaminobenzene sulfonamide ethyl-2-hydroxyethyl thioether, the optimum proportioning that control residual quantity obtains hydrogen peroxide can not be less than 2:1; Sodium wolframate consumption is 10% of thioether simultaneously, and catalytic effect is best.
The present invention relates to the hydrolysis of intermediate, esterification condition: aniline is hydrolyzed, enzymatic synthesis condition basic simlarity with 4-(2-hydroxyethyl sulfone sulfate), use special esterifier, mol ratio, temperature of reaction, the stirring velocity of adjustment esterification, strengthening mixing effect, liquid phase follow the tracks of the purity of product, control terminal and arrive., draw nitrogen reaction, coupled reaction.
Acylation reaction in preparation of dyestuff: change acidylate temperature height in the past and easily cause two acylate content inclined; transformation efficiency, purity are on the low side; this technology controlling and process temperature of reaction, acidity condition etc., improve transformation efficiency and purity, and a urea amido aniline does not need refining and acid out can be directly used in coupling to use.
Nitrogen reaction of drawing in preparation of dyestuff changes traditional method: first dissolved by naphthylamines, then after salt adding acid out of lowering the temperature goes out, adds Sodium Nitrite reaction and generate diazo component.The present invention adopts 3,6,8-trisulfonic acid-2-naphthylamines is that under the condition of 0 DEG C, making beating forms superfine suspensoid at frozen water, add sodium nitrite solution reaction again and generate diazo component, save the consumption of alkali and acid, the obtained diazo component isomery scale of construction is few, fewer by its obtained reactive yellow dyes by-product, improves its absolute degree of fixation and all other fastness.
The present invention relates to coupled reaction condition: by changing temperature, pH value, concentration, the alkaline agent of its coupled reaction, controlling low temperature 5-10 DEG C, low ph value 5.5-5.8, react and disappear for terminal arrives to diazonium salt, survey liquid phase purity and reach 90%.Its azoic dyestuff because of containing isomer number, and produce the different and application performance of absolute degree of fixation and change, optimize optimum proportioning, synthesis obtains the reactive yellow dyes more stable than known yellow dyes performance in the past.
The present invention relates to the condition of primary condensation reaction: the production technique in past is cyanuric chloride and color base solution primary condensation, regulate pH with the soda ash aqueous solution while adding color base, pH value height easily causes chlorine atom to be hydrolyzed; Change into and add rear stirring and treat that pH is down to 2-3 in 1 hour, slowly regulate pH with sodium bicarbonate, sectional-regulated, temperature controls 5 ~ 12 DEG C of reactions 1 hour, surveys liquid phase purity and reaches 88%, higher by 8% than former process purity 80%.
The present invention relates to the condition of primary condensation reaction: in the secondary condensation liquid that terminal arrives, add new intermediate 2-[2-(4-aminobenzene sulfonamide base) ethyl sulfuryl] the hydroxide ethylsulfuric acid ester industrial goods powder prepared, add rear stirring 20 minutes, then pH=6-6.5 is regulated with sodium bicarbonate, slowly be warming up to 40-45 DEG C, keep pH=6-6.5 with 6.5g sodium bicarbonate simultaneously, keep pH=6-6.5, temperature 40-45 DEG C of reaction 2-3 hour, then heat up 55 DEG C, keep pH=6-6.5 with sodium bicarbonate simultaneously, temperature 55 DEG C reaction 6-8 arrives to condensation terminal, survey liquid phase purity simultaneously and reach 78-80%.The present invention uses new intermediate 2-[2-(4-aminobenzene sulfonamide base) ethyl sulfuryl] hydroxide ethylsulfuric acid ester as two contracting components, hydroxide ethylsulfuric acid ester is introduced the larger sulfoamido of volume, ethyl sulfuryl again, carry high molecular hydrophobic and hydrophilic ratio of components, the coplanarity of its molecular structure is significantly declined, thus suitably improves the substantivity of dyestuff; New intermediate directly adds powder, regulates pH with sodium bicarbonate simultaneously, and improve concentration, the transformation efficiency of reactant, product purity increases substantially; Above-mentioned two kinds of results improved improve dye uptake, the degree of fixation of product, and washing fastness improves 0.5-1 level relatively.
Positively effect of the present invention is as follows:
Synthesized by the present invention reactive yellow dyes compound has lovely luster, solubleness is high, direct high, compatibleness is good, the features such as lifting force is high, degree of fixation is high, and every fastness is excellent.This dyestuff is applicable to the dyeing of cellulosic fibre, protein fibre, viscose fiber and tynex, stamp and pad dyeing, and washing fastness is higher than the 0.5-1 level of general kind.
Accompanying drawing explanation
Fig. 1 is the UV comparison diagram of the yellow M-3RE of standard activity and embodiment of the present invention gained reactive yellow dyes;
In figure: X-coordinate represents absorbing wavelength nm, ordinate zou Abs represents the dimensionless number of absorbancy;
In figure, lower curve is the UV curve of reactive yellow M-3RE, and maximum absorption wavelength is 412nm, and absorption value is 0.552; Top curve is the UV curve of embodiment 1, and maximum absorption wavelength is 415nm, and absorption value is 0.635, and the yellow M-3RE's of absorption value specific activity is 0.552 high by 15%, and result makes staining power high by 15%;
Fig. 2 is preparation method's schema of the reactive yellow fuel of the high washing fastness that the embodiment of the present invention provides.
Embodiment
The following examples describe in further detail of the present invention.
As shown in Figure 2, the preparation method of the reactive yellow dyes of the high washing fastness of the embodiment of the present invention, method is as follows:
S101: mphenylenediamine in acid condition and Zassol acidylate generate between urea amido aniline, obtain color base with the diazonium salt coupling of 3,6,8-trisulfonic acid-2-naphthylamines, color base and cyanuric chloride carry out primary condensation;
S102: generate p-acetaminobenzenesulfonyl chloride with being reacted by Acetanilide and chlorsulfonic acid, sulfur oxychloride again;
S103: react with 2-chloroethyl amine hydrochloride and mercaptoethanol the sulfide generated and carry out condensation and obtain thioether, thioether is reoxidized, 2-[2-(4-aminobenzene sulfonamide base) ethyl sulfuryl] hydroxide ethylsulfuric acid ester intermediate that esterification is obtained carries out secondary condensation, filter, collect filtrate, Direct spraying is dry obtains work in-process.
Embodiment 1:
One, the condensation reaction of Intermediate Preparation
16.2g Acetanilide is joined control temperature 20-30 DEG C in 13.8g chlorsulfonic acid, add rear be slowly warmed up to 40-65 DEG C reaction 2 hours, drip 28.3g sulfur oxychloride and react 2 hours, lower the temperature 25 DEG C and filter to obtain the damp product p-acetaminobenzenesulfonyl chloride of 63.1g (40%) with frozen water dilution precipitation.
Two, thioether synthesis
14.1g2-chloroethylamine hydrochloride is under agitation joined with 9.4g mercaptoethanol solution, regulate pH=4.8 with sodium bicarbonate simultaneously, within 4 hours, generate 13.8g beta-hydroxyethyl thioether ethylamine in 55 DEG C of reactions.Terminal is cooled to 0 DEG C after arriving, slowly add the damp product p-acetaminobenzenesulfonyl chloride of 63.1g (40%), add rear sodium bicarbonate and regulate pH=3.8, control temperature 0-2 DEG C is reacted 4 hours, and stratification is separated, washing secondary obtains 32.6g acetylaminobenzene sulfonamide ethyl-2-hydroxyethyl thioether.
Three, sulfide oxidation
In there-necked flask, add 3.3g sodium wolframate crystal and 6.3g water, drip the hydrochloric acid of 0.45g30%, adjust pH=5.8.Slowly add 32.6g acetylaminobenzene sulfonamide ethyl-beta-hydroxyethyl thioether, then the hydrogen peroxide dripping 11.6g30% in 1 hour is warmed up to 30-40 DEG C, use the soda ash water 45g adjust pH 6 of 10% simultaneously, the hydrogen peroxide dripping 12.6g30% after adding again in 1 hour is warmed up to 50 DEG C, use the soda ash water 15.4g adjust pH 6 of 10% simultaneously, finally be warmed up to 85 DEG C, react and be oxidized to sulfuryl in 8 hours, acidifying pH=3.5, slow cooling to 20 DEG C is separated out, filter to obtain 60.2g (damp product content is 58.2%) acetylaminobenzene sulfonamide ethyl sulfuryl-2-hydroxyethyl.
Four, esterification and hydrolysis reaction
The sulfuric acid of 10.4g98% is added in esterifier, 60.2g (damp product content is 58.2%) acetylaminobenzene sulfonamide ethyl sulfuryl-2-hydroxyethyl is added under stirring, pull an oar 15 minutes, open vacuum, slowly be warmed up to 130 DEG C, controlling vacuum tightness size is 0.2-0.3Mpa, react 8 hours terminals to arrive, cooling discharge, pulverize to obtain 43.6g (content is 96.6%) intermediate 2-[2-(4-aminobenzene sulfonamide base) ethyl sulfuryl] hydroxide ethylsulfuric acid ester.
Five, mphenylenediamine acidylate
In beaker, add 45g water, 11.25g mphenylenediamine stirs, be warming up to whole dissolving, hydrochloric acid to the congo-red test paper adding 15g30% is blue, adds 14.06g sodium-chlor, stirs 30 minutes, cooling 25-30 DEG C.2.5-3 hour, temperature 25-30 DEG C, congo-red test paper in blue condition under slowly add Zassol 9.3g, speed is first quick and back slow.Add rear insulation 25-30 DEG C reaction 1 hour, survey liquid phase purity and reach 99%.Regulate pH=7-7.5 with the caustic soda 33.8g of 10% before coupling, treat that coupling is used.
Six, nitrogen reaction is drawn
End water 10g, ice 30g is added in diazonium cup, 61.8g (content 62%) 3 is added under stirring, 6,8-trisulfonic acid-2-naphthylamines, ice grinds 2 hours, then from liquid level, add 7.11g (97%) industrial goods Sodium Nitrite (being mixed with the sodium nitrite solution of 30%), control temperature 3-8 DEG C, the micro-blue look of KI test paper, congo-red test paper avy blue, sodium nitrite solution adds rear maintenance temperature 3-8 DEG C, the micro-blue colour response of KI test paper 1 hour, eliminates micro-excessive nitrous acid before coupling with a small amount of thionamic acid.
Seven, coupled reaction
Add the mphenylenediamine acylate treating coupling under being stirred by the diazonium salt prepared, the soda ash aqueous solution 58g with 10% regulates pH=5.5-5.8, and control temperature is 5-10 DEG C simultaneously, reacts and disappears for terminal arrives to diazonium salt, survey liquid phase purity and reach 90%.The soda ash aqueous solution 16g of coupling terminal again with 10% after arriving regulates pH=6.7-7, pending primary condensation.
Eight, the primary condensation of color base
Join in condensation cup in 5g water, 30g ice, 18.6g cyanuric chloride and pull an oar 1 hour, temperature is less than 0 DEG C; Then the coupling solution that pH value regulates directly is added, add rear stirring and treat that pH is down to 2-3 in 1 hour, slow 11.6g sodium bicarbonate regulates pH=3.5-4, temperature controls 5 ~ 12 DEG C, keep pH=3-4, temperature 5 ~ 12 DEG C reaction 1 hour, regulate pH=6-7 with 5.2g sodium bicarbonate again, temperature controls 5 ~ 12 DEG C.Keep pH=6-7, temperature 5 ~ 12 DEG C reaction 3 hours, survey liquid phase purity and reach 88%, prepare secondary condensation.
Nine, the secondary condensation of new intermediate
New intermediate 2-[2-(4-aminobenzene sulfonamide base) ethyl sulfuryl] hydroxide ethylsulfuric acid ester 43.6g (content is 96.6%) the industrial goods powder prepared is added in the secondary condensation liquid that terminal arrives, add rear stirring 20 minutes, then pH=6-6.5 is regulated with 17g sodium bicarbonate, slowly be warming up to 40-45 DEG C again, keep pH=6-6.5 with 6.5g sodium bicarbonate simultaneously, keep pH=6-6.5, temperature 40-45 DEG C of reaction 2-3 hour, then heat up 55 DEG C, keep pH=6-6.5 with 1.52g sodium bicarbonate simultaneously, temperature 55 DEG C reaction 6-8 arrives to condensation terminal, survey liquid phase purity simultaneously and reach 78-80%.
Ten, aftertreatment
Suction filtration after dyestuff condensation terminal arrives, collects filtrate, and all concentrated work in-process 153g (after purifying, its MS:[M+H] +=1132.48), is processed into commodity sample according to standard or customer requirement.Product is not saltoutd, and Direct spraying is dried, and non-wastewater discharge, to eco-friendly.
Embodiment 2:
One, the condensation reaction of Intermediate Preparation
15.8g Acetanilide is joined control temperature 20-30 DEG C in 135g chlorsulfonic acid, add rear be slowly warmed up to 40-65 DEG C reaction 2 hours, drip 28.1g sulfur oxychloride and react 2 hours, lower the temperature 25 DEG C and filter to obtain the damp product p-acetaminobenzenesulfonyl chloride of 61.4g (40%) with frozen water dilution precipitation.
Two, thioether synthesis
13.8g2-chloroethylamine hydrochloride is under agitation joined with 9.1g mercaptoethanol solution, regulate pH=4.8 with sodium bicarbonate simultaneously, within 4 hours, generate 13.5g beta-hydroxyethyl thioether ethylamine in 52 DEG C of reactions.Terminal is cooled to 0 DEG C after arriving, slowly add the damp product p-acetaminobenzenesulfonyl chloride of 61.4g (40%), add rear sodium bicarbonate and regulate pH=3.5, control temperature 0-2 DEG C is reacted 4 hours, and stratification is separated, washing secondary obtains 31.7g acetylaminobenzene sulfonamide ethyl-2-hydroxyethyl thioether.
Three, sulfide oxidation
In there-necked flask, add 3.2g sodium wolframate crystal and 6..3g water, drip the hydrochloric acid of 0.45g30%, adjust pH=5.5.Slowly add 31.7g acetylaminobenzene sulfonamide ethyl-beta-hydroxyethyl thioether, then the hydrogen peroxide dripping 11.3g30% in 1 hour is warmed up to 35-40 DEG C, use the soda ash water 43.8g adjust pH 6 of 10% simultaneously, the hydrogen peroxide dripping 12.2g30% after adding again in 1 hour is warmed up to 50 DEG C, use the soda ash water 15.2g adjust pH 6 of 10% simultaneously, finally be warmed up to 82 DEG C, react and be oxidized to sulfuryl in 8 hours, acidifying pH=3.5, slow cooling to 20 DEG C is separated out, filter to obtain 58.7g (damp product content is 58%) acetylaminobenzene sulfonamide ethyl sulfuryl-2-hydroxyethyl.
Four, esterification and hydrolysis reaction
The sulfuric acid of 10.2g98% is added in esterifier, 58.7g (damp product content is 58%) acetylaminobenzene sulfonamide ethyl sulfuryl-2-hydroxyethyl is added under stirring, pull an oar 15 minutes, open vacuum, slowly be warmed up to 135 DEG C, controlling vacuum tightness size is 0.2-0.3Mpa, react 8 hours terminals to arrive, cooling discharge, pulverize to obtain 42.5g (content is 96.3%) intermediate 2-[2-(4-aminobenzene sulfonamide base) ethyl sulfuryl] hydroxide ethylsulfuric acid ester.
Five, mphenylenediamine acidylate
In beaker, add 45g water, 11.3g mphenylenediamine stirs, be warming up to whole dissolving, hydrochloric acid to the congo-red test paper adding 14.6g30% is blue, adds 13.7g sodium-chlor, stirs 30 minutes, cooling 25-35 DEG C.2.5-3 hour, temperature 30-35 DEG C, congo-red test paper in blue condition under slowly add Zassol 9.2g, speed is first quick and back slow.Add rear insulation 30-35 DEG C reaction 1 hour, survey liquid phase purity and reach 99%.Regulate pH=7-7.5 with the caustic soda 34.2g of 10% before coupling, treat that coupling is used.
Six, nitrogen reaction is drawn
End water 10g, ice 30g is added in diazonium cup, 61.8g (content 62%) 3 is added under stirring, 6,8-trisulfonic acid-2-naphthylamines, ice grinds 2 hours, then from liquid level, add 7.11g (97%) industrial goods Sodium Nitrite (being mixed with the sodium nitrite solution of 30%), control temperature 3-8 DEG C, the micro-blue look of KI test paper, congo-red test paper avy blue, sodium nitrite solution adds rear maintenance temperature 3-8 DEG C, the micro-blue colour response of KI test paper 1 hour, eliminates micro-excessive nitrous acid before coupling with a small amount of thionamic acid.
Seven, coupled reaction
Add the mphenylenediamine acylate treating coupling under being stirred by the diazonium salt prepared, the soda ash aqueous solution 56g with 10% regulates pH=4.5-5.5, and control temperature is 5-10 DEG C simultaneously, reacts and disappears for terminal arrives to diazonium salt, survey liquid phase purity and reach 88%.The soda ash aqueous solution 18g of coupling terminal again with 10% after arriving regulates pH=6.7-7, pending primary condensation.
Eight, the primary condensation of color base
Join in condensation cup in 5g water, 30g ice, 18.8g cyanuric chloride and pull an oar 1 hour, temperature is less than 0 DEG C; Then the coupling solution that pH value regulates directly is added, add rear stirring and treat that pH is down to 2-3 in 1 hour, slow 11.9g sodium bicarbonate regulates pH=3.5-4, temperature controls 5 ~ 12 DEG C, keep pH=3-4, temperature 5 ~ 12 DEG C reaction 1 hour, regulate pH=6.7 with 5.4g sodium bicarbonate again, temperature controls 5 ~ 12 DEG C.Keep pH=6-7, temperature 5 ~ 12 DEG C reaction 3 hours, survey liquid phase purity and reach 89%, prepare secondary condensation.
Nine, the secondary condensation of new intermediate
New intermediate 2-[2-(4-aminobenzene sulfonamide base) ethyl sulfuryl] hydroxide ethylsulfuric acid ester 42.5g (content is 96.3%) the industrial goods powder prepared is added in the secondary condensation liquid that terminal arrives, add rear stirring 20 minutes, then pH=6.5 is regulated with 17.2g sodium bicarbonate, slowly be warming up to 40-45 DEG C again, keep pH=6.5 with 6.7g sodium bicarbonate simultaneously, keep pH=6.5, temperature 40-45 DEG C of reaction 2-3 hour, then heat up 55 DEG C, keep pH=6.3 with 1.6g sodium bicarbonate simultaneously, temperature 55 DEG C reaction 6-8 arrives to condensation terminal, survey liquid phase purity simultaneously and reach 72%.
Ten, aftertreatment
Suction filtration after dyestuff condensation terminal arrives, collects filtrate, and all concentrated work in-process 151g (after purifying, its MS:[M+H] +=1132.48), is processed into commodity sample according to standard or customer requirement.Product is not saltoutd, and Direct spraying is dried, and non-wastewater discharge, to eco-friendly.
In example 1 and example 2, Acetanilide used, 2-chloroethyl amine hydrochloride, mercaptoethanol, hydrogen peroxide, sulfuric acid, mphenylenediamine, Zassol, 3,6,8-trisulfonic acid-2-naphthylamines, intermediates content often will criticize Exact Analysis, guarantee that content is errorless.The first five plant the content of raw material and quality to the yield of intermediate 2-[2-(4-aminobenzene sulfonamide base) ethyl sulfuryl] hydroxide ethylsulfuric acid ester and impurities affect larger; Synthesis intermediate 2-[2-(4-aminobenzene sulfonamide base) ethyl sulfuryl] hydroxide ethylsulfuric acid ester purity and content to analyze accurately, otherwise easily cause secondary condensation terminal less than, purity is on the low side; The consumption of adjustment mphenylenediamine, Zassol, coloured light, the yield of fine setting product; Lifting force, absolute degree of fixation, washing fastness etc. all increase in addition.Particular case is in table 1.
Reactive yellow dyes synthesized by embodiment 1 and reactive yellow M-3RE detect through Shimadzu UV-2450 spectrophotometer: lower curve is the UV curve of reactive yellow M-3RE, and maximum absorption wavelength is 412nm, and absorption value is 0.552; Top curve is the reactive yellow dyes that embodiment 1 is synthesized, and maximum absorption wavelength is 415nm, and absorption value is 0.635, and the yellow M-3RE's of absorption value specific activity is 0.552 high by 15%, and result makes staining power high by 15%.Particular case is in table 1 and Fig. 1.
Reactive yellow dyes synthesized by example 1 has following properties compared with reactive yellow M-3RE:
Table 1
In the test process of table 1 performance index, have employed following standard:
The general condition regulation that GB/T2374-2007 dyeing measures
The measuring method of GB/T2381-2013 dye and dye intermediate insolubles content
The mensuration of GB/T2386-2006 dye and dye intermediate moisture
The mensuration of GB/T2387-2013 reactive dye coloured light and intensity
The mensuration of GB/T2389-2006 reactive dye hydrolised dye and standard model relative content
The mensuration of GB/T2390-2013 dyestuff pH value
The mensuration of GB/T2391-2006 reactive dye degree of fixation
The measuring method of GB/T3671.1-1996 water-soluble dye solubleness and stability of solution
GB3899.1-2007 dye product nomenclature mo used for textiles
GB3899.2-2007 dye product naming standard used for textiles colour atla
The Determination by instrument of GB/T6688-2008 dyestuff relative intensity and aberration
GB/T8426-1998 textile color stability test colour fastness to light: daylight
GB/T8427-2008 textile color stability tests the colour fastness of resistance to artificial light: xenon arc
GB/T8429-1998 textile color stability test colour fastness to weathering: atmospheric exposure
GB/T8433-2008 textile color stability test colour fastness to chlorinated water (swimming-pool water)
The UV of the yellow M-3RE of standard activity and embodiment of the present invention gained reactive yellow dyes contrasts as seen from Figure 1, and concrete numerical value is as shown in table 2.
The UV of the yellow M-3RE of table 2 standard activity and embodiment gained dyestuff contrasts
Although illustrate and describe embodiments of the invention, for the ordinary skill in the art, to be appreciated that when not departing from principle of the present invention and main raw material and can to carry out multiple proportioning adjustment, condition change to these embodiments, scope of the present invention is by claims and equivalents thereof.
Claims (8)
1. a reactive yellow dyes for high washing fastness, is characterized in that: the compound structure general formula of the reactive yellow dyes of this high washing fastness is as follows:
In formula: R
1=H, CH
3, OCH
3, Cl or SO
3h.
2. the reactive yellow dyes of high washing fastness as claimed in claim 1, is characterized in that, preferred R
1the structural formula of compound of=H reactive yellow dyes is as follows:
3. prepare the reactive yellow dyes of high washing fastness as claimed in claim 2 for one kind, it is characterized in that, the preparation method of the reactive yellow dyes of this high washing fastness, as follows: mphenylenediamine in acid condition and Zassol acidylate generate between urea amido aniline, with 3, 6, the diazonium salt coupling of 8-trisulfonic acid-2-naphthylamines obtains color base, color base and cyanuric chloride carry out primary condensation, again with by Acetanilide and chlorsulfonic acid, sulfur oxychloride reaction generates p-acetaminobenzenesulfonyl chloride, react with 2-chloroethyl amine hydrochloride and mercaptoethanol the sulfide generated to carry out condensation and obtain thioether, thioether is reoxidized, 2-[2-(4-aminobenzene sulfonamide base) ethyl sulfuryl] the hydroxide ethylsulfuric acid ester intermediate that esterification obtains carries out secondary condensation, filter, collect filtrate, Direct spraying is dry obtains work in-process.
4. the reactive yellow dyes of high washing fastness as claimed in claim 3, it is characterized in that, intermediate 2-[2-(4-aminobenzene sulfonamide base) ethyl sulfuryl] hydroxide ethylsulfuric acid ester is characterised in that: joined by Acetanilide in chlorsulfonic acid in 40-65 DEG C of reaction 2 hours, drip sulfur oxychloride and react 2 hours, damp product p-acetaminobenzenesulfonyl chloride is filtered to obtain in dilution precipitation.
2-chloroethyl amine hydrochloride is under agitation joined in mercaptoethanol solution, regulate pH=4.8, within 4 hours, generate beta-hydroxyethyl thioether ethylamine in 55 DEG C of reactions; Be cooled to 0 DEG C, slowly add damp product p-acetaminobenzenesulfonyl chloride, regulate pH=3.8-5, control temperature 0-2 DEG C to react 4 hours, separation, washing obtain acetylaminobenzene sulfonamide ethyl-2-hydroxyethyl thioether;
In reactor, add water, sodium wolframate crystal, drip the hydrochloric acid of 30%, adjust pH=5.8-6.5.Slowly add acetylaminobenzene sulfonamide ethyl-beta-hydroxyethyl thioether, then the hydrogen peroxide dripping 30% is warmed up to 30-40 DEG C, the soda ash water adjust pH 5-6 of 10%, the hydrogen peroxide dripping 30% is again warmed up to 50 DEG C, the soda ash water adjust pH 6 of 10%, is finally warmed up to 80-85 DEG C of reaction and within 8 hours, is oxidized to sulfuryl, acidifying pH=3.5-4, to lower the temperature 20 DEG C of precipitations, filter and to obtain acetylaminobenzene sulfonamide ethyl sulfuryl-2-hydroxyethyl tide product;
The sulfuric acid of 98% is added in esterifier, damp product are added under stirring, open vacuum, slowly be warmed up to 130 DEG C, controlling vacuum tightness size is 0.2-0.3Mpa, react 8 hours terminals to arrive, cooling discharge, pulverize to obtain intermediate 2-[2-(4-aminobenzene sulfonamide base) ethyl sulfuryl] hydroxide ethylsulfuric acid ester.
5. the reactive yellow dyes of high washing fastness as claimed in claim 3, is characterized in that, mphenylenediamine in acid condition and Zassol acidylate generate between urea amido aniline, obtain color base with the diazonium salt coupling of 3,6,8-trisulfonic acid-2-naphthylamines.
6. the reactive yellow dyes of the high washing fastness as described in claim 3 or 4, is characterized in that, cyanuric chloride first carries out primary condensation with color base, and temperature is 5 ~ 10 DEG C, pH value is 4 ~ 6; Again with obtained intermediate 2-[2-(4-aminobenzene sulfonamide base) ethyl sulfuryl] hydroxide ethylsulfuric acid ester powder secondary condensation, temperature is 40 ~ 50 DEG C, and pH value is 6 ~ 7.
7. the reactive yellow dyes of high washing fastness as claimed in claim 6, is characterized in that, condensation course all regulates pH with sodium bicarbonate powder, and the concentration improving reactant is amassed, the yield of speed of response, transformation efficiency and product.
8. the reactive yellow dyes of high washing fastness as claimed in claim 1 or 2, is characterized in that, the compound of the reactive yellow dyes of this high washing fastness is as the purposes of reactive yellow dyes.
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| CN106317956A (en) * | 2016-07-26 | 2017-01-11 | 萧县凯奇化工科技有限公司 | Green and environment-friendly yellow G dye and preparation method thereof |
| CN108822007A (en) * | 2018-05-22 | 2018-11-16 | 福州兴创云达新材料科技有限公司 | A kind of synthetic method of N- [3- aminopropyl -2- hydroxyl ethyl sulfone] -4- nitrobenzene sulfonamide |
| CN108816230A (en) * | 2018-05-22 | 2018-11-16 | 福州兴创云达新材料科技有限公司 | A kind of novel Mg2FeAl-LDH catalyst and its application |
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| CN108816230A (en) * | 2018-05-22 | 2018-11-16 | 福州兴创云达新材料科技有限公司 | A kind of novel Mg2FeAl-LDH catalyst and its application |
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