CN1557877A - Process for preparing red benzimidazolone pigments - Google Patents
Process for preparing red benzimidazolone pigments Download PDFInfo
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- CN1557877A CN1557877A CNA2004100026328A CN200410002632A CN1557877A CN 1557877 A CN1557877 A CN 1557877A CN A2004100026328 A CNA2004100026328 A CN A2004100026328A CN 200410002632 A CN200410002632 A CN 200410002632A CN 1557877 A CN1557877 A CN 1557877A
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- 239000000049 pigment Substances 0.000 title claims abstract description 51
- MYONAGGJKCJOBT-UHFFFAOYSA-N benzimidazol-2-one Chemical compound C1=CC=CC2=NC(=O)N=C21 MYONAGGJKCJOBT-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title description 3
- 238000005859 coupling reaction Methods 0.000 claims abstract description 51
- 238000002360 preparation method Methods 0.000 claims abstract description 22
- 239000012954 diazonium Substances 0.000 claims abstract description 20
- 230000000485 pigmenting effect Effects 0.000 claims abstract description 20
- 150000004982 aromatic amines Chemical class 0.000 claims abstract description 17
- 150000001989 diazonium salts Chemical class 0.000 claims abstract description 12
- 238000006193 diazotization reaction Methods 0.000 claims abstract description 10
- 238000004381 surface treatment Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 51
- 230000008878 coupling Effects 0.000 claims description 41
- 238000010168 coupling process Methods 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000000047 product Substances 0.000 claims description 21
- 239000012065 filter cake Substances 0.000 claims description 15
- CRXVBLLLPNWFBS-UHFFFAOYSA-N 4-aminobenzimidazol-2-one Chemical compound NC1=CC=CC2=NC(=O)N=C12 CRXVBLLLPNWFBS-UHFFFAOYSA-N 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 14
- 239000000706 filtrate Substances 0.000 claims description 13
- 239000013078 crystal Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 claims description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 8
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 8
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 8
- 239000012756 surface treatment agent Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 5
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000012043 crude product Substances 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- -1 aminobenzimidazole ketone Chemical class 0.000 abstract description 6
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 32
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 24
- 239000003643 water by type Substances 0.000 description 24
- 238000003756 stirring Methods 0.000 description 19
- 235000010288 sodium nitrite Nutrition 0.000 description 16
- 238000010009 beating Methods 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- VAMXMNNIEUEQDV-UHFFFAOYSA-N methyl anthranilate Chemical compound COC(=O)C1=CC=CC=C1N VAMXMNNIEUEQDV-UHFFFAOYSA-N 0.000 description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- 238000003287 bathing Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 8
- 239000000976 ink Substances 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000004033 plastic Substances 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 239000001054 red pigment Substances 0.000 description 6
- 238000007639 printing Methods 0.000 description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- LHMQDVIHBXWNII-UHFFFAOYSA-N 3-amino-4-methoxy-n-phenylbenzamide Chemical compound C1=C(N)C(OC)=CC=C1C(=O)NC1=CC=CC=C1 LHMQDVIHBXWNII-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- HUIYGGQINIVDNW-UHFFFAOYSA-N butyl anthranilate Chemical compound CCCCOC(=O)C1=CC=CC=C1N HUIYGGQINIVDNW-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000012296 anti-solvent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- VMPITZXILSNTON-UHFFFAOYSA-N o-anisidine Chemical compound COC1=CC=CC=C1N VMPITZXILSNTON-UHFFFAOYSA-N 0.000 description 1
- 230000019612 pigmentation Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention relates to a preparation method of a red benzimidazolone pigment, which comprises 4 steps of diazotization reaction of substituted arylamine, coupling reaction of diazonium salt and 5- [2 '-hydroxy-3' -naphthoyl ] aminobenzimidazole ketone, pigmenting treatment, surface treatment of the pigment and the like.
Description
Technical field
The invention belongs to field of fine chemical, more specifically, relate to a kind of preparation method's of pigment dyestuff, particularly red benzimidazolone pigment preparation method.
Background technology
Benzimidazolone pigment is a kind of high performance pigment dyestuff, be to adopt the arylamine of different substituents to make diazo component, form with the amino benzimidazolone derivatives coupling of 5-, has the benzimidazolone structure in such pigment molecule, every application performance excellence has very high solvent resistance, unreactiveness and resistance to migration, its use general enclose very extensive, be not only applicable to the painted of plastics, resin, also be applicable to the stain for wood of senior printing-ink, industrial paint and molten Ji type.
The said red benzimidazolone pigment of the present invention is the compound with following general structure:
In the formula: R1, R2, R3, R4, R5 are selected from H, CH
3, OCH
3, COOCH
3, SO
2NHCH
3, CONHC
6H
5
United States Patent (USP) 3124565 and German Patent 1217008 disclose the molecular structure of red benzoglyoxaline ketone pigment, and have provided the preparation method of such pigment, comprise three steps altogether: one is the diazotization of single substituted aromatic amines; Its two be diazonium salt and 5-[2 '-hydroxyl-3 '-naphthoyl] coupling of amino benzimidazolone; It three is that the pigmenting of conjugates is handled.Such pigment product particle that coupling obtains in water medium is hard, tinctorial strength is low, coloured light is darker, do not have the pigment use properties, must handle by pigmenting, pigmentation method generally is to adopt organic solvents such as dimethyl formamide, pyridine, make crude pigment product boiling reflux in solvent, make it change high tinctorial strength, coloured light is bright-coloured, particle is soft beta crystal product into by alpha-crystal form.
In order to improve dispersing of pigments, United States Patent (USP) 4182708 has proposed to carry out coupled reaction in molten Ji, and carries out the method for pigmenting in this molten Ji; Also there is research to carry out diazotization under existing with 10% ethylene glycol nitrous acid ester, and coupling in ethylene glycol medium, the method that pigmenting synthesizes red benzimidazolone pigment in this medium continued again.
More than these methods all adopted a large amount of poisonous and hazardous organic solvents, not only can pollute in the production process, and can increase the pigment cost because reclaim solvent to environment.Therefore research and develop a kind of new method for preparing red benzoglyoxaline ketone pigment dyestuff and will have crucial meaning.
Summary of the invention
The technical problem to be solved in the present invention is with an organic solvent too much in the red benzimidazolone pigment preparation process, a kind of new method for preparing red benzoglyoxaline ketone pigment dyestuff is provided, environmental pollution is few in this method production process, and cost is low, the pigment particle size of output is evenly distributed, particle is soft, crystalline structure is consistent with the product of handling with organic solvent with crystallographic dimension, the tinctorial strength height of product, coloured light are bright-coloured, and fast light, solvent resistance is good.
Thinking of the present invention is such:
(1), with two kinds of substituted aromatic amines, carry out diazotization with conventional method, the ratio of two kinds of substituted aromatic amines is 1: 1-500.
(2), then diazonium salt and coupling solution are carried out coupled reaction, the coupling temperature is 0-55 ℃, coupling manner can adopt according to the character of diazonium salt along method coupling or contrary method coupling, for diazonium salt being joined the coupled reaction in the coupling solution, the pH value of this kind reaction is excessively to slightly acidic by highly basic along the method coupling; Contrary method coupling is that coupling solution is joined in the diazonium salt, and the pH value of this kind reaction is excessively to slightly acidic or weakly alkaline by strong acid.
(3), reaction finishes later on crude pigment product wet cake pigmenting in the mixed medium of water medium or a small amount of solvent and water.This organic solvent is: N-Methyl pyrrolidone, N, dinethylformamide, acetate, isopropylcarbinol, propyl carbinol etc.
(4), the filter cake water making beating that obtains of pigmenting, add specific surface treatment agent and carry out surface treatment.
For finishing purpose of the present invention, according to above-mentioned design, the contriver has proposed technical scheme as described below:
The preparation method of red benzimidazolone pigment comprises the following steps:
(1) diazotization reaction of substituted aromatic amines
Adopt two or more substituted aromatic amines to carry out diazotization reaction, described substituted aromatic amines has following general structure:
Its reaction formula is:
Wherein X is Cl or HSO4; R1, R2, R3, R4, R5 are selected from H, CH
3, OCH
3, COOCH
3, SO
2NHCH
3, CONHC
6H
5
The diazonium salt that generates is standby.
(2) diazonium salt and 5-[2 '-hydroxyl-3 '-naphthoyl] coupled reaction of amino benzimidazolone
The aqueous solution that will contain sodium hydroxide is warmed up to 100 ℃, adds earlier a small amount of Viscotrol C sodium sulfonate, add again 5-[2 '-hydroxyl-3 '-naphthoyl] amino benzimidazolone, make it dissolving, cool to 50 ℃, add proper amount of active carbon, filter, filtrate is adjusted to suitable temperature, is coupling solution, and is standby;
Coupling solution and diazonium salt are carried out coupled reaction, and temperature of reaction is 0-55 ℃;
The reaction formula of coupled reaction is:
After reaction finishes, filter also the washing filter cake to PH=7.0, with filter cake dry up to the pigment solid content be 15-40%, obtain the filter cake of crude pigment product.
(3) pigmenting is handled:
Pigmenting crude product filter cake is joined water or contain in the aqueous solution of a small amount of solvent, be heated to boiling, and maintain certain pressure, be back to crystal formation and transform fully, cooling is filtered, and washes filter cake with water;
Said organic solvent is: N, and one or more in dinethylformamide, N-Methyl pyrrolidone, acetate, formic acid, isopropylcarbinol, the propyl carbinol, the content of organic solvent is not higher than 20% in the pigmenting medium.
For obtaining better red benzimidazolone pigment, the present invention can carry out following steps after pigmenting is handled.
(4) surface treatment of pigment:
Filter cake behind the pigmenting is added to the water, adds surface treatment agent, be heated to 60-80 ℃, be incubated 1-3 hour, cooling is filtered, and filter cake is pulverized after drying; Described surface treatment agent is the rosin based compound, and add-on is the 0.5-5% (weight) of pigment.
As further technical scheme, the present invention adopts two kinds of substituted aromatic amines to carry out diazotization reaction in step (1), and the ratio of two kinds of substituted aromatic amines is 1: 1-500.
The preferred proportion of two kinds of substituted aromatic amines is 1: 1-100.
In the employed pigmenting medium of step (3), the content of organic solvent is 0.
The used surface treatment agent of step (4) is superfine rosin.
Traditional benzoglyoxaline ketone pigment prepared mainly is to have used a large amount of organic solvents in the pigmenting treating processes, thereby brings series of technical.The present invention with an organic solvent or does not only use a spot of organic solvent (not being higher than 20%) in the pigmenting treating processes, therefore avoided the problem of environmental pollution and solvent recuperation.
With the red benzimidazolone pigment of method of the present invention preparation, every excellent performances such as coloured light is bright-coloured, tinting strength is high, fast light, heat-resisting, anti-solvent can be used for the painted of products such as high-grade plastics, resin, high-grade seal China ink, industrial paint.
Embodiment
Embodiment 1
The preparation of the red benzimidazolone pigment of 171#
(1) 7.4g 4-nitro ORTHO ANISIDINE, 0.2g methyl o-aminobenzoate (two component ratios are 37: 1) join in 240 milliliters of deionized waters, stirred 30 minutes, add 10% Soxylat A 25-7 derivative solution 3.8ml, 30% hydrochloric acid 20ml, in bathing, cryosel is cooled to below 0 ℃, slowly add sodium nitrite solution (20%) 18.5ml, the terminal point Sodium Nitrite is little excessive, stirs 10 minutes, add gac, whip attachment is filtered, and filtrate is treated coupling.
(2) 5-(2 '-hydroxyl-3 '-naphthoyl) amino benzimidazolone 15g joins in 190 milliliters of deionized waters, 30% sodium hydroxide 15ml, 10% Viscotrol C sodium sulfonate 3.8ml, be stirred to whole dissolvings, adding small amount of activated filters, filtrate adds no ion frozen water to 550 milliliters of volumes, goes out fine particle with 5% glacial acetic acid solution acid out.
With 40-70 minute the diazonium drop is added in the coupling solution, the terminal point coupling solution is little excessive, stirs 20 minutes, transfers PH=2 with hydrochloric acid, is heated to 100 ℃, and insulated and stirred 120 minutes is filtered, and is washed till neutrality with deionized water.Get wet cake 115 grams.
(3) wet cake is joined in the autoclave, 400 milliliters of deionized waters, making beating was stirred 30 minutes, was warmed up to 160 ℃, stirred up to crystal formation to transform fully, filter wet cake.
(4) wet cake is added to the water, making beating evenly is warmed up to 80 ℃, adds 4g and dissolves good S-rosin solution, be incubated 2 hours, filter, add 2g and dissolve good calcium chloride solution, drying, obtain the red finished product of gold-tinted, the every fastness of this pigment is good, has the higher transparency, can be used in plastics and the paint.
Embodiment 2
The preparation of the red benzimidazolone pigment of 175#
(1) 8.0g methyl o-aminobenzoate, 0.16g3-amino-4-methoxybenzoyl aniline (two component ratios are 50: 1) join in 240 milliliters of deionized waters, stirred 30 minutes, add 10% Soxylat A 25-7 derivative solution 3.8ml, 30% hydrochloric acid 23ml, in bathing, cryosel is cooled to below 0 ℃, slowly add sodium nitrite solution (20%) 18.5ml, the terminal point Sodium Nitrite is little excessive, stirs 10 minutes, add gac, whip attachment 10 minutes is filtered, and filtrate is treated coupling.
(2) 5-(2 '-hydroxyl-3 '-naphthoyl) amino benzimidazolone 15g joins in 190 milliliters of deionized waters, 30% sodium hydroxide 15ml, 10% Viscotrol C sodium sulfonate liquid 2ml, be stirred to whole dissolvings, adding small amount of activated filters, filtrate adds no ion frozen water to 550 milliliters of volumes, goes out fine particle with 10% glacial acetic acid solution acid out.
With 40-70 minute the diazonium drop is added in the coupling solution, the terminal point coupling solution is little excessive, stirs 20 minutes, transfers PH=2 with hydrochloric acid, is heated to 100 ℃, and insulated and stirred 180 minutes is filtered, and is washed till neutrality with deionized water.Get wet cake 118 grams.
(3) wet cake is joined in the autoclave, 400 milliliters of deionized waters, 20ml pyridine, making beating stirs, and is warmed up to 160 ℃, stirs up to crystal formation to transform fully, filters, deionized water is washed till non-pyridine.
(4) wet cake is added to the water, be warmed up to 80 ℃, add 4g and dissolve good superfine rosin, be incubated 2 hours, add 2g and dissolve good calcium chloride solution, filter, drying obtains the good garnet pigment of every fastness, and this product particle is soft, particle diameter is 150-300nm, is mainly used in paint and printing ink industry.
Embodiment 3
The preparation of the red benzimidazolone pigment of 175#
(1) 12.5 gram 3-amino-4-methoxybenzoyl aniline, 0.125g methyl o-aminobenzoate (two component ratios are 100: 1) join in 240 milliliters of deionized waters, stirred 30 minutes, add 10% Soxylat A 25-7 derivative solution 3.8ml, 30% hydrochloric acid 20ml, in bathing, cryosel is cooled to below 0 ℃, slowly add sodium nitrite solution (20%) 18.5ml, the terminal point Sodium Nitrite is little excessive, stirs 10 minutes, add gac, whip attachment 10 minutes is filtered, and filtrate is treated coupling.
(2) 5-(2 '-hydroxyl-3 '-naphthoyl) amino benzimidazolone 15g joins in 190 milliliters of deionized waters, 30% sodium hydroxide 15ml, 10% Viscotrol C sodium sulfonate solution 3.8ml are stirred to whole dissolvings, add small amount of activated and filter.
With 20-50 minute the diazonium drop is added in the coupling solution, the terminal point coupling solution is little excessive, stirs 20 minutes, is heated to 100 ℃, and insulated and stirred 180 minutes is filtered, and is washed till neutrality with deionized water.Get wet cake 130 grams.
(3) wet cake is joined in the autoclave, 400 milliliters of deionized waters, 40ml N-N '-dimethyl formamide, making beating was stirred 30 minutes, was warmed up to 160 ℃, stirred up to crystal formation to transform fully, filtered, deionized water is washed till no N-N '-dimethyl formamide.
(4) wet cake is added to the water, making beating evenly is warmed up to 80 ℃, adds 4g and dissolves good semihydrogenation rosin solution, be incubated 2 hours, add 2g and dissolve good calcium chloride solution, filter drying, blue light red pigment finished product, this product easily disperses, it is painted to be mainly used in plastic prod.
Embodiment 4
The preparation of the red benzimidazolone pigment of 183#
(1) 8.35 gram 4-chlorine ORTHO ANISIDINE, 0.12g3-amino-4-methoxybenzoyl aniline (two component ratios are 70: 1) join in 240 milliliters of deionized waters, stirred 30 minutes, add 10% Soxylat A 25-7 derivative solution 3.8ml, 30% hydrochloric acid 20ml, in bathing, cryosel is cooled to below 0 ℃, slowly add sodium nitrite solution (20%) 18.5ml, the terminal point Sodium Nitrite is little excessive, stirs 10 minutes, add gac, whip attachment 10 minutes is filtered, and filtrate is treated coupling.
(2) 5-(2 '-hydroxyl-3 '-naphthoyl) amino benzimidazolone 15g joins in 190 milliliters of deionized waters, 30% sodium hydroxide 15ml, 10% Viscotrol C sodium sulfonate liquid 3.8ml, be stirred to whole dissolvings, add small amount of activated and filter, go out fine particle with 10% glacial acetic acid solution acid out.
With 40-70 minute coupling solution is joined in the diazonium liquid, the terminal point coupling solution is little excessive, stirs 20 minutes, is heated to 100 ℃, and insulated and stirred 120 minutes is filtered, and is washed till neutrality with deionized water.Get wet cake 115 grams.
(3) wet cake is joined in the autoclave, add 400 milliliters of deionized waters, making beating was stirred 30 minutes, was warmed up to 160 ℃, stirred up to crystal formation to transform fully, filtered.
(4) wet cake is added to the water, making beating evenly is warmed up to 80 ℃, adds 4g and dissolves good S-rosin solution, be incubated 1 hour, filters, and adds dissolving calcium chloride solution well, and drying obtains can be used for the red pigment finished product of plastics and printing ink.
Embodiment 5
The preparation of the red benzimidazolone pigment of 185#
(1) 12.4g2-methoxyl group-N ', 5-dimethyl sulfanilic amide, 0.083g methyl o-aminobenzoate (two component ratios are 150: 1) join in 240 milliliters of deionized waters, stirred 30 minutes, add 10% Soxylat A 25-7 derivative solution 3.8ml, 30% hydrochloric acid 20ml, in bathing, cryosel is cooled to below 0 ℃, slowly add sodium nitrite solution (20%) 18.5ml, the terminal point Sodium Nitrite is little excessive, stirred 10 minutes, add gac, whip attachment 10 minutes, filter, filtrate is treated coupling.
(2) 5-(2 '-hydroxyl-3 '-naphthoyl) amino benzimidazolone 15g joins in 190 milliliters of deionized waters, 30% sodium hydroxide 15ml, 10% Viscotrol C sodium sulfonate liquid 3.8ml are stirred to whole dissolvings, add small amount of activated, filter.
With 30-50 minute the diazonium drop is added in the coupling solution, the terminal point coupling solution is little excessive, stirs 20 minutes, transfers PH=1 with hydrochloric acid, is heated to 100 ℃, and insulated and stirred 120 minutes is filtered, and is washed till neutrality with deionized water.Get wet cake 140 grams.
(3) wet cake is joined in the autoclave, 400 milliliters of deionized waters, the 40ml isopropylcarbinol, making beating was stirred 30 minutes, was warmed up to 100 ℃, stirred up to crystal formation to transform fully, filtered, deionized water is washed till no isopropylcarbinol.
(4) wet cake is added to the water, making beating evenly is warmed up to 80 ℃, adds 4g and dissolves good superfine rosin solution, be incubated 1 hour, filter drying, gorgeous blue light red pigment product in the depth of the night of obtaining than case, this product easily disperses, particle is soft, and it is painted to be used for plastics, paint, printing ink.
Embodiment 6
The preparation of the red benzimidazolone pigment of 208#
(1) 10.4g n-butyl anthranilate, 0.087g methyl o-aminobenzoate (two component ratios are 120: 1) join in 240 milliliters of deionized waters, stirred 30 minutes, add 10% Soxylat A 25-7 derivative solution 3.8ml, 30% hydrochloric acid 20ml, in bathing, cryosel is cooled to below 0 ℃, slowly add sodium nitrite solution (20%) 18.5ml, the terminal point Sodium Nitrite is little excessive, stirs 10 minutes, add gac, whip attachment 10 minutes is filtered, and filtrate is treated coupling.
(2) 5-(2 '-hydroxyl-3 '-naphthoyl) amino benzimidazolone 15g joins in 190 milliliters of deionized waters, 30% sodium hydroxide 15ml, 10% Viscotrol C sodium sulfonate liquid 3.8ml are stirred to whole dissolvings, add small amount of activated, filter.
With 40-70 minute coupling solution is joined in the diazonium liquid, the terminal point coupling solution is little excessive, stirs 20 minutes, is heated to 100 ℃, and insulated and stirred 120 minutes is filtered, and is washed till neutrality with deionized water.Get wet cake 130 grams.
(3) wet cake is joined in the autoclave, 500 milliliters of deionized waters, 30ml acetate, making beating was stirred 30 minutes, was warmed up to 130 ℃, stirred up to crystal formation to transform fully, filtered, deionized water is washed till no acetate.
(4) wet cake is added to the water, making beating evenly, be warmed up to 80 ℃, add 4g and dissolve good S-rosin solution, be incubated 3 hours, add 2g and dissolve good calcium chloride solution, filter, drying obtains bright-coloured red pigment product, every excellent performance of this product, good dispersity can be used for the painted of solvent inkjet ink, printing ink, Masterbatch.
Embodiment 7
The preparation of the red benzimidazolone pigment of 281#
(1) 80.0g methyl o-aminobenzoate, 0.16g n-butyl anthranilate (two component ratios are 500: 1) join in 2400 milliliters of deionized waters, stirred 30 minutes, add 10% Soxylat A 25-7 derivative solution 38ml, 30% hydrochloric acid 230ml, in bathing, cryosel is cooled to below 0 ℃, slowly add sodium nitrite solution (20%) 185ml, the terminal point Sodium Nitrite is little excessive, stirs 10 minutes, add gac, whip attachment 10 minutes is filtered, and filtrate is treated coupling.
(2) 5-(2 '-hydroxyl-3 '-naphthoyl) amino benzimidazolone 150g joins in 1900 milliliters of deionized waters, 30% sodium hydroxide 150ml, 10% Viscotrol C sodium sulfonate liquid 20ml, be stirred to whole dissolvings, add small amount of activated and filter, filtrate adds no ion frozen water to 5500 milliliters of volumes.
With 40-70 minute the diazonium drop is added in the coupling solution, the terminal point coupling solution is little excessive, stirs 20 minutes, transfers PH=2 with hydrochloric acid, is heated to 100 ℃, and insulated and stirred 180 minutes is filtered, and is washed till neutrality with deionized water.Get wet cake 118 grams.
(3) wet cake is joined in the autoclave, 400 milliliters of deionized waters, 20ml pyridine, making beating stirs, and is warmed up to 160 ℃, stirs up to crystal formation to transform fully, filters, deionized water is washed till non-pyridine.
(4) wet cake is added to the water, be warmed up to 80 ℃, add 40g and dissolve good staybelite, be incubated 2 hours, add 20g and dissolve good staybelite solution, filter, drying obtains the good red pigment of every fastness, and this product particle is soft, particle diameter is 150-300nm, is mainly used in paint and printing ink industry.
Embodiment 8
The preparation of the red benzimidazolone pigment of 283#
(1) 4.75 gram 3-amino-4-methoxybenzoyl aniline, 4.75g 4-nitro ORTHO ANISIDINE (two component ratios are 1: 1) join in 240 milliliters of deionized waters, stirred 30 minutes, add 10% Soxylat A 25-7 derivative solution 3.8ml, 30% hydrochloric acid 20ml, in bathing, cryosel is cooled to below 0 ℃, slowly add sodium nitrite solution (20%) 18.5ml, the terminal point Sodium Nitrite is little excessive, stirs 10 minutes, add gac, whip attachment 10 minutes is filtered, and filtrate is treated coupling.
(2) 5-(2 '-hydroxyl-3 '-naphthoyl) amino benzimidazolone 15g joins in 190 milliliters of deionized waters, 30% sodium hydroxide 15ml, 10% Viscotrol C sodium sulfonate solution 3.8ml are stirred to whole dissolvings, add small amount of activated and filter.
With 20-50 minute the diazonium drop is added in the coupling solution, the terminal point coupling solution is little excessive, stirs 20 minutes, is heated to 100 ℃, and insulated and stirred 240 minutes is filtered, and is washed till neutrality with deionized water.Get wet cake 130 grams.
(3) wet cake is joined in the autoclave, add 400 milliliters of deionized waters, 40ml N-N '-dimethyl formamide, making beating was stirred 60 minutes, was warmed up to 160 ℃, stirred up to crystal formation to transform fully, filtered, and deionized water is washed till no N-N '-dimethyl formamide.
(4) wet cake is added to the water, making beating evenly is warmed up to 80 ℃, adds 4g and dissolves good superfine rosin solution, be incubated 2 hours, add 2g and dissolve good calcium chloride solution, filter drying, Dry Sack is compared blue red pigment finished product, and this product easily disperses, and it is painted to be mainly used in plastic prod.
Claims (6)
1. the preparation method of red benzimidazolone pigment comprises the following steps:
(1) diazotization reaction of substituted aromatic amines
Adopt two or more substituted aromatic amines to carry out diazotization reaction, described substituted aromatic amines has following general structure:
Its reaction formula is:
Wherein X is Cl or HSO4; R1, R2, R3, R4, R5 are selected from H, CH
3, OCH
3, COOCH
3, SO
2NHCH
3, CONHC
6H
5
The diazonium salt that generates is standby;
(2) diazonium salt and 5-[2 '-hydroxyl-3 '-naphthoyl] coupled reaction of amino benzimidazolone
The aqueous solution that will contain sodium hydroxide is warmed up to 100 ℃, adds earlier a small amount of Viscotrol C sodium sulfonate, add again 5-[2 '-hydroxyl-3 '-naphthoyl] amino benzimidazolone, make it dissolving, cool to 50 ℃, add proper amount of active carbon, filter, filtrate is adjusted to suitable temperature, is coupling solution, and is standby;
Coupling solution and diazonium salt are carried out coupled reaction, and temperature of reaction is 0-55 ℃;
The reaction formula of coupled reaction is:
After reaction finishes, filter also the washing filter cake to PH=7.0, with filter cake dry up to the pigment solid content be 15-40%, obtain the filter cake of crude pigment product;
(3) pigmenting is handled:
Pigmenting crude product filter cake is joined water or contain in the aqueous solution of a small amount of solvent, be heated to boiling, and maintain certain pressure, be back to crystal formation and transform fully, cooling is filtered, and washes filter cake with water;
Said organic solvent is: N, and one or more in dinethylformamide, N-Methyl pyrrolidone, acetate, formic acid, isopropylcarbinol, the propyl carbinol, the content of organic solvent is not higher than 20% in the pigmenting medium.
2. the preparation method of red benzimidazolone pigment as claimed in claim 1, further comprising the steps of:
(4) surface treatment of pigment:
Filter cake behind the pigmenting is added to the water, adds surface treatment agent, be heated to 60-80 ℃, be incubated 1-3 hour, cooling is filtered, and filter cake is pulverized after drying; Described surface treatment agent is the rosin based compound, and add-on is the 0.5-5% (weight) of pigment.
3. the preparation method of red benzimidazolone pigment as claimed in claim 1 or 2, it is characterized in that: in the step (1), adopt two kinds of substituted aromatic amines to carry out diazotization reaction, the ratio of two kinds of substituted aromatic amines is 1: 1-500.
4. the preparation method of red benzimidazolone pigment as claimed in claim 3, it is characterized in that: the ratio of two kinds of substituted aromatic amines is 1: 1-100.
5. the preparation method of red benzimidazolone pigment as claimed in claim 1 or 2, it is characterized in that: in the employed pigmenting medium of step (3), the content of organic solvent is 0.
6. the preparation method of red benzimidazolone pigment as claimed in claim 2, it is characterized in that: the used surface treatment agent of step (4) is superfine rosin.
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|---|---|---|---|
| CN 200410002632 CN1230469C (en) | 2004-01-19 | 2004-01-19 | Process for preparing red benzimidazolone pigments |
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|---|---|---|---|
| CN 200410002632 CN1230469C (en) | 2004-01-19 | 2004-01-19 | Process for preparing red benzimidazolone pigments |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101880472A (en) * | 2010-06-11 | 2010-11-10 | 丽王化工(南通)有限公司 | Pigment treatment of red and yellow organic pigment with hot water method |
| CN102391663A (en) * | 2011-09-06 | 2012-03-28 | 鞍山七彩化学股份有限公司 | Preparation method of C.I. pigment yellow 151 |
| CN106833005A (en) * | 2017-01-23 | 2017-06-13 | 浙江浩川科技有限公司 | A kind of method for preparing permeability azo organic pigment high |
| CN108047750A (en) * | 2017-12-29 | 2018-05-18 | 东营安诺其纺织材料有限公司 | A kind of production technology of disperse yellow |
-
2004
- 2004-01-19 CN CN 200410002632 patent/CN1230469C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101880472A (en) * | 2010-06-11 | 2010-11-10 | 丽王化工(南通)有限公司 | Pigment treatment of red and yellow organic pigment with hot water method |
| CN102391663A (en) * | 2011-09-06 | 2012-03-28 | 鞍山七彩化学股份有限公司 | Preparation method of C.I. pigment yellow 151 |
| CN106833005A (en) * | 2017-01-23 | 2017-06-13 | 浙江浩川科技有限公司 | A kind of method for preparing permeability azo organic pigment high |
| CN108047750A (en) * | 2017-12-29 | 2018-05-18 | 东营安诺其纺织材料有限公司 | A kind of production technology of disperse yellow |
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|---|---|
| CN1230469C (en) | 2005-12-07 |
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