CN1544529A - Method for preparing mono-azo 2:1 chromium complex dyes and and their use - Google Patents
Method for preparing mono-azo 2:1 chromium complex dyes and and their use Download PDFInfo
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- CN1544529A CN1544529A CNA2003101113795A CN200310111379A CN1544529A CN 1544529 A CN1544529 A CN 1544529A CN A2003101113795 A CNA2003101113795 A CN A2003101113795A CN 200310111379 A CN200310111379 A CN 200310111379A CN 1544529 A CN1544529 A CN 1544529A
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- monoazo
- complex dyes
- sodium nitrite
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Abstract
The invention relates to a process for preparing monoazo 2:1 chrome complex dye comprising, reacting one or more categories of aromatic ortho-aminophenol with sodium nitrite in water solution of hydrochloric acid or sulfuric acid, subjecting the reacted mixture to coupling reaction with B-naphthol queous alkali, filtering and drying the coupling product, reacting with trivalent chromium salt in organic solvent at the presence of acid-binding agent. The process according to the invention can be applied in particular to the preparation of color-developing agent for ink-ejecting ink, as well as the coloring charge modifier during the photoelectric image formation process.
Description
Technical field
The present invention relates to Monoazo 2: the Preparation method and use of 1 type chromium complex dyes.This dyestuff is specially adapted to as the painted charge adjusting agent in ink for ink-jet print and the photoelectronic imaging treating processes.Also can be used for the painted of oil product, plastics, resin, speciality coating etc.
Background technology
Do not find to be used to prepare the Monoazo 2 of ink for ink-jet print in the prior art: the preparation method of 1 type chromium complex dyes.
Summary of the invention
The purpose of this invention is to provide a kind of Monoazo 2: the Preparation method and use of 1 type chromium complex dyes, this method are not only simple, production cost is low, and productive rate is higher.The Monoazo 2 of preparation: 1 type chromium complex dyes is specially adapted to as the painted charge adjusting agent in ink for ink-jet print and the photoelectronic imaging treating processes.
Technical scheme provided by the invention is: Monoazo 2: the preparation method of 1 type chromium complex dyes, with one or more aromatics o-aminophenols II in the hydrochloric acid or aqueous sulfuric acid of 0.2～20wt%, 0-15 ℃ with Sodium Nitrite hybrid reaction 1～5 hour, wherein amino mol ratio with Sodium Nitrite is 1: 0.9～1.2 among the aromatics o-aminophenol II, carries out coupled reaction at pH value 7-12 in the 2-Naphthol alkaline solution of the 0.5-18wt% of 1-1.2 times of aromatics o-aminophenol II molar weight of post reaction mixture adding; Coupling product III after filtration, dry back in organic solvent, acid binding agent exists down, with chromic salt at 70-180 ℃, reacted 2-8 hour, promptly get Monoazo 2: 1 type chromium complex dyes I;
Monoazo 2: the structural formula of 1 chromium complex dyes is:
In the formula: R, R
1Be selected from H, halogen, alkyl, alkoxyl group, nitro and cyano group; M, n are 1-4; A is H
+, NH
4 +, Na
+, K
+Or R
2R
3R
4R
5N
+, R wherein
2, R
3, R
4, R
5Be H, C
1-C
12Alkyl, C
1-C
12Straight chain or band branched alkoxy; R
7, R
8Be H or Na
+
The aromatics o-aminophenol with the reaction of Sodium Nitrite before can account for earlier in the presence of the nonionogenic tenside of reaction mixture total amount 1-5wt% and be mixed into the solution that contains Sodium Nitrite with Sodium Nitrite, and then in hydrochloric acid or sulfuric acid, carry out diazotization reaction.Nonionogenic tenside is R
6(OCH
2CH
2)
LOH, wherein R
6Be C
4-C
20Straight chain or branched saturated alkane, L is 1-10.
The temperature of reaction of above-mentioned aromatics o-aminophenol and Sodium Nitrite is 0-15 ℃.The pH value 8-10 of coupled reaction; The temperature of reaction of coupling product and chromic salt is 100-140 ℃.
Used organic solvent is the corresponding alkyl oxide of chlorobenzene, dichloro benzene,toluene,xylene, N-Methyl pyrrolidone, ethylene glycol, glycol ether or glycol; Preferred ethylene glycol and/or ethylene glycol monoethyl ether.
Above-mentioned acid binding agent is yellow soda ash, sodium hydroxide, sodium bicarbonate, sodium-acetate, Potassium ethanoate, carbamyl amine, alkylamine or alkylamide; Carbamyl amine most preferably.The usage quantity of acid binding agent is the mole number of the 0.5-5 of monoazo pigment III, the most preferably mol ratio of 1-2.5.
The selected chromic salt of the present invention is chromium sulphate, chromium chloride, chromic formate, Chromic lactate, Whitfield's ointment chromium, chromium acetate, owing to adopt chromium sulphate, Whitfield's ointment chromium to do the chromaking agent, at the bottom of the chromium ion utilization ratio, the finished product toxicity is big.Therefore, the most preferably avirulent Chromic lactate of the present invention, its usage quantity is 0.5-0.7 for the mol ratio with formula III: 1.
Monoazo 2 provided by the invention: the preparation method of 1 type chromium complex dyes, not only simple, and also productive rate is higher.Bring great convenience on producing owing to need not prepare each plural components one by one, significantly improve plant factor, saving equipment reduces operation, reduces energy consumption, significantly lowers production cost.
The prepared Monoazo 2 according to the present invention: 1 type chromium complex dyes I shows fabulous stable solvability, as in ethanol, ethyl acetate, acetone, methyl ethyl ketone, methyl alcohol, modification ethanol, toluene, benzene in multiple organic solvent.Therefore, be particularly suitable for the developer of ink for ink-jet print.Monoazo 2 prepared in accordance with the present invention: 1 type chromium complex and composition thereof can also be used for the painted charge adjusting agent of electrophotographic imaging process.As tinting material and negative charge conditioning agent as xerographic printer and laser printer developing agent.Common using method is, Monoazo 2 with the present invention's preparation: 1 type chromium complex and composition thereof is with the 0.1-10% of photographic developer total amount, preferably 0.5-5% amount and natural or synthetic resins through grinding dispersion, as polystyrene, redix, powder such as silicone resin, polyester, urethane, resol, modified rosin, clorafin mixes, and makes carbon dust.When making carbon dust thus and being used for xerographic printer or laser printer, have development density, high-conversion rate and lower powder consumption preferably.
The present invention is because preferred Chromic lactate, makes prepared Monoazo 2 as the chromium complexing agent: 1 type chromium complex or its mixture have and are different from the special performance that adopts the product that aforementioned other chromium complexing agent obtained.As product being used for the biology medical experiment, demonstrate hypotoxicity and no supersensitivity, in carrying out the AMES test, show negative.
Embodiment
According to the present invention, Monoazo 2: 1 type chromium complex dyes I can following method prepare: the nonionogenic tenside (the HLB value is at 8-20) that adds the 1-5% of reaction mixture total amount at the aromatics o-aminophenol of choosing one or more formulas II in the alkaline medium aqueous solution, and then mix with Sodium Nitrite, in acidic medium, carry out diazotization.
The diazotization product that reacts completely can be successfully with alkaline medium in consoluet 2-Naphthol carry out coupling.Coupling product is through isolated by vacuum filtration, and drying obtains the monoazo pigment of the formula III of the high yield of 95-100%.
Selected its general formula of nonionogenic tenside of the present invention is R
6(OCH
2CH
2)
LOH, wherein R
6Be C
4-C
20Straight chain or branched saturated alkane, preferably C
6-C
20Straight chain or branched saturated alkane.L is 1-10, preferably 4-6.Selected nonionogenic tenside has the solvability of remarkable increase aromatics o-aminophenol in alkaline aqueous solution.
According to the present invention, be dried to the single or compound monoazo pigment of moisture≤3wt%, in organic solvent, add selected acid binding agent and chromic salt in 70-180 ℃, most preferably 100-140 ℃ is reacted the Monoazo 2 that made formula I in 2-8 hour: 1 type chromium complex or its mixture.
Being used for organic solvent of the present invention is the corresponding list and the alkyl oxide of chlorobenzene, dichloro benzene,toluene,xylene, N-Methyl pyrrolidone, ethylene glycol, glycol ether and glycol, most preferably ethylene glycol and ethylene glycol monoethyl ether and composition thereof.The usage quantity of organic solvent is under temperature of reaction, makes reaction mixture have good flowability, and the 1-2 that preferred usage quantity is a monoazo pigment III weight doubly.
The acid binding agent that the present invention selectes is yellow soda ash, sodium hydroxide, sodium bicarbonate, sodium-acetate, Potassium ethanoate, alkylamine, alkylamide etc., most preferably carbamyl amine.The usage quantity of acid binding agent is the mole number of the 0.5-5 of monoazo pigment III, the most preferably mol ratio of 1-2.5.
The selected chromic salt of the present invention is chromium sulphate, chromium chloride, chromic formate, Chromic lactate, Whitfield's ointment chromium, chromium acetate, Chromic lactate most preferably, and its usage quantity is 0.5-0.7 for the mol ratio with formula III: 1.
The above-mentioned chromium complex reaction mixture that contains organic solvent that makes is through subsequent disposal, as with reaction mixture dispersed with stirring in frozen water, then with its suspended substance filtration under diminished pressure, and with the second distillation water washing to specific conductivity≤200 μ S/cm.Filter cake is dried to moisture≤1% at 70-90 ℃, makes the I of Gao Deliang or the mixture of its I.
The wet cake of above-mentioned filtration under diminished pressure gained also can be nearly step dispersed with stirring in the redistilled water that 3-10 doubly measures, doubly measure alkylammonium salt by the 1-10 that adds theoretical amount, as the defined R of I formula
2R
3R
4R
5N
+,, make the A of I 40-100 ℃ of reaction 1-2 hour
+Partially or completely conversion takes place.The gained reaction mixture after filtration, the second distillation water washing is to specific conductivity≤200 μ S/cm.Filter cake is dried to moisture≤1% at 70-90 ℃, makes the I of Gao Deliang or the mixture of its I.
Following examples only illustrate the present invention, and do not limit the present invention; Wherein part and percentage number average are by weight.
Embodiment 1
With 140 parts of redistilled waters, 5.5 parts of sodium hydroxide, 31.96 parts of II (R=6-nitro and 4-neo-pentyl), 3 parts of nonionogenic tensides (HLB=18) in 20-25 ℃ of stirring 2-3 hour, add 9.4 parts of Sodium Nitrites again, stir 1 hour at 20-25 ℃.Then this mixture is added to and contains in 110 parts of water and the 52.6 parts of hydrochloric acid solns, stirred 1 hour at 0-15 ℃.With the above-mentioned doazo reaction mixture that makes, slowly add to and dissolved the good 220 parts of redistilled waters that contain, 12 parts of sodium hydroxide, 20 parts of 2-Naphthol solution carry out coupling, stir 2-3 hour at 30-40 ℃.This reaction mixture is filtered with B, washing, filter cake is at 80 ℃ of dry 54 parts of III.III reaches 99.3% through the HPLC purity assay.
With the above-mentioned III that makes and 45 parts of ethylene glycol, 30 parts of Chromic lactates, 9 parts of carbamyl amine mix, at 120-125 ℃ of hectograph hour, then reaction mixture is disperseed in 200 parts of redistilled waters, use the B suction strainer, filter cake uses the second distillation water washing to specific conductivity≤200 μ S/cm.Filter cake is dried to moisture≤1% at 80-85 ℃, gets 58 parts of I.λ max=575nm in ethanol has second absorption peak at the 487nm place in addition.In varnish, present purple.
Reference examples 1
According to the method for embodiment 1, during not with nonionogenic tenside, get only 50 parts of III, purity is 95.7%.After chromaking, have to 49 parts of I.
Embodiment 2-5
According to the method for embodiment 1, obtain different I respectively.
Embodiment 6
With three kinds of different II, be respectively 7.2 parts of R=4-neo-pentyls; The 6-nitro, 8 parts of R=5-nitros, 7.5 parts of R=4-nitros at 110 parts of redistilled waters, mix in 5.5 parts of part sodium hydroxide, 3 portions of nonionogenic tensides (HLB=18) and stirred 2 hours, add 9.7 parts of Sodium Nitrites again, stir 1 hour at 20-25 ℃ then.This mixture is added to one contains in 110 parts of water and the 52.6 parts of hydrochloric acid solns under 0-5 ℃, and be stirred to doazo reaction at 0-5 ℃ and finish.
Again with above-mentioned doazo reaction mixture under 10-20 ℃, be added to and contain 220 parts of redistilled waters, 12.3 part sodium hydroxide, 3.4 in the solution of part sodium bicarbonate and 19.9 parts of 2-Naphthols, with the sodium hydroxide solution or the hydrochloric acid soln adjustment reaction pH=8-9 of dilution, at 30-40 ℃ of stirring reaction 2-4 hour.Again 70-90 ℃ of reaction 1 hour.Filter with B under the vacuum then, filter cake uses the second distillation water washing to specific conductivity≤200 μ S/cm.Filter cake after 80-85 ℃ of drying 45 parts in the mixture of III, moisture 1.3%.
With the mixture porphyrize of above-mentioned III, with 30 portions of ethylene glycol monoethyl ethers, 15 parts of ethylene glycol, 30 parts of Chromic lactates and 8.9 parts of carbamyl amine mix.110-120 ℃ of reaction 3-5 hour, reaction mixture is disperseed to stir 10-30 minute then in 220 portions of frozen water.Vacuum B suction strainer, filter cake with the second distillation water washing to specific conductivity≤200 μ S/cm again with filter cake 80-85 ℃ of vacuum-drying to moisture≤1%, 43 parts in the mixture of I.λ max=578nm (DMF) has the second and the 3rd absorption peak at 533nm and 379nm place in addition.In varnish, present black.
The mixture of this I is shown as black in polystyrene resin.
The I that the mixture of this I demonstrates in multiple organic solvent than single structure has better solvability.As in ethanol, methyl ethyl ketone, ethyl acetate, having fabulous solvability, be used in the tinting material of making ink for ink-jet print especially.
Embodiment 7-9
With the method for embodiment 6, synthesized the mixture of other I similarly.
| Embodiment | ????????????II | ???III | ???????????????????????????I | ||||
| Structure | Umber | Umber | Structure | Umber | λmax?nm | Form and aspect | |
| ???7 | The R=4-neo-pentyl, the 6-nitro | ??11.9 | ??41 | ??I??(A) ??I??(B) ??I??(D) | ??41.5 | 571 (the 2nd absorption peaks: 369) (the 3rd absorption peak: 477) | Blue look |
| The R=5-nitro | ??10.2 | ||||||
| ???8 | The R=4-neo-pentyl; The 6-nitro | ??11.9 | ??40 | ??I??(A) ??I??(E) ??I??(C) | ??39.2 | 572 (the 2nd absorption peaks: 369) (the 3rd absorption peak: 478) | Red sauce |
| The R=4-nitro | ??8.9 | ||||||
| ???9 | The R=5-nitro | ??10.2 | ??39.5 | ??I??(D) ??I??(E) ??I??(F) | ??40 | 579 (the 2nd absorption peaks: 380) (the 3rd absorption peak: 478) | Greyish-green |
| The R=4-nitro | ??8.9 | ||||||
Claims (10)
1. Monoazo 2: the preparation method of 1 type chromium complex dyes, with one or more aromatics o-aminophenols II in the hydrochloric acid or aqueous sulfuric acid of 0.2～20wt%, 0-15 ℃ with Sodium Nitrite hybrid reaction 1～5 hour, wherein amino mol ratio with Sodium Nitrite is 1: 0.9～1.2 among the aromatics o-aminophenol II, carries out coupled reaction at pH value 7-12 in the 2-Naphthol alkaline solution of the 0.5-18wt% of 1-1.2 times of aromatics o-aminophenol II molar weight of post reaction mixture adding; Coupling product III after filtration, dry back in organic solvent, acid binding agent exists down, with chromic salt at 70-180 ℃, reacted 2-8 hour, promptly get Monoazo 2: 1 type chromium complex dyes I;
Monoazo 2: the structural formula of 1 chromium complex dyes is:
In the formula: R, R
1Be selected from H, halogen, alkyl, alkoxyl group, nitro and cyano group; M, n are 1-4; A is H
+, NH
4 +, Na
+, K
+Or R
2R
3R
4R
5N
+, R wherein
2, R
3, R
4, R
5Be H, C
1-C
12Alkyl, C
1-C
12Straight chain or band branched alkoxy; R
7, R
8Be H or Na
+
2. preparation method according to claim 1, it is characterized in that: the aromatics o-aminophenol with the reaction of Sodium Nitrite before accounting for earlier in the presence of the nonionogenic tenside of reaction mixture total amount 1-5wt% and be mixed into the solution that contains Sodium Nitrite with Sodium Nitrite, and then in hydrochloric acid or sulfuric acid, carry out diazotization reaction; Nonionogenic tenside is R
6(OCH
2CH
2)
LOH, wherein R
6Be C
4-C
20Straight chain or branched saturated alkane, L is 1-10.
3. preparation method according to claim 1 and 2 is characterized in that: the temperature of reaction of aromatics o-aminophenol and Sodium Nitrite is 0-15 ℃; The pH value 8-10 of coupled reaction; The temperature of reaction of coupling product and chromic salt is 100-140 ℃.
4. preparation method according to claim 1 and 2 is characterized in that: used organic solvent is the corresponding alkyl oxide of chlorobenzene, dichloro benzene,toluene,xylene, N-Methyl pyrrolidone, ethylene glycol, glycol ether or glycol.
5. preparation method according to claim 4 is characterized in that: used organic solvent is ethylene glycol and/or ethylene glycol monoethyl ether.
6. preparation method according to claim 1 and 2 is characterized in that: acid binding agent is yellow soda ash, sodium hydroxide, sodium bicarbonate, sodium-acetate, Potassium ethanoate, carbamyl amine, alkylamine or alkylamide.
7. preparation method according to claim 1 and 2 is characterized in that: used chromic salt is chromium sulphate, chromium chloride, chromic formate, Chromic lactate or Whitfield's ointment chromium.
8. preparation method according to claim 7 is characterized in that: used chromic salt is a Chromic lactate.
9. according to the described Monoazo 2 of claim 1: 1 type chromium complex dyes is characterized in that: the application in the preparation ink for ink-jet print.
10. according to the described Monoazo 2 of claim 1: 1 type chromium complex dyes is characterized in that: as the application of painted charge adjusting agent in photoelectronic imaging is handled.
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|---|---|---|---|
| CN 200310111379 CN1244641C (en) | 2003-11-14 | 2003-11-14 | Method for preparing mono-azo 2:1 chromium complex dyes and and their use |
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|---|---|---|---|
| CN 200310111379 CN1244641C (en) | 2003-11-14 | 2003-11-14 | Method for preparing mono-azo 2:1 chromium complex dyes and and their use |
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| CN1244641C CN1244641C (en) | 2006-03-08 |
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| US20100105884A1 (en) * | 2008-10-23 | 2010-04-29 | Hubei Dinglong Chemical Co., Ltd. | Method for producing charge control agent and toner |
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| CN102516795A (en) * | 2011-12-09 | 2012-06-27 | 青岛双桃精细化工（集团）有限公司 | Preparation method of blue dye |
| CN102718636A (en) * | 2012-06-11 | 2012-10-10 | 武汉旭日华科技发展有限公司 | Recovering and processing method of ethylene glycol monoethyl ether waste liquid containing 2:1 type chromium complex dye and by-product thereof |
| CN102731387A (en) * | 2011-03-31 | 2012-10-17 | 住友化学株式会社 | A salt for dye |
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| CN101139466B (en) * | 2007-09-29 | 2012-02-01 | 杭州下沙恒升化工有限公司 | Method for producing acid dye product |
| JP2008052306A (en) * | 2007-11-12 | 2008-03-06 | Hubei Dinglong Chemical Co Ltd | Charge controlling agent for toner, its production method, and toner |
| US8445651B2 (en) * | 2008-10-23 | 2013-05-21 | Hubei Dinglong Chemical Co., Ltd. | Method for producing charge control agent and toner |
| US20100105884A1 (en) * | 2008-10-23 | 2010-04-29 | Hubei Dinglong Chemical Co., Ltd. | Method for producing charge control agent and toner |
| CN101565555B (en) * | 2009-04-14 | 2013-01-09 | 华东理工大学 | Rare earth complex red pigment with excellent pigment performance and application thereof |
| CN102731387B (en) * | 2011-03-31 | 2016-08-03 | 住友化学株式会社 | Salt for dye |
| CN102731387A (en) * | 2011-03-31 | 2012-10-17 | 住友化学株式会社 | A salt for dye |
| CN102516795A (en) * | 2011-12-09 | 2012-06-27 | 青岛双桃精细化工（集团）有限公司 | Preparation method of blue dye |
| CN102516795B (en) * | 2011-12-09 | 2014-04-02 | 青岛双桃精细化工（集团）有限公司 | Preparation method of blue dye |
| CN102718636B (en) * | 2012-06-11 | 2014-06-25 | 武汉旭日华科技发展有限公司 | Recovering and processing method of ethylene glycol monoethyl ether waste liquid containing 2:1 type chromium complex dye and by-product thereof |
| CN102718636A (en) * | 2012-06-11 | 2012-10-10 | 武汉旭日华科技发展有限公司 | Recovering and processing method of ethylene glycol monoethyl ether waste liquid containing 2:1 type chromium complex dye and by-product thereof |
| CN103242673A (en) * | 2013-05-22 | 2013-08-14 | 南通市争妍颜料化工有限公司 | Production process of solvent black B |
| CN105385186A (en) * | 2015-10-19 | 2016-03-09 | 广州市纬庆化工科技有限公司 | Migration-resistant red dye, preparation method therefor and application thereof |
| CN107459835A (en) * | 2017-08-22 | 2017-12-12 | 南通市争妍新材料科技有限公司 | A kind of solvent yellow BL cleanly production technique |
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