CN1803930A - Photooxidation resistant red azo organic pigment and method for preparing the same - Google Patents
Photooxidation resistant red azo organic pigment and method for preparing the same Download PDFInfo
- Publication number
- CN1803930A CN1803930A CN 200510045593 CN200510045593A CN1803930A CN 1803930 A CN1803930 A CN 1803930A CN 200510045593 CN200510045593 CN 200510045593 CN 200510045593 A CN200510045593 A CN 200510045593A CN 1803930 A CN1803930 A CN 1803930A
- Authority
- CN
- China
- Prior art keywords
- solution
- add
- reaction
- tetramethyl piperidine
- naphthol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Hydrogenated Pyridines (AREA)
Abstract
The disclosed molecular structure of photooxidation-resistant red azo organic pigment comprises hindered group. Wherein, the hindered group has general formula as R1-N=N-R2; R1 belongs to the 1-R3-4-benzoate-2, 2, 6, 6-tetramethyl piperidine or 1-R3-4-benzamino-2, 2, 6, 6- tetramethyl piperidine; R3 stands for H or alkyl; R2 stands for 2-naphthol, Naphthol AS, AS-D, AS-E, AS-OL, AS-BS or AS-ITR. This product has well staining power and resistance to solvent, heat and mobility.
Description
Technical field
The present invention relates to a kind of pigment dyestuff and preparation method thereof, particularly relate to a kind of photooxidation resistant red azo organic pigment and preparation method thereof.
Background technology
As everyone knows, China's pigment dyestuff production technology is backward relatively compared with developed countries, mainly produce common azo pigment, and high-grade pigment dyestuff mainly relies on import.Common azo pigment production technique is simple, and cost is low, and consumption is big, but over-all properties such as its sun-proof, heat-resisting, anti-migration is relatively poor relatively, is mainly used in the low-grade occasion such as gas dried lacquer, emulsion paint, printing-ink, coating of general quality.And can not be used for the application scenario that outdoor advertising, automobile finish and high-grade ink-jet ink etc. are had relatively high expectations to the pigment dyestuff light fastness.
Summary of the invention
One of task of the present invention is to provide a kind of photooxidation resistant red azo organic pigment, and it has photooxidation resistant performance preferably, can remedy the deficiency of the existing above-mentioned application performance of red azo organic pigment aspect.
Two of task of the present invention is to provide a kind of preparation method of above-mentioned photooxidation resistant red azo organic pigment.
Its technical solution is:
A kind of photooxidation resistant red azo organic pigment comprises hindered amine group in the molecular structure of above-mentioned azo organic pigment, and hindered amine group is represented with following general formula:
R
1-N＝N-R
2
R wherein
1Be 1-R
3-4 benzoic acid ester group-2,2,6,6-tetramethyl piperidine or 1-R
3-4-benzoylamino-2,2,6, the 6-tetramethyl piperidine; R
3Be H or alkyl; Carbonyl in above-mentioned phenylformic acid ester group or the benzoylamino is positioned at ortho position or a position or the contraposition of the azo-group that links to each other with phenyl ring; R
2Be beta naphthal, azoic coupling component AS, Naphthol AS-D, apthol AS-E, Naphthol AS-OL, apthol AS or azoic coupling component AS-ITR.
A kind of preparation method of photooxidation resistant red monoazo pigment dyestuff comprises the step of following order:
(a) take by weighing diazo component 1-R
3The amino substituted benzoyl perester radical-2,2,6 of-4-, 6-tetramethyl piperidine or 1-R
3The amino substituted benzene formyl amido-2,2,6 of-4-, the 6-tetramethyl piperidine adds in the dilute acid soln, is stirred to dissolving fully; The above-mentioned solution that contains diazo component is cooled to below 10 ℃, add sodium nitrite solution while stirring and carry out diazotization reaction, the molar ratio of Sodium Nitrite add-on and diazo component add-on is 1.01-1.1: 1, the pH value that keeps reaction solution is less than 3, temperature of reaction is below 10 ℃, reaction solution is blue to starch potassium iodide paper, reaction times is 1-3 hour, complete until diazotization reaction, add an amount of urea to reaction solution again, stir the Sodium Nitrite of decomposing excessive, to reaction solution to the starch potassium iodide paper nondiscoloration, diazonium salt solution;
(b) dissolve coupling component R2 with the diazo component equimolar amount fully with alkali lye, filter, remove mechanical impurity, filtrate is cooled to 5-10 ℃, in 10-15min, add in the diazonium salt solution of step (a) acquisition, maintain the temperature at 5-10 ℃ after adding, the pH value is 7.5-10, continues reaction, detects with oozing the circle method, up to the diazonium salt completely dissolve, obtain coupling solution;
(c) in the coupling solution that step (b) obtains, add an amount of sodium abietate salts solution, and at room temperature continue to stir at least 0.5 hour, add an amount of barium chloride solution again, continue at room temperature to stir at least 0.5 hour, being heated to temperature then is that restir is more than at least 0.5 hour more than 65 ℃, filter immediately, filter cake washes with water, and in carrying out drying below 80 ℃, gets photooxidation resistant red azo organic pigment.
R in the above-mentioned steps (a)
3Be H or alkyl, the amino the position of substitution on amino substituted benzoyl perester radical or the amino substituted benzene formyl amido can be ortho position or a position or contraposition; Coupling component R in the above-mentioned steps (b)
2Be beta naphthal, azoic coupling component AS, Naphthol AS-D, apthol AS-E, Naphthol AS-OL, apthol AS or azoic coupling component AS-ITR.
Photooxidation resistant red azo organic pigment provided by the invention has good tinting strength, light fastness, resistance to migration energy, solvent resistance and resistance toheat.
Below by embodiment the present invention is described.
Embodiment 1, a kind of photooxidation resistant red azo organic pigment (calling pigment A in the following text) synthetic
1,4-(4-benzaminic acid ester group)-2,2,6, the producing of 6-tetramethyl piperidine:
In an exsiccant there-necked flask, thermometer and the prolong that is connected with water trap are installed, with 0.2mol (30.8g) 4-hydroxyl-2,2 respectively, 6, the 6-tetramethyl piperidine, 250ml dimethylbenzene and 0.19mol (37.05g) ethyl p-nitrobenzoate together joins in the there-necked flask, stirs and is warmed up to 140 ℃, after water in the raw material steamed, add the 0.0019mol tetra-n-butyl titanate, be incubated 140-160 ℃, react and promptly reached terminal point (utilizing thin-layer chromatography control terminal point) in 4-5 hour, after steaming solvent xylene, reactant is cooled to below 100 ℃, adds 300ml water, product precipitates immediately separates out, filter, the thorough washing filter cake, drying obtains 4-(4-nitrobenzoyl perester radical)-2,2,6,6-tetramethyl piperidine, fusing point are 120-123 ℃.
With 0.1mol (30.6g) 4-(4-nitrobenzoyl perester radical)-2,2,6, the 6-tetramethyl piperidine, 1g skeleton nickel and 200ml dehydrated alcohol add in the hydrogenation reaction kettle of band stirring, successively use nitrogen, air in the hydrogen exchange still, then hydrogen pressure in the still is promoted and be controlled at 1.0Mpa, start stirring, heat up and control reaction temperature is 80 ℃, carry out hydrogenation reaction, when reaction mass was no longer inhaled hydrogen, hydrogenation reaction finished, and obtains 4-(4-benzaminic acid ester group)-2,2,6,6-tetramethyl piperidine ethanolic soln, (while hot) filters immediately, reclaim catalyzer, filtrate is distilled the residue that reclaims behind the ethanol dissolve with 100ml dilute hydrochloric acid (1mol/L), lysate filters the back and neutralizes with diluted alkaline, and white of separating out or pale solid powder are 4-(4-benzaminic acid ester group)-2,2,6,6-tetramethyl piperidine, fusing point 234-236 ℃.
2,4-(4-benzaminic acid ester group)-2,2,6,6-tetramethyl piperidine diazotization:
With 0.01mol 4-(4-benzaminic acid ester group)-2,2,6,6-tetramethyl piperidine water 50ml and 30% hydrochloric acid 3.5ml dissolving.Put into ice-water bath and be cooled to 0 ℃.With 2.5ml concentration is that the sodium nitrite solution of 4mol/L is cooled to 0 ℃ with ice bath in advance, and under agitation joins fast in the reaction solution, and keeping temperature is 0-5 ℃, reacts 1-2 hour.Solution is little blueness to congo-red test paper in the reaction process, and starch potassium iodide paper is little blueness.It is Clear ﹠ Transparent that reaction finishes diazonium liquid, adds urea, and excessive Sodium Nitrite is decomposed, and promptly gets diazonium salt solution.Reaction formula is as follows:
3, pigment is synthetic:
In the 500ml beaker, add 30ml water, 30% sodium hydroxide solution 2.7ml, be warming up to 70 ℃, add 0.01mol azoic coupling component AS, be heated with stirring to 80 ℃, azoic coupling component AS is thoroughly dissolved.Add frozen water again and be diluted to 100ml, be cooled to 5-10 ℃.In 10-15min, join in the reaction solution equably the diazonium salt solution of above-mentioned preparation, add back adjusting pH value and be 9-10, maintain the temperature at 5-10 ℃ of fully reaction down, ooze the circle method with 2-Naphthol and check reaction end, up to the diazonium salt completely dissolve, reaction finishes.Reaction formula is as follows:
4, pigmenting:
Add an amount of water and 30% sodium hydroxide 0.22mL in the 50mL beaker, rosin 0.55g is heated with stirring to boiling, makes dissolving fully, adds while hot in the above-mentioned coupling solution, at room temperature continues to stir 1 hour.In the 50mL beaker, add an amount of water and bariumchloride two hydrate 0.22g, be heated to 60 ℃, make its dissolving, add in the above-mentioned coupling solution, at room temperature continue to stir 1 hour, be heated to 65 ℃ then, restir 1 hour, filtered while hot, filter cake washes with water, and, get photooxidation resistant red azo organic pigment A in 60 ℃ of dryings.
Embodiment 2, a kind of photooxidation resistant red azo organic pigment (calling pigment B in the following text) synthetic
1,4-(4-aminobenzoyl amido)-2,2,6, the producing of 6-tetramethyl piperidine:
In the there-necked flask that thermometer and prolong are housed, add 0.1mol (15.6g) 4-amino-2,2,6, the 6-tetramethyl piperidine, 150ml tetrahydrofuran (THF) and 10ml pyridine, under agitation add 0.11mol (20.4g) paranitrobenzoyl chloride, at room temperature react 2h, be heated to backflow, under reflux temperature, continue reaction 1h, the distillating recovering solvent tetrahydrofuran (THF) under agitation adds the diluted sodium hydroxide solution of 200ml 0.1mol, and product precipitates immediately separates out, filter, water thorough washing filter cake with filtration cakes torrefaction, gets 4-(4-nitrobenzamide base)-2 to neutral, 2,6,6-tetramethyl piperidine, fusing point 262-264 ℃.
With 0.1mol (30.6g) 4-(4-nitrobenzamide base)-2,2,6, the 6-tetramethyl piperidine, 1g skeleton nickel and 200ml dehydrated alcohol add in the hydrogenation reaction kettle of band stirring, successively use nitrogen, air in the hydrogen exchange still, then hydrogen pressure in the still is promoted and be controlled at 1.0Mpa, start stirring, heat up and control reaction temperature is 80 ℃, carry out hydrogenation reaction, when reaction mass was no longer inhaled hydrogen, hydrogenation reaction finished, and obtains 4-(4-aminobenzoyl amido)-2,2,6,6-tetramethyl piperidine ethanolic soln, (while hot) filters immediately, reclaim catalyzer, filtrate is distilled the residue that reclaims behind the ethanol dissolve with 100ml dilute hydrochloric acid (1mol/L), lysate filters the back and neutralizes with diluted alkaline, and white of separating out or pale solid powder are 4-(4-aminobenzoyl amido)-2,2,6,6-tetramethyl piperidine, fusing point 234-236 ℃.
2,4-(4-aminobenzoyl amido)-2,2,6,6-tetramethyl piperidine diazotization:
With 0.01mol 4-(4-aminobenzoyl amido)-2,2,6,6-tetramethyl piperidine water 50ml and 30% hydrochloric acid 3.5ml dissolving.Put into ice-water bath and be cooled to 0 ℃.With 2.5ml concentration is that the sodium nitrite solution of 4mol/L is cooled to 0 ℃ with ice bath in advance, and under agitation joins fast in the reaction solution, and keeping temperature is 0-5 ℃, reacts 1-2 hour.Solution is little blueness to congo-red test paper in the reaction process, and starch potassium iodide paper is little blueness.It is Clear ﹠ Transparent that reaction finishes diazonium liquid, adds urea, and excessive Sodium Nitrite is decomposed, and promptly gets diazonium salt solution.Reaction formula is as follows:
3, pigment is synthetic:
In the 500ml beaker, add 30ml water, 30% sodium hydroxide solution 2.7ml, be warming up to 70 ℃, add the 0.01mol Naphthol AS-D, be heated with stirring to 80 ℃, Naphthol AS-D is thoroughly dissolved.Add frozen water again and be diluted to 100ml, be cooled to 5-10 ℃.In 10-15min, join in the reaction solution equably the diazonium salt solution of above-mentioned preparation, add back adjusting pH value and be 9-10, maintain the temperature at 5-10 ℃ of fully reaction down, ooze the circle method with 2-Naphthol and check reaction end, up to the diazonium salt completely dissolve, reaction finishes.Reaction formula is as follows:
4, pigmenting:
Add an amount of water and 30% sodium hydroxide 0.22mL in the 50mL beaker, rosin 0.55g is heated with stirring to boiling, makes dissolving fully, adds while hot in the above-mentioned coupling solution, at room temperature continues to stir 1 hour.In the 50mL beaker, add an amount of water and bariumchloride two hydrate 0.22g, be heated to 60 ℃, make its dissolving, add in the above-mentioned coupling solution, at room temperature continue to stir 1 hour, be heated to 65 ℃ then, restir 1 hour, filtered while hot, filter cake washes with water, and, get photooxidation resistant red azo organic pigment B in 60 ℃ of dryings.
Respectively pigment performance is tested according to GB, the result shows, the tinting strength of pigment A and pigment B, light fastness, resistance to migration energy, solvent resistance, Good Heat-resistance.
Used 4-(4-benzaminic acid ester group)-2,2,6 in the above-mentioned embodiment, the 6-tetramethyl piperidine can be by 2-(4-benzaminic acid ester group)-2,2,6,6-tetramethyl piperidine, 3-(4-benzaminic acid ester group)-2,2,6,6-tetramethyl piperidine, 4-(4-benzaminic acid ester group)-1,2,2,6,6-pentamethyl-piperidines, 2-(4-benzaminic acid ester group)-1,2,2,6,6-pentamethyl-piperidines or 3-(4-benzaminic acid ester group)-1,2,2,6,6-pentamethyl-piperidines etc. substitute; 4-(4-aminobenzoyl amido)-2,2,6, the 6-tetramethyl piperidine can be by 2-(4-aminobenzoyl amido)-2,2,6,6-tetramethyl piperidine, 3-(4-aminobenzoyl amido)-2,2,6,6-tetramethyl piperidine, 4-(4-aminobenzoyl amido)-1,2,2,6,6-pentamethyl-piperidines, 2-(4-aminobenzoyl amido)-1,2,2,6,6-pentamethyl-piperidines or 3-(4-amino-benzene acid amides ester group)-1,2,2,6,6-pentamethyl-piperidines etc. substitute; Azoic coupling component AS also can be substituted by beta naphthal, Naphthol AS-D, apthol AS-E, Naphthol AS-OL, apthol AS or azoic coupling component AS-ITR etc. in the above-mentioned embodiment.Its synthetic method and effect are similar.
Claims (2)
1, a kind of photooxidation resistant red azo organic pigment comprises hindered amine group in the molecular structure of above-mentioned azo organic pigment, and hindered amine group is represented with following general formula:
R
1-N＝N-R
2
R wherein
1Be 1-R
3-4 benzoic acid ester group-2,2,6,6-tetramethyl piperidine or 1-R
3-4-benzoylamino-2,2,6, the 6-tetramethyl piperidine; R
3Be H or alkyl; Carbonyl in above-mentioned phenylformic acid ester group or the benzoylamino is positioned at ortho position or a position or the contraposition of the azo-group that links to each other with phenyl ring; R
2Be beta naphthal, azoic coupling component AS, Naphthol AS-D, apthol AS-E, Naphthol AS-OL, apthol AS or azoic coupling component AS-ITR.
2, a kind of preparation method of photooxidation resistant red monoazo pigment dyestuff comprises the step of following order:
(a) take by weighing diazo component 1-R
3The amino substituted benzoyl perester radical-2,2,6 of-4-, 6-tetramethyl piperidine or 1-R
3The amino substituted benzene formyl amido-2,2,6 of-4-, the 6-tetramethyl piperidine adds in the dilute acid soln, is stirred to dissolving fully; The above-mentioned solution that contains diazo component is cooled to below 10 ℃, add sodium nitrite solution while stirring and carry out diazotization reaction, the molar ratio of Sodium Nitrite add-on and diazo component add-on is 1.01-1.1: 1, the pH value that keeps reaction solution is less than 3, temperature of reaction is below 10 ℃, reaction solution is blue to starch potassium iodide paper, reaction times is 1-3 hour, complete until diazotization reaction, add an amount of urea to reaction solution again, stir the Sodium Nitrite of decomposing excessive, to reaction solution to the starch potassium iodide paper nondiscoloration, diazonium salt solution;
(b) dissolve coupling component R2 with the diazo component equimolar amount fully with alkali lye, filter, remove mechanical impurity, filtrate is cooled to 5-10 ℃, in 10-15min, add in the diazonium salt solution of step (a) acquisition, maintain the temperature at 5-10 ℃ after adding, the pH value is 7.5-10, continues reaction, detects with oozing the circle method, up to the diazonium salt completely dissolve, obtain coupling solution;
(c) in the coupling solution that step (b) obtains, add an amount of sodium abietate salts solution, and at room temperature continue to stir at least 0.5 hour, add an amount of barium chloride solution again, continue at room temperature to stir at least 0.5 hour, being heated to temperature then is that restir is more than at least 0.5 hour more than 65 ℃, filter immediately, filter cake washes with water, and in carrying out drying below 80 ℃, gets photooxidation resistant red azo organic pigment.
R in the above-mentioned steps (a)
3Be H or alkyl, the amino the position of substitution on amino substituted benzoyl perester radical or the amino substituted benzene formyl amido can be ortho position or a position or contraposition; Coupling component R in the above-mentioned steps (b)
2Be beta naphthal, azoic coupling component AS, Naphthol AS-D, apthol AS-E, Naphthol AS-OL, apthol AS or azoic coupling component AS-ITR.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510045593 CN1803930A (en) | 2005-12-15 | 2005-12-15 | Photooxidation resistant red azo organic pigment and method for preparing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510045593 CN1803930A (en) | 2005-12-15 | 2005-12-15 | Photooxidation resistant red azo organic pigment and method for preparing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1803930A true CN1803930A (en) | 2006-07-19 |
Family
ID=36866083
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200510045593 Pending CN1803930A (en) | 2005-12-15 | 2005-12-15 | Photooxidation resistant red azo organic pigment and method for preparing the same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1803930A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101914302A (en) * | 2010-07-17 | 2010-12-15 | 青岛大学 | K-type active light-resistant red azo dye and preparation method thereof |
| CN102746708A (en) * | 2012-05-28 | 2012-10-24 | 吴江市屯村颜料厂 | Preparation method of permanent red S2BL |
| JP2014080576A (en) * | 2012-09-27 | 2014-05-08 | Fujifilm Corp | Pigment composition, coloring curable composition, color filter for solid state imaging sensor and its manufacturing method, solid state imaging sensor, pigment dispersion composition and its manufacturing method and compound |
-
2005
- 2005-12-15 CN CN 200510045593 patent/CN1803930A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101914302A (en) * | 2010-07-17 | 2010-12-15 | 青岛大学 | K-type active light-resistant red azo dye and preparation method thereof |
| CN102746708A (en) * | 2012-05-28 | 2012-10-24 | 吴江市屯村颜料厂 | Preparation method of permanent red S2BL |
| JP2014080576A (en) * | 2012-09-27 | 2014-05-08 | Fujifilm Corp | Pigment composition, coloring curable composition, color filter for solid state imaging sensor and its manufacturing method, solid state imaging sensor, pigment dispersion composition and its manufacturing method and compound |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102337040A (en) | Preparation method of neutral metal complex dye | |
| CN1803930A (en) | Photooxidation resistant red azo organic pigment and method for preparing the same | |
| CN1789248A (en) | Hindered amine group-containing substituted benzoate intermediate compound and preparation method thereof | |
| CN102504573B (en) | Naphthol AS organic azo pigment and its synthesis method | |
| US4296028A (en) | Pyrazolonyl substituted disazo pigments | |
| CN100371393C (en) | Light resistant, mono azo organic yellow pigment and method for preparing the same | |
| CN102558906B (en) | Yellow disazo mixed pigment with high tinting strength | |
| CN100371394C (en) | Light resistant, bis-azo yellow organic pigment and method for preparing the same | |
| CH625819A5 (en) | ||
| CN111896536A (en) | Benzothiazole azo acid-base indicator and synthesis method thereof | |
| CN103160144A (en) | Mono azo organic pigment and synthetic method thereof | |
| CN102618084A (en) | Heterocyclic ring blue disperse dye and synthesizing method and application thereof | |
| CN103087544A (en) | P-phenylenediamine bisazo organic pigment and preparation method thereof | |
| CN102516814B (en) | High-strength yellow azo mixed pigment | |
| CN1789249A (en) | Hindered amine group-containing substituted benzamide intermediate compound and preparation method thereof | |
| JPH04226165A (en) | Azo dye produced by using 2- alkylamino-3-cyano-4,6-diaminopyridine as coupling component | |
| CN101294005A (en) | Red naphtocyclinon solvent dye and preparation method thereof | |
| US1947027A (en) | Azo dyes | |
| CN103952004B (en) | A kind of high temperature modification Disperse Brown dye composition and preparation method thereof | |
| DE1444729A1 (en) | Process for the production of new azo pigment dyes | |
| JP2641107B2 (en) | Method for producing azo pigment | |
| CN108587229B (en) | Preparation process and application of pyridone structure-containing disperse dye | |
| JPS63137965A (en) | Thiophene azo dye | |
| US2087706A (en) | Azo dyes and their production | |
| US888837A (en) | Red azo dye |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20060719 |