CN115247000A - Novel pigment and preparation method thereof - Google Patents
Novel pigment and preparation method thereof Download PDFInfo
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- CN115247000A CN115247000A CN202210891362.9A CN202210891362A CN115247000A CN 115247000 A CN115247000 A CN 115247000A CN 202210891362 A CN202210891362 A CN 202210891362A CN 115247000 A CN115247000 A CN 115247000A
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- 239000000049 pigment Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 12
- RWRDLPDLKQPQOW-UHFFFAOYSA-N tetrahydropyrrole Substances C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- -1 2-n-heptylphenyl Chemical group 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 15
- 239000005457 ice water Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 11
- 229910052726 zirconium Inorganic materials 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 9
- 238000000967 suction filtration Methods 0.000 claims description 8
- GCPWJFKTWGFEHH-UHFFFAOYSA-N acetoacetamide Chemical compound CC(=O)CC(N)=O GCPWJFKTWGFEHH-UHFFFAOYSA-N 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000004587 chromatography analysis Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 5
- 238000010828 elution Methods 0.000 claims description 5
- 238000012544 monitoring process Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 3
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 claims description 2
- 125000004204 2-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C(OC([H])([H])[H])C([H])=C1[H] 0.000 claims description 2
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 2
- 239000002518 antifoaming agent Substances 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000001209 o-nitrophenyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])[N+]([O-])=O 0.000 claims description 2
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 claims description 2
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 claims description 2
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 claims description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 2
- 238000004873 anchoring Methods 0.000 abstract description 3
- 230000000087 stabilizing effect Effects 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 abstract 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 abstract 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 239000012860 organic pigment Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 239000013530 defoamer Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000001053 orange pigment Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- DOQJUNNMZNNQAD-UHFFFAOYSA-N pyrrolidine-2,4-dione Chemical group O=C1CNC(=O)C1 DOQJUNNMZNNQAD-UHFFFAOYSA-N 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- QKWILNTYPDJSME-UHFFFAOYSA-N pyrrolo[3,4-c]pyrrole-3,6-dione Chemical compound C1=NC(=O)C2=C1C(=O)N=C2 QKWILNTYPDJSME-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0001—Post-treatment of organic pigments or dyes
- C09B67/0022—Wet grinding of pigments
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/006—Preparation of organic pigments
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
The invention discloses a novel pigment and a preparation method thereof, the novel pigment comprises an auxiliary agent and a solvent, wherein the auxiliary agent is a polysubstituted 2,4-pyrrolidine diketone compound, and the auxiliary agent is composed of an alpha-acetyl-alpha-carbamoyl dithioketene acetal synthon and aldehyde R 2 -CHO was synthesized. The novel pigment is simple and convenient in preparation method, the polysubstituted 2,4-pyrrolidine diketone compound is taken as an auxiliary agent, and the obtained pigment has anchoring and stabilizing functions and is suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of pigments, in particular to a novel pigment and a preparation method thereof.
Background
In the production of high-quality color pastes, the dispersibility of the pigments is one of the main influencing factors. The high dispersion and good stability of organic pigments in various environments such as aqueous color pastes or oily color pastes are one of the persistent subjects of continuous development of color pastes with excellent performance.
1,4-diketopyrrolo [3,4-c ] pyrrole pigment is a pigment which is well known at present and the synthesis of which is described in EP 94911. Diketopyrrolopyrrole pigments such as PR254 generally exhibit very good stability, brightness, good dispersibility, high color strength and color purity in a variety of application systems. At present, there are orange DPP pigments with several structures of PO71, PO73 and PO81, and these pigments are commercially available. However, these orange pigments each have some disadvantages, such as poor PO71 saturation, PO73 having excellent saturation and poor weather resistance. It is difficult to unify them, especially when they are exposed to air after they are made into a paint, the longer the time, the more serious the discoloration.
There are many companies at home and abroad that have proposed a method for improving the weatherability of diketopyrrolopyrrole pigments. In CN1068362C, the pigment is modified by using a complex of metal such as titanium or zirconium, but the method is proved not to be improved in weather resistance; the improvement in weather resistance by improving the particle size distribution of the product is mentioned in CN101370876a, which is only a minor improvement, but not the property of the molecular structure itself that is susceptible to damage. CN1665816A mentions synthesizing a new DPP structure, which can improve the coating fastness of the coating, and does not mention whether the weather resistance can be improved, but the solvent resistance is judged to be poor from the structure, and the application field is limited.
Therefore, it is an urgent technical problem to be solved by those skilled in the art to provide a polysubstituted pyrrolidone with both anchoring and stabilizing functions as an auxiliary agent to obtain a novel pigment.
Disclosure of Invention
In view of the above, the present invention provides a novel pigment, which is a slurry type, wherein the main additive of the novel pigment is a polysubstituted 2,4-pyrrolidinedione additive which has both functions of wetting and dispersing agent, and the novel pigment shows enhanced activity in the pigment of the present invention, thereby obtaining a pigment with higher processing level and having the function of improving pigment dispersibility in the mixing of multifunctional color pastes. The novel synthesis method of the pigment auxiliary agent starts from easily available raw materials, and forms a nitrogenous five-ring in one step through an alpha-acetyl-alpha-carbamoyl dithioketene intermediate.
In order to achieve the purpose, the invention adopts the following technical scheme:
the novel pigment comprises an auxiliary agent and a solvent, wherein the auxiliary agent is a polysubstituted 2,4-pyrrolidine diketone compound comp.1.
In comp.1: r is ethyl, propyl, butyl, pentyl or hexyl;
R 1 is phenyl, 2-methylphenyl, 2-methoxyphenyl, 4-chlorophenyl, 2-n-heptylphenyl, 2-n-octylphenyl, 2-n-nonylphenyl, 2-n-decylphenyl, 2-n-undecylphenyl, 2-n-tetradecylphenyl, 3-n-heptylphenyl, 3-n-octylphenyl, 3-n-nonylphenyl, 3-n-decylphenyl, 3-n-undecylphenyl, 3-n-tetradecylphenyl, 4-n-heptylphenyl, 4-n-octylphenyl, 4-n-nonylphenyl, 4-n-decylphenyl, 4-n-undecylphenyl, 4-n-tetradecylphenyl;
R 2 is p-nitrophenyl, o-methoxyphenyl, o-nitrophenyl, p-methoxyphenyl.
Preferably, the auxiliary agent is a polysubstituted 2,4-pyrrolidinedione compound comp.1 which is prepared by reacting alpha-acetyl-alpha-carbamyl dithioketene comp.2 and aldehyde R 2 -CHO comp.3, the synthetic route is shown as follows:
the specific method comprises the following steps: 2.0mmol of alpha-acetyl-alpha-carbamyl dithioketene (comp.2) and aldehyde R 2 Adding 2.2mmol of-CHO (comp.3) into 10.0mL of ethanol, stirring for 5min, dropwise adding the prepared EtONa/ethanol solution in an ice water bath under electromagnetic stirring, stirring for 50-70min at normal temperature, detecting by TLC until a reaction substrate disappears, adjusting the pH value to 6.5-7.5, performing suction filtration, washing with water, removing ethanol, continuously washing with water, combining solids obtained in two times, drying to obtain a crude product, and performing chromatography and elution to obtain comp.1;
wherein the dosage of the EtONa/ethanol solution is 2.4mL, and the concentration is 1g/L.
Preferably, the alpha-acetyl-alpha-carbamyl dithioketene comp.2 is obtained by reacting carbamyl acetone comp.4 with carbon disulfide and brominated hydrocarbon under the condition of weak alkalinity, and the synthetic route is shown as follows,
the preparation method comprises the following steps: adding anhydrous K into a reaction vessel 2 CO 3 Carbamoylacetone and DMF, stirring at room temperature for 0.5h, cooling in ice water bath, stirring for 10min, adding CS 2 And (3) rapidly turning the reaction liquid to red, stirring for 1h in ice-water bath, then dropwise adding bromohydrocarbon into the reaction system, stirring at normal temperature, monitoring the reaction by TLC until a substrate of carbamoylacetone disappears, pouring the reaction liquid into water, immediately generating a large amount of yellow precipitates, fully stirring, performing suction filtration, washing with water, and drying to obtain comp.2.
Preferably, the adjuvant polysubstituted 2,4-pyrrolidine diketone compound comp.1 specifically comprises the following structure:
preferably, the solvent comprises: diethylene glycol monomethyl ether, propylene glycol methyl ether or dipropylene glycol dimethyl ether,
the preparation method of the novel pigment comprises the following steps: according to the weight percentage, 30 to 70 percent of pigment, 15 to 30 percent of solvent, 0.1 to 1.0 percent of polysubstituted 2,4-pyrrolidine diketone compound, 0.1 to 0.5 percent of defoaming agent and water are put into a stirring cylinder to be fully stirred until the pigment and the filler are completely wetted, then zirconium balls are used as grinding media to grind for 20 to 80 minutes at the rotating speed of 2500 to 300r/min, and the zirconium balls are filtered by a screen mesh to obtain the novel pigment of the invention
According to the technical scheme, compared with the prior art, the novel pigment provided by the invention is simple and convenient to prepare, the polysubstituted 2,4-pyrrolidine diketone compound is used as an auxiliary agent, and the obtained pigment has anchoring and stabilizing functions and is suitable for industrial production.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
A novel pigment preparation method comprises the following steps: adding 70% of organic pigment, 15% of solvent, 1.0% of assistant polysubstituted 2,4-pyrrolidine diketone compound, 1.5% of defoamer Foamic 028 Tu Yile and water for complementing according to mass percentage, putting into a stirring cylinder for fully stirring until the pigment and the filler are completely wetted by the pigment, grinding for 80min at the rotating speed of 3000r/min by taking zirconium balls as grinding media, and filtering the zirconium balls by using a screen to obtain the novel pigment;
wherein, the polysubstituted 2,4-pyrrolidine diketone compound (comp.1) is shown as formula 3t (R, R in the preparation method related to the following description) 1 And R 2 Is selected in accordance with formula 3 t):
the polysubstituted 2,4-pyrrolidinedione compound (comp.1) is prepared from alpha-acetyl-alpha-carbamyl dithioketene (comp.2) and aldehyde R 2 -CHO (comp.3) reaction:
2.0mmol of alpha-acetyl-alpha-carbamoyldithioketene (comp.2) and aldehyde R 2 Adding 2.2mmol of-CHO (comp.3) compound into 10.0mL of ethanol, stirring for 5min, and dropwise adding the prepared EtONa/ethanol solution in an ice water bath under electromagnetic stirring and stirring at normal temperature for 50min. Detecting by TLC until reaction substrate disappears, adjusting pH to 6.5, vacuum filtering, washing with water, removing ethanol, washing with water, mixing the two obtained solids, drying to obtain crude product, and performing chromatography and elution to obtain comp.1;
wherein the dosage of the EtONa/ethanol solution is 2.4mL, and the concentration is 1g/L.
The synthon alpha-acetyl-alpha-carbamyl dithioketene is obtained by reacting carbamyl acetone (comp.4) with carbon disulfide and bromohydrocarbon (RBr) under the condition of weak alkaline
To a 50mL three-necked flask was added anhydrous K 2 CO 3 (40.0 mmol, 5.52g), carbamylacetone (20.0 mmol), DMF (20.0 mL), stirring at room temperature for 0.5h, cooling in ice water bath, stirring for 10min, adding CS 2 (22.0 mmol,1.3 mL), the reaction turned red rapidly, stirred for 1h in an ice water bath, and then bromohydrocarbon (22.0 mmol) was added dropwise to the reaction system. Stirring at normal temperature, monitoring the reaction by TLC until a substrate carbamoylacetone disappears, pouring the reaction solution into water, immediately generating a large amount of yellow precipitate, fully stirring, performing suction filtration, washing with water, and drying to obtain comp.2.
Example 2
A novel pigment preparation method comprises the following steps: adding 30% of organic pigment, 15% of solvent, 0.1% of auxiliary polysubstituted 2,4-pyrrolidine diketone compound, 0.1% of defoamer Foamic 028 Tu Yile and water for complement, putting into a stirring cylinder for fully stirring until the pigment is completely wetted with the pigment, grinding for 20min at the rotating speed of 2500r/min by taking zirconium balls as grinding media, and filtering the zirconium balls by using a screen to obtain the novel pigment;
wherein, the polysubstituted 2,4-pyrrolidine diketone compound (comp.1) is shown as formula 7t (R, R in the preparation method related to the following description) 1 And R 2 Is selected in accordance with formula 7 t):
the polysubstituted 2,4-pyrrolidinedione compound (comp.1) is synthesized from alpha-acetyl-alpha-carbamoyldithioketene (comp.2) and aldehyde R 2 -CHO (comp.3);
2.0mmol of alpha-acetyl-alpha-carbamyl dithioketene (comp.2) and aldehyde R 2 Adding 2.2mmol of-CHO (comp.3) compound into 10.0mL of ethanol, stirring for 5min, dropwise adding the prepared EtONa/ethanol solution in an ice water bath under electromagnetic stirring, and stirring at normal temperature for 70min. Detecting by TLC until reaction substrate disappears, adjusting pH to 7.5, vacuum filtering, washing with water, removing ethanol, washing with water, mixing the two obtained solids, drying to obtain crude product, and performing chromatography and elution to obtain comp.1;
wherein the dosage of the EtONa/ethanol solution is 2.4mL, and the concentration is 1g/L.
The synthon alpha-acetyl-alpha-carbamyl dithioketene is obtained by reacting carbamyl acetone (comp.4) with carbon disulfide and bromohydrocarbon (RBr) under the condition of weak alkaline
To a 50mL three-necked flask was added anhydrous K 2 CO 3 (40.0 mmol, 5.52g), carbamylacetone (20.0 mmol), DMF (20.0 mL), stirring at room temperature for 0.5h, cooling in ice water bath, stirring for 10min, adding CS 2 (22.0 mmol,1.3 mL), the reaction liquid rapidly turned red, and stirred for 1h in an ice-water bath, then bromohydrocarbon (22.0 mmol) was added dropwise to the reaction system. Stirring at normal temperature, monitoring the reaction by TLC until a substrate carbamoylacetone disappears, pouring the reaction solution into water, immediately generating a large amount of yellow precipitate, fully stirring, performing suction filtration, washing with water, and drying to obtain comp.2.
Example 3
A novel pigment preparation method comprises the following steps: adding 50% of organic pigment, 20% of solvent, 0.5% of auxiliary polysubstituted 2,4-pyrrolidine diketone compound, 0.3% of defoamer Foamic 028 Tu Yile and water for complement, putting into a stirring cylinder for fully stirring until the pigment is completely wetted with the pigment, grinding for 50min at the rotating speed of 2800r/min by taking zirconium balls as grinding media, and filtering the zirconium balls by using a screen to obtain the novel pigment;
<xnotran> , 5363 zxft 5363- (comp.1) 18t ( R, </xnotran>R 1 And R 2 Is consistent with formula 18 t):
wherein the polysubstituted 2,4-pyrrolidinedione compound (comp.1) is synthesized from alpha-acetyl-alpha-carbamyl dithioketene (comp.2) and aldehyde R 2 -CHO (comp.3) reaction:
2.0mmol of alpha-acetyl-alpha-carbamoyldithioketene (comp.2) and aldehyde R 2 Adding 2.2mmol of-CHO (comp.3) compound into 10.0mL of ethanol, stirring for 5min, and dropwise adding the prepared EtONa/ethanol solution in an ice water bath under electromagnetic stirring and stirring at normal temperature for 60min. Detecting by TLC until reaction substrates disappear, adjusting the pH value to 7, performing suction filtration, washing with water, removing ethanol, continuously washing with water, combining solids obtained in two times, drying to obtain a crude product, and performing chromatography and elution to obtain comp.1;
wherein the dosage of the EtONa/ethanol solution is 2.4mL, and the concentration is 1g/L.
The synthon alpha-acetyl-alpha-carbamyl dithioketene is obtained by reacting carbamyl acetone (comp.4) with carbon disulfide and bromohydrocarbon (RBr) under the condition of weak alkaline
To a 50mL three-necked flask was added anhydrous K 2 CO 3 (40.0 mmol, 5.52g), carbamylacetone (20.0 mmol), DMF (20.0 mL), stirring at room temperature for 0.5h, cooling in ice water bath, stirring for 10min, adding CS 2 (22.0 mmol,1.3 mL), the reaction liquid rapidly turned red, and stirred for 1h in an ice-water bath, then bromohydrocarbon (22.0 mmol) was added dropwise to the reaction system. Stirring at normal temperature, monitoring the reaction by TLC until the substrate carbamylacetone disappears, pouring the reaction solution into water, and immediately generating a large amount of yellow precipitatePrecipitating, fully stirring, performing suction filtration, washing with water, and drying to obtain comp.2.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (5)
1. A novel pigment is characterized by comprising an auxiliary agent and a solvent, wherein the auxiliary agent is a polysubstituted 2,4-pyrrolidine diketone compound comp.1, the structure of which is shown as the following formula comp.1,
wherein R in the formula comp.1 is ethyl, propyl, butyl, pentyl or hexyl;
R 1 is phenyl, 2-methylphenyl, 2-methoxyphenyl, 4-chlorophenyl, 2-n-heptylphenyl, 2-n-octylphenyl, 2-n-nonylphenyl, 2-n-decylphenyl, 2-n-undecylphenyl, 2-n-tetradecylphenyl, 3-n-heptylphenyl, 3-n-octylphenyl, 3-n-nonylphenyl, 3-n-decylphenyl, 3-n-undecylphenyl, 3-n-tetradecylphenyl, 4-n-heptylphenyl, 4-n-octylphenyl, 4-n-nonylphenyl, 4-n-decylphenyl, 4-n-undecylphenyl or 4-n-tetradecylphenyl;
R 2 is p-nitrophenyl, o-methoxyphenyl, o-nitrophenyl or p-methoxyphenyl.
2. A novel pigment according to claim 1, wherein the auxiliary polysubstituted 2,4-pyrrolidinedione compound comp.1 is prepared from α -acetyl- α -carbamoyl dithioketene comp.2 and aldehyde R 2 The reaction is-CHO comp.3, the synthetic route is shown as follows,
the specific method comprises the following steps: 2.0mmol of alpha-acetyl-alpha-carbamyl dithioketene (comp.2) and aldehyde R 2 Adding 2.2mmol of-CHO (comp.3) into 10.0mL of ethanol, stirring for 5min, dropwise adding the prepared EtONa/ethanol solution in an ice water bath under electromagnetic stirring, stirring for 50-70min at normal temperature, detecting by TLC until a reaction substrate disappears, adjusting the pH value to 6.5-7.5, performing suction filtration, water washing, removing ethanol, continuing water washing, combining the solids obtained in the two times, drying to obtain a crude product, and performing chromatography and elution to obtain comp.1;
wherein the dosage of the EtONa/ethanol solution is 2.4mL, and the concentration is 1g/L.
3. A novel pigment according to claim 2, characterized in that said α -acetyl- α -carbamoyl dithioketene comp.2 is prepared by reacting carbamoyl acetone comp.4 with carbon disulfide and bromohydrocarbon under weakly alkaline conditions, the synthetic route is as follows,
the preparation method comprises the following steps: adding anhydrous K into a reaction vessel 2 CO 3 Carbamoylacetone and DMF, stirring at room temperature for 0.5h, cooling in ice water bath, stirring for 10min, adding CS 2 The reaction solution turns red rapidly, is stirred for 1 hour in ice-water bath, and then reactsAdding bromohydrocarbon dropwise into the system, stirring at normal temperature, monitoring the reaction by TLC until a substrate carbamoylacetone disappears, pouring the reaction solution into water, immediately generating a large amount of yellow precipitates, fully stirring, performing suction filtration, washing with water, and drying to obtain comp.2.
4. A novel pigment according to claim 1, characterized in that said solvent comprises: diethylene glycol monomethyl ether, propylene glycol methyl ether or dipropylene glycol dimethyl ether.
5. The process for preparing the novel pigment as claimed in any of claims 1 to 4, wherein the novel pigment of the present invention is obtained by adding 30 to 70% by weight of the pigment, 15 to 30% by weight of the solvent, 0.1 to 1.0% by weight of the polysubstituted 2,4-pyrrolidinedione compound, 0.1 to 0.5% by weight of the antifoaming agent and the balance of water to a stirring tank, stirring the mixture sufficiently until the pigment completely wets the pigment and filler, grinding the mixture for 20 to 80 minutes at a rotation speed of 2500 to 300r/min by using zirconium balls as a grinding medium, and filtering the zirconium balls out by using a screen.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040060478A1 (en) * | 2001-02-10 | 2004-04-01 | Joachim Weber | Acid pigment dispersants and pigment preparations |
| CN1623991A (en) * | 2004-05-13 | 2005-06-08 | 延边大学 | Substituded acza nember 5/nember 6 ring compound and its preparation process |
| CN103339536A (en) * | 2011-01-28 | 2013-10-02 | 东洋油墨Sc控股株式会社 | Diketopyrrolopyrrole-type pigment composition for color filters, colored composition for color filters, and color filter |
| CN109554004A (en) * | 2018-12-16 | 2019-04-02 | 江苏丽王科技股份有限公司 | Pigment dispersing agent and application thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040060478A1 (en) * | 2001-02-10 | 2004-04-01 | Joachim Weber | Acid pigment dispersants and pigment preparations |
| CN1623991A (en) * | 2004-05-13 | 2005-06-08 | 延边大学 | Substituded acza nember 5/nember 6 ring compound and its preparation process |
| CN103339536A (en) * | 2011-01-28 | 2013-10-02 | 东洋油墨Sc控股株式会社 | Diketopyrrolopyrrole-type pigment composition for color filters, colored composition for color filters, and color filter |
| CN109554004A (en) * | 2018-12-16 | 2019-04-02 | 江苏丽王科技股份有限公司 | Pigment dispersing agent and application thereof |
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