CN113024889B - Organic colorant for coloring resin and preparation method thereof - Google Patents
Organic colorant for coloring resin and preparation method thereof Download PDFInfo
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- CN113024889B CN113024889B CN202110481542.5A CN202110481542A CN113024889B CN 113024889 B CN113024889 B CN 113024889B CN 202110481542 A CN202110481542 A CN 202110481542A CN 113024889 B CN113024889 B CN 113024889B
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- anthrapyridone
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3437—Six-membered rings condensed with carbocyclic rings
Abstract
The invention discloses a coloring agent for coloring resin and a preparation method thereof. The organic colorant is red light blue, has good heat resistance and resin dispersibility, and can meet the requirements of temperature resistance and migration resistance in the coloring of high-temperature processing resin such as PET and the like. The colorant is easy to prepare and has high commercial value.
Description
Technical Field
The invention belongs to the field of organic coloring agents, and particularly relates to a coloring agent for coloring resin and a preparation method thereof.
Background
The development of material science has higher and higher requirements on the performance of the colorant, and although the colorant is in a large number of markets, the application performance of the colorant is mostly poor, and particularly, the high-performance organic colorant applied to various resins is more in need of the industry. Organic colorants can be divided into two broad classes, one of which is a pigment that is insoluble in water and various application media; the other part is various dyes and solvent dyes with certain water solubility or solvent solubility. For resin coloration, only solvent dyes or pigments are generally used, while water-soluble dyes are insufficient.
Most of the commercial colorants containing anthrapyridone structures are small molecular structures. The general formula is shown as the following general formula 1:
wherein R is
The four colorants are respectively C.I. solvent red 150, C.I. solvent red 149 and C.I. solventThe colorant is bright in color, high in tinting strength and good in temperature resistance, and can be colored by thermoplastic resin. However, the small molecule cannot be applied to high-quality products, and particularly to PET and PA resins with high processing temperature, color migration occurs, i.e., migration resistance is poor.
The research report in the literature using anthrapyridone as a parent is mainly studied around the general formula 1. Such as: published in the journal of "dye and dyeing" in 2003, the Jiangsu Aolonda scientific and technical practice company Limited synthesizes a series of dyes by using reaction raw materials such as alkylamine and substituted aniline, and tests the application performance of the dyes, and the conclusion is that: the solubility of the synthesized sixteen compounds in the organic solvent is increased along with the reduction of the polarity of the solvent; the solubility gradually increases with increasing carbon chain.
Chinese patent CN101535269A discloses a thermostable colorant related to anthrapyridone compounds, which has excellent heat resistance, light resistance and bleeding resistance and can be used for coloring polycarbonate articles, and discloses two new structural anthrapyridone compounds as follows.
Four novel anthrapyridone magenta dyes are synthesized by Lishi Jade of university of great colliery and the like, and the structural general formula is shown as a general formula 2:
wherein A may be the cation M4 or substituted or unsubstituted benzyl or substituted or unsubstituted naphthylmethyl; m1, M2 and M3 are independent cations or cationic groups, and M is an integer of 0-2. The colorant with the structure is a water-soluble colorant, can be only applied to coloring fabrics and papers, and cannot be applied to coloring resin.
The research surrounding the increase of molecular structure mainly comes from the reports in japan.
Japanese patent JP 2003-192930A in 2003 discloses a fuchsin dye with an anthrapyridone structure, wherein the structure of the fuchsin dye is shown as the following general formula 3:
wherein R is selected from hydrogen atom, alkyl or cyclohexyl, Y is selected from hydrogen atom, hydroxyl, amino, mono-or dialkylamino, alkoxy, phenylamino, phenoxy, aralkyl or cycloalkyl amino, naphthyl amino and the like, and X is selected from ethylenediamine, butanediamine, hexanediamine and the like.
JP 2012-126770A published in 2012 by Japanese chemists discloses a novel anthrapyridone compound, the structure of which is shown in the following general formula 4:
the group X is ethylenediamine tetraacetic dianhydride, and the compound has a high-definition color tone and is excellent in light resistance and weather fastness. However, the research is still water-soluble dye, and the main application field is digital painting.
Furthermore, the present inventors filed a published patent application CN201811484140.5 for a colorant for coloring resin, the structure of which is shown in formula 5:
the compound is obtained by condensing 2, 4-diamino-6-substituted phenyl-1, 3, 5-triazine as a bridging group with 6-halogen-N-methyl-anthrapyridone. However, the 2, 4-diamino-6-substituted phenyl-1, 3, 5-triazines used here are more rigid and the resulting compounds are more organic pigmentary. There is still a certain problem of dispersibility in resin coloration. Furthermore, the colorant of formula 5 is yellow-red and blue colorants with similar coloring properties are still in demand by the industry.
Disclosure of Invention
In view of the above problems in the prior art, the present invention aims to provide a colorant for resin coloring, which has a novel structure, is reddish blue, has the characteristics of a solvent dye, and has good light resistance, heat resistance and migration resistance in a resin.
To achieve the above object, the present invention provides an organic colorant having a structure represented by structural formula I:
the colorant compound is a compound with large molecular weight and strong molecular polarity obtained by condensing ethylene glycol (2,2' -diamino) diphenyl ether with strong flexibility and 6-halogen-N-methyl-anthrapyridone as a bridging group. The increase of molecular weight and the increase of molecular polarity can improve the heat resistance, the light resistance and the mobility in the resin; the flexibility of the bridging group can improve the solubility of the compound in a solvent, thereby solving the problem of dispersibility in resin applications.
The invention also provides a preparation method of the organic colorant, which comprises the following steps:
wherein: x is selected from Cl and Br.
Specifically, the organic colorant is obtained by subjecting 6-halo-N-methyl-anthrapyridone and ethylene glycol (2,2' -diamino) diphenyl ether to Ullmann condensation reaction in a high-boiling-point organic solvent in the presence of an acid-binding agent and a catalyst.
In one embodiment, the catalyst is selected from copper powder, cuprous chloride, cuprous iodide, cupric acetate, or cupric sulfate; the acid-binding agent is alkali metal carbonate or alkali metal bicarbonate; the high boiling point organic solvent is alkylbenzene (such as toluene, xylene, etc.), dichlorobenzene, nitrobenzene, dimethyl sulfoxide or N-methylpyrrolidone.
In one embodiment, the catalyst is preferably cuprous chloride or cuprous iodide; the acid-binding agent is preferably sodium bicarbonate; the high boiling point organic solvent is preferably o-dichlorobenzene.
In one embodiment, the molar ratio of 6-halo-N-methyl-anthrapyridone to ethylene glycol (2,2' -diamino) diphenyl ether is 2.0:0.8 to 1.05, preferably 2.0:0.9 to 1.0, more preferably 2.0:0.95 to 1.0; the weight ratio of the catalyst to the 6-halo-N-methyl-anthrapyridone is 1:20 to 40, preferably 1:25 to 35, more preferably 1:30 to 35.
In one embodiment, the reaction is carried out at a pH of from 9.0 to 11.0, preferably from 9.5 to 10.0. The pH is adjusted by an acid-binding agent, and the dosage of the acid-binding agent is preferably adjusted to obtain the pH.
In one embodiment, the temperature of the reaction is 150 to 200 ℃, preferably 160 to 190 ℃, more preferably 170 to 180 ℃. The reaction time is 4-48 h, preferably 8-24 h, and more preferably 12-16 h.
The invention also provides the application of the organic colorant in resin or paper coloring. The resin may be Polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), Polycarbonate (PC), Polyamide (PA), ABS, Polystyrene (PS), polymethyl methacrylate (PMMA), Polyphenylene Sulfide (PPs), or the like.
To this end, the present invention also provides a method for coloring a resin or paper, characterized by subjecting the resin or paper to a step of coloring with the organic colorant of the present invention.
Furthermore, the colorant can be applied to the fields of color master batch preparation, fiber stock solution coloring, plastic film, plastic printing or injection molding and the like.
The beneficial effects of the invention are highlighted as follows:
1. the invention is a red light blue colorant, the melting point is 320 ℃, the crystal morphology of the colorant shows obvious solvent dye characteristics, and the colorant can be used for coloring various resins and particularly can meet the application requirements of high-temperature processing resins such as PET, PS and the like.
2. The colorant compound is prepared by connecting two anthrapyridone groups by using glycol (2,2' -diamino) diphenyl ether with stronger flexibility as a bridging group, has the characteristics of larger molecular weight and stronger molecular polarity, and can improve the heat resistance, the light resistance and the mobility in resin; the introduction of the flexible bridging group enables the colorant of the present invention to have good compatibility with the resin, thereby solving the problem of dispersibility in resin applications.
The test results show that the colorant of the present invention has very excellent heat resistance and migration resistance when applied to coloring of resins such as PET.
3. The colorant compound of the invention has simple preparation process, easily obtained raw materials, easy treatment of three wastes and easy large-scale preparation.
In conclusion, the organic colorant is red-light blue, has good heat resistance and easy dispersibility, and can meet the requirements of temperature resistance and migration resistance of coloring high-temperature processing resin such as PET and the like. The colorant compound is easy to prepare, has high commercial value and is suitable for being developed into the next generation resin colorant.
Drawings
FIG. 1: the product provided by the embodiment 1 of the invention has a scanning micro-topography under an electron microscope.
Detailed Description
These and other aspects of the invention will be further elucidated by the following description of a preferred embodiment and the accompanying drawings. Although variations or modifications may be made therein without departing from the spirit and scope of the novel concepts disclosed in the present disclosure.
It should be understood that the terms or words used in the specification and claims should not be construed as having meanings defined in dictionaries, but should be interpreted as having meanings that are consistent with their meanings in the context of the present invention on the basis of the following principles: the concept of terms may be defined appropriately by the inventors for the best explanation of the invention.
Synthetic examples
Example 1: preparation of Compounds of formula I
The reaction formula is as follows:
6.84g (0.02mol) of N-methyl-6-bromo-anthrapyridone, 0.22g of cuprous iodide, 150mL of o-dichlorobenzene, and 2.44g (0.01mol) of ethylene glycol (2,2' -diamino) diphenyl ether were sequentially added to a 250mL four-necked flask equipped with a reflux condenser, a water separator, and a thermometer, followed by stirring and slow warming to 170 ℃. And (3) gradually adding an acid-binding agent sodium bicarbonate in the process, and keeping the pH value of the reaction system between 9.5 and 10. And continuously heating to 180 ℃ and refluxing for 12-15 hours, and taking a sample to perform liquid chromatography detection to show that no raw material exists as a reaction end point. Adding water for azeotropic distillation to remove the solvent, carrying out hot filtration on the solid in the flask, washing residual solvent o-dichlorobenzene in the filter cake with ethanol until the filtrate is basically colorless, recovering the ethanol, continuing to wash the ethanol and inorganic salt in the filter cake with distilled water, recovering the filtrate, drying the filter cake, and weighing to obtain 7.01g of the compound shown in the structural formula I. The appearance was a dark blue powder with a yield of about 92%. UPLC-MS: the excimer ion peak M/z is 763.2569, assigned as [ M + H ═ M + H]+Confirmed as the target compound.
From the scanning electron microscope picture (figure 1), the product prepared by the invention has no obvious crystal morphology, belongs to the characteristics of solvent dye, and can be used for coloring various resins.
Example 2: preparation of Compounds of formula I
The difference from example 1 is that the procedure of example 1 is repeated using equal mass of cuprous chloride as catalyst instead of cuprous iodide in the above preparation procedure to obtain about 6.86 g of compound of formula I as dry powder with about 90% yield.
Application examples
The following examples illustrate in detail the application properties and the application effects of the colorants of the present invention, and the samples obtained in example 1 above are used as examples.
Example 3: color characterization test
0.1 g of the sample obtained in example 1 was added to 400g of PET resin, premixed uniformly, and injection-molded at 280 ℃. The resulting panels were subjected to electronic color measurement and the results are shown in table 1.
Table 1: color characteristics
The colorant of the invention is red light blue in PET resin by injection molding at 280 ℃, has better vividness and can be used as a colorant for coloring resin.
Example 4: heat resistance test
The sample of example 1 was taken to test its heat resistance in a PET resin.
The test method comprises the following steps: 0.5g of the sample of example 1, 1.2g of TiO2400g of PET resin was mixed well and injection-molded. The injection temperature was set at 290 ℃ and the residence times were 1 minute, 15 minutes and 30 minutes, respectively. Color detection is carried out by adopting an electronic colorimeter under a D65 light source by using a Lab system, and the change condition of the color difference is inspected. The results are shown in Table 2.
Table 2: heat resistance of samples in PET resin
The colorant of the invention stays for 30 minutes in PET resin at 290 ℃ during injection molding, and the total color difference is 2.72, which shows that the colorant has better heat resistance and can meet the coloring requirement of PET and other resins in high temperature processing.
Example 5: migration resistance test
The method for measuring the migration resistance comprises the following steps: the sample obtained in example 1 was uniformly mixed with Polyester (PET) powder in an amount of 2 wt%, and injection-molded at 280 ℃ to prepare a PET injection-molded sheet. Taking a block (3.2X 2.0) cm2And (3) placing the colored PET sheet on a white PET knitted fabric, applying a pressure of 7MPa, placing in a thermal cycling oven with an internal temperature of 180 ℃ for 3min, removing the colored PET sheet, and observing the contamination degree on the white PET knitted fabric. And (4) testing the blank PET knitted fabric and the test stained cloth by using an electronic color measuring instrument in a contrast mode, and calculating the total color difference. Standard evaluation according to ISO EN ISO105-A03, grade 5 indicates no migration, grade 1Indicating that migration was severe. The results are shown in Table 3.
Table 3: migration resistance of samples in PET resin
| L | a | b | DE | |
| Blank cloth | 89.46 | -0.53 | 0.15 | |
| Staining cloth | 91.53 | -0.40 | 0.73 | 2.15 |
The DE of the colorant of the invention in PET resin is 2.15<2.2, migration 4-5 grade, which shows that the colorant of the invention has better migration resistance.
The foregoing describes preferred embodiments of the present invention, but is not intended to limit the invention thereto. Modifications and variations of the embodiments disclosed herein may be made by those skilled in the art without departing from the scope and spirit of the invention.
Claims (12)
1. An organic colorant having the structure shown in formula I:
2. a process for producing the organic colorant according to claim 1,
wherein: x is selected from Cl and Br;
carrying out Ullmann condensation reaction on 6-halogen-N-methyl-anthrapyridone and ethylene glycol (2,2' -diamino) diphenyl ether in a high-boiling-point organic solvent in the presence of an acid-binding agent and a catalyst to obtain the organic colorant;
the catalyst is selected from copper powder, cuprous chloride, cuprous iodide, copper acetate or copper sulfate; the acid-binding agent is alkali metal carbonate or alkali metal bicarbonate; the high boiling point organic solvent is alkylbenzene, dichlorobenzene, nitrobenzene, dimethyl sulfoxide or N-methyl pyrrolidone.
3. The method according to claim 2, wherein the catalyst is selected from cuprous chloride or cuprous iodide; the acid-binding agent is selected from sodium bicarbonate; the high boiling point organic solvent is selected from o-dichlorobenzene.
4. The method according to claim 2, wherein the molar ratio of 6-halo-N-methyl-anthrapyridone to ethylene glycol (2,2' -diamino) diphenyl ether is 2.0:0.8 to 1.05; the weight ratio of the catalyst to the 6-halo-N-methyl-anthrapyridone is 1: 20-40.
5. The method according to claim 2, wherein the molar ratio of 6-halo-N-methyl-anthrapyridone to ethylene glycol (2,2' -diamino) diphenyl ether is 2.0:0.9 to 1.0; the weight ratio of the catalyst to the 6-halo-N-methyl-anthrapyridone is 1: 25-35.
6. The method according to claim 2, wherein the molar ratio of 6-halo-N-methyl-anthrapyridone to ethylene glycol (2,2' -diamino) diphenyl ether is 2.0:0.95 to 1.0; the weight ratio of the catalyst to the 6-halo-N-methyl-anthrapyridone is 1: 30-35.
7. The method according to claim 2, wherein the reaction is carried out at a pH of 9.0 to 11.0; the reaction temperature is 150-200 ℃.
8. The method according to claim 2, wherein the reaction is carried out at a pH of 9.5 to 10.0; the reaction temperature is 160-190 ℃.
9. Use of an organic colorant according to claim 1, characterized in that the organic colorant is used for coloring resins or paper.
10. Use according to claim 9, characterized in that the resin is selected from Polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), Polycarbonate (PC), Polyamide (PA), ABS, Polystyrene (PS), polymethyl methacrylate (PMMA) or Polyphenylene Sulfide (PPs).
11. A method for coloring a resin or paper, characterized by subjecting the resin or paper to a step of coloring with the organic colorant according to claim 1.
12. The method according to claim 11, wherein the resin is selected from Polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), Polycarbonate (PC), Polyamide (PA), ABS, Polystyrene (PS), Polymethylmethacrylate (PMMA), or Polyphenylene Sulfide (PPs).
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1323303A (en) * | 1998-10-22 | 2001-11-21 | 日本化药株式会社 | Novel anthrapyridone compounds, water-based magenta ink composition, and method of ink-jet printing |
| CN102639647A (en) * | 2009-11-24 | 2012-08-15 | 美利肯公司 | Polymeric violet anthraquinone colorant compositions and methods for producing the same |
| CN103374238A (en) * | 2012-04-28 | 2013-10-30 | 高邮市华宝颜料有限公司 | Method of preparing transparent pigment yellow 180 |
| CN109627490A (en) * | 2018-12-06 | 2019-04-16 | 沈阳化工研究院有限公司 | A kind of red toner and preparation method thereof applied to coloring resin |
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- 2021-04-30 CN CN202110481542.5A patent/CN113024889B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1323303A (en) * | 1998-10-22 | 2001-11-21 | 日本化药株式会社 | Novel anthrapyridone compounds, water-based magenta ink composition, and method of ink-jet printing |
| CN102639647A (en) * | 2009-11-24 | 2012-08-15 | 美利肯公司 | Polymeric violet anthraquinone colorant compositions and methods for producing the same |
| CN103374238A (en) * | 2012-04-28 | 2013-10-30 | 高邮市华宝颜料有限公司 | Method of preparing transparent pigment yellow 180 |
| CN109627490A (en) * | 2018-12-06 | 2019-04-16 | 沈阳化工研究院有限公司 | A kind of red toner and preparation method thereof applied to coloring resin |
Non-Patent Citations (1)
| Title |
|---|
| Soluble Functional Polymers.2 Utilization of Water-Insoluble Chromophores in Water-Soluble Polymeric Dyes;Daniel J.Dawson;《Macromolecules》;American Chemical Society;19780430;第11卷(第2期);全文 * |
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