Diketopyrrolopyrrole pigment derivative as well as preparation method and application thereof
By introducing alkyl chains to the DPP pigment, pyrrolopyrrole dione pigment derivatives containing alkyl chains were prepared, which solved the problem of poor dispersion effect of DPP pigment and achieved better thermal stability, coloring performance and dispersion performance.
Patent Information
- Application Number
- CN202510055904.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-01-14
- Publication Date
- 2025-04-18
AI Technical Summary
The dispersion effect of existing DPP pigments is poor, which affects its application in the field of photoelectric materials.
By introducing alkyl chains on DPP pigments, pyrrolopyrrole dione pigment derivatives containing alkyl chains were prepared, and the preparation was performed by reacting with alkyl halide compounds under the action of alkaline reagents.
It enhances the thermal stability of pigment derivatives, improves the coloring intensity and brightness, reduces the crystallinity and improves the dispersion performance.
Smart Images
Figure CN119841835A_ABST
Abstract
Description
Technical Field
[0001] The present application relates to the technical field of organic pigments, and in particular to a series of alkyl chain-containing pyrrolopyrrole dione pigment derivatives and a preparation method thereof, and also to the use of the derivatives as additives in the preparation of red-based filters. Background Art
[0002] The structure of 1,4-Diketopyrrolopyrroles (DPP) comes from a new type of high-performance organic pigment successfully developed by Ciba in 1983. Its molecular structure contains the structure of 1,4-Diketopyrrolopyrroles, which is called DPP pigment. Organic high-performance pigments containing 1,4-Diketopyrrolopyrroles color matrix have the characteristics of high light fastness, good chemical resistance, complete color spectrum, high fluorescence quantum yield, etc. In recent years, they have received close attention from scientific researchers and are widely used in optoelectronic materials such as organic solar cells, organic field effect transistors, and organic light-emitting diodes.
[0003] However, the current DPP pigments have poor dispersion effects. Summary of the invention
[0004] In view of the shortcomings of the existing methods, the present application proposes a diketopyrrolopyrrole pigment derivative and a preparation method and use thereof.
[0005] In the first aspect, the present invention provides a diketopyrrolopyrrole pigment derivative containing an alkyl chain, the general structural formula of which is shown below:
[0006]
[0007] In the general formula, R 1 H, Cl, CN, CH 3 , C(CH 3 ) 3 or benzene ring; R 2 Alkyl C n H 2n+1 , where n is a positive integer not less than 2 and not greater than 18.
[0008] In a second aspect, the present invention provides a method for preparing a diketopyrrolopyrrole pigment derivative containing an alkyl chain, comprising:
[0009] S1: Under the action of an alkaline reagent, a diketopyrrolopyrrole pigment monomer solution reacts with an alkyl halide compound to obtain a reactant;
[0010] S2: The reactants are washed, filtered, dried, column-passed and ground to obtain the alkyl chain-containing diketopyrrolopyrrole pigment derivative according to any one of claims 1 to 2.
[0011] In a third aspect, an embodiment of the present application provides an application of the alkyl chain-containing diketopyrrolopyrrole pigment derivative described in the first aspect as an additive for preparing a red-based filter.
[0012] The beneficial technical effects brought about by the technical solution provided by the embodiment of the present application include:
[0013] The alkyl chain-containing diketopyrrolopyrrole pigment derivative can enhance the thermal stability of the pigment derivative, improve the tinting strength and brightness, and reduce the crystallinity of the pigment derivative and improve the dispersion performance by introducing an alkyl chain into the DPP pigment.
[0014] The preparation method of the pyrrolopyrrole diketo pigment derivative containing an alkyl chain is to react the DPP pigment with an alkyl halide compound to undergo an N-alkylation substitution reaction. The reaction conditions are mild, the reagents are cheap and readily available, the experimental operation is simple, and the industrial production is easy.
[0015] Additional aspects and advantages of the present application will be partially given in the following description, which will become apparent from the following description, or will be understood through the practice of the present application. BRIEF DESCRIPTION OF THE DRAWINGS
[0016] The above and / or additional aspects and advantages of the present application will become apparent and easily understood from the following description of the embodiments in conjunction with the accompanying drawings, in which:
[0017] Figure 1 A schematic flow chart of a method for preparing a diketopyrrolopyrrole pigment derivative containing an alkyl chain provided in an embodiment of the present application;
[0018] Figure 2 A schematic diagram of the appearance of the pigment W-DPP254 (RI) provided in the examples of the present application;
[0019] Figure 3 The SEM images of the pigment DPP254 in the related art and the pigment W-DPP254 (RI) of the present application are shown;
[0020] Figure 4 FT-IR spectra of the pigment DPP254 in the related art and the pigment W-DPP254 (RI) of the present application;
[0021] Figure 5 The hydrogen nuclear magnetic resonance spectrum of the pigment W-DPP254 (RI) provided in the examples of the present application;
[0022] Figure 6 XRD spectra of the pigment DPP254 in the related art and the pigment W-DPP254 (RI) of the present application;
[0023] Figure 7 These are scanning electron microscope (SEM) images of the pigment W-DPP255 (R-II) and the N-alkylated derivative W-DPP264 (R-III) of the present application. DETAILED DESCRIPTION
[0024] The embodiments of the present application are described below in conjunction with the drawings in the present application. It should be understood that the implementation methods described below in conjunction with the drawings are exemplary descriptions for explaining the technical solutions of the embodiments of the present application and do not constitute a limitation on the technical solutions of the embodiments of the present application.
[0025] Those skilled in the art will appreciate that, unless specifically stated, the "said" and "the" used herein may also include plural forms. It should be further understood that the term "including" used in the specification of the present application refers to the presence of the features, integers, steps, operations, and / or components, but does not exclude the implementation of other features, information, data, steps, operations, components and / or combinations thereof supported by the present technical field. In order to make the purpose, technical solutions and advantages of the present application clearer, the implementation methods of the present application will be further described in detail below in conjunction with the accompanying drawings.
[0026] The technical solution of the present application and how the technical solution of the present application solves the above-mentioned technical problems are described in detail below with specific embodiments. It should be noted that the following implementation modes can refer to, draw on or combine with each other, and the same terms, similar features and similar implementation steps in different implementation modes will not be described repeatedly.
[0027] The present application provides an alkyl chain pyrrolopyrrole diketo pigment derivative, and the general structural formula of the alkyl chain pyrrolopyrrole diketo pigment derivative is as follows:
[0028] In the general formula, R 1 Including H, Cl, CN, CH 3 , C(CH 3 ) 3 , at least one of the benzene rings; R 2 Including C n H 2n+1 , where n is a positive integer not less than 2 and not greater than 18.
[0029] In this embodiment, the alkyl chain-containing diketopyrrolopyrrole pigment derivative can enhance the thermal stability of the pigment derivative, improve the tinting strength and brightness, and reduce the crystallinity of the pigment derivative and improve the dispersion performance by introducing an alkyl chain into the DPP pigment.
[0030] Optionally, R 2 C2 H 5 , C 5 H 11 or C 12 H 25 .
[0031] In this embodiment, R 2 C 2 H 5 , C 5 H 11 or C 12 H 25 The pigment derivative has good thermal stability and dispersibility.
[0032] Based on the same inventive concept, the present invention provides a method for preparing a diketopyrrolopyrrole pigment derivative containing an alkyl chain. The schematic flow chart of the method is as follows: Figure 1 As shown, the method includes:
[0033] S1: Under the action of an alkaline reagent, a diketopyrrolopyrrole pigment monomer solution reacts with an alkyl halide compound to obtain a reactant.
[0034] Optionally, in step S1, the step includes reacting the pyrrolopyrrole diketo pigment monomer solution with the alkyl halide compound at a first set temperature for a first set time to obtain a reactant; wherein the first set temperature is not less than 120°C and not more than 140°C; and the first set time is not less than 18 hours and not more than 36 hours.
[0035] In this embodiment, the temperature and reaction time set as above can make the diketopyrrolopyrrole pigment monomer solution and the alkyl halide compound react more fully.
[0036] S2: After the reactants are washed, filtered, dried, passed through a column, and ground, the alkyl chain-containing diketopyrrolopyrrole pigment derivative (ie, the target color derivative) as described above is obtained.
[0037] Optionally, in step S2, the reactants are washed, including: washing the reactants in solvent B and water, wherein solvent B includes any one or more of methanol, ethanol, isopropanol, and N,N-dimethylformamide.
[0038] In this embodiment, solvent B is cheap and readily available, which can reduce the experimental cost.
[0039] Optionally, in step S2, the reactants are washed, filtered, dried, column-filtered, and ground, comprising:
[0040] The reactants were washed in solvent B and water;
[0041] After washing, the reactants were distilled under reduced pressure to remove the solvent;
[0042] After filtration, the filter cake is dried under vacuum;
[0043] After drying, the filter cake is dissolved in an eluent and purified by column chromatography;
[0044] After purification, the target color derivative is obtained by grinding.
[0045] In this embodiment, the process is simple to operate and easy to industrialize.
[0046] Alternatively, the eluent comprises a mixture of dichloromethane and hexane or a mixture of ethyl acetate and hexane.
[0047] Optionally, before step S1, the preparation method further includes: adding diketopyrrolidine pigment monomer to solvent A to form a diketopyrrolidine pigment monomer solution; wherein solvent A is any one or more of dimethyl sulfoxide, N,N-dimethylformamide, N-methylpyrrolidone, and methanol.
[0048] In this embodiment, solvent A is cheap and readily available, which can reduce the experimental cost.
[0049] Optionally, the molar ratio of the diketopyrrolopyrrole pigment monomer, the alkyl halide compound, and the solvent A is 1: the first preset value: the second preset value, wherein the first preset value is not less than 2 and not more than 10, and the second preset value is not less than 8 and not more than 10.
[0050] In this embodiment, within the molar ratio range, the feed amounts of the solvent and the alkylating agent can be reduced as much as possible, while at the same time improving the alkylation reaction efficiency.
[0051] Optionally, the alkaline agent includes any one or more of potassium carbonate, potassium hydroxide, potassium tert-butoxide, sodium carbonate, sodium hydroxide, and sodium tert-butoxide.
[0052] In this embodiment, the alkaline reagent is cheap and easy to obtain, and the experimental operation is simple.
[0053] Optionally, in step S1, the following reaction formula is included:
[0054]
[0055] Wherein, Formula 2 is one of the diketopyrrolopyrrole pigment monomers, is one of the alkyl halogenated compounds, X is a halogenated element, and formula 1 is a reactant.
[0056] The preparation method of the pigment derivative is described below with reference to specific examples.
[0057] Example 1
[0058] Under nitrogen atmosphere, Pigment Red 254 (0.01 mol, 3.57 g) and N,N-dimethylformamide (DMF, 60 mL) were added to a 250 mL four-necked flask equipped with a condenser and a water separator. 2 CO 3 (0.04 mol, 5.5284 g) was added to the reaction solution; heated in an oil bath at 120°C and stirred for 30 min. Then 1-bromodecane (0.06 mol, 14.9538 g, dissolved in 10 mL of DMF) was added dropwise using a dropping funnel, the temperature was raised to 140°C, and the reaction was heated for 24 h to obtain a reactant containing the N-alkylated derivative W-DPP254 of DPP254.
[0059] After the reactants were cooled, they were poured into water to quench the reaction, the filtered cake was washed with methanol, the solvent was removed by distillation under reduced pressure, the red cake was vacuum dried, and dissolved in an eluent (a mixture of dichloromethane and hexane) to remove the rearrangement product and the monoalkylation product. The target N-alkylation derivative of diketopyrrolopyrrole pigment W-DPP254 (RI) was obtained by purification and grinding by gel column chromatography.
[0060]
[0061] Example 2
[0062] 1-Chlorododecane (0.06 mol, 12.2868 g) was used to replace 1-bromododecane (0.06 mol, 14.9538 g) in Example 1. The other steps were the same as in Example 1 to obtain the DPP pigment N-alkylated derivative W-DPP254 (RI).
[0063]
[0064] Example 3
[0065] 1-Fluorododecane (0.06 mol, 11.2998 g) was used to replace 1-bromododecane (0.06 mol, 14.9538 g) in Example 1. The other steps were the same as in Example 1 to obtain the DPP pigment N-alkylated derivative W-DPP254 (RI).
[0066]
[0067] It can be seen from the above Examples 1 to 3 that the pigment W-DPP254 (RI) of the present application can be obtained by using different synthesis methods.
[0068] Figure 2 This is the appearance of pigment W-DPP254 (RI). Figure 1It can be seen that the pigment W-DPP254 (RI) is a bright red powder with low crystallinity and high dispersibility.
[0069] Figure 3 The SEM images of the pigment DPP254 in the related art and the pigment W-DPP254 (RI) of the present application are shown in FIG. Figure 3 It can be seen that the N-alkylated DPP pigment derivative W-DPP254 (RI) presents dispersed flakes, which weakens the agglomeration of DPP254 pigment particles.
[0070] Figure 4 The FT-IR spectra (infrared spectra) of the pigment DPP254 in the related art and the pigment W-DPP254 (RI) of the present application, wherein (1) is the pigment DPP254 and (2) is the pigment W-DPP254 (RI). Figure 4 By comparison, we can see that at 2923cm -1 The new peak at around 9 is from the terminal -CH 3 The stretching vibration at 2850cm -1 The new peak around 9 comes from the -CH 2 This indicates that the pigment has an alkyl chain.
[0071] Figure 5 This is the H NMR spectrum of pigment W-DPP254 (RI). Figure 5 It can be known 1 H NMR (500 MHz, CDCl 3 )δ(ppm).
[0072] Figure 6 The XRD spectra of the pigment DPP254 in the related art and the pigment W-DPP254 (RI) of the present application are shown in FIG. Figure 6 By comparison, it can be seen that the crystallinity of pigment DPP254 is reduced from 91.36% to 77.29% of W-DPP254 (RI).
[0073] Example 4
[0074] Under nitrogen atmosphere, Pigment Red 255 (0.01 mol, 2.88 g) and N,N-dimethylformamide (DMF, 60 mL) were added to a four-necked flask equipped with a condenser and a water separator, and potassium tert-butoxide (0.04 mol, 4.4884 g) was weighed and added to the reaction solution, and the mixture was heated to 120°C in an oil bath and stirred for 30 min. Then 1-bromooctane (0.08 mol, 15.4496 g, dissolved in 10 mL of DMF) was added dropwise using a dropping funnel, the temperature was raised to 140°C, and the reaction was heated for 24 h to obtain a mixture containing the N-alkylated derivative W-DPP255 of DPP255. After the mixture was cooled, it was poured into water to quench the reaction, the filtered cake was washed with methanol, and the solvent was removed by distillation under reduced pressure. The red cake was vacuum dried and dissolved in the eluent dichloromethane to remove the rearrangement product and the monoalkylated product. The target N-alkylated derivative of diketopyrrolopyrrole pigment W-DPP255 (R-II) was obtained by purification and grinding by gel column chromatography.
[0075]
[0076] Example 5
[0077] 1-Chlorooctane (0.08 mol, 11.8936 g) was used to replace 1-bromooctane (0.08 mol, 15.4496 g) in Example 4. The other steps were the same as in Example 4 to obtain the DPP pigment N-alkylated derivative W-DPP255 (R-II).
[0078]
[0079] Example 6
[0080] 1-Fluorooctane (0.08 mol, 10.5776 g) was used to replace 1-bromooctane (0.08 mol, 15.4496 g) in Example 4. The other steps were the same as in Example 4 to obtain the DPP pigment N-alkylated derivative W-DPP255 (R-II).
[0081]
[0082] Example 7
[0083] Under nitrogen atmosphere, Pigment Red 264 (0.01 mol, 2.88 g) and N,N-dimethylformamide (DMF, 60 mL) were added to a four-necked flask equipped with a condenser and a water separator, and sodium tert-butoxide (0.04 mol, 3.844 g) was weighed and added to the reaction solution, and the mixture was heated to 120°C in an oil bath and stirred for 30 min. Then 1-bromobutane (0.1 mol, 13.702 g, dissolved in 10 mL of DMF) was added dropwise using a dropping funnel, the temperature was raised to 140°C, and the reaction was heated for 24 h to obtain a mixture containing the N-alkylated derivative W-DPP264 of DPP264. After the mixture was cooled, it was poured into water to quench the reaction, the filtered cake was washed with methanol, and the solvent was removed by distillation under reduced pressure. The red filter cake was vacuum dried and dissolved in an eluent (a mixture of ethyl acetate and hexane) to remove the rearrangement product and the monoalkylated product. The target N-alkylated derivative of diketopyrrolopyrrole pigment W-DPP264 (R-III) was obtained by purification and grinding by gel column chromatography.
[0084]
[0085] Example 8
[0086] 1-Iodobutane (0.1 mol, 18.402 g) was used to replace 1-bromobutane (0.1 mol, 13.702 g) in Example 7. The other steps were the same as in Example 7 to obtain the DPP pigment N-alkylated derivative W-DPP264 (R-III).
[0087]
[0088] Example 9
[0089] 1-Chlorobutane (0.1 mol, 9.257 g) was used to replace 1-bromobutane (0.1 mol, 13.702 g) in Example 7. The other steps were the same as in Example 7 to obtain the DPP pigment N-alkylated derivative W-DPP264 (R-III).
[0090]
[0091] Figure 7 The following are scanning electron microscope (SEM) images of the pigment W-DPP255 (R-II) and the pigment W-DPP264 (R-III) of the present application. Figure 7 It can be seen that pigment W-DPP255 (R-II) and pigment W-DPP264 (R-III) are both in the form of dispersed flakes, which reduces the agglomeration of pigment particles in the related art. Therefore, pigment W-DPP255 (R-II) and pigment W-DPP264 (R-III) have excellent dispersibility.
[0092] Based on the same inventive concept, an embodiment of the present application provides an application of the above-mentioned alkyl chain-containing diketopyrrolopyrrole pigment derivative as an additive for preparing a red-based filter.
[0093] In this embodiment, since the alkyl chain-containing diketopyrrolidine pigment derivatives have the advantages of low crystallinity, high light and heat stability, and strong coloring brightness, they can be used as additives in the DPP pigment processing process and can be easily prepared into color paste for the preparation of red-based filters.
[0094] Those skilled in the art will appreciate that the various operations, methods, steps, measures, and schemes in the processes discussed in this application may be alternated, changed, combined, or deleted. Furthermore, other steps, measures, and schemes in the various operations, methods, and processes discussed in this application may also be alternated, changed, rearranged, decomposed, combined, or deleted. Furthermore, steps, measures, and schemes in the related art that are similar to those disclosed in this application may also be alternated, changed, rearranged, decomposed, combined, or deleted.
[0095] In the description of this specification, specific features, structures, materials or characteristics may be combined in an appropriate manner in any one or more embodiments or examples.
[0096] The above is only a partial implementation method of the present application. It should be pointed out that for ordinary technicians in this technical field, without departing from the technical concept of the scheme of the present application, other similar implementation methods based on the technical ideas of the present application are also within the protection scope of the embodiments of the present application.
Claims
1. A diketopyrrolopyrrole pigment derivative containing an alkyl chain, characterized in that: Its general structure is shown below: In the general formula, R1 is H, Cl, CN, CH3, C(CH3)3 or a benzene ring; R2 is an alkyl C n H 2n+1 , where n is a positive integer not less than 2 and not greater than 18.
2. The diketopyrrolopyrrole pigment derivative according to claim 1, characterized in that: R2 is C2H5, C5H 11 or C 12 H 25 .
3. A method for preparing a diketopyrrolopyrrole pigment derivative containing an alkyl chain, characterized in that: include: S1: Under the action of an alkaline reagent, a diketopyrrolopyrrole pigment monomer solution reacts with an alkyl halide compound to obtain a reactant; S2: The reactants are washed, filtered, dried, column-passed and ground to obtain the alkyl chain-containing diketopyrrolopyrrole pigment derivative according to any one of claims 1 to 2.
4. The preparation method according to claim 3, characterized in that: Before the diketopyrrolopyrrole pigment monomer solution reacts with the alkyl halide compound under the action of an alkaline reagent to obtain a reactant, the preparation method further comprises: The diketopyrrolidine pigment monomer is added to solvent A to form a diketopyrrolidine pigment monomer solution; wherein the solvent A is any one or more of dimethyl sulfoxide, N,N-dimethylformamide, N-methylpyrrolidone, and methanol.
5. The preparation method according to claim 4, characterized in that: The feeding molar ratio of the diketopyrrolopyrrole pigment monomer, the alkyl halide compound and the solvent A is 1: the first preset value: the second preset value; Among them, the first preset value is not less than 2 and not greater than 10, and the second preset value is not less than 8 and not greater than 10.
6. The preparation method according to claim 3, characterized in that: The reactant is washed, comprising: The reactants are washed in solvent B and water, wherein the solvent B comprises any one or more of methanol, ethanol, isopropanol, and N,N-dimethylformamide.
7. The preparation method according to claim 3, characterized in that: The alkaline reagent includes any one or more of potassium carbonate, potassium hydroxide, potassium tert-butoxide, sodium carbonate, sodium hydroxide, and sodium tert-butoxide.
8. The preparation method according to claim 3, characterized in that: The step of reacting the diketopyrrolopyrrole pigment monomer solution with the alkyl halide compound under the action of an alkaline reagent comprises: At a first set temperature, the pyrrolopyrrole diketo pigment monomer solution reacts with the alkyl halide compound for a first set time to obtain a reactant; wherein the first set temperature is not less than 120° C. and not more than 140° C.; and the first set time is not less than 18 hours and not more than 36 hours.
9. The preparation method according to claim 3, characterized in that: Under the action of an alkaline reagent, the diketopyrrolopyrrole pigment monomer solution reacts with an alkyl halide compound to obtain a reactant, which includes the following general reaction formula: Wherein, the formula 2 is one of the diketopyrrolopyrrole pigment monomers, is one of the alkyl halogenated compounds, X is a halogenated element, and the formula 1 is the reactant.
10. Use of the alkyl chain-containing diketopyrrolopyrrole pigment derivative according to claim 1 or 2 as an additive for preparing a red-based filter.