Use of a pyrrolopyrrolodione compound in the preparation of a pigment dispersant

Abstract

The application discloses application of a pyrrolopyrrolo-diketone compound in preparation of a pigment dispersant, and the pyrrolopyrrolo-diketone compound has the following general structure: wherein R is selected from -CF3, -OCH3 or -CHO; and n is an integer from 2 to 8. The pyrrolopyrrolo-diketone compound can be used as the pigment dispersant, and the prepared product has good dispersion effect.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of preparation and performance research of force-stimulated corresponding materials, and particularly relates to application of diketopyrrolopyrrole (DPP) compounds in preparation of pigment dispersants. BACKGROUND

[0002] Diketopyrrolopyrrole (DPP) is a bright red pigment accidentally synthesized by Donald Farnum and his colleagues in the early 1970s. Later, researchers of Ciba-Geigy AG further studied and developed a series of organic high-performance pigments containing diketopyrrolopyrrole parent structure, which has the advantages of good chemical resistance, high light fastness, full color spectrum, high fluorescence quantum yield, etc. Not only is it widely used in the field of organic pigments, but in recent years it has also been applied to the field of optoelectronic materials such as organic field effect transistors, organic light emitting diodes, and organic solar cells. However, due to the aggregation-caused quenching (ACQ) characteristics of DPP molecules, the application of this organic pigment with high stability and easy chemical modification is very limited. Due to the existence of ACQ effect, the luminescent reagent has completely different luminescent ability in low-concentration and high-concentration solutions. Therefore, in the application scenarios such as biosensors, ion probes in water, and organic light emitting diodes where fluorescent molecules are aggregated, the existence of ACQ effect will seriously limit the application of organic fluorescent agents. Fortunately, in 2001, Tang Benzhong's research group discovered the aggregation-induced emission (AIE) phenomenon. Molecules with AIE characteristics can solve the problem of sharp decrease in fluorescence quantum yield of fluorescent materials in the aggregated state, and their twisted molecular configuration also provides a molecular design idea for high-efficiency luminescent materials. DPP derivatives with AIE characteristics have new applications in the fields of organic two-photon absorption materials, fluorescent probes, and humidity sensors. At the same time, organic force-induced color-changing materials have made great progress in recent years and show potential applications in pressure sensing, optical recording, security ink, data storage, etc. The twisted molecular configuration of molecules with AIE characteristics is usually the cause of force-induced color change. Therefore, developing DPP derivatives with AIE and force-induced color change properties is of great significance for expanding the application of DPP pigments in practice. SUMMARY

[0003] The first object of the present application is to provide application of diketopyrrolopyrrole compounds in preparation of pigment dispersants.

[0004] In order to achieve the above object, the technical scheme adopted by the present application is as follows:

[0005] The first aspect of the present application provides a use of a pyrrolopyrrolopyridazine compound in preparing a pigment dispersant.

[0006] The pyrrolopyrrolopyridazine compound has the following general structure:

[0007]

[0008] wherein R is selected from -CF3, -OCH3 or -CHO; and n is an integer from 2 to 8.

[0009] More preferably, in the general structure of the pyrrolopyrrolopyridazine compound, n is selected from 2, 3, 4, 6, 8.

[0010]

[0011] The pyrrolopyrrolopyridazine compound is used in an amount of 0.01-5% as the pigment dispersant.

[0012] Thanks to the above technical solution, the present application has the following advantages and beneficial effects:

[0013] The present application discloses a series of pyrrolopyrrolopyridazine derivatives, and a method for synthesizing the pyrrolopyrrolopyridazine derivatives; the DPP pigment itself has a large conjugated plane, and when the DPP pigment is aggregated, the molecules are closely overlapped due to the rigid intermolecular force, resulting in fluorescence quenching. In order to obtain the AIE property, the hydrogen bond on the amide is destroyed, a flexible alkyl chain is connected, and a carbazole group is connected at the other end of the alkyl chain, so as to weaken the original π-π interaction and increase the weak intermolecular interaction such as C-H…π. At the same time, these intermolecular forces result in a twisted molecular structure type, induce the emergence of multiple stacking modes, and promote the compound to have the mechanochromic property.

[0014] The pyrrolopyrrolopyridazine compound provided by the present application has the AIE property, has a high fluorescence quantum yield in the aggregated state (the fluorescence quantum yield of the solid is 20.7%), and exhibits a highly sensitive mechanical force response property; the color of the solid powder of the compound can rapidly change from yellow to orange, and the fluorescence can rapidly change from yellow to orange after the solid powder is ground by mechanical force; the mechanochromic property of the compound is reversible; after a benign solvent (such as tetrahydrofuran and dichloromethane) is added to the solid powder after the color change, the color of the powder rapidly changes from orange back to yellow, and the fluorescence rapidly changes from orange back to yellow; the main reason for the color change of the compound is the change of the intermolecular stacking mode from the crystal state to the amorphous state; the compound having the AIE property has a wide application as a reversible mechanochromic material, and has a good application prospect in the fields of stress sensors, anti-counterfeiting, data recording and storage, and light-emitting devices.

[0015] The pyrrolopyrrolodione-based compound of the present application can be used as a pigment dispersant, and the prepared product has good dispersion effect. BRIEF DESCRIPTION OF DRAWINGS

[0016] Figure 1 The fluorescence spectrum of compound I-1 prepared in Example 1 in different f w of THF / H2O mixed solution.

[0017] Figure 2 The fluorescence spectrum of compound I-1 prepared in Example 1 in different f w of THF / H2O mixed solution.

[0018] Figure 3 The powder X-ray diffraction (XRD) pattern of compound I-1 prepared in Example 1 before and after grinding. DETAILED DESCRIPTION

[0019] In order to more clearly illustrate the present application, the present application will be further described below in conjunction with preferred embodiments. Those skilled in the art should understand that the specific description below is illustrative rather than limiting, and should not limit the protection scope of the present application.

[0020] Example 1

[0021] An AIE compound having reversible force-induced color change property, the compound is named trifluoromethyl-substituted pyrrolopyrrolodione carbazole alkylated derivative compound I-1 (DPPA-4-Caz), and the chemical structure is as follows:

[0022]

[0023] A preparation method of an AIE compound having reversible force-induced color change property, comprising the following steps:

[0024]

[0025] Carbazole (10 mmol), 1,4-dibromobutane (50 mmol), potassium hydroxide (30 mmol) and tetrabutylammonium bromide (1 mmol) were added to a 250 mL flask, 25 mL of toluene was added as solvent, and the reaction was stirred at 35°C for 0.5 h, and then at room temperature for 12 h. After the reaction was stopped, 25 mL of saturated brine was added, stirred for 0.5 h, extracted with DCM (20 mL*3) and the organic phase was collected and dried over anhydrous sodium sulfate. After drying, the solvent was removed by distillation under reduced pressure, and the product was separated by column chromatography (DCM:PE = 1:6) to obtain 1.25 g of white powder, i.e. compound II-1, with a yield of 41%. Nuclear magnetic resonance spectrum: 1 H NMR (400 MHz, Chloroform-d) δ (ppm) 8.10 (2H, d, J = 7.7), 7.50-7.37 (4H, m), 7.26-7.22 (2H, m), 4.35 (2H, t, J = 6.9), 3.37 (2H, t, J = 6.5), 2.06 (2H, p, J = 7.0), 1.91 (2H, dt, J = 13.5, 6.6).

[0026]

[0027] Trifluoromethyl DPP, i.e. compound III-1 (1 mmol), potassium carbonate (6 mmol) were added to a 250 mL three-necked flask, 30 mL of N,N-dimethylformamide was added as solvent, and the reaction was heated to reflux at 120°C for 0.5 h, then cooled to 80°C, and compound II-1 (6 mmol) was added, and the reaction was carried out for 4 h. After the reaction was stopped, 30 mL of saturated brine was added, stirred for 0.5 h, extracted with DCM (20 mL*3) and the organic phase was collected and dried over anhydrous sodium sulfate. After drying, the solvent was removed by distillation under reduced pressure, and the product was separated by column chromatography (DCM:PE = 1:1) to obtain yellow powder compound I-1 with a yield of 46.2%. Nuclear magnetic resonance spectrum: 1 H NMR (400 MHz, DMSO-d6) δ (ppm) 8.09 (4H, d, J = 7.8), 7.61 (4H, d, J = 8.1), 7.48 (8H, d, J = 7.8), 7.41-7.33 (4H, m), 7.16 (4H, t, J = 7.4), 4.40 (4H, t, J = 6.3), 3.68 (4H, t, J = 8.0), 2.03 (4H, s), 1.23 (4H, s).

[0028] Performance test of compound I-1:

[0029] (1) AIE property test

[0030] Different water components f wThe fluorescence spectrum of compound I-1 was tested in THF / H2O mixed solution with different f (volume percentage of water in water / tetrahydrofuran mixed solvent). The fluorescence emission intensity was very weak in pure THF solution, almost no light emission, when f w >60%, it would make it aggregate in THF, the fluorescence emission intensity was enhanced, the fluorescence spectrum was changed, the results were shown in Figure 1 、 Figure 2 , Figure 1 The fluorescence spectrum of compound I-1 prepared in example 1 in THF / H2O mixed solution with different f w was shown in figure. Figure 2 The fluorescence spectrum of compound I-1 prepared in example 1 in THF / H2O mixed solution with different f w was shown in figure. From the figure, when f w reached 70%, the fluorescence intensity reached the maximum, which was 10.9 times of the initial intensity, which showed that compound I-1 had significant AIE effect.

[0031] (2) XRD test

[0032] The XRD of compound I-1 powder before and after grinding was tested by Cu-K under 40kV and 100mA. The results were shown in Figure 3 , Figure 3 The powder X-ray diffraction pattern (XRD) of compound I-1 prepared in example 1 before and after grinding was shown in figure. From the figure, the diffraction curve before force stimulation showed that compound I-1 DPPA-4-Caz had multiple sharp strong diffraction peaks, which indicated that the compound had ordered crystal structure. The sample after grinding showed broad diffuse peaks, which indicated that the molecules were accumulated in amorphous state.

[0033] Application of compound I-1 in preparing pigment dispersant: 0.096g pigment DPP dry powder and 0.192g polyvinyl butyral ester resin (PVB) were dissolved in 5.4g PGMEA (propylene glycol methyl ether acetate) to prepare a solution, 0.01g dispersant (compound I-1) was added, mixed uniformly, then film was tested, and the performance was tested, as shown in table 1:

[0034] Table 1

[0035]

[0036] From the data in table 1, it can be seen that the compound I-1 of the application used as pigment dispersant obtained the best dispersion effect of the product.

[0037] The above merely describes the preferred embodiments of the present application, and is not intended to limit the present application in any form. Although the present application has been disclosed with the preferred embodiments as above, it is not intended to limit the present application, and any person skilled in the art can make some changes or modifications to the above-mentioned technical content with the prompt as equivalent embodiments of equivalent changes without departing from the technical solution of the present application. Any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present application, which does not depart from the technical solution of the present application, still belongs to the scope of the present application.

Claims

1. Use of a pyrrolopyrrolopyridine derivative for the preparation of a pigment dispersant, characterized in that, The pyrrolopyrrolodione-based compound has the following general structure: wherein R is selected from -CF3, -OCH3 or -CHO; and n is an integer from 2 to 8.

2. The use of the pyrrolopyrrolodiketone-based compound according to claim 1 in the production of a pigment dispersant, characterized by, In the general structure of the pyrrolopyrrolodione-based compound, n is selected from 2, 3, 4, 6, 8.

3. The use of the pyrrolopyrrolodione-based compound according to claim 1 in the production of a pigment dispersant, characterized by, The pyrrolopyrrolodione-based compound is selected from one of the following compounds:

4. The use of the pyrrolopyrrolodione-based compound according to claim 1 in the production of a pigment dispersant, characterized by, The pyrrolopyrrolodione-based compound is used as a pigment dispersant in an amount of 0.01-5%.

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