Copper-based polymer metal halide material with tunable blue-yellow luminescence and preparation method of copper-based polymer metal halide material

Abstract

The invention discloses a blue-yellow luminescence tunable high-stability copper-based polymer metal halide material and a preparation method thereof.The preparation method comprises the following steps that a reaction system containing polymer cations and cuprous salt is prepared in a hydroiodic acid and hypophosphorous acid aqueous solution, precipitation is conducted in an anti-solvent, and a reaction product is obtained; the blue-yellow luminescence tunable high-stability copper-based polymer metal halide is obtained; the polymer cations are selected from at least one of polyquaternium and polyamine halate; the cuprous salt is selected from at least one of cuprous chloride, cuprous bromide and cuprous iodide. The method has universality to polymer cations, and can be used for preparing copper-based polymer metal halide materials with different structures and different luminescence colors. The amorphous material prepared by the method overcomes the limitation that only one light-emitting center is allowed in a crystal material, and meanwhile, the prepared material has excellent water stability.

Description

Technical Field

[0001] The invention relates to the field of copper-based metal halide materials and luminescent materials, and in particular to a highly stable copper-based polymer metal halide material whose luminescent color can be adjusted from blue to yellow, prepared by using polymer cations and cuprous salts as raw materials. Background Art

[0002] Copper-based metal halide materials have shown great application prospects in display lighting, X-ray detection imaging, photoelectric detection and other fields due to their excellent optical properties. Therefore, the synthesis of copper-based metal halide materials has also attracted much attention. Currently, most of the all-inorganic copper-based metal halide materials studied, such as Cs3Cu2I5 and CsCu2I3, are prepared by cooling crystallization, which has high requirements for the cooling rate. Usually, the cooling rate will affect the quality of the material, and even different cooling rates can produce different material structures. Organic-inorganic hybrid copper-based metal halide materials can be prepared by cooling crystallization, solvent volatilization and anti-solvent diffusion, but the preparation process is relatively complicated and the cycle is long. Exploring new copper-based halide material systems and preparation methods can expand the types and application range of such materials.

[0003] As an important component of polymer materials, polymer cations have been widely used in the fields of petrochemical industry, sewage treatment, etc. At the same time, the rich positive charges of polymer cations can be used to interact electrostatically with negative charges to achieve the effects of drug delivery and bactericidal and antibacterial. If polymer cations are introduced into copper-based halide luminescent materials, the types of such materials can be greatly enriched while giving the material polymer excellent processing properties. The amorphous polymer structure can allow a variety of luminescent centers to exist in the material, thereby achieving the regulation of the luminescent color of the material. Based on this, the present invention proposes a new copper-based metal halide luminescent material system, which can prepare large quantities of luminescent materials through a simple anti-solvent precipitation operation. At the same time, the presence of the polymer allows multiple luminescent centers to exist in the material, thereby achieving the regulation of luminescent properties. Furthermore, the excellent water stability of the polymer cation enables the prepared material to exhibit excellent water resistance. Summary of the invention

[0004] According to one aspect of the present application, a method for preparing a highly stable copper-based polymer metal halide material with tunable blue-yellow light emission is provided, which is used to prepare an amorphous copper-based polymer metal halide luminescent material, and can solve the problems of a single luminescent center and poor processability of brittle single crystals in existing copper-based metal halide materials. The method is simple to operate and can be used to prepare copper-based metal halide luminescent materials containing multiple luminescent centers on a large scale.

[0005] The method for preparing the blue-yellow luminescent tunable high-stability copper-based polymer metal halide material is characterized by comprising the following steps:

[0006] In a mixed solution of hydroiodic acid and hypophosphorous acid, a reaction system containing a polymer cation and cuprous halide is precipitated in an antisolvent, and after solid-liquid separation (such as suction filtration) and precipitation and drying, a copper-based polymer metal halide luminescent material is obtained;

[0007] The polymer cation is selected from at least one of a polyquaternary ammonium salt and a polyamino halide salt;

[0008] The cuprous halide is selected from at least one of cuprous chloride, cuprous bromide and cuprous iodide.

[0009] Optionally, the molecular weight M of the polyquaternary ammonium salt and the polyamino halogen acid salt is w >1000Da.

[0010] Optionally, the volume ratio of hydroiodic acid to hypophosphorous acid in the mixed solution of hydroiodic acid and hypophosphorous acid is adjustable;

[0011] Wherein, the volume ratio of hydroiodic acid to hypophosphorous acid is 1:0.1 to 1:10.

[0012] Optionally, the anti-solvent species is selectable;

[0013] Wherein, the anti-solvent is selected from at least one of methanol, ethanol, isopropanol, acetone and tetrahydrofuran.

[0014] Optionally, the amount of the anti-solvent is selectable;

[0015] The volume of the anti-solvent is 2 to 30 times the volume of the mixed solution of hydroiodic acid and hypophosphorous acid.

[0016] Optionally, the ratio of the polymer cation to the cuprous salt is adjustable;

[0017] The molar ratio of the cation in the polymer cation and the molar ratio of the cuprous salt is 1:0.01 to 1:10.

[0018] Optionally, the concentration of the polymer cation and cuprous salt in the hydroiodic acid and hypophosphorous acid is selectable;

[0019] The concentration of the polymer cation and the cuprous salt, calculated as cuprous salt, is 0.01 mol / L to 1 mol / L.

[0020] Optionally, the drying time and temperature of the precipitate obtained by precipitation in the anti-solvent are optional;

[0021] Among them, the drying time is 4 to 48 hours; the drying temperature is 40 to 180°C.

[0022] Definitions and explanations of terms

[0023] Unless otherwise defined, all technical terms used herein have the same meaning as commonly understood by those skilled in the art to which the subject matter of the claims pertains. Unless otherwise indicated, all patents, patent applications, and publications cited herein are incorporated herein by reference in their entirety. If there are multiple definitions of a term herein, the definition in this chapter shall prevail.

[0024] It should be understood that definitions of standard chemical terms can be found in the reference literature. Unless specific definitions are set forth, the terms used herein in the relevant descriptions of analytical chemistry, organic chemistry, and polymer chemistry are those known in the art.

[0025] The term polymeric cationic is understood to mean a polymer containing a positive charge in the polymer repeating unit, usually polymerized from cation-containing monomers.

[0026] The term polyquaternium is understood to mean polymers in which the positive charges in the polymer repeating units are quaternary ammonium salts.

[0027] The term polyamino halide is understood to mean a polymer containing an amino halide in the repeating polymer unit, usually a product obtained by reacting an amino group-containing polymer with a hydrohalic acid.

[0028] This method is universal for polymer cations and can be used to prepare copper-based polymer metal halide materials with different structures and different luminescent colors. The amorphous materials prepared by this method overcome the limitation that only one luminescent center is allowed in crystalline materials, and the prepared materials have excellent water stability.

[0029] The beneficial effects of this application include:

[0030] 1) The preparation method of the blue-yellow luminescent tunable high-stability copper-based polymer metal halide material provided in the present application is universal to polycations of different structures and molecular weights. At the same time, the prepared copper-based polymer metal halide material has excellent luminescent properties and excellent water stability.

[0031] 2) The preparation method of the blue-yellow luminescent tunable high-stability copper-based polymer metal halide material provided in the present application can achieve luminescence regulation by adjusting the ratio of cations to cuprous halide, which is difficult to achieve in conventional copper-based metal halide materials.

[0032] 3) The method for preparing the blue-yellow tunable high-stability copper-based polymer metal halide material provided in the present application utilizes the reaction of polymer cations and cuprous halide to prepare the copper-based luminescent material. The preparation process is simple and easy to operate, and can achieve mass production of the material.

[0033] 4) The copper-based luminescent material prepared by the preparation method of the blue-yellow tunable high-stable copper-based polymer metal halide material provided in the present application can adjust the luminescent color by controlling the ratio of polymer cations and cuprous halide, thereby obtaining white light emission. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 is the infrared spectrum of the product of Example 1 of the present invention;

[0035] Figure 2 is the X-ray photoelectron spectrum of the product of Example 1 of the present invention;

[0036] Figure 3 is the excitation and emission spectra of the product of Example 1 of the present invention;

[0037] Figure 4 This is a fluorescence emission spectrum of the product of Example 1 of the present invention before and after being immersed in water for 6 months;

[0038] Figure 5 is the infrared spectrum of the product of Example 2 of the present invention;

[0039] Figure 6 is the X-ray photoelectron spectrum of the product of Example 2 of the present invention;

[0040] Figure 7 is the excitation and emission spectra of the product of Example 2 of the present invention;

[0041] Figure 8 is the excitation and emission spectra of the product of Example 3 of the present invention;

[0042] Fig. 9 This is the fluorescence emission spectrum of the product of Example 3 of the present invention before and after being immersed in water for 6 months;

[0043] Fig.10 is the excitation and emission spectra of the product of Example 4 of the present invention;

[0044] Fig.11 It is the application spectrum diagram and actual picture of the material of Example 2 of the present invention in the white light emitting diode. DETAILED DESCRIPTION

[0045] The present application is described in detail below with reference to embodiments, but the present application is not limited to these embodiments.

[0046] Unless otherwise specified, the raw materials and solvents in the examples of the present application were purchased from commercial sources, among which polydimethyldiallylammonium chloride (M w<100000Da), cuprous chloride, cuprous bromide, cuprous iodide, hydroiodic acid and hypophosphorous acid were purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., and other chemical reagents were purchased from Sinopharm Chemical Reagent Co., Ltd.

[0047] The analysis method in the examples of this application is as follows:

[0048] The samples were analyzed by infrared spectroscopy using a Nicolet iS50 infrared spectrometer. The test samples were solid powders and the test mode was ATR mode.

[0049] The samples were analyzed and tested using X-ray photoelectron spectroscopy from Thermo Scientific. The test samples were solid powders.

[0050] The excitation and emission spectra of the samples were tested using the Edinburgh FLS1000 steady-state fluorescence spectrometer. The test samples were solid powders.

[0051] Embodiment 1:

[0052] This embodiment provides a polydimethyldiallylammonium chloride (M w A method for preparing a copper-based polymer metal halide by reacting a copper iodide (<100000Da) with cuprous iodide in a mixed solution of hydroiodic acid and hypophosphorous acid, comprising the following steps:

[0053] (1) Preparation of polycation precursor solution

[0054] Add a magnet, polydimethyldiallylammonium chloride (323 mg, 2 mmol (based on the cations in the polymer cations)), hydroiodic acid (2 mL, 47 wt%) and hypophosphorous acid (0.5 mL, 50 wt%) to a 20 mL reaction bottle and stir until the polymer is dissolved and dispersed evenly.

[0055] (2) Preparation of cuprous salt precursor solution

[0056] A magnetic particle, cuprous iodide (23.8 mg, 0.125 mmol), hydroiodic acid (1 mL, 47 wt %) and hypophosphorous acid (0.2 mL, 50 wt %) were added to a 20 mL reaction bottle and stirred until completely dissolved.

[0057] (3) Preparation of copper-based polymer metal halides

[0058] The two groups of liquids obtained in step (1) and step (2) are mixed and stirred evenly. The mixed solution is slowly added into 20 mL of isopropanol while stirring to obtain a large amount of white precipitate. After suction filtration, the precipitate is placed in a vacuum drying oven at 70° C. and dried for 12 hours to obtain a copper-based polymer metal halide product under corresponding conditions.

[0059] Embodiment 2:

[0060] This embodiment provides a polydimethyldiallylammonium chloride (M w A method for preparing a copper-based polymer metal halide by reacting a copper iodide (<100000Da) with cuprous iodide in a mixed solution of hydroiodic acid and hypophosphorous acid, comprising the following steps:

[0061] (1) Preparation of polycation precursor solution

[0062] Add a magnet, polydimethyldiallylammonium chloride (323 mg, 2 mmol (based on the cations in the polymer cations)), hydroiodic acid (3 mL, 47 wt%) and hypophosphorous acid (1 mL, 50 wt%) to a 20 mL reaction bottle and stir vigorously until the polymer is dissolved and dispersed evenly.

[0063] (2) Preparation of cuprous salt precursor solution

[0064] A magnetic particle, cuprous iodide (190.5 mg, 1.0 mmol), hydroiodic acid (3 mL, 47 wt %) and hypophosphorous acid (1 mL, 50 wt %) were added to a 20 mL reaction bottle and stirred until completely dissolved.

[0065] (3) Preparation of copper-based polymer metal halides

[0066] The two groups of liquids obtained in step (1) and step (2) are mixed and stirred evenly. The mixed solution is slowly added into 50 mL of ethanol while stirring, and a large amount of white precipitate is obtained. After suction filtration, the precipitate is placed in a vacuum drying oven at 60° C. and dried for 24 hours to obtain a copper-based polymer metal halide product under corresponding conditions.

[0067] Embodiment 3:

[0068] This embodiment provides a polydimethyldiallylammonium chloride (M w A method for preparing a copper-based polymer metal halide by reacting a copper iodide (<100000Da) with cuprous iodide in a mixed solution of hydroiodic acid and hypophosphorous acid, comprising the following steps:

[0069] (1) Preparation of polycation precursor solution

[0070] Add a magnet, polydimethyldiallylammonium chloride (323 mg, 2 mmol (based on the cations in the polymer cations)), hydroiodic acid (3 mL, 47 wt%) and hypophosphorous acid (2 mL, 50 wt%) to a 20 mL reaction bottle and stir vigorously until the polymer is dissolved and dispersed evenly.

[0071] (2) Preparation of cuprous salt precursor solution

[0072] A magnetic particle, cuprous iodide (381 mg, 2.0 mmol), hydroiodic acid (5 mL, 47 wt %) and hypophosphorous acid (2 mL, 50 wt %) were added to a 20 mL reaction bottle and stirred until completely dissolved.

[0073] (3) Preparation of copper-based polymer metal halides

[0074] The two groups of liquids obtained in step (1) and step (2) are mixed and stirred evenly. The mixed solution is slowly added into 100 mL of isopropanol while stirring to obtain a large amount of white precipitate. After suction filtration, the precipitate is placed in a vacuum drying oven at 80° C. and dried for 24 hours to obtain a copper-based polymer metal halide product under corresponding conditions.

[0075] Embodiment 4:

[0076] This embodiment provides a polydimethyldiallylammonium chloride (M w A method for preparing a copper-based polymer metal halide by reacting a copper iodide (<100000Da) with cuprous iodide in a mixed solution of hydroiodic acid and hypophosphorous acid, comprising the following steps:

[0077] (1) Preparation of polycation precursor solution

[0078] Add a magnet, polydimethyldiallylammonium chloride (323 mg, 2 mmol (based on the cations in the polymer cations)), hydroiodic acid (3 mL, 47 wt%) and hypophosphorous acid (1 mL, 50 wt%) to a 20 mL reaction bottle and stir vigorously until the polymer is dissolved and dispersed evenly.

[0079] (2) Preparation of cuprous salt precursor solution

[0080] A magnetic particle, cuprous iodide (95.2 mg, 0.5 mmol), hydroiodic acid (3 mL, 47 wt %) and hypophosphorous acid (1 mL, 50 wt %) were added to a 20 mL reaction bottle and stirred until completely dissolved.

[0081] (3) Preparation of copper-based polymer metal halides

[0082] The two groups of liquids obtained in step (1) and step (2) are mixed and stirred evenly. The mixed solution is slowly added into 60 mL of acetone while stirring, and a large amount of white precipitate is obtained. After suction filtration, the precipitate is placed in a vacuum drying oven at 60° C. and dried for 12 hours to obtain a copper-based polymer metal halide product under corresponding conditions.

[0083] Application Example 1:

[0084] The white light emitting material prepared in Example 2 is assembled with a 310nm light-emitting diode chip. The white light spectrum covers the entire visible light range, the color rendering index is as high as 92.5, and the color temperature is 4214K. This white light emitting material can be used in the field of white light emitting diodes.

[0085] The infrared spectrum of the product of Example 1 is shown in the attached Figure 1 As shown in the figure, the peak position is consistent with the corresponding polymer cation, proving that the main body of the material is the expected structure; the X-ray photoelectron spectrum of the product of Example 1 is shown in the attached Figure 2 As shown in FIG. 1 , the element types (C, N, Cu, I, etc.) are consistent with the feed, wherein the measured copper element is monovalent copper ion; the excitation and emission spectra of the product of Example 1 are shown in FIG. Figure 3 As shown, it exhibits characteristic blue emission; the material obtained in Example 1 was immersed in water for 6 months, and its fluorescence emission spectrum was similar to that of the newly prepared one as shown in the attached figure. Figure 4 The infrared spectrum of the product of Example 2 is shown in the attached figure. Figure 5 As shown in the figure, the peak position is consistent with the corresponding polymer cation, proving that the main body of the material is the expected structure; the X-ray photoelectron spectrum of the product of Example 2 is shown in the attached figure. Figure 6 As shown, the element types are consistent with the feed (C, N, Cu, I, etc.), wherein the copper element measured is monovalent copper ion; the excitation and emission spectra of the product of Example 2 are shown in the attached Figure 7 The excitation and emission spectra of the product of Example 3 are shown in the attached figure. Figure 8 As shown, the material obtained in Example 1 was immersed in water for 6 months, and its fluorescence emission spectrum was similar to that of the newly prepared material. Fig. 9 The excitation and emission spectra of the product of Example 4 are shown in the attached figure. Fig.10 As shown, it shows white light emission with dual emission centers. The spectrum and physical picture of the material used in the white light diode of Example 2 are shown in the attached figure. Fig.11 As shown, the white light spectrum covers the entire visible light range, the color rendering index is as high as 92.5, and the color temperature is 4214K.

[0086] The present invention uses polymer cations and cuprous halide as raw materials and prepares a copper-based polymer metal halide luminescent material through simple operations. The method has a wide range of applicability to polymer cations, an adjustable cation and cuprous halide feed ratio, and the luminescence of the prepared material can be tuned from blue light to yellow light, all of which provide great advantages for the method. The present invention successfully introduces polymer cations in polymer chemistry into metal halide luminescent materials in inorganic chemistry, greatly expanding the types of metal halide luminescent materials and providing a boost to the development of this field.

[0087] The above are only a few embodiments of the present application and do not constitute any form of limitation to the present application. Although the present application is disclosed as above with preferred embodiments, it is not intended to limit the present application. Any technician familiar with the profession, without departing from the scope of the technical solution of the present application, using the technical content disclosed above to make slight changes or modifications are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A method for preparing a copper-based polymer metal halide material with tunable blue-yellow luminescence, characterized in that: The following steps are involved: In a reaction system of hydroiodic acid and hypophosphorous acid aqueous solution containing polymer cations and cuprous salts, an anti-solvent is added for precipitation, and after solid-liquid separation and precipitation drying, a copper-based polymer metal halide luminescent material is obtained; The polymer cation is selected from at least one or more of polyquaternary ammonium salts and polyamino halide salts; The cuprous salt is selected from at least one or more of cuprous chloride, cuprous bromide and cuprous iodide.

2. The method for preparing the blue-yellow luminescent tunable copper-based polymer metal halide material according to claim 1, characterized in that: The polymer cation is at least one or more of a polyquaternary ammonium salt (a polymer having a repeating unit of -R1R2NXR3R4-, wherein R1-4 are alkyl groups and X is a halogen) and a polyamino halide (a polymer having an amino halide in a repeating unit); Among them, the molecular weights of polyquaternium salts and polyamino halide salts are 1000 Da < M<1000000>0 Da.​ 3. The method for preparing the blue-yellow luminescent tunable copper-based polymer metal halide material according to claim 1, characterized in that: The ratio of hydroiodic acid to hypophosphorous acid aqueous solution is adjustable; The mass concentration of the hydroiodic acid aqueous solution is 30% to 57%, preferably, the mass concentration of the hydroiodic acid aqueous solution is ≥47%; The mass concentration of the hypophosphorous acid aqueous solution is 5% to 80%, preferably, the mass concentration of the hypophosphorous acid aqueous solution is 50-60%; Optionally, the volume ratio of hydroiodic acid to hypophosphorous acid is 1:0.1 to 1:10; Preferably, the volume ratio of hydroiodic acid to hypophosphorous acid is 1:0.1 to 1:

2.

4. The method for preparing the blue-yellow luminescent tunable copper-based polymer metal halide material according to claim 1, characterized in that: The type of antisolvent is optional; Optionally, the anti-solvent is selected from at least one or more of methanol, ethanol, isopropanol, acetone, and tetrahydrofuran; Preferably, the anti-solvent is selected from at least one or two of ethanol and isopropanol.

5. The method for preparing the blue-yellow luminescent tunable copper-based polymer metal halide material according to claim 1, 3 or 4, characterized in that: The volume of the antisolvent is adjustable; Optionally, the volume ratio of the antisolvent to the mixed solvent of hydroiodic acid and hypophosphorous acid is 40:1 to 2:1; Preferably, the volume ratio of the antisolvent to the mixed solvent of hydroiodic acid and hypophosphorous acid is 30:1 to 2:1; More preferably, the volume ratio of the anti-solvent to the mixed solvent of hydroiodic acid and hypophosphorous acid is 20:1 to 5:

1.

6. The method for preparing the blue-yellow luminescent tunable copper-based polymer metal halide material according to claim 1, characterized in that: The molar ratio of cation and cuprous salt in the polymer cation is adjustable; Optionally, the molar ratio of the cation to the cuprous salt in the polymer cation is 1:0.01 to 1:10; Preferably, the molar ratio of the cation to the cuprous salt in the polymer cation is 1:0.05 to 1:

2.

7. The method for preparing the blue-yellow luminescent tunable copper-based polymer metal halide material according to claim 1, characterized in that: The concentrations of the polymer cation and the cuprous salt in the mixed solution of hydroiodic acid and hypophosphorous acid are adjustable; Optionally, the concentration of the polymer cation and the cuprous salt in the mixed solution of hydroiodic acid and hypophosphorous acid is 0.01 mol / L to 1 mol / L in terms of cuprous salt; Preferably, the concentration of the polymer cation and the cuprous salt in the mixed solution of hydroiodic acid and hypophosphorous acid is 0.02 mol / L to 0.6 mol / L in terms of cuprous salt.

8. The method for preparing the blue-yellow luminescent tunable copper-based polymer metal halide material according to claim 1, characterized in that: The drying temperature of the precipitated product obtained in the anti-solvent is adjustable; Optionally, the drying temperature is 40 to 180°C; Preferably, the drying temperature is 50-100°C.

9. The method for preparing the blue-yellow luminescent tunable copper-based polymer metal halide material according to claim 1 or 8, characterized in that: The drying time of the precipitated product obtained in the antisolvent is adjustable; Optionally, the drying time is 4 to 48 hours; Preferably, the drying time is 12 to 24 hours.

10. A copper-based polymer metal halide material with tunable blue-yellow luminescence obtained by the preparation method of claim 1.

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