High-transparency high-refractive-index organic polymer material as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of organic photoelectric materials, and discloses a high-transparency high-refractive-index organic polymer material as well as a preparation method and application thereof. According to the organic polymer material, an acrylic monomer with a spiro structure and a monomer with disulfydryl are subjected to free radical polymerization to obtain a polysulfide polymer with a main chain containing the spiro structure, and the polymer shows high transparency and high refractive index. According to the invention, the monomer with a spiro structure is polymerized with the disulfydryl monomer through sulfydryl-sparse click polymerization at normal temperature or photopolymerization reaction under ultraviolet light, so that the material has high refractive index and high transparency and also has low birefringence. The all-organic polymer material has wide application prospects in the fields of organic light-emitting diodes, micro-lens elements in double charge-coupled devices, high-performance complementary image sensors, all-polymer optoelectronic devices, polymer-based optical waveguides, photovoltaics, storage devices and the like.

Description

Technical Field

[0001] The invention belongs to the technical field of organic photoelectric materials, and specifically relates to a highly transparent and high refractive index organic polymer material and a preparation method and application thereof. Background Art

[0002] With the rapid development of science and technology, the world has entered the photon age from the electronic age. In response to this huge change, optical materials have received increasing attention in recent years. The development of high refractive index materials is crucial to the development of advanced optical devices such as image sensors, optical data storage, anti-reflective coatings, light-emitting diodes and nano-imprinting. Among them, high refractive index polymers (HRIPs) are easy to prepare and have good transparency, making their application in the optoelectronic field more and more popular.

[0003] High refractive index materials can be divided into: inorganic high refractive index materials, organic-inorganic hybrid high refractive index materials, and all-organic high refractive index materials. Although inorganic high refractive index materials have a high refractive index, their raw materials are expensive, toxic, inflexible to process, and demanding in preparation. Organic-inorganic hybrid high refractive index materials are still not the best choice because of their uneven film preparation, high Rayleigh scattering, and complex preparation process. All-organic high refractive index materials with many advantages such as convenient preparation, good processing technology, high cost-effectiveness, light weight, and high performance are considered to be promising candidate materials for highly integrated optical components and circuits. At present, the development of all-organic high refractive index materials still encounters many problems. The refractive index of most organic polymers is relatively low, only between 1.5 and 1.6. Therefore, the design and exploration of high refractive index polymers have attracted more and more attention.

[0004] With the deepening of research and the continuous advancement of technology, it is believed that the research on highly transparent and high refractive index organic materials will show a broader application prospect in the future. This material is not only expected to become an important research direction for new materials, new energy and new technologies, but also will provide strong support for the performance improvement and application expansion of organic light-emitting diode (OLED) devices. It can be foreseen that with the continuous development of highly transparent and high refractive index organic polymer material technology, the luminous efficiency of OLED devices will be further improved, promoting the development and progress of related fields. Summary of the invention

[0005] In response to the above technical problems, the present invention provides a highly transparent and high refractive index organic polymer material and a preparation method and application thereof. Sulfur atoms, aromatic rings, and spiro structures are appropriately introduced into the polymer main chain by free radical polymerization, so that the material has a low birefringence while maintaining high refractive index and high transparency.

[0006] The technical solution adopted by the present invention is as follows:

[0007] A highly transparent and high refractive index organic polymer material, the general structural formula of which is as follows:

[0008]

[0009] Wherein, n is a positive integer, Ar1 is a unit with a spiro ring structure, and Ar2 is a unit with a benzene ring or a sulfur element. Preferably, Ar1 is selected from the following structures:

[0010]

[0011] Where * is the connection location.

[0012] Preferably, Ar2 is selected from the following structures:

[0013]

[0014] * is the connection position

[0015] Preferably, the highly transparent and high refractive index organic polymer material has one or more of the following structures:

[0016]

[0017] The present invention also provides a method for preparing the above-mentioned highly transparent and high refractive index organic polymer material, the steps of the preparation method are as follows:

[0018] The highly transparent and high refractive index organic polymer material is obtained by using a monomer having a spirocyclic structure as a building unit and a monomer having an aromatic ring or sulfur element as a building unit in an organic solvent, an additive and an initiator through a thiol-ene click polymerization reaction or a photopolymerization method. The general reaction formula of the process is as follows:

[0019]

[0020] If the highly transparent and high refractive index organic polymer material is prepared by thiol-ene click polymerization, the steps are as follows: at room temperature, a monomer having an aromatic ring or sulfur element with a dithiol group as a building unit is added to an organic solvent, and stirred at room temperature until completely dissolved to obtain a solution 1; after dissolving a monomer having a building unit with a spirocyclic structure in an organic solvent, the solution 1 is added, and the stirring is continued until the mixture is uniform to obtain a mixed solution 2; an initiator used for the thiol-ene click polymerization reaction is added to the mixed solution 2, and the mixture is stirred at room temperature for 12 hours; after the reaction is completed, the final product is obtained through post-treatment as a white powder, which is a highly transparent and high refractive index organic polymer material;

[0021] If the highly transparent and high refractive index organic polymer material is prepared by photopolymerization, the steps are as follows: a monomer with a building unit having a spirocyclic structure, a monomer with an aromatic ring having a dithiol group or a sulfur element as a building unit and a photoinitiator are dissolved in an organic solvent, the solution is added dropwise onto a substrate by spin coating after stirring to obtain a prepolymer film, and the film is cured under ultraviolet light to obtain a transparent film, which is a highly transparent and high refractive index organic polymer material.

[0022] Preferably, the initiator used in the thiol-ene click polymerization reaction is selected from one or more of 1,8-diazabicyclo[5.4.0]undec-7-ene, sodium hydride, potassium iodide, triethylamine, sodium hydroxide, potassium hydroxide, and n-butyl lithium.

[0023] Preferably, the photoinitiator used in the photopolymerization reaction is selected from one or more of benzophenone, 4-methylbenzophenone, isopropylthioxanthone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholine-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinephenyl)butanone and N,N-dimethylaminobenzoic acid isooctyl ester.

[0024] Preferably, the organic solvent is selected from one or more of propylene glycol methyl ether, toluene, hexane, cyclohexane, dioxane, tetrahydrofuran, ether, acetonitrile, dichloromethane, acetone, chloroform, propylene glycol methyl ether acetate, dimethyl sulfoxide, N,N-dimethylformamide, and 1,2-dichlorobenzene.

[0025] The present invention also provides an application of the above-mentioned highly transparent and high-refractive index organic polymer material, which can be used in the fields of organic light-emitting diodes, microlens elements in double-charged coupled devices, high-performance complementary image sensors, all-polymer optoelectronic devices, polymer-based optical waveguides, photovoltaics, storage devices, etc.

[0026] The present invention has the following beneficial effects:

[0027] 1. The present invention uses an acrylic monomer with a spiro structure and a monomer with a dithiol group to obtain a polysulfide polymer with a spiro structure in the main chain through free radical polymerization. The spiro structure is well integrated into the polymer main chain, and the polarization anisotropy between the polymer main chain and the units perpendicular to the polymer main chain can be effectively offset, so that the material has high refractive index and high transparency while also having a low birefringence.

[0028] 2. This type of highly transparent and high-refractive-index organic polymer material can be used in organic light-emitting diodes, microlens elements in double-charged coupled devices, high-performance complementary image sensors, all-polymer optoelectronic devices, polymer-based optical waveguides, photovoltaics, storage devices and other fields. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 is a refractive index diagram of the polymer P1 obtained in Example 1 of the present invention;

[0030] Figure 2 is a refractive index diagram of polymer P2 obtained in Example 2 of the present invention;

[0031] Figure 3 is a refractive index diagram of the polymer P3 obtained in Example 3 of the present invention;

[0032] Figure 4 is a refractive index diagram of polymer P4 obtained in Example 4 of the present invention;

[0033] Figure 5 is a refractive index diagram of polymer P5 obtained in Example 5 of the present invention;

[0034] Figure 6 This is a transmittance diagram of the polymer P1 obtained in Example 1 of the present invention;

[0035] Figure 7 This is a transmittance diagram of the polymer P2 obtained in Example 2 of the present invention;

[0036] Figure 8 This is a transmittance diagram of the polymer P3 obtained in Example 3 of the present invention. DETAILED DESCRIPTION

[0037] In order to further describe the technical solution of the present invention, the present invention is further described below in conjunction with the accompanying drawings and specific embodiments. It should be noted that the following embodiments are only descriptions of part of the technical solution of the present invention, rather than limitations of the technical solution of the present invention.

[0038] Example 1

[0039] The highly transparent and high refractive index polymer material prepared in this embodiment has the above-mentioned P1 structure, wherein Ar1 is selected as Ar2 is The preparation process of the highly transparent and high refractive index organic polymer P1 is as follows:

[0040]

[0041] A1 (0.1 mmol, 1 equiv.), B1 (0.1 mmol, 1 equiv.) and 2-methyl-1-(4-methylthiophenyl)-2-morpholine-1-propanone (0.004 mmol, 0.04 equiv.) were dissolved in toluene (12 mL), stirred for 5 minutes, and then the solution was dropped onto a quartz plate by spin coating to obtain a prepolymer film, which was cured under ultraviolet light for 20 minutes to obtain a transparent film P1. The average refractive index of polymer P1 was 1.85 and the transparency was 99%.

[0042] Example 2

[0043] The highly transparent and high refractive index polymer material prepared in this embodiment has the above-mentioned P2 structure, wherein Ar1 is selected as Ar2 is The preparation process of the highly transparent and high refractive index organic polymer P2 is as follows:

[0044]

[0045] At room temperature, B2 (1.244 mmol, 1 equiv.) was added to the reaction vessel, nitrogen was replaced 3 to 4 times, chloroform (5 mL) was added and stirred at room temperature for 5 minutes until completely dissolved. A2 (1.244 mmol, 1 equiv.) was dissolved in chloroform (5 mL) and injected into the container, and stirring was continued for 5 minutes until mixed evenly. Then, triethylamine (1.368 mmol, 1.1 equiv.) was added to the reaction vessel and stirred at room temperature for 12 hours. After the reaction was completed, methanol (250 mL) was used for precipitation twice to completely remove the residual triethylamine to prevent it from decomposing the polymer skeleton. The final product, white powder P2, was obtained by filtration and drying with a yield of 90%. The average refractive index of polymer P2 tested was 1.8 and the transparency was 100%.

[0046] Example 3

[0047] The highly transparent and high refractive index polymer material prepared in this embodiment has the above-mentioned P3 structure, wherein Ar1 is selected as Ar2 is The preparation process of the highly transparent and high refractive index organic polymer P3 is as follows:

[0048]

[0049] At room temperature, B3 (1.244 mmol, 1 equiv.) was added to the reaction vessel, nitrogen was replaced 3 to 4 times, tetrahydrofuran (5 mL) was added and stirred at room temperature for 5 minutes until completely dissolved. A3 (1.244 mmol, 1 equiv.) was dissolved in tetrahydrofuran (5 mL) and injected into the container, and stirring was continued for 5 minutes until mixed evenly. Then, triethylamine (1.368 mmol, 1.1 equiv.) was added to the reaction vessel and stirred at room temperature for 12 hours. After the reaction was completed, water (250 mL) was precipitated twice to completely remove the residual triethylamine to prevent it from decomposing the polymer skeleton. The final product, white powder P3, was obtained by filtration and drying with a yield of 90%. The average refractive index of polymer P3 tested was 1.78 and the transparency was 96%.

[0050] Example 4

[0051] The highly transparent and high refractive index polymer material prepared in this embodiment has the above-mentioned P4 structure, wherein Ar1 is selected as Ar2 is The preparation process of the highly transparent and high refractive index organic polymer P4 is as follows:

[0052]

[0053] At room temperature, B4 (1.244 mmol, 1 equiv.) was added to the reaction vessel, nitrogen was replaced 3 to 4 times, propylene glycol methyl ether (5 mL) was added and stirred at room temperature for 5 minutes until completely dissolved. A4 (1.244 mmol, 1 equiv.) was dissolved in propylene glycol methyl ether (5 mL) and injected into the container, and stirring was continued for 5 minutes until mixed evenly. Then, sodium hydroxide (1.368 mmol, 1.1 equiv.) was added to the reaction vessel and stirred at room temperature for 12 hours. After the reaction was completed, methanol (250 mL) was precipitated twice to completely remove the residual sodium hydroxide to prevent it from decomposing the polymer skeleton. The final product, white powder P4, was obtained by filtration and drying with a yield of 87%. The average refractive index of polymer P4 tested was 1.72 and the transparency was 97%.

[0054] Example 5

[0055] The highly transparent and high refractive index polymer material prepared in this embodiment has the above-mentioned P5 structure, wherein Ar1 is selected as Ar2 is The preparation process of the highly transparent and high refractive index organic polymer P5 is as follows:

[0056]

[0057] A5 (0.1 mmol, 1 equiv.), B5 (0.1 mmol, 1 equiv.) and isopropylthioxanthone (0.004 mmol, 0.04 equiv.) were dissolved in propylene glycol methyl ether acetate (12 mL), stirred for 5 minutes, and then the solution was dropped onto a quartz plate by spin coating to obtain a prepolymer film, which was cured under ultraviolet light for 60 minutes to obtain a transparent film P5. The average refractive index of polymer P5 in the visible light region was 1.66, and the transparency was 98%.

[0058] Example 6

[0059] The highly transparent and high refractive index polymer material prepared in this embodiment has the above-mentioned P6 structure, wherein Ar1 is selected as Ar2 is The preparation process of the highly transparent and high refractive index organic polymer P6 is as follows:

[0060]

[0061] At room temperature, B8 (1.244 mmol, 1 equiv.) was added to the reaction vessel, nitrogen was replaced 3 to 4 times, 1,2-dichlorobenzene (5 mL) was added and stirred at room temperature for 5 minutes until completely dissolved. A6 (1.244 mmol, 1 equiv.) was dissolved in 1,2-dichlorobenzene (5 mL) and injected into the container, and stirring was continued for 3 minutes until mixed evenly. Then, potassium hydroxide (1.368 mmol, 1.1 equiv.) was added to the reaction vessel and stirred at room temperature for 12 hours. After the reaction was completed, ethanol (250 mL) was used for precipitation twice to completely remove the residual potassium hydroxide to prevent it from decomposing the polymer skeleton. The final product, white powder P6, was obtained by filtration and drying with a yield of 89%. The average refractive index of polymer P6 was 1.79 and the transparency was 95%.

[0062] Example 7

[0063] The highly transparent and high refractive index polymer material prepared in this embodiment has the above-mentioned P7 structure, wherein Ar1 is selected as Ar2 is The preparation process of the highly transparent and high refractive index organic polymer P7 is as follows:

[0064]

[0065] A7 (0.1 mmol, 1 equiv.), B7 (0.1 mmol, 1 equiv.) and benzophenone (0.004 mmol, 0.04 equiv.) were dissolved in N,N-dimethylformamide (12 mL), stirred for 10 minutes, and then the solution was dropped onto a quartz plate by spin coating to obtain a prepolymer film, which was cured under ultraviolet light for 45 minutes to obtain a transparent film P7. The average refractive index of polymer P7 was 1.80 and the transparency was 95%.

[0066] Example 8

[0067] The highly transparent and high refractive index polymer material prepared in this embodiment has the above-mentioned P8 structure, wherein Ar1 is selected as Ar2 is The preparation process of the highly transparent and high refractive index organic polymer P8 is as follows:

[0068]

[0069] A8 (0.1 mmol, 1 equiv.), B8 (0.1 mmol, 1 equiv.) and 1-hydroxycyclohexyl phenyl ketone (0.004 mmol, 0.04 equiv.) were dissolved in acetone (12 mL), stirred for 30 minutes, and then the solution was dropped onto a quartz plate by spin coating to obtain a prepolymer film, which was cured under ultraviolet light for 20 minutes to obtain a transparent film P8. The average refractive index of polymer P8 was 1.79 and the transparency was 100%.

[0070] Example 9

[0071] The highly transparent and high refractive index polymer material prepared in this embodiment has the above-mentioned P9 structure, wherein Ar1 is selected as Ar2 is The preparation process of the highly transparent and high refractive index organic polymer P9 is as follows:

[0072]

[0073] A2 (0.1 mmol, 1 equiv.), B9 (0.1 mmol, 1 equiv.) and N, N-dimethylaminobenzoic acid isooctyl ester (0.004 mmol, 0.04 equiv.) were dissolved in dimethyl sulfoxide (12 mL), stirred for 10 minutes, and then the solution was dropped onto a quartz plate by spin coating to obtain a prepolymer film, which was cured under ultraviolet light for 60 minutes to obtain a transparent film P9. The average refractive index of polymer P9 was 1.85 and the transparency was 97%.

Claims

1. A highly transparent and high refractive index organic polymer material, characterized in that: Its general structure is as follows: Wherein, n is a positive integer, Ar1 is a unit having a spirocyclic structure, and Ar2 is a unit having an aromatic ring or a sulfur element.

2. The highly transparent and high refractive index organic polymer material according to claim 1, characterized in that: The Ar1 is selected from the following structures: The * is the connection location.

3. The highly transparent and high refractive index organic polymer material according to claim 1, characterized in that: The Ar2 is selected from the following structures: The * is the connection location.

4. The highly transparent and high refractive index organic polymer material according to claim 1, characterized in that: The organic polymer material has one or more of the following structures:

5. A method for preparing a highly transparent and high refractive index organic polymer material as claimed in claim 1, characterized in that: The steps of the preparation method are as follows: using a monomer with a spirocyclic structure as a building unit and a monomer with an aromatic ring or sulfur element as a building unit, in the presence of an organic solvent, an additive and an initiator, through a thiol-ene click polymerization reaction or photopolymerization, the highly transparent and high refractive index organic polymer material is obtained.

6. The method for preparing a highly transparent and high refractive index organic polymer material according to claim 5, characterized in that: If the highly transparent and high refractive index organic polymer material is prepared by thiol-ene click polymerization, the steps are as follows: at room temperature, a monomer having an aromatic ring or sulfur element with a dithiol group as a building unit is added to an organic solvent, and stirred at room temperature until completely dissolved to obtain a solution 1; after dissolving a monomer having a building unit with a spirocyclic structure in an organic solvent, the solution 1 is added, and the stirring is continued until the mixture is uniform to obtain a mixed solution 2; an initiator used for the thiol-ene click polymerization reaction is added to the mixed solution 2, and the mixture is stirred at room temperature for 12 hours; after the reaction is completed, the final product is obtained through post-treatment as a white powder, which is a highly transparent and high refractive index organic polymer material; If the highly transparent and high refractive index organic polymer material is prepared by photopolymerization, the steps are as follows: a monomer with a building unit having a spirocyclic structure, a monomer with an aromatic ring having a dithiol group or a sulfur element as a building unit and a photoinitiator are dissolved in an organic solvent, the solution is added dropwise onto a substrate by spin coating after stirring to obtain a prepolymer film, and the film is cured under ultraviolet light to obtain a transparent film, which is a highly transparent and high refractive index organic polymer material.

7. The method for preparing a highly transparent and high refractive index organic polymer material according to claim 5, characterized in that: The initiator used in the thiol-ene click polymerization reaction is selected from one or more of 1,8-diazabicyclo[5.4.0]undec-7-ene, sodium hydride, potassium iodide, triethylamine, sodium hydroxide, potassium hydroxide, and n-butyl lithium.

8. The method for preparing a highly transparent and high refractive index organic polymer material according to claim 5, characterized in that: The photoinitiator used in the photopolymerization is selected from one or more of benzophenone, 4-methylbenzophenone, isopropylthioxanthone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholine-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinephenyl)butanone and N,N-dimethylaminobenzoic acid isooctyl ester.

9. The method for preparing a highly transparent and high refractive index organic polymer material according to claim 5, characterized in that: The organic solvent is selected from one or more of propylene glycol methyl ether, toluene, hexane, cyclohexane, dioxane, tetrahydrofuran, ether, acetonitrile, dichloromethane, acetone, chloroform, propylene glycol methyl ether acetate, dimethyl sulfoxide, N,N-dimethylformamide, and 1,2-dichlorobenzene.

10. An application of a highly transparent and high refractive index organic polymer material as claimed in claim 1, characterized in that: The highly transparent and high refractive index organic polymer material can be used in the fields of organic light emitting diodes, microlens elements in double charge coupled devices, high-performance complementary image sensors, all-polymer optoelectronic devices, polymer-based optical waveguides, photovoltaics, storage devices, etc.

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