Small molecule acrylate compound, preparation method therefor and use thereof

Abstract

The present invention provides a small molecule acrylate compound, a preparation method therefor, and a use thereof. The small molecule acrylate compound has a structure as represented by formula I. In formula I, L is selected from hydrogen or a group as represented by formula I-0, wherein A is selected from a biaryl ring containing a heteroatom or a fused ring containing a heteroatom; X1 and X2 are each independently selected from hydrogen or methyl; and m1 and m2 are each independently an integer from 1 to7. The present invention can improve the refractive index of the small molecule acrylate compound and achieve both a high refractive index and low viscosity of the small molecule acrylate compound, thereby satisfying applications in a nano-imprinting process.

Description

A small molecule acrylate compound and its preparation method and application

[0001] This application claims priority to the Chinese patent application filed with the China Patent Office on March 29, 2024, with application number 202410381977.6 and application name “A small molecule acrylate compound, its preparation method and application”, the entire contents of which are incorporated by reference into this application. Technical Field

[0002] The present invention relates to a small molecule acrylate compound and a preparation method and application thereof, belonging to the technical field of nanoimprint materials. Background Art

[0003] Nanoimprint lithography (NIL) has the advantages of simple operation, high efficiency, and low cost, and is considered to have broad application prospects in the field of nano-processing (such as in the fields of energy, sensors, optoelectronic devices, biology, medicine, etc.). Nanoimprint technology can be divided into hot embossing process and ultraviolet nanoimprinting technology. Compared with hot embossing, ultraviolet nanoimprinting can greatly reduce the difficulty of processing and improve device performance. Ultraviolet nanoimprinting requires the imprinting glue to have high fluidity and low viscosity, which can reduce the imprinting time and thus significantly improve the imprinting efficiency. For example, using ultraviolet nanoimprinting to manufacture microlens arrays (MLA) and gratings can significantly reduce costs. High refractive index nanoimprinting materials can reduce the height of the microlens array structure, increase the radius of curvature, reduce the angle between the curved surface and the base, and shorten the focal length of the lens.

[0004] When replacing traditional micro-nano processing technology, the UV imprinting process also puts forward many requirements for UV curing materials, such as high refractive index, low viscosity, and high reaction efficiency. In order to meet the manufacturing and processing of micro-nano devices, the resin material is usually required to be a liquid at room temperature or a relatively low temperature, preferably a low-viscosity liquid. In terms of stability, it is required to have a shelf life of more than three months in the dark. In terms of reactivity, the resin monomer is required to have a fast photocuring speed and good film-forming properties. Among them, it is particularly important to maintain a high refractive index (usually the resin refractive index (nD / 20°C) is required to reach 1.6 or above, or even higher). Optical devices made of high refractive index resins have important applications in the field of optical communications. The refractive index is usually increased by increasing the monomer molar refractive index and reducing the molar volume.

[0005] However, existing nanoimprint adhesive monomers often struggle to combine high refractive index with low viscosity. High-viscosity monomers can lead to a sharp increase in viscosity after solvent removal, rendering the nanoimprint adhesive impractical. Therefore, there is an urgent need to develop nanoimprint adhesive monomers with high refractive index and low viscosity to meet the needs of nanoimprint applications. Summary of the Invention

[0006] The present invention provides a small molecule acrylate compound and a preparation method and application thereof, which can significantly improve the refractive index of the small molecule acrylate compound, achieve a balance between high refractive index and low viscosity of the small molecule acrylate compound (monomer), and make it meet the application of nanoimprint technology.

[0007] In one aspect of the present invention, a small molecule acrylate compound is provided, which has a structure shown in the following formula I:

[0008] In the formula I, L is selected from hydrogen or a group represented by the following formula I-0:

[0009] wherein A is selected from a biaryl ring containing a heteroatom or a fused ring containing a heteroatom;

[0010] X1 and X2 are each independently selected from hydrogen or methyl;

[0011] m1 and m2 are each independently an integer of 1-7.

[0012] According to one embodiment of the present invention, the heteroatom includes sulfur or selenium.

[0013] According to one embodiment of the present invention, A in Formula I contains one or more of phenyl, thienyl, naphthyl, benzothienyl, dithienyl [3,2-B:2',3'-D] thienyl, tetrathienyl, thiazolyl, benzothiazolyl, isothiazolyl, benzisothiazolyl, imidazolyl, benzimidazolyl, selenophenyl, benzoselenophene, thieno [3,2-b] thienyl, thiadiazolyl, and tetrathiafulvalenyl.

[0014] According to one embodiment of the present invention, A in Formula I may or may not have a substituent. When A has the substituent, the substituent is selected from a straight-chain alkyl group having 1 to 10 carbon atoms, a branched-chain alkyl group having 3 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a straight-chain alkoxy group having 1 to 10 carbon atoms, a straight-chain alkylthio group having 1 to 10 carbon atoms, a branched-chain alkoxy group having 3 to 10 carbon atoms, a branched-chain alkylthio group having 3 to 10 carbon atoms, a cycloalkyloxy group having 3 to 10 carbon atoms, a cycloalkylthio group having 3 to 10 carbon atoms, a mercapto group or an acrylate group.

[0015] According to one embodiment of the present invention, the small molecule acrylate compound has a structure shown by one of Formula II to Formula I-14.

[0016] According to one embodiment of the present invention, the refractive index of the small molecule acrylate compound is greater than 1.62.

[0017] Another aspect of the present invention provides a method for preparing the above-mentioned small molecule acrylate compound, comprising the following steps: reacting a compound containing an A group with a compound represented by formula IV to obtain a small molecule acrylate compound having a structure represented by formula I; wherein the compound containing an A group includes a compound represented by formula II and / or a compound represented by formula III.

[0018] Another aspect of the present invention provides a composition for nanoimprinting, comprising the above-mentioned small molecule acrylate compound.

[0019] According to one embodiment of the present invention, the small molecule acrylate compound includes one or more compounds of Formula I-1 to Formula I-14:

[0020] According to one embodiment of the present invention, the mass fraction of the small molecule acrylate compound in the composition is 0.01%-99.9%.

[0021] According to one embodiment of the present invention, the composition further comprises a photoinitiator, and the photoinitiator comprises one or more compounds Q1 to Q8.

[0022] According to one embodiment of the present invention, the composition further comprises a photoinitiator, and the mass fraction of the photoinitiator in the composition is 0.01%-10%.

[0023] Another aspect of the present invention provides a use of the above-mentioned small molecule acrylate compound or the above-mentioned composition in nanoimprinting.

[0024] According to one embodiment of the present invention, the nanoimprinting includes ultraviolet nanoimprinting.

[0025] The small molecule acrylate compound provided by the present invention has a structure shown in Formula 1, and utilizes the low viscosity, high fluidity, and high reactivity characteristics of (meth) acrylate, while combining the high refractive index and high stability characteristics of biaryl rings and condensed rings, and introducing high refractive index heteroatoms (such as sulfur, selenium, etc.) into the aromatic heterocyclic rings, which can significantly increase the refractive index of the small molecule acrylate compound, and while increasing the refractive index, the viscosity of the small molecule acrylate compound can also be reduced, so that the small molecule acrylate compound and the resin composition comprising the small molecule acrylate compound have the advantages of low viscosity, high refractive index, high reactivity, and can be stored (stored) at low temperatures for a long time. Thus, the present invention can achieve a balance between the high refractive index and low viscosity of the small molecule acrylate compound (monomer), meeting the application of the nanoimprint process. DETAILED DESCRIPTION

[0026] In order to enable those skilled in the art to better understand the scheme of the present invention, the present invention is further described in detail below. The specific embodiments listed below are only for describing the principles and features of the present invention. The examples are only used to explain the present invention and are not intended to limit the scope of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts are within the scope of protection of the present invention.

[0027] An embodiment of the present invention provides a small molecule acrylate compound (resin monomer) having a structure shown in Formula I below:

[0028] In formula I, L is selected from hydrogen, or a group represented by the following formula I-0:

[0029] wherein A is selected from a biaryl ring containing a heteroatom or a fused ring containing a heteroatom;

[0030] X1 and X2 are each independently selected from hydrogen or methyl;

[0031] m1 and m2 are each independently an integer of 1-7.

[0032] Illustratively, m1 is 1, 2, 3, 4, 5, 6 or 7, and m2 is 1, 2, 3, 4, 5, 6 or 7, for example.

[0033] Specifically, the heteroatom includes sulfur (S) or selenium (Se), which is beneficial to further improve the refractive index of the small molecule acrylate compound.

[0034] Specifically, in Formula I, A may include an aromatic ring (Ar) and / or an aromatic heterocyclic ring (Het). For example, when A is a biaryl group, the biaryl group is formed by connecting multiple aromatic groups, and these aromatic groups can be selected from aromatic rings and / or heteroaromatic rings.

[0035] In some embodiments, A in Formula I contains one or more of phenyl, thienyl, naphthyl, benzothienyl, dithieno[3,2-B:2',3'-D]thienyl, tetrathienyl, thiazolyl, benzothiazolyl, isothiazolyl, benzisothiazolyl, imidazolyl, benzimidazolyl, selenophenyl, benzoselenophene, thieno[3,2-b]thienyl, thiadiazolyl, and tetrathiafulvalenyl.

[0036] Furthermore, A in Formula I may or may not have a substituent. When A has a substituent, the number of the substituent may be one or more.

[0037] Specifically, when A carries a substituent, the substituent can be selected from a straight-chain alkyl group having 1 to 10 carbon atoms, a branched-chain alkyl group having 3 to 10 carbon atoms (i.e., an alkyl group with a branch), a cycloalkyl group having 3 to 10 carbon atoms, a straight-chain alkoxy group having 1 to 10 carbon atoms, a straight-chain alkylthio group having 1 to 10 carbon atoms, a branched-chain alkoxy group having 3 to 10 carbon atoms, a branched-chain alkylthio group having 3 to 10 carbon atoms, a cycloalkyloxy group having 3 to 10 carbon atoms, a cycloalkylthio group having 3 to 10 carbon atoms, a mercapto group, or an acrylate group.

[0038] In the embodiment of the present invention, the carbon number of the linear alkyl group or branched alkyl group with a carbon number of 1-10 can be 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.

[0039] In the embodiment of the present invention, the carbon number of the cycloalkyl group having 3-10 carbon atoms can be 3, 4, 5, 6, 7, 8, 9 or 10.

[0040] In the embodiment of the present invention, the carbon number of the straight-chain alkoxy group with a carbon number of 1-10 can be 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.

[0041] In the embodiment of the present invention, the carbon number of the straight-chain alkylthio group with a carbon number of 1-10 can be 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.

[0042] In the embodiment of the present invention, the branched alkoxy group having 3-10 carbon atoms may have 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms.

[0043] In the embodiment of the present invention, the branched alkylthio group having 3 to 10 carbon atoms may have 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms.

[0044] In the embodiment of the present invention, the cycloalkoxy group having 3-10 carbon atoms may have 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms.

[0045] In the embodiment of the present invention, the carbon number of the cycloalkylthio group with a carbon number of 3-10 can be 3, 4, 5, 6, 7, 8, 9 or 10.

[0046] In some specific embodiments, the small molecule acrylate compound has a structure shown in one of the following Formula II to Formula I-14:

[0047] In formulas I-1 to I-14, R1, R2 and R3 are each independently selected from hydrogen, a straight-chain alkyl group having 1 to 10 carbon atoms, a branched-chain alkyl group having 3 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a straight-chain alkoxy group having 1 to 10 carbon atoms, a straight-chain alkylthio group having 1 to 10 carbon atoms, a branched-chain alkoxy group having 3 to 10 carbon atoms, a branched-chain alkylthio group having 3 to 10 carbon atoms, a cycloalkyloxy group having 3 to 10 carbon atoms, a cycloalkylthio group having 3 to 10 carbon atoms, a mercapto group or an acrylate group.

[0048] In formulas I-1 to I-14, n1, n2, n3, n4, n5, n6, and n7 are each independently an integer of 0 to 4, for example, 1, 2, 3, or 4.

[0049] Specifically, the refractive index of the small molecule acrylate compound according to the embodiment of the present invention may be greater than 1.62.

[0050] An embodiment of the present invention further provides a method for preparing the above-mentioned small molecule acrylate compound, comprising the following steps: reacting a compound containing an A group with a compound represented by Formula IV to produce a small molecule acrylate compound having a structure represented by Formula I (i.e., the compound containing an A group (Formula II and / or Formula III) is esterified with acrylic acid to produce the small molecule acrylate compound); wherein the compound containing an A group includes a compound represented by Formula II and / or a compound represented by Formula III;

[0051] Wherein, L in Formula II is hydrogen.

[0052] In formula IV, X represents X1 or X2 in formula I, and Y represents halogen, such as Cl.

[0053] For example, Formula IV includes acryloyl chloride.

[0054] In the embodiment of the present invention, Formula II, Formula III, and Formula IV can be synthesized by conventional methods in the art, without particular limitation. For example, Formula II and Formula III can be prepared by Suzuki coupling reaction, and the catalyst used can include a metal palladium catalyst.

[0055] For example, when R1, R2, and X1 in Formula I-3 are H and m1=2, Formula I-3 is a structure shown in Formula I-3-1 below. The synthesis route of Formula I-3-1 can be as follows:

[0056] Among them, S-1 and S-2 can be prepared into S-3 (Formula II) through Suzuki coupling reaction involving metal palladium catalyst, and S-3 is then esterified with acrylic acid to obtain product I-3-1.

[0057] For example, when R1, R2, R3, X1, and X2 in Formula I-14 are H and m1=m2=1, Formula I-14 is a structure shown in Formula I-14-1 below. The synthesis route of Formula I-14-1 can be as follows:

[0058] Among them, S-4 can react with N-bromosuccinimide (NBS) to obtain S-5, S-5 and S-2 can be prepared into S-6 (Formula III) through Suzuki coupling reaction involving metal palladium catalyst, and S-6 can react with acryloyl chloride to obtain Formula I-14-1.

[0059] Generally speaking, after the synthesis of small molecule acrylate compounds, a purification and refining process is also included. Specifically, the acrylate compounds can be purified and refined by methods such as chromatography and recrystallization.

[0060] An embodiment of the present invention further provides a composition for nanoimprinting, comprising the above-mentioned small molecule acrylate compound.

[0061] Specifically, the above-mentioned composition may include a small molecule acrylate compound having a structure shown in Formula I or multiple small molecule acrylate compounds having a structure shown in Formula I. In some embodiments, the small molecule acrylate compound in the above-mentioned composition may include one or more compounds of Formulas I-1 to I-14 above.

[0062] In some embodiments, the mass fraction of the small molecule acrylate compound in the composition may be 0.01%-99.9%, such as 0.5%-99.5%, preferably 1-55%, and more preferably 1-35%.

[0063] Generally, the composition further includes a photoinitiator, which includes one or more of the following compounds Q1 to Q8:

[0064] In some embodiments, the mass fraction of the photoinitiator in the composition may be 0.01%-10%, preferably 0.05%-5%, more preferably 0.1%-3%.

[0065] Specifically, the composition can be used in ultraviolet nanoimprinting, for example, as a raw material to manufacture optical devices such as microlens arrays (MLA) and gratings through ultraviolet nanoimprinting.

[0066] In specific implementation, the above-mentioned composition can be prepared by heating and dissolving the mixture, that is, mixing a small molecule acrylate compound and materials such as a photoinitiator, and then dissolving them by heat to obtain a composition, but the preparation method of the composition of the embodiment of the present invention is not limited to this.

[0067] An embodiment of the present invention further provides a use of the above-mentioned small molecule acrylate compound or the above-mentioned composition in nanoimprinting.

[0068] Specifically, nanoimprinting includes ultraviolet nanoimprinting, that is, the above-mentioned small molecule acrylate compounds or compositions containing the small molecule acrylate compounds can be applied to ultraviolet nanoimprinting processes. For example, microlens arrays (MLA), gratings, memories, sensors (such as integrated biosensors) and other devices can be manufactured through ultraviolet nanoimprinting processes.

[0069] In the embodiments of the present invention, the small molecule acrylate compounds and compositions containing the small molecule acrylate compounds can be applied in the fields of life sciences, data communications, consumer electronics, and the like.

[0070] For example, in the field of life sciences, the small molecule acrylate compounds and compositions of the embodiments of the present invention can be used as materials for preparing the following devices using nanoimprint technology:

[0071] (1) Next-generation DNA sequencing (NGS) principle integrates DNA polymerase or DNA degrading enzyme into micro-nano circuits. Each nucleotide added or removed to the structural unit of the growing DNA chain will cause a deviation in the current in the circuit, which is read by the sensor as an electronic disturbance, thereby obtaining the structural sequence of the DNA. The small molecule acrylate compounds and compositions of the embodiments of the present invention can be used as materials for manufacturing such sensors using nanoimprint technology.

[0072] (2) Point-of-care (PoC) diagnostic technology can perform rapid and dispersed detection of infectious diseases, sexually transmitted diseases, and other diseases. Biosensors for point-of-care (PoC) diagnostic technology can be manufactured using nanoimprint technology. The small molecule acrylate compounds and compositions of the embodiments of the present invention can be used as materials for manufacturing such biosensors.

[0073] (3) Organ-on-a-chip (OOC) technology, known as "organ chip", can be used to improve the efficiency of drug development. Nanoimprinting technology can provide precise micro-nano structures for high-throughput drug screening platforms that simulate living organisms. The small molecule acrylate compounds or compositions of the embodiments of the present invention can be used as materials for preparing the micro-nano structures through nanoimprinting technology.

[0074] For example, in the field of data communications, the demand for nanoimprint technology in the communications industry is increasing day by day, which has driven the research and development of nanoimprint-related equipment and processes. Imprinted polymer lenses are used to replace inorganic material lenses. In memory and diffraction optical elements, nanoimprinting can achieve high-resolution feature sizes with an economical and effective solution. The application of large-area ordered micro-nano structures in optical devices includes, for example, resonant grating filters, polarizers, wave plates, anti-reflection structures, photonic integrated circuits, and plasma devices. The small molecule acrylate compounds or compositions of the embodiments of the present invention can be used as materials for manufacturing these optical devices using nanoimprint technology. For example: (1) 3D NAND memory: The nanostructures in the memory can be manufactured using nanoimprint technology. There is also a diffractive optical element (DOE) micro-nano etching process to form a two-dimensional distributed diffraction unit, each diffraction unit can have a specific morphology, refractive index, etc., to finely control the laser wavefront phase distribution, and it can also be manufactured by nanoimprint technology. The manufacture of these structures can all use the small molecule acrylate compounds or compositions of the embodiments of the present invention; (2) Components in optical communication devices, microlens arrays (MLA) and microgratings (GRISM) can be manufactured using nanoimprint technology to achieve the purpose of reducing costs and increasing efficiency, and they can use the small molecule acrylate compounds or compositions of the embodiments of the present invention.

[0075] For example, in the field of consumer electronics, the small molecule acrylate compounds and compositions of the embodiments of the present invention can be used as materials for preparing structural components such as gratings and 3D sensors through nanoimprinting. Specifically: (1) One of the most widely used applications of nanoimprinting technology is surface relief gratings in consumer electronic AR glasses. Nanoimprinting technology is the core process of diffraction waveguides. First, a layer of organic resin is evenly coated on a glass substrate (i.e., a waveguide sheet), and then the imprinting mold is covered and cured with ultraviolet light. After curing, the mold is lifted up to form a diffraction grating with a specific structure on the waveguide; (2) One of the applications of nanoimprinting technology in the field of consumer electronics is 3D sensors. Nanoimprinting provides the ability to imprint diffraction optical elements (DOEs) at the nanoscale, including gratings and photonic crystals that generate waveguides, beam shaping elements, and pattern generators. One of the applications of nanoimprint technology in the field of consumer electronics is patterned sapphire substrate (PSS), where nanoimprint equipment replaces expensive projection mirror sets, breaking the physical limitations of the optical system and significantly reducing equipment costs; (3) Other devices in consumer electronic products can also be produced using nanoimprint technology, such as LEDs, OLEDs, AR devices, 3D sensors, etc.

[0076] The present invention is further described below through specific examples. In the following examples, the relevant test methods are as follows:

[0077] (1) Refractive index test conditions: The test was performed using an Abbe instrument at room temperature (20°C) and 589nm yellow light. The refractive index is expressed as (n D / 20℃);

[0078] (2) Viscosity test conditions: Viscosity was measured at room temperature or at a specified temperature using a cone-plate rheometer. The test instrument was the NTV-CAP1 cone-plate rheometer from Shanghai Nirun Intelligent Technology Co., Ltd., and the cone-plate used was No. 40.

[0079] (3) 1 H NMR stands for hydrogen nuclear magnetic resonance. 13 C NMR stands for carbon nuclear magnetic resonance spectroscopy, and the testing instrument is a 400 MHz or 500 MHz nuclear magnetic resonance spectrometer produced by Bruker.

[0080] Example 1

[0081] The structural formula of the resin monomer (Formula I-4-1) provided in Example 1 is as follows:

[0082] The preparation process of formula I-4-1 is as follows:

[0083] (1) Under nitrogen protection, 6-bromobenzothiophenol, 4-hydroxymethylphenylboronic acid, tetrakis(triphenylphosphine), potassium carbonate, tetrahydrofuran, and water were added to a 500 mL round-bottom flask, and the mixture was heated and stirred at 80° C. overnight; then, after the system was cooled to room temperature, ethyl acetate was added and extracted twice, the organic phases were combined, dried over magnesium sulfate, and dried under reduced pressure, and separated by column chromatography to obtain 6-(4-hydroxymethylphenyl)-benzothiophenol;

[0084] (2) In a 500 mL round-bottom flask, 6-(4-hydroxymethylphenyl)-benzothiophenol, acryloyl chloride, dichloromethane and triethylamine were added and reacted at room temperature for 12 hours; then ethyl acetate was added and extracted twice, the organic phases were combined, dried over magnesium sulfate, and dried under reduced pressure. The product of formula I-4-1 was separated by column chromatography.

[0085] Among them, the nuclear magnetic characterization results of the product of formula I-4-1 are: 1 H NMR(400MHz, CDCl3)δ8.15(s,1H),7.93(d,1H),7.72(d,2H),7.66(dd,1H),7.5 2(m,3H),7.41(d,1H),6.58(dd,1H),6.29(dd,1H),5.93(dd,1H),5.34(s,2H).

[0086] In addition, the viscosity (50°C) δ of the product of formula I-4-1 was measured to be 700 mPa·s; the refractive index (nD / 20°C) n was 1.627; and the Abbe number was 19.3.

[0087] Example 2

[0088] The structural formula of the resin monomer (Formula I-5-1) provided in Example 2 is as follows:

[0089] The preparation process of formula I-5-1 is as follows:

[0090] (1) In a 500 mL round-bottom flask, thieno[3,2-b]thiophene, N-bromosuccinimide, and N,N-dimethylformamide were added and reacted at room temperature for 12 hours; n-hexane was then added, and the mixture was washed with water three times. The organic phases were combined, dried over sodium sulfate, and dried under reduced pressure. 2-bromothieno[3,2-b]thiophene was separated by column chromatography;

[0091] (2) Under nitrogen protection, 2-bromothiophene[3,2-B]thiophene, 4-hydroxymethylphenylboronic acid, tetrakis(triphenylphosphine), potassium carbonate, tetrahydrofuran and water were added to a 500 mL round-bottom flask, and the mixture was heated and stirred at 80°C overnight; after the system was cooled to room temperature, ethyl acetate was added and extracted twice, the organic phases were combined, dried over magnesium sulfate, and dried under reduced pressure, and then separated by column chromatography to obtain 2-(4-hydroxymethylphenyl)-thiophene[3,2-B]thiophene;

[0092] (3) In a 500 mL round-bottom flask, 2-(4-hydroxymethylphenyl)-thiophene[3,2-B]thiophene, acryloyl chloride, dichloromethane and triethylamine were added and reacted at room temperature for 12 hours; ethyl acetate was added and extracted twice, the organic phases were combined, dried over magnesium sulfate, and dried under reduced pressure. The product I-5-1 was separated by column chromatography.

[0093] Among them, the nuclear magnetic characterization results of the product of formula I-5-1 are: 1 H NMR (400MHz, CDCl3) δ7.64(d,2H),7.50(s,1H),7.41(m,3H),7.26(d,1H),5.54(dd,1H),5.25(dd,1H),5.91(dd,1H),5.27(s,2H). 13 C NMR (101MHz, CDCl3) δ166.04,145.71,140.14,138.70,135.42,134.83,131.36,128.99,128.32,127.23,125.94,119.69,115.65,66.01,65.96.

[0094] In addition, the viscosity (50°C) δ of the product of formula I-5-1 was measured to be 500 mPa·s, and the refractive index (nD / 20°C) n was measured to be 1.631.

[0095] Example 3

[0096] The structural formula of the resin monomer (Formula I-3-1) provided in Example 2 is as follows:

[0097] The preparation process of formula I-3-1 is as follows:

[0098] (1) Under nitrogen protection, 2-bromothiophene, 4-hydroxymethylphenylboronic acid, tetrakis(triphenylphosphine), potassium carbonate, tetrahydrofuran and water were added to a 500 mL round-bottom flask, and the mixture was heated and stirred at 80° C. overnight; after the system was cooled to room temperature, ethyl acetate was added and extracted twice, the organic phases were combined, dried over magnesium sulfate, and dried under reduced pressure, and 2-(4-hydroxymethylphenyl)-thiophene was separated by column chromatography;

[0099] (2) In a 500 mL round-bottom flask, 2-(4-hydroxymethylphenyl)-thiophene, acryloyl chloride, dichloromethane and triethylamine were added and reacted at room temperature for 12 hours; ethyl acetate was added and extracted twice, the organic phases were combined, dried over magnesium sulfate, and dried under reduced pressure. The product I-3-1 was separated by column chromatography.

[0100] Among them, the NMR characterization results of product I-3-1 are: 1 H NMR (400MHz, CDCl3) δ7.66(d,2H),7.44(d,2H),7.35(m,2H),7.13(m,1H),5.52(dd,1H),5.24(dd,1H),5.91(dd,1H),5.26(s,2H). 13 C NMR (101MHz, CDCl3) δ166.06,143.86,135.05,134.49,131.29,128.95,128.32,128.14,126.12,125.14,123.43,66.05.

[0101] In addition, the viscosity (25°C) of the product I-3-1 was measured to be 6 mPa·s, and the refractive index (n D / 20℃)n=1.644, and the Abbe number is 22.2.

[0102] Comparative Example 1

[0103] The resin monomer of Comparative Example 1 is a commonly used high-fold commercial resin monomer (9,9-bis(4-(2-(methyl)acryloyloxyethoxy)phenyl)fluorene), and its structural formula is as follows:

[0104] The refractive index n of the resin monomer of Comparative Example 1 is 20 / D =1.606 (lit.), and its viscosity at 50°C is greater than 100,000 mPa·s.

[0105] Comparative Example 2

[0106] The resin monomer of Comparative Example 2 is a commercial resin monomer (9,9-bis(4-allyloxyphenyl)fluorene), and its structural formula is as follows:

[0107] The refractive index n of the resin monomer of Comparative Example 2 is 20 / D =1.624 (lit.), and its viscosity at 50°C is greater than 10000 mPa·s.

[0108] Comparative Example 3

[0109] The resin monomer of Comparative Example 3 is a commercial resin monomer (2-([1,1'-biphenyl]-2-oxy)ethyl 2-acrylate), and its structural formula is as follows:

[0110] The refractive index n of the resin monomer of Comparative Example 3 is 20 / D =1.576 (lit.), and its viscosity at 50°C is still greater than 500 mPa·s.

[0111] The refractive index and viscosity of the resin monomers of Examples 1 to 3 and Comparative Examples 1 to 3 are summarized in Table 1. The 50°C viscosity is the viscosity measured after heating the resin monomer to 50°C, and the 25°C viscosity is the viscosity measured at 25°C (room temperature).

[0112] Table 1

[0113] Comparative Examples 1 to 3 are commonly used nanoimprint monomers. The monomers in Comparative Examples 1 and 2 still have extremely high viscosities after heating, failing to fully wet the mold during the nanoimprint process and resulting in poor practicality. While the monomer in Comparative Example 3 has a lower viscosity, its refractive index is low, detrimental to the optical performance of the device. This demonstrates that, in practical applications, it's often difficult to achieve both a high refractive index and a low-viscosity resin monomer for nanoimprinting.

[0114] Compared with Comparative Examples 1-3, the resin monomers of Examples 1-3 have both high refractive index (>1.62) and low viscosity, and are suitable for nanoimprinting process, for example, they are conducive to fully wetting the mold in the nanoimprinting process and improving the performance of the device produced.

[0115] This demonstrates that the acrylate monomers (small molecule acrylate compounds) of the present invention, having the structure shown in Formula I, have a significantly higher refractive index than conventional resin monomers and are suitable for nanoimprinting processes. In nanoimprinting processes, the resin monomers are typically heated appropriately, typically to a temperature below 80°C. The acrylate monomers of the present invention can easily achieve extremely low viscosities at these temperatures, achieving a balance between high refractive index and low viscosity.

[0116] In addition, the acrylate monomer and the photoinitiator of the embodiment of the present invention are mixed and then coated to form a film, which also shows good film-forming properties. Specifically, the formed film has the characteristics of high gloss, good toughness and low shrinkage.

Claims

1. A small molecule acrylate compound, characterized in that: It has the structure shown in the following formula I: In the formula I, L is selected from hydrogen or a group represented by the following formula I-0: wherein A is selected from a biaryl ring containing a heteroatom or a fused ring containing a heteroatom; X1 and X2 are each independently selected from hydrogen or methyl; m1 and m2 are each independently an integer of 1-7.

2. The small molecule acrylate compound according to claim 1, characterized in that The heteroatoms include sulfur or selenium.

3. The small molecule acrylate compound according to claim 1, characterized in that: A in the formula I contains one or more of phenyl, thienyl, naphthyl, benzothienyl, dithienyl [3,2-B:2',3'-D] thienyl, tetrathienyl, thiazolyl, benzothiazolyl, isothiazolyl, benzisothiazolyl, imidazolyl, benzimidazolyl, selenophenyl, benzoselenophene, thieno [3,2-b] thienyl, thiadiazolyl, and tetrathiafulvalenyl.

4. The small molecule acrylate compound according to claim 1, characterized in that: A in the formula I may or may not have a substituent. When A has the substituent, the substituent is selected from a straight-chain alkyl group having 1 to 10 carbon atoms, a branched-chain alkyl group having 3 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a straight-chain alkoxy group having 1 to 10 carbon atoms, a straight-chain alkylthio group having 1 to 10 carbon atoms, a branched-chain alkoxy group having 3 to 10 carbon atoms, a branched-chain alkylthio group having 3 to 10 carbon atoms, a cycloalkyloxy group having 3 to 10 carbon atoms, a cycloalkylthio group having 3 to 10 carbon atoms, a mercapto group or an acrylate group.

5. The small molecule acrylate compound according to claim 1, characterized in that: The small molecule acrylate compound has a structure shown in one of the following formulas II to I-14: In Formulas I-1 to I-14, R1, R2, and R3 are each independently selected from hydrogen, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a linear alkoxy group having 1 to 10 carbon atoms, a linear alkylthio group having 1 to 10 carbon atoms, a branched alkoxy group having 3 to 10 carbon atoms, a branched alkylthio group having 3 to 10 carbon atoms, a cycloalkyloxy group having 3 to 10 carbon atoms, a cycloalkylthio group having 3 to 10 carbon atoms, a mercapto group, or an acrylate group; In the above formulas I-1 to I-14, n1, n2, n3, n4, n5, n6, and n7 are each independently an integer of 0 to 4.

6. The small molecule acrylate compound according to any one of claims 1 to 5, characterized in that: The refractive index of the small molecule acrylate compound is greater than 1.

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7. A method for preparing the small molecule acrylate compound according to any one of claims 1 to 6, characterized in that: The following steps are involved: Reacting a compound containing an A group with a compound represented by formula IV to prepare a small molecule acrylate compound having a structure represented by formula I; wherein the compound containing an A group includes a compound represented by formula II and / or a compound represented by formula III; L in the formula II is hydrogen; In the formula IV, X represents X1 or X2 in the formula I, and Y represents halogen.

8. A composition for nanoimprinting, characterized in that The invention comprises the small molecule acrylate compound according to any one of claims 1 to 7.

9. The composition according to claim 8, characterized in that The small molecule acrylate compound includes one or more compounds of the following formulas I-1 to I-14:

10. The composition according to claim 8, characterized in that The mass fraction of the small molecule acrylate compound in the composition is 0.01%-99.9%.

11. The composition according to claim 8, characterized in that The composition further includes a photoinitiator, which includes one or more of the following compounds Q1 to Q8:

12. The composition according to any one of claims 8 to 11, characterized in that The composition further comprises a photoinitiator, and the mass fraction of the photoinitiator in the composition is 0.01%-10%.

13. Use of the small molecule acrylate compound according to any one of claims 1 to 6 or the composition according to any one of claims 8 to 12 in nanoimprinting.

14. The use according to claim 13, characterized in that The nanoimprinting includes ultraviolet nanoimprinting.

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