Polymethacrylate space charge transfer polymer luminescent material, preparation method and stress strain monitoring application

Abstract

The invention relates to a polymethacrylate space charge transfer polymer luminescent material, a preparation method and stress strain monitoring application, and belongs to the technical field of organic luminescent materials. According to the high-molecular luminescent material, a non-conjugated polymethacrylate main chain structure is adopted, the electron donor and the electron acceptor are grafted on the side chain, pressure monitoring is achieved through the response characteristic of fluorescence emission brought by space interaction of donor and acceptor units to pressure, and the high-molecular luminescent material has the excellent reversible response characteristic. By adjusting the space charge transfer effect between the donor and the acceptor, the change of fluorescence wavelength and intensity is triggered, visual fluorescence signal output is formed, and a novel solution is provided for pressure sensing in the fields of intelligent sensing, flexible electronics, health monitoring and the like.

Description

Technical Field

[0001] The present invention belongs to the technical field of functional polymer materials, and particularly relates to a polymethacrylate-based through-space charge transfer polymer luminescent material, a preparation method thereof, and an application in stress and strain monitoring. Background Art

[0002] Pressure-sensitive luminescent materials have important application values in the fields of sensors, flexible electronics, and structural health monitoring. Although traditional inorganic semiconductor materials (such as quantum dots, metal complexes) have light response characteristics, they generally have problems such as poor mechanical flexibility, limited processability, and insufficient pressure response sensitivity. Although organic polymer materials (such as polydimethylsiloxane, polyurethane) have excellent deformation capabilities, they lack intrinsic luminescent properties and rely on physical doping of fluorescent dyes or phosphors to achieve optical responses, which easily cause defects such as phase separation, concentration quenching, and decline in long-term stability.

[0003] In recent years, through-space charge transfer (TSCT) luminescent systems have attracted attention due to their unique through-space electron transfer characteristics. Different from traditional intramolecular charge transfer (ICT) systems, the donor-acceptor space distance and orientation of TSCT materials can dynamically adapt and change under external pressure, showing changes in emission wavelength / intensity, and are expected to be used in pressure monitoring applications. However, existing TSCT systems are mostly based on small molecule crystals or oligomers, which are difficult to balance mechanical processability and environmental stability, and the compatibility regulation with polymer matrices has not been effectively solved.

[0004] Polymethyl methacrylate (PMMA) is a typical transparent thermoplastic polymer with excellent optical properties and molding processability, but it lacks functional luminescent groups intrinsically. Existing studies have tried to introduce fluorescent units by blending or grafting methods, but often lead to an increase in material rigidity or a decrease in luminescence efficiency. How to precisely embed the TSCT luminescent center into the PMMA main chain / side chain through molecular design while maintaining its mechanical properties and pressure response linearity is still a technical difficulty.

[0005] Based on this, developing a PMMA-based pressure-sensitive material with both efficient TSCT luminescent characteristics, mechanical adaptability, and scalable preparation, and constructing an integrated application scheme with a pressure probe device is of great significance for promoting the development of intelligent sensing technology. Summary of the Invention

[0006] In view of this, the object of the present invention is to provide a polymethacrylate-based space charge transfer polymer light-emitting material with efficient TSCT luminescence characteristics, mechanical adaptability and scalable preparation, a preparation method and a stress-strain monitoring application. The polymer light-emitting material of the present invention adopts a non-conjugated polymethacrylate main chain structure, and an electron donor and an electron acceptor are grafted on the side chain. The fluorescence emission caused by the spatial interaction between the donor and acceptor units has a response characteristic to pressure, realizing pressure monitoring and having excellent reversible response characteristics. The fluorescent polymer compound containing an arylboron acceptor in the polymer light-emitting material of the present invention also has a small singlet-triplet energy level difference (ΔEST) and a high fluorescence quantum efficiency (PLQY).

[0007] In order to achieve the above object, the technical solution of the present invention is as follows:

[0008] A polymethacrylate-based space charge transfer polymer light-emitting material has a structure shown in formula (I) or formula (II):

[0009]

[0010] Among them, x is 0.0001-0.9999, y is 0.0001-0.9999, z is 0.0001-0.9999, and y + z is 0.0001-0.9999, and n is an integer between 2 and 9999;

[0011] D is an electron donor, and A is an electron acceptor containing an arylboron unit;

[0012] H is independently selected from a straight-chain hydrocarbon group of C1-C20, a branched-chain hydrocarbon group of C3-C20, a cycloalkyl group of C3-C20, an alkoxy group of C1-C20, an aromatic unit of C6-C60 (the aromatic unit includes an aromatic condensed ring unit of C6-C60) or a heteroaromatic ring unit of C5-C60 containing N, O, S, Se, P, B, Si, Ge, ;

[0013] The D is selected from any one of the structures shown in formula (D-1) to formula (D-31):

[0014]

[0015]

[0016] The A is selected from any one of the structures shown in formula (A-1) to formula (A-16):

[0017]

[0018] In the structures of D and A, R 1 、R2 , R 3 , R 4 , R 5 and R 6 are each independently selected from H, halogen, -CN, -NO 2 , -PO(Ph) 2 , a substituted or unsubstituted straight-chain C1-C22 hydrocarbon group, a substituted or unsubstituted branched-chain C1-C22 hydrocarbon group, a substituted or unsubstituted C3-C22 cycloalkyl group, a substituted or unsubstituted C1-C22 alkoxy group.

[0019] Preferably, x is preferably 0.005 to 0.995, more preferably 0.01 to 0.99, still more preferably 0.05 to 0.95, even more preferably 0.1 to 0.9, still even more preferably 0.3 to 0.7, still still more preferably 0.4 to 0.6, most preferably 0.01 to 0.20, and most most preferably 0.05 to 0.10.

[0020] Preferably, y + z is preferably 0.005 to 0.995, more preferably 0.01 to 0.99, still more preferably 0.05 to 0.95, even more preferably 0.1 to 0.9, still even more preferably 0.3 to 0.7, still still more preferably 0.4 to 0.6, most preferably 0.01 to 0.20, and most most preferably 0.05 to 0.10.

[0021] Preferably, n is preferably an integer between 10 and 5000, more preferably an integer between 50 and 2500, still more preferably an integer between 100 and 1000, even more preferably an integer between 300 and 800, most preferably an integer between 400 and 600, and most most preferably an integer between 20 and 1000.

[0022] Most preferably, x is 0.01 to 0.20 and n is an integer between 20 and 1000.

[0023] Preferably, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 substitution in refers to one or more non-adjacent C atoms in C1-C22 being substituted by O, S, Si or -CO-O-; or also includes one or more hydrogen atoms being substituted by F.

[0024] Preferably, in the structural formulas of the above-mentioned electron donor D and electron acceptor A of the present invention, the R 1 , R 2 , R 3, R 4 , R 5 and R 6 are each independently preferably selected from H, halogen, -CN, -NO 2 , -PO(Ph) 2 , benzene ring, pyridine, pyrimidine, triazine, substituted or unsubstituted C2-C20 straight-chain hydrocarbon group, substituted or unsubstituted C2-C20 branched-chain hydrocarbon group, substituted or unsubstituted C4-C20 cycloalkyl group or substituted or unsubstituted C2-C20 alkoxy group; more preferably selected from H, halogen, -CN, -NO 2 , -PO(Ph) 2 , substituted or unsubstituted C3-C18 straight-chain hydrocarbon group, substituted or unsubstituted C3-C18 branched-chain hydrocarbon group, substituted or unsubstituted C5-C18 cycloalkyl group or substituted or unsubstituted C3-C18 alkoxy group, even more preferably selected from H, halogen, -CN, -NO 2 , -PO(Ph) 2 , substituted or unsubstituted C5-C15 straight-chain hydrocarbon group, substituted or unsubstituted C5-C15 branched-chain hydrocarbon group, substituted or unsubstituted C6-C15 cycloalkyl group, substituted or unsubstituted C5-C15 alkoxy group; most preferably selected from H, halogen, -CN, -NO 2 , -PO(Ph) 2 , substituted or unsubstituted C8-C12 straight-chain hydrocarbon group, substituted or unsubstituted C8-C12 branched-chain hydrocarbon group, substituted or unsubstituted C8-C12 cycloalkyl group or substituted or unsubstituted C8-C12 alkoxy group.

[0025] The present invention has no particular limitation on the above-mentioned substitution range, and it can be substituted with conventional substituents well-known to those skilled in the art. Those skilled in the art can make selections and adjustments according to the application situation, quality requirements and product requirements. The substitution in the present invention is preferably that one or more non-adjacent C atoms in the C1-C22 can be substituted by O, S, Si or -CO-O-. The substitution in the present invention is also preferably that one or more hydrogen atoms can be substituted by F.

[0026] The present invention has no particular limitation on the definition of the hydrocarbon group, and the concept of the hydrocarbon group well-known to those skilled in the art can be used. The hydrocarbon group in the present invention preferably includes one or more of alkyl, alkenyl and alkynyl.

[0027] In the present invention, the linking bond in the substituent represents -D, -A, -R 1 , -R 2 , -R 3 , -R 4 , -R 5 , -R 6 , R7 and R 8 The substituent can be at any position of the aromatic ring where it is located.

[0028] Preferably, the polymethacrylate-based space charge transfer polymer light-emitting material is selected from one of the structures shown in Formula (I-1) to Formula (I-60):

[0029]

[0030]

[0031]

[0032]

[0033] A method for preparing a polymethacrylate-based space charge transfer polymer light-emitting material, comprising the following steps:

[0034] Under a protective gas atmosphere, the monomer of the structure shown in Formula (X), the monomer of the structure shown in Formula (Y), an initiator and an organic solvent are mixed and then reacted to obtain the polymethacrylate-based space charge transfer polymer light-emitting material;

[0035] Or: Under a protective gas atmosphere, the monomer of the structure shown in Formula (X), the monomer of the structure shown in Formula (Y), the monomer of the structure shown in Formula (Z), an initiator and an organic solvent are mixed and then reacted to obtain the polymethacrylate-based space charge transfer polymer light-emitting material;

[0036]

[0037] The present invention has no particular limitation on the sources of the monomer of the structure shown in Formula (X) and the monomer of the structure shown in Formula (Y), and they can be prepared by conventional preparation methods well-known to those skilled in the art or purchased commercially. Those skilled in the art can select and adjust according to the application situation, quality requirements and product requirements.

[0038] The present invention has no particular limitation on the addition amounts of the monomers having the structures shown by (X) and the monomers having the structures shown by formula (Y), and the conventional amounts used in such reactions well-known to those skilled in the art may be employed. Those skilled in the art can make selections and adjustments according to production conditions, quality requirements, and product requirements. The molar ratio of the monomers having the structures shown by formula (X) to the monomers having the structures shown by formula (Y) in the present invention is preferably (0.999 - 0.001):(0.001 - 0.999), more preferably (0.99 - 0.01):(0.001 - 0.999), still more preferably (0.5 - 0.05):(0.001 - 0.999), even still more preferably (0.3 - 0.1):(0.001 - 0.999), and may also be (0.999 - 0.001):(0.01 - 0.99), may be (0.999 - 0.001):(0.05 - 0.5), or may be (0.999 - 0.001):(0.1 - 0.3).

[0039] The present invention has no particular limitation on the selection of the initiator, and the initiators conventionally used in such reactions well-known to those skilled in the art may be employed. Those skilled in the art can make selections and adjustments according to production conditions, quality requirements, and product requirements. The initiator in the present invention preferably includes one or more of azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, and tert-butyl perbenzoate, and more preferably is azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, or tert-butyl perbenzoate.

[0040] The present invention has no particular limitation on the amount of the initiator used, and the conventional amounts of initiators used in such reactions well-known to those skilled in the art may be employed. Those skilled in the art can make selections and adjustments according to production conditions, quality requirements, and product requirements. The molar ratio of the initiator to the monomers having the structures shown by formula (X) in the present invention is preferably 1% - 10%, more preferably 3% - 8%, and still more preferably 5% - 6%.

[0041] The present invention has no particular limitation on the selection of the organic solvent, and the solvents conventionally used in such reactions well-known to those skilled in the art may be employed. Those skilled in the art can make selections and adjustments according to production conditions, quality requirements, and product requirements. The organic solvent in the present invention preferably includes one or more of toluene, xylene, tert-butylbenzene, tetrahydrofuran, dioxane, and N,N-dimethylformamide, and more preferably is toluene, xylene, tert-butylbenzene, tetrahydrofuran, dioxane, or N,N-dimethylformamide.

[0042] The present invention has no particular limitation on the amount of the solvent used, and the conventional amount of the solvent used for such reactions well-known to those skilled in the art can be adopted. Those skilled in the art can make selections and adjustments according to the production situation, quality requirements and product requirements. The mass ratio of the solvent to the monomer of the structure shown in the formula (X) in the present invention is preferably 0.1% to 5%, more preferably 0.5% to 4.5%, still more preferably 1% to 4%, and even more preferably 2% to 3%.

[0043] The present invention has no particular limitation on the specific conditions of the reaction, and the conventional conditions for such reactions well-known to those skilled in the art can be adopted. Those skilled in the art can make selections and adjustments according to the production situation, quality requirements and product requirements. The temperature of the reaction in the present invention is preferably 40 to 120 °C, more preferably 50 to 110 °C, still more preferably 60 to 100 °C, and most preferably 70 to 90 °C. The reaction time is preferably 8 to 72 hours, more preferably 20 to 60 hours, and still more preferably 32 to 48 hours. The protective atmosphere in the present invention preferably includes nitrogen and / or inert gas, more preferably nitrogen and / or argon, and most preferably nitrogen.

[0044] A pressure monitoring device prepared from a polymethacrylate-based space charge transfer polymer light-emitting material based on the present invention or a polymethacrylate-based space charge transfer polymer light-emitting material prepared by the preparation method of the present invention.

[0045] In order to further optimize the preparation process of the pressure monitoring device (such as a pressure-sensitive probe) and improve its sensing performance in the present invention, the post-treatment step is preferably included after the reaction in the preparation method. The post-treatment step includes one or more of cooling, sedimentation and filtration, and more preferably cooling to room temperature and then standing for sedimentation, and then filtering to obtain a polymer solid product. The polymer solid can be formed into a pressure-sensitive thin film layer by solution spin coating, spraying or printing processes after drying.

[0046] In order to further optimize the preparation process of the pressure monitoring device (such as a pressure-sensitive probe) and improve its optical response performance in the present invention, the post-treatment step is preferably included after the reaction in the preparation method. The post-treatment step includes one or more of cooling, sedimentation and filtration, and more preferably cooling to room temperature and then standing for sedimentation, and then filtering to obtain a polymer solid product. The polymer solid can be formed into a pressure-sensitive thin film layer on a transparent substrate by solution spin coating, spraying or printing processes after drying, and is protected by an optically transparent encapsulation layer to ensure efficient transmission of optical signals.

[0047] The pressure monitoring device of the present invention may specifically be a visual pressure-sensitive probe, including a sensing functional layer; the sensing functional layer contains the polymethacrylate-based space charge transfer polymer luminescent material of the present invention, or the polymethacrylate-based space charge transfer polymer luminescent material prepared by the preparation method of the present invention. Under pressure stimulation, the polymer luminescent material undergoes intramolecular donor-acceptor spatial separation, triggering changes in the photoluminescence wavelength or color, thereby realizing visual pressure detection.

[0048] The present invention places no special restrictions on the structural design of the pressure-sensitive probe, and a conventional optical sensing architecture in the art can be adopted. Preferably, the probe includes the following layered structure:

[0049] Transparent flexible substrate: preferably polyethylene terephthalate (PET) or polydimethylsiloxane (PDMS), with a thickness of 50 - 200 μm and a light transmittance ≥ 90%;

[0050] Sensing functional layer: a pressure-sensitive polymer thin film directly disposed on the substrate, composed of the polymethacrylate-based space charge transfer polymer luminescent material of the present invention, with a thickness of 1 - 10 μm;

[0051] Optical enhancement layer (optional): a microstructured layer (such as a microlens array) disposed on the surface of the sensing functional layer for amplifying the color change signal;

[0052] Transparent encapsulation layer: a protective layer covering the sensing functional layer, made of an optically transparent elastomer (such as PDMS or polyurethane), with a thickness of 20 - 100 μm and a light transmittance ≥ 95%.

[0053] The main chain of the polymethacrylate-based space charge transfer polymer luminescent material is PMMA, and the side chains are respectively connected to an electron donor unit (such as a tetraphenylethylene derivative) and an electron acceptor unit (such as dicyanostyrene) through flexible spacer groups, with a molecular weight range of 50,000 - 300,000 g / mol and a glass transition temperature (Tg) > 80 °C;

[0054] To improve the optical contrast, the sensing functional layer may be doped with fluorescent dyes or quantum dots (doping amount 0.01 - 1 wt%) to enhance the luminescence intensity or regulate the color response range;

[0055] The surface of the transparent substrate may be pre-printed with scales or color scales for directly visually quantifying the pressure value;

[0056] The refractive index of the encapsulation layer needs to match that of the sensing functional layer (the difference ≤ 0.05) to reduce the interfacial light scattering loss.

[0057] The visual pressure-sensitive probe prepared by the above method exhibits significant color changes (such as yellow → blue) in the pressure range of 0 - 100 MPa, with the color coordinate (CIE) offset Δx / y ≥ 0.15, which can be clearly distinguished by the naked eye. The specific performance is as follows:

[0058] Sensitivity: The blue shift rate of the wavelength reaches 2.0 - 4.0 nm / kPa, and the color coordinate change rate ΔCIE ≥ 0.03 / kPa;

[0059] Response time: < 10 ms, recovery time < 50 ms;

[0060] Cyclic stability: After 10,000 pressure loading-unloading cycles, the color recovery rate > 98%;

[0061] Environmental adaptability: The color response consistency error < 5% in the range of -20°C to 60°C.

[0062] The pressure-sensitive probe is applicable to fields such as visualization detection of stress distribution in mechanical components, real-time monitoring of medical pressure patches, and indication of the sealing performance of intelligent packaging. It does not require an external circuit or power supply, and directly realizes visual judgment of pressure through color changes.

[0063] The present invention has no special restrictions on the preparation method of the visual pressure-sensitive probe, and can be implemented according to the following steps: directly prepare a sensing functional layer on a transparent flexible substrate, and protect the device integrity through a packaging layer. The sensing functional layer is composed of the polymethacrylate-based space charge transfer polymer luminescent material of the present invention, which induces the spatial separation of the donor-acceptor within the molecule through mechanical stress, triggering a change in the photoluminescence wavelength (or color), thereby realizing visual detection of pressure.

[0064] Formation of the sensing functional layer: Dissolve the polymethacrylate-based space charge transfer polymer luminescent material of the present invention in an organic solvent (such as toluene or chloroform), and form a film on a transparent substrate (such as PET or PDMS) by spin coating, spraying or doctor blading processes, with a thickness of 1 - 10 μm, preferably 2 - 5 μm

[0065] Covering with the packaging layer: Encapsulate the sensing functional layer with a transparent flexible material (such as PDMS or polyurethane), with a thickness of 20 - 100 μm, to isolate environmental interference and maintain mechanical stability.

[0066] The main chain of the polymer luminescent material is PMMA, and the side chains are respectively connected to an electron donor unit (such as a tetraphenylethylene derivative) and an electron acceptor unit (such as dicyanostyrene) through a flexible spacer group. In the stress-free state, the donor and the acceptor form a close packing through the intramolecular charge transfer (ICT) effect, and the emission wavelength is in the long-wave region (such as green or red);

[0067] When an external pressure is applied, the polymer chains deform, the spatial distance between the donor and the acceptor increases, the ICT effect weakens or even disappears, resulting in a blue shift of the emission wavelength (such as turning blue or purple), and the degree of color change is linearly related to the magnitude of the pressure;

[0068] After the pressure is removed, the polymer chains elastically recover, the donor-acceptor spatial distance is restored, and the emission wavelength reversibly returns to the initial state, realizing dynamic pressure sensing.

[0069] The molecular weight range of the polymer material is 50,000 - 300,000 g / mol, and the glass transition temperature (Tg) > 80 °C, ensuring the reversible deformation ability of the film under stress;

[0070] The emission wavelength of the sensing functional layer can be regulated with a blue shift amplitude of 50 - 120 nm in the pressure range of 0 - 100 MPa, and the change in chromaticity coordinates (CIE) Δx / y ≥ 0.15, which can be distinguished by the naked eye;

[0071] The response time < 10 ms, with excellent reversible response, and the cycle stability exceeds 20,000 times of pressure loading - unloading, suitable for high-precision tactile imaging and real-time pressure distribution monitoring.

[0072] For the structure and materials of the pressure-sensitive probe in the above preparation method of the present invention, as well as the corresponding preferred principles, they can be corresponded to the materials and structures, and the corresponding preferred principles in the aforementioned pressure-sensitive probe, which will not be elaborated one by one here.

[0073] The beneficial effects of the present invention are:

[0074] The polymethacrylate-based space charge transfer polymer luminescent material of the present invention adopts a non-conjugated polymethacrylate main chain structure, with electron donors and electron acceptors grafted on the side chains. The fluorescence emission brought by the spatial interaction between the donor and acceptor units has a response characteristic to pressure, realizing pressure monitoring and having excellent reversible response characteristics.

[0075] The polymethacrylate-based space charge transfer polymer luminescent material of the present invention realizes a highly sensitive fluorescence response to mechanical stress by embedding an electron donor (D) and an electron acceptor containing aryl boron (A) into a flexible non-conjugated polymer network through a space charge transfer (TSCT) mechanism. The non-conjugated property and flexibility of the PMMA main chain enable the electron donor-acceptor units to undergo a controllable spatial site displacement under pressure. By adjusting the space charge transfer efficiency between the donor and acceptor, it triggers dynamic changes in the fluorescence wavelength and intensity and has excellent reversible response characteristics. The weak electron-withdrawing property of the aryl boron acceptor not only endows the probe with a blue light emission characteristic of 438 - 475 nm, forming a visual fluorescence signal output, providing a new solution for pressure sensing in fields such as flexible electronic skin, intelligent packaging, and deep-sea monitoring. Brief Description of the Drawings

[0076] In order to more clearly illustrate the technical solutions of the present invention, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings in the following description are only embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on the provided drawings.

[0077] Figure 1 It is the relationship diagram of pressure - maximum emission wavelength of the pressure probe - 1 prepared in Embodiment 1 of the device of the present invention;

[0078] Figure 2 It is the relationship diagram of pressure - wavelength reversible response of the pressure probe - 1 prepared in Embodiment 1 of the device of the present invention;

[0079] Figure 3 It is the relationship diagram of pressure - maximum emission wavelength of the pressure probe - 2 prepared in Embodiment 2 of the device of the present invention;

[0080] Figure 4 It is the relationship diagram of pressure - wavelength reversible response of the pressure probe - 2 prepared in Embodiment 2 of the device of the present invention;

[0081] Figure 5 It is the relationship diagram of pressure - maximum emission wavelength of the pressure probe - 3 prepared in Embodiment 3 of the device of the present invention;

[0082] Figure 6 It is the relationship diagram of pressure - wavelength reversible response of the pressure probe - 3 prepared in Embodiment 3 of the device of the present invention;

[0083] Figure 7 It is the relationship diagram of pressure - maximum emission wavelength of the pressure probe - 4 prepared in Embodiment 4 of the device of the present invention;

[0084] Figure 8 It is the relationship diagram of pressure - wavelength reversible response of the pressure probe - 4 prepared in Embodiment 4 of the device of the present invention;

[0085] Figure 9 It is the relationship diagram of pressure - maximum emission wavelength of the pressure probe - 5 prepared in Embodiment 5 of the device of the present invention;

[0086] Figure 10 It is the relationship diagram of pressure - wavelength reversible response of the pressure probe - 5 prepared in Embodiment 5 of the device of the present invention;

[0087] Figure 11 It is the 1H NMR spectrum of the monomer MD2 prepared in Embodiment 2 of the present invention;

[0088] Figure 12 It is the 1H NMR spectrum of the monomer MA2 prepared in Embodiment 2 of the present invention. Detailed implementation manners

[0089] To further illustrate the present invention, the following provides a detailed description of a polymethacrylate-based space charge transfer polymer light-emitting material, a preparation method and a device according to the present invention in conjunction with embodiments, but it should not be construed as a limitation to the protection scope of the present invention.

[0090] For all raw materials of the present invention, there are no special restrictions on their sources, and they can be purchased on the market or prepared according to conventional methods well-known to those skilled in the art. For all raw materials of the present invention, there are no special restrictions on their purity. The present invention preferably uses analytical pure or the purity conventional in the field of organic electroluminescent materials. In the present invention, those skilled in the art can correctly understand that the two expression forms of formula (*) and formula * have the same meaning, and whether there are parentheses does not affect their actual meaning. For all compounds of the present invention, their structural expressions and abbreviations all belong to the conventional structural expressions and abbreviations in the art, and each structural expression and abbreviation is clear and definite in the field of its related uses. Those skilled in the art can clearly, accurately and uniquely understand according to the structural expression and abbreviation.

[0091] Example 1

[0092] The reaction formula is as follows:

[0093]

[0094] The synthesis route of monomer MD1 is as follows:

[0095]

[0096] Synthesis of MD1: Under an argon atmosphere, 4-diphenylaminophenol (7.5 g, 28.6 mmol), methacryloyl chloride (3.0 g, 29.0 mmol), triethylamine (7.9 g, 78.6 mmol), and dichloromethane (8.5 g, 100.0 mmol) were added to a round-bottom flask and reacted at 10 °C for 6 hours. After the reaction solution was cooled to room temperature, it was extracted with chloroform and washed three times with saturated NaCl aqueous solution. The organic phase was dried and concentrated, and the desired product MD1 5.4 g was obtained by column chromatography separation, with a yield of 51%.

[0097] C 22 H 19 NO 2 Elemental analysis: Calculated values: C, 80.22; H, 5.81; N, 4.25; O, 9.71. Measured values: C, 80.21; H, 5.85; N, 4.22; O, 9.72. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry: Calculated value: 329.14, Measured value: 329.15 [M] + .

[0098] The synthesis route of monomer MA1 is as follows:

[0099]

[0100] Synthesis of MA1: Under an argon atmosphere, 1a (9.9 g, 29.0 mmol), methacryloyl chloride (3.0 g, 29.0 mmol), triethylamine (7.9 g, 78.6 mmol), and dichloromethane (8.5 g, 100.0 mmol) were added to a 50 ml two-necked flask and reacted at 10 °C for 6 hours. After the reaction solution was cooled to room temperature, it was extracted with chloroform and washed three times with saturated NaCl aqueous solution. The organic phase was dried, concentrated, and separated by column chromatography to obtain the desired product MA1, 6.83 g, with a yield of 53%.

[0101] C 28 H 31 BO 2 Elemental analysis: Calculated values: C, 81.95; H, 7.61; B, 2.63; O, 7.80. Measured values: C, 81.96; H, 7.60; B, 2.65; O, 7.81. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry: Calculated value: 410.24, Measured value: 410.25 [M] + 。

[0102] Under an argon atmosphere, MD1 (1.28 mmol), MA1 (0.068 mmol), and azobisisobutyronitrile (AIBN, 0.026 mmol) were weighed into a 10 mL Schlenk flask. 2.5 mL of anhydrous toluene (THF) was added to the flask, and the temperature was raised to 70 °C. The reaction was stirred under argon protection for 24 hours, then quenched suddenly with liquid nitrogen. Hydroquinone as an inhibitor was added, and the reaction solution was poured into acetone. The precipitated solid was filtered, dried in vacuo, dissolved in dichloromethane, precipitated in methanol, and dried in vacuo again to obtain the polymer light-emitting material I-1 with a yield of 70%. The number-average molecular weight of the polymer was 23,600 g / mol, the weight-average molecular weight was 44,600 g / mol, the dispersity (PDI) was 1.89, and the measured values of elemental analysis were: C, 80.29; H, 5.92; N, 4.00; B, 0.18; O, 9.61.

[0103] Example 2

[0104] The reaction formula is as follows:

[0105]

[0106] The synthesis route of monomer MD2 is as follows:

[0107]

[0108] Synthesis of MD2: The synthesis steps are the same as those for the synthesis of MD1 in Example 1.

[0109] C 28 H 21 NO 2 Elemental analysis of S: Theoretical calculation: C, 77.22; H, 4.86; N, 3.22; O, 7.35; S, 7.36. Measured values: C, 77.21; H, 4.85; N, 3.23; O, 7.36; S, 7.35. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry: Calculated value: 435.13, Measured value: 435.14 [M]+; 1 1H NMR is shown in Figure 11 。

[0110] The synthesis route of monomer MA2 is as follows:

[0111]

[0112] Synthesis of monomer MA2: The synthesis steps are the same as those for the synthesis of MA1 in Example 1. Under an argon atmosphere, 2a (8.7 g, 29.0 mmol), methacryloyl chloride (3.0 g, 29.0 mmol), triethylamine (7.9 g, 78.6 mmol), and dichloromethane (8.5 g, 100.0 mmol) were added to a 50 mL two-necked flask and reacted at 10 °C for 6 hours. After the reaction solution was cooled to room temperature, it was extracted with chloroform and washed three times with saturated NaCl aqueous solution. The organic phase was dried, concentrated, and separated by column chromatography to obtain the desired product MA2 7.6 g, with a yield of 65%.

[0113] C 27 H 27 BO 2 Elemental analysis: Theoretical calculation: C, 82.24; H, 6.90; B, 2.74; O, 8.11. Measured values: C, 82.23; H, 6.92; B, 2.73; O, 8.12. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry: Calculated value: 394.21, Measured value: 394.22 [M]+; 1 1H NMR is shown in Figure 12 。

[0114] Under an argon atmosphere, MD2 (1.28 mmol), MA2 (0.068 mmol), and azobisisobutyronitrile (AIBN, 0.026 mmol) were weighed in a 10 mL Schlenk flask. 2.5 mL of anhydrous toluene (THF) was added to the flask, and the temperature was raised to 70 °C. The reaction was stirred under argon protection for 24 hours, then quenched suddenly with liquid nitrogen. Hydroquinone as an inhibitor was added, and the reaction solution was poured into acetone. The precipitated solid was filtered, dried in vacuo, dissolved in dichloromethane, precipitated in methanol, and dried in vacuo again to obtain polymer material I-30 with a yield of 58%. The number-average molecular weight of the polymer was 26,400 g / mol, the weight-average molecular weight was 47,500 g / mol, and the PDI was 1.80. The measured values of elemental analysis were: C, 77.75; H, 4.54; N, 3.10; B, 0.15; O, 7.40; S: 7.05.

[0115] Example 3

[0116] The reaction formula is as follows:

[0117]

[0118] The synthesis route of monomer MD3 is as follows:

[0119]

[0120] Synthesis of MD3: The synthesis steps were the same as those for the synthesis of MD1 in Example 1.

[0121] C 32 H 28 N 2 O 2 Elemental analysis: Theoretical calculation: C, 81.33; H, 5.97; N, 5.93; O, 6.77. Measured values: C, 81.34; H, 5.96; N, 5.94; O, 6.75. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry: Calculated value: 472.22, Measured value: 472.23 [M] + .

[0122] The synthesis route of monomer MA3 is as follows:

[0123]

[0124] Synthesis of MA3: The synthesis steps were the same as those for the synthesis of MA1 in Example 1.

[0125] C 22 H 15 BO 3Analysis of S element: Theoretical calculation: C, 71.37; H, 4.08; B, 2.92; O, 12.96; S, 8.66. Measured value: C, 71.36; H, 4.06; B, 2.94; O, 12.97; S, 8.64. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry: Calculated value: 370.08, Measured value: 370.09 [M] + .

[0126] Under an argon atmosphere, weigh MD3 (1.28 mmol), MA3 (0.068 mmol) and azobisisobutyronitrile (AIBN, 0.026 mmol) in a 10 mL Schlenk flask, add 2.5 mL of anhydrous toluene (THF) to the flask, heat up to 70 °C, stir and react for 24 hours under argon protection, then quickly cool with liquid nitrogen, add the polymerization inhibitor hydroquinone, pour the reaction solution into acetone, filter the precipitated solid, dissolve it in dichloromethane after vacuum drying, precipitate it in methanol, and dry it under vacuum again to obtain the polymer material I-32 with a yield of 58%. The number-average molecular weight of the polymer is 26,300 g / mol, the weight-average molecular weight is 50,500 g / mol, and the dispersity (PDI) is 1.92.

[0127] Example 4

[0128] The reaction formula is as follows:

[0129]

[0130] The synthesis route of MD4 is as follows:

[0131]

[0132] Synthesis of MD4: The synthesis steps are the same as those of MD1 in Example 1.

[0133] C 25 H 23 NO 2 Analysis of elements: Theoretical calculation: C, 81.27; H, 6.28; N, 3.79; O, 8.66. Measured value: C, 81.24; H, 6.29; N, 3.76; O, 8.65. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry: Calculated value: 369.17, Measured value: 369.16 [M] + .

[0134] The synthesis route of monomer MA4 is as follows:

[0135]

[0136] Synthesis of MA4: The synthesis steps are the same as those of MA1 in Example 1.

[0137] C 24 H 21 BO 2 Se elemental analysis: Theoretical calculation: C, 66.85; H, 4.91; B, 2.51; O, 7.42; Se, 18.31. Measured value: C, 66.84; H, 4.92; B, 2.53; O, 7.41; Se, 18.30. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry: Calculated value: 432.08, Measured value: 432.06 [M] + 。

[0138] Under an argon atmosphere, MD4 (1.28 mmol), MA4 (0.068 mmol), and azobisisobutyronitrile (AIBN, 0.026 mmol) were weighed in a 10 mL Schlenk flask. 2.5 mL of anhydrous toluene (THF) was added to the flask, and the temperature was raised to 70 °C. The reaction was stirred for 24 hours under argon protection, then quenched suddenly with liquid nitrogen. Hydroquinone as an inhibitor was added, and the reaction solution was poured into acetone. The precipitated solid was filtered, dried in vacuo, dissolved in dichloromethane, precipitated in methanol, and dried in vacuo again to obtain polymer material I-5 with a yield of 76%. The number-average molecular weight of the polymer was 23,700 g / mol, the weight-average molecular weight was 43,800 g / mol, and the PDI was 1.85.

[0139] Example 5

[0140] The reaction formula is as follows:

[0141]

[0142] The synthesis route of monomer MD5 is as follows:

[0143]

[0144] Synthesis of MD5: The synthesis steps are the same as those of MD1 in Example 1.

[0145] C 28 H 21 NO 3 Elemental analysis: Theoretical calculation: C, 80.17; H, 5.05; N, 3.34; O, 11.44. Measured value: C, 80.15; H, 5.06; N, 3.35; O, 11.43. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry: Calculated value: 419.15, Measured value: 419.15 [M]+.

[0146] The synthesis route of monomer MA5 is as follows:

[0147]

[0148] Synthesis of MA5: The synthesis procedure is the same as that of MA1 in Example 1.

[0149] C 24 H 21 BO 3 Elemental analysis: Theoretical calculation: C, 78.28; H, 5.75; B, 2.94; O, 13.03. Measured value: C, 78.27; H, 5.74; B, 2.95; O, 13.04. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry: Calculated value: 368.16, Measured value: 368.17 [M] + 。

[0150] Under an argon atmosphere, weigh MD5 (1.28 mmol), MA5 (0.068 mmol) and azobisisobutyronitrile (AIBN, 0.026 mmol) in a 10 mL Schlenk flask. Add 2.5 mL of anhydrous toluene (THF) to the flask, heat to 70 °C, and stir the reaction for 24 hours under argon protection. Then, rapidly cool with liquid nitrogen, add the inhibitor hydroquinone, pour the reaction solution into acetone, filter the precipitated solid, dissolve it in dichloromethane after vacuum drying, precipitate it in methanol, and dry it again under vacuum to obtain the polymer material I-36 with a yield of 58%. The number-average molecular weight of the polymer is 25,000 g / mol, the weight-average molecular weight is 50,300 g / mol, and the dispersity (PDI) is 2.01.

[0151] Example 6

[0152] The reaction formula is as follows:

[0153]

[0154] Under an argon atmosphere, weigh MD4 (1.28 mmol), MA2 (0.068 mmol) and azobisisobutyronitrile (AIBN, 0.026 mmol) in a 10 mL Schlenk flask. Add 2.5 mL of anhydrous toluene (THF) to the flask, heat to 70 °C, and stir the reaction for 24 hours under argon protection. Then, rapidly cool with liquid nitrogen, add the inhibitor hydroquinone, pour the reaction solution into acetone, filter the precipitated solid, dissolve it in dichloromethane after vacuum drying, precipitate it in methanol, and dry it again under vacuum to obtain the polymer material I-7 with a yield of 49%. The number-average molecular weight of the polymer is 22,300 g / mol, the weight-average molecular weight is 41,900 g / mol, and the PDI is 1.88.

[0155] Example 7

[0156] The reaction formula is as follows:

[0157]

[0158] The synthetic route of MD6 is as follows:

[0159]

[0160] Synthesis of MD6: The synthesis steps are the same as those of MD1 in Example 1.

[0161] C 25 H 23 NO 2 Elemental analysis: Theoretical calculation: C, 81.27; H, 6.28; N, 3.79; O, 8.66. Measured value: C, 81.24; H, 6.29; N, 3.76; O, 8.65. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry: Calculated value: 369.17, Measured value: 369.15 [M] + .

[0162] The synthetic route of MA6 is as follows:

[0163]

[0164] Synthesis of MA6: The synthesis steps are the same as those of MA1 in Example 1.

[0165] C 28 H 20 BNO 3 Elemental analysis: Theoretical calculation: C, 78.34; H, 4.70; B, 2.52; N, 3.26; O, 11.18. Measured value: C, 78.35; H, 4.71; B, 2.51; N, 3.28; O, 11.17. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry: Calculated value: C 28 H 20 BNO 3 : 429.15, Measured value: 429.16 [M] + .

[0166] Under an argon atmosphere, weigh MD6 (1.28 mmol), MA6 (0.068 mmol) and azobisisobutyronitrile (AIBN, 0.026 mmol) in a 10 mL Schlenk flask, add 2.5 mL of anhydrous toluene (THF) to the flask, heat up to 70 °C, stir and react for 24 hours under argon protection, then quench with liquid nitrogen, add the inhibitor hydroquinone, pour the reaction solution into acetone, filter the precipitated solid, dissolve it in dichloromethane after vacuum drying, precipitate it in methanol, and dry it in vacuum again to obtain the polymer material I-23 with a yield of 49%, the number-average molecular weight of the polymer is 16,300 g / mol, the weight-average molecular weight is 34,600 g / mol, and the dispersity (PDI) is 2.12.

[0167] Example 8

[0168] The reaction formula is as follows:

[0169]

[0170] The synthesis route of MD7 is as follows:

[0171]

[0172] Synthesis of MD7: The synthesis steps are the same as those of MD1 in Example 1.

[0173] C 22 H 17 NO 2 Elemental analysis: Theoretical calculation: C, 80.71; H, 5.23; N, 4.28; O, 9.77. Measured value: C, 80.72; H, 5.24; N, 4.27; O, 9.79. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry: Calculated value: 327.13, Measured value: 327.14 [M] + .

[0174] Under an argon atmosphere, weigh MD7 (1.28 mmol), MA3 (0.068 mmol) and azobisisobutyronitrile (AIBN, 0.026 mmol) in a 10 mL Schlenk flask, add 2.5 mL of anhydrous toluene (THF) to the flask, heat to 70 °C, stir and react for 24 hours under argon protection, then quench with liquid nitrogen, add the polymerization inhibitor hydroquinone, pour the reaction solution into acetone, filter the precipitated solid, dissolve it in dichloromethane after vacuum drying, precipitate it in methanol, and dry it in vacuum again to obtain the polymer material I-9 with a yield of 53%. The number-average molecular weight of the polymer is 17,800 g / mol, the weight-average molecular weight is 36,300 g / mol, and the dispersity (PDI) is 2.04.

[0175] Example 9

[0176] The reaction formula is as follows:

[0177]

[0178] The synthesis route of MD8 is as follows:

[0179]

[0180] Synthesis of MD8: The synthesis steps are the same as those of MD1 in Example 1.

[0181] C 31 H 25 N 3 O2 Elemental analysis: Theoretical calculation: C, 78.96; H, 5.34; N, 8.91; O, 6.79. Measured values: C, 78.95; H, 5.32; N, 8.92; O, 6.78. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry: Calculated value: 471.19, Measured value: 471.18 [M] + .

[0182] The synthetic route of MA7 is as follows:

[0183]

[0184] Synthesis of MA7: The synthesis steps are the same as those of MA1 in Example 1.

[0185] C 22 H 15 BO 3 Elemental analysis of Se: Theoretical calculation: C, 63.35; H, 3.62; B, 2.59; O, 11.51; Se, 18.93. Measured values: C, 63.37; H, 3.65; B, 2.58; O, 11.50; Se, 18.91. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry: Calculated value: 418.03, Measured value: 418.01 [M] + .

[0186] Under an argon atmosphere, weigh MD3 (1.28 mmol), MA9 (0.068 mmol) and azobisisobutyronitrile (AIBN, 0.026 mmol) in a 10 mL Schlenk flask. Add 2.5 mL of anhydrous toluene (THF) to the flask, heat up to 70 °C, stir and react for 24 hours under argon protection, then quickly cool with liquid nitrogen. Add the inhibitor hydroquinone, pour the reaction solution into acetone, filter the precipitated solid, dissolve it in dichloromethane after vacuum drying, precipitate it in methanol, and dry it under vacuum again to obtain the required polymer material I-40 with a yield of 59%. The number-average molecular weight of the polymer is 13,300 g / mol, the weight-average molecular weight is 26,300 g / mol, and the dispersity (PDI) is 1.98.

[0187] Example 10

[0188] The reaction formula is as follows:

[0189]

[0190] The synthetic route of MD9 is as follows:

[0191]

[0192] Synthesis of MD9: The synthesis steps are similar to those of MD1 in Example 1.

[0193] C 62 H 63 N 3 O 2 Elemental analysis: Theoretical calculation: C, 84.41; H, 7.20; N, 4.76; O, 3.63. Measured values: C, 84.42; H, 7.21; N, 4.75; O, 3.65. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry: Calculated value: 881.49, Measured value: 881.52 [M] + 。

[0194] The synthetic route of MA8 is as follows:

[0195]

[0196] Synthesis of MA8: The synthesis steps are the same as those of MA1 in Example 1.

[0197] C 22 H 15 BO 2 S 2 Elemental analysis: Theoretical calculation: C, 68.41; H, 3.91; B, 2.80; O, 8.28; S, 16.60. Measured values: C, 68.43; H, 3.90; B, 2.81; O, 8.26; S, 16.61. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry: Calculated value: 386.06, Measured value: 386.04 [M] + 。

[0198] Under an argon atmosphere, MD9 (1.28 mmol), MA8 (0.068 mmol) and azobisisobutyronitrile (AIBN, 0.026 mmol) were weighed in a 10 mL Schlenk flask. 2.5 mL of anhydrous toluene (THF) was added to the flask, and the temperature was raised to 70 °C. The reaction was stirred for 24 hours under argon protection, then quenched rapidly with liquid nitrogen. Hydroquinone as a polymerization inhibitor was added. The reaction solution was poured into acetone, and the precipitated solid was filtered. After vacuum drying, it was dissolved in dichloromethane and precipitated in methanol, and then vacuum dried again to obtain the polymer material I-41 with a yield of 63%. The number-average molecular weight of the polymer was 23,300 g / mol, the weight-average molecular weight was 44,700 g / mol, and the dispersity (PDI) was 1.92.

[0199] Example 11

[0200] The reaction formula is as follows:

[0201]

[0202] Synthesis of MA9:

[0203]

[0204] Synthesis of MA9: The synthesis steps are the same as those for the synthesis of MA1 in Example 1.

[0205] C 22 H 15 BO 2 Elemental analysis of C, H, B, O, S, and Se: Theoretical calculation: C, 61.00; H, 3.49; B, 2.50; O, 7.39; S, 7.40; Se, 18.23. Measured values: C, 61.05; H, 3.47; B, 2.51; O, 7.38; S, 7.38; Se, 18.22. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry: Calculated value: 434.01, Measured value: 433.99 [M] + .

[0206] Under an argon atmosphere, weigh MD7 (1.28 mmol), MA9 (0.068 mmol), and azobisisobutyronitrile (AIBN, 0.026 mmol) in a 10 mL Schlenk flask. Add 2.5 mL of anhydrous toluene (THF) to the flask, heat to 70 °C, and stir the reaction under argon protection for 24 hours. Then, rapidly cool with liquid nitrogen, add the polymerization inhibitor hydroquinone, pour the reaction solution into acetone, filter the precipitated solid, dissolve it in dichloromethane after vacuum drying, precipitate it in methanol, and dry it under vacuum again to obtain the polymer material with a yield of 65%. The number-average molecular weight of the polymer is 22,900 g / mol, the weight-average molecular weight is 46,900 g / mol, and the dispersity (PDI) is 2.05.

[0207] Example 12

[0208] The reaction formula is as follows:

[0209]

[0210] The synthesis route of MD10 is as follows:

[0211]

[0212] Synthesis of MD10: The synthesis steps are the same as those for the synthesis of MD1 in Example 1.

[0213] C 46 H 37 N 3 O 2Elemental analysis: Theoretical calculation: C, 83.23; H, 5.62; N, 6.33; O, 4.82. Measured value: C, 83.24; H, 5.64; N, 6.32; O, 4.81. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry: Calculated value: 663.29, Measured value: 663.30 [M] + .

[0214] The synthetic route of MA10 is as follows:

[0215]

[0216] Synthesis of MA10: The synthesis steps are the same as those of MA1 in Example 1.

[0217] C 22 H 15 BO 2 Se 2 Elemental analysis: Theoretical calculation: C, 55.04; H, 3.15; B, 2.25; O, 6.66; Se, 32.90. Measured value: C, 55.05; H, 3.16; B, 2.23; O, 6.67; Se, 32.91. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry: Calculated value: 481.95, Measured value: 481.94 [M] + .

[0218] Under an argon atmosphere, weigh MD10 (1.28 mmol), MA10 (0.068 mmol) and azobisisobutyronitrile (AIBN, 0.026 mmol) in a 10 mL Schlenk flask, add 2.5 mL of anhydrous toluene (THF) to the flask, heat to 70 °C, stir and react for 24 hours under argon protection, then quench with liquid nitrogen, add the inhibitor hydroquinone, pour the reaction solution into acetone, filter the precipitated solid, dissolve it in dichloromethane after vacuum drying, precipitate it in methanol, and dry it in vacuum again to obtain the polymer material I-42 with a yield of 70%, the number-average molecular weight of the polymer is 25,800 g / mol, the weight-average molecular weight is 48,700 g / mol, and the dispersity (PDI) is 2.01.

[0219] Example 13

[0220] The reaction formula is as follows:

[0221]

[0222] Synthesis of MD11:

[0223]

[0224] Synthesis of MD11: The synthesis steps are the same as those of MD1 in Example 1.

[0225] C 22 H 17 NO 3 Elemental analysis: Theoretical calculation: C, 76.95; H, 4.99; N, 4.08; O, 13.98. Measured values: C, 76.96; H, 4.97; N, 4.09; O, 13.99. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry: Calculated value: 343.12, Measured value: 343.11 [M] + 。

[0226] Under an argon atmosphere, MD11 (1.28 mmol), MA6 (0.068 mmol), and azobisisobutyronitrile (AIBN, 0.026 mmol) were weighed in a 10 mL Schlenk flask. 2.5 mL of anhydrous toluene (THF) was added to the flask, and the temperature was raised to 70 °C. The reaction was stirred for 24 hours under argon protection, then quenched rapidly with liquid nitrogen. Hydroquinone as an inhibitor was added. The reaction solution was poured into acetone, and the precipitated solid was filtered. After vacuum drying, it was dissolved in dichloromethane and precipitated in methanol, and then dried in vacuum again to obtain polymer material I-14 with a yield of 70%. The number-average molecular weight of the polymer was 19,100 g / mol, the weight-average molecular weight was 38,400 g / mol, and the dispersity (PDI) was 1.98.

[0227] Example 14

[0228] The reaction formula is as follows:

[0229]

[0230] The synthesis route of MA11 is as follows:

[0231]

[0232] Synthesis of MA11: The synthesis steps are the same as those of MA1 in Example 1.

[0233] C 34 H 23 BN 2 O 2 Se Elemental analysis: Theoretical calculation: C, 70.25; H, 3.99; B, 1.86; N, 4.82; O, 5.50; Se, 13.58. Measured values: C, 70.24; H, 3.97; B, 1.88; N, 4.81; O, 5.53; Se, 13.57. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry: Calculated value: 582.10, Measured value: 582.12 [M] + 。

[0234] Under an argon atmosphere, MD11 (1.28 mmol), MA11 (0.068 mmol), and azobisisobutyronitrile (AIBN, 0.026 mmol) were weighed in a 10 mL Schlenk flask. 2.5 mL of anhydrous toluene (THF) was added to the flask, and the temperature was raised to 70 °C. The reaction was stirred for 24 hours under argon protection, then rapidly cooled with liquid nitrogen. Hydroquinone, a polymerization inhibitor, was added. The reaction solution was poured into acetone, and the precipitated solid was filtered. After vacuum drying, it was dissolved in dichloromethane and precipitated in methanol, and then vacuum dried again to obtain polymer material I-15 with a yield of 67%. The number-average molecular weight of the polymer was 27,900 g / mol, the weight-average molecular weight was 49,900 g / mol, and the dispersity (PDI) was 2.10.

[0235] Example 15

[0236] The reaction formula is as follows:

[0237]

[0238] Under an argon atmosphere, MD11 (1.28 mmol), MA1 (0.068 mmol), and azobisisobutyronitrile (AIBN, 0.026 mmol) were weighed in a 10 mL Schlenk flask. 2.5 mL of anhydrous toluene (THF) was added to the flask, and the temperature was raised to 70 °C. The reaction was stirred for 24 hours under argon protection, then rapidly cooled with liquid nitrogen. Hydroquinone, a polymerization inhibitor, was added. The reaction solution was poured into acetone, and the precipitated solid was filtered. After vacuum drying, it was dissolved in dichloromethane and precipitated in methanol, and then vacuum dried again to obtain polymer material I-16 with a yield of 69%. The number-average molecular weight of the polymer was 24,900 g / mol, the weight-average molecular weight was 41,300 g / mol, and the dispersity (PDI) was 2.02.

[0239] Example 16

[0240] The reaction formula is as follows:

[0241]

[0242] The synthesis route of H1 is as follows:

[0243]

[0244] Synthesis of H1: Under an argon atmosphere, pentanol (2.6 g, 29.0 mmol), methacryloyl chloride (3.0 g, 29.0 mmol), triethylamine (7.9 g, 78.6 mmol), and dichloromethane (8.5 g, 100.0 mmol) were added to a 50 mL two-necked flask and reacted at 0 - 20 °C for 6 hours. After the reaction solution was cooled to room temperature, it was extracted with chloroform and washed three times with saturated NaCl aqueous solution. The organic phase was dried and concentrated, and the desired product H1 (3.51 g, yield 63%) was obtained by column chromatography separation;

[0245] C 9 H 16 O 2 Elemental analysis: Theoretical calculation: C, 69.19; H, 10.32; O, 20.48. Measured value: C, 69.17; H, 10.31; O, 20.46. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry: Calculated value: 156.12, Measured value: 156.11 [M] + 。

[0246] Under an argon atmosphere, H1 (2.45 mmol), MD1 (1.28 mmol), MA1 (0.068 mmol), and azobisisobutyronitrile (AIBN, 0.026 mmol) were weighed in a 10 mL Schlenk flask. 2.5 mL of anhydrous toluene (THF) was added to the flask, and the temperature was raised to 70 °C. The reaction was stirred under argon protection for 24 hours, then quenched suddenly with liquid nitrogen. Hydroquinone as a polymerization inhibitor was added. The reaction solution was poured into acetone, and the precipitated solid was filtered. After vacuum drying, it was dissolved in dichloromethane and precipitated in methanol, and then vacuum dried again to obtain the polymer material I-43 with a yield of 55%. The number-average molecular weight of the polymer was 30,200 g / mol, the weight-average molecular weight was 50,900 g / mol, and the dispersity (PDI) was 2.08. Measured values of elemental analysis: C, 75.15; H, 7.92; N, 2.17; B, 0.12; O, 14.64.

[0247] Example 17

[0248] The reaction formula is as follows:

[0249]

[0250] The synthesis route of H2 is as follows:

[0251]

[0252] Synthesis of H2: The synthesis steps are the same as those of H1 in Example 16.

[0253] C 10 H 14 O2 Elemental analysis: Theoretical calculation: C, 72.26; H, 8.49; O, 19.25. Measured values: C, 72.25; H, 8.48; O, 19.24. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry: Calculated value: 166.10, Measured value: 166.11 [M] + 。

[0254] Under an argon atmosphere, in a 10 mL Schlenk flask, weigh H2 (2.45 mmol), MD4 (1.28 mmol), MA4 (0.068 mmol) and azobisisobutyronitrile (AIBN, 0.026 mmol). Add 2.5 mL of anhydrous toluene (THF) to the flask, heat to 70 °C, stir and react for 24 hours under argon protection, then rapidly cool with liquid nitrogen. Add the polymerization inhibitor hydroquinone, pour the reaction solution into acetone, filter the precipitated solid, dissolve it in dichloromethane after vacuum drying, precipitate it in methanol, and dry it under vacuum again to obtain the polymer material I-46 with a yield of 48%. The number-average molecular weight of the polymer is 32,400 g / mol, the weight-average molecular weight is 51,600 g / mol, and the dispersity (PDI) is 2.05.

[0255] Example 18

[0256] The reaction formula is as follows:

[0257]

[0258] Synthesis of H3:

[0259]

[0260] Synthesis of H3: The synthesis procedure is the same as that of H1 in Example 16.

[0261] C 9 H 14 O 2 Elemental analysis: Theoretical calculation: C, 70.10; H, 9.15; O, 20.75. Measured values: C, 70.11; H, 9.14; O, 20.74. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry: Calculated value: 154.10, Measured value: 154.09 [M] + 。

[0262] Under an argon atmosphere, H3 (2.45 mmol), MD7 (1.28 mmol), MA3 (0.068 mmol) and azobisisobutyronitrile (AIBN, 0.026 mmol) were weighed in a 10 mL Schlenk flask. 2.5 mL of anhydrous toluene (THF) was added to the flask, and the temperature was raised to 70 °C. The reaction was stirred under argon protection for 24 hours, then quenched suddenly with liquid nitrogen. Hydroquinone, a polymerization inhibitor, was added. The reaction solution was poured into acetone, and the precipitated solid was filtered. After vacuum drying, it was dissolved in dichloromethane and precipitated in methanol, and then vacuum dried again to obtain the polymer material I-49 with a yield of 64%. The number-average molecular weight of the polymer was 31,200 g / mol, the weight-average molecular weight was 52,800 g / mol, and the dispersity (PDI) was 2.04.

[0263] Example 19

[0264] The reaction formula is as follows:

[0265]

[0266] Synthesis of H4:

[0267]

[0268] Synthesis of H4: The synthesis procedure was the same as that of H1 in Example 16.

[0269] C 10 H 10 O 2 Elemental analysis: Theoretical calculation: C, 74.06; H, 6.22; O, 19.73. Measured value: C, 74.07; H, 6.21; O, 19.72. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry: Calculated value: 162.07, Measured value: 162.06 [M] + .

[0270] Under an argon atmosphere, H4 (2.45 mmol), MD7 (1.28 mmol), MA7 (0.068 mmol) and azobisisobutyronitrile (AIBN, 0.026 mmol) were weighed in a 10 mL Schlenk flask. 2.5 mL of anhydrous toluene (THF) was added to the flask, and the temperature was raised to 70 °C. The reaction was stirred under argon protection for 24 hours, then quenched suddenly with liquid nitrogen. Hydroquinone, a polymerization inhibitor, was added. The reaction solution was poured into acetone, and the precipitated solid was filtered. After vacuum drying, it was dissolved in dichloromethane and precipitated in methanol, and then vacuum dried again to obtain the desired polymer material I-50 with a yield of 51%. The number-average molecular weight of the polymer was 33,300 g / mol, the weight-average molecular weight was 54,500 g / mol, and the dispersity (PDI) was 2.04.

[0271] Example 20

[0272] The reaction formula is as follows:

[0273]

[0274] The synthesis route of H5 is as follows:

[0275]

[0276] Synthesis of H5: The synthesis steps are the same as those of H1 in Example 16.

[0277] C 14 H 12 O 2 Elemental analysis: Theoretical calculation: C, 79.23; H, 5.70; O, 15.08. Measured value: C, 79.24; H, 5.71; O, 15.06. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry: Calculated value: 212.08, Measured value: 212.06 [M] + .

[0278] Under an argon atmosphere, weigh H5 (2.45 mmol), MD7 (1.28 mmol), MA8 (0.068 mmol) and azobisisobutyronitrile (AIBN, 0.026 mmol) in a 10 mL Schlenk flask, add 2.5 mL of anhydrous toluene (THF) to the flask, heat up to 70 °C, stir and react for 24 hours under argon protection, then quench with liquid nitrogen, add the inhibitor hydroquinone, pour the reaction solution into acetone, filter the precipitated solid, dissolve it in dichloromethane after vacuum drying, precipitate it in methanol, and dry it in vacuum again to obtain the polymer material I-51 with a yield of 53%. The number-average molecular weight of the polymer is 29,900 g / mol, the weight-average molecular weight is 48,900 g / mol, and the dispersity (PDI) is 2.01.

[0279] Device Example

[0280] Clean the glass substrate (or flexible polydimethylsiloxane (PDMS) substrate), and treat it with oxygen plasma for 5 minutes to enhance surface adhesion. Using polymethyl methacrylate (PMMA) as the main chain, graft donor (MD1) and acceptor (MA1) units on the side chains, namely the polymethacrylate-based space charge transfer polymer light-emitting material of the present invention, to form spatially separated D / A charge transfer pairs. Dissolve the PMMA-D / A copolymer (the polymethacrylate-based space charge transfer polymer light-emitting material of the present invention) in toluene (5 mg / mL), spin-coat it at 2000 rpm for 60 seconds, and anneal it at 80 °C for 20 minutes to form a light-emitting layer with a thickness of about 50 nm. Spin-coat a polyurethane (PU) elastomer (10 μm, 1000 rpm) as a flexible encapsulation layer, and cure it at 60 °C for 1 hour to protect the light-emitting layer and transfer external pressure.

[0281] The specific device structure is as follows:

[0282] PDMS / PMMA-MD1 / MA1 (50 nm) / PU (10 μm), where PMMA-MD1 / MA1 is the polymer material I-1 prepared in Example 1 of the present invention.

[0283] Device Example 1

[0284] Using the polymer in Example 1 as the implementation object, test the obtained pressure probe.

[0285] Figure 1 and 2 are respectively the relationship diagram between the fluorescence maximum emission spectrum and pressure and the reversible response diagram of pressure-fluorescence maximum emission wavelength of the device (pressure probe) prepared in Device Example 1 of the present invention.

[0286] Refer to Table 1. Table 1 is the data table of the fluorescence maximum emission spectrum and pressure of the pressure probe prepared in Device Example 1 of the present invention.

[0287] Table 1

[0288] Pressure (MPa) 1.1 2.1 5.0 7.2 10.1 13.2 Emission Wavelength (nm) 499.56 500.13 506.67 518.48 514.63 523.25 Pressure (MPa) 19.3 23.1 28.1 34.2 43.5 50.2 Emission Wavelength (nm) 532.46 537.59 538.56 547.59 565.38 570.65

[0289] Device Example 2

[0290] Using the polymer in Example 4 as the implementation object, test the obtained pressure probe.

[0291] Figure 3 and Figure 4 are respectively the relationship diagram between the fluorescence maximum emission spectrum and pressure and the reversible response diagram of pressure-fluorescence maximum emission wavelength of the pressure probe prepared in Device Example 2 of the present invention.

[0292] Refer to Table 2. Table 2 is the data table of the fluorescence maximum emission spectrum and pressure of the pressure probe prepared in Device Example 2 of the present invention.

[0293] Table 2

[0294] Pressure (MPa) 1.2 3.2 5.1 8.5 11.3 14.2 Emission Wavelength (nm) 423.92 418.56 428.63 430.65 447.53 450.12 Pressure (MPa) 18.1 23.5 29.6 36.1 43.2 54.3 Emission Wavelength (nm) 456.32 453.07 456.52 458.68 464.32 465.65 Pressure (MPa) 69.4 81.2 96.3 113.1 130.2 - Emission Wavelength (nm) 469.65 482.16 483.97 489.35 497.53 -

[0295] Device Example 3

[0296] Taking the polymer in Example 6 as the implementation object, the obtained pressure probe was tested.

[0297] Figure 5 and Figure 6 are respectively the relationship diagram between the fluorescence maximum emission spectrum and pressure and the reversible response diagram of pressure-fluorescence maximum emission wavelength of the pressure probe prepared in Device Example 3 of the present invention.

[0298] Referring to Table 3, Table 3 is the data table of the fluorescence maximum emission spectrum and pressure of the pressure probe prepared in Device Example 3 of the present invention.

[0299] Table 3

[0300] Pressure (MPa) 1.2 3.2 6.1 8.3 10.2 12.4 13.5 Emission Wavelength (nm) 432.69 436.63 435.89 438.69 446.89 446.98 447.28 Pressure (MPa) 15.1 22.3 26.1 30.5 36.2 42.3 48.4 Emission Wavelength (nm) 446.58 446.23 447.28 447.23 448.69 450.16 455.36 Pressure (MPa) 60.1 67.2 76.3 88.1 103.2 - - Emission Wavelength (nm) 465.69 467.85 475.92 488.48 502.6 - -

[0301] Device Example 4

[0302] Taking the polymer in Example 16 as the implementation object, the obtained pressure probe was tested.

[0303] Figure 7 and Figure 8 are respectively the relationship diagram between the fluorescence maximum emission spectrum and pressure and the reversible response diagram of pressure-fluorescence maximum emission wavelength of the pressure probe prepared in Device Example 4 of the present invention.

[0304] Referring to Table 4, Table 4 is the data table of the fluorescence maximum emission spectrum and pressure of the pressure probe prepared in Device Example 4 of the present invention.

[0305] Table 4

[0306] Pressure (MPa) 0 1.1 2.5 4.1 6.2 8.3 Emission Wavelength (nm) 472.02 474.36 472.80 474.36 475.91 476.69 Pressure (MPa) 10.2 12.6 14.4 16.4 20.1 23.5 Emission Wavelength (nm) 484.48 484.48 487.59 485.25 493.81 496.14 Pressure (MPa) 26.3 30.4 34.1 37.2 40.5 44.2 Emission Wavelength (nm) 495.61 499.53 504.86 510.23 517.63 520.56 Pressure (MPa) 49.6 54.7 59.2 65.1 70.9 75.8 Emission Wavelength (nm) 521.56 525.64 525.98 536.32 536.46 535.45 Pressure (MPa) 80.2 86.5 94.7 105.4 112.5 121.1 Emission Wavelength (nm) 542.92 549.25 552.16 562.92 562.48 562.98

[0307] Device Example 5

[0308] Taking the polymer in Example 18 as the implementation object, the obtained pressure probe was tested.

[0309] Figure 9 and Figure 10 are respectively the relationship diagram between the fluorescence maximum emission spectrum and pressure and the reversible response diagram of pressure-fluorescence maximum emission wavelength of the pressure probe prepared in Device Example 5 of the present invention.

[0310] Referring to Table 5, Table 5 is the data table of the fluorescence maximum emission spectrum and pressure of the pressure probe prepared in Device Example 5 of the present invention.

[0311] Table 5

[0312] Pressure (MPa) 1.8 2.1 4.2 6.1 8.4 10.2 13.1 Emission Wavelength (nm) 503.13 506.23 517.86 515.53 520.13 522.10 521.73 Pressure (MPa) 16.2 19.1 24.3 28.1 33.2 37.8 41.1 Emission Wavelength (nm) 526.31 534.23 535.80 538.61 542.56 544.31 546.47 Pressure (MPa) 48.2 56.3 64.2 73.1 82.1 96.3 110.2 Emission Wavelength (nm) 551.10 561.89 561.12 574.00 579.58 587.26 596.47

[0313] The 10 sets of experimental data graphs provided by the present invention ( Figures 1 - 10 ) are used to verify the core performance of the pressure probe, where:

[0314] Figures 1 - 10 They are the fluorescence wavelengths of the polymers prepared in Examples 1, 2, 3, 4, and 5 under different applied pressures respectively. It is not difficult to see that their fluorescence emission wavelengths increase with the increase of pressure. As the pressure decreases, their emission wavelengths will gradually decrease accordingly. The pressure change range is 1 atm to 100 MPa, and the fluorescence emission wavelength change range is 466 nm to 650 nm (i.e., the change from blue light to red light). Moreover, the pressure value and the fluorescence emission wavelength have a good linear relationship, and the change is reversible. Therefore, the magnitude of the pressure can be obtained by the change in the emission color, that is, the visual monitoring of the pressure is realized.

[0315] Obviously, the above examples are only for illustration and are not intended to limit the implementation manner. For those of ordinary skill in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation manners here. And the obvious changes or modifications derived therefrom are still within the protection scope of the present invention.

Claims

1. A polymethacrylate space charge transfer polymer luminescent material, characterized in that: It has a structure shown in formula (I) or formula (II): Wherein, x is 0.0001 to 0.9999, y is 0.0001 to 0.9999, z is 0.0001 to 0.9999, and y+z is 0.0001 to 0.9999, and n is an integer between 2 and 9999; D is an electron donor, and A is an electron acceptor containing an arylboron unit; H is independently selected from a C1-C20 straight chain hydrocarbon group, a C3-C20 branched hydrocarbon group, a C3-C20 cycloalkyl group, a C1-C20 alkoxy group, or a C6-C60 aromatic unit, or is a C1-C20 straight chain hydrocarbon group, a C3-C20 branched chain ... branched chain hydrocarbon group, a C3-C20 branched chain hydrocarbon group, a C3-C20 branched chain hydrocarbon group, a C3-C20 branched chain hydrocarbon group, a C3-C20 branched chain hydrocarbon group, a C3-C20 branched chain hydrocarbon group, a C3-C20 branched chain hydrocarbon group, a C3-C20 branched chain hydrocarbon C5-C60 aromatic heterocyclic unit; The D is selected from any one of the structures shown in formula (D-1) to formula (D-31): The A is selected from any one of the structures shown in formula (A-1) to formula (A-16): In the D and A structures, R1, R2, R3, R4, R5 and R6 are each independently selected from H, halogen, -CN, -NO2, -PO(Ph)2, substituted or unsubstituted C1~C22 straight-chain hydrocarbon groups, substituted or unsubstituted C1~C22 branched hydrocarbon groups, substituted or unsubstituted C3~C22 cycloalkyl groups, substituted or unsubstituted C1~C22 alkoxy groups.

2. The polymethacrylate space charge transfer polymer luminescent material according to claim 1, characterized in that: x is 0.01 to 0.20, and n is an integer between 20 and 1000.

3. The polymethacrylate space charge transfer polymer luminescent material according to claim 1, characterized in that: The substitution in R1, R2, R3, R4, R5 and R6 refers to one or more non-adjacent C atoms in C1 to C22 being replaced by O, S, Si or -CO-O-; or also includes one or more hydrogen atoms being replaced by F.

4. The polymethacrylate space charge transfer polymer luminescent material according to claim 1, characterized in that: It is selected from one of the structures represented by formula (I-1) to formula (I-60):

5. A method for preparing the polymethacrylate space charge transfer polymer luminescent material according to claim 1, characterized in that: The following steps are involved: In a protective gas atmosphere, a monomer having a structure represented by formula (X), a monomer having a structure represented by formula (Y), an initiator and an organic solvent are mixed and reacted to obtain a polymethacrylate-based space charge transfer polymer luminescent material; Alternatively: in a protective gas atmosphere, a monomer having a structure represented by formula (X), a monomer having a structure represented by formula (Y), a monomer having a structure represented by formula (Z), an initiator and an organic solvent are mixed and reacted to obtain a polymethacrylate-based space charge transfer polymer luminescent material; 6. The method for preparing the polymethacrylate space charge transfer polymer luminescent material according to claim 5, characterized in that: The molar ratio of the monomer having the structure represented by formula (X) to the monomer having the structure represented by formula (Y) is (0.999 to 0.001):(0.001 to 0.999).

7. The method for preparing the polymethacrylate space charge transfer polymer luminescent material according to claim 5, characterized in that: The initiator is one or more of azobisisobutyronitrile, dibenzoyl peroxide, di-tert-butyl peroxide and tert-butyl perbenzoate.

8. The method for preparing the polymethacrylate space charge transfer polymer luminescent material according to claim 5, characterized in that: The organic solvent is one or more of toluene, xylene, tert-butylbenzene, tetrahydrofuran, dioxane and N,N-dimethylformamide.

9. The method for preparing the polymethacrylate space charge transfer polymer luminescent material according to claim 5, characterized in that: The protective gas is nitrogen and / or inert gas, the reaction temperature is 40-120° C., and the reaction time is 8-72 hours.

10. A pressure monitoring device prepared based on the polymethacrylate space charge transfer polymer luminescent material according to any one of claims 1 to 4, or the polymethacrylate space charge transfer polymer luminescent material prepared by the preparation method according to any one of claims 5 to 9.

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