Space charge transfer polymer luminescent material of polynorbornene skeleton, preparation method and pressure monitoring application

Abstract

The invention relates to a space charge transfer polymer luminescent material of a polynorbornene skeleton, a preparation method and pressure monitoring application. The space charge transfer polymer luminescent material of the polynorbornene skeleton is a fluorescent compound which is based on the polynorbornene polymer skeleton, in which an electron donor and an electron acceptor are spatially separated, and has a space charge transfer effect. A space charge transfer mechanism depends on space separation between an electron donor and an electron acceptor, and the change of external pressure can change the charge transfer intensity between the electron donor and the electron acceptor, so that the wavelength and the intensity of fluorescence are changed. By adjusting the spatial distance and arrangement mode of an electron donor and an electron acceptor, the fluorescent compound can realize response in a larger pressure range and has reversible response behavior, so that the fluorescent compound has application prospects in the fields of intelligent sensing, flexible electronics, health monitoring and the like, and visual and reversible pressure monitoring can be realized.

Description

Technical Field

[0001] The present invention belongs to the technical field of functional polymer materials, and particularly relates to a space charge transfer polymer luminescent material with a norbornene backbone, a preparation method and a pressure monitoring application. Background Art

[0002] In recent years, with the rapid development of fields such as intelligent sensing, flexible electronics and health monitoring, the demand for highly sensitive and visualizable pressure sensing materials has been increasing. Traditional pressure sensors mainly rely on changes in resistance or capacitance signals, but such devices have limitations in spatial resolution, visual feedback and environmental adaptability. Pressure sensing materials based on fluorescence response have become a research hotspot due to advantages such as intuitive optical signals, fast response speed and integratability. However, the design of existing fluorescent pressure probes still faces many challenges. Currently, fluorescent pressure response materials are mainly based on the following two mechanisms: one is the conjugated polymer system, where the mechanical deformation of the conjugated main chain changes the π-π stacking state, resulting in fluorescence quenching or wavelength shift. However, the rigid structure of the conjugated main chain often limits its deformation ability, leading to insufficient response sensitivity and irreversible structural damage under high pressure. The other is the intramolecular charge transfer (ICT) system, which uses a molecular design where an electron donor and an acceptor are connected by a conjugated bridge, and the external stress regulates the electron coupling strength between the donor and the acceptor. However, such materials usually have the problem of a narrow emission wavelength tuning range, and the chemical modification of the conjugated bridge is difficult, limiting its scalability.

[0003] In addition, in the prior art, the design using covalent bonding of an electron donor and an acceptor (such as the D-π-A structure) has a charge transfer process that highly depends on the intramolecular conjugated path, and the ability of mechanical external force to regulate the spatial distance between D / A is limited, resulting in a non-linear response of the pressure-optical signal. At the same time, most fluorescent probes are prone to signal drift or phase separation phenomena under cyclic pressure loading, and the stability urgently needs to be improved. There is an urgent need in this field to develop a new type of pressure-responsive fluorescent probe that needs to have a wide dynamic response range from micro-pressure to high-pressure to achieve tunable monitoring, and at the same time needs to ensure excellent reversibility to ensure stable performance after multiple cycles of use, and its preparation process should be simple and easy to adapt to the requirements of large-scale production and probe integration. Summary of the Invention

[0004] In view of this, the object of the present invention is to provide a space charge transfer (TSCT) polymer luminescent material with a norbornene backbone, a preparation method and a pressure monitoring application. The present invention constructs a non-conjugated main chain structure, grafts an electron donor and an acceptor unit on the side chain respectively, and utilizes the flexibility and conformational adjustability of the polymer chain to realize the dynamic regulation of the spatial distance between the D / A units under external force. The present invention breaks through the limitations of the traditional conjugated system or the covalent bonding structure of the donor and acceptor, and drives the fluorescence wavelength shift through the change of the spatial charge transfer interaction intensity, so as to achieve highly sensitive and wide-range visual pressure monitoring. The present invention provides a new idea for the development of a new generation of intelligent sensing materials and devices.

[0005] In order to achieve the above object, the technical solution of the present invention is as follows:

[0006] A space charge transfer polymer luminescent material with a norbornene backbone has a structure shown in formula (I) or (II):

[0007]

[0008] wherein, x is 0.0001 to 0.9999, and n is an integer between 2 and 9999;

[0009] D is an electron donor, and A is an electron acceptor;

[0010] H is independently selected from a straight-chain hydrocarbon group with 1 to 20 carbon atoms, a branched-chain hydrocarbon group with 3 to 20 carbon atoms, a cycloalkyl group with 3 to 20 carbon atoms, an alkoxy group with 1 to 20 carbon atoms, an aromatic unit with 6 to 60 carbon atoms (including an aromatic fused-ring unit with 6 to 60 carbon atoms), or a heteroaromatic unit with 5 to 60 carbon atoms containing N, O, S, Se, P, B, Si, Ge, of the heteroaromatic unit with 5 to 60 carbon atoms.

[0011] Preferably, the D is selected from any one of the structures shown in formula (D-1) to formula (D-32):

[0012]

[0013] wherein, R 1 、R 2 are each independently selected from H, halogen, -CN, -NO 2 、-PO(Ph) 2 、benzene ring, pyridine, pyrimidine, triazine, a substituted or unsubstituted straight-chain hydrocarbon group with 1 to 22 carbon atoms, a substituted or unsubstituted branched-chain hydrocarbon group with 1 to 22 carbon atoms, a substituted or unsubstituted cycloalkyl group with 3 to 22 carbon atoms or a substituted or unsubstituted alkoxy group with 1 to 22 carbon atoms; R 3 、R 4 、R 5 、R6 Each independently selected from 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, or a substituted or unsubstituted C1-C22 alkoxy group.

[0014] More preferably, the D is selected from any one of the structures represented by formula (d-1) to formula (d-32):

[0015]

[0016] Preferably, the A is selected from any one of the structures represented by formula (A-1) to formula (A-23):

[0017]

[0018]

[0019] wherein, R 1 , R 2 Each independently selected from H, halogen, -CN, -NO 2 , -PO(Ph) 2 , benzene ring, pyridine, pyrimidine, triazine, 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, or a substituted or unsubstituted C1-C22 alkoxy group; R 3 , R 4 , R 5 Each independently selected from 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, or a substituted or unsubstituted C1-C22 alkoxy group.

[0020] Preferably, the A is selected from any one of the structures represented by formula (a-1) to formula (a-86):

[0021]

[0022]

[0023]

[0024] In the structural formulas of D and A in the present invention above, the R 1 , R 2 Each independently preferably selected from H, halogen, -CN, -NO 2 , -PO(Ph) 2, a substituted or unsubstituted C1-C22 straight-chain hydrocarbon group, a substituted or unsubstituted C1-C22 branched-chain hydrocarbon group, a substituted or unsubstituted C3-C22 cycloalkyl group, or a substituted or unsubstituted C1-C22 alkoxy group; more preferably selected from H, halogen, -CN, -NO 2 , -PO(Ph) 2 , a substituted or unsubstituted C2-C20 straight-chain hydrocarbon group, a substituted or unsubstituted C2-C20 branched-chain hydrocarbon group, a substituted or unsubstituted C4-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkoxy group; even more preferably selected from H, halogen, -CN, -NO 2 , -PO(Ph) 2 , a substituted or unsubstituted C3-C18 straight-chain hydrocarbon group, a substituted or unsubstituted C3-C18 branched-chain hydrocarbon group, a substituted or unsubstituted C5-C18 cycloalkyl group, a substituted or unsubstituted C3-C18 alkoxy group; still even more preferably selected from H, halogen, -CN, -NO 2 , -PO(Ph) 2 , a substituted or unsubstituted C5-C15 straight-chain hydrocarbon group, a substituted or unsubstituted C5-C15 branched-chain hydrocarbon group, a substituted or unsubstituted C6-C15 cycloalkyl group, a substituted or unsubstituted C5-C15 alkoxy group; most preferably selected from H, halogen, -CN, -NO 2 , -PO(Ph) 2 , a substituted or unsubstituted C8-C12 straight-chain hydrocarbon group, a substituted or unsubstituted C8-C12 branched-chain hydrocarbon group, a substituted or unsubstituted C8-C12 cycloalkyl group, a substituted or unsubstituted C8-C12 alkoxy group.

[0025] Said R 3 , R 4 , R 5 , R 6Each independently selected from 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; more preferably selected from a substituted or unsubstituted straight-chain C2-C20 hydrocarbon group, a substituted or unsubstituted branched-chain C2-C20 hydrocarbon group, a substituted or unsubstituted C4-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkoxy group; even more preferably selected from a substituted or unsubstituted straight-chain C3-C18 hydrocarbon group, a substituted or unsubstituted branched-chain C3-C18 hydrocarbon group, a substituted or unsubstituted C5-C18 cycloalkyl group, a substituted or unsubstituted C3-C18 alkoxy group; still even more preferably selected from a substituted or unsubstituted straight-chain C5-C15 hydrocarbon group, a substituted or unsubstituted branched-chain C5-C15 hydrocarbon group, a substituted or unsubstituted C6-C15 cycloalkyl group, a substituted or unsubstituted C5-C15 alkoxy group; most preferably selected from a substituted or unsubstituted straight-chain C8-C12 hydrocarbon group, a substituted or unsubstituted branched-chain C8-C12 hydrocarbon group, a substituted or unsubstituted C8-C12 cycloalkyl group, a substituted or unsubstituted C8-C12 alkoxy group.

[0026] 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, -CO-O-. The substitution in the present invention is also preferably that one or more hydrogen atoms can be substituted by F.

[0027] 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 is preferably one or more selected from alkyl, alkenyl, and alkynyl.

[0028] Preferably, the space charge transfer polymer light-emitting material of the polynorbornene backbone is selected from any one of the structures shown in formulas (1)-(90):

[0029]

[0030]

[0031]

[0032]

[0033]

[0034] A method for preparing a space charge transfer polymer light-emitting material with a polynorbornene backbone, comprising the following steps:

[0035] Under a protective atmosphere, an intermediate having the structures shown in formula (X-1), formula (Y-1) and formula (K-1), a catalyst, an aqueous alkaline solution and an organic solvent are mixed, and then a tandem Suzuki coupling reaction is carried out to obtain a space charge transfer polymer light-emitting material with a polynorbornene backbone shown in formula (I);

[0036]

[0037] Under a protective atmosphere, a compound having the structure shown in formula (K-2) is reacted with a compound containing an H group to obtain an intermediate having the structure shown in formula (N-1);

[0038] Compounds having the structures shown in formula (X-1), formula (Y-1) and formula (K-1) are reacted to obtain an intermediate having the structure shown in formula (N-2);

[0039] The intermediates having the structures shown in formula (N-1) and formula (N-2), a catalyst, an aqueous solution of a base and an organic solvent are mixed, and then a Suzuki coupling reaction is carried out to obtain a space charge transfer polymer light-emitting material with a polynorbornene backbone shown in formula (II);

[0040]

[0041] Wherein, x is a halogen atom (x is a halogen atom such as Cl, Br, I, etc.).

[0042] Preferably, in the method for preparing the polymer shown in formula (I), the molar ratio of the intermediate having the structure shown in formula (X-1) to the intermediate having the structure shown in formula (Y-1) is 1.6 to 1.1:1, more preferably 1.15:1;

[0043] In the method for preparing the polymer shown in formula (II), the molar ratio of the intermediate having the structure shown in formula (X-1) to the intermediate having the structure shown in formula (Y-1) is preferably 1:1.1 to 2.0; more preferably 1:1.5;

[0044] In the methods for preparing the polymers shown in formula (I) and formula (II), for the Suzuki coupling reaction, the temperature of the reaction is preferably 50 to 75 °C, more preferably 60 °C; in the method for preparing the polymer shown in formula (I), the reaction time is preferably 12 h to 48 h, more preferably 24 h; in the method for preparing the polymer shown in formula (II), the reaction time is preferably 6 h to 12 h, more preferably 12 h;

[0045] The protective atmosphere is nitrogen and / or inert gas; more preferably nitrogen; the present invention has no special limitation on the source of the protective atmosphere, and commercially available products well-known to those skilled in the art can be used;

[0046] The catalyst is one or more of palladium acetate, bis(triphenylphosphine)palladium dichloride, tris(dibenzylideneacetone)dipalladium, and bis(dibenzylideneacetone)palladium;

[0047] The base is one or more of potassium carbonate, sodium carbonate, sodium bicarbonate, and potassium phosphate; more preferably potassium phosphate;

[0048] The organic solvent is one or more of toluene, xylene, tert-butylbenzene, tetrahydrofuran, dioxane, dichloromethane, and N,N-dimethylformamide; more preferably tetrahydrofuran.

[0049] The present invention has no particular limitation on the sources of the monomers of the structure shown by (X) and the monomers of the structure shown by 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 make selections and adjustments according to the application situation, quality requirements, and product requirements.

[0050] A pressure probe includes a polymer luminescent material; the polymer luminescent material includes the space charge transfer polymer luminescent material with a poly(norbornene) backbone of the present invention or the space charge transfer polymer luminescent material with a poly(norbornene) backbone prepared by the preparation method of the present invention. The above-mentioned space charge transfer polymer luminescent material with a poly(norbornene) backbone of the present invention is preferably used as the luminescent material in the pressure probe.

[0051] The present invention has no particular limitation on the structure of the pressure probe, and a conventional pressure probe well-known to those skilled in the art can be used. Those skilled in the art can make selections and adjustments according to the application situation, quality requirements, and product requirements. The structure of the pressure probe of the present invention preferably includes:

[0052] A base;

[0053] A lower anvil surface disposed on the base;

[0054] A sample chamber disposed on the lower anvil surface, the sample chamber containing at least one pressure probe crystal, and the pressure probe crystal includes one or more of the space charge transfer polymer luminescent materials with a poly(norbornene) backbone of the present invention; the sample chamber is composed of gaskets, and the gaskets are between two parallel and oppositely placed upper anvil surfaces and lower anvil surfaces;

[0055] An upper anvil surface disposed on the sample chamber;

[0056] A sealing material, the sealing material is a metal gasket with a small hole, and is placed between the upper anvil surface and the lower anvil surface.

[0057] The present invention has no particular limitation on the selection of the base, and a base of a conventional pressure probe well-known to those skilled in the art can be used. Those skilled in the art can make selections and adjustments according to application situations, quality requirements, and product requirements. The substrate of the present invention is preferably a metal, plastic, or elastomer. The thickness of the substrate is preferably 1 to 2 cm, more preferably 1.3 to 1.7 cm.

[0058] According to the present invention, the lower anvil surface is made of a material with high strength and hardness, further preferably materials such as sapphire, high-strength steel, WC cemented carbide, single-crystal diamond, etc.; more preferably single-crystal diamond. The thickness of the lower anvil surface is preferably 2.0 mm to 2.6 mm.

[0059] The sample cavity is composed of gaskets, and the gaskets are made of materials such as beryllium copper, cemented carbide, and cubic boron nitride; one or more space charge transfer polymer luminescent materials with a poly(norbornene) backbone of the present invention are included in the sample cavity. Preferably in the present invention, the space charge transfer polymer luminescent material with a poly(norbornene) backbone participates in forming the pressure probe as a luminescent material.

[0060] The upper anvil surface is preferably made of materials such as sapphire, high-strength steel, WC cemented carbide, single-crystal diamond, etc., more preferably diamond; the thickness of the upper anvil surface is preferably 2.0 mm to 2.6 mm.

[0061] The sealing material is a metal gasket with a small hole; the metal gasket is made of copper sheet, T301, steel sheet, rhenium sheet, etc.; more preferably a steel sheet.

[0062] The present invention has no special limitation on the preparation method of the pressure probe device, and it can be carried out according to the following method:

[0063] Install the lower anvil surface on the base;

[0064] Install a gasket on the lower anvil surface to form a sample cavity, and a pressure probe crystal is included in the sample cavity; the pressure probe crystal includes one or more space charge transfer polymer luminescent materials with a poly(norbornene) backbone of the present invention;

[0065] Install the sealing material on the gasket;

[0066] Install the upper anvil surface on the sample cavity;

[0067] During the preparation of the pressure probe, first install the lower anvil surface on the base; the present invention has no special limitation on the formation method of the lower anvil surface, and it can be carried out according to the method well-known to those skilled in the art.

[0068] After obtaining the lower anvil surface, a sample cavity is formed on the lower anvil surface; the present invention has no special restrictions on the formation method of the sample cavity and the gasket used, and it can be carried out according to the methods well-known to those skilled in the art.

[0069] After the sample cavity is prepared, a sealing material is prepared on its surface; the present invention has no special restrictions on the formation method of the sealing material, and it is preferably a method well-known to those skilled in the art.

[0070] After obtaining the sealing material, an upper anvil surface is formed on the sample cavity; the present invention has no special restrictions on the formation method of the lower anvil surface, and it can be carried out according to the methods well-known to those skilled in the art.

[0071] The present invention can correspond the structure and material of the pressure probe in the above preparation method, as well as the corresponding preferred principles, to the corresponding materials and structures in the foregoing pressure probe, and the corresponding preferred principles, and will not be elaborated herein one by one.

[0072] The present invention first installs the lower anvil surface on the base. The present invention has no special restrictions on the formation method of the lower anvil surface, and it can be carried out according to the methods well-known to those skilled in the art. The present invention has no special restrictions on the formation methods of the sample cavity and the gasket, and it can be carried out according to the methods well-known to those skilled in the art. After the sample cavity is formed, a sealing layer can also be formed on its surface by adding a sealing material. After the sample cavity of the present invention is prepared, an upper anvil surface is prepared above it. The present invention has no special restrictions on the formation method of the upper anvil surface, and it is preferably a method well-known to those skilled in the art.

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

[0074] The space charge transfer polymer luminescent material with a polynorbornene backbone of the present invention is a class of fluorescent compounds based on a polynorbornene derivative backbone, with spatially separated electron donors and acceptors, and having a space charge transfer (Thought-space charge transfer, TSCT) effect. The space charge transfer mechanism depends on the spatial separation between the electron donor and the acceptor, and changes in the external environment will significantly affect the charge transfer intensity, thereby resulting in significant changes in the fluorescence wavelength and intensity. By adjusting the spatial distance, relative orientation, and molecular structure of the electron donor and the acceptor, the TSCT fluorescent compound can achieve a wide range of fluorescence emissions (for example: blue - red fluorescence emission), a large pressure range response (1 atm to 11 GPa), and has a reversible fluorescence response behavior. This characteristic gives it unique advantages in the fields of intelligent sensing, flexible electronics, and health monitoring, and can achieve a fluorescence response behavior of visualization and reversibility monitoring.

[0075] The spatial charge transfer polymer light-emitting material with a polynorbornene backbone of the present invention constructs a non-conjugated main chain structure, grafts an electron donor and an acceptor unit on the side chain respectively, and utilizes the flexibility and conformational tunability of the polymer chain to realize the dynamic regulation of the spatial distance between the D / A units under the action of external force. The present invention breaks through the limitations of the traditional conjugated system or the covalent bonding structure of the donor and the acceptor, and drives the fluorescence wavelength shift through the change of the spatial charge transfer interaction intensity, thereby achieving highly sensitive and wide-range visual pressure monitoring. The present invention provides a new idea for the development of a new generation of intelligent sensing materials.

[0076] The spatial charge transfer polymer light-emitting material with a polynorbornene backbone of the present invention is a type of TADF small molecule compound with non-conjugated D-A connection and spatial charge transfer effect. Compared with the conventional intramolecular charge transfer conjugated fluorescent polymer, it has great potential in the polymer fluorescence pressure probe. The spatial charge transfer mechanism depends on the spatial separation between the electron donor and the acceptor. By adjusting the spatial distance between the electron donor and the acceptor, the TSCT fluorescent compound can achieve a wide range of fluorescence emission, a large pressure range response, and a reversible fluorescence response behavior. The method for synthesizing the above small molecule compound provided by the present invention prepares a bis-substituted polynorbornene luminescent monomer through a tandem Suzuki coupling-norbornadiene insertion reaction of the donor and the boronated acceptor, obtains a small molecule compound, and applies it to the sample cavity in the pressure probe, and can obtain ideal effects and meet the requirements for preparing the pressure probe crystal by solution processing.

[0077] The experimental results show that the small molecule compounds prepared by the present invention all exhibit a wide range of fluorescence emission (for example: blue light - red light fluorescence emission), a large pressure range response (1 atm to 11 GPa), and a linear reversible fluorescence behavior, so that an efficient polymer fluorescence pressure probe can be prepared. Description of the Drawings

[0078] The present invention will be further described in detail below in conjunction with the drawings and specific embodiments.

[0079] Figure 1 It is a diagram showing the relationship between the maximum fluorescence emission spectrum and pressure of the pressure probe prepared in Device Example 1 of the present invention, wherein (a) is a diagram showing the relationship between the pressure value and the maximum fluorescence emission wavelength during the pressurization process; (b) is a diagram showing the relationship between the pressure value and the maximum fluorescence emission wavelength during the depressurization process.

[0080] Figure 2 It is a diagram showing the relationship between the maximum fluorescence emission spectrum and pressure of the pressure probe prepared in Device Example 2 of the present invention, wherein (a) is a diagram showing the relationship between the pressure value and the maximum fluorescence emission wavelength during the pressurization process; (b) is a diagram showing the relationship between the pressure value and the maximum fluorescence emission wavelength during the depressurization process.

[0081] Figure 3 Relationship diagram between the maximum fluorescence emission spectrum of the pressure probe prepared in Example 3 of the device of the present invention and pressure, where (a) is the relationship diagram between the pressure value and the maximum fluorescence emission wavelength during the pressurization process; (b) is the relationship diagram between the pressure value and the maximum fluorescence emission wavelength during the depressurization process.

[0082] Figure 4 Relationship diagram between the maximum fluorescence emission spectrum of the pressure probe prepared in Example 4 of the device of the present invention and pressure, where (a) is the relationship diagram between the pressure value and the maximum fluorescence emission wavelength during the pressurization process; (b) is the relationship diagram between the pressure value and the maximum fluorescence emission wavelength during the depressurization process.

[0083] Figure 5 1H NMR spectrum of monomer NB-1.

[0084] Figure 6 1H NMR spectrum of monomer NB-8. Detailed implementation manners

[0085] To further understand the present invention, the preferred implementation manners of the present invention will be described below in conjunction with embodiments. However, it should be understood that these descriptions are only for further explaining the features and advantages of the present invention, rather than limiting the claims of the present invention.

[0086] There is no particular limitation on the sources of all raw materials of the present invention, and they can be purchased on the market or prepared by conventional methods well-known to those skilled in the art.

[0087] There is no particular limitation on the purity of all raw materials of the present invention. The present invention preferably uses analytically pure or the purity conventional in the field of pressure probe materials.

[0088] 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 the presence or absence of parentheses does not affect their actual meaning.

[0089] For all compounds of the present invention, their structural expressions and abbreviations belong to the conventional structural expressions and abbreviations in the field. 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.

[0090] To further illustrate the present invention, a space charge transfer (TSCT) polymer light-emitting material with a norbornene backbone, its preparation method, and a pressure probe provided by the present invention will be described in detail below in conjunction with embodiments. However, it should be understood that these embodiments are implemented on the premise of the technical solution of the present invention, and the detailed implementation manners and specific operation processes are given. They are only for further explaining the features and advantages of the present invention, rather than limiting the claims of the present invention. The protection scope of the present invention is not limited to the following embodiments either.

[0091] The present invention is based on benzobicyclonene as the backbone. First, several bis-substituted luminescent monomers were synthesized, in which the acceptor and the donor are conjugated and connected at the 6,7-positions of the backbone. The charge transfer between the donor and the acceptor can be achieved through the aryl linking unit and the spatial π-π interaction. Donor units with different electron-donating abilities are beneficial to regulating the intensity of the charge transfer effect and the luminescence color. At the same time, the large steric hindrance of the acceptor is beneficial to locking the conformations of the donor and the acceptor and inhibiting non-radiative transitions. Two types of space charge transfer polymers were synthesized by the living ring-opening metathesis polymerization (ROMP) method. One type is a homopolymer containing only the bis-substituted norbornene luminescent monomer, which is used as a reference polymer to study the dual CT effect including space charge transfer and chemical bond charge transfer. The other type is a copolymer, which is composed of the bis-substituted norbornene luminescent monomer and the mono-substituted benzobicyclonene monomer containing only the donor unit.

[0092] The norbornene monomer is initiated by the Grubbs second-generation catalyst (phenylmethylene-[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolinyl]-dichloro-(tricyclohexylphosphine) ruthenium), and the target poly(norbornene) homopolymer and copolymer are obtained by the living ring-opening metathesis polymerization (ROMP) method.

[0093] Synthesis of 6,7-dibromo-1,4-dihydro-1,4-methano-naphthalene (1):

[0094]

[0095] 1,2,4,5-Tetrabromobenzene (1, 20.0 g, 50.8 mmol), freshly prepared cyclopentadiene (5.9 g, 7.3 mL, 50.8 mmol) and anhydrous toluene (800 mL) were added to a dry 2000 mL two-necked reaction flask. The reaction atmosphere was replaced with argon and the temperature was lowered to 0 °C. Under mechanical stirring, the n-butyllithium solution (22.4 mL, 2.5 M, 55.9 mmol) was added dropwise to the reaction system through a constant pressure dropping funnel. Then, after stirring at 0 °C for 2 hours, the reaction was continued at room temperature for 4 hours. 10 mL of methanol was added to the reaction system to quench the residual active lithium compounds, and then 1000 mL of saturated brine solution was added for washing three times. The toluene phase was dried, the solvent was evaporated under reduced pressure, and purified by silica gel column chromatography (eluent: petroleum ether) to obtain 8.7 g of a colorless oily liquid, which became a waxy white solid after standing for a long time, and the yield was 57%. Note that cyclopentadiene is prone to self-polymerize to form a dimer at room temperature. Therefore, the commercially purchased cyclopentadiene raw material needs to be purified by atmospheric distillation before use and stored in a -17 °C refrigerator. C 11 H 8 Br 2Elemental analysis (%) : C, 44.2; H, 2.6; Br, 53.2. Mass spectrometry (MALDI-TOF) shows a molecular weight of 461.0.

[0096] Example 1

[0097]

[0098] Add D1 (9.2 g, 25.0 mmol), 1 (15.0 g, 50.0 mmol), cuprous oxide (0.73 g, 5.0 mmol), potassium phosphate (15.9 g, 75.0 mmol), N,N'-dimethylethylenediamine (1.1 mL, 10.0 mmol) and anhydrous m-xylene (80 mL) into a 250 mL two-necked reaction flask. Replace the reaction atmosphere with argon and heat to 130 °C, then stir for 48 hours. After the reaction returns to room temperature, add 200 mL of saturated ammonium chloride aqueous solution for washing, and extract the crude product with 200 mL of chloroform. The organic phase is dried, the solvent is evaporated under reduced pressure, and purified by silica gel column chromatography (eluent: petroleum ether) to obtain 7.0 g of white solid, and the calculated yield is 61%. C 29 H 20 Elemental analysis (%) : C, 75.3; H, 4.3; Br, 17.2; N, 3.2. Mass spectrometry (MALDI-TOF) shows a molecular weight of 462.3.

[0099] Add 2 (4.2 g, 9.1 mmol) and anhydrous tetrahydrofuran (70 mL) into a pre-dried 250 mL two-necked reaction flask. Replace the reaction atmosphere with argon and cool to -78 °C. Add n-butyllithium solution (4.0 mL, 2.5 M, 10.0 mmol) dropwise to the reaction system by syringe, and then stir at -78 °C for 1.5 hours. Dissolve A1 (7.9 g, 18.2 mmol) in 20 mL of anhydrous THF, add it to the above reaction system at 0 °C under an argon atmosphere, and then react at room temperature for 8 hours. Add 5 mL of methanol to the reaction system to quench the remaining active lithium compounds, then add 100 mL of saturated brine solution for washing three times, and extract the crude product with 100 mL of ether. The organic phase is dried, the solvent is evaporated under reduced pressure, and purified by silica gel column chromatography (eluent: petroleum ether / dichloromethane = 20 / 1, volume ratio), and cooled and crystallized in a mixed solvent of n-hexane / dichloromethane / methanol at 50 °C to obtain 3.9 g of pale yellow crystals, and the calculated yield is 62%. C 50 H 34 N 4 Elemental analysis (%) : C, 86.9; H, 4.9; N, 8.2. Mass spectrometry (MALDI-TOF) shows a molecular weight of 690.8. See the NMR spectrum of monomer NB-1 in Figure 5 .

[0100] The monomer feed was NB-1 (690.8 mg, 1.00 mmol). A white fibrous polymer (379 mg) was obtained by ROMP polymerization with a yield of 55%. The preparation process was as follows: Under an argon atmosphere, the polymerization monomer NB-1 (total amount of substance 1.0 mmol) was dissolved in anhydrous THF with a concentration of 20 mg / mL. Then, the Grubbs catalyst (0.004 mmol / 2 mL) dissolved in THF was rapidly added to the reaction system through a glass syringe to initiate the polymerization, and the reaction was carried out at 25 °C under dark conditions for 1 hour. Then, the vinyl ethyl ether terminator (0.3 mL) was added through a syringe to terminate the polymerization. The reactant was precipitated in acetone (200 mL), and the polymer was filtered, dried and then dissolved in CH 2 Cl 2 (100 mL). H 2 O 2 (10 wt% aqueous solution, 75 mL) was added to the above solution and stirred under dark conditions at room temperature for 1 hour. The organic phase was dried over anhydrous Na 2 SO 4 , concentrated under reduced pressure, and then the catalyst was removed by silica gel column chromatography. The eluate was concentrated and precipitated in methanol (200 mL), and after filtration and vacuum drying, the target polymer was obtained. Elemental analysis (%) of PNB-1: C, 86.8; H, 6.7; N, 6.6. The number-average molecular weight of the polymer was 25,400 g / mol, and the weight-average molecular weight was 45,500 g / mol.

[0101] Example 2

[0102]

[0103] D2 (10.2 g, 25.0 mmol), 1 (15.0 g, 50.0 mmol), copper(I) oxide (0.73 g, 5.0 mmol), potassium phosphate (15.9 g, 75.0 mmol), N,N'-dimethylethylenediamine (1.1 mL, 10.0 mmol) and anhydrous m-xylene (80 mL) were added to a 250 mL two-necked reaction flask. The reaction atmosphere was replaced with an argon environment and heated to 130 °C and stirred for 48 hours. After the reaction returned to room temperature, 250 mL of saturated ammonium chloride aqueous solution was added for washing, and the crude product was extracted with 200 mL of chloroform. The organic phase was dried, the solvent was evaporated under reduced pressure, and purified by silica gel column chromatography (eluent: petroleum ether) to obtain 7.5 g of a white solid. The calculated yield was 60%. C 32 H 26 BrN elemental analysis (%): C, 76.2; H, 5.1; Br, 15.8; N, 2.9. Mass spectrometry (MALDI-TOF) showed that its molecular weight was 503.4.

[0104] 3 (4.6 g, 9.1 mmol) and anhydrous tetrahydrofuran (70 mL) were added to a pre-dried 250 mL two-neck reaction flask. The reaction atmosphere was replaced with an argon environment and cooled to -78 °C. A solution of n-butyllithium (4.0 mL, 2.5 M, 10.0 mmol) was added dropwise to the reaction system via a syringe, and then stirred at -78 °C for 1.5 h. A2 (7.9 g, 18.2 mmol) was dissolved in 20 mL of anhydrous THF and added to the above reaction system at 0 °C under an argon atmosphere, and then the reaction was allowed to resume at room temperature for 10 h. 5 mL of methanol was added to the reaction system to quench the remaining active lithium compounds, and then washed three times with 100 mL of saturated saline solution. The crude product was extracted with 100 mL of diethyl ether. The organic phase was dried, the solvent was evaporated under reduced pressure, and purified by silica gel column chromatography (eluent: petroleum ether / dichloromethane = 20 / 1, v / v), and cooled and crystallized in a mixed solvent of n-hexane / dichloromethane / methanol at 50 °C to obtain 4.3 g of pale yellow crystals, and the calculated yield was 65%. C 54 H 41 N 3 Elemental analysis (%) : C, 86.9; H, 5.6; N, 7.5. Mass spectrometry (MALDI-TOF) showed a molecular weight of 732.6.

[0105] The monomer feed was NB-2 (732.9 mg, 1.00 mmol), and a white fibrous polymer (381.1 mg) was obtained by ROMP polymerization with a yield of 52%. The synthesis procedure was the same as that of PNB-1 in Example 1. Elemental analysis (%) of PNB-2: C, 89.2; H, 6.4; N, 4.4. The number-average molecular weight of the polymer was 24,400 g / mol, and the weight-average molecular weight was 44,500 g / mol.

[0106] Example 3

[0107]

[0108] D3 (20.6 g, 25.0 mmol), 1 (15.0 g, 50.0 mmol), copper(I) oxide (0.73 g, 5.0 mmol), potassium phosphate (15.9 g, 75.0 mmol), N,N'-dimethylethylenediamine (1.1 mL, 10.0 mmol) and anhydrous m-xylene (80 mL) were added to a 250 mL two-neck reaction flask. The reaction atmosphere was replaced with an argon environment and heated to 130 °C and stirred for 48 h. After the reaction returned to room temperature, it was washed with 250 mL of saturated ammonium chloride aqueous solution, and the crude product was extracted with 200 mL of chloroform. The organic phase was dried, the solvent was evaporated under reduced pressure, and purified by silica gel column chromatography (eluent: petroleum ether) to obtain 13.5 g of white solid, and the calculated yield was 59%. C 62H 52 BrN 3 Elemental analysis (%) : C, 81.1; H, 5.8; Br, 8.7; N, 4.4. Mass spectrometry (MALDI-TOF) shows a molecular weight of 919.2.

[0109] 4 (8.36 g, 9.1 mmol) and anhydrous tetrahydrofuran (70 mL) were added to a pre-dried 250 mL two-neck reaction flask. The reaction atmosphere was replaced with an argon environment and cooled to -78 °C. A solution of n-butyllithium (4.0 mL, 2.5 M, 10.0 mmol) was added dropwise to the reaction system via a syringe, and then stirred at -78 °C for 1.5 hours. A3 (7.9 g, 18.2 mmol) was dissolved in 20 mL of anhydrous THF and added to the above reaction system at 0 °C under an argon atmosphere, and then the reaction was allowed to resume at room temperature for 10 hours. 5 mL of methanol was added to the reaction system to quench the remaining active lithium compounds, and then the mixture was washed three times with 100 mL of saturated saline solution. The crude product was extracted with 100 mL of diethyl ether. The organic phase was dried, the solvent was evaporated under reduced pressure, and purified by silica gel column chromatography (eluent: petroleum ether / dichloromethane = 20 / 1, volume ratio), and cooled and crystallized in a mixed solvent of n-hexane / dichloromethane / methanol at 50 °C to obtain 6.4 g of pale yellow crystals, and the calculated yield was 62%. C 87 H 68 N 6 Elemental analysis (%) : C, 86.8; H, 5.7; N, 7.5. Mass spectrometry (MALDI-TOF) shows a molecular weight of 1147.4.

[0110] The monomer feed was NB-3 (1147.4 mg, 1.00 mmol), and a white fibrous polymer (516.3 mg) was obtained by ROMP polymerization. Yield: 45%. The synthesis procedure was the same as that of PNB-1 in Example 1.

[0111] Example 4

[0112]

[0113] D4 (11.2 g, 25 mmol), 1 (15.0 g, 50.0 mmol), cuprous oxide (0.73 g, 5.0 mmol), potassium phosphate (15.9 g, 75.0 mmol), N,N'-dimethylethylenediamine (1.1 mL, 10.0 mmol) and anhydrous m-xylene (80 mL) were added to a 250 mL two-necked reaction flask. The reaction atmosphere was replaced with an argon environment and the temperature was raised to 130 °C and stirred for 48 hours. After the reaction returned to room temperature, 250 mL of saturated ammonium chloride aqueous solution was added for washing, and the crude product was extracted with 200 mL of chloroform. The organic phase was dried, the solvent was evaporated under reduced pressure, and purified by silica gel column chromatography (eluent: petroleum ether) to obtain 7.9 g of a white solid, and the calculated yield was 58%. C 35 H 30 Elemental analysis (%) of C, H, Br, N: C, 77.3; H, 5.4; Br, 14.6; N, 2.7. Mass spectrometry (MALDI-TOF) showed that its molecular weight was 544.1.

[0114] 5 (4.9 g, 9.1 mmol) and anhydrous tetrahydrofuran (70 mL) were added to a pre-dried 250 mL two-necked reaction flask. The reaction atmosphere was replaced with an argon environment and the temperature was lowered to -78 °C. n-Butyllithium solution (4.0 mL, 2.5 M, 10.0 mmol) was added dropwise to the reaction system via a syringe, and then stirred at -78 °C for 1.5 hours. A4 (7.9 g, 18.2 mmol) was dissolved in 20 mL of anhydrous THF and added to the above reaction system at 0 °C under an argon atmosphere, and then the reaction was allowed to return to room temperature for 10 hours. 5 mL of methanol was added to the reaction system to quench the remaining active lithium compounds, and then washed three times with 100 mL of saturated saline solution. The crude product was extracted with 100 mL of diethyl ether. The organic phase was dried, the solvent was evaporated under reduced pressure, and purified by silica gel column chromatography (eluent: petroleum ether / dichloromethane = 20 / 1, volume ratio), and cooled and crystallized in a mixed solvent of n-hexane / dichloromethane / methanol at 50 °C to obtain 4.2 g of a pale yellow crystal, and the calculated yield was 60%. C 56 H 50 N 4 Elemental analysis (%): C, 87.0; H, 5.6; N, 7.4. Mass spectrometry (MALDI-TOF) showed that its molecular weight was 773.0.

[0115] The monomer feed was NB-4 (773.0 mg, 1.00 mmol), and a white fibrous polymer (448.3 mg) was obtained by ROMP polymerization. Yield: 58%. The synthesis procedure was the same as that of PNB-1 in Example 1.

[0116] Example 5

[0117]

[0118] D5 (12.2 g, 25 mmol), 1 (15.0 g, 50.0 mmol), cuprous oxide (0.73 g, 5.0 mmol), potassium phosphate (15.9 g, 75.0 mmol), N,N'-dimethylethylenediamine (1.1 mL, 10.0 mmol) and anhydrous m-xylene (80 mL) were added to a 250 mL two-necked reaction flask. The reaction atmosphere was replaced with an argon environment and the temperature was raised to 130 °C and stirred for 48 hours. After the reaction returned to room temperature, 250 mL of saturated ammonium chloride aqueous solution was added for washing, and the crude product was extracted with 200 mL of chloroform. The organic phase was dried, the solvent was evaporated under reduced pressure, and purified by silica gel column chromatography (eluent: petroleum ether) to obtain 9.6 g of a white solid, and the calculated yield was 66%. C 38 H 34 Elemental analysis (%) of C, H, Br, N: C, 78.0; H, 5.9; Br, 13.6; N, 2.5. Mass spectrometry (MALDI-TOF) showed that its molecular weight was 584.6.

[0119] 6 (5.3 g, 9.1 mmol) and anhydrous tetrahydrofuran (70 mL) were added to a pre-dried 250 mL two-necked reaction flask. The reaction atmosphere was replaced with an argon environment and the temperature was lowered to -78 °C. The n-butyllithium solution (4.0 mL, 2.5 M, 10.0 mmol) was added dropwise to the reaction system via a syringe, and then stirred at -78 °C for 1.5 hours. A1 (7.9 g, 18.2 mmol) was dissolved in 20 mL of anhydrous THF and added to the above reaction system at 0 °C under an argon atmosphere, and then the reaction was allowed to return to room temperature for 10 hours. 5 mL of methanol was added to the reaction system to quench the remaining active lithium compounds, and then 100 mL of saturated saline solution was added for washing three times. The crude product was extracted with 100 mL of ether. The organic phase was dried, the solvent was evaporated under reduced pressure, and purified by silica gel column chromatography (eluent: petroleum ether / dichloromethane = 20 / 1, volume ratio), and cooled and crystallized in a mixed solvent of n-hexane / dichloromethane / methanol at 50 °C to obtain 5.0 g of white crystals, and the calculated yield was 68%. C 59 H 48 N 4 Elemental analysis (%): C, 87.0; H, 5.8; N, 6.2. Mass spectrometry (MALDI-TOF) showed that its molecular weight was 813.0.

[0120] The monomer feed was NB-5 (813.0 mg, 1.00 mmol), and a white fibrous polymer (463.4 mg) was obtained by ROMP polymerization. Yield: 57%. The synthesis procedure was the same as that of PNB-1 in Example 1.

[0121] Example 6

[0122]

[0123] D6 (13.3 g, 25 mmol), 1 (15.0 g, 50.0 mmol), cuprous oxide (0.73 g, 5.0 mmol), potassium phosphate (15.9 g, 75.0 mmol), N,N'-dimethylethylenediamine (1.1 mL, 10.0 mmol) and anhydrous m-xylene (80 mL) were added to a 250 mL two-necked reaction flask. The reaction atmosphere was replaced with an argon environment and the temperature was raised to 130 °C and stirred for 48 hours. After the reaction returned to room temperature, 250 mL of saturated ammonium chloride aqueous solution was added for washing, and the crude product was extracted with 200 mL of chloroform. The organic phase was dried, the solvent was evaporated under reduced pressure, and purified by silica gel column chromatography (eluent: petroleum ether) to obtain 8.9 g of a white solid, and the calculated yield was 57%. C 42 H 28 Elemental analysis (%) of C, H, Br, N: C, 80.6; H, 4.4; Br, 12.8; N, 2.2. Mass spectrometry (MALDI-TOF) showed that its molecular weight was 626.6.

[0124] 7 (5.7 g, 9.1 mmol) and anhydrous tetrahydrofuran (70 mL) were added to a pre-dried 250 mL two-necked reaction flask. The reaction atmosphere was replaced with an argon environment and the temperature was lowered to -78 °C. The n-butyllithium solution (4.0 mL, 2.5 M, 10.0 mmol) was added dropwise to the reaction system by syringe, and then stirred at -78 °C for 1.5 hours. A5 (7.9 g, 18.2 mmol) was dissolved in 20 mL of anhydrous THF and added to the above reaction system at 0 °C under an argon atmosphere, and then the reaction was allowed to return to room temperature for 10 hours. 5 mL of methanol was added to the reaction system to quench the residual active lithium compound, and then washed three times with 100 mL of saturated saline solution. The crude product was extracted with 100 mL of ether. The organic phase was dried, the solvent was evaporated under reduced pressure, and purified by silica gel column chromatography (eluent: petroleum ether / dichloromethane = 20 / 1, volume ratio), and crystallized by cooling in a mixed solvent of n-hexane / dichloromethane / methanol at 50 °C to obtain 4.7 g of white crystals, and the calculated yield was 60%. C 72 H 48 B N 3 Elemental analysis (%): C, 89.6; H, 5.2; B, 1.3; N, 4.1. Mass spectrometry (MALDI-TOF) showed that its molecular weight was 966.0.

[0125] The monomer feed was NB-6 (855.0 mg, 1.00 mmol), and a white fibrous polymer (496.0 mg) was obtained by ROMP polymerization. Yield: 58%. The synthesis procedure was the same as that of PNB-1 in Example 1.

[0126] Example 7

[0127]

[0128] D7 (9.6 g, 25 mmol), 1 (15.0 g, 50.0 mmol), cuprous oxide (0.73 g, 5.0 mmol), potassium phosphate (15.9 g, 75.0 mmol), N,N'-dimethylethylenediamine (1.1 mL, 10.0 mmol) and anhydrous m-xylene (80 mL) were added to a 250 mL two-necked reaction flask. The reaction atmosphere was replaced with an argon environment and the temperature was raised to 130 °C and stirred for 48 hours. After the reaction returned to room temperature, 250 mL of saturated ammonium chloride aqueous solution was added for washing, and the crude product was extracted with 200 mL of chloroform. The organic phase was dried, the solvent was evaporated under reduced pressure, and purified by silica gel column chromatography (eluent: petroleum ether) to obtain 14.3 g of a white solid, and the calculated yield was 60%. C 29 H 20 Elemental analysis (%) of C, H, Br, N, O: C, 72.7; H, 4.3; Br, 16.6; N, 3.0; O, 3.4. Mass spectrometry (MALDI-TOF) showed that its molecular weight was 478.3.

[0129] 8 (4.3 g, 9.1 mmol) and anhydrous tetrahydrofuran (70 mL) were added to a pre-dried 250 mL two-necked reaction flask. The reaction atmosphere was replaced with an argon environment and the temperature was lowered to -78 °C. n-Butyllithium solution (4.0 mL, 2.5 M, 10.0 mmol) was added dropwise to the reaction system via a syringe, and then stirred at -78 °C for 1.5 hours. A6 (7.2 g, 18.2 mmol) was dissolved in 20 mL of anhydrous THF and added to the above reaction system at 0 °C under an argon atmosphere, and then the reaction was allowed to return to room temperature for 10 hours. 5 mL of methanol was added to the reaction system to quench the remaining active lithium compounds, and then washed three times with 100 mL of saturated saline solution. The crude product was extracted with 100 mL of diethyl ether. The organic phase was dried, the solvent was evaporated under reduced pressure, and purified by silica gel column chromatography (eluent: petroleum ether / dichloromethane = 20 / 1, volume ratio), and crystallized by cooling in a mixed solvent of n-hexane / dichloromethane / methanol at 50 °C to obtain 4.2 g of white crystals, and the calculated yield was 69%. C 47 H 32 Elemental analysis (%) of C, H, B, N, O, S: C, 84.2; H, 4.8; B, 1.7; N, 2.1; O, 2.4; S, 4.9. Mass spectrometry (MALDI-TOF) showed that its molecular weight was 669.6.

[0130] The monomer feed was NB-7 (669.6 mg, 1.00 mmol), and a white fibrous polymer (368.2 mg) was obtained by ROMP polymerization. Yield: 55%. The synthesis procedure was the same as that of PNB-1 in Example 1.

[0131] Example 8

[0132]

[0133] D8 (10.2 g, 25 mmol), 1 (15.0 g, 50.0 mmol), cuprous oxide (0.73 g, 5.0 mmol), potassium phosphate (15.9 g, 75.0 mmol), N,N'-dimethylethylenediamine (1.1 mL, 10.0 mmol) and anhydrous m-xylene (80 mL) were added to a 250 mL two-necked reaction flask. The reaction atmosphere was replaced with an argon environment and the temperature was raised to 130 °C and stirred for 48 hours. After the reaction returned to room temperature, 250 mL of saturated ammonium chloride aqueous solution was added for washing, and the crude product was extracted with 200 mL of chloroform. The organic phase was dried, the solvent was evaporated under reduced pressure, and purified by silica gel column chromatography (eluent: petroleum ether) to obtain 7.6 g of a white solid, and the calculated yield was 61%. C 32 H 26 Elemental analysis (%) of C, H, Br, N: C, 76.2; H, 5.9; Br, 15.8; N, 3.1. Mass spectrometry (MALDI-TOF) showed that its molecular weight was 504.4.

[0134] 9 (4.5 g, 9.1 mmol) and anhydrous tetrahydrofuran (70 mL) were added to a pre-dried 250 mL two-necked reaction flask. The reaction atmosphere was replaced with an argon environment and the temperature was lowered to -78 °C. The n-butyllithium solution (4.0 mL, 2.5 M, 10.0 mmol) was added dropwise to the reaction system by syringe, and then stirred at -78 °C for 1.5 hours. A7 (7.2 g, 18.2 mmol) was dissolved in 20 mL of anhydrous THF and added to the above reaction system at 0 °C under an argon atmosphere, and then the reaction was allowed to return to room temperature for 10 hours. 5 mL of methanol was added to the reaction system to quench the residual active lithium compound, and then washed three times with 100 mL of saturated brine solution. The crude product was extracted with 100 mL of ether. The organic phase was dried, the solvent was evaporated under reduced pressure, and purified by silica gel column chromatography (eluent: petroleum ether / dichloromethane = 20 / 1, volume ratio), and cooled and crystallized in a mixed solvent of n-hexane / dichloromethane / methanol at 50 °C to obtain 4.2 g of white crystals, and the calculated yield was 67%. C 52 H 44 Elemental analysis (%) of C, H, B, N: C, 90.3; H, 6.0; B, 1.7; N, 2.0. Mass spectrometry (MALDI-TOF) showed that its molecular weight was 695.7. The NMR spectrum of the monomer feed NB-8 is shown in Figure 6 .

[0135] The monomer feed was NB-8 (695.7 mg, 1.00 mmol). A white fibrous polymer (403.5 mg) was obtained by ROMP polymerization with a yield of 58%. The synthesis procedure was the same as that of PNB-1 in Example 1.

[0136] Example 9

[0137]

[0138] D8 (10.2 g, 25 mmol), 1 (15.0 g, 50.0 mmol), copper(I) oxide (0.73 g, 5.0 mmol), potassium phosphate (15.9 g, 75.0 mmol), N,N'-dimethylethylenediamine (1.1 mL, 10.0 mmol) and anhydrous m-xylene (80 mL) were added to a 250 mL two-necked reaction flask. The reaction atmosphere was replaced with argon and the temperature was raised to 130 °C and stirred for 48 h. After the reaction was cooled to room temperature, 250 mL of saturated ammonium chloride aqueous solution was added for washing, and the crude product was extracted with 200 mL of chloroform. The organic phase was dried, the solvent was evaporated under reduced pressure, and purified by silica gel column chromatography (eluent: petroleum ether) to obtain 7.6 g of a white solid with a calculated yield of 61%. C 32 H 26 Elemental analysis (%) of BrN: C, 76.2; H, 5.9; Br, 15.8; N, 3.1. The molecular weight was 504.4 by mass spectrometry (MALDI-TOF).

[0139] 9 (4.5 g, 9.1 mmol) and anhydrous tetrahydrofuran (70 mL) were added to a pre-dried 250 mL two-necked reaction flask. The reaction atmosphere was replaced with argon and the temperature was cooled to -78 °C. n-Butyllithium solution (4.0 mL, 2.5 M, 10.0 mmol) was added dropwise to the reaction system via a syringe, and then stirred at -78 °C for 1.5 h. A8 (10.3 g, 18.2 mmol) was dissolved in 20 mL of anhydrous THF and added to the above reaction system at 0 °C under an argon atmosphere, and then the reaction was allowed to return to room temperature for 10 h. 5 mL of methanol was added to the reaction system to quench the remaining active lithium compounds, and then washed three times with 100 mL of saturated saline solution. The crude product was extracted with 100 mL of diethyl ether. The organic phase was dried, the solvent was evaporated under reduced pressure, and purified by silica gel column chromatography (eluent: petroleum ether / dichloromethane = 20 / 1, v / v), and crystallized by cooling in a mixed solvent of n-hexane / dichloromethane / methanol at 50 °C to obtain 10.2 g of white crystals with a calculated yield of 65%. C 55 H 38 F 6 N 4Elemental analysis (%) : C, 76.0; H, 4.5; F, 13.1; N, 6.4. Mass spectrometry (MALDI-TOF) shows a molecular weight of 868.9.

[0140] The monomer feed was NB-9 (868.9 mg, 1.00 mmol), and a white fibrous polymer (521.3 mg) was obtained by ROMP polymerization. Yield: 60%. The synthesis procedure was the same as that of PNB-1 in Example 1.

[0141] Example 10

[0142]

[0143] D8 (10.2 g, 25 mmol), 1 (15.0 g, 50.0 mmol), copper(I) oxide (0.73 g, 5.0 mmol), potassium phosphate (15.9 g, 75.0 mmol), N,N'-dimethylethylenediamine (1.1 mL, 10.0 mmol) and anhydrous m-xylene (80 mL) were added to a 250 mL two-necked reaction flask. The reaction atmosphere was replaced with argon and the temperature was raised to 130 °C and stirred for 48 hours. After the reaction returned to room temperature, 250 mL of saturated ammonium chloride aqueous solution was added for washing, and the crude product was extracted with 200 mL of chloroform. The organic phase was dried, the solvent was evaporated under reduced pressure, and purified by silica gel column chromatography (eluent: petroleum ether) to obtain 7.6 g of a white solid, and the calculated yield was 61%. C 32 H 26 Elemental analysis (%) of BrN: C, 76.2; H, 5.9; Br, 15.8; N, 3.1. Mass spectrometry (MALDI-TOF) shows a molecular weight of 504.4.

[0144] 9 (4.5 g, 9.1 mmol) and anhydrous tetrahydrofuran (70 mL) were added to a pre-dried 250 mL two-necked reaction flask. The reaction atmosphere was replaced with argon and the temperature was lowered to -78 °C. The n-butyllithium solution (4.0 mL, 2.5 M, 10.0 mmol) was added dropwise to the reaction system via a syringe, and then stirred at -78 °C for 1.5 hours. A9 (8.2 g - 18.2 mmol) was dissolved in 20 mL of anhydrous THF and added to the above reaction system at 0 °C under an argon atmosphere, and then the reaction was allowed to resume at room temperature for 10 hours. 5 mL of methanol was added to the reaction system to quench the remaining active lithium compounds, and then washed three times with 100 mL of saturated saline solution. The crude product was extracted with 100 mL of diethyl ether. The organic phase was dried, the solvent was evaporated under reduced pressure, and purified by silica gel column chromatography (eluent: petroleum ether / dichloromethane = 20 / 1, v / v), and crystallized by cooling in a mixed solvent of n-hexane / dichloromethane / methanol at 50 °C to obtain 4.3 g of white crystals, and the calculated yield was 64%. C 56 H52 Elemental analysis of BN (%) : C, 89.8; H, 7.0; B, 1.4; N, 1.8. The molecular weight was 749.8 by mass spectrometry (MALDI-TOF).

[0145] The monomer feed was NB-10 (749.8 mg, 1.00 mmol), and a white fibrous polymer (427.3 mg) was obtained by ROMP polymerization. Yield: 57%. The synthesis procedure was the same as that of PNB-1 in Example 1.

[0146] Example 11

[0147]

[0148] D8 (10.2 g, 25 mmol), 1 (15.0 g, 50.0 mmol), copper(I) oxide (0.73 g, 5.0 mmol), potassium phosphate (15.9 g, 75.0 mmol), N,N'-dimethylethylenediamine (1.1 mL, 10.0 mmol) and anhydrous m-xylene (80 mL) were added to a 250 mL two-necked reaction flask. The reaction atmosphere was replaced with argon and the temperature was raised to 130 °C and stirred for 48 h. After the reaction was cooled to room temperature, 250 mL of saturated ammonium chloride aqueous solution was added for washing, and the crude product was extracted with 200 mL of chloroform. The organic phase was dried, the solvent was evaporated under reduced pressure, and purified by silica gel column chromatography (eluent: petroleum ether) to obtain 7.6 g of a white solid. The calculated yield was 61%. C 32 H 26 Elemental analysis of C H Br N (%) : C, 76.2; H, 5.9; Br, 15.8; N, 3.1. The molecular weight was 504.4 by mass spectrometry (MALDI-TOF).

[0149] 9 (4.5 g, 9.1 mmol) and anhydrous tetrahydrofuran (70 mL) were added to a pre-dried 250 mL two-necked reaction flask. The reaction atmosphere was replaced with argon and the temperature was cooled to -78 °C. n-Butyllithium solution (4.0 mL, 2.5 M, 10.0 mmol) was added dropwise to the reaction system via a syringe, and then stirred at -78 °C for 1.5 h. A10 (6.9 g, 18.2 mmol) was dissolved in 20 mL of anhydrous THF and added to the above reaction system at 0 °C under an argon atmosphere, and then the reaction was allowed to return to room temperature for 10 h. 5 mL of methanol was added to the reaction system to quench the residual active lithium compounds, and then washed three times with 100 mL of saturated brine solution. The crude product was extracted with 100 mL of diethyl ether. The organic phase was dried, the solvent was evaporated under reduced pressure, and purified by silica gel column chromatography (eluent: petroleum ether / dichloromethane = 20 / 1, v / v), and cooled and crystallized in a mixed solvent of n-hexane / dichloromethane / methanol at 50 °C to obtain 4.2 g of white crystals. The calculated yield was 69%. C50 H 38 Elemental analysis (%) of BNO: C, 88.3; H, 5.7; B, 1.6; N, 2.0; O, 2.4. Mass spectrometry (MALDI-TOF) shows its molecular weight is 679.6.

[0150] The monomer feed was NB-11 (679.6 mg, 1.00 mmol), and a white fibrous polymer (373.7 mg) was obtained by ROMP polymerization with a yield of 55%. The synthesis procedure was the same as that of PNB-1 in Example 1.

[0151] Example 12

[0152]

[0153] D8 (10.2 g, 25 mmol), 1 (15.0 g, 50.0 mmol), copper(I) oxide (0.73 g, 5.0 mmol), potassium phosphate (15.9 g, 75.0 mmol), N,N'-dimethylethylenediamine (1.1 mL, 10.0 mmol) and anhydrous m-xylene (80 mL) were added to a 250 mL two-necked reaction flask. The reaction atmosphere was replaced with argon and the temperature was raised to 130 °C and stirred for 48 hours. After the reaction returned to room temperature, 250 mL of saturated ammonium chloride aqueous solution was added for washing, and the crude product was extracted with 200 mL of chloroform. The organic phase was dried, the solvent was evaporated under reduced pressure, and purified by silica gel column chromatography (eluent: petroleum ether) to obtain 7.6 g of a white solid with a calculated yield of 61%. C 32 H 26 Elemental analysis (%) of BrN: C, 76.2; H, 5.9; Br, 15.8; N, 3.1. Mass spectrometry (MALDI-TOF) shows its molecular weight is 504.4.

[0154] 9 (4.5 g, 9.1 mmol) and anhydrous tetrahydrofuran (70 mL) were added to a pre-dried 250 mL two-neck reaction flask. The reaction atmosphere was replaced with an argon environment and cooled to -78 °C. A solution of n-butyllithium (4.0 mL, 2.5 M, 10.0 mmol) was added dropwise to the reaction system via a syringe, and then stirred at -78 °C for 1.5 h. A11 (7.4 g, 18.2 mmol) was dissolved in 20 mL of anhydrous THF and added to the above reaction system at 0 °C under an argon atmosphere, and then the reaction was allowed to resume at room temperature for 10 h. 5 mL of methanol was added to the reaction system to quench the residual active lithium compounds, and then washed three times with 100 mL of saturated saline solution. The crude product was extracted with 100 mL of diethyl ether. The organic phase was dried, the solvent was evaporated under reduced pressure, and purified by silica gel column chromatography (eluent: petroleum ether / dichloromethane = 20 / 1, v / v), and cooled and crystallized in a mixed solvent of n-hexane / dichloromethane / methanol at 50 °C to obtain 4.1 g of white crystals, and the calculated yield was 65%. C 50 H 34 BNO 3 Elemental analysis (%) : C, 84.8; H, 4.9; B, 1.4; N, 2.0; O, 6.8. Mass spectrometry (MALDI-TOF) showed a molecular weight of 707.6.

[0155] The monomer feed was NB-12 (707.4 mg, 1.00 mmol), and a white fibrous polymer (389.0 mg) was obtained by ROMP polymerization. Yield: 55%. The synthesis procedure was the same as that of PNB-1 in Example 1.

[0156] Example 13

[0157]

[0158] D9 (11.4 g, 25 mmol), 1 (15.0 g, 50.0 mmol), copper(I) oxide (0.73 g, 5.0 mmol), potassium phosphate (15.9 g, 75.0 mmol), N,N'-dimethylethylenediamine (1.1 mL, 10.0 mmol) and anhydrous m-xylene (80 mL) were added to a 250 mL two-neck reaction flask. The reaction atmosphere was replaced with an argon environment and heated to 130 °C and stirred for 48 h. After the reaction returned to room temperature, it was washed with 250 mL of saturated ammonium chloride aqueous solution, and the crude product was extracted with 200 mL of chloroform. The organic phase was dried, the solvent was evaporated under reduced pressure, and purified by silica gel column chromatography (eluent: petroleum ether) to obtain 8.7 g of white solid, and the calculated yield was 63%. C 35 H 22Elemental analysis (%) of BrNO: C, 76.0; H, 4.1; Br, 14.5; N, 2.5; O, 3.0. Mass spectrometry (MALDI-TOF) shows its molecular weight is 552.4.

[0159] Add 10 (5.0 g, 9.1 mmol) and anhydrous tetrahydrofuran (70 mL) to a pre-dried 250 mL two-neck reaction flask. Replace the reaction atmosphere with an argon environment and cool down to -78 °C. Add n-butyllithium solution (4.0 mL, 2.5 M, 10.0 mmol) dropwise to the reaction system via a syringe, and then stir at -78 °C for 1.5 hours. Dissolve A12 (7.9 g, 18.2 mmol) in 20 mL of anhydrous THF, add it to the above reaction system at 0 °C under an argon atmosphere, and then resume the reaction at room temperature for 10 hours. Add 5 mL of methanol to the reaction system to quench the remaining active lithium compounds, then add 100 mL of saturated saline solution and wash three times. The crude product is extracted with 100 mL of ether. The organic phase is dried, the solvent is evaporated under reduced pressure, and purified by silica gel column chromatography (eluent: petroleum ether / dichloromethane = 20 / 1, volume ratio), and cooled and crystallized in a mixed solvent of n-hexane / dichloromethane / methanol at 50 °C to obtain 4.7 g of white crystals. The calculated yield is 67%. C 53 H 32 BNO 2 Elemental analysis (%) of Se: C, 79.2; H, 4.1; B, 1.1; N, 1.8; O, 3.8; Se, 9.8. Mass spectrometry (MALDI-TOF) shows its molecular weight is 804.6.

[0160] The monomer feed is NB-13 (804.6 mg, 1.00 mmol), and a white fibrous polymer (421.6 mg) is obtained by ROMP polymerization. Yield: 53%. The synthesis procedure is the same as that of PNB-1 in Example 1.

[0161] Example 14

[0162]

[0163] D10 (20.6 g, 25 mmol), (15.0 g, 50.0 mmol), copper(I) oxide (0.73 g, 5.0 mmol), potassium phosphate (15.9 g, 75.0 mmol), N,N'-dimethylethylenediamine (1.1 mL, 10.0 mmol), and anhydrous m-xylene (80 mL) were added to a 250 mL two-necked reaction flask. The reaction atmosphere was replaced with argon, and the temperature was raised to 130 °C and stirred for 48 hours. After the reaction returned to room temperature, 250 mL of saturated ammonium chloride aqueous solution was added for washing, and the crude product was extracted with 200 mL of chloroform. The organic phase was dried, the solvent was evaporated under reduced pressure, and purified by silica gel column chromatography (eluent: petroleum ether) to obtain 13.7 g of a white solid, and the calculated yield was 60%. C 62 H 52 BrN 3 Elemental analysis (%) : C, 81.1; H, 5.7; Br, 8.7; N, 4.5. Mass spectrometry (MALDI-TOF) showed a molecular weight of 919.0.

[0164] 11 (8.3 g, 9.1 mmol) and anhydrous tetrahydrofuran (70 mL) were added to a pre-dried 250 mL two-necked reaction flask. The reaction atmosphere was replaced with argon, and the temperature was lowered to -78 °C. n-Butyllithium solution (4.0 mL, 2.5 M, 10.0 mmol) was added dropwise to the reaction system via a syringe, and then stirred at -78 °C for 1.5 hours. A13 (4.0 g, 18.2 mmol) was dissolved in 20 mL of anhydrous THF and added to the above reaction system at 0 °C under an argon atmosphere, and then the reaction was allowed to return to room temperature for 10 hours. 5 mL of methanol was added to the reaction system to quench the remaining active lithium compounds, and then washed three times with 100 mL of saturated saline solution. The crude product was extracted with 100 mL of diethyl ether. The organic phase was dried, the solvent was evaporated under reduced pressure, and purified by silica gel column chromatography (eluent: petroleum ether / dichloromethane = 20 / 1, v / v), and crystallized by cooling in a mixed solvent of n-hexane / dichloromethane / methanol at 50 °C to obtain 6.2 g of white crystals, and the calculated yield was 65%. C 76 H 62 N 6 Elemental analysis (%) : C, 86.1; H, 5.9; N, 7.9. Mass spectrometry (MALDI-TOF) showed a molecular weight of 1059.3.

[0165] The monomer feed was NB-14 (1059 mg, 1.00 mmol), and a white fibrous polymer (529.5 mg) was obtained by ROMP polymerization. Yield: 50%. The synthesis procedure was the same as that of PNB-1 in Example 1.

[0166] Example 15

[0167]

[0168] D11 (8.6 g, 25 mmol), 1 (15.0 g, 50.0 mmol), cuprous oxide (0.73 g, 5.0 mmol), potassium phosphate (15.9 g, 75.0 mmol), N,N'-dimethylethylenediamine (1.1 mL, 10.0 mmol) and anhydrous m-xylene (80 mL) were added to a 250 mL two-necked reaction flask. The reaction atmosphere was replaced with an argon environment and the temperature was raised to 130 °C and stirred for 48 hours. After the reaction returned to room temperature, 250 mL of saturated ammonium chloride aqueous solution was added for washing, and the crude product was extracted with 200 mL of chloroform. The organic phase was dried, the solvent was evaporated under reduced pressure, and purified by silica gel column chromatography (eluent: petroleum ether) to obtain 9.2 g of a white solid, and the calculated yield was 67%. C 46 H 30 BrN 3 Elemental analysis (%) : C, 73.9; H, 4.2; Br, 14.3; N, 7.6. Mass spectrometry (MALDI-TOF) showed its molecular weight to be 703.6.

[0169] 12 (5.0 g, 9.1 mmol) and anhydrous tetrahydrofuran (70 mL) were added to a pre-dried 250 mL two-necked reaction flask. The reaction atmosphere was replaced with an argon environment and the temperature was lowered to -78 °C. The n-butyllithium solution (4.0 mL, 2.5 M, 10.0 mmol) was added dropwise to the reaction system via a syringe, and then stirred at -78 °C for 1.5 hours. A14 (7.2 g, 18.2 mmol) was dissolved in 20 mL of anhydrous THF and added to the above reaction system at 0 °C under an argon atmosphere, and then the reaction was allowed to return to room temperature for 10 hours. 5 mL of methanol was added to the reaction system to quench the remaining active lithium compounds, and then washed three times with 100 mL of saturated saline solution. The crude product was extracted with 100 mL of ether. The organic phase was dried, the solvent was evaporated under reduced pressure, and purified by silica gel column chromatography (eluent: petroleum ether / dichloromethane = 20 / 1, v / v), and cooled and crystallized in a mixed solvent of n-hexane / dichloromethane / methanol at 50 °C to obtain 4.4 g of white crystals, and the calculated yield was 65%. C 65 H 40 N 4 O 2 Elemental analysis (%) : C, 84.2; H, 4.4; N, 7.2; O, 4.2. Mass spectrometry (MALDI-TOF) showed its molecular weight to be 909.2.

[0170] The monomer feed was NB-15 (756.8 mg, 1.00 mmol), and a white fibrous polymer (416.2 mg) was obtained by ROMP polymerization. Yield: 55%. The synthesis procedure was the same as that of PNB-1 in Example 1.

[0171] Example 16

[0172]

[0173] D12 (10.4 g, 25 mmol), 1 (15.0 g, 50.0 mmol), cuprous oxide (0.73 g, 5.0 mmol), potassium phosphate (15.9 g, 75.0 mmol), N,N'-dimethylethylenediamine (1.1 mL, 10.0 mmol) and anhydrous m-xylene (80 mL) were added to a 250 mL two-necked reaction flask. The reaction atmosphere was replaced with an argon environment and the temperature was raised to 130 °C and stirred for 48 hours. After the reaction returned to room temperature, 250 mL of saturated ammonium chloride aqueous solution was added for washing, and the crude product was extracted with 200 mL of chloroform. The organic phase was dried, the solvent was evaporated under reduced pressure, and purified by silica gel column chromatography (eluent: petroleum ether) to obtain 8.7 g of a white solid, and the calculated yield was 63%. C 32 H 24 Elemental analysis (%) of C, H, Br, N: C, 76.4; H, 4.9; Br, 15.8; N, 2.9. Mass spectrometry (MALDI-TOF) showed that its molecular weight was 502.4.

[0174] 13 (4.5 g, 9.1 mmol) and anhydrous tetrahydrofuran (70 mL) were added to a pre-dried 250 mL two-necked reaction flask. The reaction atmosphere was replaced with an argon environment and the temperature was lowered to -78 °C. The n-butyllithium solution (4.0 mL, 2.5 M, 10.0 mmol) was added dropwise to the reaction system via a syringe, and then stirred at -78 °C for 1.5 hours. A15 (7.3 g, 18.2 mmol) was dissolved in 20 mL of anhydrous THF and added to the above reaction system at 0 °C under an argon atmosphere, and then the reaction was allowed to return to room temperature for 10 hours. 5 mL of methanol was added to the reaction system to quench the remaining active lithium compounds, and then washed three times with 100 mL of saturated saline solution. The crude product was extracted with 100 mL of ether. The organic phase was dried, the solvent was evaporated under reduced pressure, and purified by silica gel column chromatography (eluent: petroleum ether / dichloromethane = 20 / 1, volume ratio), and cooled and crystallized in a mixed solvent of n-hexane / dichloromethane / methanol at 50 °C to obtain 4.4 g of white crystals, and the calculated yield was 70%. C 50 H 38 Elemental analysis (%) of C, H, N, O, P: C, 85.9; H, 5.4; N, 2.1; O, 2.2; P, 4.4. Mass spectrometry (MALDI-TOF) showed that its molecular weight was 699.8.

[0175] The monomer feed was NB-16 (699.8 mg, 1.00 mmol), and a white fibrous polymer (398.7 mg) was obtained by ROMP polymerization. Yield: 57%. The synthesis procedure was the same as that of PNB-1 in Example 1.

[0176] Example 17

[0177]

[0178] D12 (10.4 g, 25 mmol), 1 (15.0 g, 50.0 mmol), copper(I) oxide (0.73 g, 5.0 mmol), potassium phosphate (15.9 g, 75.0 mmol), N,N'-dimethylethylenediamine (1.1 mL, 10.0 mmol) and anhydrous m-xylene (80 mL) were added to a 250 mL two-necked reaction flask. The reaction atmosphere was replaced with argon, and the temperature was raised to 130 °C and stirred for 48 h. After the reaction was cooled to room temperature, 250 mL of saturated ammonium chloride aqueous solution was added for washing, and the crude product was extracted with 200 mL of chloroform. The organic phase was dried, the solvent was evaporated under reduced pressure, and purified by silica gel column chromatography (eluent: petroleum ether) to obtain 8.7 g of a white solid, and the calculated yield was 63%. C 32 H 24 Elemental analysis (%) of BrN: C, 76.4; H, 4.9; Br, 15.8; N, 2.9. The molecular weight was 502.4 by mass spectrometry (MALDI-TOF).

[0179] 13 (4.5 g, 9.1 mmol) and anhydrous tetrahydrofuran (70 mL) were added to a pre-dried 250 mL two-necked reaction flask. The reaction atmosphere was replaced with argon and cooled to -78 °C. The n-butyllithium solution (4.0 mL, 2.5 M, 10.0 mmol) was added dropwise to the reaction system via a syringe, and then stirred at -78 °C for 1.5 h. A16 (6.0 g, 18.2 mmol) was dissolved in 20 mL of anhydrous THF and added to the above reaction system at 0 °C under an argon atmosphere, and then the reaction was allowed to return to room temperature for 10 h. 5 mL of methanol was added to the reaction system to quench the remaining active lithium compounds, and then washed three times with 100 mL of saturated saline solution. The crude product was extracted with 100 mL of diethyl ether. The organic phase was dried, the solvent was evaporated under reduced pressure, and purified by silica gel column chromatography (eluent: petroleum ether / dichloromethane = 20 / 1, v / v), and crystallized by cooling in a mixed solvent of n-hexane / dichloromethane / methanol at 50 °C to obtain 4.0 g of white crystals, and the calculated yield was 70%. C 46 H 31 NO 2Elemental analysis (%) : C, 87.8; H, 4.9; N, 2.2; O, 5.1. Mass spectrometry (MALDI-TOF) shows a molecular weight of 629.7.

[0180] The monomer feed was NB-17 (629.7 mg, 1.00 mmol), and a white fibrous polymer (352.6 mg) was obtained by ROMP polymerization with a yield of 56%. The synthesis procedure was the same as that of PNB-1 in Example 1.

[0181]

[0182] Synthesis of 6-bromo-1,4-dihydro-1,4-methano-naphthalene (14):

[0183] 2,5-Dibromoiodobenzene (4, 30.0 g, 82.9 mmol), freshly prepared cyclopentadiene (9.6 g, 11.8 mL, 145.1 mmol) and anhydrous toluene (1000 mL) were added to a dry 2000 mL two-necked reaction flask. The reaction atmosphere was replaced with argon and cooled to 0 °C. Under mechanical stirring, n-butyllithium solution (36.5 mL, 2.5 M, 91.2 mmol) was added dropwise to the reaction system through a constant pressure dropping funnel. Then, the mixture was stirred at 0 °C for 2 hours and then allowed to return to room temperature and continue the reaction for 4 hours. 10 mL of methanol was added to the reaction system to quench the remaining active lithium compounds, and then 1000 mL of saturated brine solution was added for washing three times. The toluene phase was dried, the solvent was evaporated under reduced pressure, and purified by silica gel column chromatography (eluent: petroleum ether) to obtain 14.7 g of a colorless oily liquid with a yield of 80%. C 11 H 9 Elemental analysis (%) for Br: C, 59.7; H, 4.0; Br, 36.3. Mass spectrometry (MALDI-TOF) shows a molecular weight of 221.0.

[0184] Example 18

[0185]

[0186] 14 (4.4 g, 20.0 mmol), carbazole (3.3 g, 20.0 mmol), Pd 2 (dba) 3(0.92g, 1.0mmol), tri-tert-butylphosphine tetrafluoroborate (1.2g, 4.0mmol), sodium tert-butoxide (3.8g, 40.0mmol) and anhydrous toluene (50mL) were added to a 250mL two-necked reaction bottle, the reaction atmosphere was replaced with an argon environment and the temperature was raised to 105°C and stirred for 6 hours. After the reaction returned to room temperature, 200mL of saturated ammonium chloride aqueous solution was added for washing, and the crude product was extracted with 100mL of ether. The organic phase was dried, the solvent was evaporated under reduced pressure, and purified by silica gel column chromatography (eluent: petroleum ether), and cooled and crystallized in a 50°C dichloromethane / methanol mixed solvent to obtain 5.2g of a white solid, with a calculated yield of 84%. 23 H 17 N element analysis (%): C, 89.8; H, 5.5; N, 4.7. Mass spectrometry analysis (MALDI-TOF) showed that the molecular weight was 307.4.

[0187] The monomer feed was NB-1 (333.9 mg, 0.60 mmol), IP-1 (122.9 mg, 0.40 mmol) and ROMP polymerization was performed to obtain a white fibrous polymer (225.8 mg), with a yield of 68%. Under an argon atmosphere, the polymerized monomer (total amount of substance was 1.0 mmol) was dissolved in anhydrous THF at a concentration of 20 mg / mL. Then, Grubbs catalyst (0.004 mmol / 2 mL) dissolved in THF was quickly added to the reaction system through a glass syringe to initiate polymerization, and the reaction was carried out at 25°C and protected from light for 1 hour, and then vinyl ether capping agent (0.3 mL) was added through a syringe to terminate the polymerization. The reactants were precipitated in acetone (200 mL), and the polymer was filtered, dried, and dissolved in CH 2 Cl 2 (100 mL). To the above solution was added H 2 O 2 (10 wt% aqueous solution, 75 mL) and stirred at room temperature in the dark for 1 hour. The organic phase was washed with anhydrous Na 2 SO 4 Dry, concentrate under reduced pressure, and then separate and remove the catalyst by silica gel column chromatography. The eluate is concentrated and precipitated in methanol (200 mL), filtered and vacuum dried to obtain the target polymer. Wherein, x in the formula of PNB-18 is 0.25. Elemental analysis (%) of PNB-18: C, 88.1; H, 5.2; N, 6.7. The number average molecular weight of the polymer is 27,400 g / mol, and the weight average molecular weight is 48,500 g / mol.

[0188] Embodiment 19

[0189]

[0190] 14 (4.8 g, 22.0 mmol), 3,6-di-tert-butylcarbazole (6.1 g, 22.0 mmol), Pd 2 (dba) 3 (1.0g, 1.1mmol), tri-tert-butylphosphine tetrafluoroborate (1.4g, 4.4mmol), sodium tert-butoxide (4.2g, 44.0mmol) and anhydrous toluene (80mL) were added to a 250mL two-necked reaction bottle, the reaction atmosphere was replaced with an argon environment and the temperature was raised to 105°C and stirred for 6 hours. After the reaction returned to room temperature, 200mL of saturated ammonium chloride aqueous solution was added for washing, and the crude product was extracted with 100mL of ether. The organic phase was dried, the solvent was evaporated under reduced pressure, and purified by silica gel column chromatography (eluent: petroleum ether), and cooled and crystallized in a 50°C dichloromethane / methanol mixed solvent to obtain 7.4g of a white flocculent solid with a yield of 80%. 31 H 33 N element analysis (%): C, 88.8; H, 7.9; N, 3.3. Mass spectrometry analysis (MALDI-TOF) showed that the molecular weight was 419.6.

[0191] The monomer feed is NB-1 (333.9 mg, 0.50 mmol), IP-2 (209.8 mg, 0.50 mmol) and ROMP polymerization is performed to obtain a white fibrous polymer (290.0 mg), with a yield of 87%. The synthesis steps are the same as those of PNB-18 in Example 18. Wherein, x in the formula of PNB-19 is 0.5. Elemental analysis (%) of PNB-19: C, 87.6; H, 6.1; N, 6.3. The number average molecular weight of the polymer is 26,300 g / mol, and the weight average molecular weight is 47,800 g / mol.

[0192] Embodiment 20

[0193]

[0194] 14 (4.8 g, 22.0 mmol), H1 (5.59 g, 22.0 mmol), Pd 2 (dba) 3(1.0 g, 1.1 mmol), tetra-tert-butylphosphonium tetrafluoroborate (1.4 g, 4.4 mmol), sodium tert-butoxide (4.2 g, 44.0 mmol) and anhydrous toluene (80 mL) were added to a 250 mL two-necked reaction flask. The reaction atmosphere was replaced with an argon environment and the temperature was raised to 105 °C and stirred for 6 hours. After the reaction returned to room temperature, 200 mL of saturated ammonium chloride aqueous solution was added for washing, and the crude product was extracted with 100 mL of ether. The organic phase was dried, the solvent was evaporated under reduced pressure, and purified by silica gel column chromatography (eluent: petroleum ether), and cooled and crystallized in a dichloromethane / methanol mixed solvent at 50 °C to obtain 4.6 g of a white flocculent solid, with a yield of 78%. C 21 H 16 Elemental analysis (%) : C, 94.0; H, 6.0. Mass spectrometry (MALDI-TOF) showed a molecular weight of 268.3.

[0195] The monomer feed was NB-12 (424.4 mg, 0.6 mmol), and IP-3 (107.3 mg, 0.40 mmol) was polymerized by ROMP to obtain a white fibrous polymer (237.6 mg), with a yield of 56%. The synthesis procedure was the same as that of PNB-18 in Example 18. Among them, x = 0.5 in the formula of PNB-20.

[0196] Example 21

[0197]

[0198] 14 (4.8 g, 22.0 mmol), H2 (2.8 g, 22.0 mmol), Pd 2 (dba) 3 (1.0 g, 1.1 mmol), tetra-tert-butylphosphonium tetrafluoroborate (1.4 g, 4.4 mmol), sodium tert-butoxide (4.2 g, 44.0 mmol) and anhydrous toluene (80 mL) were added to a 250 mL two-necked reaction flask. The reaction atmosphere was replaced with an argon environment and the temperature was raised to 105 °C and stirred for 6 hours. After the reaction returned to room temperature, 200 mL of saturated ammonium chloride aqueous solution was added for washing, and the crude product was extracted with 100 mL of ether. The organic phase was dried, the solvent was evaporated under reduced pressure, and purified by silica gel column chromatography (eluent: petroleum ether), and cooled and crystallized in a dichloromethane / methanol mixed solvent at 50 °C to obtain 4.7 g of a white flocculent solid, with a yield of 80%. C 20 H 17 Elemental analysis for N (%) : C, 88.5; H, 6.3; N, 5.1. Mass spectrometry (MALDI-TOF) showed a molecular weight of 271.3.

[0199] The monomer feed was NB-13 (624.6 mg, 0.80 mmol) and IP-4 (54.3 mg, 0.20 mmol) and a white fibrous polymer (337.3 mg) was obtained by ROMP polymerization with a yield of 54%. The synthesis steps were the same as those of PNB-18 in Example 18. Wherein, x in the formula of PNB-21 is 0.5.

[0200] Embodiment 22

[0201]

[0202] 14 (4.8 g, 22.0 mmol), H2 (2.8 g, 22.0 mmol), Pd2 (dba) 3 (1.0 g, 1.1 mmol), tri-tert-butylphosphine tetrafluoroborate (1.4 g, 4.4 mmol), sodium tert-butoxide (4.2 g, 44.0 mmol) and anhydrous toluene (80 mL) were added to a 250 mL two-necked reaction bottle, the reaction atmosphere was replaced with an argon environment and the temperature was raised to 105 ° C and stirred for 6 hours. After the reaction returned to room temperature, 200 mL of saturated ammonium chloride aqueous solution was added for washing, and the crude product was extracted with 100 mL of ether. The organic phase was dried, the solvent was evaporated under reduced pressure, and purified by silica gel column chromatography (eluent: petroleum ether), and cooled and crystallized in a 50 ° C dichloromethane / methanol mixed solvent to obtain 4.7 g of a white flocculent solid with a yield of 80%. C 20 H 17 N elemental analysis (%): C, 88.5; H, 6.3; N, 5.1. Mass spectrometry analysis (MALDI-TOF) showed that the molecular weight was 271.3.

[0203] The monomer feed was NB-11 (679.6 mg, 1.00 mmol) and IP-4 (108.3 mg, 0.40 mmol) and a white fibrous polymer (394.1 mg) was obtained by ROMP polymerization with a yield of 58%. The synthesis steps were the same as those of PNB-18 in Example 18. Wherein, x in the formula of PNB-22 is 0.5.

[0204] Embodiment 23

[0205]

[0206] 14 (4.8 g, 22.0 mmol), H3 (9.4 g, 22.0 mmol), Pd 2 (dba) 3(1.0 g, 1.1 mmol), tetrabutylphosphonium tetrafluoroborate (1.4 g, 4.4 mmol), sodium tert-butoxide (4.2 g, 44.0 mmol) and anhydrous toluene (80 mL) were added to a 250 mL two-necked reaction flask. The reaction atmosphere was replaced with an argon environment and the temperature was raised to 105 °C and stirred for 6 hours. After the reaction returned to room temperature, 200 mL of saturated ammonium chloride aqueous solution was added for washing, and the crude product was extracted with 100 mL of ether. The organic phase was dried, the solvent was evaporated under reduced pressure, and purified by silica gel column chromatography (eluent: petroleum ether), and cooled and crystallized in a dichloromethane / methanol mixed solvent at 50 °C to obtain 7.5 g of a white flocculent solid with a yield of 78%. C 29 H 19 BS 2 Elemental analysis (%) : C, 78.7; H, 4.3; B, 2.5; S, 14.5. Mass spectrometry (MALDI-TOF) showed a molecular weight of 442.4.

[0207] The monomer feed was NB-11 (407.7 mg, 0.6 mmol), and IP-5 (176.9 mg, 0.40 mmol) was polymerized by ROMP to obtain a white fibrous polymer (244.6 mg) with a yield of 60%. The synthesis procedure was the same as that of PNB-18 in Example 18. Among them, x = 0.75 in PNB-23.

[0208] Example 24

[0209]

[0210] 14 (4.8 g, 22.0 mmol), H3 (9.4 g, 22.0 mmol), Pd 2 (dba) 3 (1.0 g, 1.1 mmol), tetrabutylphosphonium tetrafluoroborate (1.4 g, 4.4 mmol), sodium tert-butoxide (4.2 g, 44.0 mmol) and anhydrous toluene (80 mL) were added to a 250 mL two-necked reaction flask. The reaction atmosphere was replaced with an argon environment and the temperature was raised to 105 °C and stirred for 6 hours. After the reaction returned to room temperature, 200 mL of saturated ammonium chloride aqueous solution was added for washing, and the crude product was extracted with 100 mL of ether. The organic phase was dried, the solvent was evaporated under reduced pressure, and purified by silica gel column chromatography (eluent: petroleum ether), and cooled and crystallized in a dichloromethane / methanol mixed solvent at 50 °C to obtain 7.5 g of a white flocculent solid with a yield of 78%. C 29 H 19 BS 2 Elemental analysis (%) : C, 78.7; H, 4.3; B, 2.5; S, 14.5. Mass spectrometry (MALDI-TOF) showed a molecular weight of 442.4.

[0211] The monomer feed was NB-9 (521.3 mg, 0.6 mmol) and IP-5 (176.9 mg, 0.40 mmol). Through ROMP polymerization, a white fibrous polymer (338.8 mg) was obtained with a yield of 65%. The synthesis procedure was the same as that of PNB-18 in Example 18. Among them, x = 0.75 in the formula of PNB-24.

[0212] Application Example

[0213] A diamond anvil face is installed on the alloy steel of the metal substrate. The diamond anvil faces are all 16-sided, with a height of about 2.0 - 2.6 mm and a bottom diameter generally greater than 3 mm. A cemented carbide gasket is installed to form a sample chamber. The sample chamber contains the space charge transfer polymer luminescent material of the poly(norbornene) backbone prepared in Example 1, 8, 16 or 20 of the present invention as a pressure probe. A metal gasket with a T301 steel sheet with a small hole is used as the sealing material to obtain a higher pressure. The diamond upper anvil face is designed to be chamfered or double chamfered and placed on the surface of the sealing material to obtain a fluorescent polymer pressure probe.

[0214] The specific pressure probe structure is as follows:

[0215] Base / diamond lower anvil face / sample chamber (cemented carbide gasket) / sealing material (metal gasket) / chamfered diamond upper anvil face.

[0216] Device Example 1

[0217] Taking the polymer prepared in Example 1 as the implementation object, the obtained pressure probe was tested.

[0218] See Figure 1 , Figure 1 It is a graph showing the relationship between the maximum fluorescence emission spectrum and pressure of the pressure probe prepared in Device Example 1 of the present invention.

[0219] See Table 1. Table 1 is a data table showing the relationship between the maximum fluorescence emission spectrum and pressure of the pressure probe prepared in Device Example 1 of the present invention.

[0220] Table 1. Relationship between pressure values and maximum fluorescence emission wavelength during the pressurization process and the depressurization process

[0221]

[0222]

[0223] Device Example 2

[0224] Taking the polymer prepared in Example 8 as the implementation object, the obtained pressure probe was tested.

[0225] SeeFigure 2 , Figure 2 Relationship diagram between the maximum fluorescence emission spectrum of the pressure probe prepared in Device Example 2 of the present invention and pressure. Refer to Table 2, which is the data table of the maximum fluorescence emission spectrum of the pressure probe prepared in Device Example 2 of the present invention and pressure.

[0226] Table 2. Relationship between pressure values and maximum fluorescence emission wavelengths during the pressure increase process and the pressure decrease process

[0227]

[0228] Device Example 3

[0229] Using the polymer prepared in Example 16 as the implementation object, the obtained pressure probe was tested.

[0230] Refer to Figure 3 , Figure 3 Relationship diagram between the maximum fluorescence emission spectrum of the pressure probe prepared in Device Example 3 of the present invention and pressure. Refer to Table 3, which is the data table of the maximum fluorescence emission spectrum of the pressure probe prepared in Device Example 3 of the present invention and pressure.

[0231] Table 3. Relationship between pressure values and maximum fluorescence emission wavelengths during the pressure increase process and the pressure decrease process

[0232]

[0233] Device Example 4

[0234] Using the polymer prepared in Example 20 as the implementation object, the obtained pressure probe was tested.

[0235] Refer to Figure 4 , Figure 4 Relationship diagram between the maximum fluorescence emission spectrum of the pressure probe prepared in Device Example 4 of the present invention and pressure. Refer to Table 4, which is the data table of the maximum fluorescence emission spectrum of the pressure probe prepared in Device Example 4 of the present invention and pressure.

[0236] Table 4. Relationship between pressure values and maximum fluorescence emission wavelengths during the pressure increase process and the pressure decrease process

[0237]

[0238]

[0239] Figures 1-4The fluorescence wavelengths of the polymers prepared in Examples 1, 8, 16, and 20 respectively under different applied pressures are shown. It is not difficult to see that the fluorescence emission wavelength increases with the increase of pressure. As the pressure decreases, the emission wavelength will gradually decrease accordingly. Among them, the pressure change range is 1 atm to 11.6 GPa, 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 through the change of the emission color, that is, the visual monitoring of the pressure is realized.

Claims

1. A space charge transfer polymer luminescent material with a polynorbornene skeleton, characterized in that: Having the structure shown in formula (I) or (II): Wherein, x is 0.0001 to 0.9999, and n is an integer between 2 and 9999; D is the electron donor and A is the electron acceptor; 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, a C6-C60 aromatic unit, or a C1-C20 alkyl group containing N, O, S, Se, P, B, Si, Ge, C5~C60 aromatic heterocyclic unit.

2. The space charge transfer polymer luminescent material of polynorbornene skeleton according to claim 1, characterized in that: The D is selected from any one of the structures represented by formula (D-1) to formula (D-32): Wherein, R1 and R2 are each independently selected from H, halogen, -CN, -NO2, -PO(Ph)2, benzene ring, pyridine, pyrimidine, triazine, substituted or unsubstituted C1~C22 straight chain hydrocarbon group, substituted or unsubstituted C1~C22 branched hydrocarbon group, substituted or unsubstituted C3~C22 cycloalkyl group or substituted or unsubstituted C1~C22 alkoxy group; R3, R4, R5, R6 are each independently selected from substituted or unsubstituted C1~C22 straight chain hydrocarbon group, substituted or unsubstituted C1~C22 branched hydrocarbon group, substituted or unsubstituted C3~C22 cycloalkyl group or substituted or unsubstituted C1~C22 alkoxy group.

3. The space charge transfer polymer luminescent material of polynorbornene skeleton according to claim 2, characterized in that: The D is selected from any one of the structures represented by formula (d-1) to formula (d-32):

4. The space charge transfer polymer luminescent material of polynorbornene skeleton according to claim 1, characterized in that: The A is selected from any one of the structures represented by formula (A-1) to formula (A-23): Wherein, R1 and R2 are each independently selected from H, halogen, -CN, -NO2, -PO(Ph)2, benzene ring, pyridine, pyrimidine, triazine, substituted or unsubstituted C1~C22 straight chain hydrocarbon group, substituted or unsubstituted C1~C22 branched hydrocarbon group, substituted or unsubstituted C3~C22 cycloalkyl group or substituted or unsubstituted C1~C22 alkoxy group; R3, R4, R5 are each independently selected from substituted or unsubstituted C1~C22 straight chain hydrocarbon group, substituted or unsubstituted C1~C22 branched hydrocarbon group, substituted or unsubstituted C3~C22 cycloalkyl group or substituted or unsubstituted C1~C22 alkoxy group.

5. The space charge transfer polymer luminescent material of polynorbornene skeleton according to claim 4, characterized in that: The A is selected from any one of the structures represented by formula (a-1) to formula (a-86):

6. The space charge transfer polymer luminescent material of polynorbornene skeleton according to claim 1, characterized in that: It is selected from any one of the structures represented by formula (1) to formula (90):

7. A method for preparing the space charge transfer polymer luminescent material of the polynorbornene skeleton according to claim 1, characterized in that: The following steps are involved: Under a protective atmosphere, the intermediates of the structures represented by formula (X-1), formula (Y-1) and formula (K-1), a catalyst, an alkaline aqueous solution and an organic solvent are mixed, and then a tandem Suzuki coupling reaction is performed to obtain a spatial charge transfer polymer luminescent material having a polynorbornene skeleton represented by formula (I); Under a protective atmosphere, reacting the compound of formula (K-2) and a compound containing an H group to obtain an intermediate of the structure shown in formula (N-1); Reacting compounds of the structures represented by formula (X-1), formula (Y-1) and formula (K-1) to obtain an intermediate of the structure represented by formula (N-2); After mixing the intermediates of the structures represented by formula (N-1) and formula (N-2), a catalyst, an aqueous solution of an alkali and an organic solvent, a Suzuki coupling reaction is performed to obtain a spatial charge transfer polymer luminescent material having a polynorbornene skeleton represented by formula (II); Here, x is a halogen atom.

8. The method for preparing the space charge transfer polymer luminescent material of polynorbornene skeleton according to claim 7, characterized in that: In the method for preparing the polymer represented by formula (I), the molar ratio of the intermediate represented by the structure represented by formula (X-1) to the intermediate represented by the structure represented by formula (Y-1) is 1.6 to 1.1:1; In the method for preparing the polymer represented by formula (II), the molar ratio of the intermediate represented by formula (X-1) to the intermediate represented by formula (Y-1) is 1:1.1-2.0; In the method for preparing the polymers represented by formula (I) and formula (II), the temperature of the Suzuki coupling reaction is 50 to 75°C; In the preparation method of the polymer represented by the preparation formula (I), the reaction time is 12h to 48h; In the preparation method of the polymer represented by formula (II), the reaction time is 6 h to 12 h; The protective atmosphere is nitrogen and / or an inert gas; The catalyst is one or more of palladium acetate, bistriphenylphosphine palladium dichloride, tris(dibenzylideneacetone)dipalladium and bisdibenzylideneacetonepalladium; The base is one or more of potassium carbonate, sodium carbonate, sodium bicarbonate and potassium phosphate; The organic solvent is one or more of toluene, xylene, tert-butylbenzene, tetrahydrofuran, dioxane, dichloromethane and N,N-dimethylformamide.

9. A pressure probe, characterized in that: It comprises a polymer luminescent material; the polymer luminescent material comprises the space charge transfer polymer luminescent material with a polynorbornene skeleton as described in any one of claims 1 to 4 or the space charge transfer polymer luminescent material with a polynorbornene skeleton prepared by the preparation method as described in any one of claims 5 to 8.

10. The pressure probe according to claim 9, characterized in that The pressure probe structure comprises: a base; a lower anvil surface disposed on the base; A sample cavity is arranged on the lower anvil surface, wherein the sample cavity contains at least one pressure probe crystal, wherein the pressure probe crystal comprises one or more polynorbornene skeleton space charge transfer polymer luminescent materials according to any one of claims 1 to 4 or polynorbornene skeleton space charge transfer polymer luminescent materials prepared by the preparation method according to any one of claims 5 to 8; the sample cavity is composed of a gasket, and the gasket is located between two parallel and oppositely placed upper and lower anvil surfaces; an upper anvil surface disposed on the sample chamber; Sealing material, which is a metal gasket with small holes and is placed between the upper anvil surface and the lower anvil surface.

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