Polysulfonimide and its preparation method and application

Abstract

The present invention discloses a polysulfonimide and a preparation method and application thereof, wherein the polysulfonimide shown in formula I is: #imgabs0# wherein n is an integer of 2-500; R1 and R2 are each independently an arylene group, an arylene derivative or an alkylene group, and R3 and R4 are each independently an aryl group, an aryl derivative or an alkyl group. The polysulfonimide has a brand-new structure, aggregation-induced luminescence or non-traditional luminescence properties, and has potential application value in the fields of optical display and the like.

Description

Technical Field

[0001] The present invention relates to the technical field of organic high molecular polymers, and in particular to polysulfonimide and a preparation method and application thereof. Background Art

[0002] Heteroatom-rich non-conjugated polymers can be used as various general-purpose polymers and functional polymer materials and are widely used in daily life. In recent years, luminescent polymer materials based on heteroatom-rich non-conjugated polymers have attracted much attention due to their good biocompatibility, special biological activity and optoelectronic properties, and have been widely used in the fields of fluorescence sensing, stimulus-responsive materials, bioimaging, optoelectronic devices, etc. The development of modern science and technology has increased the demand for the structural and performance diversity of functional polymers, so there is an urgent need to prepare heteroatom-rich non-conjugated luminescent polymer materials with new structures.

[0003] Therefore, the prior art still needs to be improved and developed. Summary of the invention

[0004] In view of the above-mentioned deficiencies in the prior art, the purpose of the present invention is to provide a polysulfonimide and a preparation method and application thereof, aiming to provide a heteroatom-rich non-conjugated luminescent polymer material with a completely new structure to meet the needs of the development of modern science and technology for the structural and performance diversity of functional polymers.

[0005] The technical solution of the present invention is as follows:

[0006] In the first aspect of the present invention, a polysulfonimide of formula I is provided:

[0007]

[0008] Wherein, n is an integer of 2-500; R1 and R2 are each independently an arylene group, an arylene derivative or an alkylene group; R3 and R4 are each independently an aryl group, an aryl derivative or an alkyl group.

[0009] Optionally, R1 and R2 are each independently selected from one of the following structures:

[0010]

[0011]

[0012] Wherein, * is a connection site, m, h, k are integers of 1-20, R, R' are each independently a hydrogen atom, a halogen atom, a nitro group, an ester group, an alkyl group, an alkoxy group or an aryl group, and X is selected from N, P, O, S or Si.

[0013] Optionally, the R3 is selected from one of the following structures:

[0014]

[0015]

[0016] Wherein, * is a connection site, m is an integer of 1-20, and R and R' are each independently a hydrogen atom, a halogen atom, a nitro group, an ester group, an alkyl group, an alkoxy group or an aryl group.

[0017] Optionally, the R4 is selected from one of the following structures:

[0018]

[0019] Wherein, * is a connection site, m is an integer of 1-20, and R and R' are each independently a hydrogen atom, a halogen atom, a nitro group, an ester group, an alkyl group, an alkoxy group or an aryl group.

[0020] The second aspect of the present invention provides a method for preparing the polysulfonimide as described above, comprising the steps of:

[0021] Adding a dibasic acetylene compound, a dibasic sulfonyl azide compound, an aldehyde compound, a hydrazine compound, a monovalent copper catalyst, and triethylamine into an organic solvent to react, and then filtering to obtain a filtrate;

[0022] adding the filtrate into a precipitant for precipitation to obtain the polysulfonimide;

[0023] Wherein, the general structural formula of the dibasic acetylene compound is:

[0024] The general structural formula of the dibasic sulfonyl azide compound is:

[0025] The general structural formula of the aldehyde compound is: R3-CHO;

[0026] The general structural formula of the hydrazine compound is: R4-NHNH2.

[0027] Optionally, the molar ratio of the dibasic alkyne compound, the dibasic sulfonyl azide compound, the aldehyde compound, and the hydrazine compound is 1:1:(2-3):(2-3);

[0028] and / or, the reaction concentration of the dibasic acetylene compound is 0.1 to 0.4 mol / L;

[0029] and / or, the molar amount of the monovalent copper catalyst is 2 to 10% of the molar amount of the dibasic acetylene compound;

[0030] and / or, the molar amount of the triethylamine is 1.1 to 3.3 times the molar amount of the dibasic acetylene compound;

[0031] And / or, the monovalent copper catalyst includes at least one of cuprous iodide, cuprous bromide, and cuprous chloride;

[0032] And / or, the precipitant comprises at least one of methanol, ether, acetone and n-hexane;

[0033] And / or, the organic solvent includes at least one of dichloromethane, tetrahydrofuran, N,N-dimethylformamide and toluene;

[0034] And / or, the reaction temperature is room temperature, and the reaction time is 0.5 to 24 hours.

[0035] The third aspect of the present invention provides a use of the polysulfonimide of the present invention as described above or the polysulfonimide prepared by the preparation method of the present invention as described above in the field of optical display.

[0036] The fourth aspect of the present invention provides a use of the polysulfonimide of the present invention as described above or the polysulfonimide prepared by the preparation method of the present invention as described above in the preparation of polysulfonamide.

[0037] Optionally, the preparation method comprises the steps of:

[0038] The polysulfonimide is added into an acidic solution for reaction to obtain the polysulfonamide.

[0039] In a fifth aspect of the present invention, a polysulfonamide of formula II is provided:

[0040]

[0041] The polysulfonamide is obtained by reacting the polysulfonimide of the present invention as described above or the polysulfonimide prepared by the preparation method of the present invention as described above in an acidic solution.

[0042] Beneficial effects: The present invention provides a novel structure of heteroatom-rich non-conjugated luminescent polymer material, namely, a novel structure of polysulfonimide, which is used to meet the requirements of modern science and technology for the structural and performance diversity of functional polymers. The polysulfonimide has aggregation-induced luminescence or non-traditional luminescence properties and has potential application value in the fields of optical display and the like. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] Figure 1 This is the hydrogen nuclear magnetic resonance spectrum of the polysulfonimide P1 in Example 1 of the present invention in deuterated chloroform.

[0044] Figure 2 (A) is a photoluminescence spectrum diagram of polysulfonimide P1 in Example 1 of the present invention at different excitation wavelengths, and (b) is a corresponding color coordinate change diagram.

[0045] Figure 3 This is the hydrogen nuclear magnetic resonance spectrum of the polysulfonimide P2 in deuterated chloroform in Example 2 of the present invention.

[0046] Figure 4 (A) is a photoluminescence spectrum of polysulfonimide P2 in Example 2 of the present invention in tetrahydrofuran / water mixed solvents with different water contents, and (B) is a graph showing the trend of luminescence intensity changes.

[0047] Figure 5 This is the hydrogen nuclear magnetic resonance spectrum of the polysulfonimide P3 in deuterated chloroform in Example 3 of the present invention.

[0048] Figure 6 (A) is a comparison of the H NMR spectra of polysulfonamide P1-HCl, compound 6 and polysulfonimide P1 in Example 4 of the present invention, and (B) is a H NMR spectrum of the conversion rate and product of polysulfonimide P1 in Example 1 at different reaction times in an acidic solution. DETAILED DESCRIPTION

[0049] The present invention provides a polysulfonimide and a preparation method and application thereof. To make the purpose, technical solution and effect of the present invention clearer and more specific, the present invention is further described in detail below. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0050] Unless otherwise defined, all technical terms and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used in the specification of the present invention herein are only for the purpose of describing specific embodiments and are not intended to limit the present invention.

[0051] The embodiment of the present invention provides a polysulfonimide represented by formula I:

[0052]

[0053] Wherein, n is an integer of 2-500; R1 and R2 are each independently an arylene group, an arylene derivative or an alkylene group; R3 and R4 are each independently an aryl group, an aryl derivative or an alkyl group.

[0054] The polysulfonimide with a new structure provided in this embodiment has aggregation-induced emission or non-traditional emission properties, and has potential application value in the fields of optical display and the like.

[0055] In some embodiments, R1 and R2 are each independently selected from one of the following structures:

[0056]

[0057]

[0058] Wherein, * is a connection site, m, h, k are integers of 1-20, R, R' are each independently a hydrogen atom, a halogen atom, a nitro group, an ester group, an alkyl group, an alkoxy group or an aryl group, and X is selected from N, P, O, S or Si. Exemplarily, m can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20; h can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20.

[0059] In some embodiments, the R3 is selected from one of the following structures:

[0060]

[0061] Wherein, * is a connection site, m is an integer of 1-20, R, R' are each independently a hydrogen atom, a halogen atom, a nitro group, an ester group, an alkyl group, an alkoxy group or an aryl group. Exemplarily, m can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20.

[0062] In some embodiments, the R4 is selected from one of the following structures:

[0063]

[0064] Wherein, * is a connection site, m is an integer of 1-20, and R and R' are each independently a hydrogen atom, a halogen atom, a nitro group, an ester group, an alkyl group, an alkoxy group or an aryl group.

[0065] The commonly used synthesis methods of existing polyimides are often limited to two-component step-by-step polymerization reactions of monomer combinations such as moisture-sensitive imide chlorides, diols or dianhydrides, and diisocyanates. The limitations of the types of reaction substrates severely restrict the structural diversity of the products and further functional exploration. In recent years, copper-catalyzed multi-component click polymerization, which has been developed from the frontier progress of organic chemistry, has provided new opportunities for the synthesis of functional polyimides with novel structures. Polysulfonimide derivatives with heterochain or heterocyclic structures can be generated by three-component polymerization reactions of alkynes, sulfonyl azides, and nucleophiles such as alcohols or amines or salicylaldehyde. However, the existing multi-component polymerization reactions of this type are still mainly concentrated in three-component polymerizations, which make it difficult to introduce a large number of heteroatoms and multiple substituents at the same time, and require nitrogen conditions to proceed smoothly, and are still relatively simple in terms of product structure and function. These deficiencies have greatly limited the preparation and performance research of multi-substituted polysulfonimide functional polymer materials. Based on this, an embodiment of the present invention also provides a method for preparing a polysulfonimide as described above in an embodiment of the present invention, which includes the steps of:

[0066] S1, adding a dibasic acetylene compound, a dibasic sulfonyl azide compound, an aldehyde compound, a hydrazine compound, a monovalent copper catalyst, and triethylamine to an organic solvent for reaction, and then filtering to obtain a filtrate;

[0067] S2, adding the filtrate into a precipitant for precipitation to obtain the polysulfonimide;

[0068] Wherein, the general structural formula of the dibasic acetylene compound is:

[0069] The general structural formula of the dibasic sulfonyl azide compound is:

[0070] The general structural formula of the aldehyde compound is: R3-CHO;

[0071] The general structural formula of the hydrazine compound is: R4-NHNH2.

[0072] The polymerization method provided in the embodiment of the present invention adopts cheap and readily available monomers, and in an air environment (without nitrogen conditions), a series of polysulfonimides can be efficiently synthesized by reacting four components (dibasic alkyne compounds, dibasic sulfonyl azide compounds, aldehyde compounds, hydrazine compounds) in one step, with good yield, high molecular weight of the obtained polysulfonimide, relative weight average molecular weight of up to 80,000, and polymer dispersibility index (PDI) of about 1.3. At the same time, the polysulfonimide product is easy to separate, and only needs to be precipitated once in a precipitant to obtain a high-purity polysulfonimide. The polysulfonimide prepared by the present invention has aggregation-induced luminescence or non-traditional luminescent properties, and has potential application value in the fields of optical display. Therefore, the present invention provides a polysulfonimide luminescent material that can be easily and efficiently prepared with unique structure and advanced functions, which is of great value in both academic and industrial fields.

[0073] In this embodiment, R1 in the general structural formula of the dibasic acetylene compound, R2 in the general structural formula of the dibasic sulfonyl azide compound, R3 in the general structural formula of the aldehyde compound, and R4 in the general structural formula of the hydrazine compound are respectively the same as R1, R2, R3, and R4 in the above-mentioned polysulfonimide.

[0074] In some embodiments, the molar ratio of the dibasic alkyne compound, the dibasic sulfonyl azide compound, the aldehyde compound, and the hydrazine compound is 1:1:(2-3):(2-3).

[0075] In some embodiments, the reaction concentration of the dibasic alkyne compound is 0.1 to 0.4 mol / L.

[0076] In some embodiments, the molar amount of the monovalent copper catalyst is 2-10% of the molar amount of the dibasic alkyne compound.

[0077] In some embodiments, the molar amount of the triethylamine is 1.1 to 3.3 times the molar amount of the dibasic acetylene compound.

[0078] In some embodiments, the monovalent copper catalyst includes at least one of cuprous iodide, cuprous bromide, and cuprous chloride, but is not limited thereto.

[0079] In some embodiments, the precipitant includes at least one of methanol, ether, acetone, and n-hexane, but is not limited thereto.

[0080] In some embodiments, the organic solvent includes at least one of dichloromethane, tetrahydrofuran, N,N-dimethylformamide, and toluene, but is not limited thereto.

[0081] In some embodiments, the reaction temperature is room temperature, and the reaction time is 0.5 to 24 hours.

[0082] In some embodiments, the reaction temperature is room temperature and the reaction time is 1 hour, that is, the reaction can be carried out at room temperature and air conditions, the conditions are mild, the method is simple, and it can be completed within one hour to prepare high-yield, high-molecular-weight polysulfonimide.

[0083] The embodiment of the present invention further provides an application of the polysulfonimide described above in the embodiment of the present invention or the polysulfonimide prepared by the preparation method described above in the embodiment of the present invention in the field of optical display (such as biological imaging).

[0084] The inventor unexpectedly discovered that a polysulfonamide with a completely new structure can be prepared by using the polysulfonimide. Based on this, the present invention also provides a use of the polysulfonimide described above in the present invention or the polysulfonimide prepared by the preparation method described above in the present invention in the preparation of polysulfonamide.

[0085] In one embodiment, the method of preparation comprises the steps of:

[0086] The polysulfonimide is added into an acidic solution for reaction to obtain the polysulfonamide.

[0087] The present invention also provides a polysulfonamide shown in Formula II:

[0088]

[0089] The polysulfonamide is obtained by reacting the polysulfonimide described in the embodiment of the present invention or the polysulfonimide prepared by the preparation method described in the embodiment of the present invention in an acidic solution.

[0090] The following describes it in detail through specific embodiments.

[0091] Example 1

[0092] This embodiment provides a linear polysulfonimide P1, whose structural formula is:

[0093]

[0094] The synthetic route of the linear polysulfonimide P1 is as follows:

[0095]

[0096] This embodiment also provides a method for preparing the linear polysulfonimide P1, comprising the following steps:

[0097] (1) Take a 15 mL Schlenk polymerizer tube with a branch, add a magnetron, a dibasic alkynyl compound 1a (0.30 mmol, 132 mg), a dibasic sulfonyl azide compound 2a (0.30 mmol, 114 mg), an aldehyde compound 3 (0.72 mmol, 85 μL), a hydrazine compound 4 (0.72 mmol, 72 μL) and CuI (0.012 mmol, 2.4 mg) in sequence, add 1 mL of anhydrous dichloromethane (DCM) to it with a syringe, stir the solution evenly, add triethylamine (0.33 mmol, 47 μL) dropwise with a pipette, and stir the reaction at room temperature for 1 hour. After the reaction is complete, dilute the reaction mother solution with 1 mL of dichloromethane, filter through a 1 cm thick neutral alumina column, and obtain a filtrate;

[0098] (2) The filtrate was added to 100 mL of ether for precipitation, and the precipitate was collected and dried under vacuum at 55° C. to constant weight to obtain polysulfonimide P1 with a yield of 77%, a relative weight average molecular weight of 86,000 g / mol, and a PDI of 1.27.

[0099] In the above steps, the dibasic alkynyl compound 1a is prepared according to the method disclosed in the literature (Macromolecules, 2014, 47, 1325); the dibasic sulfonyl azide compound 2a is prepared according to the method disclosed in the literature (J. Energ. Mater., 2007, 25, 79); the aldehyde compound 3 and the hydrazine compound 4 can be directly purchased.

[0100] The H NMR spectrum of the linear polysulfonimide P1 prepared by the preparation method of this embodiment in deuterated chloroform is as follows: Figure 1 As shown. Figure 1 It can be seen that at 7.26 and 1.56 ppm ( Figure 1 The characteristic peaks at * in the middle are the solvent peak and water peak of deuterated chloroform. In addition, the remaining characteristic peaks are the characteristic peaks of hydrogen atom signals in polysulfonimide. Several characteristic hydrogen atom signals can also be assigned accordingly, among which the peak at 2.35ppm ( Figure 1 b in the figure) is the characteristic peak of the methyl hydrogen atom in the polysulfonimide P1, and 5.00 ppm ( Figure 1 The a in the figure is the characteristic peak of the methylene hydrogen atom of polysulfonimide P1.

[0101] Figure 2 The photoluminescence spectrum and color coordinate changes of the linear polysulfonimide P1 prepared in Example 1 of the present invention at an excitation wavelength of 300-450 nm, wherein Figure 2 Middle (A) is the photoluminescence spectrum; Figure 2(B) is the corresponding color coordinate spectrum. It can be seen that with the increase of the excitation wavelength, the emission wavelength of polysulfonimide P1 gradually redshifts, and the corresponding color coordinates gradually change from blue light to white light and finally to the yellow light range.

[0102] Example 2

[0103] This embodiment provides a linear polysulfonimide P2, whose structural formula is:

[0104]

[0105] The synthetic route of the linear polysulfonimide P2 is as follows:

[0106]

[0107] This embodiment also provides a method for preparing the linear polysulfonimide P2, comprising the following steps:

[0108] (1) Take a 15 mL Schlenk polymerization tube with a branch, add a magnetron, a dibasic alkynyl compound 1b (0.30 mmol, 114 mg), a dibasic sulfonyl azide compound 2b (0.30 mmol, 127 mg), an aldehyde compound 3 (0.72 mmol, 85 μL), a hydrazine compound 4 (0.72 mmol, 72 μL) and CuI (0.012 mmol, 2.4 mg) in sequence, add 1 mL of anhydrous DCM to it with a syringe, stir the solution evenly, add triethylamine (0.33 mmol, 47 μL) dropwise with a pipette, and stir the reaction at room temperature for 1 h. After the reaction is complete, dilute the reaction mother liquor with 1 mL of DCM, filter through a 1 cm thick neutral alumina column, and obtain a filtrate;

[0109] (2) The filtrate was added into 100 mL of ether for precipitation, and the precipitate was collected and dried under vacuum at 55° C. to constant weight to obtain polysulfonimide P2 with a yield of 90%, a relative weight average molecular weight of 87700 g / mol, and a PDI of 1.26.

[0110] In this example, the dibasic alkynyl compound 1b was prepared according to the method disclosed in the literature (Polym.Chem.2012,3,1481), and the dibasic sulfonyl azide compound 2b was prepared according to the method disclosed in the literature (Macromolecules, 2019,52,4526 and J.Energ.Mater., 2007,25,79).

[0111] The H NMR spectrum of the polysulfonimide P2 prepared by the preparation method of this embodiment in deuterated chloroform is as follows: Figure 3 As shown. Figure 3 It can be seen that at 7.26 and 1.56 ppm ( Figure 3 The characteristic peaks at * in the middle are the solvent peak and water peak of deuterated chloroform. In addition, the remaining characteristic peaks are the characteristic peaks of hydrogen atom signals in polysulfonimide, and the characteristic hydrogen atom signals can also be assigned accordingly. Among them, the peak at 2.36ppm ( Figure 3 e) is the characteristic peak of the methyl hydrogen atom in polysulfonimide P2, and 4.26 and 4.83 ppm (corresponding to Figure 3 (d, c) are the characteristic peaks of methylene hydrogen atoms in polysulfonimide.

[0112] The photoluminescence curves of the polysulfonimide P2 prepared by the preparation method of this embodiment in tetrahydrofuran solutions with different water contents are as follows: Figure 4 Specifically, mixed solutions with a volume ratio of tetrahydrofuran to water of 100:0, 90:10, 80:20, 70:30, 60:40, 50:50, 40:60, 30:70, 20:80, 10:90, and 5:95 were prepared, and polysulfonimide P2 was dissolved in these solutions while maintaining the concentration of polysulfonimide P2 in the solutions at 10 μmol / L. Figure 4 It can be seen that as the water content increases, the fluorescence intensity of the polymer gradually increases and reaches a maximum at 95% water content. That is, as the water content in the mixed solution increases, when it increases to a certain extent, the polysulfonimide P2 aggregates and generates fluorescence, that is, the polysulfonimide P2 exhibits obvious aggregation-induced emission.

[0113] Example 3

[0114] This embodiment provides a linear polysulfonimide P3, whose structural formula is:

[0115]

[0116] The synthetic route of the linear polysulfonimide P3 is as follows:

[0117]

[0118] The embodiment of the present invention also provides a method for preparing the polysulfonimide P3, comprising the following steps:

[0119] (1) Take a 15 mL Schlenk polymerizer tube with a branch, add a magnetron, a dibasic alkynyl compound 1c (0.30 mmol, 61 mg), a dibasic sulfonyl azide compound 2a (0.30 mmol, 114 mg), an aldehyde compound 3 (0.72 mmol, 85 μL), a hydrazine compound 4 (0.72 mmol, 72 μL) and CuI (0.012 mmol, 2.4 mg) in sequence, add 1 mL of anhydrous DCM to it with a syringe, stir the solution evenly, add triethylamine (0.33 mmol, 47 μL) dropwise with a pipette, and stir the reaction at room temperature for 1 hour. After the reaction is complete, dilute the reaction mother liquor with 1 mL of DCM, filter through a 1 cm thick neutral alumina column, and obtain a filtrate;

[0120] (2) The filtrate was added into 100 mL of ether for precipitation, and the precipitate was collected and dried under vacuum at 55° C. to constant weight to obtain polysulfonimide P3 with a yield of 82%, a relative weight average molecular weight of 55,500 g / mol, and a PDI of 1.35.

[0121] The dibasic alkynyl compound 1c in this example is prepared by referring to the dibasic alkynyl compound 1a in Example 1.

[0122] The nuclear magnetic resonance hydrogen spectrum of the polysulfonimide P3 in deuterated chloroform of this example is as follows Figure 5 As shown. Figure 5 It can be seen that the positions at 7.26 and 1.56 ppm ( Figure 5 The characteristic peaks at * in the middle are the solvent peak of deuterated chloroform and the water peak, respectively, located at 1.40ppm ( Figure 5 The characteristic peak at * in the middle is the peak of cyclohexane impurity in the solvent. In addition, the remaining characteristic peaks are the characteristic peaks of hydrogen atom signals in polysulfonimide, and the characteristic hydrogen atom signals can also be assigned accordingly. Among them, the peak at 2.36ppm ( Figure 5 g) is the characteristic peak of the methyl hydrogen atom in the polysulfonimide P3, and 5.00 ppm (corresponding to Figure 5 (f) is the characteristic peak of the methylene hydrogen atom in the polysulfonimide P3.

[0123] Example 4

[0124] This embodiment provides a polysulfonamide P1-HCl, whose structural formula is:

[0125]

[0126] The synthetic route of the polysulfonamide P1-HCl is as follows:

[0127]

[0128] This embodiment also provides a method for preparing the polysulfonamide P1-HCl, comprising the following steps:

[0129] Polysulfonimide P1 (30 mg) was added to tetrahydrofuran (THF) (2 mL), and then hydrochloric acid (1 mL, HCl concentration was 36%) was added, and the reaction was stirred for 16 h to obtain polysulfonamide P1-HCl, which had a relative weight average molecular weight of 47300 g / mol and a PDI of 1.26.

[0130] In order to verify the structure of polysulfonamide P1-HCl, a model reaction was carried out on the model compound. The model compound 5 (30 mg) was added to THF (2 mL), and then hydrochloric acid (1 mL, HCl concentration was 36%) was added, and the reaction was stirred for 1 h to obtain compound 6. The synthesis route is as follows:

[0131]

[0132] The H NMR spectra of polysulfonimide P1, compound 6 and polysulfonamide P1-HCl were compared. Figure 6 As shown in (A) in FIG. 1 . After the conversion under acidic conditions, the characteristic peaks of the protons at "a" and "b" of polysulfonimide P1 significantly moved to new positions or disappeared completely in the spectra of compound 6 and polysulfonamide P1-HCl. In addition, a new characteristic peak at "i" related to NH protons was observed in the spectra of compound 6 and polysulfonamide P1-HCl.

[0133] At the same time, the conversion rate of polysulfonamide P1 at different reaction times after adding hydrochloric acid and the nuclear magnetic resonance hydrogen spectrum of the system substances were detected. The results are as follows Figure 6 As shown in (B), it was confirmed that polysulfonimide P1 was completely converted into polysulfonamide P1-HCl after 16 hours of reaction. In addition, polysulfonamide P1-HCl also has luminescent properties.

[0134] In summary, the present invention provides a polysulfonimide and its preparation method and application. The polysulfonimide has aggregation-induced luminescence or non-traditional luminescent properties, and has potential application value in the fields of optical display. The polymerization method provided by the present invention adopts cheap and readily available monomers, and a series of polysulfonimides can be efficiently synthesized in one step by four-component reaction at room temperature and air environment (without nitrogen conditions), with good yield, high molecular weight of the obtained polysulfonimide, relative weight average molecular weight of up to 80,000, polymer dispersibility index (PDI) of about 1.3, short reaction time, mild conditions, and simple method. At the same time, the polysulfonimide product is easy to separate, and only needs to be precipitated once in a precipitant to obtain a high-purity polysulfonimide. Therefore, the present invention provides a polysulfonimide luminescent material with unique structure and advanced functions that can be prepared conveniently and efficiently, which is of great value in both academic and industrial fields.

[0135] It should be understood that the application of the present invention is not limited to the above examples. For ordinary technicians in this field, improvements or changes can be made based on the above description. All these improvements and changes should fall within the scope of protection of the claims attached to the present invention.

Claims

1. Polysulfonimide represented by formula I: in, n is an integer of 2-500; R1 and R2 are each independently an arylene group, an arylene derivative or an alkylene group; R3 and R4 are each independently an aryl group, an aryl derivative or an alkyl group.

2. The polysulfonimide according to claim 1, characterized in that The R1 and R2 are each independently selected from one of the following structures: Wherein, * is a connection site, m, h, k are integers of 1-20, R, R' are each independently a hydrogen atom, a halogen atom, a nitro group, an ester group, an alkyl group, an alkoxy group or an aryl group, and X is selected from O or S.

3. The polysulfonimide according to claim 1, characterized in that The R3 is selected from one of the following structures: Wherein, * is a connection site, m is an integer of 1-20, and R and R' are each independently a hydrogen atom, a halogen atom, a nitro group, an ester group, an alkyl group, an alkoxy group or an aryl group.

4. The polysulfonimide according to claim 1, characterized in that The R4 is selected from one of the following structures: Wherein, * is a connection site, m is an integer of 1-20, and R and R' are each independently a hydrogen atom, a halogen atom, a nitro group, an ester group, an alkyl group, an alkoxy group or an aryl group.

5. A method for preparing the polysulfonimide according to any one of claims 1 to 4, characterized in that: Includes steps: Adding a dibasic acetylene compound, a dibasic sulfonyl azide compound, an aldehyde compound, a hydrazine compound, a monovalent copper catalyst, and triethylamine into an organic solvent to react, and then filtering to obtain a filtrate; adding the filtrate into a precipitant for precipitation to obtain the polysulfonimide; Wherein, the general structural formula of the dibasic alkyne compound is: The general structural formula of the dibasic sulfonyl azide compound is: The general structural formula of the aldehyde compound is: R3-CHO; The general structural formula of the hydrazine compound is: R4-NHNH2.

6. The preparation method according to claim 5, characterized in that: The molar ratio of the dibasic alkyne compound, the dibasic sulfonyl azide compound, the aldehyde compound and the hydrazine compound is 1:1:(2-3):(2-3); and / or, the reaction concentration of the dibasic acetylene compound is 0.1 to 0.4 mol / L; and / or, the molar amount of the monovalent copper catalyst is 2 to 10% of the molar amount of the dibasic acetylene compound; and / or, the molar amount of the triethylamine is 1.1 to 3.3 times the molar amount of the dibasic acetylene compound; And / or, the monovalent copper catalyst includes at least one of cuprous iodide, cuprous bromide, and cuprous chloride; And / or, the precipitant comprises at least one of methanol, ether, acetone and n-hexane; And / or, the organic solvent includes at least one of dichloromethane, tetrahydrofuran, N,N-dimethylformamide and toluene; And / or, the reaction temperature is room temperature, and the reaction time is 0.5 to 24 hours.

7. Use of the polysulfonimide according to any one of claims 1 to 4 or the polysulfonimide prepared by the preparation method according to any one of claims 5 to 6 in the field of optical display.

8. Use of the polysulfonimide according to any one of claims 1 to 4 or the polysulfonimide prepared by the preparation method according to any one of claims 5 to 6 in the preparation of polysulfonamide.

9. The use according to claim 8, characterized in that: The preparation method comprises the steps of: The polysulfonimide is added into an acidic solution for reaction to obtain the polysulfonamide.

10. Polysulfonamide represented by formula II: The polysulfonamide is obtained by reacting the polysulfonimide described in any one of claims 1 to 4 or the polysulfonimide prepared by the preparation method described in any one of claims 5 to 6 in an acidic solution.

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