A linear fluorescent polymer and its preparation method

By generating linear fluorescent polymers through the click reaction of secondary amino alcohols with activated alkyne monomers, the problem of low solid-state fluorescence quantum yield of conventional fluorescent polymers is solved, achieving efficient preparation of fluorescent materials with high yield and broad application potential.

CN119875116BActive Publication Date: 2025-10-31CHANGZHOU UNIV
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Patent Information

Application Number
CN202510014477.3
Authority / Receiving Office
CN · China
Patent Type
Patents(China)
Current Assignee / Owner
Filing Date
2025-01-06
Publication Date
2025-10-31
Estimated Expiration
2045-01-06

AI Technical Summary

Technical Problem

In existing technologies, the solid-state fluorescence quantum yield of conventional linear fluorescent polymers obtained by reacting tertiary amines with activated alkyne monomers is difficult to reach more than 10%.

Method used

A linear fluorescent polymer is generated by a click reaction between a secondary amino alcohol monomer and an activated alkyne monomer. During the reaction, the alkyne group first clicks with the primary or secondary amino group of the amino alcohol monomer, and then clicks with the hydroxyl group. The two ends of the activated alkyne monomer molecular chain are capped by alkyne groups, and the reaction is carried out at room temperature and atmospheric pressure without the need for a catalyst.

Benefits of technology

The solid-state fluorescence quantum yield of fluorescent polymers has reached over 30%, exhibiting high atom utilization, good selectivity, and excellent yield. It is applicable to a variety of temperature ranges and has promising market prospects.

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Abstract

This invention relates to the field of fluorescent polymer technology, specifically to a linear fluorescent polymer and its preparation method. The solid-state fluorescence quantum yield of linear fluorescent polymers obtained by reacting tertiary amines with activated alkyne monomers is difficult to reach 10%. Based on the above problem, this invention provides a linear fluorescent polymer obtained by triggering click reactions between a monohydric secondary amino alcohol and an activated alkyne monomer. In this invention, during the click reaction between the monohydric secondary amino alcohol and the activated alkyne monomer, the amino group first reacts with the alkyne group, followed by the hydroxyl group. This results in a higher quantum yield in the obtained fluorescent polymer, exhibiting a high solid-state fluorescence quantum yield, easily reaching over 10%, and even exceeding 20%, achieving better technical results.
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Description

Technical Field

[0001] This invention relates to the field of fluorescent polymer technology, and more specifically to a linear fluorescent polymer and its preparation method. Background Technology

[0002] In recent years, non-conjugated fluorescent polymer systems with heteroatom-rich characteristics have attracted widespread attention due to their excellent biocompatibility, environmental friendliness, and simple preparation, and have become ideal candidate materials for sensor, biological, and medical applications. However, most non-traditional fluorescent polymer materials currently emit fluorescence mainly in the blue or green region, and it is difficult to achieve full-color luminescence polymers by structural modulation. Therefore, developing new methods to synthesize non-conjugated fluorescent polymers that can obtain full-color fluorescence by directly modifying monomers is of great significance for enriching the types of fluorescent polymers and understanding fluorescence mechanisms.

[0003] Click polymerization is a highly efficient method for polymer synthesis due to its advantages such as good selectivity, wide applicability, mild conditions, high efficiency, no byproducts, and atom economy. Researchers have now achieved high-yield production of nitrogen-containing polymers by click polymerization of nucleophilic amine monomers with unsaturated monomers (double or triple bonds) at room temperature under catalytic-free conditions. Hydroxyl monomers, like amino monomers, are also commonly used nucleophiles. Compared to amines, alcohol monomers have the advantages of being more diverse, widely available, stable, and non-toxic with no irritating odor. However, the polymerization of alcohol monomers with unsaturated monomers usually requires the addition of a catalyst.

[0004] Using click reactions, the research team of this invention has developed a variety of fluorescent polymer luminescent materials. For example, Chinese invention patent CN 114736363 A discloses a fluorescent polymer and a method for controlling the emission color of the fluorescent polymer. This patent uses the reaction of tertiary amines with activated alkyne monomers to obtain macromolecular polymers with red, blue and green fluorescence properties. However, the solid fluorescence quantum yield of the fluorescent polymers obtained by this patent is all below 10%, which is difficult to reach the 10% level. Summary of the Invention

[0005] A problem with existing technologies is that the solid-state fluorescence quantum yield of conventional linear fluorescent polymers obtained by reacting tertiary amines with activated alkyne monomers is difficult to reach above 10%. To address this problem, this invention provides a linear fluorescent polymer generated by a click reaction between a secondary amino alcohol monomer and an activated alkyne monomer. During the reaction, the alkynyl group in the alkyne monomer structure first undergoes a click reaction with the primary or secondary amino group in the amino alcohol monomer structure, and then with the hydroxyl group in the amino alcohol monomer structure. The activated alkyne monomer molecular chain is end-capped with alkynyl groups at both ends, and the secondary amino alcohol monomer is a monohydric alcohol.

[0006] Preferably, the activated alkyne monomer includes an ester-activated alkyne monomer, an amide-activated alkyne monomer, or a ketone-activated alkyne monomer.

[0007] Preferably, the activated alkyne monomer includes di-alkynyl monomers and poly-alkynyl monomers whose molecular chains are both capped with alkyne groups at both ends.

[0008] Preferably, the diacetylene monomer comprises the following structural formula:

[0009]

[0010] In the above structural formula, m is 1 to 3, and n>2.

[0011] Preferably, the activated acetylene monomer comprises one or more of the following: ethylene glycol dipropynate, 1,4-butanediol dipropynate, 1,6-hexanediol dipropynate, polyethylene glycol-acetylene, ethylene glycol dipropynate, and dipropynyl acetamide.

[0012] Preferably, the polyacetylenic monomer comprises the following structural formula:

[0013]

[0014] Preferably, the secondary amino alcohol monomer comprises the following structural formula:

[0015]

[0016]

[0017] In the above structural formula, R1 includes methyl, ethyl, isopropyl, alicyclic or benzene ring, and R2 includes a methylene chain with 1 or more carbon atoms.

[0018] Preferably, the secondary amino alcohol monomer includes one or more of 3-(methylamino)-1-propanol, 1-(methylamino)prop-2-ol, 4-piperidinemethanol, 2-(cyclohexylamino)ethanol or 2-benzylaminoethanol.

[0019] Preferably, the linear fluorescent polymer comprises the following chemical structural formula:

[0020]

[0021]

[0022] In the above chemical structural formula, the value of n is determined based on the reaction temperature, reaction time, and the amount of secondary amine alcohol monomer and activated acetylene monomer used in the click reaction.

[0023] Preferably, the secondary amino alcohol monomer in the click reaction process is 3-(methylamino)-1-propanol, and the activated alkynyl monomer is ethylene glycol dipropynate.

[0024] Preferably, the click reaction occurs at room temperature and atmospheric pressure, and the molar ratio of the secondary amino alcohol monomer to the activated alkyne monomer in the click reaction is 1:1.

[0025] The present invention has the following beneficial effects:

[0026] (1) The present invention obtains a series of linear fluorescent polymers by clicking reaction of a mono-secondary amino alcohol with an activated alkyne monomer. By optimizing the type of the mono-secondary amino alcohol, the obtained fluorescent polymers have a high solid fluorescence quantum yield of more than 30%, achieving good technical results.

[0027] (2) In the process of the click reaction between the monoamine alcohol and the activated alkynyl monomer in this invention, the amino group first reacts with the alkynyl group, and then the hydroxyl group reacts with the alkynyl group, resulting in a higher photon yield of the fluorescent polymer.

[0028] (3) The method of the present invention has high atom utilization, good selectivity, and good yield. It does not require the use of any catalyst and can react in a temperature range of 0-60℃, which has good market prospects. Attached Figure Description

[0029] Figure 1 : This is the 1H NMR spectrum of the fluorescent polymer obtained in Example 1.

[0030] Figure 2 : This is the fluorescence spectrum of the fluorescent polymer obtained in Example 1.

[0031] Figure 3 : This is the 1H NMR spectrum of the fluorescent polymer obtained in Example 2.

[0032] Figure 4 : This is the fluorescence spectrum of the fluorescent polymer obtained in Example 2.

[0033] Figure 5 : This is the 1H NMR spectrum of the fluorescent polymer obtained in Example 3.

[0034] Figure 6 : This is the fluorescence spectrum of the fluorescent polymer obtained in Example 3.

[0035] Figure 7 : This is the 1H NMR spectrum of the fluorescent polymer obtained in Example 4.

[0036] Figure 8 : This is the fluorescence spectrum of the fluorescent polymer obtained in Example 4.

[0037] Figure 9 : This is the 1H NMR spectrum of the fluorescent polymer obtained in Example 5.

[0038] Figure 10: This is the fluorescence spectrum of the fluorescent polymer obtained in Example 5.

[0039] Figure 11 : This is the 1H NMR spectrum of the fluorescent polymer obtained in Example 6.

[0040] Figure 12 : This is the fluorescence spectrum of the fluorescent polymer obtained in Example 6.

[0041] Figure 13 : This is the 1H NMR spectrum of the fluorescent polymer obtained in Example 7.

[0042] Figure 14 : This is the fluorescence spectrum of the fluorescent polymer obtained in Example 7.

[0043] Figure 15 : This is the 1H NMR spectrum of the fluorescent polymer obtained in Example 8.

[0044] Figure 16 : This is the fluorescence spectrum of the fluorescent polymer obtained in Example 8.

[0045] Figure 17 : This is the fluorescence spectrum of the fluorescent polymer obtained in Example 9.

[0046] Figure 18 : This is the fluorescence spectrum of the fluorescent polymer obtained in Example 10.

[0047] Figure 19 : This is the ion-responsive fluorescence spectrum of the fluorescent polymer obtained in Example 4.

[0048] Figure 20 : This is an intracellular imaging image of the fluorescent polymer obtained in Example 4. Detailed Implementation

[0049] The present invention will be described in detail below with reference to embodiments. However, it should be understood that the following embodiments are merely illustrative examples of implementation of the present invention and are not intended to limit the scope of the present invention.

[0050] The activated alkyne monomers used in the following embodiments of the present invention are all commercially available or easily synthesized. It can be synthesized according to the method reported in the reference (ACS Appl. Polym. Mater. 2024, 6, 4127-4137).

[0051] Example 1

[0052] 3-(methylamino)-1-propanol (0.089 g, 1 equiv) and ethylene glycol dipropynate (0.166 g, 1 equiv) were added to a 5 mL single-necked polymerization flask and stirred in air at 25 °C for 24 h. After the reaction was completed, the mixture was precipitated with n-hexane to obtain a linear fluorescent polymer (LP-1) with a yield of 97% and an E configuration of 100%. The structure of the target polymer was confirmed by 1H NMR spectroscopy as shown in the appendix to the instruction manual. Figure 1 As shown. Volumetric exclusion chromatography characterization of the polymer revealed a weight-average molecular weight of 29000 g / mol and a molecular weight distribution of 1.73, indicating that this method can prepare linear polymers with high molecular weights. (See attached specification). Figure 2 As shown, the excitation and emission wavelengths of LP-1 in the fluorescence test were 572 nm and 615 nm, respectively, exhibiting red fluorescence characteristics, with a solid-state fluorescence quantum yield of 30.28%. The patterns and QR codes formed by the LP-1 solution (solvent being N,N-dimethylformamide) were invisible under visible light but clearly visible under ultraviolet light, indicating that LP-1 is a potential security and anti-counterfeiting fluorescent material.

[0053] The chemical formulas involved in the above reaction are as follows:

[0054]

[0055] Example 2

[0056] 0.089 g of 3-(methylamino)-1-propanol (1 equiv) and 0.194 g of 1,4-butanediol dipropynate (1 equiv) were added to a 5 mL single-necked polymerization flask and stirred in air at 25 °C for 24 h. After the reaction was completed, the mixture was precipitated with hexane to obtain a linear fluorescent polymer (LP-2) with a yield of 90% and an E configuration of 98%. The structure of the target polymer was confirmed by proton nuclear magnetic resonance spectroscopy as shown in the appendix to the instruction manual. Figure 3 As shown. Volume exclusion chromatography characterization revealed that the polymer's weight-average molecular weight was 30300 g / mol, and its molecular weight distribution was 1.86, indicating that this method can prepare linear fluorescent polymers with high molecular weights. Fluorescence testing showed that the excitation and emission wavelengths of this fluorescent polymer were 472 nm and 549 nm, respectively (as shown in the attached specification). Figure 4 As shown, it exhibits green fluorescence properties, with a solid-state fluorescence quantum yield of 19.88%. The patterns and QR codes formed by this fluorescent polymer solution (with N,N-dimethylformamide as the solvent) are invisible under visible light but clearly visible under ultraviolet light, indicating that it is a potential security and anti-counterfeiting fluorescent material.

[0057] The chemical formulas involved in the above reaction are as follows:

[0058]

[0059] Example 3

[0060] 3-(methylamino)-1-propanol (0.089 g, 1 equiv) and 1,6-hexanediol dipropynate (0.222 g, 1 equiv) were added to a 5 mL single-necked polymerization flask and stirred in air at 25 °C for 24 h. After the reaction was completed, the mixture was precipitated with n-hexane to obtain a linear fluorescent polymer (LP-3) with a yield of 89% and an E configuration of 100%. The target polymer was confirmed by 1H NMR spectroscopy (as per the instructions). Figure 5 (As shown). Volume exclusion chromatography characterization revealed a polymer with a weight-average molecular weight of 49300 g / mol and a molecular weight distribution of 1.84, indicating that this method can prepare fluorescent polymers with high molecular weights. The excitation and emission wavelengths of the polymer for fluorescence testing were 423 nm and 476 nm, respectively (as shown in the attached specification). Figure 6 As shown, it exhibits blue fluorescence properties, with a solid-state fluorescence quantum yield of 18.04%. The patterns and QR codes formed by this fluorescent polymer solution (with N,N-dimethylformamide as the solvent) are invisible under visible light but clearly visible under ultraviolet light, indicating that it is a potential security and anti-counterfeiting fluorescent material.

[0061] The chemical formulas involved in the above reaction are as follows:

[0062]

[0063] Example 4

[0064] 3-(methylamino)-1-propanol (0.089 g, 1 equiv) and polyethylene glycol-acetylene (0.904 g, 1 equiv) were added to a 5 mL single-necked polymerization flask and stirred in air at 60 °C for 24 h. The mixture was then precipitated with n-hexane to obtain a linear fluorescent polymer (LP-4) with a yield of 80% and an E configuration of 100%. The structure of the target polymer was confirmed by 1H NMR spectroscopy (as per the instruction manual). Figure 7 (As shown). Volume exclusion chromatography characterization revealed a polymer weight-average molecular weight of 9800 g / mol and a molecular weight distribution of 1.77, indicating that this method can prepare linear fluorescent polymers with high molecular weights. Fluorescence spectroscopy determined the polymer's excitation and emission wavelengths to be 490 nm and 556 nm, respectively (as shown in the instruction manual). Figure 8 As shown), it exhibits yellow fluorescence properties, with a solid-state fluorescence quantum yield of 9.54%. A 2 mg / ml aqueous solution of the fluorescent polymer (obtained in Example 4) was mixed with different metal ions (ion concentrations of 10... -3 After mixing (mol), Fe 3+ The fluorescence was rapidly quenched, indicating that the fluorescent polymer can effectively detect Fe. 3+(as per the instruction manual) Figure 19 As shown), is an ideal Fe 3+ Sensor. Cell experiments have shown that this fluorescent polymer can be used for intracellular imaging (as per the instruction manual). Figure 20 As shown in the figure, it is a fluorescent material with potential biomedical applications.

[0065] The chemical formulas involved in the above reaction are as follows:

[0066]

[0067] In the above chemical formula, m = 18.

[0068] Example 5

[0069] 1-(methylamino)prop-2-ol (0.089 g, 1 equiv) and ethylene glycol dipropynate (0.166 g, 1 equiv) were added to a 5 mL single-necked polymerization flask and reacted with stirring in air at 25 °C for 24 h. After the reaction was completed, the mixture was precipitated with n-hexane to obtain a linear fluorescent polymer (LP-5) with a yield of 96% and an E configuration of 98%. The structure of the target polymer was confirmed by proton NMR spectroscopy (as per the instruction manual). Figure 9 (As shown). Volume exclusion chromatography characterization revealed that the polymer's weight-average molecular weight was 12300 g / mol, and its molecular weight distribution was 1.55, indicating that this method can prepare linear fluorescent polymers with high molecular weights. Fluorescence spectroscopy showed that the polymer's excitation and emission wavelengths were 505 nm and 559 nm, respectively, exhibiting orange fluorescence characteristics. Figure 10 The solid-state fluorescent quantum yield is 24.57%.

[0070] The chemical formulas involved in the above reaction are as follows:

[0071]

[0072] Example 6

[0073] 4-Piperidinemethanol (0.115 g, 1 equiv) and ethylene glycol dipropynate (0.166 g, 1 equiv) were added to a 5 mL single-necked polymerization flask and stirred in air at 25 °C for 24 h. After the reaction was completed, the mixture was precipitated with n-hexane to obtain a linear fluorescent polymer (LP-6) with a yield of 85% and an E configuration of 95%. The structure of the linear polymer was confirmed by 1H NMR spectroscopy (as per the instruction manual). Figure 11(As shown). Volume exclusion chromatography characterization revealed a weight-average molecular weight of 5300 g / mol and a molecular weight distribution of 1.17, indicating that this method can prepare linear fluorescent polymers with higher molecular weights. Fluorescence spectroscopy analysis showed that the polymer's excitation and emission wavelengths were 487 nm and 544 nm, respectively, exhibiting yellow fluorescence (as shown in the attached instruction manual). Figure 12 As shown in the figure, the solid-state fluorescent quantum yield is 15.98%.

[0074] The chemical formulas involved in the above reaction are as follows:

[0075]

[0076] Example 7

[0077] 0.143 g (1 equiv) of 2-(cyclohexylamino)ethanol and 0.166 g (1 equiv) of ethylene glycol dipropynate were added to a 5 mL single-necked polymerization flask and stirred in air at 45 °C for 24 h. After the reaction was completed, the mixture was precipitated with n-hexane to obtain a linear fluorescent polymer (LP-7) with a yield of 80% and an E configuration of 94%. The structure of the linear polymer was confirmed by proton nuclear magnetic resonance spectroscopy (as shown in the instruction manual). Figure 13 (As shown). Volumetric exclusion chromatography characterization revealed a weight-average molecular weight of 6000 g / mol and a molecular weight distribution of 1.21, indicating that this method can prepare linear fluorescent polymers with high molecular weights. Fluorescence spectroscopy analysis showed that the polymer's excitation and emission wavelengths were 450 nm and 509 nm, respectively, exhibiting cyan fluorescence characteristics (as shown in the instruction manual). Figure 14 As shown in the figure, the solid-state fluorescent quantum yield is 14.62%.

[0078] The chemical formulas involved in the above reaction are as follows:

[0079]

[0080] Example 8

[0081] 0.151 g (1 equiv) of 2-benzylaminoethanol and 0.166 g (1 equiv) of ethylene glycol dipropynate were added to a 5 mL single-necked polymerization flask and stirred in air at 45 °C for 24 h. After the reaction was completed, the mixture was precipitated with n-hexane to obtain a linear fluorescent polymer (LP-8) with a yield of 80% and an E configuration of 90%. The structure of the linear polymer was confirmed by proton nuclear magnetic resonance spectroscopy (as shown in the instruction manual). Figure 15(As shown). Volumetric exclusion chromatography characterization revealed a weight-average molecular weight of 7300 g / mol and a molecular weight distribution of 1.46, indicating that this method can prepare linear fluorescent polymers with high molecular weights. Fluorescence spectroscopy analysis showed that the excitation and emission wavelengths of the fluorescent polymer were 458 nm and 497 nm, respectively, exhibiting blue fluorescence (as shown in the attached specification). Figure 16 As shown in the figure, the solid-state fluorescent quantum yield is 24.47%.

[0082] The chemical formulas involved in the above reaction are as follows:

[0083]

[0084] Example 9

[0085] 3-(methylamino)-1-propanol (0.089 g, 1 equiv) and dipropynyl ethylene glycol (0.134 g, 1 equiv) were added to a 5 mL single-necked polymerization flask and stirred at 25 °C in air for 12 h. After the reaction was complete, the mixture was precipitated with n-hexane to obtain a linear fluorescent polymer (LP-9) with a yield of 85% and an E configuration of 95%. Volume exclusion chromatography characterization showed that the polymer had a weight-average molecular weight of 19600 g / mol and a molecular weight distribution of 1.69, indicating that this method can prepare linear fluorescent polymers with high molecular weights. Fluorescence spectroscopy showed that the excitation and emission wavelengths of the fluorescent polymer were 522 nm and 574 nm, respectively, exhibiting orange fluorescence (as per the instruction manual). Figure 17 As shown in the figure, the solid-state fluorescent quantum yield is 20.74%.

[0086] The chemical formulas involved in the above reaction are as follows:

[0087]

[0088] Example 10

[0089] 3-(methylamino)-1-propanol (0.089 g, 1 equiv) and dipropynyl acetamide (0.134 g, 1 equiv) were added to a 5 mL single-necked polymerization flask and stirred at 25 °C in air for 12 h. After the reaction was complete, the mixture was precipitated with n-hexane to obtain the fluorescent polymer (LP-10) with a yield of 88%. Volumetric exclusion chromatography characterization showed that the polymer had a weight-average molecular weight of 17300 g / mol and a molecular weight distribution of 1.48, indicating that this method can prepare linear fluorescent polymers with high molecular weights. Fluorescence spectroscopy showed that the excitation and emission wavelengths of the fluorescent polymer were 582 nm and 627 nm, respectively, exhibiting red fluorescence characteristics (as per the instruction manual). Figure 18 As shown in the figure, the solid-state fluorescent quantum yield is 23.98%.

[0090] The chemical formulas involved in the above reaction are as follows:

[0091]

[0092] Comparative Example 1

[0093] N-methyldiethanolamine (0.119 g, 1 equiv) and 1,6-hexanediol dipropynate (0.222 g, 1 equiv) were added to a 5 mL single-necked polymerization flask and stirred. The reaction was carried out at 25 °C for 24 h at room temperature. After the reaction was completed, the mixture was precipitated with n-hexane to obtain a linear fluorescent polymer with a yield of 96% and an E configuration of 100% (the preparation method of this fluorescent polymer is the same as Example 1 in Chinese Invention Patent CN114716659A previously applied for by the research team of this invention). The weight-average molecular weight of the polymer was 26800 g / mol and the molecular weight distribution was 2.35, characterized by volume exclusion chromatography. The excitation wavelength and emission wavelength of the fluorescent polymer were measured to be 380 nm and 460 nm, respectively, exhibiting blue fluorescence characteristics and a solid-state fluorescence quantum yield of 4.82%.

[0094] Comparative Example 2

[0095] N-methyldiethanolamine (0.119 g, 1 equiv) and 1,6-hexanediol dipropynate (0.222 g, 1 equiv) were added to a 5 mL single-necked polymerization flask and reacted in air at 60 °C for 24 h. After the reaction was completed, the mixture was precipitated with n-hexane to obtain a linear fluorescent polymer (the preparation method of this fluorescent polymer is the same as Example 4 in Chinese Invention Patent CN114716659A previously applied for by the research team of this invention), with a yield of 99%. The weight-average molecular weight of the polymer was characterized by volumetric exclusion chromatography, which showed a molecular weight distribution of 71700 g / mol and a molecular weight distribution of 2.75. Fluorescence spectroscopy showed that the excitation wavelength and emission wavelength of the fluorescent polymer were 380 nm and 460 nm, respectively, exhibiting blue fluorescence characteristics, and the solid-state fluorescence quantum yield was 8.39%.

[0096] The chemical formulas involved in the above reaction are as follows:

[0097]

[0098] Comparative Example 3

[0099] N,N-bis(2-hydroxyethyl)piperazine (0.174 g, 1 equiv) and 1,6-hexanediol dipropynate (0.222 g, 1 equiv) were added to a 10 mL single-necked polymerization flask, and a water / dimethyl sulfoxide mixed solvent (0.5 mL, volume ratio 1:4) was added. The mixture was then incubated in air at 60 °C. ℃The reaction was stirred for 24 hours. After the reaction was completed, the polymer was precipitated with n-hexane to obtain a linear fluorescent polymer (the preparation method of this fluorescent polymer is the same as that in Example 8 of Chinese Invention Patent CN114716659A previously filed by our research team), with a yield of 82% and an E configuration of 97%. Volume exclusion chromatography characterized the polymer, showing a weight-average molecular weight of 11585 g / mol and a molecular weight distribution of 1.50. Fluorescence spectroscopy revealed that the excitation and emission wavelengths of the fluorescent polymer were 360 ​​nm and 415 nm, respectively, exhibiting blue fluorescence characteristics and a solid-state fluorescence quantum yield of 4.39%.

[0100] The chemical formulas involved in the above reaction are as follows:

[0101]

[0102] Based on the above-described preferred embodiments of the present invention, and through the foregoing description, those skilled in the art can make various changes and modifications without departing from the inventive concept. The technical scope of this invention is not limited to the contents of the specification, but must be determined according to the scope of the claims.

Claims

1. A linear fluorescent polymer, characterized in that, It is generated by a click reaction between a secondary amino alcohol monomer and an activated alkyne monomer. During the reaction, the alkyne group in the alkyne monomer structure first undergoes a click reaction with the secondary amino group in the secondary amino alcohol monomer structure, and then undergoes a click reaction with the hydroxyl group in the secondary amino alcohol monomer structure. Both ends of the activated alkyne monomer molecular chain are capped with alkyne groups, and the secondary amino alcohol monomer is a monohydric alcohol. The activated alkyne monomer includes ester-activated alkyne monomer, amide-activated alkyne monomer, or ketone-activated alkyne monomer.

2. The linear fluorescent polymer according to claim 1, characterized in that, The activated alkyne monomers include di-alkynyl monomers and poly-alkynyl monomers, both ends of which are end-capped with alkyne groups.

3. The linear fluorescent polymer according to claim 2, characterized in that, The diacetylene monomer includes the following structural formula: , , , , In the above structural formula, m is 1~3 and n>2.

4. The linear fluorescent polymer according to claim 3, characterized in that, The activated alkyne monomer includes one or more of the following: ethylene glycol dipropynate, 1,4-butanediol dipropynate, 1,6-hexanediol dipropynate, polyethylene glycol-alkyne, ethylene glycol dipropynate, and dipropynyl acetamide.

5. A linear fluorescent polymer according to claim 2, characterized in that, Polyacetylenic monomers include the following structural formulas: 。 6. The linear fluorescent polymer according to claim 1, characterized in that, The secondary amino alcohol monomer includes the following structural formula: , , , ; In the above structural formula, R1 includes methyl, ethyl, isopropyl, alicyclic or benzene ring, and R2 includes a methylene chain with 1 or more carbon atoms.

7. A linear fluorescent polymer according to claim 6, characterized in that, The secondary amino alcohol monomer includes one or more of 3-(methylamino)-1-propanol, 1-(methylamino)prop-2-ol, or 2-benzylaminoethanol.

8. The linear fluorescent polymer according to claim 1, characterized in that, The linear fluorescent polymer includes the following chemical structural formula: , Chemical structural formula I; , Chemical structural formula II; ; Chemical structural formula III; ; Chemical structural formula IV; ; Chemical structural formula V; ; Chemical structural formula VI; ; Chemical structural formula VII; ; Chemical structural formula VIII; ; Chemical structural formula IX; ; Chemical structural formula X; In the above chemical structural formula, the value of n is determined based on the reaction temperature, reaction time, and the amount of secondary amine alcohol monomer and activated acetylene monomer used in the click reaction.

9. A linear fluorescent polymer according to claim 1, characterized in that, The secondary amino alcohol monomer in the click reaction process is 3-(methylamino)-1-propanol, and the activated alkynyl monomer is ethylene glycol dipropynate.

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