A polymer with controllable photodegradation and upgraded recycling properties and its applications.

Abstract

This invention discloses a polymer with controllable photodegradation and upgradable recycling properties and its applications, belonging to the fields of polymer chemistry, environmental materials, and functional materials. The photodegradable monomer of this invention contains photosensitive groups and terminal active functional groups. Using the photodegradable monomer as the structural monomer, a polymer with controllable photodegradation and upgradable recycling properties can be prepared through condensation polymerization or free radical polymerization of the terminal active functional groups of the photodegradable monomer. The polymer obtained by this invention possesses high thermal stability, chemical stability (acid and alkali resistance), and high-efficiency luminescence properties, while also being controllably photodegradable under mild conditions, solving the problem of difficult degradation of traditional functional polymers. The photolysis products of this invention exhibit room-temperature phosphorescence and strong antibacterial and catalytic degradation capabilities, and can be directly used in environmental remediation and biomedicine, realizing a closed loop of "degradation-functional upgrading and transformation," and enhancing the circular economy value of materials.

Description

Technical Field

[0001] This invention relates to the fields of polymer chemistry, environmental materials and functional materials, and in particular to a sustainable luminescent polymer with aggregation-induced emission properties, controllable photodegradation performance and multifunctional upgrade and recycling potential, and its applications in photoresponsive materials, environmental remediation and biomedicine. Background Technology

[0002] With the widespread application of polymer materials, environmental problems caused by plastic waste are becoming increasingly serious. For high-performance functional polymers, their inherent rigid molecular skeleton and thermodynamic stability often make them difficult to degrade in the natural environment; while existing biodegradable polymers generally cannot balance complex structures and specific application performance. The contradiction between performance and environmental compatibility urgently needs to be resolved and further improvements are still required.

[0003] Photodegradation, as a spatiotemporally controllable chemical degradation strategy, suffers from problems such as low degradation efficiency, uncontrollable fragmentation processes, and low value of degradation products in existing systems, and lacks attention to the subsequent functionalization of degradation products. Therefore, developing novel polymer systems that combine high efficiency, controllable degradation characteristics, and the potential for functional upgrading and recycling of degradation products is of significant scientific and practical value. Summary of the Invention

[0004] The purpose of this invention is to provide a polymer with controllable photodegradation and upgraded recycling characteristics and its applications, in order to solve the problems of traditional functional polymers being difficult to degrade and having low product utilization value, while endowing the material with photoresponsiveness, multifunctionality and environmental friendliness.

[0005] To achieve the above objectives, the present invention provides the following technical solution:

[0006] One of the technical solutions of this invention is to provide a photodegradable monomer comprising a photosensitive group and a terminal active functional group; the general structural formula of the photodegradable monomer is as follows:

[0007]

[0008] Wherein, R1 and R2 are the terminal active functional groups.

[0009] Preferably, R1 and R2 have the same structure.

[0010] Preferably, the terminal active functional group is a group containing an alkyl chain; the group containing an alkyl chain is an alkyl chain in which the terminal carbon atom is replaced by a hydroxyl, amino, mercapto, carboxyl, epoxy, nitro, alkenyl or alkynyl group, and the alkyl chain is a straight chain, branched chain or cyclic alkyl chain having 2-20 carbon atoms.

[0011] The second technical solution of the present invention provides a polymer with controllable photodegradation and upgraded recycling characteristics, wherein the monomers used to prepare the polymer contain the aforementioned photodegradable monomers.

[0012] Preferably, the polymer has aggregation-induced emission properties, and its molecular backbone contains photolytic fluorescent units that can be photolyzed. After being irradiated with light, it can be controllably depolymerized into a single photolysis product with a well-defined structure.

[0013] Preferably, the polymer has the following general structural formula:

[0014]

[0015] Wherein, X1 and X2 are groups generated by polymerization of the terminal active functional groups in the photolytic monomer, and n is the degree of polymerization.

[0016] Preferably, the degree of polymerization of the polymer is 50-200.

[0017] The third technical solution of the present invention provides a method for preparing the above-mentioned polymer with controllable photodegradation and upgraded recycling characteristics, which is prepared by polycondensation reaction or free radical polymerization reaction of the terminal active functional groups of the photodegradable monomer.

[0018] The fourth technical solution of the present invention provides an application of the above-mentioned polymer with controllable photodegradation and upgraded recycling characteristics in the field of luminescent materials.

[0019] Preferably, the luminescent material is a luminescent coating, a luminescent fiber, or a photoresponsive micropattern.

[0020] More preferably, the luminescent coating is prepared by spraying; the luminescent fiber is prepared by electrospinning with polyacrylonitrile; the photoresponsive micropattern is prepared by photolithography, and after being irradiated with light, the fluorescent color can change from orange to blue, which is used for information encryption and erasure.

[0021] Fifth technical solution of the present invention: to provide an application of the above-mentioned polymer with controllable photodegradation and upgraded recycling characteristics in the field of controllable photodegradation materials.

[0022] The sixth technical solution of this invention: Provides a photodegradation method for the polymer described above, which has controllable photolysis and upgraded recycling characteristics, wherein the polymer is in an aggregated state, and then 365nm ultraviolet light (50-500mW / cm²) is used. 2 Irradiation accelerates photolysis, resulting in depolymerization into carbonyl-containing photolysis products.

[0023] The present invention achieves a light conversion efficiency of over 80% during the photolysis process, and the degradation process is accompanied by a blue shift in the fluorescence spectrum, which allows for real-time monitoring of the degradation process.

[0024] Preferably, the method for bringing the polymer to an aggregated state is to place the polymer in a CHCl3 / MeOH mixed solvent with a volume ratio of 1:3.

[0025] The seventh technical solution of the present invention provides an application of the photolysis product obtained by the above-mentioned photodegradation method in the field of room temperature phosphorescent materials.

[0026] The eighth technical solution of the present invention provides an application of the photodegradation product obtained by the above-mentioned photodegradation method in the field of organic dye degradation or antibacterial field.

[0027] The photolysis product of this invention has a phosphorescence lifetime of over 100 ms and can efficiently generate hydroxyl radicals, making it suitable for applications in dye degradation and antibacterial treatment. In the dye degradation experiment of this invention, the degradation rate of Rhodamine B by the photolysis product can reach over 90% within 1 hour; in the antibacterial experiment, the inhibition rate of 2 μM photolysis product against Escherichia coli and Staphylococcus aureus exceeds 90%.

[0028] The technical principle of this invention is as follows:

[0029] This invention diversifies polymer preparation pathways by designing multifunctional photodegradable monomers. When the photodegradable monomer contains hydroxyl, amino, or thiol groups, it can undergo condensation reactions with polybasic acids and polyesters; when it contains carbon-carbon double bonds, it can form polymer chains through free radical polymerization, ultimately constructing a polymer backbone containing photodegradable chromophores.

[0030] The photodegradation mechanism of the polymer with controllable photolysis and upgraded recycling characteristics of the present invention is as follows: photoexcitation initiates the generation of reactive oxygen species (including singlet oxygen and superoxide anion), which attack double bonds to induce selective chain scission, generating carbonyl-containing photolysis products; in the aggregated state, molecular motion is restricted, promoting intersystem crossing and the generation of reactive oxygen species, accelerating degradation and forming a self-catalytic cycle of "photoactivation-reactive oxygen species generation-polymer lysis". The carbonyl-containing photolysis products of the present invention possess both room-temperature phosphorescence emission and strong reactive oxygen species generation capabilities, thus enabling functional upgrade recycling.

[0031] The beneficial technical effects of the present invention are as follows:

[0032] 1. Balance between performance and degradability: The polymer prepared by this invention has controllable photodegradation and upgraded recycling characteristics, which combines high thermal stability, chemical stability (acid and alkali resistance) and high efficiency luminescence performance. At the same time, it can be controlled photodegraded under mild conditions, which solves the problem of difficult degradation of traditional functional polymers.

[0033] 2. Monomer design flexibility: By controlling the combination of photosensitive groups and active functional groups of the photolytic monomers of the present invention, it is possible to adapt to various synthetic routes such as polycondensation and free radical polymerization, and realize the customized construction of polymer structures.

[0034] 3. Green degradation mechanism: No external catalyst is required. It uses atmospheric oxygen as an oxidant, and the photolysis process has 100% atom economy, which is in line with the principles of green chemistry.

[0035] 4. Visualization of the degradation process: During the photodegradation process of this invention, the fluorescence color changes from orange to blue, which can be monitored in real time by the naked eye or by spectroscopy, making it convenient to assess the degree of degradation in practical applications.

[0036] 5. High-value utilization of products: The photolysis products of this invention have room temperature phosphorescence and strong antibacterial and catalytic degradation capabilities, which can be directly used in environmental remediation and biomedicine, realizing a closed loop of "degradation-functional upgrading and transformation" and enhancing the circular economy value of materials. Attached Figure Description

[0037] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0038] Figure 1 The image shows the 1H NMR spectrum of monomer 1 from Example 1, obtained by testing in deuterated chloroform solvent.

[0039] Figure 2 The image shows the 1H NMR spectrum of monomer 2 from Example 2, obtained by testing in deuterated chloroform solvent.

[0040] Figure 3 The image shows the 1H NMR spectrum of polymer P1 from Example 3, obtained by testing in deuterated chloroform solvent.

[0041] Figure 4 The image shows the 1H NMR spectrum of polymer P2 from Example 4, obtained by testing in deuterated chloroform solvent.

[0042] Figure 5 The data curves show the thermal stability of polymers P1 and P2.

[0043] Figure 6 The graph shows the change in molecular weight of polymer P2 from Example 4 after immersion in 1M hydrochloric acid and 1M sodium hydroxide solution for 24 hours.

[0044] Figure 7These are photographs of fluorescent micropatterns after exposure using photomasks of different shapes prepared with the P1 polymer in Example 3.

[0045] Figure 8 This is a diagram illustrating the fluorescence effect of the luminescent fibers and flexible textiles prepared using the P2 polymer from Example 4.

[0046] Figure 9 The image shows the 1H NMR spectrum of the photolysis product from Example 7 obtained by testing in deuterated chloroform solvent.

[0047] Figure 10 is Gel permeation chromatography data of the P1 polymer in Example 3 during the photodegradation process.

[0048] Figure 11 The fluorescence spectrum of polymer P1 after irradiation for different times under the photodegradation conditions of Example 7 is shown.

[0049] Figure 12 The fluorescence spectrum of polymer P1 changes after irradiation for different times under the photodegradation conditions of Comparative Example 1.

[0050] Figure 13 The image shows the 1H NMR spectrum of the photolysis product from Example 8 obtained by testing in deuterated chloroform solvent.

[0051] Figure 14 The fluorescence spectrum of polymer P1 after irradiation for different times under the photodegradation conditions of Example 8 is shown.

[0052] Figure 15 The fluorescence spectrum of polymer P1 changes after irradiation for different times under the photodegradation conditions of Comparative Example 2.

[0053] Figure 16 This is a statistical analysis of the changes in absorbance during the dye degradation process in Example 7.

[0054] Figure 17 The experimental results of the antibacterial effect of the photolysis product 2BAI-1 under dark and light conditions in Example 8 are statistically analyzed.

[0055] Figure 18 The phosphorescence lifetime curve of the photolysis product 2BAI-1 is shown. Detailed Implementation

[0056] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention. It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the present invention.

[0057] Furthermore, regarding the numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Any stated value or intermediate value within a stated range, as well as each smaller range between any other stated value or intermediate value within said range, are also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0058] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. It should be noted that any aspects of this invention not described in detail are conventional practices in the art and are not the focus of this invention.

[0059] The terms “comprising,” “including,” “having,” “containing,” etc., used in this invention are all open-ended terms, meaning that they include but are not limited to.

[0060] Unless otherwise specified, "room temperature" in this invention refers to 10-30°C.

[0061] Unless otherwise specified, "overnight" in this invention refers to 12 hours.

[0062] All raw materials used in the following embodiments of the present invention are commercially available products.

[0063] Example 1

[0064] A method for preparing a photolytically degradable monomer, the specific preparation steps and related reaction formulas are as follows:

[0065]

[0066] 4-Bromo-1,8-naphthalenedicarboxylic anhydride (2.77 g, 1.0 mol) and N-Boc-1,3-propanediamine (2.06 g, 1.2 mol) were added to a two-necked round-bottom flask equipped with a reflux condenser and a magnetic stir bar. Anhydrous ethanol (60 mL) was added, and the mixture was heated to 80 °C with stirring and reacted for 8 hours. After the reaction was complete, the reaction mixture was cooled to room temperature, during which time the product precipitated. The solid was collected by filtration, washed with cold ethanol, and then dried under vacuum to give compound 1. Under nitrogen protection, compound 1 (1.08 g, 2.5 mmol), 1,2-bis(4-methoxyphenyl)-1,2-bis(4-(4,4,5,5-tetramethyl-1,3,2-dioxacyclopentaborane-2-yl)phenyl)ethylene (0.64 g, 1 mmol), tetrakis(triphenylphosphine)palladium (57 mg, 0.05 mmol, Pd(PPh3)4), and potassium carbonate (0.83 g, 6 mmol, K2CO3) were added to a 100 mL double-necked flask. A deoxytoluene / ethanol / water mixed solvent (28 / 8 / 4 mL) was added, and the mixture was stirred at 80 °C for 24 hours. After the reaction was complete, the solvent was removed by rotary evaporation under reduced pressure. The solid was dissolved in dichloromethane, washed successively with saturated brine and deionized water, dried over anhydrous sodium sulfate, filtered, and concentrated by rotary evaporation. The crude product was purified by silica gel column chromatography (eluent: dichloromethane / acetone = 80:1 v / v) to give compound 2 (0.82 g, yield 75.2%) as an orange-yellow powder. Compound 2 (0.3 g) was dissolved in anhydrous dichloromethane (20 mL, DCM), and trifluoroacetic acid (10 mL, TFA) was slowly added under ice bath conditions. After stirring at room temperature for 3 hours, the solvent and excess trifluoroacetic acid were removed by rotary evaporation under reduced pressure. The residue was dissolved in dichloromethane and neutralized to pH 8-9 with saturated sodium bicarbonate solution. The organic phase was separated, and the aqueous phase was extracted with dichloromethane. The combined organic phases were dried over anhydrous sodium sulfate. After filtration and concentration, the product was purified by silica gel column chromatography (eluent: dichloromethane / methanol / ammonia = 40:10:1 v / v / v) to give monomer 1 (0.22 g, yield 87%, denoted as TPEMN-NH2).

[0067] Figure 1 The image shows the 1H NMR spectrum of monomer 1 from Example 1, obtained by testing in deuterated chloroform solvent.

[0068] Characterization data: ¹H NMR (500MHz, CDCl₃) δ 8.67–8.53 (m, 4H), 8.22 (dd, J = 20.1, 8.6 Hz, 2H), 7.70 (p, J = 7.8 Hz, 3H), 7.53 (t, J = 7.9 Hz, 1H), 7.28 (t, J = 4.6 Hz, 8H), 7.10 (dd, J = 9.0, 3.1 Hz, 4H), 6.76 (dd, J = 8.5, 6.1 Hz, 4H), 4.31 (q, J = 6.8 Hz, 4H), 3.80 (d, J = 2.2 Hz, 6H), 2.81 (t, J = 6.4 Hz, 4H), 2.01–1.89 (m, 4H).

[0069] Example 2

[0070] A method for preparing a photolytically degradable monomer, the specific preparation steps and related reaction formulas are as follows:

[0071]

[0072] 4-Bromo-1,8-naphthalenedicarboxylic anhydride (2.77 g, 1.0 mol) and 3-amino-1-propanol (0.90 g, 1.2 mol) were added to a two-necked round-bottom flask equipped with a reflux condenser and a magnetic stir bar. Anhydrous ethanol (60 mL) was added, and the mixture was heated to 80 °C with stirring and reacted for 8 hours. After the reaction was complete, the reaction mixture was cooled to room temperature, during which time the product precipitated. The solid was collected by filtration, washed with cold ethanol, and then dried under vacuum to give compound 3. Under nitrogen protection, compound 3 (0.83 g, 2.5 mmol), 1,2-bis(4-methoxyphenyl)-1,2-bis(4-(4,4,5,5-tetramethyl-1,3,2-dioxaneborane-2-yl)phenyl)ethylene (0.64 g, 1 mmol), tetrakis(triphenylphosphine)palladium (57 mg, 0.05 mmol, Pd(PPh3)4), and potassium carbonate (0.83 g, 6 mmol, K2CO3) were added to a 100 mL double-necked flask. A deoxytoluene / ethanol / water mixed solvent (28 / 8 / 4 mL) was added, and the reaction was stirred at 80 °C for 24 hours. After the reaction was complete, the solvent was removed by rotary evaporation under reduced pressure. The solid was dissolved in dichloromethane, washed successively with saturated brine and deionized water, dried over anhydrous sodium sulfate, filtered, and concentrated by rotary evaporation. The crude product was purified by silica gel column chromatography (eluent: dichloromethane / methanol = 50:1 v / v) to give an orange-yellow powder monomer 2 (0.70 g, yield 78%, denoted as TPEMN-OH).

[0073] Figure 2 The image shows the 1H NMR spectrum of monomer 2 from Example 2, obtained by testing in deuterated chloroform solvent.

[0074] Characterization data:1 H NMR (500MHz, CD2Cl2) δ8.69-8.57(m,4H),8.29(dd,J=8.4,1.2Hz,2H),7.76(d,J=7.5Hz,2H),7.61(dd,J=8.5,7.2Hz,2H),7.42-7.3 0(m,8H),7.18-7.10(m,4H),6.84-6.76(m,4H),4.36(t,J=6.3Hz,4H),3.83(s,6H),3.59(dd,J=6.2,5.1Hz,4H),2.03-1.96(m,4H).

[0075] Example 3

[0076] A method for preparing a polymer with controllable photodegradation and upgraded recycling properties, the specific preparation steps and related reaction formulas are as follows:

[0077]

[0078] In a 25 mL Schlenk reaction tube, an amine monomer containing a double bond (TPEMN-NH2 prepared in Example 1, 0.1 mmol), 2,2-bis(4-carboxyphenyl)hexafluoropropane (0.1 mmol), and anhydrous calcium chloride (60 mg, CaCl2) were added. After evacuating and purging with nitrogen three times, 3 mL of ultra-dry NMP (N-methylpyrrolidone) was added, and the mixture was stirred at room temperature for 30 minutes. Then, 0.2 mL of triphenyl phosphite (TPP) and 0.1 mL of anhydrous pyridine were added, and the mixture was heated to 130 °C and reacted for 9 hours. After cooling, the reaction solution was diluted with 2 mL of NMP and slowly poured into 50 mL of methanol. A yellow fibrous precipitate precipitated upon stirring. After filtration, the precipitate was washed successively with hot water and methanol, and dried under vacuum at 80 °C for 12 hours to obtain purified polymer P1 with a yield of 85%. The thermal decomposition temperature of P1 was determined to be 369 °C, and the fluorescence quantum yield was 29.1%.

[0079] Figure 3 The image shows the 1H NMR spectrum of polymer P1 from Example 3, obtained by testing in deuterated chloroform solvent.

[0080] Characterization data: 1H NMR (500MHz, CDCl3) δ8.70-8.57(m,4H),8.26(q,J=6.6Hz,2H),8.01(q,J=9.2Hz,4H),7.72(t,J=8.7Hz,6H),7.55(p,J=8.6Hz,6H) ,7.34-7.26(m,8H),7.08(d,J=7.7Hz,6H),6.75(d,J=8.0Hz,6H),4.36(m,4H),3.79(m,6H),3.53-3.38(m,4H),2.17-2.03(m,4H).

[0081] Example 4

[0082] A method for preparing a polymer with controllable photodegradation and upgraded recycling properties, the specific preparation steps and related reaction formulas are as follows:

[0083]

[0084] In a 25 mL Schlenk reaction tube, an amine monomer containing a double bond (TPEMN-NH2 prepared in Example 1, 0.1 mmol), adipic acid (0.1 mmol), and anhydrous calcium chloride (60 mg) were added. After evacuation and nitrogen purging three times, 3 mL of ultra-dry NMP was added, and the mixture was stirred at room temperature for 30 minutes. Then, 0.2 mL of triphenyl phosphite and 0.1 mL of anhydrous pyridine were added, and the mixture was heated to 130 °C and reacted for 6 hours. After cooling, the reaction solution was diluted with 2 mL of NMP and slowly poured into 50 mL of methanol. A yellow fibrous precipitate precipitated upon stirring. After filtration, the precipitate was washed successively with hot water and methanol, and dried under vacuum at 80 °C for 12 hours to obtain purified polymer P2 with a yield of 80%. The thermal decomposition temperature was 288 °C, and the fluorescence quantum yield was 22%.

[0085] Figure 4 The image shows the 1H NMR spectrum of polymer P2 from Example 4, obtained by testing in deuterated chloroform solvent.

[0086] Characterization data: 1 H NMR(500MHz, CDCl3)δ8.57(m,4H),8.20(m,2H),7.59(d,J=65.9Hz,4H),7.33-7.25(m,8H),7.14-7.00(m,5H),6 .82-6.66(m,5H),4.25(m,4H),3.79(d,J=4.6Hz,6H),3.29(d,J=7.0Hz,4H),2.35(d,J=8.3Hz,4H),1.95(m,4H).

[0087] Figure 5 The data curves show the thermal stability of polymers P1 and P2.

[0088] Depend on Figure 5 It is known that the polymer prepared by this invention has a high thermal decomposition temperature.

[0089] Figure 6 The graph shows the change in molecular weight of polymer P2 from Example 4 after immersion in 1M hydrochloric acid and 1M sodium hydroxide solution for 24 hours.

[0090] Depend on Figure 6 It can be seen that the molecular weight did not change significantly compared with the unsoaked sample, proving that the polymer has good acid and alkali resistance.

[0091] Example 5

[0092] Applications of luminescent polymers in micropatterned fluorescence imaging:

[0093] The P1 polymer prepared in Example 3 was dissolved in chloroform to prepare a 1 mg / mL solution. 0.5 mL of this solution was spin-coated onto a quartz substrate (spray coating parameters: 1000 rpm, 60 seconds) to form a uniform thin film. A photomask was then applied... Figure 7 The film was coated with 365nm ultraviolet light (300mW / cm²) and applied to the surface of the thin film. 2 Irradiation for 1 minute. Test results showed that, compared to the areas blocked by the photomask, the polymer in the illuminated areas underwent selective photodegradation, leading to changes in molecular structure and gaining acetone solubility. After removing the photomask, immersing the substrate in acetone for 30 seconds dissolved the polymer material in the UV-exposed areas. Subsequently, rinsing with acetone and drying with nitrogen gas resulted in the formation of high-resolution fluorescent micropatterns in the unexposed areas.

[0094] Figure 7 These are photographs of fluorescent micropatterns after exposure using photomasks of different shapes prepared with the P1 polymer in Example 3.

[0095] Example 6

[0096] Preparation of luminescent fibers:

[0097] 150,000 g / mol of PAN (polyacrylonitrile) powder and P2 (1% of PAN by mass) prepared in Example 2 were dissolved in DMAc to prepare a spinning solution containing 15% PAN. The solution was stirred at 60°C for 12 hours and then allowed to stand for 12 hours to remove bubbles. Then, 5 mL of the solution was loaded into a syringe with a 27G needle, and electrospinning was performed at 17.5 kV and a flow rate of 1.0 mL / h, with a collection distance of 15 cm. The resulting fibers were vacuum dried at 60°C for 12 hours to obtain luminescent fibers. The luminescent fibers were woven into a flexible textile displaying the "AIE" pattern, emitting orange fluorescence under ultraviolet light.

[0098] Figure 8This is a diagram illustrating the fluorescence effect of the luminescent fibers and flexible textiles prepared using the P2 polymer from Example 4.

[0099] Example 7

[0100] The photodegradation experiment and preparation of photolysis products, including the specific preparation steps and relevant reaction equations during the photolysis process, are as follows:

[0101]

[0102] The P1 polymer (50 mg) prepared in Example 2 was dissolved in a mixed solvent of 50 mL CHCl3 and 150 mL MeOH to induce polymerization, and then subjected to 365 nm ultraviolet light (300 mW / cm²). 2 Irradiate for 3 hours with stirring. After removing the solvent by rotary evaporation, the product is purified by column chromatography to obtain 46.1 mg of the photolysis product (denoted as 2BAI-1), with a yield of 90%.

[0103] Figure 9 The image shows the 1H NMR spectrum of the photolysis product from Example 7 obtained by testing in deuterated chloroform solvent.

[0104] Figure 10 is Gel permeation chromatography data of the P1 polymer in Example 3 during the photodegradation process.

[0105] Figure 11 The fluorescence spectrum of polymer P1 after irradiation for different times under the photodegradation conditions of Example 7 is shown.

[0106] Depend on Figure 11 The fluorescence spectra after irradiation for 0, 20, 40, 60, 80, 100, 120, 140, and 160 s show that the degradation rate of P1 polymer in aggregated solution is relatively fast.

[0107] Comparative Example 1

[0108] After simply replacing the MeOH in Example 7 with an equal volume of CHCl3, the fluorescence spectra of the P1 polymer were tested after irradiation for 0, 20, 40, 60, 80, 100, 120, 140, and 160 s.

[0109] Chloroform (CHCl3) is a good solvent for P1 polymers, while methanol (MeOH) is a poor solvent for P1 polymers. In a mixed solvent of chloroform and methanol, P1 polymers are in an aggregated state, while in pure chloroform, P1 polymers have good solubility and are in a dispersed state.

[0110] Figure 12 The fluorescence spectrum of polymer P1 changes after irradiation for different times under the photodegradation conditions of Comparative Example 1.

[0111] Depend on Figure 12 It can be seen that the degradation rate of P1 polymer in pure chloroform solution is relatively slow.

[0112] Figure 10 Gel permeation chromatography data showed that the polymer molecular weight gradually decreased over time. Figure 12 The fluorescence spectrum showed a decrease in the orange peak at 580 nm and an increase in the blue peak at 450 nm, indicating that the degradation process of the system could be monitored in real time through fluorescence changes.

[0113] Example 8

[0114] The preparation steps and relevant reaction formulas for another photolysis product are as follows:

[0115]

[0116] The P2 polymer (25 mg) prepared in Example 4 was dissolved in a mixed solvent of 25 mL CHCl3 and 75 mL MeOH to induce polymerization, and then subjected to 365 nm ultraviolet light (300 mW / cm²). 2 Irradiate for 3 hours with stirring. After removing the solvent by rotary evaporation, the product is purified by column chromatography to obtain 24.8 mg of the photolysis product (denoted as 2BAI-2), with a yield of 87%.

[0117] Figure 13 The image shows the 1H NMR spectrum of the photolysis product from Example 8 obtained by testing in deuterated chloroform solvent.

[0118] Figure 14 The fluorescence spectrum of polymer P1 after irradiation for different times under the photodegradation conditions of Example 8 is shown.

[0119] Depend on Figure 14 The fluorescence spectra after irradiation for 0, 20, 40, 60, 80, 100, 120, 140, and 160 s show that the degradation rate of P2 polymer in aggregated solution is relatively fast.

[0120] Comparative Example 2

[0121] After simply replacing the MeOH in Example 8 with an equal volume of CHCl3, the fluorescence spectra of the P2 polymer were tested after irradiation for 0, 20, 40, 60, 80, 100, 120, 140, and 160 s.

[0122] Figure 15 The fluorescence spectrum of polymer P1 changes after irradiation for different times under the photodegradation conditions of Comparative Example 2.

[0123] Depend on Figure 15 It can be seen that the degradation rate of P2 polymer in pure chloroform solution is relatively slow.

[0124] Example 9

[0125] Application of photolysis products in the catalytic degradation of dyes:

[0126] 10 mg of Rhodamine B dye and 10 mg of the photolysis product 2BAI-2 (insoluble in water) were added to 20 mL of deionized water and sonicated for 10 minutes to form a homogeneous suspension. The suspension was then placed at a distance of 365 nm from an ultraviolet light source (light intensity 300 mW / cm²). 2 In a beaker 5 cm directly below the surface, the mixture was magnetically stirred (600 rpm) to prevent sedimentation. During illumination, 200 μL of the reaction solution was taken every 20 minutes, filtered through a 0.45 μm polytetrafluoroethylene (PTFE) membrane to remove solid particles, and the absorbance of the filtrate at 554 nm was measured using a UV-Vis spectrophotometer. The test results are as follows. Figure 16 As shown.

[0127] Figure 16 This is a statistical analysis of the changes in absorbance during the dye degradation process in Example 7.

[0128] Example 10: Antibacterial application of photolysis products

[0129] Single colonies of Staphylococcus aureus were inoculated onto LB broth and cultured overnight at 37°C with shaking. The bacteria were collected by centrifugation, washed twice with PBS, and the concentration was adjusted to OD600 = 0.5. 1 mL of the bacterial suspension (10...) 6 Add 0.01 mL of PBS solution containing the photolysis product of Example 7 (2BAI-1, concentration 2 μM) to (CFU / mL), shake at 37°C for 20 minutes, and then irradiate with 365 nm light for 5 minutes (10 W / cm²). 2 The samples were diluted and sprayed onto LB agar plates and incubated at 37°C for 12 hours. Counting showed a bacterial inhibition rate of over 90%, which was mainly attributed to the disruption of bacterial cell membranes by the ·OH generated by photolysis products.

[0130] Figure 17 The experimental results of the antibacterial effect of the photolysis product 2BAI-1 under dark and light conditions in Example 8 are statistically analyzed.

[0131] The phosphorescence lifetime curve was tested under the conditions of microsecond lamp excitation wavelength of 360nm and phosphorescence peak monitoring wavelength of 600nm.

[0132] Figure 18 The phosphorescence lifetime curve of the photolysis product 2BAI-1 is shown.

[0133] The embodiments described above are merely preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Various modifications and improvements made by those skilled in the art to the technical solutions of the present invention without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.

Claims

1. A photodegradable monomer, characterized in that, The structural formula of the photodegradable monomer is: or 。 2. A polymer with controllable photodegradation and upgraded recycling characteristics, characterized in that, The general structural formula of the polymer is as follows: ； Wherein, X1 and X2 are groups generated from the terminal active functional groups in the photodegradable monomer after polymerization, and n is the degree of polymerization; the degree of polymerization of the polymer is 50-200; the specific structure of the general formula is as follows: or 。 3. A method for preparing the polymer with controllable photolysis and upgraded recycling characteristics as described in claim 2, characterized in that, It was prepared by polycondensation reaction of the terminal active functional groups of photolytic monomers; The structural formula of the photodegradable monomer is: 。 4. The application of the polymer with controllable photodegradation and upgraded recycling characteristics as described in claim 2 in the field of luminescent materials.

5. The application of the polymer with controllable photodegradation and upgraded recycling properties as described in claim 2 in the field of controllable photodegradation materials.

6. A method for photodegrading a polymer with controllable photolysis and upgraded recycling characteristics as described in claim 2, characterized in that, The polymer is brought into an aggregated state and then depolymerized into carbonyl-containing photodegradation products by ultraviolet light irradiation. The structural formula of the carbonyl-containing photolysis product is: or 。 7. The application of a photodegradation product obtained by the photodegradation method of claim 6 in the field of room temperature phosphorescent materials.

8. The application of a photodegradation product obtained by the photodegradation method according to claim 6 in the field of organic dye degradation or antibacterial field.

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