Ferrocenyl triazine photodegradation agent and application thereof

Abstract

The invention provides a ferrocenyl triazine photodegradation agent and an application of the ferrocenyl triazine photodegradation agent. Due to the combination of the ferrocene and the triazine ring, the disadvantage that the ferrocene can sublimate is improved; meanwhile, the photodegradation agent expands photoresponse to a visible light region through an intramolecular charge transfer effect, and the maximum photoresponse reaches 500 nm. The degradation agent is good in compatibility with materials and can be in full contact with the materials, seepage of the light degradation agent is reduced, and accurate regulation and control of the degradation rate are achieved. In addition, the degradation agent can be uniformly dispersed in a polyvinyl chloride matrix, stress concentration points formed by local enrichment are avoided, and the degradation agent can be efficiently utilized without excessive addition of compensation loss.

Description

Technical Field

[0001] This invention belongs to the field of photodegradable agents, specifically relating to a ferrocene-based triazine photodegradable agent and its application. Background Technology

[0002] Currently, commonly used photodegradable agents are mostly inorganic materials, such as nano-titanium dioxide, zinc oxide, tungsten trioxide-potassium dihydrogen phosphate, and nickel-aluminum silica. However, most of these studied photocatalysts are inorganic materials containing various metal components, with narrow spectral responses, only absorbing ultraviolet light; they tend to aggregate in polymers, exhibiting poor compatibility; and due to low solid-solid contact efficiency, inorganic photocatalysts are difficult to precisely control the degradation rate. Furthermore, the leaching of heavy metals can disperse into the natural environment, potentially causing secondary pollution. Therefore, novel photocatalysts should be developed to overcome these problems to promote the development of photodegradable polyvinyl chloride plastics. Summary of the Invention

[0003] To address the problems existing in the prior art, the present invention aims to provide a ferrocene-based triazine photodegrader and its application.

[0004] To achieve the above objectives, the present invention adopts the following technical solution: A ferrocene-based triazine photodegradant has the following structure: The application of the ferrocene-based triazine photodegradable agent in photodegradable polyvinyl chloride plastics.

[0005] Furthermore, in the aforementioned application, the amount of ferrocene-based triazine photodegrading agent added is 1×10⁻⁶. -2 mol / kg PVC.

[0006] The advantages of this invention are: This invention synthesizes four novel ferrocene-based triazine compounds as photodegraders. These photodegraders extend the photoresponse to 500 nm through intramolecular charge transfer effects, exhibit good compatibility with materials, reduce photodegrader leakage, and ensure sufficient contact between the photodegrader and the material, allowing for precise control of the degradation rate. The all-organic structure ensures no heavy metal residues in the degradation products. The combination of ferrocene and the triazine ring overcomes the sublimation problem of ferrocene while possessing excellent solubility and good compatibility with materials. The photodegraders are uniformly dispersed in the PVC matrix, avoiding localized accumulation and stress concentration points, and are not prone to leakage, allowing for efficient utilization without the need for excessive addition to compensate for losses. Attached Figure Description

[0007] Figure 1 The UV-Vis spectrum (left) and thermogravimetric analysis (right) of four ferrocene triazine compounds. Figure 2This is a diagram showing the material color change during the photoaging process in Embodiment 1 of the present invention; Figure 3 This refers to the quality changes during the photoaging process in Embodiment 1 of the present invention. Detailed Implementation

[0008] To make the above-mentioned features and advantages of the present invention more apparent and understandable, specific embodiments are described below in detail. Unless otherwise specified, the methods of the present invention are conventional methods in the art.

[0009] The synthetic steps for four ferrocene-based triazine compounds are as follows: FC-1 synthesis scheme:

[0010] Step (1): Dry the 250 mL reaction tube under vacuum using a hot air gun three times. After the reaction tube returned to room temperature, add ferrocene (372 mg, 2.00 mmol, 2.00 eq) and potassium tert-butoxide (45 mg, 0.40 mmol, 0.40 eq) under an argon atmosphere, and dissolve them in 15.0 mL of ultra-dry tetrahydrofuran solvent. Then cool to −78 °C. At this temperature, add a pentane solution of tert-butyllithium (1.3 M, 3.1 mL, 4.00 mmol, 4.00 eq) dropwise. As the tert-butyllithium solution is added, the yellow suspension gradually turns into an orange suspension. After the addition is complete, stir for 1 h. Then add the pre-dissolved zinc chloride tetrahydrofuran solution (0.4 M, 10.0 mL, 4.00 mmol, 4.00 eq), stir at −78 ℃ for 5 min, then return to room temperature and stir for another 1 h to prepare the ferrocene-zinc reagent. At this time, the orange suspension gradually becomes clear.

[0011] Another 100 mL reaction tube was dried as described above. After the reaction tube returned to room temperature, 2,4-dichloro-6-phenyl-1,3,5-triazine (226 mg, 1.00 mmol, 1.00 eq), Pd(PPh3)4 (122 mg, 0.11 mmol, 0.11 eq), and 20.0 mL of ultra-dry tetrahydrofuran solvent were added under an argon atmosphere. After mixing thoroughly, the mixture was added to the ferrocene-zinc reagent described above and reacted at room temperature for 2 h to obtain a wine-red reaction solution. After quenching with deionized water, the solution was extracted three times with dichloromethane, and the organic phase was washed multiple times with saturated brine. Finally, the solution was dried with anhydrous sodium sulfate, filtered, and the crude product after solvent removal was purified by column chromatography (petroleum ether / ethyl acetate = 50 / 1, v / v) to obtain red solid 1 (323 mg, yield: 86%). 1H NMR (500 MHz, Chloroform-d) δ 8.56 (d, J = 7.2 Hz, 2H), 7.62 (t, J= 7.3 Hz,1H), 7.54 (t, J = 7.6 Hz, 2H), 5.31 (t, J = 2.0 Hz, 2H), 4.66 (t, J= 2.0 Hz, 2H), 4.15 (s, 5H). 13C NMR (126 MHz, Chloroform-d) δ 180.4, 172.3,171.4,134.7, 133.3, 129.3, 128.8, 77.6, 73.0, 70.6, 70.5. HRMS (ESI) Exactmass calculated for C19H14ClFeN3 ([M+H]+): 376.0298, mass found: 376.0299. Step (2): Under vacuum conditions, a 100 mL Schlenk reaction tube was dried with a hot air gun. After the reaction tube returned to room temperature, compound 1 (150 mg, 0.40 mmol, 1.00 eq) was added under an argon atmosphere. Then, m-diphenylphenol (53 mg, 0.48 mmol, 1.20 eq) and anhydrous aluminum chloride powder (69 mg, 0.52 mmol, 1.30 eq) were added in three portions. 8.0 mL of ultra-dry o-dichlorobenzene was added, and the reaction was carried out at 90 °C for 24 h to obtain a deep blue-green reaction solution. After the reaction solution cooled to room temperature, the solvent was removed by passing it through a short silica gel column to obtain the crude product. This crude product was then purified again by column chromatography (petroleum ether / ethyl acetate = 10 / 1, v / v) to obtain red solid 2 (106 mg, yield: 59%). 1H NMR (500 MHz, DMSO-d6) δ 13.43(s, 1H), 10.44 (s, 1H), 8.56 (d, J = 7.0 Hz, 2H), 8.46 (d, J = 8.8 Hz, 1H), 7.71 (t, J = 7.2 Hz, 1H), 7.65 (t, J = 7.4 Hz, 2H), 6.53 (dd, J = 8.8, 2.3Hz, 1H), 6.39 (d, J = 2.4 Hz, 1H), 5.24 (t, J = 1.9Hz, 2H), 4.77 (t, J = 1.9Hz, 2H), 4.20 (s, 5H). 13C NMR (126 MHz, DMSO-d6) δ 176.3, 170.4, 164.5,164.3, 135.7, 133.5, 131.9, 129.5, 129.1, 109.5, 109.2,103.6, 78.3, 73.1,70.7, 70.1. HRMS (ESI) Exact mass calculated for C25H19FeN3O2 ([M+H]+):450.0899, mass found: 450.0899. Step (3): Synthesis of FC-1: Take a dry 10 mL Schlenk reaction tube, purge it three times with a double-row tube, and add compound 2 (45 mg, 0.10 mmol, 1.00 eq), potassium carbonate (16.6 mg, 0.12 mmol, 1.20 eq), and 1-iodohexane (16 μL, 0.11 mmol, 1.10 eq) under argon atmosphere. Add 1 mL of ultradry N,N-dimethylformamide and stir at 75 °C for 3 h to obtain a red reaction solution. Pour the reaction solution into water and extract with dichloromethane. Then wash the organic phase multiple times with water and saturated brine, dry it with anhydrous sodium sulfate, filter and remove the solvent under reduced pressure, and purify by column chromatography (petroleum ether / ethyl acetate = 50 / 1, v / v) to obtain red solid FC-1 (40 mg, yield: 74%). 1HNMR (600 MHz, Chloroform-d) δ 13.68 (s, 1H), 8.88–8.24 (m, 3H), 7.62 (t, J= 7.2 Hz, 1H), 7.57 (t, J = 7.4 Hz, 2H), 6.60 (dd, J = 8.9, 2.5 Hz, 1H), 6.54(d,J = 2.5 Hz, 1H), 5.30 (s, 2H), 4.64 (t, J = 1.9 Hz, 2H), 4.15 (s, 5H), 4.05 (t, J = 6.6 Hz, 2H), 1.88–1.78 (m, 2H), 1.49 (tt, J = 9.0, 4.8 Hz, 2H), 1.37 (h, J= 4.0, 3.5 Hz, 4H), 0.97–0.91 (m, 3H). 13C NMR (151 MHz, Chloroform-d) δ 170.5, 165.0, 164.4, 132.7, 131.2, 129.0, 128.8, 110.8,108.2, 101.9, 72.4, 70.4,70.1, 68.4, 31.7, 29.2, 25.8, 22.7, 14.1. HRMS (ESI)Exact mass calculated for C31H31FeN3O2 ([M+H]+): 534.1838, mass found:534.1838. FC-2 synthesis scheme:

[0012] Step (1): Under vacuum conditions, a 250 mL reaction tube was dried using a hot air gun. After the reaction tube returned to room temperature, ferrocene (893 mg, 4.80 mmol, 2.40 eq) and potassium tert-butoxide (108 mg, 0.96 mmol, 0.48 eq) were added under an argon atmosphere. Then, 30.0 mL of ultra-dry tetrahydrofuran was added to dissolve it. The tube was then placed in a pre-set low-temperature apparatus to cool to −78 °C. Subsequently, a pentane solution of tert-butyllithium (1.3 M, 7.4 mL, 9.60 mmol, 4.80 eq) was added dropwise. After the addition was complete, the mixture was stirred for 1 h. Then, a tetrahydrofuran solution of zinc chloride (0.4 M, 24.0 mL, 9.60 mmol, 4.80 eq) was added. The mixture was stirred at −78 °C for 5 min, then returned to room temperature and stirred for another 1 h to prepare the ferrocene-zinc reagent.

[0013] Another 100 mL reaction tube was dried as described above. After the reaction tube returned to room temperature, cyanuric chloride (369 mg, 2.00 mmol, 1.00 eq), Pd(PPh3)4 (123 mg, 0.22 mmol, 0.11 eq), and 20.0 mL of ultra-dry tetrahydrofuran solvent were added under an argon atmosphere. After mixing thoroughly, the mixture was added to the ferrocene-zinc reagent described above and reacted at room temperature for 6 h to obtain a wine-red reaction solution. After quenching with deionized water, the solution was extracted three times with dichloromethane, and the organic phase was washed multiple times with saturated brine. Finally, the solution was dried with anhydrous sodium sulfate, filtered, and the crude product after solvent removal was purified by column chromatography (petroleum ether / ethyl acetate = 50 / 1, v / v) to obtain red solid 3 (388 mg, yield: 40%). 1H NMR (600MHz, Chloroform-d) δ 5.25 (t, J = 1.9 Hz, 4H), 4.62 (t, J = 2.0 Hz, 4H), 4.15(s, 10H). 13C NMR (151 MHz, Chloroform-d) δ 179.0, 77.9, 72.6, 70.4. HRMS(ESI) Exact mass calculated for C23H18ClFe2N3 ([M+H]+): 483.9961, mass found: 483.9972. Step (2): A 100 mL Schlenk reaction tube was dried under vacuum using a hot air gun. After the reaction tube returned to room temperature, compound 3 (242 mg, 0.50 mmol, 1.00 eq) was added under an argon atmosphere, followed by 10.0 mL of ultra-dry o-dichlorobenzene. Then, m-diphenol (80 mg, 0.60 mmol, 1.20 eq) and anhydrous aluminum chloride powder (72 mg, 0.65 mmol, 1.30 eq) were added in three portions. The reaction was carried out at 130 °C for 24 h to obtain a deep blue-green reaction solution. After the reaction solution cooled to room temperature, o-dichlorobenzene was removed by passing it through a short silica gel column to obtain a red crude product. This crude product was then purified again by column chromatography (petroleum ether / ethyl acetate = 5 / 1, v / v) to obtain a red solid 4 (278 mg, yield: 45%). 1HNMR (600 MHz, DMSO-d6) δ 13.55 (s, 1H), 10.34 (s, 1H), 8.36 (d, J = 8.7 Hz, 1H), 6.51 (dd, J =8.8, 2.3 Hz, 1H), 6.38 (d, J = 2.3 Hz, 1H), 5.21 (t, J = 2.0Hz, 4H), 4.76–4.68 (m, 4H), 4.18 (s, 10H). 13C NMR (151 MHz, DMSO-d6) δ 175.4, 169.5,164.2, 164.2, 131.7, 109.6, 108.9, 103.6, 78.8, 72.8, 70.6, 70.1. HRMS(ESI)Exact mass calculated for C29H23Fe2N3O2 ([M+H]+): 558.0562, mass found:558.0573. Step (3): Synthesis of FC-2: Take a dry 10 mL Schlenk reaction tube, add compound 4 (56 mg, 0.10 mmol, 1.00 eq), potassium carbonate (17 mg, 0.12 mmol, 1.20 eq), and iodohexane (16 μL, 0.11 mmol, 1.10 eq) under an argon atmosphere, add 1 mL of ultradry N,N-dimethylformamide, and stir at 90 °C for 3 h to obtain a red reaction solution. Pour the reaction solution into distilled water, extract with dichloromethane, then wash the organic phase repeatedly with distilled water and saturated brine, dry with anhydrous sodium sulfate, filter and remove the solvent under reduced pressure, and purify by column chromatography (petroleum ether / ethyl acetate = 50 / 1, v / v) to obtain red solid FC-2 (56 mg, yield: 88%). 1H NMR (600 MHz, Chloroform-d)δ 13.83 (s, 1H), 8.48 (d, J = 8.8 Hz, 1H), 6.59 (dd, J = 8.9, 2.5 Hz, 1H), 6.53 (d, J = 2.4 Hz, 1H), 5.27 (s, 4H), 4.60 (t, J = 1.9 Hz, 4H), 4.14 (s,10H), 4.05 (t, J = 6.6 Hz, 2H), 1.83 (dq, J = 8.1, 6.6Hz, 2H), 1.53–1.45 (m,2H), 1.40–1.33 (m, 4H), 0.96–0.90 (m, 3H). 13C HRMS (ESI) Exact mass calculated for C35H35Fe2N3O2 ([M+H]+): 642.1501, mass found: 642.1512. FC-3 synthesis scheme:

[0014] Step (1): Dry the 100 mL reaction tube under vacuum conditions with a hot air gun three times. After the reaction tube returns to room temperature, add ferrocene (1.86 g, 10.00 mmol, 1.00 eq) under an argon atmosphere and dissolve it with 10.0 mL of ultra-dry dichloromethane. Then place the ferrocene solution in an ice-water mixing bath to cool to 0 °C.

[0015] Repeat the drying process in a 50 mL reaction tube. After the reaction tube has returned to room temperature, add 4-bromobenzoyl chloride (3.30 g, 15.00 mmol, 1.50 eq) and anhydrous aluminum chloride powder (2.00 g, 15.00 mmol, 1.50 eq) under an argon atmosphere. Then, dissolve the solution in 15 mL of ultra-dry dichloromethane and place it in an ice-water bath to cool to 0 °C. Then, add the solution dropwise to a ferrocene solution at 0 °C while stirring under an argon atmosphere. The two solutions will mix to form a deep blue mixture. After the addition is complete, return the solution to room temperature and stir for 1 h. Pour the mixture into a 0.1 M HCl solution to terminate the reaction, extract with dichloromethane, wash the organic phase with saturated brine and 5 wt% sodium bicarbonate solution, dry with anhydrous sodium sulfate, filter to remove the solvent, and obtain a red crude product. The crude product was then purified by column chromatography (petroleum ether / ethyl acetate = 20 / 1, v / v) to give red solid 5 (3.08 g, yield: 83%). 1HNMR (600 MHz, Chloroform-d) δ 7.78 (d, J = 8.4 Hz, 2H), 7.60 (d, J = 8.4 Hz, 2H), 4.87 (t,J = 2.0 Hz, 2H), 4.60 (t, J = 2.0 Hz, 2H), 4.19 (s, 5H). 13C NMR (151 MHz, Chloroform-d) δ 198.1, 138.6, 131.6, 129.8, 126.4, 77.9, 72.9, 71.6, 70.4.HRMS (ESI) Exact mass calculated for C17H13BrFeO ([M+H]+): 368.9572, massfound: 368.9569. Step (2): Take a 100 mL Schlenk reaction tube and add potassium acetate (294 mg, 3.00 mmol, 3.00 eq). Dry the potassium acetate under vacuum until it becomes a loose white powder. At the same time, dry the Schlenk reaction tube. Repeat the process three times. After the reaction tube returns to room temperature, add compound 5 (369 mg, 1.00 mmol, 1.00 eq), pinacol diboronate (279 mg, 1.10 mmol, 1.10 eq), and 5.0 mL of ultra-dry 1,4-dioxane under an argon atmosphere. Then, purge the tube three times. Finally, add Pd(dppf)Cl2 (37 mg, 0.05 mmol, 0.05 eq) under argon protection. After purging the tube three more times, place it in an oil bath and heat it to 100 °C under reflux for 8 h to obtain a dark brown reaction solution. After the reaction solution cooled to room temperature, it was passed through diatomaceous earth (using dichloromethane as the eluent). The collected organic phase was washed successively with water and saturated brine, dried with anhydrous sodium sulfate, filtered to remove the solvent, and then rapidly purified by column chromatography (petroleum ether / ethyl acetate = 10 / 1, v / v). After washing with a small amount of methanol and filtering, orange solid 6 (312 mg, yield: 75%) was obtained. 1HNMR (600 MHz, Chloroform-d) δ 7.91(d, J = 6.5 Hz, 2H), 7.86 (d, J = 7.5 Hz, 2H), 4.90–4.87 (m, 2H), 4.61–4.57(m, 2H), 4.19 (s, 5H), 1.38 (s, 12H). 13C NMR (151 MHz, Chloroform-d) δ 199.3,142.1, 134.7, 127.2, 84.2, 78.2, 72.8, 71.6, 70.4, 25.0. HRMS (ESI) Exactmass calculated for C23H25BFeO3 ([M+H]+): 417.1319, mass found: 417.1318. Step (3): Take a 100 mL Schlenk reaction tube and add compound 6 (416 mg, 1.00 mmol, 1.00 eq), potassium carbonate (276 mg, 2.00 mmol, 2.00 eq), and 2,4-dichloro-6-phenyl-1,3,5-triazine (452 ​​mg, 2.00 mmol, 2.00 eq), followed by 10.0 mL tetrahydrofuran and 1.0 mL deionized water. After purging the tube three times, under argon protection, add catalyst Pd(PPh3)4 (23 mg, 0.01 mmol, 0.02 eq), and continue purging the tube three times. Then heat under reflux at 80 °C for 7 h to obtain a deep purple reaction solution. After the reaction solution was cooled to room temperature, it was diluted with water and then extracted with ethyl acetate. The separated organic phase was washed with saturated brine, dried with anhydrous sodium sulfate, filtered, concentrated under reduced pressure, and purified by column chromatography (petroleum ether / ethyl acetate = 20 / 1, v / v) to give purple solid 7 (410 mg, yield: 85%). 1H NMR (600 MHz, Chloroform-d) δ 8.73 (d, J = 8.6 Hz, 2H), 8.65 (d, J = 8.4 Hz, 2H), 8.05 (d, J = 8.4 Hz, 2H), 7.66 (t, J = 7.4 Hz, 1H), 7.57 (t, J = 7.6 Hz, 2H), 4.93 (t, J = 2.0 Hz, 2H), 4.65 (t, J = 2.0 Hz, 2H), 4.24 (s, 5H). 13C NMR (151MHz, Chloroform-d) δ 198.8, 173.7, 172.8, 172.4, 144.0, 136.9, 134.3, 134.0,129.6, 129.4, 129.0, 128.4, 77.9, 73.2, 71.6, 70.5. HRMS (ESI) Exactmasscalculated for C26H18ClFeN3O ([M+H]+): 480.0561, mass found: 480.0559. Step (4): A 100 mL Schlenk reaction tube was dried under vacuum using a hot air gun. After the reaction tube returned to room temperature, compound 7 (240 mg, 0.50 mmol, 1.00 eq) was added under an argon atmosphere. Then, m-diphenylphenol (83 mg, 0.75 mmol, 1.50 eq) and anhydrous aluminum chloride powder (100 mg, 0.75 mmol, 1.50 eq) were added in three portions. 10.0 mL of ultra-dry o-dichlorobenzene was added, and the Schlenk reaction tube was then placed in a 100 °C oil bath and stirred for 24 h to obtain a dark green reaction solution. After the reaction solution cooled to room temperature, the o-dichlorobenzene was removed by passing it through a short silica gel column to obtain a black crude product. The crude product was then purified by column chromatography (petroleum ether / ethyl acetate = 2 / 1, v / v) to finally obtain a dark purple solid 8 (113.4 mg, yield: 40%). 1H NMR (600 MHz, DMSO-d6) δ 13.19 (s, 1H), 10.54 (s, 1H), 8.76–8.65 (m, 2H), 8.62–8.48 (m, 3H), 8.11 (d, J = 4.3 Hz, 2H), 7.73 (d, J =7.7 Hz, 1H), 7.67 (dt, J = 11.0, 4.9 Hz, 2H), 6.55 (d, J = 8.7 Hz, 1H), 6.40 (d, J = 3.3 Hz, 1H), 4.89 (s, 2H), 4.76 (s, 2H), 4.32 (d, J = 3.2 Hz, 5H). 13CNMR (151 MHz, DMSO-d6) δ 198.2, 171.3, 170.1, 169.6, 165.0, 164.4, 143.5,137.8, 135.1,134.0, 129.7, 129.3, 129.1, 129.0, 109.5, 103.6, 78.1, 73.7,71.6, 70.7. HRMS (ESI) Exact mass calculated for C32H23FeN3O3 ([M+H]+): 554.1162, mass found: 554.1161. Step (5): Synthesis of FC-3: Take a dry 10 mL Schlenk reaction tube, add compound 8 (111 mg, 0.20 mmol, 1.00 eq), potassium carbonate (33 mg, 0.24 mmol, 1.20 eq), and 1-iodohexane (32 μL, 0.11 mmol, 1.10 eq) under an argon atmosphere, add 2.0 mL of ultra-dry DMF, and stir at 70 °C for 6 h to obtain a red reaction solution. Dilute the reaction solution with water, extract with dichloromethane, then wash the organic phase repeatedly with water and saturated brine, dry with anhydrous sodium sulfate, filter and remove the solvent under reduced pressure, and purify by column chromatography (petroleum ether / ethyl acetate = 50 / 1, v / v) to obtain pink solid FC-3 (102 mg, yield: 80%). 1HNMR (600 MHz, Chloroform-d) δ 13.43(s, 1H), 8.98–8.51 (m, 5H), 8.11–8.05 (m, 2H), 7.65 (t, J = 7.2 Hz, 1H), 7.59(t, J = 7.4 Hz, 2H), 6.61 (d, J = 9.0 Hz,1H), 6.54 (s, 1H), 4.95 (t, J = 1.8Hz, 2H), 4.71–4.63 (m, 2H), 4.25 (s, 5H), 4.05 (t, J = 6.6 Hz, 2H), 1.83 (p,J = 6.8 Hz, 2H), 1.49 (q, J = 133.2, HRMS (ESI) Exact mass calculated forC38H35FeN3O3 ([M+H]+): 638.2101, mass found: 638.2100. FC-4 synthesis scheme:

[0016] Step (1): Take a 250 mL reaction tube and heat it under vacuum with a hot air gun three times until the reaction tube returns to room temperature. Then, under an argon atmosphere, add ferrocene (447 mg, 2.40 mmol, 1.20 eq) and potassium tert-butoxide (54 mg, 0.48 mmol, 0.24 eq) respectively, and dissolve them in 20.0 mL of ultra-dry tetrahydrofuran solvent. Then cool to −78 ℃. At this temperature, add a pentane solution of tert-butyllithium (1.3 M, 3.7 mL, 4.80 mmol, 2.40 eq) dropwise. As the tert-butyllithium solution is added, the yellow suspension gradually turns into an orange suspension. After the addition is complete, stir for 1 h. Then, add the pre-dissolved zinc chloride tetrahydrofuran solution (0.4 M, 6.0 mL, 2.40 mmol, 1.20 eq), stir at −78 ℃ for 5 min, then return to room temperature and stir for another 1 h to prepare the ferrocene-zinc reagent. At this time, the orange suspension gradually becomes clear.

[0017] (2) Synthesis of FC-4: Another 100 mL reaction tube was dried as described above. After the reaction tube returned to room temperature, 2-chloro-4,6-diphenyl-1,3,5-triazine (535 mg, 2.00 mmol, 1.00 eq), Pd(PPh3)4 (254 mg, 0.22 mmol, 0.11 eq), and 20.0 mL of ultra-dry tetrahydrofuran solvent were added under an argon atmosphere. After mixing thoroughly, the mixture was added to the ferrocene-zinc reagent described above and reacted at room temperature for 6 h to obtain a red reaction solution. After quenching with deionized water, the solution was extracted three times with dichloromethane, and the organic phase was washed multiple times with saturated brine. Finally, the solution was dried with anhydrous sodium sulfate, filtered, and the crude product after removing the solvent was purified by column chromatography (petroleum ether / ethyl acetate = 50 / 1, v / v) to obtain red solid FC-4 (667 mg, 80%). 1H NMR (600 MHz, Chloroform-d) δ 8.73 (dt, J = 8.2, 1.4 Hz,4H), 7.64–7.55 (m,6H), 5.43–5.39 (m, 2H), 4.61 (t, J = 1.9 Hz, 2H), 4.13 (s,5H). 13C NMR (151 MHz, Chloroform-d) δ 178.0, 170.8, 136.6, 132.3, 128.9,128.8, 79.8, 72.0,70.2. HRMS (ESI) Exact mass calculated for C25H19FeN3 ([M+H]+): 418.1001, massfound: 418.0995. from Figure 1 Analysis of the ultraviolet-visible spectrum revealed that the four ferrocene-based triazine compounds prepared in this invention extended the photoresponse to approximately 500 nm through intramolecular charge transfer effects, thus broadening the photoresponse range. Furthermore, thermogravimetric analysis showed that the four ferrocene-based triazine compounds also exhibited good thermal stability. At a weight loss of 5%, the thermogravimetric temperatures of FC-1, FC-2, FC-3, and FC-4 were 329 °C, 336 °C, 320 °C, and 286 °C, respectively, which can meet the processing temperature requirements of various materials.

[0018] Example 1: Preparation of PVC composite film materials: Step 1: Preparation of pure PVC film material: First, weigh 0.2 g of PVC powder and pour it into a 50 mL conical flask equipped with a rod-shaped stir bar. Place it on a magnetic stirring table and stir slowly. While stirring, add 10 mL of tetrahydrofuran and continue stirring at room temperature for 6 h to fully dissolve the PVC powder.

[0019] The dissolved PVC tetrahydrofuran solution was allowed to stand for half an hour to remove air bubbles. Then, the solution was poured entirely into a 93 mm diameter quantitative culture dish (with a smooth, unblemished bottom). The dish was placed on a level workbench at room temperature for 24 hours to allow most of the solvent to evaporate. The dish was then placed in a vacuum drying oven at 80 °C for 24 hours to ensure complete evaporation of the tetrahydrofuran and prevent any residual tetrahydrofuran from affecting subsequent tests. The final result was a transparent pure PVC film with a thickness of 20 ± 2 μm.

[0020] Step Two: Preparation of PVC Composite Material: The procedure is similar to the steps above. Weigh 2 g of PVC and mix it with 11 mg of FC-1, 13 mg of FC-2, 13 mg of FC-3, and 8 mg of FC-4, respectively. Pour the mixture into a 250 mL Erlenmeyer flask equipped with a stir bar. While stirring, add 100 mL of tetrahydrofuran. Stir in the dark for 6 hours to ensure the PVC powder is fully dissolved and the PVC and additives are evenly mixed. Then, let the dissolved solution stand for half an hour to remove air bubbles. Take 10 mL of the film-forming solution and inject it into a 93 mm diameter quantitative culture dish (with a smooth and flawless bottom). Place the dish on a horizontal experimental platform at room temperature for 24 hours, then place it in a vacuum drying oven at 80 ℃ for 24 hours to ensure complete volatilization of the tetrahydrofuran. The final film thickness is 20 ± 2 μm, and the additive content is 1 × 10⁻⁶. -2 Composite films with mol / kg PVC are FC-1 / PVC, FC-2 / PVC, FC-3 / PVC and FC-4 / PVC.

[0021] Step 3: Photoaging of Materials: Subsequently, the pure PVC film and the PVC composite film were placed 9 cm below two UV lamps (40 W UVB313 UV lamps, with a main characteristic emission wavelength of 313 nm). Photoaging was carried out at 40 °C. Then, the apparent color was observed, mass loss was measured, and molecular weight was tested.

[0022] Table 1. Changes in molecular weight of materials before and after photoaging in Example 1 of the present invention.

[0023] (1) From the change in apparent color Figure 2 Analysis showed that the addition of these four compounds reduced the lightfastness of PVC materials and accelerated PVC degradation. After 24 hours of UV irradiation, the FC-4 / PVC film showed significant yellowing, which gradually deepened with prolonged exposure, turning dark brown after 120 hours. The FC-1 / PVC and FC-2 / PVC films began to yellow with aging after 48 hours, and the aging process intensified with prolonged exposure. The FC-3 / PVC film aged more slowly, showing significant yellowing after 72 hours of UV irradiation.

[0024] (2) From Figure 3 Analysis revealed that pure PVC showed no significant mass loss during 240 hours of irradiation, while the mass loss rate of composite materials doped with ferrocene-based triazine compounds increased with aging time, and the mass loss rate of these composite materials was higher than that of pure PVC. At 240 hours of irradiation, the mass loss rate of FC-4 / PVC composite material was 6.8%, FC-1 / PVC composite material was 5.4%, FC-2 / PVC composite material was 5.8%, and FC-3 / PVC composite material was 4.8%.

[0025] (3) The molecular weight reduction of pure PVC and PVC composites doped with four ferrocene-based triazine compounds before and after 72 h of photoaging was detected by GPC. As shown in Table 1, both the number-average molecular weight (Mn) and weight-average molecular weight (Mw) decreased after photoaging. After 72 h of light exposure, the decrease rates of number-average molecular weight and weight-average molecular weight of PVC doped with FC-1, FC-2, FC-3, and FC-4 were 18% and 28%, 39% and 45%, 10% and 14%, and 49% and 51%, respectively. The decrease in Mn and Mw of PVC composites doped with ferrocene-based triazine molecules was greater than that of pure PVC.

[0026] The above description is only a preferred embodiment of the present invention. All equivalent changes and modifications made within the scope of the claims of the present invention should be included in the scope of the present invention.

Claims

1. A ferrocene-based triazine photodegradant, characterized in that, The structure is as follows: 。 2. The application of the ferrocene-based triazine photodegrader according to claim 1 in photodegradable polyvinyl chloride plastics.

3. The application according to claim 2, characterized in that, The addition amount of ferrocene-based triazine photodegrading agent is 1×10 -2 mol / kg PVC.

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