Perylene diimide-tempo photosensitizer molecules, methods of making and using the same

Abstract

The perylene diimide-TEMPO photosensitizer molecule, its preparation method and application belong to the technical field of functional materials. Based on the perylene diimide chromophore and TEMPO free radical, a new type of non-heavy atom perylene diimide-TEMPO photosensitizer based on the free radical promoted intersystem crossing mechanism is designed and synthesized. Compared with the traditional photosensitizer, the photosensitizer does not contain heavy atom, has the advantages of low toxicity, simple synthesis method, low price and the like, can efficiently generate singlet oxygen, and has a long triplet state lifetime. In addition, the triplet photosensitizer molecule can be used as a photoinitiator, has excellent performance of initiating free radical polymerization under xenon lamp, has good photobleaching performance, and can be applied to free radical photocuring of deep layer system.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of organic functional molecule synthesis, and particularly relates to a preparation method of a heavy-atom-free perylene diimide-TEMPO photosensitizer capable of efficiently generating singlet oxygen and having a free radical photopolymerization ability and application thereof. BACKGROUND

[0002] A triplet photosensitizer refers to a molecule capable of reaching a triplet excited state from a singlet excited state through an intersystem crossing process when the molecule is excited by light. A triplet photosensitizer having a long excited state lifetime and a high excited state energy level can fully utilize its excited state properties through an electron transfer or energy transfer process, and is widely used in photodynamic therapy, photocatalytic organic reactions, photopolymerization, organic photovoltaic power generation, and water splitting to produce hydrogen, and plays an important role in the development of the fields of biological medicine and energy utilization.

[0003] Since the intersystem crossing from a singlet state to a triplet state is a spin-forbidden process, in order to overcome this energy transition limitation, conventional triplet photosensitizers often rely on a heavy atom effect, and introduce transition metals such as ruthenium, platinum, and iridium, or halogen atoms such as bromine and iodine, to promote the intersystem crossing process to obtain a triplet excited state (for example, the paper In Vitro Demonstration of the Heavy-Atom Effect for Photodynamic Therapy, DOI: 10.1021 / ja047649e). Since such photosensitizers are expensive, have high synthesis costs, and have certain biological toxicity, it is necessary to develop a heavy-atom-free efficient triplet photosensitizer.

[0004] 2,2,6,6-tetramethylpiperidine oxide (TEMPO) is a kind of free radical capable of existing stably in air. The introduction of TEMPO and other free radicals into a chromophore can convert the spin-forbidden S1→T1 intersystem crossing process into a spin-allowed 2 (R-S) → 2(R-T) internal conversion process, thereby facilitating the generation of a triad of chromophores (for example, the article Radical-Enhanced Intersystem Crossing in New Bodipy Derivatives and Application for Efficient Triplet-Triplet Annihilation Upconversion, J. Am. Chem. Soc., 2017, 139, 7831-7842. DOI: 10.1021 / jacs.7b02063). The mechanism of using free radicals to promote intersystem crossing can overcome the shortcomings of traditional triplet photosensitizers, such as high cost, difficult synthesis, and high toxicity, and can be used as a new way to design non-heavy atom triplet photosensitizers. In order to better achieve the application effect in the field of photodynamic therapy, photopolymerization and the like, a good triplet photosensitizer should have an efficient intersystem crossing process, can efficiently sensitize the generation of singlet oxygen, has strong visible light absorption capacity, long triplet state lifetime and the like. However, the types of triplet photosensitizers designed based on the mechanism are few, the triplet state yield of the photosensitizer is low, and the lifetime is short, which limits its application in related fields.

[0005] Therefore, the development of a non-heavy atom triplet photosensitizer with high singlet oxygen yield, strong visible light absorption capacity and long triplet state lifetime based on the mechanism of free radical promoting intersystem crossing has become a problem that needs to be researched and solved. SUMMARY

[0006] Perylene bisimide (PBI) has a highly conjugated planar structure, strong absorption in the visible light region, good stability and easy derivatization, and is a dye molecule with unique optical properties. In view of the shortage of the types of non-heavy atom photosensitizers designed by using the mechanism of free radical promoting intersystem crossing, the present application uses perylene bisimide as a chromophore, connects it with TEMPO free radicals at different sites and lengths to form a series of perylene bisimide-TEMPO free radical molecules, which can promote the efficient intersystem crossing process of the chromophore based on the induction of free radicals, generate a long-lived triplet excited state, and do not contain heavy atoms, and can be used as a new type of photosensitizer in the field of visible light excited free radical photopolymerization.

[0007] The present application provides a perylene bisimide-TEMPO photosensitizer capable of efficiently generating singlet oxygen and having photopolymerization capacity, and the molecular structure general formula is as follows:

[0008]

[0009] wherein R1 is ; R2 is or ; m, n are integers from 8 to 10; X is hydrogen;

[0010] or, R1, R2 are each independently selected from or ; m, n are integers from 8 to 10; at least one substituent X is included in the general formula, X is or ; q1, q2 are integers from 1 to 5.

[0011] Further, R1 is ; R2 is , m, n are integers from 8 to 10; X is hydrogen.

[0012] Preferably, m is 10, n is 8.

[0013] Further, R1, R2 are ; m, n are integers from 8 to 10; one or two substituents X are included in the general formula, X is ; q1, q2 are integers from 1 to 5.

[0014] Preferably, m is 10, n is 8; q1 is 1.

[0015] Preferably, the compound structure is:

[0016] or or or or .

[0017] A second object of the present application is to provide a preparation method of the above-mentioned triplet photosensitizer, comprising the following general synthesis steps:

[0018] S1: under nitrogen protection, a mixture of raw material PBI, different amino derivatives and imidazole is stirred at 160 °C for 6 hours to obtain intermediate;

[0019] S2: under nitrogen protection, the intermediate is reacted with liquid bromine in chloroform solvent at room temperature for 48 hours to obtain a double-side bromine-substituted intermediate and a single-side bromine-substituted intermediate .

[0020] S3: under nitrogen protection, the double-side bromine-substituted intermediate or the single-side bromine-substituted intermediate is reacted with the intermediate The dry 1,4-dioxane and methanol mixed solvent at 100 °C for 36 hours, to generate double-sided substitution product Or single-sided substitution product .

[0021] In the step, A-X1 and A-X2 can be each independently selected from any one of formula (2);

[0022] In the step, B-X can be each independently selected from any one of formula (3)

[0023] A third object of the present application is to provide the application of perylene diimide-TEMPO radical type heavy atom-free photosensitizer in photopolymerization.

[0024] Further, the photopolymerization composition comprises a polymerizable monomer, a photosensitizer and a photoinitiator;

[0025] The photosensitizer is the compound of any one of claims 1-6, and the weight of the photosensitizer accounts for 0.06 wt%-0.10 wt% of the weight of the photopolymerization composition.

[0026] The photoinitiator further comprises a second photoinitiator, or a second photoinitiator and an additive;

[0027] The second photoinitiator comprises at least one of benzophenone photoinitiator, α-hydroxy ketone photoinitiator, α-amino ketone photoinitiator, dimethylamino benzophenone photoinitiator, thioxanthone photoinitiator, xanthone photoinitiator, bisimidazole photoinitiator, triazine photoinitiator, acyl oxime photoinitiator;

[0028] The additive comprises at least one of a colorant, an alkali-soluble resin, an adhesion promoter, a surfactant, and a dispersant.

[0029] Compared with the prior art, the present application has the following advantages:

[0030] 1. The photosensitizer designed and synthesized in the present application has a simple molecular structure, few synthesis steps, and does not contain heavy atoms such as transition metals and halogens, and has low toxicity and good biocompatibility;

[0031] 2. The photosensitizer molecule described in the present application is based on a perylene diimide chromophore, which has strong light absorption capacity in the visible light band. By changing the distance and connection position between the chromophore and the free radical, the intersystem crossing and the triplet quantum yield are regulated, thereby improving the singlet oxygen yield and prolonging the triplet state lifetime;

[0032] 3、The application provides a new type of non-heavy atom perylene diimide-TEMPO photosensitizer based on a radical promoting inter-system crossing mechanism, which is synthesized based on a perylene diimide chromophore and a TEMPO free radical. 1 Compared with traditional photosensitizers, the photosensitizer has the advantages of low toxicity, simple synthesis method and low price, can efficiently generate singlet oxygen (O2), and has a long triplet state lifetime.

[0033] 4、The photosensitizer molecule designed and synthesized in the application can be used as a photoinitiator and has high initiation efficiency under a xenon lamp.

[0034] 5、The photosensitizer molecule designed and synthesized in the application has good photobleaching performance and can be applied to the photocuring of deep layer systems. DETAILED DESCRIPTION

[0035] Figure 1 It is an infrared spectrum schematic diagram of compound 5-1.

[0036] Figure 2 It is a MALDI-TOF high-resolution accurate mass correction characterization diagram of compound 5-1.

[0037] Figure 3 It is an infrared spectrum schematic diagram of compound 6-1.

[0038] Figure 4 It is a MALDI-TOF high-resolution accurate mass correction characterization diagram of compound 6-1.

[0039] Figure 5 It is a diagram of the change of the absorption peak intensity of DPBF with irradiation time in the presence of compound 5-1.

[0040] Figure 6 It is a diagram of the change of the absorption peak intensity of DPBF with irradiation time in the presence of compound 6-1.

[0041] Figure 7 It is an ultraviolet-visible absorption spectrum of compound 5-1.

[0042] Figure 8 It is a nanosecond transient absorption spectrum of compound 5-1.

[0043] Figure 9 It is a triplet state lifetime decay curve of compound 5-1.

[0044] Figure 10 It is an ultraviolet-visible absorption spectrum of compound 6-1.

[0045] Figure 11 It is a nanosecond transient absorption spectrum of compound 6-1.

[0046] Figure 12Triplet lifetime decay curve for compound 6-1.

[0047] Figure 13 Photobleaching curve for compound 5-1.

[0048] Figure 14 Photobleaching curve for compound 6-1.

[0049] Figure 15 Monomer polymerization initiation plot for compound 5-1.

[0050] Figure 16 Monomer polymerization initiation plot for compound 6-1. DETAILED DESCRIPTION

[0051] The application is further described in connection with the following examples, which are not intended to limit the application.

[0052] Example 1

[0053] Synthesis of triplet photosensitizer material formula (5-1) was carried out according to the following reaction scheme:

[0054]

[0055] Synthesis of intermediate I was carried out according to the following procedure: A mixture of 3,4,9,10-perylenetetracarboxylic dianhydride (4.0 g, 10.2 mmol), imidazole (20.0 g, 294 mmol) and 2-octyldodecylamine (7.6 mL, 42.0 mmol) was heated under stirring at 160 °C for 6 h under nitrogen atmosphere. After completion of the reaction, it was cooled to room temperature, brine (200 mL) was added and the reaction mixture was extracted with dichloromethane. The organic layer was then dried over anhydrous sodium sulfate and the organic phase was concentrated using rotary evaporation. The crude product was purified by column chromatography using silica gel column with dichloromethane: n-hexane (2:3 by volume) as eluent to obtain red solid intermediate I (8.6 g, yield: 90%).

[0056] Synthesis of intermediate II was carried out according to the following procedure: A mixture of intermediate I (2.0 g, 3.3 mmol), liquid bromine (9.0 mL, 180.0 mmol) and chloroform (50 mL) was stirred at room temperature for 48 h under nitrogen atmosphere. After completion of the reaction, the organic layer was washed with saturated aqueous sodium thiosulfate solution. The organic layer was then dried over anhydrous sodium sulfate and concentrated to obtain the organic phase. The crude product was purified by column chromatography using silica gel column with dichloromethane: n-hexane (2:3 by volume) as eluent to obtain red solid intermediate II (0.67 g, yield: 31%).

[0057] Synthesis of intermediate III, the detailed synthesis protocol is as follows: Tetraisopropyl titanate (3.07 g, 10.8 mmol) was added dropwise to 4-oxo-TEMPO (1.53 g, 9 mmol) and stirred for 20 min. Then N-tert-butoxycarbonyl-1,2-ethanediamine (2.92 g, 18 mmol) was added in portions and the reaction mixture was stirred for 3 h. Before the addition of sodium cyanoborohydride (0.57 g, 9 mmol), the mixture was diluted with 500 mL of methanol. The resulting solution was stirred for 24 h. After the reaction was completed, the white precipitate was isolated by the addition of water, filtered, washed with ethyl acetate, and the combined organic layers were washed with brine. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The crude product was purified by column chromatography using a silica gel column with ethyl acetate / triethylamine / n-hexane (7:0.1:3 by volume) as the eluent. Intermediate III was obtained as a white oil (0.88 g, yield: 31%).

[0058] Synthesis of intermediate IV, the detailed synthesis protocol is as follows: To a solution of intermediate III (0.88 g, 2.8 mmol) in dichloromethane was added excess trifluoroacetic acid (0.32 g, 28 mmol) and the reaction was allowed to proceed at room temperature for 4 h. Subsequently, the solvent was removed under reduced pressure to obtain an oil, which was soaked in a mixture of methanol and dichloromethane (1:400 by volume) and anhydrous potassium carbonate (2 g) was added and stirred overnight. After filtration using celite, the filtrate was collected and the solvent was removed under reduced pressure. Intermediate IV was obtained as a white oil (0.55 g, yield: 98%).

[0059] Synthesis of triplet photosensitizer material of formula (5-1), the detailed protocol is as follows: To a dry 1,4-dioxane solution was added PBI-Br (102.9 mg, 0.1 mmol) under nitrogen protection, and a syringe was used to add a dry methanol solution containing TEMPO (214.3 mg, 1 mmol), with the volume ratio of 1,4-dioxane to methanol being 1:1, and the reaction mixture was reacted at 100 °C for 36 h. After the reaction was completed, it was cooled to room temperature, the reaction mixture was extracted with dichloromethane (3 × 15 mL), and the combined organic phase was washed with brine (2 × 10 mL) and then dried over anhydrous sodium sulfate. After the organic phase was dried over anhydrous sodium sulfate, the solvent was concentrated under reduced pressure. The crude product was purified by column chromatography using a silica gel column with dichloromethane:n-hexane (2:3 by volume) as the eluent to obtain a blue solid product (65.1 mg, yield: 56%).

[0060] Example 2

[0061] Synthesis of triplet photosensitizer material of formula (6-1), the synthesis was carried out according to the following reaction equation:

[0062]

[0063] The synthesis of the triplet photosensitizer material of formula (6-1) was carried out as follows: Under nitrogen protection, a mixture of 3,4,9,10-perylenetetracarboxylic dianhydride (196.2 mg, 0.5 mmol), imidazole (952 mg, 14 mmol), 2-octyldodecylamine (0.38 mL, 42.0 mmol), and 4-amino-TEMPO (85.6 mg, 0.5 mmol) was stirred at 160 °C for 6 hours. After the reaction was completed, the mixture was cooled to room temperature, dichloromethane was added, and the organic layer was washed with brine (3 × 200 mL). The organic phase was collected and the organic solvent was dried over anhydrous sodium sulfate. The crude product was concentrated by vacuum distillation and purified by column chromatography using silica gel column with dichloromethane as the eluent to give a red solid product (123.8 mg, yield: 30%).

[0064] Example 4

[0065] The target molecule was characterized using infrared spectroscopy and matrix-assisted laser desorption / ionization time-of-flight (MALDI-TOF) mass spectrometry, yielding accurate information about its structure. The specific results are as follows:

[0066] For equation (5-1), the infrared spectrum is shown in Figure 1 below, 3305 absorption peak corresponding Stretching vibrations indicate the presence of a secondary amine in the structure. ). 2920 and 2849 It is typical Stretching vibrations, and saturation in long-chain alkyl groups (sp) 3 The vibration corresponds to this. 1729 It is a carbonyl (C=O) stretching vibration, located at 1730°. Around 1688, consistent with the absorption characteristics of imide carbonyl groups. and 1648 It is a vibration of the aromatic ring C=C skeleton. 1510 and 1455 These are skeletal vibrations of the C=C and C=N bonds in aromatic systems. 1378 1347 1272 Belonging to Bending vibration or vibrations with CH2 and CH3 in the alkyl side chain. 1178 and 1107 Corresponding to The stretching and contracting vibration. 804 and 747 Belonging to the aromatic ring Bending vibration.

[0067]

[0068] For equation (5-1), after high-resolution precise mass correction using MALDI-TOF, as shown in Figure 2. The target molecular formula is: The theoretical mass-to-charge ratio is 1162.8663, the measured mass-to-charge ratio is 1162.8618, and the relative error is 3.9034%.

[0069] For equation (6-1), the infrared spectrum is shown in Figure 3 below, 2918 and 2853 Absorption peaks typically represent Stretching vibrations, especially those with methyl groups ( It is related to the methylene (-CH2) group. 1730 This is the carbonyl (C=O) stretching vibration peak. 1600 The absorption peak is related to the C=C stretching vibration of the aromatic ring. 1241 and 1050 Absorption peak represents Stretching vibration. 1430 The absorption peak is Bending vibration peak. 1162 and 1119 Belonging to the aromatic ring Bending vibration.

[0070] For equation (6-1), after high-resolution precise mass correction using MALDI-TOF, as shown in Figure 4. The target molecular formula is: The theoretical mass-to-charge ratio is 824.5002, and the measured mass-to-charge ratio is 824.4958.

[0071] It should be noted that the other compounds claimed in this application can be obtained by referring to the preparation methods of the examples listed above, so they will not be listed one by one here.

[0072] Example 5

[0073] The generation of singlet oxygen in photosensitizer materials in the molecular structures shown in formulas (5-1) and (6-1) is monitored using the singlet oxygen scavenger 1,3-diphenylisobenzofuran (DPBF), comprising the following steps:

[0074] Prepare a toluene solution of the photosensitizer with a concentration of mol / L, used as mother liquor A.

[0075] A chloroform solution of DPBF was prepared with a concentration of 0.1 mol / L as mother solution B.

[0076] Mother solution A was taken and added to 3 mL of toluene solution to make its absorbance at 532 nm about 0.2, and then mother solution B was added to make its absorbance at 414 nm about 1.0, to obtain a mixed solution of mother solution A and mother solution B.

[0077] Under the condition of light shielding, the mixed solution was irradiated with 532 nm light, and the decrease of the absorption peak intensity of DPBF at different irradiation time intervals was monitored to realize the detection of singlet oxygen generation state.

[0078] As shown in the following 5, the perylene diimide-radical photosensitizer material formula (5-1) generates singlet oxygen in toluene solution, and the absorption peak intensity of DPBF shows a linear change with the irradiation time (0 seconds, 60 seconds, 120 seconds, 180 seconds, 240 seconds, 300 seconds, 360 seconds, 420 seconds, 480 seconds), and the absorption peak intensity of DPBF gradually decreases with the increase of irradiation time. Specifically, the absorption peak intensity of DPBF decreases from 1.03267 to 0.85661 within 480 seconds, which indicates that formula (5-1) is a kind of triplet photosensitizer which can efficiently generate singlet oxygen.

[0079] As shown in the following 6, the perylene diimide-radical photosensitizer material formula (6-1) generates singlet oxygen in toluene solution, and the absorption peak intensity of DPBF shows a linear change with the irradiation time (0 seconds, 40 seconds, 80 seconds, 120 seconds, 160 seconds, 200 seconds, 240 seconds, 280 seconds), and the absorption peak intensity of DPBF gradually decreases with the increase of irradiation time. Specifically, the absorption peak intensity of DPBF decreases from 1.04134 to 0.88345 within 280 seconds, which indicates that formula (6-1) is a kind of triplet photosensitizer which can efficiently generate singlet oxygen.

[0080] Example 6

[0081] Test of triplet state properties of perylene diimide-radical photosensitizer materials:

[0082] ​Nanosecond transient absorption spectroscopy was performed using a nanosecond laser flash photolysis instrument (LP 980). The excitation source was a tunable nanosecond laser (Surelite I-10) with an excitation wavelength range of 210 nm–2400 nm and a laser energy of approximately 15 mJ (500 nm) per pulse. The test signal was digitized using a Tektronix TDS 3012B oscilloscope, and the data was recorded and processed using L900 software. During nanosecond transient absorption spectroscopy testing, the test sample must be placed in a nitrogen atmosphere to avoid the quenching effect of oxygen on the triplet state. Therefore, high-purity nitrogen gas was bubbled into the solution for approximately 15 minutes before the test.

[0083] The UV-Vis absorption spectrum of photosensitizer formula (5-1) in toluene solvent is shown in Figure 7. Based on the UV-Vis absorption spectrum of the photosensitizer in toluene solvent, the test concentration for nanosecond transient absorption spectroscopy was determined to be... M, with an excitation wavelength of 610 nm. The nanosecond transient absorption spectrum of the photosensitizer in a deoxytoluene solution at room temperature is shown in Figure 8. An excited-state absorption peak signal was observed within the range, which was attributed to the transition from the first triplet excited state to a higher-level triplet excited state in the amino-substituted PBI moiety. The decay curve of the transient material was measured at 520 nm, as shown in Figure 9 below. Equation (5-1) has a relatively long triplet lifetime, which, after fitting, is 7.6 μs.

[0084] The UV-Vis absorption spectrum of photosensitizer formula (6-1) in toluene solvent is shown in Figure 10. Based on the UV-Vis absorption spectrum of the photosensitizer in toluene solvent, the test concentration for nanosecond transient absorption spectroscopy was determined to be... M, with an excitation wavelength of 530 nm. The nanosecond transient absorption spectrum of the photosensitizer in a deoxytoluene solution at room temperature is shown in Figure 11. Absorption peaks were observed in the range and at 565 nm, which are typical characteristics of the transition from the first triplet excited state to a higher energy triplet excited state in unsubstituted PBI. The decay curve of the transient material was measured at 520 nm, as shown in Figure 12. Equation (6-1) has a long triplet lifetime, and the fitted triplet lifetime is 5.0 μs.

[0085] Both photosensitizers shown in equations (5-1) and (6-1) can efficiently undergo intersystem crossing processes to generate triplet states. This is due to the electron spin exchange between the free radical and the chromophore triplet state. Furthermore, the triplet lifetime of the PBI-TEMPO photosensitizer is more than ten times longer than that of the heavily atom-substituted PBI, indicating that the free radical-based triplet photosensitizer does not quench the triplet lifetime. This demonstrates the reliability of designing highly efficient, heavy-atom-free photosensitizer molecules based on this mechanism.

[0086] It should be noted that other compounds claimed in the present application can be obtained by referring to the experimental methods of the above-listed examples, and therefore are not listed one by one here.

[0087] Example 6

[0088] The mixture of the polymerizable component and the photoinitiating system in the present application can be subjected to photobleaching test (steady photolysis test) by a 35 W xenon lamp (white light intensity: 80 mW / cm 2 ). The experimental equipment is a UV-Vis absorption spectrometer from Shimadzu, Japan, the solvent is dichloromethane, and the co-initiator is tetrabutylammonium tris (3-chloro-4-methylphenyl) hexylborate (NB). The test method is as follows:

[0089] Under the condition of light shielding, dichloromethane solutions of formula (5-1) with a concentration of M and dichloromethane solutions of formula (6-1) with a concentration of M were prepared respectively. Tetrabutylammonium tris (3-chloro-4-methylphenyl) hexylborate was added to the solutions to make the concentration of the co-initiator also M. After the sample solutions were prepared, high-purity nitrogen was blown into the solutions for about 15 minutes. The absorption spectra of the samples before and after light irradiation for different time were scanned by a UV absorption spectrometer. The photobleaching curve of formula (5-1) is shown in 13, and the photobleaching curve of formula (6-1) is shown in 14.

[0090] With the increase of the light irradiation time, the absorption peak intensity of the material gradually decreased, indicating that formula (5-1) and formula (6-1) had excellent photobleaching performance, which was very rare in chromophore-radical photosensitizer materials.

[0091] Example 7

[0092] The mixture of the polymerizable component and the photoinitiating system in the present application can be subjected to photobleaching test (steady photolysis test) by a 35 W xenon lamp (white light intensity: 80 mW / cm 2 ). The experimental equipment is a UV-Vis absorption spectrometer from Shimadzu, Japan, the solvent is dichloromethane, and the co-initiator is tetrabutylammonium tris (3-chloro-4-methylphenyl) hexylborate (NB). The test method is as follows:

[0093] Further, the total amount of the photopolymerization composition is 100 wt%, and the weight of the photosensitizer accounts for 0.06 wt% to 0.10 wt% of the weight of the photopolymerization composition.

[0094] Further, the photoinitiator further comprises a second photoinitiator and / or an additive.

[0095] ​Further, the second photoinitiator includes at least one of a benzophenone-based photoinitiator, an a-hydroxyketone-based photoinitiator, an a-aminoketone-based photoinitiator, a dimethylamino phenone-based photoinitiator, a thioxanthone-based photoinitiator, an xanthone-based photoinitiator, a bisimidazole-based photoinitiator, a triazine-based photoinitiator, and an acyl oxime-based photoinitiator.

[0096] The additive includes at least one of a colorant, an alkali-soluble resin, an adhesion promoter, a surfactant, and a dispersant.

[0097] In the photopolymerization experiment, 0 wt%, 0.06 wt%, 0.08 wt%, 0.10 wt% of the perylene diimide-radical photosensitizer material of formula (5-1) or formula (6-1) was respectively added to form a co-initiation system with 0.5 wt% of tetrabutylammonium tris(3-chloro-4-methylphenyl)hexylborate (NB), which was then distributed into four small sample bottles, 0.12 mL of toluene solution was added for dissolution, followed by 1 mL of trimethylolpropane triacrylate (TMPTA) monomer, and then light and oxygen were removed, and the mixture was uniformly mixed. A 35 W xenon lamp was used for irradiation, and the time for complete curing of the monomer was recorded.

[0098] The changes of the formula (5-1) sample before and after irradiation by a 35 W xenon lamp are shown in Figure 15. As can be seen from the figure, when no perylene diimide-radical photosensitizer material is added, i.e., 0 wt% of formula (5-1), the monomer cannot be cured. When 0.06 wt% of formula (5-1) is added, the complete curing time of the monomer is 240 seconds. When 0.08 wt% of formula (5-1) is added, the complete curing time of the monomer is 85 seconds. When 0.10 wt% of formula (5-1) is added, the complete curing time of the monomer is 150 seconds.

[0099] The changes of the formula (6-1) sample before and after irradiation by a 35 W xenon lamp are shown in Figure 16. As can be seen from the figure, when no perylene diimide-radical photosensitizer material is added, i.e., 0 wt% of formula (6-1), the monomer cannot be cured. When 0.06 wt% of formula (6-1) is added, the complete curing time of the monomer is 25 seconds. When 0.08 wt% of formula (6-1) is added, the complete curing time of the monomer is 20 seconds. When 0.10 wt% of formula (6-1) is added, the complete curing time of the monomer is 32 seconds.

[0100] In summary, the application provides a synthesis method of perylene diimide-TEMPO photosensitizer based on efficient generation of singlet oxygen by radical-induced chromophore, which is simple to prepare, has high yield, does not contain heavy atoms, and realizes non-toxicity of synthesis steps and products, and conforms to the concept of green chemistry. The perylene diimide-TEMPO photosensitizer can efficiently generate triplet state and has a triplet state lifetime of up to microseconds. More importantly, the photosensitizer shows good performance in photopolymerization and achieves the purpose of polymerization under white light. Therefore, the application has certain practical and economic value in the synthesis of photosensitizer and photopolymerization.

[0101] Of course, the above embodiments of the present application are only examples and are not intended to limit the specific embodiments of the present application. For those skilled in the art, other different forms of changes or variations can be made on the basis of the above examples. It is not possible to detail all the embodiments here. Any obvious changes or variations derived from the technical solutions of the present application are still within the scope of protection of the present application.

Claims

1. A class of perylene diimide-TEMPO compounds, characterized in that: The structure of the compound is shown in general formula (1): ； Where R1 is R2 is or m and n are integers between 8 and 10; X represents hydrogen. Alternatively, R1 and R2 can be selected independently. or m and n are integers between 8 and 10; the general formula contains at least one substituent X, where X is... or q1 and q2 are integers from 1 to 5.

2. The compound according to claim 1, characterized in that: R1 is R2 is m and n are integers between 8 and 10; X is hydrogen.

3. The compound according to claim 2, characterized in that: m is 10 and n is 8.

4. The compound according to claim 1, characterized in that: R1 and R2 are m and n are integers between 8 and 10; the general formula includes one or two substituents X, where X is q1 and q2 are integers from 1 to 5.

5. The compound according to claim 4, characterized in that: m is 10, n is 8; q1 is 1.

6. The compound according to claim 1, characterized in that: or or or or or .

7. The use of the compound according to any one of claims 1-6, characterized in that: The compound is used as a reagent for generating singlet oxygen.

8. The use of the compound according to any one of claims 1-6, characterized in that: Applications of the compound in photopolymerization or photocatalysis.

9. The application according to claim 8, characterized in that, The specific application of the compound in photopolymerization is as follows: Photopolymerization compositions include polymeric monomers, photosensitizers, and photoinitiators; The photosensitizer is any one of the compounds described in claims 1-6, and the weight of the photosensitizer accounts for 0.06 wt% to 0.10 wt% of the weight of the photopolymerization composition.

10. The application according to claim 9, characterized in that, The photoinitiator further includes a second photoinitiator, or a second photoinitiator and an additive; The second photoinitiator includes at least one of the following: benzophenone photoinitiators, α-hydroxy ketone photoinitiators, α-amino ketone photoinitiators, dimethylaminobenzophenone photoinitiators, thioxanone photoinitiators, thioxanone photoinitiators, biimidazole photoinitiators, triazine photoinitiators, and acyl oxime photoinitiators; The additives include at least one of colorants, alkali-soluble resins, adhesion promoters, surfactants, and dispersants.

Images