A photo-thermal dual-effect polymer initiator, its preparation method and application

Abstract

The present invention discloses a photo-thermal dual-effect polymer initiator, its preparation method and application, so as to solve the problem that the application of photocatalytic initiators is restricted by the light transmittance of polymers. The structural formula of the photo-thermal dual-effect polymer initiator is: The preparation method of this initiator is simple, the raw materials are inexpensive, and the yield of the finished product is relatively high, with certain market economy. At the same time, its photo-thermal dual-effect characteristics enable it to be applied to opaque polymer systems, enhancing the application potential of photocatalytic initiators in fields such as biomedicine, wearable clothing, and lithography technology.

Description

Technical Field

[0001] The present invention belongs to the field of preparation of polymer initiators, and relates to a photo-thermal dual-effect polymer initiator, a preparation method thereof, and an application thereof. Background Art

[0002] With the development of the world economy, serious environmental pollution problems have emerged. Due to the high efficiency and pollution-free nature of photocatalytic initiators, and their wide application in the fields of biomedicine, wearable clothing, lithography technology, etc., they have always attracted people's attention. Photocatalysts are divided into inorganic photocatalysts and organic photocatalysts. Inorganic photocatalytic materials mainly include metal oxides (TiO2, ZnO, SnO2), sulfides (CdS, ZnS), oxohalides (BiOX (X = Cl, Br, I)), non-metal semiconductors (g-C3N4, BN), etc. However, the existing inorganic photocatalytic materials have low utilization rate of visible light, and the photocatalytic activity of some photocatalytic materials is not ideal due to the high electron-hole recombination rate. The visible light-responsive photocatalytic materials cannot be put into practical applications due to their weak visible light absorption. Therefore, there are great difficulties in the research and development of inorganic photocatalytic materials.

[0003] Related researchers have turned their attention to organic photocatalysts. Organic photocatalysts can precisely control the relative molecular mass and molecular weight distribution of polymers in reactions, and excellent chain-end fidelity helps to synthesize polymers with well-defined structures. Photocatalysis is the intersection of photochemistry and catalysis, and is usually a chemical reaction in the presence of a catalyst or initiator, etc. Therefore, in the technical center of the photocatalytic system, the research on the photocatalytic initiator system occupies an important position, and the research on new and efficient photoinitiator systems has become the focus. In the development of organic photocatalysis, although the current organic photocatalysis can proceed under visible light. However, photocatalytic initiators are often affected by the light transmittance of polymers, resulting in uneven light radiation, which limits their application.

[0004] Therefore, it is particularly important to find an effective new type of photocatalyst. Summary of the Invention

[0005] Aiming at the technical problem that photocatalytic initiators are easily affected by the light transmittance of polymers, which limits their application, the present invention proposes a photo-thermal dual-effect polymer initiator, a preparation method thereof, and an application thereof. The present invention solves the problem that the application of photocatalytic initiators is limited by the light transmittance of polymers, so that this initiator can be applied to opaque polymer systems.

[0006] In order to achieve the above object, the technical solution of the present invention is realized as follows:

[0007] A photo-thermal dual-effect polymer initiator, the structural formula of which is:

[0008]

[0009] The preparation method of the photo-thermal dual-effect polymer initiator includes the following steps:

[0010] (1) Dissolve pyrene formaldehyde and p-diacetylbenzene in methanol, add potassium hydroxide solution under stirring conditions, and the resulting product after complete stirring reaction is a yellow precipitate, which is washed with methanol to obtain 1-(4-acetylphenyl)-3-pyrenyl chalcone

[0011] (2) Add 1-(4-acetylphenyl)-3-pyrenyl chalcone, hydroxylamine hydrochloride, and sodium acetate to a tetrahydrofuran / methanol / water solution and reflux until the reaction is complete, then distill under reduced pressure and recrystallize to obtain 1-(4-(1-(oximino)ethyl)phenyl)-3-pyrenyl chalcone

[0012] (3) Dissolve 1-(4-(1-(oximino)ethyl)phenyl)-3-pyrenyl chalcone and triethylamine in dichloromethane, then add acetyl chloride, stir the reaction until complete, and after washing, drying, distilling under reduced pressure, and recrystallizing, an orange-yellow needle-like substance is obtained, namely 1-(4-(1-(acetyloxyimino)ethyl)phenyl)-3-pyrenyl chalcone

[0013]

[0014] In the above step (1), the molar ratio of pyrene formaldehyde, p-diacetylbenzene, and potassium hydroxide is 1:1, the concentration of potassium hydroxide is 2.0 - 2.5 mol / L, and the volume ratio of methanol to potassium hydroxide is 10:3.

[0015] In the above step (1), the concentration of pyrene formaldehyde is 0.03 - 0.033 mol / L, the stirring reaction is carried out at room temperature, and the stirring reaction time is 30 - 36 hours.

[0016] In the above step (2), the molar ratio of 1-(4-acetylphenyl)-3-pyrenyl chalcone, hydroxylamine hydrochloride, and sodium acetate is 1:1:1, and in the tetrahydrofuran / methanol / water solution, the volume ratio of tetrahydrofuran, methanol, and water is 10:1:1 - 12:1:1.

[0017] In the above step (3), the molar ratio of 1-(4-(1-(oximino)ethyl)phenyl)-3-pyrenyl chalcone, triethylamine, and acetyl chloride is 1.28:7.70:1.41.

[0018] In the above step (3), the content of 1-(4-(1-(oximino)ethyl)phenyl)-3-pyrenechalcone in the solution is 0.02 - 0.026 mol / L, and the stirring reaction time is 20 - 24 hours.

[0019] In the above steps (2) and (3), the solution used for washing is 6 mol / L hydrochloric acid, magnesium sulfate is used for drying, and dichloromethane / ether is used for recrystallization.

[0020] The specific preparation route of the photothermal dual-effect polymer initiator is as follows:

[0021] (1) Synthesize 1-(4-acetylphenyl)-3-pyrenechalcone

[0022]

[0023] Mix pyrene formaldehyde and p-diacetylbenzene and dissolve them in 400 mL of methanol. Add 120 mL of 2.5 mol / L potassium hydroxide solution under stirring conditions. After stirring and reacting at room temperature for 36 hours, a yellow precipitate is obtained, which is rinsed with methanol to obtain 1-(4-acetylphenyl)-3-pyrenechalcone.

[0024] (2) Synthesize 1-(4-(1-(oximino)ethyl)phenyl)-3-pyrenechalcone

[0025]

[0026] Add 1-(4-acetylphenyl)-3-pyrenechalcone, hydroxylamine hydrochloride, and sodium acetate to a tetrahydrofuran / methanol / water solution with a total volume of 480 mL and reflux for 24 hours. After vacuum distillation, recrystallize with dichloromethane / ether to obtain 1-(4-(1-(oximino)ethyl)phenyl)-3-pyrenechalcone.

[0027] (3) Synthesize 1-(4-(1-(acetyloximino)ethyl)phenyl)-3-pyrenechalcone

[0028]

[0029] Mix 1-(4-(1-(oximino)ethyl)phenyl)-3-pyrenechalcone and triethylamine and dissolve them in 50 mL of dichloromethane. Then add 0.01 mL of acetyl chloride and stir and react for 24 hours. Wash with 6 mol / L hydrochloric acid, dry with magnesium sulfate. After vacuum distillation, the product is recrystallized with dichloromethane / ether to obtain orange-yellow needles, namely 1-(4-(1-(acetyloximino)ethyl)phenyl)-3-pyrenechalcone.

[0030] The application of the above-mentioned photo-thermal dual-effect polymer initiator in the preparation of a polymer with TMPTA (trimethylolpropane triacrylate) as a monomer.

[0031] The present invention has the following beneficial effects:

[0032] 1. The present invention provides a preparation method of a photo-thermal dual-effect polymer initiator. The obtained initiator has a novel structure and can be used as a photoinitiator and a thermal initiator, solving the problem that the existing photoinitiators are easily affected by the light transmittance of polymers and thus limiting their applications. This initiator can be applied to opaque polymer systems.

[0033] 2. The present invention uses 1-(4-(1-(acetyloximino)ethyl)phenyl)-3-pyrenechalcone as a photoinitiator, and the conversion rate can reach 46% when using 405-nm ultraviolet light as the light source in TMPTA monomer, avoiding the disadvantages of using a high-pressure mercury lamp as the light source in the traditional photocuring process, such as low efficiency, short lifespan, and a main emission wavelength lower than 280 nm, meeting the requirements of the narrow emission spectrum of LEDs for the absorption spectrum of photoinitiators.

[0034] 3. The photo-thermal dual-effect polymer initiator prepared by the present invention has little environmental pollution, and there are no highly toxic and harmful substances in the whole preparation process. Some existing photoinitiators have certain organ toxicity, reproductive toxicity, and filial generation toxicity. For example, PBZ, MK, and DEAB have mutagenicity and will affect male and female reproductive performance. The toxic target organs of BP, 2-MBP, 3-MBP, 4-MBP, OMBB, and 1173 are the liver and kidneys. Description of the Drawings

[0035] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for use in the description of the embodiments or the prior art. Obviously, the following drawings are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0036] Figure 1 1H NMR of 1-(4-acetylphenyl)-3-pyrenechalcone prepared in Example 1 of the present invention 1 H NMR.

[0037] Figure 2 13C NMR of 1-(4-acetylphenyl)-3-pyrenechalcone prepared in Example 1 of the present invention 13 13C NMR.

[0038] Figure 31-(4-(1-(oximino)ethyl)phenyl)-3-pyrenyl chalcone prepared in Example 1 of the present invention 1 H NMR.

[0039] Figure 4 1-(4-(1-(oximino)ethyl)phenyl)-3-pyrenyl chalcone prepared in Example 1 of the present invention 13 C NMR.

[0040] Figure 5 1-(4-(1-(acetoxyimino)ethyl)phenyl)-3-pyrenyl chalcone prepared in Example 1 of the present invention 1 H NMR.

[0041] Figure 6 1-(4-(1-(acetoxyimino)ethyl)phenyl)-3-pyrenyl chalcone prepared in Example 1 of the present invention 13 C NMR.

[0042] Figure 7 Ultraviolet absorption spectrum of 1-(4-(1-(acetoxyimino)ethyl)phenyl)-3-pyrenyl chalcone prepared in Application Example 1 of the present invention in acetonitrile (1×10 -4 mol / L).

[0043] Figure 8 Conversion rate graph of 1-(4-(1-(acetoxyimino)ethyl)phenyl)-3-pyrenyl chalcone prepared in Application Example 1 of the present invention as a photoinitiator in TMPTA monomer (1×10 -5 mol / g) with 405 nm ultraviolet light as the light source.

[0044] Figure 9 Differential scanning calorimetry graph of 1-(4-(1-(acetoxyimino)ethyl)phenyl)-3-pyrenyl chalcone prepared in Application Example 1 of the present invention as a thermal initiator in TMPTA monomer (1×10 -5 mol / g). Detailed implementation manners

[0045] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0046] Example 1

[0047] The preparation method of the photo-thermal dual-effect high-polymer initiator in this example is as follows:

[0048] (1) Synthesis of 1-(4-acetylphenyl)-3-pyrenyl chalcone

[0049]

[0050] Pyrene formaldehyde (4 g, 17.37 mmol, M = 230.27 g / mol) and p-diacetylbenzene (2.82 g, 17.37 mmol, M = 162.19 g / mol) were mixed and dissolved in 400 mL of methanol. 120 mL of 2.5 mol / L potassium hydroxide was added with stirring. The mixture was stirred at room temperature for 36 hours to obtain a yellow precipitate. After washing with methanol, 5.42 g of solid product was obtained with a yield of 83.3%.

[0051] The 1H NMR spectrum and 13C NMR spectrum of 1-(4-acetylphenyl)-3-pyrenyl chalcone are shown in Figure 1 and Figure 2 .

[0052] (2) Synthesis of 1-(4-(1-(oximino)ethyl)phenyl)-3-pyrenyl chalcone

[0053]

[0054] Hydroxylamine hydrochloride (1.86 g, 26.71 mmol, M = 69.49 g / mol) and sodium acetate (3.63 g, 26.71 mmol, M = 136.08 g / mol) were added to 1-(4-acetylphenyl)-3-pyrenyl chalcone (10 g, 26.71 mmol, M = 374.44 g / mol). The mixture was refluxed in a mixture of tetrahydrofuran / methanol / water (volume ratio 400 mL / 40 mL / 40 mL) for 24 hours. After vacuum distillation, recrystallization from dichloromethane / ether gave 10.02 g of orange-yellow needle-like product with a yield of 96.3%.

[0055] The 1H NMR spectrum and 13C NMR spectrum of 1-(4-(1-(oximino)ethyl)phenyl)-3-pyrenyl chalcone are shown in Figure 3 and Figure 4 .

[0056] (3) Synthesis of 1-(4-(1-(acetyloximino)ethyl)phenyl)-3-pyrenyl chalcone

[0057]

[0058] At room temperature, (0.5 g, 1.28 mmol, M = 389.45 g / mol) 1-(4-(1-(oximino)ethyl)phenyl)-3-pyrenyl chalcone was mixed with (1.07 mL, 7.70 mmol, M = 101.19 g / mol, d = 0.726 g / mL) triethylamine and then dissolved in 50 mL of dichloromethane. Then, (0.10 mL, 1.41 mmol, M = 78.50 g / mol, d = 1.10 g / mL) acetyl chloride was added. After stirring for 24 hours, it was washed with 6 mol / L hydrochloric acid and then dried with magnesium sulfate. After distillation under reduced pressure, the product was recrystallized with dichloromethane / ether to obtain 0.37 g of orange-yellow needles, and the yield was 66.79%.

[0059] The 1H NMR and 13C NMR spectra of 1-(4-(1-(acetyloximino)ethyl)phenyl)-3-pyrenyl chalcone are shown in Figure 5 and Figure 6 The UV spectral absorption of the photothermal dual-effect polymer initiator prepared in this example was tested by ultraviolet spectroscopy (UV / Vis), and the results are shown in Figure 7 .

[0060] Example 2

[0061] The preparation method of the photothermal dual-effect polymer initiator in this example is as follows:

[0062] (1) Synthesis of 1-(4-acetylphenyl)-3-pyrenyl chalcone

[0063]

[0064] Pyrene formaldehyde (3.59 g, 15.60 mmol, M = 230.27 g / mol) and p-diacetylbenzene (2.53 g, 15.60 mmol, M = 162.19 g / mol) were mixed and dissolved in 400 mL of methanol. 120 mL of 2.0 mol / L potassium hydroxide was added with stirring, and the mixture was stirred at room temperature for 30 hours to obtain a yellow precipitate. After rinsing with methanol, a solid product was obtained.

[0065] (2) Synthesis of 1-(4-(1-(oximino)ethyl)phenyl)-3-pyrenyl chalcone

[0066]

[0067] Add (1.94 g, 28.00 mmol, M = 69.49 g / mol) hydroxylamine hydrochloride and (3.81 g, 28.00 mmol, M = 136.08 g / mol) sodium acetate to (10.48 g, 28.00 mmol, M = 374.44 g / mol) 1-(4-acetylphenyl)-3-pyrenyl chalcone. Reflux in (volume ratio 480 mL / 40 mL / 40 mL) tetrahydrofuran / methanol / water for 20 hours. After distillation under reduced pressure, recrystallize with dichloromethane / ether to obtain an orange-yellow needle-like product.

[0068] (3) Synthesis of 1-(4-(1-(acetoxyimino)ethyl)phenyl)-3-pyrenyl chalcone

[0069]

[0070] At room temperature, mix (0.39 g, 1.00 mmol, M = 389.45 g / mol) 1-(4-(1-(hydroxyimino)ethyl)phenyl)-3-pyrenyl chalcone with (0.84 mL, 6.02 mmol, M = 101.19 g / mol, d = 0.726 g / mL) triethylamine, dissolve in 50 ml dichloromethane, then add (0.079 mL, 1.10 mmol, M = 78.50 g / mol, d = 1.10 g / mL) acetyl chloride. Stir for 20 hours, wash with 6 mol / L hydrochloric acid, then dry with magnesium sulfate. After distillation under reduced pressure, recrystallize the product with dichloromethane / ether to obtain an orange-yellow needle-like substance.

[0071] Example 3

[0072] The preparation method of the photothermal dual-effect polymer initiator in this example is as follows:

[0073] (1) Synthesis of 1-(4-acetylphenyl)-3-pyrenyl chalcone

[0074]

[0075] Mix (3.77 g, 16.38 mmol, M = 230.27 g / mol) pyrene formaldehyde with (2.66 g, 16.38 mmol, M = 162.19 g / mol) p-diacetylbenzene and dissolve in 400 mL methanol. Stir and add 120 ml of 2.3 mol / L potassium hydroxide. Stir at room temperature for 33 hours to obtain a yellow precipitate. Rinse with methanol to obtain a solid product.

[0076] (2) Synthesis of 1-(4-(1-(hydroxyimino)ethyl)phenyl)-3-pyrenyl chalcone

[0077]

[0078] Add (1.92 g, 27.56 mmol, M = 69.49 g / mol) hydroxylamine hydrochloride and (3.75 g, 27.56 mmol, M = 136.08 g / mol) sodium acetate to (10.32 g, 27.56 mmol, M = 374.44 g / mol) 1-(4-acetylphenyl)-3-pyrenechalcone. Reflux in tetrahydrofuran / methanol / water (volume ratio 440 mL / 40 mL / 40 mL) for 22 hours. After distillation under reduced pressure, recrystallize from dichloromethane / ether to obtain an orange-yellow needle-like product.

[0079] (3) Synthesis of 1-(4-(1-(acetoxyimino)ethyl)phenyl)-3-pyrenechalcone

[0080]

[0081] At room temperature, mix (0.45 g, 1.15 mmol, M = 389.45 g / mol) 1-(4-(1-(hydroxyimino)ethyl)phenyl)-3-pyrenechalcone with (0.96 mL, 6.92 mmol, M = 101.19 g / mol, d = 0.726 g / mL) triethylamine, dissolve in 50 ml of dichloromethane, then add (0.09 mL, 1.27 mmol, M = 78.50 g / mol, d = 1.10 g / mL) acetyl chloride. Stir for 22 hours, wash with 6 mol / L hydrochloric acid, then dry with magnesium sulfate. After distillation under reduced pressure, recrystallize the product from dichloromethane / ether to obtain an orange-yellow needle-like substance.

[0082] Application Example 1

[0083] Experimental test analysis:

[0084] Under near-ultraviolet light at 405 nm, use 1-(4-(1-(acetoxyimino)ethyl)phenyl)-3-pyrenechalcone as a photoinitiator (1×10 -5 mol / g) for detection in TMPTA monomer.

[0085] Measure the conversion rate under an LED@405 nm excitation light source. The results are as Figure 8 , from Figure 8 it can be seen that when using 1-(4-(1-(acetoxyimino)ethyl)phenyl)-3-pyrenechalcone as a photoinitiator, the conversion rate of TMPTA reaches 46%.

[0086] Use 1-(4-(1-(acetoxyimino)ethyl)phenyl)-3-pyrenechalcone as a thermal initiator for DSC in TMPTA monomer. The results are as Figure 9 , from Figure 9 it can be seen that at about 200 °C, the system has an obvious endothermic peak, indicating that a thermal polymerization reaction occurs.

[0087] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A photothermal dual-effect polymer initiator, whose molecular structural formula is:

2. The preparation method of the photo-thermal dual-effect polymer initiator according to claim 1, characterized in that, The following steps: (1) Dissolve pyrene formaldehyde and p-diacetylbenzene in methanol, add potassium hydroxide solution under stirring conditions, and the resulting product after complete stirring reaction is a yellow precipitate, which is rinsed with methanol to obtain 1-(4-acetylphenyl)-3-pyrenyl chalcone (2) Add 1-(4-acetylphenyl)-3-pyrenyl chalcone, hydroxylamine hydrochloride, and sodium acetate to a tetrahydrofuran / methanol / water solution, reflux until the reaction is complete, then distill under reduced pressure and recrystallize to obtain 1-(4-(1-(oxime)ethyl)phenyl)-3-pyrenyl chalcone (3) Dissolve 1-(4-(1-(oximino)ethyl)phenyl)-3-pyrenyl chalcone and triethylamine in dichloromethane, then add acetyl chloride. After stirring until the reaction is complete, wash, dry, distill under reduced pressure, and recrystallize to obtain orange-yellow needles, namely 1-(4-(1-(acetyloxyimino)ethyl)phenyl)-3-pyrenyl chalcone 3. The preparation method of the photothermal dual-effect polymer initiator according to claim 2, wherein: In the step (1), the molar ratio of pyrene formaldehyde to p-diacetylbenzene is 1:1, the concentration of potassium hydroxide is 2.0 - 2.5 mol / L, and the volume ratio of methanol to potassium hydroxide is 10:

3.

4. The preparation method of the photo-thermal dual-effect polymer initiator according to claim 2, wherein: In the step (1), the concentration of pyrene formaldehyde is 0.03 - 0.033 mol / L, the stirring reaction is carried out at room temperature, and the stirring reaction time is 30 - 36 hours.

5. The preparation method of the photo-thermal dual-effect polymer initiator according to claim 2, wherein: In the step (2), the molar ratio of 1-(4-acetylphenyl)-3-pyrenyl chalcone, hydroxylamine hydrochloride, and sodium acetate is 1:1:1, and in the tetrahydrofuran / methanol / water solution, the volume ratio of tetrahydrofuran, methanol, and water is 10:1:1 - 12:1:

1.

6. The preparation method of the photo-thermal dual-effect polymer initiator according to claim 2, wherein: In the step (2), the concentration of 1-(4-acetylphenyl)-3-pyrenyl chalcone is 0.05 - 0.056 mol / L, and the reflux reaction time is 20 - 24 hours.

7. The preparation method of the photo-thermal dual-effect polymer initiator according to claim 2, characterized in that: In the step (3), the molar ratio of 1-(4-(1-(oxime)ethyl)phenyl)-3-pyrenyl chalcone, triethylamine, and acetyl chloride is 1.28:7.70:1.

41.

8. The preparation method of the photo-thermal dual-effect polymer initiator according to claim 2, wherein: In the step (3), the content of 1-(4-(1-(oxime)ethyl)phenyl)-3-pyrenyl chalcone is 0.02 - 0.026 mol / L, and the stirring reaction time is 20 - 24 hours.

9. The preparation method of the photo-thermal dual-effect polymer initiator according to any one of claims 2-8, characterized in that: The solution used for washing is 6 mol / L hydrochloric acid, magnesium sulfate is used for drying, and dichloromethane / ether is used for recrystallization.

10. Use of the photothermal dual-effect polymer initiator according to claim 1 in the preparation of a polymer with TMPTA as a monomer.

Images