Carbazolyl bischalcone as well as preparation method and application thereof

Abstract

The invention provides carbazolyl bischalcone as well as a preparation method and application thereof, and belongs to the technical field of photoinitiators. The chemical structural formula of the carbazolyl double chalcone provided by the invention is as shown in a formula I; in the formula I, R is-H,-SMe,-OMe, NMe2, NEt2, CF3 or-N (Ph) 2. The specific structure of the carbazolyl double chalcone is controlled, so that when the carbazolyl double chalcone is used as a photoinitiator to initiate polymerization reaction of acrylate monomers, the photoinitiation speed is high, the double bond conversion rate is high, and the carbazolyl double chalcone can be used for a deep curing system.

Description

Technical Field

[0001] The invention belongs to the technical field of photoinitiators, and specifically relates to a carbazole-based bischalcone and a preparation method and application thereof. Background Art

[0002] Acrylate polymers have excellent weather resistance, good adhesion and optical properties, good flexibility and elasticity, and are widely used in many fields. Acrylate polymers mainly generate active groups under light conditions through photoinitiators, thereby initiating polymerization reactions of monomers. Deep curing refers to the process in which the material can fully undergo polymerization reactions from the surface to the inside during the curing (polymerization) process to form a highly cross-linked three-dimensional network structure. Deeply cured materials have better properties. For example, deeply cured coatings can provide better wear resistance, corrosion resistance, and chemical resistance.

[0003] As a key component of the photocuring system, the performance of the photoinitiator directly affects the efficiency of the photocuring process, the degree of curing, and the performance of the cured product. Existing commonly used photoinitiators such as camphorquinone CQ and 2-isopropylthioxanthone ITX need to be compounded with a hydrogen donor to have high initiation activity, and there are many problems such as migration. In addition, ITX is also reproductively toxic, which limits its application in the fields of biomedicine and the like. The development of single-component initiators and low-toxicity photoinitiators has always been a research hotspot in the field of photopolymerization. Summary of the invention

[0004] The purpose of the present invention is to provide a carbazole-based bischalcone and its preparation method and application. When the carbazole-based bischalcone provided by the present invention is used as a photoinitiator to initiate the polymerization reaction of acrylate monomers, the photoinitiation speed is fast, the double bond conversion rate is high, and it can be used in a deep curing system.

[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0006] The present invention provides a carbazole-based bischalcone, the chemical structure of which is shown in Formula I:

[0007]

[0008] In the formula I, R is -H, -SMe, -OMe, NMe2, NEt2, CF3 or -N(Ph)2.

[0009] The present invention also provides a method for preparing the carbazole-based bischalcone described in the above technical solution, comprising:

[0010] 3,6-diacetyl-N-ethylcarbazole, benzaldehyde / benzaldehyde derivative, base and solvent are mixed and subjected to Claisen-Schmidt reaction to obtain carbazole-based bischalcone.

[0011] Preferably, the molar ratio of the benzaldehyde / benzaldehyde derivative to 3,6-diacetyl-N-ethylcarbazole is (2-3):1.

[0012] Preferably, the volume ratio of the amount of the 3,6-diacetyl-N-ethylcarbazole to the solvent is 5 mmol: (30-80) mL.

[0013] Preferably, the temperature of the Claisen-Schmidt reaction is 30-80° C., and the time of the Claisen-Schmidt reaction is 8-15 h.

[0014] The present invention also provides the use of the carbazole-based bischalcone described in the above technical solution or the carbazole-based bischalcone prepared by the preparation method described in the above technical solution as a photoinitiator.

[0015] Preferably, the carbazole-based bischalcone is used as a photoinitiator to initiate the polymerization reaction of the acrylic ester monomer.

[0016] Preferably, the carbazole-based bischalcone is mixed with ethyl p-dimethylaminobenzoate or iodonium salt as a photoinitiator to initiate the polymerization reaction of acrylate monomers.

[0017] Preferably, the acrylic acid ester monomers include methyl methacrylate, butyl methacrylate, methyl acrylate, n-butyl acrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, β-hydroxyethyl methacrylate or β-hydroxyethyl acrylate, 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane, triethylene glycol dimethacrylate, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctyl acrylate, hexafluorobutyl acrylate, pentafluorophenyl methacrylate, 2,2,2-trifluoroethyl acrylate, 2-(perfluorooctyl)ethyl methyl At least one of acrylate, 2-(perfluorobutyl)ethyl methacrylate, 2-(perfluorohexyl)ethyl acrylate, 2-(perfluorohexyl)ethyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 1H,1H,2H,2H-perfluorodecyl acrylate, 1H,2H,3H,4H-perfluorooctanol acrylate, 2,2,3,3,4,4,4-heptafluorobutyl acrylate, 2,2,3,3,4,4,4-heptafluorobutyl methacrylate, 2,2,3,4,4,4-hexafluorobutyl methacrylate, 1,1,1,3,3,3-hexafluoropropane-2-yl acrylate and 2,2,3,3,4,4,5,5-octafluorohexane-1,6-diyl diacrylate.

[0018] Preferably, the light source for the polymerization reaction is an LED light source.

[0019] The present invention provides a carbazole-based bischalcone, the chemical structure of which is shown in Formula I: In the formula I, R is -H, -SMe, -OMe, NMe2, NEt2, CF3 or -N(Ph)2. The present invention controls the specific structure of the carbazole-based bischalcone so that when it is used as a photoinitiator to initiate the polymerization reaction of acrylate monomers, the photoinitiation speed is fast, the double bond conversion rate is high, and it can be used in a deep curing system. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 The reaction equation for preparing the carbazole-based bischalcone of the present invention is:

[0021] Figure 2 The hydrogen nuclear magnetic resonance spectrum of the carbazole-based bischalcone prepared in Example 1;

[0022] Figure 3 The carbon NMR spectrum of the carbazole-based bischalcone prepared in Example 1;

[0023] Figure 4 The hydrogen nuclear magnetic resonance spectrum of the carbazole-based bischalcone prepared in Example 2;

[0024] Figure 5 The carbon NMR spectrum of the carbazole-based bischalcone prepared in Example 2;

[0025] Figure 6 The hydrogen nuclear magnetic resonance spectrum of the carbazole-based bischalcone prepared in Example 3;

[0026] Figure 7 The carbon NMR spectrum of the carbazole-based bischalcone prepared in Example 3;

[0027] Figure 8 The graph of carbon-carbon double bond conversion rate-time of 1,6-hexanediol diacrylate monomer in Application Examples 1 to 3;

[0028] Fig. 9 The graph of carbon-carbon double bond conversion rate-time of 1,6-hexanediol diacrylate monomer in Application Examples 4 to 6;

[0029] Fig.10 The graph of carbon-carbon double bond conversion rate-time of 1,6-hexanediol diacrylate monomer in Application Examples 7 to 9;

[0030] Fig.11 It is a graph of carbon-carbon double bond conversion rate-time of 1,6-hexanediol diacrylate monomer in Application Examples 3, 6, 9 and Comparative Application Examples 1 to 3;

[0031] Fig.12 This is a macroscopic image of the deeply cured polymer obtained in Application Example 10;

[0032] Fig.13 This is a macroscopic image of the deeply cured polymer obtained in Application Example 11. DETAILED DESCRIPTION

[0033] The present invention provides a carbazole-based bischalcone, the chemical structure of which is shown in Formula I:

[0034]

[0035] In the present invention, in the formula I, R is -H, -SMe, -OMe, NMe2, NEt2, CF3 or -N(Ph)2.

[0036] As an embodiment, when R is -N(Ph)2, the chemical structural formula of the carbazole-based bischalcone is

[0037] The carbazole-based bischalcone provided by the present invention can be used as an LED photoinitiator, and can be used as a single-component photoinitiator to initiate the polymerization of (meth) acrylate monomers and acrylate monomers or methacrylate monomers grafted with fluorine-containing segments. It can also be compounded with hydrogen donor amine (ethyl p-dimethylaminobenzoate) or iodonium salt as a photoinitiator. When compounded, it has higher photoinitiation activity and can be used in a deep curing system. Thicker polymer materials can be prepared under light. The carbazole-based bischalcone provided by the present invention does not need to add a solvent for dissolution, and does not need an auxiliary agent to effectively initiate monomer polymerization. Compared with existing photoinitiators, it has higher initiation activity.

[0038] The present invention also provides a method for preparing the carbazole-based bischalcone described in the above technical solution, comprising:

[0039] 3,6-diacetyl-N-ethylcarbazole, benzaldehyde / benzaldehyde derivative, base and solvent are mixed and subjected to Claisen-Schmidt reaction to obtain carbazole-based bischalcone.

[0040] Unless otherwise specified, the present invention has no particular limitation on the sources of the raw materials, and commercially available products known to those skilled in the art may be used.

[0041] In the present invention, the structural formula of the 3,6-diacetyl-N-ethylcarbazole is

[0042] In the present invention, the structural formula of the benzaldehyde / benzaldehyde derivative is The R is -H, -SMe, -OMe, NMe2, NEt2, CF3 or -N(Ph)2.

[0043] In the present invention, the molar ratio of the benzaldehyde / benzaldehyde derivative to 3,6-diacetyl-N-ethylcarbazole is preferably (2-3):1. As an embodiment, the molar ratio of the benzaldehyde / benzaldehyde derivative to 3,6-diacetyl-N-ethylcarbazole may be specifically 2:1, 2.1:1, 2.2:1, 2.3:1, 2.4:1, 2.5:1, 2.6:1, 2.7:1, 2.8:1, 2.9:1 or 3:1. The present invention controls the molar ratio of benzaldehyde / benzaldehyde derivative to 3,6-diacetyl-N-ethylcarbazole within the above range, so that the two can react fully and have a higher yield.

[0044] In the present invention, the base preferably comprises potassium hydroxide or sodium hydroxide. In the present invention, the base acts as a catalyst.

[0045] In the present invention, the solvent preferably includes one or both of water and ethanol.

[0046] In the present invention, the volume ratio of the amount of the substance of 3,6-diacetyl-N-ethylcarbazole to the solvent is preferably 5mmol: (30-80)mL. As an embodiment, the volume ratio of the amount of the substance of 3,6-diacetyl-N-ethylcarbazole to the solvent can be specifically 5mmol: 30mL, 5mmol: 40mL, 5mmol: 50mL, 5mmol: 60mL, 5mmol: 70mL or 5mmol: 80mL. The present invention controls the volume ratio of the amount of the substance of 3,6-diacetyl-N-ethylcarbazole to the solvent within the above range, so that the raw material can be fully dissolved.

[0047] In the present invention, the mixing of 3,6-diacetyl-N-ethylcarbazole, benzaldehyde / benzaldehyde derivatives, base and solvent is preferably: the base and solvent are mixed to obtain alkaline solution, and then 3,6-diacetyl-N-ethylcarbazole and benzaldehyde / benzaldehyde derivatives are added in sequence.

[0048] In the present invention, the mass concentration of the alkali solution is preferably 10-30%. As an embodiment, the mass concentration of the alkali solution can be specifically 10%, 15%, 20%, 25% or 30%. The present invention has no special limitation on the amount of the alkali, and the mass concentration of the alkali solution is ensured to be within the above range. The present invention controls the mass concentration of the alkali solution within the above range, so that the Claisen-Schmidt reaction can be fully carried out.

[0049] In the present invention, the temperature of the Claisen-Schmidt reaction is preferably 30 to 80° C. As an embodiment, the temperature of the Claisen-Schmidt reaction may be specifically 30° C., 40° C., 50° C., 60° C., 70° C. or 80° C.

[0050] In the present invention, the time of the Claisen-Schmidt reaction is preferably 8 to 15 hours. As an embodiment, the time of the Claisen-Schmidt reaction can be specifically 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours or 15 hours. The present invention controls the temperature and time of the Claisen-Schmidt reaction within the above range, so that the reaction can be fully carried out and the reaction yield can be improved.

[0051] After the Claisen-Schmidt reaction is completed, the product of the Claisen-Schmidt reaction is preferably cooled, filtered, washed and dried in sequence to obtain the carbazole-based bischalcone.

[0052] In the present invention, the cooling is preferably carried out in ice water. The present invention has no particular limitation on the cooling time, and cooling to room temperature is sufficient.

[0053] The present invention has no special limitation on the filtering operation, and the solid-liquid separation can be carried out by using filtering technical solutions well known to those skilled in the art.

[0054] The present invention has no special limitation on the washing operation, and the unreacted raw materials can be removed by using a washing technique known to those skilled in the art. In an embodiment of the present invention, the washing is specifically performed by washing with ethanol for 2 to 3 times, and the amount of ethanol used in each washing is 10 mL.

[0055] The present invention has no special limitation on the drying operation, and drying to constant weight can be performed using a drying technical solution well known to those skilled in the art.

[0056] The reaction equation for preparing carbazole bischalcone according to the present invention is as follows: Figure 1 shown.

[0057] The present invention also provides the use of the carbazole-based bischalcone described in the above technical solution or the carbazole-based bischalcone prepared by the preparation method described in the above technical solution as a photoinitiator.

[0058] In the present invention, the carbazole-based bischalcone is preferably used as a photoinitiator to initiate the polymerization reaction of the acrylic ester monomers.

[0059] In the present invention, the carbazole-based bischalcone is preferably compounded with ethyl p-dimethylaminobenzoate or iodonium salt as a photoinitiator to initiate the polymerization reaction of acrylate monomers.

[0060] In the present invention, the iodonium salt preferably includes diphenyl iodonium hexafluorophosphate, bis (tert-butylphenyl) iodonium hexafluorophosphate or bis (p-tolyl) iodonium hexafluorophosphate, and more preferably bis (tert-butylphenyl) iodonium hexafluorophosphate. In the present invention, when carbazole-based bischalcone is compounded with ethyl p-dimethylaminobenzoate or iodonium salt as a photoinitiator to initiate the polymerization reaction of acrylic ester monomers, it has better initiation activity.

[0061] In the present invention, the molar ratio of the carbazole-based bischalcone to ethyl p-dimethylaminobenzoate or iodonium salt is preferably 1:(1-2). The present invention controls the molar ratio of the carbazole-based bischalcone to ethyl p-dimethylaminobenzoate or iodonium salt within the above range, which can have better initiation activity.

[0062] In the present invention, the acrylic acid ester monomer preferably includes methyl methacrylate, butyl methacrylate, methyl acrylate, n-butyl acrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, β-hydroxyethyl methacrylate or β-hydroxyethyl acrylate, 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane, triethylene glycol dimethacrylate, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctyl acrylate, hexafluorobutyl acrylate, pentafluorophenyl methacrylate, 2,2,2-trifluoroethyl acrylate, 2-(perfluorooctyl)ethyl At least one of methyl methacrylate, 2-(perfluorobutyl)ethyl methacrylate, 2-(perfluorohexyl)ethyl acrylate, 2-(perfluorohexyl)ethyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 1H,1H,2H,2H-perfluorodecyl acrylate, 1H,2H,3H,4H-perfluorooctanol acrylate, 2,2,3,3,4,4,4-heptafluorobutyl acrylate, 2,2,3,3,4,4,4-heptafluorobutyl methacrylate, 2,2,3,4,4,4-hexafluorobutyl methacrylate, 1,1,1,3,3,3-hexafluoropropane-2-yl acrylate and 2,2,3,3,4,4,5,5-octafluorohexane-1,6-diyl diacrylate. The carbazole-based bischalcone provided by the present invention can be used as a photoinitiator to initiate polymerization reactions of various monomers, including fluorine-containing monomers, so that it has a broader application prospect in the development and application of various polymer materials, including fluorine-containing polymer materials.

[0063] In the present invention, the mass ratio of the amount of the carbazole-based bischalcone to the acrylate monomer is preferably 0.025 mmol: (5-15) g, more preferably 0.025 mmol: 10 g. The present invention controls the mass ratio of the amount of the carbazole-based bischalcone to the acrylate monomer within the above range, which can have better initiation activity.

[0064] In the present invention, the light source for the polymerization reaction is preferably an LED light source; the wavelength of the LED light source is preferably 365 to 405 nm; the light intensity of the light source is preferably 100 to 200 mW / cm 2 , more preferably 130m~200W / cm 2 The polymerization reaction time is preferably 1 to 30 minutes. The present invention uses a light source with the above wavelength to have better initiation activity.

[0065] The carbazole-based bischalcone provided by the present invention is used as a photoinitiator, has a fast photoinitiation speed, a high double bond conversion rate, and can be used in a deep curing system to prepare a thicker polymer.

[0066] The technical solutions in the present invention will be described clearly and completely 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, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0067] Example 1

[0068] A carbazole-based bischalcone, whose chemical structural formula is: R is -H;

[0069] The preparation method of the carbazole-based bischalcone comprises the following steps: mixing potassium hydroxide and water to obtain a potassium hydroxide aqueous solution with a mass concentration of 20%, sequentially adding 50 mL of the potassium hydroxide aqueous solution with a mass concentration of 20%, 1.395 g (5 mmol) of 3,6-diacetyl-N-ethylcarbazole and 1.272 g (12 mmol) of benzaldehyde into a 250 mL three-necked flask, heating to 50° C., reacting for 12 h, and after the reaction is completed, cooling in ice water, filtering to obtain a crude product, washing with ethanol twice (10 mL each time), and drying to obtain 1.85 g (yield 81.3%) of yellow solid carbazole-based bischalcone, which is recorded as DCZ.

[0070] The hydrogen nuclear magnetic resonance spectrum of the carbazole-based bischalcone prepared in Example 1 is as follows: Figure 2 The H NMR spectrum data is: 1 H NMR (CDCl3, 500MHz) δppm: 1.49-1.55 (t, J=7.0Hz, 3H, CH2CH3), 4.42-4.50 (q, J=7.0Hz, 2H, CH2CH3), 7.43-7.50 (m, 4H), 7.51-7.55 (d, J =8.5Hz, 2H), 7.69-7.76 (d, J=7.5Hz, 4H), 7.76-7.83 (m, 2H), 7.88-7.96 (m, 2H), 8.27-8.32 (dd, J1=8.5Hz, J2=1.5Hz, 2H), 8.94 (s, 2H).

[0071] The carbon NMR spectrum of the carbazole-based bischalcone prepared in Example 1 is as follows: Figure 3 As shown, the carbon NMR spectrum data is: 13C NMR (CDCl3, 125MHz) δppm: 189.39 (C=O), 144.15, 143.47, 135.21, 130.67, 130.40, 1 29.00, 128.51, 127.51, 123.20, 122.27, 122.18, 109.01, 38.28(NCH2), 13.94(CH3).

[0072] Example 2

[0073] A carbazole-based bischalcone, whose chemical structural formula is: R is -SMe;

[0074] The preparation method of the carbazole-based bischalcone is as follows: potassium hydroxide and water are mixed to obtain a potassium hydroxide aqueous solution with a mass concentration of 20%, 50 mL of the potassium hydroxide aqueous solution with a mass concentration of 20%, 1.395 g (5 mmol) of 3,6-diacetyl-N-ethylcarbazole and 1.824 g (12 mmol) of 4-methylthiobenzaldehyde are added in sequence into a 250 mL three-necked flask, heated to 60° C., reacted for 10 hours, and after the reaction is completed, placed in ice water for cooling, filtered to obtain a crude product, washed with ethanol 3 times (10 mL each time), and dried to obtain 2.31 g (yield 84.6%) of a yellow solid carbazole-based bischalcone, which is recorded as DCZ-SMe.

[0075] The hydrogen nuclear magnetic resonance spectrum of the carbazole-based bischalcone prepared in Example 2 is as follows: Figure 4 The H NMR spectrum data is: 1 HNMR (CDCl3, 500MHz) δppm: 1.44-1.56 (t, J=7.0Hz, 3H, CH2CH3), 2.54 (s, 6H, SCH3), 4.38-4.49 (q, J=7.0Hz, 2H, CH2CH3), 7.27-7.36 (d, J=8.5Hz, 4H), 7.47-7.55(d, J=8.5Hz, 2H), 7.60-7.67(d, J=8.0Hz, 4H), 7.71-7.78(m, 2H) , 7.82-7.91 (m, 2H), 8.23-8.31 (dd, J1=8.5Hz, J2=1.5Hz, 2H), 8.91 (s, 2H).

[0076] The carbon NMR spectrum of the carbazole-based bischalcone prepared in Example 2 is as follows: Figure 5 As shown, the carbon NMR spectrum data is: 13C NMR (CDCl3, 125MHz) δppm: 189.28 (C=O), 143.62, 143.42, 142.12, 131.72, 130.74, 128.88, 12 7.46, 126.09, 123.19, 122.19, 121.07, 108.98, 38.27(NCH2), 15.23(SCH3), 13.93(CH2CH3).

[0077] Example 3

[0078] A carbazole-based bischalcone, whose chemical structural formula is: R is -N(Ph)2;

[0079] The preparation method of the carbazole-based bischalcone comprises the following steps: mixing potassium hydroxide and water to obtain a potassium hydroxide aqueous solution with a mass concentration of 20%, sequentially adding 50 mL of the potassium hydroxide aqueous solution with a mass concentration of 20%, 1.395 g (5 mmol) of 3,6-diacetyl-N-ethylcarbazole and 3.280 g (12 mmol) of 4-diphenylaminobenzaldehyde into a 250 mL three-necked flask, heating to 60° C., reacting for 10 h, and after the reaction is completed, cooling in ice water, filtering to obtain a crude product, washing with ethanol for 3 times (10 mL each time), and drying to obtain 3.27 g (yield 82.8%) of yellow solid carbazole-based bischalcone, which is recorded as DCZ-DB.

[0080] The hydrogen nuclear magnetic resonance spectrum of the carbazole-based bischalcone prepared in Example 3 is as follows: Figure 6 The H NMR spectrum data is: 1 H NMR (500MHz, CDCl3) 1.48-1.53 ​​(3H, CH3, t, J = 7.0Hz), 4.41-4.48 (2H, CH2, q, J = 7.0Hz) ), 7.05-7.12 (8H, q, J = 8.5Hz), 7.14-7.18 (8H, d, J = 8.0Hz), 7.27-7.33 (8H, t, J = 7.0Hz ), 7.49-7.62 (2H, d, J = 8.5Hz), 7.55-7.59 (4H, d, J = 8.5Hz), 7.61-7.66 (2H, d, J = 15.5 Hz), 7.83-7.88 (2H, d, J=15.5Hz), 8.25-8.28 (2H, dd, J=1.5Hz, J=14Hz), 8.90 (2H, s).

[0081] The carbon NMR spectrum of the carbazole-based bischalcone prepared in Example 3 is as follows: Figure 7 As shown, the carbon NMR spectrum data is: 13C NMR (125MHz, CDCl3)189.50, 150.00, 146.93, 143.95, 143.27, 130.99, 129.73, 129.50, 1 28.26, 127.36, 125.40, 124.03, 123.17, 122.08, 121.80, 119.66, 108.85, 38.22, 13.91.

[0082] Application Example 1

[0083] The carbazolyl bischalcone prepared in Example 1 was weighed using a ten-thousandth analytical balance 2.5×10 -5 mol (0.0114 g) and 10.00 g of 1,6-hexanediol diacrylate (HDDA) were placed in a 10 mL centrifuge tube and ultrasonically mixed. The mixture was then placed under an LED light source with a wavelength of 385 nm and a light intensity of 130 mW / cm 2 The polymer is obtained by light curing.

[0084] Application Example 2

[0085] The carbazole-based bischalcone prepared in Example 1 in Application Example 1 was replaced with 0.0137 g of the carbazole-based bischalcone prepared in Example 2, and the other parameters were the same as those in Application Example 1.

[0086] Application Example 3

[0087] The carbazole-based bischalcone prepared in Example 1 of Application Example 1 was replaced with 0.0197 g of the carbazole-based bischalcone prepared in Example 3, and the other parameters were the same as those in Application Example 1.

[0088] The real-time infrared method was used to detect the photocuring kinetics in Examples 1 to 3, and the obtained carbon-carbon double bond conversion rate-time curve of 1,6-hexanediol diacrylate monomer was as follows: Figure 8 As shown. Figure 8 It can be seen that when the carbazole-based bischalcone in Examples 1 to 3 is used as a photoinitiator to initiate photocuring of HDDA, all three have a faster photoinitiation speed, among which the carbazole-based bischalcone in Example 3 has the fastest photoinitiation activity and the highest double bond conversion rate.

[0089] Application Example 4

[0090] The carbazolyl bischalcone prepared in Example 1 was weighed using a ten-thousandth analytical balance 2.5×10 -5 mol (0.0114 g), ethyl 4-dimethylaminobenzoate (EDB) 0.0097 g (5 × 10 -5mol) and 10.00 g of 1,6-hexanediol diacrylate (HDDA) were placed in a 10 mL centrifuge tube and ultrasonically mixed. The mixture was then placed under an LED light source with a wavelength of 385 nm and a light intensity of 130 mW / cm 2 The polymer is obtained by light curing.

[0091] Application Example 5

[0092] In Application Example 4, the carbazole-based bischalcone prepared in Example 1 was replaced with 0.0137 g of the carbazole-based bischalcone prepared in Example 2. Other parameters were the same as those in Application Example 4.

[0093] Application Example 6

[0094] In Application Example 4, the carbazole-based bischalcone prepared in Example 1 was replaced with 0.0197 g of the carbazole-based bischalcone prepared in Example 3. Other parameters were the same as those in Application Example 4.

[0095] Application Example 7

[0096] The carbazolyl bischalcone prepared in Example 1 was weighed using a ten-thousandth analytical balance 2.5×10 -5 mol (0.0114 g), di-tert-butylphenyl iodonium hexafluorophosphate (Iod) 0.0134 g (2.5 × 10 -5 mol) and 10.00 g of 1,6-hexanediol diacrylate (HDDA) were placed in a 10 mL centrifuge tube and ultrasonically mixed. The mixture was then placed under an LED light source with a wavelength of 385 nm and a light intensity of 130 mW / cm 2 The polymer is obtained by light curing.

[0097] Application Example 8

[0098] In Application Example 7, the carbazole-based bischalcone prepared in Example 1 was replaced with 0.0137 g of the carbazole-based bischalcone prepared in Example 2. Other parameters were the same as those in Application Example 7.

[0099] Application Example 9

[0100] In Application Example 7, the carbazole-based bischalcone prepared in Example 1 was replaced with 0.0197 g of the carbazole-based bischalcone prepared in Example 3. Other parameters were the same as those in Application Example 7.

[0101] The real-time infrared method was used to detect the photocuring kinetics in Examples 4 to 6, and the obtained carbon-carbon double bond conversion rate-time curve of 1,6-hexanediol diacrylate monomer was as follows: Fig. 9 shown.

[0102] The real-time infrared method was used to detect the photocuring kinetics in Examples 7 to 9, and the obtained carbon-carbon double bond conversion rate-time curve of 1,6-hexanediol diacrylate monomer was as follows: Fig.10 shown.

[0103] from Figures 8 to 10 It can be seen that the carbazole-based bischalcone provided by the present invention can be used as a single-component photoinitiator to initiate the polymerization of 1,6-hexanediol diacrylate, and can also be compounded with ethyl 4-dimethylaminobenzoate or di-tert-butylphenyl iodonium hexafluorophosphate as a photoinitiator to initiate the polymerization of 1,6-hexanediol diacrylate, and the best effect is achieved when compounded with di-tert-butylphenyl iodonium hexafluorophosphate.

[0104] Comparative application example 1

[0105] The carbazole-based bischalcone prepared in Example 3 of Application Example 3 was replaced with 0.0042 g of photoinitiator camphorquinone CQ, and the other parameters were the same as those in Application Example 3.

[0106] Comparative Application Example 2

[0107] The carbazole-based bischalcone prepared in Example 3 of Application Example 6 was replaced with 0.0042 g of photoinitiator camphorquinone CQ, and the other parameters were the same as those in Application Example 6.

[0108] Comparative Application Example 3

[0109] The carbazole-based bischalcone prepared in Example 3 of Application Example 9 was replaced with 0.0042 g of photoinitiator camphorquinone CQ, and the other parameters were the same as those in Application Example 9.

[0110] The real-time infrared method was used to detect the photocuring kinetics in Examples 3, 6, 9 and Comparative Examples 1 to 3, and the obtained carbon-carbon double bond conversion rate-time curve of 1,6-hexanediol diacrylate monomer was as follows: Fig.11 As shown. Fig.11 It can be seen that compared with the photoinitiator camphorquinone CQ, the carbazole-based bischalcone prepared in Example 3 has a better photoinitiation speed and double bond conversion rate, especially the single-component photoinitiator system has a more significant effect.

[0111] Application Example 10

[0112] The carbazolyl bischalcone prepared in Example 3 was weighed using a ten-thousandth analytical balance 2.5×10 -5 mol (0.0197 g) and 10.00 g of 1,6-hexanediol diacrylate (HDDA) were placed in a 10 mL centrifuge tube, ultrasonically mixed, transferred to a flat-mouth test tube (10 mm in diameter and 100 mm in depth), filled with argon for 2 min, sealed with a sealing film, and placed under an LED light source with a wavelength of 385 nm and a light intensity of 200 mW / cm 2 The samples were light cured for 30 min under 400 nm light conditions, and the uncured samples were washed away with ethanol to obtain a deeply cured polymer.

[0113] The macroscopic image of the deep cured polymer prepared in Application Example 10 is as follows: Fig.12 As shown. Fig.12 It can be seen that when the photocuring time is 30 minutes, the polymer curing depth is 1.5 cm. This proves that the carbazole-based bischalcone provided by the present invention can be used as a photoinitiator for the preparation of deep curing materials and has a wider range of applications.

[0114] Application Example 11

[0115] The carbazolyl bischalcone prepared in Example 3 was weighed using a ten-thousandth analytical balance 2.5×10 -5 mol (0.0197 g), di-tert-butylphenyl iodonium hexafluorophosphate (Iod) 0.0134 g (2.5 × 10 -5 mol) and 10.00 g of 1,6-hexanediol diacrylate (HDDA) were placed in a 10 mL centrifuge tube, ultrasonically mixed, and transferred to a flat-mouth test tube (10 mm in diameter and 100 mm in depth). The tube was filled with argon for 2 min and sealed with a sealing film. The tube was illuminated by an LED light source with a wavelength of 385 nm and a light intensity of 200 mW / cm 2 The samples were light cured for 30 min under 400 nm light conditions, and the uncured samples were washed away with ethanol to obtain a deeply cured polymer.

[0116] The macroscopic image of the deep cured polymer prepared in Application Example 11 is as follows: Fig.13 As shown. Fig.13 It can be seen that when the photocuring time is 30 minutes, the polymer curing depth is 3.8 cm. This proves that the carbazole-based bischalcone provided by the present invention can be used as a photoinitiator for the preparation of deep curing materials when compounded with iodonium salts, and has a wider range of applications.

[0117] In summary, the carbazole-based bischalcone provided by the present invention can be used as a photoinitiator to initiate the polymerization reaction of acrylate monomers, and has a fast photoinitiation speed, a high double bond conversion rate, and can be used in a deep curing system.

[0118] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A carbazole-based bischalcone, whose chemical structure is shown in Formula I: In the formula I, R is -H, -SMe, -OMe, NMe2, NEt2, CF3 or -N(Ph)2.

2. The method for preparing the carbazole-based bischalcone according to claim 1, comprising: 3,6-diacetyl-N-ethylcarbazole, benzaldehyde / benzaldehyde derivative, base and solvent are mixed and subjected to Claisen-Schmidt reaction to obtain carbazole-based bischalcone.

3. The preparation method according to claim 2, characterized in that: The molar ratio of the benzaldehyde / benzaldehyde derivative to 3,6-diacetyl-N-ethylcarbazole is (2-3):

1.

4. The preparation method according to claim 2, characterized in that: The volume ratio of the amount of the 3,6-diacetyl-N-ethylcarbazole to the solvent is 5 mmol: (30-80) mL.

5. The preparation method according to claim 2, characterized in that: The temperature of the Claisen-Schmidt reaction is 30-80° C., and the time of the Claisen-Schmidt reaction is 8-15 hours.

6. Use of the carbazole-based bischalcone according to claim 1 or the carbazole-based bischalcone prepared by the preparation method according to any one of claims 2 to 5 as a photoinitiator.

7. The use according to claim 6, characterized in that: The carbazole-based bischalcone is used as a photoinitiator to initiate a polymerization reaction of the acrylic ester monomers.

8. The use according to claim 6, characterized in that: The carbazole-based bischalcone is compounded with ethyl p-dimethylaminobenzoate or iodonium salt to act as a photoinitiator to initiate a polymerization reaction of acrylate monomers.

9. The use according to claim 7 or 8, characterized in that: The acrylic ester monomers include methyl methacrylate, butyl methacrylate, methyl acrylate, n-butyl acrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, β-hydroxyethyl methacrylate or β-hydroxyethyl acrylate, 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane, triethylene glycol dimethacrylate, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctyl acrylate, hexafluorobutyl acrylate, pentafluorophenyl methacrylate, 2,2,2-trifluoroethyl acrylate, 2-(perfluorooctyl)ethyl methacrylate At least one of ester, 2-(perfluorobutyl)ethyl methacrylate, 2-(perfluorohexyl)ethyl acrylate, 2-(perfluorohexyl)ethyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 1H,1H,2H,2H-perfluorodecyl acrylate, 1H,2H,3H,4H-perfluorooctanol acrylate, 2,2,3,3,4,4,4-heptafluorobutyl acrylate, 2,2,3,3,4,4,4-heptafluorobutyl methacrylate, 2,2,3,4,4,4-hexafluorobutyl methacrylate, 1,1,1,3,3,3-hexafluoropropane-2-yl acrylate and 2,2,3,3,4,4,5,5-octafluorohexane-1,6-diyl diacrylate.

10. The use according to claim 7 or 8, characterized in that: The light source of the polymerization reaction is an LED light source.

Images