A broadly-absorbed polymerizable enone photoinitiator and its preparation method and application

Abstract

The present invention discloses a wide absorption polymerizable ketene photoinitiator and a preparation method and application thereof, wherein the general structural formula of the ketene photoinitiator is as shown in the following formula (1)-(4): The molecular structure of the wide absorption polymerizable ketene photoinitiator provided by the present invention contains both a photoinitiating group and a polymerizable double bond end group, has high initiation activity, can participate in the curing reaction to avoid migration, has photobleaching characteristics, does not produce yellowing, can be used for the photopolymerization reaction of various resins, and is particularly suitable for various acrylic resins. The product of the present invention has a wide light absorption range, good compatibility with UV-LED light sources, is conducive to deep curing, can be used in inks, coatings, microelectronics, packaging, dentistry, 3D printing and other fields, and is particularly suitable for food packaging printing or medical materials with high requirements for biological toxicity.

Description

Technical Field

[0001] The invention relates to an ene ketone derivative which can be used as a photoinitiator and photosensitizer for free radical polymerization, in particular to a polymerizable ene ketone photoinitiator which has good response from long-wave ultraviolet to visible light bands, and a preparation method and application thereof. Background Art

[0002] Compared with traditional thermal polymerization, photopolymerization technology has the advantages of energy saving, environmental protection, and high efficiency. It is widely used in the fields of coatings, inks, packaging, microelectronics, photoresists, dental materials, etc. The photoinitiator is the core component of the photopolymerization system, and it plays a decisive role in whether the system can react quickly and efficiently. When the hydrogen-abstracting free radical photoinitiator is initiated, it is necessary to add a co-initiator that can provide hydrogen atoms. Tertiary amine compounds are commonly used. The hydrogen-abstracting free radical photoinitiator absorbs ultraviolet light energy and reacts with the co-initiator in the excited state. Active free radicals are generated through electron transfer to initiate photopolymerization. Common hydrogen-abstracting free radical photoinitiators include benzophenones, thioxanthones, etc. This type of photoinitiator itself has a certain yellowing, and when used in combination with tertiary amine co-initiators, the yellowing will be aggravated. In addition, small molecular amines also have migration toxicity, which affects the application effect of the coating.

[0003] In the photocuring molding of thick products or photocuring ink systems, due to the absorption of pigments, it is necessary to select a photoinitiator with good absorption in the long-wave ultraviolet range. When the absorption wavelength of the photoinitiator exceeds 400nm, it appears yellow due to the absorption of the blue end of visible light, which makes the product yellow and affects the quality. Commonly used thioxanthone photoinitiators have such problems. The enone photoinitiator itself has the characteristics of photobleaching, which can effectively solve the yellowing problem. The design and synthesis of photoinitiators that absorb long-wave ultraviolet light to visible light can reduce the damage caused by short-wave ultraviolet light sources and is conducive to deep curing. Introducing a photocurable double bond at the end of the molecule can greatly reduce the mobility and reduce the biological toxicity of the photoinitiator, which is particularly suitable for food packaging printing or medical materials with high requirements for biological toxicity. Summary of the invention

[0004] In view of the problems of yellowing and migration of long-wave ultraviolet photoinitiators in the prior art, the present invention provides a long-wavelength polymerizable enone photoinitiator and its preparation method and application. The enone photoinitiator of the present invention has high initiation activity, can participate in the photocuring reaction to avoid migration, has photobleaching characteristics, and does not produce yellowing. The product of the present invention has a wide light absorption range, has good absorption from long-wave ultraviolet to visible light bands, has good matching with UV-LED light sources, and is conducive to deep curing; and the raw materials are easily available, the reaction conditions are mild, and it is easy to purify, which is suitable for industrial production.

[0005] The broadly-absorbed polymerizable ketene photoinitiator of the present invention has the following general structural formulas (1) to (4):

[0006]

[0007]

[0008] Wherein: R1 is selected from -CH2-, -CH2CH2-, -(CH2CHCH2N)CH2-, methyleneoctyl or ethylene; R2 is selected from -H, -NO3, halogen, methyl, methoxy; R3 is selected from hydrogen, halogen; R4 is selected from hydrogen, halogen.

[0009] The preparation method of the broadly-absorbed polymerizable enone photoinitiator (1) of the present invention comprises the following steps (in terms of molar fractions): firstly preparing an enone containing a hydroxyl group, and then modifying the enone to introduce a double bond at the end group; and then preparing the enone.

[0010] Step 1: Add 1 part of diphenylaldehyde compound and 2-10 parts of NaOH (analytical grade) to water and mix evenly, control the reaction temperature at 20-50° C. with a water bath, add 2 parts of hydroxyacetophenone compound in batches, stir and react for 2-12 hours in a water bath, filter and dry, wash the obtained crude product with an alcohol-water mixed solvent (volume ratio of 4:1) to obtain a hydroxyl-containing enone;

[0011] Step 2: adding 1 part of the hydroxyl-containing enone prepared in step 1 and 2 to 5 parts of an acid-binding agent to a certain amount of an organic solvent, adding 2 to 10 parts of an organic solution of an acyl chloride or anhydride containing a double bond in batches, and then reacting at 0 to 50° C. for 3 to 12 hours. After the reaction is completed, cooling is performed, and the reaction solution is separated, washed, and the solvent is removed by rotary evaporation to obtain a primary product; the primary product is recrystallized in an alcohol-water mixed solvent (volume ratio of 1:3 to 4:1) to obtain the esterified target product (1).

[0012] The alcohol in the alcohol-water mixed solvent is methanol or ethanol, the same below.

[0013] In step 1, the diphenylaldehyde compound is selected from terephthalaldehyde, o-phthalaldehyde, isophthalaldehyde, 2-bromoisophthalaldehyde, 2-nitroterephthalaldehyde or 5-hydroxyisophthalaldehyde.

[0014] In step 1, the hydroxyacetophenone compound is selected from 2-hydroxyacetophenone, 3-hydroxyacetophenone, 4-hydroxyacetophenone, 4-hydroxy-3-nitroacetophenone or 2-chloro-3'-hydroxyacetophenone.

[0015] In step 2, the acid binding agent is selected from triethylamine, pyridine, sodium acetate, sodium carbonate, potassium carbonate, sodium hydroxide or potassium hydroxide.

[0016] In step 2, the organic solvent is selected from acetone, butanone, cyclohexanone, tetrahydrofuran, dichloromethane, chloroform or ethyl acetate.

[0017] In step 2, the double bond-containing acyl chloride is selected from methacryloyl chloride, acryloyl chloride, mono-undecenoyl chloride, monoallyl oxalyl chloride, and diallylcarbamoyl chloride.

[0018] In step 2, the acid anhydride containing a double bond is selected from methacrylic anhydride, acrylic anhydride, maleic anhydride or diallylcarbamic anhydride.

[0019] The preparation route of the broadly-absorbed polymerizable ketene photoinitiator (1) of the present invention is schematically shown as follows:

[0020]

[0021] The preparation method of the broad absorption polymerizable enone photoinitiator (2) of the present invention comprises first preparing a ketone containing a double bond, and then reacting it with an aldehyde to obtain the obtained product; the method specifically comprises the following steps (in terms of molar fractions):

[0022] Step 1: Add 1 part of diphenylaldehyde compound and 2-10 parts of NaOH (analytical grade) to water and mix them evenly, control the reaction temperature at 20-50° C. in a water bath, add 1-3 parts of aminoacetophenone compound in batches, stir and react for 2-12 hours in a water bath, filter and dry, wash the obtained crude product with a mixed solvent of alcohol and water in a volume ratio of 1:3 and recrystallize to obtain an ene ketone containing an amino group;

[0023] Step 2: Add 1 part of amino-containing enone prepared in step 1 and 2 to 10 parts of acid-binding agent to a certain amount of organic solvent, add 2 to 4 parts of organic solution containing double-bond acyl chloride in batches, then react at 0 to 50° C. for 3 to 12 hours, cool after the reaction, separate and wash the reaction solution, and remove the solvent by rotary evaporation to obtain a primary product; the primary product is recrystallized in an alcohol-water mixed solvent with a volume ratio of 1:6 to 1:3 to obtain the esterified target product (2).

[0024] The limitations of the acid-binding agent, organic solvent, double-bond-containing acyl chloride and diphenylaldehyde compound in the above preparation process are the same as those in the long-wavelength polymerizable ketene photoinitiator (1).

[0025] The aminoacetophenone compound is selected from 2-aminoacetophenone, 3-aminoacetophenone, 4-aminoacetophenone, 3,4-dihydroxyacetophenone, 2'-amino-5'-bromoacetophenone or 2-chloro-4'-aminoacetophenone.

[0026] The preparation route of the broad absorption polymerizable ketene photoinitiator (2) of the present invention is schematically shown as follows:

[0027]

[0028] The preparation method of the broadly-absorbed polymerizable enone photoinitiator (3) of the present invention comprises the following steps (in terms of molar fractions):

[0029] Step 1: Add 1 part of diphenylaldehyde compound and 2-10 parts of NaOH (analytical grade) to water and mix evenly, control the reaction temperature at 20-50° C. in a water bath, add 2 parts of hydroxyacetophenone compound in batches, stir and react in a water bath for 2-12 hours, filter and dry, and wash the obtained crude product with an alcohol-water mixed solvent in a volume ratio of 4:1 to obtain a hydroxyl-containing enone;

[0030] Step 2: adding 1 part of the hydroxyl-containing enone prepared in step 1 and 2 to 6 parts of an acid-binding agent to a certain amount of an organic solvent, adding 2 to 4 parts of an organic solution containing a double-bond halogenated hydrocarbon in batches, and then reacting at 30 to 60° C. for 3 to 12 hours. After the reaction is completed, the reaction solution is cooled, separated, washed, and the solvent is removed by rotary evaporation to obtain a primary product; the primary product is recrystallized in an alcohol-water mixed solvent with a volume ratio of 1:4 to 1:1 to obtain the target product (3);

[0031] The limitations of the acid-binding agent, organic solvent and double-bond-containing acyl chloride in the above preparation process are the same as those in the ketene photoinitiator (1).

[0032] In step 2, the double-bond halogenated hydrocarbon is bromopropylene or bromobutylene.

[0033] The preparation route of the broad absorption polymerizable ketene photoinitiator (3) of the present invention is schematically shown as follows:

[0034]

[0035] The preparation method of the broadly-absorbed polymerizable enone photoinitiator (4) of the present invention comprises first preparing a ketone containing a double bond, and then reacting the ketone with an aldehyde to obtain the photoinitiator; the method specifically comprises the following steps (in terms of molar fractions):

[0036] Step 1: Mix 1 part of a diphenylaldehyde compound and 2 to 10 parts of NaOH (analytical grade) with water and mix them evenly, control the reaction temperature at 20 to 50° C. in a water bath, add 1 to 3 parts of an aminoacetophenone compound in batches, stir and react for 2 to 12 hours in a water bath, filter and dry, wash the obtained crude product with an alcohol-water mixed solvent in a volume ratio of 1:3 and recrystallize to obtain an amino-containing enone;

[0037] Step 2: adding 1 part of amino-containing enone prepared in step 1 and 2 to 6 parts of an acid-binding agent to a certain amount of an organic solvent, and adding 1 to 4 parts of an organic solution containing a double-bond halogenated hydrocarbon in batches, and then reacting at 30 to 60° C. for 3 to 12 hours. After the reaction is completed, cooling is performed, and the reaction solution is separated, washed, and the solvent is removed by rotary evaporation to obtain a primary product; the primary product is recrystallized in an alcohol-water mixed solvent with a volume ratio of 1:3 to 1:1 to obtain the target product (4);

[0038] The limitations of the acid-binding agent, organic solvent and diphenylaldehyde compound in the above preparation process are the same as those in the ketene photoinitiator (1).

[0039] The aminoacetophenone compound is selected from 2-aminoacetophenone, 3-aminoacetophenone, 4-aminoacetophenone, 3,4-dihydroxyacetophenone, 2'-amino-5'-bromoacetophenone or 2-chloro-4'-aminoacetophenone.

[0040] The double-bond halogenated hydrocarbon is bromopropylene or bromobutylene.

[0041] The preparation route of the broad absorption polymerizable ketene photoinitiator (4) of the present invention is schematically shown as follows:

[0042]

[0043] The broadly-absorbed polymerizable ketene photoinitiator of the present invention is used as a photoinitiator in the photopolymerization reaction of resins, and is particularly suitable for various acrylic resins.

[0044] The photoinitiator of the present invention has a wide light absorption range, absorbing long-wave ultraviolet light to visible light, has good compatibility with UV-LED light sources, is conducive to deep curing, and can be used in inks, coatings, microelectronics, packaging, dentistry, 3D printing and other fields, and is particularly suitable for food packaging printing or medical materials with high requirements on biological toxicity.

[0045] Compared with the prior art, the present invention has the following beneficial effects:

[0046] The ketene photoinitiator provided by the present invention contains both a photoinitiating group and a polymerizable double bond end group in its molecular structure, has high initiating activity, can participate in the curing reaction and avoid migration; has obvious photobleaching characteristics and does not cause yellowing of the material during application; wherein the ketene photoinitiator with an amino group can self-supply hydrogen without the need for additional addition of a hydrogen donor, thereby avoiding the migration toxicity caused by small molecule amine hydrogen donors; has a wide light absorption range, reaching the wavelength range of the visible light region, and is conducive to deep curing.

[0047] The product of the present invention can be used for photopolymerization of various resins, and is particularly suitable for various acrylic resins. The raw materials of the product are easily available, the reaction conditions are mild, no heavy metal toxicity and high boiling point solvents are involved, it is easy to purify, and it is suitable for industrial production. It can be used in the fields of ink, coating, microelectronics, packaging, 3D printing, etc., and is particularly suitable for food packaging or medical materials with high requirements on biological toxicity. BRIEF DESCRIPTION OF THE DRAWINGS

[0048] Figure 1 The UV absorption spectrum of the photoinitiator (DC-6) in Example 6 (the concentration of the initiator (DC-6) is 1.8×10 -5mol / L, the solvent is ethanol).

[0049] Figure 2 is the ultraviolet absorption spectrum of the photoinitiator (DC-17) in Example 17 (the concentration of the initiator (DC-17) is 1.8×10 -5 mol / L, the solvent is ethanol).

[0050] Figure 3 The real-time infrared double bond conversion rate of 1,6-hexanediol diacrylate (HDDA) at different dosages of the photoinitiator (DC-6) in Example 6 (405nm LED light source, 70mW / cm 2 light intensity). DETAILED DESCRIPTION

[0051] The present invention will be further illustrated by the following non-limiting examples.

[0052] Embodiment 1:

[0053] 1. Mix 2.7g (0.02mol) 4-hydroxyacetophenone and 1.5g (0.01mol) terephthalaldehyde with 50mL ethanol and stir evenly, place in a 25℃ water bath and stir for half an hour, add 1g (0.025mol) sodium hydroxide, stir and react for 8h, filter and dry. The crude product is recrystallized with a mixed solvent of ethanol and water (volume ratio 4:1) to obtain the product 1,4-phenylenebis(4-hydroxyphenyl)propadienone with a yield of 78%.

[0054] 2. Place the above 3.7g (0.01mol) 1,4-phenylenebis(1-hydroxyphenyl)prop-2-enone, 1.7g (0.04mol) NaOH and 80mL deionized water solvent into a three-necked flask, stir at room temperature, then place 1.8g (0.02mol) acryloyl chloride in 40mL dichloromethane and dropwise add into the three-necked flask, react for 2h. Separate the liquid, wash with dilute hydrochloric acid, adjust the pH value to 8-9, dry the organic phase with anhydrous calcium chloride, remove dichloromethane by rotary evaporation, and then recrystallize with a mixed solvent of ethanol and water (volume ratio 4:1) in a refrigerator overnight to obtain the product (recorded as: DC-1). Yield 60%.

[0055] The structural formula of the target product (DC-1) obtained in this embodiment is:

[0056]

[0057] 1H NMR (CDCl3, δppm): 5.74 (1H, CHHCHCOO-), 6.24 (1H, CHHCHCOO-), 6.10 (1H, CHHCHCOO-), 7.52 (2H, -OCCH CH-, Ph), 8.19 (2H, -OCCHCH-, Ph), 7.60 (1H, -OCCHCH-), 8.06 (1H, -OCCHCH-), 7.29 (2H, -CCHCHC-, Ph).

[0058] Embodiment 2:

[0059] 1. The process for preparing 1,4-phenylenebis(4-hydroxyphenyl)propadienone is the same as that in Example 1.

[0060] 2. Place the above 3.7g (0.01mol) 1,4-phenylenebis(1-hydroxyphenyl)prop-2-enone, 4.0g (0.1mol) NaOH and 20mL deionized water solvent into a three-necked flask, stir at room temperature, then place 2.1g (0.02mol) methacryloyl chloride in 40mL dichloromethane and dropwise add into the three-necked flask, react for 3h. Separate the liquid, wash with dilute hydrochloric acid, adjust the pH value to 8-9, dry the organic phase with anhydrous calcium chloride, remove dichloromethane by rotary evaporation, and then recrystallize with a mixed solvent of ethanol and water (volume ratio 4:1) in a refrigerator overnight to obtain the product (recorded as: DC-2). The yield is 65%.

[0061] The structural formula of the target product (DC-2) obtained in this embodiment is:

[0062]

[0063] 1 H NMR (CDCl3, δppm): 6.18(1H, CHH(C-)CH3), 6.43(1H, CHH(C-)CH3), 2.01(3H, CHH(C-)CH3), 7.52(1H, -C CHCH-, Ph), 8.19 (1H, -CCHCH-, Ph), 7.60 (1H, -OCCHCH-), 8.06 (1H, -OCCHCH-), 7.29 (2H, -CCHCHC-, Ph).

[0064] Embodiment 3:

[0065] 1. The process for preparing 1,4-phenylenebis(4-hydroxyphenyl)propadienone is the same as that in Example 1.

[0066] 2. Place the above 3.7g (0.01mol) 1,4-phenylenebis(1-hydroxyphenyl)prop-2-enone, 2.0g (0.05mol) NaOH and 20mL deionized water solvent into a three-necked flask, stir at 50°C, then place 8.2g (0.04mol) 10-undecenoyl chloride in 50mL dichloromethane and dropwise add into the three-necked flask, react for 6h. Separate the liquid, wash with dilute hydrochloric acid, adjust the pH value to 8-9, dry the organic phase with anhydrous calcium chloride, remove dichloromethane by rotary evaporation, and then recrystallize with a mixed solvent of ethanol and water (volume ratio 1:3) in a refrigerator overnight to obtain the product (recorded as: DC-3). The yield is 68%.

[0067] The structural formula of the target product (DC-3) obtained in this embodiment is:

[0068]

[0069] 1 H NMR (CDCl3, δppm): 4.88 (1H, CHHCHCH2-), 5.13 (1H, CHHCHCH2-), 5.85 (1H, CHHCHCH2-), 2.13 (2H, C HHCHCH2-), 1.29(2H, -CH2CH2CH2-), 1.33(2H, -CH2CH2CH2-), 1.30(2H, -CH2CH2CH2-), 1.30(2H, -C H2CH2-), 1.33(2H, -CH2CH2-), 1.66(2H, -CH2CH2COO-), 2.53(2H, -CH2CH2COO-), 7.52(2H, -CCHCH -, Ph), 8.22 (2H, -CCHCH-, Ph), 7.60 (1H, -OCCHCH-), 8.09 (1H, -OCCHCH-), 7.29 (2H, -CCHCHC-, Ph).

[0070] Embodiment 4:

[0071] 1. Mix 2.7g (0.02mol) 3-hydroxyacetophenone and 1.5g (0.01mol) terephthalaldehyde with 50mL ethanol and stir evenly, place in a 25℃ water bath and stir for half an hour, add 1g (0.025mol) sodium hydroxide, stir and react for 8h, filter and dry. The crude product is recrystallized with a mixed solvent of ethanol and water (volume ratio 4:1) to obtain the product 1,4-phenylenebis(3-hydroxyphenyl)propadienone with a yield of 80%.

[0072] 2. Place the above 3.7g (0.01mol) 1,4-phenylenebis(1-hydroxyphenyl)prop-2-enone, 5.2g (0.05mol) triethylamine and 20mL dichloromethane into a three-necked flask, stir at room temperature, then place 1.8g (0.02mol) acryloyl chloride in 40mL dichloromethane and drop into the three-necked flask, react for 3h. Separate the liquid, wash with dilute hydrochloric acid, adjust the pH value to 8-9, dry the organic phase with anhydrous calcium chloride, remove dichloromethane by rotary evaporation, and then recrystallize in a mixed solvent of ethanol and water (volume ratio 4:1) in a refrigerator overnight to obtain the product (recorded as: DC-4). The yield is 70%.

[0073] The structural formula of the target product (DC-4) obtained in this embodiment is:

[0074]

[0075] 1 HNMR (CDCl3, δppm): 5.74 (1H, CHHCH2COO-), 6.24 (1H, CHHCH2COO-), 6.10 (1H, CHHCHCOO-), 7.61 (1H, -CH(CO-)CH-, Ph), 7.54 (1H, -CH(CO-) )CH-, Ph), 7.69 (1H, -CHCH(C-)CO-, Ph), 7.62 (1H, -CHCH(C-)CO-, Ph), 7.60 (1H, -OCCHCH-), 7.78 (1H, -OCCHCH-), 7.66 (2H, -CCHCHC-, Ph).

[0076] Embodiment 5:

[0077] 1. Mix 3.9g (0.02mol) 4-hydroxy-3-nitroacetophenone and 2.1g (0.01mol) 2-bromo-isophthalaldehyde with 50mL ethanol and stir evenly, place in a 50℃ water bath and stir for half an hour, add 4.0g (0.1mol) sodium hydroxide, stir and react for 8h, filter and dry. The crude product is recrystallized with a mixed solvent of methanol and water (volume ratio 4:1) to obtain an intermediate product with a yield of 70%.

[0078] 2. Place 5.1g (0.01mol) of the above intermediate product, 1.7g (0.04mol) of NaOH and 10mL of deionized water solvent into a three-necked flask, stir at room temperature, then place 1.8g (0.02mol) of acryloyl chloride in 40mL of dichloromethane and dropwise add into the three-necked flask, and react for 10h. Separate the liquid, wash with dilute hydrochloric acid, adjust the pH value to 8-9, dry the organic phase with anhydrous calcium chloride, remove dichloromethane by rotary evaporation, and then recrystallize with a mixed solvent of ethanol and water (volume ratio 2:1) in a refrigerator overnight to obtain the product (recorded as: DC-5). The yield is 53%.

[0079] The structural formula of the target product (DC-5) obtained in this embodiment is:

[0080]

[0081] 1 HNMR (CDCl3, δppm): 5.74 (2H, CHHCH2COO-), 6.24 (2H, CHHCH2COO-), 6.10 (2H, CHHCHCOO-), 8.39 (2H, 2ONCCH-, Ph), 7.60 (2H, -CHCH-, Ph), 8.59 (2H, -CHCH-, Ph), 7.29 (1H, -OCCHCH-), 7.86 (1H, -OCCHCH-), 7.11 (1H, -CHCHCH-, Ph), 7.18 (1H, -CHCHCH-, Ph), 7.11 (1H, -CHCHCH-, Ph), 8.33 (1H, -CHCHCO-), 7.43 (1H, -CHCHCO-).

[0082] Embodiment 6:

[0083] 1. The process for preparing 1,4-phenylenebis(4-hydroxyphenyl)propadienone is the same as that in Example 1.

[0084] 2. Place the above 3.7g (0.01mol) 1,4-phenylenebis(1-hydroxyphenyl)prop-2-enone, 2.8g (0.02mol) anhydrous potassium carbonate and 60mL anhydrous ethanol solvent into a three-necked flask, stir at room temperature, then place 2.4g (0.02mol) propylene bromide into 20mL anhydrous ethanol, then place into a three-necked flask, heat to 60℃ and react for 3h. Separate the liquid, remove the ethanol by rotary evaporation, and then recrystallize in a mixed solvent of ethanol and water (volume ratio 1:4) in a refrigerator overnight to obtain the product (recorded as: DC-6). The yield is 80%.

[0085] The structural formula of the target product (DC-6) obtained in this embodiment is:

[0086]

[0087] 1 H NMR (CDCl3, δppm): 5.17 (1H, CHHCHCH2-), 5.21 (1H, CHHCHCH2-), 5.86 (1H, CHHCHCH2-), 4.01 (1H, CHHCHCH2-), 6.7 2(2H,-OCCHCH-,Ph), 7.98(2H,-OCCHCH-,Ph), 7.60(1H,-OCCHCH-), 7.78(1H,-OCCHCH-), 7.66(2H,-CCHCHC-,Ph).

[0088] Table 1 below shows the molar extinction coefficient of the photoinitiator (DC-6) at different wavelengths.

[0089] Table 1

[0090] <![CDATA[λ max ]]> <![CDATA[ε max (M -1 cm -1 )]]> <![CDATA[ε 365 (M -1 cm -1 )]]> <![CDATA[ε 385 (M -1 cm -1 )]]> <![CDATA[ε 405 (M -1 cm -1 )]]> 358 55800 52600 28400 2800

[0091] Embodiment 7:

[0092] 1. The same method as the synthesis of the intermediate product in Example 4;

[0093] 2. Place the above 3.7g (0.01mol) 1,4-phenylenebis(1-hydroxyphenyl)prop-2-enone, 5.5g (0.06mol) anhydrous potassium carbonate and 60mL anhydrous ethanol solvent into a three-necked flask, stir at room temperature, then place 2.7g (0.02mol) bromobutylene into 20mL anhydrous ethanol, then place into a three-necked flask, heat to 30°C and react for 12h. Separate the liquid, remove the ethanol by rotary evaporation, and then recrystallize in a mixed solvent of ethanol and water (volume ratio 1:5) in a refrigerator overnight to obtain the product (recorded as: DC-7). The yield is 78%.

[0094] The structural formula of the target product (DC-7) obtained in this embodiment is:

[0095]

[0096] 1H NMR (CDCl3, δppm): 4.86 (1H, CHHCHCH2-), 5.13 (1H, CHHCHCH2-), 5.83 (1H, CHHCHCH2-), 2.38 (1H, CHHCHCH2-), 3.98 (2H, -CH2O-), 7.22 (1H, -CHCHCH-, Ph), 7.72 (1H, -CHCHCH-, Ph), 7.49 (1H, -CHCHCH-, Ph), 7.35 (1H, -CH(C-)CO-, Ph), 7.60 (1H, -OCCHCH-), 7.78 (1H, -OCCHCH-), 7.66 (2H, -CCHCHC-, Ph).

[0097] Embodiment 8:

[0098] 1. Mix 3.3g (0.02mol) 3,5-dimethyl-4-hydroxyacetophenone and 1.5g (0.01mol) terephthalaldehyde with 50mL ethanol and stir evenly, place in a 25℃ water bath and stir for half an hour, add 1g (0.025mol) sodium hydroxide, stir and react for 8h, filter and dry. The crude product is recrystallized with a mixed solvent of ethanol and water (volume ratio 1:3) to obtain the product with a yield of 77%.

[0099] 2. Place 4.3g (0.01mol) of the intermediate product, 5.5g (0.06mol) of anhydrous potassium carbonate and 60mL of anhydrous ethanol solvent in a three-necked flask, stir at room temperature, then place 2.4g (0.02mol) of propylene bromide in 20mL of anhydrous ethanol, then place in a three-necked flask, heat to 30°C and react for 12h. Separate the liquid, remove the ethanol by rotary evaporation, and then recrystallize in a mixed solvent of ethanol and water (volume ratio 1:5) in a refrigerator overnight to obtain the product (recorded as: DC-8). The yield is 73%.

[0100] The structural formula of the target product (DC-8) obtained in this example is:

[0101]

[0102] 1 H NMR (CDCl3, δppm): 5.43 (1H, CHHCHCH2-), 5.31 (1H, CHHCHCH2-), 6.07 (1H, CHHCHCH2-), 4.68 (2H, CHHCHCH2-), 2 .33 (6H, CH3CCH-), 7.44 (2H, CH3CCH-, Ph), 7.60 (1H, -OCCHCH-), 7.78 (1H, -OCCHCH-), 7.66 (2H, -CCHCHC-, Ph).

[0103] Embodiment 9:

[0104] 1. Mix 3.3g (0.02mol) 4-methoxy-3-hydroxyacetophenone and 1.5g (0.01mol) terephthalaldehyde with 50mL ethanol and stir evenly, place in a 35℃ water bath and stir for half an hour, add 1g (0.025mol) sodium hydroxide, stir and react for 6h, filter and dry. The crude product is recrystallized with a mixed solvent of methanol and water (volume ratio 4:1) to obtain an intermediate product with a yield of 72%.

[0105] 2. Place 4.3g (0.01mol) of the intermediate product, 5.5g (0.06mol) of anhydrous potassium carbonate and 60mL of anhydrous ethanol solvent in a three-necked flask, stir at room temperature, then place 2.4g (0.02mol) of propylene bromide in 20mL of anhydrous ethanol, then place in a three-necked flask, heat to 50°C and react for 8h. Separate and evaporate to remove ethanol, then recrystallize in a mixed solvent of ethanol and water (volume ratio 1:4) in a refrigerator overnight to obtain the product (recorded as: DC-9). Yield 86%.

[0106] The structural formula of the target product (DC-9) obtained in this example is:

[0107]

[0108] 1 H NMR (CDCl3, δppm) 5.43 (1H, CHHCHCH2-), 5.31 (1H, CHHCHCH2-), 6.07 (1H, CHHCHCH2-), 4.68 (2H, CHHCHCH2-), 3.83 (3H, CH3OCCHCH-, Ph), 7.04 (1H, CH3OCCHCH-, Ph), 7.79 (1H, CH3OCCHCH-, Ph), 7.28 (1H, -OCCH-, Ph), 7.54 (1H, -OCCHCH-), 8.03 (1H, -OCCHCH-), 7.66 (2H, -CCHCHC-, Ph).

[0109] Embodiment 10:

[0110] 1. The process for preparing 1,4-phenylenebis(4-hydroxyphenyl)propadienone is the same as that in Example 1.

[0111] 2. Place the above 3.7g (0.01mol) 1,4-phenylenebis(1-hydroxyphenyl)prop-2-enone, 1.7g (0.04mol) NaOH and 80mL deionized water solvent into a three-necked flask, stir at room temperature, then place 3.2g (0.02mol) diallylcarbamoyl chloride in 40mL chloroform and dropwise add into the three-necked flask, react for 6h. Separate the liquid, wash with dilute hydrochloric acid, adjust the pH value to 8-9, dry the organic phase with anhydrous calcium chloride, remove dichloromethane by rotary evaporation, and then recrystallize with a mixed solvent of ethanol and water (volume ratio 3.5:1) in a refrigerator overnight to obtain the product (recorded as: DC-10). The yield is 66%.

[0112] The structural formula of the target product (DC-10) obtained in this embodiment is:

[0113]

[0114] 1 H NMR (CDCl3, δppm): 5.18 (1H, CHHCHCH2-), 5.19 (1H, CHHCHCH2-), 5.85 (1H, CHHCHCH2-), 3.63 (1H, CHHCHCH2-), 7.5 2(2H,-OCCHCH-,Ph), 8.19(2H,-OCCHCH-,Ph), 7.60(1H,-OCCHCH-), 7.78(1H,-OCCHCH-), 7.66(2H,-CCHCHC-,Ph).

[0115] Embodiment 11:

[0116] 1. Mix 3.4g (0.02mol) 2-chloro-3'-hydroxyacetophenone and 1.5g (0.01mol) terephthalaldehyde with 50mL ethanol and stir evenly, place in a 25℃ water bath and stir for half an hour, add 1g (0.025mol) sodium hydroxide, stir and react for 8h, filter and dry. The crude product is recrystallized with a mixed solvent of methanol and water (volume ratio 4:1) to obtain an intermediate product with a yield of 70%.

[0117] 2. Place 4.4g (0.01mol) of the above intermediate product, 1.7g (0.04mol) of NaOH and 80mL of deionized water solvent into a three-necked flask, stir at room temperature, then place 1.8g (0.02mol) of acryloyl chloride in 40mL of dichloromethane and dropwise add into the three-necked flask, and react for 3h. Separate the liquid, wash with dilute hydrochloric acid, adjust the pH value to 8-9, dry the organic phase with anhydrous calcium chloride, remove dichloromethane by rotary evaporation, and then recrystallize with a mixed solvent of ethanol and water (volume ratio 4:1) in a refrigerator overnight to obtain the product (recorded as: DC-11). The yield is 53%.

[0118] The structural formula of the target product (DC-11) obtained in this embodiment is:

[0119]

[0120] 1 HNMR (CDCl3, δppm): 5.74 (1H, CHHCH2COO-), 6.24 (1H, CHHCH2COO-), 6.10 (1H, CHHCHCOO-), 7.61 (1H, -CH(CO-)CH-, Ph), 7.54 (1H, -CH(CO-) )CH-, Ph), 7.69 (1H, -CHCH(C-)CO-, Ph), 7.62 (1H, -CHCH(C-)CO-, Ph), 7.54 (1H, -OCCHCH-), 8.03 (1H, -OCCHCH-), 7.66 (2H, -CCHCHC-, Ph).

[0121] Embodiment 12:

[0122] 1. Add 2.7g (0.02mol) 4-aminoacetophenone, 1.5g (0.01mol) terephthalaldehyde and 40mL ethanol into a two-necked flask and stir for 0.5h to dissolve the reactants. Dissolve 1g (0.025mol) sodium hydroxide in 15mL deionized water and drop into the two-necked flask. Stir and react for 3h at room temperature. Filter, dry, dissolve with dichloromethane, acid wash and wash the organic phase with water, dry with anhydrous calcium chloride, remove dichloromethane with rotary evaporation, and then recrystallize in a mixed solvent of ethanol and water (volume ratio 1:3) in a refrigerator overnight to obtain an intermediate product. Yield 86%.

[0123] 2. Place the above 3.7g (0.01mol) intermediate product, 50mL dichloromethane and 4.1g (0.04mol) triethylamine in a single-necked flask, mix and stir evenly, place in a 25℃ water bath and stir for half an hour, then place 1.8g (0.02mol) acryloyl chloride in 40mL dichloromethane and drop into the flask, stir and react for 3h, separate the liquids, wash with dilute hydrochloric acid, adjust the pH value to 8-9, dry the organic phase with anhydrous calcium chloride, and remove dichloromethane by rotary evaporation. The crude product is recrystallized with a mixed solvent of ethanol and water (volume ratio 1:6) to obtain the product (recorded as: DC-12) with a yield of 80%.

[0124] The structural formula of the target product (DC-12) obtained in this embodiment is:

[0125]

[0126] 1H NMR (CDCl3, δppm): 5.74 (1H, CHHCHCO-), 6.09 (1H, CHHCHCO-), 6.48 (1H, CHHCHCO-), 7.83 (2H, -CCHC H-, Ph), 7.95 (2H, -CCHCH-, Ph), 7.60 (1H, -OCCHCH-), 7.78 (1H, -OCCHCH-), 7.66 (2H, -CCHCHC-, Ph).

[0127] Embodiment 13:

[0128] 1. The same method as the synthesis of the intermediate product in Example 12;

[0129] 2. Place the above 3.7g (0.01mol) intermediate product, 50mL dichloromethane and 4.1g (0.04mol) triethylamine in a single-necked flask, mix and stir evenly, place in a 25℃ water bath and stir for half an hour, then place 2.1g (0.02mol) methacryloyl chloride in 40mL dichloromethane and drop into the flask, stir and react for 4h, separate the liquid, wash with dilute hydrochloric acid, adjust the pH value to 8-9, dry the organic phase with anhydrous calcium chloride, and remove dichloromethane by rotary evaporation. The crude product is recrystallized with a mixed solvent of ethanol and water (volume ratio 1:4) to obtain the product (recorded as: DC-13) with a yield of 77%.

[0130] The structural formula of the target product (DC-13) obtained in this embodiment is:

[0131]

[0132] 1 H NMR (CDCl3, δppm): 5.72 (1H, CHH (C-)CH3), 5.79 (1H, CHH (C-)CH3), 1.98 (3H, CHH (C-)CH3), 7.83 (2H, -C CHCH-, Ph), 7.95 (2H, -CCHCH-, Ph), 7.60 (1H, -OCCHCH-), 7.78 (1H, -OCCHCH-), 7.66 (2H, -CCHCHC-, Ph).

[0133] Embodiment 14:

[0134] 1. The same method as the synthesis of the intermediate product in Example 12;

[0135] 2. Place 2.7g (0.02mol) of 4-aminoacetophenone, 50mL of dichloromethane and 4.1g (0.04mol) of triethylamine in a single-necked flask, mix and stir evenly, place in a 25℃ water bath and stir for half an hour, then place 6.2g (0.03mol) of 10-undecenoyl chloride in 40mL of dichloromethane and drop into the flask, stir and react for 4h, separate the liquids, wash with dilute hydrochloric acid, adjust the pH value to 8-9, dry the organic phase with anhydrous calcium chloride, and remove dichloromethane by rotary evaporation. The crude product is recrystallized with a mixed solvent of ethanol and water (volume ratio 1:5) to obtain the product (recorded as: DC-14), with a yield of 77%.

[0136] The structural formula of the target product (DC-14) obtained in this embodiment is:

[0137]

[0138] 1 H NMR (CDCl3, δppm): 4.88 (1H, CHHCHCH2-), 5.13 (1H, CHHCHCH2-), 5.85 (1H, CHHCHCH2-), 2.13 (2H, C HHCHCH2-), 1.29(2H,-CH2CH2CH2-), 1.33(2H,-CH2CH2CH2-), 1.30(2H,-CH2CH2CH2-), 1.30(2H,- CH2CH2-), 1.30(2H, -CH2CH2-), 1.57(2H, -CH2CH2CO-), 2.35(2H, -CH2CH2CO-), 7.83(1H, -CCHCH- , Ph), 7.95 (1H, -CCHCH-, Ph), 7.60 (1H, -OCCHCH-), 7.78 (1H, -OCCHCH-), 7.66 (2H, -CCHCHC-, Ph).

[0139] Embodiment 15:

[0140] 1. Add 4.3g (0.02mol) 2'-amino-5'-bromoacetophenone, 1.5g (0.01mol) terephthalaldehyde and 40mL ethanol into a two-necked flask and stir for 0.5h to dissolve the reactants. Dissolve 2g (0.05mol) sodium hydroxide in 15mL deionized water and drop into the two-necked flask. Stir and react for 3h at room temperature. Filter, dry, dissolve with dichloromethane, acid wash and wash the organic phase with water, dry with anhydrous calcium chloride, remove dichloromethane with rotary evaporation, and then recrystallize in a mixed solvent of ethanol and water (volume ratio 1:3) in a refrigerator overnight to obtain an intermediate product. Yield 78%.

[0141] 2. The above 6.1g (0.01mol) intermediate product, 50mL dichloromethane and 4.1g (0.04mol) triethylamine were placed in a single-necked flask and mixed and stirred evenly. They were placed in a 25°C water bath and stirred for half an hour. Then 1.8g (0.02mol) acryloyl chloride was placed in 40mL dichloromethane and added dropwise into the flask. The reaction was stirred for 3h, separated, washed with dilute hydrochloric acid, and the pH value was adjusted to 8-9. The organic phase was dried with anhydrous calcium chloride and dichloromethane was removed by rotary evaporation. The crude product was recrystallized with a mixed solvent of ethanol and water (volume ratio 1:3) to obtain the product (recorded as: DC-15) with a yield of 77%.

[0142] The structural formula of the target product (DC-15) obtained in this embodiment is:

[0143]

[0144] 1 H NMR (CDCl3, δppm): 5.74 (1H, CHHCH2CO-), 6.09 (1H, CHHCH2CO-), 6.48 (1H, CHHCHCO-), 7.94 (1H, -CHCHCBr-, Ph), 7.83 (1H, -CHCHCBr-, Ph), 7.92 (1H, -CH(C-)CO-, Ph), 7.60 (1H, -OCCHCH-), 7.78 (1H, -OCCHCH-), 7.23 (1H, -CHCH-, Ph), 7.18 (1H, -CHCH-, Ph), 7.47 (1H, -CHCBr-, Ph).

[0145] Embodiment 16:

[0146] 1. Add 3.4g (0.02mol) 2-chloro-4'-aminoacetophenone, 1.5g (0.01mol) terephthalaldehyde and 40mL ethanol into a two-necked flask and stir for 0.5h to dissolve the reactants. Dissolve 2g (0.05mol) sodium hydroxide in 15mL deionized water and drop into the two-necked flask. Stir and react for 3h at room temperature. Filter by suction, dry, dissolve with dichloromethane, acid-wash and wash the organic phase with water, dry with anhydrous calcium chloride, remove dichloromethane by rotary evaporation, and then recrystallize in a mixed solvent of ethanol and water (volume ratio 1:3) in a refrigerator overnight to obtain an intermediate product. Yield 70%.

[0147] 2. Place the above 4.4g (0.01mol) intermediate product, 50mL dichloromethane and 4.1g (0.04mol) triethylamine in a single-necked flask, mix and stir evenly, place in a 40℃ water bath and stir for half an hour, then place 1.8g (0.02mol) acryloyl chloride in 40mL dichloromethane and drop into the flask, stir and react for 3h, separate the liquid, wash with dilute hydrochloric acid, adjust the pH value to 8-9, dry the organic phase with anhydrous calcium chloride, and remove dichloromethane by rotary evaporation. The crude product is recrystallized with a mixed solvent of ethanol and water (volume ratio 1:3) to obtain the product (recorded as: DC-16) with a yield of 82%.

[0148] The structural formula of the target product (DC-16) obtained in this embodiment is:

[0149]

[0150] 1 H NMR (CDCl3, δppm): 5.74 (1H, CHHCH2CO-), 6.09 (1H, CHHCH2CO-), 6.48 (1H, CHHCHCO-), 7.22 ( 1H, -CHCH-, Ph), 8.10 (1H, -CHCH-, Ph), 5.36 (1H, -CHClCHH-), 3.10 (1H, -CHClCHH-), 2.88 (1 H, -CHClCHH-), 7.09 (1H, -CHCHCH-, Ph), 7.19 (1H, -CHCHCH-, Ph), 7.50 (1H, -CHCHCH-, Ph), 7 .20(1H,-CH(C-)-,Ph), 8.03(1H,-CHCCClCO-), 7.95(1H,-CHCH-,Ph), 7.83(1H,-CHCH-,Ph).

[0151] Embodiment 17:

[0152] 1. The same method as the synthesis of the intermediate product in Example 12;

[0153] 2. Place 3.7 g (0.01 mol) of the above intermediate product, 100 mL of ethanol, 9.6 g (0.08 mol) of propylene bromide, and 5.5 g (0.04 mol) of anhydrous potassium carbonate in a single-necked flask, mix and stir evenly, place in a 60°C water bath, stir and react for 3 h, filter, and evaporate the anhydrous ethanol to obtain a crude product. Recrystallize in a mixed solvent of ethanol and water in a volume ratio of 1:3 to obtain the product (denoted as: DC-17), with a yield of 80%.

[0154] The structural formula of the target product (DC-17) obtained in this embodiment is:

[0155]

[0156] 1 H NMR (CDCl3, δppm): 5.18 (1H, CHHCHCH2-), 5.19 (1H, CHHCHCH2-), 5.85 (1H, CHHCHCH2-), 4.02 (2H, CHHCHCH2-), 6.73 (1 H, -CCHCH-, benzene), 8.01 (1H, -CCHCH-, benzene), 7.60 (1H, -OCCHCH-), 7.78 (1H, -OCCHCH-), 7.66 (2H, -CCHCHC-).

[0157] Table 2 below shows the molar extinction coefficient of the photoinitiator (DC-17) at different wavelengths:

[0158] Table 2

[0159] <![CDATA[λ max ]]> <![CDATA[ε max (M -1 cm -1 )]]> <![CDATA[ε 365 (M -1 cm -1 )]]> <![CDATA[ε 385 (M -1 cm -1 )]]> <![CDATA[ε 405 (M -1 cm -1 )]]> 411 56500 32800 44200 55500

[0160] Embodiment 18:

[0161] 1. Add 3.3g (0.02mol) 3,5-dimethyl-4-aminoacetophenone, 1.5g (0.01mol) terephthalaldehyde and 40mL ethanol into a two-necked flask and stir for 0.5h to dissolve the reactants. Dissolve 1g (0.025mol) sodium hydroxide in 15mL deionized water and drop into the two-necked flask. Stir and react for 3h at room temperature. Filter, dry, dissolve with dichloromethane, acid wash and wash the organic phase with water, dry with anhydrous calcium chloride, remove dichloromethane with rotary evaporation, and then recrystallize in a mixed solvent of ethanol and water (volume ratio 1:3) in a refrigerator overnight to obtain the intermediate product. Yield 88%;

[0162] 2. Place 4.2 g (0.01 mol) of the above intermediate product, 100 mL of ethanol, 5.4 g (0.04 mol) of bromobutylene, and 5.5 g (0.04 mol) of anhydrous potassium carbonate in a single-necked flask, mix and stir evenly, place in a 60°C water bath, stir and react for 4 hours, filter, and evaporate the anhydrous ethanol to obtain a crude product. Recrystallize in a mixed solvent of ethanol and water in a volume ratio of 1:2 to obtain the product (denoted as: DC-18), with a yield of 76%.

[0163] The structural formula of the target product (DC-18) obtained in this embodiment is:

[0164]

[0165] 1H NMR (CDCl3, δppm): 4.88 (1H, CHHCHCH2-), 5.13 (1H, CHHCHCH2-), 5.82 (1H, CHHCHCH2-), 2.19 (2H, CHHCHCH2-), 3.39 (2H , -CH2N-), 2.12 (6H, CH3CCH-), 7.39 (2H, CH3CCH-, Ph), 7.60 (1H, -OCCHCH-), 7.78 (1H, -OCCHCH-), 7.66 (2H, -CCHCHC-).

[0166] Embodiment 19:

[0167] 1. Add 3.3g (0.02mol) 4-methoxy-3-aminoacetophenone, 1.5g (0.01mol) terephthalaldehyde and 40mL ethanol into a two-necked flask and stir for 0.5h to dissolve the reactants. Dissolve 1g (0.025mol) sodium hydroxide in 15mL deionized water and drop into the two-necked flask. Stir and react for 3h at room temperature. Filter, dry, dissolve with dichloromethane, acid wash and wash the organic phase with water, dry with anhydrous calcium chloride, remove dichloromethane with rotary evaporation, and then recrystallize in a mixed solvent of ethanol and water (volume ratio 1:3) in a refrigerator overnight to obtain the intermediate product. Yield 81%;

[0168] 2. Place 4.3 g (0.01 mol) of the above intermediate product, 100 mL of ethanol, 4.8 g (0.04 mol) of propylene bromide, and 5.5 g (0.04 mol) of anhydrous potassium carbonate in a single-necked flask, mix and stir evenly, place in a 60°C water bath and stir to react for 3 h, filter, and evaporate the anhydrous ethanol to obtain a crude product. Recrystallize in a mixed solvent of ethanol and water in a volume ratio of 1:1 to obtain the product (denoted as: DC-19), with a yield of 80%.

[0169] The structural formula of the target product (DC-19) obtained in this embodiment is:

[0170]

[0171] 1H NMR (CDCl3, δppm): 5.18 (2H, CHHCHCH2-), 5.19 (2H, CHHCHCH2-), 5.85 (2H, CHHCHCH2-), 4.02 (4H, CHHCHCH2-), 3.86 (3H, CH3OCCHCH-), 6.93 ( 1H, CH3OCCHCH-, Ph), 7.56 (1H, CH3OCCHCH-, Ph), 7.15 (1H, -OCCH-, Ph), 7.54 (1H, -OCCHCH-), 8.03 (1H, -OCCHCH-), 7.66 (2H, -CCHCHC-, Ph).

[0172] Embodiment 20:

[0173] 24g epoxy acrylate, 16g trimethylolpropane triacrylate (TMPTA), 0.04g (0.1wt%) initiator (DC-1), 0.2g (2wt%) triethanolamine (TEOA) were added into a flask, and then stirred at 25°C until the mixture was uniformly mixed. The obtained mixture was spread in a tetrafluoroethylene mold. Before ultraviolet irradiation, the color values ​​(L, a, b) were measured to be 55.26, -2.68, 20.75. The mixed liquid was placed under an ultraviolet light source (λ = 365nm, P = 200mW / cm 2 ) for 2 minutes to fully cure into a film, and the color values ​​(L, a, b) of the cured film were measured again to be 57.79, -0.94, and 10.39, indicating that the product of the present invention has obvious photobleaching phenomenon and yellowing resistance.

[0174] Determination of mobility: weigh 1g of the cured film sample into a 50mL conical flask, and measure 30mL of ethanol solution and add it to the conical flask, use ultrasonic extraction for 30min, then transfer the extract to a flask and place it on a rotary evaporator to evaporate to dryness, then add about 1-2mL of ethanol to dissolve the extraction residue and absorb 1mL of the ethanol solution containing the extract through a 0.45μm filter membrane. After the filtrate is collected, it is analyzed by gas chromatography-mass spectrometry (GC-MS). GC-MS test conditions: GC conditions: chromatographic column is HP-5MS (30m×0.25mm×0.25μm), heating rate is 10℃ / min to 280℃ and maintained for 2min, carrier gas is helium, flow rate is 1.0mL / min, injection volume is 1μL. MS conditions: electron bombardment ion source, electron energy is 70eV, ion source temperature is 230℃, solvent delay is 5min. The mobility of the initiator is measured to be 0.46%.

[0175] The pencil hardness of the cured film was tested according to GB / T 6739-2006, and the adhesion of the cured film was tested according to GB / T 9286-1998. The results showed that the cured film was smooth and transparent, with a pencil hardness of 4H and a grade 1 adhesion.

[0176] Embodiment 21:

[0177] 24g epoxy acrylate, 16g trimethylolpropane triacrylate (TMPTA), 0.04g (0.1wt%) initiator (DC-6), 0.2g (2wt%) triethanolamine (TEOA) were added into a flask, and then stirred at 25°C until uniformly mixed. The resulting mixture was spread in a tetrafluoroethylene mold. Before ultraviolet irradiation, the color values ​​(L, a, b) were measured to be 54.28, -3.42, 18.6. The mixed liquid was placed under an ultraviolet light source (λ = 365nm, P = 200mW / cm 2 ) for 2 minutes to fully cure into a film, and the color values ​​(L, a, b) of the cured film were measured again to be 55.36, -1.83, 7.8, indicating that the product of the present invention has obvious photobleaching phenomenon and yellowing resistance characteristics.

[0178] The mobility test method was the same as in Example 20, and the mobility of the initiator was measured to be 0.53%.

[0179] The pencil hardness of the cured film was tested according to GB / T 6739-2006, and the adhesion of the cured film was tested according to GB / T 9286-1998. The results showed that the cured film was smooth and transparent, with a pencil hardness of 4H and a grade 1 adhesion.

[0180] Comparative Example 1:

[0181] 24g of epoxy acrylate, 16g of trimethylolpropane triacrylate (TMPTA), 0.04g (0.1wt%) of isopropylthioxanthone (ITX), and 0.2g of triethanolamine (TEOA) were added to a flask, and then stirred at 25°C until the mixture was uniformly mixed. The resulting mixture was spread in a tetrafluoroethylene mold. Before ultraviolet irradiation, the color values ​​(L, a, b) were measured to be 40.34, -1.36, and 3.96. The mixed liquid was placed under an ultraviolet light source (λ = 365nm, P = 200mW / cm 2 ) for 2 minutes to fully cure into a film. The color values ​​(L, a, b) of the cured film were measured again and were 58.43, -0.78, 22.37, and obvious yellowing was observed.

[0182] The mobility test method was the same as in Example 20, and the mobility was measured to be 16.83%.

[0183] Embodiment 22:

[0184] 24g epoxy acrylate, 16g trimethylolpropane triacrylate (TMPTA), 0.04g (0.1wt%) initiator (DC-6), 0.2g (2wt%) triethanolamine (TEOA) were added into a flask, and then stirred at 25°C until uniformly mixed. The resulting mixture was spread in a tetrafluoroethylene mold. Before ultraviolet irradiation, the color values ​​(L, a, b) were measured to be 54.28, -3.42, 18.6. The mixed liquid was placed under an ultraviolet light source (λ = 308nm, P = 80mW / cm 2 ) for 2 minutes to fully cure into a film, and the color values ​​(L, a, b) of the cured film were measured again to be 56.09, -2.98, and 9.88, indicating that the product of the present invention can also be well cured into a film in the medium-wave ultraviolet region, and also has the characteristics of photobleaching and yellowing resistance.

[0185] The pencil hardness of the cured film was tested according to GB / T 6739-2006, and the adhesion of the cured film was tested according to GB / T 9286-1998. The results showed that the cured film was smooth and transparent, with a pencil hardness of 4H and a grade 1 adhesion.

[0186] Embodiment 23:

[0187] 24g of epoxy acrylate, 16g of trimethylolpropane triacrylate (TMPTA), 0.04g (0.1wt%) of initiator (DC-8), and 0.2g (2wt%) of polyethylene glycol diacrylate (PEGDA) were added to a flask, and then stirred at 25°C until uniformly mixed. The resulting mixture was spread in a tetrafluoroethylene mold. Before ultraviolet irradiation, the color values ​​(L, a, b) were measured to be 44.39, -1.24, and 13.94. The mixed liquid was placed under an ultraviolet light source (λ = 385nm, P = 200mW / cm 2 ) for 2 minutes to fully cure into a film, and the color values ​​(L, a, b) of the cured film were measured again to be 46.76, -2.31, and 6.37, indicating that the product of the present invention has obvious photobleaching phenomenon and yellowing resistance.

[0188] The mobility test method was the same as in Example 20, and the mobility of the initiator was measured to be 0.36%.

[0189] The pencil hardness of the cured film was tested according to GB / T 6739-2006, and the adhesion of the cured film was tested according to GB / T 9286-1998. The results showed that the cured film was smooth and transparent, with a pencil hardness of 4H and a grade 1 adhesion.

[0190] Embodiment 24:

[0191] 24g of epoxy acrylate, 16g of trimethylolpropane triacrylate (TMPTA), 0.04g (0.1wt%) of initiator (DC-12), and 0.2g (2wt%) of polyethylene glycol diacrylate (PEGDA) were added to a flask, and then stirred at 25°C until uniformly mixed. The resulting mixture was spread in a tetrafluoroethylene mold. Before ultraviolet irradiation, the color values ​​(L, a, b) were measured to be 56.36, 4.67, and 18.69. The mixed liquid was placed under an ultraviolet light source (λ = 385nm, P = 200mW / cm 2 ) for 2 minutes to fully cure into a film, and the color values ​​(L, a, b) of the cured film were measured again to be 48.73, 2.42, and 7.63, and obvious photobleaching was observed. At the same time, it also shows that this type of photoinitiator has the characteristic of self-hydrogen supply, that is, it still has good photoinitiating performance without adding amine co-initiator, and a cured film with good performance can be obtained.

[0192] The mobility test method was the same as in Example 20, and the mobility of the initiator was measured to be 0.43%.

[0193] The pencil hardness of the cured film was tested according to GB / T 6739-2006, and the adhesion of the cured film was tested according to GB / T 9286-1998. The results showed that the cured film was smooth and transparent, with a pencil hardness of 4H and a grade 1 adhesion.

[0194] Embodiment 25:

[0195] 24g epoxy acrylate, 16g trimethylolpropane triacrylate (TMPTA), 0.08g (0.2wt%) initiator (DC-14) were added into a flask, and then stirred at 25°C until the mixture was uniformly mixed. The resulting mixture was spread in a tetrafluoroethylene mold. Before ultraviolet irradiation, the color values ​​(L, a, b) were measured to be 51.64, 3.49, and 18.76. The mixed liquid was placed under an ultraviolet light source (λ = 385nm, P = 200mW / cm 2 ) for 2 minutes to fully cure into a film, and the color values ​​(L, a, b) of the cured film were measured again to be 44.38, 2.75, and 7.31, and obvious photobleaching was observed. At the same time, it also shows that this type of photoinitiator has the characteristic of self-hydrogen supply, that is, it still has good photoinitiating performance without adding amine co-initiator, and a cured film with good performance can be obtained.

[0196] The mobility test method was the same as in Example 20, and the mobility of the initiator was measured to be 0.32%.

[0197] The pencil hardness of the cured film was tested according to GB / T 6739-2006, and the adhesion of the cured film was tested according to GB / T 9286-1998. The results showed that the cured film was smooth and transparent, with a pencil hardness of 4H and a grade 1 adhesion.

[0198] Embodiment 26:

[0199] 24g of epoxy acrylate, 16g of trimethylolpropane triacrylate (TMPTA), and 0.08g (0.2wt%) of initiator (DC-19) were added to a flask, and then stirred at 25°C until the mixture was uniformly mixed. The resulting mixture was spread in a tetrafluoroethylene mold. Before ultraviolet irradiation, the color values ​​(L, a, b) were measured to be 44.74, 7.93, and 18.43. The mixed liquid was placed under an ultraviolet light source (λ = 405nm, P = 200mW / cm 2 ) for 2 minutes to fully cure into a film, and the color values ​​(L, a, b) of the cured film were measured again to be 48.34, 5.64, and 9.65, respectively, indicating a good bleaching effect. At the same time, this type of photoinitiator has the characteristic of self-hydrogen supply, that is, it still has good photoinitiating performance without adding an amine co-initiator, and a cured film with good performance can be obtained.

[0200] The mobility test method was the same as in Example 20, and the mobility was measured to be 0.29%.

[0201] The pencil hardness of the cured film was tested according to GB / T 6739-2006, and the adhesion of the cured film was tested according to GB / T 9286-1998. The results showed that the cured film was smooth and transparent, with a pencil hardness of 4H and a grade 1 adhesion.

[0202] Embodiment 27:

[0203] 40g of white ink, 0.04g (0.1wt%) initiator (DC-1), and 0.2g (2wt%) triethanolamine (TEOA) were added to a flask, and then stirred at 25°C until uniformly mixed. The resulting mixture was spread on a tetrafluoroethylene mold using a 50μm applicator. Before ultraviolet irradiation, the color values ​​(L, a, b) were measured to be 72.37, -5.46, 5.43. The mixed liquid was placed under an ultraviolet light source (λ = 385nm, P = 600mW / cm 2 ) for 50 seconds to cure into a film, and the color values ​​(L, a, b) of the cured film were measured again to be 69.58, -1.85, and 1.46, indicating that the product of the present invention also has photobleaching effect and yellowing resistance in white ink, and a cured film with good color can be obtained.

[0204] Comparative Example 2:

[0205] 40g of white ink, 0.04g (0.1wt%) initiator 2,4-diethylthioxanthone (DETX), and 0.2g (2wt%) triethanolamine (TEOA) were added to a flask, and then stirred at 25°C until the mixture was uniformly mixed. The resulting mixture was spread on a tetrafluoroethylene mold using a 50μm applicator. Before ultraviolet irradiation, the color values ​​(L, a, b) were measured to be 92.56, -0.28, and 1.79. The mixed liquid was placed under an ultraviolet light source (λ = 385nm, P = 600mW / cm 2 ) for 50s to cure into a film. The color values ​​(L, a, b) of the cured film were measured again and were 90.38, -1.24, 4.79, and a certain yellowing phenomenon was observed.

[0206] Embodiment 28:

[0207] 40g of white ink, 0.04g (0.1wt%) initiator (DC-6), and 0.2g (2wt%) triethanolamine (TEOA) were added to a flask, and then stirred at 25°C until uniformly mixed. The resulting mixture was spread on a tetrafluoroethylene mold using a 50μm applicator. Before ultraviolet irradiation, the color values ​​(L, a, b) were measured to be 89.75, 1.86, and 4.36. The mixed liquid was placed under an ultraviolet light source (λ = 385nm, P = 600mW / cm 2 ) for 50 seconds to cure into a film, and the color values ​​(L, a, b) of the cured film were measured again to be 84.86, -1.33, and 1.52, indicating that the product of the present invention also has photobleaching effect and yellowing resistance in white ink, and a cured film with good color can be obtained.

[0208] Embodiment 29:

[0209] 40g of white ink, 0.04g (0.1wt%) initiator (DC-14) and 0.2g (2wt%) triethanolamine (TEOA) were added to a flask, and then stirred at 25°C until the mixture was uniformly mixed. The resulting mixture was spread on a tetrafluoroethylene mold using a 50μm applicator. Before ultraviolet irradiation, the color values ​​(L, a, b) were measured to be 71.49, -0.58, 5.34. The mixed liquid was placed under an ultraviolet light source (λ = 385nm, P = 600mW / cm 2 ) for 50 seconds to cure into a film, and the color values ​​(L, a, b) of the cured film were measured again to be 76.16, -1.17, 2.14, indicating that the product of the present invention also has photobleaching effect and yellowing resistance in white ink, and a cured film with good color can be obtained.

[0210] Embodiment 30:

[0211] 40g of crimson ink and 0.08g (0.2wt%) of initiator (DC-19) were added to a flask, and then stirred at 25°C until uniformly mixed. The resulting mixture was spread on a tetrafluoroethylene mold using a 50μm applicator. Before ultraviolet irradiation, the color values ​​(L, a, b) were measured to be 30.43, 19.18, and 10.86. The mixed liquid was placed under an ultraviolet light source (λ = 385nm, P = 600mW / cm 2 ) for 50 seconds to cure into a film, and the color values ​​(L, a, b) of the cured film were measured again to be 26.83, 22.08, and 5.39, indicating that the product of the present invention also has photobleaching effect and yellowing resistance in crimson ink, and a cured film with good color can be obtained.

[0212] Embodiment 31:

[0213] Epoxy acrylate CN115 NS and TMPTA were mixed in a mass ratio of 4:3, and (0.1wt%) initiator (DC-1) and (2wt%) TEOA were added. After ultrasonic mixing, the mixture was vacuumed to remove bubbles and stored away from light. The prepared photosensitive resin was poured into the resin tank of an LCD 3D printer with a UV wavelength of 405nm for 3D printing to obtain a sample for performance testing. The parameter settings of the 3D printer are shown in Table 3:

[0214] Table 3 3D printing parameters

[0215]

[0216] The 3D printed samples were fully formed, and the volume shrinkage of the samples was tested by the pycnometer method, and the hardness was tested by the Shore hardness tester. The test specimens were prepared according to the ISO294-1995 standard, and the tensile properties of the specimens were tested using a universal tensile testing machine. The test temperature was room temperature and the tensile rate was 2mm / min. The test specimens were prepared according to the ISO294-1995 standard, and the impact test was performed on the specimens using a pendulum impact tester. The test temperature was room temperature. The test results show that the volume shrinkage of the 3D printed sample is 2.5%, the Shore hardness value is 72.8HD, the tensile strength is 13.54MPa, and the impact strength is 2.26KJ / m 2 .

[0217] Comparative Example 3:

[0218] Epoxy acrylate CN115 NS and TMPTA were mixed in a mass ratio of 4:3, and (0.1wt%) initiator 2,4-diethylthioxanthone (DETX) and (2wt%) TEOA were added. After ultrasonic mixing, the mixture was vacuumed to remove bubbles and stored away from light. The prepared photosensitive resin was poured into the resin tank of an LCD 3D printer with a UV wavelength of 405nm for 3D printing to obtain a sample for performance testing. The parameter settings of the 3D printer are shown in Table 3.

[0219] The 3D printed sample was completely formed. The volume shrinkage of the 3D printed sample was measured by the same test method as in Example 26 to be 6.9%, the Shore hardness value was 72.4HD, the tensile strength was 13.56MPa, and the impact strength was 1.48KJ / m 2 .

[0220] Embodiment 32:

[0221] Epoxy acrylate CN115 NS and TMPTA were mixed in a mass ratio of 4:3, and (0.1wt%) initiator (DC-6) and (2wt%) TEOA were added. After ultrasonic mixing, the mixture was vacuumed to remove bubbles and stored away from light. The prepared photosensitive resin was poured into the resin tank of an LCD 3D printer with an ultraviolet wavelength of 405nm for 3D printing to obtain a sample for performance testing. The parameter settings of the 3D printer are shown in Table 3.

[0222] The 3D printed sample was completely formed. The volume shrinkage of the 3D printed sample was measured by the same test method as in Example 26 to be 1.36%, the Shore hardness value was 67.6HD, the tensile strength was 12.73MPa, and the impact strength was 1.86KJ / m 2 .

[0223] Embodiment 33:

[0224] Epoxy acrylate CN115 NS and TMPTA were mixed in a mass ratio of 4:3, and (0.1wt%) initiator (DC-19) and (2wt%) PEGDA were added. After ultrasonic mixing, the mixture was vacuumed to remove bubbles and stored away from light. The prepared photosensitive resin was poured into the resin tank of an LCD 3D printer with a UV wavelength of 405nm for 3D printing to obtain a sample for performance testing. The parameter settings of the 3D printer are shown in Table 3.

[0225] The 3D printed sample was completely formed. The volume shrinkage of the 3D printed sample was measured by the same test method as in Example 26 to be 3.4%, the Shore hardness value was 70.6HD, the tensile strength was 15.73MPa, and the impact strength was 1.94KJ / m 2 .

[0226] Embodiment 34:

[0227] Epoxy acrylate CN115 NS and TMPTA were mixed in a mass ratio of 4:3, and (0.1wt%) initiator (DC-6), (0.1wt%) 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO), and (2wt%) TEOA were added. After ultrasonic mixing, the mixture was vacuumed to remove bubbles and stored away from light. The prepared photosensitive resin was poured into the resin tank of an LCD 3D printer with an ultraviolet wavelength of 405nm for 3D printing to obtain a sample for performance testing. The parameter settings of the 3D printer are shown in Table 1.

[0228] The 3D printed sample was completely formed. The volume shrinkage of the 3D printed sample was measured by the same test method as in Example 26. It was found that the Shore hardness value was 75.6HD, the tensile strength was 29.06MPa, and the impact strength was 2.75KJ / m 2 .

[0229] Comparative Example 4:

[0230] Epoxy acrylate CN115 NS and TMPTA were mixed in a mass ratio of 4:3, and 0.2wt% 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO) was added. After ultrasonic mixing, the mixture was vacuumed to remove bubbles and stored away from light. The prepared photosensitive resin was poured into the resin tank of an LCD 3D printer with an ultraviolet wavelength of 405nm for 3D printing to obtain a sample for performance testing. The parameter settings of the 3D printer are shown in Table 3.

[0231] The molding accuracy of the 3D printed sample is slightly poor. The volume shrinkage of the 3D printed sample measured by the same test method as in Example 26 is 5.5%, the Shore hardness value is 73.4HD, the tensile strength is 19.75MPa, and the impact strength is 2.13KJ / m 2 .

[0232] Embodiment 35:

[0233] Epoxy acrylate CN115 NS and TMPTA were mixed in a mass ratio of 4:3, and (0.1wt%) initiator (DC-17), (0.1wt%) isopropylthioxanthone (ITX), and (2wt%) TEOA were added. After ultrasonic mixing, the mixture was vacuumed to remove bubbles and stored away from light. The prepared photosensitive resin was poured into the resin tank of an LCD 3D printer with a UV wavelength of 405nm for 3D printing to obtain a sample for performance testing. The parameter settings of the 3D printer are shown in Table 3.

[0234] The 3D printed sample was completely formed. The volume shrinkage of the 3D printed sample was measured by the same test method as in Example 26 to be 3.3%, the Shore hardness value was 71.8HD, the tensile strength was 15.73MPa, and the impact strength was 1.93KJ / m 2 .

[0235] Embodiment 36:

[0236] Epoxy acrylate CN115 NS and TMPTA were mixed in a mass ratio of 4:3, and (0.1wt%) initiator (DC-19), (0.1wt%) 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO), and (2wt%) TEOA were added. After ultrasonic mixing, the mixture was vacuumed to remove bubbles and stored away from light. The prepared photosensitive resin was poured into the resin tank of an LCD 3D printer with an ultraviolet wavelength of 405nm for 3D printing to obtain a sample for performance testing. The parameter settings of the 3D printer are shown in Table 3.

[0237] The 3D printed sample was completely formed. The volume shrinkage of the 3D printed sample was measured by the same test method as in Example 26 to be 3.8%, the Shore hardness value was 76.7HD, the tensile strength was 31.36MPa, and the impact strength was 2.26KJ / m 2 .

Claims

1. A broadly absorbing polymerizable ketene photoinitiator, characterized in that Its general structure is shown below: Wherein: R1 is selected from -CH2-, -CH2CH2- or octylene; R2 is selected from -H, -NO3, halogen, methyl, methoxy; R3 is selected from hydrogen, halogen; R4 is selected from hydrogen, halogen.

2. A broadly absorbing polymerizable enone photoinitiator, characterized in that A compound selected from the following structures:

3. Use of the broad absorption polymerizable ketene photoinitiator according to claim 1 or 2, characterized in that: The ketene photoinitiator is used as a photoinitiator in the photopolymerization reaction of the material.

4. The use according to claim 3, characterized in that: The materials include ink and resin materials.

5. The use according to claim 4, characterized in that: The resin is an acrylic resin.

6. The use according to claim 3, characterized in that: The ketene photoinitiator has a wide light absorption range, has good absorption from long-wave ultraviolet to visible light bands, has good compatibility with UV-LED light sources, and is conducive to deep curing.

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