Polymerizable benzophenone photoinitiator capable of resisting oxidation inhibition as well as preparation method and application of polymerizable benzophenone photoinitiator

Abstract

The invention discloses an anti-oxygen-inhibition polymerizable benzophenone photoinitiator, and relates to the technical field of synthesis of photoinitiators in the field of photopolymerization. The invention also provides a preparation method of the photoinitiator. The anti-oxygen-inhibition polymerizable benzophenone initiator disclosed by the invention simultaneously contains a benzophenone group, vinyl and a tertiary amine group, so that the photo-initiation activity and the photolysis rate can be remarkably improved, and the migration rate can be reduced. Due to the introduction of vinyl double bonds and tertiary amine groups, the maximum absorption wavelength is increased, the initiation efficiency is greatly improved, meanwhile, the migration stability is good, the toxicity is low, the safety is high, and a certain anti-oxygen polymerization inhibition effect is achieved. The anti-oxygen-inhibition polymerizable benzophenone photoinitiator disclosed by the invention is low in migration rate, good in anti-oxygen-inhibition effect and high in LED light matching degree, and can be applied to the fields of ink printing, packaging, microelectronics and the like. The product is simple in synthesis process and suitable for industrial production.

Description

[0001] Field

[0002] The invention relates to the technical field of photopolymerization, and in particular to an anti-oxidation and anti-polymerizable benzophenone photoinitiator and a preparation method and application thereof. Background Art

[0003] Photopolymerization refers to the reaction of using light energy to initiate the polymerization of monomers. After being irradiated by an incident light source, the photoinitiator absorbs radiation energy to generate active fragments such as free radicals, cations or anions, which trigger the polymerization reaction of photosensitive materials (unsaturated acrylate monomers, cyclic monomers, thiol-ene, etc.), thereby converting the monomers into polymers. Therefore, although the amount of photoinitiator used in the photopolymerization system is small, it is a key component of the system. Benzophenone is a widely used hydrogen-abstracting photoinitiator with high initiation efficiency, but it must be used together with hydrogen donors such as tertiary amines when used, and it is very easy to cause residual small molecule initiators after the photopolymerization reaction occurs, thereby limiting its application.

[0004] In view of this, developing a photoinitiator that can effectively improve the initiation efficiency and antioxidant inhibition effect of benzophenone and overcome the disadvantages of small molecule migration has become an urgent problem to be solved by those skilled in the art. Summary of the invention

[0005] In order to solve the problems existing in the prior art, the present invention provides an anti-oxidation and anti-polymerization benzophenone photoinitiator, which introduces an unsaturated vinyl double bond in the side chain, and after the photopolymerization is initiated by light, it can undergo a polymerization reaction by itself, increase cross-linking and reduce migration, improve the migration stability of the photoinitiator, reduce toxicity, yellowing, and reduce odor. At the same time, different tertiary amine hydrogen donor groups are introduced into the side chain, which can increase the maximum absorption wavelength of the photoinitiator on the one hand, so that its tail absorption can reach the visible light region, and improve its application field; on the other hand, it can be photolyzed into highly active amino free radicals, which react with oxygen in the air, thereby avoiding oxygen inhibition of the initiator in the product, so that it has a certain anti-oxidation and anti-polymerization effect, and increases its application in the field.

[0006] One of the purposes of the present invention is to provide an anti-oxidation-inhibited polymerizable benzophenone-based photoinitiator. The structure of the anti-oxidation-inhibited polymerizable benzophenone-based photoinitiator is shown in the following formula (I):

[0007]

[0008] In formula (I), R1 and R2 are independently selected from C1-C 20Alkyl; It should be noted that R1 and R2 can be straight chain alkyl or branched chain alkyl, as long as the number of carbon atoms does not exceed 20. Further, R1 and R2 are independently selected from C1-C3 alkyl. Exemplarily, R1 and R2 are independently selected from methyl, ethyl, n-propyl or isopropyl.

[0009] R3 is selected from a hydrogen atom, a methyl group, an ethyl group, a methoxy group or a hydroxyl group; more preferably selected from a hydrogen atom, a methyl group or a hydroxyl group.

[0010] Further preferred:

[0011] The structure of the antioxidant polymerizable benzophenone photoinitiator is selected from one of the following six structures:

[0012]

[0013] The second object of the present invention is to provide a method for preparing the anti-oxidation-inhibited polymerizable benzophenone photoinitiator of the first object of the present invention. The method comprises:

[0014] (1) dissolving 3-halogenated styrene and magnesium in a solvent, stirring, and heating for reaction to obtain 3-halogenated magnesium styrene;

[0015] (2) Adding tertiary amino benzaldehyde to the 3-halogenated magnesium styrene to react, thereby obtaining the antioxidant and polymerizable benzophenone photoinitiator.

[0016] The present invention can specifically adopt the following technical solutions:

[0017] (1) dissolving 3-halogenated styrene and magnesium in a solvent, stirring, and heating for reaction to obtain 3-halogenated magnesium styrene;

[0018] (2) adding tertiary amino group-containing benzaldehyde to the 3-halogenated magnesium styrene for reaction.

[0019] (3) extracting the product of step (2) with an extractant, concentrating and purifying after the extraction, and obtaining the antioxidant and polymerizable benzophenone photoinitiator. The extractant is tertiary methyl ether. Concentration and purification are achieved by vacuum distillation.

[0020] Furthermore, the structure of the tertiary amino benzaldehyde is shown in the following formula (II):

[0021]

[0022] In formula (II), R1 and R2 are independently selected from C1-C 20Alkyl; R3 is selected from hydrogen atom, methyl, ethyl, methoxy or hydroxyl. It should be noted that R1 and R2 can be straight-chain alkyl or branched alkyl, as long as the number of carbon atoms does not exceed 20. Further, R1 and R2 are independently selected from C1-C3 alkyl. Exemplarily, R1 and R2 are independently selected from methyl, ethyl, n-propyl or isopropyl. As a preferred example of the tertiary amino group-containing benzaldehyde, the tertiary amino group-containing benzaldehyde is selected from 4-(dimethylamino)benzaldehyde, 4-diethylaminobenzaldehyde, 4-(dibutylamino)benzaldehyde, 4-(dimethylamino)-3-methylbenzaldehyde or 4-dimethylamino-2-methoxybenzaldehyde. The 3-halogenated styrene is selected from 3-fluorostyrene, 3-chlorostyrene, 3-bromostyrene or 3-iodostyrene, and the technician can choose as appropriate.

[0023] Taking 3-bromostyrene as an example, its chemical reaction is as follows:

[0024]

[0025] Further, the molar ratio of the 3-halogen magnesium styrene to the tertiary amino benzaldehyde is 1:1 to 1.5. The technician can select the appropriate molar ratio of the 3-halogen magnesium styrene to the tertiary amino benzaldehyde according to the situation. In step (1), the reaction temperature is 25 to 60°C and the reaction time is 2 to 3 hours. In step (2), the reaction temperature is -10 to 0°C and the reaction time is 6 to 12 hours. The technician can select the appropriate reaction temperature and reaction time according to the situation.

[0026] Furthermore, the solvent is at least one of dichloromethane, dichloroethane, chloroform, carbon tetrachloride, dimethyl sulfoxide, benzene, toluene, xylene, trimethylbenzene, tetramethylbenzene, acetonitrile, ethylbenzene, anisole, petroleum ether, hexane, dioxane, tetrahydrofuran, acetone, butanone, methanol, ethanol, and propanol. The technician can select the appropriate solvent type and solvent dosage according to the situation, and the type of solvent is at least one.

[0027] The third object of the present invention is to provide an antioxidant and polymerizable benzophenone photoinitiator according to the first object of the present invention and an antioxidant and polymerizable benzophenone photoinitiator prepared by the method of the second object of the present invention, and use them in ink printing, packaging, and microelectronics.

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] (1) The antioxidant and polymerizable benzophenone photoinitiator of the present invention contains unsaturated vinyl double bonds in the molecule. After being photopolymerized by light, it can undergo polymerization reaction by itself, increase cross-linking and reduce migration, improve the migration stability of the photoinitiator, reduce toxicity, yellowing, and reduce odor;

[0030] (2) The antioxidant and polymerizable benzophenone photoinitiator of the present invention introduces different tertiary amine hydrogen donor groups in the side chain to increase the maximum absorption wavelength of the photoinitiator, and the tail absorption can reach the visible light region, thereby improving its application field;

[0031] (3) The anti-oxidation and anti-polymerization benzophenone photoinitiator of the present invention introduces different tertiary amine hydrogen donor groups in the side chain, which can be photolyzed into highly active amino free radicals and react with oxygen in the air, thereby avoiding oxygen inhibition of the initiator in the product, thereby having a certain anti-oxidation and anti-polymerization effect and increasing its application in the field. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 This is a hydrogen nuclear magnetic resonance spectrum of the antioxidant, inhibited, polymerizable benzophenone photoinitiator prepared in Example 1 of the present invention;

[0033] Figure 2 This is the hydrogen nuclear magnetic resonance spectrum of the antioxidant and polymerizable benzophenone photoinitiator prepared in Example 2 of the present invention;

[0034] Figure 3 This is the hydrogen nuclear magnetic resonance spectrum of the antioxidant and polymerizable benzophenone photoinitiator prepared in Example 3 of the present invention;

[0035] Figure 4 This is the hydrogen nuclear magnetic resonance spectrum of the antioxidant and polymerizable benzophenone photoinitiator prepared in Example 4 of the present invention;

[0036] Figure 5 This is the hydrogen nuclear magnetic resonance spectrum of the antioxidant and polymerizable benzophenone photoinitiator prepared in Example 5 of the present invention;

[0037] Figure 6 This is the hydrogen nuclear magnetic resonance spectrum of the antioxidant and polymerizable benzophenone photoinitiator prepared in Example 6 of the present invention;

[0038] Figure 7 This is the ultraviolet absorption spectrum of the antioxidant, inhibited, polymerizable benzophenone photoinitiator prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0039] The present invention is described in detail below in conjunction with specific drawings and embodiments. It is necessary to point out that the following embodiments are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made to the present invention by those skilled in the art based on the content of the present invention still fall within the scope of protection of the present invention.

[0040] In the present invention, the components and raw materials involved are all conventional commercial products, and the instruments involved are all conventional commercial instruments.

[0041] In the present invention, the full chemical name of the HDDA monomer is 1,6-hexanediol diacrylate, and the full chemical name of TPGDA is tripropylene glycol diacrylate.

[0042] Example 1

[0043] An antioxidant and polymerizable benzophenone photoinitiator, the preparation method of which comprises the following steps:

[0044] (1) Synthesis of Grignard reagent: Under nitrogen protection, magnesium chips (0.1 mol, 2.4 g) were dissolved in tetrahydrofuran (50 ml) and stirred for 15 min. 3-bromostyrene (0.05 mol, 9.15 g) was dripped into the solution using a constant pressure dropping funnel at a drip rate of 1 drop / s. The reaction was initiated at 60°C. Stirring was continued after the reaction became mild. The reaction was continued at room temperature for 3 h until the magnesium chips were basically black, and a Grignard reagent solution was obtained.

[0045] (2) 4-(diethylamino)benzaldehyde (0.05 mol, 8.86 g) was added dropwise to the Grignard reagent solution in (1) above under an ice-water bath. The addition was slow and the drop rate was controlled to 2 drops / second. The temperature was controlled to 0°C and the reaction was continued for 6 hours. The reaction was quenched with 100 ml of ice water, extracted with tertiary methyl ether, and purified by vacuum distillation to obtain 9.35 g of the product with a yield of 74.44%. The structural formula of the obtained product is The structure is 1 HNMR confirmed:

[0046] 1 HNMR,7.79(d 1H),7.62(m1H),7.57(m 2H),7.39(t 1H),7.07(s 1H),6.92(d,d2H),6.72(m 1H),5.76(d 1H),5.25(d 1H),3.40(m 4H),1.12(t 6H).

[0047] Example 2

[0048] An antioxidant and polymerizable benzophenone photoinitiator, the preparation method of which comprises the following steps:

[0049] (1) Synthesis of Grignard reagent: Dissolve magnesium turnings (0.1 mol, 2.4 g) in tetrahydrofuran (50 ml) and stir for 15 min. Add 3-bromostyrene (0.05 mol, 9.15 g) dropwise at a rate of 2 drops / sec. Initiate the reaction at 60°C and allow to react at room temperature for 3 h until the magnesium turnings are substantially black, thereby obtaining a Grignard reagent solution.

[0050] (2) 3-Hydroxy-4-(diethylamino)benzaldehyde (0.06 mol, 11.595 g) was slowly added to the Grignard reagent solution in (1) under an ice-water bath, with the addition rate controlled at 1 drop / second, the temperature controlled at 0°C, and the reaction was continued for 6 hours. The reaction was quenched with 100 ml of ice water, extracted with tertiary methyl ether, and purified under reduced pressure to obtain 10.67 g of the product with a yield of 72.24%. The structural formula of the obtained product is The structure is 1 HNMR confirmed:

[0051] 1 HNMR,11.21(s 1H),7.79(d 1H),7.62(d 1H),7.57(d,d 2H),7.39(m 1H),7.33(m1H),7.13(d 2H),7.07(s 1H),6.91(s 1H),6.72(t 1H), 5.76 (d 1H), 5.25 (d 1H), 4.81 (s1H), 3.59 (m 2H), 3.41 (m 4H), 1.13 (t 6H).

[0052] Example 3

[0053] An antioxidant and polymerizable benzophenone photoinitiator, the preparation method of which comprises the following steps:

[0054] (1) Synthesis of Grignard reagent: Dissolve magnesium turnings (0.1 mol, 2.4 g) in tetrahydrofuran (50 ml) and stir for 15 min. Add 3-bromostyrene (0.05 mol, 9.15 g) dropwise at a rate of 2 drops / sec. Initiate the reaction at 60°C and allow to react at room temperature for 3 h until the magnesium turnings are substantially black, thereby obtaining a Grignard reagent solution.

[0055] (2) 3-methyl-4-(dimethylamino)benzaldehyde (0.05 mol, 8.16 g) (0.05 mol, 9.309 g) was slowly added to the Grignard reagent solution in (1) under an ice-water bath, with the addition rate controlled at 2 drops / second and the temperature controlled at 0°C for 12 hours. The reaction was quenched with 100 ml of ice water, extracted with tertiary methyl ether, and purified under reduced pressure to obtain 9.38 g of the product with a yield of 65.06%. The structural formula of the obtained product is The structure is 1 HNMR confirmed:

[0056] 1HNMR,7.79(d1H),7.62(d1H),7.47(t 1H),7.38(1H),7.07(d 1H),6.68(d 1H),6.72(m 1H),5.76(d 1H),5.25(d 1H),3.01(s 6H),2.12(s 3H).

[0057] Example 4

[0058] An antioxidant and polymerizable benzophenone photoinitiator, the preparation method of which comprises the following steps:

[0059] (1) Synthesis of Grignard reagent: Dissolve magnesium turnings (0.1 mol, 2.4 g) in tetrahydrofuran (50 ml) and stir for 15 min. Add 3-bromostyrene (0.05 mol, 9.15 g) dropwise at a rate of 2 drops / sec. Initiate the reaction at 60°C and allow to react at room temperature for 3 h until the magnesium turnings are substantially black, thereby obtaining a Grignard reagent solution.

[0060] (2) 3-Hydroxy-4-(dimethylamino)-benzaldehyde (0.05 mol, 8.161 g) was slowly added to the Grignard reagent in (1) under an ice-water bath, with the addition rate controlled at 2 drops / second, the temperature controlled at 0°C, and the reaction was carried out for 8 hours. The reaction was quenched with 100 ml of ice water, extracted with tertiary methyl ether, and purified by vacuum distillation to obtain 11.37 g of the product with a yield of 85.62%. The structural formula of the obtained product is The structure is 1 HNMR confirmed:

[0061] 1 HNMR,11.21(s 1H),7.79(d 1H),7.62(d 1H),7.47(d 1H),7.39(m 1H),7.33(m1H),7.13(t 1H),7.07(d 1H),6.91(s 1H),6.72(m 1H),5.76(d 1H),5.25(d 1H),4.43(s1H),3.01(ss 3H).

[0062] Example 5

[0063] An antioxidant and polymerizable benzophenone photoinitiator, the preparation method of which comprises the following steps:

[0064] (1) Synthesis of Grignard reagent: Under nitrogen protection, magnesium chips (0.1 mol, 2.4 g) were dissolved in tetrahydrofuran (50 ml) and stirred for 15 min. 3-bromostyrene (0.05 mol, 9.15 g) was dripped into the solution using a constant pressure dropping funnel at a drip rate of 1 drop / s. The reaction was initiated at 60°C. Stirring was continued after the reaction became mild. The reaction was continued at room temperature for 3 h until the magnesium chips were basically black, and a Grignard reagent solution was obtained.

[0065] (2) 4-(dipropylamino)benzaldehyde (0.05 mol, 10.267 g) was dripped into the Grignard reagent solution in (1) above under an ice-water bath. The dripping was slowly added, the dripping speed was controlled to 2 drops / second, the temperature was controlled to 0°C, and the reaction was carried out for 6 hours. The reaction was quenched with 100 ml of ice water, extracted with tertiary methyl ether, and purified by vacuum distillation to obtain 11.49 g of the product with a yield of 74.75%. The structural formula of the obtained product is The structure is 1 HNMR confirmed:

[0066] 1 HNMR,7.79(d 1H),7.62(m1H),7.57(m 2H),7.39(t 1H),7.07(s 1H),6.92(d,d2H),6.72(m 1H),5.76(d 1H),5.25(d 1H),3.78(m 4H), 1.57(m 4H), 0.87(t 6H).

[0067] Example 6

[0068] An antioxidant and polymerizable benzophenone photoinitiator, the preparation method of which comprises the following steps:

[0069] (1) Synthesis of Grignard reagent: Under nitrogen protection, magnesium chips (0.1 mol, 2.4 g) were dissolved in tetrahydrofuran (50 ml) and stirred for 15 min. 3-bromostyrene (0.05 mol, 9.15 g) was dripped into the solution using a constant pressure dropping funnel at a drip rate of 3 drops / second. The reaction was initiated at 60°C. Stirring was continued after the reaction became mild. The reaction was continued at room temperature for 3 h until the magnesium chips were basically black, and a Grignard reagent solution was obtained.

[0070] (2) 3-methoxy-4-(dimethylamino)-benzaldehyde (0.05 mol, 8.96 g) was slowly added to the Grignard reagent solution in (1) under an ice-water bath, with the addition rate controlled at 2 drops / second, the temperature controlled at 0°C, and the reaction was continued for 6 hours. The reaction was quenched with 100 ml of ice water, extracted with tertiary methyl ether, and purified by vacuum distillation to obtain 10.23 g of the product with a yield of 72.72%. The structural formula of the obtained product is The structure is 1 HNMR confirmed:

[0071] 1 HNMR,7.79(d 1H),7.62(m1H),7.50(d 1H),7.39(t 1H),7.25(d 1H),7.07(s2H),6.72(m 1H),5.76(d 1H),5.25(d 1H),3.86(s 3H),3.01(s 6H).

[0072] The performance of the polymerizable benzophenone photoinitiators prepared in Examples 1 to 6 was tested in the following manner:

[0073] (1) The antioxidant polymerizable benzophenone photoinitiator prepared in Example 1 was dissolved in acetonitrile solvent to a molar concentration of 5*10 -5 mol L -1 , and then perform UV spectrum test to obtain its UV spectrum (such as Figure 7 ). Figure 7 It can be seen that the maximum absorption wavelength of the antioxidant polymerization-inhibited polymerizable benzophenone photoinitiator prepared in Example 1 reaches 350nm. Under the same test conditions, the antioxidant polymerization-inhibited polymerizable benzophenone photoinitiators prepared in Examples 2 to 6 were also subjected to ultraviolet spectrum tests. The test results showed that the maximum absorption wavelength of the antioxidant polymerization-inhibited polymerizable benzophenone photoinitiators prepared in Examples 2 and 3 reached 360nm. The maximum absorption wavelength of the polymerizable benzophenone photoinitiator prepared in Example 4 reached 368nm. The maximum absorption wavelength of the polymerizable benzophenone photoinitiator prepared in Example 5 reached 345nm, and the maximum absorption wavelength of the polymerizable benzophenone photoinitiator prepared in Example 6 reached 346nm. It can be seen that the antioxidant polymerization-inhibited polymerizable benzophenone photoinitiator prepared by the present invention has a larger maximum absorption wavelength, and the tail absorption can reach the visible light region, and its application field is wide.

[0074] (2) The antioxidant and polymerizable benzophenone photoinitiator prepared in Examples 1 to 6 was dissolved in the HDDA monomer, and a real-time infrared test was performed using a double salt tablet. The mass concentration of the antioxidant and polymerizable benzophenone photoinitiator was set to 0.5%, and the real-time double bond conversion rate was obtained.

[0075] Under ultraviolet light, the monomer will undergo photopolymerization, and the decrease in the intensity of the characteristic absorption peak of the carbon-carbon double bond (-C=C-) can be reflected in the infrared spectrum. Therefore, the change in the peak area near the characteristic absorption peak of the carbon-carbon double bond can be monitored by a real-time infrared spectrometer to characterize the polymerization conversion rate. The conversion rate of the double bond in the monomer is calculated by the following formula

[0076] DC(%)=(A0-A t) / A0×100

[0077] Where A0 is the characteristic absorption peak area before illumination; A t is the characteristic absorption peak area at illumination time t.

[0078] The results of the real-time double bond conversion rate are shown in Table 1. Analysis of the data in Table 1 shows that, without adding a co-initiator and within 300 seconds, the double bond conversion rates of the anti-oxidation-inhibited polymerizable benzophenone photoinitiators prepared in Examples 1 to 6 for HDDA monomers are 98%, 99%, 98%, 96%, 98% and 97%, respectively. It can be seen that the anti-oxidation-inhibited polymerizable benzophenone photoinitiators prepared in the present invention can initiate the polymerization of photopolymerizable monomers and have excellent photopolymerization performance.

[0079] Table 1 Double bond conversion rate of the anti-oxidation-inhibited polymerizable benzophenone photoinitiator prepared in Examples 1 to 6 for the monomer HDDA within 300 seconds

[0080]

[0081] (3) The antioxidant and polymerizable benzophenone photoinitiators prepared in Examples 1 to 6 were tested for antioxidant and polymerizable benzophenone photoinitiators. The photocurable test samples were prepared according to the following weight percentages: 99 parts by weight of TPGDA and 1 part of any antioxidant and polymerizable benzophenone photoinitiator prepared in Examples 1 to 6. In order to conduct a parallel comparison, 99 parts by weight of TPGDA and 1 part by weight of commercial photoinitiator benzophenone were also selected. The above seven photocurable test samples were fully mixed, and 0.2 g of each of the above seven photocurable test samples was taken and applied on white ABS. A film scraper was used to scrape the film to form a coating of about 500 microns under air. The coating was transferred to a single glass slide and irradiated under a light intensity of 70 mW / cm 2 Under the condition of , the double bond conversion rate of 3min was measured by real-time infrared, and the results are shown in Table 2. Analysis of the data in Table 2 shows that the antioxidant and polymerizable benzophenone photoinitiators prepared in Examples 1 to 6 above all have good antioxidant and polymerization inhibition effects, which are far superior to the commercial photoinitiator benzophenone.

[0082] Table 2 Double bond conversion rate of seven photocuring test samples to monomer TPGDA within 3 min

[0083]

[0084] (4) The migration performance of the antioxidant and polymerizable benzophenone photoinitiators prepared in Examples 1 to 6 was tested. The photocuring test samples were prepared according to the following weight percentages: 99 parts by weight of HDDA and 1 part of any of the antioxidant and polymerizable benzophenone photoinitiators prepared in Examples 1 to 6. For parallel comparison, 99 parts by weight of HDDA and 1 part by weight of commercial photoinitiator benzophenone were also selected. The seven test samples were respectively injected into a square silicone pad mold and heated at a light intensity of 40 mW / cm 2 The samples were cured in a curing box for 10 minutes, and finally a sample with a length and width of 15 mm and a thickness of 1 mm was obtained. After the samples were cured by light, the surface was rinsed with anhydrous ethanol, and then 0.1 g of the samples were weighed and soaked in 20 ml of acetonitrile solution for 5 days. During the soaking process, the residual photoinitiator and photolysis fragments easily migrated out of the polymerization network, and then the ultraviolet absorption spectrum of the sample after 5 days of soaking was detected by an ultraviolet spectrophotometer to obtain the absorbance curve after soaking. By comparing the size of the absorbance, the migration comparison of the photoinitiator was achieved. The test results are shown in Table 3. Analysis of the data in Table 3 shows that the antioxidant and inhibited polymerizable benzophenone photoinitiators prepared in the above Examples 1 to 6 all have low migration performance, which is better than the commercial photoinitiator benzophenone, which indirectly reflects that it can reduce toxicity, yellowing, and reduce odor.

[0085] Table 3 Absorbance of seven test samples after 5 days

[0086]

Claims

1. An antioxidant, inhibited, polymerizable benzophenone photoinitiator, characterized in that: The structure of the anti-oxidation-inhibiting polymerizable benzophenone photoinitiator is shown in the following formula (I): In formula (I), R1 and R2 are independently selected from C1-C 20 Alkyl; R3 is selected from hydrogen atom, methyl, ethyl, methoxy or hydroxyl.

2. The antioxidant, inhibited, polymerizable benzophenone photoinitiator according to claim 1, characterized in that: R1 and R2 are independently selected from C1-C3 alkyl groups.

3. A method for preparing an antioxidant-inhibited polymerizable benzophenone photoinitiator as claimed in any one of claims 1 to 2, characterized in that The method comprises: (1) dissolving 3-halostyrene and magnesium in a solvent, stirring, and heating to react to obtain 3-halostyrene magnesium; preferably, the 3-halostyrene is selected from 3-fluorostyrene, 3-chlorostyrene, 3-bromostyrene or 3-iodostyrene; (2) Adding tertiary amino benzaldehyde to the 3-halogenated magnesium styrene to react, thereby obtaining the antioxidant and polymerizable benzophenone photoinitiator.

4. The method according to claim 3, characterized in that: The structure of the tertiary amino benzaldehyde is shown in the following formula (II): In formula (II), R1 and R2 are independently selected from C1-C 20 Alkyl; R3 is selected from hydrogen atom, methyl, ethyl, methoxy or hydroxyl.

5. The method according to claim 4, characterized in that: R1 and R2 are independently selected from C1-C3 alkyl groups.

6. The method according to claim 5, characterized in that: The tertiary amino group-containing benzaldehyde is selected from 4-(dimethylamino)benzaldehyde, 4-diethylaminobenzaldehyde, 4-(dibutylamino)benzaldehyde, 4-(dimethylamino)-3-methylbenzaldehyde or 4-dimethylamino-2-methoxybenzaldehyde.

7. The method according to claim 3, characterized in that: The molar ratio of the 3-halogenated magnesium styrene to the tertiary amino group-containing benzaldehyde is 1:1 to 1.

5.

8. The method according to claim 3, characterized in that: The solvent is at least one of dichloromethane, dichloroethane, chloroform, carbon tetrachloride, dimethyl sulfoxide, benzene, toluene, xylene, trimethylbenzene, tetramethylbenzene, acetonitrile, ethylbenzene, anisole, petroleum ether, hexane, dioxane, tetrahydrofuran, acetone, butanone, methanol, ethanol, and propanol.

9. The method according to claim 3, characterized in that: In step (1), the reaction temperature is 25-60°C and the reaction time is 2-3h; and / or In step (2), the reaction temperature is -10 to 0°C and the reaction time is 6 to 12 hours.

10. Application of the antioxidant polymerization-inhibited polymerizable benzophenone photoinitiator according to any one of claims 1 to 2 and the antioxidant polymerization-inhibited polymerizable benzophenone photoinitiator prepared by the method according to any one of claims 3 to 9 in ink printing, packaging and microelectronics.

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