CN119192004A - An anti-oxidation and polymerization-inhibiting polymerizable benzophenone photoinitiator and its preparation method and application - Google Patents

An anti-oxidation and polymerization-inhibiting polymerizable benzophenone photoinitiator and its preparation method and application Download PDF

Info

Publication number
CN119192004A
CN119192004A CN202310761215.4A CN202310761215A CN119192004A CN 119192004 A CN119192004 A CN 119192004A CN 202310761215 A CN202310761215 A CN 202310761215A CN 119192004 A CN119192004 A CN 119192004A
Authority
CN
China
Prior art keywords
photoinitiator
polymerization
styrene
polymerizable benzophenone
polymerizable
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202310761215.4A
Other languages
Chinese (zh)
Inventor
赵莹莹
李伟杰
朱晓群
聂俊
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing University of Chemical Technology
Original Assignee
Beijing University of Chemical Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Beijing University of Chemical Technology filed Critical Beijing University of Chemical Technology
Priority to CN202310761215.4A priority Critical patent/CN119192004A/en
Publication of CN119192004A publication Critical patent/CN119192004A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
    • C07C225/22—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F122/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
    • C08F122/10—Esters
    • C08F122/1006—Esters of polyhydric alcohols or polyhydric phenols, e.g. ethylene glycol dimethacrylate

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

The invention discloses an anti-oxidation polymerization 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-oxidation polymerization inhibition polymerizable benzophenone initiator contains a benzophenone group, a vinyl group and a tertiary amine group, and can obviously improve photoinitiation activity, photolysis rate and reduce mobility. The introduction of vinyl double bond and tertiary amine group increases the maximum absorption wavelength, greatly improves the initiation efficiency, and has good migration stability, low toxicity, high safety and certain antioxidant polymerization inhibition effect. The anti-oxidation polymerization inhibition polymerizable diphenyl ketone photoinitiator has low mobility, good anti-oxidation polymerization inhibition effect and high light matching degree with an LED, and can be used in the fields of printing ink, packaging, microelectronics and the like. The product of the invention has simple synthesis process and is suitable for industrial production.

Description

Anti-oxidation polymerization-inhibition polymerizable diphenyl ketone photoinitiator and preparation method and application thereof
Belonging to the field of
The invention relates to the technical field of photopolymerization, in particular to an anti-oxidation polymerization-inhibition polymerizable benzophenone photoinitiator and a preparation method and application thereof.
Background
Photopolymerization refers to a reaction that utilizes light energy to initiate polymerization of monomers. The photoinitiator is irradiated by an incident light source, absorbs radiation energy to generate active fragments such as free radicals, cations or anions, and the like, and initiates a photosensitive material (unsaturated acrylate monomers, cyclic monomers, thiol-ene, and the like) to perform polymerization reaction, so that the monomers are converted into polymers. Thus, the photoinitiator is used in small amounts in the photopolymerization system, but is a key component of the system. Benzophenone is used as a hydrogen abstraction photoinitiator with very wide application, has very wide application and high initiation efficiency, but must be used simultaneously with hydrogen donors such as tertiary amine and the like when in use, and is extremely easy to cause residual small molecular initiator after photopolymerization reaction, thereby limiting the application of the benzophenone.
In view of this, developing a photoinitiator that can effectively improve the initiation efficiency of benzophenone, the anti-oxidation polymerization inhibition effect, and overcome the drawbacks of small molecule migration is a problem to be solved by those skilled in the art.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides an anti-oxidation polymerization-inhibition polymerizable benzophenone photoinitiator, wherein unsaturated vinyl double bonds are introduced into side chains, and after light polymerization is induced by illumination, polymerization reaction can be carried out, so that crosslinking is increased, migration is reduced, migration stability of the photoinitiator is improved, toxicity and yellowing are reduced, and odor is reduced. Meanwhile, different tertiary amine hydrogen donor groups are introduced into the side chain, so that on one hand, the maximum absorption wavelength of the photoinitiator can be increased, the tail absorption of the photoinitiator can reach the visible light region, the application field of the photoinitiator is improved, and on the other hand, the photoinitiator can be photolyzed into high-activity amino free radicals which react with oxygen of air, thereby avoiding oxygen polymerization inhibition of the initiator in a product, having a certain antioxidant polymerization inhibition effect, and increasing the application in the field.
One of the purposes of the invention is to provide an anti-oxidation polymerization inhibition polymerizable benzophenone photoinitiator. The structure of the antioxidant polymerization inhibiting polymerizable benzophenone photoinitiator is shown as the following formula (I)
In the formula (I), R 1 and R 2 are independently selected from C 1-C20 alkyl, and R 1 and R 2 may be straight-chain alkyl or branched-chain alkyl, so long as the number of carbon atoms is not more than 20. Further, R 1 and R 2 are independently selected from C 1-C3 alkyl. Illustratively, R 1 and R 2 are independently selected from methyl, ethyl, n-propyl, or isopropyl.
R 3 is selected from a hydrogen atom, methyl, ethyl, methoxy or hydroxy, more preferably from a hydrogen atom, methyl or hydroxy.
Further preferred is:
the structure of the antioxidant polymerization inhibiting polymerizable benzophenone photoinitiator is selected from one of the following six structures:
it is a second object of the present invention to provide a process for preparing an antioxidant polymerization inhibiting polymerizable benzophenone-type photoinitiator which is one of the objects of the present invention. The method comprises the following steps:
(1) Dissolving 3-halogenated styrene and magnesium in a solvent, stirring, and heating for reaction to obtain 3-halogenated magnesium styrene;
(2) Adding tertiary amino benzaldehyde into the 3-halogenated magnesium styrene, and reacting to obtain the anti-oxidation polymerization-inhibition polymerizable benzophenone photoinitiator.
The invention adopts the following technical scheme:
(1) Dissolving 3-halogenated styrene and magnesium in a solvent, stirring, and heating for reaction to obtain 3-halogenated magnesium styrene;
(2) Adding tertiary amine-containing benzaldehyde into the 3-halogenated magnesium styrene for reaction.
(3) And (3) extracting the product in the step (2) by using an extracting agent, concentrating and purifying after the extraction is finished, and obtaining the anti-oxidation polymerization inhibition polymerizable benzophenone photoinitiator. Wherein the extractant is methyl tertiary ether. Reduced pressure distillation is used to effect concentration and purification.
Further, the tertiary amino benzaldehyde has a structure shown in the following formula (II)
In formula (II), R 1 and R 2 are independently selected from C 1-C20 alkyl, and R 3 is selected from hydrogen atom, methyl, ethyl, methoxy or hydroxy. It is to be noted that R 1 and R 2 may be a straight chain alkyl group or a branched alkyl group as long as the number of carbon atoms thereof is not more than 20. Still further, R 1 and R 2 are independently selected from C 1-C3 alkyl. Illustratively, R 1 and R 2 are independently selected from methyl, ethyl, n-propyl, or isopropyl. As a preferable example of the tertiary amino benzaldehyde, the tertiary amino 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-fluoro-styrene, 3-chloro-styrene, 3-bromo-styrene or 3-iodo-styrene, and can be selected by the skilled person according to the situation.
Taking 3-bromostyrene as an example, the chemical reaction mode is as follows:
Further, the molar ratio of the 3-halogenated magnesium-substituted styrene to the tertiary amino benzaldehyde is 1:1-1.5. The skilled person may optionally select a suitable molar ratio of the 3-halomagnesium styrene and the tertiary amino benzaldehyde. In the step (1), the reaction temperature is 25-60 ℃ and the reaction time is 2-3 h, and in the step (2), the reaction temperature is-10-0 ℃ and the reaction time is 6-12 h. The skilled person can choose the appropriate reaction temperature and reaction time as appropriate.
Further, 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 skilled person can optionally select a suitable kind of solvent and amount of solvent, and the kind of solvent is at least one.
The invention also provides an anti-oxidation polymerization-inhibition polymerizable benzophenone photoinitiator and application of the anti-oxidation polymerization-inhibition polymerizable benzophenone photoinitiator prepared by the method of the second object in printing ink, packaging and microelectronics.
Compared with the prior art, the invention has the following beneficial effects:
(1) The anti-oxidation polymerization inhibition polymerizable benzophenone photoinitiator contains unsaturated vinyl double bonds in molecules, can perform polymerization reaction by itself after light irradiation induced polymerization, increases crosslinking and reduces migration, improves migration stability of the photoinitiator, reduces toxicity and yellowing, and reduces odor;
(2) According to the anti-oxidation polymerization inhibition polymerizable benzophenone photoinitiator, different tertiary amine hydrogen donor groups are introduced into a side chain, so that the maximum absorption wavelength of the photoinitiator is increased, the tail absorption can reach a visible light region, and the application field of the photoinitiator is improved;
(3) The anti-oxygen polymerization-inhibition polymerizable benzophenone photoinitiator introduces different tertiary amine hydrogen donor groups into the side chain, can be photolyzed into high-activity amino free radicals and reacts with oxygen of air, thereby avoiding the polymerization inhibition of the initiator in the product, having a certain anti-oxygen polymerization-inhibition effect and increasing the application in the field.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of an anti-oxidative polymerization-inhibiting polymerizable benzophenone photoinitiator prepared in example 1 of the present invention;
FIG. 2 is a chart showing the nuclear magnetic resonance hydrogen spectrum of the anti-oxidative polymerization-inhibiting polymerizable benzophenone photoinitiator prepared in example 2 of the present invention;
FIG. 3 is a chart showing the nuclear magnetic resonance hydrogen spectrum of the anti-oxidative polymerization-inhibiting polymerizable benzophenone photoinitiator prepared in example 3 of the present invention;
FIG. 4 is a chart showing the nuclear magnetic resonance hydrogen spectrum of the anti-oxidative polymerization-inhibiting polymerizable benzophenone photoinitiator prepared in example 4 of the present invention;
FIG. 5 is a chart showing the nuclear magnetic resonance hydrogen spectrum of the anti-oxidative polymerization-inhibiting polymerizable benzophenone photoinitiator prepared in example 5 of the present invention;
FIG. 6 is a chart showing the nuclear magnetic resonance hydrogen spectrum of the anti-oxidative polymerization-inhibiting polymerizable benzophenone photoinitiator prepared in example 6 of the present invention;
FIG. 7 is a graph showing the ultraviolet absorption spectrum of the anti-oxidative polymerization-inhibiting polymerizable benzophenone-based photoinitiator prepared in example 1 of the present invention.
Detailed Description
The present invention is described in detail below with reference to the specific drawings and examples, and it is necessary to point out that the following examples are given for further illustration of the present invention only and are not to be construed as limiting the scope of the present invention, since numerous insubstantial modifications and adaptations of the invention to those skilled in the art will still fall within the scope of the present invention.
In the present invention, the components and materials involved are conventional commercial products. The instruments involved were all conventional commercially available instruments.
In the present invention, the chemical group of HDDA monomers is referred to as 1, 6-hexanediol diacrylate and the chemical group of TPGDA is referred to as tripropylene glycol diacrylate.
Example 1
An antioxidant polymerization-inhibiting polymerizable diphenyl ketone photoinitiator, the preparation method comprises the following steps:
(1) Grignard reagent was synthesized by dissolving magnesium turnings (0.1 mol,2.4 g) in tetrahydrofuran (50 ml) under nitrogen protection and stirring for 15min, dropping 3-bromostyrene (0.05 mol,9.15 g) into the solution by using a constant pressure dropping funnel, controlling the dropping speed to be 1 drop/sec, initiating reaction at 60 ℃, continuing stirring after the reaction is mild, and reacting for 3h at room temperature. Until the magnesium chips are basically blackened, and obtaining the grignard reagent solution.
(2) 4- (Diethylamino) benzaldehyde (0.05 mol,8.86 g) was dropwise added to the Grignard reagent solution in the above (1) under an ice-water bath. Slowly dripping, controlling the dripping speed to be 2 drops/second, controlling the temperature to be 0 ℃, and reacting for 6 hours. The reaction was quenched with 100ml of ice water, extracted with methyl tertiary ether, distilled under reduced pressure and purified to give 9.35g of the product in 74.44% yield. The structural formula of the obtained product isThe structural formula is confirmed by 1 HNMR:
1HNMR,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).
example 2
An antioxidant polymerization-inhibiting polymerizable diphenyl ketone photoinitiator, the preparation method comprises the following steps:
(1) Grignard reagent was synthesized by dissolving magnesium turnings (0.1 mol,2.4 g) in tetrahydrofuran (50 ml) and stirring for 15min, dropping 3-bromostyrene (0.05 mol,9.15 g) therein, controlling the dropping speed to 2 drops/sec, initiating reaction at 60℃and reacting at room temperature for 3h until the magnesium turnings become substantially black, and obtaining the grignard reagent solution.
(2) 3-Hydroxy-4- (diethylamino) benzaldehyde (0.06 mol,11.595 g) was added dropwise to the Grignard reagent solution in (1) above under an ice-water bath, and the mixture was slowly added dropwise at a controlled dropping rate of 1 drop/sec at a controlled temperature of 0℃for 6 hours. The reaction was quenched with 100ml of ice water, extracted with methyl tertiary ether, distilled under reduced pressure and purified to give 10.67g of the product in a yield of 72.24%. The structural formula of the obtained product isThe structural formula is confirmed by 1 HNMR:
1HNMR,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).
Example 3
An antioxidant polymerization-inhibiting polymerizable diphenyl ketone photoinitiator, the preparation method comprises the following steps:
(1) Grignard reagent was synthesized by dissolving magnesium turnings (0.1 mol,2.4 g) in tetrahydrofuran (50 ml) and stirring for 15min, dropping 3-bromostyrene (0.05 mol,9.15 g) therein, controlling the dropping speed to 2 drops/sec, initiating reaction at 60℃and reacting at room temperature for 3h until the magnesium turnings become substantially black, and obtaining the grignard reagent solution.
(2) 3-Methyl-4- (dimethylamino) benzaldehyde (0.05 mol,8.16 g) (0.05 mol,9.309 g) was added dropwise to the Grignard reagent solution of (1) under an ice water bath, and the mixture was slowly added dropwise at a controlled dropping speed of 2 drops/sec at a controlled temperature of 0℃for 12 hours. The reaction was quenched with 100ml of ice water, extracted with methyl tertiary ether, distilled under reduced pressure and purified to give 9.38g of the product in 65.06% yield. The structural formula of the obtained product isThe structural formula is confirmed by 1 HNMR:
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).
Example 4
An antioxidant polymerization-inhibiting polymerizable diphenyl ketone photoinitiator, the preparation method comprises the following steps:
(1) Grignard reagent was synthesized by dissolving magnesium turnings (0.1 mol,2.4 g) in tetrahydrofuran (50 ml) and stirring for 15min, dropping 3-bromostyrene (0.05 mol,9.15 g) therein, controlling the dropping speed to 2 drops/sec, initiating reaction at 60℃and reacting at room temperature for 3h until the magnesium turnings become substantially black, and obtaining the grignard reagent solution.
(2) 3-Hydroxy-4- (dimethylamino) -benzaldehyde (0.05 mol,8.161 g) was added dropwise to the Grignard reagent in (1) above under ice water bath, and the reaction was carried out for 8 hours with slow dropwise addition, 2 drops/sec drop rate and 0 ℃ temperature control. The reaction was quenched with 100ml of ice water, extracted with methyl tertiary ether, distilled under reduced pressure and purified to give 11.37g of the product in 85.62% yield. The structural formula of the obtained product isThe structural formula is confirmed by 1 HNMR:
1HNMR,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).
Example 5
An antioxidant polymerization-inhibiting polymerizable diphenyl ketone photoinitiator, the preparation method comprises the following steps:
(1) Grignard reagent was synthesized by dissolving magnesium turnings (0.1 mol,2.4 g) in tetrahydrofuran (50 ml) under nitrogen protection and stirring for 15min, dropping 3-bromostyrene (0.05 mol,9.15 g) into the solution by using a constant pressure dropping funnel, controlling the dropping speed to be 1 drop/sec, initiating reaction at 60 ℃, continuing stirring after the reaction is mild, and reacting for 3h at room temperature. Until the magnesium chips are basically blackened, and obtaining the grignard reagent solution.
(2) 4- (Dipropylamino) benzaldehyde (0.05 mol,10.267 g) was added dropwise to the Grignard reagent solution in the above (1) under ice-water bath. Slowly dripping, controlling the dripping speed to be 2 drops/second, controlling the temperature to be 0 ℃, and reacting for 6 hours. The reaction was quenched with 100ml of ice water, extracted with methyl tertiary ether, distilled under reduced pressure and purified to give 11.49g of the product in 74.75% yield. The structural formula of the obtained product isThe structural formula is confirmed by 1 HNMR:
1HNMR,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).
example 6
An antioxidant polymerization-inhibiting polymerizable diphenyl ketone photoinitiator, the preparation method comprises the following steps:
(1) Grignard reagent was synthesized by dissolving magnesium turnings (0.1 mol,2.4 g) in tetrahydrofuran (50 ml) under nitrogen protection and stirring for 15min, dropping 3-bromostyrene (0.05 mol,9.15 g) into the solution by using a constant pressure dropping funnel, controlling the dropping speed to 3 drops/sec, initiating reaction at 60 ℃, continuing stirring after the reaction is mild, and reacting for 3h at room temperature. Until the magnesium chips are basically blackened, and obtaining the grignard reagent solution.
(2) 3-Methoxy-4- (dimethylamino) -benzaldehyde (0.05 mol,8.96 g) was added dropwise to the Grignard reagent solution in (1) under ice water bath, the dropping speed was controlled to 2 drops/sec, the temperature was controlled to 0℃and the reaction was carried out for 6 hours. The reaction was quenched with 100ml of ice water, extracted with methyl tertiary ether, distilled under reduced pressure and purified to give 10.23g of the product in 72.72% yield. The structural formula of the obtained product isThe structural formula is confirmed by 1 HNMR:
1HNMR,7.79(d 1H),7.62(m1H),7.50(d 1H),7.39(t 1H),7.25(d 1H),7.07(s 2H),6.72(m 1H),5.76(d 1H),5.25(d 1H),3.86(s 3H),3.01(s 6H).
Performance tests are carried out on the polymerizable benzophenone photoinitiator prepared in the examples 1-6, and the test method is as follows:
(1) The anti-oxidation polymerization inhibition polymerizable benzophenone photoinitiator prepared in example 1 was dissolved in acetonitrile solvent to make its molar concentration be 5 x 10 -5mol L-1, and then ultraviolet spectrum test was performed to obtain its ultraviolet spectrum (as shown in fig. 7). As can be seen from FIG. 7, the maximum absorption wavelength of the anti-oxidative polymerization-inhibiting polymerizable benzophenone-based photoinitiator prepared in example 1 reaches 350nm. Under the same test conditions, ultraviolet spectrum tests are also carried out on the anti-oxidation polymerization inhibition polymerizable benzophenone type photoinitiators prepared in the examples 2-6, and test results show that the maximum absorption wavelength of the anti-oxidation polymerization inhibition polymerizable benzophenone type photoinitiators prepared in the examples 2 and 3 reaches 360nm. The maximum absorption wavelength of the polymerizable benzophenone-type photoinitiator prepared in example 4 was 368nm. The maximum absorption wavelength of the polymerizable benzophenone-type photoinitiator prepared in example 5 was 345nm and the maximum absorption wavelength of the polymerizable benzophenone-type photoinitiator prepared in example 6 was 346nm. Therefore, the anti-oxidation polymerization inhibition polymerizable benzophenone photoinitiator prepared by the invention has larger maximum absorption wavelength, and the tail absorption can reach the visible light region, so that the application field is wide.
(2) The anti-oxidation polymerization-inhibition polymerizable benzophenone photoinitiator prepared in the examples 1-6 is dissolved in an HDDA monomer, a double-salt sheet is used for real-time infrared test, the mass concentration of the anti-oxidation polymerization-inhibition polymerizable benzophenone photoinitiator is set to be 0.5%, and the real-time conversion rate of double bonds is obtained.
Under the irradiation of ultraviolet light, the monomer can undergo photopolymerization, and the reduction of the characteristic absorption peak intensity of the carbon-carbon double bond (-C=C-) can be reflected in an infrared spectrum. Thus, the polymerization conversion can be characterized by monitoring the change in peak area near the characteristic absorption peak of the carbon-carbon double bond by a real-time infrared spectrometer. The conversion of double bonds in the monomers is calculated by
DC(%)=(A0-At)/A0×100
Wherein A 0 is the characteristic absorption peak area before illumination, and A t is the characteristic absorption peak area at the time of illumination t.
The results of the conversion of double bonds in real time are shown in Table 1. Analysis of the data in Table 1 shows that the double bond conversion of the anti-oxidative polymerization-inhibiting polymerizable benzophenone-based photoinitiators prepared in examples 1 to 6 to HDDA monomers was 98%, 99%, 98%, 96%, 98% and 97%, respectively, without the addition of a co-initiator and within 300 seconds. Therefore, the anti-oxidation polymerization-inhibition polymerizable benzophenone photoinitiator prepared by the invention can initiate polymerization of the photopolymerization monomer, and has excellent photopolymerization performance.
Table 1 double bond conversion of monomer HDDA in 300s of the antioxidant polymerization inhibiting polymerizable benzophenone photoinitiator prepared in examples 1 to 6
(3) And (3) performing an antioxidant polymerization inhibition test on the anti-oxidant polymerization inhibition polymerizable benzophenone photoinitiator prepared in the examples 1-6. A photo-curing test sample was prepared according to the weight percentage of 99 parts of TPGDA and 1 part of the anti-oxidative polymerization-inhibiting polymerizable benzophenone photoinitiator prepared in any one of examples 1 to 6. For parallel comparison, 99 parts by weight of TPGDA and 1 part by weight of a commercial photoinitiator benzophenone were also selected. The seven photo-curing test samples were each thoroughly mixed, 0.2g each of the seven photo-curing test samples was taken and smeared on white ABS, and a film was scraped with a film scraper to form a coating of about 500 μm in air. The coating was transferred to a single glass slide and the double bond conversion was measured using real time infrared under light intensity 70mW/cm 2 for 3min, the results are shown in Table 2. From the analysis of the data in Table 2, it is clear that the anti-oxidative polymerization inhibition polymerizable benzophenone-type photoinitiators prepared in examples 1 to 6 have good anti-oxidative polymerization inhibition effects, and are far superior to commercial photoinitiator benzophenone.
TABLE 2 double bond conversion of seven photo-cured test samples to monomeric TPGDA in 3min
(4) Migration performance tests are conducted on the anti-oxidation polymerization inhibition polymerizable benzophenone photoinitiator prepared in the examples 1-6. A photo-curing test sample was prepared according to the following weight percentages by taking 99 parts by weight of HDDA and 1 part of the anti-oxidative polymerization-inhibiting polymerizable benzophenone photoinitiator prepared in any one of examples 1 to 6. For parallel comparison, 99 parts by weight of HDDA and 1 part by weight of a commercial photoinitiator benzophenone were also selected. And respectively injecting the seven test samples into square silica gel pad molds, and curing in a curing box with the light intensity of 40mW/cm 2 for 10min to finally obtain the sample with the length and width of 15mm and the thickness of 1 mm. After the sample is cured by illumination, the surface of the sample is washed clean by absolute ethyl alcohol, and then 0.1g of the sample is respectively weighed and soaked in 20ml of acetonitrile solution for 5 days. In the soaking process, residual photoinitiator and photolytic fragments are easy to migrate out of a polymerization network, and then ultraviolet absorption spectrum of a sample after soaking time of 5 days is detected by an ultraviolet spectrophotometer, so that an absorbance curve after soaking can be obtained. The migration contrast of the photoinitiator is achieved by comparing the absorbance. The test results are shown in Table 3. From the analysis of the data in Table 3, it is clear that all the anti-oxidative polymerization-inhibition polymerizable benzophenone-type photoinitiators prepared in examples 1 to 6 have low migration performance, and are superior to commercial photoinitiator benzophenone, and the side reflection of the benzophenone-type photoinitiator can reduce toxicity, yellowing and odor.
Table 3 absorbance of seven test samples after 5 days

Claims (10)

1. An anti-oxidation polymerization-inhibition polymerizable benzophenone photoinitiator is characterized in that the structure of the anti-oxidation polymerization-inhibition polymerizable benzophenone photoinitiator is shown as the following formula (I)
In formula (I), R 1 and R 2 are independently selected from C 1-C20 alkyl, and R 3 is selected from hydrogen atom, methyl, ethyl, methoxy or hydroxy.
2. The oxygen-resistant polymerization-inhibiting polymerizable benzophenone-type photoinitiator according to claim 1, wherein:
r 1 and R 2 are independently selected from C 1-C3 alkyl.
3. A method for preparing the anti-oxidation polymerization inhibition polymerizable benzophenone photoinitiator according to any one of claims 1 to 2, which is characterized in that the method comprises the following steps:
(1) Dissolving 3-halogenated styrene and magnesium in a solvent, stirring, heating and reacting to obtain 3-halogenated magnesium-substituted styrene, wherein the 3-halogenated styrene is preferably selected from 3-fluoro-styrene, 3-chloro-styrene, 3-bromo-styrene or 3-iodo-styrene;
(2) Adding tertiary amino benzaldehyde into the 3-halogenated magnesium styrene, and reacting to obtain the anti-oxidation polymerization-inhibition polymerizable benzophenone photoinitiator.
4. A method according to claim 3, characterized in that:
the structure of the tertiary amino benzaldehyde is shown as the following formula (II)
In formula (II), R 1 and R 2 are independently selected from C 1-C20 alkyl, and R 3 is selected from hydrogen atom, methyl, ethyl, methoxy or hydroxy.
5. The method according to claim 4, wherein:
r 1 and R 2 are independently selected from C 1-C3 alkyl.
6. The method according to claim 5, wherein:
The tertiary amino-containing benzaldehyde is selected from 4- (dimethylamino) benzaldehyde, 4-diethylamino benzaldehyde, 4- (dibutylamino) benzaldehyde, 4- (dimethylamino) -3-methylbenzaldehyde or 4-dimethylamino-2-methoxybenzaldehyde.
7. A method according to claim 3, characterized in that:
The molar ratio of the 3-halogenated magnesium styrene to the tertiary amino benzaldehyde is 1:1-1.5.
8. A 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. A method according to claim 3, characterized in that:
in the step (1), the reaction temperature is 25-60 ℃ and the reaction time is 2-3 h, and/or
In the step (2), the reaction temperature is-10-0 ℃ and the reaction time is 6-12 hours.
10. Use of an antioxidant polymerization inhibiting polymerizable benzophenone photoinitiator according to one of claims 1 to 2 and an antioxidant polymerization inhibiting polymerizable benzophenone photoinitiator prepared according to one of claims 3 to 9 in ink printing, packaging and microelectronics.
CN202310761215.4A 2023-06-26 2023-06-26 An anti-oxidation and polymerization-inhibiting polymerizable benzophenone photoinitiator and its preparation method and application Pending CN119192004A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310761215.4A CN119192004A (en) 2023-06-26 2023-06-26 An anti-oxidation and polymerization-inhibiting polymerizable benzophenone photoinitiator and its preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310761215.4A CN119192004A (en) 2023-06-26 2023-06-26 An anti-oxidation and polymerization-inhibiting polymerizable benzophenone photoinitiator and its preparation method and application

Publications (1)

Publication Number Publication Date
CN119192004A true CN119192004A (en) 2024-12-27

Family

ID=94064884

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310761215.4A Pending CN119192004A (en) 2023-06-26 2023-06-26 An anti-oxidation and polymerization-inhibiting polymerizable benzophenone photoinitiator and its preparation method and application

Country Status (1)

Country Link
CN (1) CN119192004A (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103524320A (en) * 2013-09-11 2014-01-22 西安交通大学 Substituted benzophenone and preparation method thereof
CN109280002A (en) * 2017-07-20 2019-01-29 北京化工大学常州先进材料研究院 A kind of benzophenone derivative photoinitiator and preparation method thereof
JP2022145340A (en) * 2021-03-20 2022-10-04 川崎化成工業株式会社 Radical photopolymerizable composition

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103524320A (en) * 2013-09-11 2014-01-22 西安交通大学 Substituted benzophenone and preparation method thereof
CN109280002A (en) * 2017-07-20 2019-01-29 北京化工大学常州先进材料研究院 A kind of benzophenone derivative photoinitiator and preparation method thereof
JP2022145340A (en) * 2021-03-20 2022-10-04 川崎化成工業株式会社 Radical photopolymerizable composition

Similar Documents

Publication Publication Date Title
CA1306998C (en) Propiophenone derivatives as photoinitiators for photopolymerisation
CN105001081B (en) A kind of anthracene system sensitizer and its application in UV LED light curing system
Wang et al. Novel one-component polymeric benzophenone photoinitiator containing poly (ethylene glycol) as hydrogen donor
CN105037587A (en) Sensitizer applicable to UV-LED photocuring system
CN112824432B (en) Polymerizable fluorene photoinitiator, photocurable composition containing same and application thereof
Corcione et al. UV-curable epoxy systems containing hyperbranched polymers: Kinetics investigation by photo-DSC and real-time FT-IR experiments
Chen et al. Synthesis and preliminary photopolymerization envaluation of photopolymerizalbe type II photoinitiators BRA and TXRA
CN108440688A (en) Application of a kind of curcumin derivate in visible-light curing field
CN109942475B (en) Single-component long-wavelength photoinitiator containing pyrrole derivatives and preparation method thereof
EP0242330B1 (en) Liquid blend of photoinitiators
CN117683014A (en) Chalcone structure-containing thioxanthone photoinitiator and its preparation and application
CN110387000A (en) Benzophenone derivative photoinitiator and preparation method
US6287749B1 (en) Biradical photoinitiators and photopolymerizable compositions
Chen et al. Synthesis and preliminary photopolymerization evaluation of novel photoinitiators containing phototrigger to overcome oxygen inhibition in the UV-curing system
US20230365756A1 (en) Polyfunctionalized macromolecular photoinitiator containing alpha-aminoketone, and preparation and application thereof
CN119192004A (en) An anti-oxidation and polymerization-inhibiting polymerizable benzophenone photoinitiator and its preparation method and application
Shen et al. Synthesis and photolytic properties of 1, 5-di-N, N′-dialkylaminoanthraquinones containing acryloyl groups
CN112079813B (en) UV LED photoinitiator and preparation method thereof
Matsushima et al. Non-extractable photoinitiators based on thiol-functionalized benzophenones and thioxanthones
Xiao et al. Synthesis and characterization of 4, 4′-diacryloyloxybenzophenone
CN117342977B (en) Ketoxime ester photoinitiating compound with allyloxy double bond introduced at ortho-position of carbonyl, and preparation method and application thereof
Ye et al. Low VOC bifunctional photoinitiator based on α-hydroxyalkylphenone structure
Xiao et al. Synthesis and photopolymerization kinetics of polymeric one‐component type II photoinitiator containing benzophenone moiety and tertiary amine
CN107129458A (en) Carbazole oxime ester compound and its synthetic method and application
CN110590824B (en) Thioxanthone organic zirconium complex photoinitiator and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination