CN110078761B - Acyl phosphine oxide-stilbene sulfonium salt compound and preparation method and application thereof - Google Patents

Acyl phosphine oxide-stilbene sulfonium salt compound and preparation method and application thereof Download PDF

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CN110078761B
CN110078761B CN201910361475.6A CN201910361475A CN110078761B CN 110078761 B CN110078761 B CN 110078761B CN 201910361475 A CN201910361475 A CN 201910361475A CN 110078761 B CN110078761 B CN 110078761B
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sulfonium salt
stilbene
phosphine oxide
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金明
万德成
潘海燕
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Abstract

The invention provides an acyl phosphine oxide-stilbene sulfonium salt compound, a preparation method and application thereof, wherein R in the sulfonium salt compound0Selected from hydrogen, halogen atoms, R, OR, SOR, SO2R and CH2OR, R is selected from C1‑C24Straight chain alkyl, C1‑C24Branched alkyl and-C6‑C12Aryl radical, R1Is selected from C1‑C8Alkyl radical, C6‑C20Aryl and C1‑C4More than one of alkoxy, R2And R3Are respectively selected from alkyl, aryl and alkoxy, n is an integer from 0 to 4, X‑Selected from BF4 ‑、PF6 ‑、SbF6 ‑Or B (F)5‑Ph)4 ‑(ii) a According to the invention, the function of the free radical-cation hybrid photopolymerization initiator is realized by introducing the distyryl sulfonium salt group into the acyl phosphine oxide type free radical photoinitiator, so that the ultraviolet-visible light curing photoinitiator has a wide application prospect in the field of ultraviolet-visible light curing.

Description

Acyl phosphine oxide-stilbene sulfonium salt compound and preparation method and application thereof
Technical Field
The invention belongs to the technical field of novel organic chemicals, and particularly relates to a novel free radical-cation hybrid photopolymerization initiator, and more particularly relates to an acyl phosphine oxide-stilbene sulfonium salt compound and a preparation method and application thereof.
Background
Photopolymerization initiator compounds are an important class of fine organic chemical materials, which can be decomposed to generate active species under the excitation of light so as to initiate the polymerization of corresponding monomers. Generally, the compounds can be divided into radical type initiators and cationic type initiators, and the compounds generate radical or cationic active species under the irradiation condition of ultraviolet light or visible light, are key species for inducing unsaturated systems containing alkene or epoxy to carry out high-efficiency photopolymerization, and are one of important radiation curing formula components.
Among the numerous photoinitiator products that have been commercially used, acylphosphine oxide photoinitiators are highlighted, and representative products thereof, such as TPO, TPO-L, etc. (molecular structures shown below), have good light absorption properties in the near ultraviolet and visible light regions and high photodecomposition speed, and are a type of radical photoinitiators widely used in the fields of coatings, inks, etc.
The cationic photoinitiator with obvious absorption in the near ultraviolet-visible light region has a large class of sulfonium salt, and can generate strong protonic acid under illumination by cooperating with non-electrophilic anions thereof, so that the cationic photoinitiator can efficiently initiate cationic polymerization of epoxy and vinyl ether compounds. For example, Chemistry of materials, 2012,24, 237-. Meanwhile, anions of the sulfonium salt can be used for preparing different series, such as hexafluoroantimonate and the like, through simple salt exchange reaction, and higher initiation activity is shown:
Figure BDA0002046976880000021
on the other hand, the Light-curing Light source usually uses mercury lamp, mercury vapor is not in line with the new strategic trend of the development of the world energy-saving and environment-friendly industry, so that in recent years, the LED (Light-Emitting Diode) Light source obtains increasingly wide attention and rapid development, and the application of the LED Light-curing technology greatly reduces the energy consumption and ozone generation, and the industry continues to grow strongly. For curing of LED systems, a photoinitiator with sensitive absorption for the long-wave emission wavelength of the LED (365-. Therefore, designing, developing, and industrialization of novel photoinitiator compounds is a critical technical challenge facing the current field.
However, in radical polymerization, especially in the form of a film, oxygen in the air is liable to act on radicals generated by photoexcitation, and peroxy radicals with low initiation activity are generated, so that oxygen resistance is a very important technical problem in radical polymerization; in cationic polymerization, the monomer generally has a relatively slow initiation rate, and generally requires heating, so that the rate of cationic photoinitiated polymerization can be effectively increased. If the free radical polymerization and the cationic polymerization occur together, hybrid polymerization can be realized to form an interpenetrating polymer network of the free radical polymerization and the cationic polymerization, a large amount of heat generated by the free radical polymerization can improve the speed of the cationic polymerization, and the cationic polymerization can also play a role in resisting oxygen.
In view of the above technical challenges, it is necessary to invent a class of hybrid photoinitiators sensitive to LED light sources and having dual radical/cation initiation capability. In addition, the synthesis steps of the initiator have the advantages of simplicity, low cost, environment-friendly synthesis process, less three wastes and the like. The hybrid photoinitiator can be effectively compatible with free radical and cation curing resin and compounded to form photocuring ink or paint with stable storage, and has profound influence on the fields of woodware green coating, environment-friendly printing, ink-jet printing, 3D printing, energy-saving materials and the like.
Disclosure of Invention
Aiming at the defects in the prior art, the primary object of the invention is to provide a compound containing acylphosphine oxide-stilbene sulfonium salt.
The second purpose of the invention is to provide a preparation method of the acyl phosphine oxide-stilbene sulfonium salt compound.
The third purpose of the invention is to provide the application of the acyl phosphine oxide-stilbene sulfonium salt-containing compound.
In order to achieve the above purpose, the solution of the invention is as follows:
the acyl phosphine oxide-stilbene sulfonium salt-containing compound has the following general formula:
Figure BDA0002046976880000031
wherein R is0Selected from hydrogen, halogen atoms, R, OR, SOR, SO2R and CH2OR is one OR more of.
R is selected from C1-C24Straight chain alkyl, C1-C24Branched alkyl and-C6-C12More than one aryl group.
R1Is selected from C1-C8Alkyl radical, C6-C20Aryl and C1-C4One or more alkoxy groups.
R2And R3Are respectively selected from more than one of alkyl, aryl and alkoxy.
n is an integer of 0 to 4, X-Selected from non-electrophilic anions.
Preferably, X-Selected from BF4 -、PF6 -、SbF6 -Or B (F)5-Ph)4 -。
The preparation method of the compound containing the acyl phosphine oxide-stilbene sulfonium salt comprises the following steps:
(1) reacting acyl phosphine oxide compounds, zinc dibromide and bromodimethyl ether in dried dichloromethane at 10-25 ℃ for 6h, after TLC monitoring reaction is finished, hydrolyzing, washing, drying with anhydrous sodium sulfate, and performing silica gel column chromatography (ethyl acetate/cyclohexane) to obtain a bromomethylation intermediate:
Figure BDA0002046976880000032
(2) bromomethylation intermediate (1 equivalent of bromomethyl), R0Dissolving substituted distyryl methyl sulfide (1 equivalent) in anhydrous dichloromethane, adding AgX (1 equivalent), reacting for 1-3 days at 25 ℃, centrifuging or filtering precipitated AgBr with diatomite, washing with dichloromethane, evaporating to dryness, adding n-hexane to form crystals, and performing suction filtration and drying to obtain a product with anion X, namely the product containing acyl phosphine oxide-distyryl sulfonium salt compound:
Figure BDA0002046976880000033
preferably, R0Selected from hydrogen, halogen atoms, R, OR, SOR, SO2R and CH2OR is one OR more of.
R is selected from C1-C24Straight chain alkyl, C1-C24Branched alkyl and-C6-C12More than one aryl group.
R1Is selected from C1-C8Alkyl radical, C6-C20Aryl and C1-C4One or more alkoxy groups.
R2And R3Are respectively selected from more than one of alkyl, aryl and alkoxy.
n is an integer of 0 to 4, X-Selected from non-electrophilic anions.
Preferably, X-Selected from BF4 -、PF6 -、SbF6 -Or B (F)5-Ph)4 -。
Preferably, in the step (1), the molar ratio of the acylphosphine oxide compound, the zinc dibromide and the bromodimethyl ether is 1: (1.5-2): (1.2-1.5).
Preferably, in the step (1), the catalyst is selected from more than one of zinc dibromide, anhydrous aluminum trichloride and anhydrous zinc chloride.
Preferably, in step (2), R0Position of substitution of methyl sulfide in substituted distyrylmethylthiol sulfideEither para or meta to the stilbene group.
Preferably, in step (2), AgX is selected from one or more of silver trifluoromethanesulfonate, silver tetrafluoroborate, silver hexafluorophosphate, silver hexafluoroantimonate and silver tetrakis (pentafluorophenyl) borate.
The preparation method of the compound containing the acyl phosphine oxide-stilbene sulfonium salt comprises the following steps:
(1) reacting acyl phosphine oxide compounds, anhydrous aluminum trichloride and paraformaldehyde in dried dichloromethane at 50-70 ℃, after TLC monitoring reaction, hydrolyzing, washing, drying with anhydrous sodium sulfate, and performing silica gel column chromatography (ethyl acetate/cyclohexane) to obtain a chloromethylated intermediate:
Figure BDA0002046976880000041
(2) chloromethylated intermediate (1 equivalent chloromethyl), R0Dissolving substituted distyryl methyl sulfide (1 equivalent) in anhydrous dichloromethane, adding AgX (1 equivalent), reacting for 1-3 days at 25 ℃, centrifuging or filtering precipitated AgBr with diatomite, washing with dichloromethane, evaporating to dryness, adding n-hexane to form crystals, and performing suction filtration and drying to obtain a product with anion X, namely the product containing acyl phosphine oxide-distyryl sulfonium salt compound:
Figure BDA0002046976880000042
preferably, R0Selected from hydrogen, halogen atoms, R, OR, SOR, SO2R and CH2OR is one OR more of.
R is selected from C1-C24Straight chain alkyl, C1-C24Branched alkyl and-C6-C12More than one aryl group.
R1Is selected from C1-C8Alkyl radical, C6-C20Aryl and C1-C4Alkoxy radicalMore than one of them.
R2And R3Are respectively selected from more than one of alkyl, aryl and alkoxy.
n is an integer of 0 to 4, X-Selected from non-electrophilic anions.
Preferably, X-Selected from BF4 -、PF6 -、SbF6 -Or B (F)5-Ph)4 -。
Preferably, in the step (1), the catalyst is selected from more than one of zinc dibromide, anhydrous aluminum trichloride and anhydrous zinc chloride.
Preferably, in step (2), R0The substituted position of the methyl sulfide in the substituted distyryl methyl sulfide can be para position of the distyryl group, and can also be meta position of the distyryl group.
Preferably, in step (2), AgX is selected from one or more of silver trifluoromethanesulfonate, silver tetrafluoroborate, silver hexafluorophosphate, silver hexafluoroantimonate and silver tetrakis (pentafluorophenyl) borate.
In step (2), the preparation of acylphosphine oxide-stilbene sulfonium salt-containing compounds can also be carried out in two steps, and the corresponding X is prepared by first reacting with silver trifluoromethanesulfonate-A sulfonium salt which is a trifluoromethanesulfonate; secondly, the non-electrophilic anion alkali metal salt with larger volume is used for carrying out ion exchange reaction to prepare the non-electrophilic anion alkali metal salt with different X-Target molecular structure of anion, wherein in MX, M can be potassium ion or sodium ion, and X-Represents the corresponding anion of the respective class, e.g. BF4 -、PF6 -、SbF6 -Or B (F)5-Ph)4 -And the like, but are not limited to these salts; the specific reaction process is as follows: and c, adding the product (1 equivalent) of the trifluoromethane sulfonate in the step b and MX to be subjected to salt exchange into the solvent or the mixed solvent, stirring for 2-6h at room temperature, repeating for three times, concentrating, grinding the residue by using n-hexane or a chloroform/n-hexane mixed solvent, and performing suction filtration and drying to prepare the corresponding product.
The solvent used in the salt exchange is various water-miscible organic solvents, such as acetone, acetonitrile, tetrahydrofuran, Dimethylformamide (DMF), and Dimethylsulfoxide (DMSO), and mixed solvents of these solvents and water, but is not limited thereto.
The application of the compound containing acyl phosphine oxide-stilbene sulfonium salt as a radiation curing photoinitiator. In particular to the application of the cationic hybrid polymerization system initiator containing epoxy and vinyl ether and free radical photopolymerization containing unsaturated double bonds.
Preferably, the light source of the radiation curing photoinitiator is selected from one or more of ultraviolet light and visible light.
Preferably, the light source of the radiation curing photoinitiator is selected from one or more of a mercury lamp, an LED light source, and an LDI light source, which can emit ultraviolet light, visible light.
Preferably, the radiation curing photoinitiator includes 0.01 to 30 parts by weight of the acylphosphine oxide-stilbene sulfonium salt-containing compound and 100 parts by weight of the ethylenic bond (C ═ C) containing unsaturated compound.
Preferably, the radiation curing photoinitiator includes 0.5 to 10 parts by weight of the acylphosphine oxide-stilbene sulfonium salt-containing compound and 100 parts by weight of the ethylenic bond (C ═ C) containing unsaturated compound.
Preferably, ethylenically unsaturated compound means a compound or mixture in which the ethylenic bonds are cross-linked by free radical polymerization.
Preferably, the ethylenically unsaturated compound is selected from the group consisting of monomers, oligomers and prepolymers, or mixtures or copolymers of the three, or aqueous dispersions of the three.
Exemplary compounds conforming to the structure of formula (I) are listed below:
Figure BDA0002046976880000061
wherein, X-Selected from CF3SO3 -、BF4 -、PF6 -、SbF6 -And the like.
Due to the adoption of the scheme, the invention has the beneficial effects that:
compared with the existing physical mixing method of the free radical type initiator and the cationic initiator, the acyl phosphine oxide-stilbene sulfonium salt-containing compound disclosed by the invention combines the free radical type initiator and the cationic initiator together in a chemical linking mode, has good comprehensive performance, is high in initiation efficiency of the acyl phosphine oxide free radical type photoinitiator, and can accelerate the initiation of cationic polymerization reaction by heating a polymerization system through reaction heat and light source heat in the polymerization process, so that double polymerization is realized; in addition, the molecular structure synthesis methods are simple, the steps are few, the three wastes are low, and the purification is convenient; the absorption spectrum of the UV curing light source has better overlapping with the emission spectrum of cheap light sources such as LEDs, and is consistent with the development direction of the UV curing technology.
Secondly, the function of the free radical-cation hybrid photopolymerization initiator is realized by introducing a distyryl sulfonium salt group into the acyl phosphine oxide type free radical photoinitiator, and particularly, the free radical-cation hybrid photocuring is realized under the excitation of an LED, so that the ultraviolet-visible light curing ultraviolet-ultraviolet hybrid photopolymerization initiator has wide application prospects in the field of ultraviolet-visible light curing.
Drawings
FIG. 1 shows the general structural formula of the acyl phosphine oxide-stilbene sulfonium salt-containing compound of the invention.
Detailed Description
As shown in figure 1, the invention provides an acyl phosphine oxide-stilbene sulfonium salt compound, a preparation method and application thereof.
The present invention will be further described with reference to the following examples.
Example 1: the preparation process of the intermediate substituted distyryl methyl thioether comprises the following steps:
Figure BDA0002046976880000071
R0substituted styrene (10mmol), 3-bromothioanisole or 4-bromothioanisoleAdding (10mmol), tetrakis (triphenylphosphine) palladium dichloride (0.1mmol) and potassium carbonate (10mmol) into 50mL of DMF solution, placing the mixture in an oil bath at 100 ℃ under the protection of nitrogen, stirring for reaction for 10 hours, decompressing and concentrating to recover the solvent, adding 100mL of deionized water, filtering to separate out a precipitate, dissolving the precipitate in 50mL of dichloromethane, recovering the catalyst through a short silica gel column, evaporating the filtrate to dryness, and recrystallizing with absolute ethyl alcohol to prepare a product which is white powder.
4-ethoxy-4' -methylthiostilbene, 1a, yield 92%. HR-MS (C)17H18OS): 270.1078 for m/e; the experimental results are as follows: 271.1156(M + H)+)。
4-ethoxy-3' -methylthiostilbene, 1b, yield 89%. HR-MS (C)17H18OS): 270.1078 for m/e; the experimental results are as follows: 271.1156(M + H)+)。
4-methylthiostilbene, 1c, yield 90%. HR-MS (C)15H14S): 226.0816 for m/e; the experimental results are as follows: 227.0895(M + H)+)。
3-methylthiostilbene, 1d, yield 88%. HR-MS (C)15H14S): 226.0816 for m/e; the experimental results are as follows: 227.0894(M + H)+)。
4-chloro-4' -methylthiostilbene, 1e, yield 94%. HR-MS (C)15H13ClS): 260.0426 for m/e; the experimental results are as follows: 261.0503(M + H)+)。
4-chloro-3' -methylthiostilbene, 1f, yield 92%. HR-MS (C)15H13ClS): 260.0426 for m/e; the experimental results are as follows: 261.0504(M + H)+)。
Example 2: the preparation process of the intermediate bromomethylated acylphosphine oxide comprises the following steps:
Figure BDA0002046976880000072
dissolving 2,4,6-trimethylbenzoyl diphenyl phosphine oxide (2,4,6-trimethylbenzoyl diphenyl phosphine oxide, TPO) (or TPO-L) (0.1mol) in 100mL of anhydrous dichloromethane, adding anhydrous zinc dibromide (0.15mol) in batches, dropwise adding a dichloromethane solution (0.12mol) of bromodimethyl ether at 10 ℃ under stirring, stirring at normal temperature for 0.5h after dropwise addition is finished, reacting for 6h, monitoring the reaction by a point plate, slowly adding ice water equivalent to a solvent in volume, washing an organic layer with deionized water, drying the anhydrous sodium sulfate, and carrying out ethyl acetate/cyclohexane silica gel column chromatography on the product to prepare the product.
TPO-Br, yield 87%, light yellow solid. HR-MS (C)23H22BrO2P): 440.0541 for m/e; the experimental results are as follows: 441.0615(M + H)+)。
TPO-L-Br, 82% yield, light yellow liquid. HR-MS (C)19H22BrO3P): 408.0490 for m/e; the experimental results are as follows: 409.0565(M + H)+)。
Example 3: the preparation process of the intermediate chloromethylated acylphosphine oxide comprises the following steps:
Figure BDA0002046976880000081
dissolving 2,4,6-trimethylbenzoyl diphenyl phosphine oxide (2,4,6-trimethylbenzoyl diphenyl phosphine oxide, TPO) (0.1mol) in 100mL of anhydrous dichloromethane, adding anhydrous aluminum trichloride (0.15mol) and paraformaldehyde (0.12mol) in batches, stirring at normal temperature for 10min, heating to reflux, reacting for 10h, monitoring reaction by using a dot plate, slowly adding the reaction product into ice water with the same volume as a solvent, washing an organic layer by using deionized water, drying anhydrous sodium sulfate, and separating the product by using ethyl acetate/cyclohexane silica gel column chromatography to obtain RfThe product with smaller value is intermediate TPO-Cl, i.e. chloromethylated product, yield 37%, light yellow solid. (C)23H22ClO2P): 396.1046, respectively; the experimental results are as follows: 397.1126(M + H)+)。
Example 4: preparation of acylphosphine oxide-stilbene sulfonium salt-containing compounds (1) to (12) (X ═ CF)3SO3) The process is as follows:
taking the reaction of the intermediate 1a and TPO-Br or TPO-Cl as an example: 1a (10mmol) and silver trifluoromethanesulfonate (10mmol) are placed in a dry flask and the appropriate amount of water is added by syringe under nitrogen protectionAdding dichloromethane into TPO-Br (or TPO-Cl) (10mmol) solution under stirring, stirring at room temperature for 1 day, monitoring by TLC that the raw material has disappeared, filtering out AgBr (or AgCl) separated out with diatomite, washing with dichloromethane, evaporating, adding n-hexane to form crystal, vacuum filtering, and oven drying to obtain CF anion3SO3 -The product of (1).
1-CF3SO3The yield was 93%. HR-MS (C)40H40O3PS+): 631.2436 for m/e; the experimental results are as follows: 631.2435.
2-CF3SO3to 12-CF3SO3The thioethers of example 1 and bromomethylated acylphosphine oxides of example 2 were reacted with silver trifluoromethanesulfonate in the same manner as described above to prepare the sulfonium salts of the desired products.
2-CF3SO3The yield was 92%. HR-MS (C)38H36O2PS+): 587.2174 for m/e; the experimental results are as follows: 587.2173.
3-CF3SO3the yield was 91%. HR-MS (C)38H35ClO2PS+): 621.1784 for m/e; the experimental results are as follows: 621.1782.
4-CF3SO3the yield was 90%. HR-MS (C)40H40O3PS+): 631.2436 for m/e; the experimental results are as follows: 631.2434.
5-CF3SO3the yield was 92%. HR-MS (C)38H36O2PS+): 587.2174 for m/e; the experimental results are as follows: 587.2173.
6-CF3SO3the yield was 92%. HR-MS (C)38H35ClO2PS+): 621.1784 for m/e; the experimental results are as follows: 621.1782.
7-CF3SO3the yield was 93%. HR-MS (C)36H40O4PS+): 599.2385 for m/e; the experimental results are as follows: 599.2384.
8-CF3SO3the yield was 89%. HR-MS (C)34H36O3PS+): 555.2123 for m/e; the experimental results are as follows: 555.2122.
9-CF3SO3the yield was 90%. HR-MS (C)34H35ClO3PS+): 589.1733 for m/e; the experimental results are as follows: 589.1732.
10-CF3SO3the yield was 88%. HR-MS (C)36H40O4PS+): 599.2385 for m/e; the experimental results are as follows: 599.2383.
11-CF3SO3the yield was 87%. HR-MS (C)34H36O3PS+): 555.2123 for m/e; the experimental results are as follows: 555.2122.
12-CF3SO3the yield was 89%. HR-MS (C)34H35ClO3PS+): 589.1733 for m/e; the experimental results are as follows: 589.1733.
example 5: preparation process of photoinitiator with different anions:
there are two methods for introducing different anions into the final target product, the first method is the same as in example 3 except that silver trifluoromethanesulfonate is replaced with corresponding other silver salts, such as silver tetrafluoroborate, silver hexafluorophosphate, silver hexafluoroantimonate, and the rest of the steps are the same. The second method is a salt exchange method with 1-PF6For illustration purposes:
1-CF3SO3dissolving (0.03mol) in 20mL of acetone, dissolving potassium hexafluorophosphate (0.03mol) in 25mL of water, dropwise adding the acetone solution into the salt solution, stirring for 2h at room temperature, filtering to obtain a precipitated solid, dissolving the solid in acetone again, dropwise adding the solid into the potassium hexafluorophosphate solution again, repeating the process for three times, filtering to obtain yellow powder, and vacuum drying to obtain the target product 1-PF6. The yield was 88%.
The remaining sulfonium salts with various anions can be prepared in the same manner with yields of between 83 and 89%. The anion does not influence the molecular weight of the sulfonium salt group test, and the molecular ion peak is consistent with that of the trifluoromethane sulfonate, so the description is omitted.
< experiment >
The following experiments were carried out with the products of the above examples, respectively.
< experiment 1>
Film polymerization reaction:
the photothermal dual cure test samples were formulated according to the following weight percentages: epoxy acrylate: 14 parts of (1); polyester acrylate: 16 parts of a mixture; hexanediol diacrylate: 3 parts of a mixture; pentaerythritol triacrylate: 12 parts of (1); diol or branched polyol having a molecular weight of about 400: 12 parts of (1); difunctional epoxycyclohexane EPOX: 23 parts; titanium dioxide dye: 16 parts of a mixture; acylphosphine oxide substituted sulfonium salts of selected examples: 4 parts.
A part of the mixture was sufficiently and uniformly ground and then coated on a white ABS substrate, and an image layer of about 20 μm was formed under air. Irradiation was carried out at a distance of 2cm from the sample using 365nm and 385nm LED curing testers (in Guangzhou, same as light), and the conveyor speed was 20 m/min. And judging the complete curing condition of the coating by finger-pressing and scraping. The hexafluorophosphate, hexafluoroantimonate and tetrakis (pentafluorophenyl) borate of the compounds 1-5 of the above examples all initiated complete curing of the film layer, showing good photoinitiation performance. And the heat of reaction effectively promotes cationic curing.
< experiment 2>
Thick film polymerization:
the formulation was the same as in experiment 1.
A part of the above mixture was sufficiently ground and coated on a white ABS substrate, and a pattern layer of about 200 μm was formed under air. Irradiation was carried out at a distance of 2cm from the sample using 365nm and 385nm LED curing testers (in Guangzhou, same as light), with a conveyor speed of 10 m/min. And judging the complete curing condition of the coating by pressing and scraping. The hexafluorophosphate, hexafluoroantimonate and tetrakis (pentafluorophenyl) borate initiation film layers in the compounds 1-5 of the above examples were completely cured, and showed good dual initiation of both free radicals and cations.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments and the generic principles defined herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments. Those skilled in the art should appreciate that many modifications and variations are possible in light of the above teaching without departing from the scope of the invention.

Claims (8)

1. The acyl phosphine oxide-stilbene sulfonium salt compound is characterized in that: the general formula is as follows:
Figure FDA0002965524620000011
wherein R is0Selected from hydrogen, halogen atoms, R, OR, SOR, SO2R and CH2OR is one OR more of;
r is selected from C1-C24Straight chain alkyl, C1-C24Branched alkyl and-C6-C12One or more aryl groups;
R1is selected from C1-C8Alkyl radical, C6-C20Aryl and C1-C4One or more of alkoxy groups;
R2and R3Respectively selected from more than one of alkyl, aryl and alkoxy;
n is an integer of 0 to 4, X-Selected from non-electrophilic anions.
2. The acylphosphine oxide-stilbene sulfonium salt-containing compound of claim 1, wherein: x-Selected from BF4 -、PF6 -、SbF6 -Or B (F)5-Ph)4 -。
3. A method for preparing acylphosphine oxide-stilbene sulfonium salt-containing compounds according to claim 1, wherein the method comprises the following steps: which comprises the following steps:
(1) reacting acyl phosphine oxide compounds in the following reaction formula with bromodimethyl ether in a first solvent dichloromethane under the action of a catalyst zinc dibromide in the following reaction formula to obtain a bromomethylation intermediate:
Figure FDA0002965524620000012
(2) bromomethylated intermediates in the following reaction scheme, R0Substituted distyrylmethylthioethers with AgX or bromomethylated intermediates, R0Substituted distyrylmethylthioether and AgCF3SO3Reaction with MX, AgX-Selected from BF4Ag、PF6Ag、SbF6Ag or B (F)5-Ph)4Ag to obtain the compound containing acyl phosphine oxide-stilbene sulfonium salt:
Figure FDA0002965524620000013
R0selected from hydrogen, halogen atoms, R, OR, SOR, SO2R and CH2OR is one OR more of;
r is selected from C1-C24Straight chain alkyl, C1-C24Branched alkyl and-C6-C12One or more aryl groups;
R1is selected from C1-C8Alkyl radical, C6-C20Aryl and C1-C4One or more of alkoxy groups;
R2and R3Respectively selected from more than one of alkyl, aryl and alkoxy;
n is an integer selected from 0 to 4;
m is selected from one of potassium ions and sodium ions; x-Selected from BF4 -、PF6 -、SbF6 -Or B (F)5-Ph)4 -。
4. Use of the acylphosphine oxide-stilbene sulfonium salt-containing compound as defined in claim 1 as a radiation-curing photoinitiator.
5. Use according to claim 4, characterized in that: the light source of the radiation curing photoinitiator is selected from more than one of ultraviolet light and visible light.
6. Use according to claim 5, characterized in that:
the radiation curing photoinitiator comprises 0.01-30 parts by weight of compounds containing acyl phosphine oxide-stilbene sulfonium salt and 100 parts by weight of compounds containing ethylenic bond unsaturation.
7. Use according to claim 6, characterized in that:
the radiation curing photoinitiator comprises 0.5-10 parts by weight of compounds containing acylphosphine oxide-stilbene sulfonium salt and 100 parts by weight of compounds containing ethylenic bond unsaturation.
8. Use according to claim 6 or 7, characterized in that: the ethylenic unsaturated compound refers to a compound or a mixture in which ethylenic bonds are crosslinked by radical polymerization;
the ethylenically unsaturated compound is selected from a monomer, an oligomer or a prepolymer, or a mixture or a copolymer of the three, or an aqueous dispersion of the three.
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