CN118146405A - Photoinitiator and preparation method thereof - Google Patents

Photoinitiator and preparation method thereof Download PDF

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Publication number
CN118146405A
CN118146405A CN202211511743.6A CN202211511743A CN118146405A CN 118146405 A CN118146405 A CN 118146405A CN 202211511743 A CN202211511743 A CN 202211511743A CN 118146405 A CN118146405 A CN 118146405A
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group
photoinitiator
compound
reaction
branched alkyl
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钱彬
周晓龙
张学龙
王孟雪
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Changzhou Qiangli Photoelectric Material Co ltd
Changzhou Tronly New Electronic Materials Co Ltd
Changzhou Tronly Advanced Electronic Materials Co Ltd
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Changzhou Qiangli Photoelectric Material Co ltd
Changzhou Tronly New Electronic Materials Co Ltd
Changzhou Tronly Advanced Electronic Materials Co Ltd
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Priority to CN202211511743.6A priority Critical patent/CN118146405A/en
Publication of CN118146405A publication Critical patent/CN118146405A/en
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/06—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having one or two double bonds between ring members or between ring members and non-ring members
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
    • C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
    • C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
    • C07D241/40—Benzopyrazines
    • C07D241/42—Benzopyrazines with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention provides a photoinitiator and a preparation method thereof. The photoinitiator has a structure shown in a formula I, and the preparation raw materials of the photoinitiator comprise a compound A and a compound B. The preparation method comprises the following steps: and (3) reacting the compound A with the compound B in a protective gas atmosphere to obtain the photoinitiator. The photoinitiator provided by the invention has the characteristics of low toxicity, low odor, low yellowing and low migration, and simultaneously has higher curing speed and better solubility.

Description

Photoinitiator and preparation method thereof
Technical Field
The invention belongs to the technical field of photo-curing, and particularly relates to a photoinitiator and a preparation method thereof.
Background
Ultraviolet (UV) curing is a technique for achieving rapid polymerization, cross-linking, curing and shaping using UV-initiated chemically active liquid compositions, which together with Electron Beam (EB) curing are collectively referred to as radiation curing. The photo-curing technology has the characteristics of 5E, namely efficient, enabling, economical, ENERGY SAVING, energy-saving and environmental friendly (environment-friendly). Based on the advantages, the photo-curing technology is widely applied to a plurality of industries such as printing, packaging, building materials, decoration, communication, household appliances, automobiles, aviation, medical treatment and the like. The photo-cured products are mainly in the form of UV ink, UV paint, UV adhesive, photoresist, photo-rapid prototyping material and the like. In daily life, the photo-cured products are visible everywhere.
Photoinitiators (Photoinitiator, PI) are key components in photocurable compositions and can directly affect the cure rate, heat resistance, solvent resistance, toughness, strength, and other properties of the photocurable products. Currently, photoinitiators are mainly uv-photoinitiators, but also include some other classes, such as visible photoinitiators, aqueous photoinitiators, macromolecular photoinitiators, and the like. The ultraviolet light initiator mainly comprises a free radical type photoinitiator and a cationic type photoinitiator, and the ultraviolet light initiator on the market mainly comprises a free radical type photoinitiator. The radical Type photoinitiators are largely classified into two main types, namely, norrish Type I (cleavage Type) and Norrish Type II (hydrogen abstraction Type), according to the mechanism of radical generation. The cleavage type photoinitiator mainly comprises benzoin and derivatives thereof, benzil and derivatives thereof, acetophenone and derivatives thereof, alpha-hydroxyketone, alpha-aminoketone, benzoyl formate compounds, acyl phosphine oxide, sulfur-containing photoinitiator, oxime lipid photoinitiator and the like. The hydrogen abstraction type photoinitiator mainly comprises benzophenone and derivatives thereof, thioxanthone and derivatives thereof, anthraquinone type photoinitiator and the like, does not generate free radicals, and is used together with a hydrogen donor, wherein the hydrogen donor mainly comprises tertiary amine compounds, mercapto compounds and the like.
The photoinitiator is compounded with raw materials such as reactive diluents, prepolymers, auxiliary agents or additives to form a formula product, and the formula product is applied to the production and manufacturing process of a terminal product. The photoinitiator is not used in a large amount in the formula, but plays a critical role in the production of the photo-curing material, the use amount of the photoinitiator is about 1% -5% of the total mass of the photo-curing material, and the cost is about 10% -15%. Along with the gradual change of a photocuring light source from a mercury lamp with large pollution and high energy consumption into an LED light source with more environmental protection and high efficiency, and the increasingly stringent laws and regulations of the industries such as printing ink, coating and the like, higher requirements are put forward on the performance of a photoinitiator. The ideal properties of the photoinitiator include higher absorbance and photon utilization efficiency in the light source emission spectrum region, higher solubility, high reactivity, low odor and low toxicity in the formulation, low mobility, low yellowing in the cured coating, good storage stability and the like. Based on the above requirements, various disadvantages exist more or less in the photoinitiators commercialized at present, and the development and application of novel photoinitiators with low odor, low migration, low yellowing and high sensitivity are the development trend in the field of photocuring coatings at present, and also accord with the environmental protection concepts of green photocuring and sustainable development of economic environment.
CN108948232A discloses a photoinitiator mixture APi-184S. The photoinitiator mixture APi-184S comprises a photoinitiator APi-307, a photoinitiator Darocur 1173 and other photoinitiators, a reactive amine co-initiator, an ethylenically unsaturated compound containing monomer or an ethylenically unsaturated compound containing resin. Although the initiator maintains or even improves the original excellent performance of the Irgacure 184, and eliminates or reduces the original outstanding bad performance of the Irgacure 184, small molecular fragments generated by 1173 photolysis have strong mobility and volatility due to the low molecular weight, so that the application of the initiator in packaging materials, particularly food packaging materials, is greatly limited.
Therefore, how to provide a photoinitiator with low toxicity, low odor, low yellowing, low migration, fast curing speed and good solubility has become a technical problem to be solved at present.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a photoinitiator and a preparation method thereof. The photoinitiator has the characteristics of low toxicity, low odor, low yellowing and low migration, and has high curing speed and high solubility through the structural design of the photoinitiator.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a photoinitiator having a structure according to formula I:
Wherein R 1、R2 each independently represents a hydrogen atom, a C1-C18 straight or branched alkyl group, a C3-C10 cycloalkyl group, a C4-C12 alkylcycloalkyl group, a substituted or unsubstituted C6-C20 aryl group, R 1、R2 may be linked to form a ring;
R 3 represents any one of a hydrogen atom, a C1-C18 straight-chain or branched alkyl group, a C3-C10 cycloalkyl group, a C4-C12 alkylcycloalkyl group, a C1-C10 alkoxy group, a C2-C18 alkenyl group, a C1-C8 thioalkyl group, wherein a single carbon-carbon bond (C-C) in the C1-C18 straight-chain or branched alkyl group may be replaced by an ether bond (C-O-C);
R 4 represents any one of a hydrogen atom, a halogen atom, a nitro group, a cyano group, an ester group, a hydroxyl group, a C1-C18 straight-chain or branched alkyl group, a C3-C10 cycloalkyl group, a C4-C12 alkylcycloalkyl group, a C1-C10 alkoxy group, a C1-C12 thioalkyl group, a C1-C12 haloalkyl group, a C2-C18 alkenyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted heterocyclic group, wherein a single carbon-carbon bond in the C1-C18 straight-chain or branched alkyl group may be replaced with an ether bond;
each of the substituted substituents in R 1、R2、R4 is independently selected from at least one of a halogen atom (including a fluorine atom, a chlorine atom, a bromine atom and an iodine atom), a nitro group, a cyano group, a hydroxyl group, an amino group, a C1-C6 linear or branched alkyl group, a C3-C6 cycloalkyl group, a C1-C6 alkoxy group, a phenyl group;
m, n each independently represent 0, 1 or 2, and p represents 1, 2, 3,4 or 5.
In the invention, the photoinitiator has the characteristics of low yellowing and low migration of the cracking type photoinitiator by designing the structure of the photoinitiator, and simultaneously has low toxicity, high curing speed and high solubility.
If the single carbon-carbon bond (C-C) in the C1-C18 linear or branched alkyl group is replaced with an ether bond (C-O-C), a linear or branched alkyl group having 1 to 18 carbon atoms interrupted with an oxygen atom is obtained.
In the present invention, C1-C18 may be C1, C2, C4, C6, C8, C10, C12, C14, C16, C18, or the like.
C3-C10 may be C3, C4, C5, C6, C7, C8, C9 or C10.
C4-C12 may be C4, C5, C6, C7, C8, C9, C10, C11 or C12.
C6-C20 may be C6, C8, C10, C12, C15, C18 or C20, etc.
C1-C10 may be C1, C2, C3, C4, C5, C6, C7, C8, C9 or C10.
C2-C18 may be C2, C4, C6, C8, C10, C12, C14, C16 or C18, etc.
C1-C8 may be C1, C2, C3, C4, C5, C6, C7 or C8.
C1-C12 may be C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11 or C12.
C6-C20 may be C3, C5, C8, C10, C12, C15, C18 or C20, etc.
C1-C6 may be C1, C2, C3, C4, C5 or C6.
C3-C6 may be C3, C4, C5 or C6.
The following is a preferred technical scheme of the present invention, but not a limitation of the technical scheme provided by the present invention, and the following preferred technical scheme can better achieve and achieve the objects and advantages of the present invention.
As a preferred embodiment of the present invention, each R 1、R2 independently represents a hydrogen atom, a C1-C12 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, or C12) straight-chain or branched alkyl group, or a substituted or unsubstituted C6-C20 (e.g., C6, C8, C10, C12, C15, C18, or C20, etc.) aryl group.
Preferably, the R 1、R2 is linked in a ring.
Preferably, R 3 represents a hydrogen atom, a C1-C12 (which may be C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11 or C12, for example) linear or branched alkyl, a C3-C6 (which may be C3, C4, C5 or C6, for example) cycloalkyl or a C2-C8 (which may be C2, C3, C4, C5, C6, C7 or C8, for example) alkenyl.
Preferably, R 4 represents any one of a hydrogen atom, a halogen atom, a nitro group, a cyano group, an ester group, a hydroxyl group, a C1-C12 (for example, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11 or C12) straight-chain or branched-chain alkyl group, wherein a carbon-carbon single bond in the C1-C12 straight-chain or branched-chain alkyl group may be replaced by an ether bond.
As a preferable technical scheme of the invention, the preparation raw materials of the photoinitiator comprise a compound A and a compound B;
The compound A is
The compound B is
Wherein R 1-R4, m, n and p have the same protection ranges as described above.
In a preferred embodiment of the present invention, the molar ratio of the compound a to the compound B is 1 (2 to 10), and may be, for example, 1:2, 1:2.5, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, or 1:10, etc., preferably 1 (2 to 6), and more preferably 1 (2 to 3).
Preferably, the compound B is selected from any one of the following compounds:
as a preferred technical scheme of the invention, the compound A is prepared by adopting the following method, and the method comprises the following steps:
(1) The amine compound reacts with 4,4' -dimethylbenzoyl to obtain an intermediate product 1;
(2) Uniformly mixing the intermediate product with an organic solvent B, adding an oxidant into the mixture, and reacting to obtain a compound A;
The amine compound is
Wherein R 1、R2, m and n have the same protection scope as described above.
As a preferred technical scheme of the invention, the amine compound is selected from any one of the following compounds:
Preferably, the molar ratio of the amine compound to 4,4' -dimethylbenzoyl is 1 (1-2), for example, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9 or 1:2, etc., preferably 1 (1-1.5), further preferably 1 (1-1.2).
The reaction in step (1) is preferably carried out at a temperature of 20 to 140℃and may be carried out at 20℃30℃40℃50℃60℃70℃80℃90℃100℃110℃120℃130℃140℃or 140℃and more preferably 30 to 120℃40 to 100 ℃.
Preferably, the reaction time in the step (1) is 6 to 8 hours, for example, 6 hours, 6.5 hours, 7 hours, 7.5 hours or 8 hours, etc.
Preferably, the reaction of step (1) is in the presence of an inert gas comprising nitrogen, argon.
Preferably, the reaction of step (1) is carried out in the presence of an organic solvent a.
In the present invention, the specific choice of the organic solvent a is not particularly limited, and organic solvents commonly used in the art are suitable, and exemplary include, but are not limited to: any one or a combination of at least two of methanol, ethanol, N-propanol, isopropanol, N-butanol, isobutanol, tertiary butanol, ethylene glycol, glycerol, acetone, butanone, pyridine, N-dimethylformamide, tetrahydrofuran and 1, 4-dioxane.
Preferably, the reaction in step (1) further comprises a post-treatment step.
Preferably, the post-processing method comprises: cooling, adding water for crystallization, filtering, and drying under reduced pressure.
Preferably, the pressure of the reduced pressure drying is 5-200 mbra, for example, 5mbra, 10mbra, 20mbra, 40mbra, 60mbra, 80mbra, 100mbra, 120mbra, 140mbra, 160mbra, 180mbra or 200mbra, etc.,
Preferably, the temperature of the reduced pressure drying is 40 to 60 ℃, and may be, for example, 40 ℃, 42 ℃, 44 ℃, 46 ℃, 48 ℃, 50 ℃, 52 ℃, 54 ℃, 56 ℃, 58 ℃, 60 ℃, or the like.
As a preferred embodiment of the present invention, the temperature of the oxidizing agent added in the step (2) is 0 to 5℃and may be, for example, 0℃1℃2℃3℃4℃or 5 ℃.
Preferably, the temperature of the reaction in the step (2) is 0 to 5 ℃, and for example, it may be 0 ℃,1 ℃, 2 ℃, 3 ℃,4 ℃, 5 ℃ or the like.
And (3) stopping the reaction after the reaction in the step (2) until the mass percent of the intermediate product remains less than 1%.
Preferably, the reaction of step (2) is carried out in the presence of an organic solvent B;
It should be noted that, in the present invention, the specific choice of the organic solvent B is not limited, and any organic solvent commonly used in the art is suitable, and exemplary examples include, but are not limited to: any one or a combination of at least two of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, ethylene glycol, glycerol, acetone, butanone, acetonitrile, dioxane, tetrahydrofuran, acetic acid, acetic anhydride and pyridine.
Preferably, the mole percentage of the oxidizing agent is 1% to 5%, for example, 1%, 2%, 3%, 4% or 5%, etc., based on 100% of the mole percentage of the intermediate product.
Preferably, the oxidizing agent includes an inorganic oxidizing agent and an organic oxidizing agent.
Preferably, the inorganic oxidant comprises 30-35wt% of hydrogen peroxide, ozone, ammonium persulfate, chromium trioxide, selenium dioxide, manganese dioxide, sodium bromate, potassium bromate, ammonium ceric nitrate, ferric sulfate, sodium hypochlorite and sodium perborate.
Preferably, the organic oxidizing agent includes peracetic acid, acetic anhydride, and trifluoroacetic anhydride.
Preferably, the oxidizing agent is an organic oxidizing agent, and the reaction in the step (2) further comprises a hydrolysis reaction.
Preferably, the hydrolysis reaction is carried out in the presence of pure water and a strong acid.
The strong acid solution is selected from concentrated sulfuric acid with the mass fraction of 60-98wt% and/or concentrated hydrochloric acid with the mass fraction of 20-37 wt%;
The hydrolysis reaction is preferably carried out at a temperature of 40 to 90℃and may be carried out at 40℃45℃50℃55℃60℃65℃70℃75℃80℃85℃90℃and more preferably 60 to 80 ℃.
Preferably, the hydrolysis reaction time is 1 to 3 hours, and may be, for example, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, or the like.
The hydrolysis reaction comprises the following specific steps: adding pure water, strong acid and organic solvent B into the reaction system after the reaction in the step (2), and carrying out hydrolysis reaction for 1-3 h at 40-90 ℃.
Preferably, the step (2) further comprises a post-treatment step after the reaction or after the hydrolysis reaction;
preferably, the post-processing method comprises: cooling, adding water for crystallization, filtering, drying under reduced pressure, separating and purifying.
Preferably, the pressure of the reduced pressure drying is 5-200 mbra, for example, 5mbra, 10mbra, 20mbra, 40mbra, 60mbra, 80mbra, 100mbra, 120mbra, 140mbra, 160mbra, 180mbra or 200mbra, etc.,
Preferably, the temperature of the reduced pressure drying is 40 to 60 ℃, and may be, for example, 40 ℃, 42 ℃, 44 ℃, 46 ℃, 48 ℃, 50 ℃, 52 ℃, 54 ℃, 56 ℃, 58 ℃, 60 ℃, or the like.
Preferably, the separation and purification method is to perform separation and purification by using silica gel column chromatography.
In the invention, the preparation method of the compound A specifically comprises the following steps:
(1) In a protective gas atmosphere, uniformly stirring and mixing an organic solvent A, an amine compound and 4,4' -dimethylbenzoyl, reacting at 20-140 ℃ for 6-8 hours, keeping stirring, cooling to room temperature, adding water for crystallization, filtering, and drying under reduced pressure under the conditions that the pressure is 5-200 mbra and the temperature is 40-60 ℃ to obtain an intermediate product;
(2) Dissolving the intermediate product obtained in the step (1) in an organic solvent B, uniformly mixing, cooling to 0-5 ℃, adding an oxidant, and stopping the reaction after the intermediate product is reacted at 0-5 ℃ until the mass percentage of the intermediate product is less than 1%;
Optionally, adding pure water, strong acid and an organic solvent B into the reaction system, heating to 40-90 ℃, carrying out hydrolysis reaction for 1-3 h, cooling to room temperature, adding water for crystallization, filtering, drying under reduced pressure under the conditions that the pressure is 5-200 mbra and the temperature is 40-60 ℃, and then separating and purifying by adopting a silica gel column chromatography to obtain the compound A.
The synthetic route for compound a is as follows:
in a second aspect, the present invention provides a method for preparing a photoinitiator according to the first aspect, the method comprising the steps of:
and (3) reacting the compound A with the compound B in a protective gas atmosphere to obtain the photoinitiator.
As a preferable mode of the present invention, the reaction temperature is 20 to 120℃and may be, for example, 20℃30℃40℃50℃60℃70℃80℃90℃100℃110℃120 ℃.
Preferably, the reaction time is 6 to 24 hours, and may be, for example, 6 hours, 8 hours, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours, 24 hours, or the like.
Preferably, the reaction is carried out in the presence of an organic solvent C.
The specific kind of the organic solvent C is not particularly limited in the present invention, and organic solvents commonly used in the art are suitable, and the organic solvent C illustratively includes, but is not limited to: any one or a combination of at least two of methanol, ethanol, N-propanol, isopropanol, N-butanol, isobutanol, tertiary butanol, ethylene glycol, glycerol, acetone, butanone, toluene, xylene, chlorobenzene, dichlorobenzene, N-dimethylformamide, tetrahydrofuran, 1, 4-dioxane, pyridine and N-methylpyrrolidone.
Preferably, the reaction is carried out in the presence of a catalyst;
preferably, the catalyst comprises a basic catalyst and an acidic catalyst;
The basic catalyst comprises: at least one of sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium carbonate, potassium bicarbonate, potassium hydroxide, ammonium hydroxide, sodium hydride, triethylamine, tripropylamine, ethylenediamine, aniline, N-dimethylaniline, tetramethylammonium hydroxide, sodium methoxide, sodium ethoxide, potassium tert-butoxide, lithium diisopropylamide, preferably at least one of sodium hydroxide, sodium carbonate, sodium bicarbonate, triethylamine, aniline, sodium N, N-dimethylaniline methoxide; the acidic catalyst comprises at least one of concentrated hydrochloric acid with the mass fraction of 20-37 wt%, concentrated sulfuric acid with the mass fraction of 60-98 wt%, nitric acid, perchloric acid, hydroiodic acid, hydrobromic acid, acetic acid, mellitic acid, trichloroacetic acid, trifluoromethanesulfonic acid, trinitrobenzenesulfonic acid, amberlyst 123, amberlyst 15WET, amberlyst119,119 WET.
As a preferable technical scheme of the invention, the reaction further comprises a post-treatment step.
Preferably, the method of post-treatment comprises: cooling, filtering, pulping, filtering and drying under reduced pressure.
Preferably, the pressure of the reduced pressure drying is 5-200 mbra, for example, 5mbra, 10mbra, 20mbra, 40mbra, 60mbra, 80mbra, 100mbra, 120mbra, 140mbra, 160mbra, 180mbra, 200mbra, or the like.
Preferably, the temperature of the reduced pressure drying is 40 to 60 ℃, and may be, for example, 40 ℃, 42 ℃, 44 ℃, 46 ℃, 48 ℃, 50 ℃, 52 ℃, 54 ℃, 56 ℃, 58 ℃, 60 ℃, or the like.
In the invention, the preparation method of the photoinitiator specifically comprises the following steps:
And in a protective gas atmosphere, stirring and mixing the compound A, the compound B and the organic solvent C uniformly, adding a catalyst, heating to 20-120 ℃, reacting for 6-24 hours, keeping stirring, slowly cooling to room temperature, filtering to obtain a solid, pulping the solid and the organic solvent B, filtering, and drying under reduced pressure under the conditions that the pressure is 5-200 mbra and the temperature is 40-60 ℃ to obtain the photoinitiator.
The synthetic route of the initiator is as follows:
compared with the prior art, the invention has the following beneficial effects:
The photoinitiator has the characteristics of low toxicity, low odor, low yellowing and low migration, and has high curing speed and high solubility through the structural design of the photoinitiator.
Detailed Description
To facilitate understanding of the present invention, examples are set forth below. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Preparation example 1
The preparation example provides a compound A-1 and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) Under the condition of room temperature, introducing nitrogen into a 250mL four-neck flask, adding 100mL of ethanol, 0.82g of o-phenylenediamine and 2.0g of 4,4' -dimethylbenzoyl under the nitrogen atmosphere, and stirring and mixing uniformly; heating to 80 ℃, preserving heat, stirring and reacting for 6 hours, and ending the reaction; slowly cooling the reaction solution to room temperature, adding 200mL of pure water for crystallization, filtering, and drying the filter cake at 150mbar and 40 ℃ under reduced pressure to obtain an intermediate product;
(2) Placing the intermediate product into a 250mL four-necked flask, sequentially adding 32.5g of acetic acid and 28.8g of acetic anhydride, and stirring and uniformly mixing; cooling the reaction system to 0-5 ℃ by using ice water bath, adding 0.5g of chromium trioxide, and stopping the reaction after keeping the temperature for 4 hours;
60mL of pure water, 60mL of ethanol and 1.2g of 98wt% concentrated sulfuric acid are sequentially added into the four-necked flask, the temperature is raised to 80 ℃, and the mixture is kept warm and stirred for 2 hours; slowly cooling the reaction solution to room temperature, adding 200mL of pure water for crystallization, filtering, and drying the filter cake at 150mbar and 40 ℃ under reduced pressure to obtain a solid; the obtained solid is separated and purified by adopting a silica gel column chromatography, and the mobile phase is n-hexane: ethyl acetate=4:1 (volume ratio) to give compound a-1 (milky white solid powder) with a purity of 99.0% by HPLC with a yield of 55.9%.
The results of the nuclear magnetic resonance hydrogen spectrum of the compound A-1 are as follows: 1H-NMR(CDCl3 400 MHz): 7.52 (4H, d), 7.60 (4H, d), 7.84 (2H, dt), 8.25 (2H, dt), 10.06 (2H, s).
Preparation example 2
The preparation example provides a compound A-2 and a preparation method thereof, wherein the preparation method comprises the following steps:
Specific production method of Compound A-2 referring to the method of production example 1, except that 0.82g of o-phenylenediamine was replaced with 0.86g of trans-1, 2-cyclohexanediamine, the other conditions were the same as in production example 1, to obtain Compound A-2 as a white solid powder with a purity of 97.9% and a yield of 52.2%.
The result of the nuclear magnetic resonance hydrogen spectrum of the compound A-2 is as follows ：1H-NMR(CDCl3,400MHz)：1.50-1.70(4H,m),1.88-2.26(4H,m),5.10-5.16(2H,t),7.28(4H,d),7.47(4H,d),9.98(2H,s).
Preparation example 3
The preparation example provides a compound A-3 and a preparation method thereof, wherein the preparation method comprises the following steps:
Specific production method of Compound A-3 referring to the method of production example 1, except that 0.82g of o-phenylenediamine was replaced with 0.69g of 1, 2-diamino-2-methylpropane, the other conditions were the same as in production example 1, to obtain Compound A-3 as a white solid powder with a purity of 98.9% and a yield of 53.1%.
The results of the nuclear magnetic resonance hydrogen spectrum of the compound A-3 are as follows: 1H NMR(CDCl3 400 MHz): 1.29 (6H, s), 3.98 (2H, s), 7.77-7.64 (8H, m), 9.94 (2H, s).
Preparation example 4
The preparation example provides a compound A-4 and a preparation method thereof, wherein the preparation method comprises the following steps:
specific production method of Compound A-4 referring to the method of production example 1, except that 0.82g of o-phenylenediamine was replaced with 0.56g of 1, 2-propanediamine, the other conditions were the same as in production example 1, to obtain Compound A-4 as a white solid powder with a purity of 99.0% and a yield of 54.5%.
The result of the nuclear magnetic resonance hydrogen spectrum of the compound A-4 is as follows ：1H NMR(CDCl3,400MHz)：1.33(3H,d),3.69(1H,dd),3.77(1H,dd),4.23(1H,h),7.76–7.63(m,8H),9.94(s,2H).
Example 1
The embodiment provides a photoinitiator 1 (I) and a preparation method thereof, wherein the preparation method comprises the following steps:
Introducing nitrogen into a 250mL four-necked flask, adding 100mL of ethanol, 3.0g of compound 1 (a) and 2.2g of compound 1 (b) into the four-necked flask under the nitrogen atmosphere, stirring and mixing uniformly, and keeping the system temperature at 20-30 ℃; slowly dropwise adding 0.8g 30wt% liquid alkali, heating to 40 ℃ and reacting for 10 hours, and stopping the reaction; slowly cooling the reaction solution to room temperature, filtering to obtain a filter cake, adding 30mL of ethanol into the filter cake, pulping for 60min, and filtering to obtain a solid; the solid was dried under reduced pressure at 150mbar at 60℃to give photoinitiator 1 (I) as a pale yellow solid powder, 97.5% purity by HPLC, 78.1% yield.
The nuclear magnetic resonance hydrogen spectrum of photoinitiator 1 (I) gave the following results ：1H-NMR(CDCl3,400MHz)：7.42(2H,d),7.45-7.50(6H,m),7.55(2H,m),7.68(2H,d),7.70-7.80(4H,m),7.82(2H,d),7.95(4H,d),8.15(2H,m).
Example 2
The embodiment provides a photoinitiator 2 (I) and a preparation method thereof, wherein the preparation method comprises the following steps:
Specific preparation method of photoinitiator 2 (I) referring to the preparation method of example 1, except that 3.0g of compound 1 (a) was replaced with 2.8g of compound 2 (a), the other conditions were the same as in example 1, to obtain photoinitiator 2 (I) as pale yellow solid powder with a purity of 98.1% and a yield of 77.7%.
The nuclear magnetic resonance hydrogen spectrum of photoinitiator 2 (I) gave the following results ：1H-NMR(CDCl3,400MHz)：1.30(6H,s),3.92(2H,s),7.05(1H,d),7.12(1H,d),7.41-7.58(10H,m),7.78-7.82(4H,m),8.05-8.10(4H,m).
Example 3
The embodiment provides a photoinitiator 3 (I) and a preparation method thereof, wherein the preparation method comprises the following steps:
Specific preparation method of photoinitiator 3 (I) referring to the preparation method of example 1, except that 2.2g of compound 1 (b) was replaced with 3.4g of compound 3 (b), the other conditions were the same as in example 1, to obtain photoinitiator 3 (I) as pale yellow solid powder, purity 97.7%, yield 65.1%.
The result of the nuclear magnetic resonance hydrogen spectrum of the photoinitiator 3 (I) is as follows ：1H NMR(CDCl3,400MHz)：0.94–0.83(6H,m),1.37–1.21(12H,m),1.56(4H,p),2.66(4H,tt),7.13(4H,dt),7.45(2H,d),7.58(2H,t),7.75(2H,dt),7.86–7.79(4H,m),8.00–7.87(10H,m).
Example 4
The embodiment provides a photoinitiator 4 (I) and a preparation method thereof, wherein the preparation method comprises the following steps:
specific preparation method of photoinitiator 4 (I) referring to the preparation method of example 1, except that 2.2g of compound 1 (b) was replaced with 3.2g of compound 4 (b), the other conditions were the same as in example 1, to obtain photoinitiator 4 (I) as pale yellow solid powder, purity 97.9%, yield 53.9%.
The nuclear magnetic resonance hydrogen spectrum of photoinitiator 4 (I) gave the following results ：1H NMR(CDCl3,400MHz)：0.95–0.83(6H,m),1.32–1.18(10H,m),1.38–1.28(2H,m),1.59–1.46(3H,m),1.68–1.55(1H,m),2.23–2.08(2H,m),2.61–2.46(2H,m),2.76–2.61(2H,m),3.18–3.08(1H,m),6.01(1H,dtt),6.17–6.08(1H,m),6.21(1H,ddd),6.33(1H,ddt),7.11(1H,d),7.27(1H,t),7.47–7.38(2H,m),7.55–7.47(1H,m),7.63–7.53(4H,m),7.88–7.82(2H,m),7.99–7.89(6H,m),7.89(2H,d),7.90(2H,s).
Example 5
The embodiment provides a photoinitiator 5 (I) and a preparation method thereof, wherein the preparation method comprises the following steps:
Specific preparation method of photoinitiator 5 (I) referring to the preparation method of example 1, except that 2.2g of compound 1 (b) was replaced with 3.0g of compound 5 (b), and the other conditions were the same as in example 1, to obtain photoinitiator 5 (I) as pale yellow solid powder with a purity of 98.3% and a yield of 66.0%.
The nuclear magnetic resonance hydrogen spectrum of photoinitiator 5 (I) gave the following results ：1H NMR(CDCl3,400MHz)0.98(6H,t),1.54–1.40(4H,m),1.78(4H,p),4.02(4H,t),7.00–6.92(4H,m),7.52(2H,d),7.58(2H,t),7.74(2H,dt),8.02–7.88(14H,m).
Example 6
The present embodiment provides a photoinitiator 6 (I) and a preparation method thereof, the preparation method is as follows:
Specific preparation method of photoinitiator 6 (I) referring to the preparation method of example 1, except that 2.2g of compound 1 (b) was replaced with 2.9g of compound 6 (b), the other conditions were the same as in example 1, to obtain photoinitiator 6 (I) as pale yellow solid powder, purity 97.8%, yield 56.8%.
The nuclear magnetic resonance hydrogen spectrum of photoinitiator 6 (I) gave the following results ：1H NMR(CDCl3,400MHz)3.87(12H,d),6.92(2H,d),7.51(2H,d),7.61–7.55(4H,m),7.65(2Hd,d),7.74(2Hd,t),8.00–7.88(10H,m).
Example 7
The present embodiment provides a photoinitiator 7 (I) and a preparation method thereof, the preparation method is as follows:
Specific preparation method of photoinitiator 7 (I) referring to the preparation method of example 1, except that 3.0g of compound 1 (a) was replaced with 2.7g of compound 7 (a), the other conditions were the same as in example 1, to obtain photoinitiator 7 (I) as pale yellow solid powder, purity 98.8%, yield 72.4%.
The nuclear magnetic resonance hydrogen spectrum of photoinitiator 7 (I) gave the following results ：1H NMR(CDCl3,400MHz)1.34(3H,d),3.74(1H,dd),3.81(1H,dd),4.32(1H,h),7.47–7.38(4H,m),7.53–7.47(2H,m),7.55–7.48(2H,m),7.71–7.63(4H,m),7.75(2H,dd),7.88–7.80(4H,m),8.01–7.94(4H,m).
Example 8
The present embodiment provides a photoinitiator 8 (I) and a preparation method thereof, the preparation method is as follows:
Specific preparation method of photoinitiator 8 (I) referring to the preparation method of example 1, except that 3.0g of compound 1 (a) was replaced with 3.0g of compound 8 (a), the other conditions were the same as in example 1, to obtain photoinitiator 8 (I) as pale yellow solid powder, purity 98.8%, yield 72.4%.
The nuclear magnetic resonance hydrogen spectrum of photoinitiator 8 (I) gave the following results ：1H NMR(CDCl3,400MHz)1.66–1.51(4H,m),2.00–1.87(2H,m),2.14–2.01(2H,m),4.12(2H,ddd),7.47–7.38(6H,m),7.55–7.47(2H,m),7.70–7.64(4H,m),7.73(2H,dt),7.87–7.80(4H,
m),8.01–7.93(4H,m)。
Comparative example 1
This comparative example provides a photoinitiator TPO, available from Changsha Xinyu high molecular technology Co.
Comparative example 2
This comparative example provides a photoinitiator 819, available from Chenoptery, inc.
Comparative example 3
This comparative example provides a photoinitiator, esacure 3644, available from IGM corporation.
The solubility of the photoinitiators provided in the examples above and the photoinitiators provided in the comparative examples in ethyl acetate was tested as follows: adding 50mL of ethyl acetate serving as a solvent into a 250mL glass beaker at the room temperature of 25+/-0.5 ℃, taking 0.1g of a test sample, adding the test sample into the solvent, stirring and mixing for 30min, and visually observing whether the sample is insoluble; if the sample is dissolved, adding 0.1g of the sample to be tested, stirring and mixing for 30min until insoluble substances exist, stopping adding the sample, recording the mass of the added sample to be tested, and calculating the solubility of the sample according to the following formula:
The solubility results of the photoinitiators provided in some of the examples above and those provided in the comparative examples are shown in table 1 below:
TABLE 1
Solubility (wt%)
Comparative example 1 26.0
Comparative example 2 7.9
Comparative example 3 22.5
Example 3 35.5
Example 4 38.1
Example 5 26.2
Example 6 30.3
As can be seen from the contents of table 1, the photoinitiators provided by the present invention have higher solubility than the photoinitiators provided in the prior art.
The UV light-cured ink (namely light-cured composition) is prepared by adopting a commercially available photoinitiator and the photoinitiator provided by the invention, wherein the UV light-cured ink refers to ink in which a photosensitizer in the ink initiates polymerization of monomers in an ink binder into a polymer under ultraviolet irradiation, so that the ink is formed into a film and dried. The specific composition of the UV light curable ink is shown in table 2 below:
TABLE 2
Wherein, the photo-curing compositions 1-3 are photo-curing compositions prepared by using the photo-initiators sold in the market, and the photo-curing compositions 4-7 are photo-curing compositions prepared by using the photo-initiators 3 (I) -6 (I) provided in the embodiments 3-6 of the invention.
The properties of the above photocurable composition were tested by the following specific test methods:
Curing speed: the above photocurable compositions were each roll-coated onto a PET film (ordinary industrial film FP2 of Lekai group) using a10 μm bar, and a UV-LED caterpillar type exposure machine (Shenzhen Ruo electromechanical Co., ltd.) having a wavelength of 385nm was used as a radiation light source, and the irradiation intensity of the UV-LED light source was 20W/cm 2. After the illumination is finished, the method is carried out according to the method for measuring the drying time of paint film and putty film of GB1728-1979, and a finger touch method is adopted for measuring, namely, the coating is lightly touched by fingers, and the complete solidification is confirmed by smooth surface, no sticking to hands and no fingerprint pressing; the curing speed is expressed as the maximum exposure energy to achieve a complete curing effect in mJ/cm 2. The smaller the maximum exposure energy value, the faster the curing speed, and vice versa.
Yellowing test: the above-mentioned photo-setting compositions 1 to 7 were each roll-coated onto a white cardboard with a 10 μm bar, and fully exposed to energy of 1000mJ/cm 2 using a UV-LED caterpillar type exposure machine (Runfo electromechanical Co., ltd. In Shenzhen) having a wavelength of 385nm as a radiation light source; after curing, a reflectance test was performed using a Color difference meter (alic X-Rite Color i 7), and the yellowing was evaluated by reading the Δb value, with smaller Δb indicating less pronounced yellowing, whereas more severe yellowing.
Migration test: the above-mentioned photo-setting compositions 1 to 7 were roll-coated onto PET film (common industrial film FP2 of Lekai groups) with 10 μm wire rod, respectively, and the migration amount of the photoinitiator in the soak was measured by external standard quantitative method using UV-LED crawler type exposure machine (Shenzhen Ruo electromechanical Co., ltd.) with wavelength of 385nm as radiation light source, after 500mJ/cm 2 energy radiation setting, 100cm 2 of PET film with setting layer was immersed in 100mL 95% ethanol solution, after 10 days immersion at 40 ℃.
The results of the performance test of the above photocurable composition are shown in table 3 below:
TABLE 3 Table 3
Full curing energy/mJ.cm -2 Yellowing/Δb Migration volume/. Times.10 -9g·mL-1
Photoinitiator TPO 175 3.2 5.9
Esacure 3644 293 4.2 2.1
Photoinitiator ITX 204 23.1 2.8
4(I) 112 5.4 Not detected
5(I) 127 5.5 Not detected
6(I) 101 5.8 Not detected
7(I) 98 6.2 Not detected
As can be seen from the contents of Table 3, the photoinitiator prepared by designing the structure of the photoinitiator has low yellowing and migration characteristics, and has a high curing speed, the complete curing energy is 98-127 mJ.cm -2, the yellowing index delta b is 5.4-6.2, and no photoinitiator is detected after migration test.
Compared with the photoinitiator provided by the invention, the commercially available cleavage type photoinitiator (photoinitiator TPO, esacure 3644) has better yellowing resistance, but has poorer solubility and higher mobility, and the photocuring composition prepared from the photoinitiator has slower curing speed and higher energy required for complete curing; commercial hydrogen abstraction photoinitiators have poor yellowing resistance, a yellowing index delta b of 23.1, high mobility, low curing speed and high energy required for complete curing.
In summary, the structure of the photoinitiator is designed, so that the photoinitiator has the characteristics of low toxicity, low odor, low yellowing and low migration, and simultaneously has high curing speed and high solubility.
The applicant states that the detailed process flow of the present invention is illustrated by the above examples, but the present invention is not limited to the above detailed process flow, i.e. it does not mean that the present invention must be implemented depending on the above detailed process flow. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.

Claims (10)

1. A photoinitiator, wherein the photoinitiator has a structure according to formula I:
Wherein R 1、R2 each independently represents a hydrogen atom, a C1-C18 straight or branched alkyl group, a C3-C10 cycloalkyl group, a C4-C12 alkylcycloalkyl group, a substituted or unsubstituted C6-C20 aryl group, R 1、R2 may be linked to form a ring;
R 3 represents any one of a hydrogen atom, a C1-C18 straight-chain or branched-chain alkyl group, a C3-C10 cycloalkyl group, a C4-C12 alkylcycloalkyl group, a C1-C10 alkoxy group, a C2-C18 alkenyl group, a C1-C8 thioalkyl group, wherein a single carbon-carbon bond in the C1-C18 straight-chain or branched-chain alkyl group may be replaced by an ether bond;
R 4 represents any one of a hydrogen atom, a halogen atom, a nitro group, a cyano group, an ester group, a hydroxyl group, a C1-C18 straight-chain or branched alkyl group, a C3-C10 cycloalkyl group, a C4-C12 alkylcycloalkyl group, a C1-C10 alkoxy group, a C1-C12 thioalkyl group, a C1-C12 haloalkyl group, a C2-C18 alkenyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted C3-C20 heterocyclic group, wherein a carbon-carbon single bond in the C1-C18 straight-chain or branched alkyl group may be replaced with an ether bond;
Each of the substituents substituted in R 1、R2、R4 is independently selected from at least one of halogen atom, nitro, cyano, hydroxy, amino, C1-C6 straight or branched alkyl, C3-C6 cycloalkyl, C1-C6 alkoxy, phenyl;
m, n each independently represent 0, 1 or 2, and p represents 1, 2, 3,4 or 5.
2. The photoinitiator according to claim 1, wherein each R 1、R2 independently represents a hydrogen atom, a C1-C12 linear or branched alkyl group or a substituted or unsubstituted C6-C20 aryl group;
Preferably, the R 1、R2 is linked in a ring;
preferably, R 3 represents a hydrogen atom, a C1-C12 straight or branched alkyl group, a C3-C6 cycloalkyl group or a C2-C8 alkenyl group;
Preferably, R 4 represents any one of a hydrogen atom, a halogen atom, a nitro group, a cyano group, an ester group, a hydroxyl group, and a C1-C12 linear or branched alkyl group, wherein a single carbon-carbon bond in the C1-C12 linear or branched alkyl group may be replaced with an ether bond.
3. The photoinitiator according to claim 1 or 2, wherein the photoinitiator is prepared from a raw material comprising a compound a and a compound B;
The compound A is
The compound B is
Wherein R 1-R4, m, n and p have the same protection scope as claim 1.
4. A photoinitiator according to claim 3, wherein the molar ratio of compound a to compound B is 1 (2-10), preferably 1 (2-6), further preferably 1 (2-3);
preferably, the compound B is selected from any one of the following compounds:
5. the photoinitiator according to claim 3 or 4, wherein the compound a is prepared by a process comprising the steps of:
(1) The amine compound reacts with 4,4' -dimethylbenzoyl to obtain an intermediate product;
(2) Uniformly mixing the intermediate product with an organic solvent B, adding an oxidant into the mixture, and reacting to obtain a compound A;
The amine compound is
Wherein R 1、R2, m and n have the same protection scope as claim 1.
6. The photoinitiator according to claim 5, wherein the amine compound is selected from any one of the following compounds:
Preferably, the molar ratio of the amine compound to 4,4' -dimethylbenzoyl is 1 (1-2), preferably 1 (1-1.5), and more preferably 1 (1-1.2);
Preferably, the temperature of the reaction in step (1) is 20 to 140 ℃, more preferably 30 to 120 ℃, still more preferably 40 to 100 ℃;
preferably, the reaction time in the step (1) is 6-8 hours;
Preferably, the reaction of step (1) is carried out in the presence of an inert gas;
Preferably, the reaction of step (1) is carried out in the presence of an organic solvent a;
Preferably, the reaction in step (1) further comprises a post-treatment step;
Preferably, the post-processing method comprises: cooling, adding water for crystallization, filtering, and drying under reduced pressure.
7. The photoinitiator according to claim 5 or 6, wherein the temperature of the oxidant addition in step (2) is 0 to 5 ℃;
preferably, the temperature of the reaction in the step (2) is 0-5 ℃;
preferably, the reaction of step (2) is carried out in the presence of an organic solvent B;
preferably, the mole percent of the oxidant is 1-5% based on 100% of the mole percent of the intermediate;
Preferably, the oxidizing agent comprises an inorganic oxidizing agent and an organic oxidizing agent;
Preferably, the oxidant is an organic oxidant, and the reaction in the step (2) further comprises a hydrolysis reaction;
preferably, the hydrolysis reaction is carried out in the presence of pure water and a strong acid;
preferably, the temperature of the hydrolysis reaction is 40-90 ℃, and more preferably 60-80 ℃;
preferably, the hydrolysis reaction time is 1-3 hours;
preferably, the step (2) further comprises a post-treatment step after the reaction or after the hydrolysis reaction;
preferably, the post-processing method comprises: cooling, adding water for crystallization, filtering, drying under reduced pressure, separating and purifying.
8. A process for the preparation of a photoinitiator according to any one of claims 1 to 7, comprising the steps of:
and (3) reacting the compound A with the compound B in a protective gas atmosphere to obtain the photoinitiator.
9. The method of claim 8, wherein the temperature of the reaction is 20-120 ℃;
Preferably, the reaction time is 6 to 24 hours;
preferably, the reaction is carried out in the presence of an organic solvent C;
preferably, the reaction is carried out in the presence of a catalyst.
10. The method according to claim 8 or 9, wherein the post-reaction further comprises a post-treatment step;
Preferably, the method of post-treatment comprises: cooling, filtering, pulping and drying under reduced pressure;
Preferably, the pressure of the reduced pressure drying is 5-200 mbra;
preferably, the temperature of the reduced pressure drying is 40-60 ℃.
CN202211511743.6A 2022-11-29 2022-11-29 Photoinitiator and preparation method thereof Pending CN118146405A (en)

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