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CN112441953A - Water-soluble photopolymerization initiator containing diphenyl sulfide group ketone formate and preparation method thereof - Google Patents

Water-soluble photopolymerization initiator containing diphenyl sulfide group ketone formate and preparation method thereof Download PDF

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CN112441953A
CN112441953A CN202011316129.5A CN202011316129A CN112441953A CN 112441953 A CN112441953 A CN 112441953A CN 202011316129 A CN202011316129 A CN 202011316129A CN 112441953 A CN112441953 A CN 112441953A
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photoinitiator
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金明
万德成
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Tongji University
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/62—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light

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Abstract

本发明涉及新材料有机化学品技术领域，含二苯硫醚基酮甲酸酯水溶性光聚合引发剂及其制备方法。特别涉及式(A)所示以二苯硫醚基酮甲酸酯为核心结构的新化合物。本发明通过在核心结构中引入季胺盐、磺酸根等亲水基团，实现其水溶性。本发明的合成步骤简单，制备成本低，产物的水溶解性能良好，可直接作为光解型光引发剂使用，在紫外‑可见光固化领域有广泛的应用前景。

Figure DDA0002791472690000011
The invention relates to the technical field of new material organic chemicals, a water-soluble photopolymerization initiator containing diphenyl sulfide group ketone formate and a preparation method thereof. In particular, it relates to a new compound represented by formula (A) with diphenyl sulfide ketone formate as the core structure. The invention realizes its water solubility by introducing hydrophilic groups such as quaternary ammonium salt and sulfonate into the core structure. The invention has simple synthesis steps, low preparation cost, good water solubility of the product, can be directly used as a photolysis type photoinitiator, and has wide application prospects in the field of ultraviolet-visible light curing.
Figure DDA0002791472690000011

Description

Water-soluble photopolymerization initiator containing diphenyl sulfide group ketone formate and preparation method thereof
[ technical field ] A method for producing a semiconductor device
The invention relates to the technical field of new materials, organic chemicals, in particular to a diphenyl sulfide ketone formate photoinitiator, which realizes water solubility by introducing hydrophilic groups such as quaternary ammonium salt, sulfonic acid group and the like into a core structure. Has wide application prospect in the field of ultraviolet-visible light curing.
[ background of the invention ]
Photoinitiator compounds are an important class of fine organic chemical materials. Photoinitiator compounds which generate free radical active species under the irradiation of ultraviolet light or visible light are key species for inducing high-efficiency photopolymerization of ethylenically unsaturated systems, and therefore are one of important radiation curing formula components. Among the numerous photoinitiator products that have been commercially available, diphenyl sulfide compounds have taken an outstanding position, and representative products such as diphenyl sulfide-based ketoxime photoinitiators (trade name OXE-01) are mainly used for curing color photoresist polymerizable systems. However, such highly efficient photoinitiators are not water soluble, which also limits their use in such environmentally friendly solvents.
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. Photoinitiators that absorb sensitively to both the long-wavelength emission wavelength of the LED (365-. Therefore, designing, developing, and industrialization of novel photoinitiator compounds is a critical technical challenge facing the current field.
In view of the above technical challenges, it is necessary to invent a class of photoinitiators that are sensitive to LED light sources and have good water solubility. 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 water-soluble photoinitiator can be effectively compatible with water-soluble photocuring resin and compounded to form water-soluble photocuring ink or paint with stable storage, and has profound influence on the fields of woodware green coating, environment-friendly printing, ink-jet printing, energy-saving materials and the like.
[ summary of the invention ]
The purpose of the application is to provide a diphenyl sulfide ether ketone formate photoinitiator with water solubility, and the molecular structure of the photoinitiator is shown as the following formula (A):
Figure RE-GDA0002891267670000021
in the formula (A), R1Independently represent a group of compounds having+N(R)3X-and-SO3M and bonded to the carbonyl group of the formula (A) through a carbon chain or a carbon-oxygen chain, wherein R represents a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group, and X is F, Br or I; m is K or Na ion; r2Each independently represents an alkyl group, an aryl group or an alkoxy group, and m each independently represents an integer of 0 to 4; r3Each independently represents an alkyl group, an aryl group, a benzyl group, or an aralkyl group.
The invention also provides a preparation method of the photo-initiation, and the general synthesis process is shown as the following formula:
Figure RE-GDA0002891267670000022
during the preparation of the initiator:
in the step a, halogenated benzene, aluminum trichloride and oxalyl chloride monoester (the molar ratio is 1: 2: 1) react for 2-6h at 0-10 ℃ in dry dichloromethane, and 4-halogenated phenyl ketone formate can be prepared by hydrolysis, water washing, drying by anhydrous sodium sulfate and reduced pressure distillation;
in the step b, dissolving the product 4-halogenated phenyl ketone formate (1 equivalent) and thiophenol or substituted thiophenol (1 equivalent) in a proper amount of N, N-Dimethylformamide (DMF), adding alkali (1.2 equivalents) and a small amount of CuI for catalysis, stirring and reacting for 4-10 hours at 40-60 ℃ under the protection of nitrogen, recovering DMF under reduced pressure, adding the residue into a proper amount of water, extracting twice by using 1, 2-dichloroethane, combining 1, 2-dichloroethane solutions, and recrystallizing the residue after concentration to obtain diphenyl sulfide ketone formate;
in step c, the product of step b (1 eq) is added to dichloromethane, anhydrous aluminum trichloride (1.5 eq) is added in portions, a solution of bromoalkyl acid chloride (1.2 eq) in dichloromethane is added dropwise at 0-10 ℃ and stirred at room temperature for 3-10 hours. Slowly adding the reaction solution into ice water, extracting with ethyl acetate, washing with water, drying with anhydrous magnesium sulfate, concentrating, and recrystallizing with ethanol;
in step d, the product of step c (1 eq) is dissolved in ethyl acetate, triethylamine (1 eq) is added, the precipitated solid is filtered off and washed with isopropanol and hexane to give the target product containing the quaternary ammonium salt.
In step d, the product of step c (1 eq) was dissolved in dimethyl sulfoxide and sodium 2-hydroxyethanesulfonate (1 eq) was added and stirred at 90 ℃ for 24 h. Adding 10 equivalents of saturated saline solution into the reaction solution, extracting with acetonitrile, drying with magnesium sulfate, and recrystallizing the solid obtained after concentration with isopropanol to obtain the target product containing the sulfonate.
In the above preparation step, the base added in step b may be an organic base or an inorganic base, preferably sodium methoxide and potassium carbonate;
in the above preparation steps, chloro or iodoacyl chloride can also be used in step c;
in the above preparation steps, step d may be substituted with other various kinds of tertiary amines, such as tributyl amine and trimethyl amine, but not limited to these tertiary amines.
In the above preparation step, step d may also be carried out by reacting potassium 2-hydroxyethanesulfonate with the product of step c.
Compared with the existing water-soluble photoinitiator, the invention has the advantages that on one hand, the molecule has good water solubility, the synthetic method is simple, no expensive catalyst is involved, and the purification is convenient; the molecule takes diphenyl sulfide ketone group as a core, and the absorption spectrum of the molecule has better overlap with the emission spectrum of cheap light sources such as LED, which is consistent with the development direction of UV curing technology.
Exemplary compounds conforming to the structure of formula (A) are listed below, but are not limited to these structures:
Figure RE-GDA0002891267670000031
for the gist of the present invention, we will further describe it in connection with the following series of examples.
[ detailed description ] embodiments
Hereinafter, embodiments of the present invention will be specifically described with reference to examples, but the embodiments of the present invention are not limited to these examples.
Example 1: (A) synthesis of (E) -1 to (A) -18
Process for producing Compound (A) -1
Figure RE-GDA0002891267670000041
(a) Bromobenzene (0.1mol) is dissolved in 100 ml of anhydrous dichloromethane, anhydrous aluminum trichloride (0.2mol) is added in batches, oxalyl chloride monomethyl ester (0.1mol) is added dropwise at 0-10 ℃, the dropwise addition is completed in half an hour, the reaction is stirred at normal temperature for 2-6h, the reaction is monitored by a point plate, the reaction is completed, the mixture is slowly added into volumetric ice water which is equal to a solvent, an organic layer is washed by deionized water, anhydrous sodium sulfate is dried, and reduced pressure distillation is carried out, so that the 4-bromophenyl ketone methyl formate can be prepared and directly used for the next reaction.
(b) Dissolving methyl 4-bromophenyl ketone formate (0.05mol) and thiophenol (0.05mol) in N, N-Dimethylformamide (DMF) (100 ml), adding potassium carbonate (0.06mol) and CuI (0.006mol), stirring and reacting at 140 ℃ for 4 hours under the protection of nitrogen, after the reaction is monitored by a point plate, recovering DMF under reduced pressure, adding the residue into 100 ml of deionized water, extracting twice by using 100 ml of 1, 2-dichloroethane, combining the 1, 2-dichloroethane solutions, and recrystallizing the concentrated residue by using ethanol to obtain the methyl diphenylsulfide ketone formate with the yield of 82%.
(c) Diphenyl sulfide ether ketone methyl formate (0.04mol) was added to anhydrous dichloromethane (50 ml), anhydrous aluminum trichloride (0.12mol) was added in portions, a dichloromethane solution (20 ml) of chloroacetyl chloride (0.04mol) was added dropwise at 0 to 10 ℃ and stirred at room temperature for 3 to 10 hours, and the end of the reaction was monitored by spotting plates. Slowly adding the reaction solution into ice water with the same amount as the solvent, extracting with ethyl acetate, washing with water, drying with anhydrous magnesium sulfate, concentrating, and recrystallizing with ethanol to obtain a light yellow product with a yield of 90%;
(d) the product of step c (0.03mol) was dissolved in 50 ml of ethyl acetate, triethylamine (0.06mol) was added, and the precipitated solid was filtered off and washed with isopropanol and hexane to give the desired product (A) -1 in 95% yield.
EI-MS(C23H28NO4S+): 414.2; the experimental results are as follows: 414.2.
for the synthesis of (A) -2 to (A) -18, the same synthesis procedure was carried out except that the reactants were changed, and the end point of the reaction was determined by thin plate chromatography. Wherein (a) -2, (a) -3 utilizes oxalyl chloride monoethyl ester and oxalyl chloride monobenzyl ester in step (a); (A) -4, (a) -5, (a) -6 using tributylamine instead of triethylamine in step (d); trimethylthiophenol is added in the step (b) of e.g. (A) -7, (A) -8, (A) -9; (A) -10 to (a) -18, (a) -9 replacing bromoacetyl chloride in step (c) with bromopropionyl chloride, bromobutyryl chloride, bromohexanoyl chloride, respectively, (d) replacing triethylamine with trimethylamine. The overall yield of the four steps is 60-75%.
(A)-2：EI-MS(C24H30NO4S+): 428.2; the experimental results are as follows: 428.2;
(A)-3：EI-MS(C29H32NO4S+): 490.2, respectively; the experimental results are as follows: 490.2, respectively;
(A)-4：EI-MS(C29H40NO4S+): 498.3, respectively; the experimental results are as follows: 498.3, respectively;
(A)-5：EI-MS(C30H42NO4S+): 512.3, respectively; the experimental results are as follows: 512.3, respectively;
(A)-6：EI-MS(C35H44NO4S+): 574.3; the experimental results are as follows: 574.3;
(A)-7：EI-MS(C26H34NO4S+): 456.2, respectively; the experimental results are as follows: 456.2, respectively;
(A)-8：EI-MS(C27H36NO4S+): 470.2; the experimental results are as follows: 470.2;
(A)-9：EI-MS(C32H38NO4S+): 532.2; the experimental results are as follows: 532.2;
(A)-10：EI-MS(C21H24NO4S+)：386.1; the experimental results are as follows: 386.1 of the total weight of the steel;
(A)-11：EI-MS(C22H26NO4S+): 400.2; the experimental results are as follows: 400.2;
(A)-12：EI-MS(C27H28NO4S+): 462.2 of the first step; the experimental results are as follows: 462.2 of the first step;
(A)-13：EI-MS(C22H26NO4S+): 400.2; the experimental results are as follows: 400.2;
(A)-14：EI-MS(C23H28NO4S+): 414.2; the experimental results are as follows: 414.2;
(A)-15：EI-MS(C28H30NO4S+): 476.2; the experimental results are as follows: 476.2;
(A)-16：EI-MS(C24H30NO4S+): 428.2; the experimental results are as follows: 428.2;
(A)-17：EI-MS(C25H32NO4S+): 442.2; the experimental results are as follows: 442.2;
(A)-18：EI-MS(C30H34NO4S+): 504.2; the experimental results are as follows: 504.2;
example 2: (A) synthesis of (E) -19 to (A) -24
Structural formula of Compound (A) -19
Figure RE-GDA0002891267670000051
To (A) -1c (0.05mol) obtained in the same manner as above was added dimethyl sulfoxide (100 ml) and sodium 2-hydroxyethanesulfonate (0.05mol), and the reaction mixture was stirred at 90 ℃ for 24 hours, and after completion of the reaction, 200 ml of saturated saline was added to the reaction mixture, followed by three-time extraction with 200 ml of acetonitrile, drying over magnesium sulfate, concentration under reduced pressure to give a pale yellow solid, and recrystallization from isopropanol to give (A) -19 in 90% yield.
(A) -20 was synthesized by the same reaction except that sodium 2-hydroxyethanesulfonate was changed to potassium 2-hydroxyethanesulfonate.
With respect to (A) -21 and (A) -22, the synthesis was carried out in the same reactions as in (A) -20 and (A) -21, respectively, except that oxalyl chloride monoethyl ester was used instead of oxalyl chloride monomethyl ester.
Example 3: (A) synthesis of (E) -23
Figure RE-GDA0002891267670000052
(a) Methyl 4-bromophenyl ketone formate (0.05mol) and 2,4, 6-trimethylthiophenol (0.05mol) were dissolved in 100 ml of DMF, anhydrous potassium carbonate (0.06mol) and CuI (0.006mol) were added, the reaction was stirred at 100 ℃ for 4 hours under nitrogen protection, after completion of the reaction, DMF was recovered under reduced pressure, the residue was added to 100 ml of water, extracted twice with 100 ml of 1, 2-dichloroethane, dried over anhydrous sodium sulfate, concentrated, and recrystallized from ethanol to give the product as pale yellow powder (A) -7b in 85% yield.
(b) (A) -7b (0.04mol) was added to 50 ml of anhydrous dichloromethane, anhydrous aluminum trichloride (0.12mol) was added in portions, a dichloromethane solution of chloroacetyl chloride (0.04mol) was added dropwise at 0 to 10 ℃ and stirred at room temperature for 10 hours, and the reaction was monitored by spotting plates after completion. Slowly adding the reaction solution into ice water with the same amount as the solvent, extracting with ethyl acetate, washing with water, drying with anhydrous magnesium sulfate, concentrating, and recrystallizing with ethanol to obtain a light yellow product (A) -7c with a yield of 83%;
(c) to (A) -7c (0.03mol) obtained above was added dimethyl sulfoxide (50 ml) and sodium 2-hydroxyethanesulfonate (0.03mol), and the reaction mixture was stirred at 90 ℃ for 24 hours, and after completion of the reaction, 100 ml of saturated saline was added to the reaction mixture, followed by three-time extraction with 100 ml of acetonitrile, drying over magnesium sulfate, concentration under reduced pressure to give a pale yellow solid, and recrystallization from isopropanol to give (A) -23 in 93% yield.
(A) -24 was synthesized by the same reaction except that sodium 2-hydroxyethanesulfonate was changed to potassium 2-hydroxyethanesulfonate.
Example 5: thin film polymerization
The photocuring test samples were formulated according to the following weight percentages: 28 parts of epoxy acrylate; 32 parts of polyester acrylate; 6 parts of hexanediol diacrylate; 24 parts of pentaerythritol triacrylate; 16 parts of titanium dioxide dye; 4 parts of the selected photoinitiator of example (A)1- (A) 18.
And taking part of the mixture, fully grinding the mixture uniformly, coating the mixture on a white ABS substrate, and forming a pattern layer of about 20 micrometers under air. Irradiation was carried out with a 385nm LED curing tester (light, Guangzhou) 2 cm from the sample, at a conveyor speed of 20 m/min. And judging the complete curing condition of the coating by finger-pressing and scraping. The photoinitiators in the compounds of the above examples all initiate complete curing of the film layer, and show good photoinitiation performance.
Example 6: thick film polymerization
The formulation was the same as in example 5.
A portion of the above mixture was ground thoroughly to a thickness of about 200 μm under air on a white ABS substrate. Irradiation was carried out with a 385nm LED curing tester (light, Guangzhou) 2 cm from the sample, at a conveyor speed of 10 m/min. And judging the complete curing condition of the coating by pressing and scraping. The photoinitiators in the compounds of example (A)1- (A)18 all initiate complete curing of the film layer and show good photoinitiating properties.
Example 7: aqueous polymerization
The photocuring test samples were formulated according to the following weight percentages: 12 parts of acrylamide; 70 parts of deionized water; 16 parts of titanium dioxide dye; 2 parts of the photoinitiator of example (A)19- (A) 24.
A portion of the above mixture was ground thoroughly to a thickness of about 200 μm under air on a white ABS substrate. Irradiation was carried out with a 385nm LED curing tester (light, Guangzhou) 2 cm from the sample, at a conveyor speed of 10 m/min. And judging the complete curing condition of the coating by pressing and scraping. The photoinitiators in the compounds of the above examples all initiate complete curing of the film layer, and show good photoinitiation performance.
Example 8: aqueous polymerization
A hydrogel (1% w/w at room temperature) was constructed by mixing hydroxyethyl methacrylate HEMA (0.5M), maleimido polyethylene glycol monomethyl ether mtthoxy PEGMA (0.2M, Mn ≈ 300) and polyethylene glycol dimethacrylate PEGDMA (0.02M, Mn ≈ 2000) in water and with the initiator of example 1. The mixture was stirred and poured into a mold for crosslinking for 3 hours. The resulting hydrogel was extracted with fresh PBS to remove unreacted monomers and residual chemicals, and then tested after placing the hydrogel in PBS for further stabilization in the dark for 48 hours.
The test shows that the polymerization conversion rate of the hydrogel is 7.5 percent, the dynamic equilibrium water content is 90.2 percent, wherein the calculation formula of the polymerization conversion rate is
Figure RE-GDA0002891267670000071
Wherein m is0Is the mass of all monomers and initiators, mdryIs the actual quality of the hydrogel obtained.
The calculation formula of the dynamic Equilibrium Water Content (EWC) is
Figure RE-GDA0002891267670000072
Wherein m iswetIs the actual mass of the hydrogel, mdryThe mass was obtained after the hydrogel was dried by blotting the surface water with filter paper.
Hydrogel samples after equilibration with PBS for at least 48 hours were cut into cylinders of 20mm diameter. The dynamic viscoelasticity of the hydrogels was measured at 25 ℃ on a stress control rheometer (HAAKE MARS III) using a 20mm parallel plate. The gap between the upper plate and the sample plate was set by first moving the upper plate about 2mm above the sample surface. The upper plate descends very slowly (5 μms)-1) The normal force was monitored simultaneously and stopped at a limit normal force of 100 mN. Dynamic stress and frequency sweep rheology experiments were performed on the hydrogels. A stress sweep was first performed to explore the linear viscoelastic region (LVER) at a constant frequency of 1Hz over a stress range of 1-100 Pa. Recording frequency sweep vibration in constant stress (10pa) modeTested on an oscillation and controlled in the frequency range of 0.1-50 Hz to keep the measured values in the linear range. The values of G' and G "are determined at 1 Hz. The final test results were G' ═ 1660.2Pa and G ═ 171.5 Pa.
It is emphasized that the above-described examples are merely illustrative of some tests and are not to be considered as limiting tests or conditions. The scope of the innovation covered by this application is defined by the claims.

Claims (6)

1. A hydrosoluble diphenyl sulfide ketone formate photoinitiator is characterized in that the molecular structure of the photoinitiator is shown as a general formula (A):
Figure RE-FDA0002891267660000011
in the formula (A), the compound (A),
R1represents having a structure selected from-+N(R)3X-and-SO3M and bonded to the carbonyl group of the formula (A) through a carbon chain or a carbon-oxygen chain, wherein R represents a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group, and X is F, Br or I; m is K or Na ion;
R2represents an alkyl group, an aryl group or an alkoxy group, and m represents an integer of 0 to 4;
R3represents an alkyl group, an aryl group, a benzyl group or an aralkyl group.
2. The method for synthesizing the water-soluble diphenyl sulfide ketone formate photoinitiator as claimed in claim 1, wherein the general synthesis process is as shown in the following formula:
Figure RE-FDA0002891267660000012
3. the method of claim 2, wherein the initiator is prepared by a process comprising the steps of:
(1) in the step a, halogenated benzene (chlorobenzene, bromobenzene or fluorobenzene) reacts with oxalyl chloride monoester under the catalysis of aluminum trichloride to obtain 4-halogenated phenyl ketone formate, and a used solvent is dichloromethane;
(2) in step b, the product of step a is 4-halophenyl ketoformate with R2The substituted thiophenol is used for preparing diphenyl sulfide ketone formate under the alkaline condition, wherein the alkali can be organic alkali and inorganic alkali, preferably sodium methoxide and potassium carbonate, and is catalyzed by CuI when necessary;
(3) in the step c, bromoalkyl acyl chloride is used to react under the catalysis of aluminum trichloride to generate a target product, and the used solvent is dichloromethane;
(4) in step d, the product of step c is reacted with a tertiary amine or 2-hydroxyethanesulfonate (sodium or potassium salt) to prepare a photoinitiator represented by the general formula (A).
4. A process according to claim 2 or 3, wherein in step c n-1-11 of the bromoalkyl acid chloride.
5. A mixture according to claim 1 containing a compound of the above general formula (a), curable by irradiation with light (uv or visible or LED light or equivalent light sources); the light radiation curing formula system is characterized in that:
(1) containing at least one compound described by the general formula (I) as a photoinitiator or one of its components;
(2) containing at least one free-radically polymerizable compound containing an ethylenic bond (C ═ C);
the compound of the formula (I) is suitably contained in an amount of 0.01 to 30 parts by weight, preferably 0.5 to 10 parts by weight, per 100 parts by weight of the total amount of the ethylenically unsaturated components in the system; suitable radiation-curable systems comprise polymerizable ethylenically unsaturated components which are compounds or mixtures which can be crosslinked by free-radical polymerization of the double bonds, which ethylenically unsaturated components can be monomers, oligomers or prepolymers, or mixtures or copolymers thereof, or aqueous dispersions of the above-mentioned components.
6. A process for preparing a mixture of light radiation curable formulations according to claim 5, characterized by the following specific steps:
(1) according to the monomer: photoinitiator (2): the mass ratio of the auxiliary agent is 100: 1-1.5: 0-4.5 parts of raw materials;
(2) stirring to fully dissolve; (3) irradiating the polymerization system by light sources with different wavelengths or different light intensities;
(4) researching the polymerization conversion rate by the change of the characteristic peak by an online infrared method;
wherein: the light source in the step (3) can be a mercury lamp (high pressure, medium pressure and low pressure), LEDs with the emission wavelength of 313-425 nm, and an LDI light source.
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