CN100447127C - One-component hydrogen abstraction type photoinitiator and its preparation method and use - Google Patents

Abstract

The present invention relates to compounds represented by general formulas (I) and (II) and their preparation methods and uses. Wherein: R and R' are independently selected from hydrogen, alkyl, and alkoxy; A represents the formula -[(CH₂)_nO]-, -[( CH₂)_nCOO]-, or -[(CH₂)_nNH]-group;n=0～3;R₁ and R₂ are independently selected from C_1-18 alkyl, C_{1- 18} Hydroxyalkyl, phenyl, benzyl, N,N-dimethylpropyl. As a single-component hydrogen abstraction type photoinitiator, the above compound of the present invention has good solubility, low mobility, low preparation cost, simple operation and high product yield, and can directly replace benzophenone as a photoinitiator , and its performance is superior to that of benzophenone, and it has broad application prospects in the field of UV curing.

Description

One-component hydrogen abstraction type photoinitiator and its preparation method and use

technical field

The invention relates to a single-component hydrogen abstraction photoinitiator, a preparation method and application thereof, and belongs to the field of photosensitive polymer materials.

Background technique

As a new type of green technology, UV curing technology has a wide range of applications in coatings, adhesives, printing inks, photolithography and biomaterials. UV curing systems generally include the following three main components: oligomers (or prepolymers, resins), which endow materials with basic physical and chemical properties; monomers, also known as reactive diluents, are mainly used to adjust the Viscosity, but also has an effect on cure rate and material properties; Photoinitiators, used to generate free radicals or ions that can initiate polymerization.

Photoinitiator (photoinitiator) is a key component of UV curing system, which is directly related to whether the oligomer and diluent of the formulation system can quickly change from liquid to solid when light is irradiated. Moreover, photoinitiators are required to have good curing rate, good surface curing activity, low odor, low yellowing and good solubility. In addition, with consumers becoming increasingly sensitive to chemical contamination in food and compliance with relevant food processing laws that may be formulated and improved in the future, the tendency of photoinitiators to migrate and be captured after the curing process should be minimized .

Benzophenone, due to its low price, good surface curing, low yellowing and good solubility, has become one of the most widely used photoinitiators in UV curing systems. However, its low molecular weight, strong odor, and extremely easy migration from the cured product to the surface limit its application, especially in packaging materials that come into contact with food.

Benzophenones have a severe tendency to migrate or be captured from cured products. Because of its bimolecular reaction with the amine co-initiator, two free radicals are generated, of which the amine alkyl radical has a higher activity and can react with the (meth)acrylate double bond of the oligomer or monomer to generate Incorporated into the cured product, while the carbonyl radical generated by benzophenone is less reactive with the (meth)acrylate double bond, plays a role in the termination reaction, or remains in the in cured products. Therefore, there is a wide demand for benzophenone substitutes with good reactivity, good surface curing ability, low migration, low yellowing and good solubility properties.

The invention combines benzophenone and amine in one molecule through a chemical method to make a single-component hydrogen abstraction type photoinitiator, which can significantly improve its migration and odor problems.

Contents of the invention

The problem to be solved by the present invention is to provide a compound and its preparation method and use. The obtained compound is used as a single-component hydrogen abstraction type photoinitiator for UV curing, which not only has good reactivity, good surface curing ability, good solubility, not easy to yellow, and low migration, low odor.

The technical scheme provided by the present invention is: a kind of compound, its structural formula is as shown in (I) or (II):

A represents a group of the formula -[(CH ₂ ) _n O]-, -[(CH ₂ ) _n COO]-, or -[(CH ₂ ) _n NH]-, where n=0~3;

R and R' are independently selected from hydrogen, C _1-18 alkyl, C _1-18 alkoxy;

R ₁ and R ₂ are independently selected from C _1-18 alkyl, C _1-18 hydroxyalkyl, phenyl, benzyl, N,N-dimethylpropyl.

The present invention also provides a preparation method of the above-mentioned single-component hydrogen abstraction type photoinitiator:

Dissolve 1 molar fraction of 4-hydroxyalkylbenzophenone, 4-carboxyalkylbenzophenone or 4-aminoalkylbenzophenone and 1-2 molar fractions of triethylamine in room temperature Obtain solution A in an organic solvent, then place solution A in an ice-water bath, stir to lower the temperature to 0-5°C; dissolve 1-2 molar parts of acryloyl chloride in an organic solvent at room temperature to obtain solution B, and then With the rate of 0.2-0.6mL per second, solution B is added dropwise in the solution A of stirring, after dropwise addition, continue stirring reaction 4-12 hour; Filter and remove the triethylamine hydrochloride white solid that generates, wash ( Such as washing the reaction solution with 5%-10% aqueous sodium hydroxide solution and deionized water for 1-3 times), drying (such as drying the reaction solution with anhydrous sodium sulfate), and removing the solvent in the reaction solution under reduced pressure to obtain acrylic acid Esterified 4-hydroxyalkylbenzophenones, 4-carboxyalkylbenzophenones or 4-aminoalkylbenzophenones;

1 mole fraction of the acrylated 4-hydroxyalkylbenzophenone, 4-carboxyalkylbenzophenone or 4-aminoalkylbenzophenone obtained in step a is dissolved in a protic solvent at room temperature Solution C is obtained; then 1 molar fraction of secondary amine or 0.5 molar fraction of primary amine is dissolved in a protic solvent at room temperature, and is added dropwise to the stirred solution C at a rate of 0.2-0.6 mL per second at room temperature During the Michael addition reaction, after the dropwise addition, the stirring reaction was continued for 0.5-5 hours; the protic solvent was distilled off under reduced pressure, and then treated by column chromatography to obtain the compound described in formula (I) or (II).

The preparation of such photoinitiators is carried out in the presence of solvents. For acrylate reactions, the nature of the solvent is not critical to the invention so long as it has no adverse effect on the reagents or reaction. Solvents suitable for this step reaction include: methylene chloride, chloroform, benzene, toluene or xylene and the like. For the Michael addition reaction, a protic solvent needs to be used because it catalyzes the reaction. Suitable solvents include: methanol or ethanol, etc.

The present invention also provides a UV curable composition, comprising:

(a) A polymerizable component comprising at least one ethylenically unsaturated photoreactive resin and a reactive diluent; the reactive diluent is a monofunctional, difunctional or multifunctional acrylate monomer or methacrylate monomer ;

(b) Compounds with structural formulas as described in (I) or (II).

The unsaturated photoreactive resin is epoxy acrylic resin, epoxy methacrylic resin, polyester acrylic resin, polyester methacrylic resin, polyurethane acrylic resin, polyurethane methacrylic resin, polyacrylate acrylic resin, polyester Acrylate methacrylate, polyether acrylic or polyether methacrylate.

The one-component hydrogen abstraction type photoinitiator of the present invention combines benzophenone and amine in one molecule through a chemical method, and the obtained product is liquid, and has good solubility in an ultraviolet curing system. At the same time, in the UV curing process, the amine alkyl free radical has a high activity and can be combined into the cured product by reacting with the (meth)acrylate double bond of the oligomer or monomer. The ketone and amine are linked into one molecule, so the benzophenone is also incorporated into the cured product, effectively reducing the mobility of the benzophenone. The preparation cost is low, the operation is simple, the yield of the product is high, the product has good reactivity, good surface curing ability, good solubility, is not easy to yellow, and has low migration and low odor. It can directly replace benzophenone as a photoinitiator, and its performance is better than that of benzophenone, so it has broad application prospects in the field of ultraviolet light curing.

Detailed ways

The following examples illustrate the invention in detail, but do not limit the scope of the invention.

Synthetic Example:

Example 1:

Dissolve 0.1mol 4-hydroxybenzophenone and 0.11mol triethylamine in 100mL dichloromethane at room temperature, place it in an ice-water bath, stir to lower the temperature to 0-5°C; then dissolve 0.11mol Dissolve acryloyl chloride in 50mL of dichloromethane at room temperature, add it to the constant pressure dropping funnel, and slowly add the acryloyl chloride solution dropwise to the stirred solution at a rate of 0.2mL per second. After the dropwise addition, continue Stir the reaction for 12 hours; remove the white solid triethylamine hydrochloride generated by filtration, wash the reaction solution twice with 10wt% aqueous sodium hydroxide solution and deionized water, then dry the reaction solution with anhydrous sodium sulfate; distill under reduced pressure The solvent in the reaction solution was removed to obtain acrylated 4-hydroxybenzophenone.

Dissolve 0.05 mol of the above-mentioned acrylated 4-hydroxybenzophenone in 80 mL of ethanol at room temperature; then dissolve 0.05 mol of diethylamine in 50 mL of ethanol and add it to a constant pressure dropping funnel. At room temperature, at a rate of 0.2 mL per second, slowly drop the diethylamine solution in the constant pressure dropping funnel into the stirred acrylated 4-hydroxybenzophenone solution to perform Michael addition reaction. After the dropwise addition, the stirring reaction was continued for 2 hours; the ethanol was distilled off under reduced pressure, and then purified by column chromatography to obtain a light yellow liquid product III. The structure of the product was identified by ¹ HNMR. ¹ H-NMR (CDCl ₃ , 600MHz): δ (ppm): 1.33 (CH ₃ ); 2.74, 3.62 (CH ₂ ); 7.25, 7.48, 7.59, 7.80, 7.87 (CH, Ar).

Example 2:

Dissolve 0.05mol 4-hydroxybenzophenone and 0.055mol triethylamine in 50mL toluene at room temperature, place it in an ice-water bath, stir to lower the temperature to 0-5°C; then add 0.055mol acryloyl chloride Dissolve it in 30mL toluene at room temperature, add it to the constant pressure dropping funnel, and slowly add the acryloyl chloride solution dropwise to the stirred solution at a rate of 0.3mL per second. After the dropwise addition, continue to stir for 8 hours. ; Remove the triethylamine hydrochloride white solid generated by filtration, wash the reaction solution 2 times with 6wt% sodium hydroxide aqueous solution and deionized water respectively, then dry the reaction solution with anhydrous sodium sulfate; solvent to obtain acrylated 4-hydroxybenzophenone.

Dissolve 0.03 mol of the above-mentioned acrylated 4-hydroxybenzophenone in 60 mL of ethanol at room temperature; then dissolve 0.03 mol of diethanolamine in 30 mL of ethanol, and add it to a constant pressure dropping funnel. At room temperature, at a rate of 0.4 mL per second, slowly drop the diethanolamine solution in the constant pressure dropping funnel into the stirred acrylated 4-hydroxybenzophenone solution to perform Michael addition reaction. After the dropwise addition, the stirring reaction was continued for 2 hours; the ethanol was distilled off under reduced pressure, and then purified by column chromatography to obtain the light yellow liquid product IV. The product was identified by ¹ HNMR. ¹ H-NMR (CDCl ₃ , 600MHz): δ (ppm): 2.88, 3.64, 3.97 (CH ₂ ); 7.25, 7.48, 7.59, 7.80, 7.87 (CH, Ar).

Example 3:

Dissolve 0.05mol 4-hydroxybenzophenone and 0.055mol triethylamine in 50mL dichloromethane at room temperature, place it in an ice-water bath, stir to lower the temperature to 0-5°C; then dissolve 0.055mol Dissolve acryloyl chloride in 30 mL of dichloromethane at room temperature, add it to the constant pressure dropping funnel, and slowly add the acryloyl chloride solution dropwise to the stirred solution at a rate of 0.6 mL per second. Stir the reaction for 8 hours; remove the white solid triethylamine hydrochloride generated by filtration, wash the reaction solution twice with 10wt% aqueous sodium hydroxide solution and deionized water, then dry the reaction solution with anhydrous sodium sulfate; distill under reduced pressure The solvent in the reaction solution was removed to obtain acrylated 4-hydroxybenzophenone.

Dissolve 0.03 mol of the above-mentioned acrylated 4-hydroxybenzophenone in 60 mL of methanol at room temperature; then dissolve 0.03 mol of piperidine in 30 mL of methanol and add it to a constant pressure dropping funnel. At room temperature, at a rate of 0.2 mL per second, slowly drop the piperidine solution in the constant pressure dropping funnel into the stirred acrylated 4-hydroxybenzophenone solution to perform Michael addition reaction. After the dropwise addition, the stirring reaction was continued for 2 hours; the methanol was distilled off under reduced pressure, and then purified by column chromatography to obtain a light yellow liquid product V. The structure of the product was identified by ¹ HNMR. ¹ H-NMR (CDCl ₃ , 600MHz): δ (ppm): 1.83, 2.68, 3.64 (CH ₂ ); 7.25, 7.48, 7.59, 7.80, 7.87 (CH, Ar).

Example 4:

Dissolve 0.05mol 4-hydroxymethylbenzophenone and 0.055mol triethylamine in 50mL dichloromethane at room temperature, place it in an ice-water bath, stir to lower the temperature to 0-5°C; then place Dissolve 0.055mol of acryloyl chloride in 30mL of dichloromethane at room temperature, add it to the constant pressure dropping funnel, and slowly add the acryloyl chloride solution dropwise to the stirred solution at a rate of 0.2mL per second. , continue to stir and react for 8 hours; remove the triethylamine hydrochloride white solid generated by filtration, wash the reaction solution 2 times with 9wt% sodium hydroxide aqueous solution and deionized water respectively, then dry the reaction solution with anhydrous sodium sulfate; The solvent in the reaction solution was distilled off under pressure to obtain acrylated 4-hydroxymethylbenzophenone.

Dissolve 0.03 mol of the above-mentioned acrylated 4-hydroxymethylbenzophenone in 60 mL of methanol at room temperature; then dissolve 0.03 mol of morpholine in 30 mL of methanol and add it to a constant pressure dropping funnel. At room temperature, at a rate of 0.2 mL per second, slowly drop the morpholine solution in the constant pressure dropping funnel into the stirred acrylated 4-hydroxymethylbenzophenone solution to perform Michael addition reaction . After the dropwise addition, the stirring reaction was continued for 2 hours; the methanol was distilled off under reduced pressure, and then purified by column chromatography to obtain the light yellow liquid product VI. The structure of the product was identified by ¹ HNMR. ¹ H-NMR (CDCl ₃ , 600MHz): δ (ppm): 2.70, 3.68, 4.01, 5.67 (CH ₂ ); 7.25, 7.48, 7.59, 7.80, 7.87 (CH, Ar).

Example 5:

Dissolve 0.1mol 4-hydroxypropyl benzophenone and 0.11mol triethylamine in 100mL dichloromethane at room temperature, place it in an ice-water bath, stir to lower the temperature to 0-5°C; then place Dissolve 0.11mol of acryloyl chloride in 50mL of dichloromethane at room temperature, add it to the constant pressure dropping funnel, and slowly add the acryloyl chloride solution dropwise to the stirred solution above at a rate of 0.3mL per second. , continue to stir and react for 12 hours; remove the triethylamine hydrochloride white solid generated by filtration, wash the reaction solution 2 times with 10wt% sodium hydroxide aqueous solution and deionized water respectively, then dry the reaction solution with anhydrous sodium sulfate; The solvent in the reaction solution was distilled off under pressure to obtain acrylated 4-hydroxypropyl benzophenone.

Dissolve 0.06 mol of the above-mentioned acrylated 4-hydroxypropyl benzophenone in 100 mL of methanol at room temperature; then dissolve 0.03 mol of n-butylamine in 30 mL of methanol and add it to a constant pressure dropping funnel. At room temperature, at a rate of 0.3 mL per second, slowly drop the n-butylamine solution in the constant pressure dropping funnel into the stirred acrylated 4-hydroxypropyl benzophenone solution to perform Michael addition reaction. After the dropwise addition, the stirring reaction was continued for 2 hours; the methanol was distilled off under reduced pressure, and then purified by column chromatography to obtain the light yellow viscous liquid product VII. The structure of the product was identified by ¹ HNMR. ¹ H-NMR (CDCl ₃ , 600MHz): δ(ppm): 1.40 (CH ₃ ); 1.67, 1.73, 2.24, 2.69, 2.88, 3.65, 4.43 (CH ₂ ); 7.25, 7.48, 7.59, 7.80, 7.87 ( CH, Ar).

Embodiment 6:

Dissolve 0.1mol of 4-amino-4'-methylbenzophenone and 0.11mol of triethylamine in 100mL of dichloromethane at room temperature, place it in an ice-water bath, stir to lower the temperature to 0- 5°C; then dissolve 0.11 mol of acryloyl chloride in 50 mL of dichloromethane at room temperature, add it to the constant pressure dropping funnel, and slowly drop the acryloyl chloride solution into the stirred solution at a rate of 0.2 mL per second , after the dropwise addition, continue to stir and react for 12 hours; remove the white solid of triethylamine hydrochloride generated by filtration, wash the reaction solution twice with 8wt% aqueous sodium hydroxide solution and deionized water, and then wash the reaction solution with anhydrous sodium sulfate The reaction solution was dried; the solvent in the reaction solution was distilled off under reduced pressure to obtain acrylated 4-amino-4'-methylbenzophenone.

Dissolve 0.05mol of the above-mentioned acrylated 4-amino-4'-methylbenzophenone in 80mL of ethanol at room temperature; then dissolve 0.05mol of diisopropylamine in 50mL of ethanol and add to the constant pressure dropping funnel middle. At room temperature, at a rate of 0.3 mL per second, slowly drop the diisopropylamine solution in the constant pressure dropping funnel into the stirred acrylated 4-amino-4'-methylbenzophenone solution , for a Michael addition reaction. After the dropwise addition, the stirring reaction was continued for 2 hours; the ethanol was distilled off under reduced pressure, and then purified by column chromatography to obtain the light yellow liquid product VIII. The structure of the product was identified by ¹ HNMR. ¹ H-NMR (CDCl ₃ , 600MHz): δ (ppm): 1.38, 2.68 (CH ₃ ); 3.64 (CH ₂ ); 3.31 (CH); 7.25, 7.48, 7.59, 7.80, 7.87 (CH, Ar).

Embodiment 7:

Dissolve 0.1mol 4-amino-4'-octadecylbenzophenone and 0.11mol triethylamine in 100mL toluene at room temperature, place it in an ice-water bath, stir to lower the temperature to 0- 5°C; then dissolve 0.11mol of acryloyl chloride in 50mL of toluene at room temperature, add it to the constant pressure dropping funnel, slowly add the acryloyl chloride solution dropwise to the stirred solution above at a rate of 0.4mL per second, drop After the addition is complete, continue to stir the reaction for 12 hours; remove the white solid triethylamine hydrochloride generated by filtration, wash the reaction solution twice with 7wt% aqueous sodium hydroxide solution and deionized water, and then dry the reaction solution with anhydrous sodium sulfate solution; the solvent in the reaction solution was distilled off under reduced pressure to obtain acrylated 4-amino-4'-octadecylbenzophenone.

Dissolve 0.05mol of the above-mentioned acrylated 4-amino-4'-octadecylbenzophenone in 80mL of methanol at room temperature; then dissolve 0.05mol of dicyclohexylamine in 50mL of methanol and add to constant pressure in the dropping funnel. At room temperature, at a rate of 0.2 mL per second, slowly drop the dicyclohexylamine solution in the constant pressure dropping funnel into the stirred acrylated 4-amino-4'-octadecylbenzidine In the ketone solution, the Michael addition reaction takes place. After the dropwise addition, the stirring reaction was continued for 2 hours; the methanol was distilled off under reduced pressure, and then purified by column chromatography to obtain a light yellow viscous liquid product IX. The structure of the product was identified by ¹ HNMR. ¹ H-NMR (CDCl ₃ , 600MHz): δ(ppm): 1.66 (CH ₃ ); 1.62, 1.66, 1.71-1.96, 2.88, 3.83 (CH ₂ ); 2.91 (CH); 7.25, 7.48, 7.59, 7.80 , 7.87 (CH, Ar).

Embodiment 8:

Dissolve 0.1mol of 4-aminoethyl-4'-nonyloxybenzophenone and 0.11mol of triethylamine in 100mL of toluene at room temperature, place it in an ice-water bath, stir to lower the temperature to 0- 5°C; then dissolve 0.11 mol of acryloyl chloride in 50 mL of toluene at room temperature, add it to the constant pressure dropping funnel, slowly add the acryloyl chloride solution dropwise to the stirred solution at a rate of 0.5 mL per second, drop After the addition is complete, continue to stir and react for 12 hours; remove the white solid triethylamine hydrochloride generated by filtration, wash the reaction solution twice with 8wt% aqueous sodium hydroxide solution and deionized water, and then dry the reaction solution with anhydrous sodium sulfate solution; the solvent in the reaction solution was distilled off under reduced pressure to obtain acrylated 4-aminoethyl-4'-nonyloxybenzophenone.

Dissolve 0.05mol of the above-mentioned acrylated 4-aminoethyl-4'-nonyloxybenzophenone in 80mL of methanol at room temperature; then dissolve 0.05mol of N-methylethanolamine in 50mL of methanol and add to constant In the dropping funnel. At room temperature, at a rate of 0.5 mL per second, slowly drop the N-methylethanolamine solution in the constant pressure dropping funnel into the stirred acrylated 4-aminoethyl-4'-nonyloxydiphenyl In the ketone solution, the Michael addition reaction was carried out. After the dropwise addition, the stirring reaction was continued for 2 hours; the methanol was distilled off under reduced pressure, and then purified by column chromatography to obtain a light yellow liquid product X. The structure of the product was identified by ¹ HNMR. ¹ H-NMR (CDCl ₃ , 600MHz): δ(ppm): 1.67, 2.61 (CH ₃ ); 1.62, 1.66, 1.71-1.96, 2.88, 3.15, 3.58, 3.86, 3.96 (CH ₂ ); 7.25, 7.48, 7.59, 7.80, 7.87 (CH, Ar).

Embodiment 9:

Dissolve 0.1mol 4-aminobenzophenone and 0.11mol triethylamine in 100mL benzene at room temperature, place it in an ice-water bath, stir to lower the temperature to 0-5°C; then add 0.11mol propylene Dissolve acryloyl chloride in 50mL of benzene at room temperature, add it to the constant pressure dropping funnel, and slowly add the acryloyl chloride solution dropwise to the stirred solution at a rate of 0.4mL per second. After the dropwise addition, continue to stir for 12 hour; remove the triethylamine hydrochloride white solid generated by filtration, wash the reaction solution 2 times with 7wt% sodium hydroxide aqueous solution and deionized water respectively, then dry the reaction solution with anhydrous sodium sulfate; remove the reaction solution by distillation under reduced pressure In the solvent, the acrylated 4-aminobenzophenone was obtained.

Dissolve 0.05 mol of the above-mentioned acrylated 4-aminobenzophenone in 80 mL of ethanol at room temperature; then dissolve 0.05 mol of diphenylamine in 50 mL of ethanol and add it to a constant pressure dropping funnel. At room temperature, at a rate of 0.3 mL per second, slowly drop the diphenylamine solution in the constant pressure dropping funnel into the stirred acrylated 4-aminobenzophenone solution to perform Michael addition reaction. After the dropwise addition, the stirring reaction was continued for 2 hours; the ethanol was distilled off under reduced pressure, and then purified by column chromatography to obtain the light yellow viscous liquid product XI. The structure of the product was identified by ¹ HNMR. ¹ H-NMR (CDCl ₃ , 600MHz): δ (ppm): 4.34 (CH ₂ ); 6.43, 6.58, 7.04, 7.25, 7.48, 7.59, 7.80, 7.87 (CH, Ar).

Example 10:

Dissolve 0.1mol 4-aminobenzophenone and 0.11mol triethylamine in 100mL benzene at room temperature, place it in an ice-water bath, stir to lower the temperature to 0-5°C; then add 0.11mol propylene Dissolve acryloyl chloride in 50mL of benzene at room temperature, add it to the constant pressure dropping funnel, and slowly add the acryloyl chloride solution dropwise to the stirred solution at a rate of 0.5mL per second. After the dropwise addition, continue to stir for 12 hour; remove the triethylamine hydrochloride white solid generated by filtration, wash the reaction solution 2 times with 9wt% sodium hydroxide aqueous solution and deionized water respectively, then dry the reaction solution with anhydrous sodium sulfate; remove the reaction solution by distillation under reduced pressure In the solvent, the acrylated 4-aminobenzophenone was obtained.

Dissolve 0.05 mol of the above-mentioned acrylated 4-aminobenzophenone in 80 mL of ethanol at room temperature; then dissolve 0.025 mol of cyclohexylamine in 50 mL of ethanol and add it to a constant pressure dropping funnel. At room temperature, at a rate of 0.4 mL per second, slowly drop the cyclohexylamine solution in the constant pressure dropping funnel into the stirred acrylated 4-aminobenzophenone solution to perform Michael addition reaction . After the dropwise addition, the stirring reaction was continued for 2 hours; the ethanol was distilled off under reduced pressure, and then purified by column chromatography to obtain the light yellow viscous liquid product XII. The structure of the product was identified by ¹ HNMR. ¹ H-NMR (CDCl ₃ , 600MHz): δ (ppm): 1.72-1.96, 3.63 (CH ₂ ); 2.91 (CH); 7.25, 7.48, 7.59, 7.80, 7.87 (CH, Ar).

Example 11:

Dissolve 0.1mol 4-carboxybenzophenone and 0.11mol triethylamine in 100mL toluene at room temperature, place it in an ice-water bath, stir to lower the temperature to 0-5°C; then add 0.11mol acryloyl chloride Dissolve in 50mL of toluene at room temperature, add it to the constant pressure dropping funnel, and slowly add the acryloyl chloride solution dropwise to the stirred solution at a rate of 0.2mL per second. After the dropwise addition, continue to stir for 8 hours. Remove the triethylamine hydrochloride white solid that generates by filtration, wash the reaction solution 3 times with 6wt% sodium hydroxide aqueous solution and deionized water respectively, then dry the reaction solution with anhydrous sodium sulfate; solvent to obtain acrylated 4-carboxybenzophenone.

Dissolve 0.05 mol of the above-mentioned acrylated 4-carboxybenzophenone in 80 mL of ethanol at room temperature; then dissolve 0.05 mol of N-methylaniline in 50 mL of ethanol and add it to a constant pressure dropping funnel. At room temperature, at a rate of 0.3 mL per second, slowly drop the N-methylaniline solution in the constant pressure dropping funnel into the stirred acrylated 4-carboxybenzophenone solution to perform Michael addition reaction. After the dropwise addition, the stirring reaction was continued for 3 hours; the ethanol was distilled off under reduced pressure, and then purified by column chromatography to obtain a light yellow liquid product X III. The structure of the product was identified by ¹ HNMR. ¹ H-NMR (CDCl ₃ , 600MHz): δ (ppm): 3.18 (CH ₃ ); 4.63 (CH ₂ ); 6.59, 6.93, 7.25, 7.42, 7.48, 7.59, 7.80, 7.87 (CH, Ar).

Example 12:

Dissolve 0.1mol 4-carboxybenzophenone and 0.11mol triethylamine in 100mL benzene at room temperature, place it in an ice-water bath, stir to lower the temperature to 0-5°C; then add 0.11mol acryloyl chloride Dissolve in 50mL of benzene at room temperature, add it to the constant pressure dropping funnel, and slowly add the acryloyl chloride solution dropwise to the stirred solution at a rate of 0.2mL per second. After the dropwise addition, continue to stir and react for 8 hours ; Remove the triethylamine hydrochloride white solid generated by filtration, wash the reaction solution 2 times with 6wt% sodium hydroxide aqueous solution and deionized water respectively, then dry the reaction solution with anhydrous sodium sulfate; solvent to obtain acrylated 4-carboxybenzophenone.

Dissolve 0.05 mol of the above-mentioned acrylated 4-carboxybenzophenone in 80 mL of methanol at room temperature; then dissolve 0.05 mol of tetrahydropyrrole in 30 mL of methanol and add it to a constant pressure dropping funnel. At room temperature, at a rate of 0.2 mL per second, slowly drop the tetrahydropyrrole solution in the constant pressure dropping funnel into the stirred acrylated 4-carboxybenzophenone solution to perform Michael addition reaction. After the dropwise addition, the stirring reaction was continued for 4 hours; the methanol was distilled off under reduced pressure, and then purified by column chromatography to obtain a light yellow liquid product X IV. The product was identified by ¹ HNMR. ¹ H-NMR (CDCl ₃ , 600MHz): δ (ppm): 1.93, 2.58, 3.63 (CH ₂ ); 7.25, 7.48, 7.59, 7.80, 7.87 (CH, Ar).

Example 13:

Dissolve 0.1mol 4-carboxyethylbenzophenone and 0.11mol triethylamine in 100mL toluene at room temperature, place it in an ice-water bath, stir to lower the temperature to 0-5°C; then dissolve 0.11mol Dissolve acryloyl chloride in 50mL of toluene at room temperature, add it to the constant pressure dropping funnel, and slowly add the acryloyl chloride solution dropwise to the stirred solution at a rate of 0.2mL per second. After the dropwise addition, continue to stir the reaction 10 hours; Remove the triethylamine hydrochloride white solid generated by filtration, wash the reaction solution twice with 9wt% sodium hydroxide aqueous solution and deionized water respectively, then dry the reaction solution with anhydrous sodium sulfate; remove the reaction solution by distillation under reduced pressure Solvent in the solution to obtain acrylated 4-carboxyethyl benzophenone.

Dissolve 0.05mol of the above-mentioned acrylated 4-carboxyethylbenzophenone in 80mL of methanol at room temperature; then dissolve 0.05mol of N-ethylethanolamine in 30mL of methanol and add it to a constant pressure dropping funnel. At room temperature, at a rate of 0.6 mL per second, slowly drop the N-ethylethanolamine solution in the constant pressure dropping funnel into the stirred acrylated 4-carboxyethyl benzophenone solution to perform Michael Addition reaction. After the dropwise addition, the stirring reaction was continued for 3 hours; the methanol was distilled off under reduced pressure, and then purified by column chromatography to obtain the light yellow liquid product XV. The product was identified by ¹ HNMR. ¹ H-NMR (CDCl ₃ , 600MHz): δ(ppm): 1.33 (CH ₃ ); 2.73, 2.88, 2.90, 3.16, 3.64, 3.96 (CH ₂ ); 7.25, 7.48, 7.59, 7.80, 7.87 (CH, Ar).

Example 14:

Dissolve 0.1mol 4-carboxybenzophenone and 0.11mol triethylamine in 100mL toluene at room temperature, place it in an ice-water bath, stir to lower the temperature to 0-5°C; then add 0.11mol acryloyl chloride Dissolve in 50mL of toluene at room temperature, add it to the constant pressure dropping funnel, and slowly add the acryloyl chloride solution dropwise to the stirred solution at a rate of 0.6mL per second. After the dropwise addition, continue to stir for 8 hours. ; Remove the triethylamine hydrochloride white solid generated by filtration, wash the reaction solution 2 times with 6wt% sodium hydroxide aqueous solution and deionized water respectively, then dry the reaction solution with anhydrous sodium sulfate; solvent to obtain acrylated 4-carboxybenzophenone.

Dissolve 0.05mol of the above-mentioned acrylated 4-carboxybenzophenone in 80mL of ethanol at room temperature; then dissolve 0.025mol of N,N-dimethyl-1,3-propanediamine in 50mL of ethanol and add to constant pressure dropping funnel. At room temperature, at a rate of 0.4 mL per second, slowly drop the N-methylaniline solution in the constant pressure dropping funnel into the stirred acrylated 4-carboxybenzophenone solution to perform Michael addition reaction. After the dropwise addition, the stirring reaction was continued for 3 hours; the ethanol was distilled off under reduced pressure, and then purified by column chromatography to obtain a light yellow viscous liquid product XVI. The product was identified by ¹ HNMR. ¹ H-NMR (CDCl ₃ , 600MHz): δ (ppm): 2.61 (CH ₃ ); 1.83, 2.69, 3.64 (CH ₂ ); 7.25, 7.48, 7.59, 7.80, 7.87 (CH, Ar).

Example 15:

Dissolve 0.1mol 4-carboxybenzophenone and 0.11mol triethylamine in 100mL benzene at room temperature, place it in an ice-water bath, stir to lower the temperature to 0-5°C; then add 0.11mol acryloyl chloride Dissolve in 50mL of benzene at room temperature, add it to the constant pressure dropping funnel, and slowly add the acryloyl chloride solution dropwise to the stirred solution at a rate of 0.2mL per second. After the dropwise addition, continue to stir and react for 8 hours ; Remove the triethylamine hydrochloride white solid generated by filtration, wash the reaction solution 2 times with 8wt% sodium hydroxide aqueous solution and deionized water respectively, then dry the reaction solution with anhydrous sodium sulfate; solvent to obtain acrylated 4-carboxybenzophenone.

Dissolve 0.05 mol of the above-mentioned acrylated 4-carboxybenzophenone in 80 mL of ethanol at room temperature; then dissolve 0.025 mol of hexadecylamine in 80 mL of ethanol, and add it to a constant pressure dropping funnel. At room temperature, at a rate of 0.2 mL per second, slowly drop the hexadecylamine solution in the constant pressure dropping funnel into the stirred acrylated 4-carboxybenzophenone solution to perform Michael addition reaction. After the dropwise addition, the stirring reaction was continued for 4 hours; the ethanol was distilled off under reduced pressure, and then purified by column chromatography to obtain a light yellow viscous liquid product X VII. The structure of the product was identified by ¹ HNMR. ¹ H-NMR (CDCl ₃ , 600MHz): δ(ppm): 1.29 (CH ₃ ); 1.62, 1.66, 2.88, 3.83 (CH ₂ ); 7.25, 7.48, 7.59, 7.80, 7.87 (CH, Ar).

Example 16:

Dissolve 0.1mol 4-carboxybenzophenone and 0.11mol triethylamine in 100mL benzene at room temperature, place it in an ice-water bath, stir to lower the temperature to 0-5°C; then add 0.11mol acryloyl chloride Dissolve in 50mL of benzene at room temperature, add it to the constant pressure dropping funnel, and slowly add the acryloyl chloride solution dropwise to the stirred solution at a rate of 0.2mL per second. After the dropwise addition, continue to stir and react for 8 hours ; Remove the triethylamine hydrochloride white solid generated by filtration, wash the reaction solution 2 times with 8wt% sodium hydroxide aqueous solution and deionized water respectively, then dry the reaction solution with anhydrous sodium sulfate; solvent to obtain acrylated 4-carboxybenzophenone.

Dissolve 0.05 mol of the above-mentioned acrylated 4-carboxybenzophenone in 80 mL of ethanol at room temperature; then dissolve 0.025 mol of piperazine in 60 mL of ethanol, and add it to a constant pressure dropping funnel. At room temperature, at a rate of 0.6 mL per second, slowly drop the piperazine solution in the constant pressure dropping funnel into the stirred acrylated 4-carboxybenzophenone solution to perform Michael addition reaction. After the dropwise addition, the stirring reaction was continued for 3 hours; the ethanol was distilled off under reduced pressure, and then purified by column chromatography to obtain the light yellow solid powder product XVIII. The product was identified by ¹ HNMR. ¹ H-NMR (CDCl ₃ , 600MHz): δ (ppm): 2.79, 3.63 (CH ₂ ); 7.25, 7.48, 7.59, 7.80, 7.87 (CH, Ar).

Application example:

Application Example 1:

Under light-shielding conditions, add 3 g of the single-component hydrogen abstraction type photoinitiator prepared in Synthesis Example 1 into a glass container equipped with a stirrer, and stir and dissolve 23 g of aliphatic urethane acrylate resin (6000) at 40 ° C. Then add 8g of tripropylene glycol diacrylate (TPGDA), 8g of talcum powder, 42g of barite powder and 16g of dolomite powder and mix well. The free radical photocurable coating material can be obtained.

Use the coating equipment to coat the prepared above-mentioned components on the substrate with a coating thickness of 50um. Place it under a 500W high-pressure mercury lamp and illuminate it for 1 minute (the illumination distance is 10cm) to obtain a light-cured coating film. The coating film has no irritating odor and no obvious yellowing.

Application Example 2:

Aliphatic urethane acrylate resin (6000) 45g

TPGDA 25g

Dolomite powder 25g

The one-component hydrogen abstraction type photoinitiator that synthesis embodiment 4 makes 3.5g

Antioxidant 1.5g

Prepare according to the method of application example 1. Use the coating equipment to coat the prepared above-mentioned components on the substrate with a coating thickness of 10um. Place it under a 500W high-pressure mercury lamp and illuminate for 0.5 minutes (the light distance is 10cm) to obtain a light-cured coating film. The coating film has no irritating odor and no obvious yellowing.

Application Example 3

Aliphatic urethane acrylate resin (6000) 50g

TPGDA 19g

Barite powder 27g

The one-component hydrogen abstraction type photoinitiator that synthesis embodiment 5 makes 4g

Prepare according to the method of application example 1. Use the coating equipment to coat the prepared above-mentioned components on the substrate with a coating thickness of 1um. Place it under a 500W high-pressure mercury lamp and illuminate it for 20 seconds (the illumination distance is 10cm) to obtain a light-cured coating film. The coating film has no irritating odor and no obvious yellowing.

Application Example 4

Aliphatic urethane acrylate resin (6000) 50g

TPGDA 19g

Barite powder 27g

The one-component hydrogen abstraction type photoinitiator that synthetic embodiment 6 makes is 4g

Prepare according to the method of application example 1. Use the coating equipment to coat the prepared above-mentioned components on the substrate with a coating thickness of 50um. Place it under a 500W high-pressure mercury lamp and illuminate for 2 minutes (the illumination distance is 10cm) to obtain a light-cured coating film. The coating film has no irritating odor and no obvious yellowing.

Application Example 5

Aliphatic urethane acrylate resin (6000) 50g

TPGDA 19g

Barite powder 27g

The one-component hydrogen abstraction type photoinitiator 4g that synthesis embodiment 7 makes

Prepare according to the method of application example 1. Use the coating equipment to coat the prepared above-mentioned components on the substrate with a coating thickness of 1um. Place it under a 500W high-pressure mercury lamp and illuminate it for 1 minute (the illumination distance is 10cm) to obtain a light-cured coating film. The coating film has no irritating odor and no obvious yellowing.

Application Example 6:

Aliphatic urethane acrylate resin (6000) 45g

TPGDA 25g

Dolomite powder 25g

The one-component hydrogen abstraction type photoinitiator that synthesis embodiment 9 makes 3.5g

Antioxidant 1.5g

Prepare according to the method of application example 1. Use the coating equipment to coat the prepared above-mentioned components on the substrate with a coating thickness of 50um. Place it under a 500W high-pressure mercury lamp and illuminate for 2 minutes (the illumination distance is 10cm) to obtain a light-cured coating film. The coating film has no irritating odor and no obvious yellowing.

Application Example 7

Aliphatic urethane acrylate resin (6000) 50g

TPGDA 19g

Barite powder 27g

The one-component hydrogen abstraction type photoinitiator that synthetic embodiment 12 makes is 4g

Prepare according to the method of application example 1. Use the coating equipment to coat the prepared above-mentioned components on the substrate with a coating thickness of 1um. Place it under a 500W high-pressure mercury lamp and illuminate for 0.5 minutes (the light distance is 10cm) to obtain a light-cured coating film. The coating film has no irritating odor and no obvious yellowing.

Application Example 8:

Aliphatic urethane acrylate resin (6000) 45g

TPGDA 25g

Dolomite powder 25g

The one-component hydrogen abstraction type photoinitiator that synthesis embodiment 16 makes 3.5g

Antioxidant 1.5g

Prepare according to the method of application example 1. Use the coating equipment to coat the prepared above-mentioned components on the substrate with a coating thickness of 10um. Place it under a 500W high-pressure mercury lamp and illuminate it for 1.5 minutes (the illumination distance is 10cm) to obtain a light-cured coating film. The coating film has no irritating odor and no obvious yellowing.

Claims (6)

1. A compound whose structural formula is:

in: R and R' are independently selected from hydrogen, C _1-18 alkyl, C _1-18 alkoxy; A represents a group of the formula -[(CH ₂ ) _n O]-, -[(CH ₂ ) _n COO]-, or -[(CH ₂ ) _n NH]-, n=0~3; R ₁ and R ₂ are independently selected from C _1-18 alkyl, C _1-18 hydroxyalkyl, phenyl, benzyl, N,N-dimethylpropyl. 2. the preparation method of the described compound of claim 1 is characterized in that reaction divides a, b to carry out in two steps: a. the triethylamine of 1 mole fraction 4-hydroxyalkyl benzophenone, 4-carboxyalkyl benzophenone or 4-aminoalkyl benzophenone and 1-2 mole fraction is at room temperature Dissolve in an organic solvent to obtain solution A, then place solution A in an ice-water bath, stir to lower the temperature to 0-5°C; dissolve 1-2 mole parts of acryloyl chloride in an organic solvent at room temperature to obtain solution B , and then at a rate of 0.2-0.6mL per second, dropwise add solution B to the stirred solution A, after the dropwise addition, continue to stir for 4-12 hours; filter and remove the generated triethylamine hydrochloride white solid, Washing, drying, and distillation under reduced pressure to obtain acrylated 4-hydroxyalkylbenzophenone, 4-carboxyalkylbenzophenone or 4-aminoalkylbenzophenone; b. 1 mole fraction of acrylated 4-hydroxyalkylbenzophenone, 4-carboxyalkylbenzophenone or 4-aminoalkylbenzophenone obtained in step a is dissolved in protons at room temperature Solution C was obtained in a solvent; then 1 mole fraction of secondary amine or 0.5 mole fraction of primary amine was dissolved in a protic solvent at room temperature, and was added dropwise to the stirred In solution C, a Michael addition reaction was carried out, and after the dropwise addition, the stirring reaction was continued for 0.5-5 hours; the protic solvent was distilled off under reduced pressure, and then processed by column chromatography to obtain the compound described in claim 1. 3. preparation method according to claim 2 is characterized in that: the organic solvent of a step reaction is methylene dichloride, chloroform, benzene, toluene or xylene; The protic solvent of b step reaction is methyl alcohol or ethanol. 4. The application of the compound according to claim 1 as a UV-curable single-component hydrogen abstraction type photoinitiator in the field of photosensitive polymer materials. 5. A UV curable composition, comprising: (a) A polymerizable component comprising at least one ethylenically unsaturated photoreactive resin and a reactive diluent; the reactive diluent is a monofunctional, difunctional or multifunctional acrylate monomer or methacrylate monomer ; (b) The compound of claim 1. 6. The UV-curable composition according to claim 5, characterized in that: the unsaturated photoreactive resin is epoxy acrylic resin, epoxy methacrylic resin, polyester acrylic resin, polyester methacrylic resin, Urethane acrylic resin, polyurethane methacrylate resin, polyacrylate acrylic resin, polyacrylate methacrylate resin, polyether acrylic resin or polyether methacrylate resin.