CN111138290B - Aromatic ring-containing benzophenone derivative and preparation method and application thereof - Google Patents

Aromatic ring-containing benzophenone derivative and preparation method and application thereof Download PDF

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CN111138290B
CN111138290B CN201911352758.0A CN201911352758A CN111138290B CN 111138290 B CN111138290 B CN 111138290B CN 201911352758 A CN201911352758 A CN 201911352758A CN 111138290 B CN111138290 B CN 111138290B
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benzophenone
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aromatic ring
benzophenone derivative
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张变香
赵子任
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Shanxi University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D333/38—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
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    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16

Abstract

The invention provides a benzophenone derivative containing aromatic rings, a preparation method and application thereof. Preparation of derivatives: 2-hydroxy-4-methoxy benzophenone is used as a raw material to react with aromatic acyl chloride to synthesize three benzophenone derivatives containing aromatic rings. The preparation method has the advantages of simple operation, mild reaction conditions, high yield and the like. The derivative has strong ultraviolet light absorption performance, can effectively absorb ultraviolet light of 250-310 nm, and increases the utilization rate of a light source; the cured film has the characteristics of good compatibility with resin or monomer, no odor and the like, and has better hardness and adhesive force. The three aromatic ring-containing benzophenone derivatives synthesized by the invention can be respectively used as ultraviolet initiators to be applied to the fields of photocuring compositions such as coatings, printing ink, adhesives and the like.

Description

Aromatic ring-containing benzophenone derivative and preparation method and application thereof
Technical Field
The invention relates to a benzophenone derivative, in particular to a benzophenone derivative containing aromatic rings and a preparation method and application thereof.
Background
The photocuring technology has the advantages of energy conservation, environmental protection, high efficiency, high speed and the like, and is widely applied to the traditional fields of coatings, printing ink, adhesives and the like and high and new technical products such as 3D printing and the like. Photoinitiators are key components in photocuring systems, which determine the photocuring speed, and the development of cured products depends to some extent on the development of photoinitiators. Benzophenone is a common photoinitiator which is low in price, simple to synthesize and easy to store, and is widely applied to ultraviolet curing coatings. However, the ultraviolet absorption intensity of benzophenone is not strong, and the absorption range is narrow, so that the photoinitiation activity is not ideal. With the rapid development of the industry, the requirements of environmental protection and high initiation efficiency of the photoinitiator are improved. On the basis of the benzophenone molecular structure, a better structure-activity relationship is established through reasonable molecular design, and the research and development of the photoinitiator with high efficiency, low toxicity and low mobility has wide application prospect.
Disclosure of Invention
The invention aims to provide a benzophenone derivative containing aromatic rings, a preparation method and application thereof aiming at the defects in the prior art. The preparation method has the advantages of simple operation, mild reaction conditions and high total yield, and the synthesized benzophenone derivative containing aromatic rings can be used as an ultraviolet initiator.
The invention provides a benzophenone derivative containing aromatic rings, which has a structural formula of 1 or 2 or 3:
Figure BDA0002335038550000011
the synthesis reaction formula is as follows:
Figure BDA0002335038550000021
the preparation method comprises the following steps:
1) adding 2-hydroxy-4-methoxybenzophenone into a container, dissolving the benzophenone by using an organic solvent, slowly adding triethylamine, stirring uniformly under the condition of ice-water bath, slowly adding aromatic acyl chloride, and stirring to react for 2-6 hours;
2) after the reaction is finished, adding water into the reaction solution, extracting with ethyl acetate, collecting an organic phase, washing with water, drying, and removing the organic solvent by rotary evaporation; separating and purifying by using a chromatographic silica gel column to obtain the benzophenone derivative containing aromatic rings.
The molar ratio of the 2-hydroxy-4-methoxybenzophenone to the triethylamine to the aromatic acyl chloride is 1: 1.4-2: 1.2-2. Preferably 1:1.5: 1.2.
The aromatic acyl chloride is 4-methylbenzoyl chloride or 2-thiophenoyl chloride or 2-furanoyl chloride.
The organic solvent is tetrahydrofuran or dichloromethane.
The reaction time is preferably 3 hours.
The benzophenone derivative containing aromatic rings can be used as an ultraviolet initiator to be applied to a photocuring composition.
The photocurable composition comprises, in addition to an aromatic ring-containing benzophenone derivative:
A. at least one ethylene unsaturated compound prepolymer;
B. at least one ethylenically unsaturated compound monomer;
C. and (4) an auxiliary agent.
The ethylene unsaturated compound prepolymer is epoxy acrylate resin, polyester acrylate resin or polyurethane acrylate resin.
The ethylene unsaturated compound monomer is monohydric or more than dihydric fatty alcohol acrylate.
The content of the aromatic ring-containing benzophenone derivative is 2-4%.
The auxiliary agent is triethanolamine.
The photocurable composition is a coating, an ink, an adhesive, or the like.
Compared with the prior art, the invention has the beneficial effects that: the benzophenone derivative containing aromatic rings synthesized by the invention has the advantages of simple preparation, easily obtained raw materials and higher yield; the ultraviolet light with the wavelength of 250-310 nm can be effectively absorbed, and the absorption intensity is strong; due to the introduction of ester groups in the molecular structure, the derivatives have the characteristics of good compatibility with resin and monomers, no odor and the like. Meanwhile, the release and migration of benzene can be reduced in the process of curing and film forming and products, the phenomena of oxygen inhibition and yellowing of cured coatings can be effectively relieved, and the hardness and the adhesive force of the cured film are superior to those of a commercially available free radical photoinitiator 1173 and BP. Therefore, the compounds can be used as ultraviolet initiators in photocuring compositions such as coatings, printing inks and adhesives.
Drawings
FIG. 1 nuclear magnetic resonance hydrogen spectrum of derivative 1
FIG. 2 NMR carbon spectrum of derivative 1
FIG. 3 NMR chart of derivative 2
FIG. 4 NMR carbon spectrum of derivative 2
FIG. 5 NMR hydrogen spectra of derivative 3
FIG. 6 NMR carbon spectrum of derivative 3
FIG. 7 is a graph comparing ultraviolet absorption spectra of derivatives 1, 2, 3 with Benzophenone (BP)
Detailed Description
Example 1
0.228g (1mmol) of 2-hydroxy-4-methoxybenzophenone and 0.150g (1.5mmol) of triethylamine were charged into a vessel, and the mixture was dissolved in 3ml of dichloromethane, and 0.185g (1.2mmol) of 4-methylbenzoyl chloride was slowly added thereto in an ice-water bath, followed by stirring for 3 hours. After the reaction is finished, adding water into the reaction solution, extracting with ethyl acetate, collecting an organic phase, washing with water, drying with anhydrous sodium sulfate, and removing the organic solvent by rotary evaporation; and carrying out column chromatography separation by using petroleum ether/ethyl acetate (volume ratio is 12:1) as an eluent to obtain the derivative 1.
Derivative 1: a colorless transparent liquid with the yield of 94 percent,1H NMR(600MHz,CDCl3)δ7.78–7.72(m,4H),7.60(t,J＝8.0Hz,1H),7.45(dt,J＝8.6,4.1Hz,1H),7.37(dd,J＝16.1,8.3Hz,2H),7.16(t,J＝8.7Hz,2H),6.93–6.86(m,2H),3.96–3.86(m,3H),2.43–2.36(m,3H).13C NMR(151MHz,CDCl3)δ194.30,164.74,163.05,151.03,144.35,138.51,132.59,132.40,130.10,129.62,129.03,128.21,126.12,124.17,111.57,108.92,55.76,21.74.
example 2
0.228g (1mmol) of 2-hydroxy-4-methoxybenzophenone and 0.150g (1.5mmol) of triethylamine were charged into a vessel, and the mixture was dissolved in 3ml of methylene chloride, and 0.175g (1.2mmol) of 2-thiophenecarbonyl chloride was slowly added thereto in an ice-water bath, followed by stirring for 3 hours. After the reaction is finished, adding water into the reaction solution, extracting with ethyl acetate, collecting an organic phase, washing with water, drying with anhydrous sodium sulfate, and removing the organic solvent by rotary evaporation; and carrying out column chromatography separation by using petroleum ether/ethyl acetate (volume ratio is 12:1) as an eluent to obtain the derivative 2.
Derivative 2: white solid, 96% yield, m.p.86-88 ℃.1H NMR(600MHz,CDCl3)δ7.75(t,J＝7.9Hz,2H),7.69–7.65(m,1H),7.60(dd,J＝10.4,5.5Hz,1H),7.58–7.55(m,1H),7.47(dd,J＝14.3,7.0Hz,1H),7.41–7.35(m,2H),7.04(dd,J＝11.1,6.4Hz,1H),6.93–6.86(m,2H),3.94–3.88(m,3H).13C NMR(151MHz,CDCl3)δ194.18,163.01,160.00,150.48,138.43,134.79,133.67,132.67,132.42,132.11,129.61,128.24,127.78,124.05,111.78,108.88,55.80.
Example 3
0.228g (1mmol) of 2-hydroxy-4-methoxybenzophenone and 0.150g (1.5mmol) of triethylamine were charged into a vessel, and the mixture was dissolved in 3ml of dichloromethane, and 0.156g (1.2mmol) of 2-furoyl chloride was slowly added thereto in an ice-water bath, followed by stirring for 3 hours. After the reaction is finished, adding water into the reaction solution, extracting with ethyl acetate, collecting an organic phase, washing with water, drying with anhydrous sodium sulfate, and removing the organic solvent by rotary evaporation; and performing column chromatography with petroleum ether/ethyl acetate (volume ratio 12:1) as eluent to obtain derivative 3.
Derivative 3: white solid, 91% yield, m.p.105-108 ℃.1H NMR(600MHz,CDCl3)δ7.74(d,J＝7.7Hz,2H),7.63–7.55(m,2H),7.47(q,J＝7.3Hz,1H),7.39(t,J＝7.6Hz,2H),7.05–6.99(m,1H),6.94–6.86(m,2H),6.46(dd,J＝3.3,1.5Hz,1H),3.94–3.87(m,3H).13C NMR(151MHz,CDCl3)δ194.09,163.05,156.27,150.18,147.23,143.37,138.41,132.78,132.40,129.61,128.20,123.93,119.57,112.05,111.70,108.94,55.79.
At the same time, the concentration is 1 x 10-5mol·L-1And under the condition that the solvent is dichloromethane, testing ultraviolet absorption spectra of the derivatives 1, 2 and 3 at 200-400 nm, determining characteristic absorption peaks of the derivatives, calculating molar extinction coefficients of the derivatives at the maximum absorption wavelength by applying Lambert-Beer law, and comparing the molar extinction coefficients with benzophenone BP (see table 1 and figure 7). The result shows that the compound can effectively absorb ultraviolet light of 250-310 nm compared with benzophenone, has stronger ultraviolet light absorption performance, has higher photoinitiation activity than benzophenone, and has an ultraviolet spectrum shown in figure 7.
TABLE 1
Derivative 1 Derivative 2 Derivative 3 BP
Maximum absorption wavelength/nm 285 283 295 280
Molar extinction system/L.mol-1·cm-1 5.10×10-4 5.24×10-4 3.53×10-4 1.21×10-4
The following examples are applications of the aromatic ring-containing benzophenone derivatives 1, 2 and 3 of the present invention as radical type photoinitiators in uv curable coatings, but are not limited to the uses of the following examples.
The prepolymer used therein was a modified epoxy acrylate (UV1005-65 produced by Chinesian Kabushiki Kaisha chemical plant ) and the monomer was 1, 6-hexanediol diacrylate (HDDA produced by Chineshiki Kabushiki Kaisha chemical plant ).
Example 4: evaluation of application Properties of aromatic Ring-containing benzophenone derivative 1
The experimental formula is as follows:
Figure BDA0002335038550000041
Figure BDA0002335038550000051
working conditions
Under the condition of keeping out of the sun, 10.03 g of benzophenone derivative, 0.45g of 1, 6-hexanediol diacrylate (HDDA), 0.5g of modified epoxy acrylate (UV1005-65) and 0.02g of triethanolamine are added into a glass container, and the mixture is uniformly stirred to obtain a transparent coating liquid. The mixture was coated on a glass plate with a coater to give a film having a thickness of 75 μm, and cured by irradiation with a medium-pressure mercury lamp at a mercury lamp power of 400W.
Example 5: evaluation of application Properties of aromatic Ring-containing benzophenone derivative 2
The experimental formula is as follows:
Figure BDA0002335038550000052
working conditions were the same as in example 4
Example 6: evaluation of application Properties of aromatic Ring-containing benzophenone derivative 3
The experimental formula is as follows:
Figure BDA0002335038550000053
working conditions were the same as in example 4
Comparative example 1: evaluation of application Properties of photoinitiator 1173
The experimental formula is as follows:
Figure BDA0002335038550000054
working conditions were the same as in example 4
Comparative example 2: evaluation of application Properties of photoinitiator BP
The experimental formula is as follows:
Figure BDA0002335038550000055
Figure BDA0002335038550000061
working conditions were the same as in example 4
The coating films of the compositions of examples 4 to 6 and comparative examples 1 to 2 were subjected to a performance test:
a, testing the dry time: it refers to dry method or cotton ball method.
b hardness test pencil hardness method test according to GB/T6739-1996. And observing the scratch marks of the paint film by using a film coating pencil scratch hardness instrument, and taking the pencil without the scratch as the pencil hardness of the coating film.
c, testing adhesive force: the cross-cut method (see GB 9286-88). And judging whether the adhesive force of the coating is good or not by a grid-scribing experimental method. The grade can be 0-5, 6 grades, preferably 0 grade, the film surface does not fall off any small grid, 5 grades are extremely poor, and the film surface is seriously peeled off.
The evaluation results are shown in Table 2.
TABLE 2 comparison of the properties of benzophenone derivatives containing aromatic rings with 1173 and BP
Figure BDA0002335038550000062
From the test results in the table above, it can be seen that: the aromatic ring-containing benzophenone derivative 2 provided by the invention has relatively slow curing speed, but the adhesive force between a cured film and a glass substrate is strong; the curing speed, film-forming hardness and adhesion of the aromatic ring-containing benzophenone derivatives 1 and 3 are superior to those of the commercially available free radical photoinitiator 1173 and benzophenone BP.

Claims (3)

1. The benzophenone derivative containing aromatic ring is used as ultraviolet light initiator in the light-cured composition; the structural formula of the aromatic ring-containing benzophenone derivative is 1, 2 or 3:
Figure 911892DEST_PATH_IMAGE001
。
2. the use according to claim 1, wherein the photocurable composition comprises, in addition to the aromatic ring-containing benzophenone derivative:
A. at least one ethylene unsaturated compound prepolymer;
B. at least one ethylenically unsaturated compound monomer;
C. and (4) an auxiliary agent.
3. Use according to claim 1 or 2, wherein the photocurable composition is a coating, an ink or an adhesive.
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