CN109942449B - Visible light alkali-producing agent and preparation method thereof - Google Patents
Visible light alkali-producing agent and preparation method thereof Download PDFInfo
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Abstract
The invention provides a visible light alkali-producing agent and a preparation method thereof, wherein the chemical structure of the visible light alkali-producing agent is shown as the following formula:
wherein Z represents any one of the following chemical structural formulas:
B+represents:
the photobase generator prepared by the invention has a wider spectral absorption range, a strong absorption band in a visible light region and higher quantum yield, solves the problem that the absorption range of a photosensitizer in a long wavelength cannot be enlarged by a method for increasing the conjugation degree, can generate an alkaline active substance by virtue of photodecarboxylation under the excitation of visible light, enhances alkalinity, and has the capability of carrying out base catalytic polymerization on systems such as Michael addition reaction, mercapto-epoxy resin, mercapto-isocyanate resin and the like. The invention realizes that the photoinitiator has wide application prospect in the aspects of high-molecular photosensitive systems, photoresists, epoxy resin curing, coatings, printing ink and the like.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a visible light alkali-producing agent and a preparation method thereof.
Background
Photoinitiators play an important role in many areas, such as coatings, adhesives, dental materials, microelectronic materials, and 3D printing. Photobase generators (Photobase generators) are a class of photoinitiators which are newly developed in recent years, and are compounds which can release alkaline active substances after being excited by irradiation, and can realize effective alkali catalytic reaction under certain conditions. The photopolymerization reaction system catalyzed by alkali has the advantages of small polymerization shrinkage rate of materials, no oxygen inhibition, no corrosion to base materials and the like.
As early as the late 80s in the last century, Kutal et al first proposed a first class of photobase generators, cobalt-amine complexes, and later developed a number of different photobases in succession. The early photobase generators generally have the problems of weak alkalinity and low quantum yield, so the application of the photobase generators in a photopolymerization system is limited. In recent years, strong organic bases are often used as active species released after photobase generation agents are photolyzed to improve the initiation activity, such as amidines and guanidines, and the initiation efficiency is improved. However, most photobase generators usually use ultraviolet light as a light source to initiate polymerization, but the energy of the ultraviolet light is high, and the photobase generators can cause non-negligible damage in certain application fields, such as life sciences, medical diagnosis and treatment, functional coatings, surface treatment and the like, thereby preventing the photobase generators from being applied in partial fields. The coumarin-based photobase generator is reported to use coumarin as a molecular center, introduces carboxyl and amino to promote the maximum absorption peak red shift, and realizes visible light initiation, however, the absorption peak of the initiator has small coverage in visible light (400 nm and 750nm), and has limited initiation capability under the excitation of the visible light, and the requirements of some fields on a mild excitation light source cannot be met. Therefore, the development of a visible light alkali-producing agent has been a hotspot. However, photosensitizers in the long wavelength absorption range are difficult to work with in the usual way of increasing the absorption wavelength, i.e. by increasing the degree of conjugation. On the one hand, increasing the degree of conjugation tends to decrease the energy gap between the HOMO-LUMO orbitals, and the limited cleavage of chemical bonds due to the lower absorbed energy of long wavelengths is difficult to cause and the initiation reaction of active species cannot occur. In addition, increasing the degree of conjugation tends to cause energy cross-over between σ and π in the LUMO orbital, and the absorbed energy tends to dissipate through the formation of fluorescence, causing quenching of the excited state and failure of the bond to initiate the reaction.
Disclosure of Invention
In order to solve the problems, the invention provides a visible light alkali-producing agent and a preparation method thereof. The initiator molecule takes cyclic ketone as a center, and constructs a chromophore with long conjugation by the principle that C ═ C double bonds are formed through the classical reaction of aldehyde groups and ketone, and introduces a carboxyl structure at the tail end to form an ionic visible light alkali generator with various strong bases; the photobase generator prepared by the invention not only has a wider spectral absorption range and a strong absorption band in a visible light region, but also solves the problem that the absorption range of a photosensitizer in a long wavelength cannot be enlarged by a method for increasing the conjugation degree. The invention realizes that the photoinitiator has wide application prospect in the aspects of high-molecular photosensitive systems, such as photoresist, epoxy resin curing, paint, printing ink and the like.
The purpose of the invention is realized by the following modes:
the chemical structure of the visible light alkali-producing agent is shown as the following formula:
z represents any one of the following chemical structural formulas:
b is+Represents:
preferably, Z represents:
the spectral absorption range of the photobase generator is 200-500 nm.
The preparation method of the visible light alkali-producing agent comprises the following preparation steps:
(1) dissolving N- (4-formylphenyl) -N-methyl glycine methyl ester and cycloalkyl ketone in a solvent, and performing aldehyde-ketone condensation reaction to obtain a precipitate a; the molar ratio of the N- (4-formylphenyl) -N-methyl glycine methyl ester to the cycloalkyl ketone is 1: 1-3: 1; (2) dispersing the precipitate a and organic base in a solvent for reaction, and removing the solvent to obtain the visible light alkali-producing agent; the molar ratio of the precipitate a to the organic base is 1: 1-1: 3, preferably 1: 1.5-1: 2.
The structural formula of the N- (4-formylphenyl) -N-methyl glycine methyl ester is as follows:
the N- (4-formylphenyl) -N-methyl glycine methyl ester in the structure can realize effective decarboxylation reaction.
The naphthenic ketone is any one of cyclic acetone, cyclobutanone, cyclopentanone, cyclohexanone, 3-methylcyclopentanone, 4-methylcyclohexanone, 3-ethylcyclopentanone or 4-ethylcyclohexanone.
Preferably, the cycloalkyl ketone is cyclopentanone or 4-methylcyclohexanone.
In the aldehyde ketone condensation reaction, the reaction is carried out for 4-24 hours at 20-60 ℃ under the catalysis of alkali, and then acid is dripped to generate precipitation.
Preferably, in the aldehyde ketone condensation reaction, the reaction is carried out for 18-24 hours at 40-50 ℃ under the catalysis of alkali, and then acid is dripped to generate precipitation.
In the aldehyde ketone condensation reaction, the molar ratio of N- (4-formylphenyl) -N-methyl glycine methyl ester to alkali is 1: 2-1: 5.
In the aldehyde ketone condensation reaction, the alkali is any one or the mixture of sodium hydroxide and potassium hydroxide.
In the aldehyde ketone condensation reaction, the acid is any one or the mixture of two of hydrochloric acid, sulfuric acid, nitric acid and acetic acid.
The organic base is 1,5, 7-triazabicyclo [4.4.0] undec-5-ene (TBD) or 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU).
The solvent is any one or more than two of water, methanol, ethanol, tetrahydrofuran and N, N-dimethylformamide.
In the step (2), the reaction temperature of the precipitate a and the organic base dispersed in the solvent is 20-60 ℃, and the reaction time is 1-12 hours.
The reaction is carried out under the protection of light and inert gas.
The drying is vacuum drying; the separation is any one or combination of two of the following: centrifuging and filtering; the solvent removing method is any one or combination of reduced pressure distillation and freeze drying.
In the preparation method, the reaction formula of the chemical reaction is as follows:
the visible light alkali-producing agent is applied to photolysis catalytic polymerization and curing in a high-molecular photosensitive system, such as photoresist, epoxy resin curing, coating and ink.
The invention has the beneficial effects that:
(1) the photobase generator disclosed by the invention contains a long conjugated structure, has a large absorption peak range coverage, has a wider spectral absorption range, not only comprises an ultraviolet light range, but also increases a visible light excitation range, meets the requirements of partial fields on a mild excitation light source, and has higher quantum yield.
(2) The photoinitiator prepared by the invention solves the problem that the absorption range of the photosensitizer at long wavelength cannot be enlarged by a method for increasing the conjugation degree, namely, the method for increasing the conjugation degree enlarges the absorption range of the photosensitizer at long wavelength.
(3) The reaction process of the alkali-producing agent is simple, the alkali-producing agent and strong acid and strong base are subjected to simple multi-step reaction, the reaction condition is mild, the synthesis method is simple and convenient, and the synthesized initiator has strong alkalinity and huge commercial application prospect;
(4) the photobase generator can generate free radicals and amine under the illumination condition, and can perform free radical curing and alkali catalytic curing;
(5) the photobase generator can be photolyzed and cured under visible light LED lamps of 450nm and 405 nm;
(6) the photobase generator is mainly applied to a high-molecular photosensitive system, and has wide application prospects in the aspects of photoresist, epoxy resin curing, coating, printing ink and the like;
(7) the photobase generator generates amine under the illumination condition, is used for crosslinking and curing the epoxy monomer, and can avoid the defects that the traditional epoxy resin curing agent (amine compound) starts to be cured once being mixed and can not control the initiation process.
Drawings
FIG. 1 is a diagram showing UV-VIS absorption spectra of photobase generators obtained in example 1 (denoted by VA) and example 2 (denoted by VB) of the present invention;
wherein the concentration of the photobase generator in example 1 is 1.18X 10-4mol/L (methanol as solvent), concentration of photobase generator in example 2 is 4.97X 10-5mol/L (methanol is used as a solvent);
FIG. 2 is a photolysis curve of the photobase generator obtained in example 1 of the present invention under 450nm visible light.
FIG. 3 is a photolysis curve of the photobase generator obtained in example 2 of the present invention under 450nm visible light.
FIG. 4 is a photolysis curve of the photobase generator obtained in example 3 of the present invention under 450nm visible light.
The specific implementation mode is as follows:
the invention is further illustrated by the following specific examples:
example 1:
30mL of ethanol was added to a 100mL single-neck flask, and 1.04g of methyl N- (4-formylphenyl) -N-methylglycine was stirred and added to the flask to sufficiently dissolve the methyl N- (4-formylphenyl) -N-methylglycine, and after the methyl N- (4-formylphenyl) -N-methylglycine was dissolved sufficiently, 0.20g of cyclopentanone and 1.02g of sodium hydroxide were added to the flask, and the mixture was heated to 50 ℃ to react for 18 hours. Slowly dripping hydrochloric acid into the reaction liquid to separate out a red-black precipitate, performing suction filtration and drying, and performing column chromatography separation, wherein the eluent is a dichloromethane-methanol mixed solvent with the ratio of 20:1, and 0.40g of a product is obtained, and the yield is 36.8%. 0.24g of the product was dispersed in 10mL of methanol, a methanol solution containing 0.12g of TBD was added dropwise thereto, and the mixture was reacted at 30 ℃ for 1 hour in a 50mL single-neck flask, and the methanol was distilled off under reduced pressure to obtain 0.34g of a visible light base generator (yield 94.4%). The ultraviolet-visible light absorption spectrum of the obtained alkali-producing agent is shown in FIG. 1 (indicated by V A).
1H NMR(400MHz,Chloroform-d)δ7.51(d,J＝8.6Hz,6H),6.76(d,J＝8.9Hz,4H),3.97(s,4H),3.26(q,J＝5.6Hz,20H),3.17(s,6H),3.06(s,4H),1.97(p,J＝5.9Hz,10H).
The chemical structural formula of the product is as follows:
example 2:
30mL of methanol was put into a 100mL single-neck flask, 1.03g of methyl N- (4-formylphenyl) -N-methylglycinate was added with stirring, 0.24g of 4-methylcyclohexanone and 1.11g of potassium hydroxide were added after sufficient dissolution, and the temperature was raised to 40 ℃ to react for 24 hours. Slowly dropwise adding sulfuric acid into the reaction liquid to separate out a black precipitate, carrying out suction filtration and drying, and then carrying out column chromatography separation, wherein the eluent is a dichloromethane-methanol mixed solvent with the ratio of 20:1, and 0.29g of a product is obtained, and the yield is 28.6%. 0.29g of the product was dispersed in 10mL of methanol, a methanol solution containing 0.14g of TBD was added dropwise thereto, and the mixture was reacted at 20 ℃ for 12 hours in a 50mL single-neck flask, and the methanol was distilled off under reduced pressure to obtain 0.41g of a visible light base generator (yield 95.3%). The ultraviolet-visible light absorption spectrum of the obtained alkali-producing agent is shown in FIG. 1 (denoted by VB).
1H NMR(400MHz,Chloroform-d)δ7.74(s,2H),7.41(d,J＝8.8Hz,4H),6.73(d,J＝8.9Hz,4H),3.97(s,4H),3.24(s,16H),3.14(s,6H),1.95(p,J＝5.9Hz,8H),1.10(d,J＝6.5Hz,3H)。
The chemical structural formula of the product is as follows:
example 3
30mL of ethanol was added to a 100mL single-neck flask, 1.6g of methyl N- (4-formylphenyl) -N-methylglycine was stirred and added to the flask to dissolve the methyl N- (4-formylphenyl) -N-methylglycine sufficiently, 0.3g of cyclopentanone and 0.86g of potassium hydroxide were added thereto, and the mixture was heated to 60 ℃ to react for 4 hours. Slowly dripping nitric acid into the reaction liquid to separate out a red-black precipitate, performing suction filtration and drying, and performing column chromatography separation, wherein the eluent is a dichloromethane-methanol mixed solvent with the ratio of 20:1, and 0.35g of a product is obtained, and the yield is 21.6%. 0.3g of the product was dispersed in 10mL of N, N-dimethylformamide, and a methanol solution containing 0.15g of DBU was added dropwise thereto, followed by reaction at 60 ℃ for 5 hours in a 50mL single-necked flask, and N, N-dimethylformamide was distilled off under reduced pressure to obtain 0.42g of a visible light alkali-producing agent (yield 93.3%).
1H NMR(400MHz,Chloroform-d)δ7.50(d,J＝8.6Hz,6H),6.79(d,J＝8.9Hz,4H),4.01(s,4H),3.57-3.31(m,6H),3.23(q,J＝5.6Hz,20H),2.73(d,J＝2.2Hz,3H),1.92-1.79(m,2H),1.45-1.72(m,6H).
The chemical structural formula of the product is as follows:
example 4
30mL of methanol was put into a 100mL one-neck flask, 1.1g of methyl N- (4-formylphenyl) -N-methylglycinate was added with stirring, and after sufficiently dissolving, 0.2g of 4-methylcyclohexanone and a mixture of 0.31g of sodium hydroxide and 0.4g of potassium hydroxide were added, and the temperature was raised to 20 ℃ to react for 12 hours. Slowly dripping acetic acid into the reaction liquid to separate out black precipitate, carrying out suction filtration and drying, and then carrying out column chromatography separation, wherein the eluent is a dichloromethane-methanol mixed solvent with the ratio of 20:1, and 0.22g of a product is obtained, and the yield is 19.6%. 0.22g of the product was dispersed in 10mL of tetrahydrofuran, and a methanol solution containing 0.12g of DBU was added dropwise thereto, followed by reaction at 45 ℃ for 8 hours in a 50mL single-neck flask, followed by evaporation of tetrahydrofuran under reduced pressure to obtain 0.31g of a visible light base generator (yield 91.2%).
1H NMR(400MHz,Chloroform-d)δ7.74(s,2H),7.41(d,J＝8.8Hz,4H),6.73(d,J＝8.9Hz,4H),3.97(s,4H),3.58-3.30(m,6H),3.24(s,16H),2.74(d,J＝2.2Hz,3H),1.94-1.80(m,2H),1.47-1.74(m,6H)。
The chemical structural formula of the product is as follows:
test example 1: photolysis of visible light alkali-producing agent under visible light
The visible light alkali generators obtained in example 1 and example 2 were dissolved in acetonitrile, respectively, and set to the optimum concentration for uv-vis absorption test. Two samples were placed in quartz cuvettes, respectively, and an LED light source of 450nm was prepared for irradiation steady state photolysis. The intensity of a light source used for testing by using an ultraviolet energy meter in the experimental process is 102.1mW/cm2. The whole testing process adopts a point control mode, and ultraviolet-visible light absorption spectrum scanning is immediately carried out after the cuvette filled with the sample solution is irradiated for a period of time. And drawing the spectrum change trend of the photobase generator after different irradiation times. The photolytic changes of the photobase generators obtained in example 1 and example 2 were analyzed in experiments using uv-vis absorption spectra after scanning irradiation for 0s, 5s, 10s, 30s, 60s, 120s, 240s, 420s, 600 s. The photolysis curve of the photobase generator of example 1 is shown in fig. 2, and the photolysis curve of the photobase generator of example 2 is shown in fig. 3; as shown in fig. 2 and 3, the light absorption intensity gradually decreases from 0s to 600s, the absorption intensity of 0s is the maximum, and the absorption intensity of 600 is close to 0s, which indicates that the photobase generator has a better photolysis effect when irradiated by a visible light source.
Test example 2: photolysis curing of visible light alkali-producing agent in high-molecular photosensitive system
116mg of mercapto resin PETMP (49 mol%), 79mg of epoxy resin E51 (49%) and 5mg of the visible light alkaligenerator obtained in example 1 of the present invention (2 mol%) were weighed out accurately and mixed. And (3) carrying out ultrasonic minutes on the mixed resin to dissolve and uniformly mix the resin to obtain the photosensitive resin I, and storing the photosensitive resin I in a dark place for later use.
116mg of mercapto resin PETMP (49 mol%), 79mg of epoxy resin E51 (49%) and 6mg of the visible light alkaligenerator (2 mol%) obtained in example 2 of the present invention were weighed out accurately and mixed. And (3) carrying out ultrasonic minutes on the mixed resin to dissolve and uniformly mix the resin to obtain a photosensitive resin II, and storing the photosensitive resin II in a dark place for later use.
The curing process was monitored in real time using a Nicolet 6700FT-IR infrared spectrometer for conversion testing. Respectively dripping the photosensitive resin I and the photosensitive resin II on the surface of a KBr salt plate, controlling the film thickness to be about 0.5mm, controlling the irradiation time to be 600s, and controlling the light source intensity to be 49.8mW/cm2。
The conversion rate of sulfydryl in the photosensitive resin I adopting the photobase generator obtained in the example 1 reaches 91 percent, the conversion rate of epoxy reaches 59 percent, the conversion rate of sulfydryl in the photosensitive resin II adopting the photobase generator obtained in the example 2 reaches 52 percent, and the conversion rate of epoxy reaches 49 percent.
From the conversion result of the test example 2, it can be seen that the examples and the implementation of the photobase generator well initiate the polymerization of the photosensitive resin under the illumination condition, which indicates that the effect of the photobase generator in the polymer photosensitive system is better. Therefore, the epoxy resin can be applied to photoresist, epoxy resin curing, coating, ink and the like, and has the potential of commercial application.
Test example 3: detection of alkali production behavior of visible light alkali production agent under visible light
The photobase generators obtained in example 3 were dissolved in acetonitrile, respectively, and set to the optimum concentration for uv-vis absorption test. Placing the sample solution into a quartz cuvette, dropwise adding a drop of phenol red acetonitrile saturated solution as an alkali indicator, and preparing an LED light source with the wavelength of 450nm for irradiation steady-state photolysis. Purple was used in the experimental procedureThe intensity of a light source used for the external energy meter test is 99.1mW/cm2. The whole testing process adopts a point control mode, and ultraviolet-visible light absorption spectrum scanning is immediately carried out after the cuvette filled with the sample solution is irradiated for a period of time. And drawing the spectrum change trend of the photobase generator after different irradiation times. In the experiment, the photobase generation behavior of the photobase generator obtained in example 3 was analyzed by scanning the ultraviolet-visible absorption spectrum after irradiation for 0s, 1s, 3s, 8s, 15s, 25s, 45s, 80s, and 120 s. Example 3 photolysis curve of photobase generator as shown in fig. 4, with irradiation, characteristic peak of deprotonation of phenol red appears at 580nm, which proves that example 3 can release alkaline substance under 450nm LED light source irradiation, and is effective photobase generator.
Test example 4: visible light alkali-producing agent for catalyzing curing of mercapto-epoxy resin under visible light
1.20g of mercapto resin PETMP (49 mol%), 0.80g of epoxy resin E51 (49%) and 50mg of the visible light alkaligenic agent (2 mol%) obtained in inventive example 4 were weighed out accurately and mixed. And ultrasonically dissolving the mixed resin, and uniformly mixing to obtain a third photosensitive resin, and storing in dark for later use. Coating photosensitive resin with a thickness of 60 μm on a tin plate, and irradiating under 450nm LED light source to cure with light intensity of 198.9mW/cm2The irradiation time is 20min, and the surface drying of the mercapto-epoxy resin coating is realized after the post-baking is carried out for 40min at the temperature of 60 ℃.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (16)
1. The visible light alkali-producing agent is characterized by being prepared by carrying out aldehyde ketone condensation reaction on N- (4-formylphenyl) -N-methyl glycine methyl ester and cycloalkyl ketone and then dispersing the obtained product with organic alkali, wherein the chemical structure of the visible light alkali-producing agent is shown as the following formula:
wherein Z represents:
B + represents:
2. The visible light alkali-producing agent as claimed in claim 1, wherein the spectral absorption range of the light alkali-producing agent is 200-500 nm.
3. The method for preparing the visible light alkali-producing agent according to claim 1, comprising the steps of:
(1) dissolving N- (4-formylphenyl) -N-methyl glycine methyl ester and cycloalkyl ketone in a solvent, and performing aldehyde-ketone condensation reaction to obtain a precipitate a; wherein the molar ratio of the N- (4-formylphenyl) -N-methyl glycine methyl ester to the cycloalkyl ketone is 1: 1-3: 1;
(2) dispersing the precipitate a and organic base in a solvent for reaction, and removing the solvent to obtain the visible light alkali-producing agent; the molar ratio of the precipitate a to the organic base is 1: 1-1: 3.
4. The method for preparing the visible light alkali-producing agent according to claim 3, wherein the molar ratio of the precipitate a to the organic base is 1:1.5 to 1: 2.
5. The method according to claim 3, wherein the cyclic alkyl ketone is any one of cyclic acetone, cyclobutanone, cyclopentanone, cyclohexanone, 3-methylcyclopentanone, 4-methylcyclohexanone, 3-ethylcyclopentanone, or 4-ethylcyclohexanone.
6. The method according to claim 5, wherein the cyclic alkyl ketone is cyclopentanone or 4-methylcyclohexanone.
7. The method for preparing a visible light alkali-producing agent according to claim 3, wherein the reaction conditions of the aldehyde-ketone condensation reaction are as follows: reacting for 4-24 hours at 20-60 ℃ under the catalysis of alkali, and then dropwise adding acid to generate precipitate.
8. The method for preparing a visible light alkali-producing agent according to claim 7, wherein the reaction conditions of the aldehyde-ketone condensation reaction are as follows: reacting for 18-24 hours at 40-50 ℃ under the catalysis of alkali, and then dropwise adding acid to generate precipitate.
9. The method for preparing a visible light alkali-producing agent according to claim 7 or 8, wherein in the aldehyde ketone condensation reaction, the molar ratio of N- (4-formylphenyl) -N-methylglycine methyl ester to the base is 1:2 to 1: 5.
10. The method for preparing a visible light alkali-producing agent according to claim 7 or 8, wherein in the aldehyde ketone condensation reaction, the alkali is one or a mixture of sodium hydroxide and potassium hydroxide.
11. The method of claim 7, wherein the acid is any one or a mixture of hydrochloric acid, sulfuric acid, nitric acid, and acetic acid.
12. The method of claim 3, wherein the organic base is 1,5, 7-triazabicyclo [4.4.0] undec-5-ene or 1, 8-diazabicyclo [5.4.0] undec-7-ene.
13. The method according to claim 3, wherein the solvent is one or a mixture of two or more of water, methanol, ethanol, tetrahydrofuran, and N, N-dimethylformamide.
14. The method for preparing the visible light alkali-producing agent according to claim 3, wherein the reaction temperature of the precipitate a and the organic base dispersed in the solvent in the step (2) is 20 to 60 ℃ and the reaction time is 1 to 12 hours.
15. The method according to claim 3, wherein the reaction is carried out under protection of inert gas and light.
16. The use of the visible light base generator of claim 1 in photolytic catalytic polymerization and curing of polymeric photosensitive systems.
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