CN105152945A - Triphenylamine visible light photosensitizer containing two aromatic substituent groups and application thereof - Google Patents
Triphenylamine visible light photosensitizer containing two aromatic substituent groups and application thereof Download PDFInfo
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- CN105152945A CN105152945A CN201510452296.5A CN201510452296A CN105152945A CN 105152945 A CN105152945 A CN 105152945A CN 201510452296 A CN201510452296 A CN 201510452296A CN 105152945 A CN105152945 A CN 105152945A
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- visible light
- triphenylamine
- photosensitizer
- light photosensitizer
- styryl
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Abstract
The invention provides a triphenylamine visible light photosensitizer containing two aromatic substituent groups, and belongs to the field of visible light photosensitizers. The photosensitizer has a chemical structural general formula as shown in the specification, wherein R in the structural formula is methyl, nitryl, dimethylamino, methoxyl, cyano and hydrogen. The triphenylamine visible light photosensitizer containing two aromatic substituent groups is synthesized by a simple and convenient method, and the ultraviolet visible absorption peak of the photosensitizer is subjected to redshift to a visible region and can be used as a visible light photosensitizer to form a photosensitizer initiation system with 2,4,6-trichloromethyl-s-triazine, so that acrylic monomer polymerization can be initiated under visible light irradiation.
Description
Technical field
The invention belongs to visible light photosensitizer technical field, particularly containing triphen amine visible light photosensitizer and the application thereof of two aromatic substituents.
Background technology
Traditional light trigger 2,4,6-trichloromethyl s-triazine and derivative thereof, light-initiated efficiency is very high, widely applies in actual production, but they can only absorb the UV-light of 200-300nm, cannot realize visible light polymerization.
Summary of the invention
Object of the present invention is exactly the deficiency in order to overcome above-mentioned background technology, there is provided synthesis containing the triphen amine photosensitizers of two aromatic substituents, the peak value red shift of its ultravioletvisible absorption, to visible region, can cause the polymerization of acrylic monomer as visible light photosensitizer.
Triphen amine photosensitizers containing two aromatic substituents involved in the present invention, belong to visible light photosensitizer field, its chemical structure of general formula is as follows:
Wherein in structural formula (I), R is methyl, nitro, dimethylamino, methoxyl group, cyano group, hydrogen.
The synthetic method of above-mentioned triphenylamine analog derivative, step is as follows:
Triphenylamine analog derivative, phenylboronic acid derivative, salt of wormwood and tetrakis triphenylphosphine palladium (0) are added in 50mL tri-mouthfuls of ground flasks with the ratio of mol ratio 1:2.5:10:0.1, adding volume is triphenylamine derivative 200-300 dry tetrahydrofuran doubly, reflux 24 hours under argon shield, reaction terminates, be cooled to normal temperature, underpressure distillation is except desolventizing, take methylene dichloride as developping agent, silica gel chromatography column separating purification, product normal hexane recrystallization, obtains the compound of claim 1;
Wherein in structural formula (I), R is methyl, nitro, dimethylamino, methoxyl group, cyano group, hydrogen.
The triphen amine visible light photosensitizer tool containing two aromatic substituents that the present invention relates to has the following advantages:
(1) simply, raw material sources are convenient, low price for the synthesis of the triphen amine visible light photosensitizer containing two aromatic substituents involved in the present invention and separation method;
(2) the triphen amine visible light photosensitizer ultraviolet absorption peak containing two aromatic substituents involved in the present invention is extensible to visible region, can be used as near-ultraviolet light sensitizing agent and causes acrylic monomer polymerization under light illumination;
(3) to be involved in the present inventionly connected with benzophenone containing conjugated double bond containing in the triphen amine visible light photosensitizer molecular structure of two aromatic substituents, therefore to can be used as efficient photosensitizers.
Accompanying drawing explanation
Fig. 1. 4-benzoyl-styryl-4 '-4 " proton nmr spectra of-Dimethvl-phenyl-triphenylamine of the embodiment of the present invention 1;
Fig. 2. 4-benzoyl-styryl-4 '-4 " proton nmr spectra of-dinitro-phenyl-triphenylamine of the embodiment of the present invention 2;
Fig. 3. 4-benzoyl-styryl-4 '-4 " proton nmr spectra of-two Dimethylamino-phenyl-triphenylamine of the embodiment of the present invention 3;
Fig. 4. 4-benzoyl-styryl-4 '-4 " proton nmr spectra of-dimethoxy-phenylf-triphenylamine of the embodiment of the present invention 4;
Fig. 5. "-Dimethvl-phenyl-triphenylamine is dissolved in the relation curve of absorbancy in methylene dichloride and wavelength to the 4-benzoyl-styryl-4 '-4 of the embodiment of the present invention 5;
Fig. 6. "-dinitro-phenyl-triphenylamine is dissolved in the relation curve of absorbancy in methylene dichloride and wavelength to the 4-benzoyl-styryl-4 '-4 of the embodiment of the present invention 6;
Fig. 7. "-two Dimethylamino-phenyl-triphenylamine is dissolved in the relation curve of absorbancy in methylene dichloride and wavelength to the 4-benzoyl-styryl-4 '-4 of the embodiment of the present invention 7;
Fig. 8. "-dimethoxy-phenylf-triphenylamine is dissolved in the relation curve of absorbancy in methylene dichloride and wavelength to the 4-benzoyl-styryl-4 '-4 of the embodiment of the present invention 8;
Embodiment
The present invention is further illustrated below in conjunction with examples of implementation and accompanying drawing:
Embodiment 1
4-benzoyl-styryl-4 '-4 " synthesis of-Dimethvl-phenyl-triphenylamine
By 4-benzoyl styryl-4 '-4 "-dibromo triphenylamine (1mmol; 0.609g), add in the ground flask of three mouthfuls to methylphenylboronic acid (2.5mmol; 0.339g); add the tetrahydrofuran (THF) of 20mL drying again; after material dissolution, then the salt of wormwood (10mmol, 1.380g) added through hot water dissolving and tetrakis triphenylphosphine palladium (0) (0.1mmol; 0.109g), back flow reaction 24 hours under argon shield; After reaction terminates, solvent removed in vacuo take methylene dichloride as eluent; use silica gel chromatography column separating purification, normal hexane is solvent recrystallization, and vacuum drying oven is dry; obtain 4-benzoyl-styryl-4 '-4 "-Dimethvl-phenyl-triphenylamine, productive rate 65%, its proton nmr spectra is as Fig. 1.
1H-NMR(D6-DMSO,400MHz)δ(ppm):7.699-7.718(d,6H,J＝7.6Hz,Ar-H),7.630-7.667(t,1H,J＝7.6Hz,Ar-H),7.586-7.608(d,5H,J＝8.8Hz,Ar-H),7.512-7.564(m,7H,Ar-H),7.368-7.409(d,1H,J＝16.4Hz,Ar-H),7.200-7.240(m,5H,Ar-H),7.104-7.125(d,4H,J＝8.4Hz,Ar-H),7.033-7.054(d,2H,J＝8.4Hz,Ar-CH＝CH),2.465(s,6H,Ar-CH
3).
Embodiment 2
4-benzoyl-styryl-4 '-4 " synthesis of-dinitro-phenyl-triphenylamine
By 4-benzoyl-styryl-4 '-4, "-two bromo-triphenylamines (1mmol; 0.609g), p-nitrophenyl boric acid (2.5mmol; 0.415g) add in the ground flask of three mouthfuls; add the THF of 30mL drying again; after material dissolution, then the salt of wormwood (10mmol, 1.380g) added through hot water dissolving and tetrakis triphenylphosphine palladium (0) (0.1mmol; 0.109g), back flow reaction 24 hours under argon shield; After reaction terminates; solvent removed in vacuo; take methylene dichloride as eluent; use silica gel chromatography column separating purification; methylene dichloride is solvent recrystallization, and vacuum drying oven is dry, and "-dinitro-phenyl-triphenylamine; productive rate 70%, its proton nmr spectra is as Fig. 2 to obtain 4-benzoyl-styryl-4 '-4.
1H-NMR(D6-DMSO,400MHz)δ(ppm):8.233-8.255(d,4H,J＝8.8Hz,Ar-H),7.905-7.927(d,4H,J＝8.8Hz,Ar-H),7.621-7.777(m,10H,Ar-H),7519-7.557(m,3H,Ar-H),7.394-7.435(t,2H,J＝16.4Hz,Ar-H),7.287-7.246(d,1H,J＝16.4Hz,Ar-H),7.163-7.185(d,4H,J＝8.8Hz,Ar-H),7.108-7.129(d,2H,J＝8.4Hz,Ar-CH＝CH)。
Embodiment 3
4-benzoyl-styryl-4 '-4 " synthesis of-two Dimethylamino-phenyl-triphenylamine
4-benzoyl-styryl-4 '-4 "-two bromo-triphenylamines (1mmol; 0.609g), is added in the ground flask of three mouthfuls to dimethylamino phenylo boric acid (2.5mmol; 0.415g); add the tetrahydrofuran (THF) of 20mL drying again; after material dissolution; add the Anhydrous potassium carbonate (10mmol through hot water dissolving again, 1.380g) and tetrakis triphenylphosphine palladium (0) (0.1mmol, 0.109g), back flow reaction 24 hours under argon shield; After reaction terminates; solvent removed in vacuo; take methylene dichloride as eluent; use silica gel chromatography column separating purification; normal hexane is solvent recrystallization, and vacuum drying oven is dry, and "-two Dimethylamino-phenyl-triphenylamine; productive rate 55%, its proton nmr spectra is as Fig. 3 to obtain 4-benzoyl-styryl-4 '-4.
1H-NMR(D6-DMSO,400MHz)δ(ppm):7.714(s,6H,Ar-H),7.629-7.666(t,1H,J＝14.8Hz,Ar-H),7.542-7.578(t,8H,J＝14.4Hz,Ar-H),7.484-7.522(d,4H,J＝15.2Hz,Ar-H),7.355-7.396(d,1H,J＝16.4Hz,Ar-H),7.175-7.216(d,1H,J＝16.4Hz,Ar-H),7.066-7.087(d,4H,J＝8.4Hz,Ar-H),6.991-7.013(d,2H,J＝0.022Hz,Ar-H),6.749-6.747(d,4H,J＝8.8Hz,Ar-H),2.900(s,12H,N-CH
3)。
Embodiment 4
4-benzoyl-styryl-4 '-4 " synthesis of-dimethoxy-phenylf-triphenylamine
By 4-benzoyl-styryl-4 '-4, "-two bromo-triphenylamines (1mmol; 0.609g), p-dimethyoxy benzene boric acid (2.5mmol; 0.375g) add in the ground flask of three mouthfuls; add the tetrahydrofuran (THF) of 20mL drying again; after material dissolution; add the salt of wormwood (10mmol through hot water dissolving again, 1.380g) and tetrakis triphenylphosphine palladium (0) (0.01mol, 0.109g), back flow reaction 24 hours under argon shield; After reaction terminates; solvent removed in vacuo; take methylene dichloride as eluent; use silica gel chromatography column separating purification; hexanaphthene is solvent recrystallization, and vacuum drying oven is dry, and "-dimethoxy-phenylf-triphenylamine; productive rate 60%, its proton nmr spectra is as Fig. 4 to obtain 4-benzoyl-styryl-4 '-4.
1H-NMR(D6-DMSO,400MHz)δ(ppm):7.723-7.739(d,6H,J＝6.4Hz,Ar-H),7.650-7.669(d,1H,J＝7.6Hz,Ar-H),7.541-7.599(m,12H,Ar-H),7.386-7.427(d,1H,J＝16.4Hz,Ar-CH＝CH),7.215-7.256(d,1H,J＝16.4Hz,Ar-CH＝CH),7.115-7.136(d,4H,J＝8.4Hz,Ar-H),7.042-7.063(d,4H,J＝8.4Hz,Ar-H),6.989-7.011(d,4H,J＝8.8Hz,Ar-H),3.780(s,6H,-OCH
3)。
Embodiment 5
By 4-benzoyl-styryl-4 '-4, "-Dimethvl-phenyl-triphenylamine is dissolved in methylene dichloride, and concentration is 1 × 10
-5mol/L, measures ultraviolet-visible absorption spectroscopy, as Fig. 5.
Embodiment 6
By 4-benzoyl-styryl-4 '-4 "-dinitro-phenyl-triphenylamine is dissolved in methylene dichloride, and concentration is 1 × 10
-5mol/L, measures ultraviolet-visible absorption spectroscopy, as Fig. 6.
Embodiment 7
By 4-benzoyl-styryl-4 '-4 "-two Dimethylamino-phenyl-triphenylamine is dissolved in methylene dichloride, and concentration is 1 × 10
-5mol/L, measures ultraviolet-visible absorption spectroscopy, as Fig. 7.
Embodiment 8
By 4-benzoyl-styryl-4 '-4 "-dimethoxy-phenylf-triphenylamine is dissolved in methylene dichloride, and concentration is 1 × 10
-5mol/L, measures ultraviolet-visible absorption spectroscopy, as Fig. 8.
Embodiment 9
"-Dimethvl-phenyl-triphenylamine visible light photosensitizer causes the polymerization of the methyl methacrylate in solution to 4-benzoyl-styryl-4 '-4
In the horminess glass tube that 10cm is long; add the ethyl acetate of 5mL and the methyl methacrylate of 5mL; add 10mg4-benzoyl-styryl-4 '-4 "-Dimethvl-phenyl-triphenylamine; 2mg2; 4; 6-trichloromethyl s-triazine; lead to argon gas 15 minutes in lucifuge situation, is placed in illumination under the tungsten-iodine lamp of 1kw, before tungsten-iodine lamp, places spectral filter under room temperature; only allow a visible ray to pass through; after 3 hours, stop polymerization with cold methyl alcohol, obtain white polymer; i.e. polymethylmethacrylate, productive rate 80%.
Embodiment 10
"-dinitro-phenyl-triphenylamine visible light photosensitizer causes the polymerization of the methyl methacrylate in solution to 4-benzoyl-styryl-4 '-4
In the horminess glass tube that 10cm is long; add the ethyl acetate of 5mL and the methyl methacrylate of 5mL; "-dinitro-phenyl-triphenylamine; 2mg2; 4; 6-trichloromethyl s-triazine; lead to argon gas 15 minutes in lucifuge situation, is placed in illumination under the tungsten-iodine lamp of 1kw, before tungsten-iodine lamp, places spectral filter under room temperature; only allow a visible ray to pass through to add 10mg4-benzoyl-styryl-4 '-4; after 3 hours, stop polymerization with cold methyl alcohol, obtain white polymer; i.e. polymethylmethacrylate, productive rate 75%.
Embodiment 11
4-benzoyl-styryl-4 '-4 "-two Dimethylamino-phenyl-triphenylamine visible light photosensitizer cause the polymerization of the methyl methacrylate in solution
In the horminess glass tube that 10cm is long; add the ethyl acetate of 5mL and the methyl methacrylate of 5mL; "-two Dimethylamino-phenyl-triphenylamine; 2mg2; 4; 6-trichloromethyl s-triazine; lead to argon gas 15 minutes in lucifuge situation, is placed in illumination under the tungsten-iodine lamp of 1kw, before tungsten-iodine lamp, places spectral filter under room temperature; only allow a visible ray to pass through to add 10mg4-benzoyl-styryl-4 '-4; after 3 hours, stop polymerization with cold methyl alcohol, obtain white polymer; i.e. polymethylmethacrylate, productive rate 89%.
Embodiment 12
4-benzoyl-styryl-4 '-4 " visible light photosensitizer of-dimethoxy-phenylf-triphenylamine causes the polymerization of the methyl methacrylate in solution
In the horminess glass tube that 10cm is long; add the ethyl acetate of 5mL and the methyl methacrylate of 5mL; "-dimethoxy-phenylf-triphenylamine; 2mg2; 4; 6-trichloromethyl s-triazine; lead to argon gas 15 minutes in lucifuge situation, is placed in illumination under the tungsten-iodine lamp of 1kw, before tungsten-iodine lamp, places spectral filter under room temperature; only allow a visible ray to pass through to add 10mg4-benzoyl-styryl-4 '-4; after 3 hours, stop polymerization with cold methyl alcohol, obtain white polymer; i.e. polymethylmethacrylate, productive rate 85%.
Claims (3)
1., containing the triphen amine visible light photosensitizer of two aromatic substituents, belong to visible light photosensitizer field, its chemical structure of general formula is as follows:
R wherein in structural formula (I) is methyl, nitro, dimethylamino, methoxyl group, cyano group, hydrogen.
2. the synthetic method of the triphen amine visible light photosensitizer containing two aromatic substituents as claimed in claim 1 is as follows:
Triphenylamine analog derivative, phenylboronic acid derivative, salt of wormwood and tetrakis triphenylphosphine palladium (0) are added in 50mL tri-mouthfuls of ground flasks with the ratio of mol ratio 1:2.5:10:0.1, adding volume is triphenylamine derivative 200-300 dry tetrahydrofuran doubly, reflux 24 hours under argon shield, reaction terminates, be cooled to normal temperature, underpressure distillation is except desolventizing, take methylene dichloride as developping agent, silica gel chromatography column separating purification, product normal hexane recrystallization, obtains the compound of claim 1;
Wherein in structural formula (I), R is methyl, nitro, dimethylamino, methoxyl group, cyano group, hydrogen.
3. the visible light photosensitizer of the triphen amine containing two aromatic substituents as claimed in claim 1, its purposes is: this photosensitizers is as visible light photosensitizer and 2,4,6-trichloromethyl s-triazine forms optical sensing system together and causes acrylic monomer polymerization under visible light illumination.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114634480A (en) * | 2022-04-18 | 2022-06-17 | 内蒙古大学 | Aggregation-induced emission photosensitizer and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103980392A (en) * | 2014-05-16 | 2014-08-13 | 重庆大学 | Star-like visible light initiator having conjugated structure and containing benzophenone fragments as well as synthesis and application of visible light initiator |
| CN104693322A (en) * | 2015-03-25 | 2015-06-10 | 重庆大学 | Phenyl vinyl imino group class visible light photosensitizer of conjugated structure and application thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103980392A (en) * | 2014-05-16 | 2014-08-13 | 重庆大学 | Star-like visible light initiator having conjugated structure and containing benzophenone fragments as well as synthesis and application of visible light initiator |
| CN104693322A (en) * | 2015-03-25 | 2015-06-10 | 重庆大学 | Phenyl vinyl imino group class visible light photosensitizer of conjugated structure and application thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114634480A (en) * | 2022-04-18 | 2022-06-17 | 内蒙古大学 | Aggregation-induced emission photosensitizer and preparation method and application thereof |
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