CN103044344A - Benzotriazol derivatives containing o-nitro-diphenyl ethylene fragments - Google Patents
Benzotriazol derivatives containing o-nitro-diphenyl ethylene fragments Download PDFInfo
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- CN103044344A CN103044344A CN2013100240000A CN201310024000A CN103044344A CN 103044344 A CN103044344 A CN 103044344A CN 2013100240000 A CN2013100240000 A CN 2013100240000A CN 201310024000 A CN201310024000 A CN 201310024000A CN 103044344 A CN103044344 A CN 103044344A
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- 0 Nc1ccc(C=C[C@]2C=CC=CC2[N+]([O-])=O)cc1*1I=C(C=CC=C2)C2=N1 Chemical compound Nc1ccc(C=C[C@]2C=CC=CC2[N+]([O-])=O)cc1*1I=C(C=CC=C2)C2=N1 0.000 description 1
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Abstract
The invention relates to a benzotriazol derivative containing o-nitro-diphenyl ethylene fragments. The chemical structural general formula of the benzotriazol derivatives is shown in the specification; when a functional group R of the benzotriazol derivatives containing the o-nitro-diphenyl ethylene fragments is hydroxyl, the chemical structural formula of the benzotriazol derivatives is shown in the specification; and when the functional group R of the benzotriazol derivatives containing the o-nitro-diphenyl ethylene fragments is methoxyl, the chemical structural formula of the benzotriazol derivative is shown in the specification. When the diameter of the benzotriazol derivatives is between 300 and 400 nm, the benzotriazol derivatives have an obvious function of absorbing near ultraviolet, the benzotriazol derivatives and an assistant initiator triethanolamine are mixed together to form a photoinitiator system, and the benzotriazol derivatives can be used for performing near ultraviolet polymerization on acrylic acid type monomers in a solution.
Description
Technical field
The invention belongs to photosensitive dose of field of near ultraviolet, particularly contain the Benzotriazole Derivative of adjacent nitro diphenyl ethylene fragment.
Background technology
Ultraviolet-curing paint refers to be subject to after the UV-irradiation photochemical reaction occurs, and makes coating rapid polymerization, crosslinked and solidify.After entering the nineties in last century, along with post and telecommunications, computer, printing and electron trade development and living standards of the people improve constantly, ultraviolet-curing paint has been produced very large demand.Jianwen Xu etc. (is published in " coating technology magazine " at " progress of radiotherapy market and technology " (Progress in radiation curing-marketing and technology), " Journal ofCoatings Technology ", 2002,74 (928): 67-72) estimate in the article that ultraviolet photocureable material will be with the speed sustainable growth of average annual growth rate 25%.Most important component is light trigger in the free radical reaction system of ultraviolet light polymerization, namely can produce the material of living radical under UV-irradiation.Its effect is to produce the active group that causes curing reaction, such as living radical, active cation, thereby makes reaction system generation polymerization.The performance of light trigger has determined state of cure and the curing speed of ultraviolet-curing paint.Traditional light trigger mainly contains benzophenone, benzoin ether and derivative thereof etc., and the efficiency of initiation of these light triggers is not high, and oneself widely applies in actual production by warp, but they can only absorb the UV-light of 200 ~ 300nm, can't realize the near-ultraviolet light polymerization.
Summary of the invention
The object of the invention is to overcome the deficiency of above-mentioned background technology, and a kind of Benzotriazole Derivative that contains adjacent nitro diphenyl ethylene fragment that obvious near ultraviolet absorbs that has is provided.Mix composition photoinitiator system with the aided initiating trolamine, can be used for the near-ultraviolet light polymerization of acrylic monomer in the solution, and polymerization efficiency is high.
The Benzotriazole Derivative that contains adjacent nitro diphenyl ethylene fragment involved in the present invention, its chemical structure of general formula is as follows:
When the R of functional group was hydroxyl in the said structure formula, this Benzotriazole Derivative was 2-(2-hydroxyl-5-(2-nitro) styryl)-2H-benzotriazole, and its chemical structural formula is:
When the R of functional group was methoxyl group in the said structure formula, this Benzotriazole Derivative was 2-(2-methoxyl group-5-(2-nitro) styryl)-2H-benzotriazole, and its chemical structural formula is:
When Benzotriazole Derivative was 2-(2-hydroxyl-5-(2-nitro) styryl)-2H-benzotriazole, its synthesis step was as follows:
2-(2-hydroxyl-5-(2-nitro) styryl)-2H-benzotriazole
O-Nitrophenylacetic acid is mixed in three-necked flask take mol ratio as 4:1 with 2-(2-hydroxy-5-methyl aldehyde radical)-2H-benzotriazole; stir lower a small amount of hexahydropyridine that drips; be warming up to 100 ℃ under the argon shield; reflux and be warming up to 130 ℃ of continuation backflows 4 hours after 3 hours; separate with silica gel chromatographic column; take volume ratio as the 1:1 methylene dichloride and cyclohexane give as developping agent, obtain the 2-(2-hydroxyl-5-(2-nitro) styryl) of claim 1-2H-benzotriazole.
When Benzotriazole Derivative was 2-(2-methoxyl group-5-(2-nitro) styryl)-2H-benzotriazole, its synthesis step was as follows:
2-(2-methoxyl group-5-(2-nitro) styryl)-2H-benzotriazole
2-(2-hydroxyl-5-(2-nitro) styryl)-2H-benzotriazole and salt of wormwood (mol ratio 1:2) are dissolved in 100～500 times dry acetone of these two kinds of reactant cumulative volumes, add a small amount of phase-transfer catalyst 18-C-6, drip methyl iodide (molar weight that adds methyl iodide is 4 times of 2-(2-hydroxyl-5-(2-nitro) styryl)-2H-benzotriazole), argon shield stirring at room 24 hours, reaction finishes; Solids removed by filtration, removal of solvent under reduced pressure is separated with silica gel chromatographic column, take volume ratio as the 5:3 methylene dichloride and cyclohexane give as developping agent, obtain getting the 2-(2-methoxyl group-5-(2-nitro) styryl)-2H-benzotriazole of claim 1.
The Benzotriazole Derivative that contains adjacent nitro diphenyl ethylene fragment of the present invention, having obvious near ultraviolet absorbs, mix composition photoinitiator system with the aided initiating trolamine, can be used for the near-ultraviolet light polymerization of acrylic monomer in the solution, and polymerization efficiency is high.
Consumption (with mass percent represent), preparation and the using method of light trigger of the present invention during as above purposes is as follows:
Initiator: 0.1wt%-10wt%
Organic solvent: 30wt%-60wt%
Acrylic monomer: 20wt%-50wt%
Aided initiating trolamine: 0.1wt%-5wt%
Concrete operation step is as follows:
In colorimetric cylinder, add mass percent and be respectively the Benzotriazole Derivative that contains adjacent nitro diphenyl ethylene fragment that is synthesized in the claim 1 of 0.1wt%-10wt%, the organic solvent of 20wt%-50wt%, the acrylic monomer of 30wt%-60wt%, the aided initiating trolamine of 0.1wt%-5wt%, then the logical argon gas 20-30 minute deoxygenation of lucifuge, sealing.1KW straight pipe type tungsten-iodine lamp is placed from reaction flask 10cm place as the near ultraviolet light source.With the light between the spectral filter elimination 200-300nm, the near-ultraviolet light initiated polymerization at room temperature carries out, and uses magnetic stirring apparatus to continue to stir, and reduces the temperature of reaction system with water of condensation and high-power fan, avoids producing thermopolymerization.After reaction reaches the scheduled time, take out immediately the solution after the illumination is poured in the beaker of cold methanol of 50ml, until precipitating rear filtration fully, place 50 ℃ of thermostatic drying chambers to be dried to constant weight, can get the acrylic monomer polymkeric substance.
In the above-mentioned prescription, described acrylic monomer comprises methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate or their mixture.
Described organic solvent comprises ethyl acetate, acetonitrile, methylene dichloride, benzene, hexanaphthene etc.
The Benzotriazole Derivative that contains adjacent nitro diphenyl ethylene fragment of the present invention has following advantage:
(1) synthetic method of the Benzotriazole Derivative that contains adjacent nitro diphenyl ethylene fragment of the present invention and separate simple.
(2) Benzotriazole Derivative that contains adjacent nitro diphenyl ethylene fragment of the present invention, it has obvious near ultraviolet absorption at 300 ~ 400nm, satisfies the requirement that near ultraviolet absorbs fully.
(3) Benzotriazole Derivative that contains adjacent nitro diphenyl ethylene fragment of the present invention shows good fluorescent emission.
Description of drawings
Fig. 1. the nuclear-magnetism H spectrum of the 2-of the embodiment of the invention 1 (2-hydroxyl-5-(2-nitro) styryl)-2H-benzotriazole.
Fig. 2. the nuclear-magnetism H spectrum of the 2-of the embodiment of the invention 2 (2-methoxyl group-5-(2-nitro) styryl)-2H-benzotriazole.
Fig. 3. 1 * 10 in the embodiment of the invention 1
-5The 2-of mol/L (2-hydroxyl-5-(2-nitro) styryl)-2H-benzotriazole is dissolved in absorbancy in the DMF and the relation curve of wavelength.
Fig. 4. 1 * 10 in the embodiment of the invention 1
-5The 2-of mol/L (2-hydroxyl-5-(2-nitro) styryl)-2H-benzotriazole is dissolved in N, the intensity in the N-METHYLFORMAMIDE and the relation curve of wavelength.
Fig. 5. 1 * 10 in the embodiment of the invention 2
-5The 2-of mol/L (2-methoxyl group-5-(2-nitro) styryl)-2H-benzotriazole is dissolved in absorbancy in the DMF and the relation curve of wavelength.
Fig. 6. 1 * 10 in the embodiment of the invention 2
-5The 2-of mol/L (2-methoxyl group-5-(2-nitro) styryl)-2H-benzotriazole is dissolved in fluorescent emission intensity in the DMF and the relation curve of wavelength.
Embodiment
Further specify the present invention below in conjunction with example and accompanying drawing:
When Benzotriazole Derivative was 2-(2-hydroxyl-5-(2-nitro) styryl)-2H-benzotriazole, its synthesis step was as follows:
2-(2-hydroxyl-5-(2-nitro) styryl)-2H-benzotriazole
With o-Nitrophenylacetic acid (4mmol; 0.724g) and 2-(2-hydroxy-5-methyl aldehyde radical)-2H-benzotriazole (1mmol; 0.239g) add in the three-necked flask; under constantly stirring, drip a small amount of hexahydropyridine; under argon shield, be warming up to 100 ℃; reflux and be warming up to 130 ℃ of continuation backflows 4 hours after 3 hours; separate with silica gel chromatographic column; take volume ratio as the 1:1 methylene dichloride and cyclohexane give as developping agent, obtain the 2-(2-hydroxyl-5-(2-nitro) styryl) of claim 1-2H-benzotriazole.216 ° of C of fusing point, productive rate 40%.Its nuclear-magnetism H composes as shown in Figure 1,
1H-NMR (500MHz, DMSO-d6) δ (ppm): 10.826 (s, 1H, Ar-OH), (8.080-8.049 m, 3H, Ar-H), 7.979-7.951 (t, 2H, J=7Hz, Ar-H), 7.751-7.712 (m, 2H, Ar-CH=CH), 7.558-7.502 (m, 3H, Ar-H), 7.439-7.353 (m, 2H, Ar-H), (7.224-7.207 d, 1H, J=8.5Hz, Ar-H).
When Benzotriazole Derivative was 2-(2-methoxyl group-5-(2-nitro) styryl)-2H-benzotriazole, its synthesis step was as follows:
2-(2-methoxyl group-5-(2-nitro) styryl)-2H-benzotriazole
With 2-(2-hydroxyl-5-(2-nitro) styryl)-2H-benzotriazole (2.5mmol, 0.895g) and salt of wormwood (5mmol, 0.69g) add in the two neck bottles, mix rear adding 60ml dry acetone, add a small amount of phase-transfer catalyst 18-C-6, drip methyl iodide (10mmol, 0.4ml), argon shield stirring at room 24 hours, reaction finishes; Solids removed by filtration, removal of solvent under reduced pressure is separated with silica gel chromatographic column, take volume ratio as the 5:3 methylene dichloride and cyclohexane give as developping agent, obtain getting the 2-(2-methoxyl group-5-(2-nitro) styryl)-2H-benzotriazole of claim 1.148 ℃ of fusing points, productive rate 95%.Its nuclear-magnetism H composes as shown in Figure 2,
1H-NMR (500MHz, DMSO-d6) δ (ppm): 8.063-8.026 (m, 2H, Ar-H), 7.990-7.968 (m, 2H, Ar-H), 7.966-7.945 (m, 1H, Ar-H), 7.883-7.861 (m, 1H, Ar-CH=CH), (7.763-7.732 t, 1H, J=7.75Hz, Ar-CH=CH), (7.554-7.515 m, 3H, Ar-H), 7.493-7.361 (m, 3H, Ar-H) 3.858 (s, 3H, Ar-OCH
3).
Embodiment 3
2-(2-hydroxyl-5-(2-nitro) styryl)-2H-benzotriazole is mixed with 1 * 10 at DMF
-5The solution of mol/L is measured its ultra-violet absorption spectrum, as shown in Figure 3.
Embodiment 4
2-(2-hydroxyl-5-(2-nitro) styryl)-2H-benzotriazole is mixed with 1 * 10 in DMF
-5The solution of mol/L is measured its fluorescence emission spectrum, as shown in Figure 4.
2-(2-methoxyl group-5-(2-nitro) styryl)-2H-benzotriazole is mixed with 1 * 10 in DMF
-5The solution of mol/L is measured its ultra-violet absorption spectrum, as shown in Figure 5.
2-(2-methoxyl group-5-(2-nitro) styryl)-2H-benzotriazole is mixed with 1 * 10 in DMF
-5The solution of mol/L is measured its fluorescence emission spectrum, as shown in Figure 6.
Photosensitive dose of methyl methacrylate polymerization that causes in the solution of the near ultraviolet of 2-(2-hydroxyl-5-(2-nitro) styryl)-2H-benzotriazole.
The 2-that is synthesized (2-hydroxyl-5-(2-nitro) styryl) of adding 0.049g-2H-benzotriazole in the long horminess glass tube of 10cm, the ethyl acetate of 5ml, the methyl methacrylate of 5ml, 0.01ml the aided initiating trolamine, then the logical argon gas deoxygenation in 20 ~ 30 minutes of lucifuge, sealing.1KW straight pipe type tungsten-iodine lamp is placed from reaction flask 10cm place as the near ultraviolet light source.Utilize the light between the spectral filter elimination 200-300nm, the near-ultraviolet light initiated polymerization at room temperature carries out, and uses magnetic stirring apparatus to continue to stir, and reduces the temperature of reaction system with water of condensation and high-power fan, avoids producing thermopolymerization.After reaction reaches the scheduled time, take out immediately, the solution after the illumination is poured in the beaker of cold methanol of 50ml, filter after the precipitation fully, weigh after placing 50 ℃ of thermostatic drying chamber dryings, can get the acrylic monomer polymkeric substance, monomer conversion is 95%.
Photosensitive dose of methyl methacrylate polymerization that causes in the solution of the near ultraviolet of 2-(2-methoxyl group-5-(2-nitro) styryl)-2H-benzotriazole.
The 2-that is synthesized (2-methoxyl group-5-(2-nitro) styryl) of adding 0.026g-2H-benzotriazole-2H-benzotriazole in the long horminess glass tube of 10cm, the ethyl acetate of 5ml, the methyl methacrylate of 5ml, 0.01ml the aided initiating trolamine, then the logical argon gas deoxygenation in 20 ~ 30 minutes of lucifuge, sealing.1KW straight pipe type tungsten-iodine lamp is placed from reaction flask 10cm place as the near ultraviolet light source.Utilize the light between the spectral filter elimination 200-300nm, the near-ultraviolet light initiated polymerization at room temperature carries out, and uses magnetic stirring apparatus to continue to stir, and reduces the temperature of reaction system with water of condensation and high-power fan, avoids producing thermopolymerization.After reaction reaches the scheduled time, take out immediately, the solution after the illumination is poured in the beaker of cold methanol of 50ml, filter after the precipitation fully, weigh after placing 50 ℃ of thermostatic drying chamber dryings, can get the acrylic monomer polymkeric substance, monomer conversion is 89%.
Claims (3)
1. the Benzotriazole Derivative that contains adjacent nitro diphenyl ethylene fragment, its chemical structure of general formula is as follows:
。
2. the Benzotriazole Derivative that contains adjacent nitro diphenyl ethylene fragment according to claim 1, when it is characterized in that sense R is hydroxyl, this Benzotriazole Derivative is 2-(2-hydroxyl-5-(2-nitro) styryl)-2H-benzotriazole, and its chemical structural formula is:
3. the Benzotriazole Derivative that contains adjacent nitro diphenyl ethylene fragment according to claim 1, when it is characterized in that the R of functional group is methoxyl group, this Benzotriazole Derivative is 2-(2-methoxyl group-5-(2-nitro) styryl)-2H-benzotriazole, and its chemical structural formula is:
。
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3850855A (en) * | 1972-03-14 | 1974-11-26 | Daicel Ltd | Photolytic polyisobutylene oxide resin molded products of vanishing type |
| WO1997012882A2 (en) * | 1995-10-06 | 1997-04-10 | Hoechst Celanese Corporation | Family of monomeric, reactive, and polymeric benzotriazoles |
| CN101654570A (en) * | 2009-09-24 | 2010-02-24 | 中国海洋石油总公司 | Water-based ultraviolet curing coating |
| CN101885924A (en) * | 2010-06-21 | 2010-11-17 | 重庆大学 | Benzotriazole dye as well as synthesis and application thereof |
| CN102558397A (en) * | 2012-01-17 | 2012-07-11 | 重庆大学 | Benzotriazole near ultraviolet photosensitizer with conjugation structure as well as synthesis and application of benzotriazole near ultraviolet photosensitizer |
-
2013
- 2013-01-22 CN CN2013100240000A patent/CN103044344A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3850855A (en) * | 1972-03-14 | 1974-11-26 | Daicel Ltd | Photolytic polyisobutylene oxide resin molded products of vanishing type |
| WO1997012882A2 (en) * | 1995-10-06 | 1997-04-10 | Hoechst Celanese Corporation | Family of monomeric, reactive, and polymeric benzotriazoles |
| CN101654570A (en) * | 2009-09-24 | 2010-02-24 | 中国海洋石油总公司 | Water-based ultraviolet curing coating |
| CN101885924A (en) * | 2010-06-21 | 2010-11-17 | 重庆大学 | Benzotriazole dye as well as synthesis and application thereof |
| CN102558397A (en) * | 2012-01-17 | 2012-07-11 | 重庆大学 | Benzotriazole near ultraviolet photosensitizer with conjugation structure as well as synthesis and application of benzotriazole near ultraviolet photosensitizer |
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Application publication date: 20130417 |