Indocyanine anti-glare dye and preparation method and application thereof
阅读说明：本技术 一种吲哚方酸菁防眩光染料及其制备方法和应用 (Indocyanine anti-glare dye and preparation method and application thereof ) 是由 李曼 李行 宋亚 于 2021-07-26 设计创作，主要内容包括：本发明公开了一种吲哚方酸菁防眩光染料及其制备方法和应用,属于有机功能材料技术领域。其制备方法主要包括以下步骤,S1、季铵盐中间体的合成,S2、吲哚方酸菁的制备。本发明制备的吲哚方酸菁防眩光染料是一种具有高稳定性的可见光吸收剂,该吸收剂在视见函数明视觉曲线的峰值附近有强吸收,在强光照射时可有效削减进入人眼的敏感波段的光,从而降低强光对人眼造成的炫光作用,同时其在视见函数暗视觉曲线的峰值附近吸收较弱,因此并不影响较暗光线下人眼对周围环境的观察效果,相比于其他防眩光技术,该吸收剂可制成涂料直接涂布,工艺简单,成本更低。(The invention discloses an indocyanine anti-glare dye, and a preparation method and application thereof, and belongs to the technical field of organic functional materials. The preparation method mainly comprises the following steps of S1, synthesis of a quaternary ammonium salt intermediate, S2 and preparation of indocyanine squarate. The indocyanine squarylium anti-glare dye prepared by the invention is a visible light absorbent with high stability, the absorbent has strong absorption near the peak value of a visual function photopic curve, and can effectively reduce light entering a sensitive wave band of human eyes during strong light irradiation, so that the glare effect of strong light on the human eyes is reduced, and meanwhile, the absorption near the peak value of the visual function scotopic curve is weaker, so that the observation effect of the human eyes on the surrounding environment under darker light is not influenced.)
1. An indocyanine anti-glare dye is characterized in that the molecular structure of the indocyanine anti-glare dye is as follows:
wherein R1 and R1' are the same and are C6-C12 alkyl (C)mH2m+1Wherein m is 6,7,8,9,10,11,12 '), benzene ring, one of p-cyanobenzyl and p-methylbenzyl, R2 and R2' are the same and are C4-C10 alkyl (C)mH2m+1Where m is 4,5,6,7,8,9,10), hydroxy, C4-C10 alkoxy (C)mH2m+1O, m ═ 4,5,6,7,8,9, 10).
2. The preparation method of the indocyanine anti-glare dye according to claim 1, comprising the following steps:
s1 and synthesis of intermediate of quaternary ammonium salt
Adding an indole compound (M1), an alkyl halide X-R1 and ethanol into a reaction container, stirring until the indole compound, the alkyl halide X-R1 and the ethanol are dissolved, adding potassium perchlorate, carrying out reflux reaction under the protection of nitrogen for a certain time, and then treating a reaction liquid to prepare a quaternary ammonium salt intermediate (M2), wherein the reaction formula is as follows:
wherein R1 is C6-C12 alkyl (C)mH2m+1Wherein m is 6,7,8,9,10,11, 12'), benzene ring, one of p-cyanobenzyl and p-methylbenzyl, R2 is C4-C10 alkyl (C)mH2m+1Where m is 4,5,6,7,8,9,10), hydroxy, C4-C10 alkoxy (C)mH2m+1O, m ═ 4,5,6,7,8,9,10), and X is Cl, I, or Br.
S2 preparation of indocyanine squarate
Heating and dissolving a certain mass of squaric acid in a mixed solvent, adding a pyridine solution of a quaternary ammonium salt intermediate M2, continuously carrying out reflux reaction for a period of time, and treating a reaction solution to prepare indole squaraine M3, wherein the reaction formula is as follows:
3. the method for preparing indocyanine anti-glare dye according to claim 2, wherein: in S1, the dosage of haloalkane X-R1 is 1.2-1.5 times of M1 molar number, the dosage of ethanol is 10-20 times of M1 molar number, the dosage of potassium perchlorate is 0.2-0.5 time of M1 molar number, the reflux reaction time is 6 hours, after the reaction is finished, the reaction solution is cooled to room temperature, dichloromethane with the mass of 1-2 times of ethanol is used for treating the reaction solution, the reaction solution is stirred, filtered, filtrate is rotated to be viscous, ethanol with the mass of 3-5 times of M1 is added to precipitate solid, and white-like powder M2 is obtained by suction filtration, water washing, suction filtration and drying.
4. The method for preparing indocyanine anti-glare dye according to claim 2, wherein: in S2, the dosage of the mixed solvent is 15-25 times of the mass number of the squaric acid, the dosage of M2 is 0.7-0.8 time of the molar number of the squaric acid, the concentration of M2 pyridine solution is 25 wt%, the reflux reaction time is 5-10h, after the reaction is finished, the reaction solution is cooled to room temperature, acetone 0.5-1.5 times of the mass number of the mixed solvent is used for treating the reaction solution, solid is precipitated and filtered, methanol is washed, filtered and dried to obtain blue-green powder M3.
5. The method for preparing indocyanine anti-glare dye according to claim 4, wherein: the mixed solvent is obtained by mixing one of methanol, ethanol, ethylene glycol, n-propanol, isopropanol and n-butanol with one of toluene, xylene and chlorobenzene.
6. The use of M3 prepared by the method of preparing an indocyanine anti-glare dye according to any one of claims 2 to 5, wherein: it is applied to preparing coating, sunglasses, automobile windows, rearview mirror coating films and the like.
7. An indocyanine anti-glare dye according to claim 6, for use in the preparation of coatings, characterized in that: wherein the coating comprises the following components (in wt%):
50-72.3 of solvent; 0.5-1 part of antioxidant; 0.2-1 part of light stabilizer, 25-47.3 parts of resin and 4 parts of M32.
8. An indocyanine anti-glare dye according to claim 7, for use in the preparation of coatings, characterized in that: the solvent is one of ethyl acetate, butanone, cyclohexanone, toluene and xylene, and the antioxidant is one of benzotriazole, phenols and phosphite esters; the light stabilizer is hindered amine, benzophenone; the resin is one of single-component or double-component materials of acrylic acid, epoxy modified acrylic acid, polyester modified acrylic acid and polyurethane.
Technical Field
The invention relates to an indocyanine anti-glare dye, and a preparation method and application thereof, and belongs to the technical field of organic functional materials.
Background
The human eyes have brightness adaptability, which means that the human vision needs a certain time to adapt and adjust in the process of rapid brightness change. The process of human eyes basically adapting to darkness needs 4-6min, and the human eyes stay in the dark place for about 30min when completely adapting. The time for clear adaptation is short, and the complete adaptation is usually carried out in about 1 min. In the process of adaptation, the normal function of eyes can suffer destruction and lead to the reduction of visibility, and when the driving at night, luminance in the driver's eye often changes fast, especially when the light of other vehicle high beam shines driver's eyes, will take place dazzling phenomenon, makes driver's eyesight decline temporarily, seriously influences driving safety. The visual perception that glare causes discomfort to the driver is mainly manifested in three aspects: 1. miosis, reducing the illumination on the retina; 2. the dazzling light is scattered in the eyeball, so that the contrast between the observed object and the background is weakened; 3. the visual cells are stimulated by strong light to cause the interaction between cerebral cortex cells, so that the observation result of the observed object is in a fuzzy state. Dazzling light irradiation can not only cause discomfort in physiology of people, but also can cause fatigue in psychology, so that a driver is difficult to timely and accurately judge road conditions and make correct countermeasures.
At present, the anti-dazzling method at home and abroad mainly comprises the following aspects:
the method 1, manually switching the high beam and the low beam to avoid or reduce strong light irradiation;
method 2, anti-glare by using an automatic light changing device;
method 3, adopting monochromatic light to prevent dazzling;
method 4, anti-dazzling by using an electrochromic lens;
method 5, anti-glare using polarized light.
Method 1 and method 2 reduce the irradiation of the high beam by switching the light source, the process is tedious, and the effect is poor in practical application, method 3 mainly utilizes the principle that the vision recovery is faster under the same dazzling condition of the white light by the single color light to prevent dazzling, but the defect that the illumination effect is not ideal by adopting the single color light illumination, method 4 realizes the deepening of the color of the lens during the strong light illumination by the combination of the sensor, the control circuit and the photochromic lens, and the method for reducing the incidence of visible light to prevent dazzling is realized, but the technology is not mature enough, the visual fatigue is easily caused under the condition of frequent change of brightness, the technical requirement is high, the process is complex, the cost is high, method 5 can theoretically ensure that the direct headlamp light can not penetrate through the automobile window by designing the lens and the automobile glass with the vertical polarization direction, and the light scattered back by the object can realize the dazzling prevention purpose by the mode of not influencing the visual field of the driver, however, in a real scene, the front windshield of the automobile is inclined, which causes the polarization extinction effect to be greatly deteriorated, and the problem of great process difficulty also exists.
Therefore, the development of a material with simple process and good anti-glare effect has important market value.
Disclosure of Invention
The present invention is implemented by the following technical solutions in view of the technical problems mentioned in the background art:
an indocyanine anti-glare dye, which has the following molecular structure:
wherein R1 and R1' are the same and are C6-C12 alkyl (C)mH2m+1Wherein m is 6,7,8,9,10,11,12 '), benzene ring, one of p-cyanobenzyl and p-methylbenzyl, R2 and R2' are the same and are C4-C10 alkyl (C)mH2m+1Where m is 4,5,6,7,8,9,10), hydroxy, C4-C10 alkoxy (C)mH2m+1O, m ═ 4,5,6,7,8,9, 10);
2. a preparation method of indocyanine anti-glare dye comprises the following steps:
s1 and synthesis of intermediate of quaternary ammonium salt
Adding an indole compound (M1), an alkyl halide X-R1 and ethanol into a reaction container, stirring until the indole compound, the alkyl halide X-R1 and the ethanol are dissolved, adding potassium perchlorate, carrying out reflux reaction under the protection of nitrogen for a certain time, and then treating a reaction liquid to prepare a quaternary ammonium salt intermediate (M2), wherein the reaction formula is as follows:
wherein R1 is C6-C12 alkyl (C)mH2m+1Wherein m is 6,7,8,9,10,11, 12'), benzene ring, one of p-cyanobenzyl and p-methylbenzyl, R2 is C4-C10 alkyl (C)mH2m+1Where m is 4,5,6,7,8,9,10), hydroxy, C4-C10 alkoxy (C)mH2m+1O, m ═ 4,5,6,7,8,9,10), and X is Cl, I, or Br.
S2 preparation of indocyanine squarate
Heating and dissolving a certain mass of squaric acid in a mixed solvent, adding a pyridine solution of a quaternary ammonium salt intermediate M2, continuously carrying out reflux reaction for a period of time, and treating a reaction solution to prepare indole squaraine M3, wherein the reaction formula is as follows:
as a preferable example, in S1, the alkyl halide X-R1 is 1.2-1.5 times of M1 mol number, the ethanol is 10-20 times of M1 mass number, the potassium perchlorate is 0.2-0.5 times of M1 mol number, the reflux reaction time is 6h, after the reaction is finished, the reaction solution is cooled to room temperature, dichloromethane with the ethanol mass number of 1-2 times is used for treating the reaction solution, the reaction solution is stirred, filtered, the filtrate is rotated to be viscous, ethanol with the M1 mass number of 3-5 times is added to precipitate a solid, and the white-like powder M2 is obtained by suction filtration, water washing, suction filtration and drying.
As a preferable example, in S2, the amount of the mixed solvent used is 15 to 25 times the mass number of the squaric acid, the amount of M2 added is 0.7 to 0.8 times the molar number of the squaric acid, the concentration of the M2 pyridine solution is 25 wt%, the reflux reaction time is 5 to 10 hours, after the reaction is finished and cooled to room temperature, the reaction solution is treated with acetone 0.5 to 1.5 times the mass number of the mixed solvent, the precipitated solid is filtered by suction, washed with methanol, filtered by suction, and dried to obtain a blue-green powder M3.
As a preferable example, the mixed solvent is one of methanol, ethanol, ethylene glycol, n-propanol, isopropanol and n-butanol mixed with one of toluene, xylene and chlorobenzene.
The application of M3 prepared by the preparation method of the indocyanine anti-glare dye is characterized in that: it is applied to preparing coating, sunglasses, automobile windows, rearview mirror coating films and the like.
An indocyanine anti-glare dye applied to preparing a coating, wherein the coating comprises the following components (in weight percent):
50-72.3 of solvent; 0.5-1 part of antioxidant; 0.2-1 part of light stabilizer, 25-47.3 parts of resin and 4 parts of M32.
As a preferred example, the solvent is one of ethyl acetate, butanone, cyclohexanone, toluene and xylene, and the antioxidant is one of benzotriazoles, phenols and phosphites; the light stabilizer is hindered amine, benzophenone; the resin is one of single-component or double-component materials of acrylic acid, epoxy modified acrylic acid, polyester modified acrylic acid and polyurethane.
The invention has the beneficial effects that: the indocyanine anti-glare dye prepared by the invention is a visible light absorbent with high stability, the absorbent has strong absorption near the peak value of a photopic vision curve of an eye function, and can effectively reduce light entering a sensitive wave band of human eyes during strong light irradiation, so that the glare effect of strong light on the human eyes is reduced, and meanwhile, the absorption near the peak value of a photopic vision curve of the eye function is weaker, so that the observation effect of the human eyes on the surrounding environment under darker light is not influenced. Compared with other anti-glare technologies, the absorbent can be prepared into a coating for direct coating, and has the advantages of simple process and lower cost.
Drawings
FIG. 1 is a graph illustrating a viewing function according to the present invention;
FIG. 2 is a chart of the UV-VIS absorption spectrum of a film coated with a coating containing Compound M3 in accordance with the present invention.
Detailed Description
In order to make the technical means, the original characteristics, the achieved purposes and the effects of the invention easy to understand, the invention is further explained by combining the specific drawings and the embodiments.
Example one
The preparation method of the indocyanine anti-glare dye comprises the following steps:
s1, synthesis of a quaternary ammonium salt intermediate (M1), and reaction formula:
2.15g (10mmol) of 2,3, 3-trimethyl-5-butyl-3H-indole (M1), 1.568g (13mmol) of chloron-hexane and 25g of ethanol are added into a 100ml three-neck flask, stirred until dissolved, 0.277g (2mmol) of potassium perchlorate is added, reflux reaction is carried out for 6 hours under the protection of nitrogen, the reaction solution is cooled to room temperature after the reaction is finished, 30g of dichloromethane is used for treating the reaction solution, stirring and filtering are carried out, the filtrate is rotated to be viscous, 10g of ethanol is added to precipitate solid, and white-like powder M2(1.517g, the yield is 45.2%) is obtained after suction filtration, water washing, suction filtration and drying.
S2, preparing the indocyanine squaraine according to the following reaction formula:
dissolving squaric acid 1.14g (10mmol) in a mixed solvent of n-butanol and toluene (volume ratio 1:1) 25g, adding a solution of quaternary ammonium salt intermediate (M2)2.349g (7mmol) and pyridine 7.048g, continuously refluxing for reaction for 7h, cooling to room temperature after the reaction is finished, treating the reaction solution with acetone 30g, separating out a solid, performing suction filtration, washing with methanol, performing suction filtration, and drying to obtain indocyanine M3(3.681g, yield 78%) as a blue-green powder.
Example two
Preparation and function test of anti-glare dye coating containing indocyanine squaraine
Coating the above coating with a thickness of 20 μm on a PET base film, drying at 120 ℃ for 1min, covering a layer of PET film on the surface, pressing and compounding, taking the compounded film for testing, wherein the ultraviolet visible absorption spectrum is shown as figure 2, and in addition, the film is placed in front of a strong light flashlight, so that the light is obviously softened by human eyes, and the obvious anti-dazzling effect is shown.
EXAMPLE III
The preparation method of the indocyanine anti-glare dye comprises the following steps:
s1, synthesis of a quaternary ammonium salt intermediate (M1), and reaction formula:
adding 2.15kg (10mol) of 2,3,3, -trimethyl-5-butyl-3H-indole (M1), 1.568kg (13mol) of chloron-hexane and 25kg of ethanol into a 100L reaction kettle, stirring until the materials are dissolved, adding 0.277kg (2mol) of potassium perchlorate, carrying out reflux reaction for 6 hours under the protection of nitrogen, cooling to room temperature after the reaction is finished, treating the reaction solution with 30kg of dichloromethane, stirring, filtering, adding 10kg of ethanol into the filtrate until the filtrate is viscous, precipitating solids, carrying out suction filtration, washing with water, carrying out suction filtration, and drying to obtain white-like powder M2(1.498kg, yield 44.7%).
S2, preparing the indocyanine squaraine according to the following reaction formula:
dissolving squaric acid 1.14kg (10mol) in a mixed solvent of n-butanol and toluene (volume ratio 1:1) 25kg, adding a solution of quaternary ammonium salt intermediate (M2) (2.349 kg (7mmol) and pyridine 7.719kg), continuously refluxing for reaction for 7h, cooling to room temperature after the reaction is finished, treating the reaction solution with acetone 30kg, separating out a solid, performing suction filtration, washing with methanol, performing suction filtration, and drying to obtain indocyanine M3(3.645kg, yield 77.3%) as a blue-green powder.
Example four
The preparation method of the indocyanine anti-glare dye comprises the following steps:
s1, synthesis of a quaternary ammonium salt intermediate (M1), and reaction formula:
2.15g (10mmol) of 2,3, 3-trimethyl-5-butyl-3H-indole (M1), 1.809g (15mmol) of chloron-hexane and 21.5g of ethanol are added into a 100mL reaction kettle and stirred to be dissolved, 0.693g (5mmol) of potassium perchlorate is added, reflux reaction is carried out for 6 hours under the protection of nitrogen, the reaction solution is cooled to room temperature after the reaction is finished, 30g of dichloromethane is used for treating the reaction solution, stirring and filtering are carried out, 10g of ethanol is added until the filtrate is viscous, solid is separated out, suction filtration, water washing, suction filtration and drying are carried out, and white-like powder M2(1.524g, the yield is 45.4%) is obtained.
S2, preparing the indocyanine squaraine according to the following reaction formula:
dissolving squaric acid 1.14g (10mol) in a mixed solvent of n-propanol and toluene (the volume ratio is 1:1) 25g, adding a solution of (quaternary ammonium salt intermediate (M2)2.684g (8mmol) and pyridine 8.052g), continuously refluxing and reacting for 10h, cooling to room temperature after the reaction is finished, treating the reaction solution with acetone 30g, separating out a solid, performing suction filtration, washing with methanol, performing suction filtration, and drying to obtain indocyanine M3(4.126g, yield 76.5%) as a blue-green powder.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.