阅读说明：本技术 一种大分子防蓝光助剂及其制备方法 (Macromolecular anti-blue-light auxiliary agent and preparation method thereof ) 是由 陈广凯 汤峰 欧阳晓勇 于 2021-11-16 设计创作，主要内容包括：本发明属于光学材料领域,具体涉及一种大分子防蓝光助剂及其制备方法；该方法以3,5-二羟基苯甲醛、4-氨基偶氮苯、双酚A钠盐、光气作为原料,经过偶联、缩聚等多步骤反应得到大分子防蓝光助剂材料；其中含有-C＝N-不饱和结构、PC大分子链结构；一方面,-C＝N-不饱和结构、PC的大分子链结构中含有大量的苯环,有利于进一步吸收UV、蓝光等短波光；另一方面,PC的大分子链结构,可与体系形成大分子链缠结,提供与体系的分散性、优异的相容性、不迁移性,延长制品使用寿命且安全性高；有效解决了目前常用蓝光吸收剂小分子特有的易迁移析出、使用寿命短的问题。所得材料可广泛用于光学材料中,尤其适用于PC类光学材料。(The invention belongs to the field of optical materials, and particularly relates to a macromolecular blue light-proof auxiliary agent and a preparation method thereof; the method comprises the steps of taking 3, 5-dihydroxybenzaldehyde, 4-aminoazobenzene, bisphenol A sodium salt and phosgene as raw materials, and carrying out multi-step reactions such as coupling, polycondensation and the like to obtain a macromolecular blue-light-proof auxiliary material; wherein, the structure contains-C ═ N-unsaturated structure and PC macromolecular chain structure; on one hand, the-C ═ N-unsaturated structure and the macromolecular chain structure of PC contain a large number of benzene rings, which is beneficial to further absorbing short-wave light such as UV, blue light and the like; on the other hand, the macromolecular chain structure of the PC can form macromolecular chain entanglement with the system, so that the dispersibility with the system, excellent compatibility and non-migration property are provided, the service life of the product is prolonged, and the safety is high; effectively solves the problems of easy migration and precipitation and short service life of the existing common blue light absorbent micromolecules. The obtained material can be widely used in optical materials, and is particularly suitable for PC optical materials.)

1. The macromolecular anti-blue-light additive is characterized in that: the structural formula is as follows:

wherein, m is 15-52, n is 78-135; -R₁is-H or-N (CH)₃)₂；-R₂is-H or-Cl; -R₃is-H, -CH₃or-Cl.

2. A method for preparing the macromolecular blue light prevention auxiliary agent as claimed in claim 1, which is characterized in that: comprises the following steps:

(1) dissolving 3, 5-dihydroxy benzaldehyde in ethanol A, and magnetically stirring to obtain a mixed solution A; adding the 4-aminoazobenzene derivative into the ethanol B to obtain a mixed solution B;

then, dropwise adding the mixed solution B into the mixed solution A, carrying out heating reflux reaction, and cooling, standing, filtering, vacuum concentrating and drying a product after reaction to obtain an intermediate product I;

(2) adding sodium hydroxide into the aqueous solution to prepare a sodium hydroxide aqueous solution, then adding the intermediate product I prepared in the step (1), and stirring the mixture at room temperature until the intermediate product I is completely dissolved to obtain a transparent solution, namely the aqueous solution of the intermediate product II;

(3) adding sodium hydroxide into the aqueous solution to prepare a sodium hydroxide aqueous solution, then adding bisphenol A, and stirring at room temperature until the bisphenol A is completely dissolved to obtain a transparent solution, namely a bisphenol A sodium salt aqueous solution;

mixing the aqueous solution of the intermediate product II prepared in the step (2) with the aqueous solution of bisphenol A sodium salt, adding phenol and sodium bisulfite, and uniformly mixing to obtain a sodium salt solution for later use;

dissolving phosgene in dichloromethane, and uniformly mixing at a certain temperature; adding triethylamine into a dichloromethane solution containing phosgene to obtain a mixed solution;

and mixing the mixed solution with a sodium salt solution at a certain temperature, stirring for reaction, taking an organic phase, regulating by using a formic acid aqueous solution, taking the organic phase, and finally drying to obtain a target product III.

3. The preparation method of the macromolecular blue light prevention auxiliary agent according to claim 2, characterized in that: the 4-aminoazobenzene derivative in the step (1) is 4-aminoazobenzene, N-dimethyl-4, 4 '-azodiphenylamine, 4-amino-3' -chloroazobenzene, 3-methyl-4-aminoazobenzene or 3-chloro-4-aminoazobenzene.

4. The preparation method of the macromolecular blue light prevention auxiliary agent according to claim 2, characterized in that: the dosage relation of the 3, 5-dihydroxy benzaldehyde and the ethanol A in the step (1) is 1 mol: 1L; the dosage relation of the 4-aminoazobenzene derivative and the ethanol B is 1-1.2 mol: 0.5L.

5. The preparation method of the macromolecular blue light prevention auxiliary agent according to claim 2, characterized in that: the volume ratio of the mixed solution B to the mixed solution A in the step (1) is 1: 2; the heating reflux reaction time is 3-5h, and the temperature is 80-100 ℃;

6. the preparation method of the macromolecular blue light prevention auxiliary agent according to claim 2, characterized in that: in the step (2), the dosage ratio of the sodium hydroxide to the intermediate product I is 3.5 mol: 1 mol; the concentration of the aqueous sodium hydroxide solution was 7 wt%.

7. The preparation method of the macromolecular blue light prevention auxiliary agent according to claim 2, characterized in that: in the step (3), the dosage ratio of the sodium hydroxide to the bisphenol A is 3.5 mol: 1 mol; the concentration of the sodium hydroxide aqueous solution is 7 wt%; the dosage ratio of the aqueous solution of the intermediate product II, the aqueous solution of the sodium salt of bisphenol A, phenol and sodium bisulfite is 0.1-0.4 mol: 0.6-0.9 mol: 0.005-0.01 mol: 0.01 mol.

8. The preparation method of the macromolecular blue light prevention auxiliary agent according to claim 2, characterized in that: in the step (3), the dosage relationship of the phosgene, the dichloromethane and the triethylamine is 1.25 mol: 1.2L: 2.5 mol; the phosgene is dissolved in dichloromethane, and the temperature of the mixture is 0-5 ℃ under certain temperature conditions.

9. The preparation method of the macromolecular blue light prevention auxiliary agent according to claim 2, characterized in that: when the mixed solution in the step (3) is mixed with the sodium salt solution, the dosage relation between the sodium bisulfite in the sodium salt solution and the dichloromethane in the mixed solution is 0.01 mol: 1.2L; the temperature of the mixed solution mixed with the sodium salt solution under a certain temperature condition is 12-20 ℃; the stirring reaction time is 1h, the volume fraction of the formic acid aqueous solution is 5%, and the pH is adjusted to 3-5.

10. Use of a macromolecular blue-light preventing adjuvant according to claim 1 for the preparation of blue-light preventing lenses.

Technical Field

The invention belongs to the field of optical materials, and particularly relates to a macromolecular blue-light-proof auxiliary agent and a preparation method thereof.

Background

With the improvement of living standard, the popularization of electronic products such as computers, smart phones and tablet computers and the penetration of electronic products into the aspect of life, the health problems of people are increasingly prominent, especially the vision health problems. For this reason, blue light is widely used as a background light source of liquid crystal displays in various electronic products and LED display screens. The blue light is not harmful blue light, the really harmful blue light with the energy of 400-440nm (short-wave blue light) has relatively high energy, so that the toxin amount in the macular region in the eyes is increased, and the health of people is seriously threatened, and the 480-500nm blue light has the function of adjusting the biological rhythm, and the sleep, the emotion, the memory and the like are all related to the biological rhythm and are beneficial to the human body.

In addition, Polycarbonate (PC) is a major material for manufacturing lenses because of its good transparency, strong impact strength, excellent thermal stability, and other mechanical and optical properties. The existing process for producing PC mainly comprises a phosgene method and an ester exchange method. Among them, the phosgene method has toxicity hazard, but the produced PC has controllable molecular weight, and is especially suitable for optical materials; and the PC produced by the ester exchange method has wide molecular weight distribution and excellent processing performance.

According to the reported technical route, the preparation of the PC lens with blue light resisting function is obtained by directly adding blue light absorbent into PC to form, such as UV360, solvent red and the like, and is widely applied to various blue light absorbent/UV absorbent. But inevitably has migration problems inherent to small molecule species. At present, a common means is to graft a reaction functional group on a modified small molecular structure, and the functional group reacts with a system in a forming processing process without migration, but in an actual operation process, due to the influence of viscosity, diffusion factors and the like of the reaction system, the functional group can finally participate in the reaction and is grafted to the system. Therefore, the mobility of the small molecule structure of both the additive type and the reactive type is inevitably present. Migration and precipitation not only affect the performance and service life of the final product, but also can be harmful to human health.

In consideration of the problems of the existing small molecular blue light absorbent, the development of a blue light prevention material with excellent compatibility and no migration is very important while ensuring the blue light absorption effect.

Disclosure of Invention

The invention aims to solve the problems that the additive blue light absorbent in the prior art has poor compatibility and is easy to migrate and separate out; the reactive blue light absorbent has the defects of insufficient reaction and influence on the service life of a product, and provides a macromolecular blue light prevention auxiliary agent, wherein 3, 5-dihydroxybenzaldehyde, 4-amino azobenzene derivatives, bisphenol A sodium salt and phosgene are used as raw materials, and a macromolecular blue light prevention auxiliary agent material is obtained through multi-step reactions such as coupling, polycondensation and the like, has excellent functions of blue light absorption, system dispersibility, compatibility and the like, is non-migratory and long in service life, can be widely used in optical materials, and is particularly suitable for PC optical materials.

The technical scheme adopted by the invention for solving the technical problems is as follows:

a macromolecular anti-blue-light additive has a structural formula as follows:

wherein, m is 15-52, n is 78-135; -R₁is-H or-N (CH)₃)₂；-R₂is-H or-Cl; -R₃is-H, -CH₃or-Cl.

A preparation method of a macromolecular anti-blue-light additive comprises the following steps:

(1) dissolving 3, 5-dihydroxy benzaldehyde in ethanol A, and magnetically stirring to obtain a mixed solution A; adding the 4-aminoazobenzene derivative into the ethanol B to obtain a mixed solution B;

then, dropwise adding the mixed solution B into the mixed solution A, carrying out heating reflux reaction, and cooling, standing, filtering, vacuum concentrating and drying a product after reaction to obtain an intermediate product I;

(2) adding sodium hydroxide into the aqueous solution to prepare a sodium hydroxide aqueous solution, then adding the intermediate product I prepared in the step (1), and stirring the mixture at room temperature until the intermediate product I is completely dissolved to obtain a transparent solution, namely the aqueous solution of the intermediate product II;

(3) adding sodium hydroxide into the aqueous solution to prepare a sodium hydroxide aqueous solution, then adding bisphenol A, and stirring at room temperature until the bisphenol A is completely dissolved to obtain a transparent solution, namely a bisphenol A sodium salt aqueous solution;

mixing the aqueous solution of the intermediate product II prepared in the step (2) with the aqueous solution of bisphenol A sodium salt, adding phenol and sodium bisulfite, and uniformly mixing to obtain a sodium salt solution for later use;

dissolving phosgene in dichloromethane, and uniformly mixing at a certain temperature; adding triethylamine into a dichloromethane solution containing phosgene to obtain a mixed solution;

and mixing the mixed solution with a sodium salt solution at a certain temperature, stirring for reaction, taking an organic phase, regulating by using a formic acid aqueous solution, taking the organic phase, and drying to obtain a target product III, namely the macromolecular blue-light-proof auxiliary agent.

Preferably, the 4-aminoazobenzene derivative in the step (1) is 4-aminoazobenzene, N-dimethyl-4, 4 '-azodiphenylamine, 4-amino-3' -chloroazobenzene, 3-methyl-4-aminoazobenzene or 3-chloro-4-aminoazobenzene.

Preferably, the 3, 5-dihydroxybenzaldehyde and ethanol a in step (1) are used in an amount of 1 mol: 1L; the dosage relation of the 4-aminoazobenzene derivative and the ethanol B is 1-1.2 mol: 0.5L.

Preferably, the volume ratio of the mixed solution B to the mixed solution A in the step (1) is 1: 2; the heating reflux reaction time is 3-5h, and the temperature is 80-100 ℃;

preferably, the amount ratio of the sodium hydroxide to the intermediate product I in the step (2) is 3.5 mol: 1 mol; the concentration of the aqueous sodium hydroxide solution was 7 wt%.

Preferably, the amount ratio of the sodium hydroxide to the bisphenol A in the step (3) is 3.5 mol: 1 mol; the concentration of the sodium hydroxide aqueous solution is 7 wt%; the dosage ratio of the aqueous solution of the intermediate product II, the aqueous solution of the sodium salt of bisphenol A, phenol and sodium bisulfite is 0.1-0.4 mol: 0.6-0.9 mol: 0.005-0.01 mol: 0.01 mol.

Preferably, the phosgene, the dichloromethane and the triethylamine in the step (3) are used in the relation of 1.25 mol: 1.2L: 2.5 mol; the phosgene is dissolved in dichloromethane, and the temperature of the mixture is 0-5 ℃ under certain temperature conditions.

Preferably, when the mixed solution in the step (3) is mixed with the sodium salt solution, the amount of the sodium bisulfite in the sodium salt solution and the dichloromethane in the mixed solution is 0.01 mol: 1.2L; the temperature of the mixed solution mixed with the sodium salt solution under a certain temperature condition is 12-20 ℃; the stirring reaction time is 1h, the volume fraction of the formic acid aqueous solution is 5%, and the pH is adjusted to 3-5.

In the above method, the drying conditions in step (1) or (2) are both: the temperature is 60-80 ℃, and the time is 1-3 h.

The invention provides a macromolecular anti-blue-light auxiliary agent, which is prepared by the following steps:

the invention has the beneficial effects that:

(1) the invention provides a macromolecular anti-blue-light auxiliary agent, and a target product contains azobenzene and a PC macromolecular chain structure. Firstly, the azobenzene structure has an excellent short-wave blue light absorption effect; secondly, the macromolecular chain structure is beneficial to energy transfer, and the blue light absorption efficiency is further improved.

(2) The invention provides a macromolecular anti-blue-light auxiliary agent, wherein a target product contains a-C ═ N-unsaturated structure and a PC macromolecular chain structure. On one hand, the-C ═ N-unsaturated structure and the macromolecular chain structure of PC contain a large number of benzene rings, which is beneficial to further absorbing short-wave light such as UV, blue light and the like; on the other hand, the macromolecular chain structure of PC can form macromolecular chain entanglement with the system, thereby providing dispersibility with the system, excellent compatibility, non-migration, prolonged product service life and high safety.

(3) The invention provides a preparation method of a macromolecular anti-blue-light auxiliary agent, wherein a phosgene method is adopted to prepare PC macromolecules, the molecular weight of a target product is controllable, the distribution is narrow, the mechanical property and the optical property are excellent, the macromolecular anti-blue-light auxiliary agent can be used as an auxiliary agent and can also be used as anti-blue-light main body resin, and the macromolecular anti-blue-light auxiliary agent is particularly suitable for optical materials.

(4) The invention provides a macromolecular anti-blue-light auxiliary agent which has excellent blue-light absorption effect, system compatibility and dispersibility; has the advantages of no toxicity, environmental protection, no migration, and improved mechanical property and optical property.

The specific implementation mode is as follows:

the present invention will be described in detail with reference to examples. It is to be understood, however, that the following examples are illustrative of embodiments of the present invention and are not to be construed as limiting the scope of the invention.

Example 1:

a preparation method of a macromolecular anti-blue-light additive comprises the following steps:

(1) dissolving 1mol of 3, 5-dihydroxy benzaldehyde in 1L of ethanol, and magnetically stirring to obtain a mixed solution A;

1.1mol of 4-aminoazobenzene (-R)₁：-H、-R₂：-H、-R₃: -H) to 0.5L of ethanol to obtain a mixed solution B;

then, dropwise adding the mixed solution B into the mixed solution A in a volume ratio of 1: 2; heating and refluxing for 4h at the heating temperature of 90 ℃, cooling, standing, filtering, concentrating in vacuum, and drying to obtain an intermediate product I;

(2) adding 3.5mol of sodium hydroxide into the aqueous solution to prepare a 7 wt% aqueous solution of sodium hydroxide, then adding 1mol of intermediate product I, and stirring at room temperature until the intermediate product I is completely dissolved to obtain a transparent solution, namely an aqueous solution of intermediate product II;

(3) adding 3.5mol of sodium hydroxide into the aqueous solution to prepare a 7 wt% aqueous solution of sodium hydroxide, then adding 1mol of bisphenol A, and stirring at room temperature until the bisphenol A is completely dissolved to obtain a transparent solution, namely a bisphenol A sodium salt aqueous solution;

uniformly mixing the aqueous solution containing the intermediate product II and the aqueous solution of bisphenol A sodium salt, adding phenol and sodium bisulfite, and dissolving to obtain a sodium salt solution for later use; wherein, the intermediate product II, bisphenol A and phenol: the using ratio of the sodium bisulfite is 0.3 mol: 0.7 mol: 0.005 mol: 0.01 mol;

dissolving phosgene in dichloromethane, and uniformly mixing at 0 ℃; adding triethylamine into a dichloromethane solution containing phosgene to obtain a mixed solution; the dosage relation of the phosgene, the dichloromethane and the triethylamine is 1.25 mol: 1.2L: 2.5 mol;

mixing the mixed solution with a sodium salt solution at 12 ℃, wherein the amount of sodium bisulfite in the sodium salt solution and dichloromethane in the mixed solution is 0.01 mol: 1.2L; after stirring the reaction for 1 hour, the organic phase was taken out, the pH was adjusted to 5 with 5 wt% aqueous formic acid, and the organic phase was taken out and dried to obtain the target product III (m ═ 42, n ═ 98).

The infrared data are as follows: 3052cm^-1: a benzene ring is present; 2977cm^-1：-CH₃(ii) present; 1749cm^-1: -C ═ O is present; 1261cm^-1: -O-C-O-is present; 1654cm^-1: -C-is present; 1597cm^-1: -N-is present.

The nuclear magnetic hydrogen spectrum data is as follows:¹H NMR(400MHz，CDCl₃δ ppm): 7.2-8.5(20H, benzene ring); 1.23(6H, -CH)₃)。

Example 2:

a preparation method of a macromolecular anti-blue-light additive comprises the following steps:

(1) dissolving 1mol of 3, 5-dihydroxy benzaldehyde in 1L of ethanol, and magnetically stirring to obtain a mixed solution A;

1.1mol of N, N-dimethyl-4, 4' -azodiphenylamine (-R)₁：-N(CH₃)₂、-R₂：-H、-R₃: -H) to 0.5L of ethanol to obtain a mixed solution B;

then, dropwise adding the mixed solution B into the mixed solution A, wherein the volume ratio of the mixed solution B to the mixed solution A is 1: 2; then heating and refluxing for 5h at the heating temperature of 80 ℃, cooling, standing, filtering, concentrating in vacuum, and drying to obtain an intermediate product I;

(2) adding 3.5mol of sodium hydroxide into the aqueous solution to prepare a 7 wt% aqueous solution of sodium hydroxide, then adding 1mol of intermediate product I, and stirring at room temperature until the intermediate product I is completely dissolved to obtain a transparent solution, namely an aqueous solution of intermediate product II;

(3) adding 3.5mol of sodium hydroxide into the aqueous solution to prepare a 7 wt% aqueous solution of sodium hydroxide, then adding 1mol of bisphenol A, and stirring at room temperature until the bisphenol A is completely dissolved to obtain a transparent solution, namely a bisphenol A sodium salt aqueous solution;

uniformly mixing the aqueous solution containing the intermediate product II and the aqueous solution of bisphenol A sodium salt, adding phenol and sodium bisulfite, and dissolving to obtain a sodium salt solution for later use; in the sodium salt solution, intermediate II, bisphenol a, phenol: the using ratio of the sodium bisulfite is 0.2 mol: 0.8 mol: 0.01 mol: 0.01 mol;

dissolving phosgene in dichloromethane, and uniformly mixing at 3 ℃; adding triethylamine into a dichloromethane solution containing phosgene to obtain a mixed solution; the dosage relation of the phosgene, the dichloromethane and the triethylamine is 1.25 mol: 1.2L: 2.5 mol;

mixing the mixed solution with a sodium salt solution at 20 ℃, wherein the amount of sodium bisulfite in the sodium salt solution and dichloromethane in the mixed solution are in a relationship of 0.01 mol: 1.2L; after stirring the reaction for 1 hour, the organic phase was taken out, the pH was adjusted to 3 with 5 wt% aqueous formic acid, and the organic phase was taken out and dried to obtain the target product III (m ═ 28, n ═ 112).

The infrared data are as follows: 3052cm^-1: a benzene ring is present; 2977cm^-1：-CH₃(ii) present; 1749cm^-1: -C ═ O is present; 1261cm^-1: -O-C-O-is present; 1654cm^-1: -C-is present; 1597cm^-1: -N-is present.

The nuclear magnetic hydrogen spectrum data is as follows:¹H NMR(400MHz，CDCl₃δ ppm): 7.2-8.5(19H, benzene ring); 1.23(6H, -CH)₃)；2.92(6H，-CH₃)。

Example 3:

a preparation method of a macromolecular anti-blue-light additive comprises the following steps:

(1) dissolving 1mol of 3, 5-dihydroxy benzaldehyde in 1L of ethanol, and magnetically stirring to obtain a mixed solution A;

1.2mol of 3-chloro-4-aminoazobenzene (-R)₁：-H、-R₂：-H、-R₃: -Cl) to 0.5L of ethanol to obtain a mixed solution B;

then, dropwise adding the mixed solution B into the mixed solution A, wherein the volume ratio of the mixed solution B to the mixed solution A is 1: 2; then heating and refluxing for 3h at the heating temperature of 100 ℃, cooling, standing, filtering, concentrating in vacuum, and drying to obtain an intermediate product I;

(2) adding 3.5mol of sodium hydroxide into water to prepare a 7 wt% sodium hydroxide aqueous solution, then adding 1mol of intermediate product I, and stirring at room temperature until the intermediate product I is completely dissolved to obtain a transparent solution, namely an aqueous solution of intermediate product II;

(3) adding 3.5mol of sodium hydroxide into the aqueous solution to prepare a 7 wt% aqueous solution of sodium hydroxide, then adding 1mol of bisphenol A, and stirring at room temperature until the bisphenol A is completely dissolved to obtain a transparent solution, namely a bisphenol A sodium salt aqueous solution;

uniformly mixing the aqueous solution containing the intermediate product II and the aqueous solution of bisphenol A sodium salt, adding phenol and sodium bisulfite, and dissolving to obtain a sodium salt transparent solution for later use; in the solution, intermediate II, bisphenol a, phenol: the using ratio of the sodium bisulfite is 0.4 mol: 0.6 mol: 0.07 mol: 0.01 mol;

dissolving phosgene in dichloromethane, and uniformly mixing at 5 ℃; adding triethylamine into a dichloromethane solution containing phosgene to obtain a mixed solution; the dosage relation of the phosgene, the dichloromethane and the triethylamine is 1.25 mol: 1.2L: 2.5 mol;

mixing the mixed solution with a sodium salt solution at 16 ℃, wherein the amount of sodium bisulfite in the sodium salt solution and dichloromethane in the mixed solution is 0.01 mol: 1.2L; after stirring the reaction for 1 hour, the organic phase was taken out, the pH was adjusted to 4 with 5 wt% aqueous formic acid, and the organic phase was taken out and dried to obtain the target product III (m 52, n 78).

The infrared data are as follows: 3052cm^-1: a benzene ring is present; 2977cm^-1：-CH₃(ii) present; 1749cm^-1: -C ═ O is present; 1261cm^-1: -O-C-O-is present; 1654cm^-1: -C-is present; 1597cm^-1: -N-is present; 713cm^-1: -C-Cl.

The nuclear magnetic hydrogen spectrum data is as follows:¹H NMR(400MHz，CDCl₃δ ppm): 7.2-8.5(19H, benzene ring); 1.23(6H, -CH)₃)。

Example 4:

a preparation method of a macromolecular anti-blue-light additive comprises the following steps:

(1) dissolving 1mol of 3, 5-dihydroxy benzaldehyde in 1L of ethanol, and magnetically stirring to obtain a mixed solution A;

1.1mol of 3-methyl-4-aminoazobenzene (-R)₁：-H、-R₂：-H、-R₃：-CH₃) Adding into 0.5L ethanol to obtain mixed solution B;

then, dropwise adding the mixed solution B into the mixed solution A, wherein the volume ratio of the mixed solution B to the mixed solution A is 1: 2; then heating and refluxing for 3h at the heating temperature of 100 ℃, cooling, standing, filtering, concentrating in vacuum, and drying to obtain an intermediate product I;

(2) adding 3.5mol of sodium hydroxide into the aqueous solution to prepare a 7 wt% aqueous solution of sodium hydroxide, then adding 1mol of intermediate product I, and stirring at room temperature until the intermediate product I is completely dissolved to obtain a transparent solution, namely an aqueous solution of intermediate product II;

(3) adding 3.5mol of sodium hydroxide into the aqueous solution to prepare a 7 wt% aqueous solution of sodium hydroxide, then adding 1mol of bisphenol A, and stirring at room temperature until the bisphenol A is completely dissolved to obtain a transparent solution, namely a bisphenol A sodium salt aqueous solution;

uniformly mixing the aqueous solution containing the intermediate product II and the aqueous solution of bisphenol A sodium salt, adding phenol and sodium bisulfite, and dissolving to obtain a sodium salt solution for later use; wherein, the intermediate product II, bisphenol A and phenol: the using ratio of the sodium bisulfite is 0.1 mol: 0.9 mol: 0.06 mol: 0.01 mol;

dissolving phosgene in dichloromethane, and uniformly mixing at 3 ℃; adding triethylamine into a dichloromethane solution containing phosgene to obtain a mixed solution; the dosage relation of the phosgene, the dichloromethane and the triethylamine is 1.25 mol: 1.2L: 2.5 mol;

mixing the mixed solution with a sodium salt solution at 18 ℃, wherein the amount of sodium bisulfite in the sodium salt solution and dichloromethane in the mixed solution are in a relationship of 0.01 mol: 1.2L; after stirring the reaction for 1 hour, the organic phase was taken out, the pH was adjusted to 3 with 5 wt% aqueous formic acid, and the organic phase was taken out and dried to obtain the target product III (m ═ 15, n ═ 135).

The infrared data are as follows: 3052cm^-1: a benzene ring is present; 2977cm^-1：-CH₃(ii) present; 1749cm^-1: -C ═ O is present; 1261cm^-1: -O-C-O-is present; 1654cm^-1: -C-is present; 1597cm^-1: -N-is present.

The nuclear magnetic hydrogen spectrum data is as follows:¹H NMR(400MHz，CDCl₃δ ppm): 7.2-8.5(19H, benzene ring); 1.23(6H, -CH)₃)；2.35(3H，-CH₃)。

Example 5:

a preparation method of a macromolecular anti-blue-light additive comprises the following steps:

(1) dissolving 1mol of 3, 5-dihydroxy benzaldehyde in 1L of ethanol, and magnetically stirring to obtain a mixed solution A;

1mol of 4-amino-3' -chloroazobenzene (-R)₁：-H、-R₂：-Cl、-R₃: -H) into 0.5L ethanol to obtain a mixed solution B;

then, dropwise adding the mixed solution B into the mixed solution A, wherein the volume ratio of the mixed solution B to the mixed solution A is 1: 2; heating and refluxing for 4h at the heating temperature of 90 ℃, cooling, standing, filtering, concentrating in vacuum, and drying to obtain an intermediate product I;

(2) adding 3.5mol of sodium hydroxide into the aqueous solution to prepare a 7 wt% aqueous solution of sodium hydroxide, then adding 1mol of intermediate product I, and stirring at room temperature until the intermediate product I is completely dissolved to obtain a transparent solution, namely an aqueous solution of intermediate product II;

(3) adding 3.5mol of sodium hydroxide into the aqueous solution to prepare a 7 wt% aqueous solution of sodium hydroxide, then adding 1mol of bisphenol A, and stirring at room temperature until the bisphenol A is completely dissolved to obtain a transparent solution, namely a bisphenol A sodium salt aqueous solution;

uniformly mixing the aqueous solution containing the intermediate product II and the aqueous solution of bisphenol A sodium salt, adding phenol and sodium bisulfite, and dissolving to obtain a sodium salt transparent solution for later use; in the solution, intermediate II, bisphenol a, phenol: the using ratio of the sodium bisulfite is 0.3 mol: 0.7 mol: 0.05 mol: 0.01 mol;

dissolving phosgene in dichloromethane, and uniformly mixing at 5 ℃; adding triethylamine into a dichloromethane solution containing phosgene to obtain a mixed solution; the dosage relation of the phosgene, the dichloromethane and the triethylamine is 1.25 mol: 1.2L: 2.5 mol;

mixing the mixed solution with a sodium salt solution at 16 ℃, wherein the amount of sodium bisulfite in the sodium salt solution and dichloromethane in the mixed solution is 0.01 mol: 1.2L; after stirring the reaction for 1 hour, the organic phase was taken out, the pH was adjusted to 5 with 5 wt% aqueous formic acid, and the organic phase was taken out and dried to obtain the target product III (m ═ 42, n ═ 98).

The infrared data are as follows: 3052cm^-1: a benzene ring is present; 2977cm^-1：-CH₃(ii) present; 1749cm^-1: -C ═ O is present; 1261cm^-1: -O-C-O-is present; 1654cm^-1: -C-is present; 1597cm^-1: -N-is present; 716cm^-1: -C-Cl.

The nuclear magnetic hydrogen spectrum data is as follows:¹H NMR(400MHz，CDCl₃δ ppm): 7.2-8.5(19H, benzene ring); 1.23(6H, -CH)₃)。

Example 6:

a preparation method of a macromolecular anti-blue-light additive comprises the following steps:

(1) dissolving 1mol of 3, 5-dihydroxy benzaldehyde in 1L of ethanol, and magnetically stirring to obtain a mixed solution A;

1.1mol of 4-aminoazobenzene (-R)₁：-H、-R₂：-H、-R₃: -H) into 0.5L ethanol to obtain a mixed solution B;

then, dropwise adding the mixed solution B into the mixed solution A, wherein the volume ratio of the mixed solution B to the mixed solution A is 1: 2; then heating and refluxing for 3h at the heating temperature of 90 ℃, cooling, standing, filtering, concentrating in vacuum, and drying to obtain an intermediate product I;

(2) adding 3.5mol of sodium hydroxide into the aqueous solution to prepare a 7 wt% aqueous solution of sodium hydroxide, then adding 1mol of intermediate product I, and stirring at room temperature until the intermediate product I is completely dissolved to obtain a transparent solution, namely an aqueous solution of intermediate product II;

(3) adding 3.5mol of sodium hydroxide into the aqueous solution to prepare a 7 wt% aqueous solution of sodium hydroxide, then adding 1mol of bisphenol A, and stirring at room temperature until the bisphenol A is completely dissolved to obtain a transparent solution, namely a bisphenol A sodium salt aqueous solution;

uniformly mixing the aqueous solution containing the intermediate product II and the aqueous solution of bisphenol A sodium salt, adding phenol and sodium bisulfite, and dissolving to obtain a sodium salt transparent solution for later use; in the solution, intermediate II, bisphenol a, phenol: the using ratio of the sodium bisulfite is 0.35 mol: 0.65 mol: 0.05 mol: 0.01 mol;

dissolving phosgene in dichloromethane, and uniformly mixing at 0 ℃; adding triethylamine into a dichloromethane solution containing phosgene to obtain a mixed solution; the dosage relation of the phosgene, the dichloromethane and the triethylamine is 1.25 mol: 1.2L: 2.5 mol;

mixing the mixed solution with a sodium salt solution at 12 ℃, wherein the amount of sodium bisulfite in the sodium salt solution and dichloromethane in the mixed solution is 0.01 mol: 1.2L; after stirring the reaction for 1 hour, the organic phase was taken out, the pH was adjusted to 5 with 5 wt% aqueous formic acid, and the organic phase was taken out and dried to obtain the target product III (m ═ 42, n ═ 98).

The infrared data are as follows: 3052cm^-1: a benzene ring is present; 2977cm^-1：-CH₃(ii) present; 1749cm^-1: -C ═ O is present; 1261cm^-1: -O-C-O-is present; 1654cm^-1: -C-is present; 1597cm^-1: -N-is present.

The nuclear magnetic hydrogen spectrum data is as follows:¹H NMR(400MHz，CDCl₃δ ppm): 7.2-8.5(20H, benzene ring); 1.23(6H, -CH)₃)。

The macromolecular blue light prevention auxiliary agent prepared by the invention is used for preparing a blue light prevention lens of blue light prevention resin;

the macromolecular blue-light-proof auxiliary agent obtained in the specific example 1 is used as a base material of an application example to prepare a blue-light-proof lens:

application example 1

The preparation steps of the blue light prevention lens are as follows:

(1) material preparation:

putting 1000 parts by weight of lens grade PC L-1225Z granules into a drying box, and drying at 120 ℃ for 5 hours; weighing 3 parts by weight of the target product III in the example 1, and premixing the target product III with PC granules for 30 min; then 0.86 weight part of liquid paraffin is added, mixed for 2 hours and injected for standby.

(2) And (3) injection molding:

and setting technological parameters for injection molding, setting the temperatures of the front section, the middle section and the rear section as 290 ℃, 295 and 290 ℃, setting the temperature of a mold as 80 ℃, setting the injection pressure as 110MPa, setting the injection time as 15s, cooling for 25s, and performing injection molding on the granules to obtain the blue-light-proof PC lens.

The procedure of practical examples 2 to 6 was the same as that of practical example 1 except that: the target products III obtained in examples 2 to 6 were used, respectively.

The percentage of the molecular weight of the azobenzene structure which plays a role of blue light prevention in the target product III to the molecular weight of the whole macromolecular blue light prevention auxiliary agent is as follows: example 1: 34-36%; example 2: 24 to 26 percent; example 3: 44-46%; example 4: 12-15%; example 5: 34-36%; example 6: 39-41%.

Application example comparative example 1:

the preparation steps of the blue light prevention lens are as follows:

(1) material preparation:

putting 1000 parts by weight of lens grade PC L-1225Z granules into a drying box, and drying at 120 ℃ for 5 hours; weighing 3 parts by weight of PC2400 synthesized by an ester exchange method, and premixing the PC2400 with PC granules for 30 min; then 0.86 weight part of liquid paraffin is added, mixed for 2 hours and injected for standby.

(2) And (3) injection molding:

and setting technological parameters for injection molding, setting the temperatures of the front section, the middle section and the rear section as 290 ℃, 295 and 290 ℃, setting the temperature of a mold as 80 ℃, setting the injection pressure as 110MPa, setting the injection time as 15s, cooling for 25s, and performing injection molding on the granules to obtain the blue-light-proof PC lens.

Application example comparative example 2:

(1) putting 1000 parts by weight of lens grade PC L-1225Z granules into a drying box, and drying at 120 ℃ for 5 hours; 3 parts by weight of ester phosgene method is weighed to synthesize PC2400, and the PC2400 is premixed with PC granules for 30 min; then 0.86 weight part of liquid paraffin is added, mixed for 2 hours and injected for standby.

Application example comparative example 3:

putting 1000 parts by weight of lens grade PC L-1225Z granules into a drying box, and drying at 120 ℃ for 5 hours; weighing 2 parts by weight of ester phosgene method to synthesize PC2400 and 1 part by weight of solvent yellow 2, and premixing the mixture with PC granules for 30 min; then 0.86 weight part of liquid paraffin is added, mixed for 2 hours and injected for standby.

Application example comparative example 4:

putting 1000 parts by weight of lens grade PC L-1225Z granules into a drying box, and drying at 120 ℃ for 5 hours; weighing 3 parts by weight of solvent yellow 2, and premixing with PC granules for 30 min; then 0.86 weight part of liquid paraffin is added, mixed for 2 hours and injected for standby.

Comparative examples 2-4 the process parameters of the injection moulding stage were used as in comparative example 1.

The physical property results of the blue light-proof lenses prepared in application examples 1 to 6 and application examples 1 to 4 of the present invention were measured, respectively, wherein the test methods were as follows:

(1) absorption effect: the PC lens was subjected to UV-visible absorption testing with a scan range of 380-455nm and a scan interval of 1 nm. The expression method of ultraviolet-visible light absorption: the absorption effect is expressed as a numerical value of the average transmittance, and the absorption effect is more excellent as the transmittance is lower.

(2) Migration performance: soaking the PC lens in acetonitrile for 24h, taking the soaking solution, measuring the ultraviolet-visible spectrum, and setting the wavelength to be within the range of 200-500 nm. The expression method of the mobility is as follows: 5 is the lowest molar absorption coefficient, namely the optimal mobility; 1 is the highest molar absorption coefficient, i.e. the worst migration.

(3) Transmittance: the test was carried out according to the method described in JIS K7105-1981.

(4) Haze: the test was carried out according to the method described in JIS K7105-1981.

Specific test results are shown in table 1.

Table 1 physical test properties of the examples

As can be seen from Table 1, compared with the common micromolecule blue light prevention auxiliary agent, the macromolecule blue light prevention auxiliary agent has excellent blue light absorption effect within the range of 380-455 nm; and has excellent non-migration performance. By comparing the transmittance and the haze, the product of the invention has better optical performance.

In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.