WO2018032967A1 - 9-phenylacridine macromolecule photosensitizer, and preparing method and use thereof - Google Patents

Abstract

Disclosed are a 9-phenylacridine macromolecule photosensitizer, and a preparing method and use thereof. The 9-phenylacridine macromolecule photosensitizer comprises at least one of the compounds having a structure as shown in formula (I), in which R₁ is a linear or branched C₁-C₆₀ alkyl group with a valency of m + n, wherein a -CH₂- thereof may be optionally substituted by oxygen, sulphur or 1,4-phenylene; each A independently represents -[(CHR₄)_x-O]_y-, wherein each R₄ independently represents hydrogen, a methyl group, or an ethyl group, x is an integer of 1-10, and y is an integer of 1-20; R₂ represents a linear or branched C₁-C₂₀ alkylene group, wherein a -CH₂- thereof may be optionally substituted by oxygen, sulphur or a phenylene; R₃ represents hydrogen or a substituent group; m represents an integer of 0-20, and n represents an integer of 1-20. When used in a photocuring system, the photosensitizer has good compatibility and good photosensitivity improving effect, and a film prepared therefrom has excellent resolution, adhesion, and high solubility in water.

Description

9-phenyl acridine macromolecular photosensitizer and preparation method and application thereof Technical field

The invention belongs to the field of organic chemistry, and particularly relates to a 9-phenyl acridine macromolecular photosensitizer and a preparation method thereof, and the application of the photosensitizer in the field of photocuring.

Background technique

The acridine compound is a macrocyclic conjugated system with a rigid planar structure and excellent fluorescence performance. It is a good fluorescent reagent and can be used as a photoinitiator in a photopolymerization system. It can also be used as a sensitizer to initiate photoinitiation. The agent is photopolymerized. 9-phenyl acridine is a derivative of acridine which belongs to the biphenyl type structure and can emit a photocurable material mainly composed of an unsaturated resin and a monomer material thereof under ultraviolet light, X-ray or light (photocurable coating, Cross-linking curing of inks and photoresists, etc., and stable properties, and good photosensitivity in photocurable materials composed of unsaturated resins and their monomer materials, and thus are widely used in the field of photocuring.

The use of acridine compounds as photosensitizers is known, as disclosed in Chinese Patent Application Nos. CN101525392A, CN102675203A, etc., which disclose the use of different acridine compounds in photosensitive resins. However, the conventional acridine compounds have disadvantages such as unsatisfactory solubility and poor sensitivity improvement effect when used as a photosensitizer. 9-phenyl acridine is one of the most widely used products in the existing acridine photosensitizers. As a small molecule photosensitizer, it often appears to be difficult to separate from the reactants during use, difficult to recover or not compatible with the system. Good, easy to agglomerate and precipitate problems, resulting in reduced reaction efficiency and affect material properties. In particular, 9-phenyl acridine has extremely low water solubility, which seriously affects its use as a photosensitizer in the field of photocuring, especially dry film photoresist. In the dry film development stage, the unexposed portion is usually washed away with an alkaline aqueous solution, and 9-phenyl acridine is precipitated and adsorbed on the surface of the circuit board due to its extremely low water solubility, thus not only affecting the use of the dry film, It also reduces the precision of the product, so it is necessary to increase the surface cleaning process of the board, which leads to cumbersome process and greatly increased cost.

Summary of the invention

In view of the deficiencies in the prior art, the present invention is directed to a 9-phenyl acridine macromolecular photosensitizer. Compared with the conventional photosensitizer, the photosensitizer of the invention has good compatibility when applied to a photocuring system, has good effect on sensitivity improvement, and has excellent resolution and adhesion, and high water solubility (easy to be used). Washed off).

Specifically, the 9-phenyl acridine macromolecular photosensitizer of the present invention comprises at least one of the compounds having a structure represented by the formula (I):

among them,

R ₁ represents a C ₁ -C ₆₀ linear or branched m+n valent alkyl group, wherein -CH ₂ - may be optionally substituted with oxygen, sulfur or 1,4-phenylene;

A each independently represents -[(CHR ₄ ) _x -O] _y -, wherein R ₄ each independently represents hydrogen, methyl or ethyl, x is an integer from 1 to 10, and y is an integer from 1 to 20;

R ₂ represents a C ₁ -C ₂₀ linear or branched alkylene group, wherein -CH ₂ - may be optionally substituted by oxygen, sulfur or phenylene;

R ₃ represents hydrogen or a substituent;

m represents an integer of 0-20, and n represents an integer of 1-20.

Preferably, R ₁ represents a C ₁ -C ₂₀ linear or branched m+n valent alkyl group, wherein -CH ₂ - may be optionally substituted by oxygen or 1,4-phenylene, with the conditions It is not directly connected between the two oxygen.

Further preferably, in the structure represented by the above formula (I), R _{1 is} selected from the group consisting of the following groups:

Preferably, A represents -[(CHR ₄ ) _x -O] _y - wherein R ₄ each independently represents hydrogen, methyl or ethyl, x is an integer from 1 to 10, and y is an integer from 1 to 20. -[(CHR ₄ ) _x -O] The terminal oxygen atom of the _y - group is bonded to R ₁ .

Further preferably, A is selected from the group consisting of:

-[CH ₂ O] _y -, -[CH ₂ CH ₂ O] _y -, -[CH ₂ CH ₂ CH ₂ O] _y -, -[CH ₂ CH ₂ CH ₂ CH ₂ O] _y -, -[ CH(CH ₃ )-CH ₂ O] _y -, -[CH ₂ -CH(CH ₃ )-CH ₂ O] _y -, wherein y represents an integer from 1-20.

Preferably, R ₂ represents a C ₁ -C ₈ linear or branched alkylene group, wherein -CH ₂ - may be optionally substituted by oxygen or 1,4-phenylene, provided that two oxygens Not directly connected.

Further preferably, R _{2 is} selected from the group consisting of:

*CH ₂ *, *CH ₂ -CH ₂ *, *CH ₂ -CH ₂ -CH ₂ *, *CH(CH ₃ )-CH ₂ *, *CH ₂ CH ₂ CH ₂ CH ₂ *, *CH ₂ - O-CH ₂ *, *CH ₂ -CH ₂ -O-CH ₂ *, *CH ₂ -CH ₂ -O-CH ₂ -CH ₂ *.

Preferably, R _{3 is} selected from H, CH ₃ , NO ₂ , or a halogen (such as F, Cl, Br).

Preferably, m represents an integer from 0 to 7, and n represents an integer from 1 to 8, and the sum of m and n is an integer from 2 to 8.

Accordingly, the present invention also relates to a method for preparing the above-mentioned 9-phenyl acridine macromolecular photosensitizer, comprising the following steps:

(1) The raw material a and the raw material b are reacted under the action of a catalyst to obtain an intermediate a;

(2) intermediate a and starting material c are reacted in a solvent containing an acid binding agent to obtain intermediate b;

(3) intermediate b and starting material d undergo transesterification under the action of a catalyst to obtain a product;

The reaction equation is as follows:

Wherein R ₅ represents a C ₁ -C ₈ linear or branched alkyl group.

The photosensitizer of the present invention is an improvement and optimization of the structure of existing compounds. As shown in the above reaction equation, the synthesis involved in the preparation method involves acridine structure construction, esterification, transesterification, etc., all of which are conventional processes in the field of organic chemistry. In the case where the synthesis process and its principles are clarified, specific process parameters are readily ascertainable to those skilled in the art. For example, reference is made to the content described in the Chinese patent CN101525392A, which is incorporated herein in its entirety by reference.

Preferably, in the step (1), the catalyst is a composite catalyst of zinc chloride and 85% phosphoric acid. The reaction temperature varies slightly depending on the type of the raw material, and is usually 150-220 ° C, and the reaction time is 4-8 h.

Preferably, in the step (2), R ₅ in the structure of the starting material c represents a C ₁ -C ₄ linear or branched alkyl group, particularly CH ₃ , CH ₂ CH ₃ , CH ₂ CH ₂ CH ₃ . The type of the solvent to be used is not particularly limited as long as it can dissolve the reaction raw material and has no adverse effect on the reaction, and examples thereof include acetone, acetonitrile, methanol, ethanol, and N,N-dimethylformamide. The acid binding agent may be sodium carbonate, sodium hydroxide, potassium carbonate, sodium methoxide, pyridine, triethylamine or the like. The reaction temperature is 40-100 ° C, and the reaction time is usually 4-18 h.

Preferably, in the step (3), the transesterification reaction is carried out in a solvent. However, the type of the solvent is not particularly limited as long as it can dissolve the reaction raw material and has no adverse effect on the reaction, for example, toluene, xylene, benzene, cyclohexane or the like. The catalyst may be one of sodium hydroxide, lithium hydroxide, potassium hydroxide, sodium methoxide, methanesulfonic acid, p-toluenesulfonic acid, sulfuric acid, hypophosphorous acid or a combination of two or more thereof. The amount of the catalyst used is preferably from 5 ‰ to 15 总 based on the total mass of the reaction raw materials. The reaction temperature is usually from 70 to 130 °C. The reaction time is usually from 1 to 8 hours.

The person skilled in the art can see from the transesterification reaction of the step (3) that m+n of hydroxyl groups which can be transesterified with the intermediate b are present in the starting material d. This results in an inconsistency in the amount of intermediate b reacted with a single R ₁ (AOH) _m+n molecule when m+n is greater than 1 and the intermediate b is insufficient relative to the hydroxyl group, resulting in a single product that is not single. A structural compound, but a mixture of structural compounds of formula (I). This mixture falls within the scope defined by the above 9-phenyl acridine macromolecular photosensitizer.

The 9-phenyl acridine macromolecular photosensitizer of the invention has excellent water-solubility and is particularly suitable for use as a photosensitizer in a photocuring system, and has excellent effect on sensitivity improvement, and the prepared film has good resolution. And adhesion. Accordingly, the present invention also relates to the use of the 9-phenyl acridine macromolecular photosensitizer in a photocurable composition, the photoinitiator used in the photocurable composition preferably being photogenerated by photoacid generator, photoproduction Alkaline agent and free radical photoinitiator.

The beneficial effects of the invention also include:

1. The energy migration and intermolecular reaction in the macromolecular chain become easier, and the macromolecular photosensitizer has higher photosensitivity;

2. obtaining a product having different reactivity by copolymerizing with an inactive group, adjusting and designing the distance between the photosensitive groups, or changing the distance between the photoactive group and the main chain;

3. The macromolecularization of the photosensitive group limits the migration of the photosensitive group, thereby preventing the yellowing and aging of the coating;

4. Since most photolysis fragments are still attached to the polymer matrix, the odor and toxicity of the system can be reduced.

detailed description

The invention is further described in detail below with reference to the specific embodiments, but should not be construed as limiting the scope of the invention.

Preparation example

Example 1

(1) Preparation of intermediate 1a

To a 1000 ml four-necked flask, 165.6 g (1.2 mol) of p-hydroxybenzoic acid, 169.0 g (1.0 mol) of diphenylamine, 244.8 g (1.8 mol) of zinc chloride, and 115.3 g (1.0 mol) of 85% phosphoric acid were added, and the mixture was heated to stir. 200-210 ° C, reaction for 6 h. Then cool down to 130-140 ° C, add 30% sulfuric acid 400g, stir at 80 ° C for 2h, add 80 ° C water 300g stir for 0.5h, let stand to remove the lower layer of water, then add 300g water to repeat the above operation, and finally to the reaction bottle 300 g of ammonia water was added thereto to precipitate a large amount of orange solid. The material in the reaction flask is subjected to suction filtration at room temperature, rinsed with methanol, and dried to obtain 257.4 g of solid, ie, intermediate 1a, purity 98%;

The structure of the intermediate 1a was confirmed by LCMS.

Mass spectrometry analysis gave the 272 and 273 molecular fragment peaks with the software supplied with the instrument. The molecular weight of the product was 271, which was consistent with T+1 and T+2.

(2) Preparation of intermediate 1b

To a 500 mL four-necked flask, 27.1 g (0.1 mol) of Intermediate 1a, 16.6 g (0.12 mol) of potassium carbonate and 167 g of acetonitrile were added, and the mixture was heated under reflux at 80 ° C, and 12.0 g (0.11 mol) of methyl chloroacetate was added dropwise for about 1 hour. After the completion of the dropwise addition, the reaction was continued for 8 hours, and the reaction was completed. The unreacted potassium carbonate was removed by filtration while hot, and most of the solvent was evaporated under reduced pressure to precipitate a solid. The material in the reaction flask is subjected to suction filtration, rinsed with methanol, and dried to obtain 32.5 g of a pale yellow solid, that is, intermediate 1b, purity 98%;

The structure of the intermediate 1b was confirmed by LCMS and ¹ H-NMR.

Mass spectrometry The 344 and 345 molecular fragment peaks were obtained with the software supplied with the instrument. The molecular weight of the product was 343, which was consistent with T+1 and T+2.

¹ H-NMR (CDCl 3 , 500 MHz): 3.6721 (3H, s), 4.9034 (2H, s), 6.7254-6.8351 (2H, d), 7.2812-7.3708 (2H, d), 7.3424-7.4765 (2H, d) , 7.5432-7.6278 (4H, d), 7.9234-8.0509 (2H, d).

(3) Preparation of product 1

154.3 g (0.45 mol) of intermediate 1b, 166.2 g (0.3 mol) of raw material 1d, lithium hydroxide 1.3 g, and toluene 540 g were placed in a 1000 mL four-necked flask, and the mixture was heated and stirred at a controlled internal temperature of 90-100 ° C, and steamed while heating. The methanol produced by the reaction is added, and toluene is added in a timely manner until no methanol is distilled off, and the filtrate is filtered while being vacuumed, and the obtained filtrate is distilled under reduced pressure until the residue of toluene is less than 5000 ppm, and 304.4 g of a pale yellow viscous substance is obtained, that is, product 1 .

It is not difficult to understand that there are three hydroxyl groups with the same or similar activity in the raw material 1d, which are different from the degree of reaction of the single raw material 1d molecule, and the product 1 should contain the products 1-1, 1-2 and 1-3.

Example 2

(1) Preparation of intermediate 2a

To a 1000 ml four-necked flask was added 219.6 g (1.2 mol) of 4-hydroxy-3-nitrobenzoic acid benzoic acid, 169.0 g (1.0 mol) of diphenylamine, 244.8 g (1.8 mol) of zinc chloride and 115.3 g of 85% phosphoric acid. (1.0 mol), the temperature was raised to 200-210 ° C with stirring, and the reaction was carried out for 6 h, and the liquid phase was traced to the reaction. Cool down to 130-140 ° C, add 30% sulfuric acid 400g, stir at 80 ° C for 2h, add 80 ° C water 300g stir for 0.5h, let stand to remove the lower layer of water, then add 300g water to repeat the above operation, and finally into the reaction bottle 300 g of ammonia water was added to precipitate a large amount of orange solid. The material in the reaction flask is suction filtered, rinsed with methanol, and dried to obtain 300.2 g of solid, ie, intermediate 2a, purity 98%, yield 95%;

The structure of intermediate 2a was confirmed by LCMS.

Mass spectrometry The 317 and 318 molecular fragment peaks were obtained with the software supplied with the instrument. The molecular weight of the product was 316, which was consistent with T+1 and T+2.

(2) Preparation of intermediate 2b

31.6 g (0.1 mol) of Intermediate 2a, 16.6 g (0.12 mol) of potassium carbonate and 156 g of acetonitrile were added to a 500 mL four-necked flask, and the mixture was heated under reflux at 80 ° C, and 13.4 g (0.11 mol) of ethyl chloroacetate was added dropwise for about 1 hour. After the completion of the dropwise addition, the reaction was continued for 8 hours, and the reaction was completed. The unreacted potassium carbonate was removed by filtration while hot, and most of the solvent was evaporated under reduced pressure to precipitate a solid. The material in the reaction flask is subjected to suction filtration, rinsed with methanol, and dried to obtain 36.8 g of a pale yellow solid, that is, intermediate 2b, purity 98%, yield 91.5;

The structure of intermediate 2b was confirmed by LCMS.

Mass spectrometry The 403 and 404 molecular fragment peaks were obtained with the software supplied with the instrument. The molecular weight of the product was 402, which was consistent with T+1 and T+2.

The structure of the intermediate 2b was confirmed by 1 H-NMR.

1H-NMR (CDCl3, 500MHz): 3.6721-3.7232 (3H, t), 4.9034-4.9985 (2H, q), 7.0942 (2H, s), 7.3424-7.4765 (2H, d), 7.5432-7.6278 (2H, q ), 7.6082-7.6191 (2H, d), 7.7634-7.7705 (2H, d), 7.9234-8.0509 (2H, d), 8.3233 (1H, s).

(3) Preparation of product 2:

180.4 g (0.45 mol) of the intermediate 2b, 79.8 g (0.3 mol) of the raw material 2d, lithium hydroxide 1.3 g, and toluene 540 g were placed in a 1000 mL four-necked flask, and the mixture was heated and stirred at a temperature of 90-100 ° C, and distilled while heating. The methanol produced by the reaction is added with toluene in a timely manner until no methanol is distilled off, and filtered while hot, and the obtained filtrate is subjected to distillation under reduced pressure until the residue of toluene is less than 5000 ppm, and 221 g of a pale yellow viscous substance is obtained, yield is 92.4%. This mixture is the product 2.

Example 3-9

The product 3-9 having the following structure was synthesized by the method of Example 1 or 2.

Product 3:

Product 4:

Product 5:

Product 6:

Product 7:

Product 8:

Product 9:

Performance evaluation

The application properties of the photosensitizer of the present invention were evaluated by formulating an exemplary photocurable composition (i.e., a photosensitive resin composition).

1. Preparation of performance evaluation object

<Preparation of Photosensitive Resin Laminate>

The photosensitive resin composition having the composition shown in Table 1 and propylene glycol monoethyl ether acetate were thoroughly stirred and mixed, and coated on the surface of a 19 μm-thick polyethylene terephthalate film as a support using a rod. The film was uniformly coated, and then dried in a dryer at 95 ° C for 4 minutes to form a photosensitive resin layer having a thickness of 40 μm. Then, a 23 μm-thick polyethylene film which is a protective layer is bonded to the surface of the photosensitive resin layer on which the polyethylene terephthalate film is not laminated, to obtain a photosensitive resin laminate.

<The surface of the substrate is flattened>

As a substrate for sensitivity and resolution evaluation, a ketone laminate processed by a jet washing and polishing machine at a spray pressure of 0.20 MPa was used.

<Lamination>

While peeling off the polyethylene film of the photosensitive resin laminate, the surface was flattened, and the laminate was laminated to a ketone laminate preheated to 60 ° C by a hot roll laminator at a roll temperature of 105 ° C. The pressure was 0.35 MPa and the lamination speed was 1.5 m/min.

<exposure>

The exposure was performed by an exposure amount of a stepwise exposure level of 8 which was evaluated by the following sensitivity using a hray type direct drawing exposure apparatus (Digital Light Processing).

<development>

After peeling off the polyethylene terephthalate film, it was developed with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide at 23 ° C for 2 min to dissolve and remove the unexposed portion of the photosensitive resin layer, and then washed with ultrapure water for one minute. . At this time, the minimum time required to completely dissolve the photosensitive resin layer of the unexposed portion was taken as the minimum development time.

Table 1

Note: The names/compositions of the components indicated by the symbols in Table 1 are shown in Table 2.

Table 2

2, performance evaluation method

(1) Compatibility test

The photosensitive resin composition having the composition shown in Table 1 was sufficiently stirred and mixed, and uniformly applied onto the surface of a 19 μm-thick polyethylene terephthalate film as a support using a bar coater. It was dried in a dryer at 95 ° C for 4 minutes to form a photosensitive resin layer. Thereafter, the coated surface was visually observed and classified as follows:

◇: uniform coating surface;

◆: Undissolved matter precipitated on the coated surface.

(2) Sensitivity evaluation

The laminated substrate was exposed to light for 15 min using a 21-stage stage exposure meter manufactured by Stouffer, which has a 21 degree brightness change from transparent to black, to evaluate its sensitivity. After the exposure, the development was performed twice as long as the minimum development time, and the exposure was performed according to the exposure amount of the staged exposure level of 8 which was completely left by the resist film, and was classified as follows:

○: the exposure amount is 20 mJ/cm ² or less;

◎: the exposure amount is 20 mJ/cm ² -50 mJ/cm ² (excluding the end value);

●: The exposure amount is 50 mJ/cm ² or more.

(3) Resolution evaluation

The laminated substrate was exposed for 15 minutes by a line pattern mask having a ratio of the exposed portion and the unexposed portion having a width of 1:1, and then developed with twice the minimum development time to form a cured resist line normally. The minimum mask line width is used as the resolution value. Perform the following classification:

○: The resolution value is 30 μm or less;

◎: The resolution value is 30 μm-50 μm (excluding the end value);

●: The resolution value is 50 μm or more.

(4) Adhesion evaluation

The laminated substrate was exposed for 15 minutes by a line pattern mask having a ratio of the exposed portion and the unexposed portion having a width of 1:100, and then developed with twice the minimum development time to form a cured resist line normally. The minimum mask line width is used as the adhesion value. Perform the following classification:

○: The adhesion value is 30 μm or less;

◎: adhesion value is 30μm-50μm (excluding end value);

●: The adhesion value is 50 μm or more.

(5) Water solubility evaluation

After peeling off the polyethylene terephthalate film, it was developed with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide at 23 ° C for 2 min to dissolve and remove the unexposed portion of the photosensitive resin layer, and then washed with ultrapure water for one minute. . Perform the following classification:

◇: completely dissolved, no solid residue;

◆: Solids are deposited on the coated surface.

3. Performance evaluation results

The performance evaluation results are shown in Table 3.

table 3

Note: *1—The resist line cannot be formed and is not fully cured. It cannot be used for evaluation of resolution and adhesion.

As can be seen from the evaluation results of Table 3, the composition using the 9-phenyl acridine type photosensitizer of the present invention (Schemes 1-5) has good compatibility with the other components being the same. The sensitivity is high and exhibits good resolution and adhesion, and the water solubility is good, which is superior to Comparative Example 1-2 using the existing photosensitizer. In Comparative Example 3, the compatibility, sensitivity, resolution, adhesion and water solubility of the composition were far lower than those of the 9-phenyl group using the present invention in the case of containing only the TPS photoacid generator. A composition of an acridine photosensitizer (Schemes 1-5). Comparative Example 4 shows that the composition does not cure at all in the absence of TPS and the photosensitizer.

4. Further characterization

A photosensitive resin composition as formulated in Table 4 was prepared.

Table 4

Note: The names/compositions of the components indicated by the symbols in Table 4 are shown in Table 5.

table 5

The sensitivity was evaluated by referring to the above evaluation method, and the evaluation results are shown in Table 6.

Table 6

Note: *1 - not fully cured.

Experiments have shown that when the photosensitizer of the present invention is used alone, the photosensitivity is not good and the composition cannot be sufficiently cured. When used together with a photoinitiator such as a radical photoinitiator or a photobase generator, the higher the sensitivity, the higher the sensitivity than the photoinitiator alone.

In summary, the photosensitizer of the present invention exhibits excellent application performance in the field of photocuring and has broad application prospects. In addition, the photosensitizer of the present invention is not limited to the application fields indicated by the above formula, and all the photosensitizers of the present invention are used in all of the photocurable coatings, inks, and photoresists, and are all within the scope of this patent.

Claims (10)

1. A 9-phenyl acridine macromolecular photosensitizer characterized by comprising at least one of the compounds having the structure represented by the formula (I):

   

   among them,

   R ₁ represents a C ₁ -C ₆₀ linear or branched m+n valent alkyl group, wherein -CH ₂ - may be optionally substituted by oxygen, sulfur or 1,4-phenylene;

   A each independently represents -[(CHR ₄ ) _x -O] _y -, wherein R ₄ each independently represents hydrogen, methyl or ethyl, x is an integer from 1 to 10, and y is an integer from 1 to 20;

   R ₂ represents a C ₁ -C ₂₀ linear or branched alkylene group, wherein -CH ₂ - may be optionally substituted by oxygen, sulfur or phenylene;

   R ₃ represents hydrogen or a substituent;

   m represents an integer of 0-20, and n represents an integer of 1-20.
2. The 9-phenyl acridine macromolecular photosensitizer according to claim 1, wherein R ₁ represents a C ₁ - C ₂₀ linear or branched m + n valent alkyl group, wherein -CH ₂ - may optionally be substituted by oxygen or 1,4-phenylene, provided that the two oxygens are not directly linked.
3. The 9-phenyl acridine macromolecular photosensitizer according to claim 1, wherein A represents -[(CHR ₄ ) _x -O] _y -, wherein R ₄ each independently represents hydrogen, methyl or Ethyl, x is an integer from 1 to 10, and y is an integer from 1 to 20.
4. The 9-phenyl acridine macromolecular photosensitizer according to claim 1 or 3, wherein a terminal oxygen atom of the -[(CHR ₄ ) _x -O] _y - group is bonded to R ₁ .
5. The 9-phenyl acridine macromolecular photosensitizer according to claim 1, wherein R ₂ represents a C ₁ - C ₈ linear or branched alkylene group, wherein -CH ₂ - is optional The ground is replaced by oxygen or 1,4-phenylene, provided that the two oxygens are not directly connected.
6. The 9-phenyl acridine macromolecular photosensitizer according to claim 1, wherein R _{3 is} selected from the group consisting of H, CH ₃ , NO ₂ , or halogen.
7. The 9-phenyl acridine macromolecular photosensitizer according to claim 1, wherein m represents an integer of 0-7, n represents an integer of 1-8, and the sum of m and n is 2-8. Integer.
8. The method for preparing a 9-phenyl acridine macromolecular photosensitizer according to any one of claims 1 to 7, comprising the steps of:

   (1) The raw material a and the raw material b are reacted under the action of a catalyst to obtain an intermediate a;

   (2) The intermediate a and the starting material c are reacted in a solvent containing an acid binding agent to obtain an intermediate b;

   (3) subjecting the intermediate b and the raw material d to a transesterification reaction under the action of a catalyst to obtain a product;

   The reaction equation is as follows:

   

   Wherein R ₅ represents a C ₁ -C ₈ linear or branched alkyl group.
9. Use of the 9-phenyl acridine macromolecular photosensitizer according to any one of claims 1 to 7 in a photocurable composition.
10. The use according to claim 9, wherein the photoinitiator used in the photocurable composition is selected from the group consisting of a photoacid generator, a photobase generator and a radical photoinitiator.