Diformic anhydride photosensitive monomer as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of organic synthesis and high polymer materials, and particularly relates to a dicarboxylic anhydride photosensitive monomer as well as a preparation method and application thereof. The structural formula of the dicarboxylic anhydride photosensitive monomer is shown as a formula I: # imgabs0 #, n is an integer ranging from 1 to 5, and R1 and R2 are respectively and independently selected from hydrogen, fluorine, nitryl, monofluoromethyl, difluoromethyl, trifluoromethyl or trifluoromethoxy. According to the invention, the variety of binary anhydride is expanded, the polyimide polymer can be obtained through polymerization, and the light transmittance, the refractive index, the haze, the impedance performance and other functions of the polyimide polymer are improved; the obtained polyimide polymer shows excellent performances in the aspects of light transmittance, refractive index, haze, impedance and the like, and can improve the photoelectric conversion efficiency and reduce the transmission loss.

Description

Technical Field

[0001] The invention belongs to the technical field of organic synthesis and polymer materials, and specifically relates to a diformic anhydride photosensitive monomer, a preparation method and application thereof. Background Art

[0002] Polyimide (PI) is a high-performance polymer material developed in the 1950s to meet the needs of aerospace for heat-resistant, lightweight and high-strength materials. It has increased the use temperature of polymer materials by more than 200°C. Polyimide monomers are abundant in source and have diverse synthetic routes. They show excellent structural and performance designability and flexible molding processability. They have been widely used in many fields such as power and electrical, printed circuits, new displays and energy conversion. In the early semiconductor industry, researchers gave polyimide photosensitivity, namely synthetic photosensitive polyimide (PSPI). In recent years, PSPI has shown increasingly prominent importance as a practical new material in many fields such as multi-chip packaging, integrated circuits, microelectromechanical systems (MEMS), special optical lenses, optical anti-counterfeiting materials and new displays.

[0003] PI is mainly synthesized from dibasic acid anhydrides and diamines. Compared with many other heterocyclic polymers, such as polybenzimidazole, polybenzimidazole, polybenzothiazole, polyquinoline and other monomers, these two monomers have a wide source of raw materials and are easier to synthesize. There are many varieties of dibasic acid anhydrides and diamines, and different combinations can obtain polyimides with different properties. As a monomer material for preparing PI, the structure of dibasic acid anhydrides is closely related to the performance of PI. At present, traditional dibasic acid anhydrides mainly include aromatic dibasic acid anhydrides, maleic anhydride, etc., but the PI prepared by these dibasic acid anhydrides has a high curing temperature, poor photosensitivity, large shrinkage (more than 45%), and a complicated preparation process, which is easy to cause waste of resources.

[0004] Therefore, the existing technology needs to be improved and developed. Summary of the invention

[0005] In view of the above-mentioned deficiencies in the prior art, the purpose of the present invention is to provide a dicarboxylic anhydride photosensitive monomer and a preparation method and application thereof, aiming to expand the varieties of dicarboxylic anhydride. It can also be used as one of the monomers of PI to obtain PI by polymerization, thereby improving the transmittance, refractive index, haze, impedance and other functions of PI. The obtained polyimide polymer exhibits excellent performance in terms of transmittance, refractive index, haze, impedance, etc., which can improve the photoelectric conversion efficiency and reduce transmission loss.

[0006] The technical solution of the present invention is as follows:

[0007] In a first aspect of the present invention, a dicarboxylic anhydride-based photosensitive monomer is provided, wherein the structural formula of the dicarboxylic anhydride-based photosensitive monomer is as shown in Formula I:

[0008]

[0009] wherein n is an integer of 1 to 5, and R1 and R2 are each independently selected from hydrogen, fluorine, nitro, monofluoromethyl, difluoromethyl, trifluoromethyl or trifluoromethoxy.

[0010] In a preferred technical solution, the structural formula of the diformic anhydride photosensitive monomer is:

[0011]

[0012]

[0013] One of them.

[0014] The second aspect of the present invention provides a method for preparing the diformic anhydride photosensitive monomer as described in the first aspect, comprising:

[0015] The first step: reacting tetrahydrophthalic anhydride as shown in formula II with hydrobromic acid to obtain 5-bromo-tetrahydrophthalic anhydride as shown in formula III;

[0016] Step 2: subjecting 5-bromo-tetrahydrophthalic anhydride as shown in Formula III to a nucleophilic substitution reaction with substituted 3-hydroxybenzyl alcohol as shown in Formula IV to obtain a 5-((5-hydroxy-2,3-dimethylphenyl)oxy)hexahydroisobenzofuran-1,3-dione derivative as shown in Formula V;

[0017] Step 3: reacting the 5-((5-hydroxy-2,3-dimethylphenyl)oxy)hexahydroisobenzofuran-1,3-dione derivative shown in Formula V with the dibromoalkane shown in Formula VI through a nucleophilic substitution reaction to obtain a dicarboxylic anhydride photosensitive monomer shown in Formula I;

[0018] The general reaction formula is as follows:

[0019]

[0020] Wherein, n=1-5, wherein R1 and R2 are each independently selected from hydrogen, fluorine, nitro, monofluoromethyl, difluoromethyl, trifluoromethyl or trifluoromethoxy.

[0021] The preferred technical solution is that the structural formula of Formula IV is:

[0022]

[0023] One of them.

[0024] The preferred technical solution is that the structural formula of Formula V is:

[0025]

[0026] One of them.

[0027] The preferred technical solution is that the structural formula of Formula VI is: One of them.

[0028] According to a preferred technical solution, in the first step, the molar ratio of the hydrobromic acid to the tetrahydrophthalic anhydride is (1.5-3):1.

[0029] The reaction conditions of the first step include: reaction temperature of 0 to 50° C., and reaction time of 2 to 12 h.

[0030] The first step is to carry out the reaction in the presence of solvent one;

[0031] The ratio of the volume of the solvent 1 to the mass of tetrahydrophthalic anhydride is (2-10) mL:1 g;

[0032] The solvent one is selected from at least one of dioxane, toluene, xylene, dimethyl sulfoxide, N,N-dimethylformamide, acetonitrile and tetrahydrofuran.

[0033] After the first step of reaction is completed, the method further comprises the step of using a neutralizing agent to neutralize excess hydrobromic acid, wherein the neutralizing agent is selected from at least one of sodium carbonate and sodium bicarbonate.

[0034] In a preferred technical solution, the second step is to carry out the reaction in the presence of solvent 2 and catalyst 1;

[0035] The ratio of the volume of the second solvent to the mass sum of the 5-bromo-tetrahydrophthalic anhydride and the substituted 3-hydroxybenzyl alcohol is (4-12) mL:1 g;

[0036] The second solvent is selected from at least one of toluene, xylene, dimethyl sulfoxide, N,N-dimethylformamide, acetonitrile, tetrahydrofuran, and acetone;

[0037] The molar ratio of the catalyst 1 to the 5-bromo-tetrahydrophthalic anhydride is (1.2-3):1;

[0038] The catalyst is selected from at least one of potassium carbonate, cesium carbonate, triethylamine, sodium hydride, sodium carbonate and sodium bicarbonate.

[0039] A preferred technical solution is that in the second step, the molar ratio of the 5-bromo-tetrahydrophthalic anhydride to the substituted 3-hydroxybenzyl alcohol is 1:(2-5);

[0040] According to the preferred technical solution, the reaction conditions of the second step include: a reaction temperature of 60 to 120° C. and a reaction time of 2 to 20 hours.

[0041] In a preferred technical solution, the third step is to carry out the reaction in the presence of catalyst 2 and solvent 3;

[0042] The molar ratio of the catalyst 2 to the 5-((5-hydroxy-2,3-dimethylphenyl)oxy)hexahydroisobenzofuran-1,3-dione derivative is (1.2-3):1;

[0043] The second catalyst is selected from at least one of potassium carbonate, cesium carbonate, triethylamine, sodium hydride, sodium carbonate, and sodium bicarbonate;

[0044] The ratio of the volume of the solvent three to the mass sum of the 5-((5-hydroxy-2,3-dimethylphenyl)oxy)hexahydroisobenzofuran-1,3-dione derivative and the dibromoalkane is (4-10) mL:1 g;

[0045] The solvent three is selected from at least one of toluene, xylene, dimethyl sulfoxide, N,N-dimethylformamide, acetonitrile, tetrahydrofuran and acetone.

[0046] According to a preferred technical solution, in the third step, the molar ratio of the 5-((5-hydroxy-2,3-dimethylphenyl)oxy)hexahydroisobenzofuran-1,3-dione derivative to the dibromoalkane is (2-5):1.

[0047] In the preferred technical solution, the reaction conditions of the third step include: the reaction temperature is 60 to 120° C. and the reaction time is 2 to 20 hours.

[0048] The third aspect of the present invention provides a use of the dicarboxylic anhydride photosensitive monomer as described in the first aspect or the dicarboxylic anhydride photosensitive monomer obtained by the preparation method as described in the second aspect as a polymer monomer in the preparation of polyimide.

[0049] Beneficial effects: The flexible dicarboxylic anhydride photosensitive monomer of the present invention is a new type of photosensitive monomer, which not only expands the variety of dibasic acid anhydrides, but more importantly, can be used as one of the monomers to polymerize PI, and can improve the transmittance, refractive index, haze, impedance and other functions of PI. The obtained polyimide polymer shows excellent performance in terms of transmittance, refractive index, haze, impedance and other aspects, which can improve the photoelectric conversion efficiency and reduce transmission loss.

[0050] The reason why the diformic anhydride photosensitive monomer of the present invention has the above advantages is that:

[0051] On the basis of the parent structure of dicarboxylic anhydride, the introduction of benzene rings can increase the planarity of the material, reduce light refraction, improve the light transmittance of the material, and reduce haze. The benzene ring can reduce the polarization degree of the material and thus reduce the impedance of the material. The introduction of electron-withdrawing groups can reduce the π-π conjugation of the polymer after polymerization and play a decolorizing role. The introduction of flexible chains can increase the flexibility and plasticity of the material, making it easier to process and shape, which is conducive to the preparation of various forms of photosensitive materials.

[0052] Moreover, the preparation method of the diformic anhydride photosensitive monomer of the present invention is simple and controllable, has a high yield and has a high application value. DETAILED DESCRIPTION

[0053] The present invention provides a diformic anhydride photosensitive monomer and a preparation method and application thereof. To make the purpose, technical scheme and effect of the present invention clearer and more specific, the present invention is further described in detail below.

[0054] An embodiment of the present invention provides a diformic anhydride photosensitive monomer, and the structural formula of the diformic anhydride photosensitive monomer is shown in Formula I:

[0055]

[0056] Wherein, n=1-5, R1 and R2 are each independently selected from hydrogen, fluorine, nitro, monofluoromethyl, difluoromethyl, trifluoromethyl or trifluoromethoxy.

[0057] According to the present invention, n=an integer of 1 to 5, for example, 1, 2, 3, 4, or 5.

[0058] Photosensitive monomer refers to a small molecule functional monomer. This type of monomer can form a macromolecular polymer with other small molecules. The resulting macromolecular polymer has special functions such as refraction and reflection of light and can be used as an optical anti-counterfeiting material. It is called a photosensitive monomer. The present invention provides a dicarboxylic anhydride photosensitive monomer with a new structure. The dicarboxylic anhydride photosensitive monomer can be polymerized to obtain a polymer PI, which has the functions of improving the light transmittance, refractive index, haze, impedance performance and the like of PI.

[0059] The dicarboxylic anhydride photosensitive monomer of the present invention has a group containing n methylene groups, which is equivalent to introducing a flexible chain. Therefore, the dicarboxylic anhydride photosensitive monomer of the present invention can also be called a flexible dicarboxylic anhydride photosensitive monomer.

[0060] In some embodiments, the structural formula of the dicarboxylic anhydride photosensitive monomer is:

[0061]

[0062] One of them.

[0063] The embodiment of the present invention provides a method for preparing the diformic anhydride photosensitive monomer as described above, comprising:

[0064] The first step: reacting tetrahydrophthalic anhydride as shown in formula II with hydrobromic acid to obtain 5-bromo-tetrahydrophthalic anhydride as shown in formula III;

[0065] Step 2: subjecting 5-bromo-tetrahydrophthalic anhydride as shown in Formula III to a nucleophilic substitution reaction with substituted 3-hydroxybenzyl alcohol as shown in Formula IV to obtain a 5-((5-hydroxy-2,3-dimethylphenyl)oxy)hexahydroisobenzofuran-1,3-dione derivative as shown in Formula V;

[0066] Step 3: reacting the 5-((5-hydroxy-2,3-dimethylphenyl)oxy)hexahydroisobenzofuran-1,3-dione derivative shown in Formula V with the dibromoalkane shown in Formula VI through a nucleophilic substitution reaction to obtain a dicarboxylic anhydride photosensitive monomer shown in Formula I;

[0067] The general reaction formula is as follows:

[0068]

[0069] Wherein, n=1-5, wherein R1 and R2 are each independently selected from hydrogen, fluorine, nitro, monofluoromethyl, difluoromethyl, trifluoromethyl or trifluoromethoxy.

[0070] In some embodiments, the structural formula of Formula IV is:

[0071]

[0072] One of, but not limited to.

[0073] In some embodiments, the structural formula of Formula V is:

[0074]

[0075] One of, but not limited to.

[0076] In some embodiments, the structural formula of Formula VI is: One of, but not limited to.

[0077] In a specific embodiment, when R1 is hydrogen, R2 is hydrogen, and n=1, the structural formula of Formula IV is: The structural formula of Formula V is The structural formula of formula VI is: The reaction formula for preparing the flexible diformic anhydride photosensitive monomer is:

[0078]

[0079] In another specific embodiment, when R1 is fluorine, R2 is nitro, and n=2, the structural formula of Formula IV is The structural formula of Formula V is The structural formula of formula VI is: The reaction formula for preparing the flexible diformic anhydride photosensitive monomer is:

[0080]

[0081] In some embodiments, in the first step, the molar ratio of the hydrobromic acid to the tetrahydrophthalic anhydride is (1.5-3):1, preferably (1.8-2.8):1.

[0082] In some embodiments, the reaction conditions of the first step include: reaction temperature of 0 to 50° C., and reaction time of 2 to 12 h.

[0083] In some embodiments, the first step is carried out in the presence of solvent one;

[0084] The ratio of the volume of the solvent 1 to the mass of tetrahydrophthalic anhydride is (2-10) mL:1 g, preferably (2-8) mL:1 g;

[0085] The solvent one is selected from at least one of dioxane, toluene, xylene, dimethyl sulfoxide, N,N-dimethylformamide, acetonitrile and tetrahydrofuran.

[0086] In some embodiments, after the first step of the reaction is completed, the step of neutralizing the excess hydrobromic acid with a neutralizer is further included, and the neutralizer is selected from at least one of sodium carbonate and sodium bicarbonate.

[0087] In some embodiments, the second step is carried out in the presence of solvent two and catalyst one;

[0088] The ratio of the volume of the second solvent to the mass sum of the 5-bromo-tetrahydrophthalic anhydride and the substituted 3-hydroxybenzyl alcohol is (4-12) mL:1 g, preferably (5-10) mL:1 g;

[0089] The second solvent is selected from at least one of toluene, xylene, dimethyl sulfoxide, N,N-dimethylformamide, acetonitrile, tetrahydrofuran, and acetone;

[0090] The molar ratio of the catalyst 1 to the 5-bromo-tetrahydrophthalic anhydride is (1.2-3):1, preferably (1.5-2.5):1;

[0091] The catalyst is selected from at least one of potassium carbonate, cesium carbonate, triethylamine, sodium hydride, sodium carbonate and sodium bicarbonate.

[0092] In some embodiments, in the second step, the molar ratio of the 5-bromo-tetrahydrophthalic anhydride to the substituted 3-hydroxybenzyl alcohol is 1:(2-5), preferably 1:(2.5-4.5);

[0093] In some embodiments, the reaction conditions of the second step include: reaction temperature of 60 to 120° C., and reaction time of 2 to 20 h.

[0094] In some embodiments, the third step is carried out in the presence of catalyst two and solvent three;

[0095] The molar ratio of the catalyst 2 to the 5-((5-hydroxy-2,3-dimethylphenyl)oxy)hexahydroisobenzofuran-1,3-dione derivative is (1.2-3):1, preferably (1.5-2.5):1;

[0096] The second catalyst is selected from at least one of potassium carbonate, cesium carbonate, triethylamine, sodium hydride, sodium carbonate, and sodium bicarbonate;

[0097] The ratio of the volume of the solvent three to the mass sum of the 5-((5-hydroxy-2,3-dimethylphenyl)oxy)hexahydroisobenzofuran-1,3-dione derivative and the dibromoalkane is (4-10) mL:1 g, preferably (5-10) mL:1 g;

[0098] The solvent three is selected from at least one of toluene, xylene, dimethyl sulfoxide, N,N-dimethylformamide, acetonitrile, tetrahydrofuran and acetone.

[0099] In some embodiments, in the third step, the molar ratio of the 5-((5-hydroxy-2,3-dimethylphenyl)oxy)hexahydroisobenzofuran-1,3-dione derivative to the dibromoalkane is (2-5):1, preferably (2.5-4.5):1.

[0100] In some embodiments, the reaction conditions of the third step include: reaction temperature of 60 to 120° C. and reaction time of 2 to 20 h.

[0101] For the convenience of explaining the present invention, as an example, according to some more preferred embodiments of the present invention, the preparation method comprises:

[0102] The first step: adding solvent 1, tetrahydrophthalic anhydride as shown in formula II and hydrobromic acid in a reactor in sequence, reacting at 0-50° C. for 2-12 hours, tracking the reaction progress by TLC, adding a neutralizing agent to neutralize excess hydrobromic acid after the reaction is completed, extracting with ethyl acetate, drying the organic phase with anhydrous sodium sulfate, spin-drying the organic phase, and vacuum drying at 60-100° C. to obtain the intermediate 5-bromo-tetrahydrophthalic anhydride as shown in formula III;

[0103] Step 2: Solvent 2, the intermediate 5-bromo-tetrahydrophthalic anhydride shown in Formula III prepared in the first step, substituted 3-hydroxybenzyl alcohol shown in Formula IV, and catalyst 1 are sequentially added into a reactor, reacted at 60-120° C. for 2-20 hours, and the reaction progress is tracked by TLC. After the reaction is completed, water and ethyl acetate are added for extraction, the organic phase is dried over anhydrous sodium sulfate, the organic phase is spin-dried, and vacuum dried at 60-100° C. to obtain a 5-((5-hydroxy-2,3-dimethylphenyl)oxy)hexahydroisobenzofuran-1,3-dione derivative shown in Formula V;

[0104] Step 3: Add solvent 3, 5-((5-hydroxy-2,3-dimethylphenyl)oxy)hexahydroisobenzofuran-1,3-dione derivative as shown in formula V prepared in step 2, dibromoalkane as shown in formula VI and catalyst 2 into the reactor in sequence, react at 60-120° C. for 2-20 h, and track the reaction progress by TLC. After the reaction, add water and ethyl acetate for extraction, dry the organic phase with anhydrous sodium sulfate, spin dry the organic phase, wash with petroleum ether, and dry in vacuo at 60-100° C. to obtain a flexible dicarboxylic anhydride photosensitive monomer as shown in formula I.

[0105] Based on the above technical solutions:

[0106] Furthermore, in the preparation method, the ratio of the volume of solvent one to the mass of tetrahydrophthalic anhydride is (2-10) mL:1 g, preferably (2-8) mL:1 g. When the ratio of solvent one is less than 2, the solubility of the reaction raw materials decreases, and the probability of collision between the raw materials decreases, resulting in a decrease in reaction rate; when the ratio of solvent one is greater than 10, the concentration of the reaction raw materials is too low, which also leads to a decrease in reaction rate and waste of solvent. Therefore, the ratio of the volume of solvent one to the mass of tetrahydrophthalic anhydride is in the range of (2-10) mL:1 g, which is more appropriate.

[0107] Furthermore, in the preparation method, the molar ratio of hydrobromic acid to tetrahydrophthalic anhydride is (1.5-3): 1, preferably (1.8-2.8): 1. When the ratio of hydrobromic acid is less than 1.5, the reaction is incomplete, and when it is greater than 3, the excess hydrobromic acid is difficult to neutralize, affecting subsequent reactions.

[0108] Further, in the preparation method, the solvent one is selected from dioxane, toluene, xylene, dimethyl sulfoxide, N,N-dimethylformamide, acetonitrile, tetrahydrofuran. Preferably, in the preparation method, the solvent one is selected from dioxane.

[0109] Furthermore, in the preparation method, the neutralizing agent is selected from sodium carbonate and sodium bicarbonate aqueous solution, preferably, sodium bicarbonate aqueous solution.

[0110] Further, in the preparation method, the ratio of the volume of the solvent two to the mass sum of the intermediate 5-bromo-tetrahydrophthalic anhydride and the substituted 3-hydroxybenzyl alcohol is (4-12) mL: 1g, preferably (5-10) mL: 1g. When the ratio of the solvent two is less than 4, the solubility of the reaction raw materials is reduced, and the probability of collision between the raw materials is reduced, resulting in a decrease in the reaction rate; when the ratio of the solvent two is greater than 12, the concentration of the reaction raw materials is too low, which also leads to a decrease in the reaction rate and a waste of solvent. Therefore, the ratio of the volume of the solvent two to the mass sum of the intermediate 5-bromo-tetrahydrophthalic anhydride and the substituted 3-hydroxybenzyl alcohol is in the range of (4-12) mL: 1g, which is more suitable.

[0111] Furthermore, in the preparation method, the molar ratio of catalyst 1 to 5-bromo-tetrahydrophthalic anhydride is (1.2-3):1, preferably (1.5-2.5):1. When the equivalent ratio of catalyst 1 is less than 1.2, the reaction is incomplete, and when it is greater than 3, the alkali concentration of the system is too high, interfering with the reaction. Catalyst 1 is selected from at least one of potassium carbonate, cesium carbonate, triethylamine, sodium hydride, sodium carbonate, and sodium bicarbonate, preferably potassium carbonate.

[0112] Furthermore, in the preparation method, the molar ratio of 5-bromo-tetrahydrophthalic anhydride to substituted 3-hydroxybenzyl alcohol is 1:(2-5), preferably 1:(2.5-4.5). Properly increasing the ratio of substituted 3-hydroxybenzyl alcohol can accelerate the reaction rate, shorten the reaction time, and reduce the generation of by-products; however, a feed ratio greater than 5 causes excess raw materials to accumulate in the reaction system, making it difficult to remove and causing a waste of raw materials.

[0113] Further, in the preparation method, the second solvent is selected from toluene, xylene, dimethyl sulfoxide, N,N-dimethylformamide, acetonitrile, tetrahydrofuran, acetone. Preferably, in the preparation method, the second solvent is selected from acetonitrile.

[0114] Furthermore, in the preparation method, the ratio of the volume of solvent three to the mass sum of the intermediate 5-((5-hydroxy-2,3-dimethylphenyl)oxy)hexahydroisobenzofuran-1,3-dione derivative and dibromoalkane is (4-10) mL:1g, preferably (5-10) mL:1g. When the ratio of solvent three is less than 4, the solubility of the reaction raw materials decreases, and the probability of collision between the raw materials decreases, resulting in a decrease in the reaction rate; when the ratio of solvent three is greater than 10, the concentration of the reaction raw materials is too low, which also leads to a decrease in the reaction rate and a waste of solvent. Therefore, the ratio of the volume of the solvent three to the mass sum of the intermediate 5-((5-hydroxy-2,3-dimethylphenyl)oxy)hexahydroisobenzofuran-1,3-dione derivative and dibromoalkane is in the range of (4-12) mL:1g, which is more suitable.

[0115] Furthermore, in the preparation method, the molar ratio of the catalyst 2 to the 5-((5-hydroxy-2,3-dimethylphenyl)oxy)hexahydroisobenzofuran-1,3-dione derivative is (1.2-3):1, preferably (1.5-2.5):1. When the molar ratio of the catalyst 2 is less than 1.2, the reaction is incomplete, and when it is greater than 3, the alkali concentration of the system is too high, interfering with the reaction. The catalyst 2 is selected from potassium carbonate, cesium carbonate, triethylamine, sodium hydride, sodium carbonate, sodium bicarbonate, preferably potassium carbonate.

[0116] Furthermore, in the preparation method, the molar ratio of the 5-((5-hydroxy-2,3-dimethylphenyl)oxy)hexahydroisobenzofuran-1,3-dione derivative to the dibromoalkane is (2-5):1, preferably (2.5-4.5):1. The reaction is a disubstitution reaction, and appropriately increasing the ratio of the dibromoalkane can accelerate the reaction rate, shorten the reaction time, and reduce the generation of by-products; however, a feed ratio greater than 5 leads to the enrichment of excess dibromoalkane in the reaction system, which is difficult to remove and causes a waste of raw materials.

[0117] Further, in the preparation method, the solvent three is selected from toluene, xylene, dimethyl sulfoxide, N,N-dimethylformamide, acetonitrile, tetrahydrofuran, and acetone. Preferably, in the preparation method, the solvent three is selected from acetonitrile.

[0118] The embodiment of the present invention also provides a use of the above-mentioned dicarboxylic anhydride photosensitive monomer or the dicarboxylic anhydride photosensitive monomer obtained by the above-mentioned preparation method as a polymer monomer in preparing polyimide, preferably in synthesizing photosensitive polyimide.

[0119] As described above, the present invention also provides the use of the compound as shown in Formula I defined above as a flexible dicarboxylic anhydride photosensitive monomer capable of increasing the light transmittance of a material, reducing the refractive index, reducing the haze, and reducing the impedance. For example, the dicarboxylic anhydride photosensitive monomer of the present invention can be polymerized with propylene diamine to obtain a polyimide, the general structural formula of which is:

[0120]

[0121] Wherein, n=1-5, R1 and R2 are independently selected from hydrogen, fluorine, nitro, monofluoromethyl, difluoromethyl, trifluoromethyl or trifluoromethoxy. The polyimide polymer exhibits excellent performance in terms of transmittance, refractive index, haze, impedance, etc., and can improve photoelectric conversion efficiency and reduce transmission loss.

[0122] The present invention is further described below in conjunction with specific examples, but the examples do not limit the present invention in any form. If specific conditions are not specified in the examples, they are carried out according to conventional conditions or conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments used is not specified, they are all conventional products that can be purchased commercially.

[0123] In the following examples, the calculation method of the yield of the product is:

[0124] (Actual product mass / theoretical product mass) × 100%;

[0125] The structural formulas of the intermediate products and final products of the following examples are shown in the reaction formulas by hydrogen nuclear magnetic resonance spectroscopy.

[0126] Example 1

[0127] Dioxane (150 mL), tetrahydrophthalic anhydride (15.20 g, 0.1 mol) and hydrobromic acid (11.99 g, 0.15 mol) were added to the reactor in sequence, and the mixture was reacted at 20 °C for 5 h. The reaction progress was monitored by TLC. After the reaction, saturated aqueous sodium bicarbonate solution was added to neutralize the excess hydrobromic acid until the solution was neutral. The mixture was extracted with ethyl acetate, and the organic phase was dried over anhydrous sodium sulfate. The organic phase was spin-dried and dried in vacuo at 60 °C. Toluene (100 mL) and (24.81g, 0.2mol) and potassium carbonate (17.97g, 0.13mol), react at 60℃ for 10h, follow the reaction progress by TLC, add water and ethyl acetate to extract after the reaction, dry the organic phase with anhydrous sodium sulfate, spin dry the organic phase, and dry it in vacuum at 60℃; then add acetonitrile (120mL), (9.99 g, 0.05 mol) and potassium carbonate (17.97 g, 0.13 mol) were reacted at 80 °C for 15 h. The reaction progress was monitored by TLC. After the reaction was completed, water and ethyl acetate were added for extraction. The organic phase was dried over anhydrous sodium sulfate, the organic phase was spin-dried, washed with petroleum ether, and dried in vacuo at 65 °C to obtain Yield: 99.8%, reaction formula:

[0128]

[0129] Example 2

[0130] Toluene (150 mL), tetrahydrophthalic anhydride (15.20 g, 0.1 mol) and hydrobromic acid (12.79 g, 0.16 mol) were added to the reactor in sequence, and the mixture was reacted at 20 °C for 6 h. The reaction progress was monitored by TLC. After the reaction, saturated aqueous sodium bicarbonate solution was added to neutralize the excess hydrobromic acid until the solution became neutral. The mixture was extracted with ethyl acetate, and the organic phase was dried over anhydrous sodium sulfate. The organic phase was spin-dried and dried in vacuo at 60 °C. Tetrahydrofuran (100 mL) and (37.40 g, 0.2 mol) and potassium carbonate (19.35 g, 0.14 mol), react at 70 ° C for 11 h, and track the reaction progress by TLC. After the reaction, water and ethyl acetate are added for extraction, and the organic phase is dried over anhydrous sodium sulfate, and the organic phase is dried by rotary evaporation and dried in vacuo at 60 ° C; then toluene (120 mL) and (10.69 g, 0.05 mol) and potassium carbonate (17.97 g, 0.13 mol), react at 60 ° C for 20 h, and track the reaction progress by TLC. After the reaction, water and ethyl acetate are added for extraction, and the organic phase is dried over anhydrous sodium sulfate, the organic phase is spin-dried, washed with petroleum ether, and dried in vacuo at 80 ° C to obtain Yield: 98.8%, reaction formula:

[0131]

[0132] Example 3

[0133] Dimethyl sulfoxide (150 mL), tetrahydrophthalic anhydride (15.20 g, 0.1 mol) and hydrobromic acid (15.99 g, 0.20 mol) were added to the reactor in sequence, and the mixture was reacted at 30 °C for 2 h. The reaction progress was monitored by TLC. After the reaction, saturated sodium bicarbonate aqueous solution was added to neutralize the excess hydrobromic acid until the solution was neutral. The mixture was extracted with ethyl acetate, and the organic phase was dried over anhydrous sodium sulfate. The organic phase was spin-dried and dried in vacuo at 80 °C. Toluene (100 mL) and (33.81 g, 0.2 mol) and cesium carbonate (45.61 g, 0.14 mol), react at 80 ° C for 10 h, and track the reaction progress by TLC. After the reaction is completed, water and ethyl acetate are added for extraction, and the organic phase is dried over anhydrous sodium sulfate, and the organic phase is spin-dried and dried in a vacuum at 60 ° C; then xylene (120 mL) and (11.40 g, 0.05 mol) and triethylamine (13.15 g, 0.13 mol), react at 100 ° C for 10 h, TLC tracking the reaction progress, after the reaction is completed, water and ethyl acetate are added for extraction, the organic phase is dried over anhydrous sodium sulfate, the organic phase is spin-dried, washed with petroleum ether, and dried in vacuo at 80 ° C to obtain Yield: 97.2%, reaction formula:

[0134]

[0135] Example 4

[0136] N,N-dimethylformamide (150 mL), tetrahydrophthalic anhydride (15.20 g, 0.1 mol) and hydrobromic acid (12.79 g, 0.16 mol) were added to the reactor in sequence, and the mixture was reacted at 50°C for 2 h. The reaction progress was monitored by TLC. After the reaction, saturated aqueous sodium carbonate solution was added to neutralize the excess hydrobromic acid until the solution became neutral. The mixture was extracted with ethyl acetate, and the organic phase was dried over anhydrous sodium sulfate. The organic phase was spin-dried and dried under vacuum at 70°C. Tetrahydrofuran (100 mL) and (38.41 g, 0.2 mol) and sodium carbonate (14.84 g, 0.14 mol), react at 80 ° C for 10 h, and track the reaction progress by TLC. After the reaction, water and ethyl acetate are added for extraction, and the organic phase is dried over anhydrous sodium sulfate, and the organic phase is dried by rotary evaporation and dried in vacuo at 60 ° C; then xylene (120 mL) and (12.09 g, 0.05 mol) and sodium carbonate (13.78 g, 0.13 mol), reacted at 110 ° C for 10 h, TLC followed the reaction progress, after the reaction was completed, water and ethyl acetate were added for extraction, the organic phase was dried over anhydrous sodium sulfate, the organic phase was spin-dried, washed with petroleum ether, and dried in vacuo at 80 ° C to obtain Yield: 96.5%, reaction formula:

[0137]

[0138] Example 5

[0139] Xylene (150 mL), tetrahydrophthalic anhydride (15.20 g, 0.1 mol) and hydrobromic acid (15.98 g, 0.20 mol) were added to the reactor in sequence, and the mixture was reacted at 40°C for 2 h. The reaction progress was monitored by TLC. After the reaction, saturated aqueous sodium carbonate solution was added to neutralize the excess hydrobromic acid until the solution became neutral. The mixture was extracted with ethyl acetate, and the organic phase was dried over anhydrous sodium sulfate. The organic phase was spin-dried and dried under vacuum at 70°C. Tetrahydrofuran (100 mL) and

[0140] (38.41 g, 0.2 mol) and sodium carbonate (14.84 g, 0.14 mol), react at 80 ° C for 10 h, and track the reaction progress by TLC. After the reaction, water and ethyl acetate are added for extraction, and the organic phase is dried over anhydrous sodium sulfate, and the organic phase is dried by rotary evaporation and dried in vacuo at 60 ° C; then xylene (120 mL) and (12.79 g, 0.05 mol) and sodium carbonate (13.78 g, 0.13 mol), reacted at 110 ° C for 10 h, TLC tracking the reaction progress, after the reaction was completed, water and ethyl acetate were added for extraction, the organic phase was dried over anhydrous sodium sulfate, the organic phase was spin-dried, washed with petroleum ether, and dried in vacuo at 80 ° C to obtain Yield: 97.2%, reaction formula:

[0141]

[0142] Example 6

[0143] Toluene (150 mL), tetrahydrophthalic anhydride (15.20 g, 0.1 mol) and hydrobromic acid (15.98 g, 0.20 mol) were added to the reactor in sequence, and the mixture was reacted at 40°C for 2 h. The reaction progress was monitored by TLC. After the reaction, saturated aqueous sodium carbonate solution was added to neutralize the excess hydrobromic acid until the solution became neutral. The mixture was extracted with ethyl acetate, and the organic phase was dried over anhydrous sodium sulfate. The organic phase was spin-dried and dried in vacuo at 70°C. Dimethyl sulfoxide (100 mL) and (45.20 g, 0.2 mol) and sodium carbonate (14.84 g, 0.14 mol), react at 70 ° C for 8 h, and track the reaction progress by TLC. After the reaction is completed, water and ethyl acetate are added for extraction, and the organic phase is dried over anhydrous sodium sulfate, and the organic phase is spin-dried and dried in vacuo at 60 ° C; then xylene (120 mL) and (12.79 g, 0.05 mol) and sodium carbonate (13.78 g, 0.13 mol), reacted at 110 ° C for 10 h, TLC tracking the reaction progress, after the reaction was completed, water and ethyl acetate were added for extraction, the organic phase was dried over anhydrous sodium sulfate, the organic phase was spin-dried, washed with petroleum ether, and dried in vacuo at 80 ° C to obtain Yield: 95.4%, reaction formula:

[0144]

[0145] Example 7

[0146] Acetonitrile (150 mL), tetrahydrophthalic anhydride (15.20 g, 0.1 mol) and hydrobromic acid (15.98 g, 0.20 mol) were added to the reactor in sequence, and the mixture was reacted at 40°C for 2 h. The reaction progress was monitored by TLC. After the reaction, saturated aqueous sodium carbonate solution was added to neutralize the excess hydrobromic acid until the solution became neutral. The mixture was extracted with ethyl acetate, and the organic phase was dried over anhydrous sodium sulfate. The organic phase was spin-dried and dried in vacuo at 70°C. Acetonitrile (100 mL) and (47.40 g, 0.2 mol) and sodium carbonate (14.84 g, 0.14 mol), react at 65 ° C for 9 h, and track the reaction progress by TLC. After the reaction is completed, water and ethyl acetate are added for extraction, and the organic phase is dried over anhydrous sodium sulfate, and the organic phase is dried by rotary evaporation and dried in vacuo at 60 ° C; then xylene (120 mL) and (12.79 g, 0.05 mol) and sodium carbonate (13.78 g, 0.13 mol), reacted at 110 ° C for 10 h, TLC tracking the reaction progress, after the reaction was completed, water and ethyl acetate were added for extraction, the organic phase was dried over anhydrous sodium sulfate, the organic phase was spin-dried, washed with petroleum ether, and dried in vacuo at 75 ° C to obtain Yield: 94.4%, reaction formula:

[0147]

[0148] Example 8

[0149] Dimethyl sulfoxide (150 mL), tetrahydrophthalic anhydride (15.20 g, 0.1 mol) and hydrobromic acid (15.98 g, 0.20 mol) were added to the reactor in sequence, and the mixture was reacted at 40°C for 2 h. The reaction progress was monitored by TLC. After the reaction, saturated aqueous sodium carbonate solution was added to neutralize the excess hydrobromic acid until the solution became neutral. The mixture was extracted with ethyl acetate, and the organic phase was dried over anhydrous sodium sulfate. The organic phase was spin-dried and dried in vacuo at 70°C. Tetrahydrofuran (100 mL) and (41.61g, 0.2mol) and sodium hydride (4.80g, 0.2mol), react at 65℃ for 9h, follow the reaction progress by TLC, add water and ethyl acetate to extract after the reaction, dry the organic phase with anhydrous sodium sulfate, spin dry the organic phase, and dry it in vacuum at 60℃; then add acetone (120mL), (12.79 g, 0.05 mol) and sodium carbonate (13.78 g, 0.13 mol), react at 70 ° C for 10 h, TLC to track the reaction progress, after the reaction, add water and ethyl acetate to extract, dry the organic phase with anhydrous sodium sulfate, spin dry the organic phase, wash with petroleum ether, and dry in vacuo at 75 ° C to obtain Yield: 94.4%, reaction formula:

[0150]

[0151] Example 9

[0152] Dimethyl sulfoxide (150 mL), tetrahydrophthalic anhydride (15.20 g, 0.1 mol) and hydrobromic acid (15.98 g, 0.20 mol) were added to the reactor in sequence, and the mixture was reacted at 40°C for 2 h. The reaction progress was monitored by TLC. After the reaction was completed, saturated aqueous sodium carbonate solution was added to neutralize the excess hydrobromic acid until the solution became neutral. The mixture was extracted with ethyl acetate, and the organic phase was dried over anhydrous sodium sulfate. The organic phase was spin-dried and dried under vacuum at 70°C. Tetrahydrofuran (110 mL) and (50.60g, 0.2mol) and sodium hydride (4.80g, 0.2mol), react at 65℃ for 9h, follow the reaction progress by TLC, add water and ethyl acetate to extract after the reaction, dry the organic phase with anhydrous sodium sulfate, spin dry the organic phase, and dry it in vacuo at 60℃; then add acetone (120mL), (12.79 g, 0.05 mol) and sodium carbonate (13.78 g, 0.13 mol) were reacted at 70 °C for 10 h. The reaction progress was monitored by TLC. After the reaction was completed, water and ethyl acetate were added for extraction. The organic phase was dried over anhydrous sodium sulfate, the organic phase was spin-dried, washed with petroleum ether, and dried in vacuo at 65 °C to obtain Yield: 94.4%, reaction formula:

[0153]

[0154] Comparative Example 1

[0155] The photosensitive monomer is a commercially available product: 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (i.e. 6FDA):

[0156]

[0157] Application Examples

[0158] The flexible diformic anhydride photosensitive monomers prepared in Examples 1 to 9 and the photosensitive monomers in Comparative Example 1 were placed in N,N-dimethylformamide with propylene diamine, and stirred evenly in the presence of a polymerization initiator, diphenylacetophenone, wherein the amount of the photosensitive monomer was 1 equiv, the amount of propylene diamine was 2 equiv, the amount of N,N-dimethylformamide was 100 mL, and the amount of the polymerization initiator was 0.2 equiv;

[0159] At UV light intensity 400mJ / cm 2 After irradiation for 10 minutes, the reactant was concentrated by vacuum distillation, and anhydrous methanol was added to produce a precipitate. The insoluble matter was filtered out, and the insoluble matter was rinsed with anhydrous methanol and dried in vacuum at 40°C for 12 hours to obtain the corresponding polyimide polymers 1 to 10, and relevant performance tests were carried out. The test results are shown in Table 1.

[0160] The general structural formula of the polyimide polymer obtained from the flexible dicarboxylic anhydride photosensitive monomer prepared in Examples 1 to 9 is:

[0161]

[0162] In the general formula, n, R1 and R2 correspond to the structural formulas of the flexible diformic anhydride photosensitive monomers prepared in Examples 1 to 9, respectively.

[0163] Among them, the detection methods of relevant performance tests are as follows:

[0164] The test method of light transmittance refers to GB / T 2410-2008;

[0165] The detection method of refractive index refers to GB / T 39691-2020;

[0166] The detection method of haze refers to GB / T 2410-2008;

[0167] The detection method of impedance refers to GB / T 39482.1-2023.

[0168] Table 1

[0169]

[0170]

[0171] The above experimental results show that the polyimide polymer prepared by polymerizing the flexible dicarboxylic anhydride photosensitive monomer of the present invention with propylene diamine has high transmittance and refractive index, low haze, and reduced impedance. It exhibits excellent performance in terms of transmittance, refractive index, haze, impedance, etc., can improve the photoelectric conversion efficiency, reduce transmission loss, and achieve unexpected technical effects.

[0172] It should be understood that the application of the present invention is not limited to the above examples. For ordinary technicians in this field, improvements or changes can be made based on the above description. All these improvements and changes should fall within the scope of protection of the claims attached to the present invention.

Claims

1. A diformic anhydride photosensitive monomer, characterized in that: The structural formula of the diformic anhydride photosensitive monomer is shown in Formula I: wherein n is an integer of 1 to 5, and R1 and R2 are each independently selected from hydrogen, fluorine, nitro, monofluoromethyl, difluoromethyl, trifluoromethyl or trifluoromethoxy.

2. The diformic anhydride photosensitive monomer according to claim 1, characterized in that: The structural formula of the diformic anhydride photosensitive monomer is: One of them.

3. A method for preparing a diformic anhydride photosensitive monomer as claimed in any one of claims 1 to 2, characterized in that: include: The first step: reacting tetrahydrophthalic anhydride as shown in formula II with hydrobromic acid to obtain 5-bromo-tetrahydrophthalic anhydride as shown in formula III; Step 2: subjecting 5-bromo-tetrahydrophthalic anhydride as shown in Formula III to a nucleophilic substitution reaction with substituted 3-hydroxybenzyl alcohol as shown in Formula IV to obtain a 5-((5-hydroxy-2,3-dimethylphenyl)oxy)hexahydroisobenzofuran-1,3-dione derivative as shown in Formula V; Step 3: reacting the 5-((5-hydroxy-2,3-dimethylphenyl)oxy)hexahydroisobenzofuran-1,3-dione derivative shown in Formula V with the dibromoalkane shown in Formula VI through a nucleophilic substitution reaction to obtain a dicarboxylic anhydride photosensitive monomer shown in Formula I; The general reaction formula is as follows: Wherein, n=1-5, wherein R1 and R2 are each independently selected from hydrogen, fluorine, nitro, monofluoromethyl, difluoromethyl, trifluoromethyl or trifluoromethoxy.

4. The preparation method according to claim 3, characterized in that: The structural formula of Formula IV is: One of; And / or, the structural formula of Formula V is: One of; And / or, the structural formula of Formula VI is: One of them.

5. The preparation method according to claim 3, characterized in that: In the first step, the molar ratio of the hydrobromic acid to the tetrahydrophthalic anhydride is (1.5-3):1; The reaction conditions of the first step include: reaction temperature of 0 to 50°C, reaction time of 2 to 12 hours; The first step is to carry out the reaction in the presence of solvent 1; The ratio of the volume of the solvent 1 to the mass of tetrahydrophthalic anhydride is (2-10) mL:1 g; The solvent is selected from at least one of dioxane, toluene, xylene, dimethyl sulfoxide, N,N-dimethylformamide, acetonitrile and tetrahydrofuran; After the first step of reaction is completed, the method further comprises the step of using a neutralizing agent to neutralize excess hydrobromic acid, wherein the neutralizing agent is selected from at least one of sodium carbonate and sodium bicarbonate.

6. The preparation method according to claim 3, characterized in that: The second step is to carry out the reaction in the presence of solvent 2 and catalyst 1; The ratio of the volume of the second solvent to the mass sum of the 5-bromo-tetrahydrophthalic anhydride and the substituted 3-hydroxybenzyl alcohol is (4-12) mL:1 g; The second solvent is selected from at least one of toluene, xylene, dimethyl sulfoxide, N,N-dimethylformamide, acetonitrile, tetrahydrofuran, and acetone; The molar ratio of the catalyst 1 to the 5-bromo-tetrahydrophthalic anhydride is (1.2-3):1; The catalyst is selected from at least one of potassium carbonate, cesium carbonate, triethylamine, sodium hydride, sodium carbonate and sodium bicarbonate.

7. The preparation method according to claim 3, characterized in that: In the second step, the molar ratio of the 5-bromo-tetrahydrophthalic anhydride to the substituted 3-hydroxybenzyl alcohol is 1:(2-5); And / or, the reaction conditions of the second step include: reaction temperature of 60-120° C., reaction time of 2-20 h.

8. The preparation method according to claim 3, characterized in that: The third step is to carry out the reaction in the presence of the catalyst 2 and the solvent 3; The molar ratio of the catalyst 2 to the 5-((5-hydroxy-2,3-dimethylphenyl)oxy)hexahydroisobenzofuran-1,3-dione derivative is (1.2-3):1; The second catalyst is selected from at least one of potassium carbonate, cesium carbonate, triethylamine, sodium hydride, sodium carbonate, and sodium bicarbonate; The ratio of the volume of the solvent three to the mass sum of the 5-((5-hydroxy-2,3-dimethylphenyl)oxy)hexahydroisobenzofuran-1,3-dione derivative and the dibromoalkane is (4-10) mL:1 g; The solvent three is selected from at least one of toluene, xylene, dimethyl sulfoxide, N,N-dimethylformamide, acetonitrile, tetrahydrofuran and acetone.

9. The preparation method according to claim 3, characterized in that: In the third step, the molar ratio of the 5-((5-hydroxy-2,3-dimethylphenyl)oxy)hexahydroisobenzofuran-1,3-dione derivative to the dibromoalkane is (2-5):1; And / or, the reaction conditions of the third step include: reaction temperature of 60-120° C. and reaction time of 2-20 h.

10. Use of the dicarboxylic anhydride photosensitive monomer as claimed in any one of claims 1 to 2 or the dicarboxylic anhydride photosensitive monomer obtained by the preparation method as claimed in any one of claims 3 to 9 as a polymer monomer in the preparation of polyimide.

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