A low-yellowing fluorine-free semi-crystalline polyimide composition and a method for preparing the same

Abstract

The application provides a low-yellowing fluorine-free semi-alicyclic polyimide composition and a preparation method thereof, and relates to the technical field of polyimide preparation.The semi-alicyclic polyimide composition is prepared by polymerization reaction of diamine and dianhydride; the diamine comprises first diamine and second diamine; the first diamine is 4,4'-diamino diphenyl ether-2,2'-disulfonic acid and / or 4-(4-aminophenoxy)-2,6-dimethyl aniline; the second diamine is 4,4'-diamino dicyclohexyl methane and / or 3,3'-dimethyl-4,4'-diamino dicyclohexyl methane; and the dianhydride is fluorine-free dianhydride. The semi-alicyclic polyimide composition prepared by the application significantly improves the optical performance of the polyimide film prepared therefrom, and the anti-yellowing effect is significantly improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of polyimide preparation, in particular to a low-yellowing fluorine-free semi-alicyclic polyimide composition and a preparation method thereof. BACKGROUND

[0002] Polyimide (PI) refers to a kind of polymer containing imide ring in the main chain, and is one of the best organic polymer materials in comprehensive performance. The specific structural characteristics in the molecular structure of PI material, including highly conjugated molecular chain structure, strong molecular chain internal and intermolecular chain interaction and other characteristics, endow this kind of material with excellent comprehensive performance, including low density, light weight, high strength, high and low temperature resistance, excellent chemical corrosion resistance and the like. As a kind of special engineering material, polyimide has been widely used in flexible electronics, electrical engineering, display, new energy and other new industries. In recent years, with the continuous development of human space exploration technology, the application of PI film in the field of aerospace and space exploration is also expanding, and has been gradually applied to solar cell array protective layer, solar sail main material, flexible solar cell substrate, antenna and solar concentrator and other large space deployable structures.

[0003] The development of future optoelectronic devices gradually presents the trend of lightweight, large-scale, ultra-thin and flexible. Glass, as a traditional transparent substrate material, has been unable to meet the development requirements of future flexible packaging technology. High-transparency polymer materials have become the first choice for future flexible optoelectronic packaging substrate materials due to their transparency, flexibility, light weight, high impact resistance and other advantages. Traditional PI film presents brown or yellow due to the presence of high aromatic ring, and its transmittance in the visible light (wavelength 400nm-700nm) range is low. And because it also has high birefringence, it seriously limits its application in the field of optoelectronics, such as optical waveguide materials, optoelectronic packaging materials, photovoltaic materials, nonlinear optical materials, optical edge materials, optoelectronic materials, and alignment film materials in liquid crystal display field.

[0004] The existing colorless transparent polyimide film preparation technology mainly adds fluorine-containing monomers to block or reduce intermolecular and intramolecular electron transition (such as introducing fluorine-containing groups), or reduces the content of aromatic structure in the molecular structure (such as bulky substituents, alicyclic structure, etc.), or avoids or reduces conjugated units by introducing main chain bending structure, asymmetric structure and reducing conjugated double bond structure, reduces the charge transfer effect between molecules or molecules, and improves the light transmittance and transparency of PI film.

[0005] Chinese patent application CN111073008A discloses a preparation method of a low-yellowing colorless transparent polyimide film, including a polymerization reaction of a polyamide acid and / or polyimide resin solution, adding a first yellowing inhibitor and a yellowing catalyst before or after the polymerization reaction, and adding a second yellowing inhibitor to the polyamide acid and / or polyimide resin solution generated after the polymerization reaction. The first yellowing inhibitor is at least one of 1-cyclohexyl-2-(3-furyl)-1H-benzimidazole-5-carboxylic acid, 2-(2-thienyl)-1H-benzimidazole-6-carboxylic acid, and 1-isopropyl-2-(trifluoromethyl)-1H-benzimidazole-5-carboxylic acid; the second yellowing inhibitor is at least one of 2-(3-aminophenyl)-1H-benzimidazole-6-carboxylic acid, 2-(2-aminophenyl)-1H-benzimidazole-6-carboxylic acid, and 2-(4-aminophenyl)-1H-benzimidazole-6-carboxylic acid; and the yellowing catalyst is an amide catalyst.

[0006] “Preparation and performance of low-yellow-index polyimide film” (Wang Yuxuan, Hou Yu, Cheng Zhiguan, et al., Engineering Plastics Application, 1001-3539 (2022) 07-0035-05) discusses the influence of different solvents on the molecular chain structure of polyimide precursor and the performance of the film, and studies the preparation of a low-yellow-index and high-performance polyimide film. Using 2,2'-bis(3,4-dicarboxylic acid) hexafluoropropane dianhydride (6FDA) and 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (TFMB) as reaction monomers, three different solvents: N,N-dimethylacetamide (DMAc), N-methyl pyrrolidone (NMP), and gamma-butyrolactone (GBL) are used, and a two-step method is used to prepare a polyimide film.

[0007] Therefore, through research and development of raw materials and preparation methods, it is still the focus of researchers in the field to prepare new low-yellowing fluorine-free semi-alicyclic polyimide compositions. SUMMARY

[0008] The present application is directed to the above problems, and provides a low-yellowing fluorine-free semi-alicyclic polyimide composition and a preparation method thereof.

[0009] To achieve the above-mentioned purpose, the technical solutions adopted by the present application are as follows:

[0010] In a first aspect, the present application provides a low-yellowing fluorine-free semi-alicyclic polyimide composition prepared by polymerization of diamine and dianhydride;

[0011] The diamine comprises a first diamine and a second diamine.

[0012] the first diamine is 4,4'-diaminodiphenyl ether-2,2'-disulfonic acid (ODADS) and / or 4-(4-aminophenoxy)-2,6-dimethylaniline (APDMA); the second diamine is 4,4'-diaminodicylohexyl methane (DCHM) and / or 3,3'-dimethyl-4,4'-diaminodicylohexyl methane (MDCHM);

[0013] the dianhydride is a fluorine-free dianhydride.

[0014] Preferably, the dianhydride comprises a first dianhydride and a second dianhydride.

[0015] Preferably, the first dianhydride is norbornane-2-spi-α-cyclopentanone-α'-spι-2'-norbornane-5,5',6,6'-tetra carboxylic dianhydride (CpODA) and / or 1,3-dimethyl-cyclobutane-1,2,3,4-tetracarboxylic dianhydride (DM-CBDA).

[0016] Preferably, the second dianhydride is 2,5-bis(3,4-dicarboxyphenoxy)-4'-phenylethynyl biphenyl dianhydride (PEPHQDA) and / or 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride (TDA).

[0017] Preferably, the molar ratio of the total amount of diamines and the total amount of dianhydrides is 0.9-1.1:1.

[0018] Preferably, the molar ratio of the first diamine and the second diamine is 4-6:7-10; further preferably, the molar ratio of the first diamine and the second diamine is 5:8.

[0019] Preferably, the molar ratio of the first dianhydride and the second dianhydride is 2-5:1. Further preferably, the molar ratio of the first dianhydride and the second dianhydride is 3:1.

[0020] Preferably, the polymerization reaction is carried out in the presence of a solvent.

[0021] Further preferably, the organic solvent is selected from at least one of N-methyl-2-pyrrolidone, dimethylacetamide, γ-butyrolactone, dimethylsulfoxide, N,N-dimethylformamide, m-cresol, ethyl acetate, acetone.

[0022] Preferably, the polymerization reaction further comprises an auxiliary agent; the auxiliary agent comprises a composite anti-yellowing agent and a catalyst.

[0023] Preferably, the composite anti-yellowing agent is composed of nanoparticles, 2,2'-methylene-bis[4-t-octyl-6-(2H benzotriazolyl-2)]phenol (UV-360), β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl alcohol (antioxidant 1076) and menthol salicylate.

[0024] Preferably, the nanoparticles are a mixture of nanometer titanium dioxide and nanometer zinc oxide.

[0025] Further preferably, the mass ratio of the nanometer titanium dioxide and nanometer zinc oxide is 3-6:5-9. Further preferably, the mass ratio of the nanometer titanium dioxide and nanometer zinc oxide is 4:7.

[0026] Preferably, the molar ratio of the nanoparticles, 2,2'-methylene-bis[4-t-octyl-6-(2H benzotriazolyl-2)]phenol (UV-360), β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl alcohol (antioxidant 1076) and menthol salicylate is 2-3:2-5:2-5:0.5-1.5.

[0027] Further preferably, the molar ratio of the nanoparticles, 2,2'-methylene-bis[4-t-octyl-6-(2H benzotriazolyl-2)]phenol (UV-360), β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl alcohol (antioxidant 1076) and menthol salicylate is 2.5:3:3:1.5.

[0028] Preferably, the addition amount of the composite anti-yellowing agent is 0.5-3% of the total molar amount of diamine and dianhydride.

[0029] Further preferably, the addition amount of the composite anti-yellowing agent is 1.5% of the total molar amount of diamine and dianhydride.

[0030] Preferably, the catalyst is a mixture of dibutyltin dilaurate and 2-phenylimidazole.

[0031] Preferably, the molar ratio of the dibutyltin dilaurate and 2-phenylimidazole is 2-5:3-8.

[0032] Further preferably, the molar ratio of the dibutyltin dilaurate and 2-phenylimidazole is 4:5.

[0033] Preferably, the addition amount of the catalyst is 0.1-1% of the total molar amount of diamine and dianhydride.

[0034] Further preferably, the addition amount of the catalyst is 0.3% of the total molar amount of diamine and dianhydride.

[0035] In a second aspect, the present application provides a preparation method of the semi-alicyclic polyimide composition, comprising the following steps:

[0036] S1: mixing diamine and dianhydride with solvent to obtain a mixed solution;

[0037] S2: mixing the mixed solution with the composite anti-yellowing agent and catalyst to obtain the semi-alicyclic polyimide composition.

[0038] In a third aspect, the present application provides an application of the semi-alicyclic polyimide composition in preparing a polyimide film.

[0039] Compared with the prior art, the present application has the following beneficial effects:

[0040] 1. The present application realizes the significant improvement of the optical performance of the polyimide film prepared by the semi-alicyclic polyimide composition, and the significant improvement of the anti-yellowing effect, by mixing specific multiple dianhydrides and specific multiple diamines in a specific ratio to prepare the polyimide composition.

[0041] 2. The present application realizes the significant improvement of the optical performance of the polyimide film prepared by the semi-alicyclic polyimide composition, and the effect of reducing the yellowing index, by mixing the composite anti-yellowing agent prepared by the nanoparticles, 2,2'-methylene-bis[4-t-octyl-6-(2H benzotriazolyl-2)]phenol (UV-360), β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl alcohol (antioxidant 1076) and menthol salicylate with the diamine and the dianhydride of the present application. DETAILED DESCRIPTION

[0042] In order to make the technical means, creative features, purposes and effects realized by the present application easy to understand, the present application is further illustrated by specific examples. However, the following examples are only preferred examples of the present application, and are not all. Based on the examples in the embodiments, other examples obtained by those skilled in the art without creative labor are within the protection scope of the present application. It is worth noting that the raw materials used in the present application are all ordinary commercially available products, and their sources are not specifically limited. The technical and scientific terms used in the examples have the meanings generally understood by those skilled in the art to which the present application belongs.

[0043] Nano-titanium dioxide: purchased from Ningbo Jimo Nano New Material Technology Co., Ltd., particle size is 10-30 nm.

[0044] Nano-zinc oxide: purchased from Shanghai Xu Tian New Material Technology Co., Ltd., average particle size is 20 nm.

[0045] Example 1

[0046] A low-yellowing fluorine-free semi-alicyclic polyimide composition is prepared by polymerization reaction of diamine and dianhydride.

[0047] Raw material composition:

[0048] (1) The molar ratio of diamine and dianhydride is shown in Table 1:

[0049] (2) The addition amount of the composite anti-yellowing agent is 1.5% of the total molar amount of diamine and dianhydride, and the specific amount is as follows:

[0050] The mixture is composed of nanoparticles, 2,2'-methylene-bis[4-t-octyl-6-(2H benzotriazolyl-2)] phenol (UV-360), β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl alcohol (antioxidant 1076) and menthol salicylate according to the molar ratio of 2.5:3:3:1.5, wherein the nanoparticles are a mixture of nano-titanium dioxide and nano-zinc oxide (mass ratio of 4:7).

[0051] (3) Catalyst: a mixture of dibutyltin dilaurate and 2-phenylimidazole according to the molar ratio of 4:5, the addition amount is 0.3% of the total molar amount of diamine and dianhydride.

[0052] Preparation method:

[0053] S1: The diamine and dianhydride are stirred with the solvent N-methyl-2-pyrrolidone for 20 min to obtain a mixed solution;

[0054] S2: The mixed solution is stirred with the composite anti-yellowing agent and the catalyst for 30 min to obtain the product.

[0055] Example 2

[0056] A low-yellowing fluorine-free semi-alicyclic polyimide composition is prepared by polymerization reaction of diamine and dianhydride;

[0057] Raw material composition:

[0058] (1) The molar ratio of diamine and dianhydride is shown in Table 1:

[0059] (2) The addition amount of the composite anti-yellowing agent is 0.5% of the total molar amount of diamine and dianhydride, and the specific amount is as follows:

[0060] The mixture is composed of nanoparticles, 2,2'-methylene-bis[4-t-octyl-6-(2H benzotriazolyl-2)] phenol (UV-360), β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl alcohol (antioxidant 1076) and menthol salicylate according to the molar ratio of 2:2:2:0.5, wherein the nanoparticles are a mixture of nano-titanium dioxide and nano-zinc oxide (mass ratio of 3:5).

[0061] (3) Catalyst: a mixture of dibutyltin dilaurate and 2-phenylimidazole with a molar ratio of 2:3, and the addition amount is 0.1% of the total molar amount of diamine and dianhydride.

[0062] Preparation method:

[0063] S1: The diamine and dianhydride were stirred with the solvent dimethyl sulfoxide for 20 min to obtain a mixed solution;

[0064] S2: The mixed solution was stirred with the composite anti-yellowing agent and the catalyst for 30 min to obtain the product.

[0065] Example 3

[0066] A low-yellowing fluorine-free semi-alicyclic polyimide composition prepared by polymerization reaction of diamine and dianhydride;

[0067] Raw material composition:

[0068] (1) The diamine and dianhydride and the molar ratio are shown in Table 1:

[0069] (2) The addition amount of the composite anti-yellowing agent is 3% of the total molar amount of diamine and dianhydride, and the specific amount is as follows:

[0070] A mixture of nanoparticles, 2,2'-methylene-bis[4-t-octyl-6-(2H benzotriazolyl-2)] phenol (UV-360), β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl alcohol (antioxidant 1076), and menthol salicylate with a molar ratio of 3:5:5:1.5, wherein the nanoparticles are a mixture of nano-titanium dioxide and nano-zinc oxide (mass ratio of 5:8).

[0071] (3) Catalyst: a mixture of dibutyltin dilaurate and 2-phenylimidazole with a molar ratio of 2:3, and the addition amount is 1% of the total molar amount of diamine and dianhydride.

[0072] Preparation method:

[0073] S1: The diamine and dianhydride were stirred with the solvent N,N-dimethylformamide for 20 min to obtain a mixed solution;

[0074] S2: The mixed solution was stirred with the composite anti-yellowing agent and the catalyst for 30 min to obtain the product.

[0075] Example 4

[0076] A low-yellowing fluorine-free semi-alicyclic polyimide composition prepared by polymerization reaction of diamine and dianhydride;

[0077] Raw material composition:

[0078] (1) The diamine and dianhydride and the molar ratio are shown in Table 1:

[0079] The rest is the same as Example 1.

[0080] Example 5

[0081] A low-yellowing fluorine-free semi-alicyclic polyimide composition prepared by polymerization of diamine and dianhydride;

[0082] Raw material composition:

[0083] (1) The diamine and dianhydride and the molar ratio are as shown in Table 1:

[0084] The rest is the same as Example 1.

[0085] Example 6

[0086] A low-yellowing fluorine-free semi-alicyclic polyimide composition prepared by polymerization of diamine and dianhydride;

[0087] Raw material composition:

[0088] (1) The diamine and dianhydride and the molar ratio are as shown in Table 1:

[0089] The rest is the same as Example 1.

[0090] Table 1. Diamine and dianhydride of Examples 1-6

[0091]

[0092] Comparative Example 1

[0093] A low-yellowing fluorine-free semi-alicyclic polyimide composition prepared by polymerization of diamine and dianhydride;

[0094] Only the first diamine and the second diamine are changed compared with Example 1, as shown in Table 2.

[0095] The rest is the same as Example 1.

[0096] Comparative Example 2

[0097] A low-yellowing fluorine-free semi-alicyclic polyimide composition prepared by polymerization of diamine and dianhydride;

[0098] Only the first dianhydride and the second dianhydride are changed compared with Example 1, as shown in Table 2.

[0099] The rest is the same as Example 1.

[0100] Comparative Example 3

[0101] A low-yellowing fluorine-free semi-alicyclic polyimide composition prepared by polymerization of diamine and dianhydride;

[0102] Comparing with example 1, only the component of the composite anti-yellowing agent is changed, which is as follows:

[0103] The adding amount of the composite anti-yellowing agent is 1.5% of the total mole of the diamine and dianhydride, which is as follows:

[0104] The mixture is composed of nano zinc oxide, 2-(2'-hydroxy-3',5'-dipentyl phenyl) benzotriazole (UV-328), antioxidant 1010 and menthol salicylate according to the molar ratio of 2.5:3:3:1.5.

[0105] The rest is consistent with example 1.

[0106] Comparative example 4

[0107] A low-yellowing fluorine-free semi-alicyclic polyimide composition is prepared by polymerization reaction of diamine and dianhydride;

[0108] Comparing with example 1, only the catalyst is changed, which is as follows:

[0109] The catalyst is a mixture of triethylamine and pyridine according to the molar ratio of 4:5, and the adding amount is 0.3% of the total mole of the diamine and dianhydride.

[0110] The rest is consistent with example 1.

[0111] Comparative example 5

[0112] A low-yellowing fluorine-free semi-alicyclic polyimide composition is prepared by polymerization reaction of diamine and dianhydride;

[0113] Comparing with example 1, the ratio of raw materials is changed, which is as follows:

[0114] (1) The molar ratio of the diamine and dianhydride is shown in table 2:

[0115] (2) The adding amount of the composite anti-yellowing agent is 4% of the total mole of the diamine and dianhydride, which is as follows:

[0116] The mixture is composed of nanoparticles, 2,2'-methylene-bis[4-t-octyl-6-(2H benzotriazolyl-2)] phenol (UV-360), β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl alcohol (antioxidant 1076) and menthol salicylate according to the molar ratio of 1:1:1:0.1, wherein the nanoparticles are a mixture of nano titanium dioxide and nano zinc oxide (mass ratio of 7:4).

[0117] (3) The catalyst is a mixture of dibutyl tin dilaurate and 2-phenyl imidazole according to the molar ratio of 1:1, and the adding amount is 1.2% of the total mole of the diamine and dianhydride.

[0118] Preparation method:

[0119] S1: The diamine and dianhydride were stirred with the solvent N-methyl-2-pyrrolidone for 20 min to obtain a mixture;

[0120] S2: The mixture was stirred with the composite anti-yellowing agent and catalyst for 30 min to obtain the product.

[0121] Table 2. Diamines and dianhydrides of Example 1 and Comparative Examples 1-5

[0122]

[0123] Test Example

[0124] The semi-alicyclic polyimide compositions prepared from Example 1-Example 5 and Comparative Examples 1-Comparative Example 5 were prepared into polyimide films, which were then tested as follows.

[0125] The preparation method was as follows:

[0126] The semi-alicyclic polyimide compositions prepared from Example 1-Example 5 and Comparative Examples 1-Comparative Example 5 were mixed with the solvent DMAc to obtain a precursor solution, which was then coated onto a PET substrate with a thickness of 250 pm using an automatic coating machine, and then placed in an oven at 60°C for 8 min, and then transferred to an inert gas oven, and imidized at a high temperature of 260°C for 30 min to obtain the product.

[0127] The film performance test method was as follows:

[0128] (1) The light transmittance (Tr 550 nm), yellowness index, and haze of the polyimide film were tested using an X-rite Ci7800 spectrophotometer.

[0129] (2) The tensile strength, elongation at break, and elastic modulus of the polyimide film were tested using a Shimadzu AG-X plus, 1 KN, at a test speed of 5 mm / min, with a sample size of 10 mm wide * 15 mm long, a test gauge of 50 mm, and a gauge length of 20 mm.

[0130] (3) The glass transition temperature (Tg) was measured using a dynamic mechanical analyzer (DMA850) under the following test conditions:

[0131] The measurement was performed at a load of 0.05 N and a heating rate of 3°C / min under a nitrogen atmosphere in the temperature range of 200-400°C, and the inflection point of the curve with the maximum value was recorded as the glass transition temperature.

[0132] (4) Thermal shrinkage (dimensional stability) was tested according to GB / T 13542.2-2009 "Films for electrical insulation - Part 2: Test methods" (150℃), and the testing instrument was E04501 type 2.5 dimension (CNC image testing instrument).

[0133] The results are shown in Table 3.

[0134] Table 3. Film performance test results

[0135]

[0136] As shown in Table 3, the polyimide film prepared from the semi-alicyclic polyimide composition prepared by the embodiment of the present application has good optical transmittance, heat resistance, and good mechanical properties, and the yellowing index is significantly reduced.

[0137] Finally, it should be noted that the above content is only used to illustrate the technical solutions of the present application, and is not a limitation on the protection scope of the present application. Simple modifications or equivalent replacements of the technical solutions of the present application made by those skilled in the art do not deviate from the essence and scope of the technical solutions of the present application.

Claims

1. A low-yellowing, fluorine-free hemicyclic polyimide composition, characterized in that, Prepared by polymerization of diamine and dianhydride; The diamine is a first diamine and a second diamine; The first diamine is 4,4'-diaminodiphenyl ether-2,2'-disulfonic acid and / or 4-(4-aminophenoxy)-2,6-dimethylaniline; the second diamine is 4,4'-diaminodicyclohexylmethane and / or 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane. The dianhydride is a fluorine-free dianhydride; the dianhydride is a first dianhydride and a second dianhydride; the first dianhydride is norbornane-2-spiro-α-cyclopentanone-α'-spiro-2'-norbornane-5,5',6,6'-tetracarboxylic acid dianhydride and / or 1,3-dimethyl-cyclobutane-1,2,3,4-tetracarboxylic acid dianhydride; the second dianhydride is 2,5-bis(3,4-dicarboxyphenoxy)-4'-phenylethynylbiphenyl dianhydride and / or 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthous succinic acid dianhydride; the molar ratio of the first dianhydride and the second dianhydride is 2-5:1; the molar ratio of the total amount of diamine to the total amount of dianhydride is 0.9-1.1:1; the molar ratio of the first diamine to the second diamine is 4-6:7-10.

2. The hemicyclic polyimide composition according to claim 1, characterized in that, The polymerization reaction is carried out in the presence of a solvent; the solvent is selected from N-methyl-2-pyrrolidone, dimethylacetamide, γ-butyrolactone, dimethyl sulfoxide, N,N At least one of dimethylformamide, m-cresol, ethyl acetate, and acetone.

3. The hemicyclic polyimide composition according to claim 1, characterized in that, The polymerization reaction further includes auxiliaries; the auxiliaries include a composite anti-yellowing agent and a catalyst; the amount of the composite anti-yellowing agent added is 0.5-3% of the total molar amount of diamine and dianhydride; the amount of the catalyst added is 0.1-1% of the total molar amount of diamine and dianhydride.

4. The hemicyclic polyimide composition according to claim 3, characterized in that, The composite anti-yellowing agent is composed of nanoparticles, 2,2'-methylene-bis[4-tert-octyl-6-(2H-benzotriazolyl-2)]phenol, β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate n-octadecyl alcohol, and menthol salicylate; the molar ratio of the nanoparticles, 2,2'-methylene-bis[4-tert-octyl-6-(2H-benzotriazolyl-2)]phenol, β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate n-octadecyl alcohol, and menthol salicylate is 2-3:2-5:2-5:0.5-1.

5.

5. The hemicyclic polyimide composition according to claim 4, characterized in that, The nanoparticles are a mixture of nano-titanium dioxide and nano-zinc oxide; the mass ratio of nano-titanium dioxide to nano-zinc oxide is 3-6:5-9.

6. The hemicyclic polyimide composition according to claim 3, characterized in that, The catalyst is dibutyltin dilaurate and 2 A mixture of phenylimidazoles; the dibutyltin dilaurate and 2 The molar ratio of phenylimidazole is 2-5:3-8.

7. A method for preparing the hemicyclic polyimide composition according to any one of claims 1-6, characterized in that, Includes the following steps: S1: Diamine and dianhydride are mixed with solvent to obtain a mixture; S2: The mixture is obtained by mixing the mixed liquid with the composite anti-yellowing agent and catalyst.

8. Use of the hemicyclic polyimide composition according to any one of claims 1-6 in the preparation of polyimide films.

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