CN113292727B - Ultraviolet radiation resistant polyimide and preparation method thereof - Google Patents

Ultraviolet radiation resistant polyimide and preparation method thereof Download PDF

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CN113292727B
CN113292727B CN202110495574.0A CN202110495574A CN113292727B CN 113292727 B CN113292727 B CN 113292727B CN 202110495574 A CN202110495574 A CN 202110495574A CN 113292727 B CN113292727 B CN 113292727B
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diamine monomer
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张清华
张家霖
董晗
邹合权
郝一帆
郑森森
赵昕
董杰
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Donghua University
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    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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Abstract

The invention relates to ultraviolet radiation resistant polyimide and a preparation method thereof. The method comprises the following steps: under the protection of nitrogen or argon, dissolving diamine monomer containing ortho-hydroxyl benzophenone structure or diamine monomer containing ortho-hydroxyl benzophenone structure and other diamine monomers and dianhydride monomer in polar aprotic solvent, stirring to react, and then carrying out thermal cyclization or chemical cyclization on the obtained polyimide stock solution. The method is simple and easy to obtain, is suitable for industrial production, can obtain the polyimide material with required special performance by reasonably adjusting the variety and the proportion of the comonomer, and further expands the application range of the material; the prepared polyimide has excellent ultraviolet irradiation resistance and mechanical properties.

Description

Ultraviolet radiation resistant polyimide and preparation method thereof
Technical Field
The invention belongs to the technical field of material science, and particularly relates to ultraviolet radiation resistant polyimide and a preparation method thereof.
Background
In recent years, with the continuous development of the aerospace field, the requirements on the material performance are higher and higher. The objective factors of high load, large change of the internal and external pressure difference in the lifting process, strong action of ultraviolet radiation and ozone in the service environment, large temperature difference between day and night and the like all provide more rigorous requirements for service materials. Currently, aromatic polyester (Vectran), aromatic polyamide fiber (Kevlar), poly (p-Phenylene Benzobisoxazole) (PBO), ultra-high molecular weight polyethylene (Spectra), and the like are mainly used. Although Kevlar and PBO have higher mechanical properties and dimensional stability compared with Vectran, the strong ultraviolet absorption effect of benzoxazole and amide structural units contained in a molecular chain structure can accelerate the degradation under ultraviolet irradiation, and the service life and comprehensive properties of the material are influenced.
An Aromatic Polyimide (PI) molecular chain contains an imide ring, and the polyimide is a special high polymer material with excellent comprehensive performance. The molecular chain structure with high rigidity endows the material with the advantages of excellent mechanical property, thermal stability, irradiation resistance and the like, has lower thermal expansion coefficient and dielectric constant, and is widely applied to the high and new technical fields of aerospace, national defense construction, microelectronics and the like. Because of the higher electron cloud packing density in the molecule, polyimide has better radiation resistance, and is one of the representatives of organic polymer materials with better ultraviolet radiation resistance. However, under the irradiation of high-intensity and long-term ultraviolet rays, the surface of the material still inevitably undergoes photochemical reaction, which causes degradation and aging of chemical structures, and leads to the reduction of related properties of the material. Therefore, the method has important significance for modifying the ultraviolet radiation resistance of the polyimide material.
At present, chinese patent CN105348750A discloses a heat-insulating ultraviolet-proof automobile film and a preparation method thereof, which specifically comprises compounding polyimide and nano zinc oxide coated by nano cerium dioxide to improve the ultraviolet resistance and heat resistance of the material. Chinese patent No. 103255501A discloses a preparation method of ultraviolet-resistant polyimide fibers, which specifically comprises the steps of adding one or more of triazole type, benzophenone type or hindered amine type organic light stabilizers into polyamide acid spinning solution, forming by a wet spinning method, a dry spinning method or a dry-jet wet spinning method, and obtaining the ultraviolet-resistant polyimide fibers through cyclization and hot drawing. Chinese patent CN110845345A discloses an ultraviolet resistant aromatic diamine monomer and a preparation method thereof, which specifically comprises the following steps: the side chain of aromatic diamine is introduced into the structure of ortho-position hydroxy benzophenone, and the polyimide obtained by polymerization with dianhydride monomer has improved ultraviolet resistance. In the method, most of inorganic ultraviolet shielding agents or organic ultraviolet absorbers are used as ultraviolet radiation resistant objects to be doped into corresponding polyimide materials, so that the ultraviolet radiation resistance of the polyimide materials is improved. The problem of poor dispersibility in polyimide materials is difficult to completely solve due to the large specific surface area of the nano particles using the inorganic ultraviolet shielding agent, so that the uniform polyimide materials with stable performance cannot be prepared. The added organic ultraviolet absorbent can volatilize at high temperature, so that the heat resistance is poor, and meanwhile, the surface compactness of the material is not facilitated, so that the ultraviolet irradiation resistance of the polyimide material is reduced. The preparation of the intrinsic ultraviolet radiation resistant polyimide can effectively solve the problems, and the introduction of an o-hydroxybenzophenone structure into a side chain of a polyimide structure is reported at present, but the introduction of a large side chain can damage the original polymerization degree and aggregation state structure of the polyimide, has adverse effects on the mechanical properties, heat resistance and the like of the material, and the ultraviolet resistance improvement effect is not ideal. Therefore, the introduction of ultraviolet absorption and dissipation groups into the main chain structure of polyimide is of great importance for preparing a material with excellent mechanical properties and ultraviolet irradiation resistance.
Disclosure of Invention
The invention aims to solve the technical problem of providing a polyimide with ultraviolet radiation resistance and a preparation method thereof, so as to overcome the defects of poor ultraviolet radiation resistance and poor mechanical property of polyimide materials in the prior art.
The invention provides ultraviolet radiation resistant polyimide, which is prepared from a diamine monomer containing an ortho-position hydroxybenzophenone structure, wherein the structural formula of the diamine monomer containing the ortho-position hydroxybenzophenone structure comprises:
Figure BDA0003054126570000021
wherein R is OH or H.
The invention also provides a preparation method of the ultraviolet radiation resistant polyimide, which comprises the following steps:
under the protection of nitrogen or argon, dissolving diamine monomer containing an ortho-position hydroxyl benzophenone structure or diamine monomer containing an ortho-position hydroxyl benzophenone structure and other diamine monomers and dianhydride monomers in a polar aprotic solvent, stirring for reaction to obtain polyamic acid stock solution, and then carrying out cyclization to obtain ultraviolet radiation resistant polyimide, wherein the molar ratio of the diamine monomer containing the ortho-position hydroxyl benzophenone structure to the other diamine monomers is 1:9 to 10:0, the ratio of the total molar amount of the diamine monomer to the total molar amount of the dianhydride monomer is 1.9-1, and the structural formula of the diamine monomer containing the ortho-hydroxy benzophenone structure comprises:
Figure BDA0003054126570000022
wherein R is OH or H.
Preferably, in the above method, the other diamine monomer comprises:
Figure BDA0003054126570000031
Figure BDA0003054126570000032
Figure BDA0003054126570000033
one or more of them.
Preferably, in the above method, the dianhydride monomer comprises:
Figure BDA0003054126570000034
Figure BDA0003054126570000035
Figure BDA0003054126570000036
one or more of them.
Preferably, in the above method, the method for preparing the diamine monomer containing an ortho-hydroxybenzophenone structure comprises:
(a) Reacting 4-aminophenol or 3-aminophenol with acetic anhydride in deionized water to obtain acetamidophenol, wherein the molar ratio of the 4-aminophenol or 3-aminophenol to the acetic anhydride is (0.8-1.25): 1;
(b) Adding Lewis acid into the acetamidophenol and the nitrobenzoyl chloride in the step (a) in an anhydrous solvent, and obtaining an ortho-Fries rearrangement product through Friedel-crafts acylation reaction, wherein the nitrobenzoyl chloride comprises one or more of 3-nitrobenzoyl chloride, 4-nitrobenzoyl chloride, 2-hydroxy-3-nitrobenzoyl chloride and 2-hydroxy-4-nitrobenzoyl chloride, and the molar ratio of the acetamidophenol, the Lewis acid and the nitrobenzoyl chloride is (0.8-1.25): (1.25-3.25): 1;
(c) Hydrolyzing the product of the ortho Fries rearrangement in the step (b) under an acidic condition, dissolving the obtained hydrolysis product in a solvent under the protection of nitrogen or argon, and adding a reducing agent for reduction reaction to obtain the diamine monomer containing the ortho-hydroxybenzophenone structure.
More preferably, in the above method, the reaction temperature in the step (a) is 5 to 95 ℃ and the reaction time is 0.5 to 12 hours.
More preferably, in the above method, the anhydrous solvent in step (b) comprises one or more of dichloromethane, trichloromethane, 1, 2-dichloroethane, carbon disulfide, carbon tetrachloride, chlorobenzene and nitrobenzene.
More preferably, in the above method, the lewis acid in step (b) includes one or more of anhydrous aluminum chloride, anhydrous zinc chloride, titanium tetrachloride and ferric chloride.
More preferably, in the above method, the temperature of the friedel-crafts acylation reaction in the step (b) is 40 ℃ to 180 ℃ and the time is 8h to 24h.
More preferably, in the above method, the reaction solution obtained by friedel-crafts acylation reaction in the step (b) (following the progress of the reaction by thin layer chromatography) is cooled to room temperature, and then added into a hydrochloric acid-ice water system, separated, dried over anhydrous magnesium sulfate, and concentrated in solvent to obtain a refined product.
More preferably, in the above method, the acidic condition in the step (c) is under dilute hydrochloric acid acidic condition; the hydrolysis is as follows: refluxing for 3-5 h.
More preferably, in the above method, the solvent in step (c) comprises one or more of methanol, ethanol, tetrahydrofuran, ethyl acetate and 1, 4-dioxane.
More preferably, in the above method, the reducing agent in step (c) comprises at least one of stannous chloride, ferric chloride, palladium/carbon; the reduction reaction temperature is 25-80 ℃. The reduction reaction time depends on specific reaction substrates and reaction conditions, the specific reaction time adopts Thin Layer Chromatography (TLC) to track the reaction progress, and the industrial preparation can be tracked by High Performance Liquid Chromatography (HPLC).
More preferably, in the above method, after the reduction reaction in step (c) is cooled to room temperature, a saturated sodium bicarbonate solution is added dropwise until the reaction is weakly alkaline, thereby terminating the reaction; and (3) separating the reaction liquid obtained by reduction, drying by using anhydrous sodium carbonate, carrying out rotary evaporation and concentration to obtain a crude product, and recrystallizing to obtain the diamine monomer containing the ortho-hydroxy benzophenone structure.
Preferably, in the above method, the polar aprotic solvent comprises one or more of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, and dimethylsulfoxide.
Preferably, in the above method, the total mass of the diamine monomer and the dianhydride monomer accounts for 10 to 28wt% of the total mass of the diamine monomer, the dianhydride monomer and the polar aprotic solvent.
Preferably, in the method, the stirring reaction temperature is 5-45 ℃, and the stirring reaction time is 8-24 h.
Preferably, in the above method, the cyclization includes thermal cyclization or chemical cyclization, and the process parameters of the thermal cyclization are: the temperature is raised to 90 to 110 ℃, 180 to 210 ℃ and 280 to 320 ℃ and the mixture is respectively kept for 0.8 to 1.5 hours.
The invention also provides application of the ultraviolet radiation resistant polyimide in an ultraviolet radiation resistant material.
Chinese patent CN110669337B and Chinese patent CN110863258B disclose that the introduction of o-hydroxybenzophenone structure on polyimide main chain is carried out by etherification reaction of substituted nitrobenzene under alkaline condition, friedel-crafts acylation, reduction reaction to obtain diamine monomer containing o-hydroxybenzophenone structure, although this method introduces ultraviolet absorbing group o-hydroxybenzophenone, ether linkage is inevitably introduced at the same time. The ether bond is easy to break under the ultraviolet irradiation condition, and can be subjected to degradation reaction before the imide ring, so that the improvement effect of the polyimide has certain limitation. The diamine monomer related by the invention is directly subjected to Friedel-crafts acylation and reduction reaction through structural design to obtain the diamine monomer containing the ortho-hydroxy benzophenone structure, and the monomer has the advantages of simple structure, high design efficiency and no introduction of any other unfavorable groups. Meanwhile, due to the regular structure of the diamine monomer, the crystallization of polyimide is facilitated, and the ultraviolet irradiation resistance, the mechanical property and the like are greatly improved.
Advantageous effects
(1) According to the invention, the aromatic diamine monomer containing the ortho-position hydroxybenzophenone structure is prepared through molecular structure design, an ultraviolet absorption group is introduced into the main chain of the polyimide high molecular material, an intramolecular hydrogen bond is formed between a ketone carbonyl group and the ortho-position hydroxyl group, ultrafast conversion is realized between a ketone structure and an enol structure, low-wavelength and high-energy ultraviolet radiation is rapidly dissipated without damaging the structure, the intrinsic ultraviolet radiation resistance of the material can be greatly improved, and the polyimide with excellent intrinsic ultraviolet radiation resistance is obtained.
(2) According to the invention, diamine containing an ortho-hydroxy benzophenone structure is designed, and an ultraviolet absorption group is introduced into a main chain of a polyimide structure, so that the polyimide material has obvious advantages in mechanical properties and the like compared with doping or introducing a side chain absorption group.
(3) The invention is simple and easy to obtain, is suitable for industrial production, can obtain the polyimide material with required special performance by reasonably adjusting the variety and the proportion of the comonomer, and further expands the application range of the material.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention can be made by those skilled in the art after reading the teaching of the present invention, and these equivalents also fall within the scope of the claims appended to the present application.
The raw materials used in the following examples of the present invention are all commercially available products.
The polyimide film adopts an Instron 5969 type electronic universal material testing machine to represent the tensile property of the polymer film, and the test is carried out at room temperature, wherein the width of a sample is 5mm, the original gauge length is 40mm, and the tensile rate is 20mm/min. Each group was tested more than 10 times and averaged.
The mechanical property of the polyimide fiber is tested by an XQ-1 single fiber strength instrument, and the fiber number is tested by an XD-1 type fiber number instrument. Each group was tested more than 15 times and averaged.
Example 1
(1) 32.73g (0.30 mol) of 3-aminophenol and 300mL of deionized water were added to an Erlenmeyer flask, followed by addition of 32mL of acetic anhydride in portions, and stirred well. And after reacting for 2 hours, transferring the reaction mixture into a beaker, cooling, performing suction filtration, and washing to obtain a crude product N- (3-hydroxyphenyl) acetamide. Transferring the crude product into a beaker, adding a proper amount of deionized water to prepare a saturated solution at 80 ℃, adding excessive deionized water with the concentration of 20%, adding 2g of activated carbon, boiling, filtering while the solution is hot, cooling, crystallizing, filtering, washing with a small amount of deionized water, and drying in a forced air oven at 60 ℃ to obtain refined N- (3-hydroxyphenyl) acetamide with the yield of 91%.
1 H-NMR(600MHz,DMSO-d 6 )δ＝9.78(s,1H),δ＝9.32(s,1H),δ＝7.18(d,J＝1.8Hz,1H),δ＝7.03(t,J＝8.0Hz,1H),6.91(d,J＝8.0Hz,1H),6.46-6.34(m,1H),2.00(s,3H)。
(2) 15.12g (0.1 mol) of N- (3-hydroxyphenyl) acetamide, 33.34g (0.25 mol) of anhydrous aluminum trichloride, 350mL1, 2-dichloroethane and 16.70g (0.09 mol) of 4-nitrobenzoyl chloride were successively added to a reaction flask, and stirred under reflux for 15 hours. Then pouring into hydrochloric acid-ice water solution while stirring, filtering to obtain a product, washing with deionized water and saturated sodium bicarbonate solution in sequence to obtain a crude product, and recrystallizing with ethanol to obtain 17.50g of a refined product of N- (3-hydroxy-4- (4-nitrobenzoyl) phenyl) acetamide, wherein the yield is 64.8%.
1 H-NMR(600MHz,DMSO-d 6 )δ＝11.12(s,1H),δ＝10.31(s,1H),δ＝8.37-8.32(m,1H),δ＝7.92-7.86(m,2H),δ＝7.52(d,J＝2.0Hz,1H),δ＝7.41(d,J＝8.6Hz,1H),δ＝7.04(dd,J＝8.6,2.0Hz,1H),δ＝2.09(s,3H)。
(3) 12.01g (0.04 mol) of N- (3-hydroxy-4- (4-nitrobenzoyl) phenyl) acetamide was dissolved in 60mL of 20% dilute hydrochloric acid and refluxed for 4 hours, cooled, neutralized with a saturated sodium bicarbonate solution, filtered by suction, and the product was recrystallized from methanol to give 8.78g of purified (4-amino-2-hydroxyphenyl) (4-nitrophenyl) methanone in 85% yield.
1 H-NMR(600MHz,DMSO-d 6 )δ＝12.65(s,1H),δ＝8.37-8.32(m,2H),δ＝7.83-7.79(m,2H),δ＝7.09(d,J＝8.8Hz,1H),δ＝6.74(s,2H),δ＝6.14(dd,J＝8.9,2.1Hz,1H),δ＝6.05(d,J＝2.1Hz,1H)。
(4) 7.15g (0.03 mol) (4-amino-2-hydroxyphenyl) (4-nitrophenyl) methanone, 0.71g Pd/C and 60mL methanol were added in sequence to a reaction flask, stirred well, 10mL85% hydrazine hydrate was slowly added dropwise, heated to reflux, and reacted for 12h. The mixture is filtered while the mixture is hot, filtrate is concentrated by rotary evaporation and washed by 300mL of deionized water, a crude product (4-amino-2-hydroxyphenyl) (4-aminophenyl) ketone is obtained, and the crude product (4-amino-2-hydroxyphenyl) (4-aminophenyl) ketone is recrystallized by ethanol to obtain 5.85g of a refined product (4-amino-2-hydroxyphenyl) (4-aminophenyl) ketone (the structural formula is shown in the specification), wherein the yield is 85 percent.
Figure BDA0003054126570000061
1 H-NMR(600MHz,DMSO-d 6 )δ＝13.14(s,1H),δ＝7.38(d,J＝8.3Hz,2H),δ＝7.33(d,J＝8.7Hz,1H),δ＝6.61(d,J＝8.2Hz,2H),δ＝6.30(s,2H),δ＝6.15-6.09(m,1H),δ＝6.01(d,J＝2.2Hz,1H),δ＝5.90(s,2H)。
(5) Under the protection of nitrogen, 200mL of N, N-dimethylacetamide (DMAc) and 14.38g (0.063 mol) of (4-amino-2-hydroxyphenyl) (4-aminophenyl) ketone are sequentially added into a three-neck flask, fully stirred and dissolved, then 18.54g (0.063 mol) of 3,3', 4' -o-phthalic acid dianhydride (BPDA) is added, stirred for 12 hours at the temperature of 5 ℃ to obtain a polyamic acid stock solution, a film is formed by a tape casting method, and the polyamic acid stock solution is heated to 100 ℃, 200 ℃ and 300 ℃ and respectively kept for 1 hour to obtain a polyimide film with the tensile strength of 180MPa, the elastic modulus of 4.8GPa and the elongation at break of 7.0 percent. After 168h, 16mV/cm 2 The intensity retention rate of the intensity by xenon lamp irradiation is 95%, and the modulus retention rate is 109%.
Example 2
(1) 21.82g (0.20 mol) of 3-aminophenol and 200mL of deionized water were added to an Erlenmeyer flask, followed by addition of 23mL of acetic anhydride in portions, and stirred well. And after the reaction is carried out for 1h, transferring the reaction mixture into a beaker, cooling, carrying out suction filtration, and washing to obtain a crude product N- (3-hydroxyphenyl) acetamide. Transferring the crude product into a beaker, adding a proper amount of deionized water to prepare a saturated solution at 80 ℃, adding excessive 20 percent of deionized water, adding 1.5g of activated carbon, boiling, filtering while the solution is hot, cooling, crystallizing, filtering, washing with a small amount of deionized water, and drying in a forced air oven at 60 ℃ to obtain refined N- (3-hydroxyphenyl) acetamide with the yield of 90 percent.
1 H-NMR(600MHz,DMSO)δ＝9.78(s,1H),δ＝9.32(s,1H),δ＝7.18(d,J＝1.8Hz,1H),δ＝7.03(t,J＝8.0Hz,1H),6.91(d,J＝8.0Hz,1H),6.46-6.34(m,1H),2.00(s,3H)。
(2) 18.14g (0.12 mol) of N- (3-hydroxyphenyl) acetamide, 48.00g (0.36 mol) of anhydrous aluminum trichloride, 250mL1, 2-dichloroethane and 18.56g (0.10 mol) of 3-nitrobenzoyl chloride were successively charged into a reaction flask and stirred under reflux for 10 hours. Then pouring into hydrochloric acid-ice water solution while stirring, filtering to obtain a product, washing with deionized water and saturated sodium bicarbonate solution in sequence to obtain a crude product, and recrystallizing with ethanol to obtain 15.20g of a refined product of N- (3-hydroxy-4- (3-nitrobenzoyl) phenyl) acetamide with the yield of 50.6%.
(3) 12.61g (0.042 mol) of N- (3-hydroxy-4- (3-nitrobenzoyl) phenyl) acetamide was dissolved in 60mL of 20% dilute hydrochloric acid and refluxed for 3 hours, and after cooling, the product was neutralized with a saturated sodium bicarbonate solution, and the suction-filtered product was recrystallized from methanol to obtain 9.76g of purified (4-amino-2-hydroxyphenyl) (3-nitrophenyl) methanone with a yield of 90%.
(4) 7.15g (0.03 mol) (4-amino-2-hydroxyphenyl) (3-nitrophenyl) methanone, 120mL ethanol and 45.02g (0.20 mol) stannous chloride dihydrate were added in sequence to a reaction flask, and the mixture was stirred well under reflux conditions and reacted for 2 hours. After cooling to room temperature, saturated sodium bicarbonate solution was added to adjust the pH to be alkaline, ethyl acetate extraction was performed, liquid separation was performed, anhydrous sodium carbonate was dried, and rotary evaporation and concentration were performed to obtain a crude product (4-amino-2-hydroxyphenyl) (3-aminophenyl) methanone, and ethanol was recrystallized to obtain a refined product (4-amino-2-hydroxyphenyl) (3-aminophenyl) methanone 5.48g, with a yield of 80%.
Figure BDA0003054126570000081
(5) Under the protection of nitrogen, 120mL of N-methylpyrrolidone (NMP) and 7.53g (0.033 mol) of (4-amino-2-hydroxyphenyl) (3-aminophenyl) methanone are sequentially added into a three-neck flask, fully stirred and dissolved, then 10.00g (0.034 mol) of 3,3', 4' -o-phthalic acid dianhydride (BPDA) is added, stirred for 15 hours at the temperature of 5 ℃ to obtain a polyamic acid stock solution, a casting method is adopted to form a film, the film is heated to 100 ℃, the temperature is increased to 200 ℃, the temperature is kept for 1 hour respectively at 300 ℃, and a polyimide film is obtained, wherein the tensile strength is 190MPa, the elastic modulus is 4.30GPa, and the breaking elongation is 7.3%. After 168h, 16mV/cm 2 The intensity retention rate of the intensity by xenon lamp irradiation is 92%, and the modulus retention rate is 108%.
Example 3
(1) 10.91g (0.10 mol) of 4-aminophenol and 120mL of deionized water were added to an Erlenmeyer flask, followed by 13mL of acetic anhydride in portions and stirred well. And after 4 hours of reaction, transferring the reaction mixture into a beaker, cooling, performing suction filtration, and washing to obtain a crude product N- (4-hydroxyphenyl) acetamide. Transferring the crude product into a beaker, adding a proper amount of deionized water to prepare a saturated solution at 80 ℃, adding 20% of excessive deionized water, adding 0.8g of activated carbon, boiling, filtering while hot, cooling for crystallization, filtering, washing with a small amount of deionized water, and drying in a forced air oven at 60 ℃ to obtain refined N- (4-hydroxyphenyl) acetamide with the yield of 86%.
1 H-NMR(600MHz,DMSO-d 6 )δ＝9.65(s,1H),δ＝9.14(d,J＝1.2Hz,1H),δ＝7.34(d,J＝8.8Hz,2H),δ＝6.67(d,J＝8.8Hz,2H),1.98(s,3H).
(2) 9.07g (0.06 mol) of N- (4-hydroxyphenyl) acetamide, 26.68g (0.20 mol) of anhydrous aluminum trichloride, 90mL of nitrobenzene and 9.28g (0.05 mol) of 4-nitrobenzoyl chloride were successively charged into a reaction flask and stirred under reflux for 12 hours. Then pouring the mixture into hydrochloric acid-ice water solution while stirring, filtering the product, washing the product by using deionized water and saturated sodium bicarbonate solution in sequence, removing nitrobenzene by rotary evaporation, and recrystallizing the product by using ethanol to obtain 8.00g of a refined product of the N- (4-hydroxy-3- (4-nitrobenzoyl) phenyl) acetamide with the yield of 53 percent.
(3) 6.30g (0.021 mol) of N- (4-hydroxy-3- (4-nitrobenzoyl) phenyl) acetamide was dissolved in 30mL of 20% dilute hydrochloric acid, refluxed for 4 hours, cooled, neutralized with a saturated sodium bicarbonate solution, suction-filtered, and the product was recrystallized from methanol to obtain 9.73g of purified (5-amino-2-hydroxyphenyl) (4-nitrophenyl) methanone in a yield of 91%.
(4) 4.77g (0.02 mol) of (5-amino-2-hydroxyphenyl) (4-nitrophenyl) methanone, 85mL of ethanol, and 36.02g (0.16 mol) of stannous chloride dihydrate were sequentially added to a reaction flask, and the mixture was sufficiently stirred under reflux conditions to react for 3 hours. After cooling to room temperature, saturated sodium bicarbonate solution was added to adjust the pH to be alkaline, ethyl acetate extraction was performed, liquid separation was performed, anhydrous sodium carbonate was dried, rotary evaporation was performed and concentration was performed to obtain a crude product (5-amino-2-hydroxyphenyl) (4-aminophenyl) methanone, and ethanol recrystallization was performed to obtain a refined product (5-amino-2-hydroxyphenyl) (4-aminophenyl) methanone 3.88g, with a yield of 85%.
Figure BDA0003054126570000091
(5) Under the protection of nitrogen, 120mL of N-methylpyrrolidone (NMP), 5.71g (0.025 mol) of (5-amino-2-hydroxyphenyl) (4-aminophenyl) ketone and 2.70g of p-phenylenediamine (p-PDA) are sequentially added into a three-neck flask, fully stirred and dissolved, then 14.71g (0.05 mol) of 3,3', 4' -phthalic dianhydride (BPDA) is added, stirred for 10 hours at the temperature of 5 ℃ to obtain a polyamic acid stock solution, and the polyamic acid stock solution is subjected to film casting to obtain a polyimide film, wherein the polyimide film is heated to 100 ℃, 200 ℃ and 300 ℃ and stays for 1 hour respectively, and the tensile strength is 280MPa, the elastic modulus is 5.2GPa, and the elongation at break is 6.8%. Passing through 168h16mV/cm 2 The intensity retention rate of the intensity by xenon lamp irradiation is 95%, and the modulus retention rate is 104%.
Example 4
(1) 16.36g (0.15 mol) of 4-aminophenol and 175mL of deionized water were added to an Erlenmeyer flask, followed by addition of 20mL of acetic anhydride in portions, and stirred well. And after 4 hours of reaction, transferring the reaction mixture into a beaker, cooling, performing suction filtration, and washing to obtain a crude product N- (4-hydroxyphenyl) acetamide. Transferring the crude product into a beaker, adding a proper amount of deionized water to prepare a saturated solution at 80 ℃, adding 20% excess deionized water, adding 1.0g of activated carbon, boiling, filtering while the solution is hot, cooling, crystallizing, filtering, washing with a small amount of deionized water, and drying in a forced air oven at 60 ℃ to obtain refined N- (4-hydroxyphenyl) acetamide with the yield of 85%.
1 H-NMR(600MHz,DMSO-d 6 )δ＝9.65(s,1H),δ＝9.14(d,J＝1.2Hz,1H),δ＝7.34(d,J＝8.8Hz,2H),δ＝6.67(d,J＝8.8Hz,2H),1.98(s,3H).
(2) 7.56g (0.05 mol) of N- (4-hydroxyphenyl) acetamide, 16.00g (0.12 mol) of anhydrous aluminum trichloride, 80mL of nitrobenzene, and 7.42g (0.04 mol) of 3-nitrobenzoyl chloride were successively charged into a reaction flask, and stirred under reflux for 24 hours. Then pouring into hydrochloric acid-ice water solution while stirring, filtering to obtain a product, washing with deionized water and saturated sodium bicarbonate solution in sequence, removing nitrobenzene by rotary evaporation, and recrystallizing with ethanol to obtain 5.43g of a refined product of N- (4-hydroxy-3- (3-nitrobenzoyl) phenyl) acetamide with the yield of 45%.
(3) 6.00g (0.020 mol) of N- (4-hydroxy-3- (3-nitrobenzoyl) phenyl) acetamide was dissolved in 30mL of 20% dilute hydrochloric acid and refluxed for 4 hours, cooled and then neutralized with a saturated sodium bicarbonate solution, filtered by suction, and the product was recrystallized from methanol to obtain 9.16g of purified (5-amino-2-hydroxyphenyl) (3-nitrophenyl) methanone with a yield of 90%.
(4) 2.38g (0.01 mol) (5-amino-2-hydroxyphenyl) (3-nitrophenyl) methanone, 35mL ethanol and 18.01g (0.08 mol) stannous chloride dihydrate were added in sequence to a reaction flask, and the mixture was stirred well under reflux conditions and reacted for 5 hours. After cooling to room temperature, saturated sodium bicarbonate solution was added to adjust the pH to be alkaline, ethyl acetate extraction was performed, liquid separation was performed, anhydrous sodium carbonate was dried, rotary evaporation was performed and concentration was performed to obtain a crude product (5-amino-2-hydroxyphenyl) (3-aminophenyl) methanone, and ethanol recrystallization was performed to obtain a refined product (5-amino-2-hydroxyphenyl) (3-aminophenyl) methanone 3.88g, with a yield of 85%.
Figure BDA0003054126570000101
(5) 120mL of N-methylpyrrolidone (NMP) and 5.71g (0.025 mo) are added in sequence into a three-neck flask under the protection of nitrogenl) of (5-amino-2-hydroxyphenyl) (3-aminophenyl) ketone and 5.60g (0.025 mol) of 2- (diaminophenyl) benzimidazol-5-amine (BIA) were sufficiently stirred and dissolved, and then 14.71g (0.05 mol) of 3,3', 4' -pyromellitic dianhydride (BPDA) was added thereto, and stirred at 5 ℃ for 10 hours to obtain a polyamic acid stock solution, and a film was formed by a tape casting method, and the polyamic acid stock solution was heated to 100 ℃, 200 ℃, 300 ℃ and left for 1 hour each to obtain a polyimide film having a tensile strength of 270MPa, an elastic modulus of 5.2GPa, and an elongation at break of 6.8%. Passing through 168h16mV/cm 2 The intensity retention rate of the intensity by xenon lamp irradiation is 92%, and the modulus retention rate is 110%.
Example 5
(1) 32.73g (0.30 mol) of 3-aminophenol and 300mL of deionized water were added to an Erlenmeyer flask, followed by 32mL of acetic anhydride in portions, and stirred well. And after 4 hours of reaction, transferring the reaction mixture into a beaker, cooling, performing suction filtration, and washing to obtain a crude product N- (3-hydroxyphenyl) acetamide. Transferring the crude product into a beaker, adding a proper amount of deionized water to prepare a saturated solution at 80 ℃, adding 20% of excessive deionized water, adding 2g of activated carbon, boiling, filtering while hot, cooling for crystallization, filtering, washing with a small amount of deionized water, and drying in a blast oven at 60 ℃ to obtain refined N- (3-hydroxyphenyl) acetamide with the yield of 91%.
1 H-NMR(600MHz,DMSO-d 6 )δ＝9.78(s,1H),δ＝9.32(s,1H),δ＝7.18(d,J＝1.8Hz,1H),δ＝7.03(t,J＝8.0Hz,1H),6.91(d,J＝8.0Hz,1H),6.46-6.34(m,1H),2.00(s,3H)。
(2) 15.12g (0.1 mol) of N- (3-hydroxyphenyl) acetamide, 33.34g (0.25 mol) of anhydrous aluminum trichloride, 350mL1, 2-dichloroethane and 18.14g (0.09 mol) of 2-hydroxy-4-nitrobenzoyl chloride were successively charged into a reaction flask, and stirred under reflux for 15 hours. Then pouring the mixture into hydrochloric acid-ice water solution while stirring, filtering the product, washing the product by using deionized water and saturated sodium bicarbonate solution in turn to obtain a crude product, and recrystallizing the crude product by using ethanol to obtain 17.64g of a refined product of the N- (3-hydroxy-4- (2-hydroxy-4-nitrobenzoyl) phenyl) acetamide, wherein the yield is 62%.
(3) 12.65g (0.04 mol) of N- (3-hydroxy-4- (2-hydroxy-4-nitrobenzoyl) phenyl) acetamide was dissolved in 60mL of 20% dilute hydrochloric acid, refluxed for 4 hours, cooled, neutralized with a saturated sodium bicarbonate solution, suction filtered, and the product was recrystallized with methanol to obtain 8.78g of purified (4-amino-2-hydroxyphenyl) (2-hydroxy-4-nitrophenyl) methanone with a yield of 85%.
(4) 8.23g (0.03 mol) (4-amino-2-hydroxyphenyl) (2-hydroxy-4-nitrophenyl) methanone, 0.82g Pd/C and 70mL ethanol were added in sequence to a reaction flask, stirred well, 8mL85% hydrazine hydrate was slowly added dropwise, heated to reflux, and reacted for 18h. The solution is filtered while the solution is hot, filtrate is evaporated and concentrated in a rotary manner, 380mL of deionized water is used for washing to obtain a crude product bis (4-amino-2-hydroxyphenyl) ketone, and the crude product bis (4-amino-2-hydroxyphenyl) ketone is recrystallized by ethanol to obtain a refined product bis (4-amino-2-hydroxyphenyl) ketone with the yield of 80 percent.
Figure BDA0003054126570000111
(5) 200mL of N, N-dimethylacetamide (DMAc) and 15.39g (0.063 mol) of bis (4-amino-2-hydroxyphenyl) methanone were added in this order to a three-necked flask under nitrogen atmosphere, and sufficiently stirred to dissolve the N, N-dimethylacetamide (DMAc), followed by adding 18.62g (0.063 mol) of 3,3', 4' -pyromellitic dianhydride (BPDA) and stirring at 5 ℃ for 24 hours to obtain a polyamic acid stock solution. And (3) defoaming the spinning solution in vacuum for 10 hours, and conveying the spinning solution to a wet spinning assembly through a metering pump, wherein the volume ratio of a coagulating bath is 5:5 DMAc and water, the coagulating bath temperature is 25 ℃, and the stretching ratio is 1.5 times, so as to obtain the polyamic acid nascent fiber. The obtained nascent fiber was dried under vacuum at 80 ℃ for 5 hours, subjected to static cyclization at 100-200-300 ℃ for 1 hour each in a cyclization oven, and then thermally stretched by a heat pipe of 4m length at a thermal stretching temperature of 420 ℃ and a stretching ratio of 3 times in a nitrogen atmosphere to obtain a polyimide fiber having a tensile strength of 3.0GPa, a modulus of 121GPa, and an elongation at break of 7.2%. After 168h, 16mV/cm 2 The intensity retention rate is 92% and the modulus retention rate is 112% under the irradiation of a xenon lamp with the intensity.
Comparative example 1
200mL of N, N-dimethylacetamide (DMAc) and 6.81g (0.063 mol) of p-phenylenediamine (p-PDA) were placed in a three-necked flask in this order under a nitrogen atmosphere, sufficiently stirred and dissolved, and then 18.54g (0.063 mol) of 3,3', 4' -pyromellitic dianhydride (B) was addedPDA) is stirred for 12 hours at the temperature of 5 ℃ to obtain polyamic acid stock solution, the polyamic acid stock solution is subjected to tape casting to form a film, the polyamic acid stock solution is heated to 100 ℃, 200 ℃ and 300 ℃ and stays for 1 hour respectively to obtain a polyimide film, the tensile strength of the polyimide film is 200MPa, the elastic modulus of the polyimide film is 4.8GPa, and the elongation at break of the polyimide film is 7.2%. Passing through 168h16mV/cm 2 The intensity retention rate of the intensity by xenon lamp irradiation is 85 percent, and the modulus retention rate is 95 percent.
Comparative example 2
Under the protection of nitrogen, 200mL of N, N-dimethylacetamide (DMAc) and 14.13g (0.063 mol) of 2- (diaminophenyl) benzimidazole-5 amine are sequentially added into a three-neck flask, fully stirred and dissolved, then 18.54g (0.063 mol) of 3,3', 4' -phthalic acid dianhydride (BPDA) is added, stirred for 12 hours at the temperature of 5 ℃ to obtain a polyamic acid stock solution, a film is formed by a tape casting method, and the polyamic acid stock solution is heated to 100 ℃, 200 ℃ and 300 ℃ and stays for 1 hour respectively to obtain a polyimide film with the tensile strength of 165MPa, the elastic modulus of 4.8GPa and the elongation at break of 7.2%. After 168h, 16mV/cm 2 The intensity retention rate is 83 percent and the modulus retention rate is 110 percent when the xenon lamp is used for irradiation.
Comparative example 3
Under the protection of nitrogen, 200mL of N, N-dimethylacetamide (DMAc) and 20.18g (0.063 mol) of (4- (4-aminophenoxy) -2-hydroxyphenyl) (4-aminophenyl) ketone (the structural formula is shown in the specification) are sequentially added into a three-neck flask, fully stirred and dissolved, then 18.54g (0.063 mol) of 3,3', 4' -o-phthalic acid dianhydride (BPDA) is added, stirred for 12 hours at the temperature of 5 ℃ to obtain a polyamic acid stock solution, a film is formed by a tape casting method, and the polyamic acid stock solution is heated to 100 ℃, 200 ℃ and 300 ℃ and respectively stays for 1 hour to obtain a polyimide film, wherein the tensile strength is 165MPa, and the elastic modulus is 4.0GPa. After 168h, 16mV/cm 2 The intensity retention rate of the intensity by xenon lamp irradiation is 89%, and the modulus retention rate is 90%.
Figure BDA0003054126570000121
Therefore, according to the ultraviolet radiation resistant polyimide and the preparation method thereof provided by the invention, the aromatic diamine monomer containing the ortho-position hydroxybenzophenone structure is prepared through molecular structure design, the ultraviolet absorption group is introduced into the main chain of the polyimide high polymer material, and the obtained polyimide has excellent intrinsic ultraviolet radiation resistance and keeps excellent mechanical properties through a copolymerization method; the diamine monomer can be widely used for preparing materials such as ultraviolet-resistant polyimide films, fibers and the like, and can also be used for preparing high-performance polymers such as ultraviolet-resistant functionalized polyamide, polyamide-imide, polyester-imide and the like.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention, and the invention is therefore not to be limited to the embodiments illustrated herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (9)

1. The polyimide with the ultraviolet radiation resistance is characterized in that raw materials of the polyimide comprise diamine monomers containing an ortho-position hydroxybenzophenone structure, and the structural formula of the diamine monomers containing the ortho-position hydroxybenzophenone structure comprises:
Figure FDA0003600827240000011
wherein R is OH or H.
2. A preparation method of polyimide with ultraviolet radiation resistance comprises the following steps:
under the protection of nitrogen or argon, dissolving diamine monomer containing an ortho-position hydroxyl benzophenone structure or diamine monomer containing an ortho-position hydroxyl benzophenone structure and other diamine monomers and dianhydride monomers in a polar aprotic solvent, stirring for reaction to obtain polyamic acid stock solution, and then carrying out cyclization to obtain ultraviolet radiation resistant polyimide, wherein the molar ratio of the diamine monomer containing the ortho-position hydroxyl benzophenone structure to the other diamine monomers is 1:9 to 10:0, the ratio of the total molar amount of the diamine monomer to the total molar amount of the dianhydride monomer is 1.9-1, and the structural formula of the diamine monomer containing the ortho-hydroxy benzophenone structure comprises:
Figure FDA0003600827240000012
wherein R is OH or H;
the preparation method of the diamine monomer containing the ortho-hydroxyl benzophenone structure comprises the following steps:
(a) Reacting 4-aminophenol or 3-aminophenol with acetic anhydride in deionized water to obtain acetamidophenol, wherein the molar ratio of the 4-aminophenol or 3-aminophenol to the acetic anhydride is (0.8-1.25): 1;
(b) Adding Lewis acid into the acetamidophenol and the nitrobenzoyl chloride in the step (a) in an anhydrous solvent, and obtaining an ortho-Fries rearrangement product through Friedel-crafts acylation reaction, wherein the nitrobenzoyl chloride comprises one or more of 3-nitrobenzoyl chloride, 4-nitrobenzoyl chloride, 2-hydroxy-3-nitrobenzoyl chloride and 2-hydroxy-4-nitrobenzoyl chloride, and the molar ratio of the acetamidophenol, the Lewis acid and the nitrobenzoyl chloride is (0.8-1.25): (1.25-4.0): 1;
(c) Hydrolyzing the product of the ortho Fries rearrangement in the step (b) under an acidic condition, dissolving the obtained hydrolysis product in a solvent under the protection of nitrogen or argon, and adding a reducing agent for reduction reaction to obtain the diamine monomer containing the ortho-hydroxybenzophenone structure.
3. The method of claim 2, wherein the other diamine monomer comprises:
Figure FDA0003600827240000021
Figure FDA0003600827240000022
Figure FDA0003600827240000023
one or more of the above; the dianhydride monomer comprises:
Figure FDA0003600827240000024
Figure FDA0003600827240000025
Figure FDA0003600827240000026
one or more of them.
4. The method according to claim 2, wherein the reaction temperature in the step (a) is 5 to 95 ℃ and the reaction time is 0.5 to 12 hours.
5. The method of claim 2, wherein the anhydrous solvent in step (b) comprises one or more of dichloromethane, chloroform, 1, 2-dichloroethane, carbon disulfide, carbon tetrachloride, chlorobenzene, and nitrobenzene; the Lewis acid comprises one or more of anhydrous aluminum chloride, anhydrous zinc chloride, titanium tetrachloride and ferric trichloride; the Friedel-crafts acylation reaction is carried out at the temperature of 40-180 ℃ for 8-24 h.
6. The method of claim 2, wherein the acidic condition in step (c) is under dilute hydrochloric acid acidic condition; the hydrolysis is as follows: refluxing for 3-5 h; the solvent comprises one or more of methanol, ethanol, tetrahydrofuran, ethyl acetate and 1, 4-dioxane; the reducing agent comprises at least one of stannous chloride, ferric trichloride and palladium/carbon; the temperature of the reduction reaction is 25-80 ℃.
7. The preparation method according to claim 2, wherein the polar aprotic solvent comprises one or more of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide and dimethylsulfoxide; the total mass of the diamine monomer and the dianhydride monomer accounts for 10-28 wt% of the total mass of the diamine monomer, the dianhydride monomer and the polar aprotic solvent.
8. The preparation method of claim 2, wherein the stirring reaction temperature is 5-45 ℃ and the stirring reaction time is 8-24 h; the cyclization comprises thermal cyclization or chemical cyclization, and the process parameters of the thermal cyclization are as follows: the temperature is raised to 90 to 110 ℃, 180 to 210 ℃ and 280 to 320 ℃ and the mixture is respectively kept for 0.8 to 1.5 hours.
9. Use of the polyimide according to claim 1 in a material resistant to ultraviolet radiation.
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