CN110669337B - Aromatic diamine monomer and preparation method thereof - Google Patents

Aromatic diamine monomer and preparation method thereof Download PDF

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CN110669337B
CN110669337B CN201911173013.8A CN201911173013A CN110669337B CN 110669337 B CN110669337 B CN 110669337B CN 201911173013 A CN201911173013 A CN 201911173013A CN 110669337 B CN110669337 B CN 110669337B
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CN110669337A (en
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姚海波
董志鑫
杜志军
矫龙
王汉夫
邱雪鹏
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Changchun Institute of Applied Chemistry of CAS
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Abstract

The invention provides an aromatic diamine monomer which has a structure shown in a formula (V); in the formula (V), R1And R2Independently selected from hydroxy or
Figure DDA0002289231010000011
And R is1And R2In a different sense, R3、R4、R5、R6Independently selected from hydrogen or amino, and R3And R4In a different sense, R5And R6Different. Compared with the prior art, the aromatic diamine monomer provided by the invention contains an o-hydroxybenzophenone structural unit, the o-hydroxybenzophenone structural unit can be introduced into the main chain of the polyimide high polymer material through copolymerization, when the material is exposed to an ultraviolet irradiation environment, the o-hydroxybenzophenone structure can absorb ultraviolet light and release the ultraviolet light in the form of heat, so that the damage of ultraviolet irradiation on the polyimide material is prevented or delayed, and the obtained polyimide material has excellent intrinsic ultraviolet irradiation resistance;

Description

Aromatic diamine monomer and preparation method thereof
the present application claims priority from chinese patent application filed on 2019, month 07 and 08, having application number 201910610423.8 and entitled "a polyimide-based towing tape" and chinese patent application filed on 2019, month 07 and 08, having application number 201910609959.8 and entitled "a polyimide composite foam precursor powder and polyimide composite foam", the entire contents of which are incorporated herein by reference.
Technical Field
The invention relates to the technical field of high polymer materials, in particular to an aromatic diamine monomer and a preparation method thereof.
Background
Polyimide is a special high polymer material with excellent comprehensive performance, has excellent high and low temperature resistance, mechanical performance and chemical stability, has lower dielectric constant and thermal expansion coefficient, and is widely applied to the high and new technical fields of aerospace, microelectronics and the like.
When the polyimide material is used in an ultraviolet environment, the performance of the polyimide material is reduced, and particularly, the polyimide material serving as an aerospace vehicle is in a high-intensity ultraviolet irradiation environment, so that the degradation and aging of the polyimide material are accelerated, and the service life of the polyimide material is seriously influenced. Due to the higher cost of the related technology, the preparation of the ultraviolet radiation resistant polyimide material is less reported. Chinese patent publication No. CN105348750A discloses a method for preparing a heat-insulating ultraviolet-proof automobile film, which specifically comprises: the nano zinc oxide coated by the nano cerium dioxide has the ultraviolet radiation resistance, and the nano zinc oxide is added into a polyimide substrate to prepare the polyimide composite material used as an ultraviolet-proof automobile film, wherein the automobile film has the characteristic of ultraviolet radiation resistance. And Chinese patent with publication number CN104804435A discloses a preparation method of an outdoor ultraviolet-resistant plastic, which specifically comprises the following steps: the anti-ultraviolet agent is added into the polyimide resin to prepare the material used outdoors, and the polyimide plastic has the characteristic of anti-ultraviolet radiation.
However, in the above methods, a component having an ultraviolet radiation resistant effect is added to a polyimide host material as an object to obtain an ultraviolet radiation resistant polyimide material, wherein, in the method for preparing the ultraviolet radiation resistant polyimide material by adding the ultraviolet radiation resistant nanoparticles, the problem of poor dispersibility of the nanoparticles in the polyimide host material exists, and the nanoparticles are easy to agglomerate mainly due to large specific surface area; the ultraviolet radiation resistant polyimide material prepared by adding the ultraviolet resistant agent has the problems that the ultraviolet absorbent is organic micromolecule, has poor heat resistance and cannot be used in a high-temperature environment.
Disclosure of Invention
In view of the above, the present invention provides an aromatic diamine monomer and a preparation method thereof, wherein the aromatic diamine monomer provided by the present invention contains an o-hydroxybenzophenone structural unit, and the o-hydroxybenzophenone structural unit can be introduced into a main chain of a polyimide polymer material through copolymerization, so that the obtained polyimide material has excellent intrinsic ultraviolet radiation resistance.
The invention provides an aromatic diamine monomer, which has a structure shown in a formula (V):
Figure BDA0002289229990000021
in the formula (V), R1And R2Independently selected from hydroxy or
Figure BDA0002289229990000022
And R is1And R2In a different sense, R3、R4、R5、R6Independently selected from hydrogen or amino, and R3And R4In a different sense, R5And R6Different.
The invention also provides a preparation method of the aromatic diamine monomer in the technical scheme, which comprises the following steps:
a) carrying out etherification reaction on methoxyphenol and substituted nitrobenzene with the structure shown in the formula (I) in the presence of an alkaline catalyst to obtain a compound with the structure shown in the formula (II); the methoxyphenol is 3-methoxyphenol or 4-methoxyphenol;
Figure BDA0002289229990000023
in the formula (I), X is fluorine, chlorine, bromine, iodine, methylsulfonyloxy, trifluoromethanesulfonyloxy or p-toluenesulfonyloxy, R7And R8Independently selected from hydrogen or nitro, and R7And R8Different;
Figure BDA0002289229990000031
in the formula (II), R9And R10Independently selected from hydrogen or methoxy, and R9And R10Different;
b) carrying out Friedel-crafts acylation reaction on a compound with a structure shown in a formula (II) and nitrobenzoyl halide in the presence of a catalyst to obtain a compound with a structure shown in a formula (III); the nitrobenzoyl halide is 3-nitrobenzoyl halide or 4-nitrobenzoyl halide;
Figure BDA0002289229990000032
in the formula (III), R11And R12Independently selected from methoxy or
Figure BDA0002289229990000033
And R is11And R12In a different sense, R13And R14Independently selected from hydrogen or nitro, and R13And R14Different;
c) carrying out reduction reaction on the compound with the structure shown in the formula (III) to obtain a compound with the structure shown in the formula (IV);
Figure BDA0002289229990000034
in the formula (IV), R15And R16Independently selected from methoxy or
Figure BDA0002289229990000035
And R is15And R16Different;
then carrying out demethylation reaction on the compound with the structure shown in the formula (IV) to obtain an aromatic diamine monomer with the structure shown in the formula (V);
or the like, or, alternatively,
carrying out demethylation reaction on the compound with the structure shown in the formula (III) to obtain a compound with the structure shown in the formula (VI);
Figure BDA0002289229990000036
in the formula (VI), R17And R18Independently selected from hydroxy or
Figure BDA0002289229990000041
And R is17And R18Different;
and then carrying out reduction reaction on the compound with the structure shown in the formula (VI) to obtain the aromatic diamine monomer with the structure shown in the formula (V).
Preferably, the molar ratio of the substituted nitrobenzene, the basic catalyst and the methoxyphenol in the step a) is (0.8-1.25): (1-1.5): 1.
preferably, the temperature of the etherification reaction in step a) is 140 ℃ to 170 ℃.
Preferably, the molar ratio of the nitrobenzoyl halide, the catalyst and the compound with the structure shown in the formula (II) in the step b) is (1-2): (1.1-1.8): 1.
preferably, the temperature of the friedel-crafts acylation reaction in step b) is between 0 ℃ and 40 ℃.
Preferably, stannous chloride is used as a reducing agent in the reduction reaction in the step c); the molar ratio of the reducing agent to the compound having the structure represented by the formula (III) is (7-12): 1.
preferably, the temperature of the reduction reaction in step c) is 50 ℃ to 80 ℃.
Preferably, the demethylation reaction in step c) employs a hydrobromic acid-acetic acid system; the mass ratio of acetic acid to hydrobromic acid in the hydrobromic acid-acetic acid system is (2-5): 1; the molar ratio of hydrobromic acid to a compound with a structure shown in a formula (IV) in the hydrobromic acid-acetic acid system is (3-8): 1.
the invention also provides an application of the aromatic diamine monomer in the technical scheme in synthesizing an ultraviolet-resistant functional high-performance polymer.
The invention provides an aromatic diamine monomer, which has a structure shown in the following formula:
Figure BDA0002289229990000042
in the formula, R1And R2Independently selected from hydroxy or
Figure BDA0002289229990000043
And R is1And R2In a different sense, R3、R4、R5、R6Independently selected from hydrogen or amino, and R3And R4In a different sense, R5And R6Different. Compared with the prior art, the aromatic diamine monomer provided by the invention contains an o-hydroxybenzophenone structural unit, the o-hydroxybenzophenone structural unit can be introduced into the main chain of the polyimide high polymer material through copolymerization, and when the material is exposed to an ultraviolet irradiation environment, the o-hydroxybenzophenone structure can absorb ultraviolet light and release the ultraviolet light in the form of heat, so that the damage of ultraviolet irradiation on the polyimide material is prevented or delayed, and the obtained polyimide material has excellent intrinsic ultraviolet irradiation resistance.
In addition, the preparation method provided by the invention has the advantages of simple route, low cost, high process controllability, easiness for large-scale production and higher total yield.
Drawings
FIG. 1 is a UV-VIS absorption spectrum of a structural compound (V-1) represented by the formula (V) obtained in example 1 of the present invention;
FIG. 2 shows an ultraviolet-visible absorption spectrum of a structural compound (V-3) represented by the formula (V) obtained in example 2 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides an aromatic diamine monomer, which has a structure shown in a formula (V):
Figure BDA0002289229990000051
in the formula (V), R1And R2Independently selected from hydroxy or
Figure BDA0002289229990000052
And R is1And R2In a different sense, R3、R4、R5、R6Independently selected from hydrogen or amino, and R3And R4In a different sense, R5And R6Different.
Benzophenone absorbers are currently commonly used ultraviolet absorbers, hydrogen of hydroxyl groups at the ortho positions of the benzophenone absorbers and carbonyl oxygen can form hydrogen bonds, after ultraviolet light is absorbed, the hydrogen bonds are destroyed and changed into enol structures, the structure stability is poor, the original structures can be restored after heat is released, and harmful ultraviolet light energy is changed into heat energy to be released along with the process.
In the invention, the aromatic diamine monomer is diamine containing an o-hydroxy benzophenone structural unit, and has the structural characteristics that: when the connecting structural unit of two amino groups is taken as a main chain, the structural unit of o-hydroxybenzophenone contained in the diamine monomer of the type is positioned on the main chain; the polycondensation reaction of diamine monomers and dianhydride monomers is a typical and common method for synthesizing polyimide; the formed characteristic imide ring is positioned at the main chain of the polyimide macromolecule, and the main chain group of the polyimide macromolecule is carried by diamine or dianhydride monomer in the polymerization process; the structural unit of o-hydroxybenzophenone contained in the diamine monomer is polymerized and then is remained in the main chain of the polyimide macromolecule; because the o-hydroxybenzophenone structural unit has the characteristic of absorbing ultraviolet radiation, the polyimide high polymer material is endowed with the intrinsic ultraviolet radiation resistance; the method is characterized in that a part of the structure of the material has the capability of absorbing ultraviolet, and the material is endowed with the performance of ultraviolet radiation resistance; the common conventional method is to endow the mixed material with the performance of resisting ultraviolet radiation by adding other foreign materials with the capability of absorbing ultraviolet.
In the present invention, the structure represented by formula (V) specifically includes:
Figure BDA0002289229990000061
the invention also provides a preparation method of the aromatic diamine monomer in the technical scheme, which comprises the following steps:
a) carrying out etherification reaction on methoxyphenol and substituted nitrobenzene with the structure shown in the formula (I) in the presence of an alkaline catalyst to obtain a compound with the structure shown in the formula (II); the methoxyphenol is 3-methoxyphenol or 4-methoxyphenol;
Figure BDA0002289229990000071
in the formula (I), X is fluorine, chlorine, bromine, iodine, methylsulfonyloxy, trifluoromethanesulfonyloxy or p-toluenesulfonyloxy, R7And R8Independently selected from hydrogen or nitro, and R7And R8Different;
Figure BDA0002289229990000072
in the formula (II), R9And R10Independently selected from hydrogen or methoxy, and R9And R10Different;
b) carrying out Friedel-crafts acylation reaction on a compound with a structure shown in a formula (II) and nitrobenzoyl halide in the presence of a catalyst to obtain a compound with a structure shown in a formula (III); the nitrobenzoyl halide is 3-nitrobenzoyl halide or 4-nitrobenzoyl halide;
Figure BDA0002289229990000073
in the formula (III), R11And R12Independently selected from methoxy or
Figure BDA0002289229990000074
And R is11And R12In a different sense, R13And R14Independently selected from hydrogen or nitro, and R13And R14Different;
c) carrying out reduction reaction on the compound with the structure shown in the formula (III) to obtain a compound with the structure shown in the formula (IV);
Figure BDA0002289229990000075
in the formula (IV), R15And R16Independently selected from methoxy or
Figure BDA0002289229990000076
And R is15And R16Different;
then carrying out demethylation reaction on the compound with the structure shown in the formula (IV) to obtain an aromatic diamine monomer with the structure shown in the formula (V);
or the like, or, alternatively,
carrying out demethylation reaction on the compound with the structure shown in the formula (III) to obtain a compound with the structure shown in the formula (VI);
Figure BDA0002289229990000081
in the formula (VI), R17And R18Independently selected from hydroxy or
Figure BDA0002289229990000082
And R is17And R18Different;
and then carrying out reduction reaction on the compound with the structure shown in the formula (VI) to obtain the aromatic diamine monomer with the structure shown in the formula (V).
Firstly, carrying out etherification reaction on methoxyphenol and substituted nitrobenzene with a structure shown in a formula (I) in the presence of an alkaline catalyst to obtain a compound with a structure shown in a formula (II). In the present invention, the methoxyphenol is 3-methoxyphenol or 4-methoxyphenol. The source of the methoxyphenol in the present invention is not particularly limited, and commercially available products of the above-mentioned 3-methoxyphenol and 4-methoxyphenol, which are well known to those skilled in the art, may be used.
In the present invention, the structure represented by formula (I) specifically includes:
Figure BDA0002289229990000083
in the formula (I), X is fluorine, chlorine, bromine, iodine, methylsulfonyloxy, trifluoromethanesulfonyloxy or p-toluenesulfonyloxy, preferably chlorine, bromine or p-toluenesulfonyloxy; the above groups are easy to leave, which is beneficial to carrying out etherification reaction to obtain corresponding reaction products.
In the present invention, when the substituted nitrobenzene has the structure represented by the formula (I-1), the basic catalyst is preferably an alkali metal carbonate and/or an alkaline earth metal carbonate, more preferably sodium carbonate and/or potassium carbonate, and still more preferably potassium carbonate. When the substituted nitrobenzene has the structure shown in the formula (I-2), the basic catalyst is preferably co-catalyzed by carbonate and copper salt of alkali metal carbonate and/or alkaline earth metal; more preferably sodium carbonate and/or potassium carbonate, more preferably potassium carbonate; the cupric salt is preferably cuprous chloride, cuprous bromide or cuprous iodide, and more preferably cuprous iodide; wherein the dosage of the copper salt is 0.01 to 0.05 times of the molar weight of the substituted nitrobenzene. The source of the basic catalyst in the present invention is not particularly limited, and commercially available products known to those skilled in the art may be used.
In the invention, the molar ratio of the substituted nitrobenzene, the basic catalyst and the methoxyphenol is preferably (0.8-1.25): (1-1.5): 1, more preferably (0.9 to 1.1): (1.1-1.3): 1.
in a preferred embodiment of the present invention, X is chlorine or bromine, and on this basis, the etherification reaction is preferably carried out using a first reaction solvent; the first reaction solvent is preferably one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, and dimethylsulfoxide. When the substituted nitrobenzene has the structure shown in the formula (I-1), dimethyl sulfoxide and/or N-methylpyrrolidone are more preferable; when the substituted nitrobenzene has the structure represented by the formula (I-2), N-dimethylformamide is more preferable. The source of the first reaction solvent is not particularly limited in the present invention, and commercially available ones of the above-mentioned high-boiling polar aprotic solvents known to those skilled in the art may be used. In the present invention, the mass of the first reaction solvent is preferably 1 to 3 times, more preferably 1.2 to 1.8 times the sum of the masses of the substituted nitrobenzene and the methoxyphenol.
In the present invention, the temperature of the etherification reaction is preferably 140 to 170 ℃, more preferably 150 to 165 ℃.
After the etherification reaction is completed, the present invention preferably further comprises:
and (3) carrying out primary post-treatment on a reaction product obtained after the etherification reaction to obtain a compound with a structure shown in a formula (II). In the present invention, the first post-treatment process preferably includes:
cooling a reaction product obtained after etherification reaction to 50-70 ℃, adding the reaction product into water with the volume 5-15 times of that of a first reaction solvent, separating out a crude product, filtering, washing with water, dissolving in dichloromethane, drying with anhydrous magnesium sulfate, concentrating the solvent to obtain the crude product again, and recrystallizing to obtain a refined product of the compound with the structure shown in the formula (II);
more preferably:
cooling a reaction product obtained after etherification reaction to 60 ℃, adding the reaction product into water with the volume 10 times that of the first reaction solvent, separating out a crude product, filtering, washing with water, dissolving in dichloromethane, drying with anhydrous magnesium sulfate, concentrating the solvent to obtain the crude product again, and recrystallizing to obtain a refined product of the structural compound shown in the formula (II).
In the present invention, the structure represented by formula (II) specifically includes:
Figure BDA0002289229990000091
Figure BDA0002289229990000101
after the compound with the structure shown in the formula (II) is obtained, the compound with the structure shown in the formula (II) and nitrobenzoyl halide are subjected to Friedel-crafts acylation reaction in the presence of a catalyst to obtain the compound with the structure shown in the formula (III). In the present invention, the nitrobenzoyl halide is 3-nitrobenzoyl halide or 4-nitrobenzoyl halide; among them, the acid halide is preferably an acid fluoride, an acid chloride, an acid bromide or an acid iodide, and more preferably an acid chloride or an acid bromide. The source of the nitrobenzoyl halide is not particularly limited in the present invention and commercially available products well known to those skilled in the art may be used.
In the present invention, the catalyst is preferably a lewis acid, more preferably aluminum trichloride. The source of the catalyst is not particularly limited in the present invention, and a commercially available Lewis acid known to those skilled in the art may be used.
In the invention, the molar ratio of the nitrobenzoyl halide, the catalyst and the compound with the structure shown in the formula (II) is preferably (1-2): (1.1-1.8): 1, more preferably (1.1 to 1.5): (1.2-1.5): 1.
in the present invention, the friedel-crafts acylation reaction is preferably carried out using a second reaction solvent; the second reaction solvent is preferably one or more of dichloromethane, trichloromethane, 1, 2-dichloroethane, carbon disulfide, carbon tetrachloride, chlorobenzene and nitrobenzene, and more preferably dichloromethane and/or 1, 2-dichloroethane. The source of the second reaction solvent in the present invention is not particularly limited, and commercially available products of the above-mentioned dichloromethane, chloroform, 1, 2-dichloroethane, carbon disulfide, carbon tetrachloride, chlorobenzene and nitrobenzene, which are well known to those skilled in the art, may be used. In the present invention, the mass of the second reaction solvent is preferably 3 to 8 times, more preferably 4.5 to 6 times the sum of the masses of the nitrobenzoyl halide, the catalyst and the compound having the structure represented by formula (II).
In the invention, the temperature of the Friedel-crafts acylation reaction is preferably 0-40 ℃, and more preferably 10-30 ℃; the time of the Friedel-crafts acylation reaction depends on specific reaction substrates and reaction conditions, the specific reaction time can be determined by tracking the reaction process through thin-layer chromatography in a laboratory, and the industrial preparation can be determined by tracking the reaction process through high performance liquid chromatography; meanwhile, the mixed solution obtained after the reaction for a certain time is slowly added into ice-hydrochloric acid for treatment, and the reaction termination can be realized.
In the present invention, after the friedel-crafts acylation reaction is completed, the present invention preferably further comprises:
and carrying out secondary post-treatment on a reaction product obtained after the Friedel-crafts acylation reaction to obtain a compound with a structure shown in a formula (III). In the present invention, the second post-treatment process preferably includes:
separating the reaction product obtained after the Friedel-crafts acylation reaction, drying the reaction product with anhydrous magnesium sulfate, concentrating the solvent to obtain a crude product, and recrystallizing the crude product to obtain a refined product of the compound with the structure shown in the formula (III).
In the present invention, the structure represented by formula (III) specifically includes:
Figure BDA0002289229990000111
after the compound with the structure shown in the formula (III) is obtained, the compound with the structure shown in the formula (III) is subjected to reduction reaction to obtain a compound with the structure shown in the formula (IV); and then carrying out demethylation reaction on the compound with the structure shown in the formula (IV) to obtain the aromatic diamine monomer with the structure shown in the formula (V).
In the invention, stannous chloride is preferably adopted as a reducing agent in the reduction reaction; the present invention is not particularly limited in its origin. The invention adopts the reducing agent to carry out reduction reaction, has high reaction speed and simple operation process.
In the present invention, the molar ratio of the reducing agent to the compound having the structure represented by formula (III) is preferably (7 to 12): 1, more preferably (8-10): 1.
in the present invention, the reduction reaction preferably employs a solvent having a boiling point in the range of 50 ℃ to 100 ℃, more preferably methanol, ethanol, tetrahydrofuran, ethyl acetate, ethylene glycol dimethyl ether or 1, 4-dioxane, more preferably ethyl acetate or ethanol; the solvent adopted by the invention has low price and low toxicity. In the present invention, the mass ratio of the solvent having a boiling point in the range of 50 to 100 ℃ to the compound having the structure represented by the formula (III) is preferably (10 to 20): 1, more preferably (12-16): 1.
in the invention, the temperature of the reduction reaction is preferably 50-80 ℃, and more preferably 60-75 ℃; the time of the reduction reaction depends on specific reaction substrates and reaction conditions, the specific reaction time can be determined by tracking the reaction process through thin-layer chromatography in a laboratory, and the industrial preparation can be determined by tracking the reaction process through high performance liquid chromatography; meanwhile, the mixed solution obtained after the reaction is carried out for a certain time is cooled to room temperature, and the mixed solution is added into a saturated sodium carbonate solution to be neutralized to be alkaline, so that the reaction termination can be realized.
In the present invention, after the reduction reaction is completed, the present invention preferably further comprises:
and (3) carrying out third post-treatment on the reaction product obtained after the reduction reaction to obtain the compound with the structure shown in the formula (IV). In the present invention, the third post-treatment process preferably includes:
separating the reaction product obtained after the reduction reaction, drying the reaction product by using anhydrous sodium carbonate, concentrating the solvent to obtain a crude product, and recrystallizing the crude product to obtain a refined product of the compound with the structure shown in the formula (IV).
In the present invention, the structure represented by formula (IV) specifically includes:
Figure BDA0002289229990000121
Figure BDA0002289229990000131
in the present invention, the demethylation reaction preferably employs a hydrobromic acid-acetic acid system; the system has low cost, can selectively remove methyl in methoxyl adjacent to carbonyl, has simple and convenient operation, and can conveniently recycle hydrobromic acid and acetic acid. In the invention, the mass ratio of acetic acid to hydrobromic acid in the hydrobromic acid-acetic acid system is preferably (2-5): 1, more preferably (3-4): 1.
in the present invention, the molar ratio of hydrobromic acid to the compound having the structure represented by formula (IV) in the hydrobromic acid-acetic acid system is preferably (3-8): 1, more preferably (4-6): 1.
in the invention, the compound with the structure shown in the formula (IV) is preferably converted into a common strong acid salt before the demethylation reaction, and more preferably reacts with hydrochloric acid to generate hydrochloride.
In the invention, the temperature of the demethylation reaction is preferably 80-110 ℃, and more preferably 90-100 ℃; the time of the demethylation reaction depends on the specific reaction substrate and reaction conditions, and the present invention is not particularly limited thereto; meanwhile, the reaction termination can be realized by cooling the mixed solution obtained after the reaction for a certain time to room temperature.
In the present invention, after the demethylation reaction is completed, the present invention preferably further comprises:
and (3) carrying out fourth post-treatment on the reaction product obtained after the demethylation reaction to obtain the aromatic diamine monomer with the structure shown in the formula (V). In the present invention, the fourth post-treatment process is preferably specifically:
concentrating the reaction product obtained after the demethylation reaction to recover hydrobromic acid and acetic acid, neutralizing the residue with saturated sodium carbonate solution to be alkaline, extracting with dichloromethane, separating liquid, drying with anhydrous sodium carbonate, concentrating the solvent to obtain a crude product, and recrystallizing to obtain a refined product of the compound with the structure shown in the formula (V).
Or the like, or, alternatively,
carrying out demethylation reaction on the compound with the structure shown in the formula (III) to obtain a compound with the structure shown in the formula (VI); and then carrying out reduction reaction on the compound with the structure shown in the formula (VI) to obtain the aromatic diamine monomer with the structure shown in the formula (V).
In the present invention, the demethylation reaction preferably employs a hydrobromic acid-acetic acid system; the system has low cost, can selectively remove methyl in methoxyl adjacent to carbonyl, has simple and convenient operation, and can conveniently recycle hydrobromic acid and acetic acid. In the invention, the mass ratio of acetic acid to hydrobromic acid in the hydrobromic acid-acetic acid system is preferably (2-5): 1, more preferably (3-4): 1.
in the present invention, the molar ratio of hydrobromic acid to the compound having the structure represented by formula (III) in the hydrobromic acid-acetic acid system is preferably (3-8): 1, more preferably (4-6): 1.
in the invention, the temperature of the demethylation reaction is preferably 80-110 ℃, and more preferably 90-100 ℃; the time of the demethylation reaction depends on the specific reaction substrate and reaction conditions, and the present invention is not particularly limited thereto; meanwhile, the reaction termination can be realized by cooling the mixed solution obtained after the reaction for a certain time to room temperature.
In the present invention, after the demethylation reaction is completed, the present invention preferably further comprises:
and (3) carrying out fifth post-treatment on the reaction product obtained after the demethylation reaction to obtain the compound with the structure shown in the formula (VI). In the present invention, the fifth post-treatment process is preferably specifically:
concentrating a reaction product obtained after the demethylation reaction to recover hydrobromic acid and acetic acid, dissolving residues with dichloromethane, neutralizing a saturated sodium carbonate solution to be alkaline, separating liquid, drying with anhydrous magnesium sulfate, concentrating a solvent to obtain a crude product, and recrystallizing to obtain a refined product of the compound with the structure shown in the formula (VI).
In the present invention, the structure represented by formula (VI) specifically includes:
Figure BDA0002289229990000141
in the invention, stannous chloride is preferably adopted as a reducing agent in the reduction reaction; the present invention is not particularly limited in its origin. The invention adopts the reducing agent to carry out reduction reaction, has high reaction speed and simple operation process.
In the present invention, the molar ratio of the reducing agent to the compound having the structure represented by formula (VI) is preferably (7 to 12): 1, more preferably (8-10): 1.
in the present invention, the reduction reaction preferably employs a solvent having a boiling point in the range of 50 ℃ to 100 ℃, more preferably methanol, ethanol, tetrahydrofuran, ethyl acetate, ethylene glycol dimethyl ether or 1, 4-dioxane, more preferably ethyl acetate or ethanol; the solvent adopted by the invention has low price and low toxicity. In the present invention, the mass ratio of the solvent having a boiling point in the range of 50 to 100 ℃ to the compound having a structure represented by the formula (VI) is preferably (10 to 20): 1, more preferably (12-16): 1.
in the invention, the temperature of the reduction reaction is preferably 50-80 ℃, and more preferably 60-75 ℃; the time of the reduction reaction depends on specific reaction substrates and reaction conditions, the specific reaction time can be determined by tracking the reaction process through thin-layer chromatography in a laboratory, and the industrial preparation can be determined by tracking the reaction process through high performance liquid chromatography; meanwhile, the mixed solution obtained after the reaction is carried out for a certain time is cooled to room temperature, and the mixed solution is added into a saturated sodium carbonate solution to be neutralized to be alkaline, so that the reaction termination can be realized.
In the present invention, after the reduction reaction is completed, the present invention preferably further comprises:
and carrying out sixth post-treatment on the reaction product obtained after the reduction reaction to obtain the aromatic diamine monomer with the structure shown in the formula (V). In the present invention, the sixth post-treatment process preferably includes:
separating the reaction product obtained after the reduction reaction, drying the reaction product by using anhydrous sodium carbonate, concentrating the solvent to obtain a crude product, and recrystallizing the crude product to obtain a refined product of the compound with the structure shown in the formula (V).
In the present invention, when the compound having the structure represented by formula (III) is not dissolved in the reaction solvent for the demethylation reaction, a preparation process of performing the reduction reaction first and then performing the demethylation reaction is employed.
The invention also provides an application of the aromatic diamine monomer in the technical scheme in synthesizing an ultraviolet-resistant functional high-performance polymer. In the present invention, the functional high performance polymer includes, but is not limited to, polyimide, polyamide, polyamideimide, and polyesterimide.
The invention provides an aromatic diamine monomer, which has a structure shown in the following formula:
Figure BDA0002289229990000151
in the formula, R1And R2Independently selected from hydroxy or
Figure BDA0002289229990000152
And R is1And R2In a different sense, R3、R4、R5、R6Independently selected from hydrogen or amino, and R3And R4In a different sense, R5And R6Different. Compared with the prior art, the aromatic diamine monomer provided by the invention contains an o-hydroxybenzophenone structural unit, the o-hydroxybenzophenone structural unit can be introduced into the main chain of the polyimide high polymer material through copolymerization, and when the material is exposed to an ultraviolet irradiation environment, the o-hydroxybenzophenone structure can absorb ultraviolet light and release the ultraviolet light in the form of heat, so that the damage of ultraviolet irradiation on the polyimide material is prevented or delayed, and the obtained polyimide material has excellent intrinsic ultraviolet irradiation resistance.
In addition, the preparation method provided by the invention has the advantages of simple route, low cost, high process controllability, easiness for large-scale production and higher total yield.
To further illustrate the present invention, the following examples are provided for illustration. The raw materials used in the following examples of the present invention are all commercially available products.
Example 1
(1) Adding 69.52g (0.56mol) of 3-methoxyphenol, 88.23g (0.56mol) of p-nitrochlorobenzene, 85.14g (0.616mol) of potassium carbonate and 200g of dimethyl sulfoxide into a reactor in sequence, and heating to 160 ℃ for reaction for 6 hours; cooling to 60 ℃, adding the mixture into 2000mL of water, precipitating a crude product, filtering, washing with water, dissolving in dichloromethane, drying with anhydrous magnesium sulfate, concentrating the solvent to obtain the crude product again, and recrystallizing to obtain 114.23g of a refined product of a structural compound (II-1) shown in a formula (II); the yield thereof was found to be 83.2%.
The obtained compound (II-1) with the structure shown in the formula (II) is characterized by utilizing nuclear magnetic resonance, and the obtained hydrogen spectrum result of the nuclear magnetic resonance is as follows:1H NMR(400MHz，DMSO)＝8.280–8.205(m，2H)，7.389(t，J＝8.2Hz，1H)，7.170–7.095(m，2H)，6.875(dd，J＝8.3Hz，2.2Hz，1H)，6.776(t，J＝2.2Hz，1H)，6.731(dd，J＝8.0Hz，2.0Hz，1H)，3.765(s，3H)。
(2) 89.07g (0.48mol) of 4-nitrobenzoyl chloride, 69.34g (0.52mol) of aluminum trichloride, 1000mL of dichloromethane and 105.45g (0.43mol) of a structural compound (II-1) shown in the formula (II) are sequentially added into a reactor and stirred to react for 18 hours at the temperature of 20 ℃; then slowly adding the crude product into ice-hydrochloric acid for treatment, separating liquid, drying by anhydrous magnesium sulfate, concentrating the solvent to obtain a crude product, and recrystallizing to obtain 90.43g of a refined product of a structural compound (III-1) shown in a formula (III); the yield thereof was found to be 53.3%.
The obtained compound (III-1) with the structure shown in the formula (III) is characterized by utilizing nuclear magnetic resonance, and the obtained hydrogen spectrum result of the nuclear magnetic resonance is as follows:1H NMR(400MHz，DMSO)＝8.325(dd，J＝12.6Hz，9.0Hz，4H)，7.942(d，J＝8.7Hz，2H)，7.575(d，J＝8.4Hz，1H)，7.320(d，J＝9.2Hz，2H)，7.087(d，J＝1.8Hz，1H)，6.871(dd，J＝8.3Hz，1.9Hz，1H)，3.643(s，3H)。
(3) 23.66g (0.06mol) of the structural compound (III-1) shown in the formula (III), 121.85g (0.54mol) of stannous chloride dihydrate and 350mL of ethyl acetate are sequentially added into a reactor, and stirred and reacted for 3 hours at 70 ℃; cooling to room temperature, adding into saturated sodium carbonate solution to neutralize to alkalinity, separating liquid, drying with anhydrous sodium carbonate, concentrating solvent to obtain crude product, and recrystallizing to obtain 15.78g refined product of compound (IV-1) with structure shown in formula (IV); the yield thereof was found to be 78.7%.
The obtained compound (IV-1) with the structure shown in the formula (IV) is characterized by using nuclear magnetic resonance, and the obtained hydrogen spectrum result of the nuclear magnetic resonance is as follows:1H NMR(400MHz，DMSO)＝7.410(d，J＝8.4Hz，2H)，7.100(d，J＝8.3Hz，1H)，6.838(d，J＝8.4Hz，2H)，6.666(s，1H)，6.621(d，J＝8.4Hz，2H)，6.535(d，J＝8.4Hz，2H)，6.375(d，J＝8.2Hz，1H)，6.069(s，2H)，5.009(s，2H)，3.624(s，3H)。
(4) 44g (0.108mol) of a hydrochloride of the structural compound (IV-1) represented by the formula (IV), 109.24g (40%, 0.54mol) of hydrobromic acid and 330g of acetic acid were sequentially added to a reactor, and the reaction was stirred at 100 ℃ for 84 hours; concentrating to recover hydrobromic acid and acetic acid, neutralizing the residue with saturated sodium carbonate solution to alkalinity, extracting with dichloromethane, separating, drying with anhydrous sodium carbonate, concentrating the solvent to obtain crude product, and recrystallizing to obtain 29.75g refined product of compound (V-1) with structure shown in formula (V); the yield thereof was found to be 86.0%.
The obtained compound (V-1) with the structure shown in the formula (V) is characterized by utilizing nuclear magnetic resonance, and the obtained hydrogen spectrum result of the nuclear magnetic resonance is as follows:1H NMR(400MHz，DMSO)＝11.440(s，1H)，7.462(d，J＝8.2Hz，2H)，7.412(d，J＝8.7Hz，1H)，6.832(d，J＝8.3Hz，2H)，6.606(dd，J＝13.3Hz，8.5Hz，4H)，6.417(d，J＝8.7Hz，1H)，6.315(s，1H)，6.090(s，2H)，5.069(s，2H)。
example 2
(1) Referring to step (1) of example 1, a purified product of the compound (II-1) having the structure represented by the formula (II) was obtained.
(2) 18.56g (0.1mol) of 3-nitrobenzoyl chloride, 14.67g (0.11mol) of aluminum trichloride, 250g of 1, 2-dichloroethane and 22.07g (0.09mol) of the structural compound (II-1) shown in the formula (II) are sequentially added into a reactor and stirred for reaction for 30 hours at the temperature of 20 ℃; then slowly adding the crude product into ice-hydrochloric acid for treatment, separating liquid, drying by anhydrous magnesium sulfate, concentrating the solvent to obtain a crude product, and recrystallizing to obtain 21.02g of a refined product of a structural compound (III-3) shown in a formula (III); the yield thereof was found to be 59.2%.
The obtained compound (III-3) with the structure shown in the formula (III) is characterized by utilizing nuclear magnetic resonance, and the obtained compoundThe result of the hydrogen spectrum of the nuclear magnetic resonance is as follows:1HNMR(400MHz，DMSO)＝8.490(d，J＝8.0Hz，1H)，8.425(s，1H)，8.312(d，J＝9.1Hz，2H)，8.129(d，J＝7.6Hz，1H)，7.832(t，J＝7.9Hz，1H)，7.579(d，J＝8.3Hz，1H)，7.330(d，J＝9.0Hz，2H)，7.104(s，1H)，6.881(d，J＝8.3Hz，1H)，3.660(s，3H)。
(3) 39.43g (0.1mol) of the structural compound (III-3) represented by the formula (III), 101.15g (40%, 0.5mol) of hydrobromic acid and 350g of acetic acid were sequentially added to a reactor, and the reaction was stirred at 100 ℃ for 48 hours; after hydrobromic acid and acetic acid were recovered by concentration, the residue was dissolved in methylene chloride, neutralized to alkaline with a saturated sodium carbonate solution, separated, dried over anhydrous magnesium sulfate, and the solvent was concentrated to obtain a crude product, which was recrystallized to obtain 33.65g of a purified product of the structural compound (VI-3) represented by the formula (VI), in a yield of 88.5%.
The obtained compound (VI-3) with the structure shown in the formula (VI) is characterized by utilizing nuclear magnetic resonance, and the obtained hydrogen spectrum result of the nuclear magnetic resonance is as follows:1H NMR(400MHz，DMSO)＝10.889(s，1H)，8.520–8.400(m，2H)，8.316(d，J＝9.0Hz，2H)，8.149(d，J＝7.6Hz，1H)，7.834(t，J＝7.9Hz，1H)，7.569(d，J＝8.5Hz，1H)，7.350(d，J＝9.0Hz，2H)，6.748(d，J＝8.5Hz，1H)，6.701(s，1H)。
(4) adding 45.64g (0.12mol) of a structural compound (VI-3) shown in a formula (VI), 243.7g (1.08mol) of stannous chloride dihydrate and 700mL of ethyl acetate into a reactor in sequence, and stirring and reacting at 70 ℃ for 3 h; cooling to room temperature, adding into saturated sodium carbonate solution, neutralizing to alkalinity, separating, drying with anhydrous sodium carbonate, concentrating solvent to obtain crude product, and recrystallizing to obtain 32.59g refined product of structural compound (V-3) shown in formula (V); the yield thereof was found to be 84.8%.
The obtained compound (V-3) with the structure shown in the formula (V) is characterized by utilizing nuclear magnetic resonance, and the obtained hydrogen spectrum result of the nuclear magnetic resonance is as follows:1HNMR(400MHz，DMSO)＝11.727(s，1H)，7.466(d，J＝8.8Hz，1H)，7.149(t，J＝7.8Hz，1H)，6.868-6.810(m，3H)，6.806–6.723(m，2H)，6.628(d，J＝8.7Hz，2H)，6.452(dd，J＝8.8Hz，2.3Hz，1H)，6.318(d，J＝2.3Hz，1H)，5.342(s，2H)，5.136(s，2H)。
example 3
(1) Adding 69.52g (0.56mol) of 4-methoxyphenol, 88.23g (0.56mol) of p-nitrochlorobenzene, 85.14g (0.616mol) of potassium carbonate and 200g of dimethyl sulfoxide into a reactor in sequence, and heating to 160 ℃ for reaction for 6 hours; cooling to 60 ℃, adding the mixture into 2000mL of water, precipitating a crude product, filtering, washing with water, dissolving in dichloromethane, drying with anhydrous magnesium sulfate, concentrating the solvent to obtain the crude product again, and recrystallizing to obtain 117.56g of a refined product of a structural compound (II-3) shown in a formula (II); the yield thereof was found to be 85.6%.
(2) 89.07g (0.48mol) of 4-nitrobenzoyl chloride, 69.34g (0.52mol) of aluminum trichloride, 1000mL of dichloromethane and 105.45g (0.43mol) of a structural compound (II-3) shown in the formula (II) are sequentially added into a reactor and stirred to react for 15 hours at the temperature of 30 ℃; then slowly adding the crude product into ice-hydrochloric acid for treatment, separating liquid, drying by anhydrous magnesium sulfate, concentrating the solvent to obtain a crude product, and recrystallizing to obtain 84.66g of a refined product of a structural compound (III-5) shown in a formula (III); the yield thereof was found to be 49.9%.
(3) 23.66g (0.06mol) of the structural compound (III-5) shown in the formula (III), 121.85g (0.54mol) of stannous chloride dihydrate and 350mL of ethyl acetate are sequentially added into a reactor, and stirred and reacted for 3 hours at 70 ℃; after cooling to room temperature, the solution was neutralized to alkaline by adding a saturated sodium carbonate solution, separated, dried with anhydrous sodium carbonate, and concentrated in the solvent to obtain a crude product, which was recrystallized to obtain 17.72g of a purified product of the structural compound (IV-5) represented by the formula (IV) in a yield of 88.4%.
(4) 44g (0.108mol) of a hydrochloride of the structural compound (IV-5) represented by the formula (IV), 109.24g (40%, 0.54mol) of hydrobromic acid and 330g of acetic acid were sequentially added to a reactor, and the reaction was stirred at 100 ℃ for 84 hours; concentrating to recover hydrobromic acid and acetic acid, neutralizing the residue with saturated sodium carbonate solution to alkalinity, extracting with dichloromethane, separating, drying with anhydrous sodium carbonate, concentrating the solvent to obtain crude product, and recrystallizing to obtain 30.21g refined product of compound (V-5) with structure shown in formula (V); the yield thereof was found to be 87.3%.
Example 4
(1) Referring to step (1) of example 3, a purified product of the compound (II-3) having a structure represented by the formula (II) was obtained.
(2) 18.56g (0.1mol) of 3-nitrobenzoyl chloride, 14.67g (0.11mol) of aluminum trichloride, 250g of 1, 2-dichloroethane and 22.07g (0.09mol) of the structural compound (II-3) shown in the formula (II) are sequentially added into a reactor and stirred for reaction for 18 hours at the temperature of 30 ℃; then slowly adding the crude product into ice-hydrochloric acid for treatment, separating liquid, drying by anhydrous magnesium sulfate, concentrating the solvent to obtain a crude product, and recrystallizing to obtain 22.45g of a refined product of a structural compound (III-7) shown in a formula (III); the yield thereof was found to be 64%.
(3) 39.43g (0.1mol) of the structural compound (III-7) represented by the formula (III), 101.15g (40%, 0.5mol) of hydrobromic acid and 350g of acetic acid were sequentially added to a reactor, and the reaction was stirred at 100 ℃ for 48 hours; after hydrobromic acid and acetic acid were recovered by concentration, the residue was dissolved in methylene chloride, neutralized to alkaline with a saturated sodium carbonate solution, separated, dried over anhydrous magnesium sulfate, and the solvent was concentrated to obtain a crude product, which was recrystallized to obtain 34.22g of a purified product of the structural compound (VI-7) represented by the formula (VI), with a yield of 90%.
(4) Adding 45.64g (0.12mol) of a structural compound (VI-7) shown in a formula (VI), 243.7g (1.08mol) of stannous chloride dihydrate and 700mL of ethyl acetate into a reactor in sequence, and stirring and reacting at 70 ℃ for 3 h; cooling to room temperature, adding into saturated sodium carbonate solution, neutralizing to alkaline, separating, drying with anhydrous sodium carbonate, concentrating solvent to obtain crude product, and recrystallizing to obtain 33.05g refined product of compound (V-7) with structure shown in formula (V); the yield thereof was found to be 86%.
Example 5
(1) Adding 62.07g (0.50mol) of 3-methoxyphenol, 101.0g (0.50mol) of m-bromonitrobenzene, 4.76g (0.025mol) of cuprous iodide, 76.02g (0.55 mol) of potassium carbonate and 200g of N, N-dimethylformamide into a reaction bottle in sequence, and heating the reaction system to 150 ℃ under the protection of nitrogen to react for 12 hours; cooling to 60 ℃, adding the mixture into 2000ml of water, separating out a crude product, filtering, washing with water, dissolving in dichloromethane, drying with anhydrous magnesium sulfate, concentrating a solvent, and purifying to obtain 90.59g of a refined product of a compound (II-2) with a structure shown in a formula (II); the yield thereof was found to be 73.9%.
(2) 89.07g (0.48mol) of 4-nitrobenzoyl chloride, 69.34g (0.52mol) of aluminum trichloride, 1000mL of dichloromethane and 105.45g (0.43mol) of a structural compound (II-2) shown in the formula (II) are sequentially added into a reactor and stirred to react for 18 hours at the temperature of 20 ℃; then slowly adding the crude product into ice-hydrochloric acid for treatment, separating liquid, drying by anhydrous magnesium sulfate, concentrating the solvent to obtain a crude product, and recrystallizing to obtain 96.56g of a refined product of a structural compound (III-2) shown in a formula (III); the yield thereof was found to be 56.9%.
(3) 23.66g (0.06mol) of the structural compound (III-2) shown in the formula (III), 121.85g (0.54mol) of stannous chloride dihydrate and 350mL of ethyl acetate are sequentially added into a reactor, and stirred and reacted for 3 hours at 70 ℃; cooling to room temperature, adding into saturated sodium carbonate solution, neutralizing to alkaline, separating, drying with anhydrous sodium carbonate, concentrating solvent to obtain crude product, and recrystallizing to obtain 14.23g refined product of compound (IV-2) with structure shown in formula (IV); the yield thereof was found to be 71.0%.
(4) 44g (0.108mol) of a hydrochloride of the structural compound (IV-2) represented by the formula (IV), 109.24g (40%, 0.54mol) of hydrobromic acid and 330g of acetic acid were sequentially added to a reactor, and the reaction was stirred at 100 ℃ for 84 hours; concentrating to recover hydrobromic acid and acetic acid, neutralizing the residue with saturated sodium carbonate solution to alkalinity, extracting with dichloromethane, separating, drying with anhydrous sodium carbonate, concentrating the solvent to obtain crude product, and recrystallizing to obtain 28.37g refined product of compound (V-2) with structure shown in formula (V); the yield thereof was found to be 82.0%.
Example 6
(1) Referring to step (1) of example 5, a purified product of the compound (II-2) having the structure represented by the formula (II) was obtained.
(2) 18.56g (0.1mol) of 3-nitrobenzoyl chloride, 14.67g (0.11mol) of aluminum trichloride, 250g of 1, 2-dichloroethane and 22.07g (0.09mol) of the structural compound (II-2) shown in the formula (II) are sequentially added into a reactor and stirred for reaction for 30 hours at the temperature of 20 ℃; then slowly adding the crude product into ice-hydrochloric acid for treatment, separating liquid, drying by anhydrous magnesium sulfate, concentrating the solvent to obtain a crude product, and recrystallizing to obtain 22.98g of a refined product of a structural compound (III-4) shown in a formula (III); the yield thereof was found to be 64.7%.
(3) 39.43g (0.1mol) of the structural compound (III-4) represented by the formula (III), 101.15g (40%, 0.5mol) of hydrobromic acid and 350g of acetic acid were sequentially added to a reactor, and the reaction was stirred at 100 ℃ for 48 hours; after concentrating and recovering hydrobromic acid and acetic acid, dissolving the residue with dichloromethane, neutralizing with saturated sodium carbonate solution to alkalinity, separating liquid, drying with anhydrous magnesium sulfate, concentrating the solvent to obtain a crude product, and recrystallizing to obtain 32.54g of a refined product of a compound (VI-4) with a structure shown in formula (VI); the yield thereof was found to be 85.6%.
(4) Adding 45.64g (0.12mol) of a structural compound (VI-4) shown in a formula (VI), 243.7g (1.08mol) of stannous chloride dihydrate and 700mL of ethyl acetate into a reactor in sequence, and stirring and reacting at 70 ℃ for 3 h; cooling to room temperature, adding into saturated sodium carbonate solution, neutralizing to alkaline, separating, drying with anhydrous sodium carbonate, concentrating solvent to obtain crude product, and recrystallizing to obtain 33.72g refined product of compound (V-4) with structure shown in formula (V); the yield thereof was found to be 87.7%.
Example 7
(1) Adding 62.07g (0.50mol) of 4-methoxyphenol, 101.0g (0.50mol) of m-bromonitrobenzene, 4.76g (0.025mol) of cuprous iodide, 76.02g (0.55 mol) of potassium carbonate and 200g of N, N-dimethylformamide into a reaction bottle in sequence, and heating the reaction system to 150 ℃ under the protection of nitrogen to react for 12 hours; cooling to 60 ℃, adding the mixture into 2000ml of water, separating out a crude product, filtering, washing with water, dissolving in dichloromethane, drying with anhydrous magnesium sulfate, concentrating a solvent, and purifying to obtain 92.12g of a refined product of a compound (II-4) with a structure shown in a formula (II); the yield thereof was found to be 75.1%.
(2) 89.07g (0.48mol) of 4-nitrobenzoyl chloride, 69.34g (0.52mol) of aluminum trichloride, 1000mL of dichloromethane and 105.45g (0.43mol) of a structural compound (II-4) shown in the formula (II) are sequentially added into a reactor and stirred to react for 15 hours at the temperature of 30 ℃; then slowly adding the crude product into ice-hydrochloric acid for treatment, separating liquid, drying by anhydrous magnesium sulfate, concentrating the solvent to obtain a crude product, and recrystallizing to obtain 87.63g of a refined product of a structural compound (III-6) shown in a formula (III); the yield thereof was found to be 51.7%.
(3) 23.66g (0.06mol) of the structural compound (III-6) shown in the formula (III), 121.85g (0.54mol) of stannous chloride dihydrate and 350mL of ethyl acetate are sequentially added into a reactor, and stirred and reacted for 3 hours at 70 ℃; cooling to room temperature, adding into saturated sodium carbonate solution, neutralizing to alkaline, separating, drying with anhydrous sodium carbonate, concentrating solvent to obtain crude product, and recrystallizing to obtain 16.36g refined product of compound (IV-6) with structure shown in formula (IV); the yield thereof was found to be 81.6%.
(4) 44g (0.108mol) of a hydrochloride of the structural compound (IV-6) represented by the formula (IV), 109.24g (40%, 0.54mol) of hydrobromic acid and 330g of acetic acid were sequentially added to a reactor, and the reaction was stirred at 100 ℃ for 84 hours; concentrating to recover hydrobromic acid and acetic acid, neutralizing the residue with saturated sodium carbonate solution to alkalinity, extracting with dichloromethane, separating, drying with anhydrous sodium carbonate, concentrating the solvent to obtain crude product, and recrystallizing to obtain 28.62g refined product of compound (V-6) with structure shown in formula (V); the yield thereof was found to be 82.7%.
Example 8
(1) Referring to step (1) of example 7, a purified product of the compound (II-4) having a structure represented by the formula (II) was obtained.
(2) 18.56g (0.1mol) of 3-nitrobenzoyl chloride, 14.67g (0.11mol) of aluminum trichloride, 250g of 1, 2-dichloroethane and 22.07g (0.09mol) of the structural compound (II-4) shown in the formula (II) are sequentially added into a reactor and stirred for reaction for 18 hours at the temperature of 30 ℃; then slowly adding the mixture into ice-hydrochloric acid for treatment, separating liquid, drying by anhydrous magnesium sulfate, concentrating the solvent to obtain a crude product, and recrystallizing to obtain 20.78g of a refined product of a structural compound (III-8) shown in a formula (III); the yield thereof was found to be 59.2%.
(3) 39.43g (0.1mol) of the structural compound (III-8) represented by the formula (III), 101.15g (40%, 0.5mol) of hydrobromic acid and 350g of acetic acid were sequentially added to a reactor, and the reaction was stirred at 100 ℃ for 48 hours; after hydrobromic acid and acetic acid were recovered by concentration, the residue was dissolved in methylene chloride, neutralized to alkaline with a saturated sodium carbonate solution, separated, dried over anhydrous magnesium sulfate, and the solvent was concentrated to obtain a crude product, which was recrystallized to obtain 32.03g of a purified product of the structural compound (VI-8) represented by the formula (VI), with a yield of 84.2%.
(4) Adding 45.64g (0.12mol) of a structural compound (VI-8) shown in a formula (VI), 243.7g (1.08mol) of stannous chloride dihydrate and 700mL of ethyl acetate into a reactor in sequence, and stirring and reacting at 70 ℃ for 3 h; cooling to room temperature, adding into saturated sodium carbonate solution, neutralizing to alkaline, separating, drying with anhydrous sodium carbonate, concentrating solvent to obtain crude product, and recrystallizing to obtain 31.14g refined product of compound (V-8) with structure shown in formula (V); the yield thereof was found to be 81.0%.
Example 9
Under the condition of nitrogen at normal temperature and normal pressure, adding 0.1mol (32.04g) of V-1 diamine monomer, 0.5mol (100.12g) of 4,4' -diaminodiphenyl ether and 12.08mol (1052.13g) of N, N-dimethylacetamide into a reactor, stirring and dissolving, then adding 0.6mol (130.87g) of pyromellitic dianhydride, and stirring for 24 hours to obtain a viscous polyamic acid solution; spin-coating the obtained polyamic acid solution on a dry and clean glass plate, heating at constant temperature of 80 ℃, 150 ℃, 250 ℃, 280 ℃ and 300 ℃ for 1h respectively to remove the solvent and carry out imidization reaction, then cooling to room temperature, and soaking the glass plate attached with the film in deionized water to obtain the polyimide film.
According to the test (test standard GB/T13022-.
Comparative example 1
Adding 0.6mol (120.14g) of 4,4' -diaminodiphenyl ether and 12.08mol (1052.13g) of N, N-dimethylacetamide into a reactor under the condition of normal temperature and pressure and nitrogen, stirring for dissolving, adding 0.6mol (130.87g) of pyromellitic dianhydride, and stirring for 24 hours to obtain a viscous polyamic acid solution; spin-coating the obtained polyamic acid solution on a dry and clean glass plate, heating at constant temperature of 80 ℃, 150 ℃, 250 ℃, 280 ℃ and 300 ℃ for 1h respectively to remove the solvent and carry out imidization reaction, then cooling to room temperature, and soaking the glass plate attached with the film in deionized water to obtain the polyimide film.
According to the test (test standard GB/T13022-.
Comparative example 2
Adding 0.6mol (120.14g) of 4,4' -diaminodiphenyl ether and 12.08mol (1052.13g) of N, N-dimethylacetamide into a reactor under the condition of normal temperature and pressure and nitrogen, stirring and dissolving, then adding 0.6mol (130.87g) of pyromellitic dianhydride and 25.10g of titanium dioxide nanoparticles, and stirring for 24 hours to obtain a viscous polyamide acid solution containing the titanium dioxide nanoparticles; spin-coating the obtained solution on a dry and clean glass plate, heating at constant temperature of 80 ℃, 150 ℃, 250 ℃, 280 ℃ and 300 ℃ for 1h respectively to remove the solvent and carry out imidization reaction, then cooling to room temperature, and soaking the glass plate attached with the film in deionized water to obtain the polyimide film containing the titanium dioxide nano-particles.
Through tests (test standard GB/T13022-.
The ultraviolet-visible absorption spectra (in tetrahydrofuran) of the compound (V-1) having the structure represented by the formula (V) obtained in example 1 and the compound (V-3) having the structure represented by the formula (V) obtained in example 2 were respectively characterized, and the results are shown in fig. 1 to 2.
Therefore, the aromatic diamine monomer obtained by the preparation method provided by the invention is diamine containing an o-hydroxy benzophenone structural unit, the o-hydroxy benzophenone structural unit can be introduced into the main chain of the polyimide high polymer material by a copolymerization method, the obtained polyimide material has excellent intrinsic ultraviolet radiation resistance, and various defects of preparing an ultraviolet radiation resistant polyimide material by a doping method are overcome; the diamine monomer can be widely applied to the preparation of various ultraviolet radiation resistant polyimide materials, can be used for preparing polyimide materials with intrinsic ultraviolet resistance functions, and can also be used for preparing high-performance polymers such as ultraviolet resistant functional 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. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (8)

1. A preparation method of aromatic diamine monomer comprises the following steps:
a) carrying out etherification reaction on methoxyphenol and substituted nitrobenzene with the structure shown in the formula (I) in the presence of an alkaline catalyst to obtain a compound with the structure shown in the formula (II); the methoxyphenol is 3-methoxyphenol or 4-methoxyphenol;
Figure FDA0002532587580000011
in the formula (I), X is fluorine, chlorine, bromine, iodine, methylsulfonyloxy, trifluoromethanesulfonyloxy or p-toluenesulfonyloxy, R7And R8Independently selected from hydrogen or nitro, and R7And R8Different;
Figure FDA0002532587580000012
in the formula (II), R9And R10Independently selected from hydrogen or methoxy, and R9And R10Different;
b) carrying out Friedel-crafts acylation reaction on a compound with a structure shown in a formula (II) and nitrobenzoyl halide in the presence of a catalyst to obtain a compound with a structure shown in a formula (III); the nitrobenzoyl halide is 3-nitrobenzoyl halide or 4-nitrobenzoyl halide;
Figure FDA0002532587580000013
in the formula (III), R11And R12Independently selected from methoxy or
Figure FDA0002532587580000014
And R is11And R12In a different sense, R13And R14Independently selected from hydrogen or nitro, and R13And R14Different;
c) carrying out reduction reaction on the compound with the structure shown in the formula (III) to obtain a compound with the structure shown in the formula (IV);
Figure FDA0002532587580000015
in the formula (IV), R15And R16Independently selected from methoxy or
Figure FDA0002532587580000021
And R is15And R16Different;
then carrying out demethylation reaction on the compound with the structure shown in the formula (IV) to obtain an aromatic diamine monomer with the structure shown in the formula (V);
Figure FDA0002532587580000022
in the formula (V), R1And R2Independently selected from hydroxy or
Figure FDA0002532587580000023
And R is1And R2In a different sense, R3、R4、R5、R6Independently selected from hydrogen or amino, and R3And R4In a different sense, R5And R6Different;
or the like, or, alternatively,
carrying out demethylation reaction on the compound with the structure shown in the formula (III) to obtain a compound with the structure shown in the formula (VI);
Figure FDA0002532587580000024
in the formula (VI), R17And R18Independently selected from hydroxy or
Figure FDA0002532587580000025
And R is17And R18Different;
and then carrying out reduction reaction on the compound with the structure shown in the formula (VI) to obtain the aromatic diamine monomer with the structure shown in the formula (V).
2. The preparation method according to claim 1, wherein the molar ratio of the substituted nitrobenzene, the basic catalyst and the methoxyphenol in step a) is (0.8-1.25): (1-1.5): 1.
3. the process according to claim 1, wherein the temperature of the etherification reaction in step a) is 140 to 170 ℃.
4. The preparation method according to claim 1, wherein the molar ratio of the nitrobenzoyl halide, the catalyst and the compound having the structure shown in the formula (II) in the step b) is (1-2): (1.1-1.8): 1.
5. the method according to claim 1, wherein the temperature of the friedel-crafts acylation in step b) is between 0 ℃ and 40 ℃.
6. The preparation method according to claim 1, wherein stannous chloride is used as a reducing agent in the reduction reaction in the step c); the molar ratio of the reducing agent to the compound having the structure represented by the formula (III) is (7-12): 1.
7. the method according to claim 1, wherein the temperature of the reduction reaction in step c) is 50 to 80 ℃.
8. The method according to claim 1, wherein the demethylation reaction in step c) is carried out using a hydrobromic acid-acetic acid system; the mass ratio of acetic acid to hydrobromic acid in the hydrobromic acid-acetic acid system is (2-5): 1; the molar ratio of hydrobromic acid to a compound with a structure shown in a formula (IV) in the hydrobromic acid-acetic acid system is (3-8): 1.
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