CN110713718A - Polyimide-based traction belt - Google Patents

Polyimide-based traction belt Download PDF

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CN110713718A
CN110713718A CN201911174141.4A CN201911174141A CN110713718A CN 110713718 A CN110713718 A CN 110713718A CN 201911174141 A CN201911174141 A CN 201911174141A CN 110713718 A CN110713718 A CN 110713718A
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polyimide
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fibers
polyimide resin
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CN110713718B (en
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矫龙
代学民
杜志军
姚海波
王汉夫
邱雪鹏
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Changchun Institute of Applied Chemistry of CAS
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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 provides a polyimide-based traction belt, which is prepared by the following steps: uniformly spreading untwisted continuous fibers, preheating, fully impregnating the untwisted continuous fibers with polyimide resin, and shaping to obtain a polyimide-based dragging tape; the polyimide resin is prepared by the following method: polymerizing aromatic dianhydride, aromatic diamine and a capping agent in an organic solvent to obtain polyamic acid solution; adding nonpolar aromatic hydrocarbon into the polyamic acid solution, heating for cyclization and dehydration, separating out powder, washing, drying and granulating to obtain polyimide resin; the aromatic diamine is selected from any one or more of structures of a formula V-1 to a formula V-8. The traction belt has high mechanical properties such as tensile strength; has excellent ray irradiation resistance(ii) a The paint also has the excellent performances of small specific gravity, high temperature resistance grade, long service life, low thermal expansion coefficient, low content of volatile matters in vacuum environment and the like. It can be applied to the fields of aviation, aerospace, nuclear industry, civil traction and the like.

Description

Polyimide-based traction belt
The present application claims priority from a chinese patent application filed by the chinese patent office on 2019, month 07, 08, under the application serial number 201910610423.8 entitled "a polyimide-based towing tape," the entire contents of which are incorporated herein by reference.
Technical Field
The invention belongs to the technical field of traction belts, and particularly relates to a polyimide-based traction belt.
Background
The composite material traction belt is a traction material composed of fibers and resin, plays an important role in the aspects of traction and bearing due to the advantages of flexibility, light weight, high tensile strength and the like, and is widely applied to the fields of war industry, buildings, production and the like. The common resins comprise epoxy resin, polyester resin, polypropylene resin, polysulfone resin, polyimide resin and the like, wherein the polyimide resin is a high-performance resin containing imide rings, has the advantages of high and low temperature resistance, good mechanical properties, high dimensional stability and the like, and the high-performance traction belt prepared by compounding the polyimide resin with fibers is widely applied to the high-technology field.
The traditional composite material traction belt generally adopts general engineering plastics as a resin matrix, and the general engineering plastics have the problems of solvent intolerance, low heat-resistant grade, poor mechanical property, poor environmental adaptability and the like. Moreover, the prior composite material dragging belt resistant to ray irradiation is less, and the application of the composite material dragging belt in the high-tech field is limited.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a polyimide-based traction tape having a high tensile strength.
The invention provides a polyimide-based traction belt, which is prepared by the following steps:
uniformly spreading untwisted continuous fibers, preheating, fully impregnating the untwisted continuous fibers with polyimide resin, and shaping to obtain a polyimide-based dragging tape;
the polyimide resin is prepared by the following method:
polymerizing aromatic dianhydride, aromatic diamine and a capping agent in an organic solvent to obtain polyamic acid solution;
adding nonpolar aromatic hydrocarbon into the polyamic acid solution, heating for cyclization and dehydration, separating out powder, washing, drying and granulating to obtain polyimide resin;
the aromatic diamine is selected from any one or more of structures of a formula V-1 to a formula V-8:
Figure BDA0002289525080000021
preferably, the aromatic dianhydride is selected from one or more of formula 101, formula 102 and formula 103;
Figure BDA0002289525080000022
Figure BDA0002289525080000023
in formula 103A is selected from-O-),
Figure BDA0002289525080000024
Figure BDA0002289525080000025
Preferably, the aromatic diamine further comprises one or more of formulae 301 to 306:
Figure BDA0002289525080000026
Figure BDA0002289525080000031
preferably, the untwisted continuous fibers are selected from one or more of carbon fibers, glass fibers, polyimide fibers, aramid fibers, PBO fibers;
the number of the untwisted continuous fibers is 1k to 50 k.
Preferably, the polymerization temperature is-10 to 50 ℃; the polymerization time is 1-24 h.
Preferably, the temperature of the cyclodehydration is 100-170 ℃; the time for cyclodehydration is 1-15 h.
Preferably, the organic solvent is selected from polar aprotic solvents; the polar aprotic solvent is selected from one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, and N-methylpyrrolidone.
Preferably, the mass ratio of the aromatic dianhydride to the aromatic diamine is 0.9: 1-1: 0.9.
preferably, the preheating temperature is 200-300 ℃;
the dipping temperature is 350-400 ℃.
Preferably, the width of the dragging belt is 1.0-50.0 mm, and the thickness of the dragging belt is 0.1-1.0 mm.
The invention provides a polyimide-based traction belt, which is prepared by the following steps: uniformly spreading untwisted continuous fibers, preheating, fully impregnating the untwisted continuous fibers with polyimide resin, and shaping to obtain a polyimide-based dragging tape; the polyimide resin is prepared by the following method: polymerizing aromatic dianhydride, aromatic diamine and a capping agent in an organic solvent to obtain polyamic acid solution; adding nonpolar aromatic hydrocarbon into the polyamic acid solution, heating for cyclization and dehydration, separating out powder, washing, drying and granulating to obtain polyimide resin; the aromatic diamine is selected from any one or more of structures of a formula V-1 to a formula V-8. The dragging belt is prepared by tightly coating untwisted continuous fibers with polyimide resin, the polyimide resin is prepared into polyimide matrix resin by adopting aromatic diamine with a V-1-V-8 structure and other polymerization monomers, and an o-hydroxy benzophenone structural unit is introduced into a polyimide molecular chain, so that hydrogen bonds are formed in the polyimide molecular chain, the interface bonding capability with the fibers is enhanced, and the mechanical properties of the dragging belt, such as tensile strength, are effectively improved; polyimide resin containing an o-hydroxybenzophenone structure enables the traction belt to have excellent radiation irradiation resistance. Meanwhile, the traction belt also has the excellent performances of small specific gravity, high temperature resistance grade, long service life, low thermal expansion coefficient, low volatile matter content in vacuum environment and the like. It can be applied to the fields of aviation, aerospace, nuclear industry, civil traction and the like. The experimental results show that: after 2000 hours of ultraviolet irradiation of the dragging belt, the tensile strength is 580-1090 MPa, and the tensile strength retention rate is 99-100%; the tensile strength after electron beam irradiation is 586-1075 MPa, and the tensile strength retention rate is 98-100%.
Drawings
Fig. 1 is a schematic view showing the appearance of a traction tape produced in example 1 of the present invention.
Detailed Description
The invention provides a polyimide-based traction belt, which is prepared by the following steps:
uniformly spreading untwisted continuous fibers, preheating, fully impregnating the untwisted continuous fibers with molten polyimide resin, and shaping to obtain a polyimide-based dragging belt;
the polyimide resin is prepared by the following method:
polymerizing aromatic dianhydride, aromatic diamine and a capping agent in an organic solvent to obtain polyamic acid solution;
adding nonpolar aromatic hydrocarbon into the polyamic acid solution, heating for cyclization and dehydration, separating out powder, washing, drying and granulating to obtain polyimide resin;
the aromatic diamine is selected from any one or more of structures of a formula V-1 to a formula V-8:
the dragging belt is prepared by tightly coating untwisted continuous fibers with polyimide resin, the polyimide resin is prepared into polyimide matrix resin by adopting aromatic diamine with a V-1-V-8 structure and other polymerization monomers, and an o-hydroxy benzophenone structural unit is introduced into a polyimide molecular chain, so that hydrogen bonds are formed in the polyimide molecular chain, the interface bonding capability with the fibers is enhanced, and the mechanical properties of the dragging belt, such as tensile strength, are effectively improved; polyimide resin containing an o-hydroxybenzophenone structure enables the traction belt to have excellent radiation irradiation resistance. Meanwhile, the traction belt also has the excellent performances of small specific gravity, high temperature resistance grade, long service life, low thermal expansion coefficient, low volatile matter content in vacuum environment and the like. It can be applied to the fields of aviation, aerospace, nuclear industry, civil traction and the like.
In the present invention, the untwisted continuous fibers are selected from one or more of carbon fibers, glass fibers, polyimide fibers, aramid fibers, PBO fibers; the number of the untwisted continuous fibers is 1k to 50 k. In particular embodiments, the untwisted continuous fibers are selected from one or more of 24k carbon fibers, 36k carbon fibers, 50k carbon fibers, 12k carbon fibers, 6k carbon fibers, 1k polyimide fibers, and 5k glass fibers.
In the present invention, the polyimide resin is prepared by the following method:
polymerizing aromatic dianhydride, aromatic diamine and a capping agent in an organic solvent to obtain polyamic acid solution;
adding nonpolar aromatic hydrocarbon into the polyamic acid solution, heating for cyclization and dehydration, separating out powder, washing, drying and granulating to obtain polyimide resin;
the invention adopts aromatic dianhydride, aromatic diamine and end capping agent to polymerize in organic solvent to obtain polyamic acid solution. In the present invention, the aromatic dianhydride is selected from one or more of formula 101, formula 102 and formula 103;
Figure BDA0002289525080000051
Figure BDA0002289525080000052
in formula 103A is selected from-O-),
Figure BDA0002289525080000053
Figure BDA0002289525080000054
In a particular embodiment of the invention, the aromatic dianhydride is selected from bisphenol A type diether dianhydrides, i.e. bisphenol A type diether dianhydrides
Or 4, 4' -biphenyldianhydride, i.e.
Figure BDA0002289525080000061
Or pyromellitic dianhydride; or 3, 3' -triphenyldiether dianhydride, i.e.
Figure BDA0002289525080000062
Or 4, 4' -diphenyl ether dianhydride, i.e.
Figure BDA0002289525080000063
In the present invention, the aromatic diamine is selected from any one or more of structures from V-1 to formula V-8:
the aromatic diamine with the V-1-type V-8 structure is diamine with an o-hydroxybenzophenone structure, and the monomer is polymerized with other monomers, so that an o-hydroxybenzophenone structural unit is introduced into a polyimide molecular chain, and a hydrogen bond is formed in the polyimide molecular chain, so that the interfacial bonding capability with fibers is enhanced, and the mechanical property of a dragging belt is effectively improved; and the structure can make the dragging belt have excellent radiation irradiation resistance.
In the present invention, the aromatic diamine is preferably produced by the following method:
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;
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 BDA0002289525080000072
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 BDA0002289525080000073
in the formula (III), R11And R12Independently selected from methoxy or
Figure BDA0002289525080000074
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 BDA0002289525080000075
in the formula (IV), R15And R16Independently selected from methoxy orAnd 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 BDA0002289525080000081
in the formula (VI), R17And R18Independently selected from hydroxy or
Figure BDA0002289525080000082
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:
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:
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 BDA0002289525080000111
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 BDA0002289525080000121
Figure BDA0002289525080000131
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 BDA0002289525080000141
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.
In order to adjust the thermal, processing, mechanical and radiation resistance properties of the traction tape, it is preferable to further add another kind of aromatic diamine during the preparation of the polyamic acid solution. The aromatic diamine preferably further comprises one or more of formulae 301 to 306:
Figure BDA0002289525080000151
in the present invention, the ratio of the aromatic dianhydride to the aromatic diamine is 0.9:1 to 1: 0.9.
In the present invention, the end-capping agent is preferably selected from Phthalic Anhydride (PA), benzoyl chloride or aniline; the mass ratio of the end-capping agent to the aromatic diamine is 0:10 to 2: 9.
In the specific embodiment of the invention, the types and the amounts of the raw materials are as follows:
the mass ratio of bisphenol A type diether dianhydride, m-phenylenediamine, diamine with a structure shown in a formula V-1 and pyromellitic anhydride is 9.6:9:1: 0.8;
or the mass ratio of the bisphenol A type diether dianhydride, the p-phenylenediamine, the diamine with the structure shown in the formula V-4 and the pyromellitic dianhydride is 9.6:9:1: 0.8;
or the mass ratio of the bisphenol A type diether dianhydride, the m-phenylenediamine, the diamine with the structure shown in the formula V-8 and the pyromellitic dianhydride is 9.6:7:3: 0.8;
or the mass ratio of 4,4 '-diphenyl ether dianhydride, 3, 4' -diaminodiphenyl ether, diamine with the structure shown in the formula V-1 and pyromellitic anhydride is 9.7:9:1: 0.6;
or the mass ratio of the pyromellitic dianhydride, the 4, 4' -bis (3-aminophenoxy) biphenyl, the diamine with the structure shown in the formula V-2 and the pyromellitic anhydride is 9.7:9:1: 0.6;
or the mass ratio of the 3,3 '-triphenyl diether dianhydride, the 4, 4' -diaminodiphenyl ether, the diamine with the structure shown in the formula V-6 and the pyromellitic dianhydride is 9.7:9:1: 0.6;
or the mass ratio of 4,4 '-biphenyl dianhydride, 1, 3' -bis (4-aminophenoxy) benzene, diamine of the structure shown in the formula V-7 and pyromellitic anhydride is 9.7:9:1: 0.6;
or 4,4 '-biphenyl dianhydride, 1, 3' -bis (4-aminophenoxy) benzene, diamine having a structure represented by V-7 and pyromellitic anhydride in a ratio of 9.6:5:5: 0.8.
The organic solvent is preferably selected from polar aprotic solvents; the polar aprotic solvent is preferably selected from one or more of N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), Dimethylsulfoxide (DMSO), and N-methylpyrrolidone (NMP).
The polymerization temperature is preferably-10-50 ℃, and more preferably 10-30 ℃; in a specific embodiment, the temperature of the polymerization is room temperature. The polymerization time is preferably 1-24 h, and more preferably 7-15 h; in a specific embodiment, the time for polymerization is 12 h.
In the invention, the solid content of the polyamic acid solution is preferably 5-35 wt%.
After the polyamic acid solution is obtained, the polyamic acid solution is added with nonpolar aromatic hydrocarbon to be heated and cyclized for dehydration, and the polyimide resin is obtained after powder is separated out, washed, dried and granulated. In the present invention, the non-polar aromatic hydrocarbon is preferably selected from one or more of toluene, xylene, chlorobenzene, and o-dichlorobenzene; the mass of the nonpolar aromatic hydrocarbon accounts for 10-100% of the mass of the organic solvent. The temperature of the cyclodehydration is preferably 100-170 ℃; in specific embodiments, the temperature of the cyclodehydration is specifically 160 ℃, 165 ℃ or 170 ℃. The time for the cyclodehydration is preferably 1-15 h, more preferably 4-8 h; in a specific example, the time for cyclodehydration is specifically 5 h.
Washing preferably with acetone or ethanol; the number of washing is preferably 2 to 6. The drying temperature is preferably 80-200 ℃. In a specific example, drying was carried out at 200 ℃ for 10 h.
In order to adjust the properties of the matrix resin, the polyimide resin powder and one or more of polyether-ether-ketone resin, polyphenylene sulfide resin and polyether sulfone resin are preferably blended before granulation, and then extrusion granulation is performed.
Preferably, the invention adopts a tractor to lead out the untwisted continuous fibers from a creel shaft, uniformly spreads the untwisted continuous fibers through a yarn spreading roller, and preheats the untwisted continuous fibers through a drying tunnel; the preheating temperature is preferably 200-300 ℃; in specific embodiments, the preheating temperature is 270 ℃, 290 ℃, 265 ℃, 260 ℃, 230 ℃ or 220 ℃.
The invention preferably impregnates in a dipping tank; the dipping temperature is preferably 350-400 ℃; in the examples, the impregnation temperature was 385 ℃, 395 ℃, 390 ℃, 380 ℃, 375 ℃ or 370 ℃. The expanded and preheated fibers enter a glue dipping tank connected with an extruder, the fibers are fully dipped by thermoplastic resin through a dipping roller, and the shape and the size of the dragging belt are adjusted through a shaping die. The extruding temperature of the extruder is 350-400 ℃; in specific embodiments, the temperature of extrusion is 370 ℃, 380 ℃, 390 ℃, 385 ℃ or 395 ℃.
The invention is preferably cooled and shaped in air. And obtaining the polyimide-based dragging belt through a traction roller and a winding device. The traction speed is 0.5 m/min-10 m/min; in a specific embodiment, the speed of the traction is 5m/min, 3m/min, 10m/min, 6m/min or 7 m/min.
The tensile strength and the maximum tensile load of the composite material traction belt provided by the invention are tested by adopting the GB/T3362-2005 carbon fiber multifilament tensile property test method, and the test result shows that the tensile strength of the composite material traction belt provided by the invention is 600-1300 MPa, and the maximum tensile load is 80-7000N.
To further illustrate the present invention, a polyimide-based traction tape provided by the present invention will be described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Preparatory 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)δ＝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)δ＝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)δ＝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)δ＝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)。
preparatory example 2
(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 (0.55mol) of potassium carbonate and 200g N, N-dimethylformamide into a reaction bottle in sequence, and heating the reaction system to 150 ℃ under the protection of nitrogen for reaction 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%.
Preparatory example 3
(1) Referring to step (1) of preparative example 2, 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%.
Preparatory example 4
(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 (0.55mol) 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 for reaction 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%.
Preparatory example 5
(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) 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%.
Preparatory example 6
(1) Referring to step (1) of preparative example 4, 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 1
The polyimide resin was prepared according to the following method
To a 100 liter reaction vessel equipped with a mechanical stirrer, nitrogen blanket, water and a condensing reflux apparatus were charged 4.997kg (9.6mol) of bisphenol A type diether dianhydride, 0.973kg (9mol) of m-phenylenediamine, 0.32kg (1mol) of the diamine having the structure represented by formula V-1 prepared in preparative example 1, 0.118kg (0.8mol) of phthalic anhydride, and 40kg of N, N-dimethylacetamide (DMAc) and reacted at room temperature for 12 hours to obtain a polyamic acid solution. Adding 10kg of dimethylbenzene into the obtained polyamic acid solution, refluxing at 160 ℃ for 5 hours with water, filtering, washing with ethanol for 4 times, and drying at 200 ℃ for 10 hours to finally obtain polyimide resin powder.
The composite traction belt is prepared according to the following method
The 24k carbon fibers are led out from a creel shaft through a tractor, uniformly spread through a spreading roller, preheated through a drying tunnel, enter an impregnation tank, an extruder is started, molten polyimide resin enters the impregnation tank, the carbon fibers fully impregnate the resin, then pass through a sizing die, and finally are cooled and wound in the air. In the preparation process, the temperature of the drying tunnel is 220 ℃, the temperature of the glue dipping tank is 370 ℃, the temperature of the extruder is 370 ℃, the size of the shaping neck ring mold is 20 multiplied by 0.3mm, and the speed of the tractor is 5 m/min.
According to the method of the technical scheme, the tensile strength and the maximum tensile load of the composite traction tape prepared in the embodiment 1 of the invention are tested, and the test result shows that the tensile strength of the composite traction tape prepared in the embodiment 1 of the invention is 930MPa, and the maximum tensile load is 3030N.
Fig. 1 is a schematic view showing the appearance of a traction tape produced in example 1 of the present invention.
Example 2:
the polyimide resin was prepared according to the following method
To a 100 liter reaction vessel equipped with a mechanical stirrer, nitrogen blanket, water and a condensing reflux unit were charged 4.997kg (9.6mol) of bisphenol A type diether dianhydride, 0.973kg (9mol) of p-phenylenediamine, 0.32kg (1mol) of the diamine having the structure represented by formula V-4 prepared in preparative example 3, 0.118kg (0.8mol) of phthalic anhydride, and 36kg of N, N-dimethylacetamide (DMAc) and reacted at room temperature for 12 hours to obtain a polyamic acid solution. Adding 10kg of dimethylbenzene into the obtained polyamic acid solution, refluxing at 165 ℃ for 5 hours with water, filtering, washing with ethanol for 4 times, and drying at 200 ℃ for 10 hours to finally obtain polyimide resin powder.
The composite traction belt is prepared according to the following method
The 36k carbon fibers are led out from a creel shaft through a tractor, are uniformly spread through a spreading roller, enter an impregnation tank after being preheated through a drying channel, are started through an extruder, are made to enter the impregnation tank through molten polyimide resin, pass through a sizing neck mold after being fully impregnated with the resin, and are finally cooled and wound in the air. In the preparation process, the temperature of the drying tunnel is 230 ℃, the temperature of the gum dipping tank is 375 ℃, the temperature of the extruder is 380 ℃, the size of the sizing neck ring mold is 30 multiplied by 0.3mm, and the speed of the tractor is 6 m/min.
According to the method of the technical scheme, the tensile strength and the maximum tensile load of the composite traction tape prepared in the embodiment 2 of the invention are tested, and the test result shows that the tensile strength of the composite traction tape prepared in the embodiment 2 of the invention is 949MPa, and the maximum tensile load is 4230N.
Example 3:
the polyimide resin was prepared according to the following method
4.997kg (9.6mol) of bisphenol A type diether dianhydride, 0.757kg (7mol) of m-phenylenediamine, 0.961kg (3mol) of the diamine having the structure represented by the formula V-8 prepared in the above preparative example 6, 0.118kg (0.8mol) of phthalic anhydride, and 36kg of N, N-dimethylacetamide (DMAc) were charged into a 100 liter reaction vessel equipped with a mechanical stirring, nitrogen protection, water and a condensing reflux device, and reacted at room temperature for 12 hours to obtain a polyamic acid solution. Adding 8kg of dimethylbenzene into the obtained polyamic acid solution, refluxing at 160 ℃ for 5 hours with water, filtering, washing with ethanol for 4 times, and drying at 200 ℃ for 10 hours to finally obtain polyimide resin powder.
The composite traction belt is prepared according to the following method
Leading 50k carbon fibers out of a creel shaft through a tractor, uniformly spreading the fibers through a spreading roller, preheating the fibers through a drying tunnel, then entering an impregnation tank, starting an extruder, enabling molten polyimide resin to enter the impregnation tank, fully impregnating the resin with the carbon fibers, then passing through a sizing die, and finally cooling and winding in air. In the preparation process, the temperature of the drying tunnel is 260 ℃, the temperature of the gum dipping tank is 380 ℃, the temperature of the extruder is 380 ℃, the size of the shaping neck ring mold is 30 multiplied by 0.4mm, and the speed of the tractor is 3 m/min.
According to the method of the technical scheme, the tensile strength and the maximum tensile load of the composite traction belt prepared in the embodiment 3 of the invention are tested, and the test result shows that the tensile strength of the composite traction belt prepared in the embodiment 3 of the invention is 910MPa, and the maximum tensile load is 5620N.
Example 4:
the polyimide resin was prepared according to the following method
To a 100 liter reaction vessel equipped with a mechanical stirrer, nitrogen blanket, water, and a condensing reflux apparatus were charged 3.009kg (9.7mol) of 4,4 '-diphenylether dianhydride, 1.802kg (9mol) of 3, 4' -diaminodiphenylether, 0.32kg (1mol) of the diamine having the structure represented by formula V-1 prepared in preparative example 1, 0.089kg (0.6mol) of phthalic anhydride, and 30kg of N, N-dimethylacetamide (DMAc), and reacted at room temperature for 12 hours to obtain a polyamic acid solution. Adding 5kg of dimethylbenzene into the obtained polyamic acid solution, refluxing at 165 ℃ for 5 hours with water, filtering, washing with ethanol for 4 times, and drying at 200 ℃ for 10 hours to finally obtain polyimide resin powder.
The composite traction belt is prepared according to the following method
The 12k carbon fibers are led out from a creel shaft through a tractor, are uniformly unfolded through a yarn unfolding roller, enter an impregnation tank after being preheated through a drying tunnel, an extruder is started, molten polyimide resin enters the impregnation tank, the carbon fibers fully impregnate the resin, then pass through a sizing neck mold, and finally are cooled and wound in the air. In the preparation process, the temperature of the drying tunnel is 260 ℃, the temperature of the gum dipping tank is 380 ℃, the temperature of the extruder is 380 ℃, the size of the shaping neck ring mold is 10 multiplied by 0.3mm, and the speed of the tractor is 10 m/min.
According to the method of the technical scheme, the tensile strength and the maximum tensile load of the composite traction belt prepared in the embodiment 4 of the invention are tested, and the test result shows that the tensile strength of the composite traction belt prepared in the embodiment 4 of the invention is 1005MPa, and the maximum tensile load is 1600N.
Example 5:
the polyimide resin was prepared according to the following method
Into a 100 liter reaction vessel equipped with a mechanical stirrer, nitrogen blanket, water and a reflux condenser were charged 2.116kg (9.7mol) of pyromellitic dianhydride, 3.316kg (9mol) of 4, 4' -bis (3-aminophenoxy) biphenyl, 0.32kg (1mol) of diamine having the structure represented by formula V-2 prepared in the above preparative example 2, 0.089kg (0.6mol) of pyromellitic anhydride, and 35kg of N, N-dimethylacetamide (DMAc), and reacted at room temperature for 12 hours to obtain a polyamic acid solution. Adding 5kg of dimethylbenzene into the obtained polyamic acid solution, refluxing at 170 ℃ for 5 hours with water, filtering, washing with ethanol for 4 times, and drying at 200 ℃ for 10 hours to finally obtain polyimide resin powder.
The composite traction belt is prepared according to the following method
The 12k carbon fibers are led out from a creel shaft through a tractor, are uniformly unfolded through a yarn unfolding roller, enter an impregnation tank after being preheated through a drying tunnel, an extruder is started, molten polyimide resin enters the impregnation tank, the carbon fibers fully impregnate the resin, then pass through a sizing neck mold, and finally are cooled and wound in the air. In the preparation process, the temperature of the drying tunnel is 290 ℃, the temperature of the gum dipping tank is 390 ℃, the temperature of the extruder is 390 ℃, the size of the sizing neck ring mold is 10 multiplied by 0.3mm, and the speed of the tractor is 7 m/min.
According to the method of the technical scheme, the tensile strength and the maximum tensile load of the composite traction tape prepared in the embodiment 5 of the invention are tested, and the test result shows that the tensile strength of the composite traction tape prepared in the embodiment 5 of the invention is 1090MPa, and the maximum tensile load is 1689N.
Example 6:
the polyimide resin was prepared according to the following method
Into a 100 liter reaction vessel equipped with a mechanical stirrer, nitrogen blanket, water-carrying and condensing reflux apparatus were charged 3.903kg (9.7mol) of 3,3 '-triphendiether dianhydride, 1.802kg (9mol) of 4, 4' -diaminodiphenyl ether, 0.32kg (1mol) of diamine having the structure represented by formula V-6 prepared in preparative example 4, 0.089kg (0.6mol) of phthalic anhydride, and 35kg of N, N-dimethylacetamide (DMAc), and reacted at room temperature for 12 hours to obtain a polyamic acid solution. Adding 6kg of dimethylbenzene into the obtained polyamic acid solution, refluxing at 170 ℃ for 5 hours with water, filtering, washing with ethanol for 4 times, and drying at 200 ℃ for 10 hours to finally obtain polyimide resin powder.
The composite traction belt is prepared according to the following method
The 6k carbon fibers are led out from a creel shaft through a tractor, are uniformly spread through a spreading roller, enter an impregnation tank after being preheated through a drying tunnel, are started through an extruder, are made to enter the impregnation tank through molten polyimide resin, pass through a sizing neck mold after being fully impregnated with the resin, and are finally cooled and wound in the air. In the preparation process, the temperature of the drying tunnel is 265 ℃, the temperature of the glue dipping tank is 385 ℃, the temperature of the extruder is 385 ℃, the size of the shaping neck ring mold is 3 multiplied by 0.5mm, and the speed of the tractor is 6 m/min.
According to the method of the technical scheme, the tensile strength and the maximum tensile load of the composite traction tape prepared in the embodiment 6 of the invention are tested, and the test result shows that the tensile strength of the composite traction tape prepared in the embodiment 6 of the invention is 910MPa, and the maximum tensile load is 839N.
Example 7:
the polyimide resin was prepared according to the following method
Into a 100 liter reaction vessel equipped with a mechanical stirrer, nitrogen blanket, water-carrying and condensing reflux apparatus were charged 2.854kg (9.7mol) of 4,4 '-biphenyldianhydride, 2.631kg (9mol) of 1, 3' -bis (4-aminophenoxy) benzene, 0.32kg (1mol) of diamine having the structure represented by formula V-7 prepared in preparative example 5, 0.089kg (0.6mol) of phthalic anhydride, and 38kg of N, N-dimethylacetamide (DMAc), and reacted at room temperature for 12 hours to obtain a polyamic acid solution. Adding 5.5kg of dimethylbenzene into the obtained polyamic acid solution, refluxing at 170 ℃ for 5 hours with water, filtering, washing with ethanol for 4 times, and drying at 200 ℃ for 10 hours to finally obtain polyimide resin powder.
The composite traction belt is prepared according to the following method
Leading out 1k polyimide fibers from a creel shaft through a tractor, uniformly spreading the fibers through a yarn spreading roller, preheating the fibers through a drying tunnel, then entering an impregnation tank, starting an extruder, enabling molten polyimide resin to enter the impregnation tank, fully impregnating the resin with the polyimide fibers, then passing through a sizing die, and finally cooling and winding in air. In the preparation process, the temperature of the drying tunnel is 290 ℃, the temperature of the glue dipping tank is 395 ℃, the temperature of the extruder is 395 ℃, the size of the shaping neck ring is 3 multiplied by 0.1mm, and the speed of the tractor is 10 m/min.
According to the method of the technical scheme, the tensile strength and the maximum tensile load of the composite traction tape prepared in the embodiment 7 of the invention are tested, and the test result shows that the tensile strength of the composite traction tape prepared in the embodiment 7 of the invention is 610MPa, and the maximum tensile load is 359N.
Example 8:
the polyimide resin was prepared according to the following method
To a 100 liter reaction vessel equipped with a mechanical stirrer, nitrogen blanket, water and a condensing reflux device were charged 2.825kg (9.6mol) of 4,4 '-biphenyldianhydride, 1.462kg (5mol) of 1, 3' -bis (4-aminophenoxy) benzene, 1.601kg (5mol) of the diamine having the structure represented by the formula V-7 prepared in the above preparative example 5, 1.185kg (0.8mol) of phthalic anhydride, and 32kg of N, N-dimethylacetamide (DMAc), and reacted at room temperature for 12 hours to obtain a polyamic acid solution. Adding 5.5kg of dimethylbenzene into the obtained polyamic acid solution, refluxing at 170 ℃ for 5 hours with water, filtering, washing with ethanol for 4 times, and drying at 200 ℃ for 10 hours to finally obtain polyimide resin powder.
The composite traction belt is prepared according to the following method
Leading out 5k glass fiber from a creel shaft through a tractor, uniformly spreading the fiber through a fiber spreading roller, preheating the fiber through a drying tunnel, then entering an impregnation tank, starting an extruder, enabling molten polyimide resin to enter the impregnation tank, fully impregnating the resin with the glass fiber, then passing through a sizing die, and finally cooling and winding in air. In the preparation process, the temperature of the drying tunnel is 270 ℃, the temperature of the glue dipping tank is 385 ℃, the temperature of the extruder is 385 ℃, the size of the shaping neck ring mold is 5 multiplied by 0.3mm, and the speed of the tractor is 3 m/min.
According to the method of the technical scheme, the tensile strength and the maximum tensile load of the composite traction belt prepared in the embodiment 8 of the invention are tested, and the test result shows that the tensile strength of the composite traction belt prepared in the embodiment 8 of the invention is 710MPa, and the maximum tensile load is 646N.
Comparative example 1:
the polyimide resin was prepared according to the following method
4.997kg (9.6mol) of bisphenol A type diether dianhydride, 1.081kg (10mol) of m-phenylenediamine, 0.118kg (0.8mol) of phthalic anhydride, and 40kg of N, N-dimethylacetamide (DMAc) were charged into a 100 liter reaction vessel equipped with a mechanical stirring, nitrogen protection, water, and a condensing reflux unit, and reacted at room temperature for 12 hours to obtain a polyamic acid solution. Adding 10kg of dimethylbenzene into the obtained polyamic acid solution, refluxing at 160 ℃ for 5 hours with water, filtering, washing with ethanol for 4 times, and drying at 200 ℃ for 10 hours to finally obtain polyimide resin powder.
The composite traction belt is prepared according to the following method
The 24k carbon fibers are led out from a creel shaft through a tractor, uniformly spread through a spreading roller, preheated through a drying tunnel, enter an impregnation tank, an extruder is started, molten polyimide resin enters the impregnation tank, the carbon fibers fully impregnate the resin, then pass through a sizing die, and finally are cooled and wound in the air. In the preparation process, the temperature of the drying tunnel is 220 ℃, the temperature of the glue dipping tank is 370 ℃, the temperature of the extruder is 370 ℃, the size of the shaping neck ring mold is 20 multiplied by 0.3mm, and the speed of the tractor is 5 m/min.
According to the method of the technical scheme, the tensile strength and the maximum tensile load of the composite traction tape prepared in the comparative example 1 of the invention are tested, and the test result shows that the tensile strength of the composite traction tape prepared in the comparative example 1 of the invention is 879MPa, and the maximum tensile load is 2812N.
Comparative example 2:
the polyimide resin was prepared according to the following method
4.997kg (9.6mol) of bisphenol A type diether dianhydride, 1.081kg (10mol) of p-phenylenediamine, 0.118kg (0.8mol) of phthalic anhydride, and 36kg of N, N-dimethylacetamide (DMAc) were charged into a 100-liter reaction vessel equipped with a mechanical stirring, nitrogen protection, water, and a condensing reflux unit, and reacted at room temperature for 12 hours to obtain a polyamic acid solution. Adding 10kg of dimethylbenzene into the obtained polyamic acid solution, refluxing at 165 ℃ for 5 hours with water, filtering, washing with ethanol for 4 times, and drying at 200 ℃ for 10 hours to finally obtain polyimide resin powder.
The composite traction belt is prepared according to the following method
The 36k carbon fibers are led out from a creel shaft through a tractor, are uniformly spread through a spreading roller, enter an impregnation tank after being preheated through a drying channel, are started through an extruder, are made to enter the impregnation tank through molten polyimide resin, pass through a sizing neck mold after being fully impregnated with the resin, and are finally cooled and wound in the air. In the preparation process, the temperature of the drying tunnel is 230 ℃, the temperature of the gum dipping tank is 375 ℃, the temperature of the extruder is 380 ℃, the size of the sizing neck ring mold is 30 multiplied by 0.3mm, and the speed of the tractor is 6 m/min.
According to the method of the technical scheme, the tensile strength and the maximum tensile load of the composite traction belt prepared in the comparative example 2 are tested, and the test result shows that the tensile strength of the composite traction belt prepared in the comparative example 2 is 882MPa and the maximum tensile load is 4011N.
Polyimide-based composite materials obtained in examples 1 to 8 and comparative examples 1 to 2 of the present inventionThe drag belt was subjected to ultraviolet ray irradiation test and electron beam irradiation test, and the results are shown in Table 1, where Table 1 shows the tensile strength test results of the drag belt of composite material before and after ultraviolet irradiation and electron beam irradiation, and the ultraviolet irradiation intensity was 10.43w/m2The wavelength range is 280-315 nm, and the total irradiation dose of the electron beams is 3 multiplied by 109rad：
TABLE 1 test results of irradiation resistance of the traction tapes of examples 1 to 8 and comparative examples 1 to 2
Figure BDA0002289525080000281
Example 8 710 710 100 705 99
Comparative example 1 879 615 70 729 83
Comparative example 2 882 582 66 751 85
As can be seen from the above examples, the present invention provides a polyimide-based traction tape, which is prepared by the following method: uniformly spreading untwisted continuous fibers, preheating, fully impregnating the untwisted continuous fibers with polyimide resin, and shaping to obtain a polyimide-based dragging tape; the polyimide resin is prepared by the following method: polymerizing aromatic dianhydride, aromatic diamine and a capping agent in an organic solvent to obtain polyamic acid solution; adding nonpolar aromatic hydrocarbon into the polyamic acid solution, heating for cyclization and dehydration, separating out powder, washing, drying and granulating to obtain polyimide resin; the aromatic diamine is selected from any one or more of structures of a formula V-1 to a formula V-8. The dragging belt is prepared by tightly coating untwisted continuous fibers with polyimide resin, the polyimide resin is prepared into polyimide matrix resin by adopting aromatic diamine with a V-1-V-8 structure and other polymerization monomers, and an o-hydroxy benzophenone structural unit is introduced into a polyimide molecular chain, so that hydrogen bonds are formed in the polyimide molecular chain, the interface bonding capability with the fibers is enhanced, and the mechanical properties of the dragging belt, such as tensile strength, are effectively improved; polyimide resin containing an o-hydroxybenzophenone structure enables the traction belt to have excellent radiation irradiation resistance. The paint also has the excellent performances of small specific gravity, high temperature resistance grade, long service life, low thermal expansion coefficient, low content of volatile matters in vacuum environment and the like. It can be applied to the fields of aviation, aerospace, nuclear industry, civil traction and the like. The experimental results show that: after 2000 hours of ultraviolet irradiation of the dragging belt, the tensile strength is 580-1090 MPa, and the tensile strength retention rate is 99-100%; the tensile strength after electron beam irradiation is 586-1075 MPa, and the tensile strength retention rate is 98-100%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A polyimide-based traction belt is prepared by the following method:
uniformly spreading untwisted continuous fibers, preheating, fully impregnating the untwisted continuous fibers with polyimide resin, and shaping to obtain a polyimide-based dragging tape;
the polyimide resin is prepared by the following method:
polymerizing aromatic dianhydride, aromatic diamine and a capping agent in an organic solvent to obtain polyamic acid solution;
adding nonpolar aromatic hydrocarbon into the polyamic acid solution, heating for cyclization and dehydration, separating out powder, washing, drying and granulating to obtain polyimide resin;
the aromatic diamine is selected from any one or more of structures of a formula V-1 to a formula V-8:
Figure FDA0002289525070000011
2. the polyimide-based traction tape of claim 1, wherein the aromatic dianhydride is selected from one or more of formula 101, formula 102, and formula 103;
Figure FDA0002289525070000012
Figure FDA0002289525070000021
in formula 103A is selected from-O-),
Figure FDA0002289525070000022
Figure FDA0002289525070000023
3. The polyimide-based traction tape of claim 2, wherein the aromatic diamine further comprises one or more of formula 301 to formula 306:
Figure FDA0002289525070000024
4. the polyimide-based traction belt according to claim 1, wherein the untwisted continuous fibers are selected from one or more of carbon fibers, glass fibers, polyimide fibers, aramid fibers, PBO fibers;
the number of the untwisted continuous fibers is 1k to 50 k.
5. The polyimide-based traction tape according to claim 1, wherein the polymerization temperature is-10 to 50 ℃; the polymerization time is 1-24 h.
6. The polyimide-based traction tape according to claim 1, wherein the temperature of the cyclodehydration is 100 to 170 ℃; the time for cyclodehydration is 1-15 h.
7. The polyimide-based traction tape of claim 1, wherein the organic solvent is selected from the group consisting of polar aprotic solvents; the polar aprotic solvent is selected from one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, and N-methylpyrrolidone.
8. The polyimide-based traction tape according to claim 1, wherein the aromatic dianhydride and the aromatic diamine are present in a mass ratio of 0.9:1 to 1: 0.9.
9. the polyimide-based traction tape according to claim 1, wherein the pre-heating temperature is 200 to 300 ℃;
the dipping temperature is 350-400 ℃.
10. The polyimide-based traction tape according to claim 1, wherein the traction tape has a width of 1.0 to 50.0mm and a thickness of 0.1 to 1.0 mm.
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