CN105064038B - Preparation method and application of water-soluble polyimide sizing agent for polyimide fibers - Google Patents
Preparation method and application of water-soluble polyimide sizing agent for polyimide fibers Download PDFInfo
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Abstract
A preparation method and application of a water-soluble polyimide sizing agent for polyimide fibers comprise the following steps: adding triethylamine, triethanolamine or other weak base reagents into the polyamic acid solution slowly, and reacting fully to form a polyamic acid salt solution; precipitating the polyamic acid salt solution in a poor solvent, and fully removing the residual solvent to obtain polyamic acid salt solid; the solid is dissolved in water to obtain the water-soluble polyimide sizing agent for the polyimide fiber. And dehydrating the polyimide fiber impregnated with the sizing agent by a high-temperature heating furnace and imidizing to finish fiber sizing. The sizing agent can improve the surface energy of the fiber, improve the wettability and the interface bonding strength of the fiber and a resin matrix, improve the wear resistance and the bundling property of the fiber, effectively ensure the high temperature resistance of the fiber in use, is approximate to zero pollution in the application process, and has the use characteristic of environmental friendliness.
Description
The technical field is as follows:
the invention relates to the field of preparation and application of a high-performance organic fiber sizing agent, in particular to a preparation method and application of a water-soluble polyimide sizing agent for polyimide fibers.
Background art:
polyimide (PI) fiber is a newly-emerged high-performance organic fiber, has the performance characteristics of high strength, high modulus, high temperature resistance, radiation resistance, corrosion resistance, low dielectric constant and the like, and has great research value and application prospect which are gradually accepted by wide researchers. The high-strength high-modulus P1 fiber has the characteristics of high strength, high modulus and high and low temperature resistance of carbon fiber, light weight and toughness of organic fiber, and good ultraviolet radiation resistance, so that the fiber not only can be used for preparing products such as bulletproof fabrics, high-specific-strength ropes, space suits, fire-fighting suits and the like, but also can be used as a reinforcing material to prepare a high-performance composite material to be applied to advanced weaponry and national defense high-technology products such as novel satellites, airships, airplanes and the like. In the environmental protection industry, in order to reduce the generation and emission of harmful gases such as dioxin and the like and improve the incineration temperature of the incineration rate, the high-temperature resistant polyimide fiber is the only dust removal filter material which can be used as an incinerator and can be used for a long time at the temperature of 250-350 ℃. Patents with publication numbers CN102345177A and CN102560707A and CN102168317A describe a series of polyimide fiber preparation methods. The polyimide fiber obtained by the method has smooth surface appearance, and the excellent mechanical property of the polyimide fiber is ensured by few surface defects. However, when the composite material is used as a reinforcement to prepare a composite material, the smooth surface structure affects the wettability of the composite material and a resin matrix to a certain extent, and further affects the interface bonding strength of the composite material. Meanwhile, since the nascent fiber is not surface-treated with any sizing agent, the bundling property and abrasion resistance of the fiber are also to be improved.
In order to solve the problems, the invention develops a water-soluble polyimide sizing agent for polyimide fibers, which is prepared by adding a weak base reagent into polyamic acid to generate water-soluble polyamic acid salt, then precipitating the polyamic acid salt in a poor solvent such as acetone and preparing the poor solvent into an aqueous solution of the polyamic acid salt according to the required concentration. The main component of the product is polyamic acid salt, the solution contains a large amount of amino groups (-NH-) and carboxylate groups (-COOR-), and R represents salified cation. When the polyimide fiber which is not fully imidized passes through the solution, active groups in the solution can react with amino groups or carboxylic acid groups (-COOH) on the surface of the fiber, the condensation polymerization reaction can be generated after the polyimide fiber continuously passes through a high-temperature imidization furnace, and macromolecular chains grafted on the surface of the fiber form a film layer continuously wrapping the fiber, so that the surface roughness of the fiber is increased, the wettability of the fiber and a resin matrix is improved, and the interface bonding strength of the composite material can be improved by winding or reacting the macromolecular chains and molecular chains of a wax matrix. Meanwhile, the film layer formed by the polyimide macromolecular chains can also play a role in protecting the main structure of the fibers for bearing load, effectively improving the abrasion resistance of the fibers and improving the bundling property among the fibers.
Because the polyimide fiber is a new technical product, no sizing agent material designed and matched according to the chemical structure characteristics of the polyimide fiber is produced at present, and the water-soluble polyimide sizing agent for the polyimide fiber and the preparation and application methods thereof described by the invention are not reported in documents. The product and the technology provided by the invention can be used together with polyimide fibers for production, and the surface energy, the wear resistance, the bundling property and other properties of the polyimide fibers are effectively improved. The chemical structure of the product after curing is polyimide as well as the fiber matrix, thereby effectively ensuring the service performance of the fiber under the high-temperature condition and avoiding the problem that the sizing agent of other systems is not matched with the high-temperature resistance of the fiber matrix when in use. More importantly, the water-soluble characteristic of the product is realized, no pollutant is generated in the using process, and the environmental friendliness of the product in the using process is fully ensured. The invention is a product and technology urgently needed in polyimide fiber production, and has very important practical significance for solving series problems in polyimide fiber production and perfecting the process link of polyimide fiber production.
The invention content is as follows:
the invention aims to provide a preparation method and application of a water-soluble polyimide sizing agent for polyimide fibers. Meanwhile, the chemical structure of the cured fiber is still the structural characteristic of polyimide, so that the high-temperature resistance of the fiber in use is effectively ensured, and the water-solubility characteristic of the fiber enables the fiber to be approximate to zero pollution in the application process, so that the fiber has the use characteristic of environmental friendliness.
A preparation method of a water-soluble polyimide sizing agent for polyimide fibers is characterized by comprising the following steps:
a: adding triethylamine, triethanolamine or other weak base reagents into the polyamic acid solution slowly, and reacting fully to form a polyamic acid salt solution;
b: precipitating the polyamic acid salt solution in a poor solvent, and fully removing the residual solvent to obtain polyamic acid salt solid;
c; the solid is dissolved in water to obtain the water-soluble polyimide sizing agent for the polyimide fiber.
The polyamic acid solution in the step A is polyimide precursor solution obtained by mixed polycondensation or copolycondensation of any type of dianhydride or polyanhydride and diamine or polyamine.
The weak base reagent in the step A is selected according to the following principle: can form a water-soluble salt with the polyamic acid.
The selection principle of the poor solvent in the step B is as follows: has good compatibility with the solvent used by the polyamic acid, does not dissolve the polyamic acid salt, has better volatility, and is beneficial to drying the polyamic acid salt and removing the residual solvent.
The concentration of the polyamic acid salt dissolved in water in step C is any concentration.
The sizing agent is applied to the polyimide fiber, and the polyimide fiber dipped with the sizing agent is dehydrated and imidized by a high-temperature hot furnace to finish fiber sizing.
The reaction mechanism of the application is as follows: the polyimide fiber is not fully imidized, part of polyamic acid units are still remained on the surface of the polyimide fiber, and a compact film layer is formed on the surface of the fiber through the reaction of the polyamic acid units and polyamic acid salt in a sizing agent at high temperature.
The polyimide fiber can also be any aromatic heterocyclic organic fiber.
The sizing agent has the following action characteristics: the fiber can be protected from abrasion; the surface roughness and the surface energy of the fiber are increased, and the wettability of the fiber and a resin matrix is improved; the interfacial bonding strength of the fiber and the resin matrix is improved through the entanglement or chemical bonding reaction of the macromolecular chain segment of the fiber surface film layer and the molecular chain segment of the resin matrix.
Compared with the prior art, the invention has the following beneficial effects:
the chemical structure of the sizing agent is still polyimide after being cured, so that the high-temperature service performance of the polyimide fiber can be ensured, and the matching problem of the sizing agent of other systems and the polyimide fiber under the high-temperature condition is avoided.
The preparation method and the application of the sizing agent can graft polyimide macromolecular chains on the surface of polyimide through chemical bonds and form a film layer on the surface of fibers, can effectively improve the surface energy of the fibers, improve the wettability and the interface bonding strength of the fibers and a resin matrix, and can also improve the wear resistance and the bundling property of the fibers.
The sizing agent is water-soluble liquid, is approximately zero in pollution in the using process, and has the characteristic of environmental friendliness.
Description of the drawings:
FIG. 1: a schematic diagram of a preparation principle of the water-soluble polyimide sizing agent for the polyimide fiber;
FIG. 2: the water-soluble polyimide sizing agent for the polyimide fiber is used in a schematic diagram.
The specific implementation mode is as follows:
the invention will be further illustrated with reference to the following specific examples. It should be noted that: the following examples are only for illustrating the present invention and are not intended to limit the technical solutions described in the present invention. All such modifications and variations are intended to be included herein within the scope of this disclosure and the present invention and protected by the following claims.
Example 1:
A. adding triethylamine into the polyamic acid solution, and fully reacting to form polyamic acid salt under the condition of continuous stirring, wherein the molar ratio of the triethylamine to carboxyl in the polyamic acid is 1: 1;
B. b, precipitating the polyamic acid salt solution obtained in the step A into an acetone solution, washing for multiple times, and drying to remove residual solvent to obtain polyamic acid salt solid;
C. dissolving the solid obtained in the step B in a deionized water solution at the concentration of 8 wt% to obtain the sizing agent;
D. and D, diluting the sizing agent obtained in the step C to a concentration of 2 wt%, placing the diluted sizing agent in a polyimide fiber production line, fully soaking the fiber in the solution, dehydrating the fiber in a high-temperature heating furnace, and fully cyclizing the fiber to obtain the polyimide fiber with the polyimide macromolecular chain coating film layer on the surface.
Example 2:
A. adding triethanolamine into the polyamic acid solution, and fully reacting to form polyamic acid salt under the condition of continuous stirring, wherein the molar ratio of the triethanolamine to carboxyl in the polyamic acid is 1: 1;
B. b, precipitating the polyamic acid salt solution obtained in the step A in a blending solution of acetone and methanol, washing for multiple times, and drying to remove residual solvent to obtain polyamic acid salt solid;
C. dissolving the solid obtained in the step B in a deionized water solution at the concentration of 12 wt% to obtain the sizing agent;
D. and D, diluting the sizing agent obtained in the step C to a concentration of 2.5 wt%, placing the diluted sizing agent in a polyimide fiber production line, fully soaking the fiber in the solution, dehydrating the fiber through a high-temperature heating furnace, and fully cyclizing the fiber to obtain the polyimide fiber with the polyimide macromolecular chain coating film layer on the surface.
Example 3:
A. adding tripropylamine into the polyamic acid solution, and fully reacting to form polyamic acid salt under the condition of continuous stirring, wherein the molar ratio of the tripropylamine to carboxyl in the polyamic acid is 0.5: 1;
B. b, precipitating the polyamic acid salt solution obtained in the step A in a methanol solution, washing for multiple times, and drying to remove residual solvent to obtain polyamic acid salt solid;
C. dissolving the solid obtained in the step B in a deionized water solution at the concentration of 6 wt% to obtain the sizing agent;
D. and D, diluting the sizing agent obtained in the step C to a concentration of 2.5 wt%, placing the diluted sizing agent in a polyimide fiber production line, fully soaking the fiber in the solution, dehydrating the fiber through a high-temperature heating furnace, and fully cyclizing the fiber to obtain the polyimide fiber with the polyimide macromolecular chain coating film layer on the surface.
Example 4:
A. adding triethylamine into the polyamic acid solution, and fully reacting to form polyamic acid salt under the condition of continuous stirring, wherein the molar ratio of the triethylamine to carboxyl in the polyamic acid is 0.3: 1;
B. b, precipitating the polyamic acid salt solution obtained in the step A into an acetone solution, washing for multiple times, and drying to remove residual solvent to obtain polyamic acid salt solid;
C. dissolving the solid obtained in the step B in a deionized water solution at a concentration of 5 wt% to obtain the sizing agent;
D. and D, diluting the sizing agent obtained in the step C to a concentration of 2 wt%, placing the diluted sizing agent in a polyimide fiber production line, fully soaking the fiber in the solution, dehydrating the fiber in a high-temperature heating furnace, and fully cyclizing the fiber to obtain the polyimide fiber with the polyimide macromolecular chain coating film layer on the surface.
Example 5:
A. adding triisopropanolamine into the polyamic acid solution, and fully reacting to form polyamic acid salt under the condition of continuous stirring, wherein the molar ratio of triisopropanolamine to carboxyl in the polyamic acid is 0.25: 1;
B. b, precipitating the polyamic acid salt solution obtained in the step A into an acetone solution, washing for multiple times, and drying to remove residual solvent to obtain polyamic acid salt solid;
C. dissolving the solid obtained in the step B in a deionized water solution at the concentration of 6 wt% to obtain the sizing agent;
D. and D, diluting the sizing agent obtained in the step C to a concentration of 2 wt%, placing the diluted sizing agent in a polyimide fiber production line, fully soaking the fiber in the solution, dehydrating the fiber in a high-temperature heating furnace, and fully cyclizing the fiber to obtain the polyimide fiber with the polyimide macromolecular chain coating film layer on the surface.
Example 6:
A. adding tripentylamine into the polyamic acid solution, and fully reacting to form polyamic acid salt under the condition of continuous stirring, wherein the molar ratio of the tripentylamine to carboxyl in the polyamic acid is 0.25: 1;
B. b, precipitating the polyamic acid salt solution obtained in the step A into an acetone solution, washing for multiple times, and drying to remove residual solvent to obtain polyamic acid salt solid;
C. dissolving the solid obtained in the step B in a deionized water solution at the concentration of 8 wt% to obtain the sizing agent;
D. and D, diluting the sizing agent obtained in the step C to a concentration of 4 wt%, placing the sizing agent in a polyimide fiber production line, fully soaking the fiber in the solution, dehydrating the fiber in a high-temperature heating furnace, and fully cyclizing the fiber to obtain the polyimide fiber with the polyimide macromolecular chain coating film layer on the surface.
Claims (2)
1. The application of the water-soluble polyimide sizing agent for the polyimide fiber in the polyimide fiber is characterized by comprising the following steps:
a: adding triethylamine, triethanolamine, tripropylamine, triisopropanolamine or tripentylamine slowly into the polyamic acid solution, and reacting fully to form a polyamic acid salt solution;
b: precipitating the polyamic acid salt solution in a poor solvent, and fully removing the residual solvent to obtain polyamic acid salt solid;
c: dissolving the solid in water to obtain a water-soluble polyimide sizing agent for polyimide fibers;
d: dehydrating the polyimide fiber impregnated with the sizing agent by a high-temperature heating furnace, and imidizing to finish fiber sizing, wherein the polyimide fiber is not completely imidized, a part of polyamic acid units are still remained on the surface of the polyimide fiber, and a compact film layer is formed on the surface of the fiber by reacting with polyamic acid salt in the sizing agent at a high temperature, so that the polyimide fiber with a polyimide macromolecular chain coating film layer on the surface is obtained; the solvent is selected from acetone, a blended solution of acetone and methanol or methanol.
2. The use of claim 1, wherein the polyamic acid solution in step a is a polyimide precursor solution obtained by mixed polycondensation or copolycondensation of any type of dianhydride or polyanhydride with diamine or polyamine.
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| CN110551372B (en) * | 2018-05-31 | 2021-06-18 | 比亚迪股份有限公司 | Sizing agent and preparation method thereof, chopped glass fiber and preparation method thereof, and sheet and preparation method thereof |
| CN108755144B (en) * | 2018-06-12 | 2022-08-16 | 北京化工大学常州先进材料研究院 | Preparation method of crosslinked polyimide fiber membrane |
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| CN110258058B (en) * | 2019-07-01 | 2021-12-03 | 江苏先诺新材料科技有限公司 | Polyimide fiber sizing device |
| CN110295494B (en) * | 2019-07-01 | 2021-09-24 | 江苏先诺新材料科技有限公司 | Sizing process of polyimide fibers |
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| CN114957989B (en) * | 2022-05-19 | 2024-02-27 | 江苏先诺新材料科技有限公司 | Bulletproof composite material and preparation method thereof |
| CN116145428B (en) * | 2022-12-05 | 2024-08-30 | 东华大学 | Preparation method and application of water-soluble polyamic acid salt sizing agent |
| WO2024250173A1 (en) * | 2023-06-06 | 2024-12-12 | 中国科学院化学研究所 | High-temperature-resistant water-based sizing agent for carbon fibers, and preparation method therefor and use thereof |
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| CN103174026A (en) * | 2013-04-09 | 2013-06-26 | 中国科学院山西煤炭化学研究所 | Polyamide acid aqueous sizing agent as well as preparation method and application thereof |
| CN103614923A (en) * | 2013-11-25 | 2014-03-05 | 中国科学院山西煤炭化学研究所 | Carbon nano tube modified polyamide acid waterborne sizing agent and production method thereof |
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| US20130309925A1 (en) * | 2012-05-15 | 2013-11-21 | Satoshi Seike | Carbon fiber fabric |
| US20140343218A1 (en) * | 2013-05-16 | 2014-11-20 | Toray Carbon Fibers America, Inc. | Carbon fiber |
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| CN103174026A (en) * | 2013-04-09 | 2013-06-26 | 中国科学院山西煤炭化学研究所 | Polyamide acid aqueous sizing agent as well as preparation method and application thereof |
| CN103614923A (en) * | 2013-11-25 | 2014-03-05 | 中国科学院山西煤炭化学研究所 | Carbon nano tube modified polyamide acid waterborne sizing agent and production method thereof |
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