CN116180264A - Porous aramid fiber and preparation method thereof - Google Patents
Porous aramid fiber and preparation method thereof Download PDFInfo
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- CN116180264A CN116180264A CN202310097628.7A CN202310097628A CN116180264A CN 116180264 A CN116180264 A CN 116180264A CN 202310097628 A CN202310097628 A CN 202310097628A CN 116180264 A CN116180264 A CN 116180264A
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
- D01F6/905—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides of aromatic polyamides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
Abstract
The invention relates to a porous aramid fiber and a preparation method thereof, wherein the porous aramid fiber is prepared from heterocyclic aramid resin slurry containing imidazole groups and metal ions. The porous aramid fiber has the advantages of uniform cavity structure, high porosity, high specific surface area, good mechanical strength, low thermal conductivity, good thermal stability and good application prospect in the field of heat insulation and protection materials.
Description
Technical Field
The invention belongs to the field of high-performance fiber manufacturing, and particularly relates to a porous aramid fiber and a preparation method thereof.
Background
The porous material has the characteristics of high specific surface area, high porosity, low density and the like, and has wide application prospect in the fields of heat preservation and insulation, energy storage conversion, photoelectrocatalysis, shock absorption and explosion prevention and the like. The traditional porous material mainly comprises a block material, has the defects of high brittleness, easiness in cracking, difficulty in forming and processing and the like, and is difficult to meet the application of the porous material to wearable and flexible protective equipment, while the fibrous porous material has excellent flexibility and braiding property, so that the application of the porous material in the fields of wearable fabrics and the like is widened.
However, the currently reported porous fiber preparation methods, such as a phase separation method, a template method, an ice crystal growth method, and the like, are difficult to obtain porous fibers with uniform structures, and result in uneven voids, low porosity, small specific surface area, poor mechanical properties, and the like. The spinning solution is extruded from a spinning nozzle and then converted into sol-gel, so that the porous fiber with uniform structure is expected to be continuously prepared. However, the sol-gel transition is too fast to cause the blockage of the spinneret orifices and can not be molded, while the transition is too slow to cause phase separation in the coagulation process of the coagulating bath and the structure is uneven. It remains a challenge to develop a suitable sol-gel system to continuously produce porous fibers of uniform structure. On the other hand, the aramid fiber has the advantages of excellent mechanical property, high and low temperature resistance, good flame retardance, good chemical resistance and the like. The aramid fiber is processed into the porous structure fiber, which is more beneficial to the application of the aramid fiber in high-temperature heat insulation protective clothing and other flexible protective equipment. However, the solubility of the aramid fiber is poor, the molding processing is difficult, and the porous aramid fiber with uniform structure is difficult to prepare in the prior art. The patent CN113463375A firstly etches the aramid fiber into the aramid nanofiber in an organic alkaline solvent, then takes the aramid nanofiber as a raw material, and prepares the porous aramid fiber by wet spinning through a phase separation principle. However, the method is long in time consumption and complex in operation, and the obtained porous aramid fiber is poor in mechanical property and small in specific surface area.
Disclosure of Invention
The invention aims to solve the technical problem of providing the porous aramid fiber and the preparation method thereof, and the prepared porous aramid fiber has a uniform cavity structure, high porosity, high specific surface area, good mechanical strength, low thermal conductivity, good thermal stability and good application prospect in the field of heat insulation and protection materials.
The invention provides a porous aramid fiber which is prepared from heterocyclic aramid resin slurry containing imidazole groups and metal ion compounds; wherein the structural formula of the heterocyclic aramid fiber containing the imidazole group is as follows:
the m, n ranges from 50 to 300.
The metal ion compound comprises one or more of copper acetate, zinc acetate, cobalt acetate and nickel acetate.
The porous aramid fiber has the following technical parameters and properties:
density of 0.03-0.13 g/cm 3 The porosity is 90.5-97.8%, the specific surface area is 281-350 m 2 And/g, the breaking strength is 8.6-13.0 MPa, the breaking elongation is 15.1-61.2%, and the thermal conductivity is 0.0262-0.0416W/(m.K).
The invention also provides a preparation method of the porous aramid fiber, which comprises the following steps:
(1) Taking anhydrous calcium chloride as a cosolvent and anhydrous N-methylpyrrolidone as a solvent, and taking p-phenylenediamine, 5 (6) -amino-2- (4-aminophenyl) benzimidazole and terephthaloyl chloride as raw materials to synthesize heterocyclic aramid resin slurry containing imidazole groups through solution polymerization; the solution polymerization reaction conditions are as follows: the temperature is between minus 5 and 0 ℃ and the reaction time is between 15 and 40 minutes;
(2) Adding a metal ion compound into the resin slurry synthesized in the step (1), adding a solvent for dilution, and uniformly mixing by magnetic stirring to obtain mixed slurry; wherein the molar ratio of the metal ion compound to the imidazole group in the imidazole group-containing heterocyclic aramid resin is 1:2-1:4;
(3) Preparing organic gel nascent fibers by wet spinning with the mixed slurry obtained in the step (2) as a spinning solution;
(4) And (3) replacing the organic gel primary fiber obtained in the step (3) by a gradient solvent to obtain an organic gel fiber, and drying to obtain the porous aramid fiber.
The sum of the moles of p-phenylenediamine and 5 (6) -amino-2- (4-aminophenyl) benzimidazole in step (1) is equal to the moles of terephthaloyl chloride; the molar ratio of the p-phenylenediamine to the 5 (6) -amino-2- (4-aminophenyl) benzimidazole is 1:0.6-4; the mole number of the anhydrous calcium chloride is equal to the mole number of amino groups in the system.
The solid content of the resin slurry in the step (1) is 5-10%.
The solvent in the step (2) is one or two of N 'N-dimethylformamide and N' N-dimethylacetamide.
The concentration of the mixed slurry in the step (2) is 0.5 to 2.5wt%.
The wet spinning conditions in the step (3) are as follows: the diameter of the spinning hole is 80-500 mu m, and the spinning speed is 2-10 m/min; the volume ratio of the organic solvent to the water in the coagulating bath is 1:1, and the temperature of the coagulating bath is 60-80 ℃; the negative stretch ratio is-70 to-20 percent.
The solvent adopted in the solvent replacement in the step (4) is acetone or tertiary butanol.
The gradient solvent specifically comprises the following components: water, a mixed solution of water and acetone or tertiary butanol with the volume ratio of 1:1, and acetone or tertiary butanol.
The drying method in the step (4) is a supercritical carbon dioxide drying method or a freeze drying method.
According to the invention, benzimidazole units are introduced into the main chain of the aramid fiber, so that the aramid fiber has the capability of coordinating with various metal ions, and a crosslinking system of the aramid fiber and the metal ions can be constructed through metal coordination bonds. The coordination of the metal ion and the imidazole group on the aramid fiber main chain can lead the metal ion-aramid fiber resin solution system to form a physical crosslinking network, and the sol-gel conversion speed of the system can be conveniently regulated and controlled through the regulation of the reaction temperature, so that the sol-gel conversion speed is matched with the dynamic spinning process, the sol-gel conversion of the yarn is realized in the wet spinning process, a uniform three-dimensional crosslinking network is formed, and the porous fiber with uniform structure is obtained. In addition, the crosslinking effect of the metal coordination bonds can further improve the mechanical strength and the thermal stability of the fiber, develop a type of high-performance porous aramid fiber, and provide a new thought for the continuous preparation of other high-performance porous fibers.
Advantageous effects
(1) The metal coordination bond crosslinked aramid fiber system can quickly and uniformly generate sol-gel conversion in the wet spinning process to form a uniform three-dimensional crosslinked structure, and finally the porous aramid fiber with uniform structure is obtained, so that the high porosity, the high specific surface area, the low thermal conductivity and the good thermodynamic property are further realized.
(2) The aramid porous fiber of the invention also has the characteristic of recycling due to the reversible crosslinking characteristic of the metal coordination bond. (3) The method is simple and convenient to operate, can realize continuous preparation of the porous aramid fiber by the traditional wet spinning technology, and is easier to realize large-scale production of products.
(4) The invention can be popularized to the preparation of other high-performance porous fibers.
Drawings
FIG. 1 is a digital photograph of a porous aramid fiber prepared in example 1 of the present invention;
FIG. 2 is a scanning electron micrograph of a cross section of a porous aramid fiber prepared in example 1 of the present invention;
FIG. 3 is a scanning electron micrograph of the surface of a porous aramid fiber prepared in example 1 of the present invention.
Detailed Description
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
Example 1
150mL of anhydrous N-methylpyrrolidone, 3.329g of anhydrous calcium chloride and 3.329g of 5 (6) -amino-2- (4-aminophenyl) benzimidazole are added into a 500mL three-neck flask, stirring is carried out, after complete dissolution, 1.622g of p-phenylenediamine and 3.264 g of 5 (6) -amino-2- (4-aminophenyl) benzimidazole are added, stirring is carried out, after complete dissolution, the solution is cooled to-5-0 ℃, then 6.091g of terephthaloyl chloride is added, and after intense stirring is carried out for 30min, the heterocyclic aramid resin slurry containing imidazole groups is obtained. Subsequently, 1.370g of copper acetate was added to the slurry, and anhydrous N' -N-dimethylacetamide was added to dilute the slurry concentration to 0.5wt%, and the mixture was uniformly mixed by magnetic stirring, to obtain a mixed slurry. The obtained mixed slurry is used as spinning slurry for wet spinning, wherein the diameter of a spinneret orifice is 80 mu m, the spinning speed is 4m/min, the negative stretching ratio is-50%, the composition of a coagulating bath is a mixed solvent of N' N-dimethylacetamide and water (volume ratio is 1:1), and the temperature of the coagulating bath is 70 ℃. The spinning solution is extruded by a spinneret plate and enters a coagulating bath, and filaments are subjected to sol-gel conversion under the temperature condition of the coagulating bath to form the organic gel nascent fiber. Finally, the obtained nascent fiber is subjected to gradient solvent replacement, finally acetone is replaced, and then the porous aramid fiber is prepared by drying through a supercritical carbon dioxide drying method.
The obtained porous aramid fiber is shown in FIG. 1, and the surface SEM image and the cross-sectional SEM image are shown in FIG. 2.
The structural parameters and the performances of the obtained porous aramid fiber are as follows: density of 0.0384g/cm 3 Porosity 97.31%, specific surface area 331m 2 And/g, the breaking strength is 8.59MPa, the breaking elongation is 35.9%, and the thermal conductivity is 0.0306W/(m.K).
Example 2
500mL of anhydrous N-methylpyrrolidone, 13.316g of anhydrous calcium chloride and stirring are added into a 1000mL three-neck flask, 6.488g of p-phenylenediamine and 13.456g of 5 (6) -amino-2- (4-aminophenyl) benzimidazole are added after complete dissolution, stirring is performed, after complete dissolution, the solution is cooled to-5-0 ℃, 24.364g of terephthaloyl chloride is added, and after intense stirring is performed for 40min, the heterocyclic aramid resin slurry containing imidazole groups is obtained. Subsequently, 5.480g of copper acetate was added to the slurry, and anhydrous N' N-dimethylacetamide was added to dilute the slurry concentration to 1wt%, followed by magnetic stirring and mixing to obtain a mixed slurry. The obtained mixed slurry is used as spinning slurry for wet spinning, wherein the diameter of a spinneret orifice is 80 mu m, the spinning speed is 6m/min, the negative stretching ratio is-70%, the coagulating bath composition is a mixed solvent of N' N-dimethylacetamide and water (volume ratio is 1:1), and the coagulating bath temperature is 80 ℃. The spinning solution is extruded by a spinneret plate and enters a coagulating bath, and filaments are subjected to sol-gel conversion under the temperature condition of the coagulating bath to form the organic gel nascent fiber. Finally, the obtained nascent fiber is subjected to gradient solvent replacement, finally acetone is replaced, and then the porous aramid fiber is prepared by drying through a supercritical carbon dioxide drying method.
The obtained porous aromaticThe parameters and properties of the fiber structure are as follows: density of 0.0619g/cm 3 Porosity 95.67%, specific surface area 312m 2 And/g, breaking strength of 11.21MPa, elongation at break of 53.3%, thermal conductivity of 0.0317W/(m.K).
Claims (10)
1. A porous aramid fiber characterized in that: the preparation method comprises the steps of preparing heterocyclic aramid resin slurry containing imidazole groups and a metal ion compound; wherein the structural formula of the heterocyclic aramid fiber containing the imidazole group is as follows:
the m, n ranges from 50 to 300.
2. The porous aramid fiber of claim 1, wherein: the metal ion compound comprises one or more of copper acetate, zinc acetate, cobalt acetate and nickel acetate.
3. A preparation method of porous aramid fiber comprises the following steps:
(1) Taking anhydrous calcium chloride as a cosolvent and anhydrous N-methylpyrrolidone as a solvent, and taking p-phenylenediamine, 5 (6) -amino-2- (4-aminophenyl) benzimidazole and terephthaloyl chloride as raw materials to synthesize heterocyclic aramid resin slurry containing imidazole groups through solution polymerization; the solution polymerization reaction conditions are as follows: the temperature is between minus 5 and 0 ℃ and the reaction time is between 15 and 40 minutes;
(2) Adding a metal ion compound into the resin slurry synthesized in the step (1), adding a solvent for dilution, and uniformly mixing by magnetic stirring to obtain mixed slurry; wherein the molar ratio of the metal ion compound to the imidazole group in the imidazole group-containing heterocyclic aramid resin is 1:2-1:4;
(3) Preparing organic gel nascent fibers by wet spinning with the mixed slurry obtained in the step (2) as a spinning solution;
(4) And (3) replacing the organic gel primary fiber obtained in the step (3) by a gradient solvent to obtain an organic gel fiber, and drying to obtain the porous aramid fiber.
4. A method of preparation according to claim 3, characterized in that: the sum of the moles of p-phenylenediamine and 5 (6) -amino-2- (4-aminophenyl) benzimidazole in step (1) is equal to the moles of terephthaloyl chloride; the molar ratio of the p-phenylenediamine to the 5 (6) -amino-2- (4-aminophenyl) benzimidazole is 1:0.6-4; the mole number of the anhydrous calcium chloride is equal to the mole number of amino groups in the system.
5. A method of preparation according to claim 3, characterized in that: the solid content of the resin slurry in the step (1) is 5-10%.
6. A method of preparation according to claim 3, characterized in that: the solvent in the step (2) is one or two of N 'N-dimethylformamide and N' N-dimethylacetamide.
7. A method of preparation according to claim 3, characterized in that: the concentration of the mixed slurry in the step (2) is 0.5 to 2.5wt%.
8. A method of preparation according to claim 3, characterized in that: the wet spinning conditions are as follows: the diameter of the spinning hole is 80-500 mu m, and the spinning speed is 2-10 m/min; the volume ratio of the organic solvent to the water in the coagulating bath is 1:1, and the temperature of the coagulating bath is 60-80 ℃; the negative stretch ratio is-70 to-20 percent.
9. A method of preparation according to claim 3, characterized in that: the solvent adopted in the solvent replacement in the step (4) is acetone or tertiary butanol.
10. A method of preparation according to claim 3, characterized in that: the drying method in the step (4) is a supercritical carbon dioxide drying method or a freeze drying method.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117103809A (en) * | 2023-07-14 | 2023-11-24 | 南通雄风服装有限公司 | Fire-retardant heat-insulating fabric for fire control and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117103809A (en) * | 2023-07-14 | 2023-11-24 | 南通雄风服装有限公司 | Fire-retardant heat-insulating fabric for fire control and preparation method thereof |
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