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CN116641148B - Meta-aramid fiber and preparation method and application thereof - Google Patents

Meta-aramid fiber and preparation method and application thereof

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Publication number
CN116641148B
CN116641148B CN202310795486.1A CN202310795486A CN116641148B CN 116641148 B CN116641148 B CN 116641148B CN 202310795486 A CN202310795486 A CN 202310795486A CN 116641148 B CN116641148 B CN 116641148B
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meta
aramid fiber
temperature
filtrate
prepolymerization reaction
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CN116641148A (en
Inventor
陆赵情
黄吉振
花莉
贾峰峰
陈珊珊
宁逗逗
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Shaanxi University of Science and Technology
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Shaanxi University of Science and Technology
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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
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
    • D01F6/605—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides from aromatic polyamides
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/10—Organic non-cellulose fibres
    • D21H13/20—Organic non-cellulose fibres from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H13/26—Polyamides; Polyimides
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/48—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances fibrous materials
    • H01B3/52—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances fibrous materials wood; paper; press board
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Artificial Filaments (AREA)
  • Polyamides (AREA)

Abstract

本发明公开了一种间位芳纶纤维及其制备方法和应用，方法包括：将间苯二胺溶于第一溶剂中，加入间苯二甲酰氯，反应后加入碱液，过滤得到一次滤液；在一次滤液中加入间苯二甲酰氯，反应后加入碱液，过滤得到二次滤液；在二次滤液中加入间苯二甲酰氯，反应后加入碱液和乙二胺，过滤得到终滤液；喷丝成型处理，之后依次进行两级凝固成型处理，得到间位芳纶纤维长丝；其中，两级凝固成型均采用在第二溶剂、氯化钙及水的凝固浴中完成；第二溶剂为N,N‑二甲基乙酰胺或N‑甲基吡咯烷酮；进行水浴拉伸、淬火，得到间位芳纶纤维；本发明采用分步预聚法和分段凝固浴工艺制备出间位芳纶纤维，具有良好的线密度、拉伸强度、断裂伸长率、模量和热稳定性能。This invention discloses a meta-aramid fiber, its preparation method, and its application. The method includes: dissolving m-phenylenediamine in a first solvent, adding isophthaloyl chloride, reacting, adding alkali solution, and filtering to obtain a primary filtrate; adding isophthaloyl chloride to the primary filtrate, reacting, adding alkali solution, and filtering to obtain a secondary filtrate; adding isophthaloyl chloride to the secondary filtrate, reacting, adding alkali solution and ethylenediamine, and filtering to obtain a final filtrate; spinning and forming the fiber, followed by two-stage coagulation and forming processes to obtain meta-aramid fiber filaments; wherein both stages of coagulation and forming are completed in a coagulation bath of a second solvent, calcium chloride, and water; the second solvent is N,N-dimethylacetamide or N-methylpyrrolidone; and performing water bath stretching and quenching to obtain meta-aramid fibers. This invention uses a stepwise prepolymerization method and a segmented coagulation bath process to prepare meta-aramid fibers, which have good linear density, tensile strength, elongation at break, modulus, and thermal stability.

Description

Meta-aramid fiber and preparation method and application thereof
Technical Field
The invention belongs to the technical field of aramid fibers, and particularly relates to a meta-aramid fiber and a preparation method and application thereof.
Background
Along with the gradual rise of the speed of the high-speed train, the power of the high-speed motor for supplying power is required to be higher, meta-aramid insulation paper is used as a winding insulation layer of the high-speed motor, so that the meta-aramid insulation paper provides necessary insulation performance for the high-speed motor, and is widely applied to the high-speed motor.
The meta-aramid fiber is used as an important component in aramid fiber insulation paper, has the advantages of high insulation, high mechanical strength, high temperature resistance and low shrinkage, the performance of the meta-aramid fiber is mainly influenced by a fiber spinning process, and the meta-aramid fiber is prepared by a wet spinning method generally at present, but the polymerization degree of aramid fiber molecules and the synergistic effect of coagulation bath conditions are not subjected to deep research in the spinning preparation process, so that the crystallinity, mechanical property and thermal stability of the synthesized meta-aramid fiber cannot meet the requirements of a high-speed motor.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides meta-aramid fiber and a preparation method and application thereof, and aims to solve the technical problems that the crystallinity, mechanical property and thermal stability of the synthesized meta-aramid fiber cannot meet the requirements of a high-speed motor when the meta-aramid fiber is prepared by adopting a wet spinning method.
In order to achieve the above purpose, the invention adopts the following technical scheme:
The invention provides a preparation method of meta-aramid fiber, which comprises the following steps:
Step 1, after m-phenylenediamine is dissolved in a first solvent, adding isophthaloyl dichloride for a prepolymerization reaction, adding alkali liquor to neutralize HCl molecules after the reaction, and filtering to obtain primary filtrate;
Step 2, adding isophthaloyl dichloride into the primary filtrate, performing a prepolymerization reaction, adding alkali liquor after the reaction to neutralize HCl molecules, and filtering to obtain a secondary filtrate;
Step 3, adding isophthaloyl dichloride into the secondary filtrate to perform a prepolymerization reaction, adding alkali liquor to neutralize HCl molecules after the reaction, adding ethylenediamine to neutralize residual isophthaloyl dichloride after the prepolymerization reaction, and filtering to obtain a final filtrate;
Step 4, carrying out spinning forming treatment on the final filtrate to obtain fiber filaments, and sequentially carrying out two-stage coagulation forming treatment on the fiber filaments to obtain meta-aramid fiber filaments, wherein the two-stage coagulation forming is completed in a coagulation bath of a second solvent, calcium chloride and water, and the second solvent is N, N-dimethylacetamide or N-methylpyrrolidone;
And 5, carrying out water bath stretching and quenching on the meta-aramid fiber filaments to obtain the meta-aramid fiber.
Further, in step 1, the first solvent is N, N-dimethylacetamide or N-methylpyrrolidone.
Further, in the step 1, the prepolymerization is carried out at a temperature of-15 to-5 ℃.
Further, in the step 2, the prepolymerization is carried out at a temperature of-15 to-5 ℃.
Further, in the step 3, the prepolymerization is carried out at a temperature of 0 to 6 ℃.
In the step 4, the solidification forming temperature is 6-10 ℃ during the first-stage solidification forming, the mass concentration of calcium chloride in a solidification bath is 8-10%, and the mass percentage of water is 10% -15%.
In the step 4, the second-stage solidification molding is performed at a solidification molding temperature of 10-15 ℃, the mass concentration of calcium chloride in a solidification bath is 5-7%, and the mass percentage of water is 15-20%.
Further, in the step5, when the water bath is used for stretching, the water bath temperature is 15-20 ℃, the stretching length is 2-2.5 times, and the quenching temperature is 400-410 ℃.
The invention also provides meta-aramid fiber, which is prepared by adopting the preparation method of the meta-aramid fiber, wherein the fineness of the meta-aramid fiber is 1.4-2.0 dtex, the breaking strength is 4.2-6.5 cN/dtex, the elongation at break is 1.3% -3.0%, the elastic modulus is 210-460 cN/dtex, and the thermal weight loss at 400 ℃ is 1.2-2.4%.
The invention also provides application of the meta-aramid fiber, wherein the meta-aramid fiber is used as a matrix material of aramid insulation paper.
Compared with the prior art, the invention has the beneficial effects that:
The invention provides meta-aramid fiber, a preparation method and application thereof, wherein meta-phenylenediamine and isophthaloyl dichloride are used as synthetic monomers, the occurrence of byproducts in the reaction is reduced by a multi-step prepolymerization method, the negative effects of HCl on the reduction of molecular weight, the reduction of crystallinity and the like of meta-aramid fiber synthesis are solved by a step-by-step method, HCl molecules generated in an alkali liquor absorption reaction are used after each prepolymerization reaction, and finally excess isophthaloyl dichloride is neutralized by ethylenediamine, the gradient graded coagulation bath is utilized to strengthen the molding completeness of the meta-aramid fiber, the meta-aramid fiber is converted from raw liquid to fiber step by step, the crystallinity, the mechanical property and the thermal stability of the meta-aramid fiber are improved, the meta-aramid fiber is prepared by the step-prepolymerization method and the step coagulation bath technology, and has good linear density, tensile strength, elongation at break, modulus and thermal stability, wherein the fiber titer of the meta-aramid fiber is 1.4-2.2.5 dtex, the breaking strength is 4.2-6.5 cN/dtex, the elongation at break is 1.3-0.0% and the elastic fiber is 1-2.0.0% of the thermal insulation material, and the thermal insulation performance of the meta-aramid fiber is high in the range of 1.0-400 DEG.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects solved by the invention more clear, the following specific embodiments are used for further describing the invention in detail. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The invention provides a preparation method of meta-aramid fiber, which comprises the following steps:
1, dissolving 1-1.1 kg of m-phenylenediamine in 10-12 kg of a first solvent, adding 0.35-0.4 kg of m-phthaloyl chloride under the condition of stirring speed of 300-500r/min, and performing prepolymerization at a temperature of-15 to-5 ℃ to obtain a primary prepolymerization reaction product, wherein the first solvent is N, N-dimethylacetamide or N-methylpyrrolidone.
And 2, adding Ca (OH) 2 into the primary prepolymerization reaction product to neutralize HCl molecules generated by the prepolymerization reaction in the step 1, and then filtering by using a multi-layer filter cloth to remove a byproduct CaCl 2, so as to obtain a pale yellow transparent liquid, namely a primary filtrate.
And step 3, adding 0.35-0.4 kg of isophthaloyl dichloride into the primary filtrate, and performing prepolymerization at the temperature of-15 to-5 ℃ to obtain a secondary prepolymerization reaction product.
And step 4, adding Ca (OH) 2 into the secondary prepolymerization reaction product to neutralize HCl molecules generated by the prepolymerization reaction in the step 3, and filtering to obtain secondary filtrate.
And 5, adding 0.35-0.4 kg of isophthaloyl dichloride into the secondary filtrate, and performing prepolymerization reaction at the temperature of 0-6 ℃ to obtain a three-time prepolymerization reaction product.
And 6, adding Ca (OH) 2 into the product of the three-time prepolymerization reaction to neutralize HCl molecules generated by the prepolymerization reaction in the step 5, adding ethylenediamine to neutralize residual isophthaloyl dichloride after the prepolymerization reaction, and finally filtering by using filter cloth to obtain yellow transparent polymer solution, thus obtaining the final filtrate.
And 7, feeding the final filtrate into a spinning device after passing through a metering pump, and carrying out spinning forming treatment on the final filtrate by using the spinning device to obtain fiber filaments, wherein in the spinning device, hole sites on a spinneret plate are distributed circularly or in a square shape, the aperture is 0.02-0.3 mm, and the number of the holes is 200-1200.
And 8, sequentially carrying out two-stage coagulation forming treatment on the fiber filaments to obtain meta-aramid fiber filaments, wherein the two-stage coagulation forming is completed in a coagulation bath of a second solvent, calcium chloride and water, wherein the second solvent is N, N-dimethylacetamide or N-methylpyrrolidone, the coagulation forming temperature is 6-10 ℃ in the first-stage coagulation forming, the mass concentration of the calcium chloride in the coagulation bath is 8-10%, the mass percentage of the water is 10-15%, the coagulation forming temperature is 10-15 ℃ in the second-stage coagulation forming, the mass concentration of the calcium chloride in the coagulation bath is 5-7%, and the mass percentage of the water is 15-20%.
And 9, carrying out water bath stretching and quenching on the meta-aramid fiber filaments to obtain the meta-aramid fibers, wherein the water bath temperature is 15-20 ℃ during water bath stretching, the stretching length is 2-2.5 times, and the quenching temperature is 400-410 ℃.
The preparation principle is as follows:
When the meta-aramid fiber is prepared, part of m-phthaloyl chloride is firstly mixed with m-phenylenediamine to perform polycondensation reaction to form a poly-m-phthaloyl m-phenylenediamine oligomer, and byproduct HCl is generated, and the degree of polymerization reaction can be influenced by the byproduct HCl, so that alkali liquor such as Ca (OH) 2 is added to neutralize the byproduct HCl and filter out water and CaCl 2, the reaction degree of reaction is improved, and the degree of polymerization and crystallinity of a product are influenced by the byproduct HCl when the poly-m-phthaloyl m-phenylenediamine polymer is directly prepared by a one-step forming method.
Example 1
The embodiment 1 provides a preparation method of meta-aramid fiber, which comprises the following steps:
1, dissolving 1kg of m-phenylenediamine in 12kg of a first solvent, adding 0.35kg of m-phthaloyl chloride under the condition of stirring speed of 500r/min, and carrying out a prepolymerization reaction at a temperature of-15 ℃ to obtain a primary prepolymerization reaction product, wherein the first solvent is N, N-dimethylacetamide.
And 2, adding Ca (OH) 2 into the primary prepolymerization reaction product to neutralize HCl molecules generated by the prepolymerization reaction in the step 1, and then filtering by using a multi-layer filter cloth to remove a byproduct CaCl 2, so as to obtain a pale yellow transparent liquid, namely a primary filtrate.
And step3, adding 0.35kg of isophthaloyl dichloride into the primary filtrate, and performing prepolymerization reaction at the temperature of-15 ℃ to obtain a secondary prepolymerization reaction product.
And step 4, adding Ca (OH) 2 into the secondary prepolymerization reaction product to neutralize HCl molecules generated by the prepolymerization reaction in the step 3, and filtering to obtain secondary filtrate.
And 5, adding 0.35kg of isophthaloyl dichloride into the secondary filtrate, and performing prepolymerization reaction at the temperature of 6 ℃ to obtain a product of three prepolymerization reactions.
And 6, adding Ca (OH) 2 into the product of the three-time prepolymerization reaction to neutralize HCl molecules generated by the prepolymerization reaction in the step 5, adding ethylenediamine to neutralize residual isophthaloyl dichloride after the prepolymerization reaction, and finally filtering by using filter cloth to obtain yellow transparent polymer solution, thus obtaining the final filtrate.
And 7, feeding the final filtrate into a spinning device after passing through a metering pump, and carrying out spinning forming treatment on the final filtrate by using the spinning device to obtain fiber filaments, wherein in the spinning device, hole sites on a spinneret plate are distributed circularly, the aperture is 0.05mm, and the number of the holes is 1000.
And 8, sequentially carrying out two-stage solidification forming treatment on the fiber filaments to obtain meta-aramid fiber filaments, wherein the two-stage solidification forming is completed in a solidification bath of a second solvent, calcium chloride and water, wherein the second solvent is N, N-dimethylacetamide or N-methylpyrrolidone, the solidification forming temperature is 6 ℃ in the first-stage solidification forming, the mass concentration of calcium chloride in the solidification bath is 8% and the mass percentage of water is 10%, the solidification forming temperature is 10 ℃ in the second-stage solidification forming, and the mass concentration of calcium chloride in the solidification bath is 5% and the mass percentage of water is 15%.
And 9, carrying out water bath stretching and quenching on the meta-aramid fiber filaments to obtain the meta-aramid fiber, wherein the water bath temperature is 15 ℃ and the stretching length is 2 times when the meta-aramid fiber filaments are stretched in a water bath, and the quenching temperature is 400 ℃.
And (3) performance detection:
the meta-aramid fiber prepared in example 1 was tested for properties, and it was found that the meta-aramid fiber had a fineness of 1.6dtex, a breaking strength of 6.0cN/dtex, an elongation at break of 1.6%, an elastic modulus of 380cN/dtex, and a thermal weight loss at 400 ℃ of 1.5%.
Example 2
The embodiment 1 provides a preparation method of meta-aramid fiber, which comprises the following steps:
Step 1, after 1.1kg of m-phenylenediamine is dissolved in 10kg of first solvent, 0.4kg of m-phthaloyl chloride is added under the condition of stirring speed of 300r/min, and the pre-polymerization reaction is carried out at the temperature of-5 ℃ to obtain a primary pre-polymerization reaction product, wherein the first solvent is N-methylpyrrolidone.
And 2, adding Ca (OH) 2 into the primary prepolymerization reaction product to neutralize HCl molecules generated by the prepolymerization reaction in the step 1, and then filtering by using a multi-layer filter cloth to remove a byproduct CaCl 2, so as to obtain a pale yellow transparent liquid, namely a primary filtrate.
And step 3, adding 0.4kg of isophthaloyl dichloride into the primary filtrate, and performing prepolymerization at the temperature of-5 ℃ to obtain a secondary prepolymerization reaction product.
And step 4, adding Ca (OH) 2 into the secondary prepolymerization reaction product to neutralize HCl molecules generated by the prepolymerization reaction in the step 3, and filtering to obtain secondary filtrate.
And 5, adding 0.4kg of isophthaloyl dichloride into the secondary filtrate, and performing prepolymerization reaction at the temperature of 0 ℃ to obtain a product of three prepolymerization reactions.
And 6, adding Ca (OH) 2 into the product of the three-time prepolymerization reaction to neutralize HCl molecules generated by the prepolymerization reaction in the step 5, adding ethylenediamine to neutralize residual isophthaloyl dichloride after the prepolymerization reaction, and finally filtering by using filter cloth to obtain yellow transparent polymer solution, thus obtaining the final filtrate.
And 7, feeding the final filtrate into a spinning device after passing through a metering pump, and carrying out spinning forming treatment on the final filtrate by using the spinning device to obtain fiber filaments, wherein hole sites on a spinneret plate in the spinning device are distributed circularly, the aperture is 0.02mm, and the number of the holes is 1200.
And 8, sequentially carrying out two-stage solidification forming treatment on the fiber filaments to obtain meta-aramid fiber filaments, wherein the two-stage solidification forming is completed in a solidification bath of a second solvent, calcium chloride and water, wherein the second solvent is N, N-dimethylacetamide or N-methylpyrrolidone, the solidification forming temperature is 10 ℃ during the first-stage solidification forming, the mass concentration of calcium chloride in the solidification bath is 10%, the mass percentage of water is 15%, the solidification forming temperature is 15 ℃ during the second-stage solidification forming, the mass concentration of calcium chloride in the solidification bath is 7%, and the mass percentage of water is 20%.
And 9, carrying out water bath stretching and quenching on the meta-aramid fiber filaments to obtain the meta-aramid fiber, wherein the water bath temperature is 20 ℃, the stretching length is 2.5 times, and the quenching temperature is 410 ℃ during water bath stretching.
And (3) performance detection:
the meta-aramid fiber prepared in example 2 was tested for properties, and it was found that the meta-aramid fiber had a fineness of 1.4dtex, a breaking strength of 6.5cN/dtex, an elongation at break of 1.3%, an elastic modulus of 465cN/dtex, and a thermal weight loss at 400 ℃ of 1.2%.
Example 3
The embodiment 1 provides a preparation method of meta-aramid fiber, which comprises the following steps:
Step 1, after 1.05kg of m-phenylenediamine is dissolved in 11kg of first solvent, 0.38kg of m-phthaloyl chloride is added under the condition of stirring speed of 400r/min, and the pre-polymerization reaction is carried out at the temperature of-12 ℃ to obtain a primary pre-polymerization reaction product, wherein the first solvent is N, N-dimethylacetamide.
And 2, adding Ca (OH) 2 into the primary prepolymerization reaction product to neutralize HCl molecules generated by the prepolymerization reaction in the step 1, and then filtering by using a multi-layer filter cloth to remove a byproduct CaCl 2, so as to obtain a pale yellow transparent liquid, namely a primary filtrate.
And step3, adding 0.39kg of isophthaloyl dichloride into the primary filtrate, and performing prepolymerization at the temperature of-10 ℃ to obtain a secondary prepolymerization reaction product.
And step 4, adding Ca (OH) 2 into the secondary prepolymerization reaction product to neutralize HCl molecules generated by the prepolymerization reaction in the step 3, and filtering to obtain secondary filtrate.
And 5, adding 0.39kg of isophthaloyl dichloride into the secondary filtrate, and performing prepolymerization reaction at the temperature of 3 ℃ to obtain a three-time prepolymerization reaction product.
And 6, adding Ca (OH) 2 into the product of the three-time prepolymerization reaction to neutralize HCl molecules generated by the prepolymerization reaction in the step 5, adding ethylenediamine to neutralize residual isophthaloyl dichloride after the prepolymerization reaction, and finally filtering by using filter cloth to obtain yellow transparent polymer solution, thus obtaining the final filtrate.
And 7, feeding the final filtrate into a spinning device after passing through a metering pump, and carrying out spinning forming treatment on the final filtrate by using the spinning device to obtain fiber filaments, wherein in the spinning device, hole sites on a spinneret plate are distributed in a square shape, the aperture is 0.1mm, and the number of the holes is 800.
And 8, sequentially carrying out two-stage solidification forming treatment on the fiber filaments to obtain meta-aramid fiber filaments, wherein the two-stage solidification forming is completed in a solidification bath of a second solvent, calcium chloride and water, wherein the second solvent is N, N-dimethylacetamide or N-methylpyrrolidone, the solidification forming temperature is 8 ℃ in the first-stage solidification forming, the mass concentration of calcium chloride in the solidification bath is 9% and the mass percentage of water is 13%, the solidification forming temperature is 13 ℃ in the second-stage solidification forming, and the mass concentration of calcium chloride in the solidification bath is 6% and the mass percentage of water is 18%.
And 9, carrying out water bath stretching and quenching on the meta-aramid fiber filaments to obtain the meta-aramid fiber, wherein the water bath temperature is 18 ℃ during water bath stretching, the stretching length is 2.3 times, and the quenching temperature is 405 ℃.
And (3) performance detection:
The meta-aramid fiber prepared in example 3 was tested for properties, and it was found that the meta-aramid fiber had a fineness of 1.8dtex, a breaking strength of 4.2cN/dtex, an elongation at break of 3.0%, an elastic modulus of 210cN/dtex, and a thermal weight loss at 400 ℃ of 2.4%.
Example 4
The embodiment 1 provides a preparation method of meta-aramid fiber, which comprises the following steps:
Step 1, after 1kg of m-phenylenediamine is dissolved in 1.08kg of first solvent, 0.36kg of m-phthaloyl chloride is added under the condition of stirring speed of 350r/min, and the pre-polymerization reaction is carried out at the temperature of-13 ℃ to obtain a primary pre-polymerization reaction product, wherein the first solvent is N-methylpyrrolidone.
And 2, adding Ca (OH) 2 into the primary prepolymerization reaction product to neutralize HCl molecules generated by the prepolymerization reaction in the step 1, and then filtering by using a multi-layer filter cloth to remove a byproduct CaCl 2, so as to obtain a pale yellow transparent liquid, namely a primary filtrate.
And step3, adding 0.38kg of isophthaloyl dichloride into the primary filtrate, and performing prepolymerization reaction at the temperature of-12 ℃ to obtain a secondary prepolymerization reaction product.
And step 4, adding Ca (OH) 2 into the secondary prepolymerization reaction product to neutralize HCl molecules generated by the prepolymerization reaction in the step 3, and filtering to obtain secondary filtrate.
And 5, adding 0.38kg of isophthaloyl dichloride into the secondary filtrate, and performing prepolymerization reaction at the temperature of 4 ℃ to obtain a product of three prepolymerization reactions.
And 6, adding Ca (OH) 2 into the product of the three-time prepolymerization reaction to neutralize HCl molecules generated by the prepolymerization reaction in the step 5, adding ethylenediamine to neutralize residual isophthaloyl dichloride after the prepolymerization reaction, and finally filtering by using filter cloth to obtain yellow transparent polymer solution, thus obtaining the final filtrate.
And 7, feeding the final filtrate into a spinning device after passing through a metering pump, and carrying out spinning forming treatment on the final filtrate by using the spinning device to obtain fiber filaments, wherein in the spinning device, hole sites on a spinneret plate are distributed in a square shape, the aperture is 0.3mm, and the number of the holes is 200.
And 8, sequentially carrying out two-stage solidification forming treatment on the fiber filaments to obtain meta-aramid fiber filaments, wherein the two-stage solidification forming is completed in a solidification bath of a second solvent, calcium chloride and water, wherein the second solvent is N, N-dimethylacetamide or N-methylpyrrolidone, the solidification forming temperature is 9 ℃ in the first-stage solidification forming, the mass concentration of calcium chloride in the solidification bath is 8.5% and the mass percentage of water is 12%, the solidification forming temperature is 12 ℃ in the second-stage solidification forming, the mass concentration of calcium chloride in the solidification bath is 5.5% and the mass percentage of water is 17%.
And 9, carrying out water bath stretching and quenching on the meta-aramid fiber filaments to obtain the meta-aramid fiber, wherein the water bath temperature is 17 ℃, the stretching length is 2.2 times, and the quenching temperature is 407 ℃ during water bath stretching.
And (3) performance detection:
The meta-aramid fiber prepared in example 1 was tested for properties, and it was found that the meta-aramid fiber had a fineness of 2.0dtex, a breaking strength of 5.5cN/dtex, an elongation at break of 2.0%, an elastic modulus of 408cN/dtex, and a thermal weight loss at 400 ℃ of 2.0%.
The meta-aramid fiber and the preparation and application thereof, which are disclosed by the invention, are prepared by adopting a step-by-step prepolymerization method and a sectional coagulation bath process, and have good linear density, tensile strength, elongation at break, modulus and thermal stability, wherein the fineness of the meta-aramid fiber is 1.4-2.0 dtex, the breaking strength is 4.2-6.5 cN/dtex, the elongation at break is 1.3% -3.0%, the elastic modulus is 210-460 cN/dtex, and the thermal weight loss at 400 ℃ is 1.2-2.4%. Can be applied to the matrix material of high-performance insulating paper.
The above embodiment is only one of the implementation manners capable of implementing the technical solution of the present invention, and the scope of the claimed invention is not limited to the embodiment, but also includes any changes, substitutions and other implementation manners easily recognized by those skilled in the art within the technical scope of the present invention.

Claims (4)

1.一种间位芳纶纤维的制备方法，其特征在于，包括以下步骤：1. A method for preparing meta-aramid fibers, characterized by comprising the following steps: 步骤1、将间苯二胺溶于第一溶剂中后，加入间苯二甲酰氯，进行预聚合反应，反应后加入碱液以中和HCl分子，过滤，得到一次滤液；步骤1中，预聚合反应在-15~-5℃的温度条件下进行；Step 1: After dissolving m-phenylenediamine in the first solvent, add isophthaloyl chloride to carry out a prepolymerization reaction. After the reaction, add alkali solution to neutralize HCl molecules, filter, and obtain a primary filtrate. In Step 1, the prepolymerization reaction is carried out at a temperature of -15~-5℃. 步骤2、在一次滤液中加入间苯二甲酰氯，进行预聚合反应，反应后加入碱液以中和HCl分子，过滤，得到二次滤液；步骤2中，预聚合反应在-15~-5℃的温度条件下进行；Step 2: Add isophthaloyl chloride to the primary filtrate to carry out a prepolymerization reaction. After the reaction, add alkali solution to neutralize HCl molecules, filter, and obtain a secondary filtrate. In Step 2, the prepolymerization reaction is carried out at a temperature of -15~-5℃. 步骤3、在二次滤液中加入间苯二甲酰氯，进行预聚合反应，反应后加入碱液以中和HCl分子，再加入乙二胺中和预聚合反应后剩余的间苯二甲酰氯，过滤，得到终滤液；步骤3中，预聚合反应在0~6℃的温度条件下进行；Step 3: Add isophthaloyl chloride to the secondary filtrate to carry out a prepolymerization reaction. After the reaction, add alkali solution to neutralize HCl molecules, and then add ethylenediamine to neutralize the remaining isophthaloyl chloride after the prepolymerization reaction. Filter to obtain the final filtrate. In step 3, the prepolymerization reaction is carried out at a temperature of 0~6℃. 步骤4、对所述终滤液进行喷丝成型处理，得到纤维长丝；对所述纤维长丝依次进行两级凝固成型处理，得到间位芳纶纤维长丝；其中，两级凝固成型均采用在第二溶剂、氯化钙及水的凝固浴中完成；其中，第二溶剂为N,N-二甲基乙酰胺或N-甲基吡咯烷酮；Step 4: The final filtrate is spun into fibers to obtain filaments; the filaments are then subjected to two-stage coagulation to obtain meta-aramid fiber filaments; wherein, both stages of coagulation are completed in a coagulation bath of a second solvent, calcium chloride and water; wherein, the second solvent is N,N-dimethylacetamide or N-methylpyrrolidone. 步骤5、对所述间位芳纶纤维长丝进行水浴拉伸、淬火，得到所述的间位芳纶纤维；步骤5中，水浴拉伸时，水浴温度为15~20℃，拉伸长度为2~2.5倍，淬火温度为400~410℃；Step 5: The meta-aramid fiber filament is subjected to water bath stretching and quenching to obtain the meta-aramid fiber; in Step 5, the water bath temperature is 15~20℃, the stretching length is 2~2.5 times, and the quenching temperature is 400~410℃. 步骤4中，第一级凝固成型时，凝固成型温度为6~10℃；凝固浴中氯化钙的质量浓度为8~10%、水的质量百分数为10%~15%；In step 4, during the first stage of solidification, the solidification temperature is 6~10℃; the mass concentration of calcium chloride in the solidification bath is 8~10%, and the mass percentage of water is 10%~15%. 步骤4中，第二级凝固成型时，凝固成型温度为10~15℃；凝固浴中氯化钙的质量浓度为5~7%、水的质量百分数为15%~20%。In step 4, during the second stage of solidification, the solidification temperature is 10~15℃; the mass concentration of calcium chloride in the solidification bath is 5~7%, and the mass percentage of water is 15%~20%. 2.根据权利要求1所述的一种间位芳纶纤维的制备方法，其特征在于，步骤1中，所述第一溶剂为N,N-二甲基乙酰胺或N-甲基吡咯烷酮。2. The method for preparing meta-aramid fiber according to claim 1, characterized in that, in step 1, the first solvent is N,N-dimethylacetamide or N-methylpyrrolidone. 3.一种间位芳纶纤维，其特征在于，所述间位芳纶纤维采用如权利要求1-2任意一项所述的一种间位芳纶纤维的制备方法制备得到；其中，所述间位芳纶纤维的纤度为1.4~2.0dtex，断裂强度为4.2~6.5cN/dtex，断裂伸长率为1.3%~3.0%，弹性模量为210~465cN/dtex，在400℃的热失重为1.2~2.4%。3. A meta-aramid fiber, characterized in that the meta-aramid fiber is prepared by the preparation method of a meta-aramid fiber as described in any one of claims 1-2; wherein the meta-aramid fiber has a fineness of 1.4~2.0 dtex, a breaking strength of 4.2~6.5 cN/dtex, a breaking elongation of 1.3%~3.0%, an elastic modulus of 210~465 cN/dtex, and a thermal weight loss of 1.2~2.4% at 400℃. 4.如权利要求3所述的一种间位芳纶纤维的应用，其特征在于，所述间位芳纶纤维用于作为芳纶绝缘纸的基体材料。4. The application of a meta-aramid fiber as described in claim 3, wherein the meta-aramid fiber is used as a matrix material for aramid insulating paper.
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