WO2016127465A1 - Preparation method for high-strength polyacrylonitrile nano composite fibres - Google Patents

Preparation method for high-strength polyacrylonitrile nano composite fibres Download PDF

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WO2016127465A1
WO2016127465A1 PCT/CN2015/074140 CN2015074140W WO2016127465A1 WO 2016127465 A1 WO2016127465 A1 WO 2016127465A1 CN 2015074140 W CN2015074140 W CN 2015074140W WO 2016127465 A1 WO2016127465 A1 WO 2016127465A1
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polyacrylonitrile
graphene
preparing
strength
fiber according
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PCT/CN2015/074140
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French (fr)
Chinese (zh)
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拜永孝
胡新军
沙嫣
沙晓林
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上海史墨希新材料科技有限公司
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D1/00—Treatment of filament-forming or like material
    • D01D1/02—Preparation of spinning solutions
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/06—Wet spinning methods
    • 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
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/54—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D1/00—Treatment of filament-forming or like material
    • D01D1/10—Filtering or de-aerating the spinning solution or melt
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/02—Heat treatment
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/06—Washing or drying
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/12—Stretch-spinning methods
    • 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

Definitions

  • the invention relates to a preparation method of high-strength polyacrylonitrile nano composite fiber.
  • Carbon is widely found in nature and is one of the basic elements that make up living organisms.
  • graphene consists of a dense layer of monoatomic layers formed by sp 2 hybridization of carbon atoms entrapped on the lattice of honeycomb crystals. It is the basic structure of other carbon allotropes. Unit, which can be folded into zero-dimensional fullerenes, crimped into one-dimensional carbon nanotubes, stacked into three-dimensional graphite and diamond, has excellent crystallinity and electrical quality and excellent mechanical properties, and has high graphene strength. The performance is comparable to that of diamond.
  • the measured tensile strength and elastic modulus are 125GPa and 1.1T Pa, respectively.
  • the graphene sheet has only one atomic layer thickness (0.335nm), which is only one hundred thousandth of the hair. It is currently in the world. Know the thinnest and hardest material.
  • graphene has many other properties in terms of electricity and magnetism, such as room temperature quantum, Hall effect, bipolar electric field effect, ferromagnetism, superconductivity and high electron mobility, which quickly become materials, chemistry, and physics. And research topics in the field of engineering. In particular, its large specific surface area and excellent mechanical properties are widely used in new high-strength composite materials.
  • Carbon fiber refers to a microcrystalline quasi-graphite material with a carbon content of more than 90%, usually obtained by high-temperature carbonization and graphitization of organic fibers, and its microscopic molecular structure is similar to artificial graphite, which is a disordered graphite structure.
  • Carbon fiber has excellent comprehensive properties such as high axial specific strength, high specific modulus, fatigue creep resistance, good stability, good electric heating conductor, good X-ray permeability, low density, and small thermal expansion coefficient. Aerospace, automotive, construction and sports. Carbon fiber is usually used as a structural reinforcement material to be composited with other matrix materials to form a composite material, which can be directly used as a structural component in aerospace, sports equipment, construction, transportation vehicles, machinery and the like.
  • the raw yarns for preparing high-performance carbon fibers are mainly polyacrylonitrile (PAN)-based fibers, rayon fibers and pitch-based fibers.
  • PAN fiber has high molecular orientation, high melting point and high carbon fiber yield, and heat treatment of PAN fiber at low temperature can form a highly thermally stable, highly oriented molecular structure. The heat-stable structure is not severely damaged during the carbonization treatment, and the carbon fiber having the best comprehensive performance can be obtained.
  • the domestic production of polyacrylonitrile raw yarn for carbon fiber adopts the wet spinning method.
  • the biggest advantage of the method for preparing the carbon fiber precursor is that the production process is simple, the carbon fiber produced is low in cost, the obtained PAN molecular defect is small, and the pre-oxidation process is released.
  • the heat peak temperature is low, but the hot stretching ratio in the spinning is small, and the degree of orientation of the PAN molecules is not high.
  • the de-orientation due to the molecular thermal motion, the de-orientation is caused, so that the orientation of the graphite-like sheet layer of the final product carbon fiber is poor, and the tensile strength and modulus of the carbon fiber are low.
  • the object of the present invention is to provide a preparation method of high-strength polyacrylonitrile nano-composite fiber, in particular to a preparation method of high-strength polyacrylonitrile nano-composite fiber with simple production process and low cost.
  • the invention utilizes the ultra-large specific surface area of graphene and excellent mechanical properties to prepare high-strength and high-modulus graphene/PAN fibers by gel spinning.
  • Gel spinning is the use of polyacrylonitrile with high molecular weight, dissolved into a semi-dilute solution, the entanglement between macromolecular chains is greatly reduced, and quenching after spinning causes unwinding of such macromolecular chains.
  • the state is maintained in the prepared gel precursor, and the crystallinity and degree of orientation of the fiber are increased by ultra-high heat stretching, and the platelets in the folded chain are transformed into a straight chain to obtain ultra-high-strength high-modulus fibers.
  • the graphene sheets can be aligned to further improve the performance of the fiber.
  • the sheet-like rigid structure of graphene can guide the arrangement of molecular chains in the fiber during fiber fiber forming and stretching, and improve the crystallinity thereof.
  • the graphene is oriented under the action of drawing, and the fiber molecular chain can be induced to be aligned along the direction of the graphene layer; the fiber will undergo physical shrinkage during heat treatment, and the degree of orientation will also decrease.
  • the olefin can inhibit the misorientation of the molecular chain by restricting the movement of the molecular chain, thereby increasing the degree of orientation of the fiber.
  • the structure of the pre-oxidized fiber will change to the graphite-like structure, and the graphene of the monolithic graphite structure can act as a template to guide the transformation of the fiber structure while being melted therein without causing structural damage.
  • the defects caused by the mismatch ultimately promote the fiber to form a more complete graphitized structure, and as a separate structure to connect the surrounding crystals, which is beneficial to improve the performance of the carbon fiber.
  • the invention provides a preparation method of high-strength polyacrylonitrile nano-composite fiber, and the preparation method comprises the following steps:
  • Step 1 Adding graphene to an organic solvent or a mixed solution of an organic solvent and water, dispersing uniformly, adding polyacrylonitrile, and dissolving at 30 to 120 ° C to obtain a spinning dope;
  • Step 2 the spinning dope is filtered at 20 to 80 ° C, defoamed, and then sprayed through a spinneret into a coagulation bath of -40 to 5 ° C to form nascent fibers;
  • Step 3 The nascent fiber is subjected to extraction, drying, hot stretching, and heat setting to obtain the high-strength polyacrylonitrile nano-composite fiber.
  • the dispersion specifically refers to high speed stirring or ultrasonic dispersion; the high speed stirring or ultrasonic dispersion time is 1 to 6 hours; and the high speed stirring speed is 3000 to 10000 rpm.
  • the weight ratio of the organic solvent to the water in the mixed solution ranges from 98:2 to 70:30.
  • the organic solvent comprises one of ethylene carbonate, ethylene carbonate, dimethyl sulfoxide, dimethylformamide, and dimethylacetamide.
  • the concentrated acid is concentrated nitric acid having a mass concentration greater than 65%; and the inorganic salt comprises one of thiocyanate, zinc chloride or lithium bromide.
  • the graphene comprises one of graphene oxide, modified or modified graphene, and electrically stripped graphene.
  • the polyacrylonitrile comprises a homopolymer of acrylonitrile or a copolymer of acrylonitrile and other monomers; the polyacrylonitrile has a viscosity average molecular weight ranging from 50,000 to 150,000;
  • the body includes methyl acrylate, methyl methacrylate, vinyl acetate, sodium propylene sulfonate, itaconic acid, sodium methacrylate or sodium methacrylate.
  • the weight percentage of the polyacrylonitrile in the spinning dope is 15-30%, and the weight percentage of the graphene is 0.05-20%.
  • the defoaming method comprises vacuum defoaming or atmospheric degassing; the spinneret has a pore size ranging from 0.06 to 0.25 mm.
  • the coagulation bath is a mixed solution of an organic solvent including dimethyl sulfoxide (DMSO) or dimethylformamide (DMF); and an organic solvent in the mixed solution.
  • DMSO dimethyl sulfoxide
  • DMF dimethylformamide
  • the volume ratio to water ranges from 50:50 to 80:20.
  • the extracting agent in the extraction comprises methanol or ethanol; the extraction temperature is -20 to 60 ° C, and the time is 2 to 60 min.
  • the drying temperature is 60 to 120 ° C; the drying time is 2 to 24 hours; the hot stretching temperature is 120 to 240 ° C, and the thermal stretching is 4 to 40 times, heat setting The time is 0.5 to 15 minutes.
  • the intrinsic non-polar carbon chain containing a polar nitrile group and a molecular skeleton can be used as a dispersing agent for a dilute graphite solution to uniformly disperse graphene in a mixed solvent;
  • gel spinning is the use of polyacrylonitrile with high molecular weight, dissolved into a semi-dilute solution, the entanglement between macromolecular chains is greatly reduced, and quenching after spinning makes this large
  • the unwrapped state between the molecular chains is maintained in the prepared gel precursor, and the crystallinity and orientation degree of the fiber are increased by the ultra-high heat stretching, so that the platelets in the folded chain are transformed into the straight chain, thereby obtaining ultra-high strength.
  • High-mold fiber in high-stretching, not only can the macromolecular chain in the finished fiber be stretched in a regular arrangement, but also the graphene sheets can be aligned to further improve the fiber properties; at the same time, rigid graphene molecules are added. It is beneficial to limit the disorientation of PAN molecules due to thermal motion.
  • graphene can be incorporated into the crystal structure of the fiber to induce the formation of highly oriented graphite-like crystals, and as a separate structure to connect the surrounding crystals, Conducive to improving the performance of carbon fiber.
  • Figure 1 is a photograph of the appearance of polyacrylonitrile fiber
  • Figure 2 is an SEM image (scanning electron micrograph) of a cross section of a polyacrylonitrile fiber.
  • This embodiment provides a method for preparing a high-strength polyacrylonitrile nanocomposite fiber, and the preparation method comprises the following steps:
  • DMSO dimethyl sulfoxide
  • Polyacrylonitrile having a molecular weight of 88,000 was added to the mixed solvent, and dissolved by stirring at 50 ° C for 2 hours.
  • the weight percentage of graphene oxide is 0.3%, and the weight percentage of polyacrylonitrile is 30%;
  • the jelly fiber was drawn and extracted in a methanol bath at -20 ° C to remove dimethyl sulfoxide; the extraction time was 60 min, and dried in an oven at 80 ° C for 4 hours; then, it was hot-drawn at 120 ° C and set for 0.5 minutes, and stretched. The multiple is 13 times.
  • FIG. 1 is a macro photograph of a graphene nanocomposite fiber prepared by the present invention, wherein the fiber surface is smooth and thick uniform.
  • Figure 2 is a cross-sectional scanning electron micrograph of graphene nanocomposite fiber. The cross-section shows that the internal structure of the fiber is compact and compact, the graphene is uniformly distributed in the polyacrylonitrile matrix, and the two-phase interface is firmly bonded, and there is no common material recombination and condensation. The generation of the sheath-core structure due to phase separation occurs.
  • This embodiment provides a method for preparing a high-strength polyacrylonitrile nanocomposite fiber, and the preparation method comprises the following steps:
  • the jelly fiber was drawn and extracted in a methanol bath at 60 ° C to remove dimethyl sulfoxide; the extraction time was 60 min, and dried in an oven at 100 ° C; then, it was hot-drawn at 200 ° C and set for 5 minutes, and the stretching ratio was 4 Times.
  • the polyacrylonitrile fiber obtained in this example had a tensile strength of 7.8 cN/dtex and a Young's modulus of 28 N/dtex.
  • This embodiment provides a method for preparing a high-strength polyacrylonitrile nanocomposite fiber, and the preparation method comprises the following steps:
  • the jelly fiber was subjected to drawing extraction in a methanol bath at 30 ° C to remove the solvent; the extraction time was 60 min, and it was dried in an oven at 120 ° C; then, it was hot-drawn at 240 ° C and set for 15 minutes, and the stretching ratio was 9 times.
  • the polyacrylonitrile fiber obtained in this example had a tensile strength of 7.9 cN/dtex and a Young's modulus of 31 cN/dtex.
  • This embodiment provides a method for preparing a high-strength polyacrylonitrile nanocomposite fiber, and the preparation method comprises the following steps:
  • silane coupling agent modified graphene oxide Adding silane coupling agent modified graphene oxide to concentrated nitric acid, ultrasonic dispersion for 6h; molecular weight is 150,000
  • the polyacrylonitrile was added to concentrated nitric acid and dissolved by stirring at 40 ° C for 1 h.
  • the weight percentage of the modified graphene is 20%, and the weight percentage of the polyacrylonitrile is 25%;
  • the jelly fiber was subjected to drawing extraction in a methanol bath at 20 ° C to remove nitric acid; the extraction time was 160 min, and it was dried in an oven at 120 ° C; then, it was hot-drawn at 130 ° C and set for 5 minutes, and the stretching ratio was 30 times.
  • the polyacrylonitrile fiber obtained in this example had a tensile strength of 8.9 cN/dtex and a Young's modulus of 36 cN/dtex.
  • This embodiment provides a method for preparing a high-strength polyacrylonitrile nanocomposite fiber, and the preparation method comprises the following steps:
  • DMSO dimethyl sulfoxide
  • a copolymer of acrylonitrile methyl acrylate having an average molecular weight of 75,000 was added to the mixed solvent, and stirred and dissolved at 50 ° C for 2 hours.
  • the weight percentage of graphene oxide is 0.5%, and the weight percentage of polyacrylonitrile is 20%;
  • the jelly fiber was drawn and extracted in a methanol bath at -30 ° C to remove dimethyl sulfoxide; the extraction time was 160 min, and dried in an oven at 80 ° C for 4 hours; then, it was hot-drawn at 120 ° C and set for 3 minutes, and stretched. The multiple is 10 times.
  • the polyacrylonitrile fiber obtained in this example had a tensile strength of 7.5 cN/dtex and a Young's modulus of 28 cN/dtex.
  • the present invention can be realized at a high speed stirring speed of between 3,000 and 10,000 rpm, and the copolymer monomer of the polyacrylonitrile is methyl methacrylate, vinyl acetate, sodium propylene sulfonate.
  • the present invention can be achieved by itaconic acid, sodium methacrylate sulfonate or sodium methacrylate sulfonate.

Abstract

A preparation method for high-strength polyacrylonitrile nano composite fibres. The preparation method comprises the following steps: step I, adding graphene into an organic solvent or a mixed solution of the organic solvent and water, uniformly dispersing, then adding a homopolymer or copolymer of acrylonitrile, and dissolving at 30°C to 120°C to obtain a spinning solution; or directly mixing the homopolymer or copolymer of the acrylonitrile and the graphene to obtain a mixture, then dispersing the mixture in a concentrated acid or an aqueous solution of an inorganic salt to obtain a spinning solution; step II, filtering and defoaming the spinning solution at 20°C to 80°C, and spraying the spinning solution to a coagulating bath at -40°C to 5°C through a spinneret plate to form nascent fibres; and step III, extracting, drying, thermally stretching and thermally stereotyping the nascent fibres to obtain the high-strength polyacrylonitrile nano composite fibres. The method is simple in production process, high in production performance and easy for realizing the industrialized mass production.

Description

一种高强聚丙烯腈纳米复合纤维的制备方法Preparation method of high-strength polyacrylonitrile nano composite fiber 技术领域Technical field
本发明涉及一种高强聚丙烯腈纳米复合纤维的制备方法。The invention relates to a preparation method of high-strength polyacrylonitrile nano composite fiber.
背景技术Background technique
碳广泛存在于自然界中，是构成生命有机体的基本元素之一。石墨烯作为一种碳质新材料，由一层密集的、包裹在蜂巢晶体点阵上的碳原子以sp2杂化连接而成的单原子层组成，是构成其他碳同素异形体的基本单元，它可折叠成零维的富勒烯，卷曲成一维的碳纳米管，堆垛成三维的石墨和金刚石，具有极好的结晶性及电学质量和优异的力学性能，石墨烯强度高，性能可与金刚石媲美，实测抗拉强度和弹性模量分别为125GPa和1.1T Pa，石墨烯薄片只有一个原子层厚(0.335nm)，仅为头发的20万分之一，是目前世界上已知的最薄最硬的材料。此外，石墨烯在电和磁等方面有很多其他的性质，如室温量子、霍尔效应、双极性电场效应、铁磁性、超导性及高的电子迁移率，迅速成为材料、化学、物理和工程领域的热点研究课题。尤其是其超大的比表面积和优异的机械性能，广泛应用于新型高强度复合材料之中。Carbon is widely found in nature and is one of the basic elements that make up living organisms. As a new carbonaceous material, graphene consists of a dense layer of monoatomic layers formed by sp 2 hybridization of carbon atoms entrapped on the lattice of honeycomb crystals. It is the basic structure of other carbon allotropes. Unit, which can be folded into zero-dimensional fullerenes, crimped into one-dimensional carbon nanotubes, stacked into three-dimensional graphite and diamond, has excellent crystallinity and electrical quality and excellent mechanical properties, and has high graphene strength. The performance is comparable to that of diamond. The measured tensile strength and elastic modulus are 125GPa and 1.1T Pa, respectively. The graphene sheet has only one atomic layer thickness (0.335nm), which is only one hundred thousandth of the hair. It is currently in the world. Know the thinnest and hardest material. In addition, graphene has many other properties in terms of electricity and magnetism, such as room temperature quantum, Hall effect, bipolar electric field effect, ferromagnetism, superconductivity and high electron mobility, which quickly become materials, chemistry, and physics. And research topics in the field of engineering. In particular, its large specific surface area and excellent mechanical properties are widely used in new high-strength composite materials.
碳纤维是指碳含量大于90％，通常由有机纤维经高温碳化及石墨化处理后而得到的微晶准石墨材料，其微观分子结构类似人造石墨，为乱层石墨结构。碳纤维具有轴向比强度高、比模量高、耐疲劳蠕变、稳定性好、电热良导体、X射线透过性好、密度小、热膨胀系数小等优异的综合性能，而被广泛应用于航空航天、汽车、建筑和体育等领域。碳纤维通常作为结构增强型材料与其它基体材料进行复合，组成复合材料，在航空航天、体育器材、建筑、运输车辆、机械等领域可直接用作结构性部件。Carbon fiber refers to a microcrystalline quasi-graphite material with a carbon content of more than 90%, usually obtained by high-temperature carbonization and graphitization of organic fibers, and its microscopic molecular structure is similar to artificial graphite, which is a disordered graphite structure. Carbon fiber has excellent comprehensive properties such as high axial specific strength, high specific modulus, fatigue creep resistance, good stability, good electric heating conductor, good X-ray permeability, low density, and small thermal expansion coefficient. Aerospace, automotive, construction and sports. Carbon fiber is usually used as a structural reinforcement material to be composited with other matrix materials to form a composite material, which can be directly used as a structural component in aerospace, sports equipment, construction, transportation vehicles, machinery and the like.
制备高性能碳纤维的原丝主要有聚丙烯腈(PAN)基纤维，人造丝纤维和沥青基纤维三大类。其中PAN纤维具有高的分子取向，较高的熔点以及较高的碳纤维产率，在低温时对PAN纤维进行热处理，可以形成一种热稳定性好的，高度取向的分子结构。这种热稳定性结构在进行碳化处理时也不会受到严重破坏，能制得综合性能最好的碳纤维。PAN纤维的这些优点使它成为当今制造碳纤维的最重要和最有发展前途的原丝。材料的结构决定性能，碳纤维的结构是由原丝结构经过预氧化和碳化过程演变来的，因此，碳纤维的性能好坏关键在于原丝的质量(原丝中PAN分子的轴向取向和缺陷)。 The raw yarns for preparing high-performance carbon fibers are mainly polyacrylonitrile (PAN)-based fibers, rayon fibers and pitch-based fibers. Among them, PAN fiber has high molecular orientation, high melting point and high carbon fiber yield, and heat treatment of PAN fiber at low temperature can form a highly thermally stable, highly oriented molecular structure. The heat-stable structure is not severely damaged during the carbonization treatment, and the carbon fiber having the best comprehensive performance can be obtained. These advantages of PAN fiber make it the most important and promising raw yarn for the manufacture of carbon fiber today. The structure of the material determines the properties. The structure of the carbon fiber evolves from the pre-oxidation and carbonization process of the raw silk structure. Therefore, the key performance of the carbon fiber lies in the quality of the original yarn (axial orientation and defects of PAN molecules in the original filament) .
国内生产碳纤维用聚丙烯腈原丝都采用湿法纺丝法，该方法制备碳纤维原丝最大的优点是生产工艺简单，生产的碳纤维成本低，所得PAN分子缺陷较小、预氧化过程中的放热峰值温度较低，但纺丝中热拉伸倍数小，PAN分子的取向度不高。在预氧化过程中，由于分子热运动会产生解取向，使得最终产物碳纤维的类石墨片层的取向度差，碳纤维的拉伸强度和模量低。The domestic production of polyacrylonitrile raw yarn for carbon fiber adopts the wet spinning method. The biggest advantage of the method for preparing the carbon fiber precursor is that the production process is simple, the carbon fiber produced is low in cost, the obtained PAN molecular defect is small, and the pre-oxidation process is released. The heat peak temperature is low, but the hot stretching ratio in the spinning is small, and the degree of orientation of the PAN molecules is not high. In the pre-oxidation process, due to the molecular thermal motion, the de-orientation is caused, so that the orientation of the graphite-like sheet layer of the final product carbon fiber is poor, and the tensile strength and modulus of the carbon fiber are low.
发明内容Summary of the invention
针对上述技术缺陷，本发明的目的是提供一种高强聚丙烯腈纳米复合纤维的制备方法，具体是一种生产工艺简单、成本低的高强聚丙烯腈纳米复合纤维的制备方法。In view of the above technical drawbacks, the object of the present invention is to provide a preparation method of high-strength polyacrylonitrile nano-composite fiber, in particular to a preparation method of high-strength polyacrylonitrile nano-composite fiber with simple production process and low cost.
本发明利用石墨烯超大的比表面积和优异的机械性能，用凝胶纺丝的方法制备高强高模的石墨烯/PAN纤维。凝胶纺丝是利用相对分子质量高的聚丙烯腈，经溶解成半稀溶液，大分子链之间的缠结大幅度减小，纺丝后骤冷使这种大分子链间的解缠状态得以保持在制备的凝胶原丝中，通过超倍热拉伸，提高纤维结晶度和取向度，使呈折叠链的片晶向伸直链转化，从而获得超高强高模纤维。在高倍拉伸时，不仅可以使成品纤维中大分子链呈现规整排列的伸展状态，也可以让石墨烯片成定向排列，进一步提高纤维的性能。片层刚性结构的石墨烯在纤维成纤和拉伸过程中可以引导纤维中分子链的排列，提高其结晶度。其次石墨烯在牵伸的作用下进行取向，可以诱导纤维分子链沿着石墨烯层片方向进行取向排列；纤维在热处理时将会发生物理收缩，其取向程度也将随之下降，此时石墨烯通过限制分子链的运动可以抑制分子链的解取向，从而提高纤维的取向度。最后在炭化时预氧化纤维的结构将向类石墨的结构转变，这时单片层石墨结构的石墨烯可以起到模板的作用引导纤维结构的转变同时融于其中但又不会造成结构上的不匹配带来的缺陷，最终促进纤维形成更加完善的石墨化结构，并且作为独立的结构连接周围晶体，有利于提高碳纤维的性能。The invention utilizes the ultra-large specific surface area of graphene and excellent mechanical properties to prepare high-strength and high-modulus graphene/PAN fibers by gel spinning. Gel spinning is the use of polyacrylonitrile with high molecular weight, dissolved into a semi-dilute solution, the entanglement between macromolecular chains is greatly reduced, and quenching after spinning causes unwinding of such macromolecular chains. The state is maintained in the prepared gel precursor, and the crystallinity and degree of orientation of the fiber are increased by ultra-high heat stretching, and the platelets in the folded chain are transformed into a straight chain to obtain ultra-high-strength high-modulus fibers. In the case of high-stretching, not only the macromolecular chain in the finished fiber can be stretched in a regular arrangement, but also the graphene sheets can be aligned to further improve the performance of the fiber. The sheet-like rigid structure of graphene can guide the arrangement of molecular chains in the fiber during fiber fiber forming and stretching, and improve the crystallinity thereof. Secondly, the graphene is oriented under the action of drawing, and the fiber molecular chain can be induced to be aligned along the direction of the graphene layer; the fiber will undergo physical shrinkage during heat treatment, and the degree of orientation will also decrease. The olefin can inhibit the misorientation of the molecular chain by restricting the movement of the molecular chain, thereby increasing the degree of orientation of the fiber. Finally, in the carbonization, the structure of the pre-oxidized fiber will change to the graphite-like structure, and the graphene of the monolithic graphite structure can act as a template to guide the transformation of the fiber structure while being melted therein without causing structural damage. The defects caused by the mismatch ultimately promote the fiber to form a more complete graphitized structure, and as a separate structure to connect the surrounding crystals, which is beneficial to improve the performance of the carbon fiber.
本发明的目的是通过以下技术方案实现的：The object of the invention is achieved by the following technical solutions:
本发明提供一种高强聚丙烯腈纳米复合纤维的制备方法，所述制备方法包括以下步骤：The invention provides a preparation method of high-strength polyacrylonitrile nano-composite fiber, and the preparation method comprises the following steps:
步骤一、向有机溶剂或有机溶剂与水的混合溶液中加入石墨烯，分散均匀，再加入聚丙烯腈，于30～120℃条件下溶解，得纺丝原液；Step 1. Adding graphene to an organic solvent or a mixed solution of an organic solvent and water, dispersing uniformly, adding polyacrylonitrile, and dissolving at 30 to 120 ° C to obtain a spinning dope;
或将聚丙烯腈与石墨烯直接溶解、分散于浓酸或无机盐的水溶液中，得纺丝原液；Or directly dissolving polyacrylonitrile and graphene in an aqueous solution of concentrated acid or inorganic salt to obtain a spinning dope;
步骤二、将所述纺丝原液于20～80℃条件下，过滤、脱泡后，经喷丝板喷出到-40～5℃的凝固浴中，形成初生纤维； Step 2, the spinning dope is filtered at 20 to 80 ° C, defoamed, and then sprayed through a spinneret into a coagulation bath of -40 to 5 ° C to form nascent fibers;
步骤三、所述初生纤维经萃取、干燥、热拉伸、热定型，得所述高强聚丙烯腈纳米复合纤维。Step 3: The nascent fiber is subjected to extraction, drying, hot stretching, and heat setting to obtain the high-strength polyacrylonitrile nano-composite fiber.
优选地，步骤一中，所述分散具体指高速搅拌或超声分散；所述高速搅拌或超声分散的时间为1～6h；所述高速搅拌的速度为3000～10000转/分。Preferably, in the first step, the dispersion specifically refers to high speed stirring or ultrasonic dispersion; the high speed stirring or ultrasonic dispersion time is 1 to 6 hours; and the high speed stirring speed is 3000 to 10000 rpm.
优选地，步骤一中，所述混合溶液中有机溶剂与水的重量比范围98:2～70:30，Preferably, in step 1, the weight ratio of the organic solvent to the water in the mixed solution ranges from 98:2 to 70:30.
优选地，步骤一中，所述有机溶剂包括硝酸亚乙基酯、碳酸乙烯酯、二甲基亚砜、二甲基甲酰胺、二甲基乙酰胺的一种。Preferably, in the first step, the organic solvent comprises one of ethylene carbonate, ethylene carbonate, dimethyl sulfoxide, dimethylformamide, and dimethylacetamide.
优选地，步骤一中，所述浓酸为质量浓度大于65％的浓硝酸；所述无机盐包括硫氰酸盐、氯化锌或溴化锂中的一种。Preferably, in the first step, the concentrated acid is concentrated nitric acid having a mass concentration greater than 65%; and the inorganic salt comprises one of thiocyanate, zinc chloride or lithium bromide.
优选地，步骤一中，所述石墨烯包括氧化石墨烯、修饰或改性的石墨烯、电剥离石墨烯的一种。Preferably, in the first step, the graphene comprises one of graphene oxide, modified or modified graphene, and electrically stripped graphene.
优选地，步骤一中，所述聚丙烯腈包括丙烯腈的均聚物或丙烯腈与其他单体的共聚物；所述聚丙烯腈的粘均分子量范围为5～15万；所述其他单体包括丙烯酸甲酯、甲基丙烯酸甲酯、醋酸乙烯酯、丙烯磺酸钠、衣康酸、甲基丙烯磺酸钠或甲基丙烯苯磺酸钠。Preferably, in the first step, the polyacrylonitrile comprises a homopolymer of acrylonitrile or a copolymer of acrylonitrile and other monomers; the polyacrylonitrile has a viscosity average molecular weight ranging from 50,000 to 150,000; The body includes methyl acrylate, methyl methacrylate, vinyl acetate, sodium propylene sulfonate, itaconic acid, sodium methacrylate or sodium methacrylate.
优选地，步骤一中，所述纺丝原液中聚丙烯腈的重量百分比为15～30％，所述石墨烯的重量百分比为0.05～20％。Preferably, in the first step, the weight percentage of the polyacrylonitrile in the spinning dope is 15-30%, and the weight percentage of the graphene is 0.05-20%.
优选地，步骤二中，所述脱泡方式包括真空脱泡或常压静置脱泡；所述喷丝板孔径范围为0.06～0.25mm。Preferably, in the second step, the defoaming method comprises vacuum defoaming or atmospheric degassing; the spinneret has a pore size ranging from 0.06 to 0.25 mm.
优选地，步骤二中，所述凝固浴为有机溶剂与水的混合溶液，所述有机溶剂包括二甲基亚砜(DMSO)或二甲基甲酰胺(DMF)；所述混合溶液中有机溶剂与水的体积比范围50:50～80:20。Preferably, in the second step, the coagulation bath is a mixed solution of an organic solvent including dimethyl sulfoxide (DMSO) or dimethylformamide (DMF); and an organic solvent in the mixed solution. The volume ratio to water ranges from 50:50 to 80:20.
优选地，步骤三中，所述萃取中的萃取剂包括甲醇或乙醇；萃取的温度为-20～60℃，时间为2～60min。Preferably, in the third step, the extracting agent in the extraction comprises methanol or ethanol; the extraction temperature is -20 to 60 ° C, and the time is 2 to 60 min.
优选地，步骤三中，所述干燥的温度为60～120℃；干燥的时间为2～24h；热拉伸的温度为120～240℃，热拉伸的倍数为4～40倍，热定型的时间为0.5～15min。Preferably, in the third step, the drying temperature is 60 to 120 ° C; the drying time is 2 to 24 hours; the hot stretching temperature is 120 to 240 ° C, and the thermal stretching is 4 to 40 times, heat setting The time is 0.5 to 15 minutes.
本发明与现有技术相比具有以下优点：The present invention has the following advantages over the prior art:
1、聚丙烯腈含有极性的腈基和分子骨架的本征非极性碳链可作为石墨稀溶液的分散剂，使石墨烯均匀分散在混合溶剂中；1. Polyacrylonitrile The intrinsic non-polar carbon chain containing a polar nitrile group and a molecular skeleton can be used as a dispersing agent for a dilute graphite solution to uniformly disperse graphene in a mixed solvent;
2、用石墨烯超大的比表面积和优异的机械性能，用凝胶纺丝的方法制备高强的石 墨烯/PAN纤维；凝胶纺丝是利用相对分子质量高的聚丙烯腈，经溶解成半稀溶液，大分子链之间的缠结大幅度减小，纺丝后骤冷使这种大分子链间的解缠状态得以保持在制备的凝胶原丝中，通过超倍热拉伸，提高纤维结晶度和取向度，使呈折叠链的片晶向伸直链转化，从而获得超高强高模纤维；在高倍拉伸时，不仅可以使成品纤维中大分子链呈现规整排列的伸展状态，也可以让石墨烯片成定向排列，进一步提高纤维的性能；同时，加入刚性的石墨烯分子，有利于限制PAN分子由于热运动引起的解取向，在碳化过程中，石墨烯能融入到纤维的晶体结构中，诱导生成高取向的类石墨片晶体，并且作为独立的结构连接周围晶体，有利于提高碳纤维的性能。2, using graphene super large specific surface area and excellent mechanical properties, using gel spinning method to prepare high-strength stone Moenol/PAN fiber; gel spinning is the use of polyacrylonitrile with high molecular weight, dissolved into a semi-dilute solution, the entanglement between macromolecular chains is greatly reduced, and quenching after spinning makes this large The unwrapped state between the molecular chains is maintained in the prepared gel precursor, and the crystallinity and orientation degree of the fiber are increased by the ultra-high heat stretching, so that the platelets in the folded chain are transformed into the straight chain, thereby obtaining ultra-high strength. High-mold fiber; in high-stretching, not only can the macromolecular chain in the finished fiber be stretched in a regular arrangement, but also the graphene sheets can be aligned to further improve the fiber properties; at the same time, rigid graphene molecules are added. It is beneficial to limit the disorientation of PAN molecules due to thermal motion. In the carbonization process, graphene can be incorporated into the crystal structure of the fiber to induce the formation of highly oriented graphite-like crystals, and as a separate structure to connect the surrounding crystals, Conducive to improving the performance of carbon fiber.
附图说明DRAWINGS
通过阅读参照以下附图对非限制性实施例所作的详细描述，本发明的其它特征、目的和优点将会变得更明显：Other features, objects, and advantages of the present invention will become apparent from the Detailed Description of Description
图1为聚丙烯腈纤维外观照片；Figure 1 is a photograph of the appearance of polyacrylonitrile fiber;
图2为聚丙烯腈纤维截面的SEM图(扫描电子显微镜照片)。Figure 2 is an SEM image (scanning electron micrograph) of a cross section of a polyacrylonitrile fiber.
具体实施方式detailed description
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。The invention will now be described in detail in connection with specific embodiments. The following examples are intended to further understand the invention, but are not intended to limit the invention in any way. It should be noted that a number of variations and modifications may be made by those skilled in the art without departing from the inventive concept. These are all within the scope of protection of the present invention.
实施例1Example 1
本实施例提供一种高强聚丙烯腈纳米复合纤维的制备方法，所述制备方法包括以下步骤：This embodiment provides a method for preparing a high-strength polyacrylonitrile nanocomposite fiber, and the preparation method comprises the following steps:
将氧化石墨烯加入到含二甲基亚砜(DMSO)∶水＝95∶5的混合溶剂中，超声分散1h后。将分子量为8.8万的聚丙烯腈加入到混合溶剂中，在50℃下搅拌溶解2h。氧化石墨烯的重量百分数为0.3％，聚丙烯腈的重量百分数为30％；The graphene oxide was added to a mixed solvent containing dimethyl sulfoxide (DMSO): water = 95:5, and ultrasonically dispersed for 1 hour. Polyacrylonitrile having a molecular weight of 88,000 was added to the mixed solvent, and dissolved by stirring at 50 ° C for 2 hours. The weight percentage of graphene oxide is 0.3%, and the weight percentage of polyacrylonitrile is 30%;
常压脱泡8小时，脱泡温度30℃，制得纺丝原液温度30℃，通过过滤，经孔径0.10mm的喷丝板进入到-10℃的60/40(V/V)DMSO/水的凝固浴中，形成冻胶态的初生纤维；Atmospheric defoaming for 8 hours, defoaming temperature of 30 ° C, the spinning dope temperature of 30 ° C, through filtration, through a 0.10 mm orifice spinneret into the -10 ° C 60 / 40 (V / V) DMSO / water In the coagulation bath, a nascent fiber in a jelly state is formed;
使冻胶纤维于-20℃甲醇浴中牵伸萃取除去二甲基亚砜；萃取时间为60min，在80℃烘箱中干燥4小时；然后，经120℃热拉伸并定型0.5分钟，拉伸倍数为13倍。The jelly fiber was drawn and extracted in a methanol bath at -20 ° C to remove dimethyl sulfoxide; the extraction time was 60 min, and dried in an oven at 80 ° C for 4 hours; then, it was hot-drawn at 120 ° C and set for 0.5 minutes, and stretched. The multiple is 13 times.
本实施例制得的聚丙烯腈纤维的拉伸强度为7.2cN/dtex，杨氏模量为26cN/dtex，具体见图1、2。图1为本发明制备石墨烯纳米复合纤维宏观照片，纤维表面光滑粗丝均 匀。图2为石墨烯纳米复合纤维横截面扫描电子显微镜照片，从横截面看出纤维内部结构致密紧凑、石墨烯在聚丙烯腈基体里分布均匀，两相界面结合牢固，未出现通常材料复合和凝聚时因发生相分离而导致的皮芯结构的产生。The tensile strength of the polyacrylonitrile fiber obtained in this example was 7.2 cN/dtex, and the Young's modulus was 26 cN/dtex, as shown in detail in Figures 1 and 2. 1 is a macro photograph of a graphene nanocomposite fiber prepared by the present invention, wherein the fiber surface is smooth and thick uniform. Figure 2 is a cross-sectional scanning electron micrograph of graphene nanocomposite fiber. The cross-section shows that the internal structure of the fiber is compact and compact, the graphene is uniformly distributed in the polyacrylonitrile matrix, and the two-phase interface is firmly bonded, and there is no common material recombination and condensation. The generation of the sheath-core structure due to phase separation occurs.
实施例2Example 2
本实施例提供一种高强聚丙烯腈纳米复合纤维的制备方法，所述制备方法包括以下步骤：This embodiment provides a method for preparing a high-strength polyacrylonitrile nanocomposite fiber, and the preparation method comprises the following steps:
将电化学剥离石墨烯加入到含二甲基甲酰胺∶水＝70∶30的混合溶剂中，超声分散2h后。将分子量为5万的聚丙烯腈加入到混合溶剂中，在80℃下搅拌溶解2h；氧化石墨烯的重量百分数为0.05％，聚丙烯腈的重量百分数为15％；The electrochemically stripped graphene was added to a mixed solvent containing dimethylformamide:water = 70:30, and ultrasonically dispersed for 2 hours. Adding polyacrylonitrile having a molecular weight of 50,000 to a mixed solvent, and dissolving and dissolving at 80 ° C for 2 h; the weight percentage of graphene oxide is 0.05%, and the weight percentage of polyacrylonitrile is 15%;
常压脱泡6小时，脱泡温度50℃，制得纺丝原液温度50℃，通过过滤，经孔径0.25mm的喷丝板进入到-40℃的60/40(V/V)二甲基甲酰胺/水的凝固浴中，形成冻胶态的初生纤维；Atmospheric defoaming for 6 hours, defoaming temperature of 50 ° C, the spinning dope temperature of 50 ° C, through filtration, through a 0.25 mm orifice spinneret into the 40 / 40 (V / V) dimethyl at -40 ° C In the coagulation bath of formamide/water, a nascent fiber in a jelly state is formed;
使冻胶纤维于60℃甲醇浴中牵伸萃取除去二甲基亚砜；萃取时间为60min，在100℃烘箱中干燥；然后，经200℃热拉伸并定型5分钟，拉伸倍数为4倍。The jelly fiber was drawn and extracted in a methanol bath at 60 ° C to remove dimethyl sulfoxide; the extraction time was 60 min, and dried in an oven at 100 ° C; then, it was hot-drawn at 200 ° C and set for 5 minutes, and the stretching ratio was 4 Times.
本实施例制得的聚丙烯腈纤维的拉伸强度7.8cN/dtex，杨氏模量28N/dtex。The polyacrylonitrile fiber obtained in this example had a tensile strength of 7.8 cN/dtex and a Young's modulus of 28 N/dtex.
实施例3Example 3
本实施例提供一种高强聚丙烯腈纳米复合纤维的制备方法，所述制备方法包括以下步骤：This embodiment provides a method for preparing a high-strength polyacrylonitrile nanocomposite fiber, and the preparation method comprises the following steps:
将氨基改性氧化石墨烯加入到硫氰酸钠的溶液中，超声分散4h后；将分子量为12万的聚丙烯腈加入到混合溶剂中，在80℃下搅拌溶解2h；改性石墨烯的重量百分数为10％，聚丙烯腈的重量百分数为25％；Adding amino-modified graphene oxide to a solution of sodium thiocyanate, ultrasonically dispersing for 4 hours; adding polyacrylonitrile having a molecular weight of 120,000 to a mixed solvent, stirring and dissolving at 80 ° C for 2 h; modifying graphene The weight percentage is 10%, and the weight percentage of polyacrylonitrile is 25%;
常压脱泡8小时，脱泡温度80℃，制得纺丝原液温度80℃；通过过滤，经孔径0.06mm的喷丝板进入到-5℃的60/40(V/V)蒸馏水凝固浴中，形成冻胶态的初生纤维；Atmospheric defoaming for 8 hours, defoaming temperature of 80 ° C, the spinning dope temperature of 80 ° C; by filtration, through a spinneret with a pore size of 0.06 mm into a 60 / 40 (V / V) distilled water coagulation bath at -5 ° C Forming a nascent fiber in a jelly state;
使冻胶纤维于30℃甲醇浴中牵伸萃取除去溶剂；萃取时间为60min，在120℃烘箱中干燥；然后，经240℃热拉伸并定型15分钟，拉伸倍数为9倍。The jelly fiber was subjected to drawing extraction in a methanol bath at 30 ° C to remove the solvent; the extraction time was 60 min, and it was dried in an oven at 120 ° C; then, it was hot-drawn at 240 ° C and set for 15 minutes, and the stretching ratio was 9 times.
本实施例制得的聚丙烯腈纤维的拉伸强度为7.9cN/dtex，杨氏模量为31cN/dtex。The polyacrylonitrile fiber obtained in this example had a tensile strength of 7.9 cN/dtex and a Young's modulus of 31 cN/dtex.
实施例4Example 4
本实施例提供一种高强聚丙烯腈纳米复合纤维的制备方法，所述制备方法包括以下步骤：This embodiment provides a method for preparing a high-strength polyacrylonitrile nanocomposite fiber, and the preparation method comprises the following steps:
将硅烷偶联剂改性氧化石墨烯加入到浓硝酸中，超声分散6h后；将分子量为15万 的聚丙烯腈加入到浓硝酸中，在40℃下搅拌溶解1h。改性石墨烯的重量百分数为20％，聚丙烯腈的重量百分数为25％；Adding silane coupling agent modified graphene oxide to concentrated nitric acid, ultrasonic dispersion for 6h; molecular weight is 150,000 The polyacrylonitrile was added to concentrated nitric acid and dissolved by stirring at 40 ° C for 1 h. The weight percentage of the modified graphene is 20%, and the weight percentage of the polyacrylonitrile is 25%;
常压脱泡8小时，脱泡温度40℃，制得纺丝原液温度40℃，通过过滤，经孔径0.20mm的喷丝板进入到-40℃的60/40(V/V)乙醇的凝固浴中，形成冻胶态的初生纤维；Atmospheric defoaming for 8 hours, defoaming temperature of 40 ° C, the spinning dope temperature of 40 ° C, through the filtration, through the orifice plate of 0.20 mm into the coagulation of 60 / 40 (V / V) ethanol at -40 ° C In the bath, a jelly-like nascent fiber is formed;
使冻胶纤维于20℃甲醇浴中牵伸萃取除去硝酸；萃取时间为160min，在120℃烘箱中干燥；然后，经130℃热拉伸并定型5分钟，拉伸倍数为30倍。The jelly fiber was subjected to drawing extraction in a methanol bath at 20 ° C to remove nitric acid; the extraction time was 160 min, and it was dried in an oven at 120 ° C; then, it was hot-drawn at 130 ° C and set for 5 minutes, and the stretching ratio was 30 times.
本实施例制得的聚丙烯腈纤维的拉伸强度为8.9cN/dtex，杨氏模量为36cN/dtex。The polyacrylonitrile fiber obtained in this example had a tensile strength of 8.9 cN/dtex and a Young's modulus of 36 cN/dtex.
实施例5Example 5
本实施例提供一种高强聚丙烯腈纳米复合纤维的制备方法，所述制备方法包括以下步骤：This embodiment provides a method for preparing a high-strength polyacrylonitrile nanocomposite fiber, and the preparation method comprises the following steps:
将氧化石墨烯加入到含二甲基亚砜(DMSO)∶水＝95∶5的混合溶剂中，高速搅拌(3000转/分)分散1h后。将平均分子量为7.5万的丙烯腈丙烯酸甲酯的共聚物加入到混合溶剂中，在50℃下搅拌溶解2h。氧化石墨烯的重量百分数为0.5％，聚丙烯腈的重量百分数为20％；The graphene oxide was added to a mixed solvent containing dimethyl sulfoxide (DMSO): water = 95:5, and dispersed at a high speed stirring (3000 rpm) for 1 hour. A copolymer of acrylonitrile methyl acrylate having an average molecular weight of 75,000 was added to the mixed solvent, and stirred and dissolved at 50 ° C for 2 hours. The weight percentage of graphene oxide is 0.5%, and the weight percentage of polyacrylonitrile is 20%;
常压脱泡8小时，脱泡温度30℃，制得纺丝原液温度30℃，通过过滤，经孔径0.10mm的喷丝板进入到5℃的60/40(V/V)DMSO/水的凝固浴中，形成冻胶态的初生纤维；Atmospheric defoaming for 8 hours, defoaming temperature of 30 ° C, the spinning dope temperature of 30 ° C, through the filter, through a 0.10 mm orifice spinneret into the 5 ° C 60 / 40 (V / V) DMSO / water In the coagulation bath, a nascent fiber in a jelly state is formed;
使冻胶纤维于-30℃甲醇浴中牵伸萃取除去二甲基亚砜；萃取时间为160min，在80℃烘箱中干燥4小时；然后，经120℃热拉伸并定型3分钟，拉伸倍数为10倍。The jelly fiber was drawn and extracted in a methanol bath at -30 ° C to remove dimethyl sulfoxide; the extraction time was 160 min, and dried in an oven at 80 ° C for 4 hours; then, it was hot-drawn at 120 ° C and set for 3 minutes, and stretched. The multiple is 10 times.
本实施例制得的聚丙烯腈纤维的拉伸强度为7.5cN/dtex，杨氏模量为28cN/dtex。The polyacrylonitrile fiber obtained in this example had a tensile strength of 7.5 cN/dtex and a Young's modulus of 28 cN/dtex.
在本发明的实施过程中，高速搅拌的速度在3000～10000转/分之间均可实现本发明，聚丙烯腈的共聚物单体为甲基丙烯酸甲酯、醋酸乙烯酯、丙烯磺酸钠、衣康酸、甲基丙烯磺酸钠或甲基丙烯苯磺酸钠均可实现本发明。In the practice of the present invention, the present invention can be realized at a high speed stirring speed of between 3,000 and 10,000 rpm, and the copolymer monomer of the polyacrylonitrile is methyl methacrylate, vinyl acetate, sodium propylene sulfonate. The present invention can be achieved by itaconic acid, sodium methacrylate sulfonate or sodium methacrylate sulfonate.
以上对本发明的具体实施例进行了描述。需要理解的是，本发明并不局限于上述特定实施方式，本领域技术人员可以在权利要求的范围内做出各种变形或修改，这并不影响本发明的实质内容。 The specific embodiments of the present invention have been described above. It is to be understood that the invention is not limited to the specific embodiments described above, and various modifications and changes may be made by those skilled in the art without departing from the scope of the invention.

Claims (10)

  1. 一种高强聚丙烯腈纳米复合纤维的制备方法，其特征在于，所述制备方法包括以下步骤：A method for preparing a high-strength polyacrylonitrile nanocomposite fiber, characterized in that the preparation method comprises the following steps:
    步骤一、向有机溶剂或有机溶剂与水的混合溶液中加入石墨烯，分散均匀，再加入聚丙烯腈，于30～120℃条件下溶解，得纺丝原液；Step 1. Adding graphene to an organic solvent or a mixed solution of an organic solvent and water, dispersing uniformly, adding polyacrylonitrile, and dissolving at 30 to 120 ° C to obtain a spinning dope;
    或将聚丙烯腈与石墨烯直接溶解和分散于浓酸或无机盐的水溶液中，得纺丝原液；Or directly dissolving and dispersing polyacrylonitrile and graphene in an aqueous solution of a concentrated acid or an inorganic salt to obtain a spinning dope;
    步骤二、将所述纺丝原液于20～80℃条件下，过滤、脱泡后，经喷丝板喷出到-40～5℃的凝固浴中，形成初生纤维；Step 2, the spinning dope is filtered at 20 to 80 ° C, defoamed, and then sprayed through a spinneret into a coagulation bath of -40 to 5 ° C to form nascent fibers;
    步骤三、所述初生纤维经萃取、干燥、热拉伸、热定型，得所述高强聚丙烯腈纳米复合纤维。Step 3: The nascent fiber is subjected to extraction, drying, hot stretching, and heat setting to obtain the high-strength polyacrylonitrile nano-composite fiber.
  2. 根据权利要求1所述的高强聚丙烯腈纳米复合纤维的制备方法，其特征在于，步骤一中，所述分散具体指高速搅拌或超声分散；所述高速搅拌或超声分散的时间为1～6h；所述高速搅拌的速度具体为3000～10000转/分。The method for preparing a high-strength polyacrylonitrile nanocomposite fiber according to claim 1, wherein in the first step, the dispersing specifically refers to high-speed stirring or ultrasonic dispersion; and the high-speed stirring or ultrasonic dispersing time is 1 to 6 hours. The speed of the high-speed stirring is specifically 3,000 to 10,000 rpm.
  3. 根据权利要求1所述的高强聚丙烯腈纳米复合纤维的制备方法，其特征在于，步骤一中，所述混合溶液中有机溶剂与水的重量比范围98:2～70:30。The method for preparing a high-strength polyacrylonitrile nanocomposite fiber according to claim 1, wherein in the first step, the weight ratio of the organic solvent to the water in the mixed solution ranges from 98:2 to 70:30.
  4. 根据权利要求1或3所述的高强聚丙烯腈纳米复合纤维的制备方法，其特征在于，步骤一中，所述有机溶剂包括硝酸亚乙基酯、碳酸乙烯酯、二甲基亚砜、二甲基甲酰胺、二甲基乙酰胺的一种。The method for preparing a high-strength polyacrylonitrile nanocomposite fiber according to claim 1 or 3, wherein in the first step, the organic solvent comprises ethylene carbonate, ethylene carbonate, dimethyl sulfoxide, and A type of methylformamide or dimethylacetamide.
  5. 根据权利要求1所述的高强聚丙烯腈纳米复合纤维的制备方法，其特征在于，步骤一中，所述石墨烯包括氧化石墨烯、修饰或改性的石墨烯、电剥离石墨烯的一种；所述聚丙烯腈包括丙烯腈的均聚物或丙烯腈与其他单体的共聚物；所述其他单体包括丙烯酸甲酯。The method for preparing a high-strength polyacrylonitrile nanocomposite fiber according to claim 1, wherein in the first step, the graphene comprises graphene oxide, modified or modified graphene, and electrically stripped graphene. The polyacrylonitrile comprises a homopolymer of acrylonitrile or a copolymer of acrylonitrile with other monomers; the other monomer comprises methyl acrylate.
  6. 根据权利要求1所述的高强聚丙烯腈纳米复合纤维的制备方法，其特征在于，步骤一中，所述纺丝原液中聚丙烯腈的重量百分比为15～30％，所述石墨烯的重量百分比为0.05～20％。The method for preparing a high-strength polyacrylonitrile nanocomposite fiber according to claim 1, wherein in the first step, the weight percentage of the polyacrylonitrile in the spinning dope is 15 to 30%, and the weight of the graphene The percentage is 0.05-20%.
  7. 根据权利要求1所述的高强聚丙烯腈纳米复合纤维的制备方法，其特征在于，步骤二中，所述脱泡方式包括真空脱泡或常压静置脱泡；The method for preparing a high-strength polyacrylonitrile nanocomposite fiber according to claim 1, wherein in the second step, the defoaming method comprises vacuum defoaming or standing degassing at atmospheric pressure;
    所述喷丝板的孔径范围为0.06～0.25mm。The spinneret has a pore size ranging from 0.06 to 0.25 mm.
  8. 根据权利要求1所述的高强聚丙烯腈纳米复合纤维的制备方法，其特征在于，步骤二中，所述凝固浴为有机溶剂与水的混合溶液；所述有机溶剂包括二甲基亚砜或二 甲基甲酰胺。The method for preparing a high-strength polyacrylonitrile nanocomposite fiber according to claim 1, wherein in the second step, the coagulation bath is a mixed solution of an organic solvent and water; and the organic solvent comprises dimethyl sulfoxide or Two Methylformamide.
  9. 根据权利要求1所述的高强聚丙烯腈纳米复合纤维的制备方法，其特征在于，步骤三中，所述萃取中的萃取剂包括甲醇或乙醇；萃取的温度为-20～60℃，时间为2～60min。The method for preparing a high-strength polyacrylonitrile nanocomposite fiber according to claim 1, wherein in the third step, the extracting agent in the extracting comprises methanol or ethanol; and the extraction temperature is -20 to 60 ° C, and the time is 2 to 60 minutes.
  10. 根据权利要求1所述的高强聚丙烯腈纳米复合纤维的制备方法，其特征在于，步骤三中，所述干燥的温度为60～120℃，干燥的时间为2～24h；The method for preparing a high-strength polyacrylonitrile nanocomposite fiber according to claim 1, wherein in the third step, the drying temperature is 60 to 120 ° C, and the drying time is 2 to 24 hours;
    所述热拉伸的温度为120～240℃，热拉伸的倍数为4～40倍；The hot stretching temperature is 120 to 240 ° C, and the thermal stretching is 4 to 40 times;
    所述热定型的时间为0.5～15min。 The heat setting time is 0.5 to 15 min.
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