KR101726822B1

KR101726822B1 - Ultrafine carbon fibers and their preparation method

Info

Publication number: KR101726822B1
Application number: KR1020150073060A
Authority: KR
Inventors: 조성무; 이성호; 조한익; 구본철; 여현욱; 박세준
Original assignee: 한국과학기술연구원
Priority date: 2015-05-26
Filing date: 2015-05-26
Publication date: 2017-04-13
Also published as: KR20160138776A

Abstract

The present invention relates to a production method capable of lowering the production cost of high-performance ultrafine carbon fiber by using the island-shaped composite fiber composed of the ultrafine continuous fiber aggregate of the carbon fiber-forming resin as an ultrafine carbon fiber precursor by using an electron beam, The present invention relates to a microfine carbon fiber produced by the method, and more particularly, to a method for manufacturing a microfine fiber, A marine component removing step of removing marine component from the sea-island type conjugate fiber; A step of preparing an ultrafine carbon fiber precursor to irradiate an electron beam so that cross-linking for improving the heat resistance of the ultrafine continuous fiber aggregate of the carbon fiber-forming resin from which the sea component is removed; Oxidizing and stabilizing the ultrafine carbon fiber precursor by oxidizing and stabilizing the ultrafine carbon fiber precursor; And a carbonization step of carbonizing the oxidized and stabilized ultrafine carbon fiber precursor, and a microfine carbon fiber produced by the method.

Description

[0001] ULTRAFINE CARBON FIBERS AND THEIR PREPARATION METHOD [0002]

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to produce an ultrafine carbon fiber precursor by crosslinking a sea-island composite fiber composed of a composite of ultrafine continuous fiber aggregates of carbon fiber forming ability resin by irradiation of electron beams and to form the precursor canopy fiber by thermal energy or plasma- It is possible to greatly reduce the energy consumption of the ultra-fine carbon fiber by further oxidizing and stabilizing the carbon fiber. Further, the ultrafine carbon fiber of excellent physical properties can be manufactured by further strengthening the effect of increasing the physical properties of the ultrafine carbon fiber by the added nano-carbon.

Carbon fiber is one-fifth the weight of steel, but its strength is more than ten times stronger. Accordingly, carbon fiber is used as a high-strength structural material in various industrial fields such as aerospace, sports, automobiles, and bridges. Carbon fiber has begun to attract attention as a next-generation material due to the rapid development and upgrading of the automobile and aerospace industries, and demand is increasing as the automobile industry aims for environment-friendly, low-energy consumption futuristic automobile. In the field of automobiles, there is a growing demand for lighter automobiles as well as environmental regulations related to automobile exhaust gas, which will be a problem in the future. Therefore, the demand for carbon fiber reinforced composites that can maintain the structural mechanical strength while increasing the weight of automobiles has increased rapidly .

The highest level of tensile strength and elastic modulus of existing carbon fibers is 6 ~ 7 GPa and 300 ~ 320 GPa. Compared to the theoretical carbon fiber tensile strength of 100 to 150 GPa, the increase in tensile strength of carbon fiber is a big problem. In general, defects and structural forms of the fibers are limiting factors in the tensile strength of the carbon fibers. Control of the number and size of such defect structures can greatly improve the performance of the carbon fibers. Since the number and size of the defects greatly depend on the thickness of the precursor fibers, it is possible to greatly improve the performance of the carbon fibers by reducing the number of defects by making the carbon fibers thin. In addition, the carbon fiber is finally impregnated into a resin or the like to be used as a reinforcing agent for the carbon fiber-reinforced composite material. The performance of the composite material has a great influence not only on the physical properties of the carbon fiber itself but also on the adhesiveness according to the interface characteristics with the resin. As the diameter of the fiber decreases, the specific surface area of the fiber increases and the surface reactivity increases. If the carbon fiber is made thinner, the adhesion of the composite material to the resin can be improved and the performance of the composite material is greatly improved Lt; / RTI >

Another way to improve the mechanical properties of carbon fibers is to composite nano-carbons with excellent mechanical properties such as carbon nanotubes (CNTs). The tensile strength and elastic modulus of carbon nanotubes are 23 ~ 63 GPa and 640 ~ 1060 GPa, respectively, which are superior to those of existing carbon fibers. However, since they are not long fibers such as carbon fibers, they are used only as reinforcing agents for fibers. It is possible. Therefore, there is an attempt to produce carbon fibers in which carbon nanotubes having excellent tensile strength and elastic modulus are combined. As a carbon fiber precursor, nano-carbon composite polyacrylonitrile fibers were prepared by various methods such as wet spinning, dry / wet spinning. In order to improve the mechanical properties of polymers including polyacrylonitrile, to improve electrical conductivity, and to impart functionality such as electrostatic fibers, carbon nanotubes (RU 2534779 C1, CN 101619509 A, CN 101250770 A; Fibers having nanocarbons such as carbon nanotubes, carbon nanotubes, carbon nanotubes, carbon nanotubes, carbon nanotubes, carbon nanotubes, carbon nanotubes, carbon nanotubes, Attempts have been made to carbonize polyacrylonitrile fibers to produce carbon fibers with better physical properties.

Introduction of carbon nanotubes (CNTs) and graphenes to polymer fibers can be carried out by polymerizing nano-carbon grains by polymerization in the presence of CNTs in the polymerization of polyacrylonitrile polymers, To prepare a nano-carbon composite polyacrylonitrile fiber, stabilize it, and then carbonize it to produce a carbon fiber having improved physical properties. However, the tensile strength of carbon nanotubes complexed with carbon nanotubes shows a significant improvement in physical properties such as tensile strength at the level of general-purpose carbon fibers. However, the effect of carbon nanotubes in high-performance carbon fibers is still unknown. During high-strength nano-carbon composite polyacrylonitrile precursor fibers, a high-degree stretching process is likely to cause a defect structure such as tearing at the interface between CNT and polyacrylonitrile in the composite polyacrylonitrile fiber. Therefore, attempts have been made to overcome this problem by applying chemical bonds using polyacrylonitrile polymer grafted CNTs. However, interfacial problems between CNTs and polyacrylonitriles still remain to improve the mechanical properties of the produced carbon fibers. It is homework.

If nanocarbon composite polyacrylonitrile fibers such as carbon nanotubes are miniaturized, it is possible to greatly contribute to improvement of physical properties of carbon fibers due to reduction of defect structure and excellent surface characteristics of microfine fibers. However, There is an interfacial problem, and therefore, the problem is solved.

On the other hand, in the production of ultra-fine carbon fibers, blend fibers are prepared by blending a resin forming carbon fibers in a carbonization process with a resin dissolving by thermal decomposition in a carbonization process or a water-soluble polymer capable of being removed by washing with water, Methods for producing microfine carbon fibers have been attempted. In such blend spinning, the size of the component is determined by the compatibility and mixing state between the component and the sea component resin, and the size of the component is irregular, which is difficult to control. In addition, when mixed, the spherical shaped component is a bundle of short fibers having a very short and constant length, which does not become a continuous fiber but is stretched in the direction of the fiber axis in the spinning process. Therefore, there is a problem that it can not be used as a reinforcing material for a long fiber reinforced material, which is widely used as a structural material for aircraft and the like.

On the other hand, ultra-fine carbon fiber manufacturing technology has been developed using a sea-island composite fiber manufacturing technology using a sea-island nozzle, in which the resin of the island component and the resin of the sea component are not mixed beforehand, Using a molten acrylonitrile polymer as a carbon precursor and a pyrolytic polyester as a sea component, a graphite sheet having a diameter of 1 to 10 μm is prepared, superextracted and carbonized to form a continuous phase microfibre (See JP 2006-265788 A). In the case of melt spinning, the presence of pyrolytic decomposition hinders oxidation and stabilization of the carbon fiber-forming fiber as a component, and if it can not be recycled, the cost of the produced ultra-fine carbon fiber is greatly increased.

As described above, the ultrafine continuous-phase carbon fibers have a very high cost structure as compared with conventional micro-sized carbon fibers, and uncertainties remain regarding the properties of ultrafine carbon fibers. Therefore, ultra-fine continuous-phase carbon fibers having excellent mechanical properties of a swinging structure are still required.

Generally, carbon fibers are oxidized by applying heat in an oxidizing atmosphere to infuse precursor fibers. Stabilization process, and a carbonization process in which oxidized and stabilized fibers are carbonized at a high temperature. And subsequently subjected to a graphitization process. At this time, the precursor fibers of the carbon fiber include polyacrylonitrile (PAN), pitch, rayon, lignin, and polyethylene. Of these, polyacrylonitrile (PAN) fibers are the best precursors for producing high-performance carbon fibers as compared to other precursors because they have a high carbon yield of 50% or higher and a high melting point. Accordingly, most current carbon fibers are made from polyacrylonitrile fibers.

The polyacrylonitrile fiber for the carbon fiber precursor is an acrylic resin having a carboxylic functional group such as itaconic acid capable of serving as a catalyst for the stabilization reaction and having about 95% by weight or more of an acrylonitrile (AN) And about 5% by weight or less of a comonomer. Such polyacrylonitrile fibers are capable of producing carbon fibers having high performance.

However, such a polyacrylonitrile fiber for a carbon fiber precursor is very expensive compared to a general fiber. In general, carbon fibers account for 43% of the precursor fibers, 18% of the oxidation and stabilization process, 13% of the carbonization process and 15% of the graphitization process. Therefore, oxidation and stabilization processes as well as cost reduction of precursor fibers can be a core technology of carbon fiber cost reduction technology. Oxidation and stabilization processes are the most energy consuming processes in the carbon fiber manufacturing process because they are very slow reactions compared to the carbonization process.

The oxidation and stabilization process is a process in which oxygen and fiber react with each other to cause a dehydrogenation reaction and a cyclization reaction, thereby stabilizing the molecular structure of the fiber. In the carbon fiber manufacturing process, the oxidation and stabilization process using heat, , There have been various attempts to reduce the stabilization process time.

Therefore, instead of the thermal stabilization process, the oxygen molecules reacting with the fibers are converted into reactive oxygen species (oxygen atom, ozone, NxOy, etc.) by plasma generated using RF, DC, microwave or pulsed power ), And there have been a lot of studies to increase the reaction rate of the oxygen reacting with the fibers to cause a quick reaction.

However, when the number of bundles of fibers used in the general thermal stabilization process or oxidation and stabilization process using plasma is large, it is difficult to penetrate deeply into the inside of the bundle due to heat or oxygen species, so that the stabilization of the inner fiber strands In this case, the strength of the finished carbon fiber is remarkably lowered after the carbonization process, resulting in a deterioration in overall quality.

In recent years, attention has been paid to polymer modification such as polymer crosslinking using an electron beam and introduction of a reactor. Electron beam irradiation causes various polymer structure changes such as polymer crosslinking, polymer chain cleavage, introduction of a reactor, change in crystallinity. When the polyacrylonitrile fiber is irradiated with an electron beam, cross-linking occurs between the polymer chains due to the carbon radicals generated in the polymer chain, and a part of them is added to the side chain nitrile group to generate an imine group. Therefore, it is more efficient and environmentally friendly than the radiation process such as thermal process, gamma ray, and ultraviolet ray. When the polyacrylonitrile fiber is irradiated with an electron beam, the electron beam penetrates a few centimeters in depth to cause cross-linking, so that it can be uniformly crosslinked even in the case of Rajitosu. Therefore, there is an attempt to use electron beams to oxidize and stabilize polyacrylonitrile fibers, but it is known that electron beams only cause crosslinking and do not cause a cyclization reaction of polyacrylonitrile fibers with nitrile groups.

On the other hand, electron beam irradiation is used for modifying polymers and composites by crosslinking polymers or cutting polymer chains. However, irradiation of electron beams to carbon nanotubes and graphenes generates new covalent bonds between carbon nanotubes, (AIP Conference Proceedings (2004), 723, 107), the carbon nanomaterials generate heat when irradiated with a high energy beam, and thus may be used for graphitization reactions using the nanomaterials. When the sheet containing the carbon nanotubes and the crosslinking agent is irradiated with the electron beam, the strength of the carbon nanotube sheet can be improved. This is because the crosslinking agent to be added by the action of the electron beam forms a crosslinked structure between the carbon nanotubes and between the bundles of the carbon nanotubes. That is, carbon-carbon single bonds are efficiently formed between carbon nanotubes and bundles formed by carbon nanotubes by electron beam irradiation, and thus it is known that the carbon nanotubes are intensified in strength.

RU 2534779 C1 CN 101619509 A CN 101250770 A CN 102586951 A CN 102534870A JP 2006-265788 A

Polymer, 48, (2007) 3781, Carbon, 77 (2014) 442. AIP Conference Proceedings (2004), 723, 107.

Accordingly, the present invention minimizes the energy consumption of the oxidizing and stabilizing process when the island component oxidizes and stabilizes the sea-island composite fiber composed of the ultrafine continuous fiber aggregate of the carbon fiber forming ability resin, It is an object of the present invention to provide a high-performance ultrafine continuous-phase carbon fiber according to a method of manufacturing carbon fiber and a method of manufacturing the same.

When the sea-island composite fiber containing nanocarbon is used in the fiber structure of the ultrafine continuous fiber aggregate of the carbon fiber forming ability resin as a component, the defect structure is generated by the stretching process at the interface between the nanocarbon and the carbon fiber- The present invention provides a method capable of solving the problem of generation of a defect structure due to disappearance of a volatile component during a stabilization process and a carbonization process and a problem of degradation of mechanical properties caused by failure to completely remove such a defect structure in a carbon fiber manufacturing process.

In order to accomplish the above object, the present invention provides a method for producing a carbon fiber-reinforced resin composite material, which comprises crosslinking a sea-island composite fiber composed of an ultrafine continuous fiber aggregate of a carbon fiber-forming resin as an ultrafine carbon fiber precursor, Thereby providing the ultrafine carbon fiber to be produced.

The ultrafine continuous fiber aggregate of the carbon fiber forming ability resin contains nanocarbon in the fiber structure, and cross-linking with the nanocarbon can be performed by electron beam irradiation.

The content of the ultrafine continuous fiber aggregate of the carbon fiber forming ability resin as the conductive component may be 10 to 60% by weight, and the ultrafine carbon fiber precursor to be irradiated with the electron beam may be an ultrafine continuous fiber The amount of? T in the aggregate may be 60 to 100% by weight.

The average diameter of the ultrafine continuous fibers of the carbon fiber forming ability resin may be 5 占 퐉 or less and the diameter of the sea-island composite fiber crosslinked by the electron beam irradiation may be 100 占 퐉 or less.

The ultrafine carbon fiber may have a diameter of 50 to 3000 nm, preferably 100 to 1000 nm.

The carbon fiber forming ability resin as a component of the sea-island type composite fiber is selected from the group consisting of polyacrylonitrile (PAN), pitch, rayon, lignin and polyethylene fibers And the carbon fiber precursor fibers may be acrylic fibers for producing carbon fiber precursors having a polyacrylonitrile or an acrylonitrile (AN) monomer content of 95 wt% or more for a fabric.

The nano-carbon may be a carbon nanotube (CNT), a carbon nanofiber (CNF), a graphite nano fiber (GNF), a graphene, a graphene oxide, fullerene, and the nano-carbon may be selected from the group consisting of no functional group, a functional group containing -COOH, -OH, -SO ₃ H, or a heteroatom including nitrogen Or may be grafted with a polymer comprising polyacrylonitrile or polyacrylonitrile copolymer.

The content of the nano-carbon may be 0.1 to 10 wt%, more preferably 0.1 to 1 wt%, based on the weight of the carbon fiber-forming resin.

The method for producing ultrafine carbon fiber according to the present invention comprises the steps of: preparing a sea-island complex fiber comprising an ultrafine continuous fiber aggregate of a carbon fiber-forming resin as a starting material; A marine component removing step of removing marine component from the sea-island type conjugate fiber; A step of preparing an ultrafine carbon fiber precursor to irradiate an electron beam so that cross-linking for improving the heat resistance of the ultrafine continuous fiber aggregate of the carbon fiber-forming resin from which the sea component is removed; Oxidizing and stabilizing the ultrafine carbon fiber precursor by oxidizing and stabilizing the ultrafine carbon fiber precursor; And a carbonization step of carbonizing the oxidized and stabilized ultrafine carbon fiber precursor.

The step of preparing the sea-island type composite fiber may further include a step of containing the nano-carbon in the fiber structure of the ultrafine continuous fiber aggregate of the carbon fiber-forming resin.

The ultrafine carbon fiber precursor may be prepared by irradiating an electron beam having an energy of 50 kGy to 5000 kGy and at a temperature ranging from room temperature to 300 ^° C in air.

In the oxidation and stabilization step, the ultrafine carbon fiber precursor may be thermally coupled with air by using thermal energy in air or under atmospheric pressure or vacuum. In the oxidizing and stabilizing step using the thermally coupled plasma, 350 ^° C for 30 minutes to 250 minutes using a plasma.

The carbonization step may include carbonizing the oxidized and stabilized nanocarbon composite carbon fiber precursor fiber by heat energy or microwave assisted plasma.

The method of producing the ultra-fine carbon fiber according to the present invention may further include a graphitization step by thermal energy or a microwave assisted plasma at a temperature higher than the carbonization temperature after the carbonization step.

In the production of ultrafine continuous-phase carbon fibers from sea-island composite fibers consisting of an ultrafine continuous fiber aggregate of a carbon fiber-forming resin, the conductive component has an appropriate amount of undissolved components, and the component is a sea-island complex composed of an ultrafine continuous fiber aggregate of carbon fiber- When the fibers are irradiated with electron beams, crosslinking occurs and the heat resistance can be increased. Especially, when the nanocarbon is complexed with the metallic component, the reactivity of the nanocarbon is increased by the electron beam energy, so that the chemical reaction at the interface between the nanocarbon and the carbon fiber- Bond and can be used as the ultrafine carbon fiber precursor.

In the present invention, by irradiating the ultrafine continuous fiber aggregate of the carbon fiber forming ability resin with the electron beam and then conducting the oxidation stabilization process by thermal energy or thermally coupled plasma, it is possible to oxidize and stabilize only the electron beam irradiation The problems of the prior art can be overcome.

According to the present invention, after irradiating electron beam onto the sea-island composite fiber of the ultrafine continuous fiber aggregate of the carbon fiber-forming resin in which the island component is composed of the ultrafine continuous fiber aggregate of the carbon fiber forming ability resin and the nano carbon, By using it as an ultrafine carbon fiber precursor, the oxidation and stabilization at a lower temperature and a much shorter time are completed in the oxidation and stabilization reaction step by thermal energy or plasma-coupled thermal energy, so that the energy consumption can be greatly reduced, There is an advantage that continuous-phase carbon fibers can be produced.

FIG. 1 shows a process for producing an ultrafine continuous-phase carbon fiber using a sea-island composite fiber composed of an ultrafine continuous fiber aggregate of a carbon fiber-forming resin according to an embodiment of the present invention.
FIG. 2 is a schematic view of a sea-island spinning nozzle for producing sea-island composite fibers according to an embodiment of the present invention and a process for manufacturing sea-island composite fibers as a precursor for producing ultrafine continuous-phase carbon fibers produced therefrom.

Hereinafter, the present invention will be described in detail.

The present invention relates to a method for producing a sea-island composite fiber, comprising the steps of: preparing a sea-island complex fiber comprising an aggregate of ultrafine continuous fibers of a carbon fiber forming resin; A marine component removing step of removing marine component from the sea-island type conjugate fiber; A step of preparing an ultrafine carbon fiber precursor to irradiate an electron beam so that cross-linking for improving the heat resistance of the ultrafine continuous fiber aggregate of the carbon fiber-forming resin from which the sea component is removed; Oxidizing and stabilizing the ultrafine carbon fiber precursor using thermal energy in air or using a heat-coupled plasma under atmospheric pressure or vacuum; A carbonization step of carbonizing the oxidized and stabilized nano-carbon composite carbon fiber precursor fibers by thermal energy or microwave assisted plasma; And a graphitization step by thermal energy or a microwave assisted plasma at a temperature higher than the carbonization temperature after the carbonization step, and a microfine carbon fiber produced by such a manufacturing method ,

FIG. 1 is a process diagram for producing an ultrafine continuous-phase carbon fiber using a sea-island composite fiber composed of an ultrafine continuous fiber aggregate of a carbon fiber-forming resin according to an embodiment of the present invention. The process will be described as follows.

1) A sea-island complex fiber for ultrafine carbon fiber precursor Manufacturing stage

In the present invention, the sea-island composite fiber bridged by the electron beam irradiation has an ultrafine continuous fiber aggregate content of 60 to 98% by weight, preferably 90 to 98% by weight, of the carbon fiber- And the like.

That is, in the present invention, as shown in Fig. 2, the sea-island fiber to be crosslinked by electron beam irradiation is a carbon fiber-forming resin, which is a conductive component produced by composite spinning of a cast resin and a sea component resin using a sea- The sea component is removed from the sea-island composite fiber having the ultrafine continuous fibrous aggregate content of 10 to 60% by weight to make the component having 90% by weight or more and 98% by weight or less of the conductive component by crosslinking.

When a sea-island type composite fiber having 10 to 60% by weight of a manufactured island-shaped composite spinning nozzle is directly irradiated with an electron beam, a large amount of a harmful component is also cross-linked or a polymer chain is cut off, Which adversely affects the physical properties of the ultrafine carbon fiber and can not be reused. Therefore, the cost may increase.

If the marine component remains too much, the stabilization reaction temperature must be elevated in the oxidation and stabilization process, and the ultrafine continuous fiber aggregate of the carbon fiber forming ability resin as the component can be melt-cut. In addition, the gas permeability may be lowered in the oxidation / stabilization step, and the oxidation / stabilization reaction may not proceed sufficiently.

Meanwhile, as in the present invention, cross-linking using an electron beam can reduce the stabilization temperature and thus reduce energy. If the residual amount of the harmful component is large, there arises a problem of canceling the electron beam crosslinking effect. Therefore, the conjugated fiber used as the ultrafine carbon fiber precursor after crosslinking of the electron beam should have a few harmful components.

However, if the residual amount of the sea component is too low or there is no residual matter, only the ultrafine continuous fiber aggregate of the carbon fiber forming ability resin as the component remains, and in the course of carrying out the carbonization process through the electron beam irradiation process, oxidation and stabilization process, The microfibers are cut and handling becomes very difficult. Therefore, the above problem can be solved if an adequate amount of the sea component remains. A composite fiber for an ultrafine carbon fiber precursor in which an adequate amount of a marine component remains and an electron beam crosslinked composite fiber in which a carbon fiber forming ability resin is a component is entangled, , The bundling of the ultrafine continuous fiber aggregate increases during the oxidizing / stabilizing process and the carbonization process, and the problem that the ultrafine fibers are cut by the tension in the process can be overcome.

In the present invention, since the diameter of the ultrafine carbon fibers obtained by finally carbonizing the precursor fibers is reduced to about half, the mean diameter of the ultrafine continuous fibers of the carbon fiber forming ability resin as the above-mentioned conductive component is 5 占 퐉 or less. Preferably 1 mu m or less, and the sea-island composite fiber cross-linked by electron beam irradiation has a diameter of 100 mu m or less.

In the present invention, the precursor fiber used in the oxidation / stabilization reaction is a composite fiber for an ultrafine carbon fiber precursor in which the sea component remains at a maximum of 15 wt% or less and the composite fiber as a component of the carbon fiber forming ability resin is subjected to electron beam crosslinking. Since the microfine continuous fibrous aggregate has a very small fiber diameter as compared with the general microfibers, the oxidation stabilization reaction can be completed more uniformly and quickly, and the calorific value is also rapidly diffused, so that the problem of ignition due to excessive calorific value can be further suppressed, The stabilization temperature and the calorific value can be significantly reduced by electron beam crosslinking. Therefore, the diameter of the sea-island composite fiber bridged by the electron beam irradiation used in the present invention can be successfully completed in a shorter time even if the diameter of the sea-island composite fiber is larger than that of the conventional carbon fiber precursor fiber, It is preferable to use a conjugated fiber.

According to the present invention, the carbon fiber-forming resin as a component of the sea-island composite fiber, which is the ultrafine carbon fiber precursor, is selected from the group consisting of polyacrylonitrile resins, coal- and petroleum-based pitches including isotropic pitches and anisotropic pitches, And bio-pitch produced from biomass such as cellulose and cellulose derivatives such as cellulose acetate, phenol resin, polyimide and polyamide resin, polyfurfuryl alcohol, etc. And a carbon fiber-forming polymeric resin including the carbon fiber-forming polymeric resin.

According to the present invention, in producing the ultrafine continuous carbon fiber, the polyacrylonitrile polymer used as the ultrafine carbon fiber forming ability component is a poly (acrylonitrile) polymer used for a fabric (for clothing) having an acrylonitrile monomer content of less than 95 wt% Acrylonitrile or acrylonitrile monomer may be used in an amount of 95% by weight or more. However, in order to lower the production cost, the acrylonitrile monomer is used for a fabric (for clothing, etc.) having less than 95% by weight of acrylonitrile monomer It may be desirable to use polyacrylonitrile.

According to the present invention, the polymer resin used as the sea component of the conjugated fiber is selected from the group consisting of polyvinyl alcohols such as polyvinyl alcohol (PVA), polyvinylacetate (PVAc) and the like, polyvinyl esters and polyacrylic acid , PAA), polymethacrylic acid and water-soluble or soluble polymers such as polyacrylic acid esters, polyethylene oxide (PEO), and polypropylene oxide, polyether types such as polyalkylene glycols And the like, and polyolefin types such as polyethylene and polypropylene. In addition, an emulsion such as an amino-modified silicone, an epoxy-modified silicone, an alkylene oxide-modified silicone, a polyalkylene glycol and a mixture thereof, which can inhibit fusion between fibers in the oxidation and stabilization process and carbonization process, It might

In addition, in the present invention, the sea-island composite fiber in which the ultrafine continuous fiber aggregate of the carbon fiber forming ability resin complexed with nano carbon is formed as a component, the nano carbon includes single wall carbon nanotube (SWCNT) Carbon nanotubes (CNT), carbon nanofibers (CNF), graphitic carbon nanofibers (GNF), graphene, oxide graphene oxide, fullerene, and the like, including multiwall carbon nanotubes (MWCNT) And the like. The carbon nanotubes may be one-dimensional and two-dimensional carbon-based nanocarbons.

The nano-carbon is either attached to the surface or the edges or the functional group is a functional group-functional features, such as -COOH, -OH, -SO ₃ H, or doped with a hetero-element such as nitrogen, polyacrylonitrile, polyacrylonitrile Or a nano-carbon in which a polymer including a copolymer is grafted.

The content of nano-carbon in the sea-island composite fiber in which the ultrafine continuous fiber aggregate of the carbon fiber-forming resin complexed with nano-carbon is formed as a component is 0.1 to 70% by weight based on the weight of the carbon fiber- If the nanocarbon is dispersed very uniformly throughout the fiber, the higher the nanocarbon content, the better. As the content of nano - carbon is higher, carbon fiber is expected to have better mechanical properties due to an increase in reactor formation by electron beam irradiation and an increase in chemical bonding of polymerization. However, the higher the content of nano-carbon, the greater the dispersibility is. Therefore, the content of nano-carbon is preferably 0.1 to 10% by weight, more preferably 0.1 to 1% by weight.

The electron beam crosslinking according to the present invention is characterized in that the ultrafine continuous fibrous aggregate of the carbon fiber forming ability resin is irradiated with an electron beam energy of 50 kGy to 5000 kGy on the sea-island composite fiber constituting the conductive component to crosslink the sea-island composite fiber. The penetration depth of the electron beam differs depending on the material, but in the case of the fiber sample, the penetration penetrates up to a few centimeters deep and crosslinking occurs. Therefore, even the 100 kg of Rajitow of the sea-island composite fiber for the ultrafine carbon fiber precursor in the present invention is sufficiently crosslinked so that a large exothermic reaction is suppressed in a subsequent oxidation and stabilization process, so that oxidation and stabilization can be stably performed Carbon fibers are formed successfully when carbonized. This shows that the electron beam crosslinking reaction can make a great contribution to the production of Rajitot carbon fibers.

In the case of polyacrylonitrile fiber, the cyclization reaction of -CN group did not proceed by electron beam irradiation, and crosslinking only proceeded. The DSC curve of the electron beam irradiated sample shows that the exothermic peak for the cyclization of polyacrylonitrile by electron beam crosslinking is significantly lowered. This indicates that the oxidation / stabilization reaction can proceed at a lower temperature.

In accordance with an embodiment of the present invention, the production of a sea-island composite fiber in which an ultrafine continuous fiber aggregate of a polyacrylonitrile copolymer that is a carbon fiber precursor as a component constitutes a component, will be described in detail.

The polyacrylonitrile copolymer solution dissolved in dimethyl sulfoxide (DMSO) is injected into the isotrope inlet 1 shown in Fig. The weight average molecular weight of the polyacrylonitrile copolymer is not limited in the present invention. However, as the molecular weight is increased, the mechanical properties of the fiber can be improved, but since the viscosity of the spinning solution is increased, the polymer concentration must be lowered. It is usually about 200,000 to 400,000.

In order to obtain the nano-carbon composite conductive component, the carbon nanotubes are dispersed in N, N-dimethylformamide (DMF) or dimethyl sulfoxide (DMSO), polyacrylonitrile powder is added at room temperature or lower, After swelling, the polyacrylonitrile was completely dissolved by heating at a temperature of about 80 ^° C., and the solution was filtered and deaerated to prepare a flushing solution, which was then injected into the flushing inlet of FIG.

A marine solution prepared by dissolving polyvinyl alcohol having a degree of saponification of 99.5 mol% or more and a viscosity average degree of polymerization of 1,500 as a sea component in dimethyl sulfoxide (DMSO) is injected into the sea water inlet 4 of FIG. The discharged sea-island composite fibers (5) regulate the discharge amount of the conductive component and the sea component so that the conductive component is 10 to 60% by weight. When the discharge amount of the conductive material is increased, the ultrafine continuous fiber aggregate, which is a component of the sea-island composite fibers, adheres to each other, and when the discharge amount of the conductive material is decreased, the ultrafine continuous fiber aggregate can not obtain continuous fibers. Therefore, the preferable amount of the conductive component is about 20 to 40% by weight, more preferably 20 to 30% by weight.

The above-mentioned sea-island composite fibers can be spin-wet, dry-wet-laid, melt-laid, or the like in accordance with a conventional method. In the case of the polyacrylonitrile microfine fiber, however, dry-wet spinning can obtain better physical properties.

The organic solvent to be used as the coagulating solution is not particularly limited as long as it is a solvent for coagulating the spinning solution. Usually, alcohols such as methanol and ethanol, and ketones such as acetone and methyl ethyl ketone can be used. These organic solvents may be used alone or in admixture of two or more. Methanol is preferable in consideration of coagulation power and the like, and it is preferable to set the coagulating solution temperature to 10 占 폚 or less, particularly 2 to 8 占 폚.

2) Oxidation and stabilization step

Oxidation and stabilization processes in producing carbon fibers using the sea-island composite fibers are very important processes. This is because the molecular structure in the fiber must be changed so as to have a salt resistance before the carbonization reaction in order to prevent the fiber as the polymer material from melting at the high temperature of the carbonization or graphitization step and to induce intermolecular bonding. In particular, in the case of a polyacrylonitrile polymer, the oxidation / stabilization reaction can be largely divided into a cyclization reaction, a dehydrogenation reaction and an oxidation reaction. The cyclization reaction is caused by a radical reaction in the fiber molecule due to external energy, and the dehydrogenation reaction and the oxidation reaction cause the hydrogen atoms to fall off into molecules in the oxidizing atmosphere or induce the intermolecular bonding due to the oxygen bonding. At this time, the crucial role is to transfer the oxygen atoms that react to the inside of the fiber evenly, so that a stable ladder structure of the whole fiber is formed and excellent salt resistance is obtained.

This oxidation and stabilization step is a step of making the steel so as to have salt resistance upon carbonization or graphitization, and it is preferable to proceed as follows.

The present invention relates to an ultrafine carbon fiber precursor which is obtained by crosslinking a sea-island composite fiber composed of an ultrafine continuous fiber aggregate of a carbon fiber-forming resin as an ultrafine carbon fiber precursor, Is 60 wt% or more, preferably 90 wt% or more. The oxidation and stabilization process is performed in an atmosphere of air through a heat treatment in an electric furnace capable of temperature control. Oxidation and stabilization by thermal energy is carried out in an oxidizing gas or air at 180 to 350 ^° C under tension. However, compared with the case where the precursor fiber which is not crosslinked by electron beam is oxidized and stabilized, the oxidation / stabilization time is 1 / Since it is greatly reduced to about 3 to 1/4, energy consumption is greatly reduced.

In the oxidizing and stabilizing step, it is preferable that the ultrafine carbon fiber precursor which is sea-island hybrid fiber crosslinked by the above-mentioned electron beam is subjected to heat-induced bonding under atmospheric pressure or vacuum using plasma. That is, it is preferable that plasma is generated and oxidized and stabilized while mixing and injecting, for example, argon gas as a plasma generating gas into the reaction chamber and oxygen gas as a reactive gas. As described above, when oxidation and stabilization are carried out by using plasma, active oxygen species having a high energy density and a high reactivity are produced. As a result, the oxidation and stabilization of the fibers are uniform and occur rapidly in a short time, and have better physical properties than the thermal energy treatment method. Specifically, during the generation of plasma, oxygen species such as oxygen monomers, superoxide (O ₂ -), hydrogen peroxide (H ₂ O ₂ ) and hydroxyl radical (OH) A stable oxidation / stabilization reaction takes place, and the oxidation / stabilization reaction time can be shortened.

Oxidation and stabilization reactions due to plasma-bonded heat energy can significantly reduce oxidation and stabilization reaction time and temperature compared to heat energy alone, but there is a problem in that uniform oxidation and stabilization reaction of the fiber samples can not be obtained when used alone. However, when the sea-island composite fiber crosslinked by the electron beam irradiation is used, the oxidation / stabilization reaction can be completed in a batch and excellent physical properties can be obtained.

However, the oxidizing and stabilizing step of the plasma treatment according to the present invention is characterized by oxidation and stabilization using plasma in a temperature range of 180 to 350 ^° C. in an oxidizing atmosphere in which oxygen exists, and is usually 30 minutes to 250 minutes .

According to the present invention, the oxidation-stabilization reaction by the plasma-coupled thermal energy generates plasma in the plasma generating unit to supply plasma to the sea-island composite fiber tow for the ultra-fine carbon fiber precursor, and heat is supplied to the fiber by the heat- Type composite fiber is oxidized and stabilized at the same time by using plasma.

Wherein the plasma generator comprises: a power supply for supplying high frequency power; An electrode receiving the high frequency power from the power supply unit; And a ground electrode that is grounded or supplied with a separate high frequency power, and the plasma may be generated between the electrode and the ground electrode. At this time, the power supply unit may be any one selected from the group consisting of DC, RF power, and positive power. At this time, the power applied to the plasma can be controlled by electric power supplied to the electrode or the ground electrode.

The heat source is supplied by a heating device, the supply of heat energy is controlled by electric power applied to the heating device, and the ratio of the electric power applied to the heating device and the electric power applied to the plasma can be adjusted. The heat supply unit may be an air inlet for supplying heated air to the sea-island composite fibers. The heat source is supplied from the heated air supplied through the air inlet, and the supply of heat energy is controlled by the flow rate and the temperature of the heated air supplied through the air inlet, and the flow rate and temperature of the heated air, The stabilization can be controlled by controlling the ratio of the power applied to the plasma. At this time, the heated air may contain oxygen or an oxygen compound.

3) Carbonization step

Next, after the electron beam is crosslinked, the carbonization process is carried out at a high temperature by thermal energy in order to convert the sea-island composite fiber for ultrafine carbon fiber precursor oxidized and stabilized by plasma-bonded thermal energy into carbon fiber. At this time, the carbonization process proceeds in an inert atmosphere such as nitrogen through a high temperature carbonization furnace or the like. When an inert atmosphere such as nitrogen is maintained, an unnecessary chemical reaction will act as a large defect in carbonization when another reactive gas is introduced. In addition, nitrogen atmosphere such as nitrogen is kept to separate the nitrogen element in the nitrile group. The carbonization reaction is preferably carried out under a nitrogen atmosphere at a temperature of, for example, 1,000 to 1,500 ^° C.

Also, in the carbonization process, a carbonization reaction can be performed by a microwave assisted plasma (MAP) instead of thermal energy. As described above, when the carbonization reaction proceeds using the microwave-induced plasma (MAP), it is possible to produce carbon fibers having the same level of physical properties as those of the method using thermal energy, There is an advantage that it can be reduced.

Meanwhile, the method for producing carbon fibers according to the present invention may further include a graphitization step of graphitizing the carbon fibers in addition to the above steps. At this time, the graphitization step proceeds after the carbonization step. That is, the ultrafine continuous-phase carbon fibers carbonized through the carbonization process proceeds at a temperature higher than the carbonization temperature. This graphitization step can proceed by thermal energy. For example, in a carbonization furnace or the like, the carbonized fiber can be graphitized by heat treatment at a high temperature region of 2,000 to 3,000 ^° C.

In the graphitization step, a graphitization reaction can be induced by a microwave-induced plasma so as to reduce energy consumption as in a carbonation reaction.

As described above, according to the present invention, when the plasma-bonded thermal energy is used in the oxidation and stabilization step after the electron beam crosslinking of the sea-island composite fiber for ultrafine continuous carbon fiber precursor, it is possible to obtain a high- Of ultrafine continuous-phase carbon fibers can be easily produced.

The average fiber diameter of the ultrafine carbon fibers of the present invention produced by this method is 50 nm to 3000 nm, preferably 100 nm to 1000 nm.

Example 1

(PAN) for carbon fiber precursors having an Mv of 280,000 was dissolved in dimethylsulfoxide (DMSO), and a 15% by weight solution of polyvinyl alcohol having a polymerization degree of 1700 and a degree of saponification of 99.8 mol% A 21 wt% solution in which alcohol (PVA) was dissolved in dimethyl sulfoxide was used as the sea component. Using a sea-island spinning nozzle having a spinneret diameter of 0.25 μm shown in FIG. 2, dry and wet spinning were carried out at 80 ^° C so that the weight ratio of PVA / PAN of the sea-island composite fiber was 70/30. The spinning speed was 12 m / min and spun into a coagulating liquid of DMSO / methanol (weight ratio 45/55) at 5 ° C and wound at 36 m / min. After removing the residual DMSO by washing with water, it was dried and heated 15 times at 170 ^° C.

The composite fiber using a high-pressure reactor to remove the PVA is washed with water at 120 ^o C. The cross-section of this composite fiber was observed, but the PVA was almost removed, but the PAN ultra-fine continuous fiber aggregate with an average fiber diameter of 0.2 μm was observed, and the PAN microfine fiber aggregate was partially adhered by the PVA partially removed .

The marine unremoved composite fiber and the marine composite fiber were crosslinked by electron beam irradiation at a beam current of 1 mA and an acceleration voltage of 1.14 MeV at 1500 kGy. The electron beam fiber specimens were oxidized and stabilized in an air atmosphere at 230 ^° C for 30 minutes in a temperature-controlled electric furnace. After electron beam crosslinking, the oxidized / stabilized composite fibers were carbonized to investigate the electron beam crosslinking effect. Carbonization was carried out at a temperature of 1300 ^° C and a heating rate of 5 ^° C / min. At this time, the nitrogen gas was continuously injected into the chamber during the progress of the carbonization reaction to prevent other reactions (oxidation reaction) from occurring.

In the case of the fiber which is not crosslinked by electron beam, when the heat treatment is carried out at 230 ^° C for 60 minutes, the ultrafine carbon fiber is not formed in the continuous phase as a result of incomplete oxidation and stabilization after the carbonization, . When the heat treatment was performed for 120 minutes, the oxidation and stabilization reaction was completed, but ultrafine continuous phase carbon fibers were formed. In the case of electron beam cross-linking, ultra-fine continuous-phase carbon fibers were formed because the oxidation and stabilization reaction was sufficiently completed even after heat treatment at 230 ^° C for 30 minutes

On the other hand, when the seawater is not removed and subjected to oxidation and stabilization after electron beam irradiation, a large amount of residual carbon components of the marine components after the carbonization reaction can not be formed, and ultrafine continuous carbon fibers of high purity can not be formed. However, , It showed excellent properties without cutting the ultrafine carbon fiber even in the stabilization process and the carbonization process.

Example 2

A sea - island composite fiber, which is a carbon nanotube composite polyacrylonitrile ultrafine continuous fibrous aggregate, was prepared as an isotropic component. The same polyacrylonitrile and polyvinyl alcohol as those in Example 1 were used as the polymer of the lead component and the sea component. First, PAN was dissolved in dimethyl sulfoxide (DMSO) at 15 wt%. SWCNTs were dispersed in DMSO at a concentration of 4 mg / 100 mL for 24 hours by ultrasonication. The PAN solution was added to the SWCNT dispersion solution dispersed by ultrasonic waves and dissolved, and excess DMSO was removed by distillation under reduced pressure. The SWCNT dispersion was added to the PAN so that the amount of added SWCNT was 1 wt%, and excess DMSO was removed to finally prepare PAN / SWCNT complex spinning solution having a solid content (PAN + SWCNT) of 15.5 wt% Min. A solution of 21 wt% of PMMA dissolved in DMSO was used as the sea component. A sea-island type spinning nozzle having a spinning nozzle diameter of 250 m shown in Fig. 2 was used to produce a sea-island conjugate fiber. Wet spinning at a spinning temperature of 100 ^° C in a coagulating liquid at 5 ° C in DMSO / methanol (weight ratio 45/55) at a spinning rate of 40 m / min and winding at 120 m / min. After removing the residual DMSO by washing with water, the product was stretched 1.42 times in air, then stretched 7.6 times in a glycerol bath at 170 ^° C, and stretched 32.4 times in total.

The composite fiber using a high-pressure reactor to remove the PVA is washed with water at 120 ^o C. The cross-section of the composite fiber was observed, but the ultrafine continuous fiber aggregate of PAN having an average fiber diameter of 0.12 μm, in which the PVA was almost removed, was observed, and the PAN microfine fibrous aggregate Were partially adhered to each other.

In the case of electron beam cross-linking, the oxidation and stabilization reaction was sufficiently completed even after heat treatment at 230 ^° C for 30 minutes, so that a carbon fiber composite ultrafine continuous carbon fiber was formed

On the other hand, when the seawater is not removed and subjected to oxidation and stabilization after electron beam irradiation, a large amount of residual carbon components of the marine components after the carbonization reaction can not be formed, and ultrafine continuous carbon fibers of high purity can not be formed. However, Carbon nanotube composite ultrafine carbon fibers were formed in the electron beam crosslinked arc stabilization process and carbonization process.

Example 3

(PVdF, Kynar 761) was prepared by using a 15 wt% spinning solution prepared by dissolving polyacrylonitrile (PAN) for a carbon fiber precursor of Mv 280,000 in dimethylformamide (DMF) 14% by weight in DMF was used as a sea component. Using a sea-island spinning nozzle having a spinning nozzle diameter of 0.25 탆 shown in Fig. 2, the sea-island composite fibers were dry-wet-laid at room temperature so that the weight ratio of PVdF / PAN was 50/50. The spinning speed was 10 m / min, spun into a 30% DMSO aqueous solution at room temperature, and wound at 50 m / min. After removing the residual DMSO by washing with water, it was dried and heated 12 times at 170 ^° C.

PVdF was removed by immersing the composite fiber in acetone at 60 < ⁰ > C. The cross-section of the composite fiber was observed. The PVdF was almost removed, and PAN ultra-fine continuous fiber aggregate with an average fiber diameter of 0.15 μm was observed, and the PAN microfine fiber aggregate was partially adhered by PVdF partially removed .

The marine unremoved composite fiber and the marine composite fiber were crosslinked by electron beam irradiation at a beam current of 1 mA and an acceleration voltage of 1.14 MeV at 1500 kGy. Instead of heat treating the electron beam fiber samples in an oxidizing atmosphere, a temperature controllable chamber is formed in a plasma module using a RF generator as a power source to keep the temperature in the chamber constant. An argon gas and a reactive gas And oxygen plasma was generated and the oxidation and stabilization reaction was promoted at 230 ^° C for 30 minutes, respectively. Carbonization proceeded at a temperature of 1300 ^° C and a temperature of 5 ^° C per minute.

In the case of electron beam cross-linking, the oxidation and stabilization reaction was sufficiently completed even after heat treatment for 30 minutes by thermal bonding plasma at 230 ^° C, so that ultrafine continuous-phase carbon fibers showed excellent properties without cutting.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the subject matter encompassed by way of the present invention is not limited to those precise embodiments, . The embodiments described above are therefore to be considered in all respects as illustrative and not restrictive.

a: Sea-island composite fiber
b: crosslinking by electron beam irradiation
c: Oxidation and stabilization by air thermal energy or thermal energy coupled plasma treatment
d: thermal carbonization furnace
e: Carbonization and graphitization by microwave-induced plasma
f: carbon fiber
1:
2: Distribution board
3: Discharging nozzle hole
4: Seawater inlet
5: Sea-island composite fiber

Claims

The present invention relates to a method for producing a carbon fiber-forming resin, which comprises mixing 0.1 to 10% by weight of carbon nanotube (CNT), carbon nanofiber (CNF), graphite nano fiber (GNF) The present invention relates to a method for preparing a sea-island composite fiber comprising a carbon fiber-forming resin ultrafine continuous fiber aggregate containing nanocarbons selected from the group consisting of graphene, graphene oxide, and fullerene, Characterized in that it is produced through an oxidation / stabilization step and a carbonization step by using it as an ultrafine carbon fiber precursor.

The method according to claim 1,
Wherein the ultrafine continuous fiber aggregate of the carbon fiber forming ability resin contains nanocarbon in the fiber structure and can be crosslinked with the nanocarbon by electron beam irradiation.

The method according to claim 1,
Wherein the content of the ultrafine continuous fiber aggregate of the carbon fiber-forming resin as the conductive component is 10 to 60% by weight.

The method according to claim 1,
Wherein the microfine carbon fiber precursor has a? T content of 60 to 100 wt% in the ultrafine continuous fiber aggregate of the carbon fiber forming ability resin as a conductive component.

The method according to claim 1,
Wherein the mean diameter of the ultrafine continuous fibers of the carbon fiber forming ability resin as the conductive component is 5 占 퐉 or less and the diameter of the sea type composite fiber crosslinked by the electron beam irradiation is 100 占 퐉 or less.

The method according to claim 1,
Wherein the ultrafine carbon fiber has a diameter of 50 to 3000 nm.

The method according to claim 1,
The carbon fiber forming ability resin as a component of the sea-island type composite fiber is selected from the group consisting of polyacrylonitrile (PAN), pitch, rayon, lignin and polyethylene fibers Wherein the carbon fiber is a carbon fiber.

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The method of claim 2,
The nano-carbon has no functional group, or contains a functional group containing -COOH, -OH, -SO ₃ H, a hetero-element containing nitrogen, or a polyacrylonitrile or polyacrylonitrile copolymer Wherein the polymer is grafted.

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Carbon nanotube, carbon nano fiber, graphite nano fiber (GNF), graphene, graphene oxide, fullerene, (Fullerene) is contained in the fiber structure of the ultrafine continuous fiber aggregate of the carbon fiber forming ability resin;
A step of preparing a sea-island complex fiber comprising an ultrafine continuous fiber aggregate of a carbon fiber-forming resin containing a nano-carbon as a starting material;
A marine component removing step of removing marine component from the sea-island type conjugate fiber;
A step of preparing an ultrafine carbon fiber precursor to irradiate an electron beam so that cross-linking for improving the heat resistance of the ultrafine continuous fiber aggregate of the carbon fiber-forming resin from which the sea component is removed;
Oxidizing and stabilizing the ultrafine carbon fiber precursor by oxidizing and stabilizing the ultrafine carbon fiber precursor; And
And a carbonization step of carbonizing the ultrafine carbon fiber precursor oxidized and stabilized.

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The method of claim 11,
Wherein the ultrafine carbon fiber precursor is irradiated with an electron beam having an energy of 50 kGy to 5000 kGy.

The method of claim 11,
Wherein the oxidation and stabilization step comprises using a superfine carbon fiber precursor with heat energy in the air, or using a heat-coupled plasma under atmospheric pressure or vacuum.

15. The method of claim 14,
Wherein the oxidation and stabilization step using the thermally coupled plasma is performed using plasma in a temperature range of 180 to 350 ^° C. for 30 minutes to 250 minutes in an oxidizing atmosphere in which oxygen is present.

The method of claim 11,
Wherein the carbonization step comprises carbonizing the oxidized and stabilized nano-carbon composite carbon fiber precursor fiber by heat energy or microwave assisted plasma (Microwave Assisted Plasma).

The method according to any one of claims 11 to 16,
Wherein the carbonization step further comprises a graphitization step by thermal energy or a microwave assisted plasma at a temperature higher than the carbonization temperature after the carbonization step.