WO2014204282A1 - 탄소섬유용 폴리아크릴로니트릴계 전구체 섬유 및 그 제조방법 - Google Patents
탄소섬유용 폴리아크릴로니트릴계 전구체 섬유 및 그 제조방법 Download PDFInfo
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- WO2014204282A1 WO2014204282A1 PCT/KR2014/005523 KR2014005523W WO2014204282A1 WO 2014204282 A1 WO2014204282 A1 WO 2014204282A1 KR 2014005523 W KR2014005523 W KR 2014005523W WO 2014204282 A1 WO2014204282 A1 WO 2014204282A1
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- polyacrylonitrile
- fiber
- precursor fiber
- carbon material
- conductive carbon
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/18—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D10B2321/10—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/16—Physical properties antistatic; conductive
Definitions
- the present invention relates to a polyacrylonitrile-based precursor fiber for carbon fiber and a method of manufacturing the same.
- carbon fiber is thermally stabilized acrylonitrile oxide fiber (Oxi-PAN fiber) by cyclization of the molecular structure through a flame-resistant process to heat the polyacrylonitrile-based precursor fiber at a temperature of about 200 ⁇ 300 Finally, it is manufactured by finally forming a hexagonal structure of carbon only through a carbonization process of heat treatment at a high temperature of about 800 or more.
- Oxi-PAN fiber thermally stabilized acrylonitrile oxide fiber
- the polyacrylonitrile-based (PAN) precursor for carbon fiber is a flameproofing process is performed by a heat treatment step of 3 to 4 steps .
- the individual polyacrylonitrile-based (PAN) precursor fibers are thermally stabilized from the surface toward the inner surface due to the heat treatment effect.
- the surface layer portion is thermally stabilized and flameproofed by oxygen contact and diffusion.
- the thermal stabilization and flame resistance region in contact with oxygen, and the inside of the precursor fiber is divided into a thermal stabilization section in which oxygen does not penetrate only in the flame resistance process and merely thermal stabilization.
- the present invention is to provide a polyacrylonitrile-based precursor fiber for carbon fiber and a method for manufacturing the same that can shorten the flame-resistant heat treatment time in the production of carbon fiber.
- the present invention provides a polyacrylonitrile-based precursor fiber for carbon fiber including a conductive carbon material as a first embodiment.
- the conductive carbon material according to the embodiment may be one or more selected from the group consisting of carbon black, CNT, graphene and graphene oxide.
- the conductive carbon material according to the embodiment may have a content of 0.03 to 3.0% by weight of the polyacrylonitrile-based precursor fiber for all carbon fibers.
- the conductive carbon material according to the embodiment has an electrical resistivity of 3.5 ⁇ 10 ⁇ 5 ⁇ -cm to 10 3 ⁇ -cm, its purity is 95% or more, and its particle diameter may be 0.1 to 200 nm.
- Polyacrylonitrile-based precursor fiber for carbon fiber according to the embodiment may have a single yarn fineness of 0.8 ⁇ 2.0 denier.
- the present invention also provides a process for preparing a polyacrylonitrile-based polymer solution; Spinning a spinning solution comprising a polyacrylonitrile-based polymer; Extracting the solvent from the spun fiber in the coagulated solution to produce a coagulated yarn; Washing process; Stretching process; Tanning process; And a method for producing a polyacrylonitrile precursor fiber for carbon fibers comprising a drying step, wherein the polyacrylonitrile solution is prepared by adding a conductive carbon material in the process of preparing the polyacrylonitrile solution.
- a method for producing a polyacrylonitrile-based precursor fiber for carbon fibers is provided by adding a conductive carbon material in the process of preparing the polyacrylonitrile solution.
- the process for preparing the polyacrylonitrile-based solution according to the embodiment may be polymerization after adding the conductive carbon material to a solution containing monomers of the polyacrylonitrile copolymer.
- the content thereof may be added so as to be 0.03 to 3.0% by weight of the polyacrylonitrile-based precursor fiber for all carbon fibers.
- the conductive carbon material according to the embodiment may be one or more selected from the group consisting of carbon black, CNT, graphene and graphene oxide.
- the conductive carbon material according to the embodiment has an electrical resistivity of 3.5 ⁇ 10 ⁇ 5 ⁇ -cm to 10 3 ⁇ -cm, its purity is 95% or more, and its particle diameter may be 0.1 to 200 nm.
- the stretching ratio in the stretching process according to the embodiment may be 4 to 20 times.
- the polyacrylonitrile-based precursor fiber for carbon fiber by using a conductive carbon material that has low thermal conductivity and specific resistance and is not volatilized in the carbonization process, the polyacrylonitrile-based precursor fiber for carbon fiber is used.
- the thermal stabilization can be performed quickly, thereby shortening the time for flameproofing of the polyacrylonitrile-based precursor fiber for the carbon fiber, thereby economically manufacturing carbon fiber. can do.
- Figure 1 shows a flame-resistant process in the manufacturing process of the polyacrylonitrile precursor fiber for carbon fiber according to the prior art.
- the present invention relates to a polyacrylonitrile-based precursor fiber for carbon fiber, comprising a conductive carbon material.
- the conductive carbon material of the present invention means a carbon material having an electrical resistivity of 3.5 ⁇ 10 ⁇ 5 ⁇ m-cm to 10 3 ⁇ m-cm.
- the polyacrylonitrile-based precursor fiber for carbon fiber of the present invention is composed of a polymer containing a polyacrylonitrile-based polymer (sometimes abbreviated as PAN-based polymer), wherein the polyacrylonitrile-based polymer is acrylonitrile It means a polymer containing as a main component. Specifically, it is preferable to contain acrylonitrile in 95 mol% or more of all the monomers.
- the conductive carbon material is a carbon material that is lower in thermal conductivity and specific resistance than a carbon precursor, such as polyacrylonitrile (PAN), and is not volatilized in a carbonization process.
- PAN polyacrylonitrile
- the carbon material may be one or more selected from the group consisting of carbon black, CNT, graphene and graphene oxide.
- the mixing ratio of CNT and graphene is 30 wt%: 70 wt% to 70 in consideration of optimization of the particle dispersibility.
- % By weight may be 30% by weight.
- the conductive carbon material may be that content of 0.03 to 3.0% by weight of the polyacrylonitrile precursor fiber for the carbon fiber as a whole.
- the content of the conductive carbon material is less than 0.03% by weight, the thermal conduction effect is insufficient, and when the content of the conductive carbon material is greater than 3.0% by weight, dispersibility may be reduced.
- the dosage may be changed according to the type of the conductive carbon material.
- the conductive carbon material rapidly transfers heat received from the outside into the precursor to minimize the difference in flame resistance between the inside and the outside of each precursor cross section.
- the content of the conductive carbon material is less than 0.03%, there is no meaning of substantial heat transfer rate improvement due to the conductive carbon material.
- the content of the conductive carbon material is more than 3.0wt%, the particle dispersibility of the conductive carbon material is weakened, and thus the fairness due to the strength and uneven dispersion of the precursor itself. There is a problem that the productivity is sharply lowered due to degradation is uneconomical.
- the conductive carbon material means that the electrical resistivity is 3.5x10 -5 ⁇ -cm to 10 3 ⁇ -cm.
- the electrical resistivity of the conductive carbon material may not be less than 3.5x10 -5 ⁇ -cm, if it is more than 10 3 ⁇ -cm of the substantially conductive carbon material.
- the electrical resistivity is 1.47 x 10 -3 ⁇ -cm
- copper (Cu) is 1.72 x 10 -3 ⁇ -cm
- iron (Fe) is 1.0 x 10 -7 ⁇ -cm
- the resistivity is about 3.5 x 10 -5 ⁇ -cm and has a very good heat transfer performance.
- conductive metals are expected to have high thermal conductivity due to their relatively low resistivity values. However, metals are easily ionized due to their nature, which acts as an anxiety factor in the flameproofing process through a catalytic reaction. have.
- a conductive carbon material having an electrical resistivity of 3.5x10 -5 ⁇ -cm to 10 3 ⁇ -cm, which is stable even in the flameproofing process.
- the conductive carbon material may have a purity of 95 to 99.9%. At this time, if the purity of the conductive carbon material is less than 95%, impurity inhibits the covalent bonding of carbon in the salt and carbonization process due to impurities, resulting in poor mechanical properties and final yield. In particular, when a metal component other than the conductive carbon material remains, it may be preferable not to use the ignition possibility because it increases.
- the conductive carbon material has a particle diameter of 200 nm or less, and preferably, 0.1 to 200 nm. In this case, if the particle diameter of the conductive carbon material is less than 0.1 nm, the dispersion stability becomes weak and the price of the conductive carbon material is rapidly increased. If the particle diameter is more than 200 nm, it is basically impossible to fiberize the polymer by forming the precursor there is a problem.
- the polyacrylonitrile-based precursor fiber for carbon fiber according to the present invention may have a single yarn fineness of 0.8 to 2.0 denier.
- the single yarn fineness of the polyacrylonitrile precursor fiber is less than 0.8 denier, cutting may occur during the carbonization process, and when it is 2.0 denier or more, there is a high possibility of uneven quality of the precursor and thermal stability unevenness during the flameproofing process. .
- the present invention also provides a process for preparing a polyacrylonitrile-based polymer solution; Spinning a spinning solution comprising a polyacrylonitrile-based polymer; Extracting the solvent from the spun fiber in the coagulated solution to produce a coagulated yarn; Washing process; Stretching process; Tanning process; And a method for producing a polyacrylonitrile precursor fiber for carbon fibers comprising a drying step, wherein the polyacrylonitrile solution is prepared by adding a conductive carbon material in the process of preparing the polyacrylonitrile solution.
- a method for producing a polyacrylonitrile-based precursor fiber for carbon fibers is provided by adding a conductive carbon material in the process of preparing the polyacrylonitrile solution.
- the precursor fiber for carbon fiber of the present invention consists of a polymer containing a polyacrylonitrile-based polymer (sometimes abbreviated as PAN-based polymer), wherein the polyacrylonitrile-based polymer is a polymer containing acrylonitrile as a main component. Means. Specifically, it is preferable to contain acrylonitrile in 95 mol% or more of all the monomers.
- the polyacrylonitrile-based polymer may be obtained by solution polymerization by introducing a polymerization initiator into a solution containing a monomer composed mainly of acrylonitrile (sometimes referred to as AN) and a conductive carbon material. Besides the solution polymerization method, suspension polymerization method or emulsion polymerization method can be applied.
- the conductive carbon material is preferably dispersed and used in a solvent before the polymerization.
- the reason for introducing the conductive carbon material before the polymerization is because the viscosity of the solvent is very low, so that the conductive carbon material is uniformly dispersed to improve the amount of the conductive carbon material. .
- the viscosity of the spinning stock solution is maintained at a high viscosity of 400 poise or more, so even if a reactor for dispersion is added to the conductive carbon material, it is difficult to realize a uniform spinning stock solution. Many agglomeration points due to unevenness are found inside, and high magnification stretching required to secure precursor strength of 6g / denier or more becomes difficult.
- monomers copolymerizable with acrylonitrile may be included, which may serve to promote flame resistance, and examples thereof include acrylic acid, methacrylic acid, or itaconic acid. It is preferable that such a copolymerizable monomer is 5 weight% or less of all the polymer components.
- the polymerization After the polymerization, it usually involves a process of neutralizing using a polymerization terminator, which serves to prevent rapid solidification in the coagulation bath when spinning the spinning stock solution containing the obtained polyacrylonitrile-based polymer.
- a polymerization terminator which serves to prevent rapid solidification in the coagulation bath when spinning the spinning stock solution containing the obtained polyacrylonitrile-based polymer.
- ammonia may be used as the polymerization terminator, but is not limited thereto.
- a polymer is obtained from a monomer containing acrylonitrile as a main component, and then neutralized using the polymerization terminator described above to prepare a solution containing a polyacrylonitrile-based polymer in the form of a salt with ammonium ions.
- the polymerization initiator used for the polymerization is not particularly limited, and oil-soluble azo compounds, water-soluble azo compounds, peroxides, and the like are preferable, and from the viewpoint of polymerization in terms of safety in handling and industrial efficiency,
- polymerization at the time of decomposition is used preferably, and when superposing
- polymerization initiator examples include 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2,4'-dimethylvaleronitrile), and 2 And 2'-azobisisobutyronitrile.
- polymerization temperature according to the kind and quantity of a polymerization initiator, Preferably it may be 30 degreeC or more and 90 degrees C or less.
- the solution containing the obtained polyacrylonitrile-based polymer has a solid content of 7.5 to 25% by weight, which is easy to remove the solvent during spinning when applied as a spinning solution for the production of precursor fibers for carbon fiber It may be advantageous in terms of preventing tar and impurities generated during the flameproofing process and maintaining a uniform density of the filament.
- the solution containing the polyacrylonitrile-based polymer thus obtained can be used as a spinning solution in the precursor fiber manufacturing process for carbon fibers, and the spinning solution can be spun to obtain precursor fibers for carbon fibers.
- the spinning solution may include an organic or inorganic solvent as the solvent together with the polyacrylonitrile copolymer.
- the organic solvent include dimethyl sulfoxide, dimethyl formamide, dimethyl acetamide, and the like.
- the spinning method is preferably a wet spinning method or a dry wet spinning method.
- the wet spinning method is a method of discharging the spinning solution from the cap hole in the coagulation liquid of the coagulation bath.
- the winding speed is increased because the solidification proceeds with three times or more swelling occurring immediately after the spinning solution is discharged from the cap hole.
- the draft is not greatly increased even if it is raised, there is a problem that thread breakage may occur in terms of detention as the actual draft rate is rapidly increased, and there may be a limit in setting the winding speed high.
- the wet and dry spinning method is induced in the coagulation bath after the spinning solution is discharged into the air (air gap) and then the surface crystallization proceeds, the actual spinning draft rate is absorbed by the stock solution in the air gap to enable high-speed spinning. Can be.
- the solidification rate and the stretching method can be appropriately set according to the purpose of the refractory fiber or carbon fiber.
- the coagulation solution of the coagulation bath may contain so-called coagulation-promoting components in addition to solvents such as dimethyl sulfoxide, dimethylformamide, dimethyl acetamide, zinc chloride (ZnCl 2 ) aqueous solution, and sodium endocyanate (NaSCN) aqueous solution.
- solvents such as dimethyl sulfoxide, dimethylformamide, dimethyl acetamide, zinc chloride (ZnCl 2 ) aqueous solution, and sodium endocyanate (NaSCN) aqueous solution.
- the concentration of the solvent contained in the coagulation solution is preferably 15 to 75% of the solvent concentration contained in the spinning solution. In other words, by being 15% or more, it is possible to prevent the extraction rate of the solvent from the spun fiber from becoming too fast, and by using 75% or less, the solvent can be extracted from the spun fiber at a minimum amount or more. .
- the temperature of the coagulation liquid is -35 to +15 based on the temperature of the spinning solution to moderately slow the extraction rate of the solvent from the spun fiber, improve the surface crystallinity to achieve densification of the yarn to improve strength will be.
- the temperature of the coagulation solution is low, the solvent concentration of the coagulation solution is also good to be low.
- the temperature is high, it is advantageous that the solvent concentration of the coagulation solution is also increased. This is all to properly control the extraction rate of the solvent.
- the precursor fibers for the carbon fibers can be obtained by washing with water, stretching, emulsifying (oiling) and drying.
- the draw ratio can be 4 to 20 times to improve the strength of the precursor fiber, in particular, it is preferable that the single yarn fiber strength of the precursor fiber to 6g / denier or more. In order to improve the carbon fiber strength is more preferably 8.0g / denier or more, and the single fiber strength of the precursor fiber may be 6g / denier ⁇ 15g / denier.
- an oil agent to a fiber in order to prevent adhesion of monofilaments, and to give an oil agent which consists of silicone etc. as an example. It is preferable that such silicone emulsion is modified silicone, and it may be preferable to contain network modified silicone having high heat resistance.
- the fineness of the monofilament of the precursor fiber for carbon fiber obtained in this way is 0.7-2.0 denier / filament. If the short fiber fineness is too small, the process stability of the spinning process and the carbon fiber firing process may be lowered due to the occurrence of thread breakage due to contact with the roller or the guide. On the other hand, when the short fiber fineness is too large, the structural difference between the cross sections and the inner and outer layers in each short fiber after flame-proofing becomes large, and the processability fall in the subsequent carbonization process, and the tensile strength and tensile elastic modulus of the carbon fiber obtained may fall. That is, outside the above range, the firing efficiency may be drastically lowered. Particularly, in the present invention, the fineness of the monofilament is 0.7 to 2.0 denier / filament, thereby minimizing the difference between the degree of thermal stabilization and flame resistance between inner and outer layers, thereby ensuring uniformity of high strength properties.
- a copolymer of 95 mol% of acrylonitrile, 3 mol% of methacrylic acid and 2 mol% of itaconic acid was dissolved in dimethyl sulfoxide as a solvent, and 0.2 wt% of CNT, which is a carbon material before polymerization, was added to the acrylonitrile content.
- Polymerization was carried out by polymerization method, and ammonia was added thereto and neutralized in the same amount with itaconic acid to prepare a polyacrylonitrile copolymer in the form of ammonium salt to obtain a spinning stock solution containing a content of the copolymer component of 20% by weight.
- This spinning stock solution was discharged through a spinneret (temperature 45, 0.10 mm in diameter, and a 3,000 hole number of holes) and introduced into a coagulation bath made of an aqueous solution of 40% dimethyl sulfoxide controlled by 45 to prepare a coagulated yarn. .
- the calorific value (H) was measured on a DSC, and the results are shown in Table 1. At this time, the calorific value (H) on the DSC is polyacrylonitrile molecules to form a condensed pyridine ring as the flame resistance proceeds. Since the ring structure is thermally stabilized, the calorific value H on the DSC is reduced.
- the coagulated yarn was stretched five times as a whole in the washing and stretching step to obtain an intermediate stretched yarn.
- the intermediate stretched yarn was dried using a heating roller, and then stretched in pressurized steam to obtain a polyacrylonitrile-based fiber bundle having an 8 times total winding magnification, 1.5 denier single yarn fineness, and 3,000 filament number. This is called polyacrylonitrile precursor fiber for carbon fiber.
- the polyacrylonitrile-based fiber bundle thus obtained was subjected to flameproofing (stretching) at regular time intervals for each oven in a four-stage hot air oven having a temperature distribution of 220 to 270 ° C. in an air atmosphere without substantially imparting twist.
- carbonization was performed by preliminary carbonization in an inert atmosphere of 400 to 700 ° C. to remove off-gas, followed by carbonization at 1,350 ° C. (stretching) to improve strength, thereby preparing carbon fibers.
- a polyacrylonitrile-based precursor fiber and a carbon fiber were manufactured in the same manner as in Example 1-1, except that the type and amount of the conductive carbon material charged were as shown in Table 1 below.
- Comparative Examples 1-3, 2-2 and 3-2 were prepared by a solution polymerization method using a copolymer of 95 mol% acrylonitrile, 3 mol% methacrylic acid and 2 mol% itaconic acid as a solvent using dimethyl sulfoxide. Polymerization was carried out and neutralized by addition of ammonia in the same amount with itaconic acid to prepare a polyacrylonitrile-based copolymer in the form of an ammonium salt to obtain a spinning stock solution having a content of the copolymer component of 20% by weight, wherein conductive carbon was added thereto. The materials were added and mixed according to the type and dosage given in Table 1. The method of manufacturing other PAN precursor fiber and carbon fiber was the same as that of Example 1-1.
- the calorific value of DSC was measured after flameproof using DSC (Differential scanning calorimeter, Model DSC 7), and the sample was analyzed under an air atmosphere at a temperature increase rate of 10 / min. It was.
- Carbon fiber strength was measured according to ASTM D4018 method.
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Abstract
Description
Claims (11)
- 전도성 탄소물질을 포함하는 탄소섬유용 폴리아크릴로니트릴계 전구체 섬유.
- 제1항에 있어서,상기 전도성 탄소물질은 카본블랙, CNT, 그래핀 및 그래핀옥사이드로 구성된 군에서 선택되는 1종 이상인 것임을 특징으로 하는 탄소섬유용 폴리아크릴로니트릴계 전구체 섬유.
- 제1항에 있어서,상기 전도성 탄소물질은 그 함량이 전체 탄소섬유용 폴리아크릴로니트릴계 전구체 섬유 중 0.03~3.0중량%인 것임을 특징으로 하는 탄소섬유용 폴리아크릴로니트릴계 전구체 섬유.
- 제1항에 있어서,상기 전도성 탄소물질은 그 전기 비저항이 3.5x10-5Ω-cm 내지 103Ω-cm이고, 그 순도는 95% 이상이며, 그 입자 직경은 0.1~200nm인 것임을 특징으로 하는 탄소섬유용 폴리아크로니트릴계 전구체 섬유.
- 제1항에 있어서,단사섬도가 0.8 ~ 2.0 데니어인 것임을 특징으로 하는 탄소섬유용 폴리아크릴로니트릴계 전구체 섬유.
- 폴리아크릴로니트릴계 중합체 용액을 제조하는 공정; 폴리아크릴로니트릴계 중합체를 포함하는 방사 용액을 방사하는 공정; 방사된 섬유를 응고액 속에서 용매를 추출하여 응고사를 제조하는 공정; 수세 공정; 연신 공정; 유제처리 공정; 및 건조 공정을 포함하는 탄소섬유용 폴리아크릴로니트릴계 전구체 섬유의 제조방법에 있어서,상기 폴리아크릴로니트릴계 용액을 제조하는 공정에서 전도성 탄소재료를 첨가하여 폴리아크릴로니트릴계 용액을 제조하는 것임을 특징으로 하는 탄소섬유용 폴리아크릴로니트릴계 전구체 섬유의 제조방법.
- 제6항에 있어서,상기 폴리아크릴로니트릴계 용액을 제조하는 공정은 폴리아크릴로니트릴 공중합체의 단량체들를 포함하는 용액에 상기 전도성 탄소물질을 첨가한 후 중합하는 것을 특징으로 하는 탄소섬유용 폴리아크릴로니트릴계 전구체 섬유의 제조방법.
- 제7항에 있어서,상기 전도성 탄소물질을 첨가할 때 그 함량은 전체 탄소섬유용 폴리아크릴로니트릴계 전구체 섬유중 0.03~3.0중량%가 되도록 투입하는 것임을 특징으로 하는 탄소섬유용 폴리아크릴로니트릴계 전구체 섬유의 제조방법.
- 제6항에 있어서,상기 전도성 탄소물질은 카본블랙, CNT, 그래핀 및 그래핀옥사이드로 구성된 군에서 선택되는 1종 이상인 것임을 특징으로 하는 탄소섬유용 폴리아크릴로니트릴계 전구체 섬유의 제조방법.
- 제6항에 있어서,상기 전도성 탄소물질은 그 전기 비저항이 3.5x10-5Ω-cm 내지 103Ω-cm이고, 그 순도는 95% 이상이며, 그 입자 직경은 0.1~200nm인 것임을 특징으로 하는 탄소섬유용 폴리아크릴로니트릴계 전구체 섬유의 제조방법.
- 제6항에 있어서,상기 연신 공정에서 연신비율은 4~20배인 것임을 특징으로 하는 탄소섬유용 폴리아크릴로니트릴계 전구체 섬유의 제조방법.
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US14/899,206 US20160145772A1 (en) | 2013-06-21 | 2014-06-23 | Polyacrylonitrile-based precursor fiber for carbon fiber, and production method therefor |
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CN105392930A (zh) | 2016-03-09 |
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US20160145772A1 (en) | 2016-05-26 |
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