KR20170077612A - Preparing method for carbon fiber using hybrid crosslinking and carbon fiber - Google Patents

Preparing method for carbon fiber using hybrid crosslinking and carbon fiber Download PDF

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KR20170077612A
KR20170077612A KR1020150187673A KR20150187673A KR20170077612A KR 20170077612 A KR20170077612 A KR 20170077612A KR 1020150187673 A KR1020150187673 A KR 1020150187673A KR 20150187673 A KR20150187673 A KR 20150187673A KR 20170077612 A KR20170077612 A KR 20170077612A
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polyolefin
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fibers
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황선환
이동철
류진영
김병주
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주식회사 엘지화학
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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
    • 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
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
    • D01F11/16—Chemical after-treatment of artificial filaments or the like during manufacture of carbon by physicochemical methods
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/003—Treatment with radio-waves or microwaves
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/06—Inorganic compounds or elements
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/40—Fibres of carbon
    • 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
    • D10B2321/02—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins
    • 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
    • D10B2401/06—Load-responsive characteristics
    • D10B2401/061—Load-responsive characteristics elastic
    • 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
    • D10B2401/06—Load-responsive characteristics
    • D10B2401/063—Load-responsive characteristics high strength
    • 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
    • D10B2505/00—Industrial
    • D10B2505/02—Reinforcing materials; Prepregs

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Abstract

(1) primary crosslinking the surface of the polyolefin fiber by irradiating the polyolefin fiber with an electron beam; (2) subjecting the polyolefin fibers to secondary crosslinking by adding sulfuric acid to the polyolefin fibers having the primary crosslinked surface; And (3) a carbonization step of carbonizing the secondary crosslinked polyolefin fibers in a carbonization furnace, which is an inert atmosphere, at a temperature of 600 to 1,200, wherein the carbon fiber production method of the present invention is characterized by comprising: The carbon fiber is produced by the method of improving the thermal property by cyclizing the chain structure of the polyolefin fiber by using the sulfuric acid crosslinking, so that the carbon fiber having a lower unit cost than the conventional carbon fiber can be produced, It is possible to solve the problem that the polyolefin fibers may be damaged due to cross-linking of sulfuric acid because the surface of the polyolefin fibers is crosslinked through electron beam irradiation crosslinking. Since the carbon fiber thus produced has a low unit price, it can be usefully used as various reinforcing agents for reinforcing various carbon fiber reinforced plastics.

Description

TECHNICAL FIELD [0001] The present invention relates to a method for producing carbon fibers using a composite crosslink,

The present invention relates to a method for producing carbon fiber by using a composite crosslinking method, and more particularly, to a method for producing carbon fiber by a method of producing a carbon fiber having improved thermal properties by cyclizing a polyolefin chain structure by electron beam irradiation and sulfuric acid crosslinking And a method for manufacturing carbon fibers at a low unit price.

Carbon fiber has much better mechanical strength, electrical conductivity and thermal conductivity than glass fiber and is used for a wide range of applications such as plastic reinforced materials, gas storage materials and electrode materials.

Today, the use of carbon fiber, which is a high strength and high-elasticity material, is becoming popular, but due to the high production cost of carbon fiber, it is difficult to supply it, and research for reducing the production cost of carbon fiber is increasing.

Examples of the method for producing carbon fibers include a method of carbonizing organic fibers such as synthetic fibers and petroleum pitch fibers and a method of producing carbon fibers by thermally decomposing hydrocarbons such as benzene or methane in the presence of a catalyst Method) is well known.

Among them, the method of carbonizing organic fibers such as synthetic fibers and petroleum pitch fibers is mostly made from petroleum-based precursors such as polyacrylonitrile and pitch. In the method using polyacrylonitrile, A carbon fiber is produced by carbonizing after oxidizing stabilization process using air or an oxidizing gas or a mixed gas thereof in an appropriate ratio, and a method using pitch is a method of melt spinning the pitch, An oxidizing gas such as sulfuric acid, nitrogen oxide (NOx), or the like, or a mixed gas obtained by mixing them in an appropriate ratio is used for oxidation stabilization and then carbonized to produce carbon fibers. However, since the method of carbonizing organic fibers such as synthetic fibers and petroleum pitch fibers uses a petroleum-based precursor, the production cost of carbon fibers due to the high precursor unit cost and the high processing cost generated in the stabilization step peculiar to the petroleum precursor There is a problem that the unit price is increased.

Therefore, by using a low cost precursor instead of the existing expensive petroleum precursor, the cost of the precursor in the production of carbon fibers can be lowered, and the stabilization step can be omitted, thereby developing a carbon fiber manufacturing method having a low production cost .

A problem to be solved by the present invention is to provide a method of producing a carbon fiber using a polyolefin, which can produce a carbon fiber having a lower unit cost than conventional carbon fibers.

Another object of the present invention is to provide a carbon fiber produced using a polyolefin.

In order to solve the above problems,

(1) primary crosslinking the surface of the polyolefin fiber by irradiating the polyolefin fiber with an electron beam;

(2) subjecting the polyolefin fibers to secondary crosslinking by adding sulfuric acid to the polyolefin fibers having the primary crosslinked surface; And

(3) carbonizing the secondary cross-linked polyolefin fibers in the carbonization furnace, which is an inert atmosphere, at a temperature of 600 to 1,200.

In addition, in order to solve the above-mentioned problem, the present invention provides a method for producing a carbon fiber-reinforced polyolefin fiber, which comprises the steps of: applying sulfuric acid to a polyolefin fiber whose surface has been firstly crosslinked by electron beam irradiation to carbon fiber the secondary crosslinked polyolefin fiber at a temperature of 600 to 1,200 Lt; / RTI >

The carbon fiber manufacturing method of the present invention produces a carbon fiber by a method of cycling the chain structure of a polyolefin fiber by electron beam irradiation and sulfuric acid crosslinking to improve the thermal property. Therefore, carbon having a lower unit cost Fiber can be produced. In particular, since the surface of the polyolefin fiber is crosslinked through the electron beam irradiation crosslinking before the sulfuric acid crosslinking, the problem that the polyolefin fiber may be damaged due to the sulfuric acid crosslinking can be solved. Since the carbon fiber thus produced has a low unit price, it can be usefully used as various reinforcing agents for reinforcing various carbon fiber reinforced plastics.

1 is a graph showing the results of measurement of the calorie of the secondary crosslinked polyolefin fibers produced in Examples 1 to 5 and the polyolefin fibers of Comparative Example 1. Fig.
Fig. 2 is a graph showing the results of measurement of calories of the secondary crosslinked polyolefin fibers produced in Examples 6 to 10 and the polyolefin fibers of Comparative Example 2. Fig.

Hereinafter, the present invention will be described in detail in order to facilitate understanding of the present invention.

The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms and the inventor may appropriately define the concept of the term in order to best describe its invention It should be construed as meaning and concept consistent with the technical idea of the present invention.

The method for producing a carbon fiber of the present invention comprises the steps of (1) primary crosslinking the surface of the polyolefin fiber by irradiating the polyolefin fiber with an electron beam; (2) subjecting the polyolefin fibers to secondary crosslinking by adding sulfuric acid to the polyolefin fibers having the primary crosslinked surface; And (3) carbonizing the secondary crosslinked polyolefin fibers at a temperature of 600 to 1,200 in a carbide furnace, which is an inert atmosphere.

Hereinafter, the carbon fiber manufacturing method of the present invention will be described in detail for each step.

(1) a step of primary crosslinking the surface of the polyolefin fiber by irradiating the polyolefin fiber with an electron beam

In step (1), a low-density crosslinked layer is formed on the surface of the polyolefin fiber by irradiating the polyolefin fiber with an electron beam (e-beam) to primary crosslink the surface of the polyolefin fiber.

The low-density crosslinked layer means that a part of the surface of the polyolefin fiber is crosslinked. The low-density crosslinked layer can alleviate the rapid thermal shock that is experienced when the polyolefin fibers are exposed to sulfuric acid in the subsequent sulfuric acid crosslinking process. The thermal shock causes the fiber surface to have a high crosslinking density, The cross-linking density of the fiber surface and the cross-linking density of the inside of the fiber can be prevented from becoming large. When the polyolefin fiber is made of carbon fiber, the portion having low cross-linking density inside is thermally decomposed, It is possible to prevent the phenomenon of being produced.

An example of the reaction at the time of the primary crosslinking can be schematically shown as follows.

<Example of reaction>

Figure pat00001

As shown in the example of the above reaction, when an electron beam (e-beam) is applied to the polyolefin fibers, chain scission of the molecular chains constituting the polyolefin fibers can occur (in the example of the reaction (a)), and crosslinking may occur, which is connected to the neighboring molecular chain at the site where the chain is cut as described above.

When the polyolefin fiber is irradiated with an electron beam, the reaction as described above may occur between molecular chains positioned on the surface portion of the polyolefin fiber to which the electron beam can reach. Therefore, the polyolefin fibers The low-density cross-linked layer can be formed.

The polyolefin fibers may be fibers based on polyolefins and the polyethylene may be selected from the group consisting of low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE), polypropylene and polyisobutylene It can be more than a species.

The polyolefin fibers may have a weight average molecular weight of 150,000 g / mol or more, and preferably 150,000 to 500,000 g / mol. When the molecular weight of the polyolefin fiber is 150,000 g / mol or more, it has appropriate mechanical properties. Therefore, it is possible to prevent the fiber state from being damaged or the strength to be lowered after the carbonization step, and thus the carbon fiber can be suitably produced.

The irradiation dose of the electron beam may be 50 to 600 kGy, preferably 100 to 500 kGy, and more preferably 100 to 300 kGy.

If the irradiation dose of the electron beam is 50 kGy or more, the surface of the polyolefin fiber can be properly crosslinked. If the irradiation dose of the electron beam is 600 kGy or less, the surface of the polyolefin fiber can be properly crosslinked, Can be prevented.

The electron beam may have an energy of 50 to 400 eV, preferably 100 to 300 eV, and more preferably 150 to 250 eV.

If the energy of the electron beam is 50 eV or more, the surface of the polyolefin fiber can be properly crosslinked. If the electron beam irradiation dose is 400 eV or less, the surface of the polyolefin fiber can be properly crosslinked, .

The primary crosslinking can form a low-density crosslinked layer of 0.05 to 5 탆, preferably 0.1 to 3 탆, more preferably 0.2 to 1 탆 on the surface of the polyolefin fiber.

If the thickness of the low-density cross-linked layer is more than 5 mu m, the cross-linking layer may exhibit the effect of the above-mentioned cross-linking layer. However, if the thickness of the low- May be destroyed.

(2) a step of secondary crosslinking the polyolefin fiber by adding sulfuric acid to the surface-crosslinked polyolefin fiber

In step (2), sulfuric acid is added to the surface-crosslinked polyolefin fibers to cause secondary crosslinking of the polyolefin fibers. The polyolefin fibers having the primary cross-linked surfaces of the polyolefin fibers are cyclized in the chain structure of the polyolefin through the dehydrogenation reaction and the cross-linking reaction in the secondary cross-linking, thereby improving the fiber retention of the produced carbon fibers and improving the thermal properties do.

The dehydrogenation reaction of the polyolefin fibers can be represented by the following reaction formula (1). [Reaction Scheme 1]

Figure pat00002

As shown in Reaction Scheme 1, in the molecular chain structure of the polyolefin fiber produced by the dehydrogenation reaction, the pi (pi) bond of the terminal double bond is opened, and the double bond of the neighboring molecular chain can be connected and crosslinked. The crosslinking of the polyolefin chain structure occurs in the crosslinking process, which is considered to be caused by forming a polygonal structure when the molecular chains of the polyolefin fibers are connected to each other. According to the production method of the present invention, by the cyclization of the polyolefin chain structure, the fiber holding state of the carbon fiber to be produced can be improved and the thermal property can be improved. At this time, the ring may be a hexagonal ring.

The sulfuric acid may be concentrated sulfuric acid, and when the concentrated sulfuric acid is used, the crosslinking reaction of the polyolefin fibers can proceed more smoothly.

The secondary crosslinking may be carried out by adding polyolefin fibers having the primary crosslinked surface to a suitable container and then adding sulfuric acid thereto. For example, after putting the polyolefin fibers into a crucible, sulfuric acid is added so that the polyolefin fibers are completely carried, Followed by heating. Specifically, the secondary crosslinking can be carried out under reaction conditions in which the sulfuric acid-added polyolefin fibers are maintained at a specific temperature range for a specific period of time.

The temperature of the secondary crosslinking may be from 150 to 180, preferably from 160 to 170. [ If the temperature of the furnace is less than 150, the degree of crosslinking of the polyolefin fibers becomes insufficient and is not suitable for progressing carbonization. When the temperature of the furnace exceeds 180, the polyolefin fibers are severely damaged, There is a problem that it becomes difficult.

On the other hand, the temperature holding time of the furnace may be 10 minutes to 1 hour, preferably 10 to 30 minutes. When the temperature holding time of the furnace is less than 10 minutes, the degree of crosslinking of the polyolefin fibers becomes insufficient and the polyolefin fibers are damaged when the temperature holding time of the furnace exceeds 1 hour There arises a problem that it is difficult to maintain the fiber form.

At this time, the secondary crosslinking may be performed in an inert atmosphere, and the inert atmosphere may be constituted by an inert gas. For example, the polyolefin fibers to which the sulfuric acid has been added may be subjected to a crosslinking reaction in a furnace filled with an inert gas to be secondary crosslinked.

As the furnace, it is preferable to use a furnace capable of precisely controlling the temperature to control the crosslinking reaction of the polyolefin fibers with sulfuric acid according to the temperature. The furnace may be equipped with a heating means so as to control the temperature of the furnace, and the heating means can preferably be used to precisely control the heating rate and the temperature of the furnace.

The heating means may include a heating element, and the polyolefin fiber to which the sulfuric acid has been added is placed in a tube and the tube is charged into a furnace, and then the tube is heated using the heating body. .

The tube may be made of various materials such as iron, steel, copper, nickel, stainless steel, aluminum or alumina, and may be corroded by the sulfuric acid in step (1) It may be coated with Teflon.

The heating element may be positioned above or below the tube. When the heating element is located on both the top and bottom of the tube, the heating rate and the temperature of the furnace can be precisely controlled.

The tube may be filled with an inert gas to prevent the polyolefin fibers supported on the sulfuric acid from reacting with other materials. In particular, when the polyolefin fibers are crosslinked with concentrated sulfuric acid having a characteristic of absorbing moisture, It is necessary to remove all of the oxygen.

Since the secondary crosslinking is performed in an inert atmosphere, the polyolefin fibers supported on the sulfuric acid may not react with other substances. Particularly, when the polyolefin fibers are crosslinked with concentrated sulfuric acid having moisture absorbing characteristics, it is necessary to remove all the oxygen inside the tube, and therefore, it is necessary to further make the atmosphere inert.

In an embodiment of the present invention, when the secondary crosslinking is performed using a furnace, the furnace may be stabilized by filling the inside with an inert gas for a certain period of time for the composition of the inert atmosphere, The charging time may be 10 minutes to 3 hours, preferably 20 minutes to 2 hours, more preferably 30 minutes to 1 hour.

After the stabilization, the polyolefin fibers to which the sulfuric acid has been added are introduced into the tube, and then a further inert gas charging process can be performed. The polyolefin fibers to which the sulfuric acid has been added are introduced into the tube through the additional inert gas charging process to remove water and oxygen that may be introduced into the furnace and the additional inert gas charging process is performed for 5 to 30 minutes, For 10 to 20 minutes.

The inert gas may be helium, neon, argon, krypton, xenon, radon, nitrogen, or the like, specifically, helium in the process of filling the inert gas with the inert gas and stabilizing the inert gas.

In one embodiment of the present invention, the step of neutralizing the secondary crosslinked polyolefin fibers may further comprise during the step (2) and the step (3), wherein the neutralization is carried out using distilled water to remove residual sulfuric acid . &Lt; / RTI &gt;

The neutralization may be carried out by using distilled water to wash all the sulfuric acid components, and the washing may be performed until the polyolefin fiber crosslinked with the sulfuric acid shows a pH of 7.

(3) Carbonization step of carbonizing the secondary crosslinked polyolefin fiber at a temperature of 600 to 1,200 in a carbonization furnace, which is an inert atmosphere

In step (3), the secondary crosslinked polyolefin fibers are carbonized at a temperature of 600 to 1,200 in an inert atmosphere carbonization furnace.

The carbonization can be performed in an inert atmosphere, and the inert atmosphere can be formed by filling the interior with an inert gas such as helium, neon, argon, krypton, xenon, or radon or an inert gas such as nitrogen (N 2 ) The inert gas may preferably be nitrogen.

The carbonization may be performed at a temperature of 600 to 1,200, preferably 700 to 1,100, more preferably 800 to 1,000.

If the carbonization temperature is lower than the proper temperature, other elements constituting the polyolefin fiber may remain, which may result in an unsatisfactory quality. If the carbonization temperature exceeds the proper temperature, unstable ring chains may not maintain a hexagonal ring shape when carbonization proceeds Can be decomposed.

The carbonization may be performed for 1 to 10 minutes, and more specifically for 1 to 5 minutes.

If the carbonization time is less than the proper time, the other elements constituting the polyolefin fiber may remain and may not have proper quality. If the carbonization temperature exceeds the proper time, unstable ring chains may not form a hexagonal ring shape when carbonization proceeds Can be decomposed.

The carbon fiber can be produced through the manufacturing method of the present invention as described above. Accordingly, the present invention provides the carbon fiber produced according to the above production method.

That is, the carbon fiber of the present invention may be produced by adding sulfuric acid to the polyolefin fiber whose surface has been primarily crosslinked by electron beam irradiation and carbonizing the secondary crosslinked polyolefin fiber at a temperature of 600 to 1,200.

The polyolefin may be at least one selected from the group consisting of low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE), polypropylene and polyisobutylene.

The electron beam irradiated during the primary crosslinking may have an energy of 50 to 400 eV and the irradiation dose may be 50 to 600 kGy. Further, the electron beam may preferably have an energy of 100 to 300 eV, more preferably 150 to 250 eV, and the irradiation dose of the electron beam may be preferably 100 to 500 kGy, more preferably 100 To 300 kGy.

If the energy of the electron beam irradiated is 50 to 400 eV and the irradiation dose of the electron beam is 50 to 600 kGy, the surface of the polyolefin fiber is adequately crosslinked while the surface is not broken by over-crosslinking, It may have a surface structure.

The primary crosslinking can form a low-density crosslinked layer of 0.05 to 5 탆, preferably 0.1 to 3 탆, more preferably 0.2 to 1 탆 on the surface of the polyolefin fiber.

The secondary crosslinking may be carried out by adding sulfuric acid to the polyolefin fibers whose surfaces are first crosslinked and then heating the polyolefin fibers. The heating may be performed in a furnace filled with an inert gas.

The temperature of the secondary crosslinking may be 150 to 180, preferably 160 to 170, and the crosslinking temperature may be maintained for 10 minutes to 1 hour, preferably 10 to 30 minutes.

When the crosslinking temperature is 150 to 180 and the crosslinking temperature is maintained for 10 minutes to 1 hour, the degree of crosslinking of the polyolefin fibers is not less than a suitable level, and the polyolefin fibers themselves are not damaged, Appropriate fiber morphology can be maintained.

The inert atmosphere may be an inert gas such as helium, neon, argon, krypton, xenon, or radon, or a nitrogen (N 2 ) atmosphere, and the inert gas is preferably nitrogen Lt; / RTI &gt;

The carbonization may be performed at a temperature of 600 to 1,200, preferably 700 to 1,100, more preferably 800 to 1,000.

The integral thermal decomposition progress temperature (IPDT) of the carbon fiber according to an exemplary embodiment of the present invention may be 500 or more, preferably 1,000 to 3,000, and more preferably 1,000 to 2,200.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples, but the present invention is not limited by these Examples and Experimental Examples. The embodiments according to the present invention can be modified into various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. The embodiments of the present invention are provided to enable those skilled in the art to more fully understand the present invention.

Example 1

Ebeam engine (EBR-200/270, Comet group, ebeam Tech.) Was applied to low density polyethylene (LDPE, LUTENE MB9205, manufactured by LG Chem) having a fiber diameter of 0.4 mm and a weight average molecular weight of 150,000 g / The primary crosslinking was carried out by irradiating electron beams at an energy intensity of 200 keV to an irradiation dose of 50 kGy.

The primary crosslinked polyolefin fibers were impregnated in concentrated sulfuric acid (98%), placed in a stainless steel tube coated with Teflon, and charged into a furnace. The temperature of the furnace was raised to 160 ° C. and maintained for 20 minutes. The mixture was neutralized by washing with distilled water until the pH reached 7, and then dried at 60 ° C. for 24 hours using a dry oven to obtain a second crosslinked polyolefin Fiber.

The crosslinked polyolefin fibers thus prepared were carbonized at a carbonization temperature of 900 for 3 minutes in a nitrogen (N 2 ) atmosphere using a vertical furnace to produce carbon fibers.

Example 2

Secondary crosslinked polyolefin fibers were prepared in the same manner as in Example 1 except that the irradiation dose of the electron beam was changed to 100 kGy in Example 1 to prepare carbon fibers.

Example 3

Secondary crosslinked polyolefin fibers were prepared in the same manner as in Example 1 except that the irradiation dose of the electron beam was changed to 150 kGy in Example 1 to prepare carbon fibers.

Example 4

Secondary crosslinked polyolefin fibers were prepared in the same manner as in Example 1 except that the irradiation dose of the electron beam was changed to 200 kGy in Example 1 to prepare carbon fibers.

Example 5

Secondary crosslinked polyolefin fibers were prepared in the same manner as in Example 1 except that the irradiation dose of the electron beam was changed to 250 kGy in Example 1 to prepare carbon fibers.

Examples 6 to 10

In the same manner as in Examples 1 to 5 except that polyolefin fibers having a diameter of 0.2 mm were used in place of the polyolefin fibers having a diameter of 0.4 mm in Example 1, crosslinked polyolefin Fibers were prepared, and carbon fibers were produced.

Example 11

Ebeam engine (EBR-200/270, Comet group, ebeam Tech.) Was applied to low density polyethylene (LDPE, LUTENE MB9205, manufactured by LG Chem) having a fiber diameter of 0.4 mm and a weight average molecular weight of 150,000 g / And irradiated with electron beams at an energy intensity of 80 keV so as to achieve an irradiation dose of 100 kGy.

The primary crosslinked polyolefin fibers were impregnated in concentrated sulfuric acid (98%), placed in a stainless steel tube coated with Teflon, and charged into a furnace. The temperature of the furnace was raised to 160 ° C. and maintained for 20 minutes. The mixture was neutralized by washing with distilled water until the pH reached 7, and then dried at 60 ° C. for 24 hours using a dry oven to obtain a second crosslinked polyolefin Fiber.

The crosslinked polyolefin fibers thus prepared were carbonized at a carbonization temperature of 900 for 3 minutes in a nitrogen (N 2 ) atmosphere using a vertical furnace to produce carbon fibers.

Example 12

Secondary crosslinked polyolefin fibers were prepared in the same manner as in Example 11 except that the energy intensity of the electron beam was changed to 110 keV in Example 11 to prepare carbon fibers.

Example 13

Secondary crosslinked polyolefin fibers were prepared in the same manner as in Example 11 except that the energy intensity of the electron beam was changed to 140 keV in Example 11 to prepare carbon fibers.

Example 14

Secondary crosslinked polyolefin fibers were prepared in the same manner as in Example 11 except that the energy intensity of the electron beam was changed to 170 keV in Example 11 to prepare carbon fibers.

Example 15

Secondary crosslinked polyolefin fibers were prepared in the same manner as in Example 11 except that the energy intensity of the electron beam was changed to 200 keV in Example 11 to prepare carbon fibers.

Examples 16 to 20

In the same manner as in Examples 11 to 15 except that polyolefin fibers having a diameter of 0.2 mm were used in place of the polyolefin fibers having a diameter of 0.4 mm in Example 11, Fibers were prepared, and carbon fibers were produced.

Comparative Example 1

Low density polyethylene (LDPE, LUTENE MB9205, manufactured by LG Chemie) having a weight average molecular weight of 150,000 g / mol and a diameter of 0.4 mm was used. The fiber was heated in a nitrogen furnace (N 2 ) atmosphere at a carbonization temperature of 900 for 3 minutes Carbon fiber was produced by carbonization.

Comparative Example 2

Low density polyethylene (LDPE, LUTENE MB9205, manufactured by LG Chemical) having a weight average molecular weight of 150,000 g / mol and a diameter of 0.2 mm was used. The fiber was heated in a nitrogen furnace (N 2 ) atmosphere at 900 carbonization temperature for 3 minutes Carbon fiber samples were prepared by carbonization.

Experimental Example: Calorimetric measurement of crosslinked polyolefin-based fibers

The secondary crosslinked polyolefin fibers prepared in Examples 1 to 20 and the polyolefin fibers used in Comparative Examples 1 and 2 were subjected to calorimetric measurement. The calorimetric method is a method of measuring the amount of heat absorption and calorific value by exposing a sample to nitrogen (N 2 ) atmosphere at a temperature of 400 or less by differential scanning calorimetry (DSC) using a differential scanning calorimeter (DSC-60, manufactured by Shimadzu Corporation) Respectively.

Fig. 1 shows the amounts of heat of the secondary crosslinked polyolefin fibers prepared in Examples 1 to 5 and the polyolefin fibers of Comparative Example 1. Fig. 2 shows the secondary crosslinked polyolefin fibers prepared in Examples 6 to 10, FIG. 3 shows the calorie amounts of the polyolefin fibers of the secondarily crosslinked polyolefin fibers prepared in Examples 11 to 15 and the polyolefin fibers of Comparative Example 1, and FIG. 4 shows the heat amount of the polyolefin fibers of Comparative Example 2, To 20, and the polyolefin fibers of Comparative Example 2. The results are shown in Table 1. &lt; tb &gt; &lt; TABLE &gt;

Fiber Diameter (mm) Energy intensity
(keV) Radiation dose
(kGy) Drawing symbol Example 1 0.4 200 50 200 keV-50 kGy Example 2 0.4 200 100 200 keV-100 kGy Example 3 0.4 200 150 200 keV-150 kGy Example 4 0.4 200 200 200 keV-200 kGy Example 5 0.4 200 250 200 keV-250 kGy Example 6 0.2 200 50 200 keV-50 kGy Example 7 0.2 200 100 200 keV-100 kGy Example 8 0.2 200 150 200 keV-150 kGy Example 9 0.2 200 200 200 keV-200 kGy Example 10 0.2 200 250 200 keV-250 kGy Example 11 0.4 80 100 80 keV-100 kGy Example 12 0.4 110 100 110 keV-100 kGy Example 13 0.4 140 100 140 keV-100 kGy Example 14 0.4 170 100 170 keV-100 kGy Example 15 0.4 200 100 200 keV-100 kGy Example 16 0.2 80 100 80 keV-100 kGy Example 17 0.2 110 100 110 keV-100 kGy Example 18 0.2 140 100 140 keV-100 kGy Example 19 0.2 170 100 170 keV-100 kGy Example 20 0.2 200 100 200 keV-100 kGy Comparative Example 1 0.4 - - LDPE fiber Comparative Example 2 0.2 - - LDPE fiber

As can be seen from FIGS. 1 to 4, the secondary crosslinked polyolefin fibers prepared in Examples 1 to 20 exhibited a smaller heat absorbing amount and calorific value than the polyolefin fibers of Comparative Examples 1 and 2, respectively, It was confirmed that the crosslinked polyolefin fibers prepared in Examples 1 to 20, respectively, were crosslinked smoothly through primary crosslinking and secondary crosslinking.

Claims (18)

(1) primary crosslinking the surface of the polyolefin fiber by irradiating the polyolefin fiber with an electron beam;
(2) subjecting the polyolefin fibers to secondary crosslinking by adding sulfuric acid to the polyolefin fibers having the primary crosslinked surface; And
(3) carbonizing the secondary crosslinked polyolefin fibers in a carbonization furnace in an inert atmosphere at a temperature of 600 to 1,200.
The method according to claim 1,
Wherein the polyolefin fibers have a molecular weight of at least 150,000 g / mol.
The method according to claim 1,
Wherein the polyolefin is at least one selected from the group consisting of low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE), polypropylene and polyisobutylene.
The method according to claim 1,
Wherein an irradiation dose of the electron beam is 50 to 600 kGy.
The method according to claim 1,
Wherein the electron beam has an energy of 50 to 400 eV.
The method according to claim 1,
Wherein a low-density crosslinked layer having a thickness of 0.05 to 5 占 퐉 is formed on the surface of the polyolefin fiber by the primary crosslinking.
The method according to claim 1,
Wherein the secondary crosslinking in the step (2) is carried out under reaction conditions in which the sulfuric acid-added polyolefin fibers are maintained at a temperature of 150 to 180 for 10 minutes to 1 hour.
8. The method of claim 7,
Wherein the temperature is 160 to 170 under the reaction conditions.
8. The method of claim 7,
Wherein the holding time is 10 to 30 minutes under the reaction conditions.
The method according to claim 1,
The secondary crosslinking is carried out in an inert atmosphere,
Wherein the inert atmosphere is constituted by an inert gas of helium, neon, argon, krypton, xenon, or radon.
The method according to claim 1,
Further comprising, between the step (2) and the step (3), neutralizing the secondary crosslinked polyolefin fiber,
Wherein the neutralization comprises removing residual sulfuric acid using distilled water.
The method according to claim 1,
Wherein the carbonization of step (3) is carried out at a temperature of 700 to 1,100.
The method according to claim 1,
And carbonization of the step (3) is performed for 1 to 10 minutes.
A carbon fiber produced by applying sulfuric acid to a polyolefin fiber whose surface is first crosslinked by electron beam irradiation to carbonize the secondary crosslinked polyolefin fiber at a temperature of 600 to 1,200.
15. The method of claim 14,
Wherein the polyolefin is at least one selected from the group consisting of low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE), polypropylene and polyisobutylene.
15. The method of claim 14,
Wherein the electron beam has an energy of 50 to 400 eV and an irradiation dose of 50 to 600 kGy.
15. The method of claim 14,
And a low-density crosslinked layer having a thickness of 0.05 to 5 占 퐉 is formed on the surface of the polyolefin fiber by the primary crosslinking.
15. The method of claim 14,
Wherein an integral thermal decomposition progress temperature (IPDT) of the carbon fiber is 500 or more.
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