KR101140940B1 - Oil solution for carbon fiber and method of preparing carbon fiber using the same - Google Patents

Abstract

The present invention relates to an emulsion for producing a carbon fiber comprising an uncrosslinked silicone-based compound and a method for producing a carbon fiber in which a silicon on a net is produced by spinning and heat-treating the same.

According to the manufacturing method of the present invention, since the silicone component of the emulsion exists uncrosslinked during the spinning process, it is not deposited on the spinning roller and the guide, and crosslinking occurs by the heat treatment in the spinning step, such as flameproofing and carbonization. In the firing process, since it exists as a net silicon, it is possible to maximize the physical properties of the carbon fiber by minimizing scattering.

Silicone, carbon fiber, spinning, emulsion

Description

Oil for producing carbon fiber and method for preparing carbon fiber using same {Oil solution for carbon fiber and method of preparing carbon fiber using the same}

The present invention relates to an emulsion for producing a carbon fiber comprising an uncrosslinked silicone-based compound and a method for producing a carbon fiber in which a silicon on a net is produced by spinning and heat-treating the same.

Carbon fiber is widely used in aerospace, sports, general industrial use, and the like as a reinforcing fiber for composite materials with plastics called matrix resins by utilizing its excellent mechanical properties.

As a method for producing the carbon fiber, a method of converting a precursor into a flame resistant fiber under an oxidizing atmosphere and then carbonizing it under a high temperature inert atmosphere is common. However, when baking these at high heat, fusion of short fibers arises, and there exists a problem of reducing the quality and quality of the obtained carbon fiber.

In order to prevent the fusion, a technique for imparting a silicone-based emulsion having excellent heat resistance and excellent peelability due to smoothness between fibers and fibers, particularly an amino-modified silicone-based emulsion capable of further improving heat resistance by a crosslinking reaction, to the precursor Is being developed and widely used industrially.

In particular, Japanese Laid-Open Patent Publication No. 1999-012855 attempts to prevent fusion of short-sized cows using amino-modified silicone-based fibers, but there is a problem in that the strength of carbon fibers is reduced due to contamination in the oxidation furnace by particulate components scattered in the oxidation furnace.

In Japanese Laid-Open Patent Publication No. 2005-264361, although the adhesion is increased by using a compound having a reactive functional group, there is a problem that deposition occurs on the spinning roller and the guide, thereby lowering the productivity.

In addition, the use of an amino-modified silicone emulsion causes the silicone emulsion to fall off from the fiber and become an adhesive, which is deposited on a drying roller or a guide in the precursor manufacturing process to reduce the operability such as the fibers being wound up or the thread broken. There was a problem that caused it. Then, silicon oxide is produced from a part thereof under an oxidizing atmosphere of the salt-resistant treatment step, and silicon nitride is produced when nitrogen is used as an inert gas under an inert atmosphere of the carbonization step. As a result, the scale accumulates, causing problems such as deterioration of operability and operability or damage to the kiln.

Accordingly, the present inventors have studied and tried to solve the above problems, and as a result, an uncrosslinked silicone-based compound including a polar reactor was used as an emulsion of an acrylic fiber composition and spun under specific conditions, spinning, flameproofing, and carbonizing The present invention has been completed by discovering that the deposition of rollers and guides and the damage of the kiln can be minimized.

Accordingly, an object of the present invention is to provide an oil agent for producing carbon fibers including a silicon-based compound in an uncrosslinked state, and a method for producing carbon fibers having excellent physical properties by spinning, flameproofing, and carbonizing under high temperature conditions.

The present invention is characterized by an oil agent for producing carbon fibers containing a silicone-based compound of the formula (1).

     CH3 R1 R3 CH3

      ｜ ｜ ｜ ｜

CH3-Si-O-(-Si-O-) a-(-Si-O-) b-Si-CH3 [Formula 1]

      ｜ ｜ ｜ ｜

      CH3 R2 R4 CH3

However, R1, R2 and R3 are organic compounds having the structure of CnH2n + 1 (n = 0 to 3)

    b / a = 0.03 to 0.3

    R4 is an organic compound having the structure of CnH2nX

      n = 0 to 3,

      X = epoxy, carboxylic acid, amine, acid halide type reactive terminal

In addition, the present invention,

Mixing an acrylic fiber composition with an emulsion containing a silicone-based compound of Formula 1;

Spinning an emulsion in which the acrylic fiber composition is mixed to obtain acrylic fibers;

Converting the acrylic fiber into a flame resistant fiber under an oxidizing atmosphere; And

Carbonization treatment step of carbonizing the flame resistant fiber under an inert atmosphere

Another method of producing a carbon fiber comprising a.

According to the manufacturing method of the present invention, since the silicone component of the emulsion exists uncrosslinked during the spinning process, it is not deposited on the spinning roller and the guide, and crosslinking occurs by the heat treatment in the spinning step, such as flameproofing and carbonization. In the firing process, since it exists as a net silicon, it is possible to maximize the physical properties of the carbon fiber by minimizing scattering.

The present invention relates to an emulsion for producing a carbon fiber comprising an uncrosslinked silicone-based compound and a method for producing a carbon fiber in which a silicon on a net is produced by spinning and heat-treating the same, which will be described in more detail below.

Emulsion for producing carbon fiber of the present invention comprises a silicone-based compound of formula (1).

     CH3 R1 R3 CH3

      ｜ ｜ ｜ ｜

CH3-Si-O-(-Si-O-) a-(-Si-O-) b-Si-CH3 [Formula 1]

      ｜ ｜ ｜ ｜

      CH3 R2 R4 CH3

However, R1, R2 and R3 are organic compounds having the structure of CnH2n + 1 (n = 0 to 3)

    b / a = 0.03 to 0.3

    R4 is an organic compound having the structure of CnH2nX

      n = 0 to 3,

      X = epoxy, carboxylic acid, amine, acid halide type reactive terminal

 The silicon-based compound includes at least one polar reactor, polysilicon is formed by polymerization by heat treatment, and further crosslinked to form a network structure. Examples of the silicon-based compound capable of forming the silicon compound of the network structure include epoxy, amine, carboxylic acid, acid halide, and other carboxylic compounds reactive to Si or an alkyl unit directly connected to Si, as illustrated in compound 1. Compounds containing derivatives and the like may be used, and amine and epoxy compounds may be preferably used.

In addition, the emulsion of the present invention may further include an antioxidant or a surfactant.

Antioxidant is a component which suppresses thermal decomposition of an oil agent effectively by the heating in a flameproofing process, and improves the fusion prevention effect between fiber and fiber.

Although it does not specifically limit as antioxidant, For example, 4,4'-butylidenebis (3-methyl-6-t-butylphenol, a trioctadecyl phosphite, N, N'- diphenyl-p- Phenylenediamine, triethylene glycol bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate], dioleyl-thiodipropionate and the like can be used.

Moreover, surfactant is used as an emulsifier, and it is a component which emulsifies or disperse | distributes an oil agent in water, and can improve the uniform adhesiveness to a fiber, and safety of a work environment.

Although it does not specifically limit as surfactant, A well-known thing can be selected suitably from nonionic surfactant, anionic surfactant, cationic surfactant, and amphoteric surfactant, and can be used. As a nonionic surfactant, For example, Nonionic surfactant to which alkylene oxide was added (higher alcohol, higher fatty acid, alkylphenol, styrenated phenol, benzyl phenol, sorbitan, sorbitan ester, castor oil, Products obtained by adding at least one alkylene oxide, such as ethylene oxide and propylene oxide, to hardened castor oil, products obtained by adding higher fatty acids to polyalkylene glycol, ethylene oxide / propylene oxide copolymers, and the like. . Examples of the anionic surfactants include carboxylates, higher alcohols, sulfate ester salts of higher alcohol ethers, sulfonates, higher alcohols, and phosphate ester salts of higher alcohol ethers. As cationic surfactants, quaternary ammonium salt type cationic surfactants (lauryltrimethylammonium chloride, oleylmethylethylammonium ethosulfate, etc.), amine salt type cationic surfactants (polyoxyethylene laurylamine lactate, etc.) Can be used. As the amphoteric surfactant, amino acid type amphoteric surfactants (such as sodium laurylaminopropionate), betaine type amphoteric surfactants (stearyl dimethyl betaine, lauryl dihydroxyethyl betaine and the like) and the like can be used.

The present invention is to prepare a carbon fiber by mixing the acrylic fiber composition in the emulsion, spinning it to obtain an acrylic fiber, and then converting the acrylic fiber into a flame resistant fiber under an oxidizing atmosphere, and carbonization treatment to carbonize under an inert atmosphere It is characterized by.

The spinning is carried out through the process of solidification, washing, drawing, emulsion, drying by passing through a 3000 hole nozzle through a wet or dry spinning method of a dope in which an acrylic copolymer having an acrylonitrile content of 93% or more is dissolved in a DMSO solvent. Prepare a precursor for carbon fiber. After the emulsion is added to the acrylic fiber composition in an appropriate weight ratio, a heat treatment for 2 minutes is performed at a temperature of 160 to 190 degrees after the emulsion addition process so that a crosslinking reaction can occur. At this time, if the temperature is 160 degrees or less, sufficient crosslinking degree cannot be obtained. If the temperature is 190 degrees or more, the oxidation reaction of the fiber occurs.

At this time, it is preferable that the emulsion and the acrylic fiber composition including the silicone-based compound are mixed and spun at a weight ratio of 0.5: 95.5 to 2.5: 97.5, and when the ratio is less than 0.5: 95.5, carbon fibers manufactured by insufficient fusion resistance between the fibers and the fibers. There is a problem that the strength of the resin is lowered, and when it exceeds 95.5 to 2.5: 97.5, there is a problem that the operability at the time of firing is deteriorated and the manufacturing cost is increased.

The flame retardant process converts the spun acrylic fiber into flame resistant fiber under an oxidizing atmosphere of 200 to 300 ° C. and the carbonization treatment process of carbonizing the flame resistant fiber under an inert atmosphere of 300 to 2000 ° C. again. Excellent carbon fiber can be obtained.

In this case, the oxidizing atmosphere is preferably an air atmosphere, and the intramolecular cyclization and ringing are performed when the heat treatment is performed for 20 to 100 minutes while applying a tension of 0.90 to 1.10 to the spun acrylic fiber. The flame resistant fiber which has a flameproof structure is manufactured through oxygen addition to the furnace.

In addition, the carbonization process is heat-treated for several minutes while applying a tension ratio of 0.95 to 1.15 with respect to the flame-resistant fiber in a firing furnace having a temperature gradient of 300 ℃ to 800 ℃ in an inert atmosphere such as nitrogen, argon, pre-carbonization After performing the treatment step (first carbonization treatment), in order to proceed with the graphite, heat treatment for several minutes while applying a tension ratio of 0.95 to 1.05 with respect to the first carbonization treatment process under an inert atmosphere such as nitrogen and argon. It is preferable to carry out the second carbonization treatment step to carbonize the flame resistant fiber, and to control the heat treatment temperature in the second carbonization treatment step, the maximum temperature is set to 1000 ° C or higher while applying a temperature gradient. It is better to do this, which can be adjusted according to the required properties of the carbon fiber.

Hereinafter, the present invention will be described in more detail based on the following examples. However, the following examples are not intended to limit the present invention, but are not limited thereto. Various physical property evaluations of the companies manufactured in Examples and Comparative Examples of the present invention were performed by the following method.

(1) Emulsion grant rate (OPU)

Take 5 g of the finished product and measure the weight of the fiber after vacuum drying at 120 ° C for 4 hours (W1), and dry the fiber using 200 ml of Ethylacetate / n-Hexane = 50/50 (wt%) mixed solvent. After removing the emulsion by Soxhlet extraction method for more than 10 hrs and dried in the same manner as before to measure the weight (W2). After that, the emulsion emulsification rate is measured by applying the following equation.

              O P U = (W1-W2) / W1 X 100 (%)

(2) memorial serviceability

The fiber immediately after emulsification is passed through a Heating Roll Dryer with a temperature of 150 ° C and a residence time of 1 minute to produce 1 ton of fiber, and then the weight of the deposited gum on the surface of the roll is measured.

(◎: 0.1 g or less, ○: 0.1 to 0.3 g, △: 0.3 g to 0.5, ×: 0.5 g or more)

(3) plastic operation

Oxidation heat treatment of silicon (Si) using ICP using silicon content of carbon and silicon in the PAN precursor fiber (T1) and PAN precursor fiber at 220 degrees 30 minutes and 240 degrees 30 minutes After pre-carbonization at 650 ° C for 30 seconds, multiply by 100 by dividing the content ratio (T2) of carbon and silicon among residual components (based on silicon residual = T1 / T2 X 100). (◎: 105 or more, (circle): 102-105, (triangle | delta): 100-102, x: 100 or less).

(4) carbon fiber strength

Tensile carbon fiber strands impregnated and cured in epoxy resin were tensioned according to JIS R 7601 to evaluate the strength of carbon fiber.

Example 1

[Production of emulsion]

The emulsion used in the preparation of the PAN precursor for carbon fiber of the present invention contains 30 to 60% of the main component of the silicone-based compound having the structure of Formula 1 below.

     CH3 R1 R3 CH3

      ｜ ｜ ｜ ｜

CH3-Si-O-(-Si-O-) a-(-Si-O-) b-Si-CH3 [Formula 1]

      ｜ ｜ ｜ ｜

      CH3 R2 R4 CH3

However, R1, R2 and R3 are organic compounds having the structure of CnH2n + 1 (n = 0 to 3)

    b / a = 0.03 to 0.3

    R4 is an organic compound having the structure of CnH2nX

      n = 0 to 3,

      X = epoxy, carboxylic acid, amine, acid halide type reactive terminal

Additional components other than the silicone-based compound include 30 to 50% of ester-based emulsifiers, antistatic agents, antioxidants and the like. This emulsion is prepared by preparing emulsified stock solution and preparing dilution solution of 1 ~ 15% of silicone-based compound and giving it to fiber during spinning process.

[Production of PAN Precursor Fiber]

Dope obtained by dissolving acrylic copolymer with acrylonitrile content of 93% or more in DMSO solvent through 3000-hole nozzle by wet or dry spinning method, and then solidifying, washing, stretching, emulsion, drying, etc. Prepare a precursor. At this time, the amount of oil impregnated (OPU) is adjusted to about 1.0% and a heat treatment for 2 minutes is performed at a temperature of 170 degrees after the process of impregnation so that crosslinking reaction can occur.

[Production of Carbon Fiber]

In order to evaluate the physical properties of the carbon fiber using the prepared PAN precursor fiber, the precursor fiber was subjected to oxidation heat treatment for 210 to 230 degrees 30 minutes and 240 to 250 degrees 30 minutes, and then again 1200 to 1200 for 40 seconds. In the figure, a carbon fiber is manufactured through a carbonization process and a post-treatment process for 40 seconds.

[Examples 2 to 4 and Comparative Examples 1 to 5]

Table 1 shows the results of experiments performed in the same manner as in Example 1 while varying the amount of reactive terminals and heat treatment temperature in the silicone-based compound in the emulsion.

Remarks Among the silicon compounds
Reactivity terminal ratio (b / a) After emulsification
Heat treatment temperature (℃) Operability Strength (GPa) radiation Firing Example 1 0.05 170 ◎ ◎ 4.5 Example 2 0.05 185 ◎ ◎ 4.3 Example 3 0.2 170 ○ ◎ 4.3 Example 4 0.2 185 ○ ◎ 4.2 Comparative Example 1 0 - ◎ X 3.8 Comparative Example 2 0 170 ◎ X 3.7 Comparative Example 3 0.5 170 △ ◎ 4.1 Comparative Example 4 0.05 150 ◎ △ 3.8 Comparative Example 5 0.2 150 ○ △ 3.7

As can be seen from the results of Table 1, when the reactive terminal ratio of the silicone compound falls within the scope of the present invention, it can be confirmed that the strength is maintained excellent and spinning and firing are advantageous.

Claims (5)

To include a silicon-based compound comprising at least one polar reactor of the formula (1), The silicon-based compound is a silicon-based compound capable of forming a silicon compound having a network structure, and includes a reactive group selected from epoxy, carboxylic acid, and reactive carboxylic derivative compounds in an alkyl unit directly connected to Si or Si. Emulsions for textile manufacture.      CH3 R1 R3 CH3       ｜ ｜ ｜ ｜ CH3-Si-O-(-Si-O-) a-(-Si-O-) b-Si-CH3 [Formula 1]       ｜ ｜ ｜ ｜       CH3 R2 R4 CH3 However, R1, R2 and R3 are organic compounds having the structure of CnH2n + 1 (n = 0 to 3)     b / a = 0.03 to 0.3     R4 is an organic compound having the structure of CnH2nX       n = 0 to 3,       -X = epoxy, carboxylic acid, acid halide reactive terminal delete Mixing an acrylic fiber composition with an emulsion including a silicone-based compound including at least one polar reactor of Formula 1;      CH3 R1 R3 CH3       ｜ ｜ ｜ ｜ CH3-Si-O-(-Si-O-) a-(-Si-O-) b-Si-CH3 [Formula 1]       ｜ ｜ ｜ ｜       CH3 R2 R4 CH3 However, R1, R2 and R3 are organic compounds having the structure of CnH2n + 1 (n = 0 to 3)     b / a = 0.03 to 0.3     R4 is an organic compound having the structure of CnH2nX       n = 0 to 3,       -X = epoxy, carboxylic acid, acid halide reactive terminal Spinning an emulsion in which the acrylic fiber composition is mixed to obtain acrylic fibers; Converting the acrylic fiber into a flame resistant fiber under an oxidizing atmosphere under an oxidizing atmosphere undergoing heat treatment for 20 to 100 minutes while drawing a tension of 0.90 to 1.10; And Carbonization treatment step of carbonizing the flame resistant fiber in a kiln having a temperature gradient of 300 to 800 ° C. under an inert atmosphere Carbon fiber manufacturing method comprising a.  The method of claim 3, wherein the reactive group of the silicon compound is an epoxy compound. 4. The method of claim 3, wherein the emulsion containing the silicone compound and the acrylic fiber composition are mixed in a weight ratio of 0.5: 95.5 to 2.5: 97.5.