Patent Application
20210230330
The present invention relates to an acrylonitrile-based copolymer for a carbon fiber, and specifically, to an acrylonitrile-based copolymer for a carbon fiber which is capable of being manufactured as an acrylonitrile-based fiber exhibiting excellent circularity.
Carbon fibers are fibrous carbon materials that are composed of carbon atoms at 90 wt % or more of the total weight and mean fibers obtained by pyrolyzing, in an inert atmosphere, an acrylonitrile-based polymer and a fiber-shaped precursor made from pitch or rayon which is a petroleum- or coal-based hydrocarbon residue.
Carbon fibers are materials having both the structural and textural characteristics of carbon and a fiber shape and are excellent in heat resistance, chemical stability, electrical and thermal conductivity, dimensional stability according to low-temperature expandability, low density, friction/wear properties, X-ray transmittance, electromagnetic shielding, biocompatibility, flexibility, and the like. In addition, carbon fibers may be provided with outstanding adsorbability according to an activation condition.
The acrylonitrile-based copolymer is being widely used as a raw material of a carbon fiber precursor. As a method of preparing the acrylonitrile-based copolymer, solution polymerization is commonly used. Solution polymerization is a method using a monomer, an initiator, and a reaction solvent and has an advantage in which, since a copolymer solution itself can be used as a spinning solution, a process of dissolving a copolymer in a spinning solvent is not required.
Meanwhile, since the mechanical properties of carbon fiber are affected by the morphology of an acrylonitrile-based fiber which is a precursor, the morphology of an acrylonitrile-based fiber needs to be adjusted from a spinning process. In particular, when an acrylonitrile-based fiber is manufactured by wet spinning, a coagulation rate of an acrylonitrile-based copolymer which is a raw material is known to greatly affect the morphology of a fiber. Accordingly, ammonia was conventionally added to an acrylonitrile-based copolymer solution to adjust the coagulation rate of an acrylonitrile-based copolymer. However, an ammonia addition process was additionally required, and additional safety management equipment for ammonia which is a toxic gas, needed to be installed, causing manufacturing costs to be increased.
Therefore, there is a demand for the development of an acrylonitrile-based copolymer that can be manufactured as an acrylonitrile-based fiber for a carbon fiber with excellent morphology by wet spinning without separate ammonia treatment.
The present invention provides an acrylonitrile-based copolymer for a carbon fiber which exhibits excellent circularity without separately carrying out a hydrophilization process.
Also, the present invention provides an acrylonitrile-based copolymer for a carbon fiber which exhibits excellent spinnability and minimized side reactions during a fireproofing process.
One aspect of the present invention provides an acrylonitrile-based copolymer for a carbon fiber which includes a sulfonate-based monomer unit, a carboxylic acid-based monomer unit, and an acrylonitrile-based monomer unit, wherein the acrylonitrile-based copolymer includes the sulfonate-based monomer unit at 0.55 to 1.55 mol % and the carboxylic acid-based monomer unit at 0.60 to 1.40 mol %.
An acrylonitrile-based copolymer for a carbon fiber according to the present invention can be manufactured as an acrylonitrile-based fiber exhibiting excellent circularity without separately carrying out a hydrophilization process. In addition, excellent spinnability and the minimization of side reactions occurring during a fireproofing process can be realized.
Hereinafter, the present invention will be described in more detail to facilitate understanding of the present invention.
Terms and words used in this specification and the claims should not be interpreted as being limited to commonly used meanings or meanings in dictionaries, and, based on the principle that the inventors can appropriately define concepts of terms in order to describe their invention in the best way, the terms and words should be interpreted with meanings and concepts which are consistent with the technological spirit of the present invention.
In the present invention, the circularity may be measured by manufacturing coagulated yarn using an acrylonitrile-based copolymer solution and then analyzing the coagulated yarn through a scanning electron microscope (SEM) image to determine the ratio of the major axis to the minor axis (major axis/minor axis).
In the present invention, the C1 to C3 linear alkyl group may be a C1 to C3 straight-chain or branched-chain alkyl group. The C1 to C3 linear alkyl group may be one or more selected from the group consisting of a methyl group, an ethyl group, a propyl group, and an isopropyl group and is preferably a methyl group.
In the present invention, the C1 to C3 linear alkylene group may be a C1 to C3 straight-chain or branched-chain alkylene group. The C1 to C3 linear alkylene group may mean that the C1 to C3 linear alkyl group has two binding sites (i.e., a divalent alkyl group).
In the present invention, an alkali metal may be one or more selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, and francium and is preferably sodium.
1. Acrylonitrile-Based Copolymer for Carbon Fiber
An acrylonitrile-based copolymer for a carbon fiber according to an embodiment of the present invention includes a sulfonate-based monomer unit, a carboxylic acid-based monomer unit, and an acrylonitrile-based monomer unit.
The sulfonate-based monomer unit may be included at 0.55 to 1.55 mol %, preferably 0.60 to 1.50 mol %, and more preferably 0.80 to 1.30 mol %, with respect to the total molar amount of the acrylonitrile-based copolymer. When the above-described condition is satisfied, the acrylonitrile-based copolymer for a carbon fiber can be manufactured as a fiber which exhibits excellent circularity without separately carrying out a hydrophilization process. In addition, a spinning solution including the acrylonitrile-based copolymer has an appropriate viscosity, and thus spinnability can be improved. Additionally, a fireproofing process can be carried out at an appropriate temperature, and thus manufacturing efficiency can be enhanced. Below the above-described range, a fiber which exhibits excellent circularity may not be manufactured. In addition, the viscosity of a spinning solution including the acrylonitrile-based copolymer for a carbon fiber is increased, and thus spinnability may be degraded, and a coagulation rate may be significantly lowered during a coagulation process. Above the above-described range, a fiber may not be coagulated but swelled by a coagulation solution during a coagulation process. In addition, a fiber may be manufactured with a skin-core structure in which only the surface of coagulated yarn manufactured by a coagulation process is coagulated and the inside thereof is not coagulated. Additionally, side reactions occur in addition to cyclization during a fireproofing process, and thus the material properties of carbon fiber which is a final product may be degraded.
The sulfonate-based monomer unit may be a unit derived from a monomer represented by Chemical Formula 1:
In Chemical Formula 1,
R is hydrogen or a C1 to C3 linear alkyl group,
L is a C1 to C3 linear alkylene group, and
X is an alkali metal.
Since L of the compound represented by Chemical Formula 1 is an alkylene group, L is not reactive to a radical, and thus a polymerization conversion rate may be increased. In addition, since the size of the molecular structure of the compound is small, the compound may be less likely to serve as a defect during a fireproofing process.
However, when L includes an arylene group, an amide group, or the like, the size of the molecular structure of the compound becomes larger, and thus the cyclization between acrylonitrile-based monomers, which proceeds during a fireproofing process, may not be smoothly carried out due to steric hindrance caused by the compound represented by Chemical Formula 1.
Since X of the compound represented by Chemical Formula 1 is an alkali metal, the conventional problems caused by ammonia gas generated during a spinning process, that is, degradation of a working environment and a safe environment may be avoided.
The sulfonate-based monomer unit is preferably a unit derived from one or more selected from the group consisting of sodium allyl sulfonate and sodium methallyl sulfonate.
The carboxylic acid-based monomer unit may be included at 0.60 to 1.40 mol %, preferably, 0.80 to 1.30 mol % with respect to the total molar amount of the acrylonitrile-based copolymer for a carbon fiber. When the above-described range is satisfied, a fireproofing initiation temperature can be lowered, and side reactions can be prevented from occurring during a fireproofing process. At amounts below the above-described range, a fireproofing initiation temperature may be increased. At amounts above the above-described range, side reactions may occur during a fireproofing process.
The carboxylic acid-based monomer unit may be a unit derived from a carboxylic acid-based monomer. The carboxylic acid-based monomer may be one or more selected from the group consisting of acrylic acid, methacrylic acid, ethacrylic acid, itaconic acid, crotonic acid, citraconic acid, maleic acid, and mesaconic acid. The carboxylic acid-based monomer may preferably be itaconic acid.
The acrylonitrile-based monomer unit may be a unit derived from an acrylonitrile-based monomer. The acrylonitrile-based monomer may be one or more selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile. The acrylonitrile-based monomer may preferably be acrylonitrile.
The acrylonitrile-based monomer unit is included as the remainder so that the total molar amount of the acrylonitrile-based copolymer for a carbon fiber is 100 mol %.
Meanwhile, the acrylonitrile-based copolymer for a carbon fiber according to an embodiment of the present invention may be in a state of a copolymer solution prepared by solution polymerization.
2. Method of Preparing Acrylonitrile-Based Copolymer for Carbon Fiber
The acrylonitrile-based copolymer for a carbon fiber according to an embodiment of the present invention may be prepared by a method comprising the steps of: 1) preparing a reaction solution comprising a monomer mixture including a sulfonate-based monomer, a carboxylic acid-based monomer, an acrylonitrile-based monomer, and an organic solvent; and 2) subjecting the reaction solution to polymerization.
Hereinafter, each step of the method of preparing the acrylonitrile-based copolymer for a carbon fiber according to an embodiment of the present invention will be described in detail.
Step 1): Preparation of Reaction Solution
First, a reaction solution including a monomer mixture and an organic solvent is prepared.
The monomer mixture includes a sulfonate-based monomer, a carboxylic acid-based monomer, and an acrylonitrile-based monomer.
The sulfonate-based monomer may be included at 0.55 to 1.55 mol %, preferably 0.60 to 1.50 mol %, and more preferably 0.80 to 1.30 mol % with respect to the total molar amount of the monomer mixture.
The carboxylic acid-based monomer may be included at 0.60 to 1.40 mol %, preferably, 0.80 to 1.30 mol % with respect to the total molar amount of the monomer mixture.
The acrylonitrile-based monomer may be included as the remainder so that the total molar amount of the monomer mixture is 100 mol %.
The reason why the types and contents of the sulfonate-based monomer, carboxylic acid-based monomer, and acrylonitrile-based monomer are limited has been described in “1. Acrylonitrile-based copolymer for carbon fiber.”
The organic solvent, which is a reaction solvent, is favorable for increasing the weight-average molecular weight and concentration of a copolymer in a polymerization process, as compared to an inorganic solvent. In addition, a copolymer solution after the polymerization can be directly used in a spinning process, and thus the process steps can be reduced, which can ultimately contribute to an enhancement in productivity of a precursor fiber.
The organic solvent may be one or more selected from the group consisting of dimethyl sulfoxide, dimethyl formamide, and dimethyl acetamide and is preferably dimethyl sulfoxide.
The organic solvent may be included in an amount of 200 to 500 parts by weight or 250 to 400 parts by weight with respect to 100 parts by weight of the monomer mixture and is preferably included in an amount of 250 to 400 parts by weight. When the above-described range is satisfied, the weight-average molecular weight of the acrylonitrile-based copolymer for a carbon fiber is appropriately maintained, and the viscosity of a spinning solution including the acrylonitrile-based copolymer for a carbon fiber is also appropriately maintained, and thereby a spinning process can be easily carried out.
Step 2): Polymerization
Subsequently, the reaction solution is subjected to polymerization.
The polymerization may be carried out in the presence of an initiator.
The initiator may be one or more selected from the group consisting of azobisisobutyronitrile, 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2′-azobis(2-methylpropionate), 2,2′-azobis(2-methylbutyronitrile), 1,1′-azobis(cyclohexane-1-carbonitrile), 2,2′-azobis [N-(2-propenyl)-2-methylpropionamide], [(cyano-1-methylethyl)azo]formamide, 2,2′-azobis(N-butyl-2-methylpropionamide), and 2,2′-azobis(N-cyclohexyl-2-methylpropionamide). The initiator can preferably be one or more selected from the group consisting of azobisisobutyronitrile, dimethyl 2,2′-azobis(2-methylpropionate), and 2,2′-azobis(2-methylbutyronitrile). The initiator may be added in an amount of 0.5 to 1.0 part by weight or 0.6 to 0.8 parts by weight, with respect to 100 parts by weight of the monomer mixture.
The initiator can be preferably added in an amount of 0.6 to 0.8 parts by weight. When the above-described condition is satisfied, a polymerization rate can be appropriately maintained, and thus a polymerization conversion rate relative to a reference time can be increased. In addition, an acrylonitrile-based copolymer for a carbon fiber which has a weight-average molecular weight suitable for a spinning process can be prepared.
The polymerization may be solution polymerization.
Meanwhile, the polymerization may include: primary polymerization of the reaction solution at a first temperature; and secondary polymerization of the reaction solution at a second temperature higher than the first temperature.
The first temperature may be 55 to 80° C. or 60 to 70° C., and preferably 60 to 70° C. When the above-described condition is satisfied, a polymerization rate can be appropriately maintained, and thus a polymerization conversion rate relative to a reference time can be increased. In addition, an acrylonitrile-based copolymer for a carbon fiber which has a weight-average molecular weight suitable for a spinning process can be prepared.
The second temperature may be 65 to 90° C. or 70 to 80° C., and preferably 70 to 80° C. When the above-described condition is satisfied, a polymerization rate can be appropriately maintained, and thus a polymerization conversion rate relative to a reference time can be increased. In addition, an acrylonitrile-based copolymer for a carbon fiber which has a weight-average molecular weight suitable for a spinning process can be prepared.
The secondary polymerization may be initiated 4 to 9 hours or 6 to 8 hours after the initiation of the primary polymerization and is preferably initiated 6 to 8 hours after the initiation of the primary polymerization. When the above-described condition is satisfied, a polymerization rate can be appropriately maintained, and thus a polymerization conversion rate relative to a reference time can be increased. In addition, an acrylonitrile-based copolymer for a carbon fiber which has a weight-average molecular weight suitable for a spinning process can be prepared.
The secondary polymerization may be carried out for 4 to 9 hours or 6 to 8 hours and is preferably carried out for 6 to 8 hours. When the above-described condition is satisfied, a polymerization rate can be appropriately maintained, and thus a polymerization conversion rate relative to a reference time can be increased. In addition, an acrylonitrile-based copolymer for a carbon fiber which has a weight-average molecular weight suitable for a spinning process can be prepared.
After the secondary polymerization is completed, an acrylonitrile-based copolymer for a carbon fiber is obtained.
3. Acrylonitrile-Based Fiber for Carbon Fiber
An acrylonitrile-based fiber for a carbon fiber according to another embodiment of the present invention is made of the acrylonitrile-based copolymer for a carbon fiber according to an embodiment of the present invention and has a circularity of 1.13 or less and, preferably, 1.1 or less.
When the above-described condition is satisfied, the appearance quality of a carbon fiber which is a final product can be improved.
Hereinafter, exemplary embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily carry out the present invention. However, it should be understood that the present invention can be implemented in various forms, and that the exemplary embodiments are not intended to limit the present invention thereto.
100 parts by weight of a monomer mixture including sodium methallyl sulfonate at 0.60 mol %, itaconic acid at 1.00 mol %, and acrylonitrile at 98.40 mol % was uniformly dissolved in 318 parts by weight of dimethyl sulfoxide to prepare a reaction solution.
The reaction solution was put into a reactor equipped with a stirrer, the inside of the reactor was filled with nitrogen, and then a temperature inside the reactor was raised to 60° C. at a rate of 1° C./min. 0.6 parts by weight of azobisisobutyronitrile (AIBN) as an initiator was added, and solution polymerization was carried out for 8 hours. Afterward, a temperature inside the reactor was raised to 70° C. at a rate of 1° C./min, and solution polymerization was further carried out for another 6 hours. After the polymerization was completed, an acrylonitrile-based copolymer solution was obtained.
An acrylonitrile-based copolymer solution was obtained in the same manner as in Example 1 except that a reaction solution prepared by uniformly dissolving 100 parts by weight of a monomer mixture including sodium methallyl sulfonate at 1.00 mol %, itaconic acid at 1.00 mol %, and acrylonitrile at 98.00 mol % was used.
An acrylonitrile-based copolymer solution was obtained in the same manner as in Example 1 except that a reaction solution prepared by uniformly dissolving 100 parts by weight of a monomer mixture including sodium methallyl sulfonate at 1.50 mol %, itaconic acid at 1.00 mol %, and acrylonitrile at 97.50 mol % was used.
An acrylonitrile-based copolymer solution was obtained in the same manner as in Example 1 except that a reaction solution prepared by uniformly dissolving 100 parts by weight of a monomer mixture including sodium allyl sulfonate at 0.60 mol %, itaconic acid at 1.00 mol %, and acrylonitrile at 98.40 mol % was used.
An acrylonitrile-based copolymer solution was obtained in the same manner as in Example 1 except that a reaction solution prepared by uniformly dissolving 100 parts by weight of a monomer mixture including sodium allyl sulfonate at 1.50 mol %, itaconic acid at 1.00 mol %, and acrylonitrile at 97.50 mol % was used.
An acrylonitrile-based copolymer solution was obtained in the same manner as in Example 1 except that a reaction solution prepared by uniformly dissolving 100 parts by weight of a monomer mixture including itaconic acid at 1.00 mol % and acrylonitrile at 99.00 mol % was used.
An acrylonitrile-based copolymer solution was obtained in the same manner as in Example 1 except that a reaction solution prepared by uniformly dissolving 100 parts by weight of a monomer mixture including sodium methallyl sulfonate at 0.50 mol %, itaconic acid at 1.00 mol %, and acrylonitrile at 98.50 mol % was used.
An acrylonitrile-based polymer solution was obtained in the same manner as in Example 1 except that a reaction solution prepared by uniformly dissolving 100 parts by weight of a monomer mixture including sodium methallyl sulfonate at 1.60 mol %, itaconic acid at 1.00 mol %, and acrylonitrile at 97.40 mol % was used.
An acrylonitrile-based polymer solution was obtained in the same manner as in Example 1 except that a reaction solution prepared by uniformly dissolving 100 parts by weight of a monomer mixture including sodium methallyl sulfonate at 1.00 mol %, itaconic acid at 0.50 mol %, and acrylonitrile at 98.50 mol % was used.
An acrylonitrile-based polymer solution was obtained in the same manner as in Example 1 except that a reaction solution prepared by uniformly dissolving 100 parts by weight of a monomer mixture including sodium methallyl sulfonate at 1.00 mol %, itaconic acid at 1.50 mol %, and acrylonitrile at 97.50 mol % was used.
Meanwhile, the components of the monomer mixtures according to Examples and Comparative Examples are summarized and shown in Table 1 and Table 2.
The viscosity and coagulation rate of the acrylonitrile-based copolymer solutions (acrylonitrile-based copolymer: 20 wt %) according to Examples and Comparative Examples were measured and shown in Table 1 and Table 2.
(1) Viscosity (poise): measured by the following conditions using a Brookfield viscometer.
Spindle type: Cone type (CPA-52Z), Cone angle=3°, Cone radius=1.2 cm, Gap: 13 μm or less, Measurement shear rate: 10 to 20/sec, Measurement temperature: 45° C.
(2) Coagulation rate (μm/sec): Firstly, a slide glass with a size of 76 mm (width), 26 mm (length), and 1 mm (thickness) was provided as a first substrate. Two partitions with a size of 24 mm (width), 24 mm (length), and 100 μm (thickness) were disposed to be spaced an interval of 20 mm from each other on the first substrate. Then, a cover glass with a size of 40 mm (width), 24 mm (length), and 10 μm (thickness) was disposed as a second substrate on the partitions so as to manufacture a cell.
The cell was installed in an image analysis instrument (Nikon Eclipse Ti-U/DS-QilMc manufactured by Nikon), 0.01 ml of a spinning solution (polyacrylonitrile: 20 wt %, dimethyl sulfoxide: 80 wt %) was injected into the cell, and 0.05 ml of a coagulation solution was passed through the spinning solution in one direction.
In this case, the coagulation solution was composed of crosslinked melamine particles (Polybead® Crosslinked Melamine Particles manufactured by Polyscience, Inc., average particle diameter: 1 μm, shape: sphere) at 0.5 wt %, water at 49.75 wt %, and dimethyl sulfoxide at 49.75 wt %.
The moving distance and moving time of crosslinked melamine particles included in the coagulation solution were measured for 1 minute from the time point at which the particles began to move.
A temperature of the acrylonitrile-based copolymer solutions according to Examples and Comparative Examples was raised to 60° C., and then the solution was discharged into a coagulation solution (temperature: 50° C.) including water and dimethyl sulfoxide in a weight ratio of 1:1 using a spinneret (diameter of hole: 0.065 mm, number of holes: 1,000) and coagulated to manufacture coagulated yarn. Meanwhile, the spinneret was disposed in the coagulation solution. The coagulated yarn was washed with water (80° C.). The circularity of the coagulated yarn thus washed was measured by scanning electron microscope (SEM) image analysis, and results thereof are shown in Table 1 and Table 2 below. In addition, the SEM image of the washed acrylonitrile-based coagulated yarn according to Example 2 is shown in
The acrylonitrile-based coagulated yarn manufactured in Experimental Example 2 was stretched up to 15 times at 120° C. using a roller to manufacture acrylonitrile-based stretched yarn. Subsequently, while raising a temperature to 400° C. at 10° C./min, the acrylonitrile-based stretched yarn was subjected to a fireproofing process under a nitrogen atmosphere using a differential scanning calorimeter (DSC, Q100 manufactured by TA Instruments). In addition, an exothermic onset temperature, a fireproofing initiation temperature, and a temperature at a flame retardant peak were measured, and results thereof are shown in Table 1 and Table 2.
Referring to Table 1, Table 2,
In the case of Comparative Example 3 which used a monomer mixture including sodium methallyl sulfonate at 1.60 mol %, the acrylonitrile-based copolymer solution exhibited an excessively low coagulation rate, and thus the acrylonitrile-based coagulated yarn made thereof was highly likely not to be contracted but rather expanded, from which it can be predicted that the acrylonitrile-based copolymer solution will not be suitable for a spinning process. In addition, although the washed acrylonitrile-based coagulated yarn of Comparative Example 3 exhibited excellent circularity, it was manufactured with a skin-core structure. Additionally, in the case of the acrylonitrile-based stretched yarn of Comparative Example 3, two fireproofing initiation temperatures and two temperatures at a flame retardant peak were observed, from which it can be assumed that a side reaction occurred.
In the case of Comparative Example 4 which used a monomer mixture including itaconic acid at 0.50 mol %, the acrylonitrile-based stretched yarn exhibited an excessively high fireproofing initiation temperature such that fireproofing energy efficiency was degraded, and a fiber was likely to be damaged due to excessive heat storage and heat generation.
In the case of Comparative Example 5 which used a monomer mixture including itaconic acid at 1.50 mol %, the acrylonitrile-based copolymer solution exhibited an excessively high viscosity, causing a spinning process not to proceed smoothly. In addition, in the case of the acrylonitrile-based stretched yarn, two fireproofing initiation temperatures were observed, from which it can be assumed that a side reaction occurred.
In the case of Example 4 and Example 5 which used monomer mixtures including sodium allyl sulfonate at 0.60 mol % and 1.50 mol %, respectively, the acrylonitrile-based copolymer solutions exhibited an appropriate viscosity and an appropriate coagulation rate, the washed acrylonitrile-based coagulated yarn also exhibited an appropriate circularity, and the acrylonitrile-based stretched yarn also exhibited an appropriate fireproofing initiation temperature and an appropriate temperature at a flame retardant peak.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2018-0133738 | Nov 2018 | KR | national |
The present application is a National Phase entry pursuant to 35 U.S.C. § 371 of International Application No. PCT/KR2019/014748 filed on Nov. 1, 2019, and claims priority to and the benefit of Korean Patent Application No. 10-2018-0133738, filed on Nov. 2, 2018, the disclosures of which are incorporated herein by reference in their entirety.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/KR2019/014748 | 11/1/2019 | WO | 00 |
