CN103184591B - Manufacturing method of 12K binary polyacrylonitrile-based carbon fiber - Google Patents
Manufacturing method of 12K binary polyacrylonitrile-based carbon fiber Download PDFInfo
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Abstract
The invention relates to a manufacturing method of 12K binary polyacrylonitrile-based carbon fiber. The method comprises the following steps: subjecting a precursor to preoxidation treatment in four temperature zones through a preoxidation furnace; carrying out low-temperature carbonization and high-temperature carbonization on the precursor subjected to preoxidation treatment respectively in six temperature zones and four temperature zones; and carrying out subsequent treatment to obtain high-density and high-crystal orientation quaternary polyacrylonitrile-based carbon fiber. According to the invention, the spinning solution is high in homogenization degree in the solidification forming process, which is more beneficial to later drafting and dry densification of tows, and the precursor is relatively good in spinnability. The process operation is simple, and the reaction conditions are easy to control. The prepared polyacrylonitrile spinning fluid has relatively good hydrophilicity and spinnability. The concentrated heat release of the precursor in the preoxidation stage is alleviated, and the manufacturing method is relatively good in preoxidation and carbonization process property, and applicable to engineered preparation of large-tow carbon fiber.
Description
Affiliated field
The present invention relates to carbon fiber and manufacture field, the specifically preparation method of the high-performance polyacrylonitrile-based carbon fiber of a kind of 12K.
Background technology
Carbon fiber has the series of advantages such as high specific strength, high ratio modulus, thermal coefficient of expansion be little, is widely used in the fields such as Aero-Space, industrial energy and Leisure Sport.Polyacrylonitrile (PAN) base carbon fibre dominate on carbon fiber market, the stuctures and properties of PAN directly decides precursor and the final quality of carbon fiber.The feature of homopolymerization PAN generates that the structure of macromolecular chain is more regular and degree of crystallinity is higher, but because the molecule inner injection of homopolymerization PAN can be large, make the flexibility of fiber poor, stiff and not folding, therefore, need to add comonomer and carry out copolymerization, be used for the regularity of macromolecular chain, reduce the cohesive energy between macromolecular chain and suitably reduce degree of crystallinity, giving its good toughness.As the polyacrylonitrile fibril preparing carbon fiber, comonomer should have following performance: improve the hydrophily of spinning solution and the compactness of strand; Changing the radical reaction of homopolymerization PAN in preoxidation process is the reaction of ionic type; Reduce the activation energy of cyclization; The molecule level passage providing oxygen to spread to fiber core and permeate, prepares homogeneous oxidization fiber.
When selecting comonomer, often a kind of comonomer can not meet above-mentioned requirements simultaneously, therefore, needs to select multiple comonomer, adopts ternary or quarternary copolymerized.Be in the patent of CN201010191664.5 in the patent No., Shanghai Jinfa Technology Development Co., Ltd proposes a kind of preparation method adopting monomethyl itaconate ammonium compound to prepare polyacryl-nitrile spinning fluid as comonomer, be in the patent of CN200510016572.X in the patent No., Changchun Applied Chemistry Research Inst., Chinese Academy of Sciences proposes a kind of β of employing-itaconic acid acid amides prepares polyacryl-nitrile spinning fluid preparation method as comonomer, these two patent Introductions be all adopt binary copolymerization formula preparation method, but need first to synthesize second comonomer monomethyl itaconate ammonium compound or β-itaconic acid acid amides before the reaction, operating process is loaded down with trivial details, simultaneously, also the preparation method of spinning solution is just described in these two patents, and to adding due to the second comonomer, caused pre-oxidation, charing technique matching regulate and not mentioned, be in the patent of CN02130023.2 and CN02130022.4 in the patent No., Shanxi Coal-Chemical Inst., Chinese Academy of Sciences proposes a kind of by acrylonitrile, dimethyl formamide, distilled water, azodiisobutyronitrile and chain-transferring agent are after uniform temperature homopolymerization, pass into ammonia cessation reaction again, and be adjusted to certain pH value, obtained spinning solution, the polyacryl-nitrile spinning fluid of homopolymerization that what the method prepared is, ammonia is as cessation reaction agent, technique is comparatively complicated and be not easy to control, the spinnability of homo-polypropylene nitrile spinning solution for preparing of this method is poor simultaneously, in pre-oxidation, carbonization stage also easily causes concentrated heat release, especially in the carbon fiber preparation process of large tow, the fiber more easily occurring to cause due to accumulation of heat is blown, be unfavorable for preparing high performance carbon fiber.
Summary of the invention
For overcome the technique that exists in prior art comparatively complicated and be not easy to control, the spinnability of homo-polypropylene nitrile spinning solution that obtains is poor, and in the carbon fiber preparation process of large tow, the deficiency that the fiber more easily occurring to cause due to accumulation of heat is blown, the present invention proposes a kind of manufacture method of 12K binary polyacrylonitrile-bacarbon carbon fiber.
Detailed process of the present invention is:
Step 1, the preparation of precursor: the preparation of described precursor comprises prepares spinning solution and wet spinning.
Described spinning solution of preparing is with dimethyl sulfoxide (DMSO) (DMSO) for solvent, and with acrylonitrile, itaconic acid for polymerization single polymerization monomer, ammonia, as itaconic acid modifier, carries out polymerisation; Polymeric reaction temperature is 60 DEG C, and the reaction time is 26h.Obtain polyacrylonitrile-radical spinning solution.The weight ratio of described acrylonitrile, itaconic acid is 98:2.The consumption of itaconic acid modifier ammonia is the gauge of 15% according to the molar percentage accounting for carboxyl-content on itaconic acid, is passed in the dimethyl sulphoxide solution of itaconic acid and carries out ammonification after metering.
The process of described wet spinning is same as the prior art, comprises and solidifies, washes, hot water drawing-off, to oil and dry, steam drafting and steam shaping, obtain precursor.
Step 2, pre-oxidation: described pre-oxidation carries out in No. 1 warm area ~ No. 4 warm area, and the temperature of No. 1 warm area ~ No. 4 warm area is followed successively by 185 DEG C, 230 DEG C, 255 DEG C and 270 DEG C.Precursor successively by each warm area from low temperature warm area to high temperature warm area, carries out gradient heat treatment to precursor, obtains oxidization fiber.In pre-oxidation treatment, the precursor speed of service is 2.5m/min, and the preoxidation time in each warm area is identical, and pre-oxidation total time is 82min.The draft ratio of tow in each warm area is respectively: No. 1 warm area 5 ‰, No. 2 warm areas-10 ‰, No. 3 warm areas-25 ‰, No. 4 warm areas-30 ‰.
Step 3, low-temperature carbonization: the oxidization fiber obtained enters low-temperature carbonization furnace by hauling machine and carries out continuous low temperature charing process.The warm area of described low-temperature carbonization has 6 warm areas, respectively: 400 DEG C, 570 DEG C, 680 DEG C, 740 DEG C, 740 DEG C, 630 DEG C.
In low-temperature carbonization process, with the nitrogen of oxygen content≤1ppm for medium; Low-temperature carbonization drawing-off is 0 ‰, low-temperature carbonization time 115s.
Step 4, high temperature carbonization: through low-temperature carbonization oxidization fiber by hauling machine enter high temperature carbonization furnace carry out continuous high temperature charing process.Described high temperature carbonization have 4 warm areas, respectively: 780 DEG C, 1000 DEG C, 1200 DEG C, 1450 DEG C.
In high temperature carbonization process, with the nitrogen of oxygen content≤1ppm for medium; High temperature carbonization drawing-off is-40 ‰, high temperature carbonization time 115s.Obtain unsized carbon fiber.
Step 5, starching:
Sizing agent pure water being diluted to mass concentration is 4%, carries out starching to unsized carbon fiber.The starching time is 28s, sizing agent temperature 30 DEG C.
Step 6, dry: the carbon fiber after starching enters drying tower, adopt conventional method to carry out drying.6 warm areas are set in described drying tower, are respectively 165 DEG C, 165 DEG C, 165 DEG C, 170 DEG C, 170 DEG C and 170 DEG C.Carbon fiber after starching moves to high-temperature region from low-temperature space successively, completes drying.The dry time is 173s, and the carbon fiber rate of sizing is 1.65%.The medium of described drying is air.
The technical parameter of described wet spinning as shown in Table 1 to Table 3.
Table 1
Table 2
Table 3
| Title | Spinning machine | 1# draws a machine | 2# draws a machine | 1# rinsing machine | 2# rinsing machine |
| Frequency (Hz) | 32.00 | 33.63 | 35.67 | 34.27 | 29.88 |
| Title | 3# rinsing machine | 4# rinsing machine | 5# rinsing machine | 6# rinsing machine | 7# rinsing machine |
| Frequency (Hz) | 29.79 | 29.98 | 29.74 | 29.84 | 29.78 |
| Title | 8# rinsing machine | 9# rinsing machine | 10# rinsing machine | 11# rinsing machine | 1# heat-traction machine |
| Frequency (Hz) | 29.88 | 29.98 | 29.75 | 29.81 | 29.81 |
| Title | 2 hot drawing machines | 3 hot drawing machines | 1# oiling machine | 1# drying machine | 2# oiling machine |
| Frequency (Hz) | 28.87 | 42.69 | 41.89 | 38.23 | 39.67 |
| Title | 2# drying machine A | 2# drying machine B | 3# oiling machine | Hot-rolling machine | Steam drafting machine |
| Frequency (Hz) | 41.35 | 40.86 | 37.73 | 38.04 | 31.26 |
| Title | Steam forming machine | Receive silk machine | |||
| Frequency (Hz) | 29.45 | 32.76 |
The polymerization formula that the present invention adopts binary ammoniation modified, the polyacrylonitrile-based carbon fibre of preparation 12K, carbon fibre precursor prepared by the method, in pre-oxidation, carbonization stage, has good process matching, the carbon fiber mechanical property of final preparation is higher, and machinability is better.
The present invention compares with the preparation method of traditional polyacrylonitrile carbon fiber, has following characteristics:
Binary copolymerization is filled a prescription, and technological operation is simple, easy control of reaction conditions.The polyacryl-nitrile spinning fluid of preparation has good hydrophily and spinnability.Alleviate the concentrated heat release of precursor in the pre-oxidation stage, pre-oxidation, charring process better, are applicable to the through engineering approaches preparation of large-tow carbon fiber.
For verifying effect of the present invention, the present invention implements the preparation of the 12K carbon fiber under binary ammonification polymerization formula system on engineering line, and mechanical property and the coefficient of variation of the 12K carbon fiber prepared with binary polymerization formula compare, and final result is as shown in table 4:
Table 4
Detailed description of the invention
Below by embodiment, present invention process method is described in further details.
Embodiment 1
The present embodiment is a kind of manufacture method of 12K binary polyacrylonitrile-bacarbon carbon fiber.
Step 1, the preparation of precursor:
The preparation of described precursor comprises prepares spinning solution and wet spinning.
With dimethyl sulfoxide (DMSO) (DMSO) for solvent, with acrylonitrile, itaconic acid for polymerization single polymerization monomer, ammonia, as itaconic acid modifier, carries out polymerisation; Polymeric reaction temperature is 60 DEG C, and the reaction time is 26h.Obtain polyacrylonitrile-radical spinning solution.The weight ratio of described acrylonitrile, itaconic acid is 98:2.The consumption of itaconic acid modifier ammonia is the gauge of 15% according to the molar percentage accounting for carboxyl-content on itaconic acid, is passed in the dimethyl sulphoxide solution of itaconic acid and carries out ammonification after metering.
The same prior art of described wet spinning, comprises and solidifies, washes, hot water drawing-off, to oil and dry, steam drafting and steam shaping, obtain precursor.Technical parameter in wet spinning as shown in Table 1 to Table 3.
Table 1
Table 2
Table 3
| Title | Spinning machine | 1# draws a machine | 2# draws a machine | 1# rinsing machine | 2# rinsing machine |
| Frequency (Hz) | 32.00 | 33.63 | 35.67 | 34.27 | 29.88 |
| Title | 3# rinsing machine | 4# rinsing machine | 5# rinsing machine | 6# rinsing machine | 7# rinsing machine |
| Frequency (Hz) | 29.79 | 29.98 | 29.74 | 29.84 | 29.78 |
| Title | 8# rinsing machine | 9# rinsing machine | 10# rinsing machine | 11# rinsing machine | 1# heat-traction machine |
| Frequency (Hz) | 29.88 | 29.98 | 29.75 | 29.81 | 29.81 |
| Title | 2 hot drawing machines | 3 hot drawing machines | 1# oiling machine | 1# drying machine | 2# oiling machine |
| Frequency (Hz) | 28.87 | 42.69 | 41.89 | 38.23 | 39.67 |
| Title | 2# drying machine A | 2# drying machine B | 3# oiling machine | Hot-rolling machine | Steam drafting machine |
| Frequency (Hz) | 41.35 | 40.86 | 37.73 | 38.04 | 31.26 |
| Title | Steam forming machine | Receive silk machine | |||
| Frequency (Hz) | 29.45 | 32.76 |
Step 2, pre-oxidation
Conventional method is adopted to carry out pre-oxidation treatment to the precursor obtained by pre-oxidation furnace.Described pre-oxidation furnace has two, has each two-layer up and down respectively, and each formation 2 warm areas, two pre-oxidation furnaces totally 4 warm areas, are respectively No. 1 warm area ~ No. 4 warm area.The temperature of No. 1 warm area ~ No. 4 warm area is followed successively by 185 DEG C, 230 DEG C, 255 DEG C and 270 DEG C.Precursor successively by each warm area from low temperature warm area to high temperature warm area, carries out gradient heat treatment to precursor, obtains oxidization fiber.In pre-oxidation treatment, the precursor speed of service is 2.5m/min, and the preoxidation time in each warm area is identical, and pre-oxidation total time is 82min.The draft ratio of tow in each warm area is respectively: No. 1 warm area 5 ‰, No. 2 warm areas-10 ‰, No. 3 warm areas-25 ‰, No. 4 warm areas-30 ‰.Oxidization fiber density is (1.35 ~ 1.36) g/cm
3.
Step 3, low-temperature carbonization
The oxidization fiber obtained enters low-temperature carbonization furnace by hauling machine and carries out continuous low temperature charing process.The warm area of described low-temperature carbonization has 6 warm areas, respectively: 400 DEG C, 570 DEG C, 680 DEG C, 740 DEG C, 740 DEG C, 630 DEG C.
In low-temperature carbonization process, with the nitrogen of oxygen content≤1ppm for medium; Low-temperature carbonization drawing-off is 0 ‰, low-temperature carbonization time 115s.
Step 4, high temperature carbonization
Through low-temperature carbonization oxidization fiber by hauling machine enter high temperature carbonization furnace carry out continuous high temperature charing process.Described high temperature carbonization have 4 warm areas, respectively: 780 DEG C, 1000 DEG C, 1200 DEG C, 1450 DEG C.
In high temperature carbonization process, with the nitrogen of oxygen content≤1ppm for medium; High temperature carbonization drawing-off is-40 ‰, high temperature carbonization time 115s.Obtain unsized carbon fiber.
Step 5, starching
Adopt domestic 4# emulsion-type sizing agent, being diluted to mass concentration with pure water is 4%, carries out starching to unsized carbon fiber.The starching time is 28s, sizing agent temperature 30 DEG C.
Step 6, dry
Carbon fiber after starching enters drying tower, adopts conventional method to carry out drying.6 warm areas are set in described drying tower, are respectively 165 DEG C, 165 DEG C, 165 DEG C, 170 DEG C, 170 DEG C and 170 DEG C.Carbon fiber after starching moves to high-temperature region from low-temperature space successively, completes drying.The dry time is 173s, and the carbon fiber rate of sizing is 1.65%.The medium of described drying is air.
By embodiment 1 gained PAN based precursor fiber number 1.162dtex, monofilament power surveys intensity 7.1cN/dtex, modulus is 110.5cN/dtex, fracture elongation is 13.3%, and boiling water shrinkage is 5.97%.The TENSILE STRENGTH of carbon fiber is 4789MPa(CV:2.2%), elastic modelling quantity is 223GPa(CV:1.2%), fracture elongation is 2.14%(CV:2.8%), loop strength is 273.7cN.
Embodiment 2
The present embodiment is a kind of manufacture method of 12K binary polyacrylonitrile-bacarbon carbon fiber.
Step 1, the preparation of precursor:
The preparation of described precursor comprises prepares spinning solution and wet spinning.
With dimethyl sulfoxide (DMSO) (DMSO) for solvent, with acrylonitrile, itaconic acid for polymerization single polymerization monomer, ammonia, as itaconic acid modifier, carries out polymerisation; Polymeric reaction temperature is 60 DEG C, and the reaction time is 26h.Obtain polyacrylonitrile-radical spinning solution.The weight ratio of described acrylonitrile, itaconic acid is 97:3.The consumption of itaconic acid modifier ammonia is the gauge of 25% according to the molar percentage accounting for carboxyl-content on itaconic acid, is passed in the dimethyl sulphoxide solution of itaconic acid and carries out ammonification after metering.
The same prior art of described wet spinning, comprises and solidifies, washes, hot water drawing-off, to oil and dry, steam drafting and steam shaping, obtain precursor.Technical parameter in wet spinning as shown in Table 1 to Table 3.
Step 2, pre-oxidation
Conventional method is adopted to carry out pre-oxidation treatment to the precursor obtained by pre-oxidation furnace.Described pre-oxidation furnace has two, has each two-layer up and down respectively, and each formation 2 warm areas, two pre-oxidation furnaces totally 4 warm areas, are respectively No. 1 warm area ~ No. 4 warm area.The temperature of No. 1 warm area ~ No. 4 warm area is followed successively by 185 DEG C, 230 DEG C, 255 DEG C and 270 DEG C.Precursor successively by each warm area from low temperature warm area to high temperature warm area, carries out gradient heat treatment to precursor, obtains oxidization fiber.In pre-oxidation treatment, the precursor speed of service is 2.8m/min, and the preoxidation time in each warm area is identical, and pre-oxidation total time is 73min.The draft ratio of tow in each warm area is respectively: No. 1 warm area 15 ‰, No. 2 warm areas 20 ‰, No. 3 warm areas-5 ‰, No. 4 warm areas-10 ‰.Oxidization fiber density is (1.35 ~ 1.36) g/cm
3.
Step 3, low-temperature carbonization
The oxidization fiber obtained enters low-temperature carbonization furnace by hauling machine and carries out continuous low temperature charing process.The warm area of described low-temperature carbonization has 6 warm areas, respectively: 400 DEG C, 570 DEG C, 680 DEG C, 740 DEG C, 740 DEG C, 630 DEG C.
In low-temperature carbonization process, with the nitrogen of oxygen content≤1ppm for medium; Low-temperature carbonization drawing-off is 0 ‰, low-temperature carbonization time 102s.
Step 4, high temperature carbonization
Through low-temperature carbonization oxidization fiber by hauling machine enter high temperature carbonization furnace carry out continuous high temperature charing process.Described high temperature carbonization have 4 warm areas, respectively: 780 DEG C, 1000 DEG C, 1200 DEG C, 1450 DEG C.
In high temperature carbonization process, with the nitrogen of oxygen content≤1ppm for medium; High temperature carbonization drawing-off is-40 ‰, high temperature carbonization time 102s.Obtain unsized carbon fiber.
Step 5, starching
Adopt domestic 4# emulsion-type sizing agent, being diluted to mass concentration with pure water is 4%, carries out starching to unsized carbon fiber.The starching time is 25s, sizing agent temperature 30 DEG C.
Step 6, dry
Carbon fiber after starching enters drying tower, adopts conventional method to carry out drying.6 warm areas are set in described drying tower, are respectively 165 DEG C, 165 DEG C, 165 DEG C, 170 DEG C, 170 DEG C and 170 DEG C.Carbon fiber after starching moves to high-temperature region from low-temperature space successively, completes drying.The dry time is 154s, and the carbon fiber rate of sizing is 1.55%.The medium of described drying is air.
By embodiment 2 gained PAN based precursor fiber number 1.157dtex, monofilament power surveys intensity 6.9cN/dtex, modulus is 112.8cN/dtex, fracture elongation is 12.8%, and boiling water shrinkage is 6.05%.The TENSILE STRENGTH of carbon fiber is 4441MPa(CV:2.3%), elastic modelling quantity is 225GPa(CV:1.1%), fracture elongation is 1.91%(CV:3.2%), loop strength is 237.8cN.
Embodiment 3
The present embodiment is a kind of manufacture method of 12K binary polyacrylonitrile-bacarbon carbon fiber.
Step 1, the preparation of precursor:
The preparation of described precursor comprises prepares spinning solution and wet spinning.
With dimethyl sulfoxide (DMSO) (DMSO) for solvent, with acrylonitrile, itaconic acid for polymerization single polymerization monomer, ammonia, as itaconic acid modifier, carries out polymerisation; Polymeric reaction temperature is 60 DEG C, and the reaction time is 26h.Obtain polyacrylonitrile-radical spinning solution.The weight ratio of described acrylonitrile, itaconic acid is 97.5:2.5.The consumption of itaconic acid modifier ammonia is the gauge of 25% according to the molar percentage accounting for carboxyl-content on itaconic acid, is passed in the dimethyl sulphoxide solution of itaconic acid and carries out ammonification after metering.
The same prior art of described wet spinning, comprises and solidifies, washes, hot water drawing-off, to oil and dry, steam drafting and steam shaping, obtain precursor.Technical parameter in wet spinning as shown in Table 1 to Table 3.
Step 2, pre-oxidation
Conventional method is adopted to carry out pre-oxidation treatment to the precursor obtained by pre-oxidation furnace.Described pre-oxidation furnace has two, has each two-layer up and down respectively, and each formation 2 warm areas, two pre-oxidation furnaces totally 4 warm areas, are respectively No. 1 warm area ~ No. 4 warm area.The temperature of No. 1 warm area ~ No. 4 warm area is followed successively by 185 DEG C, 230 DEG C, 255 DEG C and 270 DEG C.Precursor successively by each warm area from low temperature warm area to high temperature warm area, carries out gradient heat treatment to precursor, obtains oxidization fiber.In pre-oxidation treatment, the precursor speed of service is 3.0m/min, and the preoxidation time in each warm area is identical, and pre-oxidation total time is 68min.The draft ratio of tow in each warm area is respectively: No. 1 warm area 10 ‰, No. 2 warm areas 0 ‰, No. 3 warm areas-10 ‰, No. 4 warm areas-15 ‰.Oxidization fiber density is (1.35 ~ 1.36) g/cm
3.
Step 3, low-temperature carbonization
The oxidization fiber obtained enters low-temperature carbonization furnace by hauling machine and carries out continuous low temperature charing process.The warm area of described low-temperature carbonization has 6 warm areas, respectively: 400 DEG C, 570 DEG C, 680 DEG C, 740 DEG C, 740 DEG C, 630 DEG C.
In low-temperature carbonization process, with the nitrogen of oxygen content≤1ppm for medium; Low-temperature carbonization drawing-off is 40 ‰, low-temperature carbonization time 96s.
Step 4, high temperature carbonization
Through low-temperature carbonization oxidization fiber by hauling machine enter high temperature carbonization furnace carry out continuous high temperature charing process.Described high temperature carbonization have 4 warm areas, respectively: 780 DEG C, 1000 DEG C, 1200 DEG C, 1450 DEG C.
In high temperature carbonization process, with the nitrogen of oxygen content≤1ppm for medium; High temperature carbonization drawing-off is-40 ‰, high temperature carbonization time 96s.Obtain unsized carbon fiber.
Step 5, starching
Adopt domestic 4# emulsion-type sizing agent, being diluted to mass concentration with pure water is 4%, carries out starching to unsized carbon fiber.The starching time is 23s, sizing agent temperature 30 DEG C.
Step 6, dry
Carbon fiber after starching enters drying tower, adopts conventional method to carry out drying.6 warm areas are set in described drying tower, are respectively 165 DEG C, 165 DEG C, 165 DEG C, 170 DEG C, 170 DEG C and 170 DEG C.Carbon fiber after starching moves to high-temperature region from low-temperature space successively, completes drying.The dry time is 144s, and the carbon fiber rate of sizing is 1.67%.The medium of described drying is air.
By embodiment 3 gained PAN based precursor fiber number 1.146dtex, monofilament power surveys intensity 7.3cN/dtex, modulus is 108.7cN/dtex, fracture elongation is 15.4%, and boiling water shrinkage is 6.23%.The TENSILE STRENGTH of carbon fiber is 4566MPa(CV:2.0%), elastic modelling quantity is 223GPa(CV:1.6%), fracture elongation is 1.86%(CV:3.3%), loop strength is 256.8cN.
Embodiment 4
The present embodiment is a kind of manufacture method of 12K binary polyacrylonitrile-bacarbon carbon fiber.
Step 1, the preparation of precursor:
The preparation of described precursor comprises prepares spinning solution and wet spinning.
With dimethyl sulfoxide (DMSO) (DMSO) for solvent, with acrylonitrile, itaconic acid for polymerization single polymerization monomer, ammonia, as itaconic acid modifier, carries out polymerisation; Polymeric reaction temperature is 60 DEG C, and the reaction time is 26h.Obtain polyacrylonitrile-radical spinning solution.The weight ratio of described acrylonitrile, itaconic acid is 97.5:2.5.The consumption of itaconic acid modifier ammonia is the gauge of 35% according to the molar percentage accounting for carboxyl-content on itaconic acid, is passed in the dimethyl sulphoxide solution of itaconic acid and carries out ammonification after metering.
The same prior art of described wet spinning, comprises and solidifies, washes, hot water drawing-off, to oil and dry, steam drafting and steam shaping, obtain precursor.Technical parameter in wet spinning as shown in Table 1 to Table 3.
Step 2, pre-oxidation
Conventional method is adopted to carry out pre-oxidation treatment to the precursor obtained by pre-oxidation furnace.Described pre-oxidation furnace has two, has each two-layer up and down respectively, and each formation 2 warm areas, two pre-oxidation furnaces totally 4 warm areas, are respectively No. 1 warm area ~ No. 4 warm area.The temperature of No. 1 warm area ~ No. 4 warm area is followed successively by 185 DEG C, 230 DEG C, 255 DEG C and 270 DEG C.Precursor successively by each warm area from low temperature warm area to high temperature warm area, carries out gradient heat treatment to precursor, obtains oxidization fiber.In pre-oxidation treatment, the precursor speed of service is 3.0m/min, and the preoxidation time in each warm area is identical, and pre-oxidation total time is 68min.The draft ratio of tow in each warm area is respectively: No. 1 warm area 0 ‰, No. 2 warm areas 30 ‰, No. 3 warm areas-10 ‰, No. 4 warm areas-20 ‰.Oxidization fiber density is (1.35 ~ 1.36) g/cm
3.
Step 3, low-temperature carbonization
The oxidization fiber obtained enters low-temperature carbonization furnace by hauling machine and carries out continuous low temperature charing process.The warm area of described low-temperature carbonization has 6 warm areas, respectively: 400 DEG C, 570 DEG C, 680 DEG C, 740 DEG C, 740 DEG C, 630 DEG C.
In low-temperature carbonization process, with the nitrogen of oxygen content≤1ppm for medium; Low-temperature carbonization drawing-off is 60 ‰, low-temperature carbonization time 96s.
Step 4, high temperature carbonization
Through low-temperature carbonization oxidization fiber by hauling machine enter high temperature carbonization furnace carry out continuous high temperature charing process.Described high temperature carbonization have 4 warm areas, respectively: 780 DEG C, 1000 DEG C, 1200 DEG C, 1450 DEG C.
In high temperature carbonization process, with the nitrogen of oxygen content≤1ppm for medium; High temperature carbonization drawing-off is-40 ‰, high temperature carbonization time 96s.Obtain unsized carbon fiber.
Step 5, starching
Adopt domestic 4# emulsion-type sizing agent, being diluted to mass concentration with pure water is 4%, carries out starching to unsized carbon fiber.The starching time is 23s, sizing agent temperature 30 DEG C.
Step 6, dry
Carbon fiber after starching enters drying tower, adopts conventional method to carry out drying.6 warm areas are set in described drying tower, are respectively 165 DEG C, 165 DEG C, 165 DEG C, 170 DEG C, 170 DEG C and 170 DEG C.Carbon fiber after starching moves to high-temperature region from low-temperature space successively, completes drying.The dry time is 144s, and the carbon fiber rate of sizing is 1.62%.The medium of described drying is air.
By embodiment 4 gained PAN based precursor fiber number 1.151dtex, monofilament power surveys intensity 6.8cN/dtex, modulus is 114.6cN/dtex, fracture elongation is 15.7%, and boiling water shrinkage is 5.98%.The TENSILE STRENGTH of carbon fiber is 4525MPa(CV:2.5%), elastic modelling quantity is 226GPa(CV:1.4%), fracture elongation is 1.78%(CV:2.9%), loop strength is 277.4cN.
Claims (1)
1. a manufacture method for 12K binary polyacrylonitrile-bacarbon carbon fiber, is characterized in that, detailed process is:
Step 1, the preparation of precursor: the preparation of described precursor comprises prepares spinning solution and wet spinning;
Described spinning solution of preparing is with dimethyl sulfoxide (DMSO) (DMSO) for solvent, and with acrylonitrile, itaconic acid for polymerization single polymerization monomer, ammonia, as itaconic acid modifier, carries out polymerisation; Polymeric reaction temperature is 60 DEG C, and the reaction time is 26h;
Obtain polyacrylonitrile-radical spinning solution; The weight ratio of described acrylonitrile, itaconic acid is 97 ~ 98:3 ~ 2; The consumption of itaconic acid modifier ammonia is the gauge of 15 ~ 35% according to the molar percentage accounting for carboxyl-content on itaconic acid, is passed in the dimethyl sulphoxide solution of itaconic acid and carries out ammonification after metering;
The process of described wet spinning is same as the prior art, comprises and solidifies, washes, hot water drawing-off, to oil and dry, steam drafting and steam shaping, obtain precursor;
The technical parameter of described wet spinning as shown in Table 1 to Table 3;
Table 1
Table 2
Table 3
Step 2, pre-oxidation: described pre-oxidation carries out in No. 1 warm area ~ No. 4 warm area, and the temperature of No. 1 warm area ~ No. 4 warm area is followed successively by 185 DEG C, 230 DEG C, 255 DEG C and 270 DEG C; Precursor successively by each warm area from low temperature warm area to high temperature warm area, carries out gradient heat treatment to precursor, obtains oxidization fiber; In pre-oxidation treatment, the precursor speed of service is 2.5 ~ 3.0m/min, and the preoxidation time in each warm area is identical, and pre-oxidation total time is 68 ~ 82min; The draft ratio of tow in each warm area is respectively: No. 1 warm area 0 ~ 15 ‰, No. 2 warm area-10 ~ 30 ‰, No. 3 warm areas-25 ~-5 ‰, No. 4 warm areas-30 ~-10 ‰;
Step 3, low-temperature carbonization: the oxidization fiber obtained enters low-temperature carbonization furnace by hauling machine and carries out continuous low temperature charing process; The warm area of described low-temperature carbonization has 6 warm areas, respectively: 400 DEG C, 570 DEG C, 680 DEG C, 740 DEG C, 740 DEG C, 630 DEG C;
In low-temperature carbonization process, with the nitrogen of oxygen content≤1ppm for medium; Low-temperature carbonization drawing-off is 0 ~ 60 ‰, low-temperature carbonization time 96 ~ 115s;
Step 4, high temperature carbonization: through low-temperature carbonization oxidization fiber by hauling machine enter high temperature carbonization furnace carry out continuous high temperature charing process; Described high temperature carbonization have 4 warm areas, respectively: 780 DEG C, 1000 DEG C, 1200 DEG C, 1450 DEG C; In high temperature carbonization process, with the nitrogen of oxygen content≤1ppm for medium; High temperature carbonization drawing-off is-40 ‰, high temperature carbonization time 96 ~ 115s; Obtain unsized carbon fiber;
Step 5, starching:
Sizing agent pure water being diluted to mass concentration is 4%, carries out starching to unsized carbon fiber; The starching time is 23 ~ 28s, sizing agent temperature 30 DEG C;
Step 6, dry: the carbon fiber after starching enters drying tower, adopt conventional method to carry out drying; 6 warm areas are set in described drying tower, are respectively 165 DEG C, 165 DEG C, 165 DEG C, 170 DEG C, 170 DEG C and 170 DEG C; Carbon fiber after starching moves to high-temperature region from low-temperature space successively, completes drying; The dry time is 144 ~ 173s, and the carbon fiber rate of sizing is 1.55 ~ 1.67%; The medium of described drying is air.
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| CN105177768A (en) * | 2015-09-23 | 2015-12-23 | 荣成复合材料有限公司 | Polyacrylonitrile-based carbon fiber production device and method |
| CN106637521A (en) * | 2016-12-27 | 2017-05-10 | 长春工业大学 | Preparation method of 48K polyacrylonitrile-based carbon fiber |
| CN111088540B (en) * | 2018-10-23 | 2021-05-28 | 中国石油化工股份有限公司 | Preparation method of high-performance polyacrylonitrile fiber |
| CN112708969B (en) * | 2019-10-24 | 2022-10-11 | 中国石油化工股份有限公司 | Preparation method of polyacrylonitrile pre-oxidized fiber |
| CN112708970B (en) * | 2019-10-24 | 2022-10-11 | 中国石油化工股份有限公司 | Preparation method of polyacrylonitrile pre-oxidized fiber |
| CN111074383B (en) * | 2019-12-26 | 2022-06-07 | 长春工业大学 | A kind of preparation method of pre-oxidized filament connected with large tow strands online |
| CN118272968B (en) * | 2024-05-17 | 2025-02-14 | 长盛(廊坊)科技有限公司 | A method for preparing ultra-high performance carbon fiber |
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