CN103184591A - 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 make the field, specifically is the preparation method of the high-performance polyacrylonitrile-based carbon fiber of a kind of 12K.
Background technology
Carbon fiber has series of advantages such as high specific strength, high ratio modulus, thermal coefficient of expansion be little, is widely used in fields such as Aero-Space, industrial energy and Leisure Sport.Polyacrylonitrile (PAN) base carbon fibre dominate on carbon fiber market, the structure of PAN and performance are directly determining precursor and the final quality of carbon fiber.The characteristics of homopolymerization PAN are that the structure of generation macromolecular chain is more regular and degree of crystallinity is higher, but because the molecule inner injection of homopolymerization PAN can be big, make that the flexibility of fiber is 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, give its toughness preferably.As the polyacrylonitrile fibril of preparation 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; Provide the molecular level passage of oxygen to fiber core diffusion and infiltration, the pre-oxygen silk of preparation homogeneous.
When selecting comonomer, often a kind of comonomer can not satisfy 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 has proposed a kind of preparation method who adopts monomethyl itaconate ammonium thing 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 has proposed a kind of β of employing-itaconic acid acid amides prepares polyacryl-nitrile spinning fluid as comonomer preparation method, these two patent introductions all be the preparation method of the binary copolymerization prescription that adopts, but need before reaction, synthesize the second monomer monomethyl itaconate ammonium thing or β-itaconic acid acid amides earlier, operating process is loaded down with trivial details, simultaneously, also just introduced the preparation method of spinning solution in these two patents, and to the adding owing to second comonomer, caused pre-oxidation, the matching of the technology of charing is regulated and is not mentioned; Be in the patent of CN02130023.2 and CN02130022.4 in the patent No., Shanxi Coal-Chemical Inst., Chinese Academy of Sciences has proposed a kind of with acrylonitrile, dimethyl formamide, distilled water, azodiisobutyronitrile and chain-transferring agent are after the uniform temperature homopolymerization, feed the ammonia cessation reaction again, and be adjusted to certain pH value, make spinning solution, what this method prepared is the polyacryl-nitrile spinning fluid of homopolymerization, ammonia is as the cessation reaction agent, technology is comparatively complicated and be not easy control, the spinnability of the homo-polypropylene nitrile spinning solution for preparing of this method is relatively poor simultaneously, in pre-oxidation, the charing stage is also caused concentrated heat release easily, especially in the carbon fiber preparation process of big tow, easier generation is unfavorable for preparing high performance carbon fiber owing to the fiber that accumulation of heat causes is blown.
Summary of the invention
Comparatively complicated and to be not easy the spinnability of the homo-polypropylene nitrile spinning solution controlling, obtain relatively poor for overcoming the technology that exists in the prior art, and in the carbon fiber preparation process of big tow, the deficiency that the fiber that easier generation causes owing to accumulation of heat is blown the present invention proposes a kind of manufacture method of 12K binary polyacrylonitrile-based carbon fibre.
Detailed process of the present invention is:
Step 1, the preparation of precursor: the preparation of described precursor comprises preparation spinning solution and wet spinning.
Described preparation spinning solution is to be solvent with dimethyl sulfoxide (DMSO) (DMSO), is polymerization single polymerization monomer with acrylonitrile, itaconic acid, and ammonia carries out polymerisation as itaconic acid modifier; Polymeric reaction temperature is 60 ℃, and the reaction time is 26h.Obtain the polyacrylonitrile-radical spinning solution.The weight ratio of described acrylonitrile, itaconic acid is 98:2.The consumption of itaconic acid modifier ammonia is 15% amount meter according to the molar percentage that accounts for carboxyl-content on the itaconic acid, is passed into after the metering in the dimethyl sulphoxide solution of itaconic acid to carry out ammonification.
The process of described wet spinning is same as the prior art, comprises solidifying, washing, hot water drawing-off, oiling and dry, steam drafting and steam shaping, obtains precursor.
Step 2, pre-oxidation: described pre-oxidation is to carry 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 ℃, 230 ℃, 255 ℃ and 270 ℃.Precursor successively by each warm area, carries out gradient heat treatment to precursor from the low temperature warm area to the high temperature warm area, obtains pre-oxygen silk.In the 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 drawing-off multiplying power of tow in each warm area is respectively: No. 1 warm area 5 ‰, No. 2 warm area-10 ‰, No. 3 warm area-25 ‰, No. 4 warm areas-30 ‰.
Step 3, low-temperature carbonization: the pre-oxygen silk that obtains enters the low-temperature carbonization stove by hauling machine and carries out continuous low temperature charing processing.The warm area of described low-temperature carbonization has 6 warm areas, is respectively: 400 ℃, 570 ℃, 680 ℃, 740 ℃, 740 ℃, 630 ℃.
During low-temperature carbonization is handled, be medium with the nitrogen of oxygen content≤1ppm; The low-temperature carbonization drawing-off is 0 ‰, low-temperature carbonization time 115s.
Step 4, high temperature carbonization: the pre-oxygen silk of process low-temperature carbonization enters the high temperature carbonization stove by hauling machine and carries out continuous high temperature charing processing.Described high temperature carbonization 4 warm areas are arranged, be respectively: 780 ℃, 1000 ℃, 1200 ℃, 1450 ℃.
During high temperature carbonization is handled, be medium with the nitrogen of oxygen content≤1ppm; The high temperature carbonization drawing-off is-40 ‰, high temperature carbonization time 115s.Obtain unsized carbon fiber.
Step 5, starching:
It is 4% that sizing agent is diluted to mass concentration with pure water, and unsized carbon fiber is carried out starching.The starching time is 28s, 30 ℃ of sizing agent temperature.
Step 6, drying: the carbon fiber after the starching enters drying tower, adopts conventional method to carry out drying.6 warm areas are set in the described drying tower, are respectively 165 ℃, 165 ℃, 165 ℃, 170 ℃, 170 ℃ and 170 ℃.Carbon fiber after the starching moves to the high-temperature region from low-temperature space successively, finishes 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 is shown in table 1～table 3.
Table 1
Table 2
Table 3
| Title | Spinning machine | 1# draws a machine | 2# draws a machine | The 1# rinsing machine | The 2# rinsing machine |
| Frequency (Hz) | 32.00 | 33.63 | 35.67 | 34.27 | 29.88 |
| Title | The 3# rinsing machine | The 4# rinsing machine | The 5# rinsing machine | The 6# rinsing machine | The 7# rinsing machine |
| Frequency (Hz) | 29.79 | 29.98 | 29.74 | 29.84 | 29.78 |
| Title | The 8# rinsing machine | The 9# rinsing machine | The 10# rinsing machine | The 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 | The 1# oiling machine | The 1# drying machine | The 2# oiling machine |
| Frequency (Hz) | 28.87 | 42.69 | 41.89 | 38.23 | 39.67 |
| Title | 2# drying machine A | 2# drying machine B | The 3# oiling machine | The hot-rolling machine | The steam drafting machine |
| Frequency (Hz) | 41.35 | 40.86 | 37.73 | 38.04 | 31.26 |
| Title | The steam shaping machine | Receive the silk machine | ? | ? | ? |
| Frequency (Hz) | 29.45 | 32.76 | ? | ? | ? |
The present invention adopts the ammoniation modified polymerization formula of binary, the polyacrylonitrile-based carbon fibre of preparation 12K, the carbon fibre precursor of this method preparation has technology matching preferably in pre-oxidation, charing stage, the carbon fiber mechanical property of final preparation is higher, and machinability is better.
The preparation method of the present invention and traditional polyacrylonitrile carbon fiber relatively has following characteristics:
The binary copolymerization prescription, technological operation is simple, easy control of reaction conditions.The polyacryl-nitrile spinning fluid of preparation has hydrophily and spinnability preferably.Alleviate precursor in the concentrated heat release in pre-oxidation stage, pre-oxidation, charring process are better, are applicable to the through engineering approaches preparation of large-tow carbon fiber.
For verifying effect of the present invention, the present invention has implemented the preparation of the 12K carbon fiber under the binary ammonification polymerization formula system at the engineering line, compares with mechanical property and the coefficient of variation of the 12K carbon fiber of binary polymerization formulation, and final result is as shown in table 4:
Table 4
The specific embodiment
Be described in further details below by the process of the present invention of embodiment.
Embodiment 1
Present embodiment is a kind of manufacture method of 12K binary polyacrylonitrile-based carbon fibre.
Step 1, the preparation of precursor:
The preparation of described precursor comprises preparation spinning solution and wet spinning.
Being solvent with dimethyl sulfoxide (DMSO) (DMSO), is polymerization single polymerization monomer with acrylonitrile, itaconic acid, and ammonia carries out polymerisation as itaconic acid modifier; Polymeric reaction temperature is 60 ℃, and the reaction time is 26h.Obtain the polyacrylonitrile-radical spinning solution.The weight ratio of described acrylonitrile, itaconic acid is 98:2.The consumption of itaconic acid modifier ammonia is 15% amount meter according to the molar percentage that accounts for carboxyl-content on the itaconic acid, is passed into after the metering in the dimethyl sulphoxide solution of itaconic acid to carry out ammonification.
The same prior art of described wet spinning comprises and solidifies, washing, hot water drawing-off, oils and dry, steam drafting and steam shaping, obtains precursor.Technical parameter in the wet spinning is shown in table 1～table 3.
Table 1
Table 2
Table 3
| Title | Spinning machine | 1# draws a machine | 2# draws a machine | The 1# rinsing machine | The 2# rinsing machine |
| Frequency (Hz) | 32.00 | 33.63 | 35.67 | 34.27 | 29.88 |
| Title | The 3# rinsing machine | The 4# rinsing machine | The 5# rinsing machine | The 6# rinsing machine | The 7# rinsing machine |
| Frequency (Hz) | 29.79 | 29.98 | 29.74 | 29.84 | 29.78 |
| Title | The 8# rinsing machine | The 9# rinsing machine | The 10# rinsing machine | The 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 | The 1# oiling machine | The 1# drying machine | The 2# oiling machine |
| Frequency (Hz) | 28.87 | 42.69 | 41.89 | 38.23 | 39.67 |
| Title | 2# drying machine A | 2# drying machine B | The 3# oiling machine | The hot-rolling machine | The steam drafting machine |
| Frequency (Hz) | 41.35 | 40.86 | 37.73 | 38.04 | 31.26 |
| Title | The steam shaping machine | Receive the silk machine | ? | ? | ? |
| Frequency (Hz) | 29.45 | 32.76 | ? | ? | ? |
Step 2, pre-oxidation
Adopt conventional method that the precursor that obtains is carried out pre-oxidation treatment by pre-oxidation furnace.Described pre-oxidation furnace has two, has each two-layer up and down respectively, and each forms 2 warm areas, and two pre-oxidation furnaces are totally 4 warm areas, are respectively warm area～No. 4 warm area No. 1.The temperature of No. 1 warm area～No. 4 warm area is followed successively by 185 ℃, 230 ℃, 255 ℃ and 270 ℃.Precursor successively by each warm area, carries out gradient heat treatment to precursor from the low temperature warm area to the high temperature warm area, obtains pre-oxygen silk.In the 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 drawing-off multiplying power of tow in each warm area is respectively: No. 1 warm area 5 ‰, No. 2 warm area-10 ‰, No. 3 warm area-25 ‰, No. 4 warm areas-30 ‰.Pre-oxygen silk density is (1.35～1.36) g/cm
3
Step 3, low-temperature carbonization
The pre-oxygen silk that obtains enters the low-temperature carbonization stove by hauling machine and carries out continuous low temperature charing processing.The warm area of described low-temperature carbonization has 6 warm areas, is respectively: 400 ℃, 570 ℃, 680 ℃, 740 ℃, 740 ℃, 630 ℃.
During low-temperature carbonization is handled, be medium with the nitrogen of oxygen content≤1ppm; The low-temperature carbonization drawing-off is 0 ‰, low-temperature carbonization time 115s.
Step 4, high temperature carbonization
The pre-oxygen silk of process low-temperature carbonization enters the high temperature carbonization stove by hauling machine and carries out continuous high temperature charing processing.Described high temperature carbonization 4 warm areas are arranged, be respectively: 780 ℃, 1000 ℃, 1200 ℃, 1450 ℃.
During high temperature carbonization is handled, be medium with the nitrogen of oxygen content≤1ppm; The high temperature carbonization drawing-off is-40 ‰, high temperature carbonization time 115s.Obtain unsized carbon fiber.
Step 5, starching
Adopt homemade 4# emulsion-type sizing agent, being diluted to mass concentration with pure water is 4%, and unsized carbon fiber is carried out starching.The starching time is 28s, 30 ℃ of sizing agent temperature.
Step 6, drying
Carbon fiber after the starching enters drying tower, adopts conventional method to carry out drying.6 warm areas are set in the described drying tower, are respectively 165 ℃, 165 ℃, 165 ℃, 170 ℃, 170 ℃ and 170 ℃.Carbon fiber after the starching moves to the high-temperature region from low-temperature space successively, finishes 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 is surveyed intensity 7.1cN/dtex, modulus is that 110.5cN/dtex, fracture elongation are 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
Present embodiment is a kind of manufacture method of 12K binary polyacrylonitrile-based carbon fibre.
Step 1, the preparation of precursor:
The preparation of described precursor comprises preparation spinning solution and wet spinning.
Being solvent with dimethyl sulfoxide (DMSO) (DMSO), is polymerization single polymerization monomer with acrylonitrile, itaconic acid, and ammonia carries out polymerisation as itaconic acid modifier; Polymeric reaction temperature is 60 ℃, and the reaction time is 26h.Obtain the polyacrylonitrile-radical spinning solution.The weight ratio of described acrylonitrile, itaconic acid is 97:3.The consumption of itaconic acid modifier ammonia is 25% amount meter according to the molar percentage that accounts for carboxyl-content on the itaconic acid, is passed into after the metering in the dimethyl sulphoxide solution of itaconic acid to carry out ammonification.
The same prior art of described wet spinning comprises and solidifies, washing, hot water drawing-off, oils and dry, steam drafting and steam shaping, obtains precursor.Technical parameter in the wet spinning is shown in table 1～table 3.
Step 2, pre-oxidation
Adopt conventional method that the precursor that obtains is carried out pre-oxidation treatment by pre-oxidation furnace.Described pre-oxidation furnace has two, has each two-layer up and down respectively, and each forms 2 warm areas, and two pre-oxidation furnaces are totally 4 warm areas, are respectively warm area～No. 4 warm area No. 1.The temperature of No. 1 warm area～No. 4 warm area is followed successively by 185 ℃, 230 ℃, 255 ℃ and 270 ℃.Precursor successively by each warm area, carries out gradient heat treatment to precursor from the low temperature warm area to the high temperature warm area, obtains pre-oxygen silk.In the 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 drawing-off multiplying power of tow in each warm area is respectively: No. 1 warm area 15 ‰, No. 2 warm areas 20 ‰, No. 3 warm area-5 ‰, No. 4 warm areas-10 ‰.Pre-oxygen silk density is (1.35～1.36) g/cm
3
Step 3, low-temperature carbonization
The pre-oxygen silk that obtains enters the low-temperature carbonization stove by hauling machine and carries out continuous low temperature charing processing.The warm area of described low-temperature carbonization has 6 warm areas, is respectively: 400 ℃, 570 ℃, 680 ℃, 740 ℃, 740 ℃, 630 ℃.
During low-temperature carbonization is handled, be medium with the nitrogen of oxygen content≤1ppm; The low-temperature carbonization drawing-off is 0 ‰, low-temperature carbonization time 102s.
Step 4, high temperature carbonization
The pre-oxygen silk of process low-temperature carbonization enters the high temperature carbonization stove by hauling machine and carries out continuous high temperature charing processing.Described high temperature carbonization 4 warm areas are arranged, be respectively: 780 ℃, 1000 ℃, 1200 ℃, 1450 ℃.
During high temperature carbonization is handled, be medium with the nitrogen of oxygen content≤1ppm; The high temperature carbonization drawing-off is-40 ‰, high temperature carbonization time 102s.Obtain unsized carbon fiber.
Step 5, starching
Adopt homemade 4# emulsion-type sizing agent, being diluted to mass concentration with pure water is 4%, and unsized carbon fiber is carried out starching.The starching time is 25s, 30 ℃ of sizing agent temperature.
Step 6, drying
Carbon fiber after the starching enters drying tower, adopts conventional method to carry out drying.6 warm areas are set in the described drying tower, are respectively 165 ℃, 165 ℃, 165 ℃, 170 ℃, 170 ℃ and 170 ℃.Carbon fiber after the starching moves to the high-temperature region from low-temperature space successively, finishes 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 is surveyed intensity 6.9cN/dtex, modulus is that 112.8cN/dtex, fracture elongation are 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
Present embodiment is a kind of manufacture method of 12K binary polyacrylonitrile-based carbon fibre.
Step 1, the preparation of precursor:
The preparation of described precursor comprises preparation spinning solution and wet spinning.
Being solvent with dimethyl sulfoxide (DMSO) (DMSO), is polymerization single polymerization monomer with acrylonitrile, itaconic acid, and ammonia carries out polymerisation as itaconic acid modifier; Polymeric reaction temperature is 60 ℃, and the reaction time is 26h.Obtain the 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 25% amount meter according to the molar percentage that accounts for carboxyl-content on the itaconic acid, is passed into after the metering in the dimethyl sulphoxide solution of itaconic acid to carry out ammonification.
The same prior art of described wet spinning comprises and solidifies, washing, hot water drawing-off, oils and dry, steam drafting and steam shaping, obtains precursor.Technical parameter in the wet spinning is shown in table 1～table 3.
Step 2, pre-oxidation
Adopt conventional method that the precursor that obtains is carried out pre-oxidation treatment by pre-oxidation furnace.Described pre-oxidation furnace has two, has each two-layer up and down respectively, and each forms 2 warm areas, and two pre-oxidation furnaces are totally 4 warm areas, are respectively warm area～No. 4 warm area No. 1.The temperature of No. 1 warm area～No. 4 warm area is followed successively by 185 ℃, 230 ℃, 255 ℃ and 270 ℃.Precursor successively by each warm area, carries out gradient heat treatment to precursor from the low temperature warm area to the high temperature warm area, obtains pre-oxygen silk.In the 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 drawing-off multiplying power of tow in each warm area is respectively: No. 1 warm area 10 ‰, No. 2 warm areas 0 ‰, No. 3 warm area-10 ‰, No. 4 warm areas-15 ‰.Pre-oxygen silk density is (1.35～1.36) g/cm
3
Step 3, low-temperature carbonization
The pre-oxygen silk that obtains enters the low-temperature carbonization stove by hauling machine and carries out continuous low temperature charing processing.The warm area of described low-temperature carbonization has 6 warm areas, is respectively: 400 ℃, 570 ℃, 680 ℃, 740 ℃, 740 ℃, 630 ℃.
During low-temperature carbonization is handled, be medium with the nitrogen of oxygen content≤1ppm; The low-temperature carbonization drawing-off is 40 ‰, low-temperature carbonization time 96s.
Step 4, high temperature carbonization
The pre-oxygen silk of process low-temperature carbonization enters the high temperature carbonization stove by hauling machine and carries out continuous high temperature charing processing.Described high temperature carbonization 4 warm areas are arranged, be respectively: 780 ℃, 1000 ℃, 1200 ℃, 1450 ℃.
During high temperature carbonization is handled, be medium with the nitrogen of oxygen content≤1ppm; The high temperature carbonization drawing-off is-40 ‰, high temperature carbonization time 96s.Obtain unsized carbon fiber.
Step 5, starching
Adopt homemade 4# emulsion-type sizing agent, being diluted to mass concentration with pure water is 4%, and unsized carbon fiber is carried out starching.The starching time is 23s, 30 ℃ of sizing agent temperature.
Step 6, drying
Carbon fiber after the starching enters drying tower, adopts conventional method to carry out drying.6 warm areas are set in the described drying tower, are respectively 165 ℃, 165 ℃, 165 ℃, 170 ℃, 170 ℃ and 170 ℃.Carbon fiber after the starching moves to the high-temperature region from low-temperature space successively, finishes 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 is surveyed intensity 7.3cN/dtex, modulus is that 108.7cN/dtex, fracture elongation are 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
Present embodiment is a kind of manufacture method of 12K binary polyacrylonitrile-based carbon fibre.
Step 1, the preparation of precursor:
The preparation of described precursor comprises preparation spinning solution and wet spinning.
Being solvent with dimethyl sulfoxide (DMSO) (DMSO), is polymerization single polymerization monomer with acrylonitrile, itaconic acid, and ammonia carries out polymerisation as itaconic acid modifier; Polymeric reaction temperature is 60 ℃, and the reaction time is 26h.Obtain the 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 35% amount meter according to the molar percentage that accounts for carboxyl-content on the itaconic acid, is passed into after the metering in the dimethyl sulphoxide solution of itaconic acid to carry out ammonification.
The same prior art of described wet spinning comprises and solidifies, washing, hot water drawing-off, oils and dry, steam drafting and steam shaping, obtains precursor.Technical parameter in the wet spinning is shown in table 1～table 3.
Step 2, pre-oxidation
Adopt conventional method that the precursor that obtains is carried out pre-oxidation treatment by pre-oxidation furnace.Described pre-oxidation furnace has two, has each two-layer up and down respectively, and each forms 2 warm areas, and two pre-oxidation furnaces are totally 4 warm areas, are respectively warm area～No. 4 warm area No. 1.The temperature of No. 1 warm area～No. 4 warm area is followed successively by 185 ℃, 230 ℃, 255 ℃ and 270 ℃.Precursor successively by each warm area, carries out gradient heat treatment to precursor from the low temperature warm area to the high temperature warm area, obtains pre-oxygen silk.In the 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 drawing-off multiplying power of tow in each warm area is respectively: No. 1 warm area 0 ‰, No. 2 warm areas 30 ‰, No. 3 warm area-10 ‰, No. 4 warm areas-20 ‰.Pre-oxygen silk density is (1.35～1.36) g/cm
3
Step 3, low-temperature carbonization
The pre-oxygen silk that obtains enters the low-temperature carbonization stove by hauling machine and carries out continuous low temperature charing processing.The warm area of described low-temperature carbonization has 6 warm areas, is respectively: 400 ℃, 570 ℃, 680 ℃, 740 ℃, 740 ℃, 630 ℃.
During low-temperature carbonization is handled, be medium with the nitrogen of oxygen content≤1ppm; The low-temperature carbonization drawing-off is 60 ‰, low-temperature carbonization time 96s.
Step 4, high temperature carbonization
The pre-oxygen silk of process low-temperature carbonization enters the high temperature carbonization stove by hauling machine and carries out continuous high temperature charing processing.Described high temperature carbonization 4 warm areas are arranged, be respectively: 780 ℃, 1000 ℃, 1200 ℃, 1450 ℃.
During high temperature carbonization is handled, be medium with the nitrogen of oxygen content≤1ppm; The high temperature carbonization drawing-off is-40 ‰, high temperature carbonization time 96s.Obtain unsized carbon fiber.
Step 5, starching
Adopt homemade 4# emulsion-type sizing agent, being diluted to mass concentration with pure water is 4%, and unsized carbon fiber is carried out starching.The starching time is 23s, 30 ℃ of sizing agent temperature.
Step 6, drying
Carbon fiber after the starching enters drying tower, adopts conventional method to carry out drying.6 warm areas are set in the described drying tower, are respectively 165 ℃, 165 ℃, 165 ℃, 170 ℃, 170 ℃ and 170 ℃.Carbon fiber after the starching moves to the high-temperature region from low-temperature space successively, finishes 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 is surveyed intensity 6.8cN/dtex, modulus is that 114.6cN/dtex, fracture elongation are 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 (2)
1. the manufacture method of a 12K binary polyacrylonitrile-based carbon fibre is characterized in that detailed process is:
Step 1, the preparation of precursor: the preparation of described precursor comprises preparation spinning solution and wet spinning;
Described preparation spinning solution is to be solvent with dimethyl sulfoxide (DMSO) (DMSO), is polymerization single polymerization monomer with acrylonitrile, itaconic acid, and ammonia carries out polymerisation as itaconic acid modifier; Polymeric reaction temperature is 60 ℃, and the reaction time is 26h; Obtain the 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 15～35% amount meter according to the molar percentage that accounts for carboxyl-content on the itaconic acid, is passed into after the metering in the dimethyl sulphoxide solution of itaconic acid to carry out ammonification;
The process of described wet spinning is same as the prior art, comprises solidifying, washing, hot water drawing-off, oiling and dry, steam drafting and steam shaping, obtains precursor;
Step 2, pre-oxidation: described pre-oxidation is to carry 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 ℃, 230 ℃, 255 ℃ and 270 ℃; Precursor successively by each warm area, carries out gradient heat treatment to precursor from the low temperature warm area to the high temperature warm area, obtains pre-oxygen silk; In the 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 drawing-off multiplying power of tow in each warm area is respectively: No. 1 warm area 0～15 ‰, No. 2 warm area-10～30 ‰, No. 3 warm area-25～-5 ‰, No. 4 warm area-30～-10 ‰;
Step 3, low-temperature carbonization: the pre-oxygen silk that obtains enters the low-temperature carbonization stove by hauling machine and carries out continuous low temperature charing processing; The warm area of described low-temperature carbonization has 6 warm areas, is respectively: 400 ℃, 570 ℃, 680 ℃, 740 ℃, 740 ℃, 630 ℃;
During low-temperature carbonization is handled, be medium with the nitrogen of oxygen content≤1ppm; The low-temperature carbonization drawing-off is 0～60 ‰, low-temperature carbonization time 96～115s;
Step 4, high temperature carbonization: the pre-oxygen silk of process low-temperature carbonization enters the high temperature carbonization stove by hauling machine and carries out continuous high temperature charing processing; Described high temperature carbonization 4 warm areas are arranged, be respectively: 780 ℃, 1000 ℃, 1200 ℃, 1450 ℃; During high temperature carbonization is handled, be medium with the nitrogen of oxygen content≤1ppm; The high temperature carbonization drawing-off is-40 ‰, high temperature carbonization time 96～115s; Obtain unsized carbon fiber;
Step 5, starching:
It is 4% that sizing agent is diluted to mass concentration with pure water, and unsized carbon fiber is carried out starching; The starching time is 23～28s, 30 ℃ of sizing agent temperature;
Step 6, drying: the carbon fiber after the starching enters drying tower, adopts conventional method to carry out drying; 6 warm areas are set in the described drying tower, are respectively 165 ℃, 165 ℃, 165 ℃, 170 ℃, 170 ℃ and 170 ℃; Carbon fiber after the starching moves to the high-temperature region from low-temperature space successively, finishes 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.
2. a kind of manufacture method of 12K binary polyacrylonitrile-based carbon fibre according to claim 1 is characterized in that the technical parameter of described wet spinning is shown in table 1～table 3;
Table 1
Table 2
Table 3
。
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| CN111074383A (en) * | 2019-12-26 | 2020-04-28 | 长春工业大学 | Preparation method of pre-oxidized fiber for online connection of large tow precursor |
| CN111088540A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Preparation method of high-performance polyacrylonitrile fiber |
| CN112708969A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Preparation method of polyacrylonitrile pre-oxidized fiber |
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| CN111074383A (en) * | 2019-12-26 | 2020-04-28 | 长春工业大学 | Preparation method of pre-oxidized fiber for online connection of large tow precursor |
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