CN114959951B - Preparation method of polyacrylonitrile-based pre-oxidized fiber - Google Patents
Preparation method of polyacrylonitrile-based pre-oxidized fiber Download PDFInfo
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- 239000000835 fiber Substances 0.000 title claims abstract description 60
- 229920002239 polyacrylonitrile Polymers 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 229920002545 silicone oil Polymers 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 28
- 230000001590 oxidative effect Effects 0.000 claims abstract description 10
- 238000004140 cleaning Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 19
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 9
- 230000010355 oscillation Effects 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000012459 cleaning agent Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 4
- 238000002955 isolation Methods 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 238000007598 dipping method Methods 0.000 abstract 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000007254 oxidation reaction Methods 0.000 description 13
- 230000003647 oxidation Effects 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229920000049 Carbon (fiber) Polymers 0.000 description 4
- 239000004917 carbon fiber Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000007363 ring formation reaction Methods 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 2
- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000007243 oxidative cyclization reaction Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Description
技术领域Technical field
本发明涉及一种聚丙烯腈基预氧化纤维的制备方法。The invention relates to a preparation method of polyacrylonitrile-based pre-oxidized fiber.
背景技术Background technique
聚丙烯腈原丝结构中的含有的大量氰基是极性极强的官能团，彼此之间存在着较强的作用力，导致了原丝的熔点达到了335℃，并且因为聚丙烯腈分子是热熔型高分子，反应温度达到335℃之后分子链就会发生熔融，无法保持纤维形态，最终无法制备相应的碳纤维。The large number of cyano groups contained in the polyacrylonitrile protofilament structure are extremely polar functional groups, and there is a strong interaction between them, causing the melting point of the protofilament to reach 335°C, and because the polyacrylonitrile molecule is For hot-melt polymers, the molecular chains will melt after the reaction temperature reaches 335°C, and the fiber shape cannot be maintained, and ultimately the corresponding carbon fiber cannot be prepared.
因此，要得到保持纤维形态的碳纤维，需要先将原丝进行热氧稳定化处理，增强聚丙烯腈原丝的分子结构，使其熔融性的线性分子链变成耐热稳定的梯形结构。在预氧化过程中，聚丙烯腈大分子链发生了较为复杂的物理和化学反应，线性聚丙烯腈分子发生内环化和分子间交联等。其中PAN线性分子链上含有的不饱和氰基(-C≡N)基团之间的加成环化反应是预氧化过程中的主反应，在环化反应过程中生成亚胺键(-C＝N-)，通过氢化反应分子链之间生成具有共轭的耐热梯形结构，又通过与空气气氛中的氧气发生氧化反应生成羟基，羰基等基团，增强了聚丙烯腈分子链结构的稳定性，确保了之后反应的顺利进行。Therefore, in order to obtain carbon fiber that maintains the fiber shape, the raw filaments need to be thermally oxidized and stabilized to enhance the molecular structure of the polyacrylonitrile raw filaments and turn the molten linear molecular chains into a heat-resistant and stable ladder structure. During the pre-oxidation process, the polyacrylonitrile macromolecular chain undergoes relatively complex physical and chemical reactions, and linear polyacrylonitrile molecules undergo internal cyclization and intermolecular cross-linking. Among them, the addition cyclization reaction between the unsaturated cyano (-C≡N) groups contained on the PAN linear molecular chain is the main reaction in the pre-oxidation process. During the cyclization reaction, an imine bond (-C =N-), through the hydrogenation reaction between the molecular chains, a conjugated heat-resistant ladder structure is formed, and through the oxidation reaction with oxygen in the air atmosphere, hydroxyl, carbonyl and other groups are generated, which enhances the stability of the polyacrylonitrile molecular chain structure. Stability ensures the smooth progress of subsequent reactions.
聚丙烯腈纤维传统预氧化过程通常是在高温空气气氛中进行的，在不同温度条件下经过调整反应时间、温度以及牵伸，控制原丝的氧化环化反应程度。只有在所有反应条件均适宜的情况下，才可以确保原丝的预氧化顺利完成。目前广泛应用的稳定预氧化过程需要4～6个预氧化温区，预氧化温度在210～280℃，预氧化时间在60～80min，占到了碳纤维总生产时间的90％左右。显然，长时间预氧化成为了影响预氧丝和最终碳纤维产量的主要因素。因此，在保证质量的前提下，如何有效提升氧气向纤维内部的渗透，减轻纤维的皮芯结构，降低或者缩短预氧化时间成为提高产量、大幅降低预氧化纤维生产成本的关键。The traditional pre-oxidation process of polyacrylonitrile fiber is usually carried out in a high-temperature air atmosphere. The reaction time, temperature and draft are adjusted under different temperature conditions to control the degree of oxidative cyclization reaction of the raw filaments. Only when all reaction conditions are suitable can the pre-oxidation of the precursor be ensured to be successfully completed. The currently widely used stable pre-oxidation process requires 4 to 6 pre-oxidation temperature zones. The pre-oxidation temperature is 210-280°C and the pre-oxidation time is 60-80 minutes, accounting for about 90% of the total carbon fiber production time. Obviously, long-term pre-oxidation has become the main factor affecting the yield of pre-oxidized yarn and final carbon fiber. Therefore, on the premise of ensuring quality, how to effectively increase the penetration of oxygen into the fiber, reduce the sheath-core structure of the fiber, and reduce or shorten the pre-oxidation time has become the key to increasing output and significantly reducing the production cost of pre-oxidized fiber.
本研究通过将原丝在高温硅油中预处理，大幅提升其分子内环化程度，减少后续反应热的释放，反应产生的焦油等油溶性小分子可以在反应过程中迅速溶解于高温硅油中，避免在丝束上聚集，污染丝束；之后进行过氧化氢或高锰酸盐溶液等强氧化剂浸渍处理，使聚丙烯腈纤维溶胀填充强氧化性溶液，在后续高温硅油中处理时，内部残留溶液分解出氧气直接与内层分子链反应产生耐热梯形结构，同时反应热也更容易通过液相硅油扩散出去，避免纤维聚热，最终制备出聚丙烯腈预氧化纤维。本研究中所述制备流程可以大幅缩短预氧化时间至15min以内，大幅度降低预氧化纤维的生产加工成本。In this study, by pretreating the raw silk in high-temperature silicone oil, the degree of intramolecular cyclization is greatly improved, and the release of subsequent reaction heat is reduced. The oil-soluble small molecules such as tar produced by the reaction can be quickly dissolved in the high-temperature silicone oil during the reaction process. Avoid gathering on the tow and contaminating the tow; then perform an impregnation treatment with strong oxidants such as hydrogen peroxide or permanganate solution to make the polyacrylonitrile fiber swell and fill with the strong oxidizing solution. When processed in subsequent high-temperature silicone oil, internal residues The oxygen decomposed from the solution directly reacts with the inner molecular chain to produce a heat-resistant ladder structure. At the same time, the reaction heat is more easily diffused through the liquid silicone oil to avoid heat accumulation in the fiber, and finally the polyacrylonitrile pre-oxidized fiber is prepared. The preparation process described in this study can significantly shorten the pre-oxidation time to less than 15 minutes, significantly reducing the production and processing costs of pre-oxidized fibers.
发明内容Contents of the invention
本发明针对目前制备聚丙烯腈基预氧化纤维的方法工艺复杂，设备要求高，能耗大等问题，提供一种新型高效节能的制备方法。The present invention provides a new high-efficiency and energy-saving preparation method in view of the problems that the current method for preparing polyacrylonitrile-based pre-oxidized fibers has complicated processes, high equipment requirements, and high energy consumption.
本发明通过以下技术手段实现解决上述技术问题的：The present invention solves the above technical problems through the following technical means:
(1)将聚丙烯腈原丝丝束在高温硅油中隔绝空气超声预处理；(1) Pre-treatment of polyacrylonitrile raw filament bundles in high-temperature silicone oil with air isolation and ultrasonic treatment;
(2)将步骤(1)所得丝束通过超声清洗槽，去除纤维表面硅油；(2) Pass the tow obtained in step (1) through an ultrasonic cleaning tank to remove silicone oil on the fiber surface;
(3)将步骤(2)所得丝束在强氧化性浸渍液中超声浸渍处理；(3) Ultrasonically impregnate the tow obtained in step (2) in a strong oxidizing impregnation liquid;
(4)将步骤(3)所得丝束在高温硅油中热处理；(4) Heat-treat the tow obtained in step (3) in high-temperature silicone oil;
(5)将步骤(4)所得丝束通过超声清洗槽，去除纤维表面硅油，制备出聚丙烯腈基预氧化纤维。(5) Pass the tow obtained in step (4) through an ultrasonic cleaning tank to remove silicone oil on the fiber surface to prepare polyacrylonitrile-based pre-oxidized fiber.
优选地，所述的步骤(1)中的高温硅油处理温度为230～280℃，高温硅油处理时间为0.5～5min，牵伸比为0～+20％。Preferably, the high-temperature silicone oil treatment temperature in step (1) is 230-280°C, the high-temperature silicone oil treatment time is 0.5-5 minutes, and the draft ratio is 0-+20%.
优选地，所述的步骤(1)中的高温硅油处理在超声振荡环境中进行。Preferably, the high-temperature silicone oil treatment in step (1) is performed in an ultrasonic oscillation environment.
优选地，所述的步骤(2)中的清洗剂为可溶解硅油的有机溶剂。Preferably, the cleaning agent in step (2) is an organic solvent that can dissolve silicone oil.
优选地，所述的步骤(2)中的清洗处理在超声振荡环境中进行。Preferably, the cleaning process in step (2) is performed in an ultrasonic oscillation environment.
优选地，所述的步骤(3)中的浸渍液为过氧化氢水溶液或高锰酸盐水溶液，浓度为0～40％，浸渍时间为0.5～3min。Preferably, the impregnation liquid in step (3) is a hydrogen peroxide aqueous solution or a permanganate aqueous solution, with a concentration of 0 to 40%, and an impregnation time of 0.5 to 3 minutes.
优选地，所述的步骤(3)中的强氧化性浸渍液处理在超声振荡环境中进行。Preferably, the strongly oxidizing immersion liquid treatment in step (3) is performed in an ultrasonic oscillation environment.
优选地，所述的步骤(4)中的高温硅油处理温度为240～300℃，高温硅油处理时间为3～10min，牵伸比为-10％～+10％。Preferably, the high-temperature silicone oil treatment temperature in step (4) is 240 to 300°C, the high-temperature silicone oil treatment time is 3 to 10 minutes, and the draft ratio is -10% to +10%.
优选地，所述的步骤(5)中的清洗剂为可溶解硅油的有机溶剂，清洗处理在超声振荡环境中进行。本发明的优点在于：Preferably, the cleaning agent in step (5) is an organic solvent that can dissolve silicone oil, and the cleaning process is performed in an ultrasonic oscillation environment. The advantages of the present invention are:
本研究通过将原丝在高温硅油中预处理，大幅提升其分子内环化程度，减少后续反应热的释放，反应产生的焦油等油溶性小分子可以在反应过程中迅速溶解于高温硅油中，避免在丝束上聚集，污染丝束；之后进行过氧化氢或高锰酸盐溶液等强氧化剂浸渍处理，使聚丙烯腈纤维溶胀填充强氧化性溶液，在后续高温硅油中处理时，内部残留溶液分解出氧气直接与内层分子链反应产生耐热梯形结构，同时反应热也更容易通过液相硅油扩散出去，避免纤维聚热，最终制备出聚丙烯腈预氧化纤维。本研究中所述制备流程可以大幅缩短预氧化时间至15min以内，大幅度降低预氧化纤维的生产加工成本。In this study, by pretreating the raw silk in high-temperature silicone oil, the degree of intramolecular cyclization is greatly improved, and the release of subsequent reaction heat is reduced. The oil-soluble small molecules such as tar produced by the reaction can be quickly dissolved in the high-temperature silicone oil during the reaction process. Avoid gathering on the tow and contaminating the tow; then perform an impregnation treatment with strong oxidants such as hydrogen peroxide or permanganate solution to make the polyacrylonitrile fiber swell and fill with the strong oxidizing solution. When processed in subsequent high-temperature silicone oil, internal residues The oxygen decomposed from the solution directly reacts with the inner molecular chain to produce a heat-resistant ladder structure. At the same time, the reaction heat is more easily diffused through the liquid silicone oil to avoid heat accumulation in the fiber, and finally the polyacrylonitrile pre-oxidized fiber is prepared. The preparation process described in this study can significantly shorten the pre-oxidation time to less than 15 minutes, significantly reducing the production and processing costs of pre-oxidized fibers.
附图说明Description of the drawings
图1为本发明一种聚丙烯腈基预氧化纤维的制备方法的工艺流程图。Figure 1 is a process flow chart of a method for preparing a polyacrylonitrile-based pre-oxidized fiber of the present invention.
具体实施方式Detailed ways
以下进一步描述本发明的具体技术方案，以便于本领域的技术人员进一步地理解本发明。Specific technical solutions of the present invention are further described below to facilitate those skilled in the art to further understand the present invention.
实施例1Example 1
本实施方式所述的一种聚丙烯腈预氧化纤维的制备方法，具体是按以下步骤进行的：The preparation method of polyacrylonitrile pre-oxidized fiber according to this embodiment is specifically carried out according to the following steps:
(1)将6K聚丙烯腈原丝(英国考陶尔聚丙烯腈原丝)在250℃高温硅油中超声处理1min，牵伸比为+5％；(1) Ultrasonic treatment of 6K polyacrylonitrile raw silk (British Courtauer polyacrylonitrile raw silk) in high-temperature silicone oil at 250°C for 1 minute, with a draft ratio of +5%;
(2)将步骤(1)所得丝束在四氯化碳溶液中超声清洗；(2) Ultrasonically clean the tow obtained in step (1) in a carbon tetrachloride solution;
(3)将步骤(2)所得丝束在浓度15％的双氧水溶液中超声预浸渍处理2min；(3) Ultrasonic pre-impregnating the tow obtained in step (2) in a hydrogen peroxide solution with a concentration of 15% for 2 minutes;
(4)将步骤(3)所得丝束在280℃高温硅油中热处理8min，牵伸比为0；(4) Heat-treat the tow obtained in step (3) in high-temperature silicone oil at 280°C for 8 minutes, and the draft ratio is 0;
(5)将步骤(4)所得丝束在四氯化碳溶液中超声清洗；(5) Ultrasonically clean the tow obtained in step (4) in a carbon tetrachloride solution;
按上述步骤制备出聚丙烯腈基预氧化纤维，纤维体密度为1.36g/m3，单丝强度为0.35GPa，极限氧指数为32％。The polyacrylonitrile-based pre-oxidized fiber was prepared according to the above steps, with a fiber body density of 1.36g/m3, a single filament strength of 0.35GPa, and a limiting oxygen index of 32%.
实施例2Example 2
本实施方式所述的一种聚丙烯腈预氧化纤维的制备方法，具体是按以下步骤进行的：The preparation method of polyacrylonitrile pre-oxidized fiber according to this embodiment is specifically carried out according to the following steps:
(1)将12K聚丙烯腈原丝(吉林化纤聚丙烯腈原丝)在240℃高温硅油中超声处理1.5min，牵伸比为+2％；(1) Ultrasonic treatment of 12K polyacrylonitrile raw yarn (Jilin Chemical Fiber polyacrylonitrile raw yarn) in high-temperature silicone oil at 240°C for 1.5 minutes, with a draft ratio of +2%;
(2)将步骤(1)所得丝束在四氯化碳溶液中超声清洗；(2) Ultrasonically clean the tow obtained in step (1) in a carbon tetrachloride solution;
(3)将步骤(2)所得丝束在浓度25％的双氧水溶液中超声预浸渍处理2min；(3) Ultrasonic pre-impregnating the tow obtained in step (2) in a hydrogen peroxide solution with a concentration of 25% for 2 minutes;
(4)将步骤(3)所得丝束在270℃高温硅油中热处理8min，牵伸比为+1％；(4) Heat-treat the tow obtained in step (3) in high-temperature silicone oil at 270°C for 8 minutes, and the draft ratio is +1%;
(5)将步骤(4)所得丝束在四氯化碳溶液中超声清洗；(5) Ultrasonically clean the tow obtained in step (4) in a carbon tetrachloride solution;
按上述步骤制备出聚丙烯腈基预氧化纤维，纤维体密度为1.37g/m3，单丝强度为0.38GPa，极限氧指数为34％。The polyacrylonitrile-based pre-oxidized fiber was prepared according to the above steps, with a fiber body density of 1.37g/m3, a single filament strength of 0.38GPa, and a limiting oxygen index of 34%.
实施例3Example 3
本实施方式所述的一种聚丙烯腈预氧化纤维的制备方法，具体是按以下步骤进行的：The preparation method of polyacrylonitrile pre-oxidized fiber according to this embodiment is specifically carried out according to the following steps:
(1)将48K聚丙烯腈原丝(上海石化聚丙烯腈原丝)在250℃高温硅油中超声处理2min，牵伸比为+5％；(1) Ultrasonic treatment of 48K polyacrylonitrile raw silk (Shanghai Petrochemical polyacrylonitrile raw silk) in high-temperature silicone oil at 250°C for 2 minutes, with a draft ratio of +5%;
(2)将步骤(1)所得丝束在四氯化碳溶液中超声清洗；(2) Ultrasonically clean the tow obtained in step (1) in a carbon tetrachloride solution;
(3)将步骤(2)所得丝束在浓度25％的高锰酸钾水溶液中超声预浸渍处理2min；(3) Ultrasonic pre-impregnating the tow obtained in step (2) in a potassium permanganate aqueous solution with a concentration of 25% for 2 minutes;
(4)将步骤(3)所得丝束在285℃高温硅油中热处理10min，牵伸比为+2％；(4) Heat-treat the tow obtained in step (3) in high-temperature silicone oil at 285°C for 10 minutes, and the draft ratio is +2%;
(5)将步骤(4)所得丝束在四氯化碳溶液中超声清洗；(5) Ultrasonically clean the tow obtained in step (4) in a carbon tetrachloride solution;
按上述步骤制备出聚丙烯腈基预氧化纤维，纤维体密度为1.41g/m3，单丝强度为0.25GPa，极限氧指数为42％。The polyacrylonitrile-based pre-oxidized fiber was prepared according to the above steps, with a fiber body density of 1.41g/m3, a single filament strength of 0.25GPa, and a limiting oxygen index of 42%.
实施例4Example 4
本实施方式所述的一种聚丙烯腈预氧化纤维的制备方法，具体是按以下步骤进行的：The preparation method of polyacrylonitrile pre-oxidized fiber according to this embodiment is specifically carried out according to the following steps:
(1)将96K聚丙烯腈原丝(上海石化聚丙烯腈原丝)在230℃高温硅油中超声处理3min，牵伸比为+5％；(1) Ultrasonic treatment of 96K polyacrylonitrile raw silk (Shanghai Petrochemical polyacrylonitrile raw silk) in high-temperature silicone oil at 230°C for 3 minutes, with a draft ratio of +5%;
(2)将步骤(1)所得丝束在四氯化碳溶液中超声清洗；(2) Ultrasonically clean the tow obtained in step (1) in a carbon tetrachloride solution;
(3)将步骤(2)所得丝束在浓度30％的双氧水溶液中超声预浸渍处理3min；(3) Ultrasonic pre-impregnating the tow obtained in step (2) in a hydrogen peroxide solution with a concentration of 30% for 3 minutes;
(4)将步骤(3)所得丝束在270℃高温硅油中热处理10min，牵伸比为-1％；(4) Heat-treat the tow obtained in step (3) in high-temperature silicone oil at 270°C for 10 minutes, and the draft ratio is -1%;
(5)将步骤(4)所得丝束在四氯化碳溶液中超声清洗；(5) Ultrasonically clean the tow obtained in step (4) in a carbon tetrachloride solution;
按上述步骤制备出聚丙烯腈基预氧化纤维，纤维体密度为1.43g/m3，单丝强度为0.23GPa，极限氧指数为44％。The polyacrylonitrile-based pre-oxidized fiber was prepared according to the above steps, with a fiber body density of 1.43g/m3, a single filament strength of 0.23GPa, and a limiting oxygen index of 44%.
实施例5Example 5
本实施方式所述的一种聚丙烯腈预氧化纤维的制备方法，具体是按以下步骤进行的：The preparation method of polyacrylonitrile pre-oxidized fiber according to this embodiment is specifically carried out according to the following steps:
(1)将50K聚丙烯腈原丝(吉林化纤聚丙烯腈原丝)在230℃高温硅油中超声处理2min，牵伸比为+7％；(1) Ultrasonic treatment of 50K polyacrylonitrile raw yarn (Jilin Chemical Fiber polyacrylonitrile raw yarn) in high-temperature silicone oil at 230°C for 2 minutes, with a draft ratio of +7%;
(2)将步骤(1)所得丝束在四氯化碳溶液中超声清洗；(2) Ultrasonically clean the tow obtained in step (1) in a carbon tetrachloride solution;
(3)将步骤(2)所得丝束在浓度10％的高锰酸钾水溶液中超声预浸渍处理2min；(3) Ultrasonic pre-impregnating the tow obtained in step (2) in a potassium permanganate aqueous solution with a concentration of 10% for 2 minutes;
(4)将步骤(3)所得丝束在275℃高温硅油中热处理4min，牵伸比为+2％；(4) Heat-treat the tow obtained in step (3) in high-temperature silicone oil at 275°C for 4 minutes, and the draft ratio is +2%;
(5)将步骤(4)所得丝束在四氯化碳溶液中超声清洗；(5) Ultrasonically clean the tow obtained in step (4) in a carbon tetrachloride solution;
按上述步骤制备出聚丙烯腈基预氧化纤维，纤维体密度为1.32g/m3，单丝强度为0.40GPa，极限氧指数为28％。The polyacrylonitrile-based pre-oxidized fiber was prepared according to the above steps, with a fiber body density of 1.32g/m3, a single filament strength of 0.40GPa, and a limiting oxygen index of 28%.
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| CN106637521A (en) * | 2016-12-27 | 2017-05-10 | 长春工业大学 | Preparation method of 48K polyacrylonitrile-based carbon fiber |
| CN110067044A (en) * | 2019-05-20 | 2019-07-30 | 中国科学院山西煤炭化学研究所 | A kind of PAN based graphite fiber and preparation method thereof |
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| CN106637521A (en) * | 2016-12-27 | 2017-05-10 | 长春工业大学 | Preparation method of 48K polyacrylonitrile-based carbon fiber |
| CN110067044A (en) * | 2019-05-20 | 2019-07-30 | 中国科学院山西煤炭化学研究所 | A kind of PAN based graphite fiber and preparation method thereof |
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