WO2022021486A1 - 一种pan基碳纤维及其制备方法与由其制成的碳纤维 - Google Patents

一种pan基碳纤维及其制备方法与由其制成的碳纤维 Download PDF

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WO2022021486A1
WO2022021486A1 PCT/CN2020/109446 CN2020109446W WO2022021486A1 WO 2022021486 A1 WO2022021486 A1 WO 2022021486A1 CN 2020109446 W CN2020109446 W CN 2020109446W WO 2022021486 A1 WO2022021486 A1 WO 2022021486A1
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pan
based carbon
treatment
fibers
heat treatment
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French (fr)
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黄险波
杨志军
叶南飚
常欢
马雷
黄有平
辛伟
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金发科技股份有限公司
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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
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/68—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
    • D06M11/72—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with metaphosphoric acids or their salts; with polyphosphoric acids or their salts; with perphosphoric acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/26—Polymers or copolymers of unsaturated carboxylic acids or derivatives thereof
    • D06M2101/28—Acrylonitrile; Methacrylonitrile

Definitions

  • the present invention relates to the technical field of PAN-based fibers, and more particularly, to a PAN-based carbon fiber, a preparation method thereof, and a carbon fiber made therefrom.
  • Carbon fiber is a material with high specific strength and high specific modulus, which has been widely used in aerospace, military and civil fields.
  • the PAN precursor needs to undergo a pre-oxidation process, and a series of reactions such as cyclization, dehydrogenation, oxidation, and cross-linking occur, and the linear polymer chain is transformed into a heat-resistant trapezoidal structure, so that the fiber can withstand higher temperature carbonization process.
  • Chinese patent CN201710633176.4 uses infrared laser to irradiate the PAN precursor, shortens the thermal stabilization time, and obtains pre-oxidized fibers with suitable cyclization degree, orientation degree and bulk density.
  • Chinese patent CN200910234656.9 uses a certain concentration of potassium permanganate solution before pre-oxidation of polyacrylonitrile-based carbon fiber precursor to impregnate the precursor;
  • Chinese CN201010285139.7 uses a certain concentration of ozone water to pre-treat PAN fibers. To a certain extent, the degree of pre-oxidation reaction can be improved and the pre-oxidation time can be shortened, but it is difficult to control the oxidation reaction time to less than 30min.
  • the present invention provides a preparation method of PAN-based carbon fiber, which can not only satisfy the pre-oxidation reaction degree of PAN-based carbon fiber precursor, but also shorten the Pre-oxidation reaction time, the total time of the whole pre-cyclization and pre-oxidation reaction is controlled within 30min, and the production efficiency of carbon fiber is improved.
  • Another object of the present invention is to provide a PAN-based carbon fiber.
  • Yet another object of the present invention is to provide a carbon fiber.
  • the technical scheme adopted in the present invention is:
  • a method for preparing PAN-based carbon fiber comprising the following steps:
  • Impregnation treatment the PAN precursor is dipped in a solution or emulsion of a nitrogen- and/or phosphorus-containing compound, and dried; the concentration of the nitrogen- and/or phosphorus-containing compound in the solution or emulsion is 5 ⁇ 30wt%; the temperature of the solution or emulsion is 20-90°C, and the immersion time is at least 0.01min; the nitrogen- and/or phosphorus-containing compounds are urea, melamine, hydrazine hydrate, ammonium polyphosphate, ammonium dihydrogen phosphate , a combination of one or more of diammonium hydrogen phosphate and phosphoric acid;
  • Pre-cyclization treatment the PAN precursor after the dipping treatment is placed in an inert gas atmosphere for heat treatment to obtain pre-cyclized fibers; the temperature range of the heat treatment is 190-320°C, and the heat-treatment time is 0.5-10min;
  • Oxidation treatment place the pre-cyclized fibers in an oxygen-containing atmosphere for heat treatment to obtain PAN pre-oxidized fibers; the temperature range of the heat treatment is 200 to 300°C, and the heat treatment time is 3 to 20 minutes;
  • Carbonization treatment carbonization treatment of PAN pre-oxidized fibers in an inert atmosphere to obtain PAN-based carbon fibers.
  • the PAN-based carbon fiber preparation method of the present invention firstly uses nitrogen-containing and/or phosphorus-containing compounds to impregnate the PAN raw fiber, and then conducts a deepening cyclization reaction in an inert atmosphere, so that the PAN fiber macromolecules form a uniform trapezoid resistant
  • the thermal structure can withstand subsequent rapid, high-temperature oxidation reactions, and finally carry out rapid oxidation reactions in an oxygen-containing atmosphere, thereby shortening the overall pre-oxidation reaction time of the fibers.
  • the tow specification of the PAN precursor described in the present invention includes, but is not limited to, 24k and above.
  • the inventor's research found that if only pre-ring treatment is used, it is difficult to achieve a relatively uniform reaction degree in a short period of time for large tow of 24K and above, and the degree of reaction between the surface layer of the tow and the inner fiber is inconsistent, and the appearance of the tow shows obvious color difference. , and the fibers with a low degree of reaction are difficult to withstand subsequent oxidation treatment, and are prone to breakage.
  • the preparation method of the present invention is especially suitable for the tow of PAN filaments of 24k and above. After pre-cyclization treatment after impregnation modification, the uniformity and degree of reaction of the fiber can be significantly improved, and the color difference of the tow can be reduced.
  • the pre-oxidation reaction time can be effectively shortened by reasonably adjusting the conditions of the oxidation treatment after the present invention.
  • the total time for effective pre-cyclization and oxidation treatment of modified PAN precursor can be controlled within 30 minutes, and the minimum time can be controlled within 20 minutes to reduce production energy consumption.
  • phosphorus-containing compounds such as ammonium polyphosphate
  • Some nitrogen-containing compounds such as hydrazine hydrate, can not only react with the cyano groups in the PAN polymer chain to form five-membered and six-membered cyclic structures, but also form cross-linking structures between the cyano groups in the molecules, improving PAN. thermal stability.
  • the PAN precursor is immersed in a solution or emulsion containing both a nitrogen-containing compound and a phosphorus-containing compound, and the nitrogen-containing compound is hydrazine hydrate; the phosphorus-containing compound is ammonium polyphosphate, A combination of one or more of ammonium dihydrogen phosphate, diammonium hydrogen phosphate and phosphoric acid.
  • the drying method is to pass the impregnated PAN precursor through an electric heating roller.
  • the temperature of the electric heating roller is generally 100 to 120°C.
  • the concentration of the nitrogen- and/or phosphorus-containing compound in the solution or emulsion of the present invention is 5-10 wt%.
  • the temperature of the solution or emulsion of the present invention is 40-80° C.
  • the immersion time is 2s-5min, more preferably 30s-2min.
  • the inert gas atmosphere refers to nitrogen and other inert gases.
  • the oxygen-containing atmosphere includes but is not limited to air.
  • the inert gas atmosphere refers to nitrogen and other inert gases.
  • the temperature range of the heat treatment is 250 ⁇ 300° C., and the time of the heat treatment is 3 ⁇ 4 min.
  • the pre-cyclization treatment is performed by a pre-cyclization treatment device (eg, a pre-cyclization furnace), and the pre-cyclization treatment device includes no less than one heating zone with an inert gas atmosphere.
  • a pre-cyclization treatment device eg, a pre-cyclization furnace
  • the pre-cyclization treatment device includes no less than one heating zone with an inert gas atmosphere.
  • the PAN strands are sequentially passed through no less than one heating zone in an inert gas atmosphere.
  • the number of the heating regions is 3-4.
  • step S2 when the pre-cyclization treatment is performed, the PAN precursor after the immersion treatment is placed in an inert gas atmosphere and subjected to heat treatment using 3 to 4 heating zones with gradient heating, and the temperature range of the heating zone is: At 250 ⁇ 300°C, the residence time of PAN strands in each heating zone is 1 ⁇ 2min.
  • the PAN strands were passed through four heating zones in an inert gas atmosphere in sequence, and the temperatures of the four heating zones in an inert gas atmosphere were 260, 265, 270, and 270° C., and the PAN strands were heated in each heating zone.
  • the residence time is 1 min.
  • step S2 of the present invention the draft ratio applied to the tow of the PAN raw silk after the immersion treatment is 0.9-1.2.
  • the oxidation treatment is performed by an oxidation treatment device (eg, an oxidation furnace), and the oxidation treatment device includes not less than two heating zones with an oxygen-containing atmosphere.
  • the oxidation treatment is performed, the pre-looped fibers are sequentially passed through not less than 2 (preferably 3 to 4) heating zones in an oxygen-containing atmosphere.
  • the heat treatment is carried out by means of gradient heating, the temperature range of the gradient heating is 200-300° C., and the total heat-treatment time is 3-20 min.
  • step S3 when the oxidation treatment is performed, the pre-cyclized fibers are sequentially passed through three heating zones with oxygen-containing atmospheres, and the temperatures of the three heating zones with oxygen-containing atmospheres are 235, 250, and 260° C. , the residence time of PAN strands in each heating zone is 4min.
  • step S3 when the oxidation treatment is performed, the pre-cyclized fibers are sequentially passed through four heating zones in an oxygen-containing atmosphere, and the temperatures in the four heating zones in an oxygen-containing atmosphere are 200, 230, 260, and 280 in sequence. °C, the residence time of PAN strands in each heating zone is 3.75min.
  • step S3 of the present application the draft ratio applied to the tow of the pre-looped fibers is 0.9-1.15.
  • the bulk density of the PAN pre-oxidized fiber obtained in step S3 of the present invention is 1.32-1.40 g/cm 3 , and the cyclization degree is 50-90%.
  • the carbonization treatment is to sequentially perform low-temperature carbonization and high-temperature carbonization treatment on the PAN pre-oxidized fibers.
  • the carbonization treatment is performed by a carbonization treatment device (eg, a carbonization furnace), and the carbonization treatment device includes a plurality of heating zones in an inert gas atmosphere.
  • the carbonization treatment the PAN pre-oxidized fibers are sequentially passed through a plurality of heating zones in an inert gas atmosphere.
  • the number of the heating zones is 3 to 5
  • the total effective time of the heat treatment is 3 to 10 minutes, preferably 5 to 8 minutes.
  • the PAN pre-oxidized fibers are sequentially passed through five heating regions of an inert gas atmosphere, and the temperatures of the five heating regions of an inert gas atmosphere are 350, 600, 800, 1000, 1000 At 1250 °C, the residence time of PAN preoxidized fibers in each heating zone was 1 min.
  • step S4 of the present application the draft ratio applied to the PAN pre-oxidized fiber tow is 0.85-1.1.
  • the present invention can improve the production efficiency of carbon fiber and reduce the production cost.
  • the carbon yield of the PAN-based carbon fiber prepared by the above preparation method is not less than 51%, the tensile strength is not less than 2.8GPa, and the modulus is not less than 200GPa, which can meet the application requirements in many aspects. Therefore, the PAN-based carbon fibers should also fall within the protection scope of the present invention.
  • the present invention also protects a carbon fiber comprising the PAN-based carbon fiber.
  • the preparation method of the PAN-based carbon fiber according to the present invention firstly uses nitrogen-containing and/or phosphorus-containing compounds to impregnate the PAN raw fiber, then performs pre-cyclization treatment on the fiber in an inert atmosphere, and finally performs oxidation treatment to make
  • the obtained PAN pre-oxidized fiber can form a uniform trapezoidal heat-resistant structure, significantly improve the uniformity and reaction efficiency of the fiber reaction, and reduce the color difference of the tow, and is especially suitable for the tow of PAN filaments of 24k and above. It can not only meet the pre-oxidation reaction degree of the PAN-based carbon fiber precursor, but also shorten the pre-oxidation reaction time.
  • the pre-cyclization and pre-oxidation reaction time of the present invention can be controlled within 30min in total, which can reduce production energy consumption and can Improve carbon fiber production efficiency and reduce production costs.
  • PAN raw silk (tow specifications are 12, 24K, 48K) were purchased from Jilin Chemical Fiber Co., Ltd.
  • a preparation method of PAN-based carbon fiber comprising the following steps:
  • Impregnation treatment the PAN raw silk (tow specification is 24K) is impregnated with ammonium polyphosphate aqueous solution, and then dried by 5 groups of 120 °C electric heating rollers after extrusion; the concentration of ammonium polyphosphate in the ammonium polyphosphate aqueous solution is 15wt%, the temperature of the ammonium polyphosphate aqueous solution is 50°C, and the immersion time is 2s;
  • Pre-cyclization treatment heat-treating the immersed PAN precursor through a pre-cyclization furnace in a nitrogen atmosphere to obtain pre-cyclized fibers;
  • the pre-cyclization furnace includes 4 heating zones, and the temperature of the 4 heating zones is uniform is 260°C, the residence time of PAN strands in each heating zone is 1min, and the draw ratio applied by each heating zone to the tow of PAN strands is 1;
  • Oxidation treatment heat treatment of the pre-ringed fibers through a pre-oxidation furnace in an air atmosphere to obtain PAN pre-oxidized fibers; the pre-oxidation furnace includes 3 heating zones, and the temperatures of the heating zones are 230, 250, and 260° C.
  • the residence time of the looped fibers in each heating zone was 4 min, and the oxidation treatment time was 12 min in total.
  • the draft ratios applied by each heating zone to the tow of the pre-looped fibers were 1.01, 1, and 0.95, respectively, to obtain PAN preoxidation. fiber.
  • the PAN pre-oxidized fibers are subjected to heat treatment through a carbonization furnace in a nitrogen atmosphere.
  • the carbonization furnace includes 5 heating zones.
  • the residence time of each heating zone is 1min, and the heat treatment time of carbonization treatment is 5min in total, wherein, the draft ratios applied by each heating zone to the tow of PAN pre-oxidized fibers are 1.02, 1, 1, 0.98, and 1, respectively, to obtain PAN base carbon fiber.
  • the preparation steps of the examples and comparative examples of the present invention are basically the same as those of Example 1, except that as shown in Tables 1-6, A in the table represents the type and concentration of nitrogen- and/or phosphorus-containing compounds.
  • Oxidation treatment heat treatment of the pre-ringed fibers through a pre-oxidation furnace in an air atmosphere to obtain PAN pre-oxidized fibers; the pre-oxidation furnace includes 4 heating zones, and the temperatures of the heating zones are 200, 230, 260, and 280° C. , the residence time of PAN strands in each heating zone is 3.75min, and the oxidation treatment time is 15min in total. Among them, the draft ratios applied by each heating zone to the tow of pre-ringed fibers are 1.15, 1.05, 1, and 0.9, respectively. PAN preoxidized fibers were obtained.
  • the preparation steps of this example are basically the same as those of Example 2, the difference is that the tow specification of the PAN precursor used is 48K.
  • the preparation steps of this example are basically the same as those of Example 2, the difference is that the tow specification of the PAN precursor used is 12K.
  • the preparation steps of this comparative example are basically the same as those of Comparative Example 2, and the pre-cyclization treatment is also not used, but the oxidation treatment is directly used.
  • the pre-oxidation furnace includes 4 heating zones. The temperatures of the heating zones are 200, 230, 260, and 280° C.
  • the residence time of the PAN strands in each heating zone is 7.5 minutes, and the oxidation treatment time is 30 minutes.
  • the draw ratios applied to the tow of the PAN precursor were 1.15, 1.05, 1, and 0.9, respectively, to obtain PAN preoxidized fibers.
  • Test method for bulk density refer to the density gradient column method in the national standard (GB/T 30019-2013 Determination of Carbon Fiber Density).
  • Test method The color difference of the tow is judged by visual inspection.
  • Test method for carbon yield cut 1m long PAN raw silk and weigh it on an analytical balance, its mass is recorded as m 0 , cut a 1 m long carbon fiber and weigh it on an analytical balance, its mass is recorded as m 1 , carbon
  • Test method for tensile strength and modulus The test is carried out with reference to the national standard (GBT3362-2005 Test method for tensile properties of carbon fiber multifilaments).
  • the technical solution of the present invention can not only satisfy the pre-oxidation reaction degree of PAN-based carbon fiber precursors, but also shorten the pre-oxidation reaction time.
  • the pre-cyclization and pre-oxidation of the present invention The total reaction time can be controlled within 30 minutes, which can reduce production energy consumption and improve carbon fiber production efficiency.
  • the carbon yield of the prepared PAN-based carbon fiber is not less than 51%, the tensile strength is not less than 2.8GPa, and the modulus is not less than 200GPa, and its performance can already meet many application scenarios of carbon fiber.

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Abstract

本发明提供了一种PAN基碳纤维及其制备方法与由其制成的碳纤维。所述PAN基碳纤维的制备方法，首先利用含氮和/或含磷的化合物对PAN原丝进行浸渍处理，然后依次进行惰性气氛下的预环化处理以及含氧气氛下的氧化处理，使得PAN原丝快速形成具有均匀梯形耐热结构的预氧化纤维，最后经过碳化处理，得到PAN基碳纤维。本制备方法尤其适用于24k及以上PAN原丝的丝束，既能缩短预氧化反应时间，又能达到理想的预氧化反应程度。总体上，本发明的预环化和氧化处理反应时间合计可控制在30min以内，降低生产能耗，能够提高碳纤维生产效率。

Description

一种PAN基碳纤维及其制备方法与由其制成的碳纤维 技术领域
本发明涉及PAN基纤维的技术领域，更具体地，涉及一种PAN基碳纤维及其制备方法与由其制成的碳纤维。
背景技术
碳纤维是一种高比强度、高比模量材料，已广泛应用于航空航天、军工及民用等领域。在碳纤维制备过程中，PAN原丝需要先经过预氧化过程，发生环化、脱氢、氧化、交联等一系列反应，线性高分子链转化为耐热的梯形结构，纤维才可以承受更高温度的碳化过程。
作为碳纤维制造过程中耗时最长，能耗最大的工序，目前的生产技术中预氧化通常要耗时30～90min之久，成为整个碳纤维制备过程中的主要瓶颈。近年来，围绕缩短碳纤维预氧化时间的研究成为行业热点。中国专利CN201710550785.3公开了一种聚丙烯腈基碳纤维原丝快速预氧化工艺，采用较高的预氧化起始温度，控制升温梯度和垂直循环热风风量，将预氧化时间缩短到40min内。中国专利CN201710633176.4采用红外激光对PAN原丝辐照，缩短热稳定化时间，得到适宜环化度、取向度和体密度的预氧化纤维。中国专利CN200910234656.9在聚丙烯腈基碳纤维原丝预氧化前，采用一定浓度高锰酸钾溶液中浸渍处理原丝；中国CN201010285139.7采用一定浓度的臭氧水对PAN纤维前处理虽然这些工艺在一定程度上可以提高预氧化反应程度，缩短预氧化时间，但是很难将氧化反应时间控制到30min以内。
因此，需要开发出一种新的PAN基碳纤维的制备方法，以有效将PAN基碳纤维原丝快速预氧化。
发明内容
本发明为克服上述现有技术所述的碳纤维制造过程中预氧化反应时间长的缺陷，提供一种PAN基碳纤维的制备方法，既能满足PAN基碳纤维原丝的预氧化反应程度，又能缩短预氧化反应时间，将整个预环化和预氧化反应的总时间控制到30min以内，提高碳纤维的生产效率。
本发明的另一个目的在于提供一种PAN基碳纤维。
本发明的又一个目的在于提供一种碳纤维。
为解决上述技术问题，本发明采用的技术方案是：
一种PAN基碳纤维制备方法，包括以下步骤：
S1.浸渍处理：将PAN原丝置于含氮和/或含磷的化合物的溶液或乳液中浸渍，烘干；所述溶液或乳液中含氮和/或含磷的化合物的浓度为5～30wt％；所述溶液或乳液的温度为20～90℃，浸渍时间至少为0.01min；所述含氮和/或含磷的化合物为尿素、三聚氰胺、水合肼、聚磷酸铵、磷酸二氢铵、磷酸氢二铵、磷酸中的一种或多种的组合；
S2.预环化处理：将浸渍处理后的PAN原丝置于惰性气体气氛下进行热处理，得到预环化纤维；热处理的温度范围为190～320℃，热处理的时间为0.5～10min；
S3.氧化处理：将预环化纤维置于含氧气氛下进行热处理，得到PAN预氧化纤维；热处理的温度范围为200～300℃，热处理的时间为3～20min；
S4.碳化处理：将PAN预氧化纤维在惰性气氛下进行碳化处理，得到PAN基碳纤维。
本发明所述PAN基碳纤维制备方法，首先利用含氮和/或含磷的化合物对PAN原丝进行浸渍处理，然后在惰性气氛下进行加深环化反应，使PAN纤维大分子形成均匀的梯形耐热结构，可承受后续快速、高温氧化反应，最后在含氧气氛进行快速氧化反应，从而缩短纤维的整体预氧化反应时间。
本发明所述PAN原丝的丝束规格包括但不限于24k及以上。发明人研究发现，若仅采用预环化处理，对于24K及以上的较大丝束很难短时间达到比较均匀的反应程度，且丝束表层与内部纤维反应程度不一致，丝束外观呈现明显色差，且反应程度较低的纤维难以承受后续的氧化处理，容易发生断丝。而本发明所述的制备方法尤其适用于24k及以上PAN原丝的丝束，通过浸渍改性后再进行预环化处理，可以明显提高纤维反应均匀性及反应程度，减小丝束色差。
在上述浸渍处理和预环化处理的基础上，本发明之后通过合理调整氧化处理的条件，能够有效缩短预氧化反应时间。总体上，经过改性的PAN原丝有效预环化和氧化处理的时间合计可控制在30min以内，最低可控制在20min以内完成，降低生产能耗。
发明人研究发现，一些含磷的化合物如聚磷酸铵，可以诱导PAN高分子链 上的氰基之间以离子反应机理进行环化反应，降低环化反应活化能，快速形成稳定的梯形结构；而一些含氮的化合物如水合肼，既可以与PAN高分子链内的氰基反应，形成五元和六元环状结构，又可以在分子间的氰基之间形成交联结构，提高PAN的耐热稳定性。
进一步地，发明人发现，当含磷化合物与含氮化合物配合使用时，能够同时更好地降低环化反应活化能，和提高PAN的耐热稳定性。优选地，本发明步骤S1中，将PAN原丝置于同时具有含氮化合物和含磷化合物的溶液或乳液中浸渍，所述含氮化合物为水合肼；所述含磷化合物为聚磷酸铵、磷酸二氢铵、磷酸氢二铵、磷酸中的一种或多种的组合。
优选地，所述含磷化合物的质量与所述含氮化合物的质量之比为1：(0.2～3)，更优选为1：(0.5～2)。本发明所述步骤S1中，所述烘干的方式为将浸渍后的PAN原丝通过电加热辊。电加热辊的温度一般为100～120℃。
优选地，本发明所述溶液或乳液中含氮和/或含磷的化合物的浓度为5～10wt％。
优选地，本发明所述溶液或乳液的温度为40～80℃，浸渍时间为2s～5min，更优选为30s～2min。
步骤S2中，所述惰性气体气氛指的是氮气、其它惰性气体。步骤S3中，所述含氧气氛包括但不限于空气。步骤S4中，所述惰性气体气氛指的是氮气、其它惰性气体。
优选地，步骤S2中，所述热处理的温度范围为250～300℃，热处理的时间为3～4min。
本发明步骤S2中，所述预环化处理通过预环化处理装置(例如预环化炉)进行，所述预环化处理装置包含不少于1个的惰性气体气氛的加热区域。步骤S2中，进行所述预环化处理时，将所述PAN原丝依次通过不少于1个的惰性气体气氛的加热区域。优选地，所述加热区域的数量为3～4个。
进一步地，步骤S2中，进行所述预环化处理时，将浸渍处理后的PAN原丝置于惰性气体气氛下采用3～4个加热区域梯度升温进行热处理，所述加热区域的温度范围为250～300℃，PAN原丝在各加热区域的停留时间均为1～2min。
具体地，将所述PAN原丝依次通过4个惰性气体气氛的加热区域，所述4个惰性气体气氛的加热区域的温度依次为260、265、270、270℃，PAN原丝在 各加热区域的停留时间均为1min。
本发明步骤S2中，对浸渍处理后的PAN原丝的丝束施加的牵伸比为0.9～1.2。
本发明步骤S3中，所述氧化处理通过氧化处理装置(例如氧化炉)进行，所述氧化处理装置包含不少于2个的含氧气氛的加热区域。进行所述氧化处理时，将所述预环化纤维依次通过不少于2个(优选为3～4个)的含氧气氛的加热区域。采用梯度升温的方式进行热处理，梯度升温的温度范围为200～300℃，总热处理的时间为3～20min。
具体地，步骤S3中，进行所述氧化处理时，将预环化纤维依次通过3个含氧气氛的加热区域，所述3个含氧气氛的加热区域的温度依次为235、250、260℃，PAN原丝在各加热区域的停留时间均为4min。或者，步骤S3中，进行所述氧化处理时，将预环化纤维依次通过4个含氧气氛的加热区域，所述4个含氧气氛的加热区域的温度依次为200、230、260、280℃，PAN原丝在各加热区域的停留时间均为3.75min。
本申请步骤S3中，对预环化纤维的丝束施加的牵伸比为0.9～1.15。
本发明步骤S3所获得的PAN预氧化纤维的体密度为1.32～1.40g/cm 3，环化度为50～90％。
本发明步骤S4中，所述碳化处理为将PAN预氧化纤维依次进行低温碳化、高温碳化处理。
本发明步骤S4中，所述碳化处理通过碳化处理装置(例如碳化炉)进行，所述碳化处理装置包含多个的惰性气体气氛的加热区域。进行所述碳化处理时，将所述PAN预氧化纤维依次通过多个的惰性气体气氛的加热区域。优选地，所述加热区域的数量为3～5个，热处理总有效时间为3～10min，优选为5～8min。
具体地，进行所述碳化处理时，将所述PAN预氧化纤维依次通过5个惰性气体气氛的加热区域，所述5个惰性气体气氛的加热区域的温度依次为350、600、800、1000、1250℃，PAN预氧化纤维在各加热区域的停留时间均为1min。
本申请步骤S4中，对PAN预氧化纤维丝束施加的牵伸比为0.85～1.1。
本发明通过采用上述制备方法，能够提高碳纤维生产效率，降低生产成本。且由上述制备方法所制备得到的PAN基碳纤维的碳收率不低于51％，拉伸强度不低于2.8GPa，模量不低于200GPa，能够满足很多方面的应用需求。因此所述PAN基碳纤维也应在本发明的保护范围内。
进一步地，本发明还保护一种碳纤维，所述碳纤维包含所述的PAN基碳纤维。
与现有技术相比，本发明的有益效果是：
本发明所述PAN基碳纤维的制备方法，首先利用含氮和/或含磷的化合物对PAN原丝进行浸渍处理，再在惰性气氛下对纤维进行预环化处理，最后再进行氧化处理，使获得的PAN预氧化纤维可形成均匀的梯形耐热结构，明显提高纤维反应的均匀性及反应效率，减小丝束色差，尤其适用于24k及以上PAN原丝的丝束。既能满足PAN基碳纤维原丝的预氧化反应程度，又能缩短预氧化反应时间，总体上，本发明的预环化和预氧化反应时间合计可控制在30min以内，能够降低生产能耗，能够提高碳纤维生产效率，降低生产成本。
具体实施方式
下面结合具体实施方式对本发明作进一步的说明。实施例及对比例中的原料均可通过市售得到。
其中，PAN原丝(丝束规格为12、24K、48K)均购自吉林化纤股份有限公司。
实施例1
一种PAN基碳纤维的制备方法，包括以下步骤：
S1.浸渍处理：将PAN原丝(丝束规格为24K)进行聚磷酸铵水溶液浸渍，然后经挤压后通过5组120℃电加热辊烘干；聚磷酸铵水溶液中聚磷酸铵的浓度为15wt％，聚磷酸铵水溶液的温度为50℃，浸渍时间为2s；
S2.预环化处理：将浸渍处理后的PAN原丝通过氮气气氛的预环化炉进行热处理，得到预环化纤维；该预环化炉包含4个加热区域，4个加热区域的温度均为260℃，PAN原丝在各加热区域的停留时间均为1min，各加热区域对PAN原丝的丝束施加的牵伸比均为1；
S3.氧化处理：将预环化纤维通过空气气氛的预氧化炉进行热处理，得到PAN预氧化纤维；该预氧化炉包含3个加热区域，加热区域的温度依次为230、250、260℃，预环化纤维在各加热区域的停留时间均为4min，氧化处理时间共12min，其中，各加热区域对预环化纤维的丝束施加的牵伸比分别为1.01、1、0.95，得到PAN预氧化纤维。
S4.碳化处理：将PAN预氧化纤维通过氮气气氛的碳化炉进行热处理，该 碳化炉包含5个加热区域，加热区域的温度依次为350、600、800、1000、1250℃，PAN预氧化纤维在各加热区域的停留时间均为1min，碳化处理的热处理时间共5min，其中，各加热区域对PAN预氧化纤维的丝束施加的牵伸比分别为1.02、1、1、0.98、1，得到PAN基碳纤维。
实施例2～29及对比例1～4
本发明的实施例及对比例的制备步骤与实施例1基本相同，不同之处在于如表1～6所示，其中表中A代表含氮和/或含磷的化合物的种类及浓度。
表1 实施例2～实施例8
Figure PCTCN2020109446-appb-000001
表2 实施例9～实施例15
Figure PCTCN2020109446-appb-000002
Figure PCTCN2020109446-appb-000003
表3 实施例16～实施例20
Figure PCTCN2020109446-appb-000004
表4 实施例21～实施例25
Figure PCTCN2020109446-appb-000005
表5 实施例26～实施例29
Figure PCTCN2020109446-appb-000006
Figure PCTCN2020109446-appb-000007
表6 对比例1～对比例4
Figure PCTCN2020109446-appb-000008
实施例30
本实施例的制备步骤与实施例2基本相同，不同之处在于步骤S3：
S3.氧化处理：将预环化纤维通过空气气氛的预氧化炉进行热处理，得到PAN 预氧化纤维；该预氧化炉包含4个加热区域，加热区域的温度依次为200、230、260、280℃，PAN原丝在各加热区域的停留时间均为3.75min，氧化处理时间共15min，其中，各加热区域对预环化纤维的丝束施加的牵伸比分别为1.15、1.05、1、0.9，得到PAN预氧化纤维。
实施例31
本实施例的制备步骤与实施例2基本相同，不同之处在于，所采用的PAN原丝的丝束规格为48K。
实施例32
本实施例的制备步骤与实施例2基本相同，不同之处在于，所采用的PAN原丝的丝束规格为12K。
对比例5
本对比例的制备步骤与对比例2基本相同，同样没有采用预环化处理，直接采用氧化处理，不同之处在于，将浸渍处理后的PAN原丝通过空气气氛的预氧化炉进行热处理，该预氧化炉包含4个加热区域，加热区域的温度依次为200、230、260、280℃，PAN原丝在各加热区域的停留时间均为7.5min，氧化处理时间共30min，其中，各加热区域对PAN原丝的丝束施加的牵伸比分别为1.15、1.05、1、0.9，得到PAN预氧化纤维。
测试方法或标准
对本发明的实施例和对比例制备所得的PAN预氧化纤维及PAN基碳纤维的性能进行测试，测试方法或标准如下：
1)环化度
环化度的测试方法：环化度(RCI)的计算公式如下：RCI＝f*I C＝N/(f*I C＝N+I C≡N)*100％，其中I C＝N和I C≡N分别为FTIR谱图中C＝N和C≡N的特征吸收峰强度，f为比值常数，其值为0.29。
2)体密度
体密度的测试方法：参照国家标准(GB/T 30019-2013碳纤维密度的测定)中的密度梯度柱法进行测试。
3)丝束色差
测试方法：丝束色差通过目测判断。
4)碳收率
碳收率的测试方法：截取1m长的PAN原丝并在分析天平上称量，其质量记为m 0，截取1m长的碳纤维并在分析天平上称量，其质量记为m 1，碳收率(CY)的计算方式如下：CY＝m 1/m 0*100％。
5)拉伸强度
拉伸强度及模量的测试方法：参照国家标准(GBT3362-2005碳纤维复丝拉伸性能试验方法)进行测试。
测试结果
本发明的实施例和对比例制备所得的PAN预氧化纤维及PAN基碳纤维的性能测试结果如表7～10所示：
表7
Figure PCTCN2020109446-appb-000009
表8
Figure PCTCN2020109446-appb-000010
Figure PCTCN2020109446-appb-000011
表9
Figure PCTCN2020109446-appb-000012
表10
Figure PCTCN2020109446-appb-000013
Figure PCTCN2020109446-appb-000014
从上述实施例1～32可以看出，本发明的技术方案既能满足PAN基碳纤维原丝的预氧化反应程度，又能缩短预氧化反应时间，总体上，本发明的预环化和预氧化反应时间合计可控制在30min以内，能够降低生产能耗，能够提高碳纤维生产效率。所制备得到的PAN基碳纤维的碳收率不低于51％，拉伸强度不低于2.8GPa，模量不低于200GPa，其性能已经能够满足碳纤维的较多应用场景。
而从对比例1和2的效果可知，缺少浸渍处理或预环化处理，所制备得到的PAN基碳纤维的性能要明显低于实施例的性能，即使将氧化处理的时间延长至30min(如对比例5)，也无法满足使用要求。
显然，本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明权利要求的保护范围之内。

Claims (10)

  1. 一种PAN基碳纤维的制备方法，其特征在于，包括以下步骤：
    S1.浸渍处理：将PAN原丝置于含氮和/或含磷的化合物的溶液或乳液中浸渍，烘干；所述溶液或乳液中含氮和/或含磷的化合物的浓度为5～30wt％；所述溶液或乳液的温度为20～90℃，浸渍时间至少为0.01min；所述含氮和/或含磷的化合物为尿素、三聚氰胺、水合肼、聚磷酸铵、磷酸二氢铵、磷酸氢二铵、磷酸中的一种或多种的组合；
    S2.预环化处理：将浸渍处理后的PAN原丝置于惰性气体气氛下进行热处理，得到预环化纤维；热处理的温度范围为190～320℃，热处理的时间为0.5～10min；
    S3.氧化处理：将预环化纤维置于含氧气氛下进行热处理，得到PAN预氧化纤维；热处理的温度范围为200～300℃，热处理的时间为3～20min；
    S4.碳化处理：将PAN预氧化纤维在惰性气氛下进行碳化处理，得到PAN基碳纤维。
  2. 根据权利要求1所述的PAN基碳纤维的制备方法，其特征在于，步骤S1中，所述溶液或乳液中含氮和/或含磷的化合物的浓度为5～10wt％。
  3. 根据权利要求1或2所述的PAN基碳纤维的制备方法，其特征在于，步骤S1中，将PAN原丝置于同时具有含氮化合物和含磷化合物的溶液或乳液中浸渍，所述含氮化合物为水合肼；所述含磷化合物为聚磷酸铵、磷酸二氢铵、磷酸氢二铵、磷酸中的一种或多种的组合。
  4. 根据权利要求3所述的PAN基碳纤维的制备方法，其特征在于，所述含磷化合物的质量与所述含氮化合物的质量之比为1：(0.2～3)。
  5. 根据权利要求1所述的PAN基碳纤维的制备方法，其特征在于，步骤S2中，所述热处理的温度范围为250～300℃，热处理的时间为3～4min。
  6. 根据权利要求1所述的PAN基碳纤维的制备方法，其特征在于，步骤S2中，将浸渍处理后的PAN原丝置于惰性气体气氛下采用3～4个加热区域梯度升温进行热处理，所述加热区域的温度范围为250～300℃，PAN原丝在各加热区域的停留时间均为1～2min。
  7. 根据权利要求1所述的PAN基碳纤维的制备方法，其特征在于，步骤S3中，将预环化纤维置于含氧气氛下，采用至少2个加热区域梯度升温进行热处理， 所述热处理的温度为200～300℃，热处理的时间为3～20min。
  8. 根据权利要求1所述的PAN基碳纤维的制备方法，其特征在于，步骤S4中，所述碳化处理为将PAN预氧化纤维依次进行低温碳化、高温碳化处理。
  9. 一种PAN基碳纤维，其特征在于，由权利要求1～8任一所述的制备方法制得。
  10. 一种碳纤维，其特征在于，包含权利要求9所述的PAN基碳纤维。
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CN115404568B (zh) * 2022-09-28 2023-10-03 山西钢科碳材料有限公司 一种干喷湿纺聚丙烯腈基碳纤维原丝的预氧化方法
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