WO2023088399A1 - 聚丙烯腈碳纤维原丝用油剂及其制备方法 - Google Patents

聚丙烯腈碳纤维原丝用油剂及其制备方法 Download PDF

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WO2023088399A1
WO2023088399A1 PCT/CN2022/132708 CN2022132708W WO2023088399A1 WO 2023088399 A1 WO2023088399 A1 WO 2023088399A1 CN 2022132708 W CN2022132708 W CN 2022132708W WO 2023088399 A1 WO2023088399 A1 WO 2023088399A1
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carbon fiber
parts
silicone oil
oil agent
fiber precursor
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PCT/CN2022/132708
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English (en)
French (fr)
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张国良
郭鹏宗
祝威威
刘磊
林康
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中复神鹰碳纤维股份有限公司
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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
    • 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
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
    • D01F11/14—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with organic compounds, e.g. macromolecular compounds
    • 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

Definitions

  • the present application relates to the technical field of high-performance carbon fiber preparation, in particular to an oil agent for polyacrylonitrile carbon fiber precursors and a preparation method thereof.
  • Carbon fiber oil is an indispensable key additive in the carbon fiber manufacturing process. Its function is to prevent fiber monofilaments from sticking and doubling, and can also reduce the friction and wear between the fiber surface and the roller, thereby reducing the defects on the fiber surface and improving the quality of carbon fiber. .
  • oils with modified polydimethylsiloxane commonly known as silicone oil
  • silicone oils modified with different functional groups such as amino silicone oil, epoxy silicone oil, and polyether silicone oil are used for compounding.
  • the oil agent in the prior art has the problem of fiber sticking to the roll during the production process, and the oil agent has problems such as poor heat resistance, many fluffs, and low strength of the carbon fiber.
  • the present application aims to provide an oil agent for polyacrylonitrile carbon fiber precursors and a preparation method thereof.
  • the oil agent introduces quaternary ammonium salt modified polyether silicone oil and large molecular weight epoxy silicone oil.
  • the quaternary ammonium group contained in the quaternary ammonium salt modified polyether silicone oil has no reactivity with the epoxy group, which solves the problem of crosslinking reaction of carbon fiber oil agent at high temperature.
  • the resulting problems of thermal paralleling and sticking between fibers significantly improve the quality of carbon fibers.
  • an oil agent for polyacrylonitrile carbon fiber precursor which consists of the following components in parts by weight:
  • the polyacrylonitrile carbon fiber precursor oil agent consists of the following components in parts by weight: 100 parts of quaternary ammonium salt modified polyether silicone oil, 25 parts of epoxy modified polydimethylsiloxane ⁇ 50 parts, surfactant 40 ⁇ 50 parts, organic solvent 10 ⁇ 20 parts.
  • the quaternary ammonium salt-modified polyether silicone oil described in this application is a double-ended quaternary ammonium salt-modified polyether silicone oil or a single-end quaternary ammonium salt-modified polyether silicone oil, with a molecular weight of 5,000-20,000.
  • the molecular weight of the quaternary ammonium salt modified polyether silicone oil is too low, the viscosity will be too low after drying, and it will be easily lost, and the adhesion and protection effect of the oil agent on the fiber surface will decrease, and the wool will increase, resulting in fiber loss.
  • the molar ratio of the ethoxyl (EO) unit to the propoxyl (PO) unit is 4-6:1.
  • the molecular weight of the quaternary ammonium salt-modified polyether silicone oil is 8000-15000, and the molar ratio of the ethoxy unit to the propoxy unit is 5:1.
  • the molecular weight of the quaternary ammonium salt-modified polyether silicone oil used is 10770-14000, and the molar ratio of the ethoxy unit to the propoxy unit is 5:1.
  • the epoxy-modified polydimethylsiloxane described in this application is side-chain modified epoxy silicone oil or double-end modified epoxy silicone oil.
  • the molar ratio of the main chain structure (C 2 H 6 SiO) unit to the side chain modified epoxy group (CH(O)CH 2 ) unit is 80-150:1, Preferably it is 100-120:1.
  • the molar ratio of the main chain structure (C 2 H 6 SiO) unit to the terminal epoxy group (CH(O)CH 2 ) unit is 250-600:1, preferably 300 ⁇ 500:1.
  • the molecular weight of the epoxy-modified polydimethylsiloxane is 40,000 to 100,000.
  • the molecular weight is 50,000-80,000.
  • the epoxy-modified polydimethylsiloxane used is a side-chain modified epoxy silicone oil, and the molar ratio of C 2 H 6 SiO units to CH(O)CH 2 units is 100 : 1, the molecular weight is 47200 ⁇ 96140.
  • the surfactant in the oil agent for polyacrylonitrile carbon fiber precursor of this application is selected from fatty alcohol polyoxyethylene ether, fatty amine polyoxyethylene ether, sorbitan fatty acid ester and polyoxyethylene sorbitan fatty acid ester one or any combination of several.
  • the surfactant is a mixture of AEO-3 and AEO-9.
  • the organic solvent in the oil agent for polyacrylonitrile carbon fiber precursors of this application is selected from isopropanol, dimethylformamide, ethylene glycol monobutyl ether or dipropylene glycol methyl ether. In some embodiments of the present application, the organic solvent used is isopropanol.
  • the preparation method of the polyacrylonitrile carbon fiber precursor oil is provided, which is prepared by the following steps:
  • the particles size of the emulsion is 150nm-300nm.
  • the oil agent for polyacrylonitrile carbon fiber precursors of the present application improves the hydrophilicity of the oil agent, the adhesion to the fiber surface and the antistatic performance by introducing quaternary ammonium salt modified polyether silicone oil.
  • the introduction of a suitable large molecular weight epoxy silicone oil improves the fiber bundle, heat resistance and anti-sticking performance, further solves the problem of the fiber raw silk oil agent sticking to the roller in the drying process, and reduces the occurrence of fiber breakage.
  • the oil agent for polyacrylonitrile carbon fiber precursors of the present application can enhance the protective effect of the oil agent on the fiber surface during pre-oxidation and carbonization, and effectively improve the quality of carbon fiber precursors.
  • the oil agent for polyacrylonitrile carbon fiber precursor consists of the following components in parts by weight:
  • side chain modified epoxy silicone oil 25 parts, the molecular weight is about 47200, the molar ratio of the main chain structure (C 2 H 6 SiO) unit to the side chain modified epoxy group (CH(O)CH 2 ) unit is about 100:1;
  • Surfactant 40 parts of fatty alcohol polyoxyethylene ether, including 20 parts of AEO-3 and 20 parts of AEO-9;
  • Organic solvent 10 parts of isopropanol.
  • the solid content of the prepared oil agent is 30%, the heat resistance of the oil agent is 430°C, and the residual weight is about 74%.
  • the oil content of the carbon fiber precursor produced by using the prepared oil agent is 0.82%.
  • Grade 1-5, grade 1 is the best, grade 5 is the worst); carbon fiber tensile strength is 5143MPa, carbon fiber wool grade is 1.5 (divided into grades 1-5, grade 1 is the best, grade 5 is the worst), carbon fiber ash content is 0.021% .
  • the oil agent for polyacrylonitrile carbon fiber precursor consists of the following components in parts by weight:
  • side chain modified epoxy silicone oil 50 parts of side chain modified epoxy silicone oil, the molecular weight is about 47200, the molar ratio of the main chain structure (C 2 H 6 SiO) unit to the side chain modified epoxy group (CH(O)CH 2 ) unit is about 100:1;
  • Surfactant fat 50 parts of fatty alcohol polyoxyethylene ether, including 25 parts of AEO-3 and 25 parts of AEO-9;
  • Organic solvent 10 parts of isopropanol.
  • the heat resistance of the oil agent is 430°C, and the residual weight is about 75%.
  • the oil content of the carbon fiber precursor produced by using the prepared oil agent is 0.81%, and the grade of the raw silk wool is 1; the tensile strength of carbon fiber is 5334MPa, and the grade of the carbon fiber wool is 1.5 , carbon fiber ash 0.031%.
  • Example 1 Compared with Example 1, it can be found that increasing the content of epoxy-modified polydimethylsiloxane will lead to an increase in the particle size of the emulsion, a decrease in stability, and an increase in fiber ash; the heat resistance and clustering of the oil agent are improved, The tensile strength of the fiber has been improved to a certain extent.
  • the oil agent for polyacrylonitrile carbon fiber precursor consists of the following components in parts by weight:
  • side chain modified epoxy silicone oil 25 parts, the molecular weight is about 47200, the molar ratio of the main chain structure (C 2 H 6 SiO) unit to the side chain modified epoxy group (CH(O)CH 2 ) unit is about 100:1;
  • Surfactant 40 parts of fatty alcohol polyoxyethylene ether, including 20 parts of AEO-3 and 20 parts of AEO-9;
  • Organic solvent 10 parts of isopropanol.
  • the heat resistance of the oil agent is 430°C, and the residual weight is about 74%.
  • the oil content of the carbon fiber precursor produced by using the prepared oil agent is 0.85%, and the grade of the raw silk wool is 1.5; the tensile strength of the carbon fiber is 5184MPa, and the grade of the carbon fiber wool is 2 , carbon fiber ash 0.025%.
  • the oil agent for polyacrylonitrile carbon fiber precursor consists of the following components in parts by weight:
  • side chain modified epoxy silicone oil 25 parts, the molecular weight is about 96140, and the molar ratio of the main chain structure (C 2 H 6 SiO) unit to the side chain modified epoxy group (CH(O)CH 2 ) unit is about 100:1;
  • Surfactant 40 parts of fatty alcohol polyoxyethylene ether, including 20 parts of AEO-3 and 20 parts of AEO-9;
  • Organic solvent 10 parts of isopropanol.
  • the heat resistance of the oil agent is 430°C, and the residual weight is about 77%.
  • the oil content of the carbon fiber precursor produced by using the prepared oil agent is 0.76%, and the grade of the raw silk wool is 1; the tensile strength of the carbon fiber is 5256MPa, and the grade of the carbon fiber wool is 1.5 , carbon fiber ash 0.029%.
  • Example 1 Compared with Example 1, it can be found that increasing the molecular weight of epoxy-modified polydimethylsiloxane will also lead to an increase in the particle size of the emulsion, a decrease in stability, and an increase in fiber ash; the heat resistance of the oil agent is significantly improved .
  • the oil agent for polyacrylonitrile carbon fiber precursor consists of the following components in parts by weight:
  • side chain modified epoxy silicone oil 25 parts, the molecular weight is about 96140, and the molar ratio of the main chain structure (C 2 H 6 SiO) unit to the side chain modified epoxy group (CH(O)CH 2 ) unit is about 100:1;
  • Surfactant 50 parts of fatty alcohol polyoxyethylene ether, including 25 parts of AEO-3 and 25 parts of AEO-9;
  • Organic solvent 20 parts of isopropanol.
  • the oil agent for polyacrylonitrile carbon fiber precursor consists of the following components in parts by weight:
  • side chain modified epoxy silicone oil 70 parts of side chain modified epoxy silicone oil, the molecular weight is about 47200, the molar ratio of the main chain structure (C 2 H 6 SiO) unit to the side chain modified epoxy group (CH(O)CH 2 ) unit is about 100:1;
  • Surfactant 40 parts of fatty alcohol polyoxyethylene ether, including 20 parts of AEO-3 and 20 parts of AEO-9;
  • Organic solvent 10 parts of isopropanol.
  • the heat resistance of the oil agent is 430°C, and the residual weight is about 78%.
  • the oil content of the carbon fiber precursor produced by using the prepared oil agent is 0.81%, and the grade of the raw silk is 3; the tensile strength of the carbon fiber is 4865MPa, and the grade of the carbon fiber is 4. , carbon fiber ash 0.056%.
  • Example 1 Compared with Example 1, it can be found that when the content of epoxy-modified polydimethylsiloxane reaches 70 parts, the particle size of the emulsion exceeds 500 nm, the stability is poor, and it is easy to separate. Ultimately, the fiber wool becomes poor, the ash content is too high, and the tensile strength of the fiber decreases.
  • the oil agent for polyacrylonitrile carbon fiber precursor consists of the following components in parts by weight:
  • Surfactant 40 parts of fatty alcohol polyoxyethylene ether, including 20 parts of AEO-3 and 20 parts of AEO-9;
  • Organic solvent 10 parts of isopropanol.
  • the heat resistance of the oil agent is 430°C, and the residual weight is about 72%.
  • the oil content of the carbon fiber precursor produced by using the prepared oil agent is 0.79%, and the grade of the raw silk wool is 2.5; the tensile strength of the carbon fiber is 4923MPa, and the grade of the carbon fiber wool is 3.5 , carbon fiber ash 0.017%.
  • Example 1 Compared with Example 1, it can be found that reducing the content of epoxy-modified polydimethylsiloxane will lead to a reduction in the particle size of the emulsion, an increase in stability, and a reduction in fiber ash; the heat resistance and clustering of the oil agent are reduced, and the wool Filaments increase, resulting in a decrease in fiber tensile strength.
  • the oil agent for polyacrylonitrile carbon fiber precursor consists of the following components in parts by weight:
  • side chain modified epoxy silicone oil 25 parts, the molecular weight is about 47200, the molar ratio of the main chain structure (C 2 H 6 SiO) unit to the side chain modified epoxy group (CH(O)CH 2 ) unit is about 100:1;
  • Surfactant 60 parts of fatty alcohol polyoxyethylene ether, including 20 parts of AEO-3 and 20 parts of AEO-9;
  • Organic solvent 10 parts of isopropanol.
  • the heat resistance of the oil agent is 430°C, and the residual weight is about 71%.
  • the oil content of the carbon fiber precursor produced by using the prepared oil agent is 0.83%, and the grade of the raw silk wool is 3; the tensile strength of the carbon fiber is 4812MPa, and the grade of the carbon fiber wool is 4 , carbon fiber ash 0.017%.
  • the oil agent for polyacrylonitrile carbon fiber precursor consists of the following components in parts by weight:
  • side chain modified epoxy silicone oil 25 parts, the molecular weight is about 47200, the molar ratio of the main chain structure (C 2 H 6 SiO) unit to the side chain modified epoxy group (CH(O)CH 2 ) unit is about 100:1;
  • Surfactant 40 parts of fatty alcohol polyoxyethylene ether, including 20 parts of AEO-3 and 20 parts of AEO-9;
  • Organic solvent 5 parts of isopropanol.
  • the heat resistance of the oil agent is 430°C, and the residual weight is about 72%.
  • the oil content of the carbon fiber precursor produced by using the prepared oil agent is 0.75%, and the grade of the raw silk wool is 3; the tensile strength of the carbon fiber is 4723MPa, and the grade of the carbon fiber wool is 4 , carbon fiber ash 0.016%.
  • Example 1 Compared with Example 1, it can be found that the molecular weight of the quaternary ammonium salt modified polyether silicone oil is reduced, the viscosity may be too low after drying, and it is easy to lose, the adhesion and protection effect of the oil agent on the fiber surface decreases, and the hair filaments increase, resulting in fiber pulling. Tensile strength decreased.
  • the oil agent for polyacrylonitrile carbon fiber precursor consists of the following components in parts by weight:
  • side chain modified epoxy silicone oil 25 parts, the molecular weight is about 156800, the molar ratio of the main chain structure (C 2 H 6 SiO) unit to the side chain modified epoxy group (CH(O)CH 2 ) unit is about 100:1;
  • Surfactant 50 parts of fatty alcohol polyoxyethylene ether, including 20 parts of AEO-3 and 20 parts of AEO-9;
  • Organic solvent 10 parts of isopropanol.
  • the heat resistance of the oil agent is 430°C, and the residual weight is about 81%.
  • the oil content of the carbon fiber precursor produced by using the prepared oil agent is 0.63%, and the grade of the raw silk wool is 4; the tensile strength of carbon fiber is 4780MPa, and the grade of the carbon fiber wool is 5 , carbon fiber ash 0.089%.
  • the quaternary ammonium salt modified polyether silicone oil is a single-end quaternary ammonium salt modified polyether silicone oil
  • the epoxy-modified polydimethylsiloxane is a double-end modified epoxy silicone oil.
  • the active agent is fatty amine polyoxyethylene ether
  • the organic solvent is ethylene glycol monobutyl ether or dipropylene glycol methyl ether.
  • the quaternary ammonium salt modified polyether silicone oil is a double-ended quaternary ammonium salt modified polyether silicone oil
  • the epoxy-modified polydimethylsiloxane is a side chain modified epoxy silicone oil
  • the surfactant It is polyoxyethylene sorbitan fatty acid ester
  • the organic solvent is isopropanol.
  • the quaternary ammonium salt modified polyether silicone oil is a single-ended quaternary ammonium salt modified polyether silicone oil
  • the epoxy-modified polydimethylsiloxane is a side chain modified epoxy silicone oil
  • the surfactant It is polyoxyethylene sorbitan fatty acid ester
  • the organic solvent is isopropanol.
  • Table 2 shows the performance data of the carbon fibers produced by the oil agents of the various embodiments and comparative examples.
  • comparative example 6 selects the oil agent in the prior art for use, and its formula is:
  • Surfactant 50 parts of fatty alcohol polyoxyethylene ether, including 20 parts of AEO-3 and 20 parts of AEO-9;
  • Organic solvent 10 parts of isopropanol.
  • the heat resistance of the oil agent is 430°C, and the residual weight is about 62%.
  • the oil content of the carbon fiber precursor produced by using the prepared oil agent is 0.86%, and the grade of the raw silk wool is 4; the tensile strength of the carbon fiber is 4609MPa, and the grade of the carbon fiber wool is 5 , carbon fiber ash 0.067%.
  • the polyacrylonitrile carbon fiber precursor oil agent of the present application introduces quaternary ammonium salt modified polyether silicone oil, and the quaternary ammonium group contained in the quaternary ammonium salt modified polyether silicone oil has no reactivity with epoxy groups, which solves the problem of carbon fiber oil.
  • suitable high-molecular-weight epoxy silicone oil improves the carbon fiber bundle, heat resistance and anti-stick performance, further solves the problem of raw silk oil agent sticking to the roller in the drying process, and reduces the occurrence of fiber breakage.
  • the oil agent for polyacrylonitrile carbon fiber precursors of the present application is of great significance for improving the quality of carbon fiber precursors and improving the protective effect of the oil agent on the fiber surface during preoxidation and carbonization.
  • the oil agent for polyacrylonitrile carbon fiber precursor provided by this application introduces quaternary ammonium salt modified polyether silicone oil and large molecular weight epoxy silicone oil.
  • the problems of heat paralleling and sticking between fibers caused by the reaction can significantly improve the quality of carbon fibers.

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Abstract

一种聚丙烯腈碳纤维原丝用油剂及其制备方法，该油剂由季铵盐改性聚醚硅油100份、环氧改性聚二甲基硅氧烷20～60份、表面活性剂20～50份和有机溶剂10～30份组成。聚丙烯腈碳纤维原丝用油剂引入季铵盐改性聚醚硅油，其含有的季铵基与环氧基团无反应活性，解决了碳纤维油剂在高温下交联反应导致纤维间的热并丝及粘辊问题；同时，提高了油剂的亲水性、对纤维表面的附着力以及抗静电性能。引入的大分子量环氧硅油提高了纤维的集束性、耐热性以及抗粘性能，解决了碳纤维原丝油剂在烘干工序段粘辊问题，减少了纤维断丝的产生，明显改善碳纤维原丝质量。

Description

聚丙烯腈碳纤维原丝用油剂及其制备方法
本申请要求在2021年11月18日提交中国国家知识产权局、申请号为202111369230.1、发明名称为“聚丙烯腈碳纤维原丝用油剂及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请涉及高性能碳纤维制备技术领域，尤其涉及一种聚丙烯腈碳纤维原丝用油剂及其制备方法。
背景技术
碳纤维油剂是碳纤维制造过程中不可缺少的关键助剂，其作用在于防止纤维单丝粘连、并丝，也可以减少纤维表面与辊筒的摩擦与磨损，从而减少纤维表面产生缺陷，提高碳纤维质量。在聚丙烯腈碳纤维原丝生产过程中往往使用改性聚二甲基硅氧烷(俗称硅油)为主要成分的油剂，采用不同官能团改性硅油如氨基硅油、环氧硅油、聚醚硅油复配获得。但是，现有技术中的油剂存在纤维在生产过程中的粘辊问题，以及油剂耐热性不佳、毛丝多、碳纤维强度低等问题。
发明内容
本申请旨在提供一种聚丙烯腈碳纤维原丝用油剂及其制备方法。该油剂引入季铵盐改性聚醚硅油以及大分子量环氧硅油，季铵盐改性聚醚硅油含有的季铵基与环氧基团无反应活性，解决了碳纤维油剂在高温下交联反应导致的纤维间的热并丝及粘辊问题，显著提升碳纤维质量。
为了实现以上目的，本申请通过以下技术方案实现：
根据本申请的第一个方面，提供了一种聚丙烯腈碳纤维原丝用油剂，按重量份数计，由以下成分组成：
季铵盐改性聚醚硅油100份，环氧改性聚二甲基硅氧烷20～60份，表面活性剂20～50 份，有机溶剂10～30份。
实验发现，将以上各组分控制在以上范围，可以很好地保证乳液的稳定性、耐热性、集束性，并且由其生产的碳纤维毛羽少，具备优异的拉伸强度。具体的，环氧改性聚二甲基硅氧烷含量过低会导致油剂的耐热性和集束性下降，毛丝增大，纤维拉伸强度降低等情况；而含量过高，会导致乳液粒径过大，稳定性差，容易分层；最终导致纤维毛丝变差，灰分过高，纤维拉伸强度下降。表面活性剂的含量过高会带来纤维各方面性能的下降，包括耐热性、集束性、纤维强度等。
优选的，所述的聚丙烯腈碳纤维原丝用油剂，按重量份数计，由以下成分组成：季铵盐改性聚醚硅油100份，环氧改性聚二甲基硅氧烷25～50份，表面活性剂40～50份，有机溶剂10～20份。
本申请所述的季铵盐改性聚醚硅油为双端季铵盐改性聚醚硅油或单端季铵盐改性聚醚硅油，分子量为5000～20000。实验发现，如果季铵盐改性聚醚硅油的分子量过低，会导致烘干后粘度太低，容易流失，并且会造成油剂对纤维表面的附着保护作用下降，毛丝增大，导致纤维拉伸强度的降低；而分子量过高，会导致油剂乳液的稳定性变差，粒径变大、容易分层；同时分子量过高可能带来纤维集束性过强，过程热量不能及时排出导致纤维的热并丝以及粘辊现象，导致纤维质量下降。
其中，季铵盐改性聚醚硅油中，乙氧基(EO)单元和丙氧基(PO)单元的摩尔比为4～6:1。
优选的，所述的季铵盐改性聚醚硅油分子量为8000～15000，乙氧基单元和丙氧基单元的摩尔比为5:1。
在本申请的一些具体实施方式中，采用的季铵盐改性聚醚硅油的分子量为10770～14000，乙氧基单元和丙氧基单元的摩尔比为5:1。
本申请所述的环氧改性聚二甲基硅氧烷为侧链改性环氧硅油或双端改性环氧硅油。所述的侧链环氧改性硅油中，主链结构(C 2H 6SiO)单元与侧链改性环氧基(CH(O)CH 2)单元的摩尔比为80～150：1，优选为100～120：1。所述的双端改性环氧硅油中，主链结构(C 2H 6SiO)单元与端环氧基(CH(O)CH 2)单元的摩尔比为250～600：1，优选为300～500：1。所述的环氧改性聚二甲基硅氧烷的分子量为40000～100000，如果分子量过高，会导致乳液的稳定性变差，粒径变大、容易分层；同时分子量过高会带来纤维集束性过强，过程热量不能及时排出导致纤维的热并丝以及粘辊现象，导致纤维质量下降。优选的，分子量为50000～80000。
在本申请的一些具体实施方式中，采用的环氧改性聚二甲基硅氧烷为侧链改性环氧硅油，C 2H 6SiO单元与CH(O)CH 2单元摩尔比为100：1，分子量为47200～96140。
本申请聚丙烯腈碳纤维原丝用油剂中的表面活性剂选自脂肪醇聚氧乙烯醚、脂肪胺聚氧乙烯醚、失水山梨醇脂肪酸酯和聚氧乙烯失水山梨醇脂肪酸酯中的一种或任意几种的混合。优选的，表面活性剂为AEO-3和AEO-9的混合物。
本申请聚丙烯腈碳纤维原丝用油剂中的有机溶剂选自异丙醇、二甲基甲酰胺、乙二醇单丁醚或二丙二醇甲醚。在本申请的一些具体实施方式中，采用的有机溶剂为异丙醇。
根据本申请的第二个方面，提供所述的聚丙烯腈碳纤维原丝用油剂的制备方法，通过以下步骤制备：
按配比将各组分混合搅拌均匀后，加水乳化转相，调节pH至4～6，得到粒径为150nm～500nm的稳定乳液。优选地，所述的乳液的粒径为150nm～300nm。
相对于现有技术，本申请具有以下优点：
本申请的聚丙烯腈碳纤维原丝用油剂，通过引入季铵盐改性聚醚硅油，提高了油剂的亲水性、对纤维表面的附着力以及抗静电性能。此外，引入合适的大分子量环氧硅油提高了纤维的集束性、耐热性以及抗粘性能，进一步解决了纤维原丝油剂在烘干工序段粘辊问题，减少了纤维断丝的产生。进一步的，本申请的聚丙烯腈碳纤维原丝用油剂能够提升油剂在预氧化、碳化过程中对纤维表面的保护作用，有效改善碳纤维原丝质量。
具体实施方式
下面将结合本申请实施例对本申请的技术方案进行清楚、完整地描述，显然，所描述的实施例只是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员为没有做出创造性劳动前提下所获得的所有其他实施例，都属于本申请保护的范围。需要说明的是，为不冲突的情况下，本申请中的实施例及其特征可以相互任意组合。
下面是根据本申请的聚丙烯腈碳纤维原丝用油剂中所包括的各组分的部分具体实施例。
实施例1
聚丙烯腈碳纤维原丝用油剂，按重量份数计，由以下组分组成：
双端季铵盐改性聚醚硅油100份，分子量约为10770，其含有乙氧基(EO)单元和丙氧基(PO)单元的摩尔比约在5:1；
侧链改性环氧硅油25份，分子量约47200，主链结构(C 2H 6SiO)单元与侧链改性环氧基(CH(O)CH 2)单元摩尔比约在100：1；
表面活性剂：脂肪醇聚氧乙烯醚40份，包括20份AEO-3和20份AEO-9；
有机溶剂：异丙醇10份。
将上述组分混合搅拌均匀后，加水乳化转相，调节pH至5，得到粒径分布在213nm的乳液，乳液稳定性等级为优。制得的油剂固含量为30％，油剂耐热性430℃，余重约为74％，使用制备的油剂生产的碳纤维原丝含油为0.82％，原丝毛丝等级1级(划分1-5级，1级最优，5级最差)；碳纤维拉伸强度5143MPa，碳纤维毛丝等级1.5级(划分1-5级，1级最优，5级最差)，碳纤维灰分0.021％。
实施例2
聚丙烯腈碳纤维原丝用油剂，按重量份数计，由以下组分组成：
双端季铵盐改性聚醚硅油100份，分子量约为10770，其含有乙氧基(EO)单元和丙氧基(PO)单元的摩尔比约在5:1；
侧链改性环氧硅油50份，分子量约47200，主链结构(C 2H 6SiO)单元与侧链改性环氧基(CH(O)CH 2)单元摩尔比约在100：1；
表面活性剂脂：肪醇聚氧乙烯醚50份，包括25份AEO-3和25份AEO-9；
有机溶剂：异丙醇10份。
将上述组分混合搅拌均匀后，加水乳化转相，调节pH至5，得到粒径分布在230nm的乳液，乳液稳定性等级良。油剂耐热性430℃，余重约为75％，使用制备的油剂生产的碳纤维原丝含油为0.81％，原丝毛丝等级1级；碳纤维拉伸强度5334MPa，碳纤维毛丝等级1.5级，碳纤维灰分0.031％。与实施例1对比，可以发现提升环氧改性聚二甲基硅氧烷含量会导致乳液粒径增大，稳定性降低，纤维灰分升高；油剂的耐热性和集束性得到提高，纤维拉伸强度有一定提升。
实施例3
聚丙烯腈碳纤维原丝用油剂，按重量份数计，由以下组分组成：
双端季铵盐改性聚醚硅油100份，分子量约为14000，其含有乙氧基(EO)单元和丙氧基(PO)单元的摩尔比约在5:1；
侧链改性环氧硅油25份，分子量约47200，主链结构(C 2H 6SiO)单元与侧链改性环氧基(CH(O)CH 2)单元摩尔比约在100：1；
表面活性剂：脂肪醇聚氧乙烯醚40份，包括20份AEO-3和20份AEO-9；
有机溶剂：异丙醇10份。
将上述组分混合搅拌均匀后，加水乳化转相，调节pH至5，得到粒径分布在224nm的乳液，乳液稳定性等级优。油剂耐热性430℃，余重约为74％，使用制备的油剂生产的碳纤维原丝含油为0.85％，原丝毛丝等级1.5级；碳纤维拉伸强度5184MPa，碳纤维毛丝等级2级，碳纤维灰分0.025％。
实施例4
聚丙烯腈碳纤维原丝用油剂，按重量份数计，由以下组分组成：
双端季铵盐改性聚醚硅油100份，分子量约为10770，其含有乙氧基(EO)单元和丙氧基(PO)单元的摩尔比约在5:1；
侧链改性环氧硅油25份，分子量约96140，主链结构(C 2H 6SiO)单元与侧链改性环氧基(CH(O)CH 2)单元摩尔比约在100：1；
表面活性剂：脂肪醇聚氧乙烯醚40份，包括20份AEO-3和20份AEO-9；
有机溶剂：异丙醇10份。
将上述组分混合搅拌均匀后，加水乳化转相，调节pH至5，得到粒径分布在289nm的乳液，乳液稳定性等级良。油剂耐热性430℃，余重约为77％，使用制备的油剂生产的碳纤维原丝含油为0.76％，原丝毛丝等级1级；碳纤维拉伸强度5256MPa，碳纤维毛丝等级1.5级，碳纤维灰分0.029％。与实施例1对比，可以发现提升环氧改性聚二甲基硅氧烷的分子量也会导致乳液粒径增大，稳定下降低，纤维灰分升高；油剂的耐热性有明显的提升。
实施例5
聚丙烯腈碳纤维原丝用油剂，按重量份数计，由以下组分组成：
双端季铵盐改性聚醚硅油100份，分子量约为10770，其含有乙氧基(EO)单元和丙氧基(PO)单元的摩尔比约在5:1；
侧链改性环氧硅油25份，分子量约96140，主链结构(C 2H 6SiO)单元与侧链改性环氧基(CH(O)CH 2)单元摩尔比约在100：1；
表面活性剂：脂肪醇聚氧乙烯醚50份，包括25份AEO-3和25份AEO-9；
有机溶剂：异丙醇20份。
将上述组分混合搅拌均匀后，加水乳化转相，调节pH至5，得到粒径分布在262nm的乳液，乳液稳定性等级优。油剂耐热性430℃，余重约为77％，使用制备的油剂生产的碳纤维原丝含油为0.78％，原丝毛丝等级1.5级；碳纤维拉伸强度5387MPa，碳纤维毛丝等级2级，碳纤维灰分0.029％。与实施例4对比，可以发现提升表面活性剂和有机溶剂的含量会降低乳液粒径，提升乳液稳定性。
比较例1
聚丙烯腈碳纤维原丝用油剂，按重量份数计，由以下成分组成：
双端季铵盐改性聚醚硅油100份，分子量约为10770，其含有乙氧基(EO)单元和丙氧基(PO)单元的摩尔比约在5:1；
侧链改性环氧硅油70份，分子量约47200，主链结构(C 2H 6SiO)单元与侧链改性环氧基(CH(O)CH 2)单元摩尔比约在100：1；
表面活性剂：脂肪醇聚氧乙烯醚40份，包括20份AEO-3和20份AEO-9；
有机溶剂：异丙醇10份。
将上述组分混合搅拌均匀后，加水乳化转相，调节pH至5，得到粒径分布在624nm的乳液，乳液稳定性等级差。油剂耐热性430℃，余重约为78％，使用制备的油剂生产的碳纤维原丝含油为0.81％，原丝毛丝等级3级；碳纤维拉伸强度4865MPa，碳纤维毛丝等级4级，碳纤维灰分0.056％。与实施例1对比，可以发现环氧改性聚二甲基硅氧烷含量达到70份时，乳液粒径超过500nm，稳定很差，容易分层。最终导致纤维毛丝变差，灰分过高，纤维拉伸强度下降。
比较例2
聚丙烯腈碳纤维原丝用油剂，按重量份数计，由以下组分组成：
双端季铵盐改性聚醚硅油100份，分子量约为10770，其含有乙氧基(EO)单元和丙氧基(PO)单元的摩尔比约在5:1；
侧链改性环氧硅油10份，分子量约47200，主链结构(C 2H 6SiO)单元与侧链改性环氧基(CH(O)CH 2)单元摩尔比约在100：1；
表面活性剂：脂肪醇聚氧乙烯醚40份，包括20份AEO-3和20份AEO-9；
有机溶剂：异丙醇10份。
将上述组分混合搅拌均匀后，加水乳化转相，调节pH至5，得到粒径分布在180nm的乳液，乳液稳定性等级优。油剂耐热性430℃，余重约为72％，使用制备的油剂生产的碳纤维原丝含油为0.79％，原丝毛丝等级2.5级；碳纤维拉伸强度4923MPa，碳纤维毛丝 等级3.5级，碳纤维灰分0.017％。与实施例1对比，可以发现降低环氧改性聚二甲基硅氧烷含量会导致乳液粒径减小，稳定性提高，纤维灰分下降；油剂的耐热性和集束性得到下降，毛丝增大，导致纤维拉伸强度出现降低。
比较例3
聚丙烯腈碳纤维原丝用油剂，按重量份数计，由以下组分组成：
双端季铵盐改性聚醚硅油100份，分子量约为10770，其含有乙氧基(EO)单元和丙氧基(PO)单元的摩尔比约在5:1；
侧链改性环氧硅油25份，分子量约47200，主链结构(C 2H 6SiO)单元与侧链改性环氧基(CH(O)CH 2)单元摩尔比约在100：1；
表面活性剂：脂肪醇聚氧乙烯醚60份，包括20份AEO-3和20份AEO-9；
有机溶剂：异丙醇10份。
将上述组分混合搅拌均匀后，加水乳化转相，调节pH至5，得到粒径分布在167nm的乳液，乳液稳定性等级优。油剂耐热性430℃，余重约为71％，使用制备的油剂生产的碳纤维原丝含油为0.83％，原丝毛丝等级3级；碳纤维拉伸强度4812MPa，碳纤维毛丝等级4级，碳纤维灰分0.017％。结果显示，表面活性剂含量过高会带来纤维各方面性能的下降，包括耐热性、集束性、纤维强度等。
比较例4
聚丙烯腈碳纤维原丝用油剂，按重量份数计，由以下组分组成：
双端季铵盐改性聚醚硅油100份，分子量约为4000，其含有乙氧基(EO)单元和丙氧基(PO)单元的摩尔比约在5:1；
侧链改性环氧硅油25份，分子量约47200，主链结构(C 2H 6SiO)单元与侧链改性环氧基(CH(O)CH 2)单元摩尔比约在100：1；
表面活性剂：脂肪醇聚氧乙烯醚40份，包括20份AEO-3和20份AEO-9；
有机溶剂：异丙醇5份。
将上述组分混合搅拌均匀后，加水乳化转相，调节pH至5，得到粒径分布在191nm的乳液，乳液稳定性等级优。油剂耐热性430℃，余重约为72％，使用制备的油剂生产的碳纤维原丝含油为0.75％，原丝毛丝等级3级；碳纤维拉伸强度4723MPa，碳纤维毛丝等级4级，碳纤维灰分0.016％。与实施例1对比，可以发现降低季铵盐改性聚醚硅油的分子量，可能烘干后粘度太低，容易流失，油剂对纤维表面的附着保护作用下降，毛丝增大，导致纤维拉伸强度出现降低。
比较例5
聚丙烯腈碳纤维原丝用油剂，按重量份数计，由以下组分组成：
双端季铵盐改性聚醚硅油100份，分子量约为24330，其含有乙氧基(EO)单元和丙氧基(PO)单元的摩尔比约在5:1；
侧链改性环氧硅油25份，分子量约156800，主链结构(C 2H 6SiO)单元与侧链改性环氧基(CH(O)CH 2)单元摩尔比约在100：1；
表面活性剂：脂肪醇聚氧乙烯醚50份，包括20份AEO-3和20份AEO-9；
有机溶剂：异丙醇10份。
将上述组分混合搅拌均匀后，加水乳化转相，调节pH至5，得到粒径分布在776nm的乳液，乳液稳定性等级差。油剂耐热性430℃，余重约为81％，使用制备的油剂生产的碳纤维原丝含油为0.63％，原丝毛丝等级4级；碳纤维拉伸强度4780MPa，碳纤维毛丝等级5级，碳纤维灰分0.089％。与上述实施例对比可以发现，当采用过高分子量的季铵盐改性聚醚硅油和环氧改性聚二甲基硅氧烷会带来乳液稳定性变差问题，粒径变大、容易分层；同时分子量过高可能带来纤维集束性过强，过程热量不能及时排出导致纤维的热并丝以及粘辊现象，纤维质量下降。
本申请的聚丙烯腈碳纤维原丝用油剂配方含量的具体实施例还可如表1所示。
其中，实施例6-8中，季铵盐改性聚醚硅油为单端季铵盐改性聚醚硅油，环氧改性聚二甲基硅氧烷为双端改性环氧硅油，表面活性剂为脂肪胺聚氧乙烯醚，有机溶剂为乙二醇单丁醚或二丙二醇甲醚。
实施例9-10中，季铵盐改性聚醚硅油为双端季铵盐改性聚醚硅油，环氧改性聚二甲基硅氧烷为侧链改性环氧硅油，表面活性剂为聚氧乙烯失水山梨醇脂肪酸酯，有机溶剂为异丙醇。
实施例11-12中，季铵盐改性聚醚硅油为单端季铵盐改性聚醚硅油，环氧改性聚二甲基硅氧烷为侧链改性环氧硅油，表面活性剂为聚氧乙烯失水山梨醇脂肪酸酯，有机溶剂为异丙醇。
表1各实施例的油剂配方数据
Figure PCTCN2022132708-appb-000001
Figure PCTCN2022132708-appb-000002
表2示出了各实施例及对比例的油剂生产的碳纤维的性能数据。其中，对比例6选用现有技术中的油剂，其配方为：
侧链氨基改性硅油100份，分子量约为11000，氨基改性硅油的氨值约为0.50mmol/g；
侧链改性环氧硅油25份，分子量约23000，环氧改性硅油的环氧值为0.30mmol/g；
表面活性剂：脂肪醇聚氧乙烯醚50份，包括20份AEO-3和20份AEO-9；
有机溶剂：异丙醇10份。
将上述组分混合搅拌均匀后，加水乳化转相，调节pH至5，得到粒径分布在175nm的乳液，乳液稳定性等级优。油剂耐热性430℃，余重约为62％，使用制备的油剂生产的碳纤维原丝含油为0.86％，原丝毛丝等级4级；碳纤维拉伸强度4609MPa，碳纤维毛丝等级5级，碳纤维灰分0.067％。与上述实施例对比可以发现，采用现有技术的侧链氨基改性硅油和环氧改性硅油会带来油剂耐热性下降问题；同时氨基改性与环氧硅油性受热发生交联带来粘辊问题，导致纤维表面损伤、毛丝变差，纤维拉伸性能产生下降。
表2各实施例和比较例的油剂生产的碳纤维的性能数据
Figure PCTCN2022132708-appb-000003
表2各实施例和比较例的油剂生产的碳纤维的性能数据(续)
Figure PCTCN2022132708-appb-000004
Figure PCTCN2022132708-appb-000005
综上，本申请的聚丙烯腈碳纤维原丝用油剂引入季铵盐改性聚醚硅油，季铵盐改性聚醚硅油中含有的季铵基与环氧基团无反应活性，解决了碳纤维油剂在高温下交联反应导致的纤维间的热并丝及粘辊问题；此外，也可以提高油剂的亲水性、对纤维表面的附着力以及抗静电性能。引入合适的大分子量环氧硅油提高了碳纤维集束性、耐热性以及抗粘性能，进一步解决了原丝油剂在烘干工序段粘辊问题，减少了纤维断丝的产生。本申请的聚丙烯腈碳纤维原丝用油剂对于改善碳纤维原丝质量，提升油剂在预氧化、碳化过程中对纤维表面的保护作用具有重要意义。
最后应说明的是：在本文中，术语“包括”、“包含”或者其任何其他变体意为涵盖非排他性的包含，从而使得包含一系列要素的过程、方法、物品或者设备不仅包括那些要素，而且还包括没有明确列出的其他要素，或者是还包括为这种过程、方法、物品或者设备所固有的要素。在没有更多限制的情况下，由语句“包括一个…”限定的要素，并不排除为包括所述要素的过程、方法、物品或者设备中还存在另外的相同要素。
以上实施例仅用以说明本申请的技术方案，而非对其限制。尽管参照前述实施例对本申请进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本申请各实施例技术方案的精神和范围。
工业实用性
本申请提供的聚丙烯腈碳纤维原丝用油剂，引入季铵盐改性聚醚硅油以及大分子量环氧硅油，季铵基与环氧基团无反应活性，解决了碳纤维油剂在高温下交联反应导致的纤维间的热并丝及粘辊问题，显著提升碳纤维质量。

Claims (10)

  1. 聚丙烯腈碳纤维原丝用油剂，其特征在于，按重量份数计，由以下成分组成：
    季铵盐改性聚醚硅油100份，环氧改性聚二甲基硅氧烷20～60份，表面活性剂20～50份，有机溶剂10～30份。
  2. 根据权利要求1所述的聚丙烯腈碳纤维原丝用油剂，其特征在于，所述的聚丙烯腈碳纤维原丝用油剂，按重量份数计，由以下成分组成：季铵盐改性聚醚硅油100份，环氧改性聚二甲基硅氧烷25～50份，表面活性剂40～50份，有机溶剂10～20份。
  3. 根据权利要求1所述的聚丙烯腈碳纤维原丝用油剂，其特征在于，所述的季铵盐改性聚醚硅油为双端季铵盐改性聚醚硅油或单端季铵盐改性聚醚硅油，其中乙氧基单元和丙氧基单元的摩尔比为4～6:1，分子量为5000～20000。
  4. 根据权利要求1所述的聚丙烯腈碳纤维原丝用油剂，其特征在于，所述的季铵盐改性聚醚硅油中，乙氧基单元和丙氧基单元的摩尔比为5:1，分子量为8000～15000。
  5. 根据权利要求1所述的聚丙烯腈碳纤维原丝用油剂，其特征在于，所述的季铵盐改性聚醚硅油中，乙氧基单元和丙氧基单元的摩尔比为5:1，分子量为10770～14000。
  6. 根据权利要求1所述的聚丙烯腈碳纤维原丝用油剂，其特征在于，所述的环氧改性聚二甲基硅氧烷为侧链改性环氧硅油或双端改性环氧硅油。
  7. 根据权利要求1所述的聚丙烯腈碳纤维原丝用油剂，其特征在于，所述的表面活性剂选自脂肪醇聚氧乙烯醚、脂肪胺聚氧乙烯醚、失水山梨醇脂肪酸酯和聚氧乙烯失水山梨醇脂肪酸酯中的一种或任意几种的混合。
  8. 根据权利要求1所述的聚丙烯腈碳纤维原丝用油剂，其特征在于，所述的有机溶剂选自异丙醇、二甲基甲酰胺、乙二醇单丁醚或二丙二醇甲醚。
  9. 根据权利要求1-8任一所述的聚丙烯腈碳纤维原丝用油剂的制备方法，其特征在于，具体步骤如下：
    按配比将各组分混合搅拌均匀后，加水乳化转相，调节pH至4～6，得到乳液，即所述聚丙烯腈碳纤维原丝用油剂。
  10. 根据权利要求9所述聚丙烯腈碳纤维原丝用油剂的制备方法，其特征在于，所述 的乳液的粒径为150nm～500nm。
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