WO2019019366A1 - Special impregnating agent for alumina continuous fiber twisted yarn and preparation method therefor - Google Patents

Special impregnating agent for alumina continuous fiber twisted yarn and preparation method therefor Download PDF

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Publication number
WO2019019366A1
WO2019019366A1 PCT/CN2017/104318 CN2017104318W WO2019019366A1 WO 2019019366 A1 WO2019019366 A1 WO 2019019366A1 CN 2017104318 W CN2017104318 W CN 2017104318W WO 2019019366 A1 WO2019019366 A1 WO 2019019366A1
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lubricant
fiber
sizing agent
agent
continuous fiber
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PCT/CN2017/104318
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French (fr)
Chinese (zh)
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焦秀玲
秦嘉
贾玉娜
陈代荣
郭文勇
孟强
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山东大学
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/4584—Coating or impregnating of particulate or fibrous ceramic material

Definitions

  • the invention relates to a continuous fiber surface modification technology, in particular to a special sizing agent for alumina continuous fiber twisted yarn and a preparation method thereof, and belongs to the field of inorganic ceramic fiber sizing agent.
  • Alumina continuous fiber is an important high-performance inorganic non-metallic material, belonging to a kind of ceramic fiber, with Al 2 O 3 as the main component, and also adding Fe 2 O 3 , SiO 2 and the like.
  • the alumina continuous fiber prepared by the sol-gel method combined with the dry spinning has a series of advantages such as small diameter, high strength, high temperature resistance, corrosion resistance, woven, light weight and smooth surface, and can be used as a high-temperature and high-efficiency heat insulating material.
  • High-performance composite materials and catalyst carriers are used in high-temperature industrial furnaces, new materials, chemical industry, and military, nuclear, and aerospace industries.
  • the alumina continuous fiber is prepared by the sol-gel method, and the prepared spinnable sol is added into the barrel, and the spinnable sol is extruded from the spinning hole into the spinning tunnel to form a fine flow by a certain pressure extrusion.
  • the water in the trickle is rapidly evaporated, the fiber is solidified, and the gel is elongated and formed under the action of the winding force of the collecting roller, and then the gel fiber is calcined in a high temperature furnace to form an oxidation.
  • the fiber shrinks due to thermal decomposition, and friction between the fiber filaments forms a strong electrostatic effect.
  • the fiber bundle is affected by strong electrostatic action. Sex, together with the fiber surface is not lubricated, the alumina fiber itself is less flexible.
  • the twisting force causes the fiber to break, affecting the performance of the fiber bundle, and thus affecting the finished product of the alumina continuous fiber.
  • it is necessary to surface-modify alumina continuous fibers to eliminate static electricity, impart certain flexibility and surface lubricity to the fibers, and integrate hundreds or even thousands of fiber monofilaments to make fibers. Successful completion of the joint-stock twisting process.
  • Fiber surface modification technology can be roughly divided into three categories: plasma modification, oxidation modification technology and coating modification technology.
  • the plasma modification technology can improve the properties such as fiber wettability, cohesiveness, hydrophilicity, and disinfection and cleaning of fibers (see: Bi Songmei et al., Industrial Textiles 2013, 6, 32-35);
  • the technology is further divided into electrochemical oxidation, gas phase oxidation and liquid phase oxidation.
  • the treatment of fibers by oxidation modification technology can improve the surface state of fibers (see: Zhang Meiyun, Proceedings of the 13th Annual Conference of China Paper Association (Part 2) , 2008); coating modification technology generally by preparing a fiber-specific sizing agent, using a coupling agent to graft a polymer film forming agent on the surface of the fiber, surface modification of the fiber, improve fiber bundle, lubricity, resistance Friction and other properties (see: Jiang Xue, basalt continuous fiber special sizing agent research, Harbin Institute of Technology Master thesis, 2009). Comparing the above three methods, the coating modification technology is convenient to use and simple to operate. It is suitable for continuous fiber production, has good effect on fiber surface modification and strong controllability.
  • alumina continuous fibers Compared with inorganic fibers such as continuous glass fibers and basalt continuous fibers, alumina continuous fibers have different chemical composition and different processes, resulting in different fiber diameters, strengths, surface states and properties.
  • glass fiber is made by glass ball or waste glass as high-temperature melting, drawing, winding, weaving, etc.
  • the diameter of glass fiber is generally less than 23 ⁇ m
  • the tensile strength is 2300-4300MPa.
  • the basalt fiber is a basalt rock composed of oxides of silica, alumina, calcium oxide, magnesium oxide, iron oxide and titanium dioxide, which is rapidly drawn at a high temperature and then drawn through a drain plate.
  • the diameter of the monofilament is generally less than 9 ⁇ m.
  • the strength is equivalent to that of high-strength S glass fiber, and the alumina continuous fiber is mainly composed of Al 2 O 3 , and Fe 2 O 3 and SiO 2 are also added by sol-gel combined with dry spinning technology, and the diameter is less than 10 ⁇ m.
  • the tensile strength is 1500 to 2500 MPa.
  • the difference in fiber diameter between alumina continuous fibers and glass continuous fibers and basalt continuous fibers results in different specific surface areas of different fiber surfaces; different chemical compositions lead to different fiber contact angles, surface tension and surface energy for different sizing components.
  • the sizing agent described in the patent document CN106587659A is suitable for the glass fiber sizing agent produced by the lattice beam; the sizing agent described in the patent document CN106242320A is suitable for the sizing agent for the glass fiber weaving; the sizing agent described in the patent document CN106277847A is suitable for the high-speed injection and application of the glass fiber.
  • the sizing agent; the sizing agent described in the patent document CN103936302A is suitable for basalt fiber ply-free grit; the sizing agent described in the patent document CN102898044A is suitable for the sizing agent for basalt fiber drawing operation. It can be seen that the sizing formulations used for the glass fibers and basalt fibers described in the different patent documents are different, indicating that different inorganic continuous fibers, fibers of different uses have a special sizing agent formulation, and are not universal.
  • the present invention provides a special sizing agent for alumina continuous fiber twisted yarn and a preparation method thereof, which can impart certain bundle property, antistatic property, lubricity and wear resistance to alumina continuous fiber.
  • the purpose is to solve the problem of static electricity generated by the continuous fiber of alumina in the process of twisting, the breakage of the fiber tow and the non-bundling of the fiber, improve its applicability in the post-processing, and reduce the mechanical properties of the continuous fiber of alumina in processing. Loss in the process.
  • the sizing agent of the present invention is composed of a certain weight percentage of an aqueous epoxy emulsion film-forming agent, a lubricant, an organosilane coupling agent, a pH adjuster and water, and the sizing agent is used to carry out alumina through a film applicator during heat treatment.
  • the continuous fiber surface coating is modified, and after drying and twisting, the finished alumina continuous fiber product can be obtained.
  • the utility model relates to a special sizing agent for alumina continuous fiber and twisted yarn, which comprises the following components according to the weight percentage:
  • the aqueous epoxy emulsion is a bisphenol A type aqueous epoxy emulsion, more preferably a bisphenol A type aqueous epoxy emulsion having an epoxy equivalent of 160 to 280 g/eq; more preferably EX-305 waterborne epoxy emulsion, BH-644 waterborne epoxy emulsion or BH-653 waterborne epoxy emulsion.
  • the bisphenol A type aqueous epoxy emulsion contains an epoxy resin having a molecular weight of 340 to 560/mol.
  • the aqueous epoxy resin (low- and medium-molecular-weight water-based epoxy resin) in the molecular weight range has a strong polarity, and the emulsion can be dried to form a film to impart excellent bundleability to the alumina continuous fiber strand.
  • the lubricant comprises a lubricant A and a lubricant B, and with or without a lubricant C;
  • the lubricant A is an amide type cationic lubricant, and further preferably a lubricant of the type 3760B;
  • the lubricant B is an aliphatic and non-ionic composite lubricant, and further preferably a grade 3550 lubricant;
  • the lubricant C is a cationic lubricant, and further preferably a lubricant of the type 3512;
  • the mass ratio of the lubricant A, the lubricant B, and the lubricant C is 1: (0.3 to 1): (0.3 to 0.8).
  • the lubricant may have two kinds of cationic lubricants, which can play a lubricating role and at the same time can exert an antistatic effect.
  • the principle is that the cationic sizing agent can lower the friction coefficient and make it difficult for the alumina continuous fibers to generate static electricity.
  • the antistatic agent is inorganic lithium chloride.
  • the principle is that inorganic lithium chloride has a strong tendency to form water compounds, and it becomes a salt with crystal water, which has strong moisture absorption property, and absorbs water on the infiltrant film while dissociating into ions, so the conductivity is good. .
  • the organosilane coupling agent is ⁇ -aminopropyltriethoxysilane or ⁇ -(methacryloyloxy)propyltrimethoxysilane.
  • the hydroxyl group in the triol- silane contained in the hydrolyzed organosilane coupling agent forms a hydrogen bond with the hydroxyl group on the surface of the fiber.
  • the hydroxyl group undergoes an etherification reaction at a high temperature, and a part of water is removed to form an ether group, thereby forming a strong covalent bond.
  • the pH adjusting agent is glacial acetic acid.
  • the alumina continuous fiber-twisting special sizing agent comprises the following components in terms of weight percentage:
  • a method for preparing the above-mentioned alumina continuous fiber twisted yarn sizing agent comprises the following steps:
  • the quantitative lubricant is diluted with 10 to 20 times of deionized water, and the stirring time is 0.5 to 1 h;
  • the mass percentage of all material components, including the aqueous epoxy emulsion, the lubricant, the antistatic agent, the organosilane coupling agent, the pH adjuster, and the water in the preparation method of the present invention is 100%.
  • the preparation method of the sizing agent for alumina continuous fiber twisted yarn of the invention has simple steps, is suitable for industrial production, and is easy to popularize.
  • the alumina continuous fiber coated with the sizing agent of the invention can effectively remove the static electricity between the fiber filament and the filament during the fiber twisting process, impart excellent bundleability and lubricity to the fiber, and at the same time impart good mechanical properties to the fiber. performance.
  • the preparation method of the sizing agent of the invention is simple and easy to operate.
  • each component of the alumina continuous fiber twisted yarn special sizing agent is water-soluble, has good adhesion and film forming property, and can avoid the use of volatile organic compounds in a large amount, and is remarkable. Environmental characteristics and application value.
  • Figure 1 is a photograph of an alumina continuous fiber which has not been subjected to an sizing treatment in Test Example 1 of the present invention.
  • Figure 2 is a photograph of an alumina-treated continuous fiber treated with an sizing agent in Test Example 1 of the present invention.
  • Fig. 3 is a photograph of the sizing-treated alumina continuous fiber of Comparative Example 1 in Test Example 2 of the present invention.
  • Figure 4 is a photograph of an sizing treated alumina continuous fiber of Comparative Example 2 or Comparative Example 3 in Test Example 2 of the present invention.
  • Fig. 5 is a photograph of the sizing agent-treated alumina continuous fiber of Comparative Example 4 in Test Example 2 of the present invention.
  • Fig. 6 is a photograph showing the morphology of alumina continuous fibers treated with the sizing agent of Comparative Example 5 in Test Example 2 of the present invention.
  • Fig. 7 is a photograph showing the morphology of continuous silica fibers treated with an sizing agent in Test Example 1 of the present invention.
  • the utility model relates to a special sizing agent for alumina continuous fiber and twisted yarn, which is composed of the following components according to the weight percentage:
  • the aqueous epoxy resin emulsion is a bisphenol A type aqueous epoxy emulsion having an epoxy equivalent of 160 to 180 g/eq.
  • the grade is EX-305 waterborne epoxy emulsion (molecular weight 340 ⁇ 360 / mol), purchased from Shanghai Ai Expo Organic Silicon Materials Co., Ltd.
  • the organosilane coupling agent is ⁇ -(methacryloyloxy)propyltrimethoxysilane, which is purchased from Sinopharm Chemical Reagent Co., Ltd.
  • the lubricant A is an amide type cationic lubricant of the brand 3760B, which is purchased from Xi'an Youji Composite Materials Co., Ltd.
  • the lubricant B is an aliphatic and non-ionic composite lubricant of the grade 3550, which is purchased from Xi'an Youji Composite Materials Co., Ltd.
  • the lubricant C is a cationic lubricant of the grade 3512, which is purchased from Xi'an Youji Composite Materials Co., Ltd.
  • the antistatic agent is inorganic lithium chloride.
  • the pH adjuster is glacial acetic acid.
  • the above method for preparing an alumina sizing agent for continuous fiber entangled yarn according to the above-mentioned sizing agent ratio includes the following steps:
  • the quantitative lubricant is diluted with 10 to 20 times of deionized water, and the stirring time is 0.5 to 1 h;
  • the utility model relates to a special sizing agent for alumina continuous fiber and twisted yarn, which is composed of the following components according to the weight percentage:
  • the aqueous epoxy resin emulsion is a bisphenol A type aqueous epoxy emulsion having an epoxy equivalent of 160 to 180 g/eq.
  • the grade is EX-305 waterborne epoxy emulsion (molecular weight 340 ⁇ 360 / mol), purchased from Shanghai Ai Expo Organic Silicon Materials Co., Ltd.
  • the organosilane coupling agent is ⁇ -aminopropyltriethoxysilane, which is purchased from Sinopharm Chemical Reagent Co., Ltd.
  • the lubricant A is an amide type cationic lubricant of the brand 3760B, which is purchased from Xi'an Youji Composite Materials Co., Ltd.
  • the lubricant B is an aliphatic and non-ionic composite lubricant of the grade 3550, which is purchased from Xi'an Youji Composite Materials Co., Ltd.
  • the antistatic agent is inorganic lithium chloride.
  • the pH adjuster is glacial acetic acid.
  • the preparation method of the above-mentioned alumina continuous fiber twisted yarn special sizing agent is based on the above-mentioned sizing agent ratio, and includes the following steps:
  • the quantitative lubricant is diluted with 10 to 20 times of deionized water, and the stirring time is 0.5 to 1 h;
  • the utility model relates to a special sizing agent for alumina continuous fiber and twisted yarn, which is composed of the following components according to the weight percentage:
  • aqueous epoxy resin 4.5% aqueous epoxy resin, 0.4% organosilane coupling agent, 0.3% lubricant A, 0.25% lubricant B, 0.1% lubricant C, 0.1% antistatic agent and 0.02% pH adjuster.
  • the aqueous epoxy resin emulsion is a bisphenol A type aqueous epoxy emulsion having an epoxy equivalent of 160 to 180 g/eq.
  • the grade is EX-305 waterborne epoxy emulsion (molecular weight 340 ⁇ 360 / mol), purchased from Shanghai Ai Expo Organic Silicon Materials Co., Ltd.
  • the organosilane coupling agent is ⁇ -(methacryloyloxy)propyltrimethoxysilane, which is purchased from Sinopharm Chemical Reagent Co., Ltd.
  • the lubricant A is an amide type cationic lubricant of the brand 3760B, which is purchased from Xi'an Youji Composite Materials Co., Ltd.
  • the lubricant B is an aliphatic and non-ionic composite lubricant of the grade 3550, which is purchased from Xi'an Youji Composite Materials Co., Ltd.
  • the lubricant C is a cationic lubricant of the grade 3512, which is purchased from Xi'an Youji Composite Materials Co., Ltd.
  • the antistatic agent is inorganic lithium chloride.
  • the pH adjuster is glacial acetic acid.
  • the preparation method of the above-mentioned alumina continuous fiber twisted yarn special sizing agent is based on the above-mentioned sizing agent ratio, and includes the following steps:
  • the quantitative lubricant is diluted with 10 to 20 times of deionized water, and the stirring time is 0.5 to 1 h;
  • alumina continuous fiber plus sizing special sizing agent is composed of the following components in terms of weight percentage:
  • the aqueous epoxy resin emulsion is a bisphenol A type aqueous epoxy emulsion having an epoxy equivalent of 180 to 230 g/eq.
  • the grade is BH-653 waterborne epoxy emulsion (molecular weight 360 ⁇ 460/mol), purchased from Dongguan Guangtong Chemical Products Co., Ltd.
  • the organosilane coupling agent is ⁇ -(methacryloyloxy)propyltrimethoxysilane, which is purchased from Sinopharm Chemical Reagent Co., Ltd.
  • the lubricant A is an amide type cationic lubricant of the grade 3760B, which is purchased from Xi'an Youji Composite Material Co., Ltd. the company.
  • the lubricant B is an aliphatic and non-ionic composite lubricant of the grade 3550, which is purchased from Xi'an Youji Composite Materials Co., Ltd.
  • the lubricant C is a cationic lubricant of the grade 3512, which is purchased from Xi'an Youji Composite Materials Co., Ltd.
  • the antistatic agent is inorganic lithium chloride.
  • the pH adjuster is glacial acetic acid.
  • the utility model relates to an sizing agent for alumina continuous fiber and twisted yarn, which is composed of the following components according to the weight percentage:
  • the aqueous epoxy resin emulsion is a bisphenol A type aqueous epoxy emulsion having an epoxy equivalent of 180 to 230 g/eq.
  • BH-653 waterborne epoxy emulsion (epoxy equivalent weight: 360 ⁇ 460 g / equivalent), purchased from Dongguan Guangtong Chemical Products Co., Ltd.
  • the organosilane coupling agent is ⁇ -aminopropyltriethoxysilane, which is purchased from Sinopharm Chemical Reagent Co., Ltd.
  • the lubricant A is an amide type cationic lubricant of the brand 3760B, which is purchased from Xi'an Youji Composite Materials Co., Ltd.
  • the lubricant B is a cationic lubricant of the grade 3512, which is purchased from Xi'an Youji Composite Materials Co., Ltd.
  • the antistatic agent is inorganic lithium chloride.
  • the pH adjuster is glacial acetic acid.
  • the preparation method was the same as in Example 1.
  • the difference is that only 0.6% of the lubricant B is used in the lubricant.
  • Example 2 As described in Example 1, the difference was that only 0.3% of the lubricant B and 0.3% of the lubricant C were used in the lubricant.
  • the sizing for glass fiber weaving is used for comparison as described in the patent document CN106242320A.
  • a glass fiber sizing agent suitable for the manufacture of lattice beams is used for comparison as described in the patent document CN106587659A.
  • Fig. 2 The morphology of the continuous fiber of alumina coated with the sizing agent of Example 1 of the present invention is shown in Fig. 2, and the morphology of the fiber precursor which is not coated with the sizing agent is as shown in Fig. 1.
  • the sizing-coated alumina continuous fiber morphology of Comparative Example 1 was as shown in Fig. 3, and the sizing-coated alumina continuous fiber morphology of Example 1 of the present invention was as shown in Fig. 2 for comparison.
  • the lubricant component of the sizing agent is only treated with the lubricant A.
  • the continuous fiber of the alumina has a large stiffness and a non-smooth surface, and such a fiber is not suitable for the existing twisting production process. The fiber is easily broken or broken during the twisting process.
  • the sizing-coated alumina continuous fiber morphology of Comparative Example 2 or Comparative Example 3 is as shown in FIG. 4, and the sizing-coated alumina continuous fiber morphology of Example 1 of the present invention is as shown in FIG. For comparison.
  • the lubricant component in the sizing agent is only used by using the lubricant B or the lubricants B and C.
  • the treated alumina continuous fiber is too soft, and it can be seen that the fiber bundle effect is not very good, affecting The technical properties of the whole bundle of fibers, such fibers are not suitable for the existing twisting production process, and the fibers are liable to slip or break during the twisting process.
  • the sizing-coated alumina continuous fiber morphology of Comparative Example 4 and Comparative Example 5 was as shown in FIG. 5 and FIG. 6, and the sizing-coated alumina continuous fiber morphology of Example 1 of the present invention is shown in FIG. Figure 7, shown, for comparison.
  • the treated alumina continuous fiber coating amount is applied to the glass fiber weaving sizing agent described in the patent document CN106242320A or the glass fiber sizing agent suitable for the lattice beam manufacturing described in the patent document CN106587659A.
  • Large or some components are not suitable for alumina continuous fiber, so that the fiber is bent after coating and drying, and the bundle is excessive, so that the fiber is flattened and dried by the film applicator, but the fiber is not restored to the original shape, and the fiber is removed.
  • the bundles are stuck together and the monofilament cannot be completely extracted (as shown in Fig. 6 and Fig. 7, the bundle of alumina continuous fibers shown in Fig.
  • the monofilament can be separated, and the bundle of fibers shown in Fig. 6 is bundled. Excessive, unable to separate the monofilament), and the fiber stiffness is too large, the break is broken, affecting the technical performance of the whole bundle of fibers, such fibers are unusable.
  • the alumina continuous fibers were coated with the sizing agent of Examples 1-5 and Comparative Examples 1-5 of the present invention, and the results are shown in Table 1.
  • the alumina continuous fiber treated by the sizing agent of the present invention has a slightly higher stiffness than the fiber which has not been subjected to the sizing treatment, and is in the range of stiffness suitable for twisting, and the whole bundle of fibers is pulled.
  • the tensile strength of the stretch is greatly improved, indicating that the sizing treatment can protect the continuous fibers of alumina, and the fiber twisting process is consistent with the stiffness, lubricity, tensile strength of the whole bundle of fibers, and twisting. The effect is excellent.
  • the lubricant component in the sizing agent only uses the lubricant A.
  • the continuous fiber of the alumina has an improved tensile breaking strength of the whole bundle fiber, but the fiber The stiffness is slightly larger and the lubrication effect is not good. It is not suitable for the existing twisting process. It is only used with the lubricant B or the lubricants B and C. After the coating, the continuous fiber of the continuous fiber of the alumina is stretched and broken.
  • the glass fiber sizing agent suitable for the manufacture of the lattice beam has an improved tensile breaking strength of the whole bundle fiber after coating, but the coating amount is too large, which causes the fiber to be freely carbonized after being subjected to high temperature treatment during use. The damage is serious, affecting the overall performance of the fiber, and the fiber bundle is excessive.
  • the fiber tow is stuck together and the monofilament cannot be separated, so that the continuous fiber of the alumina cannot be used normally, and the fiber is too stiff to make the fiber less resistant to folding after coating. Poor lubrication does not apply to existing twisting processes and does not produce acceptable alumina continuous fibers.

Abstract

The present invention relates to a special impregnating agent for alumina continuous fiber twisted yarn and a preparation method therefor. The impregnating agent consists of the following components in percentage by weight: 3% to 6% of an aqueous epoxy emulsion, 0.2% to 0.6% of a lubricant, 0.1% to 0.2% of an antistatic agent, 0.3% to 0.8% of an organosilane coupling agent, 0.02% to 0.05% of a pH value regulator, and the balance of water. The surface of the fibers is modified with the impregnating agent of the present invention, and the impregnating agent is directly coated onto the surface of the fibers during the process of drawing in alumina continuous fiber production and is then dried. The alumina continuous fibers are endowed with excellent flexibility, bundling and lubricity; and the problems occurring during the ply twist process of alumina continuous fibers, such as fiber hairiness being produced, the fibers being difficult to bundle, etc., due to the fact that static electricity is produced owing to friction among fiber bundles, the fiber surface is not lubricated, and the fibers per se are poor in flexibility and prone to bending and breaking, are solved; and the mechanical properties of the alumina continuous fibers are prevented from being lost.

Description

一种氧化铝连续纤维加捻纱专用浸润剂及其制备方法Special sizing agent for alumina continuous fiber twisted yarn and preparation method thereof 技术领域Technical field
本发明涉及一种连续纤维表面改性技术，具体涉及一种氧化铝连续纤维加捻纱专用浸润剂及其制备方法，属于无机陶瓷纤维浸润剂领域。The invention relates to a continuous fiber surface modification technology, in particular to a special sizing agent for alumina continuous fiber twisted yarn and a preparation method thereof, and belongs to the field of inorganic ceramic fiber sizing agent.
背景技术Background technique
氧化铝连续纤维是重要的高性能无机非金属材料，属于陶瓷纤维的一种，以Al2O3为主要成分，同时还添加Fe2O3、SiO2等。通过溶胶凝胶法结合干法纺丝制备的氧化铝连续纤维具有直径小、高强度、耐高温、耐腐蚀、可编织、重量轻、表面光洁等一系列优点，可以做高温高效隔热材料、高性能复合材料和催化剂载体等，应用在高温工业炉、新材料、化工以及军工、核工业、航天航空等领域。Alumina continuous fiber is an important high-performance inorganic non-metallic material, belonging to a kind of ceramic fiber, with Al 2 O 3 as the main component, and also adding Fe 2 O 3 , SiO 2 and the like. The alumina continuous fiber prepared by the sol-gel method combined with the dry spinning has a series of advantages such as small diameter, high strength, high temperature resistance, corrosion resistance, woven, light weight and smooth surface, and can be used as a high-temperature and high-efficiency heat insulating material. High-performance composite materials and catalyst carriers are used in high-temperature industrial furnaces, new materials, chemical industry, and military, nuclear, and aerospace industries.
目前通过溶胶凝胶法制备氧化铝连续纤维是将制备好的可纺性溶胶加入到料筒中，通过一定压力的挤压使可纺性溶胶从喷丝孔中挤出进入纺丝甬道形成细流，在甬道热空气作用下，细流中水快速挥发，纤维发生固化，在收丝辊缠绕力的作用下伸长变细形成凝胶纤维，再将凝胶纤维放入高温炉中煅烧形成氧化铝连续纤维，通过加捻收丝得到氧化铝连续纤维成品。而氧化铝凝胶纤维在高温煅烧过程中，由于纤维受热分解发生收缩，纤维单丝之间产生摩擦形成较强的静电作用，在后续的合股加捻工艺中由于强静电作用影响纤维的成束性，再加上纤维表面不润滑，氧化铝纤维本身柔韧性较差在加捻过程中受到扭曲力导致纤维发生断丝现象，影响纤维束的性能，从而影响氧化铝连续纤维的成品生产。要解决以上存在的问题就需要对氧化铝连续纤维进行表面改性，消除静电，赋予纤维一定的柔韧性、表面润滑性，同时将数百根乃至数千根纤维单丝集成一束，使纤维顺利完成合股加捻工艺。At present, the alumina continuous fiber is prepared by the sol-gel method, and the prepared spinnable sol is added into the barrel, and the spinnable sol is extruded from the spinning hole into the spinning tunnel to form a fine flow by a certain pressure extrusion. Under the action of the hot air of the ramp, the water in the trickle is rapidly evaporated, the fiber is solidified, and the gel is elongated and formed under the action of the winding force of the collecting roller, and then the gel fiber is calcined in a high temperature furnace to form an oxidation. Aluminum continuous fiber, obtained by adding twisted wire to obtain finished alumina continuous fiber. In the high-temperature calcination process of alumina gel fiber, the fiber shrinks due to thermal decomposition, and friction between the fiber filaments forms a strong electrostatic effect. In the subsequent ply twisting process, the fiber bundle is affected by strong electrostatic action. Sex, together with the fiber surface is not lubricated, the alumina fiber itself is less flexible. During the twisting process, the twisting force causes the fiber to break, affecting the performance of the fiber bundle, and thus affecting the finished product of the alumina continuous fiber. To solve the above problems, it is necessary to surface-modify alumina continuous fibers to eliminate static electricity, impart certain flexibility and surface lubricity to the fibers, and integrate hundreds or even thousands of fiber monofilaments to make fibers. Successful completion of the joint-stock twisting process.
纤维表面改性技术大体可以分成三类：等离子体改性、氧化改性技术及涂层改性技术。其中利用等离子体改性技术可以改善纤维浸润性、粘结性、亲水性等性能以及对纤维的消毒清洗等(参见：毕松梅等，产业用纺织品2013,6,32-35)；氧化改性技术又分为电化学氧化、气相氧化法和液相氧化法，利用氧化改性技术处理纤维，可以改善纤维表面状态(参见：张美云，中国造纸学会第十三届学术年会论文集(下)，2008)；涂层改性技术一般是通过制备纤维专用浸润剂，利用偶联剂在纤维表面接枝高分子成膜剂，对纤维进行表面改性，提高纤维的集束性，润滑性，耐磨擦性等性能(参见：姜雪，玄武岩连续纤维专用浸润剂的研究，哈尔滨工业大学硕士论文，2009)。对以上三种方法进行比较，涂层改性技术使用方便，操作简单， 适合于连续纤维生产，对纤维表面改性效果好，可控性强。Fiber surface modification technology can be roughly divided into three categories: plasma modification, oxidation modification technology and coating modification technology. Among them, the plasma modification technology can improve the properties such as fiber wettability, cohesiveness, hydrophilicity, and disinfection and cleaning of fibers (see: Bi Songmei et al., Industrial Textiles 2013, 6, 32-35); The technology is further divided into electrochemical oxidation, gas phase oxidation and liquid phase oxidation. The treatment of fibers by oxidation modification technology can improve the surface state of fibers (see: Zhang Meiyun, Proceedings of the 13th Annual Conference of China Paper Association (Part 2) , 2008); coating modification technology generally by preparing a fiber-specific sizing agent, using a coupling agent to graft a polymer film forming agent on the surface of the fiber, surface modification of the fiber, improve fiber bundle, lubricity, resistance Friction and other properties (see: Jiang Xue, basalt continuous fiber special sizing agent research, Harbin Institute of Technology Master thesis, 2009). Comparing the above three methods, the coating modification technology is convenient to use and simple to operate. It is suitable for continuous fiber production, has good effect on fiber surface modification and strong controllability.
氧化铝连续纤维与玻璃连续纤维、玄武岩连续纤维等无机纤维相比，由于化学成分组成不同，采用的工艺不同导致纤维直径、强度和表面状态与性质不同。如玻璃纤维是以玻璃球或废旧玻璃为原料经高温熔制、拉丝、络纱、织布等工艺制造成的，玻纤直径一般小于23μm，拉伸强度为2300～4300MPa。玄武岩纤维是由二氧化硅、氧化铝、氧化钙、氧化镁、氧化铁和二氧化钛等氧化物组成的玄武岩石料在高温熔融后，通过漏板快速拉制而成的，单丝直径一般小于9μm，强度与高强度S玻璃纤维相当，而氧化铝连续纤维以Al2O3为主要成分，同时还添加Fe2O3、SiO2通过溶胶凝胶结合干法纺丝技术制备而成，直径小于10μm，拉伸强度为1500～2500MPa。氧化铝连续纤维与玻璃连续纤维及玄武岩连续纤维相比纤维直径不同导致不同纤维表面的比表面积不同；化学成分不同导致不同纤维对不同的浸润剂成分的接触角，表面张力，表面能不同从而导致不同纤维对不同成分浸润剂的浸润性能不同；玻璃连续纤维和玄武岩连续纤维都是采用熔融纺制造工艺拉制而成，不同的是氧化铝连续纤维还要经过高温煅烧过程，这就导致氧化铝连续纤维生产过程更为复杂，对于纤维丝束的保护要求更高，对浸润剂要求也更高。Compared with inorganic fibers such as continuous glass fibers and basalt continuous fibers, alumina continuous fibers have different chemical composition and different processes, resulting in different fiber diameters, strengths, surface states and properties. For example, glass fiber is made by glass ball or waste glass as high-temperature melting, drawing, winding, weaving, etc., the diameter of glass fiber is generally less than 23μm, and the tensile strength is 2300-4300MPa. The basalt fiber is a basalt rock composed of oxides of silica, alumina, calcium oxide, magnesium oxide, iron oxide and titanium dioxide, which is rapidly drawn at a high temperature and then drawn through a drain plate. The diameter of the monofilament is generally less than 9 μm. The strength is equivalent to that of high-strength S glass fiber, and the alumina continuous fiber is mainly composed of Al 2 O 3 , and Fe 2 O 3 and SiO 2 are also added by sol-gel combined with dry spinning technology, and the diameter is less than 10 μm. The tensile strength is 1500 to 2500 MPa. The difference in fiber diameter between alumina continuous fibers and glass continuous fibers and basalt continuous fibers results in different specific surface areas of different fiber surfaces; different chemical compositions lead to different fiber contact angles, surface tension and surface energy for different sizing components. Different fibers have different wetting properties for different components of infiltrant; glass continuous fiber and basalt continuous fiber are drawn by melt spinning manufacturing process, the difference is that alumina continuous fiber is also subjected to high temperature calcination process, which leads to alumina The continuous fiber production process is more complicated, requiring higher protection for the fiber tow and higher requirements for the sizing agent.
专利文件CN106587659A所述浸润剂适用于格子梁制造的玻璃纤维浸润剂；专利文件CN106242320A所述浸润剂适用于玻璃纤维织造用浸润剂；专利文件CN106277847A所述浸润剂适用于玻璃纤维高速喷射及揉捻用浸润剂；专利文件CN103936302A所述浸润剂适用于玄武岩纤维合股无捻粗砂；专利文件CN102898044A所述浸润剂适用于玄武岩纤维拉丝作业用浸润剂。可见不同专利文件中所述的玻璃纤维和玄武岩纤维所用的浸润剂配方都不同，说明不同的无机类连续纤维，不同用途的纤维都有专门的浸润剂配方与之配合，并不能通用。The sizing agent described in the patent document CN106587659A is suitable for the glass fiber sizing agent produced by the lattice beam; the sizing agent described in the patent document CN106242320A is suitable for the sizing agent for the glass fiber weaving; the sizing agent described in the patent document CN106277847A is suitable for the high-speed injection and application of the glass fiber. The sizing agent; the sizing agent described in the patent document CN103936302A is suitable for basalt fiber ply-free grit; the sizing agent described in the patent document CN102898044A is suitable for the sizing agent for basalt fiber drawing operation. It can be seen that the sizing formulations used for the glass fibers and basalt fibers described in the different patent documents are different, indicating that different inorganic continuous fibers, fibers of different uses have a special sizing agent formulation, and are not universal.
目前，关于氧化铝连续纤维浸润剂未见报道，将其他纤维浸润剂用于浸润氧化铝连续纤维效果较差，为此，提出本发明。At present, there has been no report on alumina continuous fiber sizing agents, and the use of other fiber sizing agents for infiltrating alumina continuous fibers is inferior, and the present invention has been proposed.
发明内容Summary of the invention
针对现有技术的不足，本发明提供一种氧化铝连续纤维加捻纱专用浸润剂及其制备方法，该浸润剂能够赋予氧化铝连续纤维一定的集束性，抗静电性，润滑性，耐磨性，目的解决氧化铝连续纤维在加捻过程中产生的静电问题、纤维丝束发生断裂以及纤维不成束问题，提高其在后加工过程中的适用性，同时减少氧化铝连续纤维力学性能在加工过程中的损失。In view of the deficiencies of the prior art, the present invention provides a special sizing agent for alumina continuous fiber twisted yarn and a preparation method thereof, which can impart certain bundle property, antistatic property, lubricity and wear resistance to alumina continuous fiber. The purpose is to solve the problem of static electricity generated by the continuous fiber of alumina in the process of twisting, the breakage of the fiber tow and the non-bundling of the fiber, improve its applicability in the post-processing, and reduce the mechanical properties of the continuous fiber of alumina in processing. Loss in the process.
本发明的浸润剂采用一定重量百分比的水性环氧乳液成膜剂、润滑剂、有机硅烷偶联剂、pH值调节剂和水组成，使用该浸润剂在热处理过程中通过涂膜器进行氧化铝连续纤维表面涂层改性，经过烘干加捻后，可制得氧化铝连续纤维成品。 The sizing agent of the present invention is composed of a certain weight percentage of an aqueous epoxy emulsion film-forming agent, a lubricant, an organosilane coupling agent, a pH adjuster and water, and the sizing agent is used to carry out alumina through a film applicator during heat treatment. The continuous fiber surface coating is modified, and after drying and twisting, the finished alumina continuous fiber product can be obtained.
本发明的技术方案如下：The technical solution of the present invention is as follows:
一种氧化铝连续纤维加捻纱专用浸润剂，按照重量百分比包括以下组分组成：The utility model relates to a special sizing agent for alumina continuous fiber and twisted yarn, which comprises the following components according to the weight percentage:
3～6％水性环氧乳液、0.2～0.6％润滑剂、0.1～0.2％抗静电剂、0.3～0.8％有机硅烷偶联剂、0.02～0.05％pH值调节剂，余量为水。3 to 6% aqueous epoxy emulsion, 0.2 to 0.6% lubricant, 0.1 to 0.2% antistatic agent, 0.3 to 0.8% organosilane coupling agent, 0.02 to 0.05% pH adjuster, and the balance is water.
根据本发明，优选的，所述的水性环氧乳液为双酚A型水性环氧乳液，进一步优选为环氧当量在160～280克/当量的双酚A型水性环氧乳液；更优选为EX-305型水性环氧乳液、BH-644型水性环氧乳液或BH-653型水性环氧乳液。According to the present invention, preferably, the aqueous epoxy emulsion is a bisphenol A type aqueous epoxy emulsion, more preferably a bisphenol A type aqueous epoxy emulsion having an epoxy equivalent of 160 to 280 g/eq; more preferably EX-305 waterborne epoxy emulsion, BH-644 waterborne epoxy emulsion or BH-653 waterborne epoxy emulsion.
优选的，所述的双酚A型水性环氧乳液所含环氧树脂分子量为340～560/mol。该分子量范围内的水性环氧树脂(低、中分子量水性环氧树脂)具有强极性，其乳液烘干成膜后可以赋予氧化铝连续纤维原丝优良的集束性。Preferably, the bisphenol A type aqueous epoxy emulsion contains an epoxy resin having a molecular weight of 340 to 560/mol. The aqueous epoxy resin (low- and medium-molecular-weight water-based epoxy resin) in the molecular weight range has a strong polarity, and the emulsion can be dried to form a film to impart excellent bundleability to the alumina continuous fiber strand.
根据本发明，优选的，所述的润滑剂包括润滑剂A和润滑剂B，以及包括或不包括润滑剂C；According to the present invention, preferably, the lubricant comprises a lubricant A and a lubricant B, and with or without a lubricant C;
所述的润滑剂A为酰胺型阳离子型润滑剂，进一步优选牌号为3760B型润滑剂；The lubricant A is an amide type cationic lubricant, and further preferably a lubricant of the type 3760B;
所述的润滑剂B为脂肪族及非离子复合型润滑剂，进一步优选牌号为3550型润滑剂；The lubricant B is an aliphatic and non-ionic composite lubricant, and further preferably a grade 3550 lubricant;
所述的润滑剂C为阳离子型润滑剂，进一步优选牌号为3512型润滑剂；The lubricant C is a cationic lubricant, and further preferably a lubricant of the type 3512;
优选的，润滑剂A、润滑剂B和润滑剂C的质量比为1：(0.3～1)：(0.3～0.8)。Preferably, the mass ratio of the lubricant A, the lubricant B, and the lubricant C is 1: (0.3 to 1): (0.3 to 0.8).
所述的润滑剂中可以有两种阳离子型润滑剂，起润滑作用，同时能起到抗静电作用，原理是阳离子型浸润剂可以降低摩擦系数，使氧化铝连续纤维难于产生静电。The lubricant may have two kinds of cationic lubricants, which can play a lubricating role and at the same time can exert an antistatic effect. The principle is that the cationic sizing agent can lower the friction coefficient and make it difficult for the alumina continuous fibers to generate static electricity.
根据本发明，优选的，所述的抗静电剂为无机氯化锂。原理是无机氯化锂有强烈形成水化合物的趋势，成为带有结晶水的盐类，具有较强的吸潮性，在浸润剂膜上吸收水分的同时本身离解成离子，所以导电效果很好。According to the present invention, preferably, the antistatic agent is inorganic lithium chloride. The principle is that inorganic lithium chloride has a strong tendency to form water compounds, and it becomes a salt with crystal water, which has strong moisture absorption property, and absorbs water on the infiltrant film while dissociating into ions, so the conductivity is good. .
根据本发明，优选的，所述的有机硅烷偶联剂为γ-氨丙基三乙氧基硅烷或γ-(甲基丙烯酰氧)丙基三甲氧基硅烷。水解后的有机硅烷偶联剂含有的三醇基硅烷中的羟基与纤维表面的羟基形成氢键。烘干过程中，羟基在高温下发生醚化反应，脱去一份水生成醚基，形成牢固的共价键。According to the invention, preferably, the organosilane coupling agent is γ-aminopropyltriethoxysilane or γ-(methacryloyloxy)propyltrimethoxysilane. The hydroxyl group in the triol- silane contained in the hydrolyzed organosilane coupling agent forms a hydrogen bond with the hydroxyl group on the surface of the fiber. During the drying process, the hydroxyl group undergoes an etherification reaction at a high temperature, and a part of water is removed to form an ether group, thereby forming a strong covalent bond.
根据本发明，优选的，所述的pH值调节剂为冰醋酸。According to the present invention, preferably, the pH adjusting agent is glacial acetic acid.
根据本发明，优选的，所述的氧化铝连续纤维加捻纱专用浸润剂，按照重量百分比包括以下组分组成：According to the present invention, preferably, the alumina continuous fiber-twisting special sizing agent comprises the following components in terms of weight percentage:
3～5％水性环氧乳液、0.2～0.6％润滑剂、0.1～0.2％抗静电剂、0.3～0.6％有机硅烷偶联剂、0.02～0.05％pH值调节剂，余量为水。 3 to 5% aqueous epoxy emulsion, 0.2 to 0.6% lubricant, 0.1 to 0.2% antistatic agent, 0.3 to 0.6% organosilane coupling agent, 0.02 to 0.05% pH adjuster, and the balance is water.
根据本发明，上述氧化铝连续纤维加捻纱用浸润剂的制备方法，包括步骤如下：According to the present invention, a method for preparing the above-mentioned alumina continuous fiber twisted yarn sizing agent comprises the following steps:
(1)在水中加入pH值调节剂，将水的pH值调节为3～4，再加入定量的有机硅烷偶联剂，继续搅拌至水溶液澄清后再加入pH值调节剂，将溶液的pH值调节为4～5；(1) Adding a pH adjuster to the water, adjusting the pH of the water to 3 to 4, adding a quantitative amount of the organosilane coupling agent, continuing to stir until the aqueous solution is clarified, and then adding a pH adjuster to adjust the pH of the solution. Adjust to 4 to 5;
(2)将定量的水性环氧乳液用10～15倍的去离子水进行稀释，搅拌时间为0.5～1h；(2) The quantitative aqueous epoxy emulsion is diluted with 10 to 15 times of deionized water, and the stirring time is 0.5 to 1 h;
(3)将定量的润滑剂用10～20倍的去离子水进行稀释，搅拌时间为0.5～1h；(3) The quantitative lubricant is diluted with 10 to 20 times of deionized water, and the stirring time is 0.5 to 1 h;
(4)将定量的抗静电剂用10～20倍的去离子水进行溶解，搅拌时间为1～2h；(4) The quantitative antistatic agent is dissolved in 10 to 20 times of deionized water, and the stirring time is 1 to 2 hours;
(5)将步骤(2)、(3)、(4)中的溶液混合均匀，搅拌0.5～1h；(5) mixing the solutions in steps (2), (3), (4) uniformly, stirring 0.5 ~ 1h;
(6)将步骤(1)中水解好的有机硅烷偶联剂及余量的水加入步骤(5)得到的混合溶液中，均匀搅拌1～2h，即得氧化铝连续纤维加捻纱专用浸润剂。(6) adding the hydrolyzed organosilane coupling agent and the remaining amount of water in the step (1) to the mixed solution obtained in the step (5), and uniformly stirring for 1 to 2 hours, thereby obtaining a special infiltration of the alumina continuous fiber and the twisted yarn. Agent.
本发明的制备方法中所有物料组分，包括水性环氧乳液、润滑剂、抗静电剂、有机硅烷偶联剂、pH值调节剂和水的质量百分比加和为100％。The mass percentage of all material components, including the aqueous epoxy emulsion, the lubricant, the antistatic agent, the organosilane coupling agent, the pH adjuster, and the water in the preparation method of the present invention is 100%.
本发明的氧化铝连续纤维加捻纱用浸润剂的制备方法，步骤简单、适于工业化生产，易于推广。The preparation method of the sizing agent for alumina continuous fiber twisted yarn of the invention has simple steps, is suitable for industrial production, and is easy to popularize.
本发明的优点在于：The advantages of the invention are:
1.采用本发明中的浸润剂涂覆过的氧化铝连续纤维能够有效去除纤维加捻过程中纤维丝与丝间的静电，赋予纤维优良的成束性和润滑性，同时赋予纤维良好的力学性能。1. The alumina continuous fiber coated with the sizing agent of the invention can effectively remove the static electricity between the fiber filament and the filament during the fiber twisting process, impart excellent bundleability and lubricity to the fiber, and at the same time impart good mechanical properties to the fiber. performance.
2.采用本发明浸润剂制备方法简单，容易操作。2. The preparation method of the sizing agent of the invention is simple and easy to operate.
3.本发明中所述氧化铝连续纤维加捻纱专用浸润剂中各成分都是水溶性的，有很好的粘结性和成膜性，并且可避免挥发性有机物的大量使用，有显著的环保特色和应用价值。3. In the present invention, each component of the alumina continuous fiber twisted yarn special sizing agent is water-soluble, has good adhesion and film forming property, and can avoid the use of volatile organic compounds in a large amount, and is remarkable. Environmental characteristics and application value.
附图说明DRAWINGS
图1为本发明试验例1中未经过浸润剂处理的氧化铝连续纤维照片。BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a photograph of an alumina continuous fiber which has not been subjected to an sizing treatment in Test Example 1 of the present invention.
图2为本发明试验例1中经过浸润剂处理过的氧化铝连续纤维照片。Figure 2 is a photograph of an alumina-treated continuous fiber treated with an sizing agent in Test Example 1 of the present invention.
图3为本发明试验例2中经过对比例1的浸润剂处理过的氧化铝连续纤维照片。Fig. 3 is a photograph of the sizing-treated alumina continuous fiber of Comparative Example 1 in Test Example 2 of the present invention.
图4为本发明试验例2中经过对比例2或对比例3的浸润剂处理过的氧化铝连续纤维照片。Figure 4 is a photograph of an sizing treated alumina continuous fiber of Comparative Example 2 or Comparative Example 3 in Test Example 2 of the present invention.
图5为本发明试验例2中经过对比例4的浸润剂处理过的氧化铝连续纤维照片。Fig. 5 is a photograph of the sizing agent-treated alumina continuous fiber of Comparative Example 4 in Test Example 2 of the present invention.
图6为本发明试验例2中经过对比例5的浸润剂处理过的氧化铝连续纤维形态照片。Fig. 6 is a photograph showing the morphology of alumina continuous fibers treated with the sizing agent of Comparative Example 5 in Test Example 2 of the present invention.
图7为本发明试验例1中经过浸润剂处理过的氧化铝连续纤维形态照片。Fig. 7 is a photograph showing the morphology of continuous silica fibers treated with an sizing agent in Test Example 1 of the present invention.
具体实施方式Detailed ways
下面通过具体实施例对本发明作进一步说明，但不限于此。 The invention is further illustrated by the following specific examples, but is not limited thereto.
实施例中所用原料如无特殊说明，均为常规市购产品。The raw materials used in the examples are conventionally commercially available products unless otherwise specified.
实施例1Example 1
一种氧化铝连续纤维加捻纱专用浸润剂，按照重量百分比由以下成分组成：The utility model relates to a special sizing agent for alumina continuous fiber and twisted yarn, which is composed of the following components according to the weight percentage:
3.0％水性环氧树脂、0.4％有机硅烷偶联剂、0.3％润滑剂A、0.2％润滑剂B、0.1％润滑剂C、0.1％抗静电剂及0.02％pH值调节剂。3.0% aqueous epoxy resin, 0.4% organosilane coupling agent, 0.3% lubricant A, 0.2% lubricant B, 0.1% lubricant C, 0.1% antistatic agent and 0.02% pH adjuster.
本实施例中，所述的水性环氧树脂乳液为环氧当量160～180克/当量的双酚A型水性环氧乳液。牌号为EX-305型水性环氧乳液(分子量为340～360/mol)，购自上海爱世博有机硅材料有限公司。In the present embodiment, the aqueous epoxy resin emulsion is a bisphenol A type aqueous epoxy emulsion having an epoxy equivalent of 160 to 180 g/eq. The grade is EX-305 waterborne epoxy emulsion (molecular weight 340 ~ 360 / mol), purchased from Shanghai Ai Expo Organic Silicon Materials Co., Ltd.
所述的有机硅烷偶联剂为γ-(甲基丙烯酰氧)丙基三甲氧基硅烷，购自国药集团化学试剂有限公司。The organosilane coupling agent is γ-(methacryloyloxy)propyltrimethoxysilane, which is purchased from Sinopharm Chemical Reagent Co., Ltd.
所述的润滑剂A是牌号为3760B的酰胺型阳离子型润滑剂，购自西安友基复合材料有限公司。The lubricant A is an amide type cationic lubricant of the brand 3760B, which is purchased from Xi'an Youji Composite Materials Co., Ltd.
所述的润滑剂B是牌号为3550的脂肪族及非离子复合型润滑剂，购自西安友基复合材料有限公司。The lubricant B is an aliphatic and non-ionic composite lubricant of the grade 3550, which is purchased from Xi'an Youji Composite Materials Co., Ltd.
所述的润滑剂C是牌号为3512的阳离子型润滑剂，购自西安友基复合材料有限公司。The lubricant C is a cationic lubricant of the grade 3512, which is purchased from Xi'an Youji Composite Materials Co., Ltd.
所述的抗静电剂是无机氯化锂。The antistatic agent is inorganic lithium chloride.
所述的pH值调节剂采用的是冰醋酸。The pH adjuster is glacial acetic acid.
上述氧化铝连续纤维加捻纱用浸润剂的制备方法，根据以上所述的浸润剂配比，并包括以下几个步骤：The above method for preparing an alumina sizing agent for continuous fiber entangled yarn according to the above-mentioned sizing agent ratio includes the following steps:
(1)在水中加入pH值调节剂，将水的pH值调节为3～4，再加入定量的有机硅烷偶联剂，继续搅拌至水溶液澄清后再加入pH值调节剂，将溶液的pH值调节为4～5；(1) Adding a pH adjuster to the water, adjusting the pH of the water to 3 to 4, adding a quantitative amount of the organosilane coupling agent, continuing to stir until the aqueous solution is clarified, and then adding a pH adjuster to adjust the pH of the solution. Adjust to 4 to 5;
(2)将定量的水性环氧乳液用10～15倍的去离子水进行稀释，搅拌时间为0.5～1h；(2) The quantitative aqueous epoxy emulsion is diluted with 10 to 15 times of deionized water, and the stirring time is 0.5 to 1 h;
(3)将定量的润滑剂用10～20倍的去离子水进行稀释，搅拌时间为0.5～1h；(3) The quantitative lubricant is diluted with 10 to 20 times of deionized water, and the stirring time is 0.5 to 1 h;
(4)将定量的抗静电剂用10～20倍的去离子水进行溶解，搅拌时间为1～2h；(4) The quantitative antistatic agent is dissolved in 10 to 20 times of deionized water, and the stirring time is 1 to 2 hours;
(5)将步骤(2)、(3)、(4)中的溶液混合均匀，搅拌0.5～1h；(5) mixing the solutions in steps (2), (3), (4) uniformly, stirring 0.5 ~ 1h;
(6)将步骤(1)中水解好的有机硅烷偶联剂及余量的水加入步骤(5)得到的混合溶液中，均匀搅拌1～2h，即得氧化铝连续纤维加捻纱专用浸润剂。(6) adding the hydrolyzed organosilane coupling agent and the remaining amount of water in the step (1) to the mixed solution obtained in the step (5), and uniformly stirring for 1 to 2 hours, thereby obtaining a special infiltration of the alumina continuous fiber and the twisted yarn. Agent.
实施例2Example 2
一种氧化铝连续纤维加捻纱专用浸润剂，按照重量百分比由以下成分组成： The utility model relates to a special sizing agent for alumina continuous fiber and twisted yarn, which is composed of the following components according to the weight percentage:
3.5％水性环氧树脂、0.4％有机硅烷偶联剂、0.3％润滑剂A、0.3％润滑剂B、0.1％抗静电剂及0.02％pH值调节剂。3.5% aqueous epoxy resin, 0.4% organosilane coupling agent, 0.3% lubricant A, 0.3% lubricant B, 0.1% antistatic agent and 0.02% pH adjuster.
本实施例中，所述的水性环氧树脂乳液为环氧当量160～180克/当量的双酚A型水性环氧乳液。牌号为EX-305型水性环氧乳液(分子量为340～360/mol)，购自上海爱世博有机硅材料有限公司。In the present embodiment, the aqueous epoxy resin emulsion is a bisphenol A type aqueous epoxy emulsion having an epoxy equivalent of 160 to 180 g/eq. The grade is EX-305 waterborne epoxy emulsion (molecular weight 340 ~ 360 / mol), purchased from Shanghai Ai Expo Organic Silicon Materials Co., Ltd.
所述的有机硅烷偶联剂为γ-氨丙基三乙氧基硅烷，购自国药集团化学试剂有限公司。The organosilane coupling agent is γ-aminopropyltriethoxysilane, which is purchased from Sinopharm Chemical Reagent Co., Ltd.
所述的润滑剂A是牌号为3760B的酰胺型阳离子型润滑剂，购自西安友基复合材料有限公司。The lubricant A is an amide type cationic lubricant of the brand 3760B, which is purchased from Xi'an Youji Composite Materials Co., Ltd.
所述的润滑剂B是牌号为3550的脂肪族及非离子复合型润滑剂，购自西安友基复合材料有限公司。The lubricant B is an aliphatic and non-ionic composite lubricant of the grade 3550, which is purchased from Xi'an Youji Composite Materials Co., Ltd.
所述的抗静电剂是无机氯化锂。The antistatic agent is inorganic lithium chloride.
所述的pH值调节剂采用的是冰醋酸。The pH adjuster is glacial acetic acid.
上述氧化铝连续纤维加捻纱专用浸润剂的制备方法，根据以上所述的浸润剂配比，并包括以下几个步骤：The preparation method of the above-mentioned alumina continuous fiber twisted yarn special sizing agent is based on the above-mentioned sizing agent ratio, and includes the following steps:
(1)在水中加入pH值调节剂，将水的pH值调节为3～4，再加入定量的有机硅烷偶联剂，继续搅拌至水溶液澄清后再加入pH值调节剂，将溶液的pH值调节为4～5；(1) Adding a pH adjuster to the water, adjusting the pH of the water to 3 to 4, adding a quantitative amount of the organosilane coupling agent, continuing to stir until the aqueous solution is clarified, and then adding a pH adjuster to adjust the pH of the solution. Adjust to 4 to 5;
(2)将定量的水性环氧乳液用10～15倍的去离子水进行稀释，搅拌时间为0.5～1h；(2) The quantitative aqueous epoxy emulsion is diluted with 10 to 15 times of deionized water, and the stirring time is 0.5 to 1 h;
(3)将定量的润滑剂用10～20倍的去离子水进行稀释，搅拌时间为0.5～1h；(3) The quantitative lubricant is diluted with 10 to 20 times of deionized water, and the stirring time is 0.5 to 1 h;
(4)将定量的抗静电剂用10～20倍的去离子水进行溶解，搅拌时间为1～2h；(4) The quantitative antistatic agent is dissolved in 10 to 20 times of deionized water, and the stirring time is 1 to 2 hours;
(5)将步骤(2)、(3)、(4)中的溶液混合均匀，搅拌0.5～1h；(5) mixing the solutions in steps (2), (3), (4) uniformly, stirring 0.5 ~ 1h;
(6)将步骤(1)中水解好的有机硅烷偶联剂及余量的水加入步骤(5)得到的混合溶液中，均匀搅拌1～2h，即得氧化铝连续纤维加捻纱专用浸润剂。(6) adding the hydrolyzed organosilane coupling agent and the remaining amount of water in the step (1) to the mixed solution obtained in the step (5), and uniformly stirring for 1 to 2 hours, thereby obtaining a special infiltration of the alumina continuous fiber and the twisted yarn. Agent.
实施例3Example 3
一种氧化铝连续纤维加捻纱专用浸润剂，按照重量百分比由以下成分组成：The utility model relates to a special sizing agent for alumina continuous fiber and twisted yarn, which is composed of the following components according to the weight percentage:
4.5％水性环氧树脂、0.4％有机硅烷偶联剂、0.3％润滑剂A、0.25％润滑剂B、0.1％润滑剂C、0.1％抗静电剂及0.02％pH值调节剂。4.5% aqueous epoxy resin, 0.4% organosilane coupling agent, 0.3% lubricant A, 0.25% lubricant B, 0.1% lubricant C, 0.1% antistatic agent and 0.02% pH adjuster.
本实施例中，所述的水性环氧树脂乳液为环氧当量160～180克/当量的双酚A型水性环氧乳液。牌号为EX-305型水性环氧乳液(分子量为340～360/mol)，购自上海爱世博有机硅材料有限公司。 In the present embodiment, the aqueous epoxy resin emulsion is a bisphenol A type aqueous epoxy emulsion having an epoxy equivalent of 160 to 180 g/eq. The grade is EX-305 waterborne epoxy emulsion (molecular weight 340 ~ 360 / mol), purchased from Shanghai Ai Expo Organic Silicon Materials Co., Ltd.
所述的有机硅烷偶联剂为γ-(甲基丙烯酰氧)丙基三甲氧基硅烷，购自国药集团化学试剂有限公司。The organosilane coupling agent is γ-(methacryloyloxy)propyltrimethoxysilane, which is purchased from Sinopharm Chemical Reagent Co., Ltd.
所述的润滑剂A是牌号为3760B的酰胺型阳离子型润滑剂，购自西安友基复合材料有限公司。The lubricant A is an amide type cationic lubricant of the brand 3760B, which is purchased from Xi'an Youji Composite Materials Co., Ltd.
所述的润滑剂B是牌号为3550的脂肪族及非离子复合型润滑剂，购自西安友基复合材料有限公司。The lubricant B is an aliphatic and non-ionic composite lubricant of the grade 3550, which is purchased from Xi'an Youji Composite Materials Co., Ltd.
所述的润滑剂C是牌号为3512的阳离子型润滑剂，购自西安友基复合材料有限公司。The lubricant C is a cationic lubricant of the grade 3512, which is purchased from Xi'an Youji Composite Materials Co., Ltd.
所述的抗静电剂是无机氯化锂。The antistatic agent is inorganic lithium chloride.
所述的pH值调节剂采用的是冰醋酸。The pH adjuster is glacial acetic acid.
上述氧化铝连续纤维加捻纱专用浸润剂的制备方法，根据以上所述的浸润剂配比，并包括以下几个步骤：The preparation method of the above-mentioned alumina continuous fiber twisted yarn special sizing agent is based on the above-mentioned sizing agent ratio, and includes the following steps:
(1)在水中加入pH值调节剂，将水的pH值调节为3～4，再加入定量的有机硅烷偶联剂，继续搅拌至水溶液澄清后再加入pH值调节剂，将溶液的pH值调节为4～5；(1) Adding a pH adjuster to the water, adjusting the pH of the water to 3 to 4, adding a quantitative amount of the organosilane coupling agent, continuing to stir until the aqueous solution is clarified, and then adding a pH adjuster to adjust the pH of the solution. Adjust to 4 to 5;
(2)将定量的水性环氧乳液用10～15倍的去离子水进行稀释，搅拌时间为0.5～1h；(2) The quantitative aqueous epoxy emulsion is diluted with 10 to 15 times of deionized water, and the stirring time is 0.5 to 1 h;
(3)将定量的润滑剂用10～20倍的去离子水进行稀释，搅拌时间为0.5～1h；(3) The quantitative lubricant is diluted with 10 to 20 times of deionized water, and the stirring time is 0.5 to 1 h;
(4)将定量的抗静电剂用10～20倍的去离子水进行溶解，搅拌时间为1～2h；(4) The quantitative antistatic agent is dissolved in 10 to 20 times of deionized water, and the stirring time is 1 to 2 hours;
(5)将步骤(2)、(3)、(4)中的溶液混合均匀，搅拌0.5～1h；(5) mixing the solutions in steps (2), (3), (4) uniformly, stirring 0.5 ~ 1h;
(6)将步骤(1)中水解好的有机硅烷偶联剂及余量的水加入步骤(5)得到的混合溶液中，均匀搅拌1～2h，即得氧化铝连续纤维加捻纱专用浸润剂。(6) adding the hydrolyzed organosilane coupling agent and the remaining amount of water in the step (1) to the mixed solution obtained in the step (5), and uniformly stirring for 1 to 2 hours, thereby obtaining a special infiltration of the alumina continuous fiber and the twisted yarn. Agent.
实施例4Example 4
上述氧化铝连续纤维加捻纱专用浸润剂，按照重量百分比由以下成分组成：The above-mentioned alumina continuous fiber plus sizing special sizing agent is composed of the following components in terms of weight percentage:
4.0％水性环氧树脂、0.4％有机硅烷偶联剂、0.3％润滑剂A、0.2％润滑剂B、0.1％润滑剂C、0.1％抗静电剂及0.02％pH值调节剂。4.0% aqueous epoxy resin, 0.4% organosilane coupling agent, 0.3% lubricant A, 0.2% lubricant B, 0.1% lubricant C, 0.1% antistatic agent and 0.02% pH adjuster.
本实施例中，所述的水性环氧树脂乳液为环氧当量180～230克/当量的双酚A型水性环氧乳液。牌号为BH-653型水性环氧乳液(分子量为360～460/mol)，购自东莞广通化工制品有限公司。In the present embodiment, the aqueous epoxy resin emulsion is a bisphenol A type aqueous epoxy emulsion having an epoxy equivalent of 180 to 230 g/eq. The grade is BH-653 waterborne epoxy emulsion (molecular weight 360~460/mol), purchased from Dongguan Guangtong Chemical Products Co., Ltd.
所述的有机硅烷偶联剂为γ-(甲基丙烯酰氧)丙基三甲氧基硅烷，购自国药集团化学试剂有限公司。The organosilane coupling agent is γ-(methacryloyloxy)propyltrimethoxysilane, which is purchased from Sinopharm Chemical Reagent Co., Ltd.
所述的润滑剂A是牌号为3760B的酰胺型阳离子型润滑剂，购自西安友基复合材料有限 公司。The lubricant A is an amide type cationic lubricant of the grade 3760B, which is purchased from Xi'an Youji Composite Material Co., Ltd. the company.
所述的润滑剂B是牌号为3550的脂肪族及非离子复合型润滑剂，购自西安友基复合材料有限公司。The lubricant B is an aliphatic and non-ionic composite lubricant of the grade 3550, which is purchased from Xi'an Youji Composite Materials Co., Ltd.
所述的润滑剂C是牌号为3512的阳离子型润滑剂，购自西安友基复合材料有限公司。The lubricant C is a cationic lubricant of the grade 3512, which is purchased from Xi'an Youji Composite Materials Co., Ltd.
所述的抗静电剂是无机氯化锂。The antistatic agent is inorganic lithium chloride.
所述的pH值调节剂采用的是冰醋酸。The pH adjuster is glacial acetic acid.
实施例5Example 5
一种氧化铝连续纤维加捻纱用浸润剂，按照重量百分比由以下几组分组成：The utility model relates to an sizing agent for alumina continuous fiber and twisted yarn, which is composed of the following components according to the weight percentage:
4.5％水性环氧树脂、0.4％有机硅烷偶联剂、0.3％润滑剂A、0.3％润滑剂B、0.1％抗静电剂及0.02％pH值调节剂。4.5% aqueous epoxy resin, 0.4% organosilane coupling agent, 0.3% lubricant A, 0.3% lubricant B, 0.1% antistatic agent and 0.02% pH adjuster.
本实施例中，所述的水性环氧树脂乳液为环氧当量180～230克/当量的双酚A型水性环氧乳液。BH-653型水性环氧乳液(环氧当量为360～460克/当量)，购自东莞广通化工制品有限公司。In the present embodiment, the aqueous epoxy resin emulsion is a bisphenol A type aqueous epoxy emulsion having an epoxy equivalent of 180 to 230 g/eq. BH-653 waterborne epoxy emulsion (epoxy equivalent weight: 360 ~ 460 g / equivalent), purchased from Dongguan Guangtong Chemical Products Co., Ltd.
所述的有机硅烷偶联剂为γ-氨丙基三乙氧基硅烷，购自国药集团化学试剂有限公司。The organosilane coupling agent is γ-aminopropyltriethoxysilane, which is purchased from Sinopharm Chemical Reagent Co., Ltd.
所述的润滑剂A是牌号为3760B的酰胺型阳离子型润滑剂，购自西安友基复合材料有限公司。The lubricant A is an amide type cationic lubricant of the brand 3760B, which is purchased from Xi'an Youji Composite Materials Co., Ltd.
所述的润滑剂B是牌号为3512的阳离子型润滑剂，购自西安友基复合材料有限公司。The lubricant B is a cationic lubricant of the grade 3512, which is purchased from Xi'an Youji Composite Materials Co., Ltd.
所述的抗静电剂是无机氯化锂。The antistatic agent is inorganic lithium chloride.
所述的pH值调节剂采用的是冰醋酸。The pH adjuster is glacial acetic acid.
制备方法同实施例1。The preparation method was the same as in Example 1.
对比例1Comparative example 1
如实施例1所述，不同的是：所述的润滑剂中仅使用0.6％的润滑剂A。As described in Example 1, the difference was that only 0.6% of the lubricant A was used in the lubricant.
对比例2Comparative example 2
如实施例1所述，不同的是：所述的润滑剂中仅使用0.6％的润滑剂B。As described in Example 1, the difference is that only 0.6% of the lubricant B is used in the lubricant.
对比例3Comparative example 3
如实施例1所述，不同的是：所述的润滑剂中仅使用0.3％的润滑剂B和0.3％的润滑剂C。As described in Example 1, the difference was that only 0.3% of the lubricant B and 0.3% of the lubricant C were used in the lubricant.
对比例4Comparative example 4
使用专利文件CN106242320A所述适用于玻璃纤维织造用浸润剂作对比。The sizing for glass fiber weaving is used for comparison as described in the patent document CN106242320A.
对比例5 Comparative example 5
使用专利文件CN106587659A所述适用于格子梁制造的玻璃纤维浸润剂作对比。A glass fiber sizing agent suitable for the manufacture of lattice beams is used for comparison as described in the patent document CN106587659A.
试验例1Test example 1
应用本发明实施例1的浸润剂涂覆过的氧化铝连续纤维形态如图2所示，与未涂覆浸润剂的纤维原丝形态如图1所示，作对比。The morphology of the continuous fiber of alumina coated with the sizing agent of Example 1 of the present invention is shown in Fig. 2, and the morphology of the fiber precursor which is not coated with the sizing agent is as shown in Fig. 1.
从图1可看出未经过浸润剂处理的氧化铝连续纤维丝与丝间由于存在静电而不成束，再加上纤维本身柔韧性不好，表面不润滑，纤维没有得到很好地保护造成纤维断裂和产生毛羽，这样的纤维是无法进行加捻生产，同时影响纤维后续加工使用；相对比图2可以看出经过浸润剂处理的纤维几百根纤维丝成一束，表面光滑无毛羽，也不容易断裂，有利于加捻生产及后续加工使用。It can be seen from Fig. 1 that the continuous filaments of alumina which have not been treated with the sizing agent are not bundled due to the presence of static electricity, and the fibers themselves are not flexible, the surface is not lubricated, and the fibers are not well protected. Breaking and hairiness, such fibers can not be twisted and produced, and affect the subsequent processing of the fiber; compared with Figure 2, it can be seen that the fibers treated with the sizing agent are bundled with hundreds of filaments, and the surface is smooth and hairless, and It is easy to break, which is conducive to the production of twisting and subsequent processing.
试验例2Test example 2
应用对比例1的浸润剂涂覆过的氧化铝连续纤维形态如图3所示，与本发明实施例1的浸润剂涂覆过的氧化铝连续纤维形态如图2所示，作对比。The sizing-coated alumina continuous fiber morphology of Comparative Example 1 was as shown in Fig. 3, and the sizing-coated alumina continuous fiber morphology of Example 1 of the present invention was as shown in Fig. 2 for comparison.
从图3可看出，浸润剂中润滑剂成分仅使用润滑剂A处理过的氧化铝连续纤维硬挺度偏大，表面不太光滑，这样的纤维不太适用于现有的加捻生产工艺，纤维容易在加捻过程中折断或出现断丝现象。It can be seen from Fig. 3 that the lubricant component of the sizing agent is only treated with the lubricant A. The continuous fiber of the alumina has a large stiffness and a non-smooth surface, and such a fiber is not suitable for the existing twisting production process. The fiber is easily broken or broken during the twisting process.
应用对比例2或对比例3的浸润剂涂覆过的氧化铝连续纤维形态如图4所示，与本发明实施例1的浸润剂涂覆过的氧化铝连续纤维形态如图2所示，作对比。The sizing-coated alumina continuous fiber morphology of Comparative Example 2 or Comparative Example 3 is as shown in FIG. 4, and the sizing-coated alumina continuous fiber morphology of Example 1 of the present invention is as shown in FIG. For comparison.
从图4可看出，浸润剂中润滑剂成分仅使用润滑剂B或者润滑剂B、C混合使用，处理过的氧化铝连续纤维过于柔软，且可以看出纤维集束性效果不是很好，影响整束纤维的技术性能，这样的纤维不太适用于现有的加捻生产工艺，纤维容易在加捻过程中滑落或出现断丝现象。It can be seen from Fig. 4 that the lubricant component in the sizing agent is only used by using the lubricant B or the lubricants B and C. The treated alumina continuous fiber is too soft, and it can be seen that the fiber bundle effect is not very good, affecting The technical properties of the whole bundle of fibers, such fibers are not suitable for the existing twisting production process, and the fibers are liable to slip or break during the twisting process.
应用对比例4和对比例5的浸润剂涂覆过的氧化铝连续纤维形态如图5、图6所示，与本发明实施例1的浸润剂涂覆过的氧化铝连续纤维形态如图2、图7所示，作对比。The sizing-coated alumina continuous fiber morphology of Comparative Example 4 and Comparative Example 5 was as shown in FIG. 5 and FIG. 6, and the sizing-coated alumina continuous fiber morphology of Example 1 of the present invention is shown in FIG. Figure 7, shown, for comparison.
从图5可看出，使用专利文件CN106242320A所述适用于玻璃纤维织造用浸润剂或使用专利文件CN106587659A所述适用于格子梁制造的玻璃纤维浸润剂，处理过的氧化铝连续纤维涂覆量过大或某些成分不适合氧化铝连续纤维，使纤维涂覆烘干后变弯曲，而且集束过度，使纤维经过涂膜器将纤维丝束压扁烘干后却无法恢复原形，且将纤维丝束粘到一起无法完整抽出单丝(如图6和图7相比，图7所示的氧化铝连续纤维整束可以集成一束，也可以分开单丝，而图6所示纤维整束集束过度，无法分开单丝)，且纤维硬挺度过大，一折就断，影响整束纤维的技术性能，这样的纤维是无法使用的。 As can be seen from Fig. 5, the treated alumina continuous fiber coating amount is applied to the glass fiber weaving sizing agent described in the patent document CN106242320A or the glass fiber sizing agent suitable for the lattice beam manufacturing described in the patent document CN106587659A. Large or some components are not suitable for alumina continuous fiber, so that the fiber is bent after coating and drying, and the bundle is excessive, so that the fiber is flattened and dried by the film applicator, but the fiber is not restored to the original shape, and the fiber is removed. The bundles are stuck together and the monofilament cannot be completely extracted (as shown in Fig. 6 and Fig. 7, the bundle of alumina continuous fibers shown in Fig. 7 can be integrated into one bundle, and the monofilament can be separated, and the bundle of fibers shown in Fig. 6 is bundled. Excessive, unable to separate the monofilament), and the fiber stiffness is too large, the break is broken, affecting the technical performance of the whole bundle of fibers, such fibers are unusable.
试验例3Test Example 3
应用本发明实施例1-5和对比例1-5的浸润剂涂覆氧化铝连续纤维进行测试，结果如表1所示。The alumina continuous fibers were coated with the sizing agent of Examples 1-5 and Comparative Examples 1-5 of the present invention, and the results are shown in Table 1.
表1.氧化铝连续纤维涂浸润剂与未涂浸润剂测试结果Table 1. Test results of alumina continuous fiber coating sizing agent and uncoated sizing agent
测试项目Test items 涂覆率(％)Coating rate (%) 硬挺度(cm)Stiffness (cm) 整束纤维拉伸断裂强力(N/tex)Whole bundle fiber tensile strength (N/tex) 加捻效果Twist effect
纤维原丝Fiber strand 0.000.00 1.71.7 0.3710.371  
实施例1Example 1 1.181.18 2.02.0 0.3860.386 优excellent
实施例2Example 2 1.541.54 2.02.0 0.4150.415 优excellent
实施例3Example 3 1.711.71 2.052.05 0.4020.402 优excellent
实施例4Example 4 1.851.85 2.12.1 0.4260.426 优excellent
实施例5Example 5 1.791.79 2.22.2 0.4250.425 优excellent
对比例1Comparative example 1 1.201.20 2.52.5 0.3890.389 良good
对比例2Comparative example 2 1.191.19 1.81.8 0.3750.375 良good
对比例3Comparative example 3 1.231.23 1.851.85 0.3730.373 良good
对比例4Comparative example 4 2.692.69 4.64.6 0.3920.392 差difference
对比例5Comparative example 5 2.562.56 5.25.2 0.3950.395 差difference
从表1中可以看出，经过本发明浸润剂处理后的的氧化铝连续纤维比没有经过浸润剂处理的纤维硬挺度稍有提高且在适合加捻要求的硬挺度范围内，整束纤维拉伸断裂强力有很大提高，说明经过浸润剂处理对氧化铝连续纤维起到集束保护作用，从硬挺度、润滑性、整束纤维拉伸断裂强力等方面都符合纤维加捻工艺，且加捻效果极佳。As can be seen from Table 1, the alumina continuous fiber treated by the sizing agent of the present invention has a slightly higher stiffness than the fiber which has not been subjected to the sizing treatment, and is in the range of stiffness suitable for twisting, and the whole bundle of fibers is pulled. The tensile strength of the stretch is greatly improved, indicating that the sizing treatment can protect the continuous fibers of alumina, and the fiber twisting process is consistent with the stiffness, lubricity, tensile strength of the whole bundle of fibers, and twisting. The effect is excellent.
将本发明实施例与对比例结合数据进行对比，可以看出浸润剂中润滑剂成分仅使用润滑剂A，经涂覆后氧化铝连续纤维虽然整束纤维拉伸断裂强力有所提高，但是纤维硬挺度稍大，且润滑效果不佳，不适用于现有的加捻工艺，仅使用润滑剂B或者润滑剂B、C混合使用，经涂覆后氧化铝连续纤维整束纤维拉伸断裂强力没有明显提高，且纤维硬挺度过小，润滑稍微过度，连续纤维加捻时容易滑落，也不适用于现有的加捻工艺，必须是几种润滑剂复配使用才能从硬挺度、润滑性、整束纤维拉伸断裂强力等方面很好的达到加捻工艺要求，而使用专利文件CN106242320A所述适用于玻璃纤维织造用浸润剂或使用专利文件CN106587659A 所述适用于格子梁制造的玻璃纤维浸润剂，虽然涂覆后整束纤维拉伸断裂强力有所提高，但是涂覆量过大，会导致纤维在使用时经过高温处理后被游离的碳离子损伤严重，影响纤维的整体使用性能，且纤维集束过度，把纤维丝束粘到一起无法分开单丝导致氧化铝连续纤维无法正常使用，且涂覆后纤维硬挺度过大使纤维更不耐折，润滑效果不佳，不适用于现有的加捻工艺且无法生产出合格的氧化铝连续纤维。 Comparing the examples of the present invention with the comparative data of the comparative examples, it can be seen that the lubricant component in the sizing agent only uses the lubricant A. After the coating, the continuous fiber of the alumina has an improved tensile breaking strength of the whole bundle fiber, but the fiber The stiffness is slightly larger and the lubrication effect is not good. It is not suitable for the existing twisting process. It is only used with the lubricant B or the lubricants B and C. After the coating, the continuous fiber of the continuous fiber of the alumina is stretched and broken. There is no obvious improvement, and the fiber stiffness is too small, the lubrication is slightly excessive, the continuous fiber is easy to slip when it is twisted, and it is not suitable for the existing twisting process. It must be compounded with several lubricants to obtain stiffness and lubricity. The tensile strength of the whole bundle of fibers is well achieved in the process of twisting, and is applied to the wetting agent for glass fiber weaving or the patent document CN106587659A as described in the patent document CN106242320A. The glass fiber sizing agent suitable for the manufacture of the lattice beam has an improved tensile breaking strength of the whole bundle fiber after coating, but the coating amount is too large, which causes the fiber to be freely carbonized after being subjected to high temperature treatment during use. The damage is serious, affecting the overall performance of the fiber, and the fiber bundle is excessive. The fiber tow is stuck together and the monofilament cannot be separated, so that the continuous fiber of the alumina cannot be used normally, and the fiber is too stiff to make the fiber less resistant to folding after coating. Poor lubrication does not apply to existing twisting processes and does not produce acceptable alumina continuous fibers.

Claims (10)

  1. 一种氧化铝连续纤维加捻纱专用浸润剂，其特征在于，该浸润剂按照重量百分比包括以下组分组成：A special sizing agent for alumina continuous fiber twisted yarn, characterized in that the sizing agent comprises the following components in terms of weight percentage:
    3～6％水性环氧乳液、0.2～0.6％润滑剂、0.1～0.2％抗静电剂、0.3～0.8％有机硅烷偶联剂、0.02～0.05％pH值调节剂，余量为水。3 to 6% aqueous epoxy emulsion, 0.2 to 0.6% lubricant, 0.1 to 0.2% antistatic agent, 0.3 to 0.8% organosilane coupling agent, 0.02 to 0.05% pH adjuster, and the balance is water.
  2. 根据权利要求1所述的浸润剂，其特征在于，所述的水性环氧乳液为双酚A型水性环氧乳液。The sizing agent according to claim 1, wherein the aqueous epoxy emulsion is a bisphenol A type aqueous epoxy emulsion.
  3. 根据权利要求1所述的浸润剂，其特征在于，所述的双酚A型水性环氧乳液为环氧当量在160～280克/当量的双酚A型水性环氧乳液。The sizing agent according to claim 1, wherein the bisphenol A type aqueous epoxy emulsion is a bisphenol A type aqueous epoxy emulsion having an epoxy equivalent of from 160 to 280 g/eq.
  4. 根据权利要求1所述的浸润剂，其特征在于，所述的润滑剂包括润滑剂A和润滑剂B，以及包括或不包括润滑剂C；The sizing agent according to claim 1, wherein said lubricant comprises lubricant A and lubricant B, and or includes lubricant C;
    所述的润滑剂A为酰胺型阳离子型润滑剂；The lubricant A is an amide type cationic lubricant;
    所述的润滑剂B为脂肪族及非离子复合型润滑剂；The lubricant B is an aliphatic and non-ionic composite lubricant;
    所述的润滑剂C为阳离子型润滑剂。The lubricant C is a cationic lubricant.
  5. 根据权利要求4所述的浸润剂，其特征在于，所述的润滑剂A、润滑剂B和润滑剂C的质量比为1：(0.3～1)：(0.3～0.8)。The sizing agent according to claim 4, wherein the mass ratio of the lubricant A, the lubricant B, and the lubricant C is 1: (0.3 to 1): (0.3 to 0.8).
  6. 根据权利要求4所述的浸润剂，其特征在于，所述的酰胺型阳离子型润滑剂是西安友基复合材料有限公司的牌号为3760B型润滑剂；The sizing agent according to claim 4, wherein the amide-type cationic lubricant is a lubricant of the type 3760B of Xi'an Youji Composite Materials Co., Ltd.;
    所述的脂肪族及非离子复合型润滑剂是西安友基复合材料有限公司的牌号为3550型润滑剂；The aliphatic and non-ionic composite lubricant is a lubricant of the type 3550 type of Xi'an Youji Composite Materials Co., Ltd.;
    所述的阳离子型润滑剂是西安友基复合材料有限公司的牌号为3512型润滑剂。The cationic lubricant is the type 3512 lubricant of Xi'an Youji Composite Materials Co., Ltd.
  7. 根据权利要求1所述的浸润剂，其特征在于，所述的抗静电剂为无机氯化锂。The sizing agent according to claim 1, wherein the antistatic agent is inorganic lithium chloride.
  8. 根据权利要求1所述的浸润剂，其特征在于，所述的有机硅烷偶联剂为γ-氨丙基三乙氧基硅烷或γ-(甲基丙烯酰氧)丙基三甲氧基硅烷，所述的pH值调节剂为冰醋酸。The sizing agent according to claim 1, wherein the organosilane coupling agent is γ-aminopropyltriethoxysilane or γ-(methacryloyloxy)propyltrimethoxysilane. The pH adjusting agent is glacial acetic acid.
  9. 根据权利要求1所述的浸润剂，其特征在于，所述的氧化铝连续纤维加捻纱专用浸润剂，按照重量百分比包括以下组分组成：The sizing agent according to claim 1, wherein said alumina continuous fiber plus sizing special sizing agent comprises, by weight percentage, the following components:
    3～5％水性环氧乳液、0.2～0.6％润滑剂、0.1～0.2％抗静电剂、0.3～0.6％有机硅烷偶联剂、0.02～0.05％pH值调节剂，余量为水。3 to 5% aqueous epoxy emulsion, 0.2 to 0.6% lubricant, 0.1 to 0.2% antistatic agent, 0.3 to 0.6% organosilane coupling agent, 0.02 to 0.05% pH adjuster, and the balance is water.
  10. 权利要求1-9任一项所述的氧化铝连续纤维加捻纱用浸润剂的制备方法，包括步骤如下： The method for preparing an sizing agent for alumina continuous fiber twisted yarn according to any one of claims 1 to 9, comprising the following steps:
    (1)在水中加入pH值调节剂，将水的pH值调节为3～4，再加入定量的有机硅烷偶联剂，继续搅拌至水溶液澄清后再加入pH值调节剂，将溶液的pH值调节为4～5；(1) Adding a pH adjuster to the water, adjusting the pH of the water to 3 to 4, adding a quantitative amount of the organosilane coupling agent, continuing to stir until the aqueous solution is clarified, and then adding a pH adjuster to adjust the pH of the solution. Adjust to 4 to 5;
    (2)将定量的水性环氧乳液用10～15倍的去离子水进行稀释，搅拌时间为0.5～1h；(2) The quantitative aqueous epoxy emulsion is diluted with 10 to 15 times of deionized water, and the stirring time is 0.5 to 1 h;
    (3)将定量的润滑剂用10～20倍的去离子水进行稀释，搅拌时间为0.5～1h；(3) The quantitative lubricant is diluted with 10 to 20 times of deionized water, and the stirring time is 0.5 to 1 h;
    (4)将定量的抗静电剂用10～20倍的去离子水进行溶解，搅拌时间为1～2h；(4) The quantitative antistatic agent is dissolved in 10 to 20 times of deionized water, and the stirring time is 1 to 2 hours;
    (5)将步骤(2)、(3)、(4)中的溶液混合均匀，搅拌0.5～1h；(5) mixing the solutions in steps (2), (3), (4) uniformly, stirring 0.5 ~ 1h;
    (6)将步骤(1)中水解好的有机硅烷偶联剂及余量的水加入步骤(5)得到的混合溶液中，均匀搅拌1～2h，即得氧化铝连续纤维加捻纱专用浸润剂。 (6) adding the hydrolyzed organosilane coupling agent and the remaining amount of water in the step (1) to the mixed solution obtained in the step (5), and uniformly stirring for 1 to 2 hours, thereby obtaining a special infiltration of the alumina continuous fiber and the twisted yarn. Agent.
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