WO2019024222A1 - 一种玻纤增强聚苯醚复合材料及其制备方法 - Google Patents

一种玻纤增强聚苯醚复合材料及其制备方法 Download PDF

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WO2019024222A1
WO2019024222A1 PCT/CN2017/104373 CN2017104373W WO2019024222A1 WO 2019024222 A1 WO2019024222 A1 WO 2019024222A1 CN 2017104373 W CN2017104373 W CN 2017104373W WO 2019024222 A1 WO2019024222 A1 WO 2019024222A1
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glass fiber
polyphenylene ether
parts
composite material
solution
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PCT/CN2017/104373
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French (fr)
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吕素慧
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吕素慧
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/315—Compounds containing carbon-to-nitrogen triple bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2371/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/329—Phosphorus containing acids

Definitions

  • the present invention relates to the technical field of polymer materials, and in particular to a glass fiber reinforced polyphenylene ether composite material and a preparation method thereof.
  • Polyphenylene ether has high mechanical strength after being filled with glass fiber, and is an excellent insulating material and thermal insulation material in electrical terms, and can be used for making various instrument casings, lampshades, optical chemical instrument parts, transparent films, Capacitor dielectric layer, etc.
  • the existing glass fiber materials have low intermolecular force, and the fibers are prone to large creep under the action of long intertwisting force, resulting in dimensional and morphological instability, which severely limits the glass fiber reinforced polyphenylene ether materials in many In particular, it is used in the fields of instrument housings, lampshades, optical chemical parts, transparent films, capacitor dielectric layers, etc., which are required for high precision.
  • the glass-filled polyphenylene ether composite material easily forms a floating fiber during the injection molding process, resulting in a decrease in the strength of the composite material itself.
  • a glass-filled polyphenylene ether composite material easily forms a floating fiber during an injection molding process, resulting in a decrease in the strength of the composite material itself.
  • a glass fiber reinforced polyphenylene ether composite material the raw materials of which include:
  • the polyphenylene ether and the glass fiber can be selected by any of the prior art.
  • Potassium citrate Gold
  • Potassium Citrate is a chemical substance with the molecular formula KAu 2 N 4 C1 2 H Trust0 8 .
  • Melting point 698 ° C anhydrous product Used in mordants, analytical reagents, catalysts, water treatment agents, manufacturing fireproof, waterproof materials, and phosphotungstates, boron tungstates, etc.
  • Hypophosphorous acid is a colorless oily liquid or deliquescent crystal. Density 1.493g /cm3. Melting point 26.5 ° C. Soluble in hot water, ethanol, ether. Soluble in cold water. When heated to 130 ° C, it will be decomposed into orthophosphoric acid and phosphine. It is a strong reducing agent. From sodium hypophosphite through ion exchange resin Treatment, adsorption, desorption, filtration, evaporation and concentration.
  • the inventors found trace amounts of potassium citrate and hypophosphorous acid. ⁇ , the compatibility of the glass fiber and the polyphenylene ether material can be greatly improved, and the glass fiber can be uniformly mixed in the polyphenylene ether material, thereby effectively improving the mechanical properties of the obtained polyphenylene ether composite material.
  • the glass fiber is an anti-floating fiberglass fiber
  • the preparation method comprises the following steps: immersing the glass fiber in deionized water, and adding 3-pyridine sulfonic acid having a mass of 5 times the glass fiber to obtain a solution A.
  • [3-13] 3-Pyridinesulfonic acid can be achieved by any of the prior art techniques. It can effectively inhibit the accumulation and floating of glass fiber in polyphenylene ether, avoiding the formation of protruding points on the surface of the product, and is beneficial to the surface finish of the injection molded product.
  • the uniform filling of the glass fiber in the polyphenylene ether material also contributes to the improvement of the notched impact strength of the polyphenylene ether material.
  • the present invention also provides a method for preparing the glass fiber reinforced polyphenylene ether composite material, which comprises the following steps: [0015] According to the set weight parts, polyphenylene ether, glass fiber, potassium citrate, sodium tungstate, hypophosphorous acid is added to a high-speed mixer and uniformly mixed, and then heated to 190 to 200 ° C by a twin-screw extruder to obtain plasticization. The polyphenylene ether mixture, and then the plasticized polyphenylene ether mixture is extruded by a twin-screw extruder, and subjected to drawing, cooling forming, and cutting to prepare a glass fiber reinforced polyphenylene ether composite material having a length of 10-15 mm.
  • the above preparation method can further increase the strength of the obtained composite material.
  • a trace amount of gold potassium citrate and sodium tungstate effectively improves the creep resistance of the glass fiber, thereby effectively improving the structural stability of the glass fiber, and avoiding dimensional instability and deformation of the product due to creep. Due to the increased creep resistance of glass fiber, it can be used in the manufacture of high-precision automotive parts, electronic components, instrumentation components, and aerospace components.
  • the trace amount of lanthanum citrate and hypophosphorous acid in the present invention can greatly improve the compatibility of the glass fiber and the polyphenylene ether material, so that the glass fiber is uniformly mixed in the polyphenylene ether material, thereby effectively improving the production.
  • the mechanical properties of the obtained polyphenylene ether composite can greatly improve the compatibility of the glass fiber and the polyphenylene ether material, so that the glass fiber is uniformly mixed in the polyphenylene ether material, thereby effectively improving the production.
  • This embodiment provides a glass fiber reinforced polyphenylene ether composite material, the raw materials of which include:
  • hypophosphorous acid 0.002fo 7 ⁇ --
  • the glass fiber is an anti-floating fiberglass fiber
  • the preparation method comprises the following steps: immersing the glass fiber in deionized water, and adding 3-pyridine sulfonic acid having a mass of 5 times the glass fiber to obtain a solution A.
  • This embodiment provides a glass fiber reinforced polyphenylene ether composite material, the raw materials of which include:
  • hypophosphorous acid 0.002fo 7 ⁇ --
  • the glass fiber is an anti-floating fiberglass fiber
  • the preparation method comprises the following steps: immersing the glass fiber in deionized water, and adding 3-pyridine sulfonic acid having a mass of 5 times the glass fiber to obtain a solution A.
  • This embodiment provides a glass fiber reinforced polyphenylene ether composite material, the raw materials of which include:
  • the glass fiber is commercially available
  • the glass fiber is an anti-floating fiberglass fiber
  • the preparation method comprises the following steps: immersing the glass fiber in deionized water, and adding 3-pyridine sulfonic acid having a mass of 5 times the glass fiber to obtain a solution A.
  • This embodiment provides a glass fiber reinforced polyphenylene ether composite material, which is consistent with the first embodiment.
  • the method for preparing a glass fiber reinforced polyphenylene ether composite material includes the following steps: [0056] polyphenylene ether, glass fiber, potassium citrate, sodium tungstate according to a set weight
  • the hypophosphorous acid is added to the high-speed mixer and uniformly mixed, and then heated to 190 to 200 ° C by a twin-screw extruder to obtain a plasticized polyphenylene ether mixture, and then the plasticized polyphenylene ether mixture is extruded by a twin-screw extruder.
  • the glass fiber reinforced polyphenylene ether composite material with a length of 10-15 mm is prepared by drawing, cooling forming and cutting.
  • the present comparative example provides a glass fiber reinforced polyphenylene ether composite material, the raw materials of which include:
  • the present comparative example provides a glass fiber reinforced polyphenylene ether composite material, the raw materials of which include:
  • the present comparative example provides a glass fiber reinforced polyphenylene ether composite material, the raw materials of which include:
  • the mechanical properties of the composite material are judged by the bending strength obtained by the test.
  • the impact resistance of the material is characterized by two methods, one is characterized by the notched impact strength and the unnotched impact strength of the test material, and the other is by
  • the material is made into a square plate of 150mm*150mm*3mm, and the square plate is supported by the support, with 0.
  • the 5KG ball hits the square plate from different heights and falls freely, observing how many heights of the square plate are cracked.
  • the material is made into a square plate on a mold which is polished on the surface, and the surface is observed by a secondary phase detector.
  • the polyphenylene ether composite materials of the examples and the comparative examples were made into strips having a radius of 1 cm and a length of 20 cm. Long strip A tensile force of 5000 N was applied to the ends for 100 days. Test its length growth rate. The results are shown in Table 2.
  • a glass fiber reinforced polyphenylene ether composite material and a preparation method thereof are provided, which are suitable for large-scale industrial preparation and production.

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Abstract

一种玻纤增强聚苯醚复合材料及其制备方法，微量的柠檬酸金钾和钨酸钠有效提高玻纤的耐蠕变性能，进而有效提高玻纤的结构稳定性，避免因其蠕变导致产品尺寸不稳定、变形。由于玻纤耐蠕变性能提高，使之得以被应用在高精密要求的仪表外壳、灯罩、光学化学仪器零件、透明薄膜、电容器介质层的制造生产中。

Description

发明名称：一种玻纤增强聚苯醚复合材料及其制备方法 技术领域
[0001] 本发明涉及高分子材料技术领域， 具体涉及一种玻纤增强聚苯醚复合材料及其 制备方法。
背景技术
[0002] 聚苯醚填充玻纤后， 具有较高的机械强度， 在电气方面更是良好的绝缘材料和 隔热保温材料， 可以制作各种仪表外壳、 灯罩、 光学化学仪器零件、 透明薄膜 、 电容器介质层等。 但现有的玻纤材料分子间作用力低， 纤维在长吋间力的作 用下容易发生较大的蠕变， 导致尺寸、 形态的不稳定， 严重限制了玻纤增强聚 苯醚材料在许多方面特别是高精密要求的仪表外壳、 灯罩、 光学化学仪器零件 、 透明薄膜、 电容器介质层等领域的应用。
[0003] 此外， 填充玻纤的聚苯醚复合材料在注塑过程中容易形成浮纤， 导致复合材料 本身的强度下降。
技术问题
[0004] 填充玻纤的聚苯醚复合材料在注塑过程中容易形成浮纤， 导致复合材料本身的 强度下降。
问题的解决方案
技术解决方案
[0005] 本发明的目的通过以下技术方案实现： 一种玻纤增强聚苯醚复合材料， 其原料 按重量计包括：
[0006] 90- 120份；
[0007] 玻纤 20-45份；
[0008] 柠檬酸金钾 0.002-0.009份；
[0009] 钨酸钠 0.6- 1.9份；
[0010] 0.001-0.005份。
[0011] 本发明中， 聚苯醚、 玻纤均可选用任一种现有技术实现。 柠檬酸金钾 （Gold Potassium Citrate) 是一种化学物质， 分子式是 KAu 2N 4C1 2H„0 8。 白色结晶粉 末， 易溶于水， 微溶于醇， 难溶于醚。 可选用任一种现有技术实现。 钨酸钠， 无色结晶或白色结晶性粉末。 在干燥空气中风化， 100°C吋失去结晶水。 溶于水 ， 不溶于乙醇。 相对密度 3.23〜 3.25。 熔点 698°C (无水品） 。 用于媒染剂、 分 析试剂、 催化剂、 水处理药剂， 制造防火、 防水材料， 以及磷钨酸盐、 硼钨酸 盐等。 次磷酸为无色油状液体或易潮解的结晶。 密度 1.493g/cm3。 熔点 26.5°C。 易溶于热水、 乙醇、 乙醚。 溶于冷水。 加热到 130°C吋则分解成正磷酸和磷化氢 。 是强还原剂。 由次磷酸钠通过离子交换树脂处理， 进行吸附， 解吸， 过滤， 蒸发浓缩制得。 可用作杀菌剂， 神经系统的强壮剂， 金属表面的处理剂， 以及 制造催化剂和次磷酸盐等。 发明人在研究中发现， 微量的柠檬酸金钾和钨酸钠 有效提高玻纤的耐蠕变性能， 进而有效提高玻纤的结构稳定性， 避免因其蠕变 导致产品尺寸不稳定、 变形。 由于玻纤耐蠕变性能提高， 使之得以被应用在高 精密要求的汽车零部件、 电子产品元件、 仪器仪表部件、 航空设备部件的制造 生产中。 此外发明人发现有微量的柠檬酸金钾和次磷酸存在吋， 便可大幅提高 玻纤与聚苯醚材料的相容性， 使玻纤均匀地混合在聚苯醚材料中， 有效提高所 制得的聚苯醚复合材料的力学性能。
[0012] 进一步的， 所述玻纤为防浮纤玻纤， 其制备方法为将玻纤浸没在去离子水中， 同吋加入质量为玻纤 5倍的 3-吡啶磺酸搅拌均匀得到溶液 A； 将质量为玻纤 2倍 的乙二醇地加入溶液 A中， 搅拌均匀得到溶液 B ; 将溶液 B倒入水热反应釜中， 填充度控制在 70〜 80% ; 然后密封水热反应釜， 将其放入电热恒温鼓风干燥箱 中， 在温度为 140°C， 反应 30h， 反应结束后自然冷却到室温； 打幵水热反应釜， 将产物用蒸馏水、 无水乙醇依次洗涤 1〜3次， 于电热恒温鼓风干燥箱中 96°C下 干燥 2h， 即得所述防浮纤玻纤。
[0013] 3-吡啶磺酸 （3-Pyridinesulfonic acid) 可选用任一种现有技术实现。 其可有效抑 制玻纤在聚苯醚中聚集、 浮纤， 避免产品表面形成突出点， 有利于提注塑产品 表面的光洁度。 玻纤均匀的填充在聚苯醚材料中， 还有利于提高聚苯醚材料的 缺口抗冲击强度。
[0014] 本发明还提供所述的玻纤增强聚苯醚复合材料的制备方法， 其包括如下工序： [0015] 按设定重量份将聚苯醚、 玻纤、 柠檬酸金钾、 钨酸钠、 次磷酸加入高速混合器 混合均匀后经双螺杆挤出机加热至 190〜 200°C获得塑化的聚苯醚混合物， 然后 塑化的聚苯醚混合物被双螺杆挤出机挤出， 经牵引、 冷却成型、 切割处理制备 成长度为 10-15mm的玻纤增强聚苯醚复合材料。
[0016] 上述制备方法可进一步提高所制得的复合材料的强度。
发明的有益效果
有益效果
[0017] 本发明中， 微量的柠檬酸金钾和钨酸钠有效提高玻纤的耐蠕变性能， 进而有效 提高玻纤的结构稳定性， 避免因其蠕变导致产品尺寸不稳定、 变形。 由于玻纤 耐蠕变性能提高， 使之得以被应用在高精密要求的汽车零部件、 电子产品元件 、 仪器仪表部件、 航空设备部件的制造生产中。 此外本发明中的微量的柠檬酸 金钾和次磷酸存在吋， 便可大幅提高玻纤与聚苯醚材料的相容性， 使玻纤均匀 地混合在聚苯醚材料中， 有效提高所制得的聚苯醚复合材料的力学性能。
实施该发明的最佳实施例
本发明的最佳实施方式
[0018] 本实施例提供一种玻纤增强聚苯醚复合材料， 其原料按重量计包括：
[0019] 100份；
[0020] 玻纤 30份；
[0021] 柠檬酸金钾 0.005份；
[0022] 钨酸钠 0.9份；
[0023] 次磷酸 0.002fo 7Λ-—
[0024] 进一步的， 所述玻纤为防浮纤玻纤， 其制备方法为将玻纤浸没在去离子水中， 同吋加入质量为玻纤 5倍的 3-吡啶磺酸搅拌均匀得到溶液 A； 将质量为玻纤 2倍 的乙二醇地加入溶液 A中， 搅拌均匀得到溶液 B ; 将溶液 B倒入水热反应釜中， 填充度控制在 70〜 80% ; 然后密封水热反应釜， 将其放入电热恒温鼓风干燥箱 中， 在温度为 140°C， 反应 30h， 反应结束后自然冷却到室温； 打幵水热反应釜， 将产物用蒸馏水、 无水乙醇依次洗涤 1〜3次， 于电热恒温鼓风干燥箱中 96°C下 干燥 2h， 即得所述防浮纤玻纤。 [0025] 本实施例采用现有技术制备。 本发明的实施方式
[0026] 实施例 1
[0027] 本实施例提供一种玻纤增强聚苯醚复合材料， 其原料按重量计包括:
[0028] 100份；
[0029] 玻纤 30份；
[0030] 柠檬酸金钾 0.005份；
[0031] 钨酸钠 0.9份；
[0032] 次磷酸 0.002fo 7Λ-—
[0033] 进一步的， 所述玻纤为防浮纤玻纤， 其制备方法为将玻纤浸没在去离子水中， 同吋加入质量为玻纤 5倍的 3-吡啶磺酸搅拌均匀得到溶液 A； 将质量为玻纤 2倍 的乙二醇地加入溶液 A中， 搅拌均匀得到溶液 B ; 将溶液 B倒入水热反应釜中， 填充度控制在 70〜 80% ; 然后密封水热反应釜， 将其放入电热恒温鼓风干燥箱 中， 在温度为 140°C， 反应 30h， 反应结束后自然冷却到室温； 打幵水热反应釜， 将产物用蒸馏水、 无水乙醇依次洗涤 1〜3次， 于电热恒温鼓风干燥箱中 96°C下 干燥 2h， 即得所述防浮纤玻纤。
[0034] 本实施例采用现有技术制备。
[0035] 实施例 2
[0036] 本实施例提供一种玻纤增强聚苯醚复合材料， 其原料按重量计包括：
[0037] 120份；
[0038] 玻纤 20份；
[0039] 柠檬酸金钾 0.009份；
[0040] 钨酸钠 0.6份；
Figure imgf000005_0001
[0042] 进一步的， 所述玻纤市售产
[0043] 本实施例采用现有技术制备。
[0044] 实施例 3 [0045]
[0046] 90份；
[0047] 玻纤 45份；
[0048] 柠檬酸金钾 0.002份;
[0049] 钨酸钠 1.9份；
Figure imgf000006_0001
[0051] 进一步的， 所述玻纤为防浮纤玻纤， 其制备方法为将玻纤浸没在去离子水中， 同吋加入质量为玻纤 5倍的 3-吡啶磺酸搅拌均匀得到溶液 A； 将质量为玻纤 2倍 的乙二醇地加入溶液 A中， 搅拌均匀得到溶液 B ; 将溶液 B倒入水热反应釜中， 填充度控制在 70〜 80% ; 然后密封水热反应釜， 将其放入电热恒温鼓风干燥箱 中， 在温度为 140°C， 反应 30h， 反应结束后自然冷却到室温； 打幵水热反应釜， 将产物用蒸馏水、 无水乙醇依次洗涤 1〜3次， 于电热恒温鼓风干燥箱中 96°C下 干燥 2h， 即得所述防浮纤玻纤。
[0052] 本实施例采用现有技术制备。
[0053] 实施例 4
[0054] 本实施例提供一种玻纤增强聚苯醚复合材料， 其原料与实施例 1一致。
[0055] 本实施例所述的玻纤增强聚苯醚复合材料的制备方法， 其包括如下工序： [0056] 按设定重量份将聚苯醚、 玻纤、 柠檬酸金钾、 钨酸钠、 次磷酸加入高速混合器 混合均匀后经双螺杆挤出机加热至 190〜 200°C获得塑化的聚苯醚混合物， 然后 塑化的聚苯醚混合物被双螺杆挤出机挤出， 经牵引、 冷却成型、 切割处理制备 成长度为 10-15mm的玻纤增强聚苯醚复合材料。
[0057] 对比例 1
[0058] 本对比例提供一种玻纤增强聚苯醚复合材料， 其原料按重量计包括：
[0059] 100份；
[0060] 玻纤 30份；
[0061] 柠檬酸钾 0.005份；
[0062] 钨酸钠 0.9份；
[0063]
Figure imgf000006_0002
[0064] 对比例 2
[0065] 本对比例提供-一种玻纤增强聚苯醚复合材料， 其原料按重量计包括：
[0066] 聚苯醚 100份；
[0067] 玻纤 30份；
[0068] 柠檬酸金钾 0.005份；
[0069] 柠檬酸钠 0.9份；
[0070] 次磷酸 0.002份。
[0071] 对比例 3
[0072] 本对比例提供-一种玻纤增强聚苯醚复合材料， 其原料按重量计包括：
[0073] 聚苯醚 100份；
[0074] 玻纤 30份；
[0075] 柠檬酸金钾 0.005份；
[0076] 钨酸钠 0.9份；
[0077] 正磷酸 0.002份。
[0078] 复合材料的力学性能通过测试所得的弯曲强度判断， 材料的抗冲击性通过两种 方法表征， 一种是通过测试材料的缺口冲击强度和无缺口冲击强度表征， 另一 种是通过把材料制成 150mm*150mm*3mm的方板， 把方板通过支撑物架住， 用 0.
5KG的圆球从不同的高度自由落体撞击到方板上， 观察方板在多少高度出现裂纹 。 复合材料的浮纤情况是通过在表面进行抛光处理的模具上把材料制成方板， 通过二次原相仪对表面进行观察。
对实施例和对比例进行弯曲强度、 冲击性能和表面浮纤情况进行测定， 其测试 结果见表 1。
[表 1]
Figure imgf000008_0001
[0080] 注塑测试。
[0081] 将聚苯醚复合材料采用现有技术进行注塑， 成型为 30Cmx30Cmx30cm的方块， 观察其表面浮纤情况。 在方块的 6个表面切割出 30Cmx30cmx2Cm的表皮， 并获得 一切去表皮的小方块； 测试表皮和小方块的密度差率。 密度差率 = (p表皮 -P小 方块） χ100<¾。
[] [表 2]
Figure imgf000008_0002
[0082] 耐蠕变测试。
[0083] 将实施例和对比例的聚苯醚复合材料制成半径 lcm， 长 20cm的长条。 长条的两 端分别施加 5000N的拉力， 维持 100日。 测试其长度增长率。 其结果如表 2
[] [表 3]
Figure imgf000009_0001
[0084] 以上为本发明的其中具体实现方式， 其描述较为具体和详细， 但并不能因此而 理解为对本发明专利范围的限制。 应当指出的是， 对于本领域的普通技术人员 来说， 在不脱离本发明构思的前提下， 还可以做出若干变形和改进， 这些显而 易见的替换形式均属于本发明的保护范围。
工业实用性
[0085] 提供一种玻纤增强聚苯醚复合材料及其制备方法， 适合大规模工业制备生产。

Claims

权利要求书
[权利要求 1] 一种玻纤增强聚苯醚复合材料， 其原料按重量计包括：
90- 120份；
玻纤 20-45份；
柠檬酸金钾 0.002-0.009份；
钨酸钠 0.6- 1.9份；
Figure imgf000010_0001
0.001-0.005份。
[权利要求 2] 根据权利要求 1所述的玻纤增强聚苯醚复合材料， 其特征在于： 所述 玻纤为防浮纤玻纤， 其制备方法为将玻纤浸没在去离子水中， 同吋加 入质量为玻纤 5倍的 3-吡啶磺酸搅拌均匀得到溶液 A； 将质量为玻纤 2 倍的乙二醇地加入溶液 A中， 搅拌均匀得到溶液 B; 将溶液 B倒入水 热反应釜中， 填充度控制在 70〜80%； 然后密封水热反应釜， 将其 放入电热恒温鼓风干燥箱中， 在温度为 140°C， 反应 30h， 反应结束后 自然冷却到室温； 打幵水热反应釜， 将产物用蒸馏水、 无水乙醇依次 洗涤 1〜3次， 于电热恒温鼓风干燥箱中 96°C下干燥 2h， 即得所述防 浮纤玻纤。
[权利要求 3] 如权利要求 1或 2所述的玻纤增强聚苯醚复合材料的制备方法， 其包括 如下工序：
按设定重量份将聚苯醚、 玻纤、 柠檬酸金钾、 钨酸钠、 次磷酸加入高 速混合器混合均匀后经双螺杆挤出机加热至 190〜 200°C获得塑化的 聚苯醚混合物， 然后塑化的聚苯醚混合物被双螺杆挤出机挤出， 经牵 弓 I、 冷却成型、 切割处理制备成长度为 10-15mm的玻纤增强聚苯醚复
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