WO2022110665A1 - 一种阻燃抗静电聚酰胺复合材料及其制备方法和应用 - Google Patents

一种阻燃抗静电聚酰胺复合材料及其制备方法和应用 Download PDF

Info

Publication number
WO2022110665A1
WO2022110665A1 PCT/CN2021/092777 CN2021092777W WO2022110665A1 WO 2022110665 A1 WO2022110665 A1 WO 2022110665A1 CN 2021092777 W CN2021092777 W CN 2021092777W WO 2022110665 A1 WO2022110665 A1 WO 2022110665A1
Authority
WO
WIPO (PCT)
Prior art keywords
flame
composite material
antistatic
retardant
polyamide composite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2021/092777
Other languages
English (en)
French (fr)
Inventor
王丰
黄险波
叶南飚
丁超
金雪峰
胡泽宇
张亚军
张永
易新
吴长波
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kingfa Science and Technology Co Ltd
Original Assignee
Kingfa Science and Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kingfa Science and Technology Co Ltd filed Critical Kingfa Science and Technology Co Ltd
Publication of WO2022110665A1 publication Critical patent/WO2022110665A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • 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
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
    • 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
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives 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
    • 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
    • C08K9/10—Encapsulated ingredients
    • 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
    • C08K3/02—Elements
    • C08K2003/026—Phosphorus
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/004—Additives being defined by their length
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/04—Antistatic

Definitions

  • the present invention relates to the technical field of engineering plastics, and more particularly, to a flame-retardant and antistatic polyamide composite material and a preparation method and application thereof.
  • Polyamide has excellent mechanical properties, heat resistance, wear resistance, oil resistance, etc., and is widely used in the machinery industry, automobiles, power tools, electronic appliances, transportation and other fields. Polyamide is often used as a flame retardant material. Although it has strong polarity and strong water absorption, it still has a high surface resistance (above 10 10 ⁇ ) and is used in the occasions where gas gas is generated. The surface resistance should reach (10 8 ⁇ ) The following) can meet the requirements of use, otherwise it is easy to cause fire and explosion. Therefore, in the application of coal mining equipment, it is necessary to develop materials with both flame retardant and antistatic functions.
  • Chinese patent CN 1752142A discloses a preparation method of nylon 6/polyelectrolyte antistatic composite material. effect polyamide composite.
  • the processing temperature of PA66 is 230 ⁇ 280°C.
  • the antistatic additive will degrade, resulting in a significant deterioration of the composite material properties and a decrease in mechanical properties of more than 30%. It is impossible to obtain both good antistatic properties and Mechanical properties of flame retardant polyamide material.
  • the technical problem to be solved by the present invention is to overcome the defects and deficiencies that the existing flame retardant polyamide materials cannot have good antistatic properties and mechanical properties at the same time, and provide a flame retardant and antistatic polyamide composite material, which has good antistatic properties at the same time. performance and mechanical properties.
  • Another object of the present invention is to provide a method for preparing a flame retardant and antistatic polyamide composite material.
  • Another object of the present invention is to provide the application of a flame retardant and antistatic polyamide composite material.
  • a flame retardant and antistatic polyamide composite material comprising the following components calculated in parts by mass:
  • the composite antistatic agent is a compound of potassium diphenylsulfone sulfonate and carbon nanotubes, wherein the mass ratio of potassium diphenylsulfonesulfonate to carbon nanotubes is 1:1.5-2.5; the diameter of carbon nanotubes It is 8 to 15 nm, and the length is 10 to 70 ⁇ m.
  • the invention uses PA66 as the matrix material, which has excellent flame retardant performance, and adds a specific proportion of potassium diphenylsulfone sulfonate and carbon nanotubes of a certain size for compounding as a composite antistatic agent.
  • One is diphenylsulfone Potassium sulfonate itself has an antistatic effect.
  • potassium diphenylsulfone sulfonate can promote the dispersion of carbon nanotubes in PA66, improve the compatibility of carbon nanotubes in the system, and is conducive to the construction of a charge transfer network.
  • the obtained flame-retardant polyamide composite material can obtain good antistatic properties, and can still have good mechanical properties at the processing temperature of PA66 (230-280° C.).
  • the mass ratio of the potassium diphenylsulfone sulfonate to the carbon nanotubes is 1:2-2.5.
  • the mass ratio of potassium diphenylsulfone sulfonate to carbon nanotubes is 1:2.
  • the carbon nanotubes have a diameter of 10-12 nm and a length of 30-60 ⁇ m.
  • the number average molecular weight of the PA66 is 12000-30000.
  • the relative viscosity of the PA66 is 1.8-3.5.
  • the relative viscosity of the PA66 is 2.2-2.8.
  • test method for the relative viscosity of PA66 test standard ISO 307-2007, 96% sulfuric acid solution, sample concentration 0.005g/mL, test temperature 25°C.
  • the reinforcing material of the present invention includes, but is not limited to, one or more of glass fibers, carbon fibers, aramid fibers, and ceramic fibers.
  • the flame retardant is red phosphorus masterbatch.
  • the flame retardant is microcapsule red phosphorus masterbatch.
  • the mass content of red phosphorus in the microcapsule red phosphorus master batch is 40% to 60%.
  • the processing aids of the present invention include, but are not limited to, one or more of antioxidants, lubricants, light stabilizers, and colorants.
  • the antioxidants described in the present invention include but are not limited to N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine (1098), triethylenediamine Alcohol ether-bis(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate (antioxidant 245), tetrakis[beta-(3,5-di-tert-butyl-4-hydroxybenzene base) propionic acid] pentaerythritol ester (antioxidant 1010), tris[2.4-di-tert-butylphenyl] phosphite (antioxidant 168), phosphite antioxidant P-EPQ, copper salt antioxidant One or more of the agent (a compound of potassium iodide, cuprous iodide, and zinc stearate, with a mass ratio of 8:1:1).
  • the agent a compound of potassium iodide
  • the lubricant of the present invention includes, but is not limited to, one or more of calcium stearate, modified ethylene bis-fatty acid amide, aliphatic fatty acid ester, and ethylene-acrylic acid copolymer.
  • the light stabilizer of the present invention includes, but is not limited to, benzotriazole light stabilizer.
  • the colorants of the present invention include, but are not limited to, black masterbatch.
  • the present invention protects the preparation method of the above-mentioned flame retardant and antistatic polyamide composite material, comprising the following steps:
  • a twin-screw extruder with side feeding is used for the melt blending, and the feeding port includes a main feeding port and a side feeding port; the uniformly mixed material is fed from the main feeding port, and the reinforcing material is fed from the main feeding port.
  • Side feeding port feeding is used for the melt blending, and the feeding port includes a main feeding port and a side feeding port; the uniformly mixed material is fed from the main feeding port, and the reinforcing material is fed from the main feeding port.
  • Side feeding port feeding is used for the melt blending, and the feeding port includes a main feeding port and a side feeding port; the uniformly mixed material is fed from the main feeding port, and the reinforcing material is fed from the main feeding port.
  • the temperature of the melt blending is 230-280°C.
  • the invention also protects the application of the above flame-retardant and antistatic polyamide composite material in coal mine equipment.
  • the flame retardant and antistatic polyamide composite material of the invention has excellent flame retardant performance, reaches V-0 level, the surface resistivity is 10 8 and below, the tensile strength reaches 133MPa and above, and the impact strength reaches 8.5kJ/m 2 and above, with good antistatic properties and mechanical properties.
  • the invention takes PA66 as the matrix material, adds a certain proportion of reinforcing materials, flame retardants, processing aids, and a certain proportion of potassium diphenylsulfone sulfonate and carbon nanotubes of a certain size to be compounded as a composite antistatic agent.
  • the flame retardant and antistatic polyamide composite material can not only obtain good antistatic properties, but also obtain good mechanical properties at the processing temperature of PA66, and has good flame retardant properties. It can be used in applications requiring antistatic properties, such as coal mines. equipment, etc.
  • the raw material reagents used in the examples of the present invention are conventionally purchased raw material reagents.
  • PA66 the grade is EPR24, the number average molecular weight is 13700, the relative viscosity is 2.4, purchased from Pingdingshan Shenma Group;
  • Reinforcing material glass fiber, grade ECS10-03-568H, purchased from Jushi Group;
  • Microcapsule red phosphorus masterbatch the brand is FR9950KF, the mass content of red phosphorus is 50%, purchased from Tongcheng Xinde New Materials Co., Ltd.;
  • antistatic agent the name is polyether antistatic agent, the brand name is PELESTAT-6500, purchased from Sanyo Chemicals in Japan;
  • Conductive carbon black purchased from Yiborui (Tianjin) Chemical Co., Ltd.;
  • KSS Potassium Diphenylsulfone Sulfonate
  • Carbon nanotube A the grade is LUCAN CP1002M, purchased from LG Chem; the diameter of the carbon nanotube is 8-12 nm, and the length is 50-70 ⁇ m.
  • Carbon nanotube B the grade is GC-21, purchased from Shandong Dazhan Nanomaterials Co., Ltd.; the diameter of the carbon nanotube is 12-15 nm, and the length is 10-50 ⁇ m;
  • Black mother the grade is N54/1044, purchased from Colly Plastics, UK;
  • Antioxidant 1098 N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine, commercially available;
  • Lubricant ethylene-acrylic acid copolymer (EAA), trade name A-C540A, available from Honeywell.
  • Table 2 shows the components and mass parts of the flame-retardant and antistatic polyamide composite materials of each embodiment and comparative example.
  • a preparation method of a flame retardant and antistatic polyamide composite material comprising the following steps:
  • Composite antistatic agent 3 1 2.5 Composite antistatic agent 4 1 1 Composite antistatic agent 5 1 3 Composite antistatic agent 6 1 2
  • the flame retardant and antistatic polyamide composite material prepared by the present invention has high antistatic effect, the surface resistivity is 10 8 and below, and also has good notched impact strength, tensile strength and flame retardancy. performance, can be used in applications requiring antistatic, such as coal mining equipment.
  • Comparative Example 1 no composite antistatic agent was added, and its surface resistivity increased significantly.
  • Comparative Example 2 and Comparative Example 3 conductive carbon black and commercially available antistatic agent PELESTAT-6500 were used as substitutes for the composite antistatic agent. The ratio is still greater than 10 8 , and the mechanical properties such as notched impact strength and tensile strength are significantly reduced.
  • the existing conventional antistatic agent cannot reduce the surface resistivity of the material well, and will cause adverse effects on the mechanical properties of the material.
  • the composite antistatic agent used in Comparative Example 4 reduces the amount of carbon nanotubes, and the composite antioxidant in Comparative Example 5 increases the amount of carbon nanotubes, and the surface resistivity of the obtained material is still large, still 10 8 Above, the antistatic performance is not good enough, and the mechanical properties also have a certain degree of decline.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

本发明公开了一种阻燃抗静电聚酰胺复合材料及其制备方法和应用，以PA66为基体材料，添加一定配比的增强材料、阻燃剂、加工助剂以及特定比例的二苯甲砜磺酸钾与一定尺寸的碳纳米管复配作为复合抗静电剂制得阻燃抗静电聚酰胺复合材料，不仅可以获得良好的抗静电性能，并且力学性能、阻燃性能也同样优异，可以应用于要求抗静电的场合，比如煤矿设备等。

Description

一种阻燃抗静电聚酰胺复合材料及其制备方法和应用 技术领域
本发明涉及工程塑料技术领域，更具体地，涉及一种阻燃抗静电聚酰胺复合材料及其制备方法和应用。
背景技术
聚酰胺具有杰出的机械性能、耐热性能、耐磨性能、耐油性能等，广泛应用于机械行业、汽车、电动工具、电子电器、交通运输等领域。聚酰胺常用作阻燃材料，虽然本身极性很强，而且吸水性比较强，但仍具有较高的表面电阻(10 10Ω以上)产生瓦斯气体的场合使用，表面电阻要达到(10 8Ω以下)才能满足使用的要求，否则很容易引起火灾和爆炸，因此在煤矿设备这种应用场合，需要开发既具有阻燃又具有抗静电功能的材料。
中国专利CN 1752142A(公开日2006.3.29)公开了一种尼龙6/聚电解质抗静电复合材料的制备方法，通过添加碱金属盐或烷基苯二苯甲砜磺酸钾制备了具有良好抗静电效果的聚酰胺复合材料。然而PA66的加工温度为230～280℃，在如此高的加工温度下，抗静电助剂会发生降解，导致复合材料性能显著劣化，力学性能降低30％以上，无法获得同时具有良好抗静电性能和力学性能的阻燃聚酰胺材料。
发明内容
本发明要解决的技术问题是克服现有阻燃聚酰胺材料无法同时具有良好的抗静电性能和力学性能的缺陷和不足，提供一种阻燃抗静电聚酰胺复合材料，同时具有良好的抗静电性能和力学性能。
本发明的又一目的是提供一种阻燃抗静电聚酰胺复合材料的制备方法。
本发明的另一目的是提供一种阻燃抗静电聚酰胺复合材料的应用。
本发明上述目的通过以下技术方案实现：
一种阻燃抗静电聚酰胺复合材料，包括如下按照质量份计算的组分：
Figure PCTCN2021092777-appb-000001
Figure PCTCN2021092777-appb-000002
所述复合抗静电剂为二苯甲砜磺酸钾与碳纳米管的复配物，其中二苯甲砜磺酸钾与碳纳米管的质量比为1：1.5～2.5；碳纳米管的直径为8～15nm，长度为10～70μm。
本发明以PA66作为基体材料，具有优异的阻燃性能，并添加选择特定比例的二苯甲砜磺酸钾与一定尺寸的碳纳米管进行复配作为复合抗静电剂，一是二苯甲砜磺酸钾本身具有抗静电效果，二是二苯甲砜磺酸钾能够促进碳纳米管在PA66的分散，提高碳纳米管在体系中的相容性，有利于构建电荷的传递网络，所制得的阻燃聚酰胺复合材料可以获得良好抗静电性能，并且在PA66的加工温度下(230～280℃)，仍能具有较好的力学性能。
优选地，包括如下按照质量份计算的组分：
Figure PCTCN2021092777-appb-000003
优选地，所述二苯甲砜磺酸钾与碳纳米管质量比为1：2～2.5。
更优选地，所述二苯甲砜磺酸钾与碳纳米管质量比为1：2。
优选地，所述碳纳米管的直径10～12nm，长度30～60μm。
优选地，所述PA66的数均分子量为12000～30000。
优选地，所述PA66的相对粘度为1.8～3.5。
优选地，所述PA66的相对粘度在2.2～2.8。
其中上述PA66相对粘度的测试方法：测试标准ISO 307-2007，96％的硫酸溶液，样品浓度0.005g/mL，测试温度25℃。
本发明所述增强材料包括但不限于玻璃纤维、碳纤维、芳纶纤维、陶瓷纤维中一种或几种。
优选地，所述阻燃剂为红磷母粒。
优选地，所述阻燃剂为微胶囊红磷母粒。
优选地，所述微胶囊红磷母粒中红磷的质量含量为40％～60％。
本发明所述加工助剂包括但不限于抗氧剂、润滑剂、光稳定剂、着色剂中的一种或几种。
本发明所述抗氧剂包括但不限于N,N'-双-(3-(3,5-二叔丁基-4-羟基苯基)丙酰基)己二胺(1098)、三乙二醇醚-二(3-叔丁基-4-羟基-5-甲基苯基)丙酸酯(抗氧剂245)、四[β-(3，5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯(抗氧剂1010)、三[2.4-二叔丁基苯基]亚磷酸酯(抗氧剂168)、亚磷酸酯类抗氧剂P-EPQ、铜盐抗氧剂(碘化钾、碘化亚铜、硬脂酸锌的复配物，质量比为8:1:1)中的一种或几种。
本发明所述润滑剂包括但不限于硬脂酸钙、改性乙撑双脂肪酸酰胺、脂肪族脂肪酸酯、乙烯-丙烯酸共聚物中的一种或几种。
本发明所述光稳定剂包括但不限于苯并三唑类光稳定剂。
本发明所述着色剂包括但不限于黑色母。
本发明保护上述阻燃抗静电聚酰胺复合材料的制备方法，包括如下步骤：
将PA66、增强材料、阻燃剂、复合抗静电剂、加工助剂混合均匀，熔融共混后，经过冷却、风干、造粒制得阻燃抗静电聚酰胺复合材料。
优选地，所述熔融共混选用带侧喂的双螺杆挤出机，喂料口包括主喂料口、侧喂料口；将混合均匀的物料从主喂料口喂入，将增强材料从侧喂料口喂入。
优选地，所述熔融共混的温度为230～280℃。
本发明还保护上述阻燃抗静电聚酰胺复合材料在煤矿设备中的应用。本发明的阻燃抗静电聚酰胺复合材料具有优异的阻燃性能，达到V-0级，表面电阻率在10 8及其以下，拉伸强度达到133MPa及其以上，冲击强度达到8.5kJ/m 2及其以上，具有良好的抗静电性能和力学性能。
与现有技术相比，本发明的有益效果是：
本发明以PA66为基体材料，添加一定配比的增强材料、阻燃剂、加工助剂以及特定比例的二苯甲砜磺酸钾与一定尺寸的碳纳米管复配作为复合抗静电剂制得阻燃抗静电聚酰胺复合材料，不仅可以获得良好抗静电性能，并且在PA66的加工温度下，仍能获得较好的力学性能，阻燃性能良好，可以应用于要求抗静电的场合，比如煤矿设备等。
具体实施方式
下面结合具体实施方式对本发明作进一步的说明，但实施例并不对本发明做任何形式的限定。除非另有说明，本发明实施例采用的原料试剂为常规购买的原料试剂。
实施例和对比例中的组分：
PA66：牌号为EPR24，数均分子量为13700，相对粘度2.4，购于平顶山神马集团；
增强材料：玻璃纤维，牌号为ECS10-03-568H，购于巨石集团；
微胶囊红磷母粒：牌号为FR9950KF，红磷质量含量50％，购于桐城市信得新材料有限公司；
市售抗静电剂：名称为聚醚型抗静电剂，牌号为PELESTAT-6500，购于日本三洋化成；
导电炭黑：购于亿博瑞(天津)化工有限公司；
二苯甲砜磺酸钾(KSS)：牌号为KSS-KF，购于上海鼎耐化工有限公司；
碳纳米管A：牌号为LUCAN CP1002M，购于LG化学；碳纳米管的直径为8～12nm，长度为50～70μm。
碳纳米管B：牌号为GC-21，购于山东大展纳米材料有限公司；碳纳米管的直径为12～15nm，长度为10～50μm；
黑色母：牌号为N54/1044，购于英国高莱塑料；
抗氧剂1098：N,N'-双-(3-(3,5-二叔丁基-4-羟基苯基)丙酰基)己二胺，市售；
润滑剂：乙烯-丙烯酸共聚物(EAA)，牌号为A-C540A，购于霍尼韦尔。
实施例1
各实施例和对比例的阻燃抗静电聚酰胺复合材料，其组分及其质量份如表2所示。
一种阻燃抗静电聚酰胺复合材料的制备方法，包括如下步骤：
将PA66、增强材料、阻燃剂、复合抗静电剂、加工助剂投入混合机中进行混合直至均匀，得到混合物料；然后选用带双侧喂的双螺杆挤出机，从主喂下料；再将增强材料从侧喂口下料，然后在280℃下熔融共混、螺杆转速为450rpm，挤出、水冷、风干、造粒；再将材料烘干、注塑成相应的测试样条和样板。
表1不同配比的复合抗静电剂(质量比)
  二苯甲砜磺酸钾 碳纳米管A 碳纳米管B
复合抗静电剂1 1 1.5  
复合抗静电剂2 1 2  
复合抗静电剂3 1 2.5  
复合抗静电剂4 1 1  
复合抗静电剂5 1 3  
复合抗静电剂6 1   2
表2各实施例和对比例中的组分及其质量份
Figure PCTCN2021092777-appb-000004
  对比例1 对比例2 对比例3 对比例4 对比例5
PA66EPR24 58.5 43.5 43.5 54.5 54.5
微胶囊红磷母粒FR9950KF 14 14 14 14 14
导电炭黑   15      
市售抗静电剂     15    
PELESTAT-6500          
复合抗静电剂1          
复合抗静电剂2          
复合抗静电剂3          
复合抗静电剂4       4  
复合抗静电剂5         4
复合抗静电剂6          
黑色母N54/1044 1.5 1.5 1.5 1.5 1.5
玻璃纤维ECS10-03-568H 25 25 25 25 25
抗氧剂1098 0.5 0.5 0.5 0.5 0.5
润滑剂A-C0540A 0.5 0.5 0.5 0.5 0.5
性能测试
1、测试方法
(1)拉伸强度：按照GB/T 1040.2-2006标准进行测试；拉伸速度为10mm/min；(2)悬臂梁缺口冲击强度：按照ISO 180进行测试；
(3)阻燃性能：按照UL 94测试，样条规格125×13×0.8mm；
(4)表面电阻率：GBT 1410-2006，样板规格100*100*3.0mm矩形板。
2、测试结果
表3各实施例和对比例产品的测试结果
Figure PCTCN2021092777-appb-000005
通过表3可以发现，通过本发明制备的阻燃抗静电聚酰胺复合材料具有高效的抗静电效果，表面电阻率在10 8及其以下，还具有良好的缺口冲击强度、拉伸 强度和阻燃性能，可以应用于要求抗静电的场合，比如煤矿设备。但是其中对比例1没有添加复合抗静电剂，其表面电阻率显著增大，对比例2和对比例3分别采用导电炭黑、市售抗静电剂PELESTAT-6500作为替代复合抗静电剂，表面电阻率仍大于10 8，且缺口冲击强度、拉伸强度等力学性能显著下降，可见现有常规的抗静电剂不能很好地降低材料表面电阻率，且对材料的力学性能会造成不良影响。对比例4中使用的复合抗静电剂减少了碳纳米管的用量，对比例5中的复合抗氧化剂增加了碳纳米管的用量，制得的材料的表面电阻率仍较大，仍在10 8以上，抗静电性能不够好，且力学性能也有一定程度的下降。
显然，本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明权利要求的保护范围之内。

Claims (10)

  1. 一种阻燃抗静电聚酰胺复合材料，其特征在于，包括如下按照质量份计算的组分：
    Figure PCTCN2021092777-appb-100001
    所述复合抗静电剂为二苯甲砜磺酸钾与碳纳米管的复配物，其中二苯甲砜磺酸钾与碳纳米管的质量比为1：1.5～2.5；碳纳米管的直径为8～15nm，长度为10～70μm。
  2. 根据权利要求1所述阻燃抗静电聚酰胺复合材料，其特征在于，包括如下按照质量份计算的组分：
    Figure PCTCN2021092777-appb-100002
  3. 根据权利要求1或2所述阻燃抗静电聚酰胺复合材料，其特征在于，所述二苯甲砜磺酸钾与碳纳米管的质量比为1：2～2.5。
  4. 根据权利要求1或2所述阻燃抗静电聚酰胺复合材料，其特征在于，所述碳纳米管的直径10～12nm，长度30～60μm。
  5. 根据权利要求1所述阻燃抗静电聚酰胺复合材料，其特征在于，所述PA66的数均分子量为15000～40000。
  6. 根据权利要求1所述阻燃抗静电聚酰胺复合材料，其特征在于，所述PA66的相对粘度为1.8～3.5。
  7. 根据权利要求1所述阻燃抗静电聚酰胺复合材料，其特征在于，所述阻燃剂为红磷母粒。
  8. 权利要求1～7任一项所述阻燃抗静电聚酰胺复合材料的制备方法，其特征在于，包括如下步骤：
    将PA66、增强材料、阻燃剂、复合抗静电剂、加工助剂混合均匀，熔融共 混后，经过冷却、风干、造粒制得阻燃抗静电聚酰胺复合材料。
  9. 权利要求1～7任一项所述阻燃抗静电聚酰胺复合材料在煤矿设备领域用聚酰胺制品中的应用。
  10. 一种聚酰胺制品，其特征在于，包括权利要求1～7任一项所述阻燃抗静电聚酰胺复合材料制成。
PCT/CN2021/092777 2020-11-27 2021-05-10 一种阻燃抗静电聚酰胺复合材料及其制备方法和应用 Ceased WO2022110665A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202011360931.4 2020-11-27
CN202011360931.4A CN112552679B (zh) 2020-11-27 2020-11-27 一种阻燃抗静电聚酰胺复合材料及其制备方法和应用

Publications (1)

Publication Number Publication Date
WO2022110665A1 true WO2022110665A1 (zh) 2022-06-02

Family

ID=75046486

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/092777 Ceased WO2022110665A1 (zh) 2020-11-27 2021-05-10 一种阻燃抗静电聚酰胺复合材料及其制备方法和应用

Country Status (2)

Country Link
CN (1) CN112552679B (zh)
WO (1) WO2022110665A1 (zh)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114957987A (zh) * 2022-07-04 2022-08-30 华润化学材料科技股份有限公司 一种阻燃性抗静电母粒及其制备方法与应用
CN115926453A (zh) * 2023-01-13 2023-04-07 深圳科立尔科技有限公司 一种具有抗静电作用的尼龙母粒及其制备方法
CN115948049A (zh) * 2023-03-15 2023-04-11 广东永鑫华新型材料有限公司 一种永久抗静电挤出级尼龙材料的制备方法
CN117866429A (zh) * 2023-12-15 2024-04-12 会通特种材料科技有限公司 一种阻燃抗静电的生物基长碳链尼龙复合材料及其制备方法
CN117887252A (zh) * 2024-01-16 2024-04-16 湖南省新基源新材料科技有限公司 聚酰胺组合物及其制备方法
CN119820817A (zh) * 2023-10-08 2025-04-15 宁波弘瑞薄膜科技有限公司 多功能低静电尼龙膜的生产方法
CN120310243A (zh) * 2025-04-30 2025-07-15 宁波瑞成包装材料有限公司 一种抗静电双向拉伸尼龙膜

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112552679B (zh) * 2020-11-27 2022-01-11 金发科技股份有限公司 一种阻燃抗静电聚酰胺复合材料及其制备方法和应用
CN114621573B (zh) * 2022-03-15 2023-06-23 金发科技股份有限公司 一种无卤阻燃碳纤维增强聚碳酸酯组合物及其制备方法和应用

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101870812A (zh) * 2009-04-24 2010-10-27 上海金发科技发展有限公司 一种导电尼龙66材料及其制备方法
CN102532867A (zh) * 2010-12-17 2012-07-04 合肥杰事杰新材料股份有限公司 一种导电尼龙材料及其制备方法
CN105602245A (zh) * 2016-02-23 2016-05-25 广东思汗新材料有限公司 阻燃导电尼龙66材料及其制备方法
US9567462B2 (en) * 2006-12-28 2017-02-14 Ems-Chemie Ag Polyamide molding materials reinforced with glass fibers and injection molded parts thereof
WO2019132085A1 (ko) * 2017-12-29 2019-07-04 (주)성호폴리텍 내열성 및 내유성이 우수한 얼로이 조성물
CN109971171A (zh) * 2019-03-27 2019-07-05 宁波汇邦尼龙科技有限公司 一种阻燃导电耐冲型电缆夹板材料及其制备装置
CN111363349A (zh) * 2020-03-27 2020-07-03 苏州禾润昌新材料有限公司 一种阻燃抗静电增强尼龙复合材料及其制备方法
CN112552679A (zh) * 2020-11-27 2021-03-26 金发科技股份有限公司 一种阻燃抗静电聚酰胺复合材料及其制备方法和应用

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170107337A1 (en) * 2006-12-28 2017-04-20 Ems-Chemie Ag Polyamide molding materials reinforced with glass fibers and injection molded parts thereof
CN106566240A (zh) * 2016-11-04 2017-04-19 马鞍山市华能电力线路器材有限责任公司 一种抗静电缓蚀型玻纤增强pa66电力金具材料及其制备方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9567462B2 (en) * 2006-12-28 2017-02-14 Ems-Chemie Ag Polyamide molding materials reinforced with glass fibers and injection molded parts thereof
CN101870812A (zh) * 2009-04-24 2010-10-27 上海金发科技发展有限公司 一种导电尼龙66材料及其制备方法
CN102532867A (zh) * 2010-12-17 2012-07-04 合肥杰事杰新材料股份有限公司 一种导电尼龙材料及其制备方法
CN105602245A (zh) * 2016-02-23 2016-05-25 广东思汗新材料有限公司 阻燃导电尼龙66材料及其制备方法
WO2019132085A1 (ko) * 2017-12-29 2019-07-04 (주)성호폴리텍 내열성 및 내유성이 우수한 얼로이 조성물
CN109971171A (zh) * 2019-03-27 2019-07-05 宁波汇邦尼龙科技有限公司 一种阻燃导电耐冲型电缆夹板材料及其制备装置
CN111363349A (zh) * 2020-03-27 2020-07-03 苏州禾润昌新材料有限公司 一种阻燃抗静电增强尼龙复合材料及其制备方法
CN112552679A (zh) * 2020-11-27 2021-03-26 金发科技股份有限公司 一种阻燃抗静电聚酰胺复合材料及其制备方法和应用

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114957987A (zh) * 2022-07-04 2022-08-30 华润化学材料科技股份有限公司 一种阻燃性抗静电母粒及其制备方法与应用
CN115926453A (zh) * 2023-01-13 2023-04-07 深圳科立尔科技有限公司 一种具有抗静电作用的尼龙母粒及其制备方法
CN115926453B (zh) * 2023-01-13 2024-05-17 深圳科立尔科技有限公司 一种具有抗静电作用的尼龙母粒及其制备方法
CN115948049A (zh) * 2023-03-15 2023-04-11 广东永鑫华新型材料有限公司 一种永久抗静电挤出级尼龙材料的制备方法
CN119820817A (zh) * 2023-10-08 2025-04-15 宁波弘瑞薄膜科技有限公司 多功能低静电尼龙膜的生产方法
CN117866429A (zh) * 2023-12-15 2024-04-12 会通特种材料科技有限公司 一种阻燃抗静电的生物基长碳链尼龙复合材料及其制备方法
CN117887252A (zh) * 2024-01-16 2024-04-16 湖南省新基源新材料科技有限公司 聚酰胺组合物及其制备方法
CN120310243A (zh) * 2025-04-30 2025-07-15 宁波瑞成包装材料有限公司 一种抗静电双向拉伸尼龙膜

Also Published As

Publication number Publication date
CN112552679B (zh) 2022-01-11
CN112552679A (zh) 2021-03-26

Similar Documents

Publication Publication Date Title
WO2022110665A1 (zh) 一种阻燃抗静电聚酰胺复合材料及其制备方法和应用
CN102532823B (zh) 一种综合性能优异的抗静电pbt材料及其制备方法
WO2022110666A1 (zh) 一种红磷阻燃聚酰胺组合物及其制备方法和应用
WO2023179555A1 (zh) 一种无卤阻燃聚碳酸酯/苯乙烯类树脂合金及其制备方法和应用
CN103013104A (zh) 一种无卤填充阻燃尼龙6复合材料及其制备方法
CN101845206B (zh) 耐热薄壁阻燃pbt/pet合金材料
CN108485092B (zh) 应用于瓦斯抽放管道的阻燃抗静电氯化聚乙烯复合材料及其制备方法
CN116218210A (zh) 一种抗静电阻燃增强增韧尼龙复合材料及其制备方法
CN110551387B (zh) 一种抗静电阻燃热塑性聚氨酯弹性体及其制备方法
CN116178912A (zh) 一种pbt复合材料及其制备方法和应用
CN110760177B (zh) 导电聚苯醚/高抗冲聚苯乙烯组合物及其制备方法
CN107266786A (zh) 一种聚丙烯无卤阻燃母粒及其制备方法
CN105062072A (zh) 一种聚苯硫醚复合材料及其制备方法
CN102399430B (zh) 一种永久抗静电pa6/pa66合金及制备方法
CN115490954A (zh) 一种聚丙烯复合材料及其制备方法和应用
CN102417658B (zh) 一种永久抗静电pa66/pp合金及制备方法
CN104387742A (zh) 一种耐高温的pc复合材料
CN111825933B (zh) 阻燃耐磨pvc组合物、pvc银灰管及pvc银灰管制备方法
CN103788635A (zh) 一种阻燃型聚己内酰胺导热塑料及其制备方法
CN109233242B (zh) 聚苯醚树脂复合材料及其制备方法和应用
CN114316556A (zh) 一种高冲击永久抗静电阻燃pc材料及其制备方法
CN117924929B (zh) 一种耐黄变无卤阻燃增强的ppa复合材料及其制备方法
CN115491013B (zh) 一种阻燃玻纤增强聚碳酸酯组合物及其制备方法和应用
CN102399432B (zh) 一种永久抗静电母粒、永久抗静电pa66/pa6/poe合金及制备方法
CN102417726B (zh) 一种永久抗静电pa66/poe合金及制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21896180

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 02.10.2023)

122 Ep: pct application non-entry in european phase

Ref document number: 21896180

Country of ref document: EP

Kind code of ref document: A1