WO2023109490A1 - 一种阻燃尼龙复合材料及其制备方法和应用 - Google Patents

一种阻燃尼龙复合材料及其制备方法和应用 Download PDF

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WO2023109490A1
WO2023109490A1 PCT/CN2022/134674 CN2022134674W WO2023109490A1 WO 2023109490 A1 WO2023109490 A1 WO 2023109490A1 CN 2022134674 W CN2022134674 W CN 2022134674W WO 2023109490 A1 WO2023109490 A1 WO 2023109490A1
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Prior art keywords
flame
composite material
nylon composite
retardant
retardant nylon
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French (fr)
Inventor
郑一泉
陈平绪
叶南飚
王丰
丁超
金雪峰
胡泽宇
吴长波
刘鑫鑫
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Kingfa Science and Technology Co Ltd
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Kingfa Science and Technology Co Ltd
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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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • 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
    • C08L71/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids

Definitions

  • the invention belongs to the application field of engineering plastics, and in particular relates to a flame-retardant nylon composite material and a preparation method and application thereof.
  • Nylon has the advantages of excellent electrical properties (CTI, electrical breakdown strength) and low price, and is widely used in electronic and electrical industries.
  • CTI electrical breakdown strength
  • Melamine cyanurate is a very effective flame retardant for nylon, but due to the interaction between melamine cyanurate and nylon, it affects the processing stability of nylon.
  • Nylon materials are prone to changes in crystallinity when heated, which will also affect the flame-retardant stability of nylon materials.
  • the purpose of the present invention is to overcome the defects or insufficiencies that the nylon material in the prior art uses melamine cyanurate as a flame retardant, and the compound flame retardant stabilizer has poor flame retardant stability and affected mechanical properties.
  • Burning nylon composite The flame-retardant nylon composite material provided by the present invention uses a specific nylon resin as the base material, and at the same time adds a small amount of aromatic dicarboxylic acid for flame-retardant modification. The mechanical properties of the nylon composites were not negatively affected.
  • Another object of the present invention is to provide a method for preparing the above flame-retardant nylon composite material.
  • Another object of the present invention is to provide the application of the flame-retardant nylon composite material in the preparation of 3D printing consumables.
  • a flame-retardant nylon composite material comprising the following components in parts by weight:
  • Aromatic dicarboxylic acid 0.05-2 parts
  • the oligomer content in the nylon resin is not higher than 1.6%.
  • the inventors of the present invention have found that if only C 8 ⁇ 18 long carbon chain monobasic saturated carboxylic acid compounds or C 8 ⁇ 18 long carbon chain dibasic saturated carboxylic acid compounds are added to modify the nylon material, although its flame retardant grade can be improved. It reaches the V-2 grade, but its flame retardancy is poor, and it cannot maintain the V-2 grade after being treated at 70°C for 168 hours, and has a relatively large negative impact on the mechanical properties.
  • Nylon resin will contain a certain amount of oligomers (the content is generally 0.5-2.5%, mass content), too many oligomers, easy to appear wool during spinning, not only affect the nylon composite
  • the mechanical properties of the material also affect the flame-retardant stability of V-2
  • the aromatic dicarboxylic acid has a high melting point, which is relatively stable in the processing temperature range of nylon and is difficult to attack the amide bond, which has a negative impact on the mechanical properties Small; at the same time, during the combustion (600-700°C), the aromatic dicarboxylic acid decomposes and attacks the amide bond, and produces a dripping effect, which takes away a large amount of heat and prevents combustion, making the flame retardant stability better.
  • the present invention not only achieves a stable flame-retardant V-2 grade by selecting nylon resin with a lower oligomer content, but also adds a small amount of aromatic dicarboxylic acid to carry out flame-retardant modification, and is effective for flame-retardant nylon
  • the mechanical properties of the composites were not negatively affected.
  • the weight portion of the aromatic dicarboxylic acid in the flame-retardant nylon composite material is 0.1-1 part.
  • the nylon resin is one or more of PA6, PA66 or PA66/6.
  • the oligomer content in the nylon resin is 1.0-1.6%.
  • the number average molecular weight of the oligomer is not higher than 1000.
  • the aromatic dicarboxylic acid is one or more of naphthalene dicarboxylic acid or phthalic acid.
  • the naphthalene dicarboxylic acid is one or more of 1,4-naphthalene dicarboxylic acid or 2,6-naphthalene dicarboxylic acid.
  • the phthalic acid is one or more of terephthalic acid, isophthalic acid or phthalic acid.
  • the aromatic dicarboxylic acid is one or both of naphthalene dioic acid (1,4-naphthalene dioic acid) or terephthalic acid.
  • the flame-retardant nylon composite material also includes other processing aids.
  • the other processing aids are one or more of antioxidants, lubricants, nucleating agents or antistatic agents.
  • the antioxidant is one of hindered phenol antioxidants, copper salt antioxidants, aromatic amine antioxidants, phosphite antioxidants or thioester antioxidants or Several kinds.
  • the weight part of the antioxidant is 0.05-1 part.
  • the hindered phenolic antioxidant is N, N'-hexamethylene bis(3,5-di-tert-butyl-4-hydroxyphenylpropionamide (Irganox 1098), tetrakis[1093,5 -Di-tert-butyl-4-hydroxyphenyl)propionate]pentaerythritol (Irganox 1010), triethylene glycol bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate (Iragnox 259), n-octadecyl ⁇ -(4-hydroxy-3,5-di-tert-butylphenyl)propionate (Iragno 1076) or spiroethylene glycol bis[ ⁇ -(3-tert-butyl-4 -Hydroxy-5-methylphenyl) propionate] (ADK AO-80) in one or more.
  • Irganox 1098 N, N'-hexamethylene bis
  • the copper salt antioxidant is cuprous iodide.
  • the aromatic amine antioxidant is one of 4,4'-bis( ⁇ ( ⁇ (-dimethylbenzyl)diphenylamine (Naugard 445) or polyamine mixture (Flexamine Granular) or two.
  • the phosphite antioxidant is 2,4-di-tert-butylphenol (Irganox 168), two (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol phosphite ( One or both of ADK PEP-36).
  • the mercaptan antioxidant is bis(octadecyl)thiodipropionate (Irganox PS802) pentaerythritol tetrakis(3-lauryl thiopropionate) (THANOX 412S).
  • the lubricant is one or more of amide lubricants, ester lubricants or fatty acid salt lubricants.
  • the weight part of the lubricant is 0.2-1.5 parts.
  • the amide lubricant is one or both of ethylene bis stearamide (EBS) or ethylene bis (12 hydroxymethyl) stearamide (TAF).
  • EBS ethylene bis stearamide
  • TAF ethylene bis (12 hydroxymethyl) stearamide
  • ester lubricant is pentaerythritol tetrastearate (PETS).
  • the fatty acid salt lubricant is one or more of zinc stearate, calcium stearate or calcium montanate.
  • the nucleating agent is one or more of amide nucleating agents, silicate nucleating agents or phosphate nucleating agents.
  • the weight part of the nucleating agent is 0.1-0.5 parts.
  • the amide nucleating agent is polyethylenediamine oxalic acid, polydecanediamine terephthalic acid, polydecanediamine isophthalic acid, polynonanediamine terephthalic acid or polynonanediamine terephthalic acid.
  • diamine isophthalic acid is one or more of diamine isophthalic acid.
  • the silicate nucleating agent is one or more of talc, kaolin or hydrotalcite.
  • the phosphate nucleating agent is sodium phenylphosphinate, sodium phenylphosphite, 2,2'-methylene-di(4,6-di-tert-butylphenyl)sodium phosphate Or one or more of bis[2,2'-methylene-bis(4,6-di-tert-butylphenyl)]aluminum phosphate.
  • the antistatic agent is one or more of polyethylene glycols.
  • the weight part of the antistatic agent is preferably 10-30 parts.
  • the weight part of the antistatic agent is preferably 15-25 parts.
  • the preparation method of the above-mentioned flame-retardant nylon composite material includes the following steps: uniformly mixing each component to obtain a mixture, then melting and extruding the mixture, and granulating to obtain the flame-retardant nylon composite material.
  • the preparation method of the flame-retardant nylon composite material includes the following steps: mixing each component uniformly in a high-speed mixer to obtain a compound, then adding the compound to a twin-screw extruder for melt extrusion, and granulating , to obtain the flame-retardant nylon composite material; wherein, the screw length-to-diameter ratio of the twin-screw extruder is 40-48:1, the temperature of the screw barrel is 250-320° C., and the screw speed is 200-550 rpm.
  • the present invention has the following beneficial effects:
  • the flame-retardant nylon composite material provided by the present invention uses a specific nylon resin as the base material, and at the same time adds a small amount of aromatic dicarboxylic acid for flame-retardant modification.
  • the mechanical properties of the nylon composites were not negatively affected.
  • Nylon material 1#, 50BWFS, PA66, ASCEND company the content of oligomers with number average molecular weight less than 1000 is 1%;
  • Nylon material 2#, 88X, PA66/6, ASCEND company the content of the oligomer whose number average molecular weight is lower than 1000 is 1.6%;
  • Aromatic dicarboxylic acid 1# 1,4-naphthalene dicarboxylic acid, chemically pure, Aladdin;
  • Aromatic dicarboxylic acid 2# isophthalic acid, chemically pure, Aladdin;
  • Aromatic dicarboxylic acid 3# phthalic acid, chemically pure, Aladdin;
  • Aromatic monocarboxylic acids benzoic acid, chemically pure, Aladdin;
  • Melamine cyanurate melamine cyanurate, commercially available
  • antistatic agent polyethylene glycol, 3600, commercially available.
  • the preparation method of the nylon composite material of each embodiment and comparative example of the present invention is: take each raw material according to the proportion, premix in a high mixer to obtain a premix; then put the premix into a twin-screw extruder Melt and mix, and extrude and granulate to obtain a nylon composite material; wherein, the aspect ratio of the twin-screw extruder is 36:1; the temperature of the screw barrel is set as 250-260-270-280 -290-290-290-300-320°C; the screw speed is 350 rpm.
  • (1) Flame retardant performance test clamp the sample strip 6mm from the upper end, the length direction is downward, and the lower end of the sample is kept at a distance of 300 ⁇ 10mm from the surface of the prefabricated cotton layer.
  • the thickness of the cotton is not more than 6mm, the size is 50mm ⁇ 50mm, and the weight About 0.08g.
  • the burning appliance adopts the methane flow rate of 105ml/min, the pressure is 0.1kpa, and the flame height is 20 ⁇ 1mm.
  • the center of the flame is placed at the midpoint of the lower edge of the sample.
  • the distance from the top of the burning appliance to the lower end of the sample is 10 ⁇ 1mm, and it is maintained for 10 ⁇ 0.5 seconds.
  • the burning appliance needs to be adjusted.
  • tilt the burner to 45°, move the burner away at a speed of 300mm/min for at least 150mm after burning for 10 ⁇ 0.05 seconds, and start recording the afterflame time t1 at the same time, and burn again immediately after the afterflame stops. 0.5 seconds, record afterflame time t2 after removing.
  • pretreatments were carried out: 48 hours at 23°C and 50% RH; 5 samples were tested for each group of samples;
  • Elongation at break test perform a tensile test on the injection molded strip according to the ISO527 standard at a tensile speed of 50 mm/min, and record the elongation at break.
  • This example provides a series of flame-retardant nylon composite materials, and the dosage of each component in the formula is shown in Table 1.
  • This comparative example provides a series of nylon composite materials, and the dosage of each component in the formula is shown in Table 2.
  • the flame-retardant nylon composite materials provided by each example can reach the flame-retardant V-2 grade, and after being treated at 70°C for 168 hours, it can still maintain the flame-retardant V-2 grade, and has excellent flame-retardant stability; In addition, there is basically no negative effect on the mechanical properties.
  • Comparative Example 1 no flame retardant modification was performed, and the flame retardant grade was gradeless; in Comparative Example 2, a small amount of melamine cyanurate was added as a flame retardant, and the flame retardancy was gradeless, and the elongation at break decreased significantly; Comparative Example 3 A relatively large amount of melamine cyanurate was added as a flame retardant, although the flame retardant grade can reach the V-0 grade, but the flame retardant stability is not good, and the elongation at break is significantly reduced; in comparative example 4, aromatic monoaryl Carboxylic acid is modified, although the flame retardant grade can reach V-2, but the flame retardant stability is not good, and the mechanical properties decline more seriously; comparative example 5 is modified by adding a small amount of long carbon chain dibasic saturated carboxylic acid, Although the flame retardant grade can reach V-2, the flame retardant stability is poor, the mechanical properties are poor, and the elongation at break drops significantly; comparative example 6 is modified by adding a large amount of long carbon chain dibas

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Abstract

一种阻燃尼龙复合材料及其制备方法和应用。该阻燃尼龙复合材料包括尼龙树脂、芳香族二元羧酸等组分，本方案提供的阻燃尼龙复合材料以特定尼龙树脂为基材，同时添加较少量的芳香族二元羧酸进行阻燃改性，不仅可达到稳定的阻燃V‑2等级，且对阻燃尼龙复合材料的力学性能没有负面影响。

Description

一种阻燃尼龙复合材料及其制备方法和应用 技术领域
本发明属于工程塑料应用领域，具体涉及一种阻燃尼龙复合材料及其制备方法和应用。
背景技术
尼龙具有电性能优异(CTI，电击穿强度)，以及价格低廉等优势，广泛应用于电子电气等行业。三聚氰胺氰尿酸盐是尼龙非常有效的阻燃剂，但由于三聚氰胺氰尿酸盐会与尼龙产生相互作用，影响尼龙的加工稳定性。尼龙材料在受热情况下，容易出现结晶度的变化，也会影响尼龙材料的阻燃稳定性。
已有专利公开了一种MAC阻燃尼龙66复合材料，以MAC(三聚氰胺氰尿酸盐)作为阻燃剂，以特定碳原子数的长碳链一元饱和羧酸化合物或长碳链二元饱和羧酸化合物作为阻燃稳定剂，可达到阻燃V-0等级；同时其指出如不添加阻燃稳定剂，只可达到V-2等级。但其仍然是以三聚氰胺氰尿酸盐作为阻燃剂，阻燃稳定性不佳。并且，特定碳原子数的长碳链一元饱和羧酸化合物或长碳链二元饱和羧酸化合物加入还会对尼龙材料的力学性能产生负面影响。
因此，开发一种具有较佳的力学性能、阻燃性能及阻燃稳定性的尼龙材料具有重要的研究意义。
发明内容
本发明的目的在于克服现有技术的尼龙材料以三聚氰胺氰尿酸盐作为阻燃剂，同时复配阻燃稳定剂存在阻燃稳定性不佳、力学性能受到影响的缺陷或不足提供一种阻燃尼龙复合材料。本发明提供的阻燃尼龙复合材料以特定尼龙树脂为基材，同时添加较少量的芳香族二元羧酸进行阻燃改性，不仅可达到稳定的阻燃V-2等级，且对阻燃尼龙复合材料的力学性能没有负面影响。
本发明的另一目的在于提供上述阻燃尼龙复合材料的制备方法。
本发明的另一目的在于提供阻燃尼龙复合材料在制备3D打印耗材中的应用。
为实现上述发明目的，本发明采用如下技术方案：
一种阻燃尼龙复合材料，包括如下重量份数的组分：
尼龙树脂       97～99.95份；
芳香族二元羧酸      0.05～2份；
所述尼龙树脂中齐聚物的含量不高于1.6％。
本发明的发明人研究发现，如果仅添加C 8～18长碳链一元饱和羧酸化合物或C 8～18长碳链二元饱和羧酸化合物对尼龙材料进行改性，其阻燃等级虽然可达到V-2等级，但阻燃稳定性差，经70℃处理168H后无法保持V-2等级，且对力学性能有较大的负面影响。
经反复研究发现，当选用较低齐聚物含量的尼龙树脂作为基材，同时添加芳香族二元羧酸对尼龙材料进行改性时，只需少量添加就可达到阻燃V-2等级，且经70℃处理168H后仍可保持阻燃V-2等级，具有优异的阻燃稳定性；另外，少量芳香族二元羧酸的添加对力学性能的负面影响很小。其原因可能是：(1)尼龙树脂中会含有一定量的齐聚物(含量一般为0.5～2.5％，质量含量)，齐聚物过多，纺丝时容易出现毛丝，不单影响尼龙复合材料的力学性能，同时还影响V-2的阻燃稳定性；(2)芳香族二元羧酸的熔点较高，在尼龙的加工温度范围内较为稳定难以攻击酰胺键，对力学性能负面影响小；同时，在燃烧(600-700℃)过程中芳香族二元羧酸分解并攻击酰胺键，并产生滴落效应，带走大量热量，阻止燃烧，使得阻燃稳定性较佳。
即本发明通过选用较低齐聚物含量的尼龙树脂，同时添加较少量的芳香族二元羧酸进行阻燃改性，不仅可达到稳定的阻燃V-2等级，且对阻燃尼龙复合材料的力学性能没有负面影响。
优选地，所述阻燃尼龙复合材料中芳香族二元羧酸的重量份数为0.1～1份。
本领域常规的尼龙材料均可用于本发明中。
优选地，所述尼龙树脂为PA6、PA66或PA66/6的一种或几种。
优选地，所述尼龙树脂中齐聚物的含量为1.0～1.6％。
优选地，所述齐聚物的数均分子量不高于1000。
优选地，所述芳香族二元羧酸为萘二酸或苯二甲酸中的一种或几种。
更为优选地，所述萘二甲酸为1,4-萘二甲酸或2,6-萘二甲酸中的一种或几种。
更为优选地，所述苯二甲酸为对苯二甲酸、间苯二甲酸或邻苯二甲酸中的一种或几种。
更为优选地，所述芳香族二元羧酸为萘二酸(1,4-萘二酸)或对苯二甲酸中 的一种或两种。
优选地，所述阻燃尼龙复合材料还包括其它加工助剂。
更为优选地，所述其它加工助剂为抗氧剂、润滑剂、成核剂或抗静电剂中的一种或几种。
优选地，所述抗氧剂为受阻酚类抗氧剂、铜盐类抗氧剂、芳香胺类抗氧剂、亚磷酸酯类抗氧剂或硫代酯类抗氧剂中的一种或几种。
优选地，所述抗氧剂的重量份数为0.05～1份。
更为优选地，所述受阻酚类抗氧剂为N，N`-六亚甲基双(3,5-二叔丁基-4-羟基苯丙酰胺(Irganox 1098)、四[1093,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯(Irganox 1010)、三甘醇双-3-(3-叔丁基-4-羟基-5-甲基苯基)丙酸酯(Iragnox 259)、β-(4-羟基-3,5-二叔丁基苯基)丙酸正十八酯(Iragno 1076)或螺乙二醇双[β-(3-特丁基-4-羟基-5-甲基苯基)丙酸酯](ADK AO-80)中的一种或几种。
更为优选地，所述铜盐类抗氧剂为碘化亚铜。
更为优选地，所述芳香胺类抗氧剂为4,4`-双(α(α(-二甲基苄基)二苯胺(Naugard 445)或多元胺混合物(Flexamine Granular)中的一种或两种。
更为优选地，所述亚磷酸酯类抗氧剂为2，4-二叔丁基苯酚(Irganox 168)、双(2,6-二叔丁基-4-甲苯基)季戊四醇亚磷酸酯(ADK PEP-36)中的一种或两种。
更为优选地，所述硫醇类抗氧剂为硫代二丙酸双(十八)酯(Irganox PS802)季戊四醇四(3-月桂基硫代丙酸酯)(THANOX 412S)。
优选地，所述润滑剂为酰胺类润滑剂、酯类润滑剂或脂肪酸盐类润滑剂中的一种或几种。
优选地，所述润滑剂的重量份数为0.2～1.5份。
更为优选地，所述酰胺类润滑剂为乙撑双硬脂酰胺(EBS)或乙撑双(12羟甲基)硬脂酰胺(TAF)中的一种或两种。
更为优选地，所述酯类润滑剂为季戊四醇四硬脂酸酯(PETS)。
更为优选地，所述脂肪酸盐类润滑剂为硬脂酸锌、硬脂酸钙或蒙旦酸钙中的一种或几种。
进一步优选地，所述成核剂为酰胺类成核剂、硅酸盐类成核剂或磷酸盐类成核剂中的一种或几种。
优选地，所述成核剂的重量份数为0.1～0.5份。
更进一步优选地，所述酰胺类成核剂为聚乙二胺乙二酸、聚癸二胺对苯二甲酸、聚癸二胺间苯二甲酸、聚壬二胺对苯二甲酸或聚壬二胺间苯二甲酸中的一种或几种。
更进一步优选地，所述硅酸盐类成核剂为滑石粉、高岭土或水滑石中的一种或几种。
更进一步优选地，所述磷酸盐类成核剂为苯基次膦酸钠、苯基亚磷酸钠、2,2’-亚甲基-二(4,6-二叔丁基苯)磷酸钠或双[2,2’-亚甲基-二(4,6-二叔丁基苯基)]磷酸铝中的一种或几种。
优选地，所述抗静电剂为聚乙二醇类的一种或几种。
优选地，所述抗静电剂的重量份数优选为10～30份。
进一步优选地，所述抗静电剂的重量份数优选为15～25份。
上述阻燃尼龙复合材料的制备方法，包括如下步骤：将各组分混合均匀得混合料，然后将混合料熔融挤出，造粒，即得所述阻燃尼龙复合材料。
优选地，所述阻燃尼龙复合材料的制备方法，包括如下步骤：将各组分在高混机中混合均匀得混合料，然后将混合料加入双螺杆挤出机中熔融挤出，造粒，即得所述阻燃尼龙复合材料；其中，双螺杆挤出机的螺杆长径比为40～48:1，螺筒温度为250～320℃，螺杆转速为200～550rpm。
上述阻燃尼龙复合材料在制备电子电器(例如连接器、开关面板)中的应用也在本发明的保护范围内。
与现有技术相比，本发明具有如下有益效果：
本发明提供的阻燃尼龙复合材料以特定尼龙树脂为基材，同时添加较少量的芳香族二元羧酸进行阻燃改性，不仅可达到稳定的阻燃V-2等级，且对阻燃尼龙复合材料的力学性能没有负面影响。
具体实施方式
下面结合实施例进一步阐述本发明。这些实施例仅用于说明本发明而不用于限制本发明的范围。下例实施例中未注明具体条件的实验方法，通常按照本领域常规条件或按照制造厂商建议的条件；所使用的原料、试剂等，如无特殊说明，均为可从常规市场等商业途径得到的原料和试剂。本领域的技术人员在本发明的 基础上所做的任何非实质性的变化及替换均属于本发明所要求保护的范围。
本发明各实施例及对比例选用的部分试剂说明如下：
尼龙材料1#，50BWFS，PA66，ASCEND公司，数均分子量低于1000的齐聚物的含量为1％；
尼龙材料2#，88X，PA66/6，ASCEND公司，数均分子量低于1000的齐聚物的含量为1.6％；
尼龙材料3#，M2400，PA66，新会美达化工有限公司，数均分子量低于1000的齐聚物的含量为1.3％；
尼龙材料4#，EP-158，PA66，华峰集团有限公司，数均分子量低于1000的齐聚物的含量为2.6％；
芳香族二元羧酸1#：1,4-萘二酸，化学纯，阿拉丁；
芳香族二元羧酸2#：间苯二甲酸，化学纯，阿拉丁；
芳香族二元羧酸3#：邻苯二甲酸，化学纯，阿拉丁；
芳香族一元羧酸：苯甲酸，化学纯，阿拉丁；
长碳链二元饱和羧酸：癸二酸，化学纯，阿拉丁；
三聚氰胺氰尿酸盐：氰尿酸三聚氰胺，市售；
其它加工助剂：抗静电剂，聚乙二醇类，3600，市售。
应当理解的是，如未特殊说明，实施例或对比例所包括的某一组分(例如芳香族二元羧酸1～3#、三聚氰胺氰尿酸盐、抗氧剂、润滑剂、成核剂、抗静电剂)均为相同的市售产品。
本发明各实施例及对比例的尼龙复合材料的制备方法为：按照配比称取各原料，在高混机中进行预混合得到预混料；然后将预混物投入双螺杆挤出机中进行熔融混合，并挤出造粒，得到尼龙复合材料；其中，双螺杆挤出机的长径比为36:1；螺筒温度一-九区设定为：为250-260-270-280-290-290-290-300-320℃，；螺杆转速为350转/分钟，即得。
本发明各实施例及对比例的尼龙复合材料进行如下测试：
(1)阻燃性能测试：将样条从上端夹入6mm，长度方向朝下，样品下端离预制棉花层表面保持300±10mm的距离，棉花的厚度不超过6mm，尺寸为50mm×50mm，重量约0.08g。燃具采用甲烷流量105ml/min，被压0.1kpa，火焰高度 20±1mm。火焰中心置于样品下边沿中点处，燃具顶部到样品下端距离为10±1mm，维持10±0.5秒，如果燃烧过程中出现形状和位置的变化，燃具需要调整，若测试过程中有熔融物滴落，可将燃具倾斜到45°，燃烧10±0.05秒后以300mm/min的速度移开燃具至少150mm，同时开始记录余焰时间t1，余焰停止时立刻再次燃烧10±0.5秒，移开后记录余焰时间t2。测试前进行如下前处理：23℃，50％RH条件下处理48H；每组样品测试5块样板；
(2)阻燃稳定性测试：将制备的样品在70℃处理168H，然后在23℃下，50％湿度下处理48H，再进行UL94阻燃等级测试。
(3)断裂伸长率测试：按照ISO527标准注塑样条进行拉伸测试，拉伸速度50mm/min，记录断裂时的伸长率。
实施例1～10
本实施例提供一系列阻燃尼龙复合材料，其配方中各组分的用量如表1。
表1 实施例1～10的配方(份)
Figure PCTCN2022134674-appb-000001
对比例1～7
本对比例提供一系列尼龙复合材料，其配方中各组分的用量如表2。
Figure PCTCN2022134674-appb-000002
Figure PCTCN2022134674-appb-000003
各实施例和对比例提供的尼龙复合材料的测试结果如表3。
表3 实施例和对比例提供的尼龙复合材料的性能测试结果
Figure PCTCN2022134674-appb-000004
Figure PCTCN2022134674-appb-000005
Figure PCTCN2022134674-appb-000006
由上述测试结果可知，各实施例提供的阻燃尼龙复合材料可达到阻燃V-2等级，且经70℃处理168H后仍可保持阻燃V-2等级，具有优异的阻燃稳定性；另外，对力学性能基本无负面影响。对比例1未进行阻燃改性，阻燃级别为无级别；对比例2添加少量的三聚氰胺氰尿酸盐作为阻燃剂，阻燃为无级别，断裂伸长率大幅度下降；对比例3中添加较大量的三聚氰胺氰尿酸盐作为阻燃剂，阻燃等级虽然可达到V-0等级，但阻燃稳定性不佳，且断裂伸长率显著下降；对比例4中添加芳香族一元羧酸进行改性，阻燃等级虽可达到V-2，但阻燃稳定性不佳，力学性能下降比较严重；对比例5添加较少量的长碳链二元饱和羧酸进行改性，阻燃等级虽可达到V-2，但阻燃稳定性不佳，力学性能差，断裂伸长率下降明显；对比例6添加较大量的长碳链二元饱和羧酸进行改性，但阻燃稳定性同样不佳，力学性能差，断裂伸长率显著明显；对比例7选用较高齐聚物含量的尼龙材料，力学性能不佳，断裂伸长率低，阻燃稳定性不佳。
本领域的普通技术人员将会意识到，这里的实施例是为了帮助读者理解本发明的原理，应被理解为本发明的保护范围并不局限于这样的特别陈述和实施例。本领域的普通技术人员可以根据本发明公开的这些技术启示做出各种不脱离本发明实质的其它各种具体变形和组合，这些变形和组合仍然在本发明的保护范围内。

Claims (10)

  1. 一种阻燃尼龙复合材料，其特征在于，包括如下重量份数的组分：
    尼龙树脂                  97～99.95份；
    芳香族二元羧酸            0.05～2份；
    所述尼龙树脂中齐聚物的含量不高于1.6％。
  2. 根据权利要求1所述阻燃尼龙复合材料，其特征在于，所述阻燃尼龙复合材料中芳香族二元羧酸的重量份数为0.1～1份。
  3. 根据权利要求1所述阻燃尼龙复合材料，其特征在于，所述尼龙树脂为PA6、PA66或PA66/6的一种或几种。
  4. 根据权利要求1所述阻燃尼龙复合材料，其特征在于，所述尼龙树脂中齐聚物的含量为1.0～1.6％。
  5. 根据权利要求1所述阻燃尼龙复合材料，其特征在于，所述芳香族二元羧酸为萘二甲酸或苯二甲酸中的一种或几种。
  6. 根据权利要求5所述阻燃尼龙复合材料，其特征在于，所述萘二甲酸为1,4-萘二甲酸或2,6-萘二甲酸中的一种或两种；所述苯二甲酸为对苯二甲酸、间苯二甲酸或邻苯二甲酸中的一种或几种。
  7. 根据权利要求1所述阻燃尼龙复合材料，其特征在于，所述齐聚物的数均分子量不高于1000。
  8. 根据权利要求1所述阻燃尼龙复合材料，其特征在于，所述阻燃尼龙复合材料还包括其它加工助剂。
  9. 权利要求1～8任一所述阻燃尼龙复合材料的制备方法，其特征在于，包括如下步骤：将各组分混合均匀得混合料，然后将混合料熔融挤出，造粒，即得所述阻燃尼龙复合材料。
  10. 权利要求1～8任一所述阻燃尼龙复合材料在制备电子电器中的应用。
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