WO2025162010A1 - 一种聚酰胺组合物及其制备方法和应用 - Google Patents

一种聚酰胺组合物及其制备方法和应用

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Publication number
WO2025162010A1
WO2025162010A1 PCT/CN2025/073073 CN2025073073W WO2025162010A1 WO 2025162010 A1 WO2025162010 A1 WO 2025162010A1 CN 2025073073 W CN2025073073 W CN 2025073073W WO 2025162010 A1 WO2025162010 A1 WO 2025162010A1
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Prior art keywords
polyamide composition
hollow glass
masterbatch
polyamide resin
polyamide
Prior art date
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PCT/CN2025/073073
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English (en)
French (fr)
Inventor
周臣旭
陈平绪
叶南飚
郑一泉
姜粞
吴长波
丁超
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Kingfa Science and Technology Co Ltd
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Kingfa Science and Technology Co Ltd
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Application filed by Kingfa Science and Technology Co Ltd filed Critical Kingfa Science and Technology Co Ltd
Publication of WO2025162010A1 publication Critical patent/WO2025162010A1/zh
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    • 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
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant

Definitions

  • the present invention relates to the technical field of engineering plastics, and more particularly to a polyamide composition, a preparation method thereof, and an application thereof.
  • Polyamide resins with their excellent mechanical properties, wear resistance, and solvent resistance, are widely used in drones, automobiles, electronics, medical devices, and other fields.
  • Lowweighting helps reduce payload costs, increase effective weight, and extend service life. This is particularly true for drone applications, where miniaturization is possible.
  • drones Reducing the overall density of drones not only reduces the weight of the platform and improves accuracy, but also increases flight endurance. Components like the housing and propellers require high toughness and modulus to withstand collisions and drops. Furthermore, drones offer advantages such as strong real-time performance, flexibility, minimal environmental impact, and low cost. They hold broad potential for development and application in disaster emergency response, such as using drone systems for forest fire monitoring. This places even higher demands on the flame retardancy of the base material.
  • the current method mainly involves adding hollow glass microspheres, which can effectively reduce density but significantly reduce the toughness of the material.
  • the high density of flame retardants in current flame-retardant polyamides makes it difficult to reduce the density of the system and reduces the toughness of the material.
  • the impact strength of flame-retardant polyamide materials is no more than 5kJ/ m2 and the density is no less than 1.1g/ cm3 . If the amount of flame retardant used is too low, it is difficult to meet the higher flame retardancy requirements. Therefore, it is difficult to balance the flame retardancy of polyamide materials with low density and high toughness. Therefore, there is a need in the art to develop a flame-retardant, low-density polyamide composition that also has good toughness.
  • the purpose of the present invention is to provide a polyamide composition in order to overcome the problems or defects in the prior art that the polyamide composition is difficult to balance the flame retardant effect and low density performance, and the addition of hollow microbeads will reduce the toughness.
  • Another object of the present invention is to provide a method for preparing the polyamide composition.
  • Another object of the present invention is to provide applications of the polyamide composition.
  • the present invention adopts the following technical solutions:
  • a polyamide composition comprising the following components calculated in parts by weight:
  • the polyamide resin is a mixture of an aliphatic polyamide resin and an aromatic polyamide resin, and the content of the aromatic polyamide resin is 25wt% to 75wt% of the polyamide resin;
  • the hollow glass microbead masterbatch includes hollow glass microbeads, a first toughening agent and a first coupling agent, the content of the first coupling agent is not less than 0.3wt% of the hollow glass microbead masterbatch, and the content of the first toughening agent is not less than 3wt% of the hollow glass microbead masterbatch.
  • first toughening agent and the second toughening agent may be the same or different; the first coupling agent and the second coupling agent may be the same or different.
  • the present invention provides a polyamide composition.
  • the polyamide composition uses polyamide resin as a base resin.
  • the prepared polyamide composition has low density, high toughness, flame retardancy and high modulus properties.
  • the hollow glass microsphere masterbatch contains a first toughening agent and a first coupling agent, which can effectively improve the interface effect of the hollow glass microspheres directly added to the resin system, reduce the attenuation of toughness, and effectively reduce the pore breakage during the extrusion process; the selection of aromatic polyamide resin and red phosphorus flame retardant in synergy can achieve higher flame retardant performance with a lower amount of flame retardant added, thereby avoiding the problem of increased density; the addition of reinforcing fiber can effectively compensate for the modulus loss caused by the toughening agent and flame retardant.
  • the coupling agent is added in batches to help better disperse at the interface and prevent agglomeration during the preparation of the masterbatch.
  • the batch addition of the toughening agent can reduce the viscosity of the system during the preparation of the masterbatch, which causes pores in the hollow glass microspheres.
  • the content of the polyamide resin in the resin matrix is not less than 50 wt %, for example, but not limited to, 52.5 wt %, 55 wt %, 57.5 wt %, 60 wt %, 62.5 wt %, 65 wt %, 67.5 wt %, 70 wt %, etc.
  • the hollow glass microbead masterbatch includes the following components calculated in parts by weight: Hollow glass microspheres 68-99 parts; 5-40 parts of the first toughening agent; The first coupling agent: 0.5-2 parts.
  • the hollow glass microbead masterbatch further comprises 0 to 1 parts of an antioxidant.
  • the preparation method of hollow glass microbead masterbatch can adopt the conventional masterbatch preparation method in the prior art.
  • the method for preparing the hollow glass microbead masterbatch comprises the following steps:
  • the first coupling agent is diluted with a solvent, mixed with other components, and kneaded to obtain hollow glass microbead masterbatch.
  • the solvent is anhydrous ethanol.
  • the mass volume ratio of the first coupling agent to the solvent is 1:10 to 1:20.
  • the banburying is carried out by stirring at 90-130° C. for 5-10 minutes.
  • polyamide composition comprises the following components calculated in parts by weight:
  • the content of the aromatic polyamide resin in the polyamide resin is 25wt% to 75wt%, for example, but not limited to 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, 70wt% or 75wt%, etc. can achieve the present invention. Furthermore, the content of the aromatic polyamide resin in the polyamide resin is 45wt% to 60wt%.
  • aromatic polyamide resin can be any one or more of PA MXD6, PA MXD8, PA MXD10 or PA MXD12.
  • the density of the aliphatic polyamide resin is 1.00 to 1.03 g/cm 3 ; the density of the aromatic polyamide resin is 1.05 to 1.08 g/cm 3 .
  • the aliphatic polyamide resin is a long-chain polyamide resin.
  • Examples include, but are not limited to, AB-type PA11 and PA12 prepared by ring-opening ⁇ -amino acids or lactams, and PA612, PA610, PA1010, PA1012, and PA1212 prepared by polycondensation of dibasic acids and diamines.
  • the compressive strength of the hollow glass microspheres is 10,000 to 30,000 Psi.
  • the compressive strength of the hollow glass microspheres is tested by water isostatic pressure testing.
  • the density of the hollow glass microspheres is 0.4-0.5 g/cm 3 .
  • red phosphorus flame retardant is red phosphorus and/or red phosphorus masterbatch.
  • the red phosphorus content in the red phosphorus flame retardant is 45 to 85 wt%.
  • the flame retardant synergist includes one or more of zinc borate, magnesium hydroxide, aluminum hydroxide or montmorillonite.
  • the first coupling agent is a carboxyl-containing polymer
  • the second coupling agent is a carboxyl-containing polymer
  • the carboxyl group-containing polymer is an olefin acrylic acid copolymer and an ionic polymer thereof.
  • the olefin acrylic acid copolymer and the ionic polymer thereof are one or more of ethylene-methacrylic acid-acrylate terpolymer resin, ionic polymer of ethylene-methacrylic acid-acrylate terpolymer resin, or ethylene-methacrylic acid.
  • the first toughening agent is a polyolefin containing a polar group
  • the second toughening agent is a polyolefin containing a polar group
  • the polar group is one or more of maleic anhydride, epoxy group or ester group.
  • the polyolefin containing polar groups is one or more of MAH-g-SEBS, MAH-g-POE, ethylene-methyl acrylate copolymer or GMA-g-POE.
  • the reinforcing fibers include glass fibers and/or carbon fibers.
  • the reinforcing fiber is carbon fiber.
  • the processing aid is an antioxidant and/or a lubricant.
  • antioxidants can be selected according to existing technologies, such as but not limited to one or more of hindered phenol antioxidants, phosphite antioxidants, diphenylamine antioxidants or thioether antioxidants.
  • the hindered phenol antioxidant is one or more of N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyphenylpropionamide (Irganox 1098), pentaerythritol tetrakis[ ⁇ -3,5-di-tert-butyl-4-hydroxyphenyl)propionate (Irganox 1010), triethylene glycol bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate (Iragnox 259), ⁇ -(4-hydroxy-3,5-di-tert-butylphenyl) propionate n-octadecyl (Iragno 1076) or spiroglycol bis[ ⁇ -(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] (ADK AO-80).
  • Irganox 1098 N,N'-hexamethylenebis(3,5-di-tert-
  • the phosphite antioxidant is one or more of 2,4-di-tert-butylphenol (Irganox 168), bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol phosphite (PEP-36) or 627A.
  • the diphenylamine antioxidant is 4,4'-bis( ⁇ , ⁇ '-dimethylbenzyl)diphenylamine.
  • the thioether antioxidant is one or more of distearyl thiodipropionate, dilauryl thiodipropionate or pentaerythritol dodecylthiopropionate.
  • commonly used lubricants can be selected according to existing technologies, such as but not limited to one or more of stearic acid lubricants, polyethylene lubricants, amide lubricants, paraffin lubricants, ester lubricants or silicone lubricants.
  • the stearic acid lubricant can be calcium stearate and/or zinc stearate.
  • the polyethylene lubricant may be polyethylene wax.
  • the amide lubricant may be one or more of oleamide lubricants, EBS amide lubricants or erucamide lubricants.
  • the ester lubricant may be one or more of aliphatic stearate, oleic acid-based aliphatic polyester, or mesoic acid-based aliphatic polyester.
  • the silicone lubricant may be polydimethylsiloxane.
  • the present invention also protects a method for preparing the above-mentioned polyamide composition, comprising the following steps:
  • the polyamide resin, hollow glass microbead masterbatch, reinforcing fiber, a second toughening agent, a red phosphorus flame retardant, a flame retardant synergist, a second coupling agent and a processing aid are mixed to obtain a premix;
  • step S1 The premix in step S1 is melt-blended and extruded into pellets to obtain a polyamide composition.
  • the extrusion granulation in step S2 is carried out in a twin-screw extruder.
  • the screw length-diameter ratio of the twin-screw extruder is 40-48:1
  • the barrel temperature of the twin-screw extruder is 220-250° C.
  • the screw speed of the twin-screw extruder is 150-400 rpm.
  • the present invention also protects the use of the above-mentioned polyamide composition in the preparation of drone casings and propeller materials.
  • the present invention has the following beneficial effects:
  • the present invention provides a polyamide composition.
  • a base resin containing an aromatic polyamide resin is selected, and hollow glass microbead masterbatch is added.
  • the interfacial interaction between the hollow glass microbeads and the resin system can be effectively improved.
  • the aromatic polyamide resin and the red phosphorus flame retardant work synergistically to achieve higher flame retardant performance with a lower amount of flame retardant added, thereby avoiding density increase.
  • the density of the prepared polyamide composition is no higher than 1.1g/ m3 , the flame retardant grade meets the 1.0mm V-0 grade, and the notched impact strength is no less than 7kJ/ m2 .
  • the raw materials and reagents used in the examples of the present invention are conventionally purchased raw materials and reagents.
  • Polyamide resin 1 PA610 F150, purchased from Shandong Guangyin New Materials Co., Ltd.
  • Polyamide resin 2 PA MXD10, purchased from Yinggu Co., Ltd.
  • Hollow glass microspheres IM16K, density 0.46 g/cm 3 , compressive strength 16000 Psi, purchased from 3M Company, USA;
  • Reinforcement fiber 1 glass fiber, S1HM435TM-10-3, length 3 mm, Taishan Glass Fiber Co., Ltd.
  • Reinforcement fiber 2 carbon fiber, Type-65, length 6mm, ZOLTEK;
  • Red phosphorus flame retardant 1 microcapsule coated red phosphorus masterbatch, FR9950T, red phosphorus content 50wt%, purchased from Tongcheng Xinde Co., Ltd.
  • Red phosphorus flame retardant 2 microcapsule coated red phosphorus, FRP-950X, red phosphorus content 80wt%, Guangzhou Yinsu Flame Retardant Material Co., Ltd.
  • Brominated flame retardant brominated polystyrene, BPS 7010, Guangzhou Chengernuo Chemical Co., Ltd.
  • the first toughening agent MAH-g-SEBS, FG1901 G, purchased from Kraton;
  • Second toughening agent MAH-g-SEBS, FG1901 G, purchased from Kraton;
  • First coupling agent ethylene-methacrylic acid-acrylate terpolymer resin, AN4228C, purchased from DuPont Chemical, USA;
  • Second coupling agent ethylene-methacrylic acid-acrylate terpolymer resin, AN4228C, purchased from DuPont Chemical, USA;
  • Antioxidant Inganox@1098; Lubricant: LOXIOL G32; Both antioxidants and lubricants are commercially available, and the same antioxidants and lubricants are used in the parallel experiments of the examples and comparative examples.
  • hollow glass microbead masterbatch was prepared according to the following preparation method:
  • the first coupling agent was diluted 10 times with anhydrous ethanol, and then added into an internal mixer with hollow glass microspheres, a second toughening agent, and an antioxidant in proportion, stirred at high speed to mix evenly, and internally kneaded at 130° C. to obtain hollow glass microsphere masterbatch.
  • the polyamide resin, hollow glass microbead masterbatch, reinforcing fiber, a second toughening agent, a red phosphorus flame retardant, a flame retardant synergist, a second coupling agent and a processing aid are mixed to obtain a premix;
  • step S2 The premix in step S1 is melt blended and extruded into pellets to obtain a polyamide composition; the screw aspect ratio of the twin-screw extruder is 40 to 48:1; the barrel temperature of the twin-screw extruder is 220 to 250°C, and the screw speed of the twin-screw extruder is 150 to 400 rpm.
  • Izod notched impact strength The polyamide compositions prepared in the above examples and comparative examples were tested for notched impact strength according to ISO 180-2019; notch type: Type A;
  • the polyamide compositions prepared in various embodiments of the present invention have relatively low density and good flame retardancy, as well as good toughness and rigidity. Specifically, the density is not higher than 1.1 g/m 3 , the flame retardancy grade meets the 1.0 mm V-0 grade, and the notched impact strength is not lower than 7 kJ/m 2 .

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  • Health & Medical Sciences (AREA)
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Abstract

本发明公开了一种聚酰胺组合物及其制备方法和应用。所述聚酰胺组合物以聚酰胺树脂为基体树脂，通过加入中空玻璃微珠母粒、红磷阻燃剂和增强纤维，使制得的聚酰胺组合物具有低密度、高韧性、阻燃和高模量性能；所述中空玻璃微珠母粒中含有第一增韧剂和第一偶联剂，选用芳香族聚酰胺树脂与红磷阻燃剂协同，可以使得在较少阻燃剂添加量的情况下满足较高的阻燃性能，从而避免密度升高的问题，制得的聚酰胺组合物具有较好的阻燃性能且密度较低，同时具有较好的韧性。

Description

一种聚酰胺组合物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，涉及一种聚酰胺组合物及其制备方法和应用。
背景技术
聚酰胺树脂具有较好的机械性能、耐磨性和耐溶剂性能，而被广泛应用于无人机、汽车、电子电器、医疗器械等领域。随着行业的发展，轻量化产品的开发成为一大趋势。轻量化有助于降低载重成本和增加有效重量，延长使用时间，尤其是在无人机领域的应用，能够实现小型化。
降低无人机整体密度，不仅可以减轻无人机平台重量、提高精确度，而且可以增加续航能力。机壳和螺旋桨等面对碰撞和跌落对韧性和模量具有较高要求。另外，无人机具有实时性强、灵活方便、外界环境影响小、成本低的优点，其在灾害应急救援方面具有广阔的发展空间和应用前景，如使用无人机系统对森林火情监测等，这使得对基体材料提出了更高的阻燃要求。
为了满足在无人机等领域的使用要求，目前主要是通过加入中空玻璃微珠，可以有效的降低密度，但是会导致材料的韧性大幅度衰减；而针对目前的阻燃聚酰胺，由于阻燃剂的密度较大，会使得体系密度的降低较为困难，且会降低材料韧性，通常阻燃聚酰胺材料的冲击强度不高于5kJ/m2，密度不低于1.1g/cm3；若阻燃剂用量较少的话又难以满足较高的阻燃要求，聚酰胺材料的阻燃性能和低密度高韧性能较难平衡。因此，本领域需要开发一种阻燃低密度聚酰胺组合物，且同时具有较好的韧性。
发明内容
本发明的目的就是为了克服上述现有技术中聚酰胺组合物较难平衡阻燃效果和低密度性能，且加入中空微珠会使得韧性下降的问题或缺陷，而提供一种聚酰胺组合物。
本发明的另一目的在于，提供所述聚酰胺组合物的制备方法。
本发明的另一目的在于，提供所述聚酰胺组合物的应用。
为实现上述目的，本发明采用如下技术方案实现：
一种聚酰胺组合物，包括如下按照重量份计算的组分：

其中，聚酰胺树脂为脂肪族聚酰胺树脂和芳香族聚酰胺树脂的混合物，芳香族聚酰胺树脂的含量为聚酰胺树脂的25wt～75wt％；中空玻璃微珠母粒包括中空玻璃微珠、第一增韧剂和第一偶联剂，第一偶联剂含量不低于中空玻璃微珠母粒的0.3wt％，第一增韧剂的含量不低于中空玻璃微珠母粒的3wt％。
需要说明的是，所述第一增韧剂和第二增韧剂可以相同，也可以不同；所述第一偶联剂和第二偶联剂可以相同，也可以不同。
本发明中提供一种聚酰胺组合物，所述聚酰胺组合物以聚酰胺树脂为基体树脂，通过加入中空玻璃微珠母粒、红磷阻燃剂和增强纤维，使制得的聚酰胺组合物具有低密度、高韧性、阻燃和高模量性能。
具体地：中空玻璃微珠母粒中含有第一增韧剂和第一偶联剂，可以有效改善中空玻璃微珠直接加入树脂体系中的界面作用，能够减少韧性的衰减，可以有效减弱挤出过程中的破孔现象；选用芳香族聚酰胺树脂与红磷阻燃剂协同，可以使得在较少阻燃剂添加量的情况下满足较高的阻燃性能，从而避免密度升高的问题；增强纤维的加入可以有效弥补增韧剂和阻燃剂带来的模量损失。偶联剂分批次加入，有助于更好的分散在界面，也有助于防止在制备母粒的过程中发生结块现象。增韧剂的分批次加入可以减小在母粒制备过程中体系黏度多大，造成中空玻璃微珠破孔。
需要说明的是，本发明中所述聚酰胺组合物中，聚酰胺树脂占树脂基体的含量不低于50wt％。例如但不限于52.5wt％、55wt％、57.5wt％、60wt％、62.5wt％、65wt％、67.5wt％、70wt％等。
具体地，所述中空玻璃微珠母粒包括如下按照重量份计算的组分：
中空玻璃微珠                   68～99份；
第一增韧剂                     5～40份；
第一偶联剂                     0.5～2份。
进一步地，所述中空玻璃微珠母粒还包括0～1份抗氧剂。
中空玻璃微珠母粒的制备方法可采用现有技术中常规的母粒制备方法。
在具体实施方式中，所述中空玻璃微珠母粒的制备方法，包括如下步骤：
采用溶剂将第一偶联剂稀释，再与其他组分混合，经密炼得到中空玻璃微珠母粒。
在具体实施方式中，所述溶剂为无水乙醇。
具体地，所述第一偶联剂和溶剂的质量体积比为1：10～1：20。
具体地，所述密炼在90～130℃下搅拌5～10min。
进一步地，所述聚酰胺组合物，包括如下按照重量份计算的组分：
本发明中，所述聚酰胺树脂中芳香族聚酰胺树脂的含量为25wt～75wt％，例如但不限于25wt％、30wt％、35wt％、40wt％、45wt％、50wt％、55wt％、60wt％、65wt％、70wt％或75wt％等均能实现本发明。进一步地，所述聚酰胺树脂中芳香族聚酰胺树脂的含量为45～60wt％。
进一步地，所述芳香族聚酰胺树脂可以为PA MXD6、PA MXD8、PA MXD10或PA MXD12中的任意一种或几种。
具体地，所述脂肪族聚酰胺树脂的密度为1.00～1.03g/cm3；所述芳香族聚酰胺树脂的密度为1.05～1.08g/cm3。
具体地，所述脂肪族聚酰胺树脂为长碳链聚酰胺树脂。所述长碳链聚酰胺树脂是指重复单元中酰胺基团间，亚甲基数目≥10的聚酰胺树脂。例如但不限于：由ω-氨基酸或内酰胺开环制备的AB型PA11、PA12，通过二元酸和二元胺缩聚而成的PA612、PA610、PA1010、PA1012、PA1212等。
进一步地，所述中空玻璃微珠的抗压强度为10000～30000Psi。
进一步地，所述中空玻璃微珠的抗压强度的测试方法为水等静压检测法。
具体地，所述中空玻璃微珠的密度为0.4～0.5g/cm3。
进一步地，所述红磷阻燃剂为红磷和/或红磷母粒。
在具体实施方式中，所述红磷阻燃剂中红磷含量为45～85wt％。
进一步地，所述阻燃协效剂包括硼酸锌、氢氧化镁、氢氧化铝或蒙脱土中的一种或几种。
进一步地，所述第一偶联剂为含羧基的聚合物；第二偶联剂为含羧基的聚合物。
在具体实施方式中，所述含羧基的聚合物为烯烃丙烯酸共聚物及其离子型聚合物。
具体地，所述烯烃丙烯酸共聚物及其离子型聚合物为乙烯-甲基丙烯酸-丙烯酸酯三元共聚物树脂、乙烯-甲基丙烯酸-丙烯酸酯三元共聚物树脂的离子型聚合物或乙烯-甲基丙烯酸中的一种或几种。
进一步地，所述第一增韧剂为含有极性基团的聚烯烃；第二增韧剂为含有极性基团的聚烯烃。
进一步地，所述极性基团为马来酸酐、环氧基团或酯基中的一种或者几种。
在具体实施方式中，所述含有极性基团的聚烯烃为MAH-g-SEBS、MAH-g-POE、乙烯-丙烯酸甲酯共聚物或GMA-g-POE中的一种或几种。
进一步地，所述增强纤维包括玻璃纤维和/或碳纤维。
更进一步地，所述增强纤维为碳纤维。
进一步地，所述加工助剂为抗氧剂和/或润滑剂。
本发明中，可以根据现有技术选用常用的抗氧剂，例如但不限于受阻酚类抗氧剂、亚磷酸酯类抗氧剂、二苯胺类抗氧剂或硫醚类抗氧剂中的一种或几种。
具体地，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[β-3,5-二叔丁基-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-叔丁基-4-羟基-5-甲基苯基)丙酸酯](ADK AO-80)中的一种或几种。
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(PEP-36)或627A中的一种或几种。
所述二苯胺类抗氧剂为4，4’-双(α，α’-二甲基苄基)二苯胺。
所述硫醚类抗氧剂为硫代二丙酸二硬脂醇酯、硫代二丙酸二月桂酯或季戊四醇类十二硫代丙酯中的一种或几种。
本发明中，可以根据现有技术选用常用的润滑剂。例如但不限于硬脂酸类润滑剂、聚乙烯类润滑剂、酰胺类润滑剂、石蜡类润滑剂、酯类润滑剂或硅酮类润滑剂中的一种或几种。
具体地，所述硬脂酸类润滑剂可以为硬脂酸钙和/或硬脂酸锌。
所述聚乙烯类润滑剂可以为聚乙烯蜡。
所述酰胺类润滑剂可以为油酸酰胺类润滑剂、EBS酰胺类润滑剂或芥酸酰胺类润滑剂中的一种或几种。
所述酯类润滑剂可以为脂肪族硬脂酸酯、油酸基脂肪族聚酯或介酸基脂肪族聚酯中的一种或几种。
所述硅酮类润滑剂可以为聚二甲基硅氧烷。
本发明还保护上述聚酰胺组合物的制备方法，包括以下步骤：
S1.将聚酰胺树脂、中空玻璃微珠母粒、增强纤维、第二增韧剂、红磷阻燃剂、阻燃协效剂、第二偶联剂和加工助剂混合均匀得到预混物；
S2.将步骤S1中的预混物经熔融共混、挤出造粒得到聚酰胺组合物。
在具体实施方式中，步骤S2中所述挤出造粒在双螺杆挤出机中进行。
具体地，所述双螺杆挤出机的螺杆长径比为40～48：1，所述双螺杆挤出机的螺筒温度为220～250℃，所述双螺杆挤出机的螺杆转速为150～400rpm。
本发明还保护上述聚酰胺组合物在制备无人机机壳、螺旋桨材料中的应用。
与现有技术相比，本发明的有益效果是：
本发明提供了一种聚酰胺组合物，选用含有芳香族聚酰胺树脂的基体树脂，加入中空玻璃微珠母粒，能够有效改善中空玻璃微珠和树脂体系的界面作用，芳香族聚酰胺树脂和红磷阻燃剂相协同，能够在较少阻燃剂添加量的情况下实现较高的阻燃性能，避免密度上升，制得的聚酰胺组合物的密度不高于1.1g/m3，阻燃等级均满足1.0mm的V-0级，缺口冲击强度不低于7kJ/m2。
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。
本发明各实施例和对比例中使用的原料：
聚酰胺树脂：
聚酰胺树脂1：PA610 F150，购自山东广垠新材料有限公司；
聚酰胺树脂2：PA MXD10，购自盈固有限公司；
中空玻璃微珠：IM16K，密度为0.46g/cm3，抗压强度16000Psi，购自美国3M公司；
增强纤维：
增强纤维1：玻璃纤维，S1HM435TM-10-3，长度3mm，泰山玻璃纤维有限公司；
增强纤维2：碳纤维，Type-65，长度6mm，ZOLTEK；
红磷阻燃剂：
红磷阻燃剂1：微胶囊包覆红磷母粒，FR9950T，红磷含量为50wt％，购自桐城信得有限公司；
红磷阻燃剂2：微胶囊包覆红磷，FRP-950X，红磷含量为80wt％，广州市银塑阻燃材料有限公司；
溴系阻燃剂：溴化聚苯乙烯，BPS 7010，广州市诚而诺化工有限公司；
阻燃协效剂：硼酸锌，市售；
第一增韧剂：MAH-g-SEBS，FG1901 G，购自科腾；
第二增韧剂：MAH-g-SEBS，FG1901 G，购自科腾；
第一偶联剂：乙烯-甲基丙烯酸-丙烯酸酯三元共聚物树脂，AN4228C，购自美国杜邦化工；
第二偶联剂：乙烯-甲基丙烯酸-丙烯酸酯三元共聚物树脂，AN4228C，购自美国杜邦化工；
抗氧剂：Inganox@1098；润滑剂：LOXIOL G32；抗氧剂和润滑剂均为市售，实施例和对比例的平行实验均采用相同的抗氧剂和润滑剂。
按照表1中的配方，按照如下制备方法制备中空玻璃微珠母粒：
先采用无水乙醇将第一偶联剂稀释10倍，再将其和中空玻璃微珠、第二增韧剂、抗氧剂按比例加入到密炼机中，高速搅拌混合均匀，在130℃密炼得中空玻璃微珠母粒。
表1中空玻璃微珠母粒中各组分用量(单位：重量份)
实施例1～10和对比例1～5
按照表2～3中的配方，按照如下制备方法制备聚酰胺组合物：
S1.将聚酰胺树脂、中空玻璃微珠母粒、增强纤维、第二增韧剂、红磷阻燃剂、阻燃协效剂、第二偶联剂和加工助剂混合均匀得到预混物；
S2.将步骤S1中的预混物经熔融共混、挤出造粒得到聚酰胺组合物；所述双螺杆挤出机的螺杆长径比为40～48：1；所述双螺杆挤出机的螺筒温度为220～250℃，所述双螺杆挤出机的螺杆转速为150～400rpm。
表2实施例1～7中的聚酰胺组合物中各组分用量(单位：重量份)
表3实施例8～10和对比例1～5中的聚酰胺组合物中各组分用量(单位：重量份)
性能测试
1.测试方法
将上述实施例和对比例制备的轻量化聚酰胺组合物进行性能测试：
(1)密度测试：将上述实施例和对比例制备的聚酰胺组合物按照ISO 1183-1-2019标准进行测试，浸渍法；
(2)悬臂梁缺口冲击强度：将上述实施例和对比例制备的聚酰胺组合物按照ISO 180-2019标准测定缺口冲击强度；缺口类型：A型；
(3)阻燃性能：将上述实施例和对比例制备的聚酰胺组合物按照UL 94 2013的相关标准对样条进行阻燃性能测试，样品厚度为1.0mm；
(4)弯曲模量：将上述实施例和对比例制备的聚酰胺组合物按照ISO 178-2010标准进行测定，弯曲速度为2mm/min。
2.测试结果
各实施例和对比例制得的聚酰胺组合物的性能测试结果如表4所示。
表4实施例1～10和对比例1～5性能测试结果
从表4中可以看出，本发明各实施例制备得到的聚酰胺组合物具有较低密度和较好的阻燃性能，同时具有较好的韧性和刚性，具体地：密度不高于1.1g/m3，阻燃等级均满足1.0mm的V-0级，缺口冲击强度不低于7kJ/m2。
从对比例1中可以看出，若聚酰胺树脂中芳香族聚酰胺树脂含量过低，制得的聚酰胺组合物的阻燃性能较差。
从对比例2中可以看出，若采用其他阻燃剂，其他类型的阻燃剂密度高于红磷阻燃剂，且阻燃效率不如红磷阻燃剂，制得的聚酰胺组合物的密度和阻燃均无法达到要求。
从对比例3中可以看出，若不采用中空玻璃微珠母粒，即使在聚酰胺组合物中增加偶联剂和增韧剂的用量，也很难有效改善中空玻璃微珠与聚酰胺树脂之间的界面，使得最终的韧性较差，且制得的聚酰胺组合物的密度较高。
从对比例4中可以看出，若聚酰胺树脂中芳香族聚酰胺树脂含量过高，制得的聚酰胺组合物的密度偏高，且韧性较差。
从对比例5可以看出，若聚酰胺组合物中不添加第二增韧剂和第二偶联剂，而是将其加入到中空玻璃微珠母粒中会造成母粒制备过程中结块，体系黏度大，破孔率高等问题，制得的聚酰胺组合物的性能下降。
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. 一种聚酰胺组合物，其特征在于，包括如下按照重量份计算的组分：
    其中，聚酰胺树脂为芳香族聚酰胺树脂和脂肪族聚酰胺树脂的混合物，芳香族聚酰胺树脂的含量为聚酰胺树脂的25wt％～75wt％；中空玻璃微珠母粒包括中空玻璃微珠、第一增韧剂和第一偶联剂，第一偶联剂含量不低于中空玻璃微珠母粒的0.3wt％，第一增韧剂的含量不低于中空玻璃微珠母粒的3wt％。
  2. 根据权利要求1所述聚酰胺组合物，其特征在于，所述中空玻璃微珠母粒包括如下按照重量份计算的组分：
    中空玻璃微珠                   68～99份；
    第一增韧剂                     5～40份；
    第一偶联剂                     0.5～2份。
  3. 根据权利要求2所述聚酰胺组合物，其特征在于，所述中空玻璃微珠母粒的制备方法包括如下步骤：
    采用溶剂将第一偶联剂稀释，再与其他组分混合，经密炼得到中空玻璃微珠母粒。
  4. 根据权利要求1所述聚酰胺组合物，其特征在于，所述聚酰胺树脂中芳香族聚酰胺树脂的含量为45～60wt％。
  5. 根据权利要求1所述聚酰胺组合物，其特征在于，所述芳香族聚酰胺树脂为PA MXD6、PA MXD8、PA MXD10或PA MXD12中的任意一种或几种；所述脂肪族聚酰胺树脂为PA612、PA610、PA1010、PA1012或PA1212中的任意一种或几种。
  6. 根据权利要求1所述聚酰胺组合物，其特征在于，所述第一偶联剂为含羧基的聚合物；所述第二偶联剂为含羧基的聚合物；优选的，所述含羧基的聚合物为烯烃丙烯酸共聚物及其离子型聚合物；更优选的，所述烯烃丙烯酸共聚物及其离子型聚合物为乙烯-甲基丙烯酸-丙烯酸酯三元共聚物树脂、乙烯-甲基丙烯酸-丙烯酸酯三元共聚物树脂的离子型聚合物或乙烯-甲基丙烯酸中的一种或几种。
  7. 根据权利要求1所述聚酰胺组合物，其特征在于，所述第一增韧剂为含有极性基团的聚烯烃；所述第二增韧剂为含有极性基团的聚烯烃；优选的，所述含有极性基团的聚烯烃为MAH-g-SEBS、MAH-g-POE、乙烯-丙烯酸甲酯共聚物或GMA-g-POE中的一种或几种。
  8. 根据权利要求1所述聚酰胺组合物，其特征在于，所述增强纤维包括玻璃纤维和/或碳纤维；优选的，所述增强纤维为碳纤维。
  9. 一种权利要求1～8任一项所述聚酰胺组合物的制备方法，其特征在于，包括如下步骤：
    S1.将聚酰胺树脂、中空玻璃微珠母粒、增强纤维、第二增韧剂、红磷阻燃剂、阻燃协效剂、第二偶联剂和加工助剂混合均匀得到预混物；
    S2.将步骤S1中的预混物经熔融共混、挤出造粒得到聚酰胺组合物。
  10. 一种权利要求1～8任一项所述聚酰胺组合物在制备无人机机壳、螺旋桨材料中的应用。
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