WO2024008199A1 - 一种高韧高磁吸abs合金及其制备方法和应用 - Google Patents

一种高韧高磁吸abs合金及其制备方法和应用 Download PDF

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WO2024008199A1
WO2024008199A1 PCT/CN2023/108307 CN2023108307W WO2024008199A1 WO 2024008199 A1 WO2024008199 A1 WO 2024008199A1 CN 2023108307 W CN2023108307 W CN 2023108307W WO 2024008199 A1 WO2024008199 A1 WO 2024008199A1
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toughness
magnetic
abs alloy
resin
abs
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PCT/CN2023/108307
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English (en)
French (fr)
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何超雄
陈平绪
叶南飚
陈日平
李玉虎
黄宝奎
吴俊�
付锦锋
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金发科技股份有限公司
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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
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0856—Iron
    • 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
    • C08K2201/005—Additives being defined by their particle size in general
    • 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
    • C08K2201/01—Magnetic additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

  • the invention relates to the technical field of engineering plastics, and more specifically, to a high-tenacity and high-magnetic ABS alloy and its preparation method and application.
  • Magnetic materials are generally prepared by adding magnetic materials or high-content metallic iron.
  • the processing equipment commonly used in the processing of ABS products has many iron-containing parts, it is difficult to use magnetic materials to prepare high-magnetic ABS products. If a large amount of metal powder is added to obtain magnetic properties, the toughness of the ABS material will seriously deteriorate.
  • the present invention provides a high-toughness and high-magnetic attraction ABS alloy, which is induced-coated with high-content metal iron powder by oxidized low-density polyethylene wax and filled into In the ABS system, polyester resin is introduced to further improve the toughness of the material, and an ABS alloy with both high toughness and high magnetic properties can be obtained.
  • Another object of the present invention is to provide a method for preparing the above-mentioned high-toughness and high-magnetic ABS alloy.
  • Another object of the present invention is to provide the application of the above-mentioned high toughness and high magnetic attraction ABS alloy.
  • the technical solution adopted by the present invention is:
  • ABS resin 20 to 30 parts ABS resin 20 to 30 parts; Polyester resin 20 to 30 parts; Metal iron powder 40 to 60 parts; Surface modifier 2 to 8 parts;
  • the surface modifier is oxidized low-density polyethylene wax, and the acid value of the oxidized low-density polyethylene wax is ⁇ 15 mg KOH/g.
  • the inventor's research found that by using oxidized low-density polyethylene wax to induce coating and filling high-content metal iron powder into the ABS system, and introducing polyester resin to further improve the toughness, an ABS alloy with both high toughness and high magnetic properties can be obtained.
  • the high-toughness and high-magnetic ABS alloy of the present application contains a large amount of metallic iron powder, which brings excellent magnetic properties to the ABS material.
  • Oxidized low-density polyethylene wax contains carboxylic acid and ester functional groups. Oxidized low-density polyethylene wax with high acid value is highly polar and can be coated on the surface of metal iron powder during the extrusion process, making the metal iron powder in the ABS system. It has good dispersion and will not cause significant deterioration in the toughness of ABS.
  • polyester resin and ABS resin are compounded and blended, and the phase structure formed is more conducive to improving the toughness of the material under a high filling system.
  • the processing temperatures of ABS and polyester are similar, and the alloy material will not affect the degradation of ABS components due to higher processing temperatures.
  • the acid value of the oxidized low-density polyethylene wax is 17-60 mg KOH/g.
  • the acid value of oxidized low-density polyethylene wax is tested according to the ASTM D1386-2015 standard method.
  • the viscosity of the oxidized low-density polyethylene wax is 150 to 300 cps.
  • the viscosity of the oxidized low-density polyethylene wax is 150 to 200 cps.
  • the viscosity of oxidized low-density polyethylene wax is tested according to the ASTM D1986-2014 standard method.
  • the oxidized low-density polyethylene wax has suitable fluidity and has a better coating effect on metal iron powder.
  • the average particle size of the metallic iron powder is ⁇ 74 ⁇ m.
  • the average particle size of the metallic iron powder is 38 to 50 ⁇ m.
  • the mass ratio of the metallic iron powder to the surface modifier is 1: (0.1-0.12).
  • the surface modifier can effectively coat the metal iron powder and promote dispersion, but will not cause local phase agglomeration due to excessive surface modifier content, causing the material to stratify and lead to toughness. decline.
  • the polyester resin is polyethylene terephthalate-1,4-cyclohexanedimethanol (PCTG resin), polyethylene terephthalate-1,4-cyclohexane One or more of dimethyl glycol ester (PETG resin), polybutylene terephthalate (PBT resin), and polyethylene terephthalate (PET resin).
  • PCTG resin polyethylene terephthalate-1,4-cyclohexanedimethanol
  • PET resin polyethylene terephthalate-1,4-cyclohexanedimethanol
  • the polyester resin is a mixture of PCTG resin and PBT resin.
  • the mass ratio of PCTG resin and PBT resin in the polyester resin is 1: (0.2 ⁇ 5).
  • the high-toughness and high-magnetic ABS alloy also includes 0.1 to 2 parts of antioxidants and 0.1 to 2 parts of lubricants.
  • the antioxidant is a hindered phenolic antioxidant and/or a phosphite lipid antioxidant.
  • the lubricant is one or more of pentaerythritol stearate, erucic acid amide, oleic acid amide or ethylene bis stearic acid amide.
  • the present invention also protects the preparation method of the above-mentioned high-toughness and high-magnetic ABS alloy, which includes the following steps:
  • ABS resin After mixing the ABS resin, polyester resin, metal iron powder, surface modifier, lubricant (if any) and antioxidant (if any), add them to the extruder, melt and blend, and extrud and granulate.
  • lubricant if any
  • antioxidant if any
  • the extruder is a twin-screw extruder
  • the temperature in the first to second zones of the screw barrel is 120-190°C
  • the temperature in the third to tenth zones is 200-240°C
  • the screw speed is 350-450 rpm.
  • the invention also protects the application of the above-mentioned high-tenacity and high-magnetic ABS alloy in the preparation of household appliances and toys.
  • the invention develops a high-tenacity and high-magnetic ABS alloy.
  • oxidized low-density polyethylene wax to induce coating and filling high-content metal iron powder into the ABS system, and introducing polyester resin, an ABS alloy with both high toughness and high magnetic properties can be obtained.
  • the high-toughness and high-magnetic ABS alloy of the present application has a notched impact strength of the cantilever beam ⁇ 14kJ/m 2 and can absorb weights weighing more than 255g.
  • ABS resin purchased from Chimei Industrial, ABS PA-757;
  • PCTG resin purchased from Eastman, DN011;
  • PETG resin purchased from Eastman, GN071;
  • PBT resin purchased from Changchun, Jiangsu, 1200-211M;
  • Metal iron powder-1 purchased from Jinhe, JHF-200, with an average particle size of 74 ⁇ m;
  • Metal iron powder-2 purchased from Jinhe, JHF-300, with an average particle size of 48 ⁇ m;
  • Metal iron powder-3 purchased from Jinhe, JHF-400, with an average particle size of 38 ⁇ m;
  • Oxidized low-density polyethylene wax-1 purchased from Mitsui, 4202E, acid value 17mg KOH/g, viscosity 300cps;
  • Oxidized low-density polyethylene wax-2 purchased from Mitsui, 1105A, acid value 60mg KOH/g, viscosity 150cps;
  • Oxidized low-density polyethylene wax-3 purchased from Ruile, RL-216A, acid value 15mg KOH/g, viscosity 200cps;
  • Oxidized low-density polyethylene wax-4 purchased from Honeywell, AC629, acid value 17mg KOH/g, viscosity 200cps;
  • Oxidized low-density polyethylene wax-5 purchased from Ruile, RL-9308, acid value 10mg KOH/g, viscosity 160cps;
  • Antioxidants commercially available, hindered phenolic antioxidants
  • Lubricant commercially available, pentaerythritol stearate
  • Low-density polyethylene wax purchased from Ruile RL-617A, has not been oxidized and modified, and has a viscosity of 200cps;
  • Oxidized high-density polyethylene wax purchased from Reile RL-916A, 17mg KOH/g;
  • PVC resin purchased from LG Chem LS100E;
  • PA resin was purchased from Haiyang Chemical Fiber HY-2500A.
  • the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in this technical field.
  • Embodiments 1 to 18 respectively provide an ABS alloy, the component content is shown in Table 1, and the preparation method is as follows:
  • Comparative Examples 1 to 10 respectively provide an ABS alloy, the component content is shown in Table 2, and the preparation method is as follows:
  • Izod notch impact strength in accordance with ISO 180-2019 standard
  • Magnetic adsorption performance Inject the ABS alloy into a 3mm thick square plate, use a NdFeB strong magnetic hanging ring with a pull-off force of 18kg, add weights of different weights to adsorb the square plate, and test the maximum weight that can be absorbed. The greater the weight, the greater the magnetism. The better the suction performance.
  • the ABS alloys prepared in each embodiment of the present application have excellent magnetic properties, with an adsorption weight weight of ⁇ 255g, while maintaining good toughness, and a cantilever notched impact strength of ⁇ 14kJ/m 2 .
  • polyester resins can effectively synergize with ABS resin to improve material toughness, among which the effect is better when PCTG resin is compounded with PBT resin.
  • Example 2 and Examples 14 and 15 when the average particle size of the metallic iron powder is smaller, the impact on the toughness deterioration of the ABS alloy material is smaller under high filling amounts, and the magnetic properties of the ABS alloy are better.
  • Example 2 and Examples 16 to 18 the higher the acid value of the oxidized low-density polyethylene wax, the better the induction coating effect on metal iron powder, which contributes to better toughness and better magnetic properties of the ABS alloy. ;
  • the acid value of the oxidized low-density polyethylene wax is close to each other (Examples 2 and 18) and the viscosity is lower, the ABS alloy produced has better toughness and better magnetic properties.
  • the acid value of the oxidized low-density polyethylene wax is preferably 17 to 60 mg KOH/g and the viscosity is 150 to 200 cps.
  • Comparative Example 1 no surface modifier is included. It can be seen that when metallic iron powder is added to the ABS alloy at a high filling amount, the toughness of the material will be seriously deteriorated, and the notched impact strength of the cantilever beam is only 6kJ/m 2 , due to uneven dispersion of metal iron powder, it also affects the magnetic properties of the material.
  • Comparative Example 2 the content of metal iron powder is too small, the magnetic adsorption performance of the ABS alloy is insufficient, and the weight of the adsorbed weight is too low; in Comparative Example 3, the content of metal iron powder is too much, and even if the material contains a surface modifier, it is difficult to As a result, excessive metal iron powder is effectively dispersed and the material toughness is poor. In Comparative Example 4, the content of surface modifier Too much will deteriorate the toughness of ABS alloy.
  • Comparative Example 5 does not contain polyester resin and cannot form a phase structure with ABS resin that contributes to toughness improvement.
  • the polyester resin was replaced with other resins (PVC resin, PA resin) respectively, and it was difficult to achieve the effect of improving the toughness of the ABS material equivalent to that of the polyester resin.
  • the oxidized low-density polyethylene wax was replaced with a conventional polyethylene wax that has not been oxidized and modified.
  • the acid value is generally 0 and cannot effectively induce coating of a large amount of metal iron powder to improve the material toughness.
  • the oxidized low-density polyethylene wax was replaced by the oxidized high-density polyethylene wax. Even though the acid value was suitable, the coating effect of the oxidized high-density polyethylene wax on the metal iron powder was poor. In the highly filled ABS of the present invention, The dispersion of metallic iron powder cannot be effectively improved within the alloy system.
  • the acid value of the oxidized low-density polyethylene wax is low, the induction coating effect on metal iron powder is limited, and the toughness and magnetic properties of the alloy material are poor.

Abstract

本发明公开了一种高韧高磁吸ABS合金及其制备方法和应用。本发明的高韧高磁吸ABS合金，包括如下重量份的组分：ABS树脂20～30份；聚酯树脂20～30份；金属铁粉40～60份；表面改性剂2～8份；所述表面改性剂为氧化低密度聚乙烯蜡，酸值≥15mg KOH/g。采用氧化低密度聚乙烯蜡诱导包覆高含量金属铁粉填充至ABS体系中，并引入聚酯树脂，可以获得兼具高韧性和高磁吸性能的ABS合金。本申请的高韧高磁吸ABS合金的悬臂梁缺口冲击强度≥14kJ/m2，在18kg拉脱力的钕铁硼强磁吊环条件下能够吸附255g以上重量的砝码。

Description

一种高韧高磁吸ABS合金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，更具体的，涉及一种高韧高磁吸ABS合金及其制备方法和应用。
背景技术
近年来，仿金属塑料已被广泛应用在塑料制件的外观装饰上，一般在塑料树脂中加入少量的金属粉(如铝粉、铁粉)来改变塑料外观，使得制件成型金属效果。但是金属粉的添加会导致塑料的韧性大幅下降。对于丙烯腈-丁二烯-苯乙烯共聚物(ABS树脂)，一般使用丁二烯橡胶增韧改性，但仍无法有效弥补金属粉所造成的韧性下降，因此，ABS树脂中金属粉的添加量受限。
目前在创新家电、玩具产品领域中，市场对高磁吸特性的改性ABS制品有较大需求。磁吸材料一般是通过添加磁性材料或高含量金属铁来制备，但是由于ABS制品加工过程常用的加工设备都有不少含铁制件，制备高磁吸ABS制品难以使用磁性材料，而若是通过添加大量金属粉以获得磁吸性能的话，ABS材料的韧性劣化严重。
因此，难以制得具有磁吸性能，且兼具优异韧性的高韧高磁吸ABS材料。
发明内容
本发明为克服上述现有技术所述的韧性和磁吸性难以兼具的缺陷，提供一种高韧高磁吸ABS合金，采用氧化低密度聚乙烯蜡诱导包覆高含量金属铁粉填充至ABS体系中，并引入聚酯树脂进一步改善材料韧性，可以获得兼具高韧性和高磁吸性能的ABS合金。
本发明的另一目的在于提供上述高韧高磁吸ABS合金的制备方法。
本发明的另一目的在于提供上述高韧高磁吸ABS合金的应用。
为解决上述技术问题，本发明采用的技术方案是：
一种高韧高磁吸ABS合金，包括如下重量份的组分：
ABS树脂 20～30份；
聚酯树脂 20～30份；
金属铁粉 40～60份；
表面改性剂 2～8份；
所述表面改性剂为氧化低密度聚乙烯蜡，氧化低密度聚乙烯蜡的酸值≥15mg KOH/g。
发明人研究发现，采用氧化低密度聚乙烯蜡诱导包覆高含量金属铁粉填充至ABS体系中，并引入聚酯树脂进一步改善韧性，可以获得兼具高韧性和高磁吸性能的ABS合金。
本申请的高韧高磁吸ABS合金中含有较大量金属铁粉，为ABS材料带来了优异的磁吸性能。氧化低密度聚乙烯蜡含有羧酸和酯基官能团，酸值高的氧化低密度聚乙烯蜡极性较高，可以在挤出过程中包覆于金属铁粉表面，使得金属铁粉在ABS体系中分散性良好，从而不会造成ABS的韧性明显劣化。
在本发明的ABS合金体系中，聚酯树脂与ABS树脂复合共混，形成的相态结构更有助于在高填充体系下改善材料的韧性。同时，在高填充体系下ABS和聚酯加工温度相当，合金材料不会因较高加工温度影响ABS成分降解。
优选地，所述氧化低密度聚乙烯蜡的酸值为17～60mg KOH/g。
氧化低密度聚乙烯蜡的酸值按照ASTM D1386-2015标准方法进行检测。
优选地，所述氧化低密度聚乙烯蜡的粘度为150～300cps。
更优选地，所述氧化低密度聚乙烯蜡的粘度为150～200cps。
氧化低密度聚乙烯蜡的粘度按照ASTM D1986-2014标准方法进行检测。
在上述粘度范围内，氧化低密度聚乙烯蜡的流动性适宜，对于金属铁粉的包覆效果更优。
优选地，所述金属铁粉的平均粒径≤74μm。
更优选地，所述金属铁粉的平均粒径为38～50μm。
优选地，所述金属铁粉与表面改性剂的质量比为1∶(0.1～0.12)。
在上述质量比范围内，表面改性剂既能有效包覆金属铁粉、促进分散，又不会因表面改性剂含量过多而造成局部相态团聚，使材料出现分层现象，导致韧性下降。
优选地，所述聚酯树脂为聚对苯二甲酸乙二醇-1,4-环己烷二甲醇酯(PCTG树脂)、聚对苯二甲酸乙二醇酯-1,4-环己烷二甲醇酯(PETG树脂)、聚对苯二甲酸丁二醇酯(PBT树脂)、聚对苯二甲酸乙二醇酯(PET树脂)的一种或者几种。
更优选地，所述聚酯树脂为PCTG树脂与PBT树脂的混合物。
进一步优选地，所述聚酯树脂中PCTG树脂与PBT树脂的质量比为1：(0.2～5)。
优选地，所述高韧高磁吸ABS合金还包括抗氧剂0.1～2份，润滑剂0.1～2份。
可选地，所述抗氧剂为受阻酚类抗氧剂和/或亚磷酸脂类抗氧剂。
可选地，所述润滑剂为季戊四醇硬脂酸酯、芥酸酰胺、油酸酰胺或乙撑双硬脂酰胺中的一种或几种。
本发明还保护上述高韧高磁吸ABS合金的制备方法，包括如下步骤：
将ABS树脂、聚酯树脂、金属铁粉、表面改性剂、润滑剂(如有)和抗氧剂(如有)混合后，加至挤出机，经熔融共混，挤出造粒，得到所述高韧高磁吸ABS合金。
优选地，所述挤出机为双螺杆挤出机，螺筒一至二区温度为120～190℃，三至十区温度为200～240℃，螺杆转速为350～450rpm。
本发明还保护上述高韧高磁吸ABS合金在制备家用电器、玩具中的应用。
与现有技术相比，本发明的有益效果是：
本发明开发了一种高韧高磁吸ABS合金。采用氧化低密度聚乙烯蜡诱导包覆高含量金属铁粉填充至ABS体系中，并引入聚酯树脂，可以获得兼具高韧性和高磁吸性能的ABS合金。
本申请的高韧高磁吸ABS合金的悬臂梁缺口冲击强度≥14kJ/m2，能够吸附255g以上重量的砝码。
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。
实施例及对比例中的原料均可通过市售得到；
ABS树脂，采购自奇美实业，ABS PA-757；
PCTG树脂，采购自伊士曼，DN011；
PETG树脂，采购自伊士曼，GN071；
PBT树脂，采购自江苏长春，1200-211M；
金属铁粉-1，采购自金河，JHF-200，平均粒径为74μm；
金属铁粉-2，采购自金河，JHF-300，平均粒径为48μm；
金属铁粉-3，采购自金河，JHF-400，平均粒径为38μm；
氧化低密度聚乙烯蜡-1，采购自三井，4202E，酸值17mg KOH/g，粘度为300cps；
氧化低密度聚乙烯蜡-2，采购自三井，1105A，酸值60mg KOH/g，粘度为150cps；
氧化低密度聚乙烯蜡-3，采购自瑞勒，RL-216A，酸值15mg KOH/g，粘度为200cps；
氧化低密度聚乙烯蜡-4，采购自霍尼韦尔，AC629，酸值17mg KOH/g，粘度为200cps；
氧化低密度聚乙烯蜡-5，采购自瑞勒，RL-9308，酸值10mg KOH/g，粘度为160cps；
抗氧剂，市售，受阻酚类抗氧剂；
润滑剂，市售，季戊四醇硬脂酸酯；
低密度聚乙烯蜡，采购自瑞勒RL-617A，未经氧化改性处理，粘度为200cps；
氧化高密度聚乙烯蜡，采购自瑞勒RL-916A，17mg KOH/g；
PVC树脂，采购自LG化学LS100E；
PA树脂，采购自海阳化纤HY-2500A。
除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
实施例1～18
实施例1～18分别提供一种ABS合金，组分含量见表1，制备方法如下：
按照表1将各组分混合后，加至双螺杆挤出机，螺筒一至二区温度为120～190℃，三至十区温度为200～240℃，螺杆转速为350～450rpm，经熔融共混，挤出造粒，得到ABS合金。
表1实施例1～18ABS合金的组分含量(重量份)


对比例1～10
对比例1～10分别提供一种ABS合金，组分含量见表2，制备方法如下：
按照表2将各组分混合后，加至双螺杆挤出机，螺筒一至二区温度为120～190℃，三至十区温度为200～240℃，螺杆转速为350～450rpm，经熔融共混，挤出造粒，得到ABS合金。
表2对比例1～10的ABS合金的组分含量(重量份)

性能测试
对上述实施例及对比例制得的ABS合金进行性能测试，具体方法如下：
悬臂梁缺口冲击强度：按照ISO 180-2019标准；
磁吸性能：将ABS合金注塑为3mm厚度的方板，采用18kg拉脱力的钕铁硼强磁吊环，添加不同重量砝码吸附方板，测试可吸附砝码的最大重量，重量越大说明磁吸性能越好。
实施例和对比例的测试结果见表3和表4。
表3实施例的测试结果

根据表3的测试结果，本申请各实施例制得的ABS合金均具有优异的磁吸性能，吸附砝码重量≥255g，同时保持了良好的韧性，悬臂梁缺口冲击强度≥14kJ/m2。
由实施例1～3，可以看出随着金属铁粉含量的增加，ABS合金的韧性略微下降，磁吸性能越来越好，磁吸砝码重量更高。根据实施例2和实施例4～7的对比，可以看出，在金属铁粉在材料中的重量占比基本一致的情况下，随着表面改性剂的含量增多，金属铁粉的分散均匀度更高，ABS合金的磁吸性能更优，但当表面改性剂为8份时，可能会造成局部相态团聚，导致ABS合金的韧性略微下降。对于金属铁粉和表面改性剂，二者的质量比为1∶(0.1～0.12)时，可以兼具更优的韧性和磁吸性能。
根据实施例10～12与实施例2的测试结果，不同种聚酯树脂均可以与ABS树脂有效协同，改善材料韧性，其中PCTG树脂与PBT树脂复配时的效果更优。
根据实施例2和实施例14、15，金属铁粉的平均粒径更小时，在高填充量下对于ABS合金材料的韧性劣化影响更小，且使得ABS合金的磁吸性能更优。
根据实施例2和实施例16～18，氧化低密度聚乙烯蜡的酸值越高，对于金属铁粉的诱导包覆效果更优，有助于ABS合金的韧性更好、磁吸性能更优；氧化低密度聚乙烯蜡在酸值接近的情况下(实施例2、18)，粘度更低时，制得的ABS合金的韧性更好、磁吸性能更优。综合考虑酸值和粘度的影响，优选氧化低密度聚乙烯蜡的酸值为17～60mg KOH/g，粘度为150～200cps。
表4对比例的测试结果
对比例1中，不含表面改性剂，可以看出，在金属铁粉以高填充量加至ABS合金中时，会导致材料的韧性劣化严重，悬臂梁缺口冲击强度仅为6kJ/m2，由于金属铁粉分散不均，也影响了材料的磁吸性能。
对比例2中，金属铁粉含量过少，ABS合金的磁吸性能不足，吸附的砝码重量过低；对比例3中，金属铁粉的含量过多，即使材料含有表面改性剂也难以使得过量的金属铁粉有效分散，材料韧性较差。对比例4中，表面改性剂的含量 过多，使得ABS合金的韧性劣化。
对比例5中不含聚酯树脂，无法与ABS树脂形成有助于韧性改善的相态结构。对比例6和7中分别将聚酯树脂替换为其他树脂(PVC树脂、PA树脂)，也难以达到与聚酯树脂相当的促ABS材料韧性改善的效果。
对比例8中，氧化低密度聚乙烯蜡替换为常规的、未经氧化改性处理的聚乙烯蜡，酸值一般为0，无法有效诱导包覆大量的金属铁粉改善材料韧性。对比例9中，氧化低密度聚乙烯蜡替换为氧化高密度聚乙烯蜡，即使酸值适宜，但氧化高密度聚乙烯蜡对金属铁粉的包覆效果较差，在本发明的高填充ABS合金体系内不能有效改善金属铁粉的分散。对比例10中，氧化低密度聚乙烯蜡的酸值较低，对金属铁粉的诱导包覆效果有限，合金材料的韧性和磁吸性能较差。
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. 一种高韧高磁吸ABS合金，其特征在于，包括如下重量份的组分：
    所述表面改性剂为氧化低密度聚乙烯蜡，氧化低密度聚乙烯蜡的酸值≥15mg KOH/g。
  2. 根据权利要求1所述高韧高磁吸ABS合金，其特征在于，所述氧化低密度聚乙烯蜡的酸值为17～60mg KOH/g。
  3. 根据权利要求1所述高韧高磁吸ABS合金，其特征在于，所述氧化低密度聚乙烯蜡按照ASTM D1986-2014标准方法进行检测，其粘度为150～300cps。
  4. 根据权利要求1所述高韧高磁吸ABS合金，其特征在于，所述金属铁粉的平均粒径≤74μm。
  5. 根据权利要求1所述高韧高磁吸ABS合金，其特征在于，所述聚酯树脂为PCTG树脂、PETG树脂、PBT树脂、PET树脂的一种或者几种。
  6. 根据权利要求1所述高韧高磁吸ABS合金，其特征在于，所述聚酯树脂为PCTG树脂与PBT树脂的混合物。
  7. 根据权利要求1所述高韧高磁吸ABS合金，其特征在于，还包括抗氧剂0.1～2份，润滑剂0.1～2份。
  8. 权利要求1～7任一项所述高韧高磁吸ABS合金的制备方法，其特征在于，包括如下步骤：
    将ABS树脂、聚酯树脂、金属铁粉和表面改性剂混合后，加至挤出机，经熔融共混，挤出造粒，得到所述高韧高磁吸ABS合金。
  9. 根据权利要求8所述高韧高磁吸ABS合金的制备方法，其特征在于，所述挤出机为双螺杆挤出机，螺筒一至二区温度为120～190℃，三至十区温度为200～240℃，螺杆转速为350～450rpm。
  10. 权利要求1～7任一项所述高韧高磁吸ABS合金在制备家用电器、玩具中的应用。
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