WO2001009241A1 - High fluidible, impact resistant conductive acrylonitrile-butadiene-styrene terpolymer material and preparing method thereof - Google Patents

High fluidible, impact resistant conductive acrylonitrile-butadiene-styrene terpolymer material and preparing method thereof Download PDF

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Publication number
WO2001009241A1
WO2001009241A1 PCT/CN2000/000154 CN0000154W WO0109241A1 WO 2001009241 A1 WO2001009241 A1 WO 2001009241A1 CN 0000154 W CN0000154 W CN 0000154W WO 0109241 A1 WO0109241 A1 WO 0109241A1
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Prior art keywords
impact
abs
flow
butadiene
resistant conductive
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PCT/CN2000/000154
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English (en)
French (fr)
Inventor
Guisheng Yang
Yongdong Chen
Qing Xu
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Shanghai Genius Advanced Material Co. Ltd.
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Priority to AU53865/00A priority Critical patent/AU5386500A/en
Priority to JP2001514039A priority patent/JP2003529626A/ja
Publication of WO2001009241A1 publication Critical patent/WO2001009241A1/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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/04—Particle-shaped
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/919—Thermal treatment of the stream of extruded material, e.g. cooling using a bath, e.g. extruding into an open bath to coagulate or cool the material

Definitions

  • the invention relates to an engineering plastic material and a preparation process thereof, and particularly to a high-flow impact-resistant conductive acrylonitrile-butadiene-styrene terpolymer material and a preparation process thereof.
  • ABS resin Acrylonitrile-butadiene-styrene terpolymer (ABS) resin is widely used in the electronics, communication and other home appliance industries to manufacture casings for telephones, computers, televisions, etc. due to its excellent mechanical properties and surface gloss. component.
  • ABS resin is an insulating material, its volume and surface resistivity are relatively high, so the surface of the product is prone to generate electrostatic charges due to friction and other reasons.
  • the surface of the product can be easily dusted and affect the appearance. The accumulated static charge can cause spark discharge and affect the normal operation of the semiconductor integrated circuit. It can even cause electric shock to the user.
  • external interference electromagnetic waves easily pass through the insulated ABS shell and affect the normal operation of the internal circuit system.
  • ABS resin When the ABS resin is given a certain conductivity, it can eliminate the harm of electrostatic charges accumulated on the surface area of the product to the human body, on the other hand, it can shield electromagnetic waves, and effectively prevent the external electromagnetic waves from interfering with the normal operation of the equipment circuit system.
  • conductive fillers such as metal powder, fiber and graphite, carbon black, and carbon fiber in the ABS resin matrix.
  • metal powders and fibers have disadvantages such as the surface is easy to oxidize, it is not easy to process, the weight is heavy, and the mechanical and mechanical properties of the material are seriously deteriorated, which severely restricts its application.
  • graphite has a large electrical resistance, a poor electrical conductivity, and a relatively expensive carbon fiber. These factors have affected their widespread application in industry.
  • carbon black filled ABS is a more commonly used method.
  • the poor adhesion between carbon black and the ABS matrix will cause the impact resistance and flow properties of the carbon black filled composite to decrease sharply, which seriously affects The processing performance of the material and the end-use effect of the product.
  • the purpose of the present invention is to provide a method for preparing a conductive ABS material with good processing flow performance and impact resistance in order to overcome the defects existing in the prior art.
  • the object of the present invention can be achieved by:
  • ABS conductive acrylonitrile-butadiene-styrene terpolymer
  • the impact modifier is a thermoplastic polyester elastomer.
  • the impact modifier is a thermoplastic polyurethane TPU.
  • the impact modifier is a core-shell structure graft MBS.
  • a process for preparing a high-flow and impact-resistant conductive ABS material which is characterized in that the above components are mixed in a high-mixing machine for 1 to 2 minutes, and then the materials are placed in the hopper of a twin-screw extruder.
  • the segment temperature is 210 ⁇ 240 ° C
  • the screw speed is 300 rpm
  • the extruded material is water cooled, pelletized, and dried to obtain the product.
  • Embodiments 1 to 3 are identical to Embodiments 1 to 3:
  • the ABS resin is a high toughness and high flow material.
  • MI 3 ⁇ 4g / 10min
  • notched impact strength of simply supported beam is 25 ⁇ 35kJ / m 2
  • tensile strength is 40 ⁇ 60MPa.
  • a thermoplastic polyester elastomer was used as a toughening agent, and the elastomer was DuPont HYTREL4533.
  • the tensile strength at break was 30 MPa, and the elongation at break was 600 ° /. , Izod notch shock constantly.
  • the specific surface of the carbon black is 251 ⁇ 27g, the particle size is 30 ⁇ , the DBPA value is 188cm7100g, and the density is 97g / l.
  • the content of each composition component of the blend is shown in Table 1.
  • the components with the above contents are mixed in a high-mixer for 1 to 2 minutes, and then the materials are placed in the hopper of a twin-screw extruder, and the temperature of each section of the screw is 210-240 ° F. Screw speed is 300rpn! .
  • the extruded material is water cooled, pelletized, and dried to obtain the product.
  • the granulated product is injection molded into a standard spline for performance
  • Table 1 Component content of high impact, high flow, conductive ABS material Component content (parts by weight) 1 2 3
  • Carbon black 200 200
  • Antioxidant 2 2 UV light stabilizer 2 2 2
  • thermoplastic polyurethane TPU is a toughening agent
  • carbon black is used as a conductive filler (same as in Example 1).
  • the content of each composition component of the blend is listed in Table III.
  • the components with the above contents are mixed in a high mixer for 1 to 2 minutes, and then the materials are placed in the hopper of a twin screw extruder, and the temperature of each section of the screw is 210 to 240 ° C. The screw speed was 300 rpm. After extrusion The material is water-cooled, pelletized, and dried to obtain the product. The granulated product was injection molded into a standard spline for performance testing.
  • the test results are listed in Table IV.
  • ABS 600 620 650 Thermoplastic polyurethane TPU 200 180 150 Carbon black 200 200 200 Antioxidant 2 2 2 Ultraviolet light stabilizer 2 2 2 Total 1004 1004 1004
  • Example 1 Based on ABS (material properties are the same as in Example 1), core-shell structure graft MBS (product of ROHM HASS Company in the United States) is used as toughener, and carbon black is used as conductive filler (same as in Example 1)
  • the content of each composition component of the blend is listed in Table 5.
  • the components with the above contents are mixed in a high mixer for 1 to 2 minutes, and then the materials are placed in the hopper of a twin screw extruder, and the temperature of each section of the screw is 210 to 240 ° C. The screw speed was 300 rpm.
  • the extruded material is water-cooled, pelletized, and dried to obtain the product. After the granular product
  • Table 6 Component content of high impact, high flow, conductive ABS material Component content (parts by weight) 1 2
  • ABS 600 650 Core-shell structure graft MBS 200 150 Carbon black 200 200 Antioxidant 2 2 Ultraviolet light stabilizer 2 2 Total 1004 1004
  • a toughening agent a thermoplastic polyester elastomer having a soft-hard segment structure, a thermoplastic polyurethane TPU, and a graft having a core-shell structure MBS were used as toughening agents. While maintaining the conductive properties of the material, on the one hand, the impact resistance of carbon black-filled ABS composites is improved, and on the other hand, the processing flow properties of this composite material are greatly improved, which meets the needs of making large parts with complex structures; The surface resistivity of the invention product is reduced to 10 5 ⁇ 10 7 ⁇ , which meets the antistatic requirements of materials. It is especially suitable for manufacturing other components such as televisions, computers, telephones, printer enclosures, and electronic turnover boxes.
  • the present invention is different in that it uses conductive carbon black as a conductive filler, and in the ABS-carbon black system, several types of polymer impact modifiers with good compatibility with ABS resin are correctly selected.
  • Additives such as thermoplastic polyester elastomers, thermoplastic polyurethane TPU, grafts MBS with core-shell structure
  • the impact resistance of carbon black filled ABS composites is improved, on the other hand, the processing flow properties of this composite material are greatly improved, which meets the needs of making large parts with complex structures.

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  • Mechanical Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Conductive Materials (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)

Description

高流动耐冲击导电丙烯腈一丁二烯一苯乙烯三元共聚物材料及其制备工艺 技术领域
本发明涉及一种工程塑料材料及其制备工艺， 尤其涉及一种高流动耐冲击导 电丙烯腈一丁二烯一苯乙烯三元共聚物材料及其制备工艺。
背景技术
丙烯腈一丁二烯一苯乙烯三元共聚物 （ABS ) 树脂由于具有优良的力学综合 性能和表面光泽， 在电子、 通讯等家电行业中广泛用于制造电话、 电脑、 电视机 等的外壳等部件。 然而由于普通 ABS树脂是绝缘材料， 其体积和表面电阻率都较 高， 因此制品的表面容易因摩擦等原因而产生静电荷， 这样一方面会使制品表面 容易吸尘而影响外观， 另一方面积聚的静电荷能产生火花放电从而影响半导体集 成电路的正常工作， 严重的甚至会使操作使用者遭受电击。 此外， 外界的干扰电 磁波容易穿过绝缘的 ABS外壳而影响内部电路***的正常工作，另一方面， 电脑、 电话等***在工作时产生的电磁波等信号也会向外辐射从而干扰周围其它电子 通讯设备电路***的正常工作， 甚至影响人体的生理健康。 当赋予 ABS树脂一定 的导电性能后， 一方面能消除制品表面积聚的静电荷对人体的危害， 另一方面能 起到屏蔽电磁波的作用， 有效防止外界电磁波对设备电路***正常工作的干扰。
目前， 世界各国关于导电 ABS的研制生产主要是往 ABS树脂基体中填充金属 粉末、 纤维和石墨、 炭黑、 碳纤维等导电性填料。 但是， 金属粉末、 纤维具有表 面容易氧化， 不易加工， 重量大， 对材料的机械力学性能劣化严重等缺点， 严重 制约了其应用。 另外， 石墨的电阻较大， 导电性较差， 碳纤维的价格较贵， 这些 因素影响了它们在工业上的广泛应用。目前，炭黑填充 ABS是较常用的一种方法， 但是， 由于炭黑与 ABS基体的粘结性能较差， 会导致炭黑填充后复合材料的抗冲 击性能和流动性能急剧降低， 严重影响了材料的加工性能和制品的最终使用效 果。
发明内容
本发明的目的就是为了克服上述现有技术存在的缺陷而提供一种具有良好 的加工流动性能和抗冲击性能的导电 ABS材料的制备。 本发明的目的可通过以下方式来实现：
一种高流动耐冲击导电丙烯腈一丁二烯一苯乙烯三元共聚物 （ABS ) 材料， 其特征在于： 所述的材料配方如下（重量百分数）：
ABS 60—65
炭黑 15〜25
抗冲改性剂 15〜20
抗氧剂 0. 1〜0. 2
紫外线吸收剂 0. 2〜0. 3 所述的抗冲改性剂为热塑性聚酯弹性体。
所述的抗冲改性剂为热塑性聚氨酯 TPU。
所述的抗冲改性剂为核一壳结构的接枝物 MBS。
一种高流动耐冲击导电 ABS材料的制备工艺， 其特征在于： 将上述各组分置 于高混机中混合 1〜2 分钟， 然后将物料置于双螺杆挤出机的料斗中， 螺杆各段 温度为 210〜240°C， 螺杆转速为 300rpm， 挤出的物料经水冷、 切粒、 干燥后得 到产品。
本发明的最佳实施方式
下面结合实施例， 对本发明作进一步详细说明：
实施例 1〜3：
以 ABS 为基料， 该 ABS 树脂为高韧性高流动材料。 熔融指数（MI=3〜 4g/10min) , 简支梁缺口冲击强度为 25〜35kJ/m2， 拉伸强度为 40〜60MPa。 以热 塑性聚酯弹性体为增韧剂， 该弹性体为杜邦 HYTREL4533 , 其断裂拉伸强度为 30MPa, 断裂伸长率为 600°/。， Izod缺口冲击不断。 融指 8. 5g 0min， 熔点 193°C， 维卡软化点 158 °C。 以炭黑作为导电性填料， 该炭黑比表面为 25½7g， 粒径为 30μιη, DBPA值达 188cm7l00g， 密度 97g/l。 其共混物的各组合物组分含量列于 表一中。 将上述含量的各组分置于高混机中混合 1〜2 分钟， 然后将物料置于双 螺杆挤出机的料斗中， 螺杆各段温度为 210〜240Ό。 螺杆转速为 300rpn！。 挤出 后的物料经水冷， 切粒， 干燥后得到产品。 将该颗粒产品注塑成标准样条供性能 测试， 测试结果列于表二中 表一高抗冲、 高流动、 导电 ABS材料的组分含量 组分含量（重量份） 1 2 3
ABS 600 620 650 杜邦 HYTREL4533 200 180 150
炭黑 200 200 200 抗氧剂 2 2 2 紫外光稳定剂 2 2 2
合计 1004 1004 1004
表二高抗冲、 高流动、 导电 ABS材料的电学、 力学性能 性能 1 2 3 熔指（lOg/min) 1. 8 2. 2 1. 6 拉伸强度（MPa) 32 32. 4 33. 8 简支梁缺口冲击强度（MPa) 12. 3 11. 8 9. 1 弯曲强度（MPa) 34 34. 2 36. 5 弯曲模量 (MPa) 2100 2110 2280 表面电阻率（Ω ) 105〜107 105〜107 105〜107 模塑收縮率 (%) 0. 9〜1. 0 0. 9 0. 9 实施例 4〜6：
以 ABS为基料（材料性能与实施例 1相同）， 热塑性聚氨酯 TPU为增韧剂， 炭 黑作为导电性填料（与实施例 1 相同）， 其共混物的各组合物组分含量列于表三 中。 将上述含量的各组分置于高混机中混合 1〜2 分钟， 然后将物料置于双螺杆 挤出机的料斗中， 螺杆各段温度为 210〜240°C。 螺杆转速为 300rpm。 挤出后的 物料经水冷， 切粒， 干燥后得到产品。将该颗粒产品注塑成标准样条供性能测试， 测试结果列于表四中。
表三高抗冲、 高流动、 导电 ABS材料的组分含量 组分含量（重量份） 1 2 3
ABS 600 620 650 热塑性聚氨酯 TPU 200 180 150 炭黑 200 200 200 抗氧剂 2 2 2 紫外光稳定剂 2 2 2 合计 1004 1004 1004
表四高抗冲、 高流动 、 导电 ABS材料的电学、 力学性能 性 能 1 2 3 熔指（10g/min) 3. 8 3. 2 2. 6 拉伸强度（MPa) 36. 4 39. 8 43. 8 简支梁缺口冲击强度（MPa) 14. 3 13. 8 15. 1 弯曲强度（MPa) 32. 5 33. 2 34. 5 弯曲模量（MPa) 2000 2010 2080 表面电阻率（Ω ) 105〜107 105〜107 105〜107 模塑收縮率（％) 0. 9〜1. 0 0. 9 0. 9 实施例 7〜8：
以 ABS为基料（材料性能与实施例 1相同），核一壳结构的接枝物 MBS (为美国 ROHM HASS公司产品）为增韧剂， 炭黑作为导电性填料（与实施例 1相同）， 其共混 物的各组合物组分含量列于表五中。将上述含量的各组分置于高混机中混合 1〜2 分钟， 然后将物料置于双螺杆挤出机的料斗中， 螺杆各段温度为 210〜240°C。 螺 杆转速为 300rpm。 挤出后的物料经水冷， 切粒， 干燥得到产品。 将该颗粒产品后 塑成标准样条供性能测试 列于表六中。 表五高抗冲、 高流动、 导电 ABS材料的组分含量 组分含量（重量份） 1 2
ABS 600 650 核一壳结构的接枝物 MBS 200 150 炭黑 200 200 抗氧剂 2 2 紫外光稳定剂 2 2 合计 1004 1004
表六高抗冲、 高流动、 导电 ABS材料的电学、 力学性能 性 能 1 2
熔指（10g/min) 1. 8 1. 2 拉伸强度（MPa) 38. 4 40. 1 简支梁缺口冲击强度（MPa) 12. 7 11. 8 弯曲强度（MPa) 34. 5 36. 2 弯曲模量 (MPa) 2100 2210 表面电阻率（Ω ) 105〜107 105〜107
模塑收縮率（％) 0. 8 0. 7 总之， 以具有软一硬段结构的热塑性聚酯弹性体、 热塑性聚氨酯 TPU, 以及 具有核一壳结构的接枝物 MBS作为增韧剂， 在保持材料导电性能的同时， 一方面 改善了炭黑填充 ABS复合材料的抗冲击性能， 另一方面大大提高了此复合材料的 加工流动性能， 满足了制作复杂结构大部件制品的需要； 此外， 本发明产品表面 电阻率降低为 105〜107Ω， 达到材料抗静电要求， 特别适用于制造电视机、 电脑、 电话、 打印机外壳以及电子周转箱等其他部件。
工业应用性
与现有技术相比， 本发明的不同之处是采用导电炭黑作为导电填料， 并在 ABS——炭黑体系中正确选择了几类与 ABS 树脂具有良好相容性的高分子抗冲改 性剂， 如热塑性聚酯弹性体， 热塑性聚氨酯 TPU， 具有核一壳结构的接枝物 MBS 作为增韧剂， 一方面改善了炭黑填充 ABS复合材料的抗冲击性能， 另一方面大大 提高了此复合材料的加工流动性能， 满足了制作复杂结构大部件制品的需要。

Claims

权 利 要 求
1 . 一种高流动耐冲击导电丙烯腈一丁二烯—苯乙烯三元共聚物 （ABS )材 料， 其特征在于： 所述的材料配方如下（重量百分数）：
ABS 60—65
炭黑 15〜25
抗冲改性剂 15〜20
抗氧剂 0. 1〜0. 2
紫外线吸收剂 0. 2〜0. 3
2 . 根据权利要求 1所述的一种高流动耐冲击导电 ABS材料， 其特征在于： 所述的抗冲改性剂为热塑性聚酯弹性体。
3. 根据权利要求 1所述的一种高流动耐冲击导电 ABS材料， 其特征在于： 所述的抗冲改性剂为热塑性聚氨酯 TPU。
4. 根据权利要求 1所述的一种高流动耐冲击导电 ABS材料， 其特征在于： 所述的抗冲改性剂为核一壳结构的接枝物 MBS。
5. 一种高流动耐冲击导电丙烯腈一丁二烯一苯乙烯三元共聚物（ABS )材 料的制备工艺， 其特征在于： 将权利要求 1所述的各组分置于高混机中混合 1〜2 分钟， 然后将物料置于双螺杆挤出机的料斗中， 螺杆各段温度为 210〜240Ό， 螺 杆转速为 300rpm， 挤出的物料经水冷、 切粒、 干燥后得到产品。
PCT/CN2000/000154 1999-07-29 2000-06-12 High fluidible, impact resistant conductive acrylonitrile-butadiene-styrene terpolymer material and preparing method thereof WO2001009241A1 (en)

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JP2001514039A JP2003529626A (ja) 1999-07-29 2000-06-12 高流動性耐衝撃性導電性アクリロニトリル・ブタジエン・スチレン三次元共重合体組成物およびその製造方法

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CN102585429B (zh) * 2011-01-11 2015-02-25 合肥杰事杰新材料股份有限公司 一种树脂材料、制备方法及其应用
CN102582188A (zh) * 2012-02-16 2012-07-18 仙居县一远静电科技有限公司 一种防静电abs贴面板
CN103360718B (zh) * 2013-07-14 2015-11-18 上海秋橙新材料科技有限公司 抗老化abs-tpu塑料合金
KR101860388B1 (ko) 2017-03-10 2018-05-24 (주)티엘씨코리아 내충격성 및 저수축성이 향상된 3d 프린터 필라멘트용 abs 조성물 및 이로부터 제조된 필라멘트

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