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WO2022105134A1 - Composition de polypropylène conductrice à faible densité, son procédé de préparation et son utilisation - Google Patents

Composition de polypropylène conductrice à faible densité, son procédé de préparation et son utilisation Download PDF

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Publication number
WO2022105134A1
WO2022105134A1 PCT/CN2021/091387 CN2021091387W WO2022105134A1 WO 2022105134 A1 WO2022105134 A1 WO 2022105134A1 CN 2021091387 W CN2021091387 W CN 2021091387W WO 2022105134 A1 WO2022105134 A1 WO 2022105134A1
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WIPO (PCT)
Prior art keywords
low
polypropylene composition
density conductive
parts
conductive polypropylene
Prior art date
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Ceased
Application number
PCT/CN2021/091387
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English (en)
Chinese (zh)
Inventor
卢朝亮
叶南飚
黄险波
杨波
吴亦建
苏娟霞
罗忠富
陈延安
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Kingfa Science and Technology Co Ltd
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Kingfa Science and Technology Co Ltd
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Publication of WO2022105134A1 publication Critical patent/WO2022105134A1/fr
Anticipated expiration legal-status Critical
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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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/28—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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/04—Ingredients characterised by their shape and organic or inorganic 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
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic 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
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives

Definitions

  • the invention relates to the field of polymer material modification, in particular to a low-density conductive polypropylene composition suitable for automotive millimeter-wave radar EMI and a preparation method thereof.
  • polypropylene As a cost-effective general-purpose plastic, polypropylene (PP) has excellent mechanical properties after toughening and modification, and is easy to form and process, and is widely used in home appliances and automotive products.
  • Millimeter-wave radars will be widely used in automatic cruise (ACC), collision avoidance system (CA) and lane-change assistance systems in future automotive automated driving technologies, and with the development of technology, 77GHz millimeter-wave radars will be widely industrialized and Replacing 24GHz millimeter-wave radar has become the mainstream of automotive millimeter-wave radar applications. In this case, the anti-jamming of radar is particularly important.
  • ACC automatic cruise
  • CA collision avoidance system
  • lane-change assistance systems in future automotive automated driving technologies
  • 77GHz millimeter-wave radars will be widely industrialized and Replacing 24GHz millimeter-wave radar has become the mainstream of automotive millimeter-wave radar applications. In this case, the anti-jamming of radar is particularly important.
  • the patent with publication number CN 110951164 A uses micro-foaming technology to improve the electrical conductivity of the material, but as we all know, the use of micro-foaming technology will lead to a substantial decrease in the physical properties of the material, which limits its popularization and use to a certain extent.
  • the patent with publication number CN 104877232 A uses nanomaterials containing modified carbonized bacterial cellulose to achieve electrical conductivity. At present, the industrialization of multi-walled carbon nanotubes (MWCNT) has greatly reduced the cost of raw materials.
  • MWCNT multi-walled carbon nanotubes
  • Multi-walled carbon nanotubes have been widely used in the development of conductive materials as a common conductive filler since their industrial production. Its advantages are low price and low addition amount; Due to the strong interaction force and the high flexibility of the molecular chain of polypropylene, it is difficult for polypropylene melt to effectively transmit shear force to effectively disperse MWCNTs during processing, which makes it difficult for polypropylene systems to use MWCNTs as conductive fillers. Achieving the desired high conductivity; usually, even adding an excess of MWCNTs in the polypropylene system can only achieve antistatic effects, and the addition of excess MWCNTs on the one hand leads to a sharp increase in cost, on the other hand, it is a problem of the parts.
  • the purpose of the present invention is to overcome the above-mentioned shortcomings of the prior art and provide a low-density conductive polypropylene composition.
  • a low-density conductive polypropylene composition comprising the following components in parts by weight: 80-90 parts of PP resin, 5-15 parts of hollow glass beads, 3-8 parts of MWCNT parts and 0.1 to 3 parts of additives.
  • the weight part of the hollow glass microspheres is 5-10 parts, and the weight part of the MWCNT is 3-5 parts.
  • the PP resin is at least one of homopolypropylene and copolymerized polypropylene; the melt mass flow rate of the PP resin at 230° C. and a load of 2.16Kg is 10-100g/10min.
  • the particle size D90 of the hollow glass microbeads is 10-100 ⁇ m, and the wall thickness of the hollow glass microbeads is 1-2 ⁇ m.
  • the tube diameter of the MWCNT is 8-60 nm, and the tube length of the MWCNT is 20-100 ⁇ m.
  • the selected MWCNTs are arrayed tube CNTs or part of arrayed tube CNTs, and the array length of the selected MWCNTs is 2-80 ⁇ m.
  • the auxiliary agent is at least one of antioxidant, light stabilizer and lubricant.
  • the antioxidant is at least one of a hindered phenolic antioxidant and a phosphite antioxidant; the light stabilizer is a hindered amine light stabilizer; the lubricant is stearin Zinc acid.
  • the antioxidant is at least one of 1010, 1076, 3114, 168, and PEP-36; the light stabilizer is at least one of UV-3808PP5, LA-402XP, and LA-402AF.
  • the present invention also provides a preparation method of the low-density conductive polypropylene composition.
  • the method comprises the following steps: mixing the components uniformly, adding them into a twin-screw extruder, melting and kneading, and extruding and pelletizing, A low-density conductive polypropylene composition is obtained; wherein, the temperature of melt-kneading is 200-210° C., and the rotational speed of the screw is 350-450 rpm.
  • the present invention also provides the application of the low-density conductive polypropylene composition in automobile interior and exterior trim parts with electromagnetic signal shielding.
  • the dispersion of MWCNTs in the polypropylene system is effectively improved, so that the surface resistance of the prepared material is in the range of 10 4 -10 2 ⁇ /sq; at the same time, due to the hollow glass microspheres
  • the low density characteristic of the material makes the material exhibit the characteristic of low density
  • the production method of the low-density conductive polypropylene composition of the present invention is simple and easy to implement, and has a high degree of freedom in design;
  • the low-density conductive polypropylene composition of the present invention has very high electrical conductivity, and is suitable for use as an EMI material for automotive interior and exterior trims with EMI characteristics and other applications with EMI requirements.
  • test methods for electrical conductivity are: the surface resistance of the material is tested according to ASTM D4496-2013 and D257-2014 standards; the test standard for impact strength is ISO 527-1-2012; the test for flexural modulus The standard is ISO 178-2010; the reference standard for density testing is ISO 1183-2019.
  • PP resin 1 Copolymerized polypropylene, the melt mass flow rate at 230°C and 2.16Kg load is 40g/10min, Sinopec Maoming;
  • PP resin 2 Copolymerized polypropylene, the melt mass flow rate at 230°C and 2.16Kg load is 2g/10min, CNOOC Shell;
  • Hollow glass beads 1 D90 is 75 ⁇ m, wall thickness is 1 ⁇ m, 3M company;
  • Hollow glass beads 2 D90 is 110 ⁇ m, wall thickness is 1 ⁇ m, Zhongke Huaxing;
  • MWCNT 1 tube diameter is 8-15nm, tube length is 20-60 ⁇ m, array tube, array length is 5-50 ⁇ m, LG Chem;
  • MWCNT 2 diameter of 10-30nm, length of 30-45 ⁇ m, non-array tube, Shandong Dazhan;
  • MWCNT 3 tube diameter is 12-15nm, tube length is 3-12 ⁇ m, array tube, array length is 2-8 ⁇ m, LG Chem;
  • Filler 1 (talcum powder): the particle size is 1250 mesh, Beihai Group;
  • Filler 2 (calcium carbonate): fineness 1250 mesh, Jiangsu Yifeng;
  • UV-3808PP5 Light stabilizer
  • Lubricant (zinc stearate);
  • the preparation method of the low-density conductive polypropylene composition is as follows:
  • the components are mixed uniformly and then added to a twin-screw extruder, melt-kneaded, extruded and pelletized to obtain a low-density conductive polypropylene composition; wherein, the melt-kneading temperature is 200-210° C., and the screw speed is 350 ⁇ 450 rpm.
  • the polypropylene composition was prepared according to the above method, and then the composition was injection-molded into 100mm*100mm*2mm sample pieces and ISO standard mechanical splines.
  • Examples 1 to 10 and Comparative Examples 1 to 6 are set in this application.
  • the formulations and electrical conductivity of the low-density conductive polypropylene compositions of Examples 1 to 10 are shown in Table 1;
  • the ingredient content and properties are shown in Table 2.
  • the addition amount of hollow glass microspheres is 5-10 parts, because when the addition amount of hollow glass microspheres is higher than 10 parts, the hollow glass microsphere powder If the volume ratio of the material is too high, it is easy to cause instability of the extrusion feeding, which will affect the production stability of the material.
  • Example 1 and Comparative Example 2 show that for the same filler fraction, hollow glass microspheres have better dispersion effect on MWCNT, and the material has higher electrical conductivity, while systems using hollow glass microspheres have lower densities.
  • Example 2 Comparing Example 2 with Example 3, it can be seen that the PP resin in Example 2 has a melt mass flow rate in the range of 10-100g/10min at 230°C and a load of 2.16Kg, and the PP resin in Example 3 melts.
  • the body mass flow rate is not within the above range, and the surface resistance and density in Example 3 are higher than those in Example 2;
  • Example 4 Comparing Example 2 with Example 4, it can be seen that the particle size of the hollow glass microspheres in Example 2 is 10-100 ⁇ m, and the wall thickness is 1-2 ⁇ m; the particle size and wall thickness of the hollow glass microspheres in Example 4 are not Within the above range, the surface resistance and density in Example 4 are higher than those in Example 2;
  • Example 2 Comparing Example 2 with Example 5, it can be seen that the MWCNTs in Example 2 are array tube CNTs or part of array tube CNTs, and the array length of the selected MWCNTs is 2-80 ⁇ m; The surface resistance and density in Example 5 were higher than those in Example 2.
  • Example 2 is compared with Example 9. In Example 9, 8 parts of MWCNTs are used, and the high MWCNT content will make the processing of the material difficult and make the electrical conductivity of the material more unstable. Example 2 phase It has lower conductivity than Example 9.
  • Example 10 Comparing Example 2 with Example 10, the tube length of the MWCNT in Example 10 is not in the range of "20-100 ⁇ m", and the conductivity achieved in Example 10 is lower than that in Example 2.

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  • 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

L'invention concerne une composition de polypropylène conductrice à faible densité, comprenant les composants suivants en parties en poids : De 80 à 90 parties de résine PP, de 5 à 15 parties de billes de verre creuses, de 3 à 8 parties de MWCNT et de 0,1 à 3 parties d'un agent auxiliaire. La sélection de billes de verre creuses en tant que composant de dispersion améliore de manière efficace la dispersion de MWCNT dans le système de polypropylène, de telle sorte que la résistance de surface du matériau préparé est dans la plage de 104 à 10 2 Ω/sq ; en outre, du fait de la faible densité des billes de verre creuses, le matériau présente des caractéristiques de faible densité. L'invention concerne également un procédé de préparation de la composition de polypropylène conductrice à faible densité et son utilisation.
PCT/CN2021/091387 2020-11-23 2021-04-30 Composition de polypropylène conductrice à faible densité, son procédé de préparation et son utilisation Ceased WO2022105134A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202011325150.1A CN112409701B (zh) 2020-11-23 2020-11-23 一种低密度导电聚丙烯组合物及其制备方法与应用
CN202011325150.1 2020-11-23

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115197534A (zh) * 2022-07-15 2022-10-18 南京聚隆科技股份有限公司 一种可用于倒车雷达壳体的低介电peek改性材料及其制备方法
CN116574325A (zh) * 2023-03-31 2023-08-11 江苏金发科技新材料有限公司 一种聚丙烯复合材料及其制备方法和应用
CN117198587A (zh) * 2023-10-17 2023-12-08 北京高义创合航空科技有限公司 低密度导电泡沫材料、其浆料及制备方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112409701B (zh) * 2020-11-23 2022-04-19 金发科技股份有限公司 一种低密度导电聚丙烯组合物及其制备方法与应用
CN113637312A (zh) * 2021-08-31 2021-11-12 歌尔股份有限公司 一种抗菌材料

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WO2004026962A2 (fr) * 2002-09-20 2004-04-01 General Electric Company Composants de capot
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CN111073040A (zh) * 2019-12-11 2020-04-28 宁波多普达聚合物有限公司 一种HGM-CNTs键合物的制备方法及轻质抗静电聚丙烯材料
CN112409701A (zh) * 2020-11-23 2021-02-26 金发科技股份有限公司 一种低密度导电聚丙烯组合物及其制备方法与应用

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CN106380683A (zh) * 2016-08-31 2017-02-08 金田集团（桐城）塑业有限公司 一种爽滑聚丙烯薄膜

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004026962A2 (fr) * 2002-09-20 2004-04-01 General Electric Company Composants de capot
CN110746693A (zh) * 2019-10-31 2020-02-04 万华化学（宁波）有限公司 一种选择性激光烧结用聚丙烯粉末产品及其制备方法
CN111073040A (zh) * 2019-12-11 2020-04-28 宁波多普达聚合物有限公司 一种HGM-CNTs键合物的制备方法及轻质抗静电聚丙烯材料
CN112409701A (zh) * 2020-11-23 2021-02-26 金发科技股份有限公司 一种低密度导电聚丙烯组合物及其制备方法与应用

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115197534A (zh) * 2022-07-15 2022-10-18 南京聚隆科技股份有限公司 一种可用于倒车雷达壳体的低介电peek改性材料及其制备方法
CN116574325A (zh) * 2023-03-31 2023-08-11 江苏金发科技新材料有限公司 一种聚丙烯复合材料及其制备方法和应用
CN117198587A (zh) * 2023-10-17 2023-12-08 北京高义创合航空科技有限公司 低密度导电泡沫材料、其浆料及制备方法

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CN112409701B (zh) 2022-04-19

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