WO2023040734A1 - Composition de polypropylène résistant à l'usure et résistant aux chocs, son procédé de préparation et son utilisation - Google Patents

Composition de polypropylène résistant à l'usure et résistant aux chocs, son procédé de préparation et son utilisation Download PDF

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Publication number
WO2023040734A1
WO2023040734A1 PCT/CN2022/117707 CN2022117707W WO2023040734A1 WO 2023040734 A1 WO2023040734 A1 WO 2023040734A1 CN 2022117707 W CN2022117707 W CN 2022117707W WO 2023040734 A1 WO2023040734 A1 WO 2023040734A1
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Prior art keywords
parts
wear
resistant
polypropylene composition
carbon black
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PCT/CN2022/117707
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English (en)
Chinese (zh)
Inventor
卢朝亮
陈平绪
叶南飚
吴亦建
左立增
陈延安
吴国峰
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金发科技股份有限公司
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Publication of WO2023040734A1 publication Critical patent/WO2023040734A1/fr

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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
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene

Definitions

  • the invention relates to the field of polymer materials and their molding processing, in particular to a wear-resistant and high-impact polypropylene composition and its preparation method and application.
  • polypropylene As a cost-effective general-purpose plastic, polypropylene has excellent mechanical properties such as high strength and toughness, chemical resistance, and high heat resistance after modification, and can be widely used in home appliances and automotive products.
  • polypropylene materials For automotive interior parts made of polypropylene materials, it is usually easy to be scratched or worn by fabric shoe materials, decorations, gravel and other items, so scratch resistance and abrasion resistance are important performance requirements for automotive interior polypropylene , It is of great significance to keep the interior beautiful.
  • Patent CN109721829A adds wear-resistant agents such as hexagonal boron nitride, ⁇ -alumina, zirconium boride and polytetrafluoroethylene powder, that is, uses ceramic powder to increase rigidity and PTFE powder to reduce the surface friction coefficient.
  • Wear-resistant agents such as hexagonal boron nitride, ⁇ -alumina, zirconium boride and polytetrafluoroethylene powder, that is, uses ceramic powder to increase rigidity and PTFE powder to reduce the surface friction coefficient.
  • Modified plastics are not a general-purpose filler, and they are used in large quantities in polypropylene systems.
  • the purpose of the present invention is to provide a wear-resistant high-impact polypropylene composition.
  • the present invention realizes the effective improvement of the wear resistance and impact performance of polypropylene material by adding carbon black with high oil absorption value and optimizing and optimizing polypropylene and toughening agent, and the wear-resistant and high-impact polypropylene composition can be widely used Applied to the preparation of automotive interior parts.
  • Another object of the present invention is to provide a method for preparing the above-mentioned wear-resistant and high-impact polypropylene composition.
  • Another object of the present invention is to provide the application of the above-mentioned wear-resistant and high-impact polypropylene composition in the preparation of interior and exterior trim parts of automobiles.
  • a wear-resistant and high-impact polypropylene composition comprising the following components in parts by weight: 30-85 parts of polypropylene resin, 5-25 parts of toughening agent, 5-25 parts of filler, 5-20 parts of carbon black, 1-3 parts of lubricant, 0-0.8 parts of antioxidant, 0-0.6 parts of light stabilizer;
  • the oil absorption value of the carbon black is 120-180mL/100g.
  • Carbon black is an important reinforcing agent in the rubber industry. Because it improves the anti-fatigue properties of rubber, the wear resistance of materials is greatly improved. It has mature applications in the rubber industry, but no carbon black has been used to improve wear resistance in the plastics industry. In addition, the common automotive interior polypropylene is only colored with carbon black, without optimization and optimization of the addition amount, it cannot meet the use requirements of improving wear resistance.
  • carbon black by selecting carbon black with a higher oil absorption value as the physical cross-linking agent, carbon black can be used to absorb and entangle polypropylene molecular chains, thereby generating physical cross-linking points to limit the surface layer of polypropylene under the abrasion test. wear; if the oil absorption value of carbon black is low, the adsorption and entanglement of carbon black to polypropylene molecular chains is less, and it is difficult to meet the requirements of improving wear resistance.
  • oil absorption value of carbon black is in accordance with the ASTM D2414-09a-2017 test standard, and the specific test method is: the minimum dibutyl phthalate required for testing the gaps and surface infiltration filled with carbon black chain branches or fiber structures The amount of ester, also known as DBP oil absorption value.
  • the wear-resistant and high-impact polypropylene composition includes the following components in parts by weight: 50-70 parts of polypropylene resin, 10-15 parts of toughening agent, 10-15 parts of filler, and 10-15 parts of carbon black 1.5-2.5 parts of lubricant, 0.3-0.6 part of antioxidant, 0.2-0.4 part of light stabilizer.
  • the carbon black has an oil absorption value of 130-175mL/100g.
  • the carbon black is furnace carbon black.
  • the polypropylene resin is at least one of homopolypropylene or copolymerized polypropylene.
  • the polypropylene resin is copolymerized polypropylene.
  • the polypropylene resin has a melt flow rate of 60-115 g/10 min at a temperature of 230° C. and a load of 2.16 kg according to ASTM D-1238-2013 standard.
  • the toughening agent is ethylene-butene copolymer or ethylene-octene copolymer (POE).
  • the POE has a melt flow rate of 3-14g/10min at a temperature of 190°C and a load of 2.16Kg.
  • a polypropylene resin with a higher melt flow rate is preferred, which can improve the dispersibility of carbon black in the polypropylene system, and at the same time, due to the existence of a certain amount of carbon black with high oil absorption value, it can effectively reduce the toughening agent and polypropylene resin.
  • the melt flow rate of POE by optimizing the melt flow rate of POE, its dispersibility is significantly improved, so that the prepared polypropylene material can have higher impact strength at a lower elastomer content, which is conducive to further reducing The adverse effect of POE on the wear resistance of polypropylene system.
  • the filler is at least one of talcum powder, calcium carbonate, barium sulfate or glass fiber.
  • the lubricant is at least one of amide, amide masterbatch or silicone masterbatch.
  • the antioxidant is at least one of hindered phenols or phosphites, specifically at least one of 1010, 1076, 3114, 168 or PEP-36.
  • the light stabilizer is hindered amines, specifically at least one of UV-3808, LA-402XP or LA-402AF.
  • the present invention also provides a method for preparing the above-mentioned wear-resistant and high-impact polypropylene composition, comprising the following steps:
  • the present invention has the following beneficial effects:
  • the wear resistance of the prepared wear-resistant high-impact polypropylene composition has been significantly improved, and at the same time, by optimizing polypropylene and toughening agent, to achieve It achieves high impact resistance performance under the condition of low toughening agent addition, and is suitable for automotive interior parts with wear resistance requirements.
  • the preparation method of the wear-resistant and high-impact polypropylene composition prepared in the present invention is simple and easy to implement, has cost advantages, and has a high degree of freedom in design.
  • melt flow rate (230°C/2.16kg) is 112g/10min
  • melt flow rate (230°C/2.16kg) is 60g/10min
  • melt flow rate (230°C/2.16kg) of polypropylene copolymer is 30.9g/10min
  • POE 1 Model POE ENGAGE 7447 Manufacturer: Dow Chemical Melt flow rate (190°C/2.16kg) is 5g/10min;
  • POE 2 Model POE ENGAGE 8137 Manufacturer: Dow Chemical Melt flow rate (190°C/2.16kg) is 13g/10min;
  • POE 3 Model POE ENGAGE 7467 Manufacturer: Dow Chemical Melt flow rate (190°C/2.16kg) is 1.2g/10min;
  • SEBS Model SEBS G1657 VS Manufacturer: Kraton Polymers
  • Hindered phenols Model 1010 Manufacturer: Shandong Sanfeng;
  • Phosphite Type 168 Manufacturer: Shandong Sanfeng;
  • the polypropylene composition prepared above was injection molded into a 100mm*100mm*3mm sample piece for performance testing.
  • Wear resistance test method According to the GBT 5478-2008 test standard, the material wear resistance test is carried out, the wear wheel model is CS-10/load 2.45N/cycle number 100 times/test speed 60rpm, and visual evaluation is carried out after the test; Evaluation grades: Level 1: Wear marks are very obvious; Level 2: Wear marks are relatively obvious; Level 3: Wear marks are slight but can be clearly distinguished; Level 4: Weak wear marks can be observed but not obvious; Level 5: Completely noticeable less than wear marks;
  • This example provides a series of wear-resistant and high-impact polypropylene compositions, the formulations of which are shown in Table 1.
  • This comparative example provides a series of polypropylene compositions, the formulations of which are shown in Table 2.
  • Example 1 performance Wear resistance Notched Izod Impact Strength (KJ/m 2 ) Example 1 5 24.6 Example 2 5 15.2 Example 3 4 24.2 Example 4 4 21.5 Example 5 5 22.79 Example 6 5 24.4 Example 7 5 23.6 Example 8 5 16.5 Example 9 4 15.7 Example 10 5 21.2 Example 11 5 19.2 Example 12 5 21.8 Example 13 5 19.1 Example 14 5 20.4 Example 15 5 23.9 Example 16 4 14.6 Example 17 4 21.6 Comparative example 1 3 6.8 Comparative example 2 3 8.5 Comparative example 3 3 14.8
  • the wear-resistant and high-impact polypropylene compositions prepared have a wear-resistant appearance grade ⁇ 4, and the preferred high
  • the carbon black with oil absorption value can promote the dispersion of the toughening agent in the material, so that the notched Izod impact strength of the material is greater than 10KJ/m 2 .
  • the oil absorption value of carbon black, polypropylene resin type, melt index, and POE melt index were optimized, and the wear resistance level and notched impact strength were further improved, reaching a wear-resistant appearance level of 5, and the notch impact strength was average. >20KJ/m 2 .
  • Example 1 The comparison between Example 1 and Example 2/3 shows that the optimization of polypropylene is beneficial to further improve the wear resistance and impact resistance of the material.
  • Example 1/6 The comparison between Example 1/6 and Example 7/8/12 shows that optimizing the toughening agent is beneficial to further improve the impact resistance of the material.
  • Example 1 The comparison between Example 1 and Comparative Example 1/2/3 shows that by adding the preferred carbon black, compared with no carbon black and carbon black with low oil absorption value, the wear resistance and impact resistance of the material are significantly improved.
  • Comparing Example 1 with Comparative Example 7 it can be known that when obtaining similar impact strength, a relatively large amount of POE needs to be added in the formula without adding carbon black, thereby causing a significant decline in the wear resistance of the material; in Comparative Example 8 , The amount of the toughening agent POE added is too small, which has no obvious effect on the wear resistance, but the impact performance of the material is seriously reduced.
  • carbon black with high oil absorption value is selected as a physical crosslinking agent for polypropylene modification, and PP/POE is optimized at the same time, and the wear-resistant and high-impact polypropylene composition prepared has Excellent wear resistance and high impact performance, can be widely used in automotive interior parts.

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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)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition de polypropylène résistant aux chocs et résistant à l'usure, son procédé de préparation et son utilisation. La composition de polypropylène résistant aux chocs et résistant à l'usure comprend les constituants suivants, en parties en poids : de 30 à 85 parties d'une résine de polypropylène, de 5 à 25 parties d'un agent de renforcement, de 5 à 25 parties d'une charge, de 5 à 20 parties de noir de carbone, de 1 à 3 parties d'un lubrifiant, de 0 à 0,8 partie d'un antioxydant et de 0 à 0,6 partie d'un agent photostabilisant, le noir de carbone ayant une valeur d'absorption d'huile de 120 à 180 mL/100 g. Dans la présente invention, le matériau de polypropylène est modifié par la sélection et l'ajout de noir de carbone à haute valeur d'absorption d'huile, et la composition de polypropylène résistant aux chocs et résistant à l'usure finalement préparée présente à la fois une excellente résistance à l'usure et une excellente résistance aux chocs, et peut être utilisée efficacement pour préparer des pièces de garniture intérieure d'automobile.
PCT/CN2022/117707 2021-09-18 2022-09-08 Composition de polypropylène résistant à l'usure et résistant aux chocs, son procédé de préparation et son utilisation WO2023040734A1 (fr)

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CN202111112881.2 2021-09-18
CN202111112881.2A CN113881146A (zh) 2021-09-18 2021-09-18 一种耐磨高抗冲聚丙烯组合物及其制备方法和应用

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CN113881146A (zh) * 2021-09-18 2022-01-04 金发科技股份有限公司 一种耐磨高抗冲聚丙烯组合物及其制备方法和应用
CN114479271B (zh) * 2022-01-19 2023-10-31 金发科技股份有限公司 一种耐热氧老化聚丙烯组合物及其制备方法和应用

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CN1583867A (zh) * 2004-05-27 2005-02-23 上海交通大学 一种抗静电和导电聚丙烯共混物的制备方法
JP2016191026A (ja) * 2015-03-31 2016-11-10 新日鉄住金化学株式会社 ポリプロピレン系樹脂組成物及びその成形品
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