WO2022206611A1 - Composition de polypropylène et son procédé de préparation - Google Patents

Composition de polypropylène et son procédé de préparation Download PDF

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Publication number
WO2022206611A1
WO2022206611A1 PCT/CN2022/083107 CN2022083107W WO2022206611A1 WO 2022206611 A1 WO2022206611 A1 WO 2022206611A1 CN 2022083107 W CN2022083107 W CN 2022083107W WO 2022206611 A1 WO2022206611 A1 WO 2022206611A1
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WIPO (PCT)
Prior art keywords
polypropylene
acid amide
parts
polypropylene composition
amide
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PCT/CN2022/083107
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English (en)
Chinese (zh)
Inventor
苏娟霞
杨波
罗忠富
黄险波
叶南飚
吴亦建
卢朝亮
彭莉
吴国峰
陈延安
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金发科技股份有限公司
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Publication of WO2022206611A1 publication Critical patent/WO2022206611A1/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
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/062—HDPE

Definitions

  • the invention relates to the technical field of polypropylene materials, in particular to a polypropylene composition and a preparation method thereof.
  • the polarity of polypropylene molecular chain is low, and its own surface tension is relatively low.
  • the surface of ordinary talc-filled elastomer-toughened modified polypropylene material has a certain low surface tension, but this level of low surface tension cannot be achieved like a lotus leaf.
  • car interiors such as door panels, racks, etc. may often come into contact with some stains such as coffee, juice, tea, etc., leaving traces that are difficult to erase.
  • the performance requirements for anti-stain adhesion on the surface of automobile interiors are getting higher and higher.
  • CN101200524A discloses a low surface tension polypropylene material. By mixing polypropylene raw materials with low surface tension fluorochemical monomers with unsaturated double bonds and co-grafting monomers, the low surface tension is prepared by the method of grafting. Surface tension water resistant polypropylene material.
  • CN105440604A discloses a low surface tension PBT resin, which uses polyethylene glycol, oxidized polyethylene wax, stearate, metal soap or stearamide to reduce the surface tension of the PBT body, instead of the application of TPX resin.
  • TPX resin polyethylene glycol, oxidized polyethylene wax, stearate, metal soap or stearamide
  • the purpose of the present invention is to overcome the deficiencies of the prior art and provide a polypropylene composition, the polypropylene composition has low surface tension and good anti-stain adhesion effect, and can be used for preparing automobile interior parts.
  • the technical scheme adopted by the present invention is:
  • a polypropylene composition comprising the following components in parts by weight: 40-90 parts of polypropylene, 10-35 parts of toughening agent, 5-25 parts of filler and 0.2-1 part of secondary amide auxiliary;
  • the structural formula of the secondary amide auxiliary agent is R 1 -CO-NH-R 2 , wherein R 1 is a saturated chain segment with a carbon number of 15-22 or an unsaturated chain segment with a carbon number of 15-22, and R 2 is a saturated segment having 15-22 carbon atoms or an unsaturated segment having 15-22 carbon atoms.
  • R 1 and R 2 may be the same or different.
  • the secondary amide auxiliary agent with the above structure is used as the low surface tension auxiliary agent, which can significantly reduce the surface tension of the polypropylene material, and realize the free rolling of shoe polish stains on the surface of the sample plate, thereby improving the anti-stain adhesion on the surface of the material. effect.
  • the weight part of secondary amide additives in the formulation system of the present invention is controlled to be 0.2-1 part by weight.
  • the weight part of the secondary amide auxiliary agent in the polypropylene composition is 0.3-0.4 part, within this content range, it is beneficial to reduce the surface tension of the system, and the surface of the prepared polypropylene material has an anti-stain adhesion effect. better and better mechanical properties.
  • the obtained polypropylene composition has lower surface tension and anti-stain adhesion effect, and can meet the use requirements of automobile interior parts.
  • the secondary amide additives include oleic palmitic acid amide, stearyl stearic acid amide, stearyl erucic acid amide, oleic acid behenic acid amide, stearyl oleic acid amide, stearyl behenic acid amide
  • At least one of uric acid amide and bis-erucic acid amide is beneficial to reduce the surface tension of the polypropylene material, realize the free rolling of shoe polish stains on the surface of the sample, and improve the anti-stain adhesion effect of the material.
  • the polypropylene includes at least one of homo-polypropylene and copolymerized polypropylene, the polypropylene is tested according to ASTM D792-2013, and its density is 0.894-0.914 g/cm 3 , and the polypropylene is tested according to ASTM D792-2013 According to D1238-2013 standard, the melt mass flow rate under the test condition of 230°C and 2.16kg is 0.5 ⁇ 100g/10min.
  • the toughening agent is an ethylene-alpha olefin copolymer, and according to the ASTM D1238-2013 standard, the melt mass flow rate of the toughening agent under the test condition of 190 ° C and 2.16 kg is 0.1-30 g/10min.
  • the filler includes at least one of talc, whisker, calcium carbonate, barium sulfate, and wollastonite.
  • the polypropylene composition further comprises the following components by weight: 0-12 parts of polyethylene, 0.1-0.5 parts of antioxidant , 0.1-0.5 part of light stabilizer and 0.5-1 part of color masterbatch.
  • the polyethylene is high-density polyethylene (HDPE), and according to the ASTM D1238-2013 standard, its melt mass flow rate at 190° C. under the test condition of 2.16kg is 0.1 ⁇ 30g/10min.
  • HDPE high-density polyethylene
  • antioxidants include hindered phenolic antioxidants and phosphite antioxidants.
  • the light stabilizer is a hindered amine light stabilizer.
  • the present invention also provides a preparation method of the above polypropylene composition, comprising the following steps:
  • each component is weighed by weight proportion and added to the high mixer to mix for 1 to 3 minutes, and the rotating speed is 1000 to 2000 rpm to obtain a premix;
  • the present invention also provides the application of the above polypropylene composition in automobile interior parts.
  • the preparation process of the invention is simple and easy to control, suitable for industrial scale production, and the product has low surface tension and anti-stain adhesion effect, and can be widely used for preparing automobile interior decorations, such as instrument panels, door panels, glove boxes, storage racks, etc. Parts for anti-stain adhesion needs.
  • the present invention also provides the application of the above-mentioned secondary amide auxiliary agent in reducing the surface tension of the polypropylene composition
  • the polypropylene composition includes the following components in parts by weight: 40-90 parts of polypropylene, 10-90 parts of toughening agent 35 parts, 5-25 parts of filler and 0.2-1 part of secondary amide additives;
  • the structural formula of the secondary amide auxiliary agent is R 1 -CO-NH-R 2 , wherein R 1 is a saturated chain segment with a carbon number of 15-22 or an unsaturated chain segment with a carbon number of 15-22, and R 2 is a saturated segment having 15-22 carbon atoms or an unsaturated segment having 15-22 carbon atoms.
  • Amide additives are added to the existing polypropylene system, and their function is generally to reduce the friction coefficient of the material, thereby improving the scratch resistance of the material or increasing the slippage to facilitate the release of the material.
  • adding an appropriate amount of secondary amide additives can be used as low surface tension additives, which can significantly reduce the surface tension of polypropylene materials, thereby improving the anti-stain adhesion on the surface of the material. effect.
  • the weight part of the secondary amide auxiliary agent in the polypropylene composition is 0.3-0.4 part.
  • the prepared material has both good mechanical properties and surface anti-stain and stickiness. attached effect.
  • the secondary amide additives include oleic palmitic acid amide, stearyl stearic acid amide, stearyl erucic acid amide, oleic acid behenic acid amide, stearyl oleic acid
  • At least one of amide, stearyl behenamide and bis-erucamide can significantly reduce the surface tension of the polypropylene material, thereby improving the anti-stain adhesion effect on the surface of the material.
  • the polypropylene includes at least one of homopolymer polypropylene and copolymer polypropylene.
  • the polypropylene has a melt mass flow rate of 0.5-100 g/10min under the test conditions of 230° C. and 2.16 kg.
  • the toughening agent is an ethylene-alpha olefin copolymer
  • the melt mass flow rate of the toughening agent under the test condition of 190 ° C and 2.16 kg is 0.1 ⁇ 30g/10min.
  • the filler includes at least one of talc, whisker, calcium carbonate, barium sulfate, and wollastonite.
  • the polypropylene composition further comprises the following components in parts by weight: 0-12 parts of polyethylene, 0.1-0.5 parts of antioxidants, 0.1-0.5 parts of light stabilizers and 0.5 parts of color masterbatches -1 serving.
  • the polyethylene is high-density polyethylene, and according to the ASTM D1238-2013 standard, its melt mass flow rate under the test condition of 190 ° C and 2.16 kg is 0.1 to 30 g/10min.
  • the antioxidants include hindered phenolic antioxidants and phosphite antioxidants.
  • the light stabilizer is a hindered amine light stabilizer.
  • the invention adopts the secondary amide type auxiliary agent as the low surface tension auxiliary agent, which can significantly reduce the surface tension of the polypropylene material, and realize the free rolling of shoe polish stains on the surface of the sample plate, so as to improve the anti-stain adhesion on the surface of the material, so that the Meet the use requirements of automotive interior parts.
  • Figure 1 shows the traces left by the shoe polish droplets corresponding to each level of surface tension evaluation after rolling off the stain on the sample plate.
  • Polypropylene Homopolypropylene, PPN-Z30S, according to ASTM D1238-2013, the melt mass flow rate is 26g/10min at 230°C, 2.16kg test condition; according to ASTM D792-2013, its density is 0.897 g/cm 3 ; Maoming Petrochemical;
  • HDPE HDPE HMA025, according to ASTM D1238-2013, the melt mass flow rate at 190°C, 2.16kg test condition is 8g/10min; according to ASTM D1505-2018 test, density 0.964g/ cm3 ; ExxonMobil ;
  • Toughening agent POE Engage 8137, according to ASTM D1238-2013 standard, the melt mass flow rate at 190 ° C, 2.16kg test condition is 13g/10min; according to ASTM D1505-2018 test, density 0.864g/ cm3 ; chemistry;
  • Oleic palmitamide secondary amide additives, Croda, UK;
  • Stearyl stearic acid amide secondary amide additives, British Croda;
  • Stearyl erucamide secondary amide additives, British Croda;
  • Double erucamide secondary amide auxiliary, Jiangxi Weike;
  • Oleic acid amide primary amide auxiliary, British Croda;
  • Ethylene biserucamide Bifunctional amide auxiliary, Jiangxi Weltco;
  • Talc powder TYT-777A, Beihai Tianyuan
  • Antioxidant including main antioxidant and auxiliary antioxidant, main antioxidant is hindered phenolic antioxidant, model: Irganox 1010, BASF; auxiliary antioxidant is phosphite antioxidant, model: Irganox 168,BASF;
  • each component is weighed by weight proportion and added to the high mixer to mix for 1 to 3 minutes, and the rotating speed is 1000 to 2000 rpm to obtain a premix;
  • the device for evaluating the surface tension of the sample includes a bracket that can be used to place the sample stably.
  • the bracket can adjust the angle through the gear of the rear seat buckle.
  • the surface tension evaluation grades are as follows:
  • Level 1 droplets do not shrink and adhere
  • Level 2 The droplet shrinks and adheres continuously
  • Level 3 The droplet shrinkage breakpoint adheres and there are more than 10 adhesion points
  • Level 4 droplet shrinkage breakpoint adhesion and less than 10 adhesion points
  • Table 1 shows the surface tension evaluation grades and mechanical properties test results of the polypropylene compositions prepared in the above examples and comparative examples.
  • the weight part of the secondary amide auxiliary is preferably 0.2-1 part, but the content of the secondary amide auxiliary is too high, the effect of improving the anti-stain adhesion effect on the surface of the material is not obvious, but it will also lead to the reduction of the mechanical properties of the material.
  • the weight part of secondary amide additives in the formulation system of the present invention is preferably 0.3-0.4 parts.
  • Example 2 Comparing Example 2, Example 4-6 and Comparative Example 2-3, it was found that under the same content of amide additives, compared with oleic palmitic acid amide, stearyl stearic acid amide, stearin Secondary amide additives such as base erucamide and bis-erucamide, primary amide additives (oleic acid amide) and bifunctional amide additives (ethylene bis-erucamide) can not reduce the surface tension of the system, which has a negative impact on the material. There is no improvement in the surface anti-stain adhesion.
  • amide additives such as base erucamide and bis-erucamide
  • primary amide additives oleic acid amide
  • bifunctional amide additives ethylene bis-erucamide

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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

Sont divulgués dans la présente invention une composition de polypropylène et son procédé de préparation. La composition de polypropylène comprend les constituants suivants, en parties en poids : de 40 à 90 parties de polypropylène, de 10 à 35 parties d'agent de renforcement, de 5 à 25 parties de charge, et de 0,2 à 1 partie d'adjuvant amide secondaire ; la formule développée de l'adjuvant amide secondaire est R1-CO-NH-R2, dans laquelle R1 est un segment de chaîne saturée ayant un nombre d'atomes de carbone compris entre 15 et 22 ou un segment de chaîne insaturée ayant un nombre d'atomes de carbone compris entre 15 et 22, et R2 est un segment de chaîne saturée ayant un nombre d'atomes de carbone compris entre 15 et 22 ou un segment de chaîne insaturée ayant un nombre d'atomes de carbone compris entre 15 et 22. La présente invention utilise l'adjuvant amide secondaire en tant qu'adjuvant à faible tension superficielle qui peut réduire de manière considérable la tension superficielle du matériau de polypropylène, de telle sorte que des gouttelettes et des taches de cirage à chaussure peuvent rouler librement sur la surface d'une plaque échantillon, ce qui a pour effet d'améliorer l'anti-adhérence des taches de la surface du matériau, et de satisfaire aux exigences d'utilisation des garnitures intérieures d'automobile.
PCT/CN2022/083107 2021-03-31 2022-03-25 Composition de polypropylène et son procédé de préparation WO2022206611A1 (fr)

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CN202110353484.8 2021-03-31
CN202110353484.8A CN113150436B (zh) 2021-03-31 2021-03-31 一种聚丙烯组合物及其制备方法

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CN113150436B (zh) * 2021-03-31 2022-12-02 金发科技股份有限公司 一种聚丙烯组合物及其制备方法
CN114213762B (zh) * 2021-11-23 2023-09-26 金发科技股份有限公司 一种高表面张力聚丙烯材料及其制备方法和应用
CN114350061B (zh) * 2021-11-30 2023-09-26 金发科技股份有限公司 一种聚丙烯组合物及其制备方法和应用
CN114736454B (zh) * 2022-03-24 2023-09-26 金发科技股份有限公司 一种低吸附医用透明聚丙烯材料及其制备方法和应用

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CN1997703A (zh) * 2004-07-07 2007-07-11 西巴特殊化学品控股有限公司 抗刮伤的聚烯烃
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