WO2017045597A1 - 聚丙烯组合物及其制备方法、由其制备的薄膜或片材及应用 - Google Patents

聚丙烯组合物及其制备方法、由其制备的薄膜或片材及应用 Download PDF

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WO2017045597A1
WO2017045597A1 PCT/CN2016/098938 CN2016098938W WO2017045597A1 WO 2017045597 A1 WO2017045597 A1 WO 2017045597A1 CN 2016098938 W CN2016098938 W CN 2016098938W WO 2017045597 A1 WO2017045597 A1 WO 2017045597A1
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polypropylene
polypropylene composition
film
sheet
antioxidant
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PCT/CN2016/098938
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English (en)
French (fr)
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杨波
张广伟
罗忠富
丁超
张学庸
赵岚
侯剑锋
李文龙
周英辉
叶南飚
王鹏
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金发科技股份有限公司
延锋汽车饰件系统有限公司
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Priority to US15/759,742 priority Critical patent/US10723869B2/en
Publication of WO2017045597A1 publication Critical patent/WO2017045597A1/zh

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
    • C08L23/10Homopolymers or copolymers of propene
    • C08L23/12Polypropene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/06Polyethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/08Copolymers of ethene
    • C08L23/0807Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815Copolymers of ethene with aliphatic 1-olefins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/13Phenols; Phenolates
    • C08K5/134Phenols containing ester groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/49Phosphorus-containing compounds
    • C08K5/51Phosphorus bound to oxygen
    • C08K5/52Phosphorus bound to oxygen only
    • C08K5/524Esters of phosphorous acids, e.g. of H3PO3
    • C08K5/526Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/16Applications used for films
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00Properties characterising the ingredient of the composition
    • C08L2207/06Properties of polyethylene
    • C08L2207/062HDPE
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00Properties characterising the ingredient of the composition
    • C08L2207/10Peculiar tacticity

Definitions

  • the invention belongs to the field of polymer materials and molding processing thereof, and particularly relates to a polypropylene composition and a preparation method thereof, a film or sheet prepared therefrom and an application thereof.
  • Polypropylene has been widely used in automobiles due to its low cost, light weight, high strength, good chemical resistance, good processing technology and easy recycling. However, its disadvantage is that its low temperature toughness is poor.
  • CN 101659768 discloses a low temperature resistant impact polypropylene composition and a process for the preparation thereof and as an automotive interior part, the polypropylene composition comprising, by weight percent, the following components: polypropylene resin 40 to 79.8%, mineral filler 15 to 35%, toughener 5 to 30%, antioxidant 0.1 to 1%, and weather resistance 0.1 to 1%.
  • CN101709122A discloses a polypropylene nanocomposite for automobile and a preparation method thereof, comprising: using a twin-screw extruder, controlling PP at a temperature of 190 to 210 ° C, and making the MFR 15-30g/10min, on the basis of this PP, the ball-milled inorganic powder, elastomer and copolymerized PP are used for twin-screw blending and granulation, which has good fluidity and good high. Low temperature impact resistance and stiffness.
  • CN102838807A discloses a polypropylene composite material with good impact resistance and low temperature toughness and a preparation method thereof.
  • the composite material is made by weight of the following components: polypropylene resin 30-80%, low density low melting index polyolefin Elastomer 10-40%, filling enhancer 1-30%, interface modifier 1-10%, other additives 0.1-4%, the performance index of polypropylene composite prepared by this method meets or exceeds the predetermined
  • the requirements, especially the low temperature performance are multi-axis low temperature impact (tested according to ASTM D3763, impact velocity of 6.6 m / s) failure form is ductile failure.
  • Automotive interior components such as instrument panels, sub-dashboards, door panels, columns, glove boxes, etc., mainly use polypropylene-based thermoplastic materials and polyolefin-based thermoplastic elastomers (TPO). Under low temperature environment, polypropylene materials are prone to external forces. Breakage and embrittlement damage. During the blasting of the airbag, due to the deployment of the airbag, the airbag door is partially broken and partially broken due to interference with the windshield, the instrument panel characteristic slot, the characteristic edge or other structures, and it is easy to threaten the automobile when the accident occurs in the automobile. The rider is safe.
  • TPO polyolefin-based thermoplastic elastomers
  • the polypropylene has a crystallization peak half-width of 5 ° C to 10 ° C, preferably 7 ° C to 9 ° C, and the crystallization peak-to-peak temperature of the polypropylene is from 105 ° C to 115 ° C, preferably from 108 ° C to 112 ° C.
  • the crystallization peak half-width and the crystallization peak-to-peak temperature were tested according to the ISO 11357 standard at a cooling rate of 10 ° C/min.
  • the polypropylene is a homopolypropylene having an isotactic index of 94% to 98%, and a melt flow rate MFR of 1 g/10 min to 5 g/10 min at 230 ° C under a load of 2.16 kg.
  • the elastomer is one or more of an ethylene-hexene copolymer, an ethylene-butene copolymer or an ethylene-octene copolymer.
  • the polyethylene is a high density polyethylene HDPE, having a density of 0.94g / cm 3 -0.97g / cm 3 , a melt flow rate at 190 °C, under a load of 2.16kg conditions 0.01g / 10min-0.5g / 10min.
  • the polypropylene composition of the present invention further comprises, based on the entire composition, 0.1 parts by weight to 0.5 parts by weight of the antioxidant, and 0.1 parts by weight to 0.5 parts by weight of the lubricant.
  • the antioxidant is a compound of a hindered phenol antioxidant and a phosphite antioxidant 1:1 to 2.
  • the lubricant is a mixture of one or both of polyethylene wax or oxidized polyethylene wax.
  • the preparation method of the above polypropylene composition of the present invention comprises the following steps:
  • the premix is melt extruded through a twin-screw extruder, and the temperature of each zone of the screw is 190 to 230 ° C, and the polypropylene composition is obtained by vacuum granulation.
  • the present invention also discloses a film or sheet prepared from the above polypropylene composition.
  • the film or sheet is used Production by calendering, calendering, and rogue methods.
  • the film or sheet has a thickness of from 0.01 mm to 10 mm.
  • the invention also discloses the application of the above-mentioned film or sheet in an automobile interior product, which is an instrument panel, a sub-instrument board, a column or a door panel, and the like. It can be compounded on the back of the dashboard of the car, and participates in the production process of instrument panel injection molding, friction vibration welding process, laser weakening process, soft touch paint spraying process and other instrument panels.
  • the present invention has the following beneficial effects:
  • the present invention uses a polypropylene having a specific crystallization peak half-width and a crystallization peak-to-peak temperature as a matrix resin, and the polyethylene and the elastomer are synergistically toughened, and the prepared polypropylene composition material has excellent impact properties, particularly
  • the low temperature impact performance at -30 ° C solves the disadvantage that the polypropylene composition is prone to brittle failure when subjected to external impact at -30 ° C;
  • the film and the sheet made of the polypropylene composition material of the invention are compounded in the interior of the automobile, which not only can make the external parts less likely to produce sharp fragments when subjected to strong impact force, and also has matt characteristics;
  • the film and sheet made by the material of the invention have good compatibility with the polypropylene-based thermoplastic material, and have good compatibility with the TPO-based material, and can be compounded in the airbag door area of the B panel of the automobile instrument panel, and the instrument can be lifted.
  • the plate and the airbag frame are welded and pulled off, and the local body toughness of the instrument panel body is improved, and the low speed/high speed impact resistance of the instrument panel airbag door after the normal temperature/low temperature/high temperature/aging cycle is improved to prevent the airbag from being blasted due to the deployment of the airbag.
  • Partial breakage and partial breakage of the airbag door caused by interference between the airbag door and the windshield glass, the instrument panel characteristic slot, the characteristic edge or other structures, improve the safety of the airbag deployment of the occupant side of the vehicle dashboard, and may cause the airbag to burst when the accident occurs in the automobile. Better protect the safety of the passengers on the side of the car;
  • the invention has simple preparation process, low equipment requirement and high product yield rate, and can be widely applied to the production of automobile interior materials.
  • Polypropylene 1 isotactic index is 94%, MFR (230 ° C, 2.16 kg) is 1.0 g/10 min, polypropylene has a crystallization peak half-width of 5 ° C, and the crystallization peak-to-peak temperature of polypropylene is 110 ° C;
  • Polypropylene 2 isotacticity is 95%, MFR (230 ° C, 2.16 kg) is 3.0 g/10 min, polypropylene has a crystallization peak half-width of 7.3 ° C, and the crystallization peak-to-peak temperature of polypropylene is 105 ° C;
  • Polypropylene 3 isotacticity is 98%, MFR (230 ° C, 2.16 kg) is 5.0 g/10 min, polypropylene has a crystallization peak half-width of 10 ° C, and the crystallization peak-to-peak temperature of polypropylene is 108 ° C;
  • Polypropylene 4 isotacticity is 96%, MFR (230 ° C, 2.16 kg) is 4.0 g/10 min, polypropylene has a crystallization peak half-width of 9 ° C, and the crystallization peak-to-peak temperature of polypropylene is 112 ° C;
  • Polypropylene 5 isotacticity is 96%, MFR (230 ° C, 2.16 kg) is 2.0 g/10 min, and the crystallization peak half width of polypropylene 5 ° C, the crystallization peak-to-peak temperature of polypropylene is 115 ° C;
  • Polypropylene 6 isotacticity is 98%, MFR (230 ° C, 2.16 kg) is 8.0 g/10 min, polypropylene has a crystallization peak half-width of 12 ° C, and the crystallization peak-to-peak temperature of polypropylene is 125 ° C;
  • Polypropylene 7 isotacticity is 98%, MFR (230 ° C, 2.16 kg) is 0.5 g/10 min, polypropylene has a crystallization peak half-width of 4.8 ° C, and the crystallization peak-to-peak temperature of polypropylene is 102 ° C;
  • Ethylene-hexene copolymer density is 0.860 g/cm 3 , MFR (190 ° C, 2.16 kg) is 0.5 g/10 min;
  • Ethylene-butene copolymer density is 0.865 g / cm 3 , MFR (190 ° C, 2.16 kg) is 0.5 g/10 min;
  • Ethylene-octene copolymer density is 0.855 g/cm 3 , MFR (190 ° C, 2.16 kg) is 1.0 g/10 min;
  • Ethylene-propylene copolymer density is 0.856 g/cm 3 , MFR is (190 ° C, 2.16 kg) 1.0 g/10 min;
  • High density polyethylene 1 density is 0.94g/cm 3 , MFR (190 ° C, 2.16kg) is 0.01g/10min;
  • High density polyethylene 2 density is 0.95g/cm 3 , MFR (190 ° C, 2.16kg) is 0.05g/10min;
  • High density polyethylene 3 density is 0.97 g/cm 3 , MFR (190 ° C, 2.16 kg) is 0.5 g/10 min;
  • High density polyethylene 4 density is 0.95 g/cm 3 , MFR (190 ° C, 2.16 kg) is 8.0 g/10 min;
  • the antioxidant is a 1:1 compound of hindered phenol antioxidant 1010 and phosphite antioxidant 168.
  • Test items unit standard test The melt flow rate g/10min ISO 1133 density g/cm 2 ISO 1183 Tensile Strength MPa ISO 527-1, 527-2 Elongation at break % ISO 527-1, 527-2 Bending strength MPa ISO 178 Flexural modulus MPa ISO 178 Cantilever beam notched impact strength (23 ° C) kJ/m 2 ISO 180 Cantilever beam notched impact strength (-30 ° C) kJ/m 2 ISO 180 Gloss (60°) ASTM D523 Crystallinity half width °C ISO 11357 Crystalline peak-to-peak temperature °C ISO 11357
  • the present invention uses a polypropylene having a specific crystallization peak half-width and a peak-to-peak temperature as a matrix resin, and the polyethylene and the elastomer are synergistically toughened.
  • the impact property of the prepared polypropylene composition material is greatly improved, especially the low temperature impact property of -30 ° C, and the obtained material has a good gloss toughness, and the gloss is still low, and the film is made into a film.
  • the sheet is applied to the interior of the automobile, which can effectively solve the problem that the automobile interior parts are easily brittle under low temperature and high speed impact.

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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)
  • Air Bags (AREA)

Abstract

一种聚丙烯组合物及其制备方法、由其制备的薄膜或片材及应用。该组合物包括聚丙烯45份~75份,弹性体10份~35份,聚乙烯5份~20份,抗氧剂0.1份-0.5份,润滑剂0.1份-0.5份。所述聚丙烯的结晶峰半峰宽为5℃-10℃,所述聚丙烯的结晶峰峰值温度为105℃-115℃。所述聚丙烯组合物具有良好的韧性,特别是-30℃低温冲击性能,由该组合物制得的薄膜与片材应用于汽车内饰中,不仅能使外部零件在受强大冲击力时不易产生尖锐的碎片,保证人员安全,还具有哑光特性。

Description

聚丙烯组合物及其制备方法、由其制备的薄膜或片材及应用 技术领域
本发明属于高分子材料及其成型加工领域,具体涉及一种聚丙烯组合物及其制备方法,由其制备的薄膜或片材及应用。
背景技术
聚丙烯由于具有成本低、质量轻、强度高、耐化学性能好、加工工艺性好、易回收等优点,近来在汽车上得到广泛应用。但其不足在于,其低温韧性较差。CN 101659768公开了一种耐低温冲击聚丙烯组合物及其制备方法与作为汽车内饰件的应用,该聚丙烯组合物按重量百分比计包含如下组分:聚丙烯树脂40~79.8%,矿物填料15~35%,增韧剂5~30%,抗氧剂0.1~1%,耐候剂0.1~1%,此聚丙烯组合物通过注塑加工汽车内饰件的各种性能均达到使用要求,克服了低温性能差的缺点,特别是在0℃到-40℃具有良好的低温冲击性能。CN101709122A公开了一种无机化工技术领域的汽车用聚丙烯纳米复合物及其制备方法,包括:使用双螺杆挤出机,在温度190~210℃的条件下,可控降解PP,使其MFR为15-30g/10min,再在此PP基础上,用球磨过的无机粉体、弹性体、共聚PP进行双螺杆共混造粒,在获得良好的流动性的同时,也具备了较好的高低温抗冲性能和刚度。CN102838807A公开了一种耐冲击和低温韧性良好的聚丙烯复合材料及其制备方法,该复合材料按重量百分比计由如下组分制成:聚丙烯树脂30~80%,低密度低熔指聚烯烃弹性体10~40%,填充增强剂1~30%,界面改性剂1~10%,其他添加剂0.1~4%,采用此方法制备的聚丙烯复合材料的各项性能指标均达到或超过预定的要求,尤其是低温性能优异,其多轴低温冲击(按ASTMD3763测试,冲击速度为6.6m/s)破坏形式为韧性破坏。
汽车内饰部件如仪表板、副仪表板、门板、立柱、手套箱等,主要采用聚丙烯类热塑性材料和聚烯烃类热塑性弹性体(TPO),在低温环境下聚丙烯材料受外力作用容易出现断裂与脆化损坏现象。在气囊爆破时,由于气囊展开导致气囊门与风挡玻璃、仪表板特征槽、特征棱或者其它结构干涉引起的气囊门局部断裂与局部断裂飞出,容易在汽车发生事故引发气囊点爆时威胁汽车乘驾人员安全。
因此,对于汽车内饰部件需要在极端低温(-30℃)时保证有足够的韧性,不允许有碎片飞出伤人,另外,随着对内饰部件的要求越来越高,如何解决聚丙烯材料的低温韧性,提升仪表板与气囊框焊接拉脱力,同时提升仪表板本体局部体韧性成为聚丙烯改性材料的重要研究方向。
发明内容
为了解决上述汽车内饰件在低温高速冲击下容易脆性破坏的问题,本发明的目的在于提供一种聚丙烯组合物,该组合物既具有优良的常温和低温冲击性能,又具有低光泽的特点。
本发明是通过以下技术方案实现的:
一种聚丙烯组合物,基于整个组合物,按重量份数计,包括以下组分:
聚丙烯    45份~75份;
弹性体    10份~35份;
聚乙烯    5份~20份;
其中,所述聚丙烯的结晶峰半峰宽为5℃-10℃,优选7℃-9℃,所述聚丙烯的结晶峰峰值温度为105℃-115℃,优选108℃-112℃。结晶峰半峰宽及结晶峰峰值温度按ISO 11357标准在降温速率10℃/分钟条件下测试所得。
所述聚丙烯为均聚聚丙烯,等规指数94%-98%,熔体流动速率MFR在230℃、载荷2.16kg条件下为1g/10min-5g/10min。
所述的弹性体为乙烯-己烯共聚物、乙烯-丁烯共聚物或乙烯-辛烯共聚物的一种或几种
的混合物,其密度为0.850g/cm3-0.865g/cm3,熔体流动速率在190℃、载荷2.16kg条件下为0.1g/10min-3g/10min。
所述聚乙烯为高密度聚乙烯HDPE,其密度为0.94g/cm3-0.97g/cm3,熔体流动速率在190℃、载荷2.16kg条件下为0.01g/10min-0.5g/10min。
本发明所述的聚丙烯组合物,基于整个组合物,按重量份数计,还包括抗氧剂0.1份-0.5份;润滑剂0.1份-0.5份。
所述的抗氧剂为受阻酚抗氧剂和亚磷酸酯类抗氧剂1:1~2的复配物。
所述的润滑剂为聚乙烯蜡或氧化聚乙烯蜡的一种或两种的混合物。
本发明上述的聚丙烯组合物的制备方法,包括如下步骤:
(1)按比例称取各组分,并将聚丙烯、弹性体、聚乙烯在高混机中混合1~3分钟,然后加入抗氧剂和润滑剂后再混合1~3分钟,转速为1000~2000转分钟,得到预混料;
(2)预混料经双螺杆挤出机熔融挤出,螺杆各区温度为190~230℃,真空造粒制得聚丙烯组合物。
本发明还公开了一种由上述的聚丙烯组合物制备的薄膜或片材。该薄膜或片材采用 压延法、压光法、流涎法等方式生产。所述薄膜或片材的厚度为0.01mm~10mm。
本发明还公开了上述的薄膜或片材在汽车内饰产品中的应用,所述汽车内饰产品为仪表板、副仪表板、立柱或门板等。可复合在汽车仪表板背部,参与仪表板注塑成型、摩擦振动焊工艺、激光弱化工艺、软触漆喷涂工艺与其它仪表板等其它零部件的生产工艺。
与现有技术相比,本发明具有如下有益效果:
1.本发明通过采用特定结晶峰半峰宽及结晶峰峰值温度的聚丙烯作为基体树脂,聚乙烯和弹性体协效增韧,所制备的聚丙烯组合物材料具有优良的冲击性能,特别是-30℃低温冲击性能,解决了聚丙烯组合物在-30℃下受外界冲击时容易发生脆性破坏的缺点;
2.将本发明聚丙烯组合物材料制得的薄膜与片材复合在汽车内饰中,不仅能使外部零件在受强大冲击力时不易产生尖锐的碎片,还具有哑光特性;
3.本发明材料制得的薄膜与片材与聚丙烯类热塑性材料具有良好相容性,同时与TPO类材料具有良好相容性,可复合在汽车仪表板B面气囊门区域,可以提升仪表板与气囊框焊接拉脱力,同时提升仪表板本体局部体韧性,提升仪表板气囊门在常温/低温/高温/老化循环后的低速/高速抗冲击性,以防止气囊爆破时,由于气囊展开导致气囊门与风挡玻璃、仪表板特征槽、特征棱或者其它结构干涉引起的气囊门局部断裂与局部断裂飞出,提高汽车仪表板乘员侧气囊展开安全性,在汽车发生事故引发气囊点爆时可以更好的保护汽车乘员侧人员安全;
4.本发明制备工艺简单,设备要求低,产品良品率高,可广泛应用于汽车内饰材料的生产。
具体实施方式
下面给出实施例以对本发明进行具体的描述,但不限于此。
现对实施例及对比例所用的原材料做如下说明,但不限于这些材料:
聚丙烯1:等规指数为94%,MFR(230℃、2.16kg)为1.0g/10min,聚丙烯的结晶峰半峰宽为5℃,聚丙烯的结晶峰峰值温度为110℃;
聚丙烯2:等规度为95%,MFR(230℃、2.16kg)为3.0g/10min,聚丙烯的结晶峰半峰宽为7.3℃,聚丙烯的结晶峰峰值温度为105℃;
聚丙烯3:等规度为98%,MFR(230℃、2.16kg)为5.0g/10min,聚丙烯的结晶峰半峰宽为10℃,聚丙烯的结晶峰峰值温度为108℃;
聚丙烯4:等规度为96%,MFR(230℃、2.16kg)为4.0g/10min,聚丙烯的结晶峰半峰宽为9℃,聚丙烯的结晶峰峰值温度为112℃;
聚丙烯5:等规度为96%,MFR(230℃、2.16kg)为2.0g/10min,聚丙烯的结晶峰半峰宽 为5℃,聚丙烯的结晶峰峰值温度为115℃;
聚丙烯6:等规度为98%,MFR(230℃、2.16kg)为8.0g/10min,聚丙烯的结晶峰半峰宽为12℃,聚丙烯的结晶峰峰值温度为125℃;
聚丙烯7:等规度为98%,MFR(230℃、2.16kg)为0.5g/10min,聚丙烯的结晶峰半峰宽为4.8℃,聚丙烯的结晶峰峰值温度为102℃;
乙烯-己烯共聚物:密度为0.860g/cm3,MFR(190℃、2.16kg)为0.5g/10min;
乙烯-丁烯共聚物:密度为0.865g/cm3,MFR(190℃、2.16kg)为0.5g/10min;
乙烯-辛烯共聚物:密度为0.855g/cm3,MFR(190℃、2.16kg)为1.0g/10min;
乙烯-丙烯共聚物:密度为0.856g/cm3,MFR为(190℃、2.16kg)1.0g/10min;
高密度聚乙烯1:密度为0.94g/cm3,MFR(190℃、2.16kg)为0.01g/10min;
高密度聚乙烯2:密度为0.95g/cm3,MFR(190℃、2.16kg)为0.05g/10min;
高密度聚乙烯3:密度为0.97g/cm3,MFR(190℃、2.16kg)为0.5g/10min;
高密度聚乙烯4:密度为0.95g/cm3,MFR(190℃、2.16kg)为8.0g/10min;
抗氧剂:抗氧剂为受阻酚抗氧剂1010和亚磷酸酯类抗氧剂168按1:1的复配物。
实施例1-8:
按表1所示重量份数称取组分,将聚丙烯、弹性体、高密度聚乙烯先在高混机中混合3分钟,然后加入抗氧剂和润滑剂,再混合2分钟,转速为2000转分钟,得到预混料;预混料经双螺杆挤出机熔融挤出,螺杆各区温度维持在190~230℃,真空造粒制得良好低温韧性的聚丙烯组合物,按标准制成相应的测试样条,并测定其力学性能,具体数值列于表1。
表1实施例中聚丙烯组合物组成及性能
Figure PCTCN2016098938-appb-000001
对比例1-6:
按表2所示重量份数称取组分,制备方法同实施例,性能测试数值列于表2。
表2对比例聚丙烯组合物组成及性能
Figure PCTCN2016098938-appb-000002
各性能测试按如下表3的标准进行:
表3:
测试项目 单位 测试标准
熔体流动速率 g/10min ISO 1133
密度 g/cm2 ISO 1183
拉伸强度 MPa ISO 527-1,527-2
断裂伸长率 ISO 527-1,527-2
弯曲强度 MPa ISO 178
弯曲模量 MPa ISO 178
悬臂梁缺口冲击强度(23℃) kJ/m2 ISO 180
悬臂梁缺口冲击强度(-30℃) kJ/m2 ISO 180
光泽度(60°)   ASTM D523
结晶度半峰宽 ISO 11357
结晶峰峰值温度 ISO 11357
由各实施例与对比例的力学性能和光泽度测试结果可以看出,本发明通过采用特定结晶峰半峰宽及结晶峰峰值温度的聚丙烯作为基体树脂,聚乙烯和弹性体协效增韧,所制备的聚丙烯组合物材料的冲击性能得到很大的提高,特别是-30℃低温冲击性能,制得的材料除了具有良好的冲击韧性外,光泽度还较低,将其制成薄膜或片材应用于汽车内饰中,可有效解决汽车内饰件在低温高速冲击下容易脆性破坏的问题。

Claims (12)

  1. 一种聚丙烯组合物,其特征在于,基于整个组合物,按重量份数计,包括以下组分:
    聚丙烯   45份~75份;
    弹性体  10份~35份;
    聚乙烯   5份~20份;
    其中,所述聚丙烯的结晶峰半峰宽为5℃-10℃,优选7℃-9℃,优选所述聚丙烯的结晶峰峰值温度为105℃-115℃,优选108℃-112℃,结晶峰半峰宽及结晶峰峰温度值按ISO 11357标准在降温速率10℃/分钟条件下测试所得。
  2. 根据权利要求1所述的聚丙烯组合物,其特征在于,所述聚丙烯为均聚聚丙烯,等规指数94%-98%,熔体流动速率在230℃、载荷2.16kg条件下为1g/10min-5g/10min。
  3. 根据权利要求1所述的聚丙烯组合物,其特征在于,所述的弹性体为乙烯-己烯共聚物、乙烯-丁烯共聚物或乙烯-辛烯共聚物的一种或几种的混合物,其密度为0.850g/cm3-0.865g/cm3,熔体流动速率在190℃、载荷2.16kg条件下为0.1g/10min-3g/10min。
  4. 根据权利要求1所述的聚丙烯组合物,其特征在于,所述聚乙烯为高密度聚乙烯HDPE,其密度为0.94g/cm3-0.97g/cm3,熔体流动速率在190℃、载荷2.16kg条件下为0.01g/10min-0.5g/10min。
  5. 根据权利要求1所述的聚丙烯组合物,其特征在于,基于整个组合物,按重量份数计,还包括抗氧剂0.1份-0.5份;润滑剂0.1份-0.5份。
  6. 根据权利要求5所述的聚丙烯组合物,其特征在于,所述的抗氧剂为受阻酚抗氧剂和亚磷酸酯类抗氧剂1:1~2的复配物。
  7. 根据权利要求5所述的聚丙烯组合物,其特征在于,所述的润滑剂为聚乙烯蜡或氧化聚乙烯蜡的一种或两种的混合物。
  8. 权利要求1~7任一项所述的聚丙烯组合物的制备方法,其特征在于,包括如下步骤:
    (1)按比例称取各组分,并将聚丙烯、弹性体、聚乙烯在高混机中混合1~3分钟,然后加入抗氧剂和润滑剂后再混合1~3分钟,转速为1000~2000转分钟,得到预混料;
    (2)预混料经双螺杆挤出机熔融挤出,螺杆各区温度为190~230℃,真空造粒制得聚丙烯组合物。
  9. 一种由权利要求1~7任一项所述的聚丙烯组合物制备的薄膜或片材。
  10. 根据权利要求9所述的薄膜或片材,其特征在于,所述薄膜或片材的厚度为0.01mm~10mm。
  11. 权利要求9或10所述的薄膜或片材在汽车内饰产品中的应用。
  12. 根据权利要求11所述的应用,其特征在于,所述汽车内饰产品为仪表板、副仪表板、立柱或门板。
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