WO2023185504A1 - 一种长玻纤增强聚丙烯材料及其制备方法与应用 - Google Patents

一种长玻纤增强聚丙烯材料及其制备方法与应用 Download PDF

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WO2023185504A1
WO2023185504A1 PCT/CN2023/082077 CN2023082077W WO2023185504A1 WO 2023185504 A1 WO2023185504 A1 WO 2023185504A1 CN 2023082077 W CN2023082077 W CN 2023082077W WO 2023185504 A1 WO2023185504 A1 WO 2023185504A1
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long glass
glass fiber
parts
fiber reinforced
aluminum powder
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PCT/CN2023/082077
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English (en)
French (fr)
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刘纪庆
陈平绪
叶南飚
张超
张永
安朋
邱志强
许建稳
刘明
王飞
叶士兵
肖军华
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江苏金发科技新材料有限公司
上海金发科技发展有限公司
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Publication of WO2023185504A1 publication Critical patent/WO2023185504A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2477/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2487/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
    • 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
    • C08K3/08—Metals
    • C08K2003/0812—Aluminium
    • 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
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • 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
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • 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
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass

Definitions

  • the invention relates to the field of polymer materials, in particular to a long glass fiber reinforced polypropylene material and its preparation method and application.
  • spray-free materials can avoid the spraying process and can enhance the competitiveness of products under the dual-carbon policy of "carbon neutrality and carbon peaking".
  • CN201710383662 provides a spray-free PP material with metallic luster, including 90% to 97% PP, 1% to 5% aluminum silver bars, 0.2% to 0.3% antioxidant, 0.1% to 0.2% antioxidant UV additive, 0.1% ⁇ 0.5% wax powder.
  • This spray-free PP material uses aluminum silver bars with good dispersion and matrix resin PP materials.
  • the spray-free PP material produced has high reflectivity.
  • the aluminum silver bars (particle size 30-35 ⁇ m) are evenly dispersed in the PP material and the metallic gloss is high. high.
  • CN102942742A provides a spray-free PP material with metallic flashing effect, including 97%-99% random PP, 0.2%-0.8% antioxidant, 0.1%-1% lubricant, 0.3%-1.5% effect pigments.
  • This spray-free PP material can be directly injected without spraying to achieve good high gloss, pearlescent sparkle and metallic spray paint effect. It has a good appearance, saves costs compared with the spray paint process, and avoids the problem of paint peeling during the use of the product.
  • CN106279971A discloses a spray-free high-gloss PP material, including 6% to 9% tetrahydrofuran, 0.1% to 0.3% tetrakis triphenylphosphine palladium, 1% to 2% pearlescent powder, 1% to 2% color Powder, 0.3% to 0.5% lubricant, 0.3% to 0.5% nucleating agent, 0.3% to 0.5% liquid form of grain removal and brightening agent, 0.5% to 0.8% liquid form of flow modifier, 0.3% to 0.8% liquid phase solvent, and the balance is PP powder.
  • the product has a good surface gloss effect, forming a uniform and continuous pearlescent powder layer on the surface of the product, with no flow lines and a strong texture.
  • the above spray-free polypropylene materials are all spray-free materials without reinforcement system. This is because during the melting and blending process of aluminum powder and glass fiber in the twin-screw, the aluminum powder is easily sheared and broken by the glass fiber, and the original surface metallic luster cannot be maintained. . In addition, some metal powders or pearlescent powders are easily dispersed unevenly and accumulate in the resin system, resulting in uneven product color. Metal powders or pearlescent powders will reduce the tensile properties and toughness of the material. At the same time, this type of system material has poor scratch resistance.
  • the purpose of the present invention is to overcome the above-mentioned shortcomings of the prior art and provide a long glass fiber reinforced polypropylene material and its preparation method and application.
  • This material requires no spraying, has excellent metallic effect, and has good tensile properties, scratch resistance and high toughness.
  • the technical solution adopted by the present invention is: a long glass fiber reinforced polypropylene material, including the following components by weight: 12.8-78.2 parts of polypropylene resin, 5-20 parts of polyamide resin, 3-5 parts of compatibilizer, 3-10 parts of nylon elastomer, 10-40 parts of long glass fiber, 0.2-5 parts of aluminum powder, 0-0.7 parts of additives.
  • the long glass fiber reinforced polypropylene material includes the following components by weight: 28-70 parts of polypropylene resin, 10-15 parts of polyamide resin, 3-5 parts of compatibilizer, 4-5 parts of nylon elastomer 6 parts, 30-40 parts of long glass fiber, 2-4 parts of aluminum powder, 0.2-0.5 parts of additives.
  • the melt flow rate of the polypropylene resin is 10-150g/10min (test conditions 230°C, 2.16kg, test standard ISO1133).
  • the melt flow rate of the polypropylene resin is less than 10g/10min, the resin will not be able to fully impregnate the glass fiber, and the impregnation die will return material or break seriously, making smooth production impossible.
  • the polyamide resin is at least one of polyamide 6 (PA6), polyamide 610 (PA610), and polyamide 612 (PA612).
  • the compatibilizer is polypropylene grafted maleic anhydride (PP-G-MAH).
  • the nylon elastomer is a copolymer composed of PA6 as the hard segment and propylene oxide polyether as the soft segment.
  • the long glass fiber is twisted coarse sand, and the single filament diameter is 7-18 ⁇ m.
  • the aluminum powder is a mixture of aluminum powder with a particle size of 55-100 ⁇ m (D50) and aluminum powder with a particle size of 5-15 ⁇ m; more preferably, aluminum powder with a particle size of 55-100 ⁇ m and aluminum powder with a particle size of 5-15 ⁇ m are mixed according to the mass. Ratio (3-8): 1 compound.
  • the auxiliary agent is at least one of an antioxidant and a lubricant.
  • the preparation method of the above long glass fiber reinforced polypropylene material includes the following steps: Mix polypropylene resin, polyamide resin, compatibilizer, nylon elastomer, aluminum powder and additives evenly at 275-330°C, 400-800r/ min conditions, the resulting resin additive melt infiltrates long glass fibers at 320-350°C to obtain long glass fiber reinforced polypropylene materials.
  • the long glass fiber reinforced polypropylene material is cooled, shaped, and pelletized to obtain the finished product.
  • the pellets are cut into lengths of 6 ⁇ 3mm or 10 ⁇ 3mm.
  • the melt plasticization and homogenization are achieved using a twin-screw extruder.
  • a twin-screw extruder Through the LFT pultrusion process, aluminum powder and glass fiber will not appear in the twin-screw extruder at the same time, preventing the metal aluminum powder from being excessively damaged by the strong shearing of the glass fiber in the extruder and affecting the metal effect.
  • the infiltration is achieved using an infiltration die.
  • the resin additive melt is passed through the infiltration die, and the traction equipment pulls the long glass fiber through the infiltration die to realize the infiltration of the long glass fiber by the resin additive melt.
  • the pulling speed is 40-90m/min.
  • Appearance structural parts can be car lower fenders, foot supports, power tool handles, traffic joints, car door handles, rearview mirror brackets and other parts.
  • the present invention achieves the metallic scintillating effect of the material through long glass fibers and aluminum powder of different particle sizes: the large particle size aluminum powder orients along with the melt flow direction together with part of the long glass fiber to provide a uniform metallic effect, while small particles Diameter aluminum powder is interspersed in the long glass fiber skeleton structure to provide a glittering metal dot effect. Secondly, aluminum powder is distributed on the surface of the part to cover floating fibers. Furthermore, long glass fibers are interspersed with each other to provide a three-dimensional fiberglass skeleton structure inside the injection molded parts, avoiding the degradation of material performance caused by the addition of aluminum powder.
  • the material adopts a spray-free process to obtain a beautiful metallic effect on the surface of the product, reducing the defective rate of the product, reducing pollution, especially carbon emissions, and reducing energy consumption.
  • polyamide By adding polyamide, the surface hardness of the material is increased and the scratch resistance of the composite material is provided.
  • Nylon elastomer improves the impact resistance of modified materials, especially low-temperature impact toughness.
  • the material of the invention has excellent metallic effect, good scratch resistance, tensile properties and high toughness.
  • Figure 1 is a rendering of long glass fiber reinforced polypropylene material products with no flow marks and no floating fibers.
  • Figure 2 is a rendering of a long glass fiber reinforced polypropylene material product with severe flow marks and obvious floating fibers.
  • Figure 3 is a rendering of long glass fiber reinforced polypropylene material products with flow marks and no floating fibers.
  • the experimental methods used are conventional methods unless otherwise specified, and the materials and reagents used can be obtained from commercial sources unless otherwise specified.
  • Polypropylene resin 1 Formosa Plastics, K9026; the melt flow rate measured according to ISO 1133 standard using a weight of 2.16kg at a temperature of 230°C is 26g/10min;
  • Polypropylene resin 2 LG, MH7900; melt flow rate measured according to ISO 1133 standard using a weight of 2.16kg at a temperature of 230°C is 150g/10min;
  • Polypropylene resin 3 Zhenhai Petrochemical, PP PPH-T03; the melt flow rate measured according to ISO 1133 standard using a weight of 2.16kg at a temperature of 230°C is 4g/10min;
  • Polyamide resin 1 PA6, Haiyang chemical fiber, HY2500A;
  • Polyamide resin 2 PA610, Shandong Guangyin New Materials Co., Ltd., F120;
  • Polyamide resin 3 PA612, Shanghai Yinggu Chemical Co., Ltd., A150;
  • Polypropylene grafted with maleic anhydride Arkema, CA100;
  • Nylon elastomer Atochem, 5512MNOO; a copolymer composed of PA6 as the hard segment and propylene oxide polyether as the soft segment;
  • Polyolefin elastomer POE ENGAGE 8137, Dow;
  • Long glass fiber Chongqing International Composite Materials Co., Ltd., ER4301R-2400; twisted coarse sand, single filament diameter 17 ⁇ m respectively;
  • Short wave fiber Chongqing International Composite Materials Co., Ltd., ECS301HP-3-H;
  • Aluminum powder 1 Hefei Xuyang, TH5390 (particle size 85 ⁇ 2 ⁇ m) and XYC710 (particle size 10 ⁇ 2 ⁇ m) are compounded according to a mass ratio of 3:1;
  • Aluminum powder 2 Hefei Xuyang, TH5390 (particle size 85 ⁇ 2 ⁇ m) and XYC710 (particle size 10 ⁇ 2 ⁇ m) are compounded according to a mass ratio of 2:1;
  • Aluminum powder 3 Hefei Xuyang, TH5390 (particle size 85 ⁇ 2 ⁇ m) and XYC710 (particle size 10 ⁇ 2 ⁇ m) are compounded according to a mass ratio of 9:1;
  • Aluminum powder 4 Hefei Xuyang, TH5390 (particle size 85 ⁇ 2 ⁇ m) and XYC710 (particle size 10 ⁇ 2 ⁇ m) are compounded according to a mass ratio of 8:1;
  • antioxidant 1010, commercially available
  • lubricant erucamide, commercially available
  • the mass ratio of antioxidant and lubricant is 1:1.
  • the components and weight parts of the long glass fiber reinforced polypropylene materials of Examples 1-8 and Comparative Examples 1-12 are as shown in Tables 1 and 2.
  • the preparation method of the polypropylene composite materials of Examples 1-8 and Comparative Examples 1-12 includes the following Steps: Mix polypropylene resin, polyamide resin, compatibilizer, nylon elastomer aluminum powder and additives evenly, then feed them into the twin-screw extruder from a weighing scale for melting, plasticization and homogenization, and set the temperature of the twin-screw extruder. 290°C, rotation speed 600r/min.
  • the obtained resin additive melt is transported to the infiltration die, and the temperature of the infiltration die is set to 340°C.
  • the traction equipment pulls the long glass fiber through the infiltration die at a pulling speed of 50m/min to achieve the infiltration of the long glass fiber with the resin additive melt. After perfect infiltration, long glass fiber reinforced polypropylene material strips are obtained, and then after cooling, shaping and pelletizing, a finished product of 10mm length is obtained.
  • Low-temperature falling ball impact performance test and evaluation method Inject the material into a 2mm square plate and store it in a -40°C environment for 24 hours. Use a 500g iron ball and a 40mm falling ball to drop the impact and observe whether there are cracks.
  • Metal effect evaluation method observe whether the metal effect is uniform, whether the flashing effect is obvious, whether there are flow marks and floating fiber defects: the more uniform the metal effect, the more obvious the flashing effect, the better the spraying effect, * represents the visual effect, the more * It means the better the effect.
  • Evaluation method of scratch resistance effect According to PV3952 standard, scratch with 15N force, and test the ⁇ L value of scratch resistance effect.
  • the invention adds polyamide and nylon elastomer to improve the scratch resistance and impact resistance of the modified material. performance, especially low temperature impact toughness. Adding an appropriate proportion of aluminum powder can improve the impact strength of the material, metal flashing effect, and metal uniformity effect, and the parts will have no flow marks and floating fibers.
  • the material of the present invention combines excellent metallic effects, tensile properties, scratch resistance and high toughness.
  • Figure 1 is a rendering of the long glass fiber reinforced polypropylene material in Example 3. It can be seen that the material presents a uniform metallic effect, has a flashing metal dot effect, and covers floating fibers well without flow marks. Examples 1, 2, and 7 use less long glass fibers, but the tensile strength and normal temperature notched impact strength still reach relatively high levels.
  • Comparative Example 1 the short glass fiber has poor toughness, very poor metal effect, severe flow marks and obvious floating fibers; Comparative Example 2: No polyamide, the metal effect is OK, but the toughness is poor, and the appearance is poor.
  • Comparative Example 3 No aluminum powder added, unable to achieve metallic effect; Comparative Example 4: No nylon elastomer, poor toughness; Comparative Example 5: Too little aluminum powder, poor metallic effect, and flow marks , the scintillating effect is poor; Comparative Example 6: Too much aluminum powder is used, there are flow marks, and the scintillating effect is poor; Comparative Example 7: The proportion of small particle size aluminum powder is too large, the metal uniformity effect is poor, and there are flow marks; Comparative Example 8: The proportion of large particle size aluminum powder is too large, the scintillation effect is poor, and there are flow marks; Comparative Example 9: The resin cannot fully impregnate the glass fiber, and the impregnation die returns material or breaks seriously, making it impossible to produce smoothly; Comparative Example 10: Metal The effect and flicker effect are poor, and the low-temperature ball impact strength is poor; Comparative Example 11: The metallic effect and flicker effect are poor, the low-temperature ball impact strength is poor, and there are floating

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Abstract

本发明公开了一种长玻纤增强聚丙烯材料及其制备方法与应用，材料包括以下组分：聚丙烯树脂、聚酰胺树脂、相容剂、尼龙弹性体、长玻纤、铝粉、助剂。本发明通过长玻纤和不同粒径复配的铝粉，实现均匀金属闪烁效果；铝粉分布于制件表面，遮盖浮纤；长玻纤相互穿插，规避因添加铝粉导致的材料性能降低；添加聚酰胺、尼龙弹性体，提高耐划伤性能和耐冲击性能。本材料适用于外观结构件，免喷涂，具有广泛应用前景。

Description

一种长玻纤增强聚丙烯材料及其制备方法与应用 技术领域
本发明涉及高分子材料领域，尤其是一种长玻纤增强聚丙烯材料及其制备方法与应用。
背景技术
免喷涂材料作为一种环保产品，可避免喷漆环节，在“碳中和、碳达峰”双碳政策下，可增强产品的竞争力。
CN201710383662提供了一种具有金属光泽的免喷涂PP材料，包括90％～97％的PP、1％～5％的铝银条、0.2％～0.3％的抗氧剂、0.1％～0.2％的抗UV助剂、0.1％～0.5％的蜡粉。该免喷涂PP材料选用分散性好的铝银条以及基体树脂PP材料，制得的免喷涂PP材料反射率高，铝银条(粒径30-35μm)在PP材料中分散均匀，金属光泽度高。
CN102942742A提供了一种具有金属闪烁效果的免喷涂PP材料，包括97％-99％的无规PP、0.2％-0.8％的抗氧剂、0.1％-1％的润滑剂、0.3％-1.5％的效果颜料。该免喷涂PP材料无需喷涂直接注塑即可获得良好的高光泽和珠光闪烁以及金属喷漆效果，具备良好外观，与喷漆工艺相比节约了成本，同时避免了制品使用过程中的脱漆问题。
CN106279971A公开了一种免喷涂的高光PP材料，包括6％～9％的四氢呋喃，0.1％～0.3％的四三苯基膦钯，1％～2％的珠光粉，1％～2％的色粉，0.3％～0.5％的润滑剂，0.3％～0.5％的成核剂，0.3％～0.5％的液体形状的去纹增亮剂，0.5％～0.8％的液体形状的流动改性剂，0.3％～0.8％的液体形状的相溶剂，余量为PP粉。该产品表面高光效果好，在产品的表面形成均匀和连续的珠光粉层，且无流纹，质感强。
以上免喷涂聚丙烯材料均属于无增强体系免喷涂材料，这是因为铝粉与玻璃纤维在双螺杆熔融共混过程中，铝粉容易被玻纤剪切破碎，无法保持原有的表面金属光泽。此外，部分金属粉或珠光粉容易分散不均，在树脂体系内形成堆积，导致产品颜色不均匀，且金属粉或珠光粉会降低材料的拉伸性能和韧性。同时此类体系材料耐划伤效果比较差。
发明内容
基于此，本发明的目的在于克服上述现有技术的不足之处，提供一种长玻纤增强聚丙烯材料及其制备方法与应用。该材料免喷涂，具有优异的金属效果，同时具有良好的拉伸性能、耐划伤性能以及高韧性。
为实现上述目的，本发明所采取的技术方案为：一种长玻纤增强聚丙烯材料，包括以下重量份计的组分：聚丙烯树脂12.8-78.2份、聚酰胺树脂5-20份、相容剂3-5份、尼龙弹性体3-10份、长玻纤10-40份、铝粉0.2-5份、助剂0-0.7份。
优选地，所述长玻纤增强聚丙烯材料包括以下重量份计的组分：聚丙烯树脂28-70份、聚酰胺树脂10-15份、相容剂3-5份、尼龙弹性体4-6份、长玻纤30-40份、铝粉2-4份、助剂0.2-0.5份。
优选地，所述聚丙烯树脂的熔体流动速率为10-150g/10min(测试条件230℃、2.16kg，测试标准ISO1133)。当聚丙烯树脂的熔体流动速率小于10g/10min时，将无法实现树脂充分浸渍玻纤，浸渍模头返料或断条严重，无法顺利生产。
优选地，所述聚酰胺树脂为聚酰胺6(PA6)、聚酰胺610(PA610)、聚酰胺612(PA612)中的至少一种。
优选地，所述相容剂为聚丙烯接枝马来酸酐(PP-G-MAH)。
优选地，所述尼龙弹性体是以PA6为硬段、以环氧丙烷聚醚为软段组成的共聚物。
优选地，所述长玻纤为有捻粗砂，单丝直径为7-18μm。
优选地，所述铝粉为55-100μm粒径(D50)铝粉与5-15μm粒径铝粉的混合物；更优选地，55-100μm粒径铝粉与5-15μm粒径铝粉按照质量比(3-8)：1复配。
优选地，所述助剂为抗氧剂、润滑剂中的至少一种。
上述长玻纤增强聚丙烯材料的制备方法，包括以下步骤：将聚丙烯树脂、聚酰胺树脂、相容剂、尼龙弹性体、铝粉和助剂混合均匀，275-330℃、400-800r/min条件下熔融塑化均化，得到的树脂助剂熔体320-350℃浸润长玻纤，得到长玻纤增强聚丙烯材料。
优选地，所述长玻纤增强聚丙烯材料经过冷却、定形、切粒，即得成品。
优选地，所述切粒为切成6±3mm或10±3mm长度。
优选地，所述熔融塑化均化采用双螺杆挤出机实现。通过LFT的拉挤工艺，使铝粉和玻璃纤维不会同时出现在双螺杆挤出机中，避免金属铝粉在挤出机中被玻纤强剪切过分破坏而影响金属效果。
优选地，所述浸润采用浸润模头实现，将树脂助剂熔体通过浸润模头，牵引设备牵引长玻纤经过浸润模头，实现树脂助剂熔体对长玻纤的浸润。
优选地，所述牵引的速度为40-90m/min。
上述长玻纤增强聚丙烯材料在制备耐划伤、抗冲击的外观结构件中的应用。外观结构件可以是汽车下护板、脚撑、电动工具把手、通车关节、汽车门把手、后视镜支架等零件。
相对于现有技术，本发明的有益效果为：
本发明通过长玻纤和不同粒径复配的铝粉，实现材料的金属闪烁效果：大粒径铝粉随着熔体流动方向与部分长玻纤一起取向，提供均匀的金属效果，小粒径铝粉穿插在长玻纤骨架结构中，提供闪烁金属点效果。其次，铝粉分布于制件表面，起到遮盖浮纤的作用。再者，长玻纤相互穿插，提供注塑制件内部的玻纤三维骨架结构，规避因添加铝粉导致的材料性能降低。材料采用免喷涂工艺即可在制品表面获得绚丽金属效果，降低制品不良率，减少污染，尤其是碳排放，降低能耗。通过添加聚酰胺提高材料表面硬度，提供复合材料耐划伤性能。尼龙弹性体提高改性材料的耐冲击性能，特别是低温冲击韧性。本发明的材料具有优异的金属效果，同时具有良好的耐划伤性能、拉伸性能以及高韧性。
附图说明
图1为无流痕无浮纤的长玻纤增强聚丙烯材料制品效果图。
图2为严重流痕且明显浮纤的长玻纤增强聚丙烯材料制品效果图。
图3为有流痕无浮纤的长玻纤增强聚丙烯材料制品效果图。
具体实施方式
为更好的说明本发明的目的、技术方案和优点，下面将结合具体实施例和附图对本发明作进一步说明。
实施例中，所使用的实验方法如无特殊说明，均为常规方法，所用的材料、试剂等，如无特殊说明，均可从商业途径得到。
现对实施例及对比例所用原料做如下说明，但不限于这些材料：
聚丙烯树脂1：台塑，K9026；根据ISO 1133标准使用2.16kg重量在230℃的温度下测量的熔体流动速率为26g/10min；
聚丙烯树脂2：LG，MH7900；根据ISO 1133标准使用2.16kg重量在230℃的温度下测量的熔体流动速率为150g/10min；
聚丙烯树脂3：镇海石化，PP PPH-T03；根据ISO 1133标准使用2.16kg重量在230℃的温度下测量的熔体流动速率为4g/10min；
聚酰胺树脂1：PA6，海阳化纤，HY2500A；
聚酰胺树脂2：PA610，山东广垠新材料有限公司，F120；
聚酰胺树脂3：PA612，上海盈固化工有限公司，A150；
聚丙烯接枝马来酸酐：阿科玛，CA100；
尼龙弹性体：Atochem，5512MNOO；以PA6为硬段、以环氧丙烷聚醚为软段组成的共聚物；
聚烯烃弹性体：POE ENGAGE 8137，陶氏；
长玻纤：重庆国际复合材料有限公司，ER4301R-2400；有捻粗砂，单丝直径分别为17μm；
短波纤：重庆国际复合材料有限公司，ECS301HP-3-H；
铝粉1：合肥旭阳，TH5390(粒径85±2μm)和XYC710(粒径10±2μm)按照质量比3：1复配；
铝粉2：合肥旭阳，TH5390(粒径85±2μm)和XYC710(粒径10±2μm)按照质量比2：1复配；
铝粉3：合肥旭阳，TH5390(粒径85±2μm)和XYC710(粒径10±2μm)按照质量比9：1复配；
铝粉4：合肥旭阳，TH5390(粒径85±2μm)和XYC710(粒径10±2μm)按照质量比8：1复配；
助剂：抗氧剂，1010，市售；润滑剂，芥酸酰胺，市售；抗氧剂和润滑剂的质量比为1：1。
实施例1-8及对比例1-12
实施例1-8及对比例1-12的长玻纤增强聚丙烯材料的组分及重量份如表1和2所示。实施例1-8及对比例1-12的聚丙烯复合材料的制备方法，包括如下 步骤：将聚丙烯树脂、聚酰胺树脂、相容剂、尼龙弹性体铝粉和助剂混合均匀，由计量秤喂入双螺杆挤出机熔融塑化均化，双螺杆挤出机温度设定290℃，转速600r/min。得到的树脂助剂熔体输送至浸润模头，浸润模头温度设定为340℃。牵引设备牵引长玻纤由浸润模头经过，牵引速度为50m/min，实现树脂助剂熔体对长玻纤的浸润。浸润完善即得到长玻纤增强聚丙烯材料的料条，再经过冷却、定形、切粒，得到10mm长度的成品。
表1实施例中的原材料组分及重量份
表2对比例中的原材料组分及重量份

效果例性能测试
将实施例1-8及对比例1-12制备的长玻纤增强聚丙烯材料进行相关性能测试，具体测试方法如下：
力学性能测试评价方法：按照ISO527-1/2标准，23℃测试样条的拉伸强度；根据ISO179/1eA标准，测试样条在23℃下的缺口冲击强度。
低温落球冲击性能测试评价方法：材料注塑2mm方板，-40℃环境存放24h，用500g铁球，40mm落球跌落冲击，观察是否有裂纹。
金属效果评价方法：观察金属效果是否均匀，闪烁效果是否明显，是否有流痕和浮纤缺陷：金属效果越均匀，闪烁效果越明显，喷涂效果越好，以*代表目视效果，*越多代表效果越佳。
耐划伤效果评价方法：按照PV3952标准，15N力划伤，测试耐划伤效果△L值。
浮纤和流痕评级方法：目视。无浮纤且无流痕的状态如图1所示，严重流痕且明显浮纤的状态如图2所示，无浮纤但有流痕的状态如图3所示。
表3实施例的性能测试结果

表4对比例的性能测试结果
本发明添加聚酰胺和尼龙弹性体，提高改性材料的耐划伤性能和耐冲击性 能，特别是低温冲击韧性。添加适当比例的铝粉，提高材料冲击强度、金属闪烁效果、金属均匀效果，制件无流痕和浮纤。本发明的材料兼具优异的金属效果、拉伸性能、耐划伤性能及高韧性。图1是实施例3的长玻纤增强聚丙烯材料效果图，可以看出，该材料呈现均匀的金属效果，具有闪烁金属点效果，很好地遮盖了浮纤，没有流痕。实施例1、2、7使用较少的长玻纤少，但拉伸强度和常温缺口冲击强度仍达到比较高的水平。
表4的数据可以看出：对比例1，短玻纤韧性差，金属效果非常差，严重流痕且明显浮纤；对比例2：无聚酰胺，金属效果可以，但韧性差，外观差，耐划伤效果差；对比例3：无铝粉添加，无法实现金属效果；对比例4：无尼龙弹性体，韧性差；对比例5：铝粉用量过少，金属效果不佳，有流痕，闪烁效果不佳；对比例6：铝粉用量过多，有流痕，，闪烁效果不佳；对比例7：小粒径铝粉比例过大，金属均匀效果差，有流痕；对比例8：大粒径铝粉比例过大，闪烁效果差，有流痕；对比例9：无法实现树脂充分浸渍玻纤，浸渍模头返料或断条严重，无法顺利生产；对比例10：金属效果和闪烁效果不佳，低温落球冲击强度差；对比例11：金属效果和闪烁效果不佳，低温落球冲击强度差，有浮纤；对比例12：使用聚烯烃弹性体，金属效果和闪烁效果不佳，低温落球冲击强度差。
最后所应当说明的是，以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制，尽管参照较佳实施例对本发明作了详细说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的实质和范围。

Claims (10)

  1. 一种长玻纤增强聚丙烯材料，其特征在于，包括以下重量份计的组分：聚丙烯树脂12.8-78.2份、聚酰胺树脂5-20份、相容剂3-5份、尼龙弹性体3-10份、长玻纤10-40份、铝粉0.2-5份、助剂0-0.7份。
  2. 根据权利要求1所述长玻纤增强聚丙烯材料，其特征在于，所述长玻纤增强聚丙烯材料包括以下重量份计的组分：聚丙烯树脂28-70份、聚酰胺树脂10-15份、相容剂3-5份、尼龙弹性体4-6份、长玻纤30-40份、铝粉2-4份、助剂0.2-0.5份。
  3. 根据权利要求1所述长玻纤增强聚丙烯材料，其特征在于，
    所述聚酰胺树脂为PA6、PA610、PA612中的至少一种；
    所述相容剂为聚丙烯接枝马来酸酐；
    所述尼龙弹性体是以PA6为硬段、以环氧丙烷聚醚为软段组成的共聚物。
  4. 根据权利要求1所述长玻纤增强聚丙烯材料，其特征在于，所述聚丙烯树脂在230℃、2.16kg测试条件下的熔体流动速率为10-150g/10min。
  5. 根据权利要求1所述长玻纤增强聚丙烯材料，其特征在于，所述长玻纤为有捻粗砂，单丝直径为7-18μm。
  6. 根据权利要求1所述长玻纤增强聚丙烯材料，其特征在于，所述铝粉为55-100μm粒径铝粉与5-15μm粒径铝粉的混合物。
  7. 根据权利要求6所述长玻纤增强聚丙烯材料，其特征在于，所述55-100μm粒径铝粉与5-15μm粒径铝粉按照质量比(3-8)：1复配。
  8. 根据权利要求1所述长玻纤增强聚丙烯材料，其特征在于，所述助剂为抗氧剂、润滑剂中的至少一种。
  9. 权利要求1-8任一项所述长玻纤增强聚丙烯材料的制备方法，其特征在于，包括以下步骤：将聚丙烯树脂、聚酰胺树脂、相容剂、尼龙弹性体、铝粉和助剂混合均匀，275-330℃、400-800r/min条件下熔融塑化均化，得到的树脂助剂熔体320-350℃浸润长玻纤，得到长玻纤增强聚丙烯材料；
    所述长玻纤增强聚丙烯材料经过冷却、定形、切粒，即得成品；
    所述熔融塑化均化采用双螺杆挤出机实现；
    所述浸润采用浸润模头实现。
  10. 权利要求1-8任一项所述长玻纤增强聚丙烯材料在制备耐划伤、抗冲 击的外观结构件中的应用。
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