WO2021057355A1 - 一种低收缩、低线性膨胀系数聚丙烯复合材料及制备方法 - Google Patents

一种低收缩、低线性膨胀系数聚丙烯复合材料及制备方法 Download PDF

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WO2021057355A1
WO2021057355A1 PCT/CN2020/110657 CN2020110657W WO2021057355A1 WO 2021057355 A1 WO2021057355 A1 WO 2021057355A1 CN 2020110657 W CN2020110657 W CN 2020110657W WO 2021057355 A1 WO2021057355 A1 WO 2021057355A1
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composite material
polypropylene
expansion coefficient
linear expansion
low
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PCT/CN2020/110657
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English (en)
French (fr)
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俞飞
黄险波
叶南飚
罗忠富
陈嘉杰
李志鹏
李振华
吴国峰
杨波
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金发科技股份有限公司
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Publication of WO2021057355A1 publication Critical patent/WO2021057355A1/zh

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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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/2224—Magnesium hydroxide
    • 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
    • C08K2201/011—Nanostructured additives

Definitions

  • the invention relates to a polypropylene composite material and a preparation method thereof, in particular to a polypropylene composite material with low shrinkage and low linear expansion coefficient and a preparation method.
  • Polypropylene materials are widely used in automobiles, home appliances, packaging, electronic appliances and other fields due to their low price and light weight.
  • polypropylene is a semi-crystalline polymer, which has disadvantages such as large shrinkage rate, poor dimensional stability, and large linear expansion coefficient. It is difficult to meet the dimensional requirements of precision parts and the dimensional instability caused by temperature differences.
  • the mainstream of the modified polypropylene industry is to fill modified polypropylene with fillers such as ordinary talc or calcium carbonate.
  • This type of filled modified polypropylene composite can be widely used in automotive interior and exterior trim parts, but for parts with special requirements, such as plastics Fenders, plastic tailgates, etc. have very high requirements for shrinkage and fenders. At this time, ordinary modification cannot meet the existing requirements.
  • Chinese patent CN 106317607 A uses Sc 2 W 3 O 12 as a modifier to reduce CLTE.
  • the preparation technology of raw material Sc 2 W 3 O 12 is not mature enough and the dispersibility in polypropylene is a problem;
  • Chinese patent CN 106147034 A uses Phlogopite as a modifier, its appearance effect is not good, and the shrinkage rate is 6 ⁇ 8 ⁇ and CLTE is 5 ⁇ 7*10 -5 1/K, which is not very good.
  • the purpose of the present invention is to overcome the above-mentioned shortcomings of the prior art and provide a low-shrinkage, low linear expansion coefficient polypropylene composite material, which can meet the requirements of major automobile OEMs to replace steel with plastic and reduce the weight of automobiles. Development direction and trend.
  • the technical solution adopted by the present invention is: a low shrinkage, low linear expansion coefficient polypropylene composite material, containing the following components by weight: 15 to 65 parts of polypropylene, 20 to 40 parts of filler A, and toughening 15-30 parts of the filler, the filler A is talc, the whiteness of the talc is 80-88, the mass percentage of silica in the talc is 55-60%, and the content of the talc is 55-60%.
  • the particle size D50 is 8.5-12.5 ⁇ m, and the aspect ratio of the talc powder is 20-30.
  • the length-to-diameter ratio of the filler A of the present invention is more than twice that of ordinary talc, and the stiffness-increasing effect is obviously better than that of ordinary talc. It replaces traditional talc filled with polypropylene, and can significantly reduce shrinkage without increasing weight. And CLTE.
  • the toughening agent is an ethylene-octene random copolymer.
  • the Mooney viscosity of the toughening agent is 45-74 MU, and the testing standards for the Mooney viscosity are ASTM D1646, ML1+4@121°C.
  • the polypropylene is highly crystalline polypropylene
  • the melt index of the polypropylene at 230° C. is 30-110 g/10 min
  • the enthalpy of melting of the polypropylene obtained by the DSC test method is 100-120 J/g.
  • the polypropylene melt index of the present invention is obtained by testing at 230°C and 2.16kg.
  • the high crystalline polypropylene of the present invention can significantly reduce the CLTE of the composite material.
  • the low shrinkage, low linear expansion coefficient polypropylene composite material further contains 2-15 parts by weight of filler B, and said filler B is nano-magnesium hydroxide or/and basic magnesium sulfate whiskers.
  • the thickness of the nano-magnesium hydroxide is 60 nm
  • the aspect ratio (width/thickness) of the nano-magnesium hydroxide is 67
  • the ultra-high aspect ratio is more effective than ordinary fillers
  • the alkali The diameter of the magnesium sulfate whisker is not more than 3 ⁇ m
  • the length of the basic magnesium sulfate whisker is not less than 25 ⁇ m
  • the largest possible aspect ratio is beneficial to strengthen polypropylene, which makes the composite material CLTE decrease significantly.
  • the low-shrinkage, low linear expansion coefficient polypropylene composite material further contains the following components by weight: 0.05-0.3 parts of lubricant, 0.05-0.3 parts of light stabilizer, and 0.1-0.6 parts of antioxidant.
  • the lubricant is a stearate lubricant
  • the antioxidant is a hindered phenolic antioxidant or/and a phosphite antioxidant
  • the light stabilizer is a hindered amine light stabilizer. Stabilizer.
  • the present invention also provides a preparation method of the low shrinkage, low linear expansion coefficient polypropylene composite material, which includes the following steps:
  • step (2) Add the mixed materials in step (1) into the twin-screw extruder, while filler A is added from side feed port A, and filler B is added from side feed port B to perform melt extrusion, granulation, drying, Cooling, packaging, to obtain the low shrinkage, low linear expansion coefficient polypropylene composite material; wherein, the temperature of the twin-screw extruder from the feeding section to the die is 170°C, 200°C, 200°C, 210°C, 210°C, 205°C, 205°C, 205°C, 200°C, 200°C, the extrusion adopts a double vacuum process, and the vacuum degree is not more than -0.08MPa.
  • the specific extrusion process of the present invention can well achieve the purpose of reducing shrinkage rate and CLTE; and the production process is simple and suitable for mass production.
  • the present invention uses special fillers A and B instead of traditional talc to fill polypropylene, which can significantly reduce shrinkage and CLTE without increasing weight;
  • the present invention uses special high crystalline polypropylene, which can significantly reduce the CLTE of composite materials;
  • the invention cooperates with a specific extrusion process to achieve the purpose of reducing shrinkage rate and CLTE, and the production process is simple and suitable for mass production.
  • the bending performance in the embodiment of the present invention and the comparative example were tested in accordance with the ISO 178 standard, in which the bending speed was 2mm/min; the cantilever beam notched impact was tested in accordance with the ISO 180 standard; the shrinkage rate was tested in accordance with the ISO 294-4 standard: MD refers to the shrinkage in the flow direction, TD refers to the shrinkage in the vertical flow direction, AVG refers to the average value of MD and TD, and the difference in shrinkage refers to TD-MD. The greater the difference in shrinkage, the risk of deformation of the material after injection molding. The higher the sex;
  • CLTE coefficient of linear expansion
  • Supplier Lanzhou Petrochemical
  • Filler A (1250 mesh talc powder, diameter-to-thickness ratio 30) Supplier: Imerys, France; whiteness 84, mass percentage of silica is 56%, particle size D50 is 10.5 ⁇ m, length-to-diameter ratio is 25 ;
  • Filler B KISUMA10 (Nano Magnesium Hydroxide) (thickness 60nm, aspect ratio 67) Supplier: Kyowa Chemical Industry Co.,Ltd;
  • Filler B WS-1S2 (basic magnesium sulfate whiskers) (diameter not greater than 3 ⁇ m, length not less than 25 ⁇ m) Supplier: Yingkou Kangru Technology;
  • Toughening agent ethylene-octene copolymer (POE):
  • Hindered phenol type number 1010 Manufacturer: Shandong Sanfeng;
  • Phosphite type number 168 Manufacturer: Shandong Sanfeng;
  • Hindered amine type number UV-3808PP5 Manufacturer: Solvay, Belgium;
  • Zinc stearate model BS-2818 Manufacturer: Huamingtai Chemical;
  • the low shrinkage, low linear expansion coefficient polypropylene composite material of this embodiment contains the following components by weight:
  • Polypropylene (PP BX3920) 65 parts, toughening agent (POE 7289) 15 parts, light stabilizer (UV-3808PP5) 0.05 parts, lubricant (BS-2818) 0.05 parts, antioxidant (1010 and 168 weight ratio It is: 1010:168 1:1) 0.1 parts, filler A (HAR T84) 20 parts.
  • the preparation method of the low shrinkage and low linear expansion coefficient polypropylene composite material includes the following steps:
  • step (2) Add the mixed materials in step (1) into the twin-screw extruder, and at the same time, add filler A from the side feed port A, perform melt extrusion, granulation, drying, cooling, and packaging to obtain the Polypropylene composite material with low shrinkage and low linear expansion coefficient; wherein the temperature of the twin-screw extruder from the feeding section to the die is 170°C, 200°C, 200°C, 210°C, 210°C, 205°C, 205°C, 205°C, 200°C, 200°C, extrusion adopts double vacuum process, and the vacuum degree is not more than -0.08MPa.
  • the low shrinkage, low linear expansion coefficient polypropylene composite material of this embodiment contains the following components by weight:
  • Polypropylene (PP H9018) 15 parts, toughening agent (POE 7387) 30 parts, light stabilizer (UV-3808PP5) 0.3 part, lubricant (BS-2818) 0.3 part, antioxidant (weight ratio of 1010 to 168) It is: 1010:168 1:1) 0.6 parts, filler A (HAR T84) 40 parts, filler B nano magnesium hydroxide 15 parts.
  • the preparation method of the low shrinkage and low linear expansion coefficient polypropylene composite material includes the following steps:
  • step (2) Add the mixed materials in step (1) into the twin-screw extruder, while filler A is added from side feed port A, and filler B is added from side feed port B to perform melt extrusion, granulation, drying, Cooling, packaging, to obtain the low shrinkage, low linear expansion coefficient polypropylene composite material; wherein, the temperature of the twin-screw extruder from the feeding section to the die is 170°C, 200°C, 200°C, 210°C, 210°C, 205°C, 205°C, 205°C, 200°C, 200°C, the extrusion adopts a double vacuum process, and the vacuum degree is not more than -0.08MPa.
  • the low shrinkage, low linear expansion coefficient polypropylene composite material of this embodiment contains the following components by weight:
  • Polypropylene (PPH9018) 15 parts, polypropylene (PP BX3900) 25 parts, toughening agent (POE 8677) 25 parts, light stabilizer (UV-3808PP5) 0.12 parts, lubricant (BS-2818) 0.08 parts, antioxidant (The weight ratio of 1010 to 168 is: 1010:168 13:16) 0.29 parts, filler A (HAR T84) 33 parts, filler B nano magnesium hydroxide 1 part, filler B basic magnesium sulfate whisker 1 part.
  • the preparation method of the low shrinkage and low linear expansion coefficient polypropylene composite material includes the following steps:
  • step (2) Add the mixed materials in step (1) into the twin-screw extruder, while filler A is added from side feed port A, and filler B is added from side feed port B to perform melt extrusion, granulation, drying, Cooling, packaging, to obtain the low shrinkage, low linear expansion coefficient polypropylene composite material; wherein, the temperature of the twin-screw extruder from the feeding section to the die is 170°C, 200°C, 200°C, 210°C, 210°C, 205°C, 205°C, 205°C, 200°C, 200°C, the extrusion adopts a double vacuum process, and the vacuum degree is not more than -0.08MPa.
  • the low shrinkage, low linear expansion coefficient polypropylene composite material of this embodiment contains the following components by weight:
  • Polypropylene (PPBX3900) 20 parts, polypropylene (PP H9018) 15 parts, toughening agent (POE 8677) 25 parts, light stabilizer (UV-3808PP5) 0.16 parts, lubricant (BS-2818) 0.12 parts, antioxidant (The weight ratio of 1010 to 168 is: 1010:168 2:3) 0.3 parts, filler A (HAR T84) 28 parts, filler B nano magnesium hydroxide 8 parts, filler B basic magnesium sulfate whiskers 4 parts.
  • the preparation method of the low shrinkage and low linear expansion coefficient polypropylene composite material includes the following steps:
  • step (2) Add the mixed materials in step (1) into the twin-screw extruder, while filler A is added from side feed port A, and filler B is added from side feed port B to perform melt extrusion, granulation, drying, Cooling, packaging, to obtain the low shrinkage, low linear expansion coefficient polypropylene composite material; wherein, the temperature of the twin-screw extruder from the feeding section to the die is 170°C, 200°C, 200°C, 210°C, 210°C, 205°C, 205°C, 205°C, 200°C, 200°C, the extrusion adopts a double vacuum process, and the vacuum degree is not more than -0.08MPa.
  • the low shrinkage, low linear expansion coefficient polypropylene composite material of this embodiment contains the following components by weight:
  • Polypropylene (PPBX3900) 18 parts, polypropylene (PPH9018) 17 parts, toughening agent (POE 7387) 28 parts, light stabilizer (UV-3808PP5) 0.19 parts, lubricant (BS-2818) 0.17 parts, antioxidant (The weight ratio of 1010 to 168 is: 1010:168 19:17) 0.37 parts, filler A (HAR T84) 30 parts, and filler B basic magnesium sulfate whiskers 7 parts.
  • the preparation method of the low shrinkage and low linear expansion coefficient polypropylene composite material includes the following steps:
  • step (2) Add the mixed materials in step (1) into the twin-screw extruder, while filler A is added from side feed port A, and filler B is added from side feed port B to perform melt extrusion, granulation, drying, Cooling, packaging, to obtain the low shrinkage, low linear expansion coefficient polypropylene composite material; wherein, the temperature of the twin-screw extruder from the feeding section to the die is 170°C, 200°C, 200°C, 210°C, 210°C, 205°C, 205°C, 205°C, 200°C, 200°C, the extrusion adopts a double vacuum process, and the vacuum degree is not more than -0.08MPa.
  • control group 1 Set up control group 1 and experimental groups 1-4.
  • ordinary talc powder TYT-777A is used to replace filler A in Example 1, and the others are the same as Example 1.
  • Experimental group 1 is Example 1;
  • Experimental group 2 The ordinary toughening agent POE 8137 was used instead of POE 7289 in Example 1, and the others were the same as in Example 1.
  • the composition in experimental group 3 was the same as that in Example 1, but the preparation method was different.
  • the preparation method was as follows: first weigh 65 Parts polypropylene PP BX3920, 15 parts toughening agent POE 7289, 20 parts special filler A, 0.05 parts light stabilizer UV-3808PP5, 0.05 parts lubricant BS-2818, 0.05 parts antioxidant SONOX 1010, 0.05 parts antioxidant SONOX 168 is mixed with a high-speed mixer for 3 minutes, where the speed of the high-speed mixer is 500 rpm; the above-mentioned mixed particles are added to the twin-screw extruder for melt extrusion, granulation, drying, cooling, and packaging ; The temperature of the twin-screw extruder is 170°C, 200°C, 200°C, 210°C, 210°C, 205°C, 205°C, 200°C, 200°C in sequence from the feeding section to the die head; Double-vacuum process and the vacuum degree requirement is ⁇ -0.08MPa.
  • Experimental group 4 replaced PP BX3920 in Example 1 with ordinary polypropylene PP EP548R, and the others were the same as Example 1.
  • the polypropylene composite materials obtained in control group 1 and experimental groups 1 to 4 were tested and analyzed, and the specific test analysis was carried out. The results are shown in Table 1:
  • the shrinkage rate and CLTE of the polypropylene composite material of the present invention are relatively low.
  • the shrinkage rate-AVG of embodiment 2 can reach 1.8 ⁇ , and CLTE can reach 2.3*10 -5 1/K, which is even equivalent to metal aluminum;
  • the shrinkage rate of embodiment 4-AVG can reach 1.9 ⁇ , and CLTE can reach 2.5*10 -5 1/K level. Therefore, the polypropylene composite material of the present invention has excellent performance of low shrinkage rate and low CLTE, and can be widely used in various fields that have extremely high requirements for shrinkage rate and CLTE, such as automobiles, household appliances, and electronic appliances.
  • experimental group 1 only contains filler A, and examples 2 to 5 contain both filler A and filler B.
  • the shrinkage rate and linear expansion coefficient of experimental group 1 are both high. In Examples 2-5.

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Abstract

本发明公开了一种低收缩、低线性膨胀系数聚丙烯复合材料，包含以下重量份的成分：聚丙烯15～65份、填料A20～40份和增韧剂15～30份，所述填料A为滑石粉，所述滑石粉的白度为80～88，所述滑石粉中二氧化硅的质量百分含量为55～60％，所述滑石粉的粒径D50为8.5～12.5μm，所述滑石粉的长径比为20～30。本发明通过使用特殊填料A替代传统滑石粉填充聚丙烯，在不增加重量的前提下，可明显降低收缩率和CLTE。同时，本发明还公开一种所述低收缩、低线性膨胀系数聚丙烯复合材料的制备方法。

Description

一种低收缩、低线性膨胀系数聚丙烯复合材料及制备方法 技术领域
本发明涉及一种聚丙烯复合材料及其制备方法，尤其是一种低收缩、低线性膨胀系数聚丙烯复合材料及制备方法。
背景技术
聚丙烯材料由于其价格低廉质轻等优点，广泛应用于汽车、家电、包装、电子电器等领域。但是聚丙烯是半结晶聚合物，本身存在收缩率大、尺寸稳定性差、线性膨胀系数大等缺点，较难满足精密零部件的尺寸要求和温差变化带来的尺寸不稳定。目前改性聚丙烯行业主流是利用普通滑石粉或碳酸钙等填料填充改性聚丙烯，此类填充改性聚丙烯复合可广泛应用于汽车内外饰件，但是对于特殊要求的零部件，如塑料翼子板、塑料尾门等对收缩率和翼子板都提出了很高的要求，这时普通改性是满足不了现有要求的。
中国专利CN 106317607 A采用Sc 2W 3O 12作为降低CLTE的改性剂，目前原材料Sc 2W 3O 12的制备技术还不够成熟以及在聚丙烯中分散性是个难题；中国专利CN 106147034 A采用金云母作为改性剂，其外观效果不好，另外收缩率在6～8‰和CLTE在5～7*10 -51/K，还不是很好。
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而提供一种低收缩、低线性膨胀系数聚丙烯复合材料，可满足各大汽车主机厂要求的以塑代钢、汽车轻量化的发展方向和趋势。
为实现上述目的，本发明所采取的技术方案为：一种低收缩、低线性膨胀系数聚丙烯复合材料，包含以下重量份的成分：聚丙烯15～65份、填料A20～40份和增韧剂15～30份，所述填料A为滑石粉，所述滑石粉的白度为80～88，所述滑石粉中二氧化硅的质量百分含量为55～60％，所述滑石粉的粒径D50为8.5～12.5μm，所述滑石粉的长径比为20～30。
本发明所述填料A的长径比是普通滑石粉的2倍以上，增刚效果明显优于普通滑石粉，替代传统滑石粉填充聚丙烯，在不增加重量的前提下，可明显降低收缩率和CLTE。
优选地，所述增韧剂为乙烯-辛烯无规共聚物。
更优选地，所述增韧剂的门尼粘度为45～74MU，所述门尼粘度的测试标准为ASTM D1646、ML1+4@121℃。
优选地，所述聚丙烯为高结晶聚丙烯，所述聚丙烯在230℃的熔融指数为30～110g/10min，所述聚丙烯利用DSC测试法得到的熔融焓为100～120J/g。本发明所述聚丙烯熔融指数是在230℃、2.16kg条件下测试所得。本发明所述高结晶聚丙烯，可明显降低复合材料的CLTE。
优选地，所述的低收缩、低线性膨胀系数聚丙烯复合材料，还包含2～15重量份的填料B，所述填料B为纳米氢氧化镁或/和碱式硫酸镁晶须。
更优选地，所述纳米氢氧化镁的厚度为60nm，所述纳米氢氧化镁的纵横比(宽度/厚度)为67，超高的纵横比是的增强效果比普通填料更加优异；所述碱式硫酸镁晶须的直径不大于3μm，所述碱式硫酸镁晶须的长度不小于25μm，尽可能大的长径比有利于增强聚丙烯，使得复合材料CLTE下降明显。
优选地，所述的低收缩、低线性膨胀系数聚丙烯复合材料，还包含以下重量份的成分：润滑剂0.05～0.3份、光稳剂0.05～0.3份和抗氧剂0.1～0.6份。
更优选地，所述润滑剂为硬脂酸盐类润滑剂，所述抗氧剂为受阻酚类抗氧剂或/和亚磷酸酯类抗氧剂，所述光稳剂为受阻胺类光稳剂。
同时，本发明还提供一种所述低收缩、低线性膨胀系数聚丙烯复合材料的制备方法，包括如下步骤：
(1)将聚丙烯、增韧剂、光稳剂、润滑剂、抗氧剂在高速混合机中混合3～5分钟，其中高速混合机的转速为500～800转/分钟；
(2)将步骤(1)中混合好的物料加入双螺杆挤出机中，同时填料A从侧喂口A加入，填料B从侧喂口B加入，进行熔融挤出、造粒、干燥、冷却、装 包，即得所述低收缩、低线性膨胀系数聚丙烯复合材料；其中，所述双螺杆挤出机的温度从喂料段到机头依次为170℃、200℃、200℃、210℃、210℃、205℃、205℃、205℃、200℃、200℃，挤出采用双真空工艺，且真空度要求不大于-0.08MPa。
本发明特定的挤出工艺，可以很好的达到降低收缩率和CLTE的目的；且生产工艺简单、适合大批量生产。
相对于现有技术，本发明的有益效果为：
1、本发明通过使用特殊填料A和B替代传统滑石粉填充聚丙烯，在不增加重量的前提下，可明显降低收缩率和CLTE；
2、本发明使用特殊高结晶聚丙烯，可明显降低复合材料的CLTE；
3、本发明配合特定的挤出工艺，达到降低收缩率和CLTE的目的，且生产工艺简单、适合大批量生产。
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对本发明作进一步说明。
本发明实施例和对比例中的弯曲性能均按照ISO 178标准进行测试，其中弯曲速度为2mm/min；悬臂梁缺口冲击均按照ISO 180标准进行测试；收缩率按照ISO 294-4标准进行测试：MD是指流动方向的收缩率，TD是指垂直流动方向的收缩率，AVG是指MD与TD的平均值，收缩率差异是指TD-MD，收缩率差异越大表示材料注塑后变形的风险性越高；
线性膨胀系数(简称：CLTE)按ISO 11359标准测试，温度范围为23℃～85℃，150*150*3mm方板中间位置截取10*10*3mm尺寸样片进行测试；MD是指流动方向的CLTE，TD是指垂直流动方向的CLTE，AVG是指MD与TD的平均值。
本发明实施例和对比例中用到的主要代表材料如下：
聚丙烯(PP)：
PP-1：BX3920(嵌段共聚，MFR＝90-110g/10min，熔融焓为100～120J/g) 供应商：韩国SK；
PP-2：BX3900(嵌段共聚，MFR＝40-60g/10min，熔融焓为100～120J/g)供应商：韩国SK；
PP-3：H9018(均聚，MFR＝50-60g/10min，熔融焓为100～120J/g)供应商：兰州石化；
PP-5：EP548R(嵌段共聚，MFR＝25-35g/10min，熔融焓为85～99J/g)供应商：中海壳牌；
填料：
填料A：HAR T84(1250目滑石粉，径厚比30)供应商：法国Imerys；白度84、二氧化硅的质量百分含量为56％、粒径D50为10.5μm、长径比为25；
填料B：KISUMA10(纳米氢氧化镁)(厚度为60nm，纵横比为67)供应商：Kyowa Chemical Industry Co.,Ltd；
填料B：WS-1S2(碱式硫酸镁晶须)(直径不大于3μm，长度不小于25μm)供应商：营口康如科技；
普通填料：型号：TYT-777A(3000目滑石粉)厂家：辽宁添源；白度96、二氧化硅的质量百分含量为59％、粒径D50为5.8μm、长径比为6；
增韧剂：乙烯-辛烯共聚物(POE)：
牌号：7289(ASTM D1646 ML1+4@121℃门尼粘度74)供应商：陶氏化学；
牌号：7387(ASTM D1646 ML1+4@121℃门尼粘度54)供应商：陶氏化学；
牌号：8677(ASTM D1646 ML1+4@121℃门尼粘度45)供应商：陶氏化学；
牌号：8137(ASTM D1646 ML1+4@121℃门尼粘度4)供应商：陶氏化学；
抗氧剂：
受阻酚类型号：1010       厂家：山东三丰；
亚磷酸酯类型号：168     厂家：山东三丰；
光稳剂：
受阻胺类型号：UV-3808PP5    厂家：比利时索尔维；
润滑剂：
硬脂酸锌型号：BS-2818    厂家：华明泰化工；
实施例1
本发明所述低收缩、低线性膨胀系数聚丙烯复合材料的一种实施例，本实施例所述低收缩、低线性膨胀系数聚丙烯复合材料包含以下重量份的成分：
聚丙烯(PP BX3920)65份、增韧剂(POE 7289)15份、光稳剂(UV-3808PP5)0.05份、润滑剂(BS-2818)0.05份、抗氧剂(1010与168的重量比为：1010:168＝1:1)0.1份、填料A(HAR T84)20份。
所述低收缩、低线性膨胀系数聚丙烯复合材料的制备方法，包括如下步骤：
(1)将聚丙烯、增韧剂、光稳剂、润滑剂、抗氧剂在高速混合机中混合3分钟，其中高速混合机的转速为500转/分钟；
(2)将步骤(1)中混合好的物料加入双螺杆挤出机中，同时填料A从侧喂口A加入，进行熔融挤出、造粒、干燥、冷却、装包，即得所述低收缩、低线性膨胀系数聚丙烯复合材料；其中，所述双螺杆挤出机的温度从喂料段到机头依次为170℃、200℃、200℃、210℃、210℃、205℃、205℃、205℃、200℃、200℃，挤出采用双真空工艺，且真空度要求不大于-0.08MPa。
实施例2
本发明所述低收缩、低线性膨胀系数聚丙烯复合材料的一种实施例，本实施例所述低收缩、低线性膨胀系数聚丙烯复合材料包含以下重量份的成分：
聚丙烯(PP H9018)15份、增韧剂(POE 7387)30份、光稳剂(UV-3808PP5)0.3份、润滑剂(BS-2818)0.3份、抗氧剂(1010与168的重量比为：1010:168＝1:1)0.6份、填料A(HAR T84)40份、填料B纳米氢氧化镁15份。
所述低收缩、低线性膨胀系数聚丙烯复合材料的制备方法，包括如下步骤：
(1)将聚丙烯、增韧剂、光稳剂、润滑剂、抗氧剂在高速混合机中混合5分钟，其中高速混合机的转速为800转/分钟；
(2)将步骤(1)中混合好的物料加入双螺杆挤出机中，同时填料A从侧喂口A加入，填料B从侧喂口B加入，进行熔融挤出、造粒、干燥、冷却、装 包，即得所述低收缩、低线性膨胀系数聚丙烯复合材料；其中，所述双螺杆挤出机的温度从喂料段到机头依次为170℃、200℃、200℃、210℃、210℃、205℃、205℃、205℃、200℃、200℃，挤出采用双真空工艺，且真空度要求不大于-0.08MPa。
实施例3
本发明所述低收缩、低线性膨胀系数聚丙烯复合材料的一种实施例，本实施例所述低收缩、低线性膨胀系数聚丙烯复合材料包含以下重量份的成分：
聚丙烯(PPH9018)15份、聚丙烯(PP BX3900)25份、增韧剂(POE 8677)25份、光稳剂(UV-3808PP5)0.12份、润滑剂(BS-2818)0.08份、抗氧剂(1010与168的重量比为：1010:168＝13:16)0.29份、填料A(HAR T84)33份、填料B纳米氢氧化镁1份、填料B碱式硫酸镁晶须1份。
所述低收缩、低线性膨胀系数聚丙烯复合材料的制备方法，包括如下步骤：
(1)将聚丙烯、增韧剂、光稳剂、润滑剂、抗氧剂在高速混合机中混合3.8分钟，其中高速混合机的转速为627转/分钟；
(2)将步骤(1)中混合好的物料加入双螺杆挤出机中，同时填料A从侧喂口A加入，填料B从侧喂口B加入，进行熔融挤出、造粒、干燥、冷却、装包，即得所述低收缩、低线性膨胀系数聚丙烯复合材料；其中，所述双螺杆挤出机的温度从喂料段到机头依次为170℃、200℃、200℃、210℃、210℃、205℃、205℃、205℃、200℃、200℃，挤出采用双真空工艺，且真空度要求不大于-0.08MPa。
实施例4
本发明所述低收缩、低线性膨胀系数聚丙烯复合材料的一种实施例，本实施例所述低收缩、低线性膨胀系数聚丙烯复合材料包含以下重量份的成分：
聚丙烯(PPBX3900)20份、聚丙烯(PP H9018)15份、增韧剂(POE 8677)25份、光稳剂(UV-3808PP5)0.16份、润滑剂(BS-2818)0.12份、抗氧剂(1010与168的重量比为：1010:168＝2:3)0.3份、填料A(HAR T84)28份、填料B 纳米氢氧化镁8份、填料B碱式硫酸镁晶须4份。
所述低收缩、低线性膨胀系数聚丙烯复合材料的制备方法，包括如下步骤：
(1)将聚丙烯、增韧剂、光稳剂、润滑剂、抗氧剂在高速混合机中混合4.5分钟，其中高速混合机的转速为725转/分钟；
(2)将步骤(1)中混合好的物料加入双螺杆挤出机中，同时填料A从侧喂口A加入，填料B从侧喂口B加入，进行熔融挤出、造粒、干燥、冷却、装包，即得所述低收缩、低线性膨胀系数聚丙烯复合材料；其中，所述双螺杆挤出机的温度从喂料段到机头依次为170℃、200℃、200℃、210℃、210℃、205℃、205℃、205℃、200℃、200℃，挤出采用双真空工艺，且真空度要求不大于-0.08MPa。
实施例5
本发明所述低收缩、低线性膨胀系数聚丙烯复合材料的一种实施例，本实施例所述低收缩、低线性膨胀系数聚丙烯复合材料包含以下重量份的成分：
聚丙烯(PPBX3900)18份、聚丙烯(PPH9018)17份、增韧剂(POE 7387)28份、光稳剂(UV-3808PP5)0.19份、润滑剂(BS-2818)0.17份、抗氧剂(1010与168的重量比为：1010:168＝19:17)0.37份、填料A(HAR T84)30份、填料B碱式硫酸镁晶须7份。
所述低收缩、低线性膨胀系数聚丙烯复合材料的制备方法，包括如下步骤：
(1)将聚丙烯、增韧剂、光稳剂、润滑剂、抗氧剂在高速混合机中混合4.7分钟，其中高速混合机的转速为762转/分钟；
(2)将步骤(1)中混合好的物料加入双螺杆挤出机中，同时填料A从侧喂口A加入，填料B从侧喂口B加入，进行熔融挤出、造粒、干燥、冷却、装包，即得所述低收缩、低线性膨胀系数聚丙烯复合材料；其中，所述双螺杆挤出机的温度从喂料段到机头依次为170℃、200℃、200℃、210℃、210℃、205℃、205℃、205℃、200℃、200℃，挤出采用双真空工艺，且真空度要求不大于-0.08MPa。
设置对照组1和实验组1～4，对照组1中用普通滑石粉TYT-777A替代实施 例1中的填料A，其他均与实施例1相同；实验组1为实施例1；实验组2中用普通增韧剂POE 8137替代实施例1中的POE 7289，其他均与实施例1相同；实验组3中成分和实施例1相同，但是制备方法不同，其制备方法为：首先称取65份聚丙烯PP BX3920、15份增韧剂POE 7289、20份特殊填料A、0.05份光稳剂UV-3808PP5、0.05份润滑剂BS-2818、0.05份抗氧剂SONOX 1010、0.05份抗氧剂SONOX 168与高速混合机中混合3分钟，其中高速混合机的转速为500转/分钟；将上述混合好的粒子加入双螺杆挤出机中进行熔融挤出、造粒、干燥、冷却、装包；双螺杆挤出机的温度从喂料段到机头依次为170℃、200℃、200℃、210℃、210℃、205℃、205℃、205℃、200℃、200℃；挤出采用双真空工艺且真空度要求≤-0.08MPa。实验组4用普通聚丙烯PP EP548R替代实施例1中的PP BX3920，其他均与实施例1相同；分别对对照组1及实验组1～4中所得聚丙烯复合材料进行测试分析，具体测试分析结果如表1所示：
表1 对照组1和实验组1～4聚丙烯复合材料性能测试结果
Figure PCTCN2020110657-appb-000001
从表1可以看出，与实验组1～4相比，对照组1中不含有填料A，实验组1～4中含有填料A，其弯曲模量较低、收缩率较大、CLTE较大；由此可以得知，本申请中的填料A可以明显降低收缩率和CLTE；将实验组2与实验组1对比， 实验组1的冲击强度低于实验组2，这说明选择门尼粘度为45～74MU的乙烯-辛烯无规共聚物作为增韧剂，可以起到更好的增韧效果；将实验组3与实验组1对比可知，将填料A从侧喂改为主喂，会出现弯曲模量下降、收缩率增大和CLTE增大的情况，这也进一步说明了本申请特定挤出工艺的进步性。
同时，对本发明实施例2～5中制备所得聚丙烯复合材料进行测试分析，具体测试分析结果如表2所示：
表2 实施例2～5聚丙烯复合材料性能测试结果
测试项目 实施例2 实施例3 实施例4 实施例5
收缩率-MD/‰ 1.7 2.0 1.3 2.2
收缩率-TD/‰ 1.9 2.4 2.5 2.5
收缩率-AVG/‰ 1.8 2.2 1.9 2.4
CLTE-MD/(*10 -51/K) 2.2 2.2 2.0 2.6
CLTE-TD/(*10 -51/K) 2.4 2.6 3.0 3.0
CLTE-AVG/(*10 -51/K) 2.3 2.4 2.5 2.8
从表2可以看出，本发明聚丙烯复合材料的收缩率和CLTE均较低。比如，实施例2的收缩率-AVG可以达到1.8‰，CLTE可以达到2.3*10 -51/K，其甚至与金属铝相当；实施例4的收缩率-AVG可以达到1.9‰，CLTE可以达到2.5*10 -51/K水平。因此，本发明聚丙烯复合材料具有低收缩率、低CLTE的优异性能，可广泛应用于汽车、家电、电子电器等各个对收缩率和CLTE有极高要求的领域。
同时，通过表1、2中的性能数据可以得出，实验组1中只含有填料A，实施例2～5中同时含有填料A和填料B，实验组1的收缩率与线性膨胀系数均高于实施例2～5。
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 (9)

  1. 一种低收缩、低线性膨胀系数聚丙烯复合材料，其特征在于，包含以下重量份的成分：聚丙烯15～65份、填料A20～40份和增韧剂15～30份，所述填料A为滑石粉，所述滑石粉的白度为80～88，所述滑石粉中二氧化硅的质量百分含量为55～60％，所述滑石粉的粒径D50为8.5～12.5μm，所述滑石粉的长径比为20～30。
  2. 如权利要求1所述的低收缩、低线性膨胀系数聚丙烯复合材料，其特征在于，所述增韧剂为乙烯-辛烯无规共聚物。
  3. 如权利要求2所述的低收缩、低线性膨胀系数聚丙烯复合材料，其特征在于，所述增韧剂的门尼粘度为45～74MU，所述门尼粘度的测试标准为ASTMD1646、ML1+4@121℃。
  4. 如权利要求1所述的低收缩、低线性膨胀系数聚丙烯复合材料，其特征在于，所述聚丙烯为高结晶聚丙烯，所述聚丙烯在230℃、2.16kg测试条件下的熔融指数为30～110g/10min，所述聚丙烯利用DSC测试法得到的熔融焓为100～120J/g。
  5. 如权利要求1～4任一项所述的低收缩、低线性膨胀系数聚丙烯复合材料，其特征在于，还包含2～15重量份的填料B，所述填料B为纳米氢氧化镁或/和碱式硫酸镁晶须。
  6. 如权利要求5所述的低收缩、低线性膨胀系数聚丙烯复合材料，其特征在于，所述纳米氢氧化镁的厚度为60nm，所述纳米氢氧化镁的纵横比为67；所述碱式硫酸镁晶须的直径不大于3μm，所述碱式硫酸镁晶须的长度不小于25μm。
  7. 如权利要求5所述的低收缩、低线性膨胀系数聚丙烯复合材料，其特征在于，还包含以下重量份的成分：润滑剂0.05～0.3份、光稳剂0.05～0.3份和抗氧剂0.1～0.6份。
  8. 如权利要求7所述的低收缩、低线性膨胀系数聚丙烯复合材料，其特征 在于，所述润滑剂为硬脂酸盐类润滑剂，所述抗氧剂为受阻酚类抗氧剂或/和亚磷酸酯类抗氧剂，所述光稳剂为受阻胺类光稳剂。
  9. 一种如权利要求7或8所述低收缩、低线性膨胀系数聚丙烯复合材料的制备方法，其特征在于，包括如下步骤：
    (1)将聚丙烯、增韧剂、光稳剂、润滑剂、抗氧剂在高速混合机中混合3～5分钟，其中高速混合机的转速为500～800转/分钟；
    (2)将步骤(1)中混合好的物料加入双螺杆挤出机中，同时填料A从侧喂口A加入，填料B从侧喂口B加入，进行熔融挤出、造粒、干燥、冷却、装包，即得所述低收缩、低线性膨胀系数聚丙烯复合材料；其中，所述双螺杆挤出机的温度从喂料段到机头依次为170℃、200℃、200℃、210℃、210℃、205℃、205℃、205℃、200℃、200℃，挤出采用双真空工艺，且真空度要求不大于-0.08MPa。
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