WO2023071296A1 - 一种长玻纤增强聚丙烯复合材料及其制备方法和应用 - Google Patents

一种长玻纤增强聚丙烯复合材料及其制备方法和应用 Download PDF

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WO2023071296A1
WO2023071296A1 PCT/CN2022/105162 CN2022105162W WO2023071296A1 WO 2023071296 A1 WO2023071296 A1 WO 2023071296A1 CN 2022105162 W CN2022105162 W CN 2022105162W WO 2023071296 A1 WO2023071296 A1 WO 2023071296A1
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long glass
glass fiber
composite material
fiber reinforced
reinforced polypropylene
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PCT/CN2022/105162
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English (en)
French (fr)
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安朋
张超
刘纪庆
王飞
叶士兵
肖军华
付大炯
邱志强
许建稳
张永
夏建盟
丁正亚
罗忠富
吴国峰
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金发科技股份有限公司
上海金发科技发展有限公司
江苏金发科技新材料有限公司
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Publication of WO2023071296A1 publication Critical patent/WO2023071296A1/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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—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
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene

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  • the invention relates to the technical field of polymer materials, in particular to a long glass fiber reinforced polypropylene composite material and its preparation method and application.
  • LFT-PP Long glass fiber reinforced polypropylene
  • LFT-PP Long glass fiber reinforced polypropylene
  • Peripheral parts of automobile engines such as water chamber, thermostat, engine cover, front hatch cover and other parts need to be in contact with solvents such as coolant (ethylene glycol) and glass cleaning fluid for a long time.
  • solvents such as coolant (ethylene glycol) and glass cleaning fluid for a long time.
  • the current material is glass fiber reinforced nylon; Glass fiber reinforced polypropylene can be used as a lightweight solution due to its excellent mechanical properties.
  • Chinese patent 201910217593X discloses a preparation method of long glass fiber reinforced polypropylene material, in which the traditional long glass fiber infiltration method is adopted, and the long glass fiber (linear density 2400-2500tex) is impregnated with glass fiber and resin through an infiltration die.
  • this method cannot fully infiltrate the long glass fiber and the resin, and the improvement of the solvent resistance defect of the long glass fiber reinforced polypropylene composite material is insufficient.
  • the object of the present invention is to overcome the above-mentioned technical defects and provide a long glass fiber reinforced polypropylene composite material, which has the advantages of good solvent resistance and excellent mechanical properties.
  • a kind of long glass fiber reinforced polypropylene composite material, by weight, comprises the following components:
  • the ethylene unit content is 25mol%-45mol%
  • the long glass fibers are selected from one or more of HMG long glass fibers, S-1 long glass fibers, TM long glass fibers, and S-2 long glass fibers.
  • the ultra-high strength long glass fiber of the present invention has good wettability.
  • the average diameter of the long glass fibers is 12-20 microns, preferably, the average diameter of the long glass fibers is 14-17 microns; preferably, the long glass fibers are selected from HMG long glass fibers.
  • the long glass fibers listed above are high-strength alkali-free continuous glass fibers, which have higher strength than other types of long glass fibers, but are also more difficult to infiltrate.
  • the melt index of the homopolypropylene is 10-150g/10min, the condition is 230°C, the weight is 2.16kg, and the test standard is ISO1133.
  • the ethylene unit content in the ethylene vinyl alcohol copolymer segment is 30mol%-40mol%.
  • the melt index of the ethylene vinyl alcohol copolymer is 2-5g/10min, the condition is 210°C, 2.16kg, and the test standard is ISO1133; preferably, the melt index of the ethylene vinyl alcohol copolymer is 3-4g/10min, and the test standard is ISO 1133.
  • Described compatibilizer is selected from at least one in maleic anhydride grafted polypropylene, acrylic acid grafted polypropylene, maleic acid grafted polypropylene, glycidyl acrylate grafted polypropylene, wherein maleic anhydride, ma
  • the grafting rate of lycic acid, acrylic acid and glycidyl acrylate is 1-1.5wt%, the melt index of the compatibilizer is 50-120g/10min, and the condition is 190°C and 2.16Kg. Grafting rate can be determined by acid-base titration.
  • the compatibilizer is selected from maleic anhydride grafted polypropylene.
  • auxiliary agents are also included, and the auxiliary agents are selected from one or more of antioxidants, lubricants, and nucleating agents.
  • Antioxidants can be hindered phenolic or phosphite antioxidant compounds.
  • Lubricants can be silicones, esters, amides, polyethylenes, stearic acids, fatty acids and esters, etc.
  • the nucleating agent is an inorganic nucleating agent with a particle size of less than 1 ⁇ m, which can be talcum powder, montmorillonite, calcium carbonate and the like.
  • the long glass fiber reinforced polypropylene composite material of the present invention all components except the long glass fiber are uniformly mixed according to the proportion, melted and kneaded by a twin-screw extruder, and then the molten material is passed through an infiltration die
  • the long glass fiber enters the die pre-impregnation system through the tension dispersion system, and enters the impregnation die after impregnation in the pre-impregnation die.
  • the resin and long glass fibers are evenly dispersed, extruded to granulate, and
  • the temperature of the machine is 210-280°C, and the temperature of the infiltration die is 270-320°C to obtain long glass fiber reinforced polypropylene composite materials.
  • the application of the long glass fiber reinforced polypropylene composite material of the present invention is used for preparing automotive interior and exterior decoration, industrial fans, and electric tool structural parts.
  • the present invention can significantly improve the wettability and wettability of the ultra-high-strength long glass fiber in the homopolypropylene resin matrix by specially selecting the type of ultra-high-strength long glass fiber and adding ethylene vinyl alcohol copolymer with a specific repeating unit structure. Dispersion, thereby improving the solvent resistance and mechanical properties of long glass fiber reinforced polypropylene composites.
  • the ultra-high-strength long glass fiber of the present invention can significantly improve the wettability of the long glass fiber and the resin matrix through the dispersion of the tension system and the pre-impregnation system.
  • Figure 1 Diagram of the electrolyte resistance evaluation device.
  • Homopolypropylene A M60T, Sinopec, 60g/10min, condition 230°C, 2.16Kg;
  • Homopolypropylene B Z30S, Sinopec, 25g/10min, condition 230°C, 2.16Kg;
  • Copolymer polypropylene EP548R, China Sea Shell, 30g/10min, condition 230°C, 2.16Kg;
  • Ethylene vinyl alcohol copolymer A the content of ethylene units is 29mol%, the melt index is 3.0g/10min, the condition is 210°C, 2.16kg, commercially available;
  • Ethylene vinyl alcohol copolymer B the content of ethylene units is 32mol%, the melt index is 3.7g/10min, the condition is 210°C, 2.16kg, commercially available;
  • Ethylene vinyl alcohol copolymer C the content of ethylene units is 38mol%, the melt index is 3.7g/10min, the condition is 210°C, 2.16kg, commercially available;
  • Ethylene vinyl alcohol copolymer D the content of ethylene units is 44mol%, the melt index is 4.0g/10min, the condition is 210°C, 2.16kg, commercially available;
  • Ethylene vinyl alcohol copolymer E the content of ethylene units is 35mol%, the melt index is 2.3g/10min, the condition is 210°C, 2.16kg, commercially available;
  • Ethylene vinyl alcohol copolymer F the content of ethylene units is 35mol%, the melt index is 4.4g/10min, the condition is 210°C, 2.16kg, commercially available;
  • Compatibilizer A maleic anhydride grafted polypropylene, the grafting rate of maleic anhydride is 1wt%, the melt index is 80g/10min, the condition is 230°C, 2.16Kg;
  • Compatibilizer B acrylic acid grafted polypropylene, acrylic acid grafting rate 0.5wt%, melt index 50g/10min, condition 230°C, 2.16Kg;
  • Compatibilizer C maleic acid grafted polypropylene, maleic acid grafting rate 1.2wt%, melt index 100g/10min, condition 230°C, 2.16Kg;
  • Compatibilizer D glycidyl acrylate grafted polypropylene, glycidyl acrylate graft rate 1wt%, melt index 70g/10min, condition 230°C, 2.16Kg;
  • Long glass fiber A-1 HMG838T, with an average diameter of 17 microns;
  • Long glass fiber A-2 HMG838T, with an average diameter of 14 microns;
  • Long glass fiber A-3 HMG838T, with an average diameter of 12 microns;
  • Long glass fiber A-4 HMG838T, with an average diameter of 20 microns;
  • Long glass fiber B S-1Glass, with an average diameter of 17 microns;
  • Long glass fiber C TM4305, with an average diameter of 17 microns;
  • Long glass fiber D S-2Glass, with an average diameter of 14 microns;
  • Long glass fiber E EDR240-T838T, with an average diameter of 17 microns.
  • Antioxidant 1010/Antioxidant 168 is 1:1 compound
  • Lubricant Lubricant-A-C540A.
  • the preparation method of long glass fiber reinforced polypropylene composite material is characterized in that homopolypropylene, ethylene vinyl alcohol copolymer, compatibilizer and auxiliary agent are uniformly mixed according to the proportioning ratio, and then extruded by twin-screw Exit the machine for melting and kneading, then pass the molten material through the infiltration die, pass the long glass fiber through the tension dispersion system into the die pre-impregnation system, enter the infiltration die after impregnation in the pre-impregnation mold, and pour the resin in the infiltration die Disperse evenly with long glass fibers, extrude and granulate, the heating block of the extruder has 9 temperature sections, the temperature is 50/180/210/280/280/280//280/280/280°C, and the speed is 550rpm. The temperature of the soaking die head is 270-320° C., and the long glass fiber reinforced polypropylene composite material is obtained.
  • Charpy notched impact strength according to the ISO179/1eA standard, use an injection molding machine to mold long glass fiber reinforced polypropylene composite materials into 4mm thick test specimens. Impact strength;
  • Ethylene glycol resistance evaluation Mix ethylene glycol and deionized water according to the volume ratio of 1:1 and pour them into the reaction kettle. The prepared tensile test specimens are put into the reaction kettle and sealed. The kettle was placed in an aging box at 120°C for 1000 hours of aging, and the retention rate of tensile strength properties was tested.
  • Electrolyte resistance evaluation concentrated sulfuric acid and deionized water are configured into a 35wt% concentration sulfuric acid solution, and the sulfuric acid solution is introduced into the container, and the prepared tensile test sample is put into a device such as the accompanying drawing in the description, and the Heat at °C for 24h, and test the retention rate of tensile strength properties.
  • Table 1 Examples 1-8 long glass fiber polypropylene composite material (parts by weight) and test results
  • the preferred average diameter of the ultra-high-strength long glass fiber is 14-17 microns.
  • Table 2 Examples 9-11 long glass fiber polypropylene composite material (parts by weight) and test results
  • Example 9 Example 10
  • Example 11 Homopolypropylene A 60 60 60 Ethylene vinyl alcohol copolymer A 3 3 3 3 Compatibilizer A 3 3 3 3 long glass fiber B 30 the the long glass fiber C the 30 the long glass fiber D the the 30 antioxidant 0.8 0.8 0.8 lubricant 0.3 0.3 0.3 Charpy notched impact strength, kJ/m 2 37 38 35 Tensile strength, MPa 135 138 139 Ethylene Glycol Resistant Tensile Strength Retention Rate, % 93.5 93.2 93.9 Electrolyte resistance tensile strength performance retention rate, % 96.1 97.2 95.8
  • Table 2 Examples 12-14 long glass fiber polypropylene composite material (parts by weight) and test results
  • Example 12 Example 13
  • Example 14 Homopolypropylene A 60 60 60 Ethylene vinyl alcohol copolymer A 3 3 3 3 Compatibilizer B 3 the the Compatibilizer C the 3 the Compatibilizer D the the 3 Long Glass Fiber A 30 30 30 30 antioxidant 0.8 0.8 0.8 lubricant 0.3 0.3 0.3 Charpy notched impact strength, kJ/m 2 36 34 33 Tensile strength, MPa 136 136 132 Ethylene Glycol Resistant Tensile Strength Retention Rate, % 93.7 93.5 93.2 Electrolyte resistance tensile strength performance retention rate, % 97.8 97.4 97.1
  • the preferred ethylene vinyl alcohol copolymer has an ethylene unit content of 30mol%-40mol%, and a melt index of 3-4g/10min.
  • Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Homopolypropylene A 60 60 60 the Copolymer polypropylene the the the 60 Ethylene vinyl alcohol copolymer A 1 the 10 1 Compatibilizer A 1 1 1 1 Long Glass Fiber A the 10 10 10 Long Glass Fiber E 10 the the the antioxidant 0.8 0.8 0.8 0.8 lubricant 0.3 0.3 0.3 0.3 0.3 0.3 0.3
  • Comparative Example 1 It can be seen from Comparative Example 1 that ordinary glass fibers have low strength, and are insufficient in resistance to ethylene glycol and electrolyte.

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Abstract

本发明公开了一种长玻纤增强聚丙烯复合材料，按重量份计，包括以下组分：均聚聚丙烯30-70份；乙烯乙烯醇共聚物1-8份；相容剂1-6份；长玻璃纤维10-70份；助剂0.2-2份。本发明在均聚聚乙烯中添加一定量的乙烯乙烯醇共聚物，并且特选了长玻璃纤维的种类，明显改善了超高强度长玻璃纤维的浸润效果，解决了超高强度长玻纤增强聚丙烯耐溶剂性能差、分散不均匀的技术缺陷，提升了耐溶剂性及材料力学性能。

Description

一种长玻纤增强聚丙烯复合材料及其制备方法和应用 技术领域
本发明涉及高分子材料技术领域，特别是涉及一种长玻纤增强聚丙烯复合材料及其制备方法和应用。
背景技术
长玻纤增强聚丙烯(LFT-PP)具有密度低、抗冲击性强、翘曲度低、耐疲劳、蠕变性能优异等显著特点，且在材料或零件中的高玻纤保留长度，使其具有作为结构件和功能件所需的耐久性和可靠性，广泛应用于电子电器、家电、汽车等领域。随着对汽车轻量化的需求越来越迫切，要求越来越严，车用油箱、膨胀壶、水室等部件对材料性能的要求也越来越高，尤其是对材料的耐蠕变性能、耐热性能、耐化学药品腐蚀性能提出了更高的要求。汽车发动机周边零件如水室、节温器、发动机罩盖、前舱盖板等零件需长期与冷却液(乙二醇)、玻璃清洗液等溶剂接触接触，现用材料为玻纤增强尼龙；长玻纤增强聚丙烯由于其优异的力学性能可作为轻量化期待方案。
但是，长期以来，长玻纤增强聚丙烯复合材料的耐溶剂性较差，很难应用在车载上述制件领域。中国专利201910217593X公开了一种长玻纤增强聚丙烯材料的制备方法，其中采用传统的长玻纤浸润法，将长玻纤(线密度2400-2500tex)通过浸润模头将玻璃纤维与树脂浸润。但是，实际上采用该方法无法使长玻纤与树脂充分的浸润，对于长玻纤增强聚丙烯复合材料的耐溶剂性缺陷改善不足。
发明内容
本发明的目的在于，克服上述技术缺陷，提供一种长玻纤增强聚丙烯复合材料，具有耐溶剂性能好、力学性能优异的优点。
本发明是通过以下技术方案实现的：
一种长玻纤增强聚丙烯复合材料，按重量份计，包括以下组分：
Figure PCTCN2022105162-appb-000001
所述的乙烯乙烯醇共聚物链段中，乙烯单元含量为25mol％～45mol％；
所述长玻璃纤维选自HMG长玻璃纤维、S-1长玻璃纤维、TM长玻璃纤维、S-2长玻璃纤维中的一种或几种。
优选的，均聚聚丙烯40-50份，长玻璃纤维40-60份。现有技术中，一般玻璃纤维的含量越高，由于浸润性差会导致耐溶剂性的急速降低。而本发明的技术方案中，长玻璃纤维可以达到60份时耐溶剂性才会缓缓下降，说明本发明超高强度长玻璃纤维的浸润性好。
所述的长玻璃纤维平均直径为12-20微米，优选的，所述的长玻璃纤维平均直径为14-17微米；优选的，所述的长玻璃纤维选自HMG长玻纤。
上述列举的长玻纤为高强度无碱连续玻璃纤维，相对于其他种类的长玻纤具有更高的强度，但是浸润难度也更高。
所述的均聚聚丙烯的熔融指数为10～150g/10min，条件230℃，2.16kg，测试标准为ISO1133。
优选的，所述的乙烯乙烯醇共聚物链段中，乙烯单元含量为30mol％～40mol％。
乙烯乙烯醇共聚物的熔融指数为2～5g/10min，条件为210℃，2.16kg，测试标准为ISO1133；优选的，乙烯乙烯醇共聚物的熔融指数为3～4g/10min，测试标准为ISO 1133。
所述的相容剂选自马来酸酐接枝聚丙烯、丙烯酸接枝聚丙烯、马来酸接枝聚丙烯、丙烯酸缩水甘油酯接枝聚丙烯中的至少一种，其中马来酸酐、马来酸、丙烯酸、丙烯酸缩水甘油酯的接枝率为1-1.5wt％，相容剂的熔融指数50～120g/10min，条件190℃，2.16Kg。接枝率可以通过酸碱滴定法测定。
优选的，所述的相容剂选自马来酸酐接枝聚丙烯。
按重量份计，还包括0-2份助剂，所述的助剂选自抗氧剂、润滑剂、成核剂中的一种或多种。
抗氧剂可以是受阻酚类或亚磷酸酯类抗氧剂复配物。
润滑剂可以是硅酮类、酯类、酰胺类、聚乙烯类、硬脂酸类、脂肪酸及酯等。
成核剂为颗粒粒径小于1μm的无机成核剂，可以是滑石粉，蒙脱土、碳酸钙等。
本发明的长玻纤增强聚丙烯复合材料的制备方法，按照配比，将除长玻璃纤维之外各组分混合均匀，通过双螺杆挤出机进行熔融混炼，再将熔料通过浸润模头，将长玻璃纤维经过张力分散系统进入模头预浸渍系统，在预浸渍模具中浸渍后进入浸润模头，在浸润模头中将树脂与长玻璃纤维分散均匀，挤出造粒，挤出机温度为210-280℃、浸润模头温度为270-320℃，得到长玻纤增强聚丙烯复合材料。
本发明的长玻纤增强聚丙烯复合材料的应用，用于制备汽车内外饰、工业风扇、电动工 具结构件。
本发明具有如下有益效果：
现有技术中，很难将高强度长玻璃纤维与树脂基体完全的浸润。
关于配方，本发明通过特选超高强度长玻璃纤维的种类并且添加特定重复单元结构的乙烯乙烯醇共聚物，能够明显提升超高强度长玻璃纤维在均聚聚丙烯树脂基体中的浸润性和分散性，进而提升长玻纤增强聚丙烯复合材料的耐溶剂性和力学性能。
关于制备方法，本发明的超高强度长玻璃纤维通过张力系统和预浸渍系统的分散，能够明显提升长玻纤与树脂基体的浸润性。
附图说明
图1：耐电解液评价装置图。
具体实施方式
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。
实施例和对比例所用原材料来源如下：
均聚聚丙烯A：M60T，中石化，60g/10min，条件230℃，2.16Kg；
均聚聚丙烯B：Z30S，中石化，25g/10min，条件230℃，2.16Kg；
共聚聚丙烯：EP548R，中海壳牌，30g/10min，条件230℃，2.16Kg；
乙烯乙烯醇共聚物A：乙烯单元含量为29mol％，熔融指数3.0g/10min，条件为210℃，2.16kg，市售；
乙烯乙烯醇共聚物B：乙烯单元含量为32mol％，熔融指数3.7g/10min，条件为210℃，2.16kg，市售；
乙烯乙烯醇共聚物C：乙烯单元含量为38mol％，熔融指数3.7g/10min，条件为210℃，2.16kg，市售；
乙烯乙烯醇共聚物D：乙烯单元含量为44mol％，熔融指数4.0g/10min，条件为210℃，2.16kg，市售；
乙烯乙烯醇共聚物E：乙烯单元含量为35mol％，熔融指数2.3g/10min，条件为210℃，2.16kg，市售；
乙烯乙烯醇共聚物F：乙烯单元含量为35mol％，熔融指数4.4g/10min，条件为210℃， 2.16kg，市售；
相容剂A：马来酸酐接枝聚丙烯，马来酸酐的接枝率为1wt％，熔融指数80g/10min，条件230℃，2.16Kg；
相容剂B：丙烯酸接枝聚丙烯，丙烯酸接枝率为0.5wt％，熔融指数50g/10min，条件230℃，2.16Kg；
相容剂C：马来酸接枝聚丙烯，马来酸接枝率为1.2wt％，熔融指数100g/10min，条件230℃，2.16Kg；
相容剂D：丙烯酸缩水甘油酯接枝聚丙烯，丙烯酸缩水甘油酯接枝率为1wt％，熔融指数70g/10min，条件230℃，2.16Kg；
长玻璃纤维A-1：HMG838T，平均直径为17微米；
长玻璃纤维A-2：HMG838T，平均直径为14微米；
长玻璃纤维A-3：HMG838T，平均直径为12微米；
长玻璃纤维A-4：HMG838T，平均直径为20微米；
长玻璃纤维B：S-1Glass，平均直径为17微米；
长玻璃纤维C：TM4305，平均直径为17微米；
长玻璃纤维D：S-2Glass，平均直径为14微米；
长玻璃纤维E：EDR240-T838T，平均直径为17微米。
抗氧剂：抗氧剂1010/抗氧剂168为1:1复配；
润滑剂：润滑剂-A-C540A。
实施例和对比例长玻纤增强聚丙烯复合材料的制备方法，其特征在于，按照配比，将均聚聚丙烯、乙烯乙烯醇共聚物、相容剂、助剂混合均匀，通过双螺杆挤出机进行熔融混炼，再将熔料通过浸润模头，将长玻璃纤维经过张力分散系统进入模头预浸渍系统，在预浸渍模具中浸渍后进入浸润模头，在浸润模头中将树脂与长玻璃纤维分散均匀，挤出造粒，挤出机加热块共9个温度段，温度分别为50/180/210/280/280/280//280/280/280℃、转速为550rpm，浸润模头温度为270-320℃，得到长玻纤增强聚丙烯复合材料。
各项测试方法
(1)简支梁缺口冲击强度：按照ISO179/1eA标准，使用注塑机将长玻纤增强聚丙烯复合材料模制成4mm厚的测试样条，23℃下，测试样条的简支梁缺口冲击强度；
(2)拉伸强度：按照ISO527-1/2标准，使用注塑机将长玻纤增强聚丙烯复合材料模制成4mm厚的测试样条，23℃、5mm/min的测试速度条件下，测试样条的拉伸强度；
(3)耐乙二醇评价：将乙二醇与去离子水按照1:1体积比进行混合均匀并倒入反应釜中，制备得到的拉伸测试样条放入反应釜中密封，将反应釜放入120℃老化箱中老化1000h，测试拉伸强度性能保持率。
(4)耐电解液评价：将浓硫酸与去离子水配置成35wt％浓度硫酸溶液，并将硫酸溶液导入容器中，制备得到的拉伸测试样条放入如说明书附图的装置，在70℃下加热24h，测试拉伸强度性能保持率。
表1：实施例1-8长玻纤聚丙烯复合材料(重量份)及测试结果
Figure PCTCN2022105162-appb-000002
由实施例1-4可知，超高强度长玻纤优选的平均直径为14-17微米。
由实施例1/5/6/7/8可知，优选的均聚聚丙烯和长玻璃纤维的配比下，力学性能最好，而且耐溶剂性也较好。
表2：实施例9-11长玻纤聚丙烯复合材料(重量份)及测试结果
  实施例9 实施例10 实施例11
均聚聚丙烯A 60 60 60
乙烯乙烯醇共聚物A 3 3 3
相容剂A 3 3 3
长玻璃纤维B 30    
长玻璃纤维C   30  
长玻璃纤维D     30
抗氧剂 0.8 0.8 0.8
润滑剂 0.3 0.3 0.3
简支梁缺口冲击强度，kJ/m 2 37 38 35
拉伸强度，MPa 135 138 139
耐乙二醇拉伸强度性能保持率，％ 93.5 93.2 93.9
耐电解液拉伸强度性能保持率，％ 96.1 97.2 95.8
由实施例1/2/9/10/11可知，优选HMG玻璃纤维，相容性更好使得力学性能与耐溶剂性综合更好。
表2：实施例12-14长玻纤聚丙烯复合材料(重量份)及测试结果
  实施例12 实施例13 实施例14
均聚聚丙烯A 60 60 60
乙烯乙烯醇共聚物A 3 3 3
相容剂B 3    
相容剂C   3  
相容剂D     3
长玻璃纤维A 30 30 30
抗氧剂 0.8 0.8 0.8
润滑剂 0.3 0.3 0.3
简支梁缺口冲击强度，kJ/m 2 36 34 33
拉伸强度，MPa 136 136 132
耐乙二醇拉伸强度性能保持率，％ 93.7 93.5 93.2
耐电解液拉伸强度性能保持率，％ 97.8 97.4 97.1
由实施例1/12/13/14可知，优选马来酸酐接枝聚丙烯相容剂。
表3：实施例15-21长玻纤聚丙烯复合材料(重量份)及测试结果
Figure PCTCN2022105162-appb-000003
由实施例1/15-19可知，优选乙烯乙烯醇共聚物的乙烯单元含量为30mol％～40mol％，熔融指数为3-4g/10min。
表4：对比例长玻纤聚丙烯复合材料(重量份)及测试结果
  对比例1 对比例2 对比例3 对比例4
均聚聚丙烯A 60 60 60  
共聚聚丙烯       60
乙烯乙烯醇共聚物A 1   10 1
相容剂A 1 1 1 1
长玻璃纤维A   10 10 10
长玻璃纤维E 10      
抗氧剂 0.8 0.8 0.8 0.8
润滑剂 0.3 0.3 0.3 0.3
简支梁缺口冲击强度，kJ/m 2 15 17 15 18
拉伸强度，MPa 73 79 74 76
耐乙二醇拉伸强度性能保持率，％ 90.5 90.0 92.4 92.0
耐电解液拉伸强度性能保持率，％ 92.2 92.4 91.9 93.2
由对比例1可知，普通的玻璃纤维强度低，而且耐乙二醇、耐电解液性不足。
由对比例2/3可知，乙烯乙烯醇共聚物是本发明申请的关键，并且添加过多反而会降低强度以及耐乙二醇及耐电解液性能。
由对比例4可知，共聚聚丙烯无法实现本发明的技术效果。

Claims (10)

  1. 一种长玻纤增强聚丙烯复合材料，其特征在于，按重量份计，包括以下组分：
    Figure PCTCN2022105162-appb-100001
    所述的乙烯乙烯醇共聚物链段中，乙烯单元含量为25mol％～45mol％；
    所述长玻璃纤维选自HMG长玻璃纤维、S-1长玻璃纤维、TM长玻璃纤维、S-2长玻璃纤维中的一种或几种。
  2. 根据权利要求1所述的长玻纤增强聚丙烯复合材料，其特征在于，均聚聚丙烯40-50份，长玻璃纤维40-60份。
  3. 根据权利要求1所述的长玻纤增强聚丙烯复合材料，其特征在于，所述的长玻璃纤维平均直径为12-20微米，优选的，所述的长玻璃纤维平均直径为14-17微米；所述的长玻璃纤维选自HMG长玻璃纤维。
  4. 根据权利要求1所述的长玻纤增强聚丙烯复合材料，其特征在于，所述的均聚聚丙烯的熔融指数为10～150g/10min，条件230℃，2.16kg，测试标准为ISO 1133。
  5. 根据权利要求1所述的长玻纤增强聚丙烯复合材料，其特征在于，所述的乙烯乙烯醇共聚物链段中，优选乙烯单元含量为30mol％～40mol％。
  6. 根据权利要求1所述的长玻纤增强聚丙烯复合材料，其特征在于，所述的乙烯乙烯醇共聚物的熔融指数为2～5g/10min，条件为210℃，2.16kg，测试标准为ISO 1133；优选的，乙烯乙烯醇共聚物的熔融指数为3～4g/10min，测试标准为ISO 1133。
  7. 根据权利要求1所述的长玻纤增强聚丙烯复合材料，其特征在于，所述的相容剂选自马来酸酐接枝聚丙烯、丙烯酸接枝聚丙烯、马来酸接枝聚丙烯、丙烯酸缩水甘油酯接枝聚丙烯中的至少一种，其中马来酸酐、丙烯酸、马来酸、丙烯酸缩水甘油酯的接枝率为0.5-1.5wt％，所述的相容剂的熔融指数为50～120g/10min，条件190℃，2.16Kg；所述的相容剂选自马来酸酐接枝聚丙烯。
  8. 根据权利要求1所述的长玻纤增强聚丙烯复合材料，其特征在于，按重量份计，还包括0-2份助剂，所述的助剂选自抗氧剂、润滑剂、成核剂中的一种或多种。
  9. 权利要求1-8任一项所述的长玻纤增强聚丙烯复合材料的制备方法，其特征在于，按照配比，将除长玻璃纤维之外各组分混合均匀，通过双螺杆挤出机进行熔融混炼，再将熔料通过 浸润模头，将长玻璃纤维经过张力分散系统进入模头预浸渍系统，在预浸渍模具中浸渍后进入浸润模头，在浸润模头中将熔料与长玻璃纤维分散均匀，挤出造粒，挤出机温度为210-280℃、浸润模头温度为270-320℃，得到长玻纤增强聚丙烯复合材料。
  10. 权利要求1-8任一项所述的长玻纤增强聚丙烯复合材料的应用，其特征在于，用于制备汽车内外饰、工业风扇、电动工具结构件。
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