WO2022127857A1 - Reinforced polypropylene material, preparation method therefor and use thereof - Google Patents

Reinforced polypropylene material, preparation method therefor and use thereof Download PDF

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WO2022127857A1
WO2022127857A1 PCT/CN2021/138773 CN2021138773W WO2022127857A1 WO 2022127857 A1 WO2022127857 A1 WO 2022127857A1 CN 2021138773 W CN2021138773 W CN 2021138773W WO 2022127857 A1 WO2022127857 A1 WO 2022127857A1
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polypropylene material
reinforcing fibers
reinforced polypropylene
material according
component
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PCT/CN2021/138773
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French (fr)
Chinese (zh)
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陆湛泉
黄险波
叶南飚
陈平绪
程文建
程书文
姜向新
杨霄云
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金发科技股份有限公司
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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
    • C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/047—Reinforcing macromolecular compounds with loose or coherent fibrous material with mixed fibrous material
    • 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
    • C08J2423/10—Homopolymers or copolymers of propene
    • C08J2423/12—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
    • C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2427/18—Homopolymers or copolymers of tetrafluoroethylene
    • 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

Definitions

  • the invention relates to the technical field of engineering plastics, in particular to a reinforced polypropylene material and a preparation method and application thereof.
  • Polypropylene material is currently the most widely used polymer material. It has the advantages of excellent processing performance and mechanical properties, and is widely used in daily life and industrial production fields, such as: agricultural film, wire and cable, communication, housing construction and aviation manufacturing. Wait.
  • the polyolefin materials suitable for blow molding and blister molding are basically HDPE or PP pure resins. These resins can be molded well, but they still need to be improved in terms of heat resistance and strength.
  • the industry usually uses the high strength and high rigidity of glass fiber to improve product strength and heat resistance, but conventional glass fiber reinforced polypropylene materials have low melt strength, low melt elongation, and surface floating fibers and poor toughness. And other issues.
  • the purpose of the present invention is to provide a reinforced polypropylene material with high rigidity and heat resistance, and high melt strength, which is beneficial to blow molding and suction molding.
  • Another object of the present invention is to provide a method for preparing the above-mentioned reinforced polypropylene material.
  • a reinforced polypropylene material, by weight, comprising the following components:
  • the reinforcing fiber includes component I, component II and component III, wherein:
  • Component I It is composed of reinforcing fibers with a length of less than 0.2 mm, and the percentage of the reinforcing fibers is 10-20%, preferably 14-18%;
  • Component II It is composed of reinforcing fibers with a length of 0.2mm-0.4mm, which accounts for 50-75% of the number of reinforcing fibers, preferably 60-70%;
  • Component III It is composed of reinforcing fibers with a length of 0.5mm-0.8mm, and the percentage of the reinforcing fibers is 5-40%, preferably 15-25%.
  • the melt index MI of the linear polypropylene is 0.01-10 g/10min, and the test conditions are 230° C., 2.16Kg load; preferably 0.1-3 g/10min.
  • the melt index MI of the long-chain branched polypropylene is 0.01-10 g/10min, and the test conditions are 230° C., 2.16Kg load; preferably 0.1-3 g/10min.
  • the reinforcing fibers are selected from one or a mixture of glass fibers, quartz fibers, and basalt fibers; the average diameter of the reinforcing fibers is 5-20 microns.
  • the compatibilizer is a graft polymer of a polar monomer and polypropylene, wherein the polar monomer is selected from one or a mixture of maleic anhydride, acrylic acid, and acrylate derivatives.
  • the fluorine compound is ethylene-tetrafluoroethylene copolymer (ETFE), polytetrafluoroethylene (PTFE), fluorinated ethylene propylene copolymer (FEP), perfluoroalkoxy resin (PFA), polychlorinated One or more mixtures of trifluoroethylene (PCTFE), ethylene-monochlorotrifluoroethylene copolymer (ECTFE) or polyvinylidene fluoride (PVDF).
  • ETFE ethylene-tetrafluoroethylene copolymer
  • PTFE polytetrafluoroethylene
  • FEP fluorinated ethylene propylene copolymer
  • PFA perfluoroalkoxy resin
  • PCTFE polychlorinated One or more mixtures of trifluoroethylene
  • ECTFE ethylene-monochlorotrifluoroethylene copolymer
  • PVDF polyvinylidene fluoride
  • high molecular weight fluorine compounds are preferred, which do not melt during the molding process, and will be stretched into fibers under the action of the melt, so that the polypropylene molecular chain and the fluorine compound fibers will form an interpenetrating network, thereby further improving the The melt strength of the entire material. If the molecular weight is too low, the improvement of melt strength is not obvious, and if the molecular weight is too high, the processing performance is affected. Therefore, preferably, the weight average molecular weight of the fluorine compound is 10-10 million, preferably 5-8 million.
  • the present invention also provides a method for preparing the above-mentioned reinforced polypropylene material, comprising the following steps:
  • the reinforced polypropylene material is prepared by melt blending and extrusion granulation through a twin-screw extruder.
  • the position of the twin-screw extruder side feeding system can be adjusted, and the reinforcing fibers can be fed into the screw in the first to tenth zones, and added after the extruder die, and then directly combined with the polypropylene melt.
  • the reinforcing fibers of the present invention enter the screw through different regions, so that the residence time of the reinforcing fibers in the extruder can be adjusted, and the shearing degree of the reinforcing fibers can be controlled, thereby controlling the retention length of the reinforcing fibers.
  • the temperature of the first to second zones of the twin-screw extruder is 120°C-160°C
  • the temperature of the third to fifth zone is 180°C-300°C
  • the temperature of the fifth to tenth zone is 180°C-300°C
  • the screw speed is 300rpm-600rpm.
  • the present invention also provides the application of the above-mentioned reinforced polypropylene material in blow molding and suction molding occasions.
  • the present invention has the following beneficial effects:
  • the present invention provides a reinforced polypropylene material, including straight-chain polypropylene, long-chain branched polypropylene, a compatibilizer, reinforcing fibers and fluorine compounds, wherein the long molecular chain of the straight-chain polypropylene is used to increase the distance between the molecular chains.
  • the entanglement between them is beneficial to improve the stability of the melt during extrusion and blistering;
  • the addition of long-chain branched polypropylene can greatly improve the melt strength by using its branched structure; high molecular weight fluorine compounds are used in the molding process. It does not melt, and will be stretched into fibers under the action of the melt, so that the polypropylene molecular chain and the fluorine compound fibers will form an interpenetrating network, thereby further improving the melt strength of the entire material;
  • the present invention can further improve the melt extension of the whole material while having better rigidity and heat resistance by adjusting and controlling the length and content distribution of the reinforcing fibers. sex.
  • the polypropylene material prepared by the invention has higher melt strength, better rigidity and heat resistance, and is mainly suitable for blow molding and suction molding and other occasions.
  • the raw materials used in the examples of the present invention and the comparative examples are all from commercially available;
  • Linear polypropylene 1 MI is 3g/10min (230°C, 2.16Kg load);
  • Linear polypropylene 2 MI is 9g/10min (230°C, 2.16Kg load);
  • Linear polypropylene 3 MI is 25g/10min (230°C, 2.16Kg load);
  • MI is 2g/10min (230°C, 2.16Kg load);
  • MI is 8g/10min (230°C, 2.16Kg load);
  • MI is 20g/10min (230°C, 2.16Kg load);
  • Fluorine compound 1 weight average molecular weight 60W polytetrafluoroethylene
  • Fluorine compound 2 weight average molecular weight 800W polytetrafluoroethylene
  • Fluorine compound 3 weight average molecular weight 2W polytetrafluoroethylene.
  • Maleic anhydride grafted polypropylene PP-g-MAH manufacturer Polyram; model: 1001CN;
  • Glass fiber 1 It is a glass fiber raw material with an average diameter of 8 microns;
  • Glass fiber 2 It is the glass fiber in the reinforced polypropylene material product, with an average diameter of 8 microns and a length of 0.4-0.6 mm.
  • the reinforced polypropylene material is prepared by melt blending and extrusion granulation through a twin-screw extruder.
  • the position of the extruder side feeding system can be adjusted, and the reinforcing fibers can enter the extruder screw in the first to tenth zones, and be added after the extruder die, and then directly combined with the polypropylene melt. Reinforcing fibers with different lengths and content distributions can be obtained by adjusting the position where the reinforcing fibers enter the extruder screw.
  • the temperature of the first to second zones of the extruder is 120°C-160°C
  • the temperature of the third to fifth zone is 180°C-300°C
  • the temperature of the fifth to tenth zone is 180°C-300°C
  • the screw speed is 300rpm-600rpm.
  • Test method for the length and distribution of reinforcing fibers After injection molding, the splines are first separated from the matrix by a high-temperature sintering scheme, and then the length of the reinforcing fibers is measured by automatic imaging analysis technology;
  • Heat distortion temperature ISO 75-2 2013, test condition: 0.46MPA;
  • the polypropylene material of the present invention comprising straight-chain polypropylene, long-chain branched polypropylene, fluorine compounds and reinforcing fibers has significantly improved melt strength and melt fracture speed, and is suitable for blow molding and suction. plastic and other occasions.
  • Comparative example 1 did not add long-chain branched polypropylene, and its melt strength and melt fracture rate were poor; in comparative example 2, long-chain branched polypropylene was introduced, but no fluorine compound was added, and its melt strength and melt The breaking speed is slightly improved, but the improvement effect is not obvious, which shows that there is a synergistic effect between the components of the present invention.
  • the length and content distribution of the reinforcing fibers affect the rigidity and heat resistance of the material, and also have an impact on the melt extensibility of the material.
  • the length and content distribution of reinforcing fibers in polypropylene, the prepared modified polypropylene material has good rigidity and heat resistance, and has good melt elongation, which is mainly suitable for blow molding and suction molding.

Abstract

Disclosed are a reinforced polypropylene material, a preparation method therefor, and the use thereof. The reinforced polypropylene material comprises 20-80 parts of linear polypropylene, 5-40 parts of a long-branched-chain polypropylene, 0.5-25 parts of a compatilizer, 5-60 parts of reinforcing fibers, and 1-20 parts of a fluorine compound. The polypropylene material prepared by the present invention has a relatively high melt strength and a relatively good rigidity and heat resistance, and is mainly suitable for occasions such as blow molding and plastic uptake.

Description

一种增强聚丙烯材料及其制备方法和应用A kind of reinforced polypropylene material and its preparation method and application 技术领域technical field
本发明涉及工程塑料技术领域，特别涉及一种增强聚丙烯材料及其制备方法和应用。The invention relates to the technical field of engineering plastics, in particular to a reinforced polypropylene material and a preparation method and application thereof.
背景技术Background technique
聚丙烯材料是目前用量最大的高分子材料，具有优异的加工性能和力学性能等优点，被广泛应用于日常生活和工业生产领域，如：农用薄膜、电线电缆、通讯、房屋建筑和航空制造业等。Polypropylene material is currently the most widely used polymer material. It has the advantages of excellent processing performance and mechanical properties, and is widely used in daily life and industrial production fields, such as: agricultural film, wire and cable, communication, housing construction and aviation manufacturing. Wait.
目前适用于吹塑和吸塑用的聚烯烃材料，基本都是HDPE或者PP纯树脂，这些树脂能较好地成型，但是在耐热和强度方面还需要改善。行业内通常是利用玻璃纤维的高强度和高刚性来提高产品强度和耐热，但常规的玻璃纤维增强聚丙烯材料具有熔体强度低，熔体延伸率低，还有表面浮纤和韧性差等问题。At present, the polyolefin materials suitable for blow molding and blister molding are basically HDPE or PP pure resins. These resins can be molded well, but they still need to be improved in terms of heat resistance and strength. The industry usually uses the high strength and high rigidity of glass fiber to improve product strength and heat resistance, but conventional glass fiber reinforced polypropylene materials have low melt strength, low melt elongation, and surface floating fibers and poor toughness. And other issues.
因此，有必要研究一种适用于吹塑和吸塑用的增强聚丙烯材料。Therefore, it is necessary to study a reinforced polypropylene material suitable for blow molding and blister molding.
发明内容SUMMARY OF THE INVENTION
为了克服现有技术的缺点与不足，本发明的目的在于提供一种具有较高刚性和耐热性，且熔体强度高的利于吹塑和吸塑等场合的增强聚丙烯材料。In order to overcome the shortcomings and deficiencies of the prior art, the purpose of the present invention is to provide a reinforced polypropylene material with high rigidity and heat resistance, and high melt strength, which is beneficial to blow molding and suction molding.
本发明的另一目的是提供上述增强聚丙烯材料的制备方法。Another object of the present invention is to provide a method for preparing the above-mentioned reinforced polypropylene material.
本发明是通过以下技术方案实现的：The present invention is achieved through the following technical solutions:
一种增强聚丙烯材料，按重量份计，包括以下组分：A reinforced polypropylene material, by weight, comprising the following components:
Figure PCTCN2021138773-appb-000001
Figure PCTCN2021138773-appb-000001
所述增强纤维包括组分I、组分II和组分Ⅲ，其中：The reinforcing fiber includes component I, component II and component III, wherein:
组分I：由长度为小于0.2mm的增强纤维组成，其占增强纤维的根数百分比为10-20％，优选为14-18％；Component I: It is composed of reinforcing fibers with a length of less than 0.2 mm, and the percentage of the reinforcing fibers is 10-20%, preferably 14-18%;
组分II：由长度为0.2mm-0.4mm的增强纤维组成，其占增强纤维的根数百分比为50-75％，优选为60-70％；Component II: It is composed of reinforcing fibers with a length of 0.2mm-0.4mm, which accounts for 50-75% of the number of reinforcing fibers, preferably 60-70%;
组分Ⅲ：由长度为0.5mm-0.8mm的增强纤维组成，其占增强纤维的根数百分比为5-40％， 优选为15-25％。Component III: It is composed of reinforcing fibers with a length of 0.5mm-0.8mm, and the percentage of the reinforcing fibers is 5-40%, preferably 15-25%.
优选的，所述直链聚丙烯的熔融指数MI为0.01-10g/10min，测试条件为230℃，2.16Kg负荷；优选为0.1-3g/10min。Preferably, the melt index MI of the linear polypropylene is 0.01-10 g/10min, and the test conditions are 230° C., 2.16Kg load; preferably 0.1-3 g/10min.
优选的，所述长支链聚丙烯的熔融指数MI为0.01-10g/10min，测试条件为230℃，2.16Kg负荷；优选为0.1-3g/10min。Preferably, the melt index MI of the long-chain branched polypropylene is 0.01-10 g/10min, and the test conditions are 230° C., 2.16Kg load; preferably 0.1-3 g/10min.
优选的，所述增强纤维选自玻璃纤维、石英纤维、玄武岩纤维中的一种或几种的混合；所述增强纤维的平均直径为5-20微米。Preferably, the reinforcing fibers are selected from one or a mixture of glass fibers, quartz fibers, and basalt fibers; the average diameter of the reinforcing fibers is 5-20 microns.
优选的，所述相容剂为极性单体与聚丙烯的接枝聚合物，其中极性单体选自马来酸酐、丙烯酸、丙烯酸酯类衍生物中的一种或几种的混合物。Preferably, the compatibilizer is a graft polymer of a polar monomer and polypropylene, wherein the polar monomer is selected from one or a mixture of maleic anhydride, acrylic acid, and acrylate derivatives.
优选的，所述氟类化合物为乙烯-四氟乙烯共聚物(ETFE)、聚四氟乙烯(PTFE)、氟化乙丙共聚物(FEP)、全氟烷氧基树脂(PFA)、聚氯三氟乙烯(PCTFE)、乙烯-一氯三氟乙烯共聚合物(ECTFE)或聚偏氟乙烯(PVDF)中一种或几种的混合物。Preferably, the fluorine compound is ethylene-tetrafluoroethylene copolymer (ETFE), polytetrafluoroethylene (PTFE), fluorinated ethylene propylene copolymer (FEP), perfluoroalkoxy resin (PFA), polychlorinated One or more mixtures of trifluoroethylene (PCTFE), ethylene-monochlorotrifluoroethylene copolymer (ECTFE) or polyvinylidene fluoride (PVDF).
本发明优选高分子量的氟类化合物，其在成型过程中不熔，在熔体的作用下会给拉伸为纤维，这样聚丙烯分子链和氟类化合物纤维会形成互穿网络，从而进一步提高整个材料的熔体强度。分子量过低，对熔体强度的改善不明显，分子量过高，影响其加工性能，因此，优选的，所述氟类化合物的重均分子量为10-1000万，优选为500-800万。In the present invention, high molecular weight fluorine compounds are preferred, which do not melt during the molding process, and will be stretched into fibers under the action of the melt, so that the polypropylene molecular chain and the fluorine compound fibers will form an interpenetrating network, thereby further improving the The melt strength of the entire material. If the molecular weight is too low, the improvement of melt strength is not obvious, and if the molecular weight is too high, the processing performance is affected. Therefore, preferably, the weight average molecular weight of the fluorine compound is 10-10 million, preferably 5-8 million.
本发明还提供上述增强聚丙烯材料的制备方法，包括如下步骤：The present invention also provides a method for preparing the above-mentioned reinforced polypropylene material, comprising the following steps:
按照配方含量称量各组分，并将除增强纤维外的各组分混合均匀，随后将混合物加入双螺杆挤出机的主喂料系统；同时将增强纤维加入双螺杆挤出机的侧喂料系统，然后通过双螺杆挤出机熔融共混、挤出造粒制备得到增强聚丙烯材料。Weigh each component according to the formula content, and mix all components except the reinforcing fiber uniformly, then add the mixture to the main feeding system of the twin-screw extruder; at the same time, add the reinforcing fiber to the side feeding system of the twin-screw extruder The reinforced polypropylene material is prepared by melt blending and extrusion granulation through a twin-screw extruder.
双螺杆挤出机侧喂系统可以调节位置，增强纤维可以在第一至第十区进入螺杆，以及在挤出机模头后再加入，然后和聚丙烯熔体直接结合。本发明增强纤维通过不同区域进入螺杆，可以调节增强纤维在挤出机的停留时间，控制增强纤维受剪切的程度，从而控制增强纤维的保留长度。The position of the twin-screw extruder side feeding system can be adjusted, and the reinforcing fibers can be fed into the screw in the first to tenth zones, and added after the extruder die, and then directly combined with the polypropylene melt. The reinforcing fibers of the present invention enter the screw through different regions, so that the residence time of the reinforcing fibers in the extruder can be adjusted, and the shearing degree of the reinforcing fibers can be controlled, thereby controlling the retention length of the reinforcing fibers.
优选的，双螺杆挤出机一至二区温度为120℃-160℃，三至五区温度为180℃-300℃，五至十区温度为180℃-300℃，螺杆转速为300rpm-600rpm。Preferably, the temperature of the first to second zones of the twin-screw extruder is 120°C-160°C, the temperature of the third to fifth zone is 180°C-300°C, the temperature of the fifth to tenth zone is 180°C-300°C, and the screw speed is 300rpm-600rpm.
本发明还提供了上述增强聚丙烯材料在吹塑和吸塑场合中的应用。The present invention also provides the application of the above-mentioned reinforced polypropylene material in blow molding and suction molding occasions.
本发明与现有技术相比，具有如下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
本发明提供了一种增强聚丙烯材料，包括直链聚丙烯、长支链聚丙烯、相容剂、增强纤维和氟类化合物，其中，利用直链聚丙烯的长分子链，增加分子链之间的缠结，利于提高挤 出和吸塑时熔体的稳定；长支链聚丙烯的加入，利用其支链结构，可以极大提高熔体强度；高分子量的氟类化合物在成型过程中不熔，在熔体的作用下会被拉伸为纤维，这样聚丙烯分子链和氟类化合物纤维会形成互穿网络，从而进一步提高整个材料的熔体强度；The present invention provides a reinforced polypropylene material, including straight-chain polypropylene, long-chain branched polypropylene, a compatibilizer, reinforcing fibers and fluorine compounds, wherein the long molecular chain of the straight-chain polypropylene is used to increase the distance between the molecular chains. The entanglement between them is beneficial to improve the stability of the melt during extrusion and blistering; the addition of long-chain branched polypropylene can greatly improve the melt strength by using its branched structure; high molecular weight fluorine compounds are used in the molding process. It does not melt, and will be stretched into fibers under the action of the melt, so that the polypropylene molecular chain and the fluorine compound fibers will form an interpenetrating network, thereby further improving the melt strength of the entire material;
本发明通过调节控制增强纤维的长度和含量分布，与常规长度(0.4-0.6mm)的玻纤材料相比，在具有较好刚性和耐热性的同时，可进一步提高整个材料的熔体延伸性。Compared with glass fiber materials with conventional length (0.4-0.6mm), the present invention can further improve the melt extension of the whole material while having better rigidity and heat resistance by adjusting and controlling the length and content distribution of the reinforcing fibers. sex.
本发明制备得到的聚丙烯材料具有较高的熔体强度、较好的刚性和耐热性，主要适用于吹塑和吸塑等场合。The polypropylene material prepared by the invention has higher melt strength, better rigidity and heat resistance, and is mainly suitable for blow molding and suction molding and other occasions.
具体实施方式Detailed ways
下面通过具体实施方式来进一步说明本发明，以下实施例为本发明较佳的实施方式，但本发明的实施方式并不受下述实施例的限制。The present invention will be further described below through specific embodiments. The following examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited by the following examples.
本发明实施例和对比例所采用的原料均来源于市购；The raw materials used in the examples of the present invention and the comparative examples are all from commercially available;
直链聚丙烯1：MI为3g/10min(230℃，2.16Kg负荷)；Linear polypropylene 1: MI is 3g/10min (230℃, 2.16Kg load);
直链聚丙烯2：MI为9g/10min(230℃，2.16Kg负荷)；Linear polypropylene 2: MI is 9g/10min (230℃, 2.16Kg load);
直链聚丙烯3：MI为25g/10min(230℃，2.16Kg负荷)；Linear polypropylene 3: MI is 25g/10min (230℃, 2.16Kg load);
长支链聚丙烯1：MI为2g/10min(230℃，2.16Kg负荷)；Long-chain branched polypropylene 1: MI is 2g/10min (230℃, 2.16Kg load);
长支链聚丙烯2：MI为8g/10min(230℃，2.16Kg负荷)；Long-chain branched polypropylene 2: MI is 8g/10min (230°C, 2.16Kg load);
长支链聚丙烯3：MI为20g/10min(230℃，2.16Kg负荷)；Long-chain branched polypropylene 3: MI is 20g/10min (230℃, 2.16Kg load);
氟类化合物1：重均分子量60W聚四氟乙烯；Fluorine compound 1: weight average molecular weight 60W polytetrafluoroethylene;
氟类化合物2：重均分子量800W聚四氟乙烯；Fluorine compound 2: weight average molecular weight 800W polytetrafluoroethylene;
氟类化合物3：重均分子量2W聚四氟乙烯。Fluorine compound 3: weight average molecular weight 2W polytetrafluoroethylene.
相容剂：Compatibilizer:
马来酸酐接枝聚丙烯PP-g-MAH：厂家Polyram；型号：1001CN；Maleic anhydride grafted polypropylene PP-g-MAH: manufacturer Polyram; model: 1001CN;
增强纤维：Reinforcing fibers:
玻璃纤维1：为玻璃纤维原料，平均直径为8微米；Glass fiber 1: It is a glass fiber raw material with an average diameter of 8 microns;
玻璃纤维2：为增强聚丙烯材料产品中的玻璃纤维，平均直径为8微米，长度为0.4-0.6mm。Glass fiber 2: It is the glass fiber in the reinforced polypropylene material product, with an average diameter of 8 microns and a length of 0.4-0.6 mm.
实施例1-11及对比例1-6：增强聚丙烯材料的制备Examples 1-11 and Comparative Examples 1-6: Preparation of Reinforced Polypropylene Materials
按照配方含量称量各组分，并将除增强纤维外的各组分混合均匀，随后将混合物加入双螺杆挤出机的主喂料系统；同时将增强纤维加入双螺杆挤出机的侧喂料系统，然后通过双螺杆挤出机熔融共混、挤出造粒制备得到增强聚丙烯材料。Weigh each component according to the formula content, and mix all components except the reinforcing fiber uniformly, then add the mixture to the main feeding system of the twin-screw extruder; at the same time, add the reinforcing fiber to the side feeding system of the twin-screw extruder The reinforced polypropylene material is prepared by melt blending and extrusion granulation through a twin-screw extruder.
其中挤出机侧喂系统可以调节位置，增强纤维可以在第一至第十区进入挤出机螺杆，以 及在挤出机模头后再加入，然后和聚丙烯熔体直接结合。通过调节增强纤维进入挤出机螺杆的位置，得到不同长度和含量分布的增强纤维。The position of the extruder side feeding system can be adjusted, and the reinforcing fibers can enter the extruder screw in the first to tenth zones, and be added after the extruder die, and then directly combined with the polypropylene melt. Reinforcing fibers with different lengths and content distributions can be obtained by adjusting the position where the reinforcing fibers enter the extruder screw.
其中挤出机一至二区温度为120℃-160℃，三至五区温度为180℃-300℃，五至十区温度为180℃-300℃，螺杆转速为300rpm-600rpm。The temperature of the first to second zones of the extruder is 120℃-160℃, the temperature of the third to fifth zone is 180℃-300℃, the temperature of the fifth to tenth zone is 180℃-300℃, and the screw speed is 300rpm-600rpm.
各性能的测试标准或方法：Test standards or methods for each performance:
增强纤维的长度以及分布的测试方法：注塑后的样条首先采用高温灼烧的方案将增强纤维在基体中分离出，再使用自动成像分析技术对增强纤维长度进行测量；Test method for the length and distribution of reinforcing fibers: After injection molding, the splines are first separated from the matrix by a high-temperature sintering scheme, and then the length of the reinforcing fibers is measured by automatic imaging analysis technology;
热变形温度：ISO 75-2 2013，测试条件：0.46MPA；Heat distortion temperature: ISO 75-2 2013, test condition: 0.46MPA;
弯曲强度：ISO 178-2019；Bending strength: ISO 178-2019;
熔体强度、熔体断裂速度：熔体拉伸流变仪测试，测试条件：180℃；Melt strength, melt fracture speed: melt tensile rheometer test, test condition: 180 ℃;
表1各实施例与对比例中各组分的具体配比(重量份)及各性能测试结果The specific proportions (parts by weight) of each component in each embodiment and comparative example of table 1 and the test results of each performance
Figure PCTCN2021138773-appb-000002
Figure PCTCN2021138773-appb-000002
续表1Continued from Table 1
Figure PCTCN2021138773-appb-000003
Figure PCTCN2021138773-appb-000003
由上表可以看出，本发明包含直链聚丙烯、长支链聚丙烯、氟类化合物和增强纤维的聚丙烯材料，其熔体强度和熔体断裂速度明显提高，适用于吹塑和吸塑等场合。对比例1未加入长支链聚丙烯，其熔体强度和熔体断裂速度均较差；对比例2中引入了长支链聚丙烯，但未加入氟类化合物，其熔体强度和熔体断裂速度稍微有所提高，但提高效果不明显，由此可以表明，本发明各组分之间具有协同增效作用。As can be seen from the above table, the polypropylene material of the present invention comprising straight-chain polypropylene, long-chain branched polypropylene, fluorine compounds and reinforcing fibers has significantly improved melt strength and melt fracture speed, and is suitable for blow molding and suction. plastic and other occasions. Comparative example 1 did not add long-chain branched polypropylene, and its melt strength and melt fracture rate were poor; in comparative example 2, long-chain branched polypropylene was introduced, but no fluorine compound was added, and its melt strength and melt The breaking speed is slightly improved, but the improvement effect is not obvious, which shows that there is a synergistic effect between the components of the present invention.
由上表实施例1-2和对比例3-5可以看出，增强纤维的长度及含量分布影响材料的刚性和耐热性，且对材料熔体延伸性也有影响，本发明通过控制改性聚丙烯中的增强纤维的长度及含量分布，制备得到的改性聚丙烯材料具有较好的刚性和耐热性，且熔体延伸性好，主要适用于吹塑和吸塑等场合。As can be seen from Examples 1-2 and Comparative Examples 3-5 in the above table, the length and content distribution of the reinforcing fibers affect the rigidity and heat resistance of the material, and also have an impact on the melt extensibility of the material. The length and content distribution of reinforcing fibers in polypropylene, the prepared modified polypropylene material has good rigidity and heat resistance, and has good melt elongation, which is mainly suitable for blow molding and suction molding.
由实施例1-2和对比例6的对比可知，本发明通过调节控制增强纤维的长度和含量分布，与常规长度(0.4-0.6mm)的玻纤材料相比，在具有较好刚性和耐热性的同时，可进一步提高整个材料的熔体延伸性。From the comparison of Examples 1-2 and Comparative Example 6, it can be seen that the present invention controls the length and content distribution of the reinforcing fibers by adjusting, and has better rigidity and resistance than glass fiber materials with conventional lengths (0.4-0.6mm). At the same time, the melt extensibility of the whole material can be further improved.

Claims (10)

  1. 一种增强聚丙烯材料，其特征在于，按重量份计，包括以下组分：A reinforced polypropylene material, characterized in that, in parts by weight, it comprises the following components:
    Figure PCTCN2021138773-appb-100001
    Figure PCTCN2021138773-appb-100001
    所述增强纤维包括组分I、组分II和组分Ⅲ，其中：The reinforcing fiber includes component I, component II and component III, wherein:
    组分I：由长度为小于0.2mm的增强纤维组成，其占增强纤维的根数百分比为10-20％，优选为14-18％；Component I: It is composed of reinforcing fibers with a length of less than 0.2 mm, and the percentage of the reinforcing fibers is 10-20%, preferably 14-18%;
    组分II：由长度为0.2mm-0.4mm的增强纤维组成，其占增强纤维的根数百分比为50-75％，优选为60-70％；Component II: It is composed of reinforcing fibers with a length of 0.2mm-0.4mm, which accounts for 50-75% of the number of reinforcing fibers, preferably 60-70%;
    组分Ⅲ：由长度为0.5mm-0.8mm的增强纤维组成，其占增强纤维的根数百分比为5-40％，优选为15-25％。Component III: It is composed of reinforcing fibers with a length of 0.5mm-0.8mm, and the percentage of the reinforcing fibers is 5-40%, preferably 15-25%.
  2. 根据权利要求1所述的增强聚丙烯材料，其特征在于，所述直链聚丙烯的熔融指数MI为0.01-10g/10min，测试条件为230℃，2.16Kg负荷；优选为0.1-3g/10min。The reinforced polypropylene material according to claim 1, wherein the melt index MI of the linear polypropylene is 0.01-10g/10min, and the test conditions are 230°C, 2.16Kg load; preferably 0.1-3g/10min .
  3. 根据权利要求1所述的增强聚丙烯材料，其特征在于，所述长支链聚丙烯的熔融指数MI为0.01-10g/10min，测试条件为230℃，2.16Kg负荷；优选为0.1-3g/10min。The reinforced polypropylene material according to claim 1, wherein the melt index MI of the long-chain branched polypropylene is 0.01-10g/10min, and the test conditions are 230°C, 2.16Kg load; preferably 0.1-3g/ 10min.
  4. 根据权利要求1所述的增强聚丙烯材料，其特征在于，所述增强纤维选自玻璃纤维、石英纤维、玄武岩纤维中的一种或几种的混合；所述增强纤维的平均直径为5-20微米。The reinforced polypropylene material according to claim 1, wherein the reinforcing fibers are selected from one or a mixture of glass fibers, quartz fibers, and basalt fibers; the average diameter of the reinforcing fibers is 5- 20 microns.
  5. 根据权利要求1所述的增强聚丙烯材料，其特征在于，所述相容剂为极性单体与聚丙烯的接枝聚合物，其中极性单体选自马来酸酐、丙烯酸、丙烯酸酯类衍生物中的一种或几种的混合物。The reinforced polypropylene material according to claim 1, wherein the compatibilizer is a graft polymer of a polar monomer and polypropylene, wherein the polar monomer is selected from maleic anhydride, acrylic acid, acrylate One or more of the derivatives.
  6. 根据权利要求1所述的增强聚丙烯材料，其特征在于，所述氟类化合物为乙烯-四氟乙烯共聚物ETFE、聚四氟乙烯PTFE、氟化乙丙共聚物FEP、全氟烷氧基树脂PFA、聚氯三氟乙烯PCTFE、乙烯-一氯三氟乙烯共聚合物ECTFE或聚偏氟乙烯PVDF中的一种或几种的混合物。The reinforced polypropylene material according to claim 1, wherein the fluorine compound is ethylene-tetrafluoroethylene copolymer ETFE, polytetrafluoroethylene PTFE, fluorinated ethylene propylene copolymer FEP, perfluoroalkoxy One or more mixtures of resin PFA, polychlorotrifluoroethylene PCTFE, ethylene-monochlorotrifluoroethylene copolymer ECTFE or polyvinylidene fluoride PVDF.
  7. 根据权利要求6所述的增强聚丙烯材料，其特征在于，所述氟类化合物的重均分子量为10-1000万，优选为500-800万。The reinforced polypropylene material according to claim 6, wherein the weight average molecular weight of the fluorine compound is 10-10 million, preferably 5-8 million.
  8. 根据权利要求1-7任一项所述的增强聚丙烯材料的制备方法，其特征在于，包括如下步骤：按照配方含量称量各组分，并将除增强纤维外的各组分混合均匀，随后将混合物加入双螺杆 挤出机的主喂料系统；同时将增强纤维加入双螺杆挤出机的侧喂料系统，然后通过双螺杆挤出机熔融共混、挤出造粒制备得到增强聚丙烯材料。The preparation method of reinforced polypropylene material according to any one of claims 1-7, characterized in that it comprises the steps of: weighing each component according to the formula content, and mixing each component except the reinforcing fiber uniformly, Then, the mixture was added to the main feeding system of the twin-screw extruder; at the same time, the reinforcing fibers were added to the side-feeding system of the twin-screw extruder, and then the reinforced polymer was prepared by melt-blending and extrusion granulation through the twin-screw extruder. Acrylic material.
  9. 根据权利要求8所述的增强聚丙烯材料的制备方法，其特征在于，所述双螺杆挤出机一至二区温度为120℃-160℃，三至五区温度为180℃-300℃，五至十区温度为180℃-300℃，螺杆转速为300rpm-600rpm。The preparation method of reinforced polypropylene material according to claim 8, wherein the temperature of the first to second zones of the twin-screw extruder is 120°C-160°C, the temperature of the third to fifth zones is 180°C-300°C, and the temperature of the fifth zone is 180°C-300°C. The temperature of the tenth zone is 180℃-300℃, and the screw speed is 300rpm-600rpm.
  10. 根据权利要求1-7任一项所述的增强聚丙烯材料在吹塑或吸塑场合中的应用。Application of the reinforced polypropylene material according to any one of claims 1 to 7 in blow molding or blister molding.
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Publication number Priority date Publication date Assignee Title
CN112708196B (en) * 2020-12-18 2022-08-09 金发科技股份有限公司 Reinforced polypropylene material and preparation method and application thereof
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CN114031842B (en) * 2021-09-29 2023-10-31 金发科技股份有限公司 Impact-resistant halogen-free flame-retardant polypropylene composition and preparation method and application thereof
CN116041849A (en) * 2022-12-29 2023-05-02 上海宏盎新材料科技有限公司 High-strength automobile skylight reinforced polypropylene material and preparation method thereof

Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5595696A (en) * 1994-06-03 1997-01-21 Basf Aktiengesellschaft Plastic material, and process for the preparation thereof
US6284831B1 (en) * 1996-11-07 2001-09-04 Mitsubishi Denki Kabushiki Kaisha Fiber-reinforced resin molded article
CN102558675A (en) * 2011-12-21 2012-07-11 上海普利特复合材料股份有限公司 Polypropylene material with high melt strength and preparation method thereof
CN103044773A (en) * 2012-12-24 2013-04-17 上海普利特复合材料股份有限公司 Melt strength enhancing PP (polypropylene) material and preparation method thereof
JP2013072042A (en) * 2011-09-28 2013-04-22 Toray Ind Inc Carbon fiber-reinforced thermoplastic resin sheet
JP2013173330A (en) * 2012-02-27 2013-09-05 Toyota Motor Corp Method of manufacturing fiber-reinforced resin material
CN104130508A (en) * 2014-08-12 2014-11-05 苏州卓越工程塑料有限公司 Low-oriented extrusion grade polypropylene material and preparation method thereof
JP2014208802A (en) * 2013-03-29 2014-11-06 日本ポリプロ株式会社 Fiber-reinforced polypropylene-based flame retardant resin composition, and molding using the same
WO2015022404A1 (en) * 2013-08-15 2015-02-19 Basf Se Fibre-reinforced thermoplastic moulding composition with improved weld line strength
CN105837941A (en) * 2016-05-16 2016-08-10 上海日之升科技有限公司 Low-floating-fiber glass fiber reinforced polypropylene material and preparation method thereof
US20170218189A1 (en) * 2014-10-01 2017-08-03 Japan Polypropylene Corporation Fiber-reinforced flame-retardant polypropylene resin composition and molded article using the same
CN108084561A (en) * 2017-12-19 2018-05-29 会通新材料股份有限公司 A kind of lightweight polypropylene micro foaming composite material and preparation method thereof
CN108690259A (en) * 2017-04-10 2018-10-23 广州金发碳纤维新材料发展有限公司 A kind of fibre reinforced PP composite material and preparation method thereof
US10351693B2 (en) * 2013-09-27 2019-07-16 Sumitomo Riko Company Limited Glass-fiber-reinforced thermoplastic resin molding product, and production method therefor
CN110092872A (en) * 2019-05-31 2019-08-06 青岛海尔新材料研发有限公司 The extrusion foaming of one-step method preparation damping PP composite material and preparation method thereof
CN111500009A (en) * 2020-04-13 2020-08-07 金发科技股份有限公司 Reinforced polypropylene material and preparation method thereof
CN111534037A (en) * 2020-04-20 2020-08-14 金发科技股份有限公司 Reinforced polypropylene material and preparation method thereof
CN112724510A (en) * 2020-12-18 2021-04-30 金发科技股份有限公司 Reinforced polypropylene material and preparation method and application thereof

Patent Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5595696A (en) * 1994-06-03 1997-01-21 Basf Aktiengesellschaft Plastic material, and process for the preparation thereof
US6284831B1 (en) * 1996-11-07 2001-09-04 Mitsubishi Denki Kabushiki Kaisha Fiber-reinforced resin molded article
JP2013072042A (en) * 2011-09-28 2013-04-22 Toray Ind Inc Carbon fiber-reinforced thermoplastic resin sheet
CN102558675A (en) * 2011-12-21 2012-07-11 上海普利特复合材料股份有限公司 Polypropylene material with high melt strength and preparation method thereof
JP2013173330A (en) * 2012-02-27 2013-09-05 Toyota Motor Corp Method of manufacturing fiber-reinforced resin material
CN103044773A (en) * 2012-12-24 2013-04-17 上海普利特复合材料股份有限公司 Melt strength enhancing PP (polypropylene) material and preparation method thereof
JP2014208802A (en) * 2013-03-29 2014-11-06 日本ポリプロ株式会社 Fiber-reinforced polypropylene-based flame retardant resin composition, and molding using the same
WO2015022404A1 (en) * 2013-08-15 2015-02-19 Basf Se Fibre-reinforced thermoplastic moulding composition with improved weld line strength
US10351693B2 (en) * 2013-09-27 2019-07-16 Sumitomo Riko Company Limited Glass-fiber-reinforced thermoplastic resin molding product, and production method therefor
CN104130508A (en) * 2014-08-12 2014-11-05 苏州卓越工程塑料有限公司 Low-oriented extrusion grade polypropylene material and preparation method thereof
US20170218189A1 (en) * 2014-10-01 2017-08-03 Japan Polypropylene Corporation Fiber-reinforced flame-retardant polypropylene resin composition and molded article using the same
CN105837941A (en) * 2016-05-16 2016-08-10 上海日之升科技有限公司 Low-floating-fiber glass fiber reinforced polypropylene material and preparation method thereof
CN108690259A (en) * 2017-04-10 2018-10-23 广州金发碳纤维新材料发展有限公司 A kind of fibre reinforced PP composite material and preparation method thereof
CN108084561A (en) * 2017-12-19 2018-05-29 会通新材料股份有限公司 A kind of lightweight polypropylene micro foaming composite material and preparation method thereof
CN110092872A (en) * 2019-05-31 2019-08-06 青岛海尔新材料研发有限公司 The extrusion foaming of one-step method preparation damping PP composite material and preparation method thereof
CN111500009A (en) * 2020-04-13 2020-08-07 金发科技股份有限公司 Reinforced polypropylene material and preparation method thereof
CN111534037A (en) * 2020-04-20 2020-08-14 金发科技股份有限公司 Reinforced polypropylene material and preparation method thereof
CN112724510A (en) * 2020-12-18 2021-04-30 金发科技股份有限公司 Reinforced polypropylene material and preparation method and application thereof

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