WO2023000608A1 - High-impregnation long glass fiber reinforced polypropylene composite material and preparation method therefor - Google Patents

High-impregnation long glass fiber reinforced polypropylene composite material and preparation method therefor Download PDF

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WO2023000608A1
WO2023000608A1 PCT/CN2021/139967 CN2021139967W WO2023000608A1 WO 2023000608 A1 WO2023000608 A1 WO 2023000608A1 CN 2021139967 W CN2021139967 W CN 2021139967W WO 2023000608 A1 WO2023000608 A1 WO 2023000608A1
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glass fiber
parts
composite material
fiber reinforced
reinforced polypropylene
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PCT/CN2021/139967
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French (fr)
Chinese (zh)
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柯俊沐
陈登龙
郭振雄
吴健健
陈明鹏
刘志鹏
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福建师范大学泉港石化研究院
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Publication of WO2023000608A1 publication Critical patent/WO2023000608A1/en

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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
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
    • C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • 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
    • 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
    • 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
    • C08J2451/04—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 rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • 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
    • C08K9/00—Use of pretreated ingredients

Definitions

  • the invention belongs to the technical field of polymer materials, and in particular relates to a high impregnation degree long glass fiber reinforced polypropylene composite material and a preparation method thereof.
  • Polypropylene resin is a general-purpose plastic with a wide range of applications. It is one of the lowest-density varieties among all plastics. It has the advantages of good formability and chemical resistance. However, polypropylene resin has a large shrinkage rate and it is difficult to meet the requirements for size. It has high requirements for parts, and its mechanical properties are not as good as engineering plastics, so it cannot be used as a structural part. Glass fiber has many excellent properties such as high mechanical strength, good heat resistance and strong corrosion resistance, and is widely used in electronic equipment, building materials, sports equipment, aircraft and automobiles and other fields. The mechanical properties and dimensional stability of glass fiber reinforced polypropylene materials have been greatly improved, which can meet the requirements of replacing engineering plastics as structural parts.
  • Chinese patent CN201710528906 discloses a low-odor and low-floating long glass fiber reinforced polypropylene composite material for automotive interiors. Its advantage is that the odor measured according to the public odor detection standard is reduced from the conventional 4.0 level to 3.5 level, and it can be observed by naked eyes. The floating fiber on the surface is obviously improved.
  • Chinese patent CN201610207016 discloses a high-gloss long glass fiber flame-retardant and toughened polypropylene blend material, which is suitable for mid-to-high-end furniture products with high requirements for product structure and appearance, cost and processability.
  • Chinese patent CN201110008670 discloses a high-impact, low-floating long glass fiber reinforced polypropylene material, which has the advantages of high surface gloss, less floating fiber phenomenon, and good drop resistance.
  • the above-mentioned patents mainly use the anti-floating fiber agent to reduce the interaction force between the mold surface and the melt to reduce the floating fiber phenomenon on the surface of the part as much as possible, and do not improve the impregnation degree of the glass fiber in the material, and cannot fundamentally solve the problem of glass on the surface of the part. Fiber agglomeration defects.
  • Chinese patent CN202011594023.1 discloses a low-agglomeration long glass fiber reinforced polypropylene composite material for automotive interiors and a preparation method thereof.
  • the low-agglomeration long glass fiber reinforced polypropylene composite material for automotive interiors adds false twist to the continuous glass fiber bundle through the false twist device, so that the glass fiber monofilaments in the glass fiber bundles are completely dispersed, and the monofilaments in the glass fiber bundles can be obtained More complete impregnation can effectively reduce the agglomeration phenomenon of long glass fiber reinforced polypropylene materials, and can better meet the appearance requirements of long glass fiber reinforced polypropylene materials used in automotive interiors as exposed parts.
  • the invention uses a false twisting device to completely disperse the glass fibers.
  • the invention provides a long glass fiber reinforced polypropylene compound with high impregnation degree and long glass fiber reinforcement that has few glass fiber agglomeration defects and can be produced continuously on-line.
  • Materials, each step before and after the preparation process are closely related, all affect the wettability, the key technology is to charge the glass fiber with static electricity, so that the glass fibers repel each other to achieve the complete dispersion of the glass fiber.
  • the continuous glass fiber passes through the glass fiber heating pre-dispersion device and cooling device, then frictionally electrifies through silk, and finally passes through the static electricity generating device.
  • the pre-dispersion device By heating the pre-dispersion device, the glass fiber is dried to facilitate charging.
  • the pre-dispersion device initially spreads the glass fiber for the first time, and the contact surface increases when it is rubbed by silk, which is more conducive to charging.
  • the cooling device cools the glass fiber to prevent the silk from being scalded.
  • the cooling device adopts a blower device, and the airflow further disperses the glass fiber.
  • the silk friction and static electricity generating device makes each glass fiber charged with static electricity.
  • each glass fiber repels each other, and the glass fiber bundle will become fluffy, thereby further increasing the dispersion width of the glass fiber bundle; the static electricity generating device
  • the second part heats the glass fiber, keeps the glass fiber at a certain temperature and enters the dipping tank, prevents the cold glass fiber from meeting the melt, and the sudden cooling reduces the fluidity of the melt, which is not conducive to the infiltration of the glass fiber.
  • the polypropylene melt is fully infiltrated into the glass fiber, so that each glass fiber is wrapped with polypropylene resin.
  • a long glass fiber reinforced polypropylene composite material with high impregnation degree which is composed of the following raw materials in parts by weight: 43.2-63.2 parts of polypropylene resin, 30-50 parts of glass fiber, 1-10 parts of compatibilizer, and toughening agent 1-10 parts, 0.1-1 parts of antioxidant, 0.2-2 parts of lubricant.
  • the melting value of described polypropylene is 100 g/10min (2.16 kg, 230°C).
  • the glass fiber is direct untwisted glass fiber.
  • the compatibilizer is maleic anhydride grafted polypropylene.
  • the antioxidant is one or a combination of hindered phenol antioxidant 1010, phosphite antioxidant 168, and antioxidant GA80.
  • the toughening agent is one or a combination of maleic anhydride grafted EPDM, POE and SEBS.
  • the lubricant is one or more combinations of stearic acid, pentaerythritol stearate, glyceryl stearate, erucamide and polyethylene wax.
  • the continuous glass fiber passes through the glass fiber heating and pre-dispersing device and the cooling device on the drawing line, then passes through the silk friction and electrification, and finally passes through the static electricity generating device, and then enters the impregnation tank with polypropylene melt.
  • the electrostatic generating device is composed of two parts, the first part is composed of electrostatic electret electrostatic generator, high voltage wire, bracket, insulating support, molybdenum wire parts; the second part is composed of heating device;
  • the present invention has the following technical effects: Compared with the long glass fiber reinforced polypropylene composite materials commonly used in the market, the long glass fiber reinforced polypropylene composite material with high impregnation degree of the present invention realizes that each glass fiber is wrapped with polypropylene resin , to protect the glass fiber from being damaged during the plasticizing process of the pellets, thereby retaining the length of the glass fiber in the product, its tensile strength, flexural modulus, impact strength and other properties are greatly improved, and at the same time, the finished product is greatly reduced Occurrence ratio of surface glass fiber agglomeration defects.
  • Each step in the preparation process of the present invention is closely related, and the key technology is to charge the glass fibers with static electricity, so that the glass fibers repel each other so that the glass fibers are completely dispersed.
  • glass fibers are added in an on-line continuous manner without increasing energy consumption or affecting production capacity.
  • the continuous glass fiber passes through the glass fiber heating and pre-dispersing device and the cooling device on the drawing line, then passes through the silk friction and electrification, and finally passes through the static electricity generating device, and then enters the impregnation tank with polypropylene melt.
  • the electrostatic generating device is composed of two parts, the first part is composed of electrostatic electret electrostatic generator, high voltage wire, bracket, insulating support, molybdenum wire parts; the second part is composed of heating device;
  • the continuous glass fiber passes through the glass fiber heating and pre-dispersing device and the cooling device on the drawing line, then passes through the silk friction and electrification, and finally passes through the static electricity generating device, and then enters the impregnation tank with polypropylene melt.
  • the electrostatic generating device is composed of two parts, the first part is composed of electrostatic electret electrostatic generator, high voltage wire, bracket, insulating support, molybdenum wire parts; the second part is composed of heating device;
  • the continuous glass fiber passes through the glass fiber heating and pre-dispersing device and the cooling device on the drawing line, then passes through the silk friction and electrification, and finally passes through the static electricity generating device, and then enters the impregnation tank with polypropylene melt.
  • the electrostatic generating device is composed of two parts, the first part is composed of electrostatic electret electrostatic generator, high voltage wire, bracket, insulating support, molybdenum wire parts; the second part is composed of heating device;
  • the continuous glass fiber passes through the glass fiber heating and pre-dispersing device and the cooling device on the drawing line, then passes through the silk friction and electrification, and finally passes through the static electricity generating device, and then enters the impregnation tank with polypropylene melt.
  • the electrostatic generating device is composed of two parts, the first part is composed of electrostatic electret electrostatic generator, high voltage wire, bracket, insulating support, molybdenum wire parts; the second part is composed of heating device;
  • the continuous glass fiber passes through the glass fiber heating and pre-dispersing device and cooling device on the drawing line, then passes through the static electricity generating device, and then enters the impregnation tank with polypropylene melt.
  • the electrostatic generating device is composed of two parts, the first part is composed of electrostatic electret electrostatic generator, high voltage wire, bracket, insulating support, molybdenum wire parts; the second part is composed of heating device;
  • the continuous glass fiber is drawn on the line, passes through the glass fiber heating pre-dispersion device and cooling device, and then passes through the silk friction to electrify, and at the same time passes through the static electricity generating device, and then enters the impregnation tank with polypropylene melt.
  • the electrostatic generating device is composed of two parts, the first part is composed of electrostatic electret electrostatic generator, high voltage wire, bracket, insulating support, molybdenum wire parts; the second part is composed of heating device;
  • the continuous glass fiber passes through the glass fiber heating pre-dispersion device on the traction line, and then passes through the silk friction to electrify, and at the same time passes through the static electricity generating device, and then enters the dipping tank with polypropylene melt.
  • the electrostatic generating device is composed of two parts, the first part is composed of electrostatic electret electrostatic generator, high voltage wire, bracket, insulating support, molybdenum wire parts; the second part is composed of heating device;
  • the density is tested according to the ISO1183 standard.
  • the tensile strength is tested according to the ISO527-2 standard, and the tensile speed is 5 mm/min;
  • the bending strength is tested according to the ISO178 standard, and the bending speed is 2 mm/min;
  • the notched impact strength is tested according to the ISO179 standard.
  • the glass fibers of Examples 1-3 were drawn on the line and passed through the glass fiber heating pre-dispersion device, then passed through the silk friction and electrified, and passed through the static electricity generating device at the same time, and then entered the dipping tank with polypropylene melt; while Comparative Examples 1-3 The glass fibers go directly into the impregnation tank. According to the comparison of the data in Table 1, it is shown that the treatment method of Examples 1-3 can significantly improve the tensile strength, bending strength, impact strength and other properties of the glass fiber reinforced polypropylene composite material.
  • the obtained highly impregnated long glass fiber reinforced polypropylene composite material is injection-molded into long boards of 356*100*3.2, and 200 above-mentioned long boards are respectively injected for each embodiment and comparative example, and statistics are made for each embodiment and comparative example.
  • the proportion of surface glass fiber agglomeration defects in the obtained long board is made.
  • Example 1-3 the glass fiber is drawn on the line and passed through the glass fiber heating pre-dispersion device, then it is electrified by silk friction, and passes through the static electricity generating device at the same time, and then enters the dipping tank with polypropylene melt; Comparative Example 1-3, The glass fibers go directly into the impregnation tank. According to the comparison of the data in Table 1, it is shown that the mechanical properties of Examples 1-3 are higher than those of Comparative Examples 1-3, indicating that the treatment method improves the mechanical properties of the product. And according to the comparison of the data in Table 2, it shows that this treatment method can significantly improve the agglomeration defect after the material is injection molded into a product.
  • Comparative example 4 and comparative example 5 show that the agglomeration defect can be better improved through two steps of silk friction electrification and static electricity generating device; comparative example 6 shows that the melting value of polypropylene resin is 100 g/10min (2.16kg, 230 °C), the agglomeration defect is better improved; comparative example 7 shows that the cooling device is beneficial to the improvement of the agglomeration defect.
  • the preparation method of the invention is simple to operate and can realize on-line continuous production. Adding silk friction and static electricity generating devices to the original equipment does not affect the production capacity, and the energy consumption increases by 0.2 degrees/t, which is almost negligible, and is suitable for industrial production and application.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Reinforced Plastic Materials (AREA)
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  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)

Abstract

Disclosed are a high-impregnation long glass fiber reinforced polypropylene composite material and a preparation method therefor. Said material is composed of the following raw materials in parts by weight: 43.2-63.2 parts of polypropylene resin, 30-50 parts of glass fiber, 1-10 parts of a compatibilizer, 1-10 parts of a toughening agent, 0.1-1 part of an antioxidant, and 0.2-2 parts of a lubricant. After the glass fiber passes on-line through a glass fiber heating pre-dispersing device and a cooling device, same is electrified by silk friction, and finally passes through a static electricity generating device and directly enters a dipping tank for production. The present invention has the following technical effects: the high-impregnation long glass fiber reinforced polypropylene composite material of the present invention achieves each glass fiber being wrapped with polypropylene resin, which can protect the glass fibers from damage during plasticizing by pellets, thereby preserving the length of the glass fibers in products; moreover, the tensile strength, flexural modulus, impact strength and other properties thereof are greatly improved.

Description

一种高浸渍度长玻纤增强聚丙烯复合材料及其制备方法A long glass fiber reinforced polypropylene composite material with high impregnation degree and its preparation method 技术领域technical field
本发明属于高分子材料技术领域，具体涉及到一种高浸渍度长玻纤增强聚丙烯复合材料及其制备方法。The invention belongs to the technical field of polymer materials, and in particular relates to a high impregnation degree long glass fiber reinforced polypropylene composite material and a preparation method thereof.
背景技术Background technique
聚丙烯树脂是一种应用领域极广的通用塑料，是目前所有塑料中密度最小的品种之一，具有成型性好、耐化学性好等优点，但聚丙烯树脂收缩率大，难以满足对尺寸要求较高的制件要求，同时其机械性能相对工程塑料有所差距，无法作为结构件使用。玻璃纤维具有机械强度高、耐热性能好、抗腐蚀性强等多种优异性能，被广泛应用于电子器械、建筑材料、体育器材、飞机汽车等领域。经过玻璃纤维增强的聚丙烯材料机械性能和尺寸稳定性有大幅度提升，能够满足替代工程塑料作为结构件使用的要求。目前市场上长玻璃纤维增强聚丙烯材料制备过程中，采用数根带加热功能的预分散辊组成，通过调整玻纤的接触角度，来调整预张紧力改变玻纤的分散宽度，仅此而已。然而，这种机械展宽的方式，聚丙烯浸润效果不尽人意。在注塑成零件时频繁出现表面玻璃纤维团聚的缺陷，严重影响成品表观，难以作为直接外露件材料使用。高浸渍度长玻纤增强聚丙烯复合材料就是从市场出发，为了解决一些直接外露产品要求材料有较高力学性能，又要求表观不出现缺陷而研发的一种优质材料。Polypropylene resin is a general-purpose plastic with a wide range of applications. It is one of the lowest-density varieties among all plastics. It has the advantages of good formability and chemical resistance. However, polypropylene resin has a large shrinkage rate and it is difficult to meet the requirements for size. It has high requirements for parts, and its mechanical properties are not as good as engineering plastics, so it cannot be used as a structural part. Glass fiber has many excellent properties such as high mechanical strength, good heat resistance and strong corrosion resistance, and is widely used in electronic equipment, building materials, sports equipment, aircraft and automobiles and other fields. The mechanical properties and dimensional stability of glass fiber reinforced polypropylene materials have been greatly improved, which can meet the requirements of replacing engineering plastics as structural parts. At present, in the preparation process of long glass fiber reinforced polypropylene materials on the market, several pre-dispersion rollers with heating function are used to adjust the pre-tensioning force to change the dispersion width of glass fiber by adjusting the contact angle of glass fiber, nothing more. . However, with this mechanical broadening method, the infiltration effect of polypropylene is not satisfactory. The surface glass fiber agglomeration defect frequently occurs when injection molding into parts, which seriously affects the appearance of the finished product and is difficult to use as a material for directly exposed parts. The long glass fiber reinforced polypropylene composite material with high impregnation degree is a high-quality material developed from the market, in order to solve some directly exposed products that require the material to have high mechanical properties and require no apparent defects.
中国专利CN201710528906公布了一种汽车内饰用低气味低浮纤长玻纤增强聚丙烯复合材料，其优点在于按大众气味检测标准测得的气味由常规的4.0级降低到3.5级，且肉眼可观察表面浮纤明显改善。中国专利CN201610207016公布了一种高光洁长玻纤阻燃增韧聚丙烯共混材料，其适用于对产品结构和外观、成本及加工性有较高要求的中高端家具用品上。中国专利CN201110008670公布了一种高抗冲、低浮纤长玻纤增强聚丙烯材料，其优点在于其制备的聚丙烯材料表面光泽高、浮纤现象少、耐跌落性好。但是上述专利均主要是通过抗浮纤剂降低模具表面与熔体间相互作用力尽可能降低零件表面浮纤现象，并没有提升材料中玻璃纤维的浸渍度，无法从根本上解决零件表面出现玻璃纤维团聚缺陷。Chinese patent CN201710528906 discloses a low-odor and low-floating long glass fiber reinforced polypropylene composite material for automotive interiors. Its advantage is that the odor measured according to the public odor detection standard is reduced from the conventional 4.0 level to 3.5 level, and it can be observed by naked eyes. The floating fiber on the surface is obviously improved. Chinese patent CN201610207016 discloses a high-gloss long glass fiber flame-retardant and toughened polypropylene blend material, which is suitable for mid-to-high-end furniture products with high requirements for product structure and appearance, cost and processability. Chinese patent CN201110008670 discloses a high-impact, low-floating long glass fiber reinforced polypropylene material, which has the advantages of high surface gloss, less floating fiber phenomenon, and good drop resistance. However, the above-mentioned patents mainly use the anti-floating fiber agent to reduce the interaction force between the mold surface and the melt to reduce the floating fiber phenomenon on the surface of the part as much as possible, and do not improve the impregnation degree of the glass fiber in the material, and cannot fundamentally solve the problem of glass on the surface of the part. Fiber agglomeration defects.
中国专利CN202011594023.1公布了一种汽车内饰用低团聚长玻纤增强聚丙烯复合材料及其制备方法。汽车内饰用低团聚长玻纤增强聚丙烯复合材料通过假捻装置对连续玻璃纤维束增加假捻，使玻璃纤维束中的玻璃纤维单丝完全分散开，玻璃纤维束中的单丝能够获得更完全的浸渍，有效降低长玻纤增强聚丙烯材料的团聚现象，能够更好满足汽车内饰用长玻纤增强聚丙烯材料作为外露件时的外观要求。该发明采用假捻装置使玻纤完全分散开。Chinese patent CN202011594023.1 discloses a low-agglomeration long glass fiber reinforced polypropylene composite material for automotive interiors and a preparation method thereof. The low-agglomeration long glass fiber reinforced polypropylene composite material for automotive interiors adds false twist to the continuous glass fiber bundle through the false twist device, so that the glass fiber monofilaments in the glass fiber bundles are completely dispersed, and the monofilaments in the glass fiber bundles can be obtained More complete impregnation can effectively reduce the agglomeration phenomenon of long glass fiber reinforced polypropylene materials, and can better meet the appearance requirements of long glass fiber reinforced polypropylene materials used in automotive interiors as exposed parts. The invention uses a false twisting device to completely disperse the glass fibers.
技术问题technical problem
如何解决长玻璃纤维的浸渍度问题，从而进一步提高长玻璃纤维增强聚丙烯复合材料的力学性能。How to solve the problem of impregnation degree of long glass fibers, so as to further improve the mechanical properties of long glass fiber reinforced polypropylene composites.
技术解决方案technical solution
为了提升材料中玻璃纤维的浸渍度，从根本上解决零件表面出现玻璃纤维团聚缺陷，本发明提供一种玻璃纤维团聚缺陷极少、可在线连续化生产的高浸渍度长玻纤增强聚丙烯复合材料，制备过程中前后每个步骤紧密关联，均影响着浸润度，其关键技术在于使玻纤带静电，使玻纤相互排斥而达到玻纤完全分散开。In order to improve the degree of impregnation of glass fibers in the material and fundamentally solve the defects of glass fiber agglomeration on the surface of parts, the invention provides a long glass fiber reinforced polypropylene compound with high impregnation degree and long glass fiber reinforcement that has few glass fiber agglomeration defects and can be produced continuously on-line. Materials, each step before and after the preparation process are closely related, all affect the wettability, the key technology is to charge the glass fiber with static electricity, so that the glass fibers repel each other to achieve the complete dispersion of the glass fiber.
根据玻璃棒在丝绸上摩擦起电的原理，连续玻璃纤维通过玻纤加热预分散装置和冷却装置后，再通过丝绸摩擦起电，最后过静电发生装置。通过加热预分散装置，玻纤被干燥利于带电，同时预分散装置使玻纤第一次初步铺展，通过丝绸摩擦时接触面增大，更有利于带电。冷却装置使玻纤冷却防止烫伤丝绸，同时冷却装置采用鼓风装置，气流使玻纤进一步分散。丝绸摩擦和静电发生装置使每个玻璃纤维带上静电，受静电的作用，使每根玻璃纤维相互排斥，玻璃纤维束将会变得蓬松，从而更进一步增加玻璃纤维束分散宽度；静电发生装置的第二部分对玻纤加热，保持玻纤有一定温度进入浸渍槽，防止冷玻纤遇上熔体，骤冷降低熔体流动性，不利于玻纤的浸润。通过以上装置，使聚丙烯熔融体充分浸润玻璃纤维，实现每根玻纤都有聚丙烯树脂包裹。According to the principle of frictional electrification of glass rods on silk, the continuous glass fiber passes through the glass fiber heating pre-dispersion device and cooling device, then frictionally electrifies through silk, and finally passes through the static electricity generating device. By heating the pre-dispersion device, the glass fiber is dried to facilitate charging. At the same time, the pre-dispersion device initially spreads the glass fiber for the first time, and the contact surface increases when it is rubbed by silk, which is more conducive to charging. The cooling device cools the glass fiber to prevent the silk from being scalded. At the same time, the cooling device adopts a blower device, and the airflow further disperses the glass fiber. The silk friction and static electricity generating device makes each glass fiber charged with static electricity. Under the action of static electricity, each glass fiber repels each other, and the glass fiber bundle will become fluffy, thereby further increasing the dispersion width of the glass fiber bundle; the static electricity generating device The second part heats the glass fiber, keeps the glass fiber at a certain temperature and enters the dipping tank, prevents the cold glass fiber from meeting the melt, and the sudden cooling reduces the fluidity of the melt, which is not conducive to the infiltration of the glass fiber. Through the above device, the polypropylene melt is fully infiltrated into the glass fiber, so that each glass fiber is wrapped with polypropylene resin.
本发明解决其技术问题所采用的技术方案是：The technical solution adopted by the present invention to solve its technical problems is:
一种高浸渍度长玻纤增强聚丙烯复合材料，由以下按重量份计的原料组成：聚丙烯树脂43.2～63.2份、玻璃纤维30～50份，相容剂1～10份、增韧剂1～10份、抗氧剂0.1～1份、润滑剂0.2～2份。所述的玻璃纤维在线经过玻纤加热预分散装置和冷却装置后，再通过丝绸摩擦起电，最后过静电发生装置直接进入浸渍槽进行生产。A long glass fiber reinforced polypropylene composite material with high impregnation degree, which is composed of the following raw materials in parts by weight: 43.2-63.2 parts of polypropylene resin, 30-50 parts of glass fiber, 1-10 parts of compatibilizer, and toughening agent 1-10 parts, 0.1-1 parts of antioxidant, 0.2-2 parts of lubricant. After the glass fiber is passed through the glass fiber heating and pre-dispersing device and the cooling device online, it is electrified by silk friction, and finally passes through the static electricity generating device and directly enters the dipping tank for production.
上述高浸渍度长玻纤增强聚丙烯复合材料中，其中，In the above-mentioned high impregnation degree long glass fiber reinforced polypropylene composite material, wherein,
所述的聚丙烯的熔值为100 g/10min（2.16 kg，230℃）。The melting value of described polypropylene is 100 g/10min (2.16 kg, 230°C).
所述的玻璃纤维为直接无捻玻璃纤维。The glass fiber is direct untwisted glass fiber.
所述的相容剂为马来酸酐接枝聚丙烯。The compatibilizer is maleic anhydride grafted polypropylene.
所述抗氧剂为受阻酚抗氧剂1010、亚磷酸酯类抗氧剂168和抗氧剂GA80等中的一种或者几种组合。The antioxidant is one or a combination of hindered phenol antioxidant 1010, phosphite antioxidant 168, and antioxidant GA80.
所述的增韧剂为马来酸酐接枝的EPDM、POE和SEBS中的一种或者几种组合。The toughening agent is one or a combination of maleic anhydride grafted EPDM, POE and SEBS.
所述的润滑剂为硬脂酸、季戊四醇硬脂酸酯、硬脂酸甘油酯、芥酸酰胺和聚乙烯蜡中的一种或者几种组合。The lubricant is one or more combinations of stearic acid, pentaerythritol stearate, glyceryl stearate, erucamide and polyethylene wax.
上述高浸渍度长玻纤增强聚丙烯复合材料的制备方法，其步骤如下：The preparation method of the above-mentioned high impregnation degree long glass fiber reinforced polypropylene composite material, its steps are as follows:
1)连续玻璃纤维经牵引在线经过玻纤加热预分散装置和冷却装置后，再通过丝绸摩擦起电，最后过静电发生装置，随后进入有聚丙烯熔融体的浸渍槽。所述静电发生装置由两部分组成，第一部分由静电驻极静电发生器、高压线、支架、绝缘支柱、钼丝部件组成；第二部分由加热装置组成； 1) The continuous glass fiber passes through the glass fiber heating and pre-dispersing device and the cooling device on the drawing line, then passes through the silk friction and electrification, and finally passes through the static electricity generating device, and then enters the impregnation tank with polypropylene melt. The electrostatic generating device is composed of two parts, the first part is composed of electrostatic electret electrostatic generator, high voltage wire, bracket, insulating support, molybdenum wire parts; the second part is composed of heating device;
2)按照重量配比称取原料聚丙烯树脂、相容剂、增韧剂、抗氧剂及润滑剂，将称好的原材料投入到高速混合器中混合均匀，然后经过双螺杆挤出机进入浸渍槽；2) Weigh the raw material polypropylene resin, compatibilizer, toughening agent, antioxidant and lubricant according to the weight ratio, put the weighed raw materials into the high-speed mixer and mix them evenly, and then pass through the twin-screw extruder into Dip tank;
3)连续玻璃纤维经过浸渍槽后进行拉条、冷却、切粒、干燥处理。3) The continuous glass fiber is drawn, cooled, pelletized and dried after passing through the dipping tank.
有益效果Beneficial effect
本发明具有以下技术效果：与目前市场上常见的长玻璃纤维增强聚丙烯复合材料相比，本发明的高浸渍度长玻纤增强聚丙烯复合材料实现了每根玻纤都有聚丙烯树脂包裹，保护玻纤在粒料塑化过程中不受破坏，从而保留玻纤在制品中的长度，其拉伸强度、弯曲模量、冲击强度等性能上有较大幅度提升，同时大幅度降低成品表面玻璃纤维团聚缺陷的出现比例。本发明制备过程中前后每个步骤紧密关联，其关键技术在于使玻纤带静电，使玻纤相互排斥而达到玻纤完全分散开。另外，通过在线连续的方式加入玻璃纤维，不增加能耗，不影响产能。The present invention has the following technical effects: Compared with the long glass fiber reinforced polypropylene composite materials commonly used in the market, the long glass fiber reinforced polypropylene composite material with high impregnation degree of the present invention realizes that each glass fiber is wrapped with polypropylene resin , to protect the glass fiber from being damaged during the plasticizing process of the pellets, thereby retaining the length of the glass fiber in the product, its tensile strength, flexural modulus, impact strength and other properties are greatly improved, and at the same time, the finished product is greatly reduced Occurrence ratio of surface glass fiber agglomeration defects. Each step in the preparation process of the present invention is closely related, and the key technology is to charge the glass fibers with static electricity, so that the glass fibers repel each other so that the glass fibers are completely dispersed. In addition, glass fibers are added in an on-line continuous manner without increasing energy consumption or affecting production capacity.
本发明的最佳实施方式BEST MODE FOR CARRYING OUT THE INVENTION
1)连续玻璃纤维经牵引在线经过玻纤加热预分散装置和冷却装置后，再通过丝绸摩擦起电，最后过静电发生装置，随后进入有聚丙烯熔融体的浸渍槽。所述静电发生装置由两部分组成，第一部分由静电驻极静电发生器、高压线、支架、绝缘支柱、钼丝部件组成；第二部分由加热装置组成； 1) The continuous glass fiber passes through the glass fiber heating and pre-dispersing device and the cooling device on the drawing line, then passes through the silk friction and electrification, and finally passes through the static electricity generating device, and then enters the impregnation tank with polypropylene melt. The electrostatic generating device is composed of two parts, the first part is composed of electrostatic electret electrostatic generator, high voltage wire, bracket, insulating support, molybdenum wire parts; the second part is composed of heating device;
2)按照重量配比称取原料聚丙烯树脂（扬子石化XPJ-3100H，熔值为100g/10min，2.16kg，230℃）43.2份，并经烘箱烘干；加入3份马来酸酐接枝聚丙烯，3份马来酸酐接枝SEBS，0.3份抗氧剂GA80，0.3份芥酸酰胺在高速机中搅拌混合均匀，然后经过双螺杆挤出机进入浸渍槽；2) Weigh 43.2 parts of raw material polypropylene resin (Yangzi Petrochemical XPJ-3100H, melting value 100g/10min, 2.16kg, 230°C) according to the weight ratio, and dry in an oven; add 3 parts of maleic anhydride graft poly Propylene, 3 parts of maleic anhydride grafted SEBS, 0.3 part of antioxidant GA80, and 0.3 part of erucamide are stirred and mixed evenly in a high-speed machine, and then enter the impregnation tank through a twin-screw extruder;
3)连续玻璃纤维经过浸渍槽后进行拉条、冷却、切粒、干燥处理。3) The continuous glass fiber is drawn, cooled, pelletized and dried after passing through the dipping tank.
本发明的实施方式Embodiments of the present invention
下面结合具体实施例来进一步说明本发明的技术方案。The technical solutions of the present invention will be further described below in conjunction with specific embodiments.
实施例1：Example 1:
1)连续玻璃纤维经牵引在线经过玻纤加热预分散装置和冷却装置后，再通过丝绸摩擦起电，最后过静电发生装置，随后进入有聚丙烯熔融体的浸渍槽。所述静电发生装置由两部分组成，第一部分由静电驻极静电发生器、高压线、支架、绝缘支柱、钼丝部件组成；第二部分由加热装置组成； 1) The continuous glass fiber passes through the glass fiber heating and pre-dispersing device and the cooling device on the drawing line, then passes through the silk friction and electrification, and finally passes through the static electricity generating device, and then enters the impregnation tank with polypropylene melt. The electrostatic generating device is composed of two parts, the first part is composed of electrostatic electret electrostatic generator, high voltage wire, bracket, insulating support, molybdenum wire parts; the second part is composed of heating device;
2)按照重量配比称取原料聚丙烯树脂（扬子石化XPJ-3100H，熔值为100g/10min，2.16kg，230℃）63.2份，并经烘箱烘干；加入5份马来酸酐接枝聚丙烯，3份马来酸酐接枝的EPDM，0.2份受阻酚抗氧剂1010、0.1份亚磷酸酯类抗氧剂168，0.5份季戊四醇硬脂酸酯在高速机中搅拌混合均匀，然后经过双螺杆挤出机进入浸渍槽；2) Weigh 63.2 parts of raw material polypropylene resin (Yangzi Petrochemical XPJ-3100H, melting value 100g/10min, 2.16kg, 230°C) according to the weight ratio, and dry in an oven; add 5 parts of maleic anhydride grafted poly Propylene, 3 parts of maleic anhydride grafted EPDM, 0.2 part of hindered phenol antioxidant 1010, 0.1 part of phosphite antioxidant 168, and 0.5 part of pentaerythritol stearate were stirred and mixed evenly in a high-speed machine, and then passed through double The screw extruder enters the impregnation tank;
3)连续玻璃纤维经过浸渍槽后进行拉条、冷却、切粒、干燥处理。3) The continuous glass fiber is drawn, cooled, pelletized and dried after passing through the dipping tank.
实施例2：Example 2:
1)连续玻璃纤维经牵引在线经过玻纤加热预分散装置和冷却装置后，再通过丝绸摩擦起电，最后过静电发生装置，随后进入有聚丙烯熔融体的浸渍槽。所述静电发生装置由两部分组成，第一部分由静电驻极静电发生器、高压线、支架、绝缘支柱、钼丝部件组成；第二部分由加热装置组成； 1) The continuous glass fiber passes through the glass fiber heating and pre-dispersing device and the cooling device on the drawing line, then passes through the silk friction and electrification, and finally passes through the static electricity generating device, and then enters the impregnation tank with polypropylene melt. The electrostatic generating device is composed of two parts, the first part is composed of electrostatic electret electrostatic generator, high voltage wire, bracket, insulating support, molybdenum wire parts; the second part is composed of heating device;
2)按照重量配比称取原料聚丙烯树脂（扬子石化XPJ-3100H，熔值为100g/10min，2.16kg，230℃）53.2份，并经烘箱烘干；加入4份马来酸酐接枝聚丙烯，3份马来酸酐接枝POE，0.2份受阻酚抗氧剂1010、0.1份亚磷酸酯类抗氧剂168，0.5份硬脂酸甘油酯在高速机中搅拌混合均匀，然后经过双螺杆挤出机进入浸渍槽；2) Weigh 53.2 parts of raw material polypropylene resin (Yangzi Petrochemical XPJ-3100H, melting value 100g/10min, 2.16kg, 230°C) according to the weight ratio, and dry in an oven; add 4 parts of maleic anhydride grafted poly Propylene, 3 parts of maleic anhydride grafted POE, 0.2 part of hindered phenol antioxidant 1010, 0.1 part of phosphite antioxidant 168, and 0.5 part of glyceryl stearate were mixed evenly in a high-speed machine, and then passed through a twin-screw The extruder enters the impregnation tank;
3)连续玻璃纤维经过浸渍槽后进行拉条、冷却、切粒、干燥处理。3) The continuous glass fiber is drawn, cooled, pelletized and dried after passing through the dipping tank.
实施例3：Example 3:
1)连续玻璃纤维经牵引在线经过玻纤加热预分散装置和冷却装置后，再通过丝绸摩擦起电，最后过静电发生装置，随后进入有聚丙烯熔融体的浸渍槽。所述静电发生装置由两部分组成，第一部分由静电驻极静电发生器、高压线、支架、绝缘支柱、钼丝部件组成；第二部分由加热装置组成； 1) The continuous glass fiber passes through the glass fiber heating and pre-dispersing device and the cooling device on the drawing line, then passes through the silk friction and electrification, and finally passes through the static electricity generating device, and then enters the impregnation tank with polypropylene melt. The electrostatic generating device is composed of two parts, the first part is composed of electrostatic electret electrostatic generator, high voltage wire, bracket, insulating support, molybdenum wire parts; the second part is composed of heating device;
2)按照重量配比称取原料聚丙烯树脂（扬子石化XPJ-3100H，熔值为100g/10min，2.16kg，230℃）43.2份，并经烘箱烘干；加入3份马来酸酐接枝聚丙烯，3份马来酸酐接枝SEBS，0.3份抗氧剂GA80，0.3份芥酸酰胺在高速机中搅拌混合均匀，然后经过双螺杆挤出机进入浸渍槽；2) Weigh 43.2 parts of raw material polypropylene resin (Yangzi Petrochemical XPJ-3100H, melting value 100g/10min, 2.16kg, 230°C) according to the weight ratio, and dry in an oven; add 3 parts of maleic anhydride graft poly Propylene, 3 parts of maleic anhydride grafted SEBS, 0.3 part of antioxidant GA80, and 0.3 part of erucamide are stirred and mixed evenly in a high-speed machine, and then enter the impregnation tank through a twin-screw extruder;
3)连续玻璃纤维经过浸渍槽后进行拉条、冷却、切粒、干燥处理。3) The continuous glass fiber is drawn, cooled, pelletized and dried after passing through the dipping tank.
对比例1：Comparative example 1:
1)连续玻璃纤维经牵引进入有聚丙烯熔融体的浸渍槽；1) The continuous glass fiber is drawn into the impregnation tank with polypropylene melt;
2)按照重量配比称取原料聚丙烯树脂（扬子石化XPJ-3100H，熔值为100g/10min，2.16kg，230℃）63.2份，并经烘箱烘干；加入5份马来酸酐接枝聚丙烯，3份马来酸酐接枝的EPDM，0.2份受阻酚抗氧剂1010、0.1份亚磷酸酯类抗氧剂168，0.5份季戊四醇硬脂酸酯在高速机中搅拌混合均匀，然后经过双螺杆挤出机进入浸渍槽；2) Weigh 63.2 parts of raw material polypropylene resin (Yangzi Petrochemical XPJ-3100H, melting value 100g/10min, 2.16kg, 230°C) according to the weight ratio, and dry in an oven; add 5 parts of maleic anhydride grafted poly Propylene, 3 parts of maleic anhydride grafted EPDM, 0.2 part of hindered phenol antioxidant 1010, 0.1 part of phosphite antioxidant 168, and 0.5 part of pentaerythritol stearate were stirred and mixed evenly in a high-speed machine, and then passed through double The screw extruder enters the impregnation tank;
3)连续玻璃纤维经过浸渍槽后进行拉条、冷却、切粒、干燥处理。3) The continuous glass fiber is drawn, cooled, pelletized and dried after passing through the dipping tank.
对比例2：Comparative example 2:
1)连续玻璃纤维经牵引进入有聚丙烯熔融体的浸渍槽；1) The continuous glass fiber is drawn into the impregnation tank with polypropylene melt;
2)按照重量配比称取原料聚丙烯树脂（扬子石化XPJ-3100H，熔值为100 g/10min，2.16kg，230℃）53.2份，并经烘箱烘干；加入4份马来酸酐接枝聚丙烯，3份马来酸酐接枝POE，0.2份受阻酚抗氧剂1010、0.1份亚磷酸酯类抗氧剂168，0.5份硬脂酸甘油酯在高速机中搅拌混合均匀，然后经过双螺杆挤出机进入浸渍槽；2) Weigh the raw material polypropylene resin (Yangzi Petrochemical XPJ-3100H, melting value is 100 g/10min, 2.16kg, 230°C) 53.2 parts, and dried in an oven; add 4 parts of maleic anhydride grafted polypropylene, 3 parts of maleic anhydride grafted POE, 0.2 parts of hindered phenol antioxidant 1010, 0.1 parts Phosphite antioxidant 168, 0.5 parts of glyceryl stearate are stirred and mixed uniformly in a high-speed machine, and then enter the dipping tank through a twin-screw extruder;
3)连续玻璃纤维经过浸渍槽后进行拉条、冷却、切粒、干燥处理。3) The continuous glass fiber is drawn, cooled, pelletized and dried after passing through the dipping tank.
对比例3：Comparative example 3:
1)连续玻璃纤维经牵引进入有聚丙烯熔融体的浸渍槽；1) The continuous glass fiber is drawn into the impregnation tank with polypropylene melt;
2)按照重量配比称取原料聚丙烯树脂（扬子石化XPJ-3100H，熔值为100 g/10min，2.16kg，230℃）43.2份，并经烘箱烘干；加入3份马来酸酐接枝聚丙烯，3份马来酸酐接枝SEBS，0.3份抗氧剂GA80，0.3份芥酸酰胺在高速机中搅拌混合均匀，然后经过双螺杆挤出机进入浸渍槽；2) Weigh the raw material polypropylene resin (Yangzi Petrochemical XPJ-3100H, melting value is 100 g/10min, 2.16kg, 230℃) 43.2 parts, and dried in an oven; add 3 parts of maleic anhydride grafted polypropylene, 3 parts of maleic anhydride grafted SEBS, 0.3 parts of antioxidant GA80, 0.3 parts of erucic acid The amide is stirred and mixed evenly in a high-speed machine, and then enters the impregnation tank through a twin-screw extruder;
3)连续玻璃纤维经过浸渍槽后进行拉条、冷却、切粒、干燥处理。3) The continuous glass fiber is drawn, cooled, pelletized and dried after passing through the dipping tank.
对比例4：Comparative example 4:
1)连续玻璃纤维经牵引在线经过玻纤加热预分散装置和冷却装置后，再通过丝绸摩擦起电，随后进入有聚丙烯熔融体的浸渍槽；1) After the continuous glass fiber is drawn on the line, passes through the glass fiber heating pre-dispersion device and cooling device, and then is electrified by silk friction, and then enters the impregnation tank with polypropylene melt;
2)按照重量配比称取原料聚丙烯树脂（扬子石化XPJ-3100H，熔值为100 g/10min，2.16kg，230℃）63.2份，并经烘箱烘干；加入5份马来酸酐接枝聚丙烯，3份马来酸酐接枝的EPDM，0.2份受阻酚抗氧剂1010、0.1份亚磷酸酯类抗氧剂168，0.5份季戊四醇硬脂酸酯在高速机中搅拌混合均匀，然后经过双螺杆挤出机进入浸渍槽；2) Weigh the raw material polypropylene resin (Yangzi Petrochemical XPJ-3100H, melting value is 100 g/10min, 2.16kg, 230℃) 63.2 parts, and dried in an oven; add 5 parts of maleic anhydride grafted polypropylene, 3 parts of maleic anhydride grafted EPDM, 0.2 parts of hindered phenol antioxidant 1010, 0.1 Part of phosphite antioxidant 168, 0.5 part of pentaerythritol stearate is stirred and mixed uniformly in a high-speed machine, and then enters the dipping tank through a twin-screw extruder;
3)连续玻璃纤维经过浸渍槽后进行拉条、冷却、切粒、干燥处理。3) The continuous glass fiber is drawn, cooled, pelletized and dried after passing through the dipping tank.
对比例5：Comparative example 5:
1)连续玻璃纤维经牵引在线经过玻纤加热预分散装置和冷却装置后，再通过静电发生装置，随后进入有聚丙烯熔融体的浸渍槽。所述静电发生装置由两部分组成，第一部分由静电驻极静电发生器、高压线、支架、绝缘支柱、钼丝部件组成；第二部分由加热装置组成； 1) The continuous glass fiber passes through the glass fiber heating and pre-dispersing device and cooling device on the drawing line, then passes through the static electricity generating device, and then enters the impregnation tank with polypropylene melt. The electrostatic generating device is composed of two parts, the first part is composed of electrostatic electret electrostatic generator, high voltage wire, bracket, insulating support, molybdenum wire parts; the second part is composed of heating device;
2)按照重量配比称取原料聚丙烯树脂（扬子石化XPJ-3100H，熔值为100 g/10min，2.16kg，230℃）63.2份，并经烘箱烘干；加入5份马来酸酐接枝聚丙烯，3份马来酸酐接枝的EPDM，0.2份受阻酚抗氧剂1010、0.1份亚磷酸酯类抗氧剂168，0.5份季戊四醇硬脂酸酯在高速机中搅拌混合均匀，然后经过双螺杆挤出机进入浸渍槽；2) Weigh the raw material polypropylene resin (Yangzi Petrochemical XPJ-3100H, melting value is 100 g/10min, 2.16kg, 230℃) 63.2 parts, and dried in an oven; add 5 parts of maleic anhydride grafted polypropylene, 3 parts of maleic anhydride grafted EPDM, 0.2 parts of hindered phenol antioxidant 1010, 0.1 Part of phosphite antioxidant 168, 0.5 part of pentaerythritol stearate is stirred and mixed uniformly in a high-speed machine, and then enters the dipping tank through a twin-screw extruder;
3)连续玻璃纤维经过浸渍槽后进行拉条、冷却、切粒、干燥处理。3) The continuous glass fiber is drawn, cooled, pelletized and dried after passing through the dipping tank.
对比例6：Comparative example 6:
1)连续玻璃纤维经牵引在线经过玻纤加热预分散装置和冷却装置后，再通过丝绸摩擦起电，同时过静电发生装置，随后进入有聚丙烯熔融体的浸渍槽。所述静电发生装置由两部分组成，第一部分由静电驻极静电发生器、高压线、支架、绝缘支柱、钼丝部件组成；第二部分由加热装置组成； 1) The continuous glass fiber is drawn on the line, passes through the glass fiber heating pre-dispersion device and cooling device, and then passes through the silk friction to electrify, and at the same time passes through the static electricity generating device, and then enters the impregnation tank with polypropylene melt. The electrostatic generating device is composed of two parts, the first part is composed of electrostatic electret electrostatic generator, high voltage wire, bracket, insulating support, molybdenum wire parts; the second part is composed of heating device;
2)按照重量配比称取原料聚丙烯树脂（熔值为60 g/10min，2.16kg，230℃）63.2份，并经烘箱烘干；加入5份马来酸酐接枝聚丙烯，3份马来酸酐接枝的EPDM，0.2份受阻酚抗氧剂1010、0.1份亚磷酸酯类抗氧剂168，0.5份季戊四醇硬脂酸酯在高速机中搅拌混合均匀，然后经过双螺杆挤出机进入浸渍槽；2) Weigh 63.2 parts of raw material polypropylene resin (melting value: 60 g/10min, 2.16kg, 230°C) according to the weight ratio, and dry in an oven; add 5 parts of maleic anhydride grafted polypropylene, 3 parts of maleic anhydride EPDM grafted with anhydride, 0.2 part of hindered phenol antioxidant 1010, 0.1 part of phosphite antioxidant 168, 0.5 part of pentaerythritol stearate are stirred and mixed evenly in a high-speed machine, and then enter through a twin-screw extruder Dip tank;
3)连续玻璃纤维经过浸渍槽后进行拉条、冷却、切粒、干燥处理。3) The continuous glass fiber is drawn, cooled, pelletized and dried after passing through the dipping tank.
对比例7：Comparative example 7:
1)连续玻璃纤维经牵引在线经过玻纤加热预分散装置后，再通过丝绸摩擦起电，同时过静电发生装置，随后进入有聚丙烯熔融体的浸渍槽。所述静电发生装置由两部分组成，第一部分由静电驻极静电发生器、高压线、支架、绝缘支柱、钼丝部件组成；第二部分由加热装置组成； 1) The continuous glass fiber passes through the glass fiber heating pre-dispersion device on the traction line, and then passes through the silk friction to electrify, and at the same time passes through the static electricity generating device, and then enters the dipping tank with polypropylene melt. The electrostatic generating device is composed of two parts, the first part is composed of electrostatic electret electrostatic generator, high voltage wire, bracket, insulating support, molybdenum wire parts; the second part is composed of heating device;
2)按照重量配比称取原料聚丙烯树脂（扬子石化XPJ-3100H，熔值为100 g/10min，2.16kg，230℃）63.2份，并经烘箱烘干；加入5份马来酸酐接枝聚丙烯，3份马来酸酐接枝的EPDM，0.2份受阻酚抗氧剂1010、0.1份亚磷酸酯类抗氧剂168，0.5份季戊四醇硬脂酸酯在高速机中搅拌混合均匀，然后经过双螺杆挤出机进入浸渍槽；2) Weigh the raw material polypropylene resin (Yangzi Petrochemical XPJ-3100H, melting value is 100 g/10min, 2.16kg, 230℃) 63.2 parts, and dried in an oven; add 5 parts of maleic anhydride grafted polypropylene, 3 parts of maleic anhydride grafted EPDM, 0.2 parts of hindered phenol antioxidant 1010, 0.1 Part of phosphite antioxidant 168, 0.5 part of pentaerythritol stearate is stirred and mixed uniformly in a high-speed machine, and then enters the dipping tank through a twin-screw extruder;
3)连续玻璃纤维经过浸渍槽后进行拉条、冷却、切粒、干燥处理。3) The continuous glass fiber is drawn, cooled, pelletized and dried after passing through the dipping tank.
上述实施例和对比例中的原料共计100份。A total of 100 parts of raw materials in the above-mentioned examples and comparative examples.
性能测试：Performance Testing:
密度按照ISO1183标准进行检测；The density is tested according to the ISO1183 standard;
拉伸强度按照ISO527-2标准进行检测，拉伸速度为5 mm/min；The tensile strength is tested according to the ISO527-2 standard, and the tensile speed is 5 mm/min;
弯曲强度按照ISO178标准进行检测，弯曲速度为2 mm/min；The bending strength is tested according to the ISO178 standard, and the bending speed is 2 mm/min;
缺口冲击强度按照ISO179标准进行检测；The notched impact strength is tested according to the ISO179 standard;
材料性能测试结果见表1：The material performance test results are shown in Table 1:
Figure dest_path_image001
Figure dest_path_image001
实施例1-3的玻璃纤维经牵引在线经过玻纤加热预分散装置后，再通过丝绸摩擦起电，同时过静电发生装置，随后进入有聚丙烯熔融体的浸渍槽；而对比例1-3的玻璃纤维直接进入浸渍槽。按照表1中数据对比显示是实施例1-3的处理法可以明显提高玻璃纤维增强聚丙烯复合材料的拉伸强度、弯曲强度、冲击强度等性能。另外，通过在线连续的方式加入玻璃纤维，对产能无影响，能耗增加0.2度/t,几乎可以忽略不计；实施例1相比于对比例4和对比例5可知，玻璃纤维单独过丝绸摩擦或静电发生装置，玻璃纤维束的蓬松度不够，造成玻璃纤维的浸润程度较差，对拉伸强度、弯曲强度、冲击强度等性能提高有限；实施例1和对比例6相比较可知，聚丙烯树脂采用熔值100g/10min（2.16kg，230℃），有利于树脂浸润至玻璃纤维束内部；实施例1和对比例7相比较可知，冷却装置除了可以保护过丝绸时不会烫伤丝绸，而且可以进行进一步分散玻纤丝束，利用熔体浸润玻纤。The glass fibers of Examples 1-3 were drawn on the line and passed through the glass fiber heating pre-dispersion device, then passed through the silk friction and electrified, and passed through the static electricity generating device at the same time, and then entered the dipping tank with polypropylene melt; while Comparative Examples 1-3 The glass fibers go directly into the impregnation tank. According to the comparison of the data in Table 1, it is shown that the treatment method of Examples 1-3 can significantly improve the tensile strength, bending strength, impact strength and other properties of the glass fiber reinforced polypropylene composite material. In addition, adding glass fibers in an online continuous manner has no effect on production capacity, and the energy consumption increases by 0.2 degrees/t, which is almost negligible; compared with Comparative Examples 4 and 5 in Example 1, it can be seen that glass fibers are rubbed with silk alone Or electrostatic generating device, the bulkiness of glass fiber bundle is not enough, causes the infiltration degree of glass fiber to be relatively poor, to the performance improvement such as tensile strength, flexural strength, impact strength etc.; The resin adopts a melting value of 100g/10min (2.16kg, 230°C), which is beneficial for the resin to infiltrate into the glass fiber bundle; comparing Example 1 and Comparative Example 7, it can be seen that the cooling device will not burn the silk except for protecting the silk, and It is possible to further disperse the glass fiber bundles and use the melt to infiltrate the glass fibers.
团聚改善率测试：Reunion improvement rate test:
将制得的高浸渍长玻纤增强聚丙烯复合材料经过注塑为356*100*3.2的长板，每个实施例和对比例分别注塑200块上述长板，统计每个实施例和对比例制得的长板出现表面玻纤团聚缺陷的比例。The obtained highly impregnated long glass fiber reinforced polypropylene composite material is injection-molded into long boards of 356*100*3.2, and 200 above-mentioned long boards are respectively injected for each embodiment and comparative example, and statistics are made for each embodiment and comparative example. The proportion of surface glass fiber agglomeration defects in the obtained long board.
统计结果见表2：The statistical results are shown in Table 2:
Figure 601742dest_path_image002
Figure 601742dest_path_image002
实施例1-3，玻璃纤维经牵引在线经过玻纤加热预分散装置后，再通过丝绸摩擦起电，同时过静电发生装置，随后进入有聚丙烯熔融体的浸渍槽；对比例1-3，玻璃纤维直接进入浸渍槽。按照表1中数据对比显示：实施例1-3的力学性能要高于对比例1-3，说明该处理法提高了制品的力学性能。并且按照表2中数据对比显示该处理法对材料注塑成制品后的团聚缺陷有明显改善。对比例4和对比例5说明需经过丝绸摩擦起电和静电发生装置两个步骤，团聚缺陷才能得到较好改善；对比例6说明聚丙烯树脂的熔值为100 g/10min（2.16kg，230℃），团聚缺陷得到较好改善；对比例7说明冷却装置利于团聚缺陷地改善。In Example 1-3, the glass fiber is drawn on the line and passed through the glass fiber heating pre-dispersion device, then it is electrified by silk friction, and passes through the static electricity generating device at the same time, and then enters the dipping tank with polypropylene melt; Comparative Example 1-3, The glass fibers go directly into the impregnation tank. According to the comparison of the data in Table 1, it is shown that the mechanical properties of Examples 1-3 are higher than those of Comparative Examples 1-3, indicating that the treatment method improves the mechanical properties of the product. And according to the comparison of the data in Table 2, it shows that this treatment method can significantly improve the agglomeration defect after the material is injection molded into a product. Comparative example 4 and comparative example 5 show that the agglomeration defect can be better improved through two steps of silk friction electrification and static electricity generating device; comparative example 6 shows that the melting value of polypropylene resin is 100 g/10min (2.16kg, 230 ℃), the agglomeration defect is better improved; comparative example 7 shows that the cooling device is beneficial to the improvement of the agglomeration defect.
本发明的制备方法操作简单，可以实现在线连续化生产。在原有设备增加丝绸摩擦和静电发生装置，不影响产能，能耗增加0.2度/t，几乎可以忽略不计，适合工业化生产和应用。The preparation method of the invention is simple to operate and can realize on-line continuous production. Adding silk friction and static electricity generating devices to the original equipment does not affect the production capacity, and the energy consumption increases by 0.2 degrees/t, which is almost negligible, and is suitable for industrial production and application.

Claims (8)

  1. 一种高浸渍度长玻纤增强聚丙烯复合材料，其特征在于：由以下按重量份计的原料组成：聚丙烯树脂43.2～63.2份、玻璃纤维30～50份，相容剂1～10份、增韧剂1～10份、抗氧剂0.1～1份、润滑剂0.2～2份；其中，所述玻璃纤维在线经过玻纤加热预分散装置和冷却装置后，再通过丝绸摩擦起电，最后过静电发生装置直接进入浸渍槽进行生产。A long glass fiber reinforced polypropylene composite material with high impregnation degree is characterized in that it is composed of the following raw materials in parts by weight: 43.2-63.2 parts of polypropylene resin, 30-50 parts of glass fiber, and 1-10 parts of compatibilizer , 1 to 10 parts of toughening agent, 0.1 to 1 part of antioxidant, and 0.2 to 2 parts of lubricant; wherein, after the glass fiber is passed through the glass fiber heating pre-dispersion device and the cooling device on the line, it is electrified by silk friction, Finally, the static electricity generating device directly enters the dipping tank for production.
  2. 根据权利要求1所述的一种高浸渍度长玻纤增强聚丙烯复合材料，其特征在于：所述的聚丙烯树脂的熔值为100 g/10min(2.16 kg，230℃) 。A long glass fiber reinforced polypropylene composite material with high impregnation degree according to claim 1, characterized in that: the melting value of the polypropylene resin is 100 g/10min (2.16 kg, 230°C).
  3. 根据权利要求1所述的一种高浸渍度长玻纤增强聚丙烯复合材料，其特征在于：所述的玻璃纤维为直接无捻玻璃纤维。A long glass fiber reinforced polypropylene composite material with high impregnation degree according to claim 1, characterized in that: said glass fiber is direct untwisted glass fiber.
  4. 根据权利要求1所述的一种高浸渍度长玻纤增强聚丙烯复合材料，其特征在于：所述的相容剂为马来酸酐接枝聚丙烯。A long glass fiber reinforced polypropylene composite material with high impregnation degree according to claim 1, characterized in that: the compatibilizer is maleic anhydride grafted polypropylene.
  5. 根据权利要求1所述的一种高浸渍度长玻纤增强聚丙烯复合材料，其特征在于：所述的增韧剂为马来酸酐接枝的EPDM、POE和SEBS中的一种或者几种。A long glass fiber reinforced polypropylene composite material with high impregnation degree according to claim 1, characterized in that: the toughening agent is one or more of maleic anhydride grafted EPDM, POE and SEBS .
  6. 根据权利要求1所述的一种高浸渍度长玻纤增强聚丙烯复合材料，其特征在于：所述抗氧剂为受阻酚抗氧剂1010、亚磷酸酯类抗氧剂168和抗氧剂GA80等中的一种或者几种组合。A long glass fiber reinforced polypropylene composite material with high impregnation degree according to claim 1, characterized in that: said antioxidant is hindered phenol antioxidant 1010, phosphite antioxidant 168 and antioxidant One or several combinations of GA80, etc.
  7. 根据权利要求1所述的一种高浸渍度长玻纤增强聚丙烯复合材料，其特征在于：所述的润滑剂为硬脂酸、季戊四醇硬脂酸酯、硬脂酸甘油酯、芥酸酰胺和聚乙烯蜡中的一种或者几种。A long glass fiber reinforced polypropylene composite material with high impregnation degree according to claim 1, characterized in that: the lubricant is stearic acid, pentaerythritol stearate, glyceryl stearate, erucamide and one or more of polyethylene waxes.
  8. 权利要求1-7任意之一所述高浸渍度长玻纤增强聚丙烯复合材料的制备方法，其特征在于：其步骤如下：The preparation method of the long glass fiber reinforced polypropylene composite material with high impregnation degree according to any one of claims 1-7, characterized in that: the steps are as follows:
    1)连续玻璃纤维经牵引在线经过玻纤加热预分散装置和冷却装置后，再通过丝绸摩擦起电，最后过静电发生装置，随后进入有聚丙烯熔融体的浸渍槽。所述静电发生装置由两部分组成，第一部分由静电驻极静电发生器、高压线、支架、绝缘支柱、钼丝部件组成；第二部分由加热装置组成； 1) The continuous glass fiber passes through the glass fiber heating and pre-dispersing device and the cooling device on the drawing line, then passes through the silk friction and electrification, and finally passes through the static electricity generating device, and then enters the impregnation tank with polypropylene melt. The electrostatic generating device is composed of two parts, the first part is composed of electrostatic electret electrostatic generator, high voltage wire, bracket, insulating support, molybdenum wire parts; the second part is composed of heating device;
    2)按照重量配比称取聚丙烯树脂、相容剂、增韧剂、抗氧剂及润滑剂，将称好的原材料投入到高速混合器中混合均匀，然后经过双螺杆挤出机进入浸渍槽；2) Weigh the polypropylene resin, compatibilizer, toughening agent, antioxidant and lubricant according to the weight ratio, put the weighed raw materials into the high-speed mixer and mix them evenly, and then enter the impregnation through the twin-screw extruder groove;
    3)连续玻璃纤维经过浸渍槽后进行拉条、冷却、切粒、干燥处理。3) The continuous glass fiber is drawn, cooled, pelletized and dried after passing through the dipping tank.
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