WO2022077864A1 - 一种良外观、可喷涂的聚丙烯增强复合材料及其制备方法 - Google Patents

一种良外观、可喷涂的聚丙烯增强复合材料及其制备方法 Download PDF

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WO2022077864A1
WO2022077864A1 PCT/CN2021/082255 CN2021082255W WO2022077864A1 WO 2022077864 A1 WO2022077864 A1 WO 2022077864A1 CN 2021082255 W CN2021082255 W CN 2021082255W WO 2022077864 A1 WO2022077864 A1 WO 2022077864A1
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parts
composite material
antioxidant
polypropylene
preparation
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PCT/CN2021/082255
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French (fr)
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俞飞
黄险波
叶南飚
吴国峰
赖昂
丁正亚
杨波
罗忠富
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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
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass

Definitions

  • the invention relates to a polypropylene reinforced composite material with good appearance and can be sprayed and a preparation method thereof, belonging to the technical field of polymer material modification.
  • Glass fiber reinforced polypropylene has the advantages of high rigidity, high impact, good fatigue creep resistance, short molding cycle, and recyclability, which largely solves a series of shortcomings such as low rigidity and poor fatigue creep of pure PP.
  • GFRPP Glass fiber reinforced polypropylene
  • the phenomenon of glass fiber exposure limits the use of GFRPP materials to a large extent, and the spraying effect of glass fiber materials is not good, thus limiting its application in various aspects such as automotive functional parts.
  • anti-floating fiber agents to their products, and the types of anti-floating fiber agents are also various, such as the use of high melting index PP (MFR>500g/10min), ethylene bis-stearic acid amide dispersant and TAF Lubricants are used in combination, but ethylene bis-stearic acid amide dispersant and TAF are small molecules and there is a risk of precipitation and stickiness.
  • high melting index PP MFR>500g/10min
  • ethylene bis-stearic acid amide dispersant and TAF are small molecules and there is a risk of precipitation and stickiness.
  • the appearance spraying performance of glass fiber reinforced polypropylene materials has not been well resolved.
  • Poly-1-butene (poly-1-butene, English alias PB-1 or iPBu) is a thermoplastic resin polymerized from 1-butene. It is a translucent, colorless, odorless solid with a regular molecular structure. Chemical resistance, aging resistance and electrical insulation are similar to polypropylene. But it has a unique property, that is, after cooling and crystallization from the melt state, it needs to be placed at room temperature for three or four days before it can become a relatively stable crystal form I (melting point 124 ° C), and the strength and stiffness are also increased.
  • the outstanding advantages of poly-1-butene are excellent creep resistance, environmental stress cracking resistance and impact resistance, which are superior to polyethylene.
  • pipes such as water supply pipes, hot water pipes, and industrial pipes. and building pipes, etc.
  • Its application in film and packaging is expanding day by day. Due to its excellent heat resistance, boiling water resistance, transparency and non-toxicity, it can be widely used as medical instruments, such as syringes, three-way valves, blood separation tanks, and tube tanks for ultraviolet blood analysis, replacing quartz glass. etc.; physical and chemical utensils, such as measuring cylinders, utensils, beakers, etc.
  • medicine and food packaging such as milk containers, tableware, electronic stoves, food packaging films, and transparent packaging materials, instead of thermosetting resins and optical plastics. It can also be used to make release paper, heat-resistant lenses, etc., and has many uses in aviation and aerospace.
  • the object of the present invention is to overcome the deficiencies of the above-mentioned prior art and provide a good appearance, sprayable polypropylene reinforced composite material and its preparation method, the composite material has good tensile strength, flexural strength, flexural modulus and Izod notched impact strength, which can meet the development trends of lightweight, olefinization, and high performance required by the automotive industry at this stage.
  • the technical solution adopted in the present invention is: a polypropylene reinforced composite material with good appearance and sprayability, the composite material includes the following components in parts by weight: 55-82 parts of polypropylene, 15-82 parts of glass fiber 35 parts, 3-10 parts of special compatibilizer, 0-0.3 part of lubricant, 0-0.3 part of light stabilizer, 0.2-0.6 part of antioxidant.
  • the composite material includes the following components in parts by weight: 62-76 parts of polypropylene, 20-35 parts of glass fiber, 4-8 parts of special compatibilizer, and 0.1 part of lubricant ⁇ 0.2 part, light stabilizer 0.1 ⁇ 0.2 part, antioxidant 0.3 ⁇ 0.5 part.
  • the appearance of the composite material is higher in anti-floating fiber grade, longer in glass fiber retention length, and higher in surface tension.
  • the melt flow rate of the polypropylene is 60-1500 g/10min, and the melt flow rate of the polypropylene is according to ISO 1133 using a weight of 2.16 kg and at 230° C. temperature measurement.
  • the glass fiber is an alkali-free chopped glass fiber, and the monofilament diameter of the glass fiber is 10-13 ⁇ m.
  • the lubricant is at least one of an amide-based lubricant and a stearate-based lubricant
  • the antioxidant is a hindered phenolic antioxidant, phosphorous acid
  • the ester antioxidants is a hindered amine light stabilizer.
  • the special compatibilizer is poly-1-butene grafted sodium maleate.
  • the preparation raw materials of the special compatibilizer include the following components in parts by weight: 100 parts of poly-1 butene and 1.5 to 4.5 parts of sodium maleate.
  • the raw materials for the preparation of the special compatibilizer also include the following components in parts by weight: 0.2-0.4 parts of antioxidants, 0.2-0.4 parts of initiators, comonomer ⁇ - 2-3 parts of methyl styrene and 1-1.5 parts of comonomer 1-octene.
  • the present invention uses the self-made poly-1-butene grafted sodium maleate (PB-1-g-sodium maleate) purified product, and uses PB-1 with a lower melting point (124° C.) than PP (167° C.). In this way, at the same temperature, the low melt viscosity of PB-1 can better infiltrate the glass fiber surface, and the sodium maleate in PB-1-g-sodium maleate can be well mixed with glass fiber Combined, PB-1 has good compatibility with PP, so the purified PB-1-g-sodium maleate plays both the role of anti-floating fiber and the role of compatibilizer, which can significantly improve the properties of reinforced polypropylene. Sprayable performance.
  • the preparation method of the special compatibilizer comprises the following steps:
  • step (3) The mixed solution A obtained in step (2) is added to the mixture in step (1), the high-mixer mixes evenly, and after all the acetone is volatilized, it is added to a twin-screw extruder for melt extrusion grafting reaction , to obtain poly-1-butene grafted sodium maleate crude product;
  • step (3) (4) adding the poly-1-butene grafted sodium maleate crude product obtained in step (3) into xylene, stirring until all dissolved, to obtain mixed solution B, then pouring mixed solution B into acetone solution while hot In the process, a flocculent precipitation product is generated, and then rinsed with acetone to obtain the first purified product, and then the flocculent precipitate is dried to constant weight; the above steps are repeated for the second and third purification, and finally the obtained poly1- The butene-grafted sodium maleate purified product is vacuum-dried to constant weight for use, which is a special compatibilizer.
  • the rotating speed of the high-speed mixer is 650-750 rpm, and the antioxidant is at least one of antioxidant 1010 and antioxidant 168;
  • the mass ratio of the initiator and acetone is (0.2 ⁇ 0.4): (35 ⁇ 45), the initiator is di-tert-butyl peroxide, and the dissolution temperature is 35 ⁇ 45°C;
  • the step ( 3) in, the temperature of twin-screw extruder is 135 ⁇ 150 °C;
  • the mass ratio of poly-1-butene grafted sodium maleate crude product, xylene, acetone is 1:( 35 ⁇ 45): (60 ⁇ 70), the dissolving temperature is 70 ⁇ 80°C, the number of times of washing with acetone is 3 ⁇ 5 times, and the vacuum drying time is 24h.
  • the present invention provides a preparation method of the above-mentioned composite material.
  • the preparation method includes the following steps: mixing polypropylene, a special compatibilizer, a light stabilizer, a lubricant, and an antioxidant in a high-speed mixer;
  • the above-mentioned mixed particles are added to a twin-screw extruder for melt extrusion and granulation, and glass fibers are fed from the side for extrusion and materialization, and then dried, cooled, and packaged to obtain a good appearance and sprayable powder.
  • Polypropylene reinforced composite are the following steps: mixing polypropylene, a special compatibilizer, a light stabilizer, a lubricant, and an antioxidant in a high-speed mixer;
  • the above-mentioned mixed particles are added to a twin-screw extruder for melt extrusion and granulation, and glass fibers are fed from the side for extrusion and materialization, and then dried, cooled, and packaged to obtain a good appearance and sprayable
  • the mixing time of the high-speed mixer is 3-5 minutes, and the rotation speed is 200-300 rpm; the temperature of the twin-screw extruder is from the feeding section to the machine.
  • the heads are 230°C, 250°C, 260°C, 260°C, 270°C, 270°C, 265°C, 260°C, 250°C in sequence.
  • the extrusion process of the good appearance and sprayable polypropylene reinforced composite material of the present invention is also very critical.
  • the general extrusion temperature of glass fiber reinforced PP is generally 200-230°C, while the extrusion temperature of the present invention is 230-270°C, and the high temperature
  • the lower melt viscosity can better infiltrate the glass fiber and reduce the shear, so that the composite material has good anti-floating fiber effect, long glass fiber retention length, high mechanical properties, and better wrapping to achieve better spray performance.
  • the present invention prepares a high-performance polypropylene reinforced composite material with good appearance and sprayability by using a special compatibilizer. At this stage, the development trends of lightweight, olefinization, and high performance required by the automotive industry.
  • the present invention can better wrap and infiltrate glass fiber by using specific polypropylene, so that the appearance of anti-floating fiber effect is good; Its melting point (124°C) is lower than that of PP (167°C).
  • PB-1 has a lower melt viscosity and can better wet the glass fiber surface.
  • PB-1-g-sodium maleate purified product The sodium maleate in the product can be well combined with glass fiber, and PB-1 has good compatibility with PP, so PB-1-g-sodium maleate purified product not only plays the role of anti-floating fiber but also plays a role in To the role of the compatibilizer, it can significantly improve the spray performance.
  • the extrusion process of the good appearance and sprayable polypropylene reinforced composite material of the present invention is also very critical.
  • the commonly used glass fiber reinforced PP is generally extruded at a temperature of 200 to 230° C., while the extrusion temperature of the present invention is at 230 to 270° C. °C, low melt viscosity at high temperature can better infiltrate glass fiber and reduce shearing, so that the composite material has good anti-floating fiber effect, long glass fiber retention length and high mechanical properties, and better wrapping achieves better spraying performance.
  • the invention has a simple production process and is suitable for mass production.
  • the density of the following examples and comparative examples is tested according to ISO 1183-1-2019, the tensile properties are tested according to ISO 527-2-2016, the tensile speed is 10mm/min, the bending properties are tested according to ISO 178-2019, and the bending properties are tested according to ISO 178-2019.
  • the speed is 2mm/min and the Izod notched impact is tested according to ISO 180-2013.
  • the glass fiber retention length test method is as follows: the extruded particles are fully burned in a 650 °C muffle furnace for 4 hours, and the burned glass fiber residue is tested for retention length, and the average retention length of 500 pieces is analyzed, and the unit is mm.
  • the sprayable performance is characterized by surface tension. The larger the surface tension, the better the sprayable performance. The surface tension is in accordance with the Ford BO 116-03-2018 standard, and the unit is mN/m.
  • the surface tension solution preparation comparison table is shown in Table 1.
  • anti-floating fiber The appearance of anti-floating fiber is evaluated according to the degree of the existence of floating fiber, which is divided into five grades from 1 to 5. The specific evaluation grades are shown in Table 2.
  • the number of floating fibers is 0 ⁇ 5/cm 2 2 Slightly floating fibers, the number of floating fibers is 6 to 10/cm 2 3 Slight floating fiber, the number of floating fiber is 11 ⁇ 15/cm 2 4 Obvious floating fibers, the number of floating fibers is 16-20/cm 2 5 Severe floating fibers, the number of floating fibers is 21 to 25/cm 2
  • Alkali-free chopped glass fiber Model: E7CS13-03-508A (monofilament diameter 13 ⁇ m), manufacturer: Jushi Group; Model: E7CS10-03-508A (monofilament diameter 10 ⁇ m), manufacturer: Jushi Group.
  • Di-tert-butyl peroxide Model: DTBP, Manufacturer: Dongying Haijing Chemical Co., Ltd.
  • ⁇ -Methylstyrene Model: AMS, Manufacturer: Mitsui Chemicals, Japan.
  • 1-Octene Model: 1-Octene, Manufacturer: Nanjing Huijing Petrochemical.
  • Xylene Xylene, manufacturer: Dongguan Qifeng Chemical Co., Ltd.
  • Acetone Acetone, manufacturer: Shanghai Xinwei Chemical Co., Ltd.
  • Antioxidant Hindered phenol type number: 1010, manufacturer: Shandong Sanfeng; phosphite type number: 168, manufacturer: Shandong Sanfeng.
  • Lubricant amide type: TR016, manufacturer: STRUKTOL, USA; calcium stearate: BS-3818, manufacturer: Huamingtai Chemical; Zinc stearate: BS-2818, manufacturer: Huamingtai Chemical.
  • step (c) adding the mixed solution A obtained in the step (b) into the mixture in the step (a), mixing with the high-mixer uniformly, and adding it to the twin-screw extruder after all the acetone volatilizes to carry out the melt extrusion grafting reaction, PB-1-g-sodium maleate crude product was obtained; wherein, the temperature of the twin-screw extruder was 135°C;
  • a polypropylene reinforced composite material with good appearance and sprayability the composite material comprises the following components by weight: 55 parts of polypropylene, 35 parts of glass fiber, 10 parts of special compatibilizer, 0.3 part of lubricant, light stabilizer 0.3 part of antioxidant, 0.2 part of antioxidant.
  • the preparation method of the composite material in this example is as follows: weighing 55 parts of polypropylene PP M60T, 10 parts of the special compatibilizer PB-1-g-sodium maleate purified product of the present invention, 0.3 part of light stabilizer, 0.3 part of lubricating agent Agent BS-2818, 0.1 part of antioxidant 1010, and 0.1 part of antioxidant 168 were mixed in a high-speed mixer for 3 minutes, wherein the rotating speed of the high-speed mixer was 200 rpm.
  • the above-mentioned mixed particles were added into a twin-screw extruder for melt extrusion, granulation, drying, cooling and packaging, in which 35 parts of glass fiber E7CS10-03-508A were fed into the extrusion material from the side.
  • the temperature of the twin-screw extruder is 230°C, 250°C, 260°C, 260°C, 270°C, 270°C, 270°C, 265°C, 260°C, 250°C from the feeding section to the head.
  • melt flow rate of the polypropylene used in this comparative example is not within the scope of the present invention.
  • the only difference between this comparative example and Example 1 is the polypropylene used, and other components and preparation methods in the composite material are the same as those in the example. 1 is the same.
  • a polypropylene reinforced composite material comprises the following components by weight: 55 parts of polypropylene, 35 parts of glass fiber, 10 parts of special compatibilizer, 0.3 part of lubricant, 0.3 part of light stabilizer, antioxidant dose 0.2 servings.
  • the preparation method of the composite material of this comparative example is as follows: firstly, 55 parts of polypropylene PP EP548R, 10 parts of the special compatibilizer PB-1-g-sodium maleate purified product of the present invention, 0.3 parts of light stabilizer, 0.3 parts of Lubricant BS-2818, 0.1 part of antioxidant 1010, and 0.1 part of antioxidant 168 were mixed in a high-speed mixer for 3 minutes, wherein the rotating speed of the high-speed mixer was 200 rpm.
  • the above-mentioned mixed particles were added into a twin-screw extruder for melt extrusion, granulation, drying, cooling and packaging, in which 35 parts of glass fiber E7CS10-03-508A were fed into the extrusion material from the side.
  • the temperature of the twin-screw extruder is 230°C, 250°C, 260°C, 260°C, 270°C, 270°C, 270°C, 265°C, 260°C, 250°C from the feeding section to the head.
  • Example 1 The only difference between this comparative example and Example 1 is that it does not contain a special compatibilizer, and other components and preparation methods in the composite material are the same as those in Example 1.
  • a polypropylene reinforced composite material comprising the following components by weight: 55 parts of polypropylene, 35 parts of glass fiber, 0.3 part of lubricant, 0.3 part of light stabilizer, and 0.2 part of antioxidant.
  • the preparation method of the composite material of this comparative example is as follows: firstly, 55 parts of polypropylene PP M60T, 0.3 part of light stabilizer, 0.3 part of lubricant BS-2818, 0.1 part of antioxidant 1010, 0.1 part of antioxidant 168 are weighed and mixed with high speed Mix in the machine for 3 minutes, wherein the speed of the high-speed mixer is 200 rpm. The above-mentioned mixed particles were added into a twin-screw extruder for melt extrusion, granulation, drying, cooling and packaging, in which 35 parts of glass fiber E7CS10-03-508A were fed into the extrusion material from the side.
  • the temperature of the twin-screw extruder is 230°C, 250°C, 260°C, 260°C, 270°C, 270°C, 270°C, 265°C, 260°C, 250°C from the feeding section to the head.
  • Example 1 The only difference between this comparative example and Example 1 is that in the preparation method of the composite material, the temperature of extrusion granulation is different, and other components in the composite material and the preparation method are the same as those in Example 1.
  • a polypropylene reinforced composite material with good appearance and sprayability the composite material comprises the following components by weight: 55 parts of polypropylene, 35 parts of glass fiber, 10 parts of special compatibilizer, 0.3 part of lubricant, light stabilizer 0.3 part of antioxidant, 0.2 part of antioxidant.
  • the preparation method of the composite material of this comparative example is as follows: weighing 55 parts of polypropylene PP M60T, 10 parts of the special compatibilizer PB-1-g-sodium maleate purified product of the present invention, 0.3 part of light stabilizer, 0.3 part of lubricating agent Agent BS-2818, 0.1 part of antioxidant 1010, and 0.1 part of antioxidant 168 were mixed in a high-speed mixer for 3 minutes, wherein the rotating speed of the high-speed mixer was 200 rpm.
  • the above-mentioned mixed particles were added into a twin-screw extruder for melt extrusion, granulation, drying, cooling and packaging, in which 35 parts of glass fiber E7CS10-03-508A were fed into the extrusion material from the side.
  • the temperature of the twin-screw extruder is 200°C, 210°C, 220°C, 220°C, 220°C, 220°C, 210°C, 205°C, 200°C, 200°C from the feeding section to the head.
  • step (c) adding the mixed solution A obtained in the step (b) into the mixture in the step (a), mixing with the high-mixer uniformly, and adding it to the twin-screw extruder after all the acetone volatilizes to carry out the melt extrusion grafting reaction, PB-1-g-sodium maleate crude product was obtained; wherein, the temperature of the twin-screw extruder was 150°C;
  • a polypropylene reinforced composite material with good appearance and sprayable the composite material comprises the following components in parts by weight: 82 parts of polypropylene, 15 parts of glass fiber, 3 parts of special compatibilizer, and 0.6 part of antioxidant.
  • the preparation method of the composite material in this example is as follows: weighing 82 parts of polypropylene PP MH7900, 3 parts of the special compatibilizer PB-1-g-sodium maleate purified product of the present invention, 0.3 parts of antioxidant 1010, 0.3 parts of Antioxidant 168 was mixed in a high-speed mixer for 5 minutes, wherein the rotational speed of the high-speed mixer was 300 rpm.
  • the above-mentioned mixed particles were added into a twin-screw extruder for melt extrusion, granulation, drying, cooling and packaging, wherein 15 parts of glass fiber E7CS13-03-508A were fed into the extrusion material from the side feed.
  • the temperature of the twin-screw extruder is 230°C, 250°C, 260°C, 260°C, 270°C, 270°C, 270°C, 265°C, 260°C, 250°C from the feeding section to the head.
  • the preparation raw materials and preparation method of the special compatibilizer in this example are the same as those in Example 2.
  • a polypropylene reinforced composite material with good appearance and sprayability the composite material comprises the following components in parts by weight: 64 parts of polypropylene, 30 parts of glass fiber, 6 parts of special compatibilizer, and 0.6 part of antioxidant.
  • the preparation method of the composite material in this example is as follows: weighing 64 parts of polypropylene PP MH7900, 6 parts of the special compatibilizer PB-1-g-sodium maleate purified product of the present invention, 0.3 parts of antioxidant 1010, 0.3 parts of Antioxidant 168 was mixed in a high-speed mixer for 5 minutes, wherein the rotational speed of the high-speed mixer was 300 rpm.
  • the above-mentioned mixed particles were added into a twin-screw extruder for melt extrusion, granulation, drying, cooling and packaging, in which 30 parts of glass fiber E7CS13-03-508A were fed into the extrusion material from the side feed.
  • the temperature of the twin-screw extruder is 230°C, 250°C, 260°C, 260°C, 270°C, 270°C, 270°C, 265°C, 260°C, 250°C from the feeding section to the head.
  • a polypropylene reinforced composite material with good appearance and sprayability comprises the following components in parts by weight: 65 parts of polypropylene, 30 parts of glass fibers, 5 parts of a special compatibilizer, 0.22 parts of a lubricant, a light stabilizer 0.18 parts of antioxidants, 0.49 parts of antioxidants.
  • the preparation method of the composite material in this example is as follows: weighing 65 parts of polypropylene PP P1000, 5 parts of the special compatibilizer PB-1-g-sodium maleate purified product of the present invention, 0.18 part of light stabilizer, 0.22 part of lubricating agent Agent TR016, 0.22 part of antioxidant 1010, and 0.27 part of antioxidant 168 were mixed with a high-speed mixer for 3.8 minutes, wherein the speed of the high-speed mixer was 269 rpm.
  • the above-mentioned mixed particles were added into a twin-screw extruder for melt extrusion, granulation, drying, cooling and packaging, in which 30 parts of glass fiber E7CS13-03-508A were fed into the extrusion material from the side feed.
  • the temperature of the twin-screw extruder is 230°C, 250°C, 260°C, 260°C, 270°C, 270°C, 270°C, 265°C, 260°C, 250°C from the feeding section to the head.
  • a polypropylene reinforced composite material with good appearance and sprayability comprises the following components in parts by weight: 68 parts of polypropylene, 25 parts of glass fiber, 7 parts of special compatibilizer, 0.26 parts of lubricant, light stabilizer 0.23 parts of antioxidants and 0.46 parts of antioxidants.
  • the preparation method of the composite material in this example is as follows: weighing 68 parts of polypropylene PP P1200, 7 parts of the special compatibilizer PB-1-g-sodium maleate purified product of the present invention, 0.23 parts of light stabilizer, 0.26 parts of lubricating agent Agent TR016, 0.22 part of antioxidant 1010, 0.24 part of antioxidant 168 were mixed with a high-speed mixer for 4.7 minutes, wherein the speed of the high-speed mixer was 288 rpm.
  • the above-mentioned mixed particles were added into a twin-screw extruder for melt extrusion, granulation, drying, cooling and packaging, in which 25 parts of glass fiber E7CS10-03-508A were fed into the extrusion material from the side feed.
  • the temperature of the twin-screw extruder is 230°C, 250°C, 260°C, 260°C, 270°C, 270°C, 270°C, 265°C, 260°C, and 250°C in sequence from the feeding section to the head.
  • the preparation raw materials and preparation method of the special compatibilizer in this example are the same as those in Example 1.
  • a polypropylene reinforced composite material with good appearance and sprayability comprises the following components in parts by weight: 62 parts of polypropylene PP M60T, 35 parts of glass fiber E7CS10-03-508A, 4 parts of special compatibilizer, Lubricant BS-2818 0.1 part, light stabilizer UV-3808PP5 0.1 part, antioxidant 1010 0.3 part.
  • the preparation method of the polypropylene reinforced composite material in this example is the same as that in Example 1.
  • the specific properties of the polypropylene composite material prepared in this example are shown in Table 3.
  • the preparation raw materials and preparation method of the special compatibilizer in this example are the same as those in Example 1.
  • a polypropylene reinforced composite material with good appearance and sprayability comprises the following components in parts by weight: 76 parts of polypropylene PP M60T, 20 parts of glass fiber E7CS10-03-508A, 8 parts of special compatibilizer, Lubricant BS-2818 0.2 part, light stabilizer UV-3808PP5 0.2 part, antioxidant 1010 0.5 part.
  • the preparation method of the polypropylene reinforced composite material in this example is the same as that in Example 1.
  • the specific properties of the polypropylene composite material prepared in this example are shown in Table 3.
  • the invention prepares a high-performance polypropylene reinforced composite material with good appearance, anti-floating fiber and sprayable by using special polypropylene and special compatibilizer.
  • the glass fiber content is 35 parts
  • the tensile strength can reach 120MPa
  • the bending strength It can reach 180MPa
  • the flexural modulus can reach 9000MPa
  • the notched impact of the cantilever beam can reach 15kJ/m 2 , which can meet the development trends of lightweight, olefinization, and high performance required by the automotive industry at this stage.
  • the prepared polypropylene reinforced composite material has a higher level of anti-floating fiber appearance, longer glass fiber retention length and greater surface tension.

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Abstract

一种良外观、可喷涂的聚丙烯增强复合材料，所述复合材料包括如下重量份的组分：聚丙烯55～82份、玻璃纤维15～35份、特制相容剂3～10份、润滑剂0～0.3份、光稳剂0～0.3份、抗氧剂0.2～0.6份。通过使用特制相容剂制备出了外观良好、可喷涂的高性能聚丙烯增强复合材料，该复合材料具有良好的拉伸强度、弯曲强度、弯曲模量和悬臂梁缺口冲击强度，可满足现阶段汽车行业要求的轻量化、烯烃化、高性能化等发展趋势。

Description

一种良外观、可喷涂的聚丙烯增强复合材料及其制备方法 技术领域
本发明涉及一种良外观、可喷涂的聚丙烯增强复合材料及其制备方法，属于高分子材料改性技术领域。
背景技术
玻纤增强聚丙烯(GFRPP)具有高刚性、高冲击、耐疲劳蠕变好、成型周期短、可循环利用等优点，很大程度上解决了纯PP刚性低、疲劳蠕变差等一系列不足，在70年代投入使用后便在家电、电子电器、建筑工业、航空航天、船舶和汽车等众多领域得到了广泛的应用。但是，在工程应用方面，玻纤外露的现象又很大程度上限制了GFRPP材料的使用，另外玻纤材料的喷涂效果不好，因此限制了其在汽车功能件等多方面的应用。
近年来，随着对高分子材料使用环境、美观性要求的提高，人们对GFRPP复合材料的表面浮纤情况提出了更高的要求。目前众多研究中，有些学者使用抗浮纤母粒，如使用玻璃纤维与PB-1做抗浮纤母粒再加入成品中，这样母粒中的玻纤进行了二次过机保留长度会降低，影响产品力学性能；或者使用氧化锌做抗浮纤母粒，这种抗浮纤母粒为白色，无法应用到深色产品中。另外一些学者是在产品中加入抗浮纤剂，抗浮纤剂的种类也是各式各样，如使用高熔指PP(MFR＞500g/10min)、乙撑双硬脂酸酰胺分散剂及TAF润滑剂复配使用，但是乙撑双硬脂酸酰胺分散剂及TAF是小分子存在析出发黏的风险。另外，玻纤增强聚丙烯材料的外观喷涂性能一直得不到较好的解决。
聚1-丁烯(poly-1-butene，英文别名PB-1或iPBu)由1-丁烯聚合而成的一种热塑性树脂，是半透明、无色、无臭固体，分子结构规整，其耐化学性、耐老化性和电绝缘性均与聚丙烯相近。但它有一独特性能，即从熔体状态冷却结晶后，需在室温放置三四日方能变为较稳定的晶型I(熔点124℃)，强度和刚度也随之提高。聚1-丁烯的突出优点是抗蠕变性、耐环境应力开裂和抗冲击性能 十分优异，优于聚乙烯，因此最主要的用途是作管材，如供水管、热水管、工业用管和建筑物用管等。其在薄膜、包装方面的应用正日益扩展。由于具有优异的耐热性、耐沸水蒸煮性、透明性及无毒等特性，故可广泛用作医疗器具、如注射器、三通阀、血液分离槽、紫外线血液分析用管槽，取代石英玻璃等；理化器具，如量筒、器皿、烧杯等。还可用于医药及食品包装，如牛奶容器、餐具、电子炉、食品包装薄膜、透明包装材料，代替热固性树脂、光学塑料。也可以制作剥离纸、耐热透镜等，在航空和宇航方面的用途也很多。
发明内容
本发明的目的在于克服上述现有技术的不足之处而提供一种良外观、可喷涂的聚丙烯增强复合材料及其制备方法，该复合材料具有良好的拉伸强度、弯曲强度、弯曲模量和悬臂梁缺口冲击强度，可满足现阶段汽车行业要求的轻量化、烯烃化、高性能化等发展趋势。
为实现上述目的，本发明采取的技术方案为：一种良外观、可喷涂的聚丙烯增强复合材料，所述复合材料包括如下重量份的组分：聚丙烯55～82份、玻璃纤维15～35份、特制相容剂3～10份、润滑剂0～0.3份、光稳剂0～0.3份、抗氧剂0.2～0.6份。
作为本发明所述复合材料的优选实施方式，所述复合材料包括如下重量份的组分：聚丙烯62～76份、玻璃纤维20～35份、特制相容剂4～8份、润滑剂0.1～0.2份、光稳剂0.1～0.2份、抗氧剂0.3～0.5份。当复合材料包含上述重量份的组分时，复合材料的外观抗浮纤等级更高、玻纤保留长度更长、表面张力更大。
作为本发明所述复合材料的优选实施方式，所述聚丙烯的熔体流动速率为60～1500g/10min，所述聚丙烯的熔体流动速率是根据ISO 1133使用2.16kg重量并在230℃的温度测量。
作为本发明所述复合材料的优选实施方式，所述玻璃纤维为无碱短切玻璃纤维，所述玻璃纤维的单丝直径为10～13μm。
作为本发明所述复合材料的优选实施方式，所述润滑剂为酰胺类润滑剂、 硬脂酸盐类润滑剂中的至少一种，所述抗氧剂为受阻酚类抗氧剂、亚磷酸酯类抗氧剂中的至少一种，所述光稳剂为受阻胺类光稳剂。
作为本发明所述复合材料的优选实施方式，所述特制相容剂为聚1-丁烯接枝马来酸钠。
作为本发明所述复合材料的优选实施方式，所述特制相容剂的制备原料包含如下重量份的组分：聚-1丁烯100份和马来酸钠1.5～4.5份。
作为本发明所述复合材料的优选实施方式，所述特制相容剂的制备原料还包含如下重量份的组分：抗氧剂0.2～0.4份、引发剂0.2～0.4份、共单体α-甲基苯乙烯2～3份和共单体1-辛烯1～1.5份。
本发明使用自制的聚1-丁烯接枝马来酸钠(PB-1-g-马来酸钠)纯化物，应用PB-1本身熔点(124℃)比PP熔点(167℃)低的特点，这样在相同的温度下PB-1熔体粘度低可以更好的浸润玻纤表面，PB-1-g-马来酸钠纯化物中的马来酸钠可以很好的与玻纤相结合，PB-1与PP相容性较好，因此PB-1-g-马来酸钠纯化物既起到抗浮纤的作用又起到相容剂的作用，可明显改善增强聚丙烯的可喷涂性能。
作为本发明所述复合材料的优选实施方式，所述特制相容剂的制备方法包括以下步骤：
(1)将聚-1丁烯、马来酸钠、抗氧剂通过高速混合机混合均匀，得到混合物；
(2)将引发剂、共单体α-甲基苯乙烯、共单体1-辛烯溶解于丙酮中，得到混合溶液A待用；
(3)将步骤(2)得到的混合溶液A加入到步骤(1)的混合物中，高混机混合均匀，待丙酮全部挥发后，加入到双螺杆挤出机中进行熔融挤出接枝反应，得到聚1-丁烯接枝马来酸钠粗化物；
(4)将步骤(3)得到的聚1-丁烯接枝马来酸钠粗化物加入到二甲苯中，搅拌直至全部溶解，得到混合溶液B，然后将混合溶液B趁热倒入丙酮溶液中，生成絮状沉淀产物，再用丙酮冲洗，得到第一次纯化物，然后将絮状沉淀物干 燥至恒重；重复以上步骤进行第二次、第三次纯化，最后得到的聚1-丁烯接枝马来酸钠纯化物真空干燥至恒重备用，即为特制相容剂。
作为本发明所述复合材料的优选实施方式，所述步骤(1)中，高速混合机的转速为650～750rpm，抗氧剂为抗氧剂1010、抗氧剂168中的至少一种；所述步骤(2)中，引发剂、丙酮的质量比为(0.2～0.4)：(35～45)，引发剂为二叔丁基过氧化物，溶解温度为35～45℃；所述步骤(3)中，双螺杆挤出机的温度为135～150℃；所述步骤(4)中，聚1-丁烯接枝马来酸钠粗化物、二甲苯、丙酮的质量比为1：(35～45)：(60～70)，溶解温度为70～80℃，用丙酮冲洗的次数为3～5次，真空干燥时间为24h。
第二方面，本发明提供了上述复合材料的制备方法，所述制备方法包括以下步骤：将聚丙烯、特制相容剂、光稳剂、润滑剂、抗氧剂于高速混合机中混合；将上述混合好的粒子加入双螺杆挤出机中进行熔融挤出、造粒，将玻璃纤维从侧喂料加入进行挤出造料，然后干燥、冷却、装包，即得良外观、可喷涂的聚丙烯增强复合材料。
作为本发明所述制备方法的优选实施方式，所述高速混合机的混合时间为3～5分钟，转速为200～300转/分钟；所述双螺杆挤出机的温度从喂料段到机头依次为230℃、250℃、260℃、260℃、270℃、270℃、270℃、265℃、260℃、250℃。
本发明的良外观、可喷涂聚丙烯增强复合材料的挤出工艺也是非常关键的，常用玻纤增强PP一般挤出温度在200～230℃，而本发明挤出温度在230～270℃，高温下熔体粘度低可以更好的浸润玻纤以及降低剪切，使得复合材料抗浮纤效果好、玻纤保留长度长力学性能高、更好的包裹实现了更好的喷涂性能。
与现有技术相比，本发明的有益效果为：
(1)本发明通过使用特制相容剂制备出了外观良好、可喷涂的高性能聚丙烯增强复合材料，具有良好的拉伸强度、弯曲强度、弯曲模量和悬臂梁缺口冲击强度，可满足现阶段汽车行业要求的轻量化、烯烃化、高性能化等发展趋势。
(2)本发明通过使用特定聚丙烯能更好地包裹、浸润玻纤，使得外观抗浮 纤效果好；本发明使用自制的PB-1-g-马来酸钠纯化物，应用PB-1本身熔点(124℃)比PP熔点(167℃)低的特点，在相同的温度下PB-1熔体粘度低可以更好的浸润玻纤表面，PB-1-g-马来酸钠纯化物中的马来酸钠可以很好的与玻纤相结合，PB-1与PP相容性较好，因此PB-1-g-马来酸钠纯化物既起到抗浮纤的作用又起到相容剂的作用，可明显改善喷涂性能。
(3)本发明的良外观、可喷涂聚丙烯增强复合材料的挤出工艺也是非常关键的，常用玻纤增强PP一般挤出温度在200～230℃，而本发明挤出温度在230～270℃，高温下熔体粘度低可以更好的浸润玻纤以及降低剪切，使得复合材料抗浮纤效果好、玻纤保留长度长力学性能高，更好的包裹实现了更好的喷涂性能。本发明生产工艺简单、适合大批量生产。
具体实施方式
为更好地说明本发明的目的、技术方案和优点，下面将结合具体实施例对本发明作进一步说明。
以下实施例和对比例的密度按照ISO 1183-1-2019进行测试，拉伸性能按照ISO 527-2-2016进行测试、拉伸速度为10mm/min，弯曲性能按照ISO 178-2019进行测试、弯曲速度为2mm/min，悬臂梁缺口冲击按照ISO 180-2013进行测试。玻纤保留长度测试的方法为：挤出粒子在650℃马弗炉中充分燃烧4h，烧后的玻纤残留物进行保留长度测试，分析500根取平均保留长度，单位mm。可喷涂性能使用表面张力进行表征，表面张力越大表示可喷涂性能越好，表面张力按照Ford BO 116-03-2018标准，单位mN/m，表面张力溶液配制对比表如表1所示。
表1
序号 水/ml 乙醇/ml 表面张力/(mN/m)
1 0 50 22.3
2 1.25 48.75 22.8
3 5.25 44.75 24.2
4 9.5 40.5 26.1
5 13.25 36.75 27.5
6 17.5 32.5 29.5
7 21.25 28.75 31.5
8 24.25 25.75 33
9 27 23 34.7
10 29.5 20.5 36.9
11 31.75 18.25 39.3
12 33.75 16.25 42.5
13 35.75 14.25 48
14 37.35 12.65 48.8
15 39 11 51.7
16 40.15 9.85 53.7
17 41.5 8.5 56
18 43.5 6.5 59.5
19 45.35 4.65 62.7
20 46.85 3.15 65.7
21 48.25 1.75 68.7
22 49.5 0.5 71
23 50 0 72
外观抗浮纤按照浮纤存在的程度进行评价，分为1～5五个等级，具体评价等级如表2所示。
表2
等级 外观描述
1 无浮纤，浮纤条数为0～5条/cm 2
2 微微浮纤，浮纤条数为6～10条/cm 2
3 轻微浮纤，浮纤条数为11～15条/cm 2
4 明显浮纤，浮纤条数为16～20条/cm 2
5 严重浮纤，浮纤条数为21～25条/cm 2
本发明实施例和对比例中用到的主要代表材料如下：
聚丙烯：型号：P1000(MFR＝1000g/10min)，厂家：上海华合有限公司；型号：P1200(MFR＝1200g/10min)，厂家：上海华合有限公司；型号：P1500(MFR＝1500g/10min)，厂家：上海华合有限公司；型号：M60T(MFR＝60g/10min)，厂家：镇海炼化；型号：MH7900(MFR＝150g/10min)，厂家：LG化学；型号：EP548R(MFR＝26g/10min)，厂家：中海壳牌。
PB-1：型号：PB0800M(MFR＝200g/10min，190℃/2.16kg)，厂家：利安德巴塞尔；型号：PB0401M(MFR＝15g/10min，190℃/2.16kg)，厂家：利安德巴塞尔；。
无碱短切玻璃纤维：型号：E7CS13-03-508A(单丝直径13μm)，厂家：巨石集团；型号：E7CS10-03-508A(单丝直径10μm)，厂家：巨石集团。
马来酸钠：型号：马来酸钠，厂家：上海千峰化工有限公司。
二叔丁基过氧化物：型号：DTBP，厂家：东营市海京化工有限公司。
α-甲基苯乙烯：型号：AMS，厂家：日本三井化学。
1-辛烯：型号：1-Octene，厂家：南京汇景石油化工。
二甲苯：二甲苯，厂家：东莞市淇锋化工有限公司。
丙酮：丙酮，厂家：上海鑫魏化工有限公司。
抗氧剂：受阻酚类型号：1010，厂家：山东三丰；亚磷酸酯类型号：168，厂家：山东三丰。
光稳剂：型号：UV-3808PP5，厂家：比利时索尔维。
润滑剂：酰胺类型号：TR016，厂家：美国STRUKTOL；硬脂酸钙型号：BS-3818，厂家：华明泰化工；硬脂酸锌型号：BS-2818，厂家：华明泰化工。
实施例1
本实施例中特制相容剂的制备方法如下：
(a)首先称取100份聚-1丁烯PB0800M、1.5份马来酸钠、0.1份抗氧剂1010和0.1份抗氧剂168通过高速混合机混合均匀，高混机的转速650rpm，得到混合物；
(b)将0.2份引发剂二叔丁基过氧化物(DTBP)、2份共单体α-甲基苯乙烯(AMS)、1份共单体1-辛烯(1-Octene)在35℃条件下溶解于35份丙酮中， 得到混合溶液A待用；
(c)将步骤(b)得到的混合溶液A加入到步骤(a)的混合物中，高混机混合均匀，待丙酮全部挥发后加入到双螺杆挤出机中进行熔融挤出接枝反应，得到PB-1-g-马来酸钠粗化物；其中，双螺杆挤出机的温度为135℃；
(d)取1份PB-1-g-马来酸钠粗化物加入到35份二甲苯中在70℃温度下搅拌直至全部溶解，得到混合溶液B，然后将混合溶液B趁热倒入60份的丙酮溶液中，生成絮状沉淀产物，再用丙酮冲洗3次，得到第一次纯化物，然后将絮状沉淀物放入通风厨中干燥至恒重；重复以上步骤进行第二次、第三次纯化，最后得到的PB-1-g-马来酸钠纯化物放入真空干燥箱中干燥24h至恒重备用，即得特制相容剂。
一种良外观、可喷涂的聚丙烯增强复合材料，所述复合材料包括如下重量份的组分：聚丙烯55份、玻璃纤维35份、特制相容剂10份、润滑剂0.3份、光稳剂0.3份、抗氧剂0.2份。
本实施例复合材料的制备方法为：称取55份聚丙烯PP M60T、10份本发明的特制相容剂PB-1-g-马来酸钠纯化物、0.3份光稳剂、0.3份润滑剂BS-2818、0.1份抗氧剂1010、0.1份抗氧剂168与高速混合机中混合3分钟，其中高速混合机的转速为200转/分钟。将上述混合好的粒子加入双螺杆挤出机中进行熔融挤出、造粒、干燥、冷却、装包，其中35份玻璃纤维E7CS10-03-508A从侧喂料加入挤出造料。双螺杆挤出机的温度从喂料段到机头依次为230℃、250℃、260℃、260℃、270℃、270℃、270℃、265℃、260℃、250℃。
本实施例制备得到的聚丙烯复合材料的具体性能如表3所示。
对比例1
本对比例中使用的聚丙烯的熔体流动速率不在本发明范围内，本对比例与实施例1的区别仅在于使用的聚丙烯不同，复合材料中的其他组分及制备方法均与实施例1相同。
本对比例特制相容剂的制备原料及制备方法均同实施例1。
一种聚丙烯增强复合材料，所述复合材料包括如下重量份的组分：聚丙烯55份、玻璃纤维35份、特制相容剂10份、润滑剂0.3份、光稳剂0.3份、抗氧剂0.2份。
本对比例复合材料的制备方法为：首先称取55份聚丙烯PP EP548R、10份本发明的特制相容剂PB-1-g-马来酸钠纯化物、0.3份光稳剂、0.3份润滑剂BS-2818、0.1份抗氧剂1010、0.1份抗氧剂168与高速混合机中混合3分钟，其中高速混合机的转速为200转/分钟。将上述混合好的粒子加入双螺杆挤出机中进行熔融挤出、造粒、干燥、冷却、装包，其中35份玻璃纤维E7CS10-03-508A从侧喂料加入挤出造料。双螺杆挤出机的温度从喂料段到机头依次为230℃、250℃、260℃、260℃、270℃、270℃、270℃、265℃、260℃、250℃。
本对比例制备得到的聚丙烯复合材料的具体性能如表3所示。
对比例2
本对比例与实施例1的区别仅在于不包含特制相容剂，复合材料中的其他组分及制备方法均与实施例1相同。
一种聚丙烯增强复合材料，所述复合材料包括如下重量份的组分：聚丙烯55份、玻璃纤维35份、润滑剂0.3份、光稳剂0.3份、抗氧剂0.2份。
本对比例复合材料的制备方法为：首先称取55份聚丙烯PP M60T、0.3份光稳剂、0.3份润滑剂BS-2818、0.1份抗氧剂1010、0.1份抗氧剂168与高速混合机中混合3分钟，其中高速混合机的转速为200转/分钟。将上述混合好的粒子加入双螺杆挤出机中进行熔融挤出、造粒、干燥、冷却、装包，其中35份玻璃纤维E7CS10-03-508A从侧喂料加入挤出造料。双螺杆挤出机的温度从喂料段到机头依次为230℃、250℃、260℃、260℃、270℃、270℃、270℃、265℃、260℃、250℃。
本对比例制备得到的聚丙烯复合材料的具体性能如表3所示。
对比例3
本对比例与实施例1的区别仅在于复合材料的制备方法中，挤出造粒的温度不同，复合材料中的其他组分及制备方法均与实施例1相同。
本对比例特制相容剂的制备原料及制备方法均同实施例1。
一种良外观、可喷涂的聚丙烯增强复合材料，所述复合材料包括如下重量份的组分：聚丙烯55份、玻璃纤维35份、特制相容剂10份、润滑剂0.3份、光稳剂0.3份、抗氧剂0.2份。
本对比例复合材料的制备方法为：称取55份聚丙烯PP M60T、10份本发明的特制相容剂PB-1-g-马来酸钠纯化物、0.3份光稳剂、0.3份润滑剂BS-2818、0.1份抗氧剂1010、0.1份抗氧剂168与高速混合机中混合3分钟，其中高速混合机的转速为200转/分钟。将上述混合好的粒子加入双螺杆挤出机中进行熔融挤出、造粒、干燥、冷却、装包，其中35份玻璃纤维E7CS10-03-508A从侧喂料加入挤出造料。双螺杆挤出机的温度从喂料段到机头依次为200℃、210℃、220℃、220℃、220℃、220℃、210℃、205℃、200℃、200℃。
本对比例制备得到的聚丙烯复合材料的具体性能如表3所示。
实施例2
本实施例中特制相容剂的制备方法如下：
(a)首先称取100份聚-1丁烯PB0401M、4.5份马来酸钠、0.2份抗氧剂1010和0.2份抗氧剂168通过高速混合机混合均匀，高混机的转速750rpm，得到混合物；
(b)将0.4份引发剂二叔丁基过氧化物(DTBP)、3份共单体α-甲基苯乙烯(AMS)、1.5份共单体1-辛烯(1-Octene)在45℃条件下溶解于45份丙酮中，得到混合溶液A待用；
(c)将步骤(b)得到的混合溶液A加入到步骤(a)的混合物中，高混机混合均匀，待丙酮全部挥发后加入到双螺杆挤出机中进行熔融挤出接枝反应，得到PB-1-g-马来酸钠粗化物；其中，双螺杆挤出机的温度为150℃；
(d)取1份PB-1-g-马来酸钠粗化物加入到45份二甲苯中在80℃温度下搅 拌直至全部溶解，得到混合溶液B，然后将混合溶液B趁热倒入70份的丙酮溶液中，生成絮状沉淀产物，再用丙酮冲洗5次，得到第一次纯化物，然后将絮状沉淀物放入通风厨中干燥至恒重；重复以上步骤进行第二次、第三次纯化，最后得到的PB-1-g-马来酸钠纯化物放入真空干燥箱中干燥24h至恒重备用，即得特制相容剂。
一种良外观、可喷涂的聚丙烯增强复合材料，所述复合材料包括如下重量份的组分：聚丙烯82份、玻璃纤维15份、特制相容剂3份、抗氧剂0.6份。
本实施例复合材料的制备方法为：称取82份聚丙烯PP MH7900、3份本发明的特制相容剂PB-1-g-马来酸钠纯化物、0.3份抗氧剂1010、0.3份抗氧剂168与高速混合机中混合5分钟，其中高速混合机的转速为300转/分钟。将上述混合好的粒子加入双螺杆挤出机中进行熔融挤出、造粒、干燥、冷却、装包，其中15份玻璃纤维E7CS13-03-508A从侧喂料加入挤出造料。双螺杆挤出机的温度从喂料段到机头依次为230℃、250℃、260℃、260℃、270℃、270℃、270℃、265℃、260℃、250℃。
本实施例制备得到的聚丙烯复合材料的具体性能如表3所示。
实施例3
本实施例特制相容剂的制备原料及制备方法均同实施例2。
一种良外观、可喷涂的聚丙烯增强复合材料，所述复合材料包括如下重量份的组分：聚丙烯64份、玻璃纤维30份、特制相容剂6份、抗氧剂0.6份。
本实施例复合材料的制备方法为：称取64份聚丙烯PP MH7900、6份本发明的特制相容剂PB-1-g-马来酸钠纯化物、0.3份抗氧剂1010、0.3份抗氧剂168与高速混合机中混合5分钟，其中高速混合机的转速为300转/分钟。将上述混合好的粒子加入双螺杆挤出机中进行熔融挤出、造粒、干燥、冷却、装包，其中30份玻璃纤维E7CS13-03-508A从侧喂料加入挤出造料。双螺杆挤出机的温度从喂料段到机头依次为230℃、250℃、260℃、260℃、270℃、270℃、270℃、265℃、260℃、250℃。
本实施例制备得到的聚丙烯复合材料的具体性能如表3所示。
实施例4
本实施例中特制相容剂的制备方法如下：
(a)首先称取100份聚-1丁烯PB0401M、3.2份马来酸钠、0.16份抗氧剂1010和0.22份抗氧剂168通过高速混合机混合均匀，高混机的转速695rpm，得到混合物；
(b)将0.31份引发剂二叔丁基过氧化物(DTBP)、2.7份共单体α-甲基苯乙烯(AMS)、1.4份共单体1-辛烯(1-Octene)在40℃条件下溶解于40份丙酮中，得到混合溶液A待用；
(c)将步骤(b)得到的混合溶液A加入到步骤(a)的混合物中，高混机混合均匀，待丙酮全部挥发后加入到双螺杆挤出机中进行熔融挤出接枝反应，得到PB-1-g-马来酸钠粗化物。其中，双螺杆挤出机的温度为142℃；
(d)取1份PB-1-g-马来酸钠粗化物加入到37.9份二甲苯中在77℃温度下搅拌直至全部溶解，得到混合溶液B，然后将混合溶液B趁热倒入68份的丙酮溶液中，生成絮状沉淀产物，再用丙酮冲洗5次，得到第一次纯化物，然后将絮状沉淀物放入通风厨中干燥至恒重；重复以上步骤进行第二次、第三次纯化，最后得到的PB-1-g-马来酸钠纯化物放入真空干燥箱中干燥24h至恒重备用，即得特制相容剂。
一种良外观、可喷涂的聚丙烯增强复合材料，所述复合材料包括如下重量份的组分：聚丙烯65份、玻璃纤维30份、特制相容剂5份、润滑剂0.22份、光稳剂0.18份、抗氧剂0.49份。
本实施例复合材料的制备方法为：称取65份聚丙烯PP P1000、5份本发明的特制相容剂PB-1-g-马来酸钠纯化物、0.18份光稳剂、0.22份润滑剂TR016、0.22份抗氧剂1010、0.27份抗氧剂168与高速混合机中混合3.8分钟，其中高速混合机的转速为269转/分钟。将上述混合好的粒子加入双螺杆挤出机中进行熔融挤出、造粒、干燥、冷却、装包，其中30份玻璃纤维E7CS13-03-508A从侧喂料加入挤出造料。双螺杆挤出机的温度从喂料段到机头依次为230℃、250℃、260℃、260℃、270℃、270℃、270℃、265℃、260℃、250℃。
本实施例制备得到的聚丙烯复合材料的具体性能如表3所示。
实施例5
本实施例中特制相容剂的制备方法如下：
(a)首先称取100份聚-1丁烯PB0401M、4.2份马来酸钠、0.16份抗氧剂1010和0.22份抗氧剂168通过高速混合机混合均匀，高混机的转速725rpm，得到混合物；
(b)将0.37份引发剂二叔丁基过氧化物(DTBP)、2.8份共单体α-甲基苯乙烯(AMS)、1.5份共单体1-辛烯(1-Octene)在42℃条件下溶解于43份丙酮中，得到混合溶液A待用。
(c)将步骤(b)得到的混合溶液A加入到步骤(a)的混合物中，高混机混合均匀，待丙酮全部挥发后加入到双螺杆挤出机中进行熔融挤出接枝反应，得到PB-1-g-马来酸钠粗化物。其中，双螺杆挤出机的温度为147℃。
(d)取1份PB-1-g-马来酸钠粗化物加入到43.8份二甲苯中在79℃温度下搅拌直至全部溶解，得到混合溶液B，然后将混合溶液B趁热倒入62份的丙酮溶液中，生成絮状沉淀产物，再用丙酮冲洗5次，得到第一次纯化物，然后将絮状沉淀物放入通风厨中干燥至恒重；重复以上步骤进行第二次、第三次纯化，最后得到的PB-1-g-马来酸钠纯化物放入真空干燥箱中干燥24h至恒重备用，即得特制相容剂。
一种良外观、可喷涂的聚丙烯增强复合材料，所述复合材料包括如下重量份的组分：聚丙烯68份、玻璃纤维25份、特制相容剂7份、润滑剂0.26份、光稳剂0.23份、抗氧剂0.46份。
本实施例复合材料的制备方法为：称取68份聚丙烯PP P1200、7份本发明的特制相容剂PB-1-g-马来酸钠纯化物、0.23份光稳剂、0.26份润滑剂TR016、0.22份抗氧剂1010、0.24份抗氧剂168与高速混合机中混合4.7分钟，其中高速混合机的转速为288转/分钟。将上述混合好的粒子加入双螺杆挤出机中进行熔融挤出、造粒、干燥、冷却、装包，其中25份玻璃纤维E7CS10-03-508A从侧喂料加入挤出造料。双螺杆挤出机的温度从喂料段到机头依次为230℃、250℃、 260℃、260℃、270℃、270℃、270℃、265℃、260℃、250℃。
本实施例制备得到的聚丙烯复合材料的具体性能如表3所示。
实施例6
本实施例特制相容剂的制备原料及制备方法均同实施例1。
一种良外观、可喷涂的聚丙烯增强复合材料，所述复合材料包括如下重量份的组分：聚丙烯PP M60T 62份、玻璃纤维E7CS10-03-508A 35份、特制相容剂4份、润滑剂BS-2818 0.1份、光稳剂UV-3808PP5 0.1份、抗氧剂1010 0.3份。
本实施例聚丙烯增强复合材料的制备方法同实施例1。本实施例制备得到的聚丙烯复合材料的具体性能如表3所示。
实施例7
本实施例特制相容剂的制备原料及制备方法均同实施例1。
一种良外观、可喷涂的聚丙烯增强复合材料，所述复合材料包括如下重量份的组分：聚丙烯PP M60T 76份、玻璃纤维E7CS10-03-508A 20份、特制相容剂8份、润滑剂BS-2818 0.2份、光稳剂UV-3808PP5 0.2份、抗氧剂1010 0.5份。
本实施例聚丙烯增强复合材料的制备方法同实施例1。本实施例制备得到的聚丙烯复合材料的具体性能如表3所示。
表3
Figure PCTCN2021082255-appb-000001
Figure PCTCN2021082255-appb-000002
由表3可知，聚丙烯增强复合材料配方中的主要成分任何一种被其他替换掉之后，综合性能都达不到预期效果。本发明通过使用特殊聚丙烯和特制相容剂制备出了外观良好、抗浮纤、可喷涂的高性能聚丙烯增强复合材料，玻纤含量为35份时，拉伸强度可达120MPa，弯曲强度可达180MPa，弯曲模量可达9000MPa，悬臂梁缺口冲击可达15kJ/m 2，可满足现阶段汽车行业要求的轻量化、烯烃化、高性能化等发展趋势。
并且，当所述复合材料包括如下重量份的组分：聚丙烯62～76份、玻璃纤维20～35份、特制相容剂4～8份、润滑剂0.1～0.2份、光稳剂0.1～0.2份、抗氧剂0.3～0.5份时，制备得到的聚丙烯增强复合材料的外观抗浮纤等级更高、玻纤保留长度更长、表面张力更大。
最后所应当说明的是，以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制，尽管参照较佳实施例对本发明作了详细说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的实质和范围。

Claims (10)

  1. 一种良外观、可喷涂的聚丙烯增强复合材料，其特征在于，所述复合材料包括如下重量份的组分：聚丙烯55～82份、玻璃纤维15～35份、特制相容剂3～10份、润滑剂0～0.3份、光稳剂0～0.3份、抗氧剂0.2～0.6份。
  2. 如权利要求1所述的复合材料，其特征在于，所述复合材料包括如下重量份的组分：聚丙烯62～76份、玻璃纤维20～35份、特制相容剂4～8份、润滑剂0.1～0.2份、光稳剂0.1～0.2份、抗氧剂0.3～0.5份。
  3. 如权利要求1或2所述的复合材料，其特征在于，所述聚丙烯的熔体流动速率为60～1500g/10min，所述聚丙烯的熔体流动速率是根据ISO 1133-2011使用2.16kg重量并在230℃的温度测量；所述玻璃纤维为无碱短切玻璃纤维，所述玻璃纤维的单丝直径为10～13μm；所述润滑剂为酰胺类润滑剂、硬脂酸盐类润滑剂中的至少一种；所述抗氧剂为受阻酚类抗氧剂、亚磷酸酯类抗氧剂中的至少一种；所述光稳剂为受阻胺类光稳剂。
  4. 如权利要求1或2所述的复合材料，其特征在于，所述特制相容剂为聚1-丁烯接枝马来酸钠。
  5. 如权利要求4所述的复合材料，其特征在于，所述特制相容剂的制备原料包含如下重量份的组分：聚-1丁烯100份和马来酸钠1.5～4.5份。
  6. 如权利要求5所述的复合材料，其特征在于，所述特制相容剂的制备原料还包含如下重量份的组分：抗氧剂0.2～0.4份、引发剂0.2～0.4份、共单体α-甲基苯乙烯2～3份和共单体1-辛烯1～1.5份。
  7. 如权利要求6所述的复合材料，其特征在于，所述特制相容剂的制备方法包括以下步骤：
    (1)将聚-1丁烯、马来酸钠、抗氧剂通过高速混合机混合均匀，得到混合物；
    (2)将引发剂、共单体α-甲基苯乙烯、共单体1-辛烯溶解于丙酮中，得到混合溶液A待用；
    (3)将步骤(2)得到的混合溶液A加入到步骤(1)的混合物中，高混机混合均匀，待丙酮全部挥发后，加入到双螺杆挤出机中进行熔融挤出接枝反应，得到聚1-丁烯接枝马来酸钠粗化物；
    (4)将步骤(3)得到的聚1-丁烯接枝马来酸钠粗化物加入到二甲苯中，搅拌直至全部溶解，得到混合溶液B，然后将混合溶液B趁热倒入丙酮溶液中，生成絮状沉淀产物，再用丙酮冲洗，得到第一次纯化物，然后将絮状沉淀物干燥至恒重；重复以上步骤进行第二次、第三次纯化，最后得到的聚1-丁烯接枝马来酸钠纯化物真空干燥至恒重备用，即为特制相容剂。
  8. 如权利要求7所述的复合材料，其特征在于，所述步骤(1)中，高速混合机的转速为650～750rpm，抗氧剂为抗氧剂1010、抗氧剂168中的至少一种；所述步骤(2)中，引发剂、丙酮的质量比为(0.2～0.4)：(35～45)，引发剂为二叔丁基过氧化物，溶解温度为35～45℃；所述步骤(3)中，双螺杆挤出机的温度为135～150℃；所述步骤(4)中，聚1-丁烯接枝马来酸钠粗化物、二甲苯、丙酮的质量比为1：(35～45)：(60～70)，溶解温度为70～80℃，用丙酮冲洗的次数为3～5次，真空干燥时间为24h。
  9. 如权利要求1～8任一项所述的复合材料的制备方法，其特征在于，所述制备方法包括以下步骤：将聚丙烯、特制相容剂、光稳剂、润滑剂、抗氧剂于高速混合机中混合；将上述混合好的粒子加入双螺杆挤出机中进行熔融挤出、造粒，将玻璃纤维从侧喂料加入进行挤出造料，然后干燥、冷却、装包，即得良外观、可喷涂的聚丙烯增强复合材料。
  10. 如权利要求9所述的制备方法，其特征在于，所述高速混合机的混合时间为3～5分钟，转速为200～300转/分钟；所述双螺杆挤出机的温度从喂料段到机头依次为H1＝230℃、H2＝250℃、H3＝260℃、H4＝260℃、H5＝270℃、H6＝270℃、H7＝270℃、H8＝265℃、H9＝260℃、H10＝250℃。
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