Continuous glass fiber reinforced ASA composite material and preparation method thereof

Abstract

The invention discloses a continuous glass fiber reinforced ASA composite material and a preparation method thereof, the continuous glass fiber reinforced ASA composite material comprises the following raw materials by weight: 30-70 parts of ASA rubber powder, 50-100 parts of SAN resin, 100-150 parts of continuous glass fiber, 0.5-10 parts of a compatilizer, 1-10 parts of a wear resistant agent, 0.1-1 part of an antioxidant, 0.1-1 part of a lubricant, and 0.1-1 part of a weather resistant agent. And large-scale continuous industrial production can be achieved, infiltration is sufficient, the apparent quality is good, and the mass production quality is stable and controllable. Meanwhile, the prepared prepreg has excellent weather resistance and wear resistance and can be independently molded or attached to the surface layer of a composite material product, compared with a traditional appearance treatment process needing multi-layer spraying, the technological method can save a large amount of working hours, and meanwhile the huge requirement of the market for improving the comprehensive performance of a continuous fiber reinforced product is met.

Description

Technical Field

[0001] The present invention belongs to the field of polymer materials, and particularly relates to a novel highly weather-resistant wear-resistant continuous fiber-reinforced thermoplastic ASA composite material and a preparation method thereof. Background Art

[0002] Continuously reinforced thermoplastic materials have excellent properties such as high strength, high stiffness, high impact strength, low density, low warpage creep, and excellent dynamic fatigue resistance. At the same time, they have a high cost performance and are gradually replacing metal and short glass fiber-reinforced materials and are applied to structural components such as automobiles and household appliances and appearance parts such as the shells of power tools.

[0003] Continuous fiber-reinforced polypropylene (PP) materials, as a major category of thermoplastic continuous fiber-reinforced materials, have the widest range of applications. However, due to the molecular structure of the PP material itself, there are a large number of tertiary carbon atoms, and during granulation processing, storage, and use, it is extremely easy to age and degrade under the action of light, heat, and oxygen, with the surface turning yellow, fading, or even pulverizing. Especially during natural exposure, the aging of PP is mainly degradation, its relative molecular mass continuously decreases, and there is an obvious accelerated degradation phenomenon, thus losing excellent comprehensive physical and mechanical properties and use value. At the same time, in the harsh use environment of outdoor flying sand and falling stones, the hardness of PP is relatively low, and pits are likely to appear on the surface of the parts, or the glass fibers and the substrate material are separated and damaged from each other, resulting in uneven light scattering and scratch whitening, thereby restricting the use of continuous glass fiber-reinforced polypropylene on parts with higher scratch resistance requirements.

[0004] CN 115648776 A discloses a continuous fiber-reinforced thermoplastic resin composite board, including at least one weather-resistant layer, at least one wear-resistant layer, at least one adhesive film layer, and at least one continuous fiber-reinforced layer to achieve weather resistance and wear resistance of the material; CN 109397785 A also mentions a weather-resistant lightweight weather-resistant continuous fiber-reinforced thermoplastic composite board and a preparation method thereof by adopting a multi-layer weather-resistant coating structure. In the above patents, multiple functional layers are used, and a multi-layer coating or composite molding method is adopted to simultaneously improve the weather resistance and wear resistance of the material, with high adhesive cost, operational complexity, and a cumbersome overall process flow.

[0005] At present, there have been many studies on continuous fiber-reinforced PP composites. Relatively speaking, there are relatively few studies on acrylonitrile-styrene-acrylate graft copolymer ASA on continuous fibers. ASA is a weather-resistant engineering plastic that can be directly used outdoors without surface protection such as painting, electroplating, etc. After being exposed to sunlight for 9 to 15 months, the impact strength, elongation rate, and color hardly change. At the same time, it is easy to form and process. Compared with PP, it has better heat aging resistance and surface hardness, and is widely used in building materials, automotive exterior parts, exterior parts of electronic and electrical engineering, sports equipment and other fields. If it can be applied to continuous fiber materials, it will surely improve its comprehensive performance and can better replace PP and be used in service environments with requirements for appearance properties such as weather resistance and scratch resistance.

[0006] For continuous fiber-reinforced thermoplastic prepreg composites, when selecting substrates such as ABS and ASA for thermoplastics, due to the differences in their rheological properties, melt strength and polypropylene, it is very difficult to prepare prepreg composites, which has always been a problem that cannot be solved or mass-produced in this field for a long time. Most are still limited to the research and development level of small-scale test equipment in the laboratory. Since industrialized and mass production have stricter requirements for processing windows, quality stability, controllability, etc. than laboratory small-scale equipment. Continuous fiber-reinforced ASA prepreg composites often easily have problems such as incomplete resin infiltration, undispersed glass fiber bundles, obvious fiber exposure, longitudinal cracking and brittleness of the prepared prepreg, and narrow processing windows and difficult forming. Summary of the Invention

[0007] Aiming at the deficiencies in this field, the present invention provides a new type of highly weather-resistant and wear-resistant continuous fiber-reinforced thermoplastic ASA composite material and its preparation method, which can be mass-produced continuously in industrial scale, with sufficient infiltration, good apparent quality, and stable and controllable mass production quality. At the same time, the prepared prepreg has excellent weather resistance and wear resistance, can be molded alone or laminated on the surface of composite products. The process method can save a large amount of working hours compared with the traditional surface treatment process that requires multiple coatings, and at the same time meets the huge market demand for the improvement of the comprehensive performance of continuous fiber-reinforced products.

[0008] To achieve the above object, the technical solution adopted by the present invention is as follows: A continuous glass fiber-reinforced ASA composite material, by weight, the raw material composition includes: ASA rubber powder 30 - 70 parts SAN resin 50 - 100 parts Continuous glass fiber 100 - 150 parts Compatibilizer 0.5 - 10 parts Wear-resistant agent: 1 - 10 parts Antioxidant: 0.1 - 1 part Lubricant: 0.1 - 1 part Weather-resistant agent: 0.1 - 1 part.

[0009] The particle size of the ASA rubber powder is 100 - 1000 μm; preferably, the particle size of the ASA rubber powder is 400 - 800 μm; preferably, the manufacturer is Guangzhou Entropy Energy Innovative Materials.

[0010] The melt index of the SAN resin at 220°C and a load of 10 kg is 5 - 75 (g / 10 min); preferably, the melt index of the SAN resin at 220°C and a load of 10 kg is 40 - 65 (g / 10 min).

[0011] The ratio between the ASA rubber powder and the SAN resin is higher than 1:4 and lower than 1:1.

[0012] The continuous glass fiber is one or more of E-glass fiber, thermoplastic resin and glass fiber mixed fiber, and alkali-containing glass fiber.

[0013] The glass fiber is high-modulus E-glass continuous fiber, with a single filament diameter of 13 - 20 μm and a single fiber strand number of 1200 tex - 2400 tex, and is one of Taishan T838P type, Owens Corning SE4805 type, and Jushi 362A type.

[0014] The compatibilizer is one or more of MAH-g-poe, GMA-g-poe, and maleic anhydride styrene copolymer SMA.

[0015] The wear-resistant agent is PTFE micropowder, with a particle size range of 1 - 20 μm, and preferably a particle size of 5 - 15 μm.

[0016] The antioxidant is one or more of hindered phenol antioxidants or phosphite antioxidants. Preferably, at least two of antioxidant 1010, antioxidant 168, antioxidant 412s, and antioxidant 9228.

[0017] The lubricant is one or more of pentaerythritol stearate, ethylene bis-stearamide silicone oil, barium stearate, and paraffin polyethylene wax.

[0018] The weather-resistant agent is benzophenone-based, benzotriazole-based, or triazine-based ultraviolet absorber, and preferably triazine-based ultraviolet absorber.

[0019] A preparation method of a novel highly weather-resistant wear-resistant continuous fiber-reinforced thermoplastic ASA composite material, and the specific steps are as follows: Step 1: Weigh ASA powder, SAN resin, compatibilizer, antioxidant, lubricant and weathering agent, add them to a high-speed mixer, and mix them at high speed for 0.1 - 0.2 h until evenly stirred to obtain a mixture. Step 2: Put the uniformly mixed raw materials from the previous step into a twin-screw extruder, melt and plasticize the mixed materials, and inject them into the impregnation mold of the impregnation equipment. Then, under the action of a tractor, continuous glass fiber enters the impregnation mold and is impregnated and dispersed with the molten mixed material resin. Then, the impregnated continuous glass fiber impregnated material is drawn out at a speed of 1 - 20 m / min through a traction device. Finally, it is roll-pressed and cooled to obtain a continuous glass fiber-reinforced ASA prepreg composite plate material.

[0020] The temperature setting range of the twin-screw extruder is: 190°C - 230°C.

[0021] The temperature of the impregnation mold is 230 - 260°C, and the outlet temperature near the outlet of the impregnation mold (within a range of 10 cm) is controlled not to exceed 245°C.

[0022] Compared with the prior art, the present invention has the following advantages and beneficial effects: (1) The composite plate manufactured with the prepreg of the present invention uses an ASA base layer, has excellent ultraviolet barrier performance, good long-term weather resistance, and can reduce the use of weathering agents. (2) The present invention screens ASA powder with different rubber particle sizes, AS resins with different melt indexes, the ratio of ASA powder to AS resin, the types and combinations of compatibilizers, obtains a formulation system with suitable melt rheological properties for the impregnation tape production process, and then cooperates with appropriate process parameters to ensure good melt flow permeability during the melt impregnation process, better impregnation and dispersion of glass fibers, meet the processing requirements, and obtain better performance. (3) The present invention uses PTFE micropowder in a superimposed manner, which can improve the surface wear resistance of the finished parts, and can also avoid brittle failure of the prepreg material under the action of a certain pressing force, sliding force or lateral force during the molding and composite molding processes. (4) The present invention uses PTFE micropowder and unexpectedly finds that the tensile strength is slightly increased. The reason is that when the resin infiltrates the glass fiber, the presence of PTFE micropowder helps the melt to infiltrate into the glass fiber. (5) Using the prepreg of the present invention to manufacture composite plates, while achieving the dual properties of weather resistance and wear resistance, compared with the traditional multi-layer adhesive or hot pressing molding process methods, a large amount of working hours are shortened and the production efficiency is improved. Embodiment Example

[0023] The continuous fiber reinforced thermoplastic prepreg tape contains the following components, and the content of each component is expressed in parts by weight as follows: ASA rubber powder: 30 parts SAN resin: 70 parts Continuous glass fiber: 100 parts Compatibilizer: 2 parts Wear-resistant agent: 5 parts Antioxidant: 0.5 part Lubricant: 0.2 part Weather-resistant agent: 0.2 part.

[0024] Among them, the rubber particle size of the ASA rubber powder is 300 μm, and the melt index of the selected SAN resin at 220 °C and a load of 10 kg is 30 (g / 10 min); the selected continuous glass fiber is high-modulus alkali-free continuous glass fiber of Taishan T838P type, the selected compatibilizer is MAH-g-poe, the selected wear-resistant agent is PTFE fine powder with a particle size of 5 μm, the selected antioxidant is a combination of hindered phenol antioxidant and phosphite antioxidant, specifically the combination of antioxidant 1010 and antioxidant 168, the selected lubricant is pentaerythritol stearate, and the selected weather-resistant agent is a benzotriazole substance.

[0025] The thickness of the prepared prepreg tape is 0.3 mm.

[0026] Example 2 The continuous fiber reinforced thermoplastic prepreg tape contains the following components, and the content of each component is expressed in parts by weight as follows: ASA rubber powder: 50 parts SAN resin: 50 parts Continuous glass fiber: 100 parts Compatibilizer: 2 parts Wear-resistant agent: 5 parts Antioxidant: 0.5 part Lubricant: 0.2 part Weather-resistant agent: 0.2 part.

[0027] Among them, the rubber particle size of the ASA rubber powder is 300 μm, and the melt index of the selected SAN resin at 220 °C and a load of 10 kg is 30 (g / 10 min); the selected continuous glass fiber is high-modulus alkali-free continuous glass fiber of Taishan T838P type, the selected compatibilizer is MAH-g-poe, the selected wear-resistant agent is PTFE fine powder with a particle size of 5 μm, the selected antioxidant is a combination of hindered phenol antioxidant and phosphite antioxidant, specifically the combination of antioxidant 1010 and antioxidant 168, the selected lubricant is pentaerythritol stearate, and the selected weather-resistant agent is a benzotriazole substance.

[0028] The thickness of the prepared prepreg tape is 0.3 mm.

[0029] Example 3 The continuous fiber reinforced thermoplastic prepreg tape contains the following components, and the content of each component is expressed in parts by weight as follows: ASA rubber powder: 70 parts SAN resin: 30 parts Continuous glass fiber: 100 parts Compatibilizer: 2 parts Wear-resistant agent: 5 parts Antioxidant: 0.5 part Lubricant: 0.2 part Weather-resistant agent: 0.2 part.

[0030] Among them, the rubber particle size of the ASA rubber powder is 300 μm, the melt index of the selected SAN resin at 220 °C and 10 kg load is 30 (g / 10 min); the selected continuous glass fiber is high-modulus alkali-free continuous glass fiber, of the Taishan T838P type, the selected compatibilizer is MAH-g-poe, the selected wear-resistant agent is PTFE fine powder with a particle size of 5 μm, the selected antioxidant is a combination of hindered phenol antioxidants and phosphite antioxidants, specifically the combination of antioxidant 1010 and antioxidant 168, the selected lubricant is pentaerythritol stearate, and the selected weather-resistant agent is a benzotriazole substance.

[0031] Example 4 The continuous fiber reinforced thermoplastic prepreg tape contains the following components, and the content of each component is expressed in parts by weight as follows: ASA rubber powder: 30 parts SAN resin: 70 parts Continuous glass fiber: 100 parts Compatibilizer: 2 parts Wear-resistant agent: 5 parts Antioxidant: 0.5 part Lubricant: 0.2 part Weather-resistant agent: 0.2 part.

[0032] Among them, the rubber particle size of the ASA rubber powder is 500 μm, the melt index of the selected SAN resin at 220 °C and 10 kg load is 30 (g / 10 min); the selected continuous glass fiber is high-modulus alkali-free continuous glass fiber, of the Taishan T838P type, the selected compatibilizer is MAH-g-poe, the selected wear-resistant agent is PTFE fine powder with a particle size of 5 μm, the selected antioxidant is a combination of hindered phenol antioxidants and phosphite antioxidants, specifically the combination of antioxidant 1010 and antioxidant 168, the selected lubricant is pentaerythritol stearate, and the selected weather-resistant agent is a benzotriazole substance.

[0033] The thickness of the prepared prepreg tape is 0.3 mm.

[0034] Example 5 The continuous fiber reinforced thermoplastic prepreg tape contains the following components, and the content of each component is expressed in parts by weight as follows: ASA rubber powder: 30 parts SAN resin: 70 parts Continuous glass fiber: 100 parts Compatibilizer: 2 parts Wear-resistant agent: 5 parts Antioxidant: 0.5 part Lubricant: 0.2 part Weather-resistant agent: 0.2 part.

[0035] Among them, the rubber particle size of the ASA rubber powder is 700 μm, the melt index of the selected SAN resin at 220 °C and 10 kg load is 30 (g / 10 min); the selected continuous glass fiber is high-modulus alkali-free continuous glass fiber, of the Taishan T838P type, the selected compatibilizer is MAH-g-poe, the selected wear-resistant agent is PTFE fine powder with a particle size of 5 μm, the selected antioxidant is a combination of hindered phenol antioxidants and phosphite antioxidants, specifically the combination of antioxidant 1010 and antioxidant 168, the selected lubricant is pentaerythritol stearate, and the selected weather-resistant agent is a benzotriazole substance.

[0036] The prepared prepreg tape has a thickness of 0.3 mm.

[0037] Example 6 The continuous fiber reinforced thermoplastic prepreg tape contains the following components, and the content of each component is expressed in parts by weight as follows: ASA rubber powder: 30 parts SAN resin: 70 parts Continuous glass fiber: 100 parts Compatibilizer: 2 parts Wear-resistant agent: 5 parts Antioxidant: 0.5 part Lubricant: 0.2 part Weather-resistant agent: 0.2 part.

[0038] Among them, the rubber particle size of the ASA rubber powder is 900 μm, the melt index of the selected SAN resin at 220 °C and 10 kg load is 30 (g / 10 min); the selected continuous glass fiber is high-modulus alkali-free continuous glass fiber, of the Taishan T838P type, the selected compatibilizer is MAH-g-poe, the selected wear-resistant agent is PTFE fine powder with a particle size of 5 μm, the selected antioxidant is a combination of hindered phenol antioxidants and phosphite antioxidants, specifically the combination of antioxidant 1010 and antioxidant 168, the selected lubricant is pentaerythritol stearate, and the selected weather-resistant agent is a benzotriazole substance.

[0039] The thickness of the prepared prepreg tape is 0.3 mm.

[0040] Example 7 The continuous fiber reinforced thermoplastic prepreg tape contains the following components, and the content of each component is expressed in parts by weight as follows: ASA rubber powder: 30 parts SAN resin: 70 parts Continuous glass fiber: 100 parts Compatibilizer: 2 parts Wear-resistant agent: 5 parts Antioxidant: 0.5 part Lubricant: 0.2 part Weather-resistant agent: 0.2 part.

[0041] Among them, the rubber particle size of the ASA rubber powder is 700 μm, the melt index of the selected SAN resin at 220 °C and a load of 10 kg is 40 (g / 10 min); the selected continuous glass fiber is high-modulus alkali-free continuous glass fiber of Taishan T838P type, the selected compatibilizer is MAH-g-poe, the selected wear-resistant agent is PTFE fine powder with a particle size of 5 μm, the selected antioxidant is a combination of hindered phenol antioxidant and phosphite antioxidant, specifically the combination of antioxidant 1010 and antioxidant 168, the selected lubricant is pentaerythritol stearate, and the selected weather-resistant agent is a benzotriazole substance.

[0042] The thickness of the prepared prepreg tape is 0.3 mm.

[0043] Example 8 The continuous fiber reinforced thermoplastic prepreg tape contains the following components, and the content of each component is expressed in parts by weight as follows: ASA rubber powder: 30 parts SAN resin: 70 parts Continuous glass fiber: 100 parts Compatibilizer: 2 parts Wear-resistant agent: 5 parts Antioxidant: 0.5 part Lubricant: 0.2 part Weather-resistant agent: 0.2 part.

[0044] Among them, the rubber particle size of the ASA rubber powder is 700 μm, the melt index of the selected SAN resin at 220 °C and a load of 10 kg is 60 (g / 10 min); the selected continuous glass fiber is a high-modulus alkali-free continuous glass fiber, of the Taishan T838P type, the selected compatibilizer is MAH-g-poe, the selected wear-resistant agent is PTFE fine powder with a particle size of 5 μm, the selected antioxidant is a hindered phenol antioxidant and a phosphite antioxidant, specifically a combination of antioxidant 1010 and antioxidant 168, the selected lubricant is pentaerythritol stearate, and the selected weathering agent is a benzotriazole substance.

[0045] The thickness of the prepared prepreg tape is 0.3 mm.

[0046] Example 9 The continuous fiber reinforced thermoplastic prepreg tape contains the following components, and the content of each component is expressed in parts by weight as follows: ASA rubber powder 30 parts SAN resin 70 parts Continuous glass fiber 100 parts Compatibilizer 2 parts Wear-resistant agent 5 parts Antioxidant 0.5 part Lubricant 0.2 part Weathering agent 0.2 part. Among them, the rubber particle size of the ASA rubber powder is 700 μm, the melt index of the selected SAN resin at 220 °C and a load of 10 kg is 60 (g / 10 min); the selected continuous glass fiber is a high-modulus alkali-free continuous glass fiber, of the Taishan T838P type, the selected compatibilizer is a compound of MAH-g-poe and maleic anhydride styrene copolymer SMA, and the ratio of the two is 3:1, the selected wear-resistant agent is PTFE fine powder with a particle size of 5 μm, the selected antioxidant is a hindered phenol antioxidant and a phosphite antioxidant, specifically a combination of antioxidant 1010 and antioxidant 168, the selected lubricant is pentaerythritol stearate, and the selected weathering agent is a benzotriazole substance.

[0047] The thickness of the prepared prepreg tape is 0.3 mm.

[0048] Example 10 The continuous fiber reinforced thermoplastic prepreg tape contains the following components, and the content of each component is expressed in parts by weight as follows: ASA rubber powder 30 parts SAN resin 70 parts Continuous glass fiber 100 parts Compatibilizer 2 parts Wear-resistant agent 5 parts Antioxidant 0.5 part Lubricant 0.2 parts Weathering agent 0.2 parts

[0049] Among them, the rubber particle size of the ASA powder is 700 μm, the melt index of the selected SAN resin at 220 °C and a load of 10 kg is 70 (g / 10 min); the selected continuous glass fiber is a high-modulus alkali-free continuous glass fiber, which is Taishan T838P type, the selected compatibilizer is MAH-g-poe, the selected wear-resistant agent is PTFE fine powder with a particle size of 5 μm, the selected antioxidant is a hindered phenol antioxidant and a phosphite antioxidant, specifically a combination of antioxidant 1010 and antioxidant 168, the selected lubricant is pentaerythritol stearate, and the selected weathering agent is a benzotriazole substance

[0050] The prepared prepreg tape has a thickness of 0.3 mm

[0051] Example 11 The continuous fiber reinforced thermoplastic prepreg tape contains the following components, and the content of each component is expressed in parts by weight as follows ASA powder 30 parts SAN resin 70 parts Continuous glass fiber 100 parts Compatibilizer 2 parts Wear-resistant agent 5 parts Antioxidant 0.5 parts Lubricant 0.2 parts Weathering agent 0.2 parts

[0052] Among them, the rubber particle size of the ASA powder is 700 μm, the melt index of the selected SAN resin at 220 °C and a load of 10 kg is 60 (g / 10 min); the selected continuous glass fiber is a high-modulus alkali-free continuous glass fiber, which is Taishan T838P type, the selected compatibilizer is MAH-g-poe, the selected wear-resistant agent is PTFE fine powder with a particle size of 10 μm, the selected antioxidant is a hindered phenol antioxidant and a phosphite antioxidant, specifically a combination of antioxidant 1010 and antioxidant 168, the selected lubricant is pentaerythritol stearate, and the selected weathering agent is a benzotriazole substance

[0053] The prepared prepreg tape has a thickness of 0.3 mm

[0054] Example 12 The continuous fiber reinforced thermoplastic prepreg tape contains the following components, and the content of each component is expressed in parts by weight as follows ASA powder 30 parts SAN resin 70 parts Continuous glass fiber 100 parts Compatibilizer: 2 parts Wear-resistant agent: 5 parts Antioxidant: 0.5 part Lubricant: 0.2 part Weather-resistant agent: 0.2 part.

[0055] Among them, the rubber particle size of the ASA rubber powder is 700 μm, the melt index of the selected SAN resin at 220 °C and a load of 10 kg is 60 (g / 10 min); the selected continuous glass fiber is high-modulus alkali-free continuous glass fiber, of the Taishan T838P type, the selected compatibilizer is MAH-g-poe, the selected wear-resistant agent is PTFE fine powder with a particle size of 15 μm, the selected antioxidant is a hindered phenol antioxidant and a phosphite antioxidant, specifically a combination of antioxidant 1010 and antioxidant 168, the selected lubricant is pentaerythritol stearate, and the selected weather-resistant agent is a benzotriazole substance.

[0056] The thickness of the prepared prepreg tape is 0.3 mm.

[0057] Example 13 The continuous fiber reinforced thermoplastic prepreg tape contains the following components, and the content of each component is expressed in parts by weight as follows: ASA rubber powder: 30 parts SAN resin: 70 parts Continuous glass fiber: 100 parts Compatibilizer: 2 parts Antioxidant: 0.5 part Lubricant: 0.2 part Weather-resistant agent: 0.2 part.

[0058] Among them, the rubber particle size of the ASA rubber powder is 700 μm, the melt index of the selected SAN resin at 220 °C and a load of 10 kg is 60 (g / 10 min); the selected continuous glass fiber is high-modulus alkali-free continuous glass fiber, of the Taishan T838P type, the selected compatibilizer is MAH-g-poe, the selected antioxidant is a hindered phenol antioxidant and a phosphite antioxidant, specifically a combination of antioxidant 1010 and antioxidant 168, the selected lubricant is pentaerythritol stearate, and the selected weather-resistant agent is a benzotriazole substance.

[0059] The thickness of the prepared prepreg tape is 0.3 mm.

[0060] Example 14 The continuous fiber reinforced thermoplastic prepreg tape contains the following components, and the content of each component is expressed in parts by weight as follows: ASA rubber powder: 30 parts SAN resin: 70 parts Continuous glass fiber: 100 parts 2 parts of compatibilizer 5 parts of wear-resistant agent 0.5 part of antioxidant 0.2 part of lubricant 0.2 part of weathering agent

[0061] Among them, the rubber particle size of the ASA rubber powder is 700 μm, the melt index of the selected SAN resin at 220 °C and a load of 10 kg is 60 (g / 10 min); the selected continuous glass fiber is high-modulus alkali-free continuous glass fiber, which is Taishan T838P type. The selected compatibilizer is a compound of MAH-g-poe and maleic anhydride styrene copolymer SMA, and the ratio of the two is 3:1. The selected wear-resistant agent is PTFE fine powder with a particle size of 5 μm. The selected antioxidant is a hindered phenol antioxidant and a phosphite antioxidant, specifically a combination of antioxidant 1010 and antioxidant 168. The selected lubricant is pentaerythritol stearate, and the selected weathering agent is a benzotriazole substance.

[0062] The preparation method of the prepreg for Examples 1 to 14 is as follows: The first step: Weigh ASA rubber powder, SAN resin, compatibilizer, antioxidant, lubricant and weathering agent, add them to a high-speed mixer and mix at high speed for 0.2 h until evenly mixed to obtain a mixture; The second step: Put the uniformly mixed raw materials in the previous step into a twin-screw extruder (temperature range: 190 °C - 230 °C), melt and plasticize the mixed material and inject it into the impregnation mold of the impregnation equipment; Lead out the continuous glass fiber from the constant tension yarn frame, pass through the front guiding device and enter the preheating device for preheating (temperature 150 °C), then pass through the rear dispersion device and enter the extrusion mold. In the extrusion mold, the continuous glass fiber is impregnated in the mixed material, and then led out at a speed of 10 m / min through the traction device. The impregnated continuous glass fiber is sent into the cooling and shaping roller system to become a continuous glass fiber-reinforced ASA prepreg with a flat appearance, and finally wound up through the winding system.

[0063] Table 1 Performance comparison table of each example 1# 2# 3# 4# 5# 6# 7# 8# 9# 10# 11# 12# 13# 14# ASA / SAN 3:7 5:5 7:3 3:7 3:7 3:7 3:7 3:7 3:7 3:7 3:7 3:7 3:7 3:7 Melt index of SAN resin (g / 10min) 30 30 30 30 30 30 40 60 60 70 60 60 60 60 Particle size of ASA powder (μm) 300 300 300 500 700 900 700 700 700 700 700 700 700 700 Particle size of wear-resistant agent (μm) 5 5 5 5 5 5 5 5 5 5 10 15 0 5 Type of compatibilizer MAH-g-POE MAH-g-POE MAH-g-POE MAH-g-POE MAH-g-POE MAH-g-POE MAH-g-POE MAH-g-POE MAH-g-POE + SMA (3:1) MAH-g-POE MAH-g-POE MAH-g-POE MAH-g-POE MAH-g-poe + SMA (3:1) Tensile strength (MPa) 396 387 Unable to test 404 376 180 495 541 610 421 503 480 511 560 Flexural strength (MPa) 380 339 Unable to test 350 320 119 449 515 558 429 412 403 456 520 Flexural modulus (MPa) 22045 20799 Unable to test 21876 20395 14845 23998 25823 26145 23390 23122 22910 25240 25830 Surface quality (fiber leakage, yellow spots, cracking, thickness unevenness) Thickness uneven, prepreg tape is prone to longitudinal cracking, tolerance exceeds ±0.02mm Thickness uneven, tolerance exceeds ±0.02mm Resin is difficult to infiltrate glass fiber, resin and glass fiber are seriously delaminated, resin will fall off from glass fiber, difficult to mold Thickness uneven, there is a situation where glass fibers are not dispersed, prepreg tape is longitudinally cracked, tolerance exceeds ±0.02mm Thickness uneven, there is a situation where glass fibers are not dispersed, tolerance exceeds ±0.02mm Resin is not easy to infiltrate glass fiber, production temperature needs to be increased by 10℃ - 20℃, thickness is seriously uneven, obvious fiber leakage Thickness is uniform, and a small part of glass fibers are not dispersed Thickness is uniform, glass fibers are fully infiltrated Thickness is uniform, glass fibers are fully infiltrated Thickness is uniform, the tape is extremely easy to crack longitudinally Thickness is uniform Thickness uneven, prepreg tape is prone to longitudinal cracking, tolerance exceeds ±0.02mm Glass fibers are well infiltrated, thickness is uniform Thickness is uniform, glass fibers are fully infiltrated Color difference after 1000h of UV weathering 1.85 1.98 Unable to test 1.79 1.81 2.23 1.69 1.58 1.42 1.78 1.60 1.63 1.61 1.60 Surface condition after 1000h of UV weathering (chalking, fiber leakage) Chalking occurs Chalking occurs Unable to test, serious chalking and fiber leakage Chalking occurs Chalking occurs Serious chalking, obvious fiber leakage Surface is acceptable Surface is good Surface is good Chalking occurs Surface is acceptable Surface is acceptable, local chalking occurs Surface is good Surface is good Mass loss of the part after wear resistance test (g) 8.2 8.3 Unable to test 7.9 7.6 12.8 7.2 6.8 6.5 11.8 6.9 7.6 13.3 6.9 The temperature of the impregnation mold in the above examples is 230 - 260 °C. Among them, for Examples 1 to 13#, the outlet temperature near the outlet of the impregnation mold (within a 10 cm range) is controlled not to exceed 245 °C. Therefore, a cooling device must be set near the outlet of the impregnation mold to achieve the purpose of temperature control. The cooling medium is water cooling or oil temperature cooling; for Example 14#, the outlet temperature near the outlet of the impregnation mold (within a 10 cm range) is 255 °C.

[0064] The tensile strength test refers to GB / T 1040.2 - 2006; Flexural strength test refers to GB / T 9341-2008; UV weather resistance test: irradiate for 1000 hours. The test method for measuring the color change △E of the test materials is formulated by the enterprise itself. All materials are processed in parallel for comparison. The test conditions are as follows: use UVA340 as the irradiation light source, with a 2-hour dark interval and a 10-hour light duration; Wear resistance test: The test method for measuring the wear resistance of the test materials is formulated by the enterprise itself. The same material is prepared into test specimens. The upper specimen is a plate cut into a cuboid shape (10mm * 4mm * 2mm), and the lower specimen is a large circular plate with a thickness of 6.0mm and a diameter of 10cm. The cuboid specimen is placed vertically above and below the large circular plate specimen, and a load (1.8kg) is applied to the specimen and kept stationary. The lower specimen makes a rotational motion (rotation speed of 50 rpm) and stops after 6000 rotations. Weigh the mass changes of the specimen and the circular plate before and after the test.

Claims

1. A continuous glass fiber reinforced ASA composite material, comprising, by weight: ASA rubber powder 30~70 parts SAN resin 50~100 parts Continuous glass fiber 100~150 parts Compatibilizer 0.5~10 parts 1~10 parts of anti-wear agent Antioxidant 0.1~1 part Lubricant 0.1~1 part Weathering agent 0.1~1 part; The ratio between the ASA rubber powder and the SAN resin is higher than 1:4 and lower than 1:1; A method for preparing a continuous glass fiber reinforced ASA composite material, the specific steps of which are as follows: Step 1: Weigh ASA rubber powder, SAN resin, compatibilizer, antioxidant, lubricant and weathering agent, add them into a high-speed mixer and mix them at high speed for 0.1 to 0.2h to obtain a mixture; Step 2: Put the raw materials mixed evenly in the previous step into a twin-screw extruder, melt and plasticize the mixed material and inject it into the impregnation mold of the impregnation equipment; then the continuous glass fiber enters the impregnation mold under the action of the traction machine, and is impregnated and dispersed with the molten mixed material resin; then the impregnated continuous glass fiber impregnation material is drawn out by the traction device at a speed of 1-20 m / min; finally, the continuous glass fiber reinforced ASA prepreg tape composite plate material is obtained; The temperature setting range of the twin-screw extruder is: 190°C to 230°C; The temperature of the impregnation mold is 230-260° C., wherein the outlet temperature closest to the outlet of the impregnation mold (within 10 cm) is controlled to be no more than 245° C.

2. A continuous glass fiber reinforced ASA composite material according to claim 1, characterized in that The particle size of the ASA rubber powder is between 100 and 1000 μm.

3. A continuous glass fiber reinforced ASA composite material according to claim 1, characterized in that The SAN resin has a melting index of 5 to 75 (g / 10min) at 220°C and a load of 10kg.

4. A continuous glass fiber reinforced ASA composite material according to claim 1, characterized in that The continuous glass fiber is one or more of alkali-free glass fiber, thermoplastic resin and glass fiber mixed fiber, and alkali glass fiber.

5. The continuous glass fiber reinforced ASA composite material according to claim 1, characterized in that The compatibilizer is one or more of MAH-g-poe, GMA-g-poe and maleic anhydride styrene copolymer SMA.

6. The continuous glass fiber reinforced ASA composite material according to claim 1, characterized in that The wear-resistant agent is PTFE micropowder with a particle size ranging from 1 to 20 μm.

7. The continuous glass fiber reinforced ASA composite material according to claim 1, characterized in that The antioxidant is one or more of hindered phenol antioxidants or phosphite antioxidants.

8. The continuous glass fiber reinforced ASA composite material according to claim 1, characterized in that The lubricant is one or more of pentaerythritol stearate or ethylene bis stearamide silicone oil, barium stearate, and paraffin polyethylene wax.

9. The continuous glass fiber reinforced ASA composite material according to claim 1, characterized in that The weathering agent is a benzophenone, benzotriazole or triazine ultraviolet absorber, preferably a triazine ultraviolet absorber.

10. A method for preparing a novel highly weather-resistant and wear-resistant continuous fiber reinforced thermoplastic ASA composite material, the specific steps of which are as follows: Step 1: Weigh ASA rubber powder, SAN resin, compatibilizer, antioxidant, lubricant and weathering agent, add them into a high-speed mixer and mix them at high speed for 0.1 to 0.2h to obtain a mixture; Step 2: Put the raw materials mixed evenly in the previous step into a twin-screw extruder, melt and plasticize the mixed material and inject it into the impregnation mold of the impregnation equipment; then the continuous glass fiber enters the impregnation mold under the action of the traction machine, and is impregnated and dispersed with the molten mixed material resin; then the impregnated continuous glass fiber impregnation material is drawn out by the traction device at a speed of 1-20 m / min; finally, the continuous glass fiber reinforced ASA prepreg tape composite plate material is obtained; The temperature setting range of the twin-screw extruder is: 190°C to 230°C; The temperature of the impregnation mold is 230-260° C., wherein the outlet temperature closest to the outlet of the impregnation mold (within 10 cm) is controlled to be no more than 245° C.