Weather-resistant and corrosion-resistant composite material for automobile and preparation method thereof

Abstract

The invention discloses a weather-resistant and corrosion-resistant composite material for automobiles and a preparation method thereof, and belongs to the field of high polymer materials. The preparation method comprises the following steps: 1, preparing modified functional filler powder: 1-a, preparing a lanthanum-filled crushed plant carbon source; 1-b, preparing modified carbon composite particles; step 2, preparing functional filler powder; and step 3, preparing the weather-resistant and corrosion-resistant composite material for the automobile. According to the scheme, the weather resistance of the weather-resistant and corrosion-resistant composite material for the automobile is improved through the lanthanum-modified porous nano carbon particles; the wear resistance of the weather-resistant and corrosion-resistant composite material for the automobile is improved by modifying the carbon nanofibers with silicon and combining a rolling process and the like.

Description

Technical Field

[0001] The present invention relates to the field of polymer materials, and particularly to a weather-resistant and corrosion-resistant composite material for automobiles and a preparation method thereof. Background Art

[0002] Improving the properties such as weather resistance, corrosion resistance, and wear resistance of structural materials is an eternal theme in the application of structural materials. At present, composite materials for automobiles already have good weather resistance, corrosion resistance, and wear resistance. However, the exterior injection plastics show cracking, pitting, and even cracking during long-term use, which are all manifestations of insufficient weather resistance and corrosion resistance. The reason may be the presence of micropores on the surface and low wear resistance. Improving the radiation absorption capacity of structural materials through fillers to improve the flatness and wear resistance of materials is a feasible direction.

[0003] In the prior art, CN117887175A discloses a high weather-resistant and yellowing-resistant PP / PS alloy material for automobile interiors, which includes the following formula by weight percentage: 30-70% of polypropylene, 10-30% of compatibilizer, 30-60% of polystyrene, 0.2-2% of yellowing-resistant agent, 0.2-2% of scratch-resistant agent, 0.2-2% of antioxidant, 0.2-2% of light stabilizer, and 0-3% of other additives. The high weather-resistant and yellowing-resistant PP / PS alloy material obtained by the above technical solution has high weather resistance and yellowing resistance, and at the same time takes into account the comprehensive mechanical properties, light resistance, and scratch resistance of the PP / PS alloy material.

[0004] CN105482378A relates to a PBT composite material for automobile exteriors, which includes the following components in parts by weight: 100 parts of PBT resin, 20-30 parts of glass fiber, 5-10 parts of polyimide fiber, 1-5 parts of coupling agent, 0.5-2 parts of compatibilizer, 1-5 parts of heat-resistant agent, 2-6 parts of toughening agent, and 0.5-2 parts of antistatic agent. The reinforcing materials are used in combination of glass fiber and polyimide fiber. The obtained PBT composite material can effectively improve the impact resistance of the PBT composite material while maintaining the excellent properties such as high heat resistance, high tensile strength, weather resistance, and chemical corrosion resistance of the PBT composite material. The use of polyimide fiber can especially improve the impact resistance of the PBT composite material at low temperatures; among them, the amount of glass fiber used is large and the amount of polyimide fiber used is small, which can economically and effectively prepare a PBT composite material with excellent comprehensive properties to meet the long-term use requirements of automobile exteriors in cold regions. The above technologies can all achieve good weather resistance effects, but for the long-term use state, the wear resistance of the material is positively correlated with improving its weather resistance, and the above solutions do not mention this. Summary of the Invention

[0005] To solve the above problems, the present invention provides a weather-resistant and corrosion-resistant composite material for automobiles and a preparation method thereof. The molded part has fewer pores on the surface, not only has good weather resistance and corrosion resistance characteristics, but also has good wear resistance.

[0006] To achieve the above object, the technical solution of the present invention is as follows: The present solution proposes a preparation method of a weather-resistant and corrosion-resistant composite material for automobiles, including the following steps: Step 1, prepare modified functional filler powder: 1-a By weight, crush the plant carbon source and pass it through a 20-mesh to 50-mesh sieve to obtain the crushed plant carbon source. Take 1 part of the crushed plant carbon source and add it to 1 part to 1.5 parts of lanthanum acetate solution with a mass concentration of 0.3% - 0.5%. After soaking for 2h - 3h, filter and dehydrate to obtain lanthanum-filled crushed plant carbon source; 1-b By weight, mix 1 part of bamboo fiber, 0.3 part to 0.5 part of lanthanum-filled crushed plant carbon source, 0.5 part to 1 part of silica sol, and 0.5 part to 1 part of ethanol, and ball mill for 3 - 5h. Unload the material, evaporate the solvent under vacuum conditions to obtain a mixture. Calcinate the mixture at 600°C - 800°C under an oxygen-free condition for 2 - 3h, then raise the temperature to 1000°C - 1100°C and calcinate under an oxygen-free condition for 0.5h - 1h to obtain modified carbon composite particles; Step 2, prepare functional filler powder: By weight, mix 1 part of modified carbon composite particles, 0.05 part to 0.15 part of silicone oil, 1 part to 2 parts of filler, 0.05 part to 0.1 part of leveling agent, and 1 - 1.5 parts of water, add them to a ball mill, and ball mill for 1 - 2h. Then, mix and grind at a speed of 800 - 1000r / s for 1h - 2h, unload the material, dehydrate, and dry under an oxygen-free condition to obtain functional filler powder by dispersion; Step 3, prepare a weather-resistant and corrosion-resistant composite material for automobiles: By weight, heat 1 part of polyamide to 240°C - 300°C, add 0.2 part to 0.3 part of functional filler powder, 0.01 part to 0.05 part of dispersant, and 0.02 part to 0.05 part of weather-resistant additive under stirring conditions, stir for 30min - 60min, then cool to 180°C - 220°C, and introduce it into a calender for calendering 2 - 3 times, cut into pellets, cool, and dry to obtain a weather-resistant and corrosion-resistant composite material for automobiles.

[0007] The solution of the weather-resistant and corrosion-resistant composite material for automobiles prepared by this solution has the following characteristics: 1. Prepare modified carbon composite particles. The modified carbon composite particles consist of two parts. One part is lanthanum-modified porous nano-carbon particles, whose main function is to improve weather resistance. Lanthanum-filled crushed plant carbon sources can obtain silicon-lanthanum-modified porous nano-carbon particles under the ball milling and calcination conditions in step 1-b. The generated lanthanum oxide nanoparticles and silicon dioxide nanoparticles can adhere to the surface of the porous nano-carbon particles. During the further heating process, the lanthanum oxide nanoparticles and silicon dioxide nanoparticles can undergo a hometown reaction to form a heterojunction structure, change the surface potential of the porous nano-carbon particles, improve the microwave absorption ability of the porous nano-carbon particles, and thus improve their weather resistance. The other part is silicon-modified nano-carbon fibers, which mainly strengthen the mechanical properties through carbon fibers. The generated nano-silicon dioxide is adsorbed on the surface of the carbon fibers, improving the compatibility with the silicone oil in step 2 and further improving the compatibility with polyamide.

[0008] 2. Improve the compatibility between components. To obtain better component uniformity, in addition to subjecting the filler components to silicone oil-modified ball milling, this solution also proposes adding the remaining components to molten polyamide, and at the same time improving the component uniformity through temperature control and rolling processes. First, this solution heats the polyamide to 240°C - 300°C to obtain molten polyamide, mainly to ensure that there is sufficient fluidity when adding the remaining components, which is conducive to full dispersion. Secondly, after cooling to 180°C - 220°C, the fluidity of the polyamide becomes poor, becoming a highly elastic fluid. Through multiple rolling processes, the compatibility between components can be further strengthened, achieving more thorough mixing. More importantly, the rolling process gives a mechanical force orientation, which can improve the alignment regularity of the carbon fibers.

[0009] 3. Step 1-b is divided into two-stage calcination. The 600°C - 800°C stage is to volatilize organic substances, carbonize the plant carbon source and bamboo fibers, and at the same time, lanthanum acetate and silica sol decompose into nano-lanthanum oxide and nano-silicon dioxide, which adhere to the carbonized surface. The 1000°C - 1100°C stage is to promote the hometown reaction, enable the nano-lanthanum oxide and nano-silicon dioxide to form a heterojunction structure, and then change the surface state of the porous nano-carbon particles, making them obtain better radiation absorption ability, especially the absorption ability in the short wavelength band, that is, improving the weather resistance.

[0010] The leveling agent is used to improve the surface flatness of the automotive weather-resistant and corrosion-resistant composite material after molding, and thus improve the corrosion resistance.

[0011] Preferably, the plant carbon source described in step 1-a is one or more combinations of dry hay leaves, dry wood chips, dry tree leaves, and straw. Sieving is mainly to increase the contact area, and choosing a dry plant carbon source is mainly to ensure that the lanthanum acetate solution is fully absorbed.

[0012] Preferably, the water content ratio of the lanthanum-filled crushed plant carbon source in step 1-a is less than 10%.

[0013] Preferably, the silica sol described in step 1-b is one of aqueous silica sol or organosilica sol; the silicone oil is resin-type aqueous silicone oil.

[0014] Preferably, the oxygen-free condition in step 1-b is one of vacuum oxygen-free, nitrogen atmosphere oxygen-free, and inert gas oxygen-free; the oxygen-free condition in step 2 is one of vacuum oxygen-free, nitrogen atmosphere oxygen-free, and inert gas oxygen-free.

[0015] The oxygen-free condition in step 1-b is mainly to prevent the oxidation of plant carbon source or bamboo fiber; the oxygen-free condition in step 2 is mainly to prevent the oxidation of modified carbon composite particles.

[0016] Preferably, the drying temperature after dehydration under oxygen-free conditions in step 2 is 60°C - 90°C, and the dispersion condition is dispersion by a high-speed crusher.

[0017] Preferably, the leveling agent in step 2 is one of organosilicon leveling agents, acrylate leveling agents, or fluorocarbon compound leveling agents.

[0018] Preferably, the dispersant in step 3 is one or more of calcium stearate, zinc stearate, and copolyamide wax.

[0019] Preferably, the weather resistance aid in step 3 is carbon black; the stirring condition in step 3 is 800 r / min - 1000 r / min.

[0020] Preferably, the filler in step 2 is one or more of zinc oxide powder, magnesium oxide powder, aluminum oxide powder, titanium dioxide powder, and silicon dioxide powder. The function of the filler is to enhance wear resistance and strength.

[0021] This solution also proposes an automotive weather and corrosion resistant composite material prepared by the above-mentioned preparation method of the automotive weather and corrosion resistant composite material.

[0022] Compared with the prior art, the present invention has the following advantages: 1. Introduce modified carbon composite particles, including lanthanum-modified porous nano-carbon particles and silicon-modified nano-carbon fibers. The weather resistance of the automotive weather and corrosion resistant composite material is improved by lanthanum-modified porous nano-carbon particles; the strength of the automotive weather and corrosion resistant composite material is improved by silicon-modified nano-carbon fibers in combination with processes such as roll pressing.

[0023] 2. In order to improve the dispersibility, this solution mixes and ball-mills the modified carbon composite particles, silicone oil, filler, and leveling agent, performs surface modification on each component to obtain functional filler powder; then adds the functional filler powder to molten polyamide, and improves the dispersibility of each component by controlling temperature, stirring, and roll pressing processes. Detailed implementation mode

[0024] The following specific embodiments illustrate the implementation modes of the present invention. Those skilled in this technology can easily understand the other advantages and effects of the present invention from the content disclosed in this specification. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work belong to the scope of protection of the present invention.

[0025] Example 1 A weather-resistant and corrosion-resistant composite material for automobiles is prepared through the following steps: Step 1, prepare modified functional filler powder: 1-a By weight, crush the straw and pass it through a 50-mesh sieve to obtain crushed plant carbon source. Take 1 part of the crushed plant carbon source and add it to 1 part of lanthanum acetate solution with a mass concentration of 0.5%. After soaking for 2 h, filter and press-filter to dehydrate to obtain lanthanum-filled crushed plant carbon source with a water content ratio of 5%; 1-b By weight, mix 1 part of bamboo fiber, 0.5 part of lanthanum-filled crushed plant carbon source, 0.5 part of aqueous silica sol, and 1 part of ethanol, and ball-mill for 4 h. Unload the material, evaporate the solvent under vacuum conditions, and obtain a mixed material. The mixed material is calcined at 700 °C under nitrogen conditions for 2 h, then the temperature is raised to 1000 °C and calcined under nitrogen conditions for 0.5 h to obtain modified carbon composite particles; the aqueous silica sol is LUDOXTM-40; Step 2, prepare functional filler powder: By weight, mix 1 part of modified carbon composite particles, 0.1 part of resin-type aqueous silicone oil, 1 part of calcium carbonate, 0.2 part of magnesium oxide, 0.1 part of zinc oxide, 0.08 part of organosilicon leveling agent, and 1 part of water and add them to a ball mill. Ball-mill for 1 h, then mix and grind for 2 h. Unload the material, press-filter to dehydrate, dry at 80 °C under nitrogen conditions, and disperse through a high-speed pulverizer to obtain functional filler powder; the resin-type aqueous silicone oil is polyether-modified silicone oil; Step 3, prepare weather-resistant and corrosion-resistant composite material for automobiles: By weight, heat 1 part of polyamide to 270 °C, add 0.25 part of functional filler powder, 0.02 part of calcium stearate, and 0.03 part of carbon black under stirring conditions. Stir at a speed of 900 r / s for 60 min, then cool to 180 °C, introduce it into a calender for calendering 3 times, cut and granulate, cool, and dry to obtain a weather-resistant and corrosion-resistant composite material for automobiles.

[0026] Example 2 A weather-resistant and corrosion-resistant composite material for automobiles is prepared through the following steps: Step 1, prepare modified functional filler powder: 1-a By weight, crush dry wood chips and sieve them through a 50-mesh sieve to obtain crushed plant carbon source. Take 1 part of the crushed plant carbon source and add it to 1.2 parts of lanthanum acetate solution with a mass concentration of 0.4%. After soaking for 2 h, filter and press-filter to dehydrate, obtaining lanthanum-filled crushed plant carbon source with a water content ratio of 7%. 1-b By weight, mix 1 part of bamboo fiber, 0.5 part of lanthanum-filled crushed plant carbon source, 0.5 part of aqueous silica sol, and 0.8 part of ethanol, and ball-mill for 4 h. Unload the material, evaporate the solvent under vacuum conditions to obtain a mixed material. Calcinate the mixed material at 750 °C under nitrogen conditions for 2 h, then raise the temperature to 1050 °C and calcinate for 1 h under nitrogen conditions to obtain modified carbon composite particles; the aqueous silica sol is LUDOXTM-40. Step 2, prepare functional filler powder: By weight, mix 1 part of modified carbon composite particles, 0.08 part of resin-type aqueous silicone oil, 1 part of calcium carbonate, 0.3 part of titanium dioxide, 0.1 part of silicon dioxide, 0.12 part of silicone-based leveling agent, and 1 part of water, add them to a ball mill, and ball-mill for 1 h. After mixing and grinding for 2 h, unload the material, press-filter and dehydrate, then dry at 80 °C under nitrogen conditions, and disperse through a high-speed pulverizer to obtain functional filler powder; the resin-type aqueous silicone oil is polyether-modified silicone oil. Step 3, prepare weather-resistant and corrosion-resistant composite material for automobiles: By weight, heat 1 part of polyamide to 290 °C, add 0.28 part of functional filler powder, 0.03 part of zinc stearate, and 0.03 part of carbon black under stirring conditions. Stir at a speed of 900 r / s for 60 min, then cool to 200 °C, introduce it into a calender and roll 3 times, cut into pellets, cool, and dry to obtain a weather-resistant and corrosion-resistant composite material for automobiles.

[0027] Example 3 A weather-resistant and corrosion-resistant composite material for automobiles is prepared through the following steps: Step 1, prepare modified functional filler powder: 1-a By weight, crush dry wood chips and sieve them through a 20-mesh sieve to obtain crushed plant carbon source. Take 1 part of the crushed plant carbon source and add it to 1.2 parts of lanthanum acetate solution with a mass concentration of 0.3%. After soaking for 2 h, filter and press-filter to dehydrate, obtaining lanthanum-filled crushed plant carbon source with a water content ratio of 4%. 1-b By weight, mix 1 part of bamboo fiber, 0.5 part of lanthanum-filled crushed plant carbon source, 0.7 part of aqueous silica sol, and 1 part of ethanol, and ball-mill for 4 h. Unload the material, evaporate the solvent under vacuum conditions to obtain a mixed material. Calcinate the mixed material at 650 °C under nitrogen conditions for 2 h, then raise the temperature to 1050 °C and calcinate for 1 h under nitrogen conditions to obtain modified carbon composite particles; the aqueous silica sol is LUDOX TM-40. Step 2, preparing functional filler powder: By weight, mix 1 part of modified carbon composite particles, 0.12 part of resin-type aqueous silicone oil, 1 part of calcium carbonate, 0.3 part of titanium dioxide, 0.1 part of silicon dioxide, 0.12 part of silicone leveling agent and 1 part of water, add them to a ball mill, mix and ball mill for 1 h, mix and grind for 2 h, then unload the material, filter and dehydrate, and dry at 80 °C under nitrogen conditions, and disperse with a high-speed crusher to obtain functional filler powder; the resin-type aqueous silicone oil is polyether-modified silicone oil; Step 3, preparing weather-resistant and corrosion-resistant composite material for automobiles: By weight, heat 1 part of polyamide to 250 °C, add 0.21 part of functional filler powder, 0.03 part of calcium stearate and 0.03 part of carbon black under stirring conditions, stir at a speed of 980 r / s for 60 min, then cool to 220 °C, introduce it into a rolling mill and roll 3 times, cut and granulate, cool, and dry to obtain a weather-resistant and corrosion-resistant composite material for automobiles.

[0028] Comparative Example 1 A weather-resistant and corrosion-resistant composite material for automobiles is prepared through the following steps: Step 1, preparing modified functional filler powder: By weight, mix 1 part of bamboo fiber, 0.5 part of lanthanum-filled crushed plant carbon source, 0.5 part of aqueous silica sol and 1 part of ethanol, mix and ball mill for 4 h, unload the material, evaporate the solvent under vacuum conditions to obtain a mixed material, calcine the mixed material at 700 °C under nitrogen conditions for 2 h, then raise the temperature to 1000 °C and calcine for 0.5 h under nitrogen conditions to obtain modified carbon composite particles; the aqueous silica sol is LUDOX TM-40; Step 2, preparing functional filler powder: By weight, mix 1 part of modified carbon composite particles, 0.1 part of resin-type aqueous silicone oil, 1 part of calcium carbonate, 0.2 part of magnesium oxide and 0.1 part of zinc oxide, 0.08 part of silicone leveling agent and 1 part of water, add them to a ball mill, mix and ball mill for 1 h, mix and grind for 2 h, then unload the material, filter and dehydrate, and dry at 80 °C under nitrogen conditions, and disperse with a high-speed crusher to obtain functional filler powder; the resin-type aqueous silicone oil is polyether-modified silicone oil; Step 3, preparing weather-resistant and corrosion-resistant composite material for automobiles: By weight, heat 1 part of polyamide to 270 °C, add 0.25 part of functional filler powder, 0.02 part of calcium stearate and 0.03 part of carbon black under stirring conditions, stir at a speed of 900 r / s for 60 min, then cool to 180 °C, introduce it into a rolling mill and roll 3 times, cut and granulate, cool, and dry to obtain a weather-resistant and corrosion-resistant composite material for automobiles.

[0029] Comparative Example 2 A weather-resistant and corrosion-resistant composite material for automobiles is prepared through the following steps: Step 1, preparing modified functional filler powder: By weight, the straw is crushed and screened through a 50-mesh sieve to obtain crushed plant carbon source. Take 1 part of the crushed plant carbon source and add it to 1 part of lanthanum acetate solution with a mass concentration of 0.5%. After soaking for 2 h, filter and press-filter to dehydrate, obtaining lanthanum-filled crushed plant carbon source with a water content ratio of 5%. Calcinate for 2 h under nitrogen condition and then raise the temperature to 1000 °C, and calcinate for 0.5 h under nitrogen condition to obtain modified carbon composite particles; the aqueous silica sol is LUDOX TM-40; Step 2, prepare functional filler powder: By weight, mix 1 part of modified carbon composite particles, 0.1 part of resin-type aqueous silicone oil, 1 part of calcium carbonate, 0.2 part of magnesium oxide, 0.1 part of zinc oxide, 0.08 part of silicone-based leveling agent and 1 part of water, add them to a ball mill, mix and ball mill for 1 h, mix and grind for 2 h, then unload, press-filter to dehydrate and dry at 80 °C under nitrogen condition, and disperse through a high-speed crusher to obtain functional filler powder; the resin-type aqueous silicone oil is polyether-modified silicone oil; Step 3, prepare weather-resistant and corrosion-resistant composite material for automobile: By weight, heat 1 part of polyamide to 270 °C, add 0.25 part of functional filler powder, 0.02 part of calcium stearate and 0.03 part of carbon black under stirring condition, stir at a speed of 900 r / s for 60 min, then cool down to 180 °C, introduce it into a calender for calendering 3 times, cut and granulate, cool, and dry to obtain weather-resistant and corrosion-resistant composite material for automobile.

[0030] Comparative Example 3 A weather-resistant and corrosion-resistant composite material for automobile is prepared through the following steps: Step 1, prepare modified functional filler powder: 1-a By weight, the straw is crushed and screened through a 50-mesh sieve to obtain crushed plant carbon source. Take 1 part of the crushed plant carbon source and add it to 1 part of lanthanum acetate solution with a mass concentration of 0.5%. After soaking for 2 h, filter and press-filter to dehydrate, obtaining lanthanum-filled crushed plant carbon source; 1-b By weight, mix 1 part of bamboo fiber, 0.5 part of lanthanum-filled crushed plant carbon source, 0.5 part of aqueous silica sol and 1 part of ethanol, evaporate the solvent under vacuum condition after mixing to obtain a mixture, calcinate the mixture at 700 °C for 2 h under nitrogen condition and then raise the temperature to 1000 °C, and calcinate for 0.5 h under nitrogen condition to obtain modified carbon composite particles; the aqueous silica sol is LUDOX TM-40; Step 2, prepare functional filler powder: By weight, mix 1 part of modified carbon composite particles, 0.1 part of resin-type aqueous silicone oil, 1 part of calcium carbonate, 0.2 part of magnesium oxide, 0.1 part of zinc oxide, 0.08 part of silicone-based leveling agent and 1 part of water, add them to a ball mill, mix and ball mill for 1 h, mix and grind for 2 h, then unload, press-filter to dehydrate and dry at 80 °C under nitrogen condition, and disperse through a high-speed crusher to obtain functional filler powder; the resin-type aqueous silicone oil is polyether-modified silicone oil; Step 3, preparing a weather-resistant and corrosion-resistant composite material for automobiles: By weight, heat 1 part of polyamide to 270 °C, add 0.25 part of functional filler powder, 0.02 part of calcium stearate and 0.03 part of carbon black under stirring conditions, stir at a speed of 900 r / s for 60 min, then cool to 180 °C, introduce it into a calendering machine and calender 3 times, cut and granulate, cool, and dry to obtain a weather-resistant and corrosion-resistant composite material for automobiles.

[0031] Comparative Example 4 A weather-resistant and corrosion-resistant composite material for automobiles is prepared by the following steps: Step 1, preparing modified functional filler powder: 1-a By weight, crush straw and sieve it through a 50-mesh sieve to obtain crushed plant carbon source; 1-b By weight, mix 1 part of bamboo fiber, 0.5 part of crushed plant carbon source, 0.5 part of aqueous silica sol and 1 part of ethanol, ball-mill for 4 h, unload the material, evaporate the solvent under vacuum conditions to obtain a mixed material, calcine the mixed material at 700 °C for 2 h under nitrogen conditions and then raise the temperature to 1000 °C, calcine for 0.5 h under nitrogen conditions to obtain modified carbon composite particles; the aqueous silica sol is LUDOX TM-40; Step 2, preparing functional filler powder: By weight, add 1 part of modified carbon composite particles, 0.1 part of resin-type aqueous silicone oil, 1 part of calcium carbonate, 0.2 part of magnesium oxide and 0.1 part of zinc oxide, 0.08 part of organosilicon leveling agent and 1 part of water into a ball mill, mix and ball-mill for 1 h, mix and grind for 2 h, then unload the material, filter and dehydrate under pressure, dry at 80 °C under nitrogen conditions, and disperse with a high-speed crusher to obtain functional filler powder; the resin-type aqueous silicone oil is polyether-modified silicone oil; Step 3, preparing a weather-resistant and corrosion-resistant composite material for automobiles: By weight, heat 1 part of polyamide to 270 °C, add 0.25 part of functional filler powder, 0.02 part of calcium stearate and 0.03 part of carbon black under stirring conditions, stir at a speed of 900 r / s for 60 min, then cool to 180 °C, introduce it into a calendering machine and calender 3 times, cut and granulate, cool, and dry to obtain a weather-resistant and corrosion-resistant composite material for automobiles.

[0032] Comparative Example 5 A weather-resistant and corrosion-resistant composite material for automobiles is prepared by the following steps: Step 1, preparing modified functional filler powder: 1-a By weight, crush straw and sieve it through a 50-mesh sieve to obtain crushed plant carbon source, take 1 part of crushed plant carbon source, add it to 1 part of lanthanum acetate solution with a mass concentration of 0.5%, soak for 2 h, filter, filter and dehydrate under pressure to obtain lanthanum-filled crushed plant carbon source with a water content ratio of 5%; 1-b By weight, 1 part of bamboo fiber, 0.5 part of lanthanum-filled crushed plant carbon source and 1 part of ethanol are mixed and ball-milled for 4 h, then unloaded. After evaporating the solvent under vacuum conditions, a mixture is obtained. The mixture is calcined at 700 °C under nitrogen for 2 h and then the temperature is raised to 1000 °C and calcined at 700 °C under nitrogen for 0.5 h to obtain modified carbon composite particles; the aqueous silica sol is LUDOX TM-40; Step 2, prepare the functional filler powder: By weight, 1 part of the modified carbon composite particles, 1 part of calcium carbonate, 0.2 part of magnesium oxide, 0.1 part of zinc oxide, 0.08 part of organosilicon leveling agent and 1 part of water are mixed and added to a ball mill, and ball-milled for 1 h. After mixing and grinding for 2 h, unload, filter and dehydrate under pressure, and then dry at 80 °C under nitrogen. The functional filler powder is obtained by dispersion with a high-speed pulverizer; the resin-type aqueous silicone oil is polyether-modified silicone oil; Step 3, prepare the weather-resistant and corrosion-resistant composite material for automobiles: By weight, 1 part of polyamide is heated to 270 °C, and 0.25 part of the functional filler powder, 0.02 part of calcium stearate and 0.03 part of carbon black are added under stirring conditions. After stirring at a speed of 900 r / s for 60 min, the temperature is lowered to 180 °C, then introduced into a rolling mill and rolled 3 times, chopped and granulated, cooled, and dried to obtain the weather-resistant and corrosion-resistant composite material for automobiles.

[0033] Comparative Example 6 A weather-resistant and corrosion-resistant composite material for automobiles is prepared by the following steps: Step 1, prepare the modified functional filler powder: 1-a By weight, the straw is crushed and passed through a 50-mesh sieve to obtain a crushed plant carbon source. Take 1 part of the crushed plant carbon source and add it to 1 part of an acetic acid lanthanum solution with a mass concentration of 0.5%. After soaking for 2 h, filter and dehydrate under pressure to obtain a lanthanum-filled crushed plant carbon source with a water content ratio of 5%; 1-b By weight, 1 part of bamboo fiber, 0.5 part of lanthanum-filled crushed plant carbon source, 0.5 part of aqueous silica sol and 1 part of ethanol are mixed and ball-milled for 4 h, then unloaded. After evaporating the solvent under vacuum conditions, a mixture is obtained. The mixture is calcined at 700 °C under nitrogen for 2 h and then the temperature is raised to 1000 °C and calcined at 700 °C under nitrogen for 0.5 h to obtain modified carbon composite particles; the aqueous silica sol is LUDOXTM-40; Step 2, prepare the functional filler powder: By weight, 1 part of the modified carbon composite particles, 0.1 part of resin-type aqueous silicone oil, 1 part of calcium carbonate, 0.2 part of magnesium oxide, 0.1 part of zinc oxide and 1 part of water are mixed and added to a ball mill, and ball-milled for 1 h. After mixing and grinding for 2 h, unload, filter and dehydrate under pressure, and then dry at 80 °C under nitrogen. The functional filler powder is obtained by dispersion with a high-speed pulverizer; the resin-type aqueous silicone oil is polyether-modified silicone oil; Step 3, Preparation of weather-resistant and corrosion-resistant composite material for automobiles: By weight, heat 1 part of polyamide to 270 °C, add 0.25 part of functional filler powder, 0.02 part of calcium stearate and 0.03 part of carbon black under stirring conditions, stir for 60 min at a rotation speed of 900 r / s, then cool to 180 °C, introduce it into a rolling mill and roll it 3 times, cut it into granules, cool, and dry to obtain the weather-resistant and corrosion-resistant composite material for automobiles.

[0034] Comparative Example 7 A weather-resistant and corrosion-resistant composite material for automobiles is prepared by the following steps: Step 1, Preparation of modified functional filler powder: 1-a By weight, crush the straw and pass it through a 50-mesh sieve to obtain crushed plant carbon source. Take 1 part of the crushed plant carbon source, add it to 1 part of lanthanum acetate solution with a mass concentration of 0.5%, soak for 2 h, then filter and press-filter to dehydrate to obtain lanthanum-filled crushed plant carbon source with a water content ratio of 5%; 1-b By weight, mix 1 part of bamboo fiber, 0.5 part of lanthanum-filled crushed plant carbon source, 0.5 part of aqueous silica sol and 1 part of ethanol, ball-mill for 4 h, unload the material, evaporate the solvent under vacuum conditions to obtain a mixture, and calcine the mixture under nitrogen conditions at 1200 °C for 0.5 h to obtain modified carbon composite particles; the aqueous silica sol is LUDOX TM-40; Step 2, Preparation of functional filler powder: By weight, add 1 part of modified carbon composite particles, 0.1 part of resin-type aqueous silicone oil, 1 part of calcium carbonate, 0.2 part of magnesium oxide and 0.1 part of zinc oxide, 0.08 part of organosilicon leveling agent and 1 part of water to a ball mill, mix and ball-mill for 1 h, mix and grind for 2 h, then unload the material, press-filter and dehydrate, and dry at 80 °C under nitrogen conditions, and disperse with a high-speed pulverizer to obtain functional filler powder; the resin-type aqueous silicone oil is polyether-modified silicone oil; Step 3, Preparation of weather-resistant and corrosion-resistant composite material for automobiles: By weight, heat 1 part of polyamide to 270 °C, add 0.25 part of functional filler powder, 0.02 part of calcium stearate and 0.03 part of carbon black under stirring conditions, stir for 60 min at a rotation speed of 900 r / s, then cool to 180 °C, introduce it into a rolling mill and roll it 3 times, cut it into granules, cool, and dry to obtain the weather-resistant and corrosion-resistant composite material for automobiles.

[0035] Comparative Example 8 A weather-resistant and corrosion-resistant composite material for automobiles is prepared by the following steps: Step 1, Preparation of modified functional filler powder: 1-a By weight, crush the straw and pass it through a 50-mesh sieve to obtain crushed plant carbon source. Take 1 part of the crushed plant carbon source, add it to 1 part of lanthanum acetate solution with a mass concentration of 0.5%, soak for 2 h, then filter and press-filter to dehydrate to obtain lanthanum-filled crushed plant carbon source with a water content ratio of 5%; 1-b By weight, 1 part of bamboo fiber, 0.5 part of lanthanum-filled pulverized plant carbon source, 0.5 part of aqueous silica sol, and 1 part of ethanol are mixed and ball-milled for 4 h, then unloaded. After evaporating the solvent under vacuum conditions, a mixture is obtained. The mixture is calcined at 700 °C for 2 h under nitrogen conditions and then heated to 1000 °C and calcined at 1000 °C for 0.5 h under nitrogen conditions to obtain modified carbon composite particles; the aqueous silica sol is LUDOXTM-40; Step 2, preparing functional filler powder: By weight, 1 part of modified carbon composite particles, 0.1 part of resin-type aqueous silicone oil, 1 part of calcium carbonate, 0.2 part of magnesium oxide, 0.1 part of zinc oxide, 0.08 part of organosilicon leveling agent, and 1 part of water are mixed and added to a ball mill, and ball-milled for 1 h. After mixing and grinding for 2 h, it is unloaded, dewatered by pressure filtration, dried at 80 °C under nitrogen conditions, and dispersed by a high-speed pulverizer to obtain functional filler powder; the resin-type aqueous silicone oil is polyether-modified silicone oil; Step 3, preparing weather-resistant and corrosion-resistant composite material for automobiles: By weight, 1 part of polyamide is heated to 270 °C, and 0.25 part of functional filler powder, 0.02 part of calcium stearate, and 0.03 part of carbon black are added under stirring conditions. After stirring at a speed of 900 r / s for 60 min, it is extruded and granulated, cooled, and dried to obtain a weather-resistant and corrosion-resistant composite material for automobiles.

[0036] Testing method: Antibacterial property test: Detect whether the test sample is easily attached by mold: Refer to the standard method of GB / T31402, and the test strains are Aspergillus niger; Weather resistance test: Refer to the special standard for automotive exterior parts of SAE J2527; Surface detection: A sample plate of 60 mm × 60 mm × 3.2 mm is prepared, a section is intercepted, and the surface micropores are observed with a 500-fold optical microscope, and the number of pores in the field of view is recorded.

[0037] Abrasion resistance test: Prepare samples according to ASTM D3702, and the test conditions are: pressure: 100 N, speed: 0.5 m / s, wear time: 2 h, wear rate = wear mass / initial mass * 100%.

[0038] Detection of the use effect in the environment: A sample plate of 60 mm × 60 mm × 3.2 mm is prepared and left standing in the same outdoor environment for 100 weeks to observe the surface state.

[0039] Table 1 Serial number Glossiness (60°) Black mold Glossiness after aging (60°, 2000h) Color difference after aging (2000h) Wear rate % Surface condition after standing outdoors for 100 weeks Number of pores (pcs) Example 1 73 92.2 62 2.2 19 A small amount of scratches, no obvious change None Example 2 76 92.3 62 2.1 21 A small amount of scratches, no obvious change None Example 3 74 92.4 61 2.0 20 A small amount of scratches, no obvious change None Comparative example 1 68 91.6 48 1.7 28 Yellowing, with cracks 3 Comparative example 2 71 91.2 59 1.8 47 With cracks 4 Comparative example 3 70 91.6 54 1.3 38 With cracks 12 Comparative example 4 69 90.4 41 1.0 27 Yellowing 4 Comparative example 5 70 90.3 53 1.1 46 With pits and cracks 17 Comparative example 6 67 86.3 38 1.3 23 With pits and cracks 35 Comparative example 7 72 91.0 45 1.9 29 Yellowing 2 Comparative example 8 66 90.2 58 1.8 33 Obvious scratches, with a small number of pits 8 From the above results, it can be seen that the products obtained in Examples 1-3 are superior to Comparative Examples 1-8 in the test results, which benefits from the combination of the formula and process.

[0040] The main difference between Comparative Example 1 and Example 1 is that lanthanum-filled crushed plant carbon source was not prepared in Comparative Example 1. Therefore, the lanthanum oxide-silica heterojunction structure could not be formed in Comparative Example 1, resulting in poor absorption of radiation and poor weather resistance. The difference between Comparative Example 4 and Example 1 is that the plant carbon source was not soaked in lanthanum acetate solution, and there was also a problem of low weather resistance.

[0041] The main difference between Comparative Example 2 and Example 1 is that carbon fiber calcined from bamboo fiber was not prepared in Comparative Example 2. Comparative Example 2 could not obtain the reinforcement of carbon fiber, so the wear resistance was poor.

[0042] The difference between Comparative Example 3 and Example 1 is that ball milling was not carried out in Step 1-b, which led to poor mixing uniformity, resulting in uneven attachment of silica sol on the surfaces of bamboo fiber particles and crushed plant carbon source particles, and finally resulting in an increase in the number of surface pores and poor performance.

[0043] The difference between Comparative Example 5 and Example 1 is that silica sol was not added in Step 1-b and silicone oil was not added in Step 2. This led to poor compatibility between the prepared functional filler and polyamide, and microcracks were easily formed on the contact surface, which in turn affected the weather resistance and wear resistance, and at the same time, the number of surface pores was relatively large. Therefore, the test results of Comparative Example 5 in terms of wear resistance and weather resistance were not satisfactory.

[0044] The difference between Comparative Example 6 and Example 1 is that no leveling agent was added. This led to an uneven surface of the prepared weather-resistant and corrosion-resistant composite material for automobiles after molding, with many pores, etc., which were easily attached by bacteria and molds, and at the same time, it was also easy to form corrosion sources. From the data, it can be seen that the difference in wear resistance detection between the prepared finished product and Example 1 was not significant, but the number of pores was large, and there were pits and cracks after standing outdoors for 100 weeks, indicating that the leveling agent had a strong promoting effect on the weather-resistant and corrosion-resistant composite material for automobiles described in this scheme.

[0045] The difference between Comparative Example 7 and Example 1 is that step 1-b was not subjected to segmented calcination and the temperature was too high, which led to excessive solid-phase reaction, formation of coarse heterocrystalline grains, and at the same time, the pore structure of the porous nano-carbon particles decreased, ultimately affecting the radiation absorption ability and resulting in poor weather resistance.

[0046] The difference between Comparative Example 8 and Example 1 is that conventional extrusion granulation was selected in Step 3, which did not further enhance the binding between components, reduced the mixing uniformity, and more importantly, affected the mechanical orientation of nano-carbon fibers, thereby affecting the wear resistance and weather resistance.

[0047] The above are only the preferred specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention, according to the technical solution and inventive concept of the present invention, making equivalent substitutions or changes, shall be covered by the protection scope of the present invention.

Claims

1. A preparation method of a weather-resistant and corrosion-resistant composite material for automobiles, characterized in that, It includes the following steps: Step 1, preparing modified functional filler powder: 1-a By weight, crush the plant carbon source and sieve it through a 20-mesh to 50-mesh sieve to obtain the crushed plant carbon source. Take 1 part of the crushed plant carbon source and add it to 1 part to 1.5 parts of lanthanum acetate solution with a mass concentration of 0.3% - 0.5%. After soaking for 2h - 3h, filter and dehydrate to obtain lanthanum-filled crushed plant carbon source; 1-b By weight, mix 1 part of bamboo fiber, 0.3 part to 0.5 part of lanthanum-filled crushed plant carbon source, 0.5 part to 1 part of silica sol, and 0.5 part to 1 part of ethanol, and ball mill for 3 - 5h. Unload the material, evaporate the solvent under vacuum conditions to obtain a mixture. Calcinate the mixture at 600°C - 800°C under an oxygen-free condition for 2 - 3h, then raise the temperature to 1000°C - 1100°C and calcinate under an oxygen-free condition for 0.5h - 1h to obtain modified carbon composite particles; Step 2, preparing functional filler powder: By weight, mix 1 part of modified carbon composite particles, 0.05 part to 0.15 part of silicone oil, 1 part to 2 parts of filler, 0.05 part to 0.1 part of leveling agent, and 1 - 1.5 parts of water, add them to a ball mill, and ball mill for 1 - 2h. Then, mix and grind at a rotation speed of 800 - 1000r / s for 1h - 2h, unload the material, dehydrate, and dry under an oxygen-free condition to obtain functional filler powder by dispersion; Step 3, preparing weather-resistant and corrosion-resistant composite material for automobiles: By weight, heat 1 part of polyamide to 240°C - 300°C, add 0.2 part to 0.3 part of functional filler powder, 0.01 part to 0.05 part of dispersant, and 0.02 part to 0.05 part of weather-resistant additive under stirring conditions, stir for 30min - 60min, then cool to 180°C - 220°C, introduce it into a roller press and roll 2 - 3 times, cut and granulate, and obtain the weather-resistant and corrosion-resistant composite material for automobiles after cooling and drying.

2. The preparation method of a weather-resistant and corrosion-resistant composite material for automobiles according to claim 1, characterized in that, The plant carbon source described in step 1-a is one or a combination of hay leaves, dry wood chips, dry leaves, and straw.

3. The preparation method of a weather-resistant and corrosion-resistant composite material for automobiles according to claim 1, characterized in that, The water content ratio of the lanthanum-filled crushed plant carbon source described in step 1-a is less than 10%.

4. The preparation method of a weather-resistant and corrosion-resistant composite material for automobiles according to claim 1, characterized in that, The silica sol described in step 1-b is one of aqueous silica sol or organosilica sol; the silicone oil is resin-type aqueous silicone oil.

5. The preparation method of a weather-resistant and corrosion-resistant composite material for automobiles according to claim 1, characterized in that, The oxygen-free condition described in step 1-b is one of vacuum oxygen-free, nitrogen atmosphere oxygen-free, and inert gas oxygen-free; the oxygen-free condition described in step 2 is one of vacuum oxygen-free, nitrogen atmosphere oxygen-free, and inert gas oxygen-free.

6. The preparation method of a weather-resistant and corrosion-resistant composite material for automobiles according to claim 1, characterized in that, The drying temperature under an oxygen-free condition after dehydration in step 2 is 60°C - 90°C, and the dispersion condition is dispersion by a high-speed crusher.

7. The preparation method of a weather-resistant and corrosion-resistant composite material for automobiles according to claim 1, characterized in that, The leveling agent described in step 2 is one of organosilicon leveling agent, acrylate leveling agent, or fluorocarbon compound leveling agent; the filler described in step 2 is one or several of zinc oxide powder, magnesium oxide powder, alumina powder, titanium dioxide powder, and silica powder.

8. The preparation method of a weather-resistant and corrosion-resistant composite material for automobiles according to claim 1, characterized in that, The dispersant described in step 3 is one or several of calcium stearate, zinc stearate, and copolyamide wax.

9. The preparation method of a weather-resistant and corrosion-resistant composite material for automobiles according to claim 1, characterized in that, The weather-resistant additive described in step 3 is carbon black; the stirring condition described in step 3 is 800r / min - 1000r / min.

10. An automotive weather and corrosion resistant composite material prepared by the method for preparing an automotive weather and corrosion resistant composite material according to any one of claims 1-9.