High-impact-resistance plate and preparation method thereof

Abstract

The invention discloses a high-impact-resistance plate and a preparation method thereof, and relates to the technical field of preparation of stone-plastic plates. The raw materials comprise the following components in parts by mass: 100-120 parts of a vinyl chloride-butadiene-styrene-acrylonitrile copolymer, 50-150 parts of calcium powder, 15-35 parts of a plasticizer, 0.2-0.8 part of an antioxidant, 1.5-5 parts of a stabilizer and 5-15 parts of a processing aid. The preparation method comprises the steps of mixing, banburying, open milling, calendering and cooling traction discharging. According to the invention, the influence of the raw material formula ratio of the stone-plastic plate on the impact resistance of the plate is explored, and a proper processing mode is matched, so that the stone-plastic plate prepared by taking the ABS copolymer and the calcium powder as main raw materials has better impact resistance.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of plates, and particularly relates to the technical field of preparation of stone-plastic plates. BACKGROUND

[0002] The stone-plastic plate is generally composed of stone powder and PVC resin, mainly uses calcium powder as a raw material, is formed by plastic extrusion of a sheet, and is composed of a stone-plastic polymer base layer, a PUR crystal shield transparent layer, a wear-resistant layer, a color film decorative layer, and a soft and quiet rebound layer. The stone-plastic plate is environmentally friendly and free of formaldehyde, does not use glue in the manufacturing process, is integrally formed by one-time heating and extrusion, is a truly 0-formaldehyde green plate, and does not cause harm to the human body, and is widely used in public places such as kindergartens, hospitals, offices, office buildings, shopping malls, homes, KTVs, and the like. In use scenarios such as hospitals, office buildings, laboratories, and shopping malls, there are situations such as placement of large heavy objects and collision, and the impact resistance of the plate is often required to be high.

[0003] Acrylonitrile-butadiene-styrene copolymer, namely ABS resin, has excellent impact resistance, heat resistance, and low-temperature resistance, and also has characteristics such as easy processing, stable product size, good surface gloss, and the like, and can be easily painted, colored, and subjected to secondary processing such as surface metal spraying, electroplating, welding, hot pressing, and bonding, and is widely used in industrial fields such as machinery, automobiles, electronics and electrical appliances, instruments and meters, textiles, and construction, and is an engineering plastic with a wide range of uses.

[0004] An ABS plate and a preparation method thereof are disclosed in Chinese Patent Application No. CN201210011934.6. The ABS plate is made of the following raw materials in parts by weight: matt ABS 50-60 parts, high-heat-resistant ABS 15-20 parts, ABS toughening agent 10-15 parts, ABS heat-resistant modifier 4-8 parts, matt agent 4-6 parts, antioxidant 0.6-1.2 parts, light stabilizer 0.4-0.8 parts, heat stabilizer 0.6-0.8 parts, processing aid 1.0-1.5 parts, color powder 1-1.2 parts, and mineral oil 0.4-0.5 parts. The application also provides a preparation method of the ABS plate. The prepared plate has good matt effect, good anti-aging performance, long service life, and high heat resistance. The application obtains the matt ABS plate by adding the ABS toughening agent and other modifiers. Although the application modifies the existing ABS material, the obtained plate is a transparent plate and does not have the characteristics of the stone-plastic plate. Therefore, the application does not disclose how to fill more inorganic calcium fillers in the ABS plate to make the plate have the high-impact characteristics of the stone-plastic plate.

[0005] A composite wallboard and a preparation method thereof are disclosed in Chinese patent application No. CN201410629521.3. The composite wallboard is composed of an inner polyurethane core material and an outer plastic-wood composite material structure. The plastic-wood structure material is formed by blending, extruding modified wood powder, maleic anhydride grafted plastic particles, calcium stearate, activated basic magnesium sulfate whiskers, ABS high glue powder, white oil, and an antioxidant. The polyurethane core material is formed by injection foaming isocyanate and combined polyether. The combined polyether is formed by mixing polyester polyol, polyether polyol, silicone oil, OP-10, water, and a composite catalyst. The composite wallboard has high rigidity and is not prone to warping and deformation, and can be used to make non-permanent houses for parking lots, construction sites, holiday villages, and unit gate guards. In this application, a wooden board for temporary houses is prepared, and the main raw materials are wooden materials and other plastic modification reagents. Although ABS high glue powder and calcium stearate are mentioned, their roles are not disclosed, and the main raw material is wood. It is not explained how to achieve better combination of ABS and calcium powder to obtain a high-impact stone plastic board.

[0006] Chinese patent application No. CN202010725836.3 discloses a SPC stone plastic floor material, which includes: 100 parts by weight of PVC resin; 220-260 parts by weight of heavy calcium carbonate; 40-80 parts by weight of nano calcium carbonate; 2-4 parts by weight of stearic acid; 8-12 parts by weight of impact modifier; and 4-8 parts by weight of color masterbatch. The SPC stone plastic floor has better mechanical properties and lower dimensional deformation rate. The application points out that the mechanical properties of the SPC stone plastic floor are not satisfactory due to the adverse interface effect between the PVC resin and the heavy calcium powder. The adverse effect can be improved by adding color masterbatch and nano calcium carbonate together, but the application only improves the tensile strength of the stone plastic board, and does not explain the impact strength of the board.

[0007] A Chinese patent with the application number CN201811139203.3 discloses a stone plastic SPC composite floor and a preparation method thereof, belonging to the technical field of high polymer materials. The floor is prepared by using the following raw materials: ABS resin, heavy calcium carbonate, nano calcium carbonate, nano aluminum oxide, PVC calcium-zinc composite stabilizer, TG-60 triglyceride, PE wax, acrylic ester polymer ACR, resin type chlorinated polyethylene CPE, impact resistant PP copolymer, super dispersant, and back material. The formula of the stone plastic SPC composite floor fully plays the advantages of the raw materials and effectively improves the comprehensive performance of the stone plastic SPC floor. Although it is pointed out in the application that the floor prepared by using ABS resin and calcium powder as the main raw materials has good strength and toughness, the stone plastic board obtained by the application does not have high impact resistance, but only makes it better adapt to cutting, milling and other processing technologies.

[0008] In summary, the poor impact resistance of PVC board is mainly due to its brittleness, temperature sensitivity, notch sensitivity, and control problems in the processing process. Poor impact resistance means that the board is prone to breakage under impact during use, especially at low temperatures, and the brittleness is particularly prominent, limiting the application range. Most of the ABS boards on the market are used in the refrigerator and automobile fields. In order to effectively reduce the fuel consumption of automobiles and reduce CO2 emissions and promote the green development of the automobile industry, calcium powder is not added, and the cost of pure ABS board is high, which is not suitable for the home decoration market. In order to improve the impact resistance of the board, it is usually necessary to add impact modifiers or add materials with good impact resistance. Under the condition of controlling the cost, how to make the board prepared by using ABS copolymer and calcium powder as the main raw materials have good impact resistance becomes a technical problem to be solved in the field. SUMMARY

[0009] In view of the poor impact resistance of SPC stone plastic board due to the brittleness, temperature sensitivity, notch sensitivity, and control problems in the processing process of PVC material, the first object of the present application is to provide a high impact board, which uses chloroethylene-butadiene-styrene-acrylonitrile copolymer as the main raw material in the raw material. By controlling the proportion relationship between the raw materials, the heat resistance, stability, and especially the impact resistance of the obtained board can be greatly improved.

[0010] The second object of the present application is to provide a preparation method of a high impact board, which controls the mixing temperature and mixing and turning time, so that crosslinking reaction occurs between the raw materials, and the impact resistance of the obtained stone plastic board is better than that of pure PVC board.

[0011] The technical solution adopted by the present application to solve the technical problem is:

[0012] A kind of high impact plate, raw materials include the following mass fraction of each component: vinyl chloride-butadiene-styrene-acrylonitrile copolymer 100~120 parts, calcium powder 50~150 parts, plasticizer 15~35 parts, antioxidant 0.2~0.8 parts, stabilizer 1.5~5 parts, processing aid 5~15 parts.

[0013] Control the proportion between several raw materials, wherein vinyl chloride-butadiene-styrene-acrylonitrile copolymer should account for 42% of the total weight of all raw materials, after chemical crosslinking and physical blending reaction, the mechanical properties of vinyl chloride-butadiene-styrene-acrylonitrile copolymer are significantly improved, and its phase structure not only depends on the particle size of PB rubber particles, crosslinking degree and grafting rate of SAN copolymer, but also depends on the compatibility between grafted SAN copolymer and PVC resin. The obtained plate has good heat resistance, stability, and especially the impact resistance is greatly improved.

[0014] Wherein, the particle size of the calcium powder is 200-400 mesh, and the purity of the calcium powder is that the mass percentage content of calcium carbonate is ≥90%. Limiting the particle size of the calcium powder and the mass percentage content of calcium carbonate in it can make the filling and dispersion of the calcium powder more uniform and the filling effect better. And it can further control the melt torque in the processing process. Too high or too low torque is not conducive to production and processing.

[0015] Further, the plasticizer is dioctyl phthalate or epoxy soybean oil, and the antioxidant is antioxidant 1076 and / or antioxidant 168. The high polymer powder generated by the reaction of the raw materials needs to be dried at a temperature of 100-120 DEG C. At such a high temperature, the powdered high polymer is extremely sensitive to oxidation. Limiting the types of plasticizer and antioxidant can effectively disperse in the powder, make the performance of the product better, and avoid the performance reduction in the drying stage.

[0016] Further, the stabilizer is calcium-zinc composite stabilizer and / or organic tin stabilizer, and the processing aid is stearic acid and / or chlorinated polyethylene. The selection of the stabilizer and processing aid can be environment-friendly and further control the production cost.

[0017] A preparation method of a high impact plate, comprising the following steps:

[0018] S1, mixing: the above raw materials are put into a mixing machine for high and low temperature mixing, the high temperature mixing temperature of the mixing machine is 100-120 DEG C, the low temperature mixing temperature is 30-60 DEG C, and the mixing time is 5-15 min, to obtain a mixture.

[0019] S2, mixing: the mixture is sent into a mixing machine for heating and mixing, and the hammering and turning in the mixing machine is carried out, wherein the hammering and turning time is 5-8 min, the mixing temperature is 110-140 DEG C, to obtain a melt.

[0020] S3, milling: the above molten material is sent to a mill for milling, the milling temperature is 175-195℃, and a milled material is obtained.

[0021] S4, calendering: the above milled material is sent to a calender, and a sheet is obtained after being rolled by rollers at a temperature of 190-200℃.

[0022] S5, cooling and pulling out: the above sheet is pulled out by a cooling roller, and a high-impact plate is obtained.

[0023] The preparation process of the present application is not a simple mixing and stirring process of materials, but a chemical cross-linking reaction of different components and amounts in the formula, especially vinyl chloride-butadiene-styrene-acrylonitrile, to improve the mechanical properties of the material. The obtained copolymer can improve the melt strength and draw ratio of the material through high and low temperature mixing. Under the pushing of the high-speed rotating stirring paddle, the material spreads sharply along the inner wall of the mixer and falls from the center of the mixer, forming a vortex motion. Under the shearing action generated by the mutual impact and friction of the material, the stirring paddle and the inner wall of the mixer, the material is transformed from solid, single-phase, non-uniform state to multi-phase, uniform state, and part of gel state. With the continuous rise of the temperature of the material, the copolymer particles and other components continuously penetrate each other, and the particle surface gradually adsorbs stabilizers, processing aids and the like. DETAILED DESCRIPTION

[0024] In order to make the purpose, technical scheme and advantages of the embodiments of the present application more clear, the technical scheme in the embodiments of the present application will be clearly and completely described below. If the specific conditions are not specified in the embodiments, the conventional conditions or the conditions recommended by the manufacturer are used. If the reagents or instruments used are not specified by the manufacturer, they are all conventional products that can be purchased on the market.

[0025] It should be noted that the embodiments in the present application and the features in the embodiments can be combined with each other without conflict.

[0026] Embodiment 1

[0027] S1, mixing: according to the production raw material formula amount shown in Table 1, each raw material is taken, and the above raw materials are put into a mixer for high and low temperature mixing. The high temperature mixing temperature of the above mixer is 100℃, the low temperature mixing temperature is 50℃, the mixing time is 8min, and a mixed material is obtained. The specific selection of the raw materials is shown in Tables 2-3.

[0028] S2, banburying: the above mixed material is sent to a banburying machine for heating and banburying. The hammering and turning time in the banburying machine is 5min, the banburying temperature is 130℃, and a molten material is obtained.

[0029] S3, Milling: the above molten material is sent into a mill for milling, and the milling temperature is 190℃, to obtain a milled material.

[0030] S4, Calendering: the above milled material is sent into a calender, and after being rolled by rollers at a temperature of 200℃, a sheet with a thickness of 4mm is obtained.

[0031] S5, Cooling and pulling out: the above sheet is pulled out by a cooling roller, to obtain a high-impact plate.

[0032] The obtained plate is subjected to performance detection, and the results are shown in Table 4.

[0033] Examples 2-4

[0034] The implementation of Examples 2-4 is basically the same as that of Example 1, and the only difference is that the formula and quantity of the production raw materials are adjusted, and the specific conditions are shown in Tables 1-3.

[0035] The plate prepared in Examples 2-4 is subjected to performance detection, and the results are shown in Table 4.

[0036] Table 1 Formulation table of production raw materials of Examples 1-4

[0037] ABS copolymer Calcium powder Plasticizer Antioxidant Stabilizer Processing aid Example 1 110 110 28 0.6 3.5 8.0 Example 2 110 110 28 0.6 3.5 8.0 Example 3 110 110 28 0.6 3.5 8.0 Example 4 110 110 28 0.6 3.5 8.0

[0038] Table 2 Specific formulation table of antioxidants in Examples 1-4

[0039] Antioxidant 1076 Antioxidant 168 Example 1 0 0.6 Example 2 0.2 0.4 Example 3 0.4 0.2 Example 4 0.6 0

[0040] Table 3 Formulation table of other components in raw materials of Examples 1-4

[0041]

[0042] Table 4 Performance detection results table of high-impact plate in Examples 1-4

[0043]

[0044] As can be seen from Table 4, the new composite plate prepared by the method has stronger deformation resistance and stability, and the impact strength is as high as 9.79 KJ / m2, while the impact strength of ordinary stone-plastic plate is 4.0 KJ / m2, which significantly improves the toughness of existing stone-plastic plate, prolongs the service life of the plate, and can be well applied in the industries of home decoration, building decoration, outdoor door and window profile, etc.

[0045] The embodiments described above are only part of the embodiments of the present application, rather than all the embodiments. The detailed description of the embodiments of the present application is not intended to limit the scope of the application claimed, but only represents selected embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative labor fall within the scope of protection of the present application.

Claims

1. A high-impact sheet metal, characterized in that, The raw materials include the following components in parts by weight: 100-120 parts of vinyl chloride-butadiene-styrene-acrylonitrile copolymer, 50-150 parts of calcium powder, 15-35 parts of plasticizer, 0.2-0.8 parts of antioxidant, 1.5-5 parts of stabilizer, and 5-15 parts of processing aid.

2. The high-impact sheet metal according to claim 1, characterized in that, The calcium powder has a particle size of 200-400 mesh and a calcium carbonate content of ≥90% by mass.

3. The high-impact sheet metal according to claim 1, characterized in that, The plasticizer is dioctyl phthalate or epoxidized soybean oil.

4. The high-impact sheet metal according to claim 1, characterized in that, The antioxidant is antioxidant 1076 and / or antioxidant 168.

5. The high-impact sheet metal according to claim 1, characterized in that, The stabilizer is a calcium-zinc composite stabilizer and / or an organotin stabilizer.

6. The high-impact sheet metal according to claim 1, characterized in that, The processing aid is stearic acid and / or chlorinated polyethylene.

7. A method for preparing a high-impact sheet metal as described in claim 1, characterized in that, Includes the following steps: S1. Mixing: The raw materials are put into a mixer and mixed at high and low temperatures. The high temperature mixing temperature of the mixer is 100-120°C, the low temperature mixing temperature is 30-60°C, and the mixing time is 5-15 minutes to obtain a mixture. S2. Internal mixing: The mixture is fed into an internal mixer for heating and internal mixing. The material is turned over in the internal mixer for 5 to 8 minutes and the mixing temperature is 110 to 140°C to obtain a melt. S3. Open milling: The molten material is fed into an open mill for open milling at a temperature of 175-195°C to obtain the open milled material. S4. Calendering: The open mill material is fed into a calender and calendered by rollers at a temperature of 190-200°C to obtain a sheet. S5. Cooling and pulling out the material: The sheet is pulled out by cooling rollers to obtain a high-impact sheet.

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