CN109679314B - PC/ASA plastic for automotive interior parts and production process thereof - Google Patents
PC/ASA plastic for automotive interior parts and production process thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- B29B9/00—Making granules
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- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention discloses a PC/ASA plastic for automotive interior parts and a production process thereof, wherein the production process comprises the following steps: (1) weighing the raw materials in parts by weight; (2) mixing the raw materials by a high-speed mixer at the rotating speed of 300-900r/min for 5-15min to obtain a mixture; (3) and adding the mixture into a double-screw extruder for melt blending, and cooling, drying and dicing after extrusion to obtain the composite material. The PC/ASA plastic for the automotive upholstery takes the PC and the ASA as resin matrixes, and selects specific components and the proportion thereof, so that the production process is simple, easy to control and low in cost, and is suitable for industrial production; the PC/ASA plastic has excellent wear resistance, mechanical property and higher processing property, is easy to fill and form large-size molds, and can be used for various automotive upholsteries and the like.
Description
Technical Field
The invention belongs to the technical field of plastics, and particularly relates to a PC/ASA plastic for automotive interior parts and a production process thereof.
Background
The automobile interior decoration part mainly comprises a partition board of a carriage and door interior decoration. Parts such as instrument panel assembly, armrest, top plate, carpet, seat, etc., knitwear, felt, genuine leather, artificial leather, etc. In the manufacture of these devices for use in automobiles, it can be realized by the use of metal products, wooden products, and plastic products. The manufacturing price of the automobile can be increased in the use of the wooden products, the automobile is not favorable for sale and popularization, and the wooden products can be used in high-end automobile manufacturing. The manufacture of metal appliances is common in the manufacture of low-end automobiles, and the hand feeling and the comfort degree have certain limitations in use. The use of engineering plastics changes the current use situation of automobile manufacturing. The automobile steering wheel improves the use of automobile reflection and driving space, has the characteristic of low construction cost, and has high use cost performance and good comfort and flame retardance.
At present, engineering plastics are widely used in technical research and development, not only have the characteristic of light use, but also have lower use standards in the aspect of use cost, and have more audience groups in the society. In the application of the interior and exterior of the automobile, the use amount of engineering plastic materials is increasing in a stable environment, but in the design and manufacture of the automobile, the use of the plastic materials is an important index for measuring the manufacturing level, and the application status of the plastic materials in the interior and exterior of the automobile needs to be enhanced in the background of increasing environmental protection requirements and use quality.
Acrylic acid-styrene-acrylonitrile, english name: AcrylonitrileStyrene Acrylatecopolymer, abbreviated as ASA resin, is a ternary graft copolymer composed of acrylonitrile (acrylonitrite), Styrene (Styrene) and Acrylate (Acrylate), and is a non-crystalline polymer prepared by graft copolymerization of a polyacrylate as a main chain and acrylonitrile and Styrene monomers. ASA resin was industrially produced by BASF company in Germany at the earliest in 1962, and then Japanese Hitachi was also industrially produced, and at present, ASA resin is one of the major products of GE company in America.
The ASA is an opaque yellow amorphous polymer, is non-toxic and odorless, has the flame retardance reaching UL94HB grade, the tensile strength of 38-48MPa, the thermal deformation temperature of 85-105 ℃ under the load of 1.83MPa, can be used at the temperature of-20-75 ℃ for a long time, has better environmental stress crack resistance, and simultaneously resists oil, hydrochloric acid solution, olefine acid and alkali, but does not resist esters, ketones, aromatics, chlorides and alcohols.
Compared with ABS resin, ASA resin does not contain double bonds, so that it can resist degradation, aging and discoloration caused by ultraviolet irradiation, and can resist the action of thermal oxygen during processing to prevent decomposition and discoloration. Therefore, ASA plastic is one of the varieties with the best weather resistance in plastics, and the anti-aging performance of the ASA plastic is more than 10 times higher than that of ABS plastic. Due to the many advantages of ASA, ASA is now gradually becoming widely used in industrial applications. In the automobile field, the automobile interior trim parts with various shapes can be easily processed by an injection molding process, such as glove box inner cover plates, glove box hoppers, instrument panels, panel storage boxes and the like.
The Polycarbonate (PC) has the best impact toughness among thermoplastic resins, good dimensional stability and good heat resistance, can be used for a long time at the temperature of-60-120 ℃, and has the heat distortion temperature of 130-140 ℃, the glass transition temperature of 149 ℃ and the thermal decomposition temperature of more than 310 ℃. The polycarbonate has the advantages of small polarity, low water absorption, small shrinkage, high dimensional accuracy, light stability and good weather resistance. However, polycarbonate is less resistant to solvents, in particular to alkali, and is not resistant to abrasion.
Disclosure of Invention
The invention provides a PC/ASA plastic for automotive upholstery and a production process thereof in order to solve the problems in the prior art, and aims to solve the problem that the performance of a PC/ASA alloy material in the prior art cannot meet the requirements.
The invention is realized by the following steps:
a production process of PC/ASA plastic for automotive upholsteries comprises the following steps:
(1) weighing the following raw materials in parts by weight: 75-85 parts of polycarbonate, 15-25 parts of acrylonitrile-styrene-acrylate graft copolymer, 1-4 parts of compatilizer, 0.8-1.8 parts of lubricant, 0.3-0.9 part of antioxidant and 0.2-0.7 part of light stabilizer;
(2) mixing the raw materials by a high-speed mixer at the rotating speed of 300-900r/min for 5-15min to obtain a mixture;
(3) adding the mixture into a double-screw extruder for melt blending, wherein the temperature of a first zone is 195-plus 205 ℃, the temperature of a second zone is 205-plus 215 ℃, the temperature of a third zone is 215-plus 225 ℃, the temperature of a fourth zone is 225-plus 235 ℃, the temperature of a fifth zone is 235-plus 245 ℃, the temperature of a sixth zone is 235-plus 245 ℃, the temperature of a seventh zone is 245-plus 255 ℃, the temperature of an eighth zone is 245-plus 255 ℃, the temperature of a ninth zone is 240-plus 250 ℃, and the rotating speed of a screw is 200-plus 300r/min, and cooling, drying and pelletizing are carried out after extrusion to obtain the composite material.
The light stabilizer is at least one selected from bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate and a light stabilizer UV-944. The Light stabilizer (Light stabilizer) is an additive of high molecular products (such as plastics, rubber, paint, synthetic fiber), which can shield or absorb the energy of ultraviolet ray, quench singlet oxygen and decompose hydroperoxide into inactive substances, so that the high molecular polymer can eliminate or slow down the possibility of photochemical reaction under the irradiation of Light, and prevent or delay the process of photoaging, thereby achieving the purpose of prolonging the service life of the high molecular polymer products.
The compatilizer is at least one of maleic anhydride grafted ABS, St/MAH-g-MMA grafted copolymer and MAH-g-peroxide modified SAN. Further, the compatibilizer consists of 35-45 wt% St/MAH-g-MMA graft copolymer and 55-65 wt% MAH-g-peroxide modified SAN. The compatibilizer is also called a compatibilizer, and refers to an assistant for promoting two incompatible polymers to be combined together by virtue of intermolecular bonding force so as to obtain a stable blend, and is referred to as a high molecular compatibilizer. The compatilizer is understood as a surfactant in thermodynamic essence, but the compatilizer used in a polymer alloy system generally has higher molecular weight, and after the compatilizer is added into an incompatible polymer system and mixed at a certain temperature, the compatilizer is limited on the interface between two polymers to play the roles of reducing the interfacial tension, increasing the thickness of an interfacial layer and reducing the size of dispersed particles, so that the system finally forms a thermodynamically stable phase structure with the characteristics of macroscopic uniform microscopic phase separation.
The preparation method of the MAH-g-peroxidation modified SAN comprises the following steps: dissolving 95-105g of acrylonitrile-styrene-methacrylic acid polymer in 950-1050, N-dimethylformamide, cooling to 0 ℃ by using an ice water bath, slowly adding 27.4-27.8g of thionyl chloride by using a constant-pressure dropping funnel under the stirring of 100-300r/min at the speed of 0.01-0.05g/s, keeping the reaction system at the temperature of 5-15 ℃ for reaction for 1 hour after the thionyl chloride is added, slowly adding a mixed solution of 19-20g of sodium bicarbonate and 14-16g of tert-butyl hydrogen peroxide water solution with the mass fraction of 65-75%, wherein the adding speed of the mixed solution is 0.01-0.05g/s, keeping the reaction system at the temperature of 5-15 ℃ for standing for 10-15 hours after the mixed solution is added to obtain a reaction solution, repeatedly precipitating the reaction solution with methanol, filtering, and drying to obtain peroxide modified SAN; performing peroxidation modification on SAN and MAH according to a mass ratio of 1: (0.2-0.3) mixing for 5-15min by a high-speed mixer at the rotating speed of 300-900r/min to obtain a premix; adding the premix into a double-screw extruder for melt blending, wherein the temperature of a first zone is 195-plus 205 ℃, the temperature of a second zone is 205-plus 215 ℃, the temperature of a third zone is 215-plus 225 ℃, the temperature of a fourth zone is 225-plus 235 ℃, the temperature of a fifth zone is 235-plus 245 ℃, the temperature of a sixth zone is 235-plus 245 ℃, the temperature of a seventh zone is 245-plus 255 ℃, the temperature of an eighth zone is 245-plus 255 ℃, the temperature of a ninth zone is 240-plus 250 ℃, and the rotating speed of a screw is 200-plus 300r/min, and cooling, drying and pelletizing are carried out after extrusion to obtain the composite material.
The antioxidant is at least one of pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate and diethyl 3, 5-di-tert-butyl-4-hydroxybenzyl phosphate.
The lubricant is at least one selected from polyethylene wax, calcium stearate, stearic acid amide, zinc stearate and N, N-ethylene bis-stearic acid amide. The high polymer generally has a high viscosity after melting, and during processing, when the molten high polymer passes through a narrow slit, a sprue and the like, the polymer melt must generate friction with the surface of a processing machine, some friction is very unfavorable for processing the polymer, the friction reduces the fluidity of the melt, and the serious friction causes the surface of a film to be rough, lack of gloss or generate flow marks. For this reason, it is necessary to add an auxiliary agent for the purpose of improving lubricity, reducing friction, and reducing interfacial adhesion. This is the lubricant. Lubricants, in addition to improving flowability, may also function as melt accelerators, antiblock and antistatic agents, slip agents, and the like.
Further, the lubricant is modified polyethylene wax. The preparation method of the modified polyethylene wax comprises the following steps: polyethylene wax, maleic anhydride, acrylamide and graphene oxide are mixed according to the mass ratio of 1: (0.015-0.025): (0.003-0.009): (0.002-0.007) is added into a reaction kettle, heated and melted under the protection of nitrogen, added with di-tert-butyl peroxide with the mass of 0.2-0.7 percent of polyethylene wax, heated to 150 ℃ and 170 ℃, stirred and reacted for 2-5h at the rotating speed of 30-90r/min, cooled and discharged, thus obtaining the polyethylene wax.
The PC/ASA plastic for the automotive upholstery is prepared by adopting the production process.
The PC/ASA plastic for the automotive upholstery takes the PC and the ASA as resin matrixes, and selects specific components and the proportion thereof, so that the production process is simple, easy to control and low in cost, and is suitable for industrial production; the PC/ASA plastic has excellent wear resistance, mechanical property and higher processing property, is easy to fill and form large-size molds, and can be used for various automotive upholsteries and the like.
Detailed Description
The raw materials used in the examples were as follows:
acrylonitrile-styrene-methacrylic acid polymer is supplied by japanese UMG corporation, model number: S601N.
Polycarbonate (PC) was supplied by korean LG chemistry, brand: GP1000 LS.
Acrylonitrile-styrene-acrylate graft copolymer (ASA) was provided by korean LG chemistry under the brand number: LI-913.
N, N-dimethylformamide, CAS No.: 68-12-2.
Thionyl chloride, CAS number: 7719-09-7.
T-butyl hydroperoxide, CAS number: 75-91-2.
MAH, i.e., maleic anhydride, CAS number: 108-31-6.
The polyethylene wax is the polyethylene wax granular wax provided by a synthetic plastic additive factory in Jiangyun markets, and has the molecular weight of 2400-2800.
Acrylamide, CAS No.: 79-06-1.
Graphene oxide, provided by the islandau technologies ltd, beijing, debko, thickness: 0.55-1.2 nm, diameter: 0.5-3 μm, number of layers: 1-5 layers, color: amber in color.
Di-tert-butyl peroxide, CAS No.: 110-05-4.
Maleic anhydride grafted ABS was supplied by plastic science and technology Co., Ltd, available in Dongguan city, under the trade designation: GR-6001A.
Pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate, CAS number: 6683-19-8.
Light stabilizer UV-944, CAS number: 70624-18-9.
St/MAH-g-MMA graft copolymer was prepared as shown in example 1 in Chinese patent application No. 201410282352.0.
Example 1
The production process of the PC/ASA plastic for the automotive interior trim part comprises the following steps:
(1) weighing the following raw materials in parts by weight: 80 parts of polycarbonate, 20 parts of acrylonitrile-styrene-acrylate graft copolymer, 3 parts of compatilizer, 1.2 parts of lubricant, 0.5 part of antioxidant and 0.4 part of light stabilizer;
(2) mixing the raw materials for 8min at a rotating speed of 600r/min by using a high-speed mixer to obtain a mixture;
(3) adding the mixture into a double-screw extruder for melt blending, wherein the diameter of a screw of the extruder is 35mm, and the length-diameter ratio of the screw of the extruder is 32; the temperature of the first zone is 200 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 220 ℃, the temperature of the fourth zone is 230 ℃, the temperature of the fifth zone is 240 ℃, the temperature of the sixth zone is 240 ℃, the temperature of the seventh zone is 250 ℃, the temperature of the eighth zone is 250 ℃, the temperature of the ninth zone is 245 ℃, the rotating speed of a screw is 240r/min, the extruded materials are cooled by water, and then are dried and cut by 60 ℃ hot air, so that the PC/ASA plastic for the automotive upholstery is obtained.
The light stabilizer is a light stabilizer UV-944.
The compatilizer is maleic anhydride grafted ABS.
The antioxidant is pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate.
The lubricant is modified polyethylene wax. The preparation method of the modified polyethylene wax comprises the following steps: polyethylene wax, maleic anhydride, acrylamide and graphene oxide are mixed according to the mass ratio of 1: 0.02: 0.007: 0.005 is added into a reaction kettle, heated and melted under the protection of nitrogen, added with di-tert-butyl peroxide accounting for 0.5 percent of the mass of the polyethylene wax, heated to 160 ℃, stirred and reacted for 3.5 hours at the rotating speed of 60r/min, cooled and discharged, and the modified polyethylene wax is obtained.
Example 2
The production process of the PC/ASA plastic for the automotive interior trim part comprises the following steps:
(1) weighing the following raw materials in parts by weight: 80 parts of polycarbonate, 20 parts of acrylonitrile-styrene-acrylate graft copolymer, 3 parts of compatilizer, 1.2 parts of lubricant, 0.5 part of antioxidant and 0.4 part of light stabilizer;
(2) mixing the raw materials for 8min at a rotating speed of 600r/min by using a high-speed mixer to obtain a mixture;
(3) adding the mixture into a double-screw extruder for melt blending, wherein the diameter of a screw of the extruder is 35mm, and the length-diameter ratio of the screw of the extruder is 32; the temperature of the first zone is 200 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 220 ℃, the temperature of the fourth zone is 230 ℃, the temperature of the fifth zone is 240 ℃, the temperature of the sixth zone is 240 ℃, the temperature of the seventh zone is 250 ℃, the temperature of the eighth zone is 250 ℃, the temperature of the ninth zone is 245 ℃, the rotating speed of a screw is 240r/min, the extruded materials are cooled by water, and then are dried and cut by 60 ℃ hot air, so that the PC/ASA plastic for the automotive upholstery is obtained.
The light stabilizer is a light stabilizer UV-944.
The compatilizer is MAH-g-peroxide modified SAN.
The preparation method of the MAH-g-peroxidation modified SAN comprises the following steps: dissolving 100g of acrylonitrile-styrene-methacrylic acid polymer in 1000g N, N-dimethylformamide, cooling to 0 ℃ by using an ice water bath, slowly adding 27.6g of thionyl chloride by using a constant-pressure dropping funnel under the stirring of 150r/min, wherein the adding speed of the thionyl chloride is 0.02g/s, keeping the reaction system at 10 ℃ for reacting for 1 hour after the thionyl chloride is added, slowly adding a mixed solution of 19.5g of sodium bicarbonate and 14.5g of 70% tert-butyl hydrogen peroxide solution by mass fraction, wherein the adding speed of the mixed solution is 0.02g/s, keeping the reaction system at 10 ℃ for standing for 12 hours after the mixed solution is added to obtain a reaction solution, repeatedly precipitating the reaction solution by using methanol, performing suction filtration by using a 0.22 mu m polytetrafluoroethylene filter membrane, drying a filter cake to constant weight at 50 ℃, obtaining SAN decorated by peroxidation; performing peroxidation modification on SAN and MAH according to a mass ratio of 1: 0.25 mixing for 8min by a high-speed mixer at the rotating speed of 600r/min to obtain premix; adding the premix into a double-screw extruder for melt blending, wherein the diameter of a screw of the extruder is 35mm, and the length-diameter ratio of the screw of the extruder is 32; the temperature of the first zone is 200 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 220 ℃, the temperature of the fourth zone is 230 ℃, the temperature of the fifth zone is 240 ℃, the temperature of the sixth zone is 240 ℃, the temperature of the seventh zone is 250 ℃, the temperature of the eighth zone is 250 ℃, the temperature of the ninth zone is 245 ℃, the rotating speed of a screw is 240r/min, the mixture is extruded, cooled by water, dried by hot air at 60 ℃ and cut into particles, and the MAH-g-peroxide modified SAN is obtained.
The antioxidant is pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate.
The lubricant is modified polyethylene wax. The preparation method of the modified polyethylene wax comprises the following steps: polyethylene wax, maleic anhydride, acrylamide and graphene oxide are mixed according to the mass ratio of 1: 0.02: 0.007: 0.005 is added into a reaction kettle, heated and melted under the protection of nitrogen, added with di-tert-butyl peroxide accounting for 0.5 percent of the mass of the polyethylene wax, heated to 160 ℃, stirred and reacted for 3.5 hours at the rotating speed of 60r/min, cooled and discharged, and the modified polyethylene wax is obtained.
Example 3
The production process of the PC/ASA plastic for the automotive interior trim part comprises the following steps:
(1) weighing the following raw materials in parts by weight: 80 parts of polycarbonate, 20 parts of acrylonitrile-styrene-acrylate graft copolymer, 3 parts of compatilizer, 1.2 parts of lubricant, 0.5 part of antioxidant and 0.4 part of light stabilizer;
(2) mixing the raw materials for 8min at a rotating speed of 600r/min by using a high-speed mixer to obtain a mixture;
(3) adding the mixture into a double-screw extruder for melt blending, wherein the diameter of a screw of the extruder is 35mm, and the length-diameter ratio of the screw of the extruder is 32; the temperature of the first zone is 200 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 220 ℃, the temperature of the fourth zone is 230 ℃, the temperature of the fifth zone is 240 ℃, the temperature of the sixth zone is 240 ℃, the temperature of the seventh zone is 250 ℃, the temperature of the eighth zone is 250 ℃, the temperature of the ninth zone is 245 ℃, the rotating speed of a screw is 240r/min, the extruded materials are cooled by water, and then are dried and cut by 60 ℃ hot air, so that the PC/ASA plastic for the automotive upholstery is obtained.
The light stabilizer is a light stabilizer UV-944.
The compatilizer is MAH-g-peroxide modified SAN.
The preparation method of the MAH-g-peroxidation modified SAN comprises the following steps: dissolving 100g of acrylonitrile-styrene-methacrylic acid polymer in 1000g N, N-dimethylformamide, cooling to 0 ℃ by using an ice water bath, slowly adding 27.6g of thionyl chloride by using a constant-pressure dropping funnel under the stirring of 150r/min, wherein the adding speed of the thionyl chloride is 0.02g/s, keeping the reaction system at 10 ℃ for reacting for 1 hour after the thionyl chloride is added, slowly adding a mixed solution of 19.5g of sodium bicarbonate and 14.5g of 70% tert-butyl hydrogen peroxide solution by mass fraction, wherein the adding speed of the mixed solution is 0.02g/s, keeping the reaction system at 10 ℃ for standing for 12 hours after the mixed solution is added to obtain a reaction solution, repeatedly precipitating the reaction solution by using methanol, performing suction filtration by using a 0.22 mu m polytetrafluoroethylene filter membrane, drying a filter cake to constant weight at 50 ℃, obtaining SAN decorated by peroxidation; performing peroxidation modification on SAN and MAH according to a mass ratio of 1: 0.25 mixing for 8min by a high-speed mixer at the rotating speed of 600r/min to obtain premix; adding the premix into a double-screw extruder for melt blending, wherein the diameter of a screw of the extruder is 35mm, and the length-diameter ratio of the screw of the extruder is 32; the temperature of the first zone is 200 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 220 ℃, the temperature of the fourth zone is 230 ℃, the temperature of the fifth zone is 240 ℃, the temperature of the sixth zone is 240 ℃, the temperature of the seventh zone is 250 ℃, the temperature of the eighth zone is 250 ℃, the temperature of the ninth zone is 245 ℃, the rotating speed of a screw is 240r/min, the mixture is extruded, cooled by water, dried by hot air at 60 ℃ and cut into particles, and the MAH-g-peroxide modified SAN is obtained.
The antioxidant is pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate.
The lubricant is polyethylene wax.
Example 4
The production process of the PC/ASA plastic for the automotive interior trim part comprises the following steps:
(1) weighing the following raw materials in parts by weight: 80 parts of polycarbonate, 20 parts of acrylonitrile-styrene-acrylate graft copolymer, 3 parts of compatilizer, 1.2 parts of lubricant, 0.5 part of antioxidant and 0.4 part of light stabilizer;
(2) mixing the raw materials for 8min at a rotating speed of 600r/min by using a high-speed mixer to obtain a mixture;
(3) adding the mixture into a double-screw extruder for melt blending, wherein the diameter of a screw of the extruder is 35mm, and the length-diameter ratio of the screw of the extruder is 32; the temperature of the first zone is 200 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 220 ℃, the temperature of the fourth zone is 230 ℃, the temperature of the fifth zone is 240 ℃, the temperature of the sixth zone is 240 ℃, the temperature of the seventh zone is 250 ℃, the temperature of the eighth zone is 250 ℃, the temperature of the ninth zone is 245 ℃, the rotating speed of a screw is 240r/min, the extruded materials are cooled by water, and then are dried and cut by 60 ℃ hot air, so that the PC/ASA plastic for the automotive upholstery is obtained.
The light stabilizer is a light stabilizer UV-944.
The compatilizer is MAH-g-peroxide modified SAN.
The preparation method of the MAH-g-peroxidation modified SAN comprises the following steps: dissolving 100g of acrylonitrile-styrene-methacrylic acid polymer in 1000g N, N-dimethylformamide, cooling to 0 ℃ by using an ice water bath, slowly adding 27.6g of thionyl chloride by using a constant-pressure dropping funnel under the stirring of 150r/min, wherein the adding speed of the thionyl chloride is 0.02g/s, keeping the reaction system at 10 ℃ for reacting for 1 hour after the thionyl chloride is added, slowly adding a mixed solution of 19.5g of sodium bicarbonate and 14.5g of 70% tert-butyl hydrogen peroxide solution by mass fraction, wherein the adding speed of the mixed solution is 0.02g/s, keeping the reaction system at 10 ℃ for standing for 12 hours after the mixed solution is added to obtain a reaction solution, repeatedly precipitating the reaction solution by using methanol, performing suction filtration by using a 0.22 mu m polytetrafluoroethylene filter membrane, drying a filter cake to constant weight at 50 ℃, obtaining SAN decorated by peroxidation; performing peroxidation modification on SAN and MAH according to a mass ratio of 1: 0.25 mixing for 8min by a high-speed mixer at the rotating speed of 600r/min to obtain premix; adding the premix into a double-screw extruder for melt blending, wherein the diameter of a screw of the extruder is 35mm, and the length-diameter ratio of the screw of the extruder is 32; the temperature of the first zone is 200 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 220 ℃, the temperature of the fourth zone is 230 ℃, the temperature of the fifth zone is 240 ℃, the temperature of the sixth zone is 240 ℃, the temperature of the seventh zone is 250 ℃, the temperature of the eighth zone is 250 ℃, the temperature of the ninth zone is 245 ℃, the rotating speed of a screw is 240r/min, the mixture is extruded, cooled by water, dried by hot air at 60 ℃ and cut into particles, and the MAH-g-peroxide modified SAN is obtained.
The antioxidant is pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate.
The lubricant is modified polyethylene wax. The preparation method of the modified polyethylene wax comprises the following steps: polyethylene wax and maleic anhydride are mixed according to the mass ratio of 1: 0.02 is added into a reaction kettle, heated and melted under the protection of nitrogen, added with di-tert-butyl peroxide with the mass of 0.5 percent of that of the polyethylene wax, heated to 160 ℃, stirred and reacted for 3.5 hours at the rotating speed of 60r/min, cooled and discharged, and the modified polyethylene wax is obtained.
Example 5
The production process of the PC/ASA plastic for the automotive interior trim part comprises the following steps:
(1) weighing the following raw materials in parts by weight: 80 parts of polycarbonate, 20 parts of acrylonitrile-styrene-acrylate graft copolymer, 3 parts of compatilizer, 1.2 parts of lubricant, 0.5 part of antioxidant and 0.4 part of light stabilizer;
(2) mixing the raw materials for 8min at a rotating speed of 600r/min by using a high-speed mixer to obtain a mixture;
(3) adding the mixture into a double-screw extruder for melt blending, wherein the diameter of a screw of the extruder is 35mm, and the length-diameter ratio of the screw of the extruder is 32; the temperature of the first zone is 200 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 220 ℃, the temperature of the fourth zone is 230 ℃, the temperature of the fifth zone is 240 ℃, the temperature of the sixth zone is 240 ℃, the temperature of the seventh zone is 250 ℃, the temperature of the eighth zone is 250 ℃, the temperature of the ninth zone is 245 ℃, the rotating speed of a screw is 240r/min, the extruded materials are cooled by water, and then are dried and cut by 60 ℃ hot air, so that the PC/ASA plastic for the automotive upholstery is obtained.
The light stabilizer is a light stabilizer UV-944.
The compatilizer is St/MAH-g-MMA graft copolymer.
The preparation method of the MAH-g-peroxidation modified SAN comprises the following steps: dissolving 100g of acrylonitrile-styrene-methacrylic acid polymer in 1000g N, N-dimethylformamide, cooling to 0 ℃ by using an ice water bath, slowly adding 27.6g of thionyl chloride by using a constant-pressure dropping funnel under the stirring of 150r/min, wherein the adding speed of the thionyl chloride is 0.02g/s, keeping the reaction system at 10 ℃ for reacting for 1 hour after the thionyl chloride is added, slowly adding a mixed solution of 19.5g of sodium bicarbonate and 14.5g of 70% tert-butyl hydrogen peroxide solution by mass fraction, wherein the adding speed of the mixed solution is 0.02g/s, keeping the reaction system at 10 ℃ for standing for 12 hours after the mixed solution is added to obtain a reaction solution, repeatedly precipitating the reaction solution by using methanol, performing suction filtration by using a 0.22 mu m polytetrafluoroethylene filter membrane, drying a filter cake to constant weight at 50 ℃, obtaining SAN decorated by peroxidation; performing peroxidation modification on SAN and MAH according to a mass ratio of 1: 0.25 mixing for 8min by a high-speed mixer at the rotating speed of 600r/min to obtain premix; adding the premix into a double-screw extruder for melt blending, wherein the diameter of a screw of the extruder is 35mm, and the length-diameter ratio of the screw of the extruder is 32; the temperature of the first zone is 200 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 220 ℃, the temperature of the fourth zone is 230 ℃, the temperature of the fifth zone is 240 ℃, the temperature of the sixth zone is 240 ℃, the temperature of the seventh zone is 250 ℃, the temperature of the eighth zone is 250 ℃, the temperature of the ninth zone is 245 ℃, the rotating speed of a screw is 240r/min, the mixture is extruded, cooled by water, dried by hot air at 60 ℃ and cut into particles, and the MAH-g-peroxide modified SAN is obtained.
The antioxidant is pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate.
The lubricant is modified polyethylene wax. The preparation method of the modified polyethylene wax comprises the following steps: polyethylene wax, maleic anhydride, acrylamide and graphene oxide are mixed according to the mass ratio of 1: 0.02: 0.007: 0.005 is added into a reaction kettle, heated and melted under the protection of nitrogen, added with di-tert-butyl peroxide accounting for 0.5 percent of the mass of the polyethylene wax, heated to 160 ℃, stirred and reacted for 3.5 hours at the rotating speed of 60r/min, cooled and discharged, and the modified polyethylene wax is obtained.
Example 6
The production process of the PC/ASA plastic for the automotive interior trim part comprises the following steps:
(1) weighing the following raw materials in parts by weight: 80 parts of polycarbonate, 20 parts of acrylonitrile-styrene-acrylate graft copolymer, 3 parts of compatilizer, 1.2 parts of lubricant, 0.5 part of antioxidant and 0.4 part of light stabilizer;
(2) mixing the raw materials for 8min at a rotating speed of 600r/min by using a high-speed mixer to obtain a mixture;
(3) adding the mixture into a double-screw extruder for melt blending, wherein the diameter of a screw of the extruder is 35mm, and the length-diameter ratio of the screw of the extruder is 32; the temperature of the first zone is 200 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 220 ℃, the temperature of the fourth zone is 230 ℃, the temperature of the fifth zone is 240 ℃, the temperature of the sixth zone is 240 ℃, the temperature of the seventh zone is 250 ℃, the temperature of the eighth zone is 250 ℃, the temperature of the ninth zone is 245 ℃, the rotating speed of a screw is 240r/min, the extruded materials are cooled by water, and then are dried and cut by 60 ℃ hot air, so that the PC/ASA plastic for the automotive upholstery is obtained.
The light stabilizer is a light stabilizer UV-944.
The compatilizer is prepared by mixing 40 wt% of St/MAH-g-MMA graft copolymer and 60 wt% of MAH-g-peroxidation modified SAN.
The preparation method of the MAH-g-peroxidation modified SAN comprises the following steps: dissolving 100g of acrylonitrile-styrene-methacrylic acid polymer in 1000g N, N-dimethylformamide, cooling to 0 ℃ by using an ice water bath, slowly adding 27.6g of thionyl chloride by using a constant-pressure dropping funnel under the stirring of 150r/min, wherein the adding speed of the thionyl chloride is 0.02g/s, keeping the reaction system at 10 ℃ for reacting for 1 hour after the thionyl chloride is added, slowly adding a mixed solution of 19.5g of sodium bicarbonate and 14.5g of 70% tert-butyl hydrogen peroxide solution by mass fraction, wherein the adding speed of the mixed solution is 0.02g/s, keeping the reaction system at 10 ℃ for standing for 12 hours after the mixed solution is added to obtain a reaction solution, repeatedly precipitating the reaction solution by using methanol, performing suction filtration by using a 0.22 mu m polytetrafluoroethylene filter membrane, drying a filter cake to constant weight at 50 ℃, obtaining SAN decorated by peroxidation; performing peroxidation modification on SAN and MAH according to a mass ratio of 1: 0.25 mixing for 8min by a high-speed mixer at the rotating speed of 600r/min to obtain premix; adding the premix into a double-screw extruder for melt blending, wherein the diameter of a screw of the extruder is 35mm, and the length-diameter ratio of the screw of the extruder is 32; the temperature of the first zone is 200 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 220 ℃, the temperature of the fourth zone is 230 ℃, the temperature of the fifth zone is 240 ℃, the temperature of the sixth zone is 240 ℃, the temperature of the seventh zone is 250 ℃, the temperature of the eighth zone is 250 ℃, the temperature of the ninth zone is 245 ℃, the rotating speed of a screw is 240r/min, the mixture is extruded, cooled by water, dried by hot air at 60 ℃ and cut into particles, and the MAH-g-peroxide modified SAN is obtained.
The antioxidant is pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate.
The lubricant is modified polyethylene wax. The preparation method of the modified polyethylene wax comprises the following steps: polyethylene wax, maleic anhydride, acrylamide and graphene oxide are mixed according to the mass ratio of 1: 0.02: 0.007: 0.005 is added into a reaction kettle, heated and melted under the protection of nitrogen, added with di-tert-butyl peroxide accounting for 0.5 percent of the mass of the polyethylene wax, heated to 160 ℃, stirred and reacted for 3.5 hours at the rotating speed of 60r/min, cooled and discharged, and the modified polyethylene wax is obtained.
Test example 1
The performance of the automotive upholstery prepared in the examples was tested with PC/ASA plastic. The specific test results are shown in table 1.
And (3) testing the scratch resistance: reference test standard: ASTM D7027-2005, multi-finger scratch tester (Taber 710, Taber Inc., USA) has a scratch tip made of stainless steel with a diameter of 1mm, a test load of 15N, a scratch speed of 100mm/s and a scratch length of 100 mm. The scratch resistance was characterized by the average scratch width. The injection molding process comprises the following steps: the injection temperature is 260 ℃, the mold temperature is 85 ℃, the injection pressure is 10MPa, and the injection speed is 55cm3The specimen dimensions were 210mm by 140mm by 3mm, and the injection-molded specimens were used for the following tests.
And (3) testing the glossiness: reference is made to the standard ASTM D523-2014 Standard test method for specular gloss.
Notched impact strength: the test environment temperature was 23 ℃ according to ASTM D6110.
Table 1: test result table
The embodiments described above are presented to enable those skilled in the art to make and use the invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the embodiments described herein, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (8)
1. A production process of PC/ASA plastic for automotive interior parts is characterized by comprising the following steps:
(1) weighing the following raw materials in parts by weight: 75-85 parts of polycarbonate, 15-25 parts of acrylonitrile-styrene-acrylate graft copolymer, 1-4 parts of compatilizer, 0.8-1.8 parts of lubricant, 0.3-0.9 part of antioxidant and 0.2-0.7 part of light stabilizer;
(2) mixing the raw materials by a high-speed mixer at the rotating speed of 300-900r/min for 5-15min to obtain a mixture;
(3) adding the mixture into a double-screw extruder for melt blending, wherein the temperature of a first zone is 195-plus 205 ℃, the temperature of a second zone is 205-plus 215 ℃, the temperature of a third zone is 215-plus 225 ℃, the temperature of a fourth zone is 225-plus 235 ℃, the temperature of a fifth zone is 235-plus 245 ℃, the temperature of a sixth zone is 235-plus 245 ℃, the temperature of a seventh zone is 245-plus 255 ℃, the temperature of an eighth zone is 245-plus 255 ℃, the temperature of a ninth zone is 240-plus 250 ℃, and the rotating speed of a screw is 200-plus 300r/min, and cooling, drying and pelletizing are carried out after extrusion to obtain the composite material;
the compatilizer consists of 35-45 wt% of St/MAH-g-MMA graft copolymer and 55-65 wt% of MAH-g-peroxide modified SAN.
2. The process for producing a PC/ASA plastic for automotive upholsteries as claimed in claim 1, wherein: the light stabilizer is at least one selected from bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate and a light stabilizer UV-944.
3. The process for producing a PC/ASA plastic for automotive upholsteries as claimed in claim 1, wherein: the preparation method of the MAH-g-peroxidation modified SAN comprises the following steps: dissolving 95-105g of acrylonitrile-styrene-methacrylic acid polymer in 950-1050, N-dimethylformamide, cooling to 0 ℃ by using an ice water bath, slowly adding 27.4-27.8g of thionyl chloride by using a constant-pressure dropping funnel under the stirring of 100-300r/min at the speed of 0.01-0.05g/s, keeping the reaction system at the temperature of 5-15 ℃ for reaction for 1 hour after the thionyl chloride is added, slowly adding a mixed solution of 19-20g of sodium bicarbonate and 14-16g of tert-butyl hydrogen peroxide water solution with the mass fraction of 65-75%, wherein the adding speed of the mixed solution is 0.01-0.05g/s, keeping the reaction system at the temperature of 5-15 ℃ for standing for 10-15 hours after the mixed solution is added to obtain a reaction solution, repeatedly precipitating the reaction solution with methanol, filtering, and drying to obtain peroxide modified SAN; performing peroxidation modification on SAN and MAH according to a mass ratio of 1: (0.2-0.3) mixing for 5-15min by a high-speed mixer at the rotating speed of 300-900r/min to obtain a premix; adding the premix into a double-screw extruder for melt blending, wherein the temperature of a first zone is 195-plus 205 ℃, the temperature of a second zone is 205-plus 215 ℃, the temperature of a third zone is 215-plus 225 ℃, the temperature of a fourth zone is 225-plus 235 ℃, the temperature of a fifth zone is 235-plus 245 ℃, the temperature of a sixth zone is 235-plus 245 ℃, the temperature of a seventh zone is 245-plus 255 ℃, the temperature of an eighth zone is 245-plus 255 ℃, the temperature of a ninth zone is 240-plus 250 ℃, and the rotating speed of a screw is 200-plus 300r/min, and cooling, drying and pelletizing are carried out after extrusion to obtain the composite material.
4. The process for producing a PC/ASA plastic for automotive upholsteries as claimed in claim 1, wherein: the antioxidant is at least one of pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate and diethyl 3, 5-di-tert-butyl-4-hydroxybenzyl phosphate.
5. The process for producing a PC/ASA plastic for automotive upholsteries as claimed in claim 1, wherein: the lubricant is at least one selected from polyethylene wax, calcium stearate, stearic acid amide, zinc stearate and N, N-ethylene bis-stearic acid amide.
6. The process for producing a PC/ASA plastic for automotive upholsteries as claimed in claim 1, wherein: the lubricant is modified polyethylene wax.
7. The process for producing a PC/ASA plastic for automotive upholsteries as claimed in claim 6, wherein: the preparation method of the modified polyethylene wax comprises the following steps: polyethylene wax, maleic anhydride, acrylamide and graphene oxide are mixed according to the mass ratio of 1: (0.015-0.025): (0.003-0.009): (0.002-0.007) is added into a reaction kettle, heated and melted under the protection of nitrogen, added with di-tert-butyl peroxide with the mass of 0.2-0.7 percent of polyethylene wax, heated to 150 ℃ and 170 ℃, stirred and reacted for 2-5h at the rotating speed of 30-90r/min, cooled and discharged, thus obtaining the polyethylene wax.
8. A PC/ASA plastic for automotive interior parts, which is prepared by the production process of any one of claims 1 to 7.
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