PC / ABS composite material and preparation method thereof

Abstract

The invention relates to a PC / ABS composite material and a preparation method thereof, and belongs to the technical field of composite materials. The PC / ABS composite material is prepared from ABS plastic, PC plastic, glass fibers, an initiator, zinc borate, an ultraviolet light absorber, an antioxidant and a flame-retardant compatilizer as raw materials, the flame-retardant compatilizer with a double-bond structure and an aldehyde group structure is prepared firstly, the ABS plastic is modified in the presence of the initiator, and the modified ABS plastic is obtained; according to the present invention, the modified ABS plastic can perform the aldolization reaction with the hydroxyl group in the PC plastic to form the chemical crosslinking, such that the compatibility between the modified ABS plastic and the PC plastic is effectively improved, and the phase separation problem existing in the direct blending of the ABS plastic and the PC plastic is solved; the mechanical property of the composite material is improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of composite materials, and specifically relates to a PC / ABS composite material and a preparation method thereof. Background Art

[0002] PC / ABS composite material, also known as PC / ABS alloy, blending PC and ABS can combine the heat resistance and impact resistance of PC with the processability and cost advantages of ABS, forming an alloy material with excellent comprehensive performance, which has a wide range of applications in the fields of automotive interiors, electronic enclosures, communication equipment, etc. The main existing problem of PC / ABS alloy is that there is a large difference in solubility between the two. PC is partially compatible with SAN in ABS, but incompatible with PB therein. This difference in solubility leads to a weakening of the interfacial bonding force between ABS and PC, prone to phase separation problems, and as the proportion of ABS in the alloy increases, this phenomenon will be further aggravated.

[0003] Both PC and ABS are combustible materials. To improve the flame retardant performance of the finished composite material, a flame retardant must be added to the raw materials. Halogen flame retardants have the advantages of low addition amount and stable flame retardant effect, but they release harmful fumes during combustion and are not suitable for use in the field of automotive interiors. Phosphate flame retardants do not release halogens, are safe and environmentally friendly, but have poor flame retardant effects. To achieve good flame retardant effects, a high addition amount of additives is required, and a large amount of phosphate flame retardants may damage the interfacial bonding performance between polymers and greatly reduce the impact resistance of the material. To solve the above problems, the present invention prepares a flame retardant compatibilizer to improve the compatibility between PC and ABS, and through compounding with zinc borate, reduces the addition amount of flame retardant components. Summary of the Invention

[0004] The purpose of the present invention is to provide a PC / ABS composite material and a preparation method thereof to solve the problems mentioned in the above background art.

[0005] The purpose of the present invention can be achieved by the following technical solutions: A PC / ABS composite material contains the following raw materials in parts by mass: 30 - 40 parts of ABS plastic, 60 - 70 parts of PC plastic, 10 - 18 parts of glass fiber, 0.3 - 1.2 parts of initiator, 1 - 5 parts of zinc borate, 1 - 3 parts of ultraviolet absorber, 0.4 - 1.6 parts of antioxidant, and 6 - 12 parts of flame retardant compatibilizer.

[0006] Further, the initiator is one or a mixture of more than one of diethylbenzene peroxide propyl, benzoyl peroxide, and azobisisobutyronitrile.

[0007] Further, the ultraviolet absorber is one or a mixture of more than one of UV-P, UV-531, and UV-1164.

[0008] Further, the antioxidant is one or a mixture of antioxidants 1010, 1098, and B900.

[0009] Further, the flame retardant compatibilizer is prepared by the following steps: Step 1: Mix a benzaldehyde derivative, glycidyl methacrylate, and absolute ethanol in a three-necked flask, install a condenser and a thermometer, turn on magnetic stirring, and react at a temperature of 40 - 80°C for 2 - 6 h. After the reaction, rotary evaporate to remove the solvent, wash the remaining solid with deionized water, and dry to obtain the compatibilizer; Step 2: Mix the compatibilizer, tetrahydrofuran, and triethylamine in a three-necked flask, turn on magnetic stirring, then add a mixed solution of carbon tetrachloride and diethyl phosphite dropwise to the three-necked flask. After the dropwise addition, react at a temperature of 20 - 60°C for 2 - 8 h. After the reaction, filter to remove triethylamine hydrochloride, then rotary evaporate to remove the solvent, wash the remaining solid with deionized water, and dry to obtain the flame retardant compatibilizer.

[0010] Further, the benzaldehyde derivative is one of o-aminobenzaldehyde, m-aminobenzaldehyde, and p-aminobenzaldehyde.

[0011] Further, by mass parts, the dosage ratio of the benzaldehyde derivative, glycidyl methacrylate, and absolute ethanol used in Step 1 is 12.1 - 14.6: 11.4 - 14.2: 40 - 160.

[0012] Further, by mass parts, the dosage ratio of the compatibilizer, tetrahydrofuran, triethylamine, carbon tetrachloride, and diethyl phosphite used in Step 2 is 18 - 24: 50 - 180: 10 - 16: 12.4 - 17.8: 9.6 - 13.8.

[0013] A preparation method of a PC / ABS composite material includes the following steps: The first step: Weigh each raw material by mass parts; The second step: Mix ABS plastic, an initiator, and the flame retardant compatibilizer and add them to a twin-screw extruder for co-extrusion to obtain modified ABS plastic; The third step: Mix the modified ABS plastic, PC plastic, glass fiber, zinc borate, ultraviolet absorber, and antioxidant and add them to a twin-screw extruder for co-extrusion to obtain the PC / ABS composite material.

[0014] Further, in the second step, the melting and extrusion temperature of the modified ABS is 190 - 220°C.

[0015] Further, in the third step, the melting and extrusion temperature of the PC / ABS composite material is 240 - 260°C.

[0016] The modified ABS plastic of the present invention contains aldehyde groups, which can undergo acetalization reactions with the free hydroxyl groups in PC plastic to form chemical bonds, strengthening the bonding ability between the modified ABS plastic and PC plastic, and diffusing through their chain segments into their respective corresponding homopolymer phases, thereby enhancing the interaction between the modified ABS plastic and PC plastic. The reaction mechanism is as follows:

[0017] Advantages of the present invention: The present invention uses a benzaldehyde derivative with an amino group and glycidyl methacrylate as raw materials. An epoxy ring-opening reaction occurs between the amino group of the benzaldehyde derivative and the epoxy group of glycidyl methacrylate to obtain a compatibilizer. Then, carbon tetrachloride and diethyl phosphite are used to prepare diethylphosphoryl chloride through the Atherton-Todd reaction. A flame-retardant compatibilizer with a phosphate group is obtained through a nucleophilic substitution reaction between the hydroxyl group and imino group of the compatibilizer and diethylphosphoryl chloride. The flame-retardant compatibilizer of the present invention contains long-chain double bonds and can be grafted onto the molecular chain of ABS plastic under the action of an initiator to modify the ABS plastic, improving the compatibility between the modified ABS plastic and PC plastic, solving the phase separation problem existing in the direct blending of ABS plastic and PC plastic, and improving the tensile properties and impact resistance of the prepared composite material.

[0018] The flame-retardant compatibilizer of the present invention has a phosphate group and has good flame retardancy. By grafting it into the modified ABS plastic, the flame retardancy of the composite material can be effectively improved. The polarity difference between small-molecule phosphate flame retardants and polymer plastics is relatively large. Direct blending may cause interfacial defects in the composite material, forming unevenly dispersed particles and reducing the mechanical properties of the composite material. The present invention introduces flame-retardant components by grafting, which can effectively improve the problem that the mechanical properties of the material are affected by excessive addition of phosphate flame retardants and inhibit the migration of flame-retardant components, making the prepared composite material have flame-retardant persistence. Specific embodiments

[0019] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts fall within the scope of protection of the present invention. Example 1

[0020] A PC / ABS composite material includes the following raw materials: 30 parts of ABS plastic, 70 parts of PC plastic, 10 parts of glass fiber, 0.3 parts of initiator, 1 part of zinc borate, 1 part of ultraviolet absorber, 0.4 parts of antioxidant, and 6 parts of flame-retardant compatibilizer.

[0021] Among them, the initiator is diethylbenzene peroxide propylene, the ultraviolet absorber is UV-P, the antioxidant is antioxidant 1010, and the flame retardant compatibilizer is prepared by the following steps: Step 1: By mass, mix 12.1 parts of benzaldehyde derivative, 11.4 parts of glycidyl methacrylate, and 40 parts of absolute ethanol in a three-necked flask, install a condenser and a thermometer, turn on magnetic stirring, and react at a temperature of 40 °C for 6 h. After the reaction is completed, rotary evaporate to remove the solvent, wash the remaining solid with deionized water and then dry to obtain the compatibilizer; Step 2: By mass, mix 18 parts of the compatibilizer, 50 parts of tetrahydrofuran, and 10 parts of triethylamine in a three-necked flask, turn on magnetic stirring, and then dropwise add a mixed solution of 12.4 parts of carbon tetrachloride and 9.6 parts of diethyl phosphite to the three-necked flask. After the dropping is completed, react at a temperature of 20 °C for 8 h. After the reaction is completed, filter to remove triethylamine hydrochloride, then rotary evaporate to remove the solvent, wash the remaining solid with deionized water and then dry to obtain the flame retardant compatibilizer.

[0022] A preparation method of a PC / ABS composite material includes the following steps: The first step: Weigh each raw material by mass; The second step: Mix ABS plastic, initiator, and flame retardant compatibilizer and add them to a twin-screw extruder for blending, and extrude at a temperature of 190 °C to obtain modified ABS plastic; The third step: Mix the modified ABS plastic, PC plastic, glass fiber, zinc borate, ultraviolet absorber, and antioxidant and add them to a twin-screw extruder for blending, and extrude at a temperature of 240 °C to obtain the PC / ABS composite material. Example 2

[0023] A PC / ABS composite material includes the following raw materials: 35 parts of ABS plastic, 65 parts of PC plastic, 14 parts of glass fiber, 0.75 part of initiator, 3 parts of zinc borate, 2 parts of ultraviolet absorber, 1 part of antioxidant, and 9 parts of flame retardant compatibilizer.

[0024] Among them, the initiator is benzoyl peroxide, the ultraviolet absorber is UV-531, the antioxidant is antioxidant 1098, and the flame retardant compatibilizer is prepared by the following steps: Step 1: By mass, mix 13.3 parts of benzaldehyde derivative, 12.8 parts of glycidyl methacrylate, and 100 parts of absolute ethanol in a three-necked flask, install a condenser and a thermometer, turn on magnetic stirring, and react at a temperature of 60 °C for 4 h. After the reaction is completed, rotary evaporate to remove the solvent, wash the remaining solid with deionized water and then dry to obtain the compatibilizer; Step 2: Weigh 21 parts by mass of a compatibilizer, 115 parts of tetrahydrofuran, and 13 parts of triethylamine into a three-necked flask. Start magnetic stirring, and then add dropwise a mixed solution of 15.1 parts of carbon tetrachloride and 12.7 parts of diethyl phosphite to the three-necked flask. After the addition is complete, react at 40 °C for 5 h. After the reaction ends, filter off triethylamine hydrochloride by suction, and then remove the solvent by rotary evaporation. The remaining solid is washed with deionized water and dried to obtain a flame-retardant compatibilizer.

[0025] A preparation method of a PC / ABS composite material comprises the following steps: The first step: Weigh each raw material by mass parts; The second step: Mix ABS plastic, an initiator, and a flame-retardant compatibilizer and add them to a twin-screw extruder for blending, and extrude at 205 °C to obtain modified ABS plastic; The third step: Mix the modified ABS plastic, PC plastic, glass fiber, zinc borate, ultraviolet absorber, and antioxidant and add them to a twin-screw extruder for blending, and extrude at 250 °C to obtain a PC / ABS composite material. Example 3

[0026] A PC / ABS composite material comprises the following raw materials: 40 parts of ABS plastic, 60 parts of PC plastic, 18 parts of glass fiber, 1.2 parts of an initiator, 5 parts of zinc borate, 3 parts of an ultraviolet absorber, 1.6 parts of an antioxidant, and 12 parts of a flame-retardant compatibilizer.

[0027] Among them, the initiator is azobisisobutyronitrile, the ultraviolet absorber is UV-1164, the antioxidant is antioxidant B900, and the flame-retardant compatibilizer is prepared by the following steps: Step 1: Weigh 14.6 parts by mass of a benzaldehyde derivative, 14.2 parts of glycidyl methacrylate, and 160 parts of absolute ethanol into a three-necked flask, install a condenser and a thermometer, start magnetic stirring, and react at 80 °C for 2 h. After the reaction ends, remove the solvent by rotary evaporation. The remaining solid is washed with deionized water and dried to obtain a compatibilizer; Step 2: Weigh 24 parts by mass of the compatibilizer, 180 parts of tetrahydrofuran, and 16 parts of triethylamine into a three-necked flask. Start magnetic stirring, and then add dropwise a mixed solution of 17.8 parts of carbon tetrachloride and 13.8 parts of diethyl phosphite to the three-necked flask. After the addition is complete, react at 60 °C for 2 h. After the reaction ends, filter off triethylamine hydrochloride by suction, and then remove the solvent by rotary evaporation. The remaining solid is washed with deionized water and dried to obtain a flame-retardant compatibilizer.

[0028] A preparation method of a PC / ABS composite material comprises the following steps: The first step: Weigh each raw material by mass parts; Step 2: Mix ABS plastic, initiator, and flame retardant compatibilizer, add them to a twin-screw extruder for blending, and extrude at a temperature of 220 °C to obtain modified ABS plastic; Step 3: Mix the modified ABS plastic, PC plastic, glass fiber, zinc borate, ultraviolet absorber, and antioxidant, add them to a twin-screw extruder for blending, and extrude at a temperature of 260 °C to obtain a PC / ABS composite material.

[0029] Comparative Example 1 A PC / ABS composite material includes the following raw materials: 40 parts of ABS plastic, 60 parts of PC plastic, 18 parts of glass fiber, 5 parts of zinc borate, 3 parts of ultraviolet absorber, and 1.6 parts of antioxidant.

[0030] Among them, the ultraviolet absorber is UV-1164, and the antioxidant is antioxidant B900.

[0031] A preparation method of a PC / ABS composite material includes the following steps: Step 1: Weigh each raw material according to the mass parts; Step 2: Mix the ABS plastic, PC plastic, glass fiber, zinc borate, ultraviolet absorber, and antioxidant, add them to a twin-screw extruder for blending, and extrude at a temperature of 260 °C to obtain a PC / ABS composite material.

[0032] Comparative Example 2 A PC / ABS composite material includes the following raw materials: 40 parts of ABS plastic, 60 parts of PC plastic, 18 parts of glass fiber, 5 parts of zinc borate, 3 parts of ultraviolet absorber, 1.6 parts of antioxidant, and 12 parts of flame retardant.

[0033] Among them, the ultraviolet absorber is UV-1164, the antioxidant is antioxidant B900, and the flame retardant is diethyl ethylphosphonate: A preparation method of a PC / ABS composite material includes the following steps: Step 1: Weigh each raw material according to the mass parts; Step 2: Mix the ABS plastic and the flame retardant, add them to a twin-screw extruder for blending, and extrude at a temperature of 220 °C to obtain modified ABS plastic; Step 3: Mix the modified ABS plastic, PC plastic, glass fiber, zinc borate, ultraviolet absorber, and antioxidant, add them to a twin-screw extruder for blending, and extrude at a temperature of 260 °C to obtain a PC / ABS composite material.

[0034] Experimental Example 1 The PC / ABS composites prepared in Examples 1-3 and Comparative Examples 1-2 were subjected to performance tests. Referring to ASTM D-638, the tensile properties of each component composite were tested. Referring to ASTM D-256, the notched impact strength was tested. Referring to ASTM D-2836, the limiting oxygen index was tested. The test results are shown in Table 1: Table 1 As can be seen from Table 1, the tensile strength and notched impact strength of the PC / ABS composites in Examples 1-3 are superior to those in Comparative Examples 1-2, indicating that the addition of the flame retardant compatibilizer of the present invention can effectively improve the mechanical properties of the composite material and enable the composite material to have good flame retardant properties. Comparative Example 2 is a control experiment in which a flame retardant is used to replace the flame retardant compatibilizer of the present invention. It can be seen that although the conventional flame retardant can slightly increase the limiting oxygen index of the composite material, adding a large amount of flame retardant in a blending manner will cause a significant decrease in the tensile strength and notched impact strength of the material.

[0035] The above provides a detailed introduction to a PC / ABS composite material and its preparation method of the present invention. Specific examples are used in this article to elaborate on the principle and implementation manner of the present invention. The description of the above examples is only used to help understand the method and its core idea of the present invention, including the best mode, and also enables any person skilled in the art to practice the present invention. It should be noted that for those of ordinary skill in the art, several improvements and modifications can be made to the present invention without departing from the principle of the present invention. In particular, as long as there is no structural conflict, the various features in the embodiments disclosed in the present invention can be combined with each other in any way. The exhaustive description of these combinations is omitted in this specification only for the sake of saving space and resources. Therefore, the present invention is not limited to the specific embodiments disclosed in the text, but includes all technical solutions falling within the scope of the claims.

Claims

1. A PC / ABS composite material, characterized in that, It comprises the following raw materials: The raw materials in the following parts by mass: 30-40 parts of ABS plastic, 60-70 parts of PC plastic, 10-18 parts of glass fiber, 0.3-1.2 parts of initiator, 1-5 parts of zinc borate, 1-3 parts of ultraviolet absorber, 0.4-1.6 parts of antioxidant, 6-12 parts of flame retardant compatibilizer; Among them, the flame retardant compatibilizer is prepared by the following steps: Mix benzaldehyde derivative and glycidyl methacrylate, dissolve them with absolute ethanol, control the temperature at 40-80 °C for reaction to obtain a compatibilizer, then dissolve the compatibilizer and triethylamine with tetrahydrofuran, and then add a mixed solution of carbon tetrachloride and diethyl phosphite to the system, and then control the temperature at 20-60 °C for reaction to obtain a flame retardant compatibilizer.

2. The PC / ABS composite material according to claim 1, characterized in that, The benzaldehyde derivative is one of o-aminobenzaldehyde, m-aminobenzaldehyde, and p-aminobenzaldehyde.

3. A PC / ABS composite material according to claim 1, characterized in that, By mass, the dosage ratio of benzaldehyde derivative to glycidyl methacrylate is 12.1-14.6:11.4-14.

2.

4. A PC / ABS composite material according to claim 1, characterized in that, By mass, the dosage ratio of compatibilizer, triethylamine, carbon tetrachloride, and diethyl phosphite is 18-24:10-16:12.4-17.8:9.6-13.

8.

5. A PC / ABS composite material according to claim 1, characterized in that, The initiator is one or a mixture of diethylbenzene peroxide propyl, benzoyl peroxide, and azodiisobutyronitrile.

6. The PC / ABS composite material according to claim 1, characterized in that, The ultraviolet absorber is one or a mixture of UV-P, UV-531, and UV-1164.

7. A PC / ABS composite material according to claim 1, wherein The antioxidant is one or a mixture of antioxidant 1010, antioxidant 1098, and antioxidant B900.

8. A method for preparing a PC / ABS composite material as described in any one of claims 1 to 7, characterized in that, It includes the following steps: Blend and extrude ABS plastic, initiator, and flame retardant compatibilizer to obtain modified ABS plastic, and then blend and extrude the modified ABS plastic with PC plastic, glass fiber, zinc borate, ultraviolet absorber, and antioxidant to obtain PC / ABS composite material.

9. The preparation method of a PC / ABS composite material according to claim 5, characterized in that, The melting and extrusion temperature of modified ABS is 190-220 °C.

10. A preparation method of a PC / ABS composite material according to claim 5, characterized in that, The melting and extrusion temperature of PC / ABS composite material is 240-260 °C.

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