High-performance ABS modified material and production process thereof

Abstract

The invention discloses a high-performance ABS (Acrylonitrile Butadiene Styrene) modified material and a production process thereof. The production process comprises the following steps: (1) preparing an active substance B; (2) modifying the active substance B to obtain a functional filler; (3) preparing a functional component by taking the functional filler as a core of a polymerization reaction; (4) preparing a copolymer C from an acrylonitrile monomer and a styrene monomer; and (5) mixing the functional component and the copolymer C for reaction, adding a lubricant, melting and mixing by using a double-screw extruder, extruding, and granulating to obtain the ABS modified material. The scheme belongs to the field of functional plastics, and the functional filler is modified and added into the preparation process of the high-performance ABS modified material in the form of a polymer core, so that the high-performance ABS modified material has higher oxidation resistance, electromagnetic shielding effect and mechanical property.

Description

Technical Field

[0001] The present invention relates to the field of functional plastics, and particularly to a high-performance ABS modified material and its production process. Background Art

[0002] ABS materials have high mechanical strength, high working temperature, can be processed by various methods such as injection molding and extrusion molding, and have high corrosion resistance. They are widely used in industries such as automobiles, electronics, toys, and household appliances. In terms of electromagnetic shielding, ABS is transformed into a functional plastic by adding conductive fillers (such as carbon black, carbon fiber, metal powder or metal fiber) to endow it with the ability to shield electromagnetic interference, and can be applied to electronic devices, the automotive industry, communication devices, household appliances, etc., which helps to reduce electromagnetic radiation and protect user health. However, the addition of conductive fillers easily leads to a reduction in its performance. When exposed to ultraviolet rays, high temperature or contact with acids / solvents for a long time, ABS will also undergo oxidative degradation, thermal aging or chemical corrosion, which will further lead to cracking and failure problems.

[0003] CN115109381 A discloses an ABS composite material with electromagnetic shielding effect and its preparation method. The ABS composite material with electromagnetic shielding effect contains the following components in parts by weight: 80 - 120 parts of ABS resin; 10 - 20 parts of glass fiber; 5 - 10 parts of electromagnetic shielding agent; 0.2 - 1 part of coupling agent; 1 - 3 parts of lubricant; the electromagnetic shielding agent is made of carbon nanotubes and tungsten powder. This invention makes the prepared ABS composite material have very excellent electromagnetic shielding effect by adding an electromagnetic shielding agent prepared by a new method. CN101812214A relates to an electromagnetic shielding material and its preparation method. The electromagnetic shielding material is prepared by mixing and heating and pre-treating ABS plastic and ABS plasticizer, then adding conductive carbon black, magnetic powder and carbon fiber, mixing evenly by a high-speed mixer, and then extruding into a twin-screw extruder, and granulating to obtain the electromagnetic shielding material of the present invention; it has a good anti-electromagnetic wave radiation effect and can be applied to the fields of electric power, wireless communication, household appliances and military. The above methods all focus on the electromagnetic shielding performance and do not consider the service and failure problems of ABS. Summary of the Invention

[0004] In order to solve the above problems, the present invention proposes a high-performance ABS modified material and its production process. By modifying functional fillers and adding them in the form of polymer cores to the preparation process of the high-performance ABS modified material, the high-performance ABS modified material has high antioxidant properties, electromagnetic shielding effect and mechanical properties.

[0005] To achieve the above object, the technical solution of the present invention is:

[0006] A production process of a high-performance ABS modified material, comprising the following steps:

[0007] Step (1): By weight, add 0.1 part to 1 part of tetrabutyl titanate into an ethanol aqueous solution with a mass concentration of 10% to 20%, and disperse evenly to obtain liquid A; take 10 parts to 20 parts of liquid A, add 10 parts to 20 parts of soft magnetic powder particles, then add hydrochloric acid to adjust the pH to 5 to 7, carry out hydrolysis reaction for 5h to 8h, dry, calcine at 550°C to 650°C for 1h to 2h, after cooling to room temperature, carry out heat preservation treatment at 120°C to 150°C for 0.5h to 1h, and disperse to obtain active substance B;

[0008] Step (2): By weight, add 10 parts to 20 parts of active substance B and 0.3 part to 0.5 part of silane coupling agent into 10 parts to 15 parts of an ethanol aqueous solution with a mass concentration of 10% to 20%, adjust the pH to 5 to 6 through carboxylic acid, stir for 30min to 60min, then carry out centrifugal separation to obtain the solid phase, dry to obtain the functional filler;

[0009] Step (3): By weight, disperse 3 parts to 5 parts of the functional filler in 30 parts to 40 parts of butadiene monomer in an emulsion, add 0.15 part to 0.5 part of initiator A, polymerize at 600r / min to 800r / min and 50°C to 80°C for 2h to 3h, then add 5 parts to 10 parts of styrene monomer and 5 parts to 10 parts of acrylonitrile monomer, add 0.05 part to 0.1 part of initiator B, and react at 400r / min to 800r / min and 60°C to 80°C for 5h to 10h to obtain the functional component;

[0010] Step (4): By weight, add 10 parts to 15 parts of acrylonitrile monomer and 15 parts to 20 parts of styrene monomer into 50 parts to 80 parts of an acetone solution with a mass concentration of 5% to 10%, add 0.1 part to 0.15 part of initiator C and 0.1 part to 0.3 part of emulsifier, and react at 600r / min to 800r / min and 65°C to 80°C for 4h to 6h to obtain copolymer C;

[0011] Step (5): By weight, mix 10 parts to 20 parts of the functional component and 15 parts to 30 parts of copolymer C, add 0.1 part to 0.3 part of demulsifier, react at 200r / min to 300r / min and 60°C to 80°C for 2h to 3h, then wash and dry, add 0.1 part to 1 part of lubricant, carry out melt mixing through a twin-screw extruder, and cut into pellets after extrusion to obtain the ABS modified material.

[0012] This solution has the following characteristics:

[0013] 1. This solution selects titanium dioxide-modified soft magnetic powder particles as functional fillers, which can not only play an electromagnetic shielding role but also have an antioxidant effect. Among them, the electromagnetic shielding is mainly achieved by the soft magnetic powder particles. The electromagnetic shielding ability of soft magnetic ferrites stems from their dual characteristics of both magnetic and dielectric media, with both magnetic loss mechanisms and electrical loss mechanisms, and they are particularly good at suppressing high-frequency magnetic field interference. Since the addition amount is not high and it is a soft magnetic material, it does not exhibit magnetism macroscopically; the antioxidant effect is mainly that during the process of step (1), after tetrabutyl titanate is hydrolyzed, titanium ions adhere to the surface of the soft magnetic powder particles. During the calcination process, titanium dioxide nanocrystals are formed on the surface of the soft magnetic powder particles. This part of the titanium dioxide crystals forms a heterojunction with the soft magnetic powder particles, namely active substance B. The oxidation band of ABS resin in the environment mainly focuses on the ultraviolet light region of 290 - 400 nm, while the maximum absorption wavelength of titanium dioxide is usually between 280 - 350 nm. The heterojunction formed in this solution can reduce the interfacial energy band gap, making the absorption of the heterojunction structure in the ultraviolet light band wider and enhancing the antioxidant ability of ABS.

[0014] 2. In this solution, in order to enable active substance B to be fully dispersed in the ABS modified material, active substance B was modified in step (2) to obtain functional fillers. During the modification process of this solution, the pH adjustment is achieved through carboxylic acid. Conventional modification adjusts the pH with hydrochloric acid, but due to the presence of chloride ions, it will bring problems such as difficult ABS processing, decreased mechanical properties, and poor weather resistance. Using carboxylic acid instead can make a small amount of carboxyl groups adhere to the surface of the functional fillers, which can enhance the interfacial compatibility between the functional fillers and butadiene monomers or polymers, reduce the activation energy of butadiene polymerization, which enables the nucleation of the polymerization reaction to mainly occur on the surface of the functional fillers, enabling the functional fillers to be coated by butadiene polymers, and then in step (3) and step (5), they are further wrapped and fully dispersed.

[0015] 3. In this solution, in step (3), a core-shell structured functional component with polybutadiene encapsulating the functional fillers as the core and styrene-acrylonitrile copolymer as the shell is first prepared. Further, copolymer C is prepared through step (4), and then copolymer C is polymerized with the functional component to obtain the ABS modified material. Such a preparation method is conducive to realizing the regulation of strength and toughness, and can better disperse the functional fillers, improving the overall uniformity. The stirring rate is used to control the reaction process and the polymer particle size in steps (3) and (4). The faster the stirring, the smaller the particle size.

[0016] Preferably, in step (1), the soft magnetic powder particles are soft magnetic ferrite powder particles; the average particle size of the soft magnetic ferrite powder particles is 1 μm to 2 μm.

[0017] Preferably, in step (2), the silane coupling agent is γ-aminopropyltriethoxysilane.

[0018] Preferably, in step (2), the carboxylic acid is one of formic acid, acetic acid, propionic acid, citric acid, and tartaric acid.

[0019] Preferably, in step (2), the rotation speed for stirring for 30 min to 60 min is 800 r / min to 1000 r / min.

[0020] Preferably, in step (3), the initiator A is a persulfate, and the initiator B is benzoyl peroxide.

[0021] Preferably, in step (4), the initiator C is azobisisobutyronitrile or azobisisobutyronitrile, and the emulsifier is sodium dodecylbenzenesulfonate.

[0022] Preferably, in step (5), the demulsifier is a polyether demulsifier or a quaternary ammonium salt demulsifier.

[0023] Preferably, in step (5), the drying temperature is 80°C - 120°C; the moisture ratio after drying is <0.1%.

[0024] Preferably, in step (5), the lubricant is one of zinc stearate, glyceryl trihydroxystearate, paraffin wax, or polyethylene wax.

[0025] This solution also proposes a high-performance ABS modified material prepared by the production process of the above high-performance ABS modified material.

[0026] Compared with the prior art, the advantages of this solution are as follows:

[0027] 1. A heterojunction composed of titanium dioxide / soft magnetic ferrite powder particles is prepared as a functional filler, obtaining good electromagnetic shielding effect and antioxidant performance.

[0028] 2. Technologically, through methods such as modification and stepwise polymerization, which are closely linked, the heterojunction composed of titanium dioxide / soft magnetic ferrite powder particles is well dispersed in the finished product, ensuring the stability of performance. Specific Embodiments

[0029] The following specific embodiments illustrate the implementation manners of the present invention. Those skilled in the art 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 of them. Based on the embodiments in the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the scope of protection of the present invention.

[0030] Example 1

[0031] A production process of a high-performance ABS modified material, comprising the following steps:

[0032] Step (1): By weight, add 0.5 parts of tetrabutyl titanate to an aqueous ethanol solution with a mass concentration of 10%, disperse evenly to obtain Solution A; take 15 parts of Solution A, add 15 parts of soft magnetic ferrite powder particles with an average particle size of 1.3 μm, then add hydrochloric acid to adjust the pH to 7, carry out hydrolysis reaction for 7 h, dry, calcine at 600 °C for 2 h, after cooling to room temperature, carry out heat preservation treatment at 140 °C for 0.5 h, and disperse to obtain active substance B;

[0033] Step (2): By weight, add 15 parts of active substance B and 0.4 parts of γ-aminopropyltriethoxysilane to 13 parts of an aqueous ethanol solution with a mass concentration of 10%, adjust the pH to 6 with formic acid, stir at 900 r / min for 60 min, then carry out centrifugal separation to obtain the solid phase, dry to obtain the functional filler;

[0034] Step (3): By weight, disperse 4 parts of the functional filler in 35 parts of butadiene monomer in an emulsion, add 0.3 parts of potassium persulfate, polymerize at 700 r / min and 70 °C for 2 h, then add 8 parts of styrene monomer and 6 parts of acrylonitrile monomer, and then add 0.08 parts of benzoyl peroxide, react at 600 r / min and 70 °C for 7 h to obtain the functional component;

[0035] Step (4): By weight, add 13 parts of acrylonitrile monomer and 18 parts of styrene monomer to 70 parts of an acetone solution with a mass concentration of 6%, add 0.13 parts of azobisisobutyronitrile and 0.2 parts of sodium dodecylbenzenesulfonate, react at 700 r / min and 65 °C - 80 °C for 5 h to obtain copolymer C;

[0036] Step (5): By weight, mix 15 parts of the functional component and 25 parts of copolymer C, add 0.2 parts of polyoxyethylene demulsifier, react at 250 r / min and 70 °C for 2 h, then wash and dry at 100 °C, the water specific gravity after drying < 0.1%, add 0.5 parts of zinc stearate, carry out melt mixing through a twin-screw extruder, pelletize after extrusion to obtain the ABS modified material.

[0037] Example 2

[0038] A production process of a high-performance ABS modified material, comprising the following steps:

[0039] Step (1): By weight, add 0.3 parts of tetrabutyl titanate to an aqueous ethanol solution with a mass concentration of 17%, and disperse evenly to obtain Solution A; take 12 parts of Solution A, add 15 parts of soft magnetic ferrite powder particles with an average particle size of 1.1 μm, then add hydrochloric acid to adjust the pH to 6, carry out hydrolysis reaction for 7 h, dry, calcine at 630 °C for 1 h, cool to room temperature, carry out heat preservation treatment at 130 °C for 1 h, and disperse to obtain active substance B;

[0040] Step (2): By weight, add 20 parts of active substance B and 0.5 parts of γ-aminopropyltriethoxysilane to 15 parts of an aqueous ethanol solution with a mass concentration of 15%, adjust the pH to 6 with propionic acid, stir at 800 r / min for 60 min, then carry out centrifugal separation to obtain the solid phase, dry to obtain the functional filler;

[0041] Step (3): By weight, disperse 5 parts of the functional filler in 30 parts of butadiene monomer in an emulsion, add 0.4 parts of potassium persulfate, polymerize at 600 r / min and 70 °C for 3 h, then add 10 parts of styrene monomer and 10 parts of acrylonitrile monomer, and then add 0.05 parts of benzoyl peroxide, react at 500 r / min and 80 °C for 8 h to obtain the functional component;

[0042] Step (4): By weight, add 10 parts of acrylonitrile monomer and 15 parts of styrene monomer to 50 parts of an acetone solution with a mass concentration of 10%, add 0.14 parts of azobisisobutyronitrile and 0.3 parts of sodium dodecylbenzenesulfonate, react at 800 r / min and 75 °C for 6 h to obtain copolymer C;

[0043] Step (5): By weight, mix 10 parts of the functional component and 15 parts of copolymer C, add 0.1 parts of polyoxyethylene demulsifier, react at 200 r / min and 80 °C for 3 h, then wash, dry at 120 °C, the moisture ratio after drying is <0.1%, add 0.6 parts of glyceryl trihydroxystearate, carry out melt mixing through a twin-screw extruder, and cut into pellets after extrusion to obtain the ABS modified material.

[0044] Example 3

[0045] A production process of a high-performance ABS modified material, comprising the following steps:

[0046] Step (1): By weight, add 0.8 parts of tetrabutyl titanate to an aqueous ethanol solution with a mass concentration of 20%, and disperse evenly to obtain Solution A; take 20 parts of Solution A, add 20 parts of soft magnetic ferrite powder particles with an average particle size of 1.6 μm, then add hydrochloric acid to adjust the pH to 7, carry out hydrolysis reaction for 8 h, dry, calcine at 650 °C for 2 h, cool to room temperature, carry out heat preservation treatment at 150 °C for 1 h, and disperse to obtain active substance B;

[0047] Step (2): By weight, add 10 to 20 parts of active substance B and 0.3 to 0.5 part of γ-aminopropyltriethoxysilane to 10 to 15 parts of an ethanol aqueous solution with a mass concentration of 10% to 20%. Adjust the pH to 5 with acetic acid. After stirring at 1000 r / min for 60 min, perform centrifugal separation to obtain a solid phase, and dry it to obtain a functional filler;

[0048] Step (3): By weight, disperse 5 parts of the functional filler in 40 parts of butadiene monomer in an emulsion. Add 0.5 part of potassium persulfate, and polymerize at 800 r / min and 75 °C for 3 h. Subsequently, add 10 parts of styrene monomer and 8 parts of acrylonitrile monomer, then add 0.08 part of benzoyl peroxide, and react at 700 r / min and 65 °C for 8 h to obtain a functional component;

[0049] Step (4): By weight, add 13 parts of acrylonitrile monomer and 18 parts of styrene monomer to 75 parts of an acetone solution with a mass concentration of 8%. Add 0.14 part of azobisisobutyronitrile and 0.3 part of sodium dodecylbenzenesulfonate, and react at 800 r / min and 80 °C for 6 h to obtain copolymer C;

[0050] Step (5): By weight, mix 20 parts of the functional component and 30 parts of copolymer C, add 0.3 part of a sulfuric acid methylated alkyl methyl quaternary ammonium salt demulsifier, and react at 300 r / min and 80 °C for 3 h. Subsequently, perform cleaning and drying at 120 °C. The water proportion after drying is <0.1%. Add 0.7 part of polyethylene wax, and perform melt mixing through a twin-screw extruder. After extrusion, pelletize to obtain an ABS modified material.

[0051] Comparative Example 1

[0052] The difference from Example 1 is that nano-titanium dioxide and soft magnetic ferrite powder particles are added respectively, specifically:

[0053] Step (1): By weight, disperse 4 parts of soft magnetic ferrite powder particles with an average particle size of 1.1 microns and 0.04 part of nano-titanium dioxide in 35 parts of butadiene monomer in an emulsion. Add 0.3 part of potassium persulfate, and polymerize at 700 r / min and 70 °C for 2 h. Subsequently, add 8 parts of styrene monomer and 6 parts of acrylonitrile monomer, then add 0.08 part of benzoyl peroxide, and react at 600 r / min and 70 °C for 7 h to obtain a functional component;

[0054] Step (2): By weight, add 13 parts of acrylonitrile monomer and 18 parts of styrene monomer to 70 parts of an acetone solution with a mass concentration of 6%. Add 0.13 part of azobisisobutyronitrile and 0.2 part of sodium dodecylbenzenesulfonate, and react at 700 r / min and 65 °C - 80 °C for 5 h to obtain copolymer C;

[0055] Step (3): Mix 15 parts of the functional component and 25 parts of copolymer C by weight, add 0.2 parts of polyoxyethylene demulsifier, react at 250 r / min and 70 °C for 2 h, then wash and dry at 100 °C. The moisture proportion after drying is <0.1%, add 0.5 parts of zinc stearate, melt and knead through a twin-screw extruder, pelletize after extrusion to obtain the ABS modified material.

[0056] Comparative Example 2

[0057] The difference from Example 1 is that the functional filler is not prepared, specifically:

[0058] A production process of a high-performance ABS modified material, comprising the following steps:

[0059] Step (1): Add 0.5 parts of tetrabutyl titanate to an aqueous ethanol solution with a mass concentration of 10% by weight, disperse evenly to obtain Solution A; take 15 parts of Solution A, add 15 parts of soft magnetic ferrite powder particles with an average particle size of 1.3 μm, then add hydrochloric acid to adjust the pH to 7, carry out hydrolysis reaction for 7 h, dry, calcine at 600 °C for 2 h, cool to room temperature, carry out heat preservation treatment at 140 °C for 0.5 h, and disperse to obtain the active substance B;

[0060] Step (2): Disperse 4 parts of the active substance B in 35 parts of butadiene monomer in emulsion, add 0.3 parts of potassium persulfate, polymerize at 700 r / min and 70 °C for 2 h, then add 8 parts of styrene monomer and 6 parts of acrylonitrile monomer, and then add 0.08 parts of benzoyl peroxide, react at 600 r / min and 70 °C for 7 h to obtain the functional component;

[0061] Step (3): Add 13 parts of acrylonitrile monomer and 18 parts of styrene monomer to 70 parts of an acetone solution with a mass concentration of 6% by weight, add 0.13 parts of azobisisobutyronitrile and 0.2 parts of sodium dodecylbenzenesulfonate, react at 700 r / min and 65 °C - 80 °C for 5 h to obtain copolymer C;

[0062] Step (4): Mix 15 parts of the functional component and 25 parts of copolymer C by weight, add 0.2 parts of polyoxyethylene demulsifier, react at 250 r / min and 70 °C for 2 h, then wash and dry at 100 °C. The moisture proportion after drying is <0.1%, add 0.5 parts of zinc stearate, melt and knead through a twin-screw extruder, pelletize after extrusion to obtain the ABS modified material.

[0063] Comparative Example 3

[0064] The difference from Example 1 is that the functional component is not prepared, specifically:

[0065] A production process of a high-performance ABS modified material, comprising the following steps:

[0066] Step (1): By weight, add 0.5 parts of tetrabutyl titanate to an ethanol aqueous solution with a mass concentration of 10%, disperse evenly to obtain solution A; take 15 parts of solution A, add 15 parts of soft ferrite powder particles with an average particle size of 1.3 μm, then add hydrochloric acid to adjust the pH to 7, carry out a hydrolysis reaction for 7 h, dry, calcine at 600 °C for 2 h, after cooling to room temperature, carry out a heat preservation treatment at 140 °C for 0.5 h, and disperse to obtain active substance B;

[0067] Step (2): By weight, add 15 parts of active substance B and 0.4 parts of γ-aminopropyltriethoxysilane to 13 parts of an ethanol aqueous solution with a mass concentration of 10%, adjust the pH to 6 with formic acid, stir at 900 r / min for 60 min, then carry out centrifugal separation to obtain a solid phase, dry to obtain a functional filler;

[0068] Step (3): By weight, add 13 parts of acrylonitrile monomer and 18 parts of styrene monomer to 70 parts of an acetone solution with a mass concentration of 6%, add 0.13 parts of azobisisobutyronitrile and 0.2 parts of sodium dodecylbenzenesulfonate, react at 700 r / min and 65 °C - 80 °C for 5 h to obtain copolymer C;

[0069] Step (4): By weight, mix 15 parts of the functional filler and 25 parts of copolymer C, add 0.2 parts of polyoxyethylene demulsifier, react at 250 r / min and 70 °C for 2 h, then wash, dry at 100 °C, the water specific gravity after drying < 0.1%, add 0.5 parts of zinc stearate, carry out melt mixing through a twin-screw extruder, pelletize after extrusion to obtain the ABS modified material.

[0070] Comparative Example 4

[0071] The difference from Example 1 is that the functional filler is directly incorporated into the ABS resin, specifically:

[0072] A production process of a high-performance ABS modified material, comprising the following steps:

[0073] Step (1): By weight, add 0.5 parts of tetrabutyl titanate to an ethanol aqueous solution with a mass concentration of 10%, disperse evenly to obtain solution A; take 15 parts of solution A, add 15 parts of soft ferrite powder particles with an average particle size of 1.3 μm, then add hydrochloric acid to adjust the pH to 7, carry out a hydrolysis reaction for 7 h, dry, calcine at 600 °C for 2 h, after cooling to room temperature, carry out a heat preservation treatment at 140 °C for 0.5 h, and disperse to obtain active substance B;

[0074] Step (2): By weight, add 15 parts of active substance B and 0.4 part of γ-aminopropyltriethoxysilane to 13 parts of an ethanol aqueous solution with a mass concentration of 10%. Adjust the pH to 6 with formic acid, stir at 900 r / min for 60 min, then perform centrifugal separation to obtain the solid phase, and dry it to obtain the functional filler;

[0075] Step (3): By weight, mix 5 parts of the functional filler and 25 parts of dry ABS particles, add 0.5 part of zinc stearate, and perform melt mixing through a twin-screw extruder. After extrusion, pelletize to obtain the ABS modified material.

[0076] Comparative Example 5

[0077] It is different from Example 1 in that the calcination temperature in Step (1) is too high, specifically:

[0078] A production process of a high-performance ABS modified material includes the following steps:

[0079] Step (1): By weight, add 0.5 part of tetrabutyl titanate to an ethanol aqueous solution with a mass concentration of 10%, and disperse it evenly to obtain Solution A; Take 15 parts of Solution A, add 15 parts of soft magnetic ferrite powder particles with an average particle size of 1.3 μm, then add hydrochloric acid to adjust the pH to 7, carry out a hydrolysis reaction for 7 h, dry it, calcine at 800 °C for 2 h, cool to room temperature, and then perform heat preservation treatment at 140 °C for 0.5 h and disperse to obtain active substance B;

[0080] Step (2): By weight, add 15 parts of active substance B and 0.4 part of γ-aminopropyltriethoxysilane to 13 parts of an ethanol aqueous solution with a mass concentration of 10%. Adjust the pH to 6 with formic acid, stir at 900 r / min for 60 min, then perform centrifugal separation to obtain the solid phase, and dry it to obtain the functional filler;

[0081] Step (3): By weight, disperse 4 parts of the functional filler in 35 parts of butadiene monomer in an emulsion, add 0.3 part of potassium persulfate, polymerize at 700 r / min and 70 °C for 2 h, then add 8 parts of styrene monomer and 6 parts of acrylonitrile monomer, and then add 0.08 part of benzoyl peroxide, and react at 600 r / min and 70 °C for 7 h to obtain the functional component;

[0082] Step (4): By weight, add 13 parts of acrylonitrile monomer and 18 parts of styrene monomer to 70 parts of an acetone solution with a mass concentration of 6%, add 0.13 part of azobisisobutyronitrile and 0.2 part of sodium dodecylbenzenesulfonate, and react at 700 r / min and 65 °C - 80 °C for 5 h to obtain copolymer C;

[0083] Step (5): Mix 15 parts of functional components and 25 parts of copolymer C by weight, add 0.2 parts of polyoxyethylene demulsifier, react at 250 r / min and 70 °C for 2 h, then wash and dry at 100 °C. The moisture proportion after drying is <0.1%, add 0.5 parts of zinc stearate, melt and knead through a twin-screw extruder, pelletize after extrusion to obtain the ABS modified material.

[0084] The products prepared in Examples 1-3 and Comparative Examples 1-5 were made into test specimens according to the following standards and relevant performance tests were carried out.

[0085] Refer to ASTM D638 to test the tensile strength (23 °C);

[0086] Refer to ASTM D790 to test the flexural modulus;

[0087] Refer to ASTM D256 to test the Izod notched impact strength (23 °C);

[0088] Use a surface resistance tester to test its surface resistance;

[0089] Refer to ASTM D4935 standard to test the electromagnetic shielding effect;

[0090] Place the specimen outdoors for 60 days and observe the color change

[0091] The specific test results are shown in Table 1.

[0092] Table 1

[0093]

[0094]

[0095] From the results analysis of Examples 1-3 and Comparative Examples 1-5, this solution can obtain better mechanical properties and electromagnetic shielding effects, and has better antioxidant properties.

[0096] The difference between Comparative Example 1 and Example 1 is that nano-titanium dioxide and soft magnetic ferrite powder particles are added respectively, that is, they are not added to the preparation of the ABS modified material in the form of a heterojunction structure. The heterojunction structure of this solution broadens the absorption range of ultraviolet light waves. At the same time, since the heterojunction is the junction of two substances, that is, the grain boundary, the resistance is large, which may lead to an increase in electrical loss, thereby improving the electromagnetic shielding effect. In addition, the soft magnetic ferrite powder particles are micron-sized and are directly mixed without modification, resulting in compatibility problems with ABS, while nano-titanium dioxide has dispersion problems, so the mechanical properties of Comparative Example 1 are also poor. The difference between Comparative Example 2 and Example 1 is that the functional filler is not prepared, and there are also dispersion and compatibility problems, resulting in poor mechanical properties.

[0097] The difference between Comparative Example 3 and Example 1 is that the functional component was not prepared. In Example 1 of this solution, the most important role of the presence of the functional component is also for dispersion. At the same time, when the soft magnetic ferrite powder particles absorb electromagnetic waves, magnetic domain deflection will occur. With the soft magnetic ferrite as the core of the functional component, the magnetic domain deflection may drive the movement of a small amount of ABS chains around the soft magnetic ferrite powder particles, which may increase the energy loss and improve the electromagnetic wave absorption ability. The soft magnetic ferrite powder particles in Comparative Example 3 do not have the core function, so the dispersibility is poor. Similarly, the difference between Comparative Example 4 and Example 1 is that the functional filler was directly incorporated into the ABS resin, and there are also problems with dispersibility.

[0098] The difference between Comparative Example 5 and Example 1 is that the calcination temperature in step (1) is too high. The too high calcination temperature in step (1) causes the nanoparticles of titanium dioxide to grow, and some titanium atoms diffuse into the grain boundaries of the soft magnetic ferrite, resulting in a higher coercivity of the soft magnetic ferrite, hindering the movement of magnetic domains. At the same time, the difference at the grain boundaries decreases, resulting in a smaller resistance, making the electromagnetic shielding effect worse.

Claims

1. A production process of high-performance ABS modified materials, characterized in that: The following steps are involved: Step (1): adding 0.1 to 1 part of tetrabutyl titanate to an ethanol aqueous solution with a mass concentration of 10% to 20% by weight, uniformly dispersing to obtain liquid A; taking 10 to 20 parts of liquid A, adding 10 to 20 parts of soft magnetic powder particles, then adding hydrochloric acid to adjust the pH to 5 to 7, hydrolyzing for 5 hours to 8 hours, drying, calcining at 550° C. to 650° C. for 1 hour to 2 hours, cooling to room temperature, heat-treating at 120° C. to 150° C. for 0.5 hours to 1 hour, dispersing, and obtaining active material B; Step (2): adding 10 to 20 parts of active material B and 0.3 to 0.5 parts of silane coupling agent to 10 to 15 parts of ethanol aqueous solution with a mass concentration of 10% to 20%, adjusting the pH to 5 to 6 with carboxylic acid, stirring at 800 to 1000 r / min for 30 to 60 minutes, centrifuging to obtain a solid phase, drying, and obtaining a functional filler; Step (3): by weight, 3 to 5 parts of functional filler are dispersed in 30 to 40 parts of butadiene monomer in an emulsion, 0.15 to 0.5 parts of initiator A are added, and polymerization is carried out at 600 r / min to 800 r / min and 50° C. to 80° C. for 2 h to 3 h, followed by addition of 5 to 10 parts of styrene monomer and 5 to 10 parts of acrylonitrile monomer, and then 0.05 to 0.1 parts of initiator B are added, and the reaction is carried out at 400 to 800 r / min and 60° C. to 80° C. for 5 h to 10 h to obtain a functional component; Step (4): adding 10 to 15 parts of acrylonitrile monomer and 15 to 20 parts of styrene monomer to 50 to 80 parts of acetone solution having a mass concentration of 5% to 10%, adding 0.1 to 0.15 parts of initiator C and 0.1 to 0.3 parts of emulsifier, reacting at 600 to 800 r / min and 65° C. to 80° C. for 4 to 6 hours to obtain copolymer C; Step (5): by weight, 10 to 20 parts of the functional component and 15 to 30 parts of the copolymer C are mixed, 0.1 to 0.3 parts of a demulsifier are added, and the mixture is reacted at 200 r / min to 300 r / min and 60° C. to 80° C. for 2 h to 3 h, followed by washing and drying, and 0.1 to 1 parts of a lubricant are added, and the mixture is melt-kneaded by a twin-screw extruder, extruded and pelletized to obtain an ABS modified material.

2. The production process of high-performance ABS modified material as claimed in claim 1, characterized in that: In step (1), the soft magnetic powder particles are soft ferrite powder particles; the average particle size of the soft ferrite powder particles is 1 μm to 2 μm.

3. The production process of high-performance ABS modified material as claimed in claim 1, characterized in that: In step (2), the silane coupling agent is γ-aminopropyltriethoxysilane.

4. The production process of high-performance ABS modified material as claimed in claim 1, characterized in that: In step (2), the carboxylic acid is one of formic acid, acetic acid, propionic acid, citric acid and tartaric acid.

5. The production process of high-performance ABS modified material as claimed in claim 1, characterized in that: In step (2), the average particle size of the functional filler is 0.5 μm to 1.5 μm.

6. The production process of high-performance ABS modified material according to claim 1, characterized in that: In step (3), the initiator A is persulfate, and the initiator B is benzoyl peroxide.

7. The production process of high-performance ABS modified material as claimed in claim 1, characterized in that: In step (4), the initiator C is azobisisobutyronitrile or azobisisobutyronitrile, and the emulsifier is sodium dodecylbenzene sulfonate.

8. The production process of high-performance ABS modified material as claimed in claim 1, characterized in that: In step (5), the demulsifier is a polyether or quaternary ammonium salt demulsifier; the lubricant is one of zinc stearate, trihydroxystearate, paraffin or polyethylene wax.

9. The production process of high-performance ABS modified material as claimed in claim 1, characterized in that: In step (5), the drying temperature is 80° C.-120° C.; the moisture content after drying is less than 0.1%.

10. A high-performance ABS modified material prepared by the production process of the high-performance ABS modified material according to any one of claims 1 to 9.

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