ABS composite material and preparation method thereof

Abstract

The invention discloses an ABS (Acrylonitrile Butadiene Styrene) composite material and a preparation method thereof, and belongs to the technical field of high polymer materials, and the ABS composite material comprises the following raw materials in parts by weight: 41-70 parts of ABS resin, 14-24 parts of a flame retardant, 4-10 parts of modified basalt fiber, 10-20 parts of mint fiber antibacterial master batch and 2.2-6 parts of other auxiliaries. According to the flame retardant, the brominated flame retardant, the antimony trioxide and the piperazine pyrophosphate are compounded and have a good synergistic effect on improving the flame retardance, and the modified basalt fibers can improve the screw torque of the material, avoid the screw cracking problem and improve the flame retardance of the material at the same time. In addition, the mint fiber antibacterial master batch is adopted, so that bacterium breeding can be effectively inhibited, and the antibacterial property of the ABS material is improved.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, and in particular to an ABS composite material and its preparation method. Background Technology

[0002] ABS (acrylonitrile-butadiene-styrene) is a non-crystalline polymer that possesses excellent mechanical properties, heat resistance, and moldability, as well as good surface gloss and colorability. As an important thermoplastic, ABS is widely used in home appliances, electronics, and the automotive industry.

[0003] However, ABS has an oxygen index of only 20%, making it a flammable resin. It continues to burn after being removed from the flame, releasing large amounts of dense smoke and toxic gases. This drawback limits its application range.

[0004] Secondly, ABS material exterior parts, such as air conditioners, washing machines, and small appliance shells, are prone to bacterial growth, which is detrimental to human health. In addition, the plastic parts of the appliance shells mentioned above often have screw posts due to the need for assembly. During the assembly process, screw cracking often occurs, causing the product to be unqualified and scrapped.

[0005] Therefore, improving the flame retardant and antibacterial properties of ABS and reducing screw cracking has become an urgent problem for the industry. Summary of the Invention

[0006] The purpose of this invention is to provide an ABS composite material to solve the problems of traditional ABS in the prior art, such as easy combustion, poor antibacterial properties, and easy cracking when screws are driven into place.

[0007] The present invention also aims to provide a method for preparing ABS composite materials, which are non-flammable, have good antibacterial properties, and are not easily cracked when screwed in.

[0008] In a first aspect, the present invention provides an ABS composite material comprising the following parts by weight of raw materials: 41-70 parts of ABS resin; 14-24 parts flame retardant; 4-10 parts of modified basalt fiber; Other additives: 2.2–6 parts; 10-20 parts of antibacterial masterbatch containing peppermint fiber; Flame retardants include brominated flame retardants in a mass ratio of (9-14):(3-6):(2-4), antimony trioxide, and piperazine pyrophosphate.

[0009] By adopting the above technical solutions, ABS, as the matrix material, provides basic skeletal support for composite materials with its unique structure and comprehensive properties as a non-crystalline copolymer, while achieving synergistic compatibility with functional components such as flame retardants, modified basalt fibers, and menthol fiber antibacterial masterbatches.

[0010] The flame retardant is a compound of brominated flame retardant, antimony trioxide, and piperazine pyrophosphate in a mass ratio of (9-14):(3-6):(2-4). These components work synergistically in both the gas and condensed phases to effectively improve the flame retardant properties of ABS materials. Specifically, the brominated flame retardant reacts with antimony trioxide to generate hydrogen bromide during combustion. Hydrogen bromide can capture active free radicals that propagate the combustion chain reaction, generating low-activity bromine free radicals such as antimony oxybromine and antimony bromide, thus slowing down or terminating combustion. Furthermore, hydrogen bromide is a dense and difficult-to-ignite gas. It not only dilutes oxygen in the air but also coats the material surface, replacing air and reducing the combustion rate or causing self-extinguishing.

[0011] Piperazine pyrophosphate mainly inhibits the combustion process under the dual action of the condensed phase and the gas phase. Specifically, the acidic substances produced by decomposition at high temperature are catalyzed into carbon, forming a dense carbon layer that is heat-insulating and oxygen-barrier; at the same time, it releases non-flammable gases to dilute the oxygen concentration and interrupts the chain reaction by capturing free radicals.

[0012] Basalt fiber is rich in hydroxyl groups on its surface, exhibiting strong polarity, while ABS resin is a weakly polar polymer. The significant difference in polarity between the two results in extremely weak interfacial bonding during mixing, easily leading to fiber agglomeration or interfacial voids. After modification with a silane coupling agent, the siloxane groups at one end of the coupling agent can undergo a condensation reaction with the hydroxyl groups on the basalt fiber surface, forming stable covalent bonds; the organic functional groups at the other end can form physical entanglement or weak chemical bonds with the styrene or butadiene segments of the ABS resin, preventing fiber agglomeration during mixing and ensuring uniform fiber dispersion within the ABS matrix. Furthermore, the modified basalt fiber possesses excellent mechanical strength, significantly improved interfacial bonding, and can effectively withstand external loads during screw tightening, dispersing localized stress. The rigidity of the modified basalt fiber synergistically complements the toughness of ABS, enhancing the tensile strength, flexural strength, and impact strength of the material, particularly improving the crack resistance in the screw stud region; it also exhibits a synergistic flame-retardant effect.

[0013] Peppermint fiber antibacterial masterbatch not only has good interfacial bonding with ABS resin, but also reinforces ABS materials, improving their mechanical strength and impact resistance. Importantly, it effectively inhibits bacterial growth, enhancing the antibacterial effect of ABS materials.

[0014] Adding 2.2 to 6 parts of other additives can maintain the long-term stability of the material by resisting oxidation and photoaging. In addition, it can help improve the flame retardant properties of ABS composites, optimize the processing effect, and work synergistically with the main components to ensure the functional integrity, durability and production feasibility of ABS composites.

[0015] Preferably, the brominated flame retardant includes one or more of the following: decabromodiphenyl ether, octabromodiphenyl ether, tetrabromobisphenol A, decabromodiphenyl ethane, brominated epoxy oligomers, polydecabromostyrene, and tri(tribromophenyl)cyanurate.

[0016] Preferably, the preparation method of modified basalt fiber includes the following steps: An alkoxysilane coupling agent is added to a mixed solution of water and ethanol to prepare a mixed solution of alkoxysilane coupling agent with a mass fraction of 3% to 30%; basalt short-cut fibers are added to the mixed solution, stirred to react, filtered, and dried to obtain the final product.

[0017] Preferably, the mass ratio of water to ethanol in the mixed solution is 1:(7-15).

[0018] Preferably, the mass ratio of basalt short-cut fibers to silane coupling agent is (50-200):1.

[0019] Preferably, the stirring reaction time is 3 to 7 hours.

[0020] Preferably, the alkoxysilane coupling agent is at least one of vinyltriethoxysilane and γ-methacryloyloxypropyltrimethoxysilane.

[0021] Preferably, the raw materials for the antibacterial masterbatch of peppermint fiber include ABS resin, modified peppermint fiber, ABS-g-MAH, titanate coupling agent and lubricant in a mass ratio of (45-65):(35-45):(5-10):(1.5-2.5):(0.5-1.0).

[0022] Preferably, the preparation method of peppermint fiber antibacterial masterbatch includes the following steps: S101. Add peppermint fiber to tetramethylethylenediamine, heat and stir, add titanate coupling agent, heat and stir to react, and obtain modified peppermint fiber. S102. Add modified menthol fiber, ABS resin, ABS-g-MAH resin and lubricant to a container and stir evenly to obtain a mixture. S103. The mixture is extruded and granulated to obtain peppermint fiber antibacterial masterbatch.

[0023] Preferably, in step S101, heating and stirring are carried out at a temperature of 110-120°C for 1-2 hours; heating and stirring reaction refers to heating to 140-150°C and reacting for 3-4 hours.

[0024] Preferably, in step S101, the titanate coupling agent includes isopropyl triisostearoyl titanate and neoalkoxytris(dioctylpyrophosphate) titanate.

[0025] Preferably, in step S102, the lubricant includes EBS and CaSt.

[0026] Preferably, in step S102, the stirring speed is 180-250 r / min.

[0027] Preferably, in step S103, the extrusion temperature is 180–205°C and the rotation speed is 300–600 r / min.

[0028] Preferably, other additives include antioxidants, light stabilizers, anti-dripping agents and lubricants in a weight ratio of (0.5-1):(0.6-2):(0.6-1):(0.5-2).

[0029] Preferably, the antioxidant comprises a composition of BASF hindered phenolic antioxidant 1076 and phosphite antioxidant 168 in a weight ratio of 1:(0.5-2).

[0030] Preferably, the light stabilizer includes one or more of UV531, UV327, UV328, UV770 and UV-P.

[0031] Preferably, the anti-dripping agent includes polytetrafluoroethylene and styrene-acrylonitrile copolymer.

[0032] Preferably, the lubricant is a combination of one or more of calcium stearate, zinc stearate, magnesium stearate, EBS, PETS and silicones.

[0033] Secondly, the present invention provides a method for preparing ABS composite material, comprising the following steps: A101. Weigh out the ABS resin and flame retardant by weight and add them to a low-speed mixer. Mix at a speed of 200-300 r / min for 3-5 minutes to obtain the first mixture. A102. Weigh other additives by weight and add them to a high-speed mixer. Mix at a speed of 400-600 r / min for 6-10 min to obtain a second mixture. A103. Add the first mixture to the second mixture and mix in a high-speed mixer at a speed of 300-400 r / min for 6-10 minutes to obtain the third mixture; A104. Add the third mixture to the main feed of the parallel twin-screw extruder. Under the protection of an inert atmosphere, weigh the modified basalt fiber by weight and add it from the side feed of the 4th-5th section of the extruder. Weigh the antibacterial masterbatch of peppermint fiber by weight and add it from the side feed of the 6th-7th section of the extruder. Then, after melting, mixing, extrusion and granulation, obtain the ABS composite material.

[0034] Preferably, in step A104, the barrel temperature of the parallel twin-screw extruder is 180–210°C and the screw speed is 400–500 r / min.

[0035] By adopting the above technical solutions, the preparation method of the ABS material of the present invention uses a twin-screw extrusion process. In the main feed of the parallel twin-screw extruder, basalt fiber is added from the side feed of the 4th-5th section of the parallel twin-screw extruder under an inert atmosphere, and peppermint fiber antibacterial masterbatch is added from the side feed of the 6th-7th section of the parallel twin-screw extruder under an inert atmosphere. This reduces excessive shearing of basalt fiber and peppermint fiber, ensuring that their structure is not damaged, reducing the generation of small molecules, and ensuring the good strength of the ABS material. In addition, since the peppermint fiber is not excessively sheared, it will not produce an odor and will have the natural fragrance of peppermint fiber.

[0036] The beneficial effects of this invention are: 1. This invention employs a flame retardant system composed of brominated flame retardants, antimony trioxide, and piperazine pyrophosphate in a specific ratio, combined with the flame retardant synergistic effect of modified basalt fiber, effectively solving the problem of easy combustion of traditional ABS.

[0037] 2. This invention uses peppermint fiber antibacterial masterbatch, which is modified to achieve good bonding with ABS matrix, with an antibacterial rate of over 95%, effectively inhibiting bacterial growth on the surface of household appliance shells; at the same time, modified basalt fiber and peppermint fiber form a double reinforcement, significantly improving the screw torque of the material and solving the problem of screw cracking.

[0038] 3. This invention achieves pre-dispersion of raw materials by combining low-mixing and high-mixing. Modified basalt fiber and antibacterial masterbatch of mint fiber are added separately by side feeding in the twin-screw extrusion process, which reduces excessive shearing damage to the fibers, preserves their structural integrity and functional performance, and at the same time protects against oxidation of components by an inert atmosphere, ensuring the stability of the core properties of the composite material such as flame retardancy, antibacterial properties, and mechanical properties. Detailed Implementation

[0039] The specific embodiments of the present invention will be described in detail below, but it should be understood that the scope of protection of the present invention is not limited to the specific embodiments.

[0040] Preparation Example

[0041] Preparation Example 1: A modified basalt fiber was prepared according to the following method: An ethanol-water solution containing 15% silane coupling agent was prepared by mixing vinyltriethoxysilane, ethanol, and water in a mass ratio of 15:77:8. Basalt chopped fibers were added to the ethanol-water solution of the silane coupling agent for impregnation, stirred for 5 hours, filtered, and dried to obtain the final product. The mass ratio of basalt chopped fibers to vinyltriethoxysilane was 100:1.

[0042] Preparation Example 2-1: A peppermint fiber antibacterial masterbatch was prepared according to the following method: S101. Take 100 parts of peppermint fiber and add it to 1L of tetramethylethylenediamine. Purge with nitrogen gas, heat to 110℃ and keep for 2 hours. Then add 1 part of titanate coupling agent triisostearoyl titanate isopropyl ester, heat to 140℃ and keep for 4 hours. Cool down to 25℃ to obtain modified peppermint fiber.

[0043] S102. Add 30 parts of modified peppermint fiber, 40 parts of ABS resin, 15 parts of ABS-g-MAH, and 0.8 parts of lubricant EBS to a high-speed mixing pot and disperse and stir evenly at 200 r / min to obtain a mixture. S103. Add the mixture to a twin-screw extruder for extrusion granulation to obtain a peppermint fiber antibacterial masterbatch.

[0044] The twin-screw extruder has a temperature of 180℃ in each zone, a screw speed of 450 r / min, a melt pressure of 1.6MPa, and a vacuum of -0.04Mpa.

[0045] Preparation Example 2-2: A peppermint fiber antibacterial masterbatch was prepared according to the following method: S101. Take 100 parts of peppermint fiber and add it to 1L of tetramethylethylenediamine. Purge with nitrogen gas, heat to 120°C and keep for 1 hour. Then add 1.5 parts of titanate coupling agent triisostearoyl titanate isopropyl ester, heat to 150°C and keep for 3 hours. Cool down to 25°C to obtain modified peppermint fiber.

[0046] S102. Add 50 parts of modified peppermint fiber, 60 parts of ABS resin, 5 parts of ABS-g-MAH, and 0.2 parts of lubricant EBS to a high-speed mixing pot and disperse and stir evenly at 200 r / min to obtain a mixture. S103. Add the mixture to a twin-screw extruder for extrusion granulation to obtain a peppermint fiber antibacterial masterbatch.

[0047] The twin-screw extruder has a temperature of 180℃ in each zone, a screw speed of 450 r / min, a melt pressure of 1.6 MPa, and a vacuum of -0.08 MPa.

[0048] Preparation Example 3: A soybean stalk fiber masterbatch was prepared according to the following method: 100 parts of soybean stalk fiber were added to 1L of tetramethylethylenediamine. Nitrogen gas was introduced to make the reactor an inert environment. The temperature was raised to 125℃ and maintained for 1.5h. 1.5 parts of titanate coupling agent were added to the reactor. The temperature was then raised to 145℃ and maintained for 3.5h. The temperature was then lowered to room temperature to obtain modified soybean stalk fiber. Take 40 parts of modified soybean stalk fiber, then add 50 parts of ABS resin, 10 parts of ABS-g-MAH resin, 1.3 parts of phthalate coupling agent, and 0.5 parts of lubricant EBS. Disperse and stir evenly in a high-speed mixing pot at 200 r / min. Then extrude and granulate through a twin-screw extruder at a processing temperature of 180℃, a screw speed of 450 r / min, a melt pressure of 1.6 MPa, and a vacuum degree of -0.08 MPa to obtain soybean stalk fiber masterbatch.

[0049] Example

[0050] Example 1: An ABS composite material was prepared according to the following method: A101. Add 70 parts of ABS resin, 9 parts of brominated flame retardant, 3 parts of antimony trioxide, and 2 parts of piperazine pyrophosphate to a low-speed mixer and mix at 250 r / min for 3 min to obtain the first mixture. The brominated flame retardant is a compound of decabromodiphenyl ethane and tris(tribromophenyl)cyanurate in a weight ratio of 2:1. A102. Add 0.5 parts of antioxidant, 0.5 parts of lubricant, 0.6 parts of light stabilizer, and 0.6 parts of anti-drip agent to a high-speed mixer and mix at 500 rpm for 6 minutes to obtain a second mixture. The antioxidant is a BASF hindered phenolic antioxidant 1076 and phosphite antioxidant 168 compounded in a 1:1 weight ratio; the lubricant is a calcium stearate and EBS compounded in a 2:1 weight ratio; the light stabilizer is a UV770 and UV531 compounded in a 3:1 weight ratio; and the anti-drip agent is polytetrafluoroethylene. A103. Add the first mixture to the second mixture and mix in a high-speed mixer at a speed of 400 r / min for 6 minutes to obtain the third mixture; A104. The third mixture is added to the main feed of the parallel twin-screw extruder. Under nitrogen protection, 4 parts of the modified basalt fiber prepared in Preparation Example 1 are added from the side feed of the 5th section of the extruder, and 10 parts of the antibacterial masterbatch of peppermint fiber prepared in Preparation Example 2-1 are added from the side feed of the 7th section. After melting, mixing, extrusion and granulation, ABS composite material is obtained. The parallel twin-screw extruder has a barrel temperature of 200℃, a screw speed of 400r / min, a melt pressure of 1.5MPa, and a vacuum of -0.05Mpa.

[0051] Example 2: An ABS composite material was prepared according to the following method: A101. Add 59.5 parts of ABS resin, 10.5 parts of brominated flame retardant, 3.5 parts of antimony trioxide, and 2.5 parts of piperazine pyrophosphate to a low-speed mixer and mix at 250 r / min for 4 min to obtain the first mixture. The brominated flame retardant is a compound of decabromodiphenyl ethane and tris(tribromophenyl)cyanurate in a weight ratio of 2:1. A102. Add 0.6 parts of antioxidant, 1.2 parts of lubricant, 1 part of light stabilizer, and 0.7 parts of anti-drip agent to a high-speed mixer and mix at 500 r / min for 7 min to obtain a second mixture. The antioxidant is a BASF hindered phenolic antioxidant 1076 and phosphite antioxidant 168 compounded in a 1:1 weight ratio; the lubricant is a calcium stearate and EBS compounded in a 2:1 weight ratio; the light stabilizer is a UV770 and UV531 compounded in a 3:1 weight ratio; and the anti-drip agent is polytetrafluoroethylene. A103. Add the first mixture to the second mixture and mix in a high-speed mixer at a speed of 400 r / min for 8 minutes to obtain the third mixture; A104. The third mixture is added to the main feed of the parallel twin-screw extruder. Six parts of the modified basalt fiber prepared in Preparation Example 1 are added by side feeding through the fourth section of the extruder under nitrogen protection. Fourteen parts of the antibacterial masterbatch of peppermint fiber prepared in Preparation Example 2-1 are added by side feeding through the seventh section under nitrogen protection. After melting, mixing, extrusion and granulation, ABS composite material is obtained. The parallel twin-screw extruder has a barrel temperature of 190℃, a screw speed of 450r / min, a melt pressure of 1.6MPa, and a vacuum of -0.05Mpa.

[0052] Example 3: An ABS composite material was prepared according to the following method: A101. Add 49.4 parts of ABS resin, 11.5 parts of brominated flame retardant, 4.5 parts of antimony trioxide, and 3 parts of piperazine pyrophosphate to a low-speed mixer and mix at 250 r / min for 5 min to obtain the first mixture. The brominated flame retardant is a compound of decabromodiphenyl ethane and tris(tribromophenyl)cyanurate in a weight ratio of 2:1. A102. Add 0.9 parts of antioxidant, 1.6 parts of lubricant, 1.5 parts of light stabilizer, and 0.8 parts of anti-drip agent to a high-speed mixer and mix at 500 rpm for 8 minutes to obtain a second mixture. The antioxidant is a 1:1 weight ratio blend of BASF hindered phenolic antioxidant 1076 and phosphite antioxidant 168; the lubricant is a 2:1 weight ratio blend of calcium stearate and EBS; the light stabilizer is a 3:1 weight ratio blend of UV770 and UV531; and the anti-drip agent is polytetrafluoroethylene. A103. Add the first mixture to the second mixture and mix in a high-speed mixer at a speed of 400 r / min for 8 minutes to obtain the third mixture; A104. The third mixture is added to the main feed of the parallel twin-screw extruder. Eight parts of the modified basalt fiber prepared in Preparation Example 1 are added by side feeding under nitrogen protection in the fifth stage of the extrusion stage. Eighteen parts of the antibacterial masterbatch of peppermint fiber prepared in Preparation Example 2-2 are added by side feeding from the sixth stage under nitrogen protection. After melting, mixing, extrusion and granulation, ABS composite material is obtained. The parallel twin-screw extruder has a barrel temperature of 210℃, a screw speed of 500 r / min, a melt pressure of 1.7 MPa, and a vacuum of -0.05 MPa.

[0053] Example 4: An ABS composite material was prepared according to the following method: A101. Add 41 parts of ABS resin, 14 parts of brominated flame retardant, 6 parts of antimony trioxide, and 4 parts of piperazine pyrophosphate to a low-speed mixer and mix at 250 r / min for 5 min to obtain the first mixture. The brominated flame retardant is a compound of decabromodiphenyl ethane and tris(tribromophenyl)cyanurate in a weight ratio of 2:1. A102. Add 1 part antioxidant, 2 parts lubricant, 2 parts light stabilizer, and 1 part anti-drip agent to a high-speed mixer and mix at 500 r / min for 10 min to obtain a second mixture. The antioxidant is a BASF hindered phenolic antioxidant 1076 and phosphite antioxidant 168 compounded in a 1:1 weight ratio; the lubricant is a calcium stearate and EBS compounded in a 2:1 weight ratio; the light stabilizer is a UV770 and UV531 compounded in a 3:1 weight ratio; and the anti-drip agent is polytetrafluoroethylene. A103. Add the first mixture to the second mixture and mix in a high-speed mixer at a speed of 400 r / min for 10 min to obtain the third mixture; A104. The third mixture is added to the main feed of the parallel twin-screw extruder. 10 parts of the modified basalt fiber prepared in Preparation Example 1 are added by side feeding under nitrogen protection in the 4th stage of the extrusion stage. 20 parts of the antibacterial masterbatch of peppermint fiber prepared in Preparation Example 2-2 are added by side feeding from the 6th stage under nitrogen protection. After melting, mixing, extrusion and granulation, ABS composite material is obtained. The parallel twin-screw extruder has a barrel temperature of 210℃, a screw speed of 500 r / min, a melt pressure of 1.8 MPa, and a vacuum of -0.05 MPa.

[0054] Comparative Example

[0055] Comparative Example 1: An ABS composite material, which differs from Example 1 only in that it does not contain antimony trioxide.

[0056] Comparative Example 2, an ABS composite material, differs from Example 1 only in that piperazine pyrophosphate is not added.

[0057] Comparative Example 3, an ABS composite material, differs from Example 1 only in that the basalt fibers are not modified.

[0058] Comparative Example 4, an ABS composite material, differs from Example 1 only in that it does not contain modified basalt fibers.

[0059] Comparative Example 5, an ABS composite material, differs from Example 1 only in that the same mass of soybean stalk fiber masterbatch prepared in Preparation Example 3 is used instead of the peppermint fiber antibacterial masterbatch prepared in Preparation Example 2-1.

[0060] Comparative Example 6, an ABS composite material, differs from Example 1 only in that the same mass of peppermint fiber is used instead of peppermint fiber antibacterial masterbatch.

[0061] Comparative Example 7, an ABS composite material, was prepared according to the following method: A101. 70 parts of ABS resin, 9 parts of brominated flame retardant, 3 parts of antimony trioxide, 2 parts of piperazine pyrophosphate, and 4 parts of the modified basalt fiber prepared in Preparation Example 1 are added to a low-speed mixer and mixed at a speed of 250 r / min for 3 min to obtain the first mixture. The brominated flame retardant is composed of decabromodiphenyl ethane and tris(tribromophenyl)cyanurate in a weight ratio of 2:1. A102. Add 0.5 parts of antioxidant, 0.5 parts of lubricant, 0.6 parts of light stabilizer, 0.6 parts of anti-dripping agent, and 10 parts of the peppermint fiber antibacterial masterbatch prepared in Preparation Example 2-1 to a high-speed mixer and mix at 500 r / min for 6 min to obtain a second mixture. The antioxidant is a BASF hindered phenolic antioxidant 1076 and phosphite antioxidant 168 compounded in a weight ratio of 1:1; the lubricant is a calcium stearate and EBS compounded in a weight ratio of 2:1; the light stabilizer is a UV770 and UV531 compounded in a weight ratio of 3:1; and the anti-dripping agent is polytetrafluoroethylene. A103. Add the first mixture to the second mixture and mix in a high-speed mixer at a speed of 400 r / min for 6 minutes to obtain the third mixture; A104. The third mixture is added to the main feed of a parallel twin-screw extruder, and after melting, mixing, extrusion and granulation, modified composite ABS material is obtained. The parallel twin-screw extruder has a barrel temperature of 200℃, a screw speed of 400 r / min, a melt pressure of 1.5 MPa, and a vacuum degree of -0.05 MPa.

[0062] Performance testing

[0063] 1. Antibacterial test: The ABS composite materials prepared in Examples 1-4 and Comparative Examples 1-7 were made into plastic samples of the same thickness (50mm × 50mm) for antibacterial testing. Antibacterial test standard: QB / T2591-2003 "Test Methods and Antibacterial Effects of Antibacterial Plastics". Test bacteria: Escherichia coli ATCC25922.

[0064] 2. Combustion performance test: Prepare specimens and templates according to UL94 standard and conduct combustion performance test.

[0065] 3. Screw torque test: Screw posts were made using special molds from Examples 1-4 and Comparative Examples 1-7, and the screw torque of the materials was tested.

[0066] 4. Impact strength test of simply supported beams: prepare specimens and conduct tests according to GB / T1043.

[0067] The ABS composite materials prepared in Examples 1-4 and Comparative Examples 1-7 were subjected to the above tests, and the test results are shown in Table 1.

[0068] Table 1 Performance test results

[0069] As shown in Table 1, and in conjunction with Examples 1 to 4, it can be seen that the simultaneous addition of brominated flame retardants, antimony trioxide, piperazine pyrophosphate, and modified basalt fiber in the embodiments of the present invention has a good synergistic flame retardant effect. The four components achieve synergistic effects in both the gas phase and the condensed phase, thereby enabling the ABS composite material to achieve a higher flame retardant level of 5VA. In addition, the modified basalt fiber also has excellent strength, and the screw torque of the material is significantly improved, reaching more than 5.5 kgf.cm.

[0070] This application incorporates antibacterial masterbatch made from peppermint fiber. Peppermint fiber has the property of inhibiting bacterial growth, resulting in an antibacterial rate of over 95% for the prepared ABS composite material. Simultaneously, due to the reinforcing effect of the peppermint fiber, the ABS material exhibits excellent impact resistance in simply supported beams, reaching over 67 KJ / m².

[0071] Combining Example 1 and Comparative Example 1, the flame retardant rating of the ABS composite material in Example 1 is 5VA, while in Comparative Example 1, since only brominated flame retardants and piperazine pyrophosphate were added, but no antimony trioxide was added, the flame retardant rating of the final material was significantly reduced to only V2.

[0072] Combining Example 1 and Comparative Example 2, since piperazine pyrophosphate was not added in Comparative Example 2, the flame retardancy rating of the final ABS composite material decreased to only V2.

[0073] Combining Example 1 and Comparative Example 3, since Comparative Example 3 did not modify the basalt fiber, on the one hand, it has poor compatibility with ABS resin and cannot form a stable interfacial bond, resulting in uneven dispersion and easy agglomeration of the fiber in the matrix. This not only makes it difficult to play a stress transfer role, but also forms stress concentration points at the agglomeration points, causing the material screw torque to decrease and the screw cracking problem to occur. On the other hand, the hydroxyl groups on the surface of the unmodified fiber are prone to non-specific adsorption with flame retardants, resulting in local enrichment of flame retardants around the fiber, destroying the synergistic flame retardant system of bromine-antimony trioxide-piperazine pyrophosphate, resulting in a decrease in the flame retardant level.

[0074] Combining Example 1 and Comparative Example 4, since no modified basalt fiber was added in Comparative Example 4, the screw torque and simply supported beam impact strength of the final ABS composite material decreased significantly, and the flame retardant rating also decreased to only V1.

[0075] Combining Example 1 and Comparative Example 5, since soybean stalk fiber masterbatch was added in Comparative Example 5, the antibacterial properties of the material were significantly reduced and the flame retardant rating was lowered.

[0076] Combining Example 1 and Comparative Example 6, since Comparative Example 6 added peppermint fiber, its compatibility with ABS resin is poor, resulting in a decrease in the screw torque and simply supported beam impact strength of the material.

[0077] In comparison with Example 1 and Comparative Example 7, Comparative Example 7 involved directly adding basalt fiber and antibacterial masterbatch to the main feed of a parallel twin-screw extruder after mixing them separately with other materials. This resulted in a significant deterioration in the flame retardant properties and screw torque of the final material. Therefore, the preparation method described in this application, where basalt fiber is added from the side feed in stages 4-5 and antibacterial masterbatch is added from the side feed in stages 6-7 under an inert atmosphere, enables the ABS composite material to achieve better flame retardancy, antibacterial properties, and screw torque.

[0078] The above-disclosed embodiments are merely a few specific examples of the present invention. However, the embodiments of the present invention are not limited thereto, and any variations that can be conceived by those skilled in the art should fall within the protection scope of the present invention.

Claims

1. An ABS composite material, characterized in that, Including the following parts by weight of raw materials: 41-70 parts of ABS resin; 14-24 parts flame retardant; 4-10 parts of modified basalt fiber; Other additives: 2.2–6 parts; 10-20 parts of antibacterial masterbatch containing peppermint fiber; The flame retardant comprises a bromine-based flame retardant, antimony trioxide, and piperazine pyrophosphate in a mass ratio of (9-14):(3-6):(2-4).

2. The ABS composite material according to claim 1, characterized in that, The preparation method of the modified basalt fiber includes the following steps: An alkoxysilane coupling agent is added to a mixed solution of water and ethanol to prepare a mixed solution of alkoxysilane coupling agent with a mass fraction of 3% to 30%; basalt short-cut fibers are added to the mixed solution, stirred to react, filtered, and dried to obtain the final product.

3. The ABS composite material according to claim 2, characterized in that, The mass ratio of the basalt short-cut fiber to the alkoxysilane coupling agent is (50-200):

1.

4. The ABS composite material according to claim 1, characterized in that, The raw materials of the antibacterial masterbatch of peppermint fiber include ABS resin, modified peppermint fiber, ABS-g-MAH, titanate coupling agent and lubricant in a mass ratio of (45-65):(35-45):(5-10):(1.5-2.5):(0.5-1.0).

5. An ABS composite material according to claim 4, characterized in that, The preparation method of the peppermint fiber antibacterial masterbatch includes the following steps: S101. Add peppermint fiber to tetramethylethylenediamine, heat and stir, add titanate coupling agent, heat and stir to react, and obtain modified peppermint fiber. S102. Add modified menthol fiber, ABS resin, ABS-g-MAH resin and lubricant to a container and stir evenly to obtain a mixture. S103. The mixture is extruded and granulated to obtain peppermint fiber antibacterial masterbatch.

6. An ABS composite material according to claim 5, characterized in that, In step S101, the heating and stirring is carried out at a temperature of 110-120°C for 1-2 hours; the heating and stirring reaction refers to heating to 140-150°C and reacting for 3-4 hours.

7. An ABS composite material according to claim 1, characterized in that, The other additives include antioxidants, light stabilizers, anti-dripping agents, and lubricants in a weight ratio of (0.5-1):(0.6-2):(0.6-1):(0.5-2).

8. An ABS composite material according to claim 7, characterized in that, The antioxidant comprises a composition of hindered phenolic antioxidant 1076 and phosphite antioxidant 168 in a weight ratio of 1:(0.5-2). The light stabilizer includes one or more of UV531, UV327, UV328, UV770 and UV-P; The anti-dripping agent includes PTFE and styrene-acrylonitrile copolymer; The lubricant is one or a combination of several of the following: calcium stearate, zinc stearate, magnesium stearate, EBS, PETS, and silicones.

9. A method for preparing an ABS composite material, using the ABS composite material as described in any one of claims 1-8, characterized in that, Includes the following steps: A101. Weigh out the ABS resin and flame retardant by weight and add them to a low-speed mixer. Mix at a speed of 200-300 r / min for 3-5 minutes to obtain the first mixture. A102. Weigh other additives by weight and add them to a high-speed mixer. Mix at a speed of 400-600 r / min for 6-10 min to obtain a second mixture. A103. Add the first mixture to the second mixture and mix in a high-speed mixer at a speed of 300-400 r / min for 6-10 min to obtain the third mixture; A104. Add the third mixture to the main feed of the parallel twin-screw extruder. Under the protection of an inert atmosphere, weigh the modified basalt fiber by weight and add it from the side feed of the 4th-5th section of the extruder. Weigh the antibacterial masterbatch of peppermint fiber by weight and add it from the side feed of the 6th-7th section of the extruder. Then, after melting, mixing, extrusion and granulation, obtain the ABS composite material.

10. The method for preparing ABS composite material according to claim 9, characterized in that, In step A104, the barrel temperature of the parallel twin-screw extruder is 180-210℃, the screw speed is 400-500 r / min, the melt pressure is controlled at 1.5-1.8 MPa, and the vacuum degree is -0.04--0.08 MPa.

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