A glass fiber reinforced abs material and a method for producing the same

Abstract

This invention specifically relates to a glass fiber reinforced ABS material and its preparation method. The glass fiber reinforced ABS material comprises the following raw materials in parts by weight: 60-80 parts ABS, 15-30 parts glass fiber, 8-15 parts modifying agents, 4-8 parts toughening agent, 2-6 parts epoxy functionalized olefin copolymer, 0.1-2 parts antioxidant, 0.1-2 parts lubricant, and 0.5-3 parts silane coupling agent. The glass fiber reinforced ABS material possesses excellent heat resistance, surface properties, and mechanical properties, exhibiting superior overall performance. Its preparation method is simple, easy to operate, highly efficient, and produces stable product quality. The entire preparation process requires no special equipment and is suitable for large-scale production.

Description

Technical Field

[0001] This invention relates to the field of plastics technology, specifically to a glass fiber reinforced ABS material and its preparation method. Background Technology

[0002] ABS resin is an acrylonitrile-butadiene-styrene terpolymer, which has advantages such as good processability and high surface gloss, making it a widely used general-purpose engineering plastic. However, ABS suffers from technical bottlenecks in practical engineering applications, such as insufficient heat resistance, low strength and rigidity, and poor dimensional stability, which limit its application in high-temperature environments or load-bearing structural components.

[0003] To address the aforementioned issues, existing technologies often employ glass fiber reinforcement of ABS. Glass fiber reinforced ABS materials are prepared by melt-blending ABS resin with glass fibers. This increases the material's heat distortion temperature from 80-90℃ to over 100℃, significantly improves tensile strength and flexural modulus, and reduces molding shrinkage, making it a potential substitute for some metals or expensive engineering plastics. However, existing glass fiber reinforced ABS materials still face numerous technical challenges in preparation and application: First, reduced toughness; as the glass fiber content increases, the notched impact strength of the material decreases significantly, making it prone to brittle fracture. Second, poor surface properties; glass fibers tend to float on the product surface, forming a "floating fiber" phenomenon, leading to surface roughness and reduced gloss. Third, difficulty in achieving a balance between performance; increasing the glass fiber content to enhance rigidity leads to a decrease in toughness, while adding toughening agents reduces rigidity and heat resistance. Fourth, poor interfacial bonding; insufficient interfacial bonding between glass fibers and ABS resin easily leads to phase separation, affecting overall mechanical properties. Therefore, developing a glass fiber reinforced ABS material that can effectively improve surface floating fibers, balance toughness and rigidity, and achieve excellent overall performance has become an urgent problem to be solved in this field. Summary of the Invention

[0004] In order to overcome the shortcomings and deficiencies of the existing technology, the purpose of this invention is to provide a glass fiber reinforced ABS material, which, through the compounding and synergistic effect of raw materials, gives the material excellent heat resistance and surface properties, as well as good mechanical properties, and has superior overall performance.

[0005] Another objective of this invention is to provide a method for preparing glass fiber reinforced ABS material, wherein the preparation method is simple, easy to operate, and suitable for large-scale production.

[0006] The objective of this invention is achieved through the following technical solution: a glass fiber reinforced ABS material, comprising the following raw materials in parts by weight: 60-80 parts ABS, 15-30 parts glass fiber, 8-15 parts modifying agent, 4-8 parts toughening agent, 2-6 parts epoxy functionalized olefin copolymer, 0.1-2 parts antioxidant, 0.1-2 parts lubricant, and 0.5-3 parts silane coupling agent.

[0007] The glass fiber reinforced ABS material of this invention achieves synergistic effects through the compounding of various raw materials, solving the technical problems of decreased toughness, surface fiber floating, low gloss, and difficulty in achieving a balance of various properties in existing glass fiber reinforced ABS. Specifically, the epoxy functionalized olefin copolymer, silane coupling agent, and modifying additives synergistically enhance the interfacial bonding strength between glass fiber and ABS resin, preventing phase separation. The modifying additives effectively solve the fiber floating problem, improve surface gloss, ensure mechanical property stability, balance the rigidity and toughness of the material, and improve thermal stability.

[0008] Furthermore, the modifying agent is at least one of styrene-N-phenylmaleimide copolymer, amino-modified silicone oil, and wollastonite mineral fiber.

[0009] Preferably, the modifying agent comprises the following raw materials in parts by weight: 4-7 parts of styrene-N-phenylmaleimide copolymer, 2-4 parts of amino-modified silicone oil, and 2-4 parts of wollastonite mineral fiber. This invention modifies ABS material with amino-modified silicone oil and styrene-N-phenylmaleimide copolymer, effectively improving the dispersibility of glass fibers, reducing fiber floating, and enhancing the surface gloss and heat resistance of the material. Wollastonite mineral fiber can replace some glass fibers, reducing mold wear, while synergistically improving the rigidity and dimensional stability of the material. The combination of these three components achieves synergistic optimization of surface properties and rigidity.

[0010] Furthermore, the toughening agent is at least one of carboxyl-terminated liquid nitrile rubber and MBS resin. By adding a toughening agent, this invention can effectively compensate for the decrease in toughness of materials reinforced with glass fiber. The carboxyl-terminated liquid nitrile rubber exhibits good compatibility with ABS resin, demonstrates significant toughening effect, and can synergistically enhance interfacial bonding with epoxy-functionalized olefin copolymers.

[0011] Furthermore, the epoxy-functionalized olefin copolymer is at least one of ethylene-acrylate-glycidyl methacrylate copolymer, ethylene-vinyl acetate-glycidyl methacrylate copolymer, and maleic anhydride-grafted ethylene-octene copolymer. This invention incorporates the above-mentioned epoxy-functionalized olefin copolymer into glass fiber reinforced ABS material. Its epoxy groups can react with the active groups of glass fiber and silane coupling agent, while exhibiting excellent compatibility with ABS resin. The synergistic use of the epoxy-functionalized olefin copolymer and carboxyl-terminated liquid nitrile rubber helps to improve the interfacial bonding strength between glass fiber and ABS resin, prevents phase separation, enhances toughness, and ensures the stability of the material's mechanical properties.

[0012] Furthermore, the antioxidant is at least one of hindered phenolic antioxidants and phosphite antioxidants. ABS is prone to oxidation and decomposition, turning yellow, during high-temperature processing. Adding antioxidants can protect the resin and maintain the material's color and long-term stability.

[0013] Furthermore, the lubricant is at least one selected from zinc stearate, polyethylene wax, ethylene bis-stearamide, and pentaerythritol stearate. By using a lubricant, the dispersibility of glass fibers in the resin can be effectively improved, while reducing friction between the melt and the screw and mold, preventing "scorching".

[0014] Furthermore, the silane coupling agent is at least one selected from γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, and N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane. The silane coupling agent can modify the surface of glass fibers, introducing active groups onto the glass fiber surface and improving the interfacial bonding between the glass fibers and ABS resin or epoxy-functionalized olefin copolymers.

[0015] Furthermore, the glass fiber is chopped glass fiber with a length of 0.3-1 mm. By controlling the length of the chopped glass fiber and pre-treating it with a silane coupling agent, both the mechanical reinforcement effect of the material and the molding flowability of the material can be guaranteed.

[0016] The present invention also provides a method for preparing the above-mentioned glass fiber reinforced ABS material, comprising the following steps: (1) Raw material preparation: Weigh each raw material according to the weight parts; pretreat the glass fiber with silane coupling agent and set aside; (2) Melt mixing: Add raw materials other than glass fiber and silane coupling agent to the main feed port of the extruder and heat them to melt and mix them; (3) Side feeding: Add pretreated glass fiber to the side feeding port in the middle section of the extruder to make the glass fiber and the molten material fully mixed; (4) Extrusion pelletizing: The uniformly mixed material is extruded from the extruder head, cooled, pelletized by a pelletizer, and dried to obtain glass fiber reinforced ABS material.

[0017] Furthermore, in step (1), the method for pretreating glass fibers with silane coupling agent is as follows: mix silane coupling agent and ethanol at a mass ratio of 1:4-8, then add glass fibers and mix evenly, and then dry.

[0018] Furthermore, in steps (2)-(4), the melt extrusion adopts a twin-screw extruder, and the temperatures of each zone are set as follows: Zone 1 200-220℃, Zone 2 210-230℃, Zone 3 200-220℃, Zone 4 190-210℃, the die head temperature is 210-230℃, the screw speed is 250-500rpm, and the side feed port is set in Zone 2.

[0019] This invention uses a side-feeding method to add glass fibers, which avoids the glass fibers being scorched or broken in the high-temperature main feeding section, thus ensuring the length and reinforcing effect of the glass fibers. At the same time, by controlling the processing temperature, the materials are fully melted and mixed, and the glass fibers are fully impregnated with the molten resin, thereby improving the dispersion uniformity and interfacial bonding of the glass fibers.

[0020] The beneficial effects of this invention are as follows: By adding glass fiber to ABS material for reinforcement and compounding it with epoxy functionalized olefin copolymers, silane coupling agents, and modifying agents, a synergistic effect is achieved, effectively improving the surface fiber floating phenomenon. This results in glass fiber reinforced ABS material possessing excellent heat resistance, surface properties, and mechanical properties, exhibiting superior overall performance. The preparation method of the glass fiber reinforced ABS material is simple, easy to operate, has high production efficiency, and stable product quality. The entire preparation process requires no special equipment and is suitable for large-scale production. Detailed Implementation

[0021] To facilitate understanding by those skilled in the art, the present invention will be further described below with reference to embodiments. The content mentioned in the embodiments is not intended to limit the present invention.

[0022] In some embodiments of the present invention, a glass fiber reinforced ABS material comprises the following raw materials in parts by weight: 60-80 parts ABS, 15-30 parts glass fiber, 8-15 parts modifying agent, 4-8 parts toughening agent, 2-6 parts epoxy functionalized olefin copolymer, 0.1-2 parts antioxidant, 0.1-2 parts lubricant, and 0.5-3 parts silane coupling agent.

[0023] In some embodiments of the present invention, the modifying agent comprises the following raw materials in parts by weight: 4-7 parts of styrene-N-phenylmaleimide copolymer, 2-4 parts of amino-modified silicone oil, and 2-4 parts of wollastonite mineral fiber. The aspect ratio of the wollastonite mineral fiber is 10-15:1.

[0024] In some embodiments of the present invention, the toughening agent is at least one of carboxyl-terminated liquid nitrile rubber and MBS resin.

[0025] In some embodiments of the present invention, the epoxy-functionalized olefin copolymer is at least one selected from ethylene-acrylate-glycidyl methacrylate copolymer and ethylene-vinyl acetate-glycidyl methacrylate copolymer. In some embodiments of the present invention, the antioxidant is at least one selected from hindered phenolic antioxidants and phosphite antioxidants.

[0026] In some embodiments of the present invention, the lubricant is at least one of zinc stearate, polyethylene wax, ethylene bis-stearamide, and pentaerythritol stearate.

[0027] In some embodiments of the present invention, the silane coupling agent is at least one selected from γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, and N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane.

[0028] In some embodiments of the present invention, the present invention also provides a method for preparing the above-mentioned glass fiber reinforced ABS material, comprising the following steps: (1) Raw material preparation: Weigh each raw material according to the weight parts; pretreat the glass fiber with silane coupling agent and set aside; (2) Melt mixing: Add raw materials other than glass fiber and silane coupling agent to the main feed port of the extruder and heat them to melt and mix them; (3) Side feeding: Add pretreated glass fiber to the side feeding port in the middle section of the extruder so that the glass fiber is fully wetted with the molten material; (4) Extrusion pelletizing: The uniformly mixed material is extruded from the extruder head, cooled by a cooling water tank, pelletized by a pelletizer, and dried to obtain glass fiber reinforced ABS material.

[0029] Furthermore, in step (1), the method for pretreating glass fibers with silane coupling agent is as follows: mix silane coupling agent and ethanol at a mass ratio of 1:4-8, then add glass fibers and mix evenly, and then dry.

[0030] Furthermore, in steps (2)-(4), the melt extrusion adopts a twin-screw extruder, and the temperatures of each zone are set as follows: Zone 1 200-220℃, Zone 2 210-230℃, Zone 3 200-220℃, Zone 4 190-210℃, the die head temperature is 210-230℃, the screw speed is 250-500rpm, and the side feed port is set in Zone 2. Example 1

[0031] In this embodiment, a glass fiber reinforced ABS material comprises the following raw materials in parts by weight: 70 parts ABS, 25 parts glass fiber, 12 parts modifying agent, 6 parts toughening agent, 4 parts epoxy functionalized olefin copolymer, 1.2 parts antioxidant, 1 part lubricant, and 1.5 parts silane coupling agent. The ABS used is Formosa Plastics AG12A1.

[0032] Furthermore, the modifying agent comprises the following raw materials in parts by weight: 6 parts of styrene-N-phenylmaleimide copolymer, 3 parts of amino-modified silicone oil, and 3 parts of wollastonite mineral fiber. The styrene-N-phenylmaleimide copolymer is selected from Denki Kagaku MS-NB; the amino-modified silicone oil is selected from Dow Corning OFX-8040.

[0033] Furthermore, the toughening agent is a carboxyl-terminated liquid nitrile rubber, specifically Nipol 1072CG from Zeon Corporation. The epoxy-functionalized olefin copolymer is an ethylene-acrylate-glycidyl methacrylate copolymer, specifically Arkema AX8900.

[0034] Furthermore, the antioxidant is a mixture of antioxidant 1010 and antioxidant 168 in a mass ratio of 2:1. The lubricant is zinc stearate. The silane coupling agent is γ-aminopropyltriethoxysilane.

[0035] In this embodiment, the preparation method of the above-mentioned glass fiber reinforced ABS material includes the following steps: (1) Raw material preparation: Weigh each raw material according to the weight parts; pretreat the glass fiber with silane coupling agent and set aside; (2) Melt mixing: Add raw materials other than glass fiber and silane coupling agent to the main feed port of the twin-screw extruder to melt and mix the materials; (3) Side feeding: Add pretreated glass fiber to the side feeding port in the middle section of the twin-screw extruder to fully mix the glass fiber with the molten material; (4) Extrusion and pelletizing: The uniformly mixed material is extruded from the head of a twin-screw extruder, cooled by a cooling water tank, pelletized by a pelletizer, and dried with hot air at 40°C for 4 hours to obtain glass fiber reinforced ABS material.

[0036] Furthermore, in step (1), the method for pretreating glass fibers with silane coupling agent is as follows: mix silane coupling agent and ethanol at a mass ratio of 1:5, then add glass fibers and mix evenly, and dry at 80°C for 2 hours.

[0037] Furthermore, in steps (2)-(4), the temperatures of each zone of the twin-screw extruder are set as follows: Zone 1 210℃, Zone 2 220℃, Zone 3 210℃, Zone 4 200℃, the die head temperature is 220℃, the screw speed is 400rpm, and the side feed port is set in Zone 2. Example 2

[0038] In this embodiment, a glass fiber reinforced ABS material comprises the following raw materials in parts by weight: 65 parts ABS, 15 parts glass fiber, 8 parts modifying agent, 4 parts toughening agent, 2 parts epoxy functionalized olefin copolymer, 0.6 parts antioxidant, 0.5 parts lubricant, and 1 part silane coupling agent.

[0039] Furthermore, the modified additive comprises the following raw materials in parts by weight: 4 parts of styrene-N-phenylmaleimide copolymer, 2 parts of amino-modified silicone oil, and 2 parts of wollastonite mineral fiber.

[0040] Furthermore, the antioxidant is a mixture of antioxidant 1010 and antioxidant 168 in a mass ratio of 2:1. The lubricant is pentaerythritol stearate. The silane coupling agent is γ-glycidoxypropyltrimethoxysilane.

[0041] In this embodiment, a method for preparing the above-mentioned glass fiber reinforced ABS material includes the following steps: (1) Raw material preparation: Weigh each raw material according to the weight parts; pretreat the glass fiber with silane coupling agent and set aside; (2) Melt mixing: Add the raw materials, except for glass fiber and silane coupling agent, into the main feed port of the twin-screw extruder and heat them to 200°C to melt and mix the materials; (3) Side feeding: Add pretreated glass fiber to the side feeding port in the middle section of the twin-screw extruder so that the glass fiber is fully wetted with the molten material; (4) Extrusion and pelletizing: The uniformly mixed material is extruded from the head of the twin-screw extruder, cooled by a cooling water tank, and then pelletized by a pelletizer to obtain glass fiber reinforced ABS material.

[0042] Furthermore, in step (1), the method for pretreating glass fibers with silane coupling agent is as follows: mix silane coupling agent and ethanol at a mass ratio of 1:5, then add glass fibers and mix evenly, and then dry.

[0043] Furthermore, in steps (2)-(4), the temperatures of each zone of the twin-screw extruder are set as follows: Zone 1 200℃, Zone 2 210℃, Zone 3 210℃, Zone 4 200℃, the die head temperature is 210℃, the screw speed is 300rpm, and the side feed port is set in Zone 2.

[0044] The rest of this embodiment is the same as that in Embodiment 1. Example 3

[0045] In this embodiment, a glass fiber reinforced ABS material comprises the following raw materials in parts by weight: 75 parts ABS, 30 parts glass fiber, 15 parts modifying agent, 8 parts toughening agent, 5 parts epoxy functionalized olefin copolymer, 1.5 parts antioxidant, 1.5 parts lubricant, and 3 parts silane coupling agent.

[0046] Furthermore, the modified additive comprises the following raw materials in parts by weight: 7 parts of styrene-N-phenylmaleimide copolymer, 4 parts of amino-modified silicone oil, and 4 parts of wollastonite mineral fiber.

[0047] Furthermore, the toughening agent is a carboxyl-terminated liquid nitrile rubber.

[0048] Furthermore, the antioxidant is a mixture of antioxidant 1010 and antioxidant 168 in a mass ratio of 2.5:1. The lubricant is pentaerythritol stearate. The silane coupling agent is γ-aminopropyltriethoxysilane.

[0049] The rest of this embodiment is the same as that in Embodiment 1.

[0050] Comparative Example 1 The difference between this comparative example and Example 1 is that the glass fiber reinforced ABS material in this comparative example does not contain styrene-N-phenylmaleimide copolymer as a modifier; its amount is supplemented by equal amounts of amino-modified silicone oil and wollastonite mineral fiber in the original proportion. The remaining raw materials and preparation methods are the same as in Example 1.

[0051] Comparative Example 2 The difference between this comparative example and Example 1 is that the glass fiber reinforced ABS material in this comparative example does not contain epoxy-functionalized olefin copolymer; its amount is made up by an equal amount of ABS resin. The remaining raw materials and preparation methods are the same as in Example 1.

[0052] Comparative Example 3 The difference between this comparative example and Example 1 is that the amount of terminal carboxyl-terminated liquid nitrile rubber in the glass fiber reinforced ABS material of this comparative example is made up by an equal amount of ABS resin. The remaining raw materials and preparation methods are the same as in Example 1.

[0053] The glass fiber reinforced ABS material granules prepared in Example 1 and Comparative Examples 1-3 were dried and then injection molded into standard test specimens using an injection molding machine. The injection temperature was controlled at 220℃ and the mold temperature was controlled at 70℃. After the test specimens were placed in an environment with a pre-test temperature of 23±2℃ and a relative humidity of 50±5% for 48 hours, the test results are shown in Table 1 below: Tensile strength testing was performed according to ASTM D638. Flexural strength testing was performed according to ASTM D790. Flexural modulus testing was performed according to ASTM D790. Notched impact strength testing was performed according to ASTM D256 using a cantilever beam impact testing machine. Heat distortion temperature testing was performed according to ASTM D648, with test conditions of 1.82 MPa and a heating rate of 120 °C / h.

[0054] Surface fiber floating phenomena were tested on Examples 1 and Comparative Examples 1-3 under natural light at a distance of 30 cm. No visible fiber protrusions or white streaks indicated no fiber floating; a small number of fiber protrusions / white streaks indicated slight fiber floating; and a large number of fiber protrusions / white streaks indicated significant fiber floating. Observation revealed that the injection-molded product of Example 1 had a smooth surface with no visible fiber floating; Comparative Example 1 showed slight surface fiber floating; and Comparative Examples 2-3 showed significant surface fiber floating with visible white streaks.

[0055] In summary, the glass fiber reinforced ABS material of the present invention strengthens ABS material by adding glass fiber, and works synergistically with raw materials such as styrene-N-phenylmaleimide copolymer, epoxy functionalized olefin copolymer, and modifying agents to effectively improve surface fiber floating. This results in glass fiber reinforced ABS material with excellent heat resistance and surface properties, as well as good toughness and rigidity, and superior overall performance.

[0056] The above embodiments are preferred implementations of the present invention. In addition, the present invention can be implemented in other ways. Any obvious substitutions without departing from the concept of the present invention are within the protection scope of the present invention.

Claims

1. A glass fiber reinforced ABS material, characterized in that: The raw materials include the following parts by weight: 60-80 parts ABS, 15-30 parts glass fiber, 8-15 parts modifying agent, 4-8 parts toughening agent, 2-6 parts epoxy functionalized olefin copolymer, 0.1-2 parts antioxidant, 0.1-2 parts lubricant, and 0.5-3 parts silane coupling agent.

2. The glass fiber reinforced ABS material according to claim 1, characterized in that: The modifying agent is at least one of styrene-N-phenylmaleimide copolymer, amino-modified silicone oil, and wollastonite mineral fiber.

3. The glass fiber reinforced ABS material according to claim 1, characterized in that: The toughening agent is at least one of carboxyl-terminated liquid nitrile rubber and MBS resin.

4. The glass fiber reinforced ABS material according to claim 1, characterized in that: The epoxy-functionalized olefin copolymer is at least one of ethylene-acrylate-glycidyl methacrylate copolymer and ethylene-vinyl acetate-glycidyl methacrylate copolymer.

5. The glass fiber reinforced ABS material according to claim 1, characterized in that: The antioxidant is at least one of hindered phenolic antioxidants and phosphite antioxidants.

6. The glass fiber reinforced ABS material according to claim 1, characterized in that: The lubricant is at least one of zinc stearate, polyethylene wax, ethylene bis-stearamide, and pentaerythritol stearate.

7. The glass fiber reinforced ABS material according to claim 1, characterized in that: The silane coupling agent is at least one of γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, and N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane.

8. A method for preparing glass fiber reinforced ABS material as described in any one of claims 1-7, characterized in that: Includes the following steps: (1) Raw material preparation: Weigh each raw material according to the weight parts; pretreat the glass fiber with silane coupling agent and set aside; (2) Melt mixing: Add raw materials other than glass fiber and silane coupling agent to the main feed port of the extruder and heat them to melt and mix them; (3) Side feeding: Add pretreated glass fiber to the side feeding port in the middle section of the extruder to make the glass fiber and the molten material fully mixed; (4) Extrusion pelletizing: The uniformly mixed material is extruded from the extruder head, cooled and pelletized, and dried to obtain glass fiber reinforced ABS material.

9. The method for preparing glass fiber reinforced ABS material according to claim 8, characterized in that: In step (1), the method for pretreating glass fibers with silane coupling agent is as follows: mix silane coupling agent and ethanol, then add glass fibers and mix evenly, and then dry.

10. The method for preparing glass fiber reinforced ABS material according to claim 8, characterized in that: In steps (2)-(4), the melt extrusion uses a twin-screw extruder, and the temperatures of each zone are set as follows: Zone 1 200-220℃, Zone 2 210-230℃, Zone 3 200-220℃, Zone 4 190-210℃, the die head temperature is 210-230℃, the screw speed is 250-500rpm, and the side feed port is set in Zone 2.

Images