A glass fiber reinforced ABS composition and its preparation method and application

Abstract

The present invention discloses a glass fiber-reinforced ABS composition, its preparation method, and application, belonging to the field of polymer material technology. The glass fiber-reinforced ABS composition comprises the following components, by weight: 40-90 parts of ABS resin; 15-30 parts of glass fiber; 3-5 parts of a compatibilizer; 6-15 parts of antimony trioxide; 0.1-1 part of a silane coupling agent; 0.1-5 parts of a lubricant; and 0.1-5 parts of a processing aid. The antimony trioxide has an average particle size of 20-50 nm, and the glass fibers in the glass fiber-reinforced ABS composition have an average retention length (L) of 400-600 μm. The glass fiber-reinforced ABS composition of the present invention effectively increases the average retention length of the glass fibers through the synergistic effect of antimony trioxide of a specific particle size and the silane coupling agent, thereby improving the mechanical properties of the glass fiber-reinforced ABS composition and increasing the whiteness to above 91.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and more particularly to a glass fiber reinforced ABS composition, a preparation method thereof, and applications thereof. Background Art

[0002] ABS resin (acrylonitrile-butadiene-styrene copolymer) is a thermoplastic polymer material with high strength, good toughness, and easy processing and molding. Products processed from ABS have a smooth surface and are easy to dye and electroplate. Therefore, they are widely used in the production of mechanical and electronic products, automotive interior and exterior trim and structural parts, household appliances, toys, and other everyday items.

[0003] Using glass fiber to reinforce ABS is a very important modification method of ABS. The addition of glass fiber can significantly improve the strength and rigidity of the material and reduce its linear thermal expansion coefficient, which has better dimensional stability, making it suitable for parts with higher requirements for strength and dimensional stability, such as home appliance fans, small appliance brackets, audio brackets, printer frames, TV bases, frames, etc.

[0004] In the field of white appliances, there are many applications that require ultra-white reinforced ABS materials. Since glass fiber itself cannot be dyed, a higher hiding power of the matrix resin is required. Titanium dioxide is the most commonly used white toner in this field. Therefore, the addition of glass fiber requires more white toner to cover the surface. Therefore, to achieve the same whiteness effect, white reinforced ABS materials often require more titanium dioxide than non-reinforced ABS materials. However, during the preparation of white reinforced ABS, the mixing of the twin-screw extruder causes friction between the titanium dioxide and the glass fiber. Since titanium dioxide is hard and the amount added is relatively large, it greatly reduces the retained length of the glass fiber in the white reinforced ABS material, resulting in a significant decline in the mechanical properties of the white reinforced ABS material. Compared with the natural reinforced ABS material, the mechanical property retention rate is only about 80%, which greatly limits the application of white reinforced ABS materials.

[0005] To address the problem of titanium dioxide reducing glass fiber length and thus degrading the material's mechanical properties, existing technology discloses a flame-retardant material that incorporates 10-40 parts glass fiber, 10-20 parts brominated flame retardant, and 3-10 parts flame retardant synergist into polycaprolactam. While maintaining a V0 flame retardancy rating and maintaining tensile strength, flexural strength, and notched impact strength, the material's whiteness is enhanced. However, this material primarily improves its flame retardancy, and its whiteness cannot be raised above 91. Summary of the Invention

[0006] The technical problem to be solved by the present invention is to overcome the defects and shortcomings of existing ABS compositions, namely, the inability to increase the whiteness to above 91 and the inability to simultaneously improve both the whiteness and mechanical properties. The present invention provides a glass fiber reinforced ABS composition. The synergistic effect of antimony trioxide of a specific particle size and a silane coupling agent effectively prevents the average retention length of the glass fibers from being too short, thereby improving the mechanical properties of the glass fiber reinforced ABS composition and enabling the whiteness to be increased to above 91.

[0007] Another object of the present invention is to provide a method for preparing a glass fiber reinforced ABS composition.

[0008] Another object of the present invention is to provide an application of a glass fiber reinforced ABS composition in the preparation of fan blade materials for white household appliances.

[0009] The above-mentioned purpose of the present invention is achieved through the following technical solutions:

[0010] A glass fiber reinforced ABS composition, comprising the following components in parts by weight:

[0011]

[0012] Wherein, the average particle size of antimony trioxide is 20 to 50 nm;

[0013] The average retention length L of the glass fibers in the glass fiber reinforced ABS composition is 400-600 μm;

[0014] The mechanism of action of the components of the glass fiber reinforced ABS composition of the present invention is as follows:

[0015] Antimony trioxide commonly used in the art is generally used as a flame retardant synergist. The average particle size of antimony trioxide used as a flame retardant synergist is generally 0.6 to 0.8 μm.

[0016] In the present invention, adding a large amount of nano-antimony trioxide with a particle size of 20 to 50 nm can not only significantly improve the whiteness of the composition, but also the nano-antimony trioxide can reduce the mutual friction with the glass fiber, preventing the average retention length of the glass fiber from being too low. Since the glass fiber can have a higher average retention length, it is beneficial to improve the mechanical properties of the composition.

[0017] The silane coupling agent can improve the compatibility of antimony trioxide with ABS resin and glass fiber, which is beneficial to improving the mechanical properties of the composition.

[0018] The antimony trioxide is high-purity antimony trioxide, and the content of antimony trioxide is ≥99.9%.

[0019] The ABS resin may be an ABS resin synthesized by a bulk method.

[0020] In practical applications, the silane coupling agent can be pre-mixed and modified with antimony trioxide.

[0021] Preferably, the silane coupling agent is one or more of a bisaminosilane coupling agent, a monoaminosilane coupling agent, an epoxysilane coupling agent, a methylsilane coupling agent, a phenylsilane coupling agent or a long-chain alkylsilane coupling agent.

[0022] More preferably, the silane coupling agent is a bisaminosilane coupling agent or a monoaminosilane coupling agent.

[0023] More preferably, the silane coupling agent is a bisaminosilane coupling agent.

[0024] In order to further improve the mechanical strength of the composition, the average retention length L of the glass fibers in the glass fiber reinforced ABS composition is 450 to 600 μm.

[0025] Preferably, the average diameter of the glass fiber is 11-14 μm.

[0026] The average diameter of the glass fiber is small, which can effectively increase the specific surface area of ​​the glass fiber, thereby further improving the interaction between the glass fiber and the matrix resin and antimony trioxide, thereby further improving the mechanical properties and whiteness of the material.

[0027] Preferably, the melt mass flow rate of the ABS resin is 20 to 40 g / 10 min, the test standard is ASTM D-1238-2013, and the test conditions are 220° C. and 10 kg.

[0028] The ABS resin with a melt mass flow rate of 20 to 40 g / 10 min can promote the dispersion of glass fibers and nano-scale antimony trioxide modified by a silane coupling agent, thereby facilitating the improvement of the mechanical properties and whiteness of the composition.

[0029] Preferably, the compatibilizer is one or more of ABS-g-MAH, ABS-g-GMA, AS-g-MAH, methyl methacrylate, styrene-maleic anhydride copolymer or styrene-acrylonitrile-glycidyl methacrylate copolymer.

[0030] Preferably, the lubricant is one or more of fatty acid amide, pentaerythritol stearate, solid paraffin, liquid paraffin, stearate, silicone or N,N'-ethylene bisstearamide.

[0031] Preferably, the processing aid is an antioxidant, and the antioxidant is a hindered phenol antioxidant and / or a phosphite antioxidant.

[0032] The present invention also protects a method for preparing the above-mentioned glass fiber reinforced ABS composition, comprising the following steps:

[0033] S1. A silane coupling agent aqueous solution and antimony trioxide are mixed and reacted, washed, and dried to obtain a silane coupling agent-modified antimony trioxide; wherein the reaction temperature is 60 to 70 ° C, and the reaction time is 6 to 8h;

[0034] S2. The components except the glass fiber are mixed evenly with the silane coupling agent-modified antimony trioxide in S1 and fed into a twin-screw extruder. The glass fiber is side-fed into the twin-screw extruder. The components are melt-extruded and granulated at 210-250° C. through the twin-screw extruder, and then dried to obtain the glass fiber-reinforced ABS composition.

[0035] Among them, the feeding speed of the twin-screw extruder is 200-350rpm; the temperature of each section of the screw of the twin-screw extruder from the feeding port to the die head is preferably 220-250°C in zone 1, 220-240°C in zone 2, 210-220°C in zone 3, 210-230°C in zone 4, and 210-230°C in zone 5, the die temperature is 220-230°C, the main engine speed is 100-500r / min, and the vacuum degree is ≤0.1MPa.

[0036] The glass fiber reinforced ABS composition prepared by the present invention has excellent mechanical properties and whiteness, and can be widely used in the preparation of plastic products. The present invention particularly protects the use of the glass fiber reinforced ABS composition in the preparation of fan blade components of white household appliances.

[0037] Compared with the prior art, the present invention has the following beneficial effects:

[0038] The present invention discloses a glass fiber-reinforced ABS composition, comprising ABS resin, glass fiber, a compatibilizer, antimony trioxide, a silane coupling agent, a lubricant, and a processing aid. The antimony trioxide has an average particle size of 20 to 50 nm, and the glass fibers in the glass fiber-reinforced ABS composition have an average retention length (L) of 400 to 600 μm. The synergistic effect of antimony trioxide of a specific particle size and the silane coupling agent effectively prevents the average retention length of the glass fibers from being too short, thereby improving the mechanical properties of the glass fiber-reinforced ABS composition and increasing the whiteness to above 91.

[0039] The glass fiber reinforced ABS composition of the present invention has a whiteness of more than 91, and has good mechanical properties, and the tensile strength retention rate can reach more than 89%. DETAILED DESCRIPTION

[0040] The present invention will be further described below in conjunction with specific embodiments, but the examples do not limit the present invention in any form. Unless otherwise specified, the raw materials and reagents used in the examples of the present invention are conventionally purchased raw materials and reagents.

[0041] ABS resin 1: brand ABS 8391, melt mass flow rate 30g / 10min, manufacturer: Shanghai Gaoqiao Petrochemical;

[0042] ABS resin 2: brand ABS 275, melt mass flow rate 10g / 10min, manufacturer: Shanghai Gaoqiao Petrochemical;

[0043] ABS resin 3: brand MAGNUM TM 347EZ, melt flow rate 45g / 10min, manufacturer: Trinseo;

[0044] Glass fiber 1: Brand: glass fiber ECS13-4.5-534A, average diameter: 13 μm, manufactured by China Jushi;

[0045] Glass fiber 2: Brand: glass fiber EDR17-2400-988A, average diameter: 17 μm, manufactured by China Jushi;

[0046] Compatibilizer: styrene maleic anhydride copolymer, commercially available and the same one was used in all examples and comparative examples;

[0047] Antimony trioxide 1, brand CY-D20, average particle size 20nm, purity 99.9%, manufacturer is Nangong Leigong Alloy;

[0048] Antimony trioxide 2, brand AM-Sb2O3-001-1, average particle size 50nm, purity 99.9%, manufacturer Zhejiang Yamei Nano Technology Co., Ltd.

[0049] Antimony trioxide 3, brand S-05N, average particle size 0.6-0.8μm, purity 99.8%, manufacturer Changde Chenzhou Antimony Products;

[0050] Titanium dioxide, with an average particle size of 20 nm, is commercially available and the same one was used in all examples and comparative examples;

[0051] Silane coupling agent 1: bisaminosilane coupling agent, brand JH-A112, manufactured by Jianghan Chemical;

[0052] Silane coupling agent 2: epoxy silane coupling agent, brand JH-O186, manufacturer: Jianghan Chemical;

[0053] Silane coupling agent 3: methyl silane coupling agent, brand name JH-2150, manufactured by Jianghan Chemical;

[0054] Silane coupling agent 4: phenyl silane coupling agent, brand name JH-651, manufacturer: Jianghan Chemical;

[0055] Silane coupling agent 5: monoaminosilane coupling agent, brand name JH-A110, manufactured by Jianghan Chemical;

[0056] Lubricant: Ethylene bisstearamide lubricant, commercially available and the same one was used in all examples and comparative examples;

[0057] Antioxidants: hindered phenol antioxidants and phosphite antioxidants, the mass ratio of hindered phenol antioxidants to phosphite antioxidants is 1:2, and the same antioxidants are commercially available and used in all examples and comparative examples.

[0058] Examples 1 to 11

[0059] A glass fiber reinforced ABS composition, comprising the following components in parts by weight:

[0060] ABS resin; glass fiber; compatibilizer; antimony trioxide; silane coupling agent; lubricant and processing aid, the processing aid being an antioxidant; the specific content of each component is shown in Table 1 below.

[0061] Table 1 Composition of glass fiber reinforced ABS composition of each embodiment (in parts by weight)

[0062]

[0063]

[0064] The preparation method of the glass fiber reinforced ABS composition is as follows:

[0065] S1. A silane coupling agent aqueous solution and antimony trioxide were mixed and reacted, washed, and dried to obtain silane coupling agent-modified antimony trioxide; wherein the reaction temperature was 60 ° C and the reaction time was 6h;

[0066] The mass ratio of the silane coupling agent to water in the aqueous solution is 1:10. The rotation speed of the stirring magnet is 300 rpm during the reaction. The mixed reaction product is washed at least three times with anhydrous ethanol.

[0067] S2. Except for the glass fiber, the raw materials in the formula are mixed in a high-speed mixing mixer according to the appropriate proportions. This mixture is then fed into a twin-screw extruder, with the glass fiber added through the first vent or side feed system. All materials are extruded through the die, stretched into strands, cooled, pelletized, dried, and finally packaged to obtain a glass fiber-reinforced ABS composition.

[0068] Among them, the feeding speed of the twin-screw extruder is 200-350rpm; the temperature of each section of the screw of the twin-screw extruder from the feeding port to the die head is preferably 220-250°C in zone 1, 220-240°C in zone 2, 210-220°C in zone 3, 210-230°C in zone 4, and 210-230°C in zone 5, the die temperature is 220-230°C, the main engine speed is 100-500r / min, and the vacuum degree is ≤0.1MPa.

[0069] Example 12

[0070] A glass fiber reinforced ABS composition, wherein the contents of each component are the same as those in Example 1, but the difference from Example 1 is the preparation method, comprising the following steps:

[0071] The raw materials in the formula, except for the glass fiber, are mixed in a high-speed mixing mixer according to the appropriate proportions. The mixture is then fed into a twin-screw extruder, where the glass fiber is added through the first vent or side feed system. All materials are extruded through the die, stretched into strands, cooled, pelletized, dried, and finally packaged to obtain a glass fiber-reinforced ABS composition.

[0072] Among them, the feeding speed of the twin-screw extruder is 200-350rpm; the temperature of each section of the screw of the twin-screw extruder from the feeding port to the die head is preferably 220-250°C in zone 1, 220-240°C in zone 2, 210-220°C in zone 3, 210-230°C in zone 4, and 210-230°C in zone 5, the die temperature is 220-230°C, the main engine speed is 100-500r / min, and the vacuum degree is ≤0.1MPa.

[0073] Comparative Examples 1 to 5

[0074] A glass fiber reinforced ABS composition, comprising the following components in parts by weight:

[0075] ABS resin; glass fiber; compatibilizer; antimony trioxide or titanium dioxide; silane coupling agent; lubricant and processing aid, the processing aid is an antioxidant; the specific content of each component is shown in Table 2 below.

[0076] Table 2 Composition of glass fiber reinforced ABS compositions of each comparative example (in parts by weight)

[0077] Table 2

[0078] Components Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 ABS resin 1 75 75 75 75 75 Glass fiber 1 20 20 20 20 20 Compatibilizer 4 4 4 4 4 Titanium dioxide / 5 / / / Antimony trioxide 1 / / 30 10 / Antimony trioxide 3 / / / / 10 Silane coupling agent 1 / / 0.3 2 0.3 lubricant 0.5 0.5 0.5 0.5 0.5 antioxidants 0.3 0.3 0.3 0.3 0.3

[0079] The preparation method of Comparative Example 1 is basically the same as that of Example 1, except that antimony trioxide is not added in Comparative Document 1. The rest is the same as that of Example 1 and will not be repeated here.

[0080] The preparation method of Comparative Example 2 is basically the same as that of Example 1, except that S1 is deleted, antimony trioxide is replaced by titanium dioxide, and the titanium dioxide is not treated with a silane coupling agent. The rest is the same as that of Example 1 and will not be repeated here.

[0081] The preparation methods of the glass fiber reinforced ABS compositions of Comparative Examples 3 to 5 are the same as those of Example 1 and will not be described again here.

[0082] Result detection

[0083] The glass fiber reinforced ABS compositions of the above examples and comparative examples were injection molded into standard specimens using a Ningbo Haitian Bochuang injection molding machine BS650-III. The injection molding temperature was 230-240-240-250°C. The specimens were tested using the following performance test methods:

[0084] (1) Tensile strength: According to ISO 527-2-2012 standard method, the specimen is a type I specimen, and the testing equipment is a tensile testing machine Z020 from Zwick, Germany.

[0085] The tensile strength retention rate is the percentage of the tensile strength of the ABS composition to which antimony trioxide and a silane coupling agent, or titanium dioxide are added to the tensile strength of the ABS composition to which antimony trioxide and a silane coupling agent, or titanium dioxide are not added, under the premise that the weight proportions of ABS resin, glass fiber, compatibilizer, lubricant and antioxidant are the same.

[0086] (2) L value: The test equipment is X-Rite spectrophotometer Ci7600. The L value represents the whiteness of the color. The larger the L value, the higher the whiteness.

[0087] (3) Determination of the average retained length L of glass fibers in glass fiber reinforced ABS composition: The average retained length (average value) of glass fibers in the material was determined according to the ISO 22314-2006 standard method.

[0088] The specific test results are shown in Table 3 below:

[0089]

[0090]

[0091] It can be seen from the above data that the glass fiber reinforced ABS composition of the present invention has a whiteness of above 91 and has good mechanical properties, with a tensile strength retention rate of above 89%.

[0092] As can be seen from Example 1 and Comparative Example 1, the material in Comparative Example 1, which lacks titanium dioxide, exhibits high mechanical properties but low whiteness, specifically an L value of only around 86-87. When 5 parts of titanium dioxide are added to the system in Comparative Example 2, the whiteness rapidly increases, reaching an L value of around 93-94. However, the material's mechanical properties significantly decrease, as evidenced by a significant drop in tensile strength. Comparative Example 5, dyed with conventional synergistic flame retardant micron-sized antimony trioxide, also exhibits a significant decrease in tensile strength.

[0093] It can be seen from Example 1 and Comparative Example 3 that when the amount of antimony trioxide used is too much, the whiteness of the material does not change much, but the mechanical properties are greatly reduced.

[0094] It can be seen from Example 1 and Comparative Example 4 that when the amount of silane coupling agent is too much, the mechanical properties of the material are significantly reduced, and the whiteness of the material is also slightly reduced. This is because the excessive content of the coupling agent may result in a certain excess after the reaction of the coupling agent and antimony trioxide, affecting the interface of the composite material, thereby having a negative impact on the whiteness and mechanical properties.

[0095] It can be seen from Examples 1, 2 and 3 that when the melt flow rate of the ABS resin is 20 to 40 g / 10 min, it is more conducive to improving the tensile strength and whiteness of the composition.

[0096] It can be seen from Examples 1 and 5 that the average diameter of the glass fiber is 11 to 14 μm, which is more conducive to improving the tensile strength and L value of the composite material.

[0097] It can be seen from Examples 1 and 6 to 9 that when the silane coupling agent is a bisaminosilane coupling agent or a monoaminosilane coupling agent, it is more conducive to improving the tensile strength of the composition material.

[0098] It can be seen from Examples 1 and 12 that in Example 1, by first obtaining the silane coupling agent-modified antimony trioxide and then mixing it with other components, the glass fiber reinforced ABS composition obtained has better mechanical properties and L value.

[0099] Obviously, the above embodiments of the present invention are merely examples for the purpose of clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Those skilled in the art will appreciate that other variations or modifications can be made based on the above description. It is not necessary and impossible to enumerate all embodiments here. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention shall be included within the scope of protection of the claims of the present invention.

Claims

1. A glass fiber reinforced ABS composition, characterized in that: Calculated by weight, it includes the following components: Wherein, the average particle size of antimony trioxide is 20 to 50 nm; The average retention length L of the glass fibers in the glass fiber reinforced ABS composition is 400 to 600 μm; The average diameter of the glass fiber is 11-14 μm.

2. The glass fiber reinforced ABS composition according to claim 1, wherein: The silane coupling agent is one or more of a bisaminosilane coupling agent, a monoaminosilane coupling agent, an epoxysilane coupling agent, a methylsilane coupling agent, a phenylsilane coupling agent or a long-chain alkylsilane coupling agent.

3. The glass fiber reinforced ABS composition according to claim 1, wherein: The average retention length L of the glass fibers in the glass fiber reinforced ABS composition is 450 to 600 μm.

4. The glass fiber reinforced ABS composition according to claim 1, wherein: The melt mass flow rate of the ABS resin is 20 to 40 g / 10 min, the test standard is ASTM D-1238-2013, and the test conditions are 220° C. and 10 kg.

5. The glass fiber reinforced ABS composition according to claim 1, wherein: The compatibilizer is one or more of ABS-g-MAH, ABS-g-GMA, AS-g-MAH, methyl methacrylate, styrene-maleic anhydride copolymer or styrene-acrylonitrile-glycidyl methacrylate copolymer.

6. The glass fiber reinforced ABS composition according to claim 1, wherein: The lubricant is one or more of fatty acid amide, pentaerythritol stearate, solid paraffin, liquid paraffin, stearate, silicone or N,N'-ethylene bisstearamide.

7. The glass fiber reinforced ABS composition according to claim 1, wherein: The processing aid is an antioxidant, and the antioxidant is a hindered phenol antioxidant and / or a phosphite antioxidant.

8. The method for preparing the glass fiber reinforced ABS composition according to any one of claims 1 to 7, characterized in that: The steps include: S1. A silane coupling agent aqueous solution and antimony trioxide are mixed and reacted, washed, and dried to obtain a silane coupling agent-modified antimony trioxide; wherein the reaction temperature is 60 to 70 ° C, and the reaction time is 6 to 8h; S2. The components except the glass fiber are mixed evenly with the silane coupling agent-modified antimony trioxide in S1 and fed into a twin-screw extruder. The glass fiber is side-fed into the twin-screw extruder. The components are melt-extruded and granulated at 210-250° C. through the twin-screw extruder, and then dried to obtain the glass fiber-reinforced ABS composition.

9. Use of the glass fiber reinforced ABS composition according to any one of claims 1 to 7 in the preparation of fan blade components of white household appliances.

Images