AS (acrylonitrile-styrene) composite material as well as preparation method and application thereof

Abstract

The invention discloses an AS (acrylonitrile-styrene) composite material as well as a preparation method and application thereof, and belongs to the technical field of polymer engineering plastics. The AS composite material provided by the invention is prepared from the following components in parts by mass: 58 to 82 parts of AS resin, 18 to 42 parts of glass fiber, 2 to 8 parts of phenolic resin, 2 to 8 parts of glycidyl ester and 0.3 to 2.2 parts of compatilizer, the mass content of acrylonitrile in the AS resin is greater than or equal to 27%; the fluidity of the phenolic resin at the temperature of 125 DEG C is 22 to 52 mm; the compatilizer comprises an acrylate copolymer. The product prepared by the invention has excellent strength and modulus and relatively low specific gravity; therefore, the material can be widely applied to preparation of household appliances, automobile interior and exterior decorations and office equipment. In addition, the preparation method of the AS composite material provided by the invention is simple to operate and beneficial to actual production.

Description

Technical Field

[0001] This invention belongs to the field of polymer engineering plastics technology, and particularly relates to an AS composite material, its preparation method and application. Background Technology

[0002] As resin, or styrene-acrylonitrile copolymer, possesses high mechanical strength, excellent optical properties (good transparency and high gloss), high thermal stability, and ease of processing, making it widely used in industries such as home appliances, office equipment, and automobiles. To further improve the mechanical properties of as resin, it is often blended with glass fiber to achieve properties such as high modulus and high strength.

[0003] Glass fiber reinforced asphalt (AS) materials are widely used in axial and cross-flow fan blades for air conditioners. Air conditioner fan blades typically operate at high speeds, making them prone to deformation and cracking. Therefore, the mechanical properties of the materials are extremely important, especially high flexural modulus and high notched impact strength. Increasing the proportion of glass fiber can improve the flexural modulus and notched impact strength, but it also leads to an increase in density, increasing energy consumption during operation.

[0004] Chinese patent (CN 106751312 B) discloses a modified acrylonitrile-styrene copolymer and its preparation method. Glass fibers are added by traction through the secondary feed port of an extruder, improving the tensile and flexural strength of the material, but the improvement is limited. Chinese patent (CN110964270B) discloses a high-impact long glass fiber reinforced SAN composition, its preparation method, and its application. By replacing short-wavelength fibers with long glass fibers, a significant improvement in toughness is achieved (notched impact strength can be increased by more than four times), but the improvement in flexural modulus is insufficient. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of the prior art and provide an AS composite material with high flexural modulus and notched impact strength, as well as low specific gravity, and its preparation method and application.

[0006] To achieve the above objectives, in a first aspect of the present invention, the present invention provides an AS composite material comprising the following components in parts by weight: 58-82 parts AS resin, 18-42 parts glass fiber, 2-8 parts phenolic resin, 2-8 parts glycidyl ester, and 0.3-2.2 parts compatibilizer. The acrylonitrile content in the AS resin is ≥27% by mass; The phenolic resin has a flowability of 22-52 mm at 125°C; The compatibilizer includes acrylate copolymers.

[0007] The present invention provides an AS composite material by selecting a specific type of compatibilizer, and by selecting a specific number of components, and by ensuring that the mass content of acrylonitrile in the AS resin is within a certain range and the flowability of the phenolic resin at 125°C is within a certain range. The resulting AS composite material can simultaneously possess excellent flexural modulus and notched impact strength, and has a low specific gravity.

[0008] Specifically, this invention selects to simultaneously add phenolic resin and glycidyl ester with a certain fluidity range to a glass fiber reinforced AS resin system. The two work together and cure and crosslink at the extrusion processing temperature during the preparation process, forming an interpenetrating network, thereby improving the modulus and strength of the composite material while ensuring a low specific gravity. Furthermore, by selecting acrylate copolymers as compatibilizers and ensuring the acrylonitrile content of the AS resin is within a certain range, the compatibility between the AS resin and other components, as well as the bonding strength between the AS resin and glass fiber, can be effectively improved, thereby enhancing the strength and modulus of the composite material.

[0009] For example, the mass fraction of the AS resin can be any point value or any two points within a range of 58-82 parts, such as 60-80 parts, or 58, 60, 62, 65, 68, 70, 72, 75, 78, 80, 82, etc.; the glass fiber can be any point value or any two points within a range of 18-42 parts, such as 20-40 parts, or 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, etc.; the phenolic resin can be 2 The concentration of the glycidyl ester can be any point value or any two-point range between 2 and 8 parts, for example, it can be 3-7 parts, or 2, 3, 4, 5, 6, 7, 8 parts, etc.; the concentration of the glycidyl ester can be any point value or any two-point range between 2 and 8 parts, for example, it can be 3-7 parts, or 2, 3, 4, 5, 6, 7, 8 parts, etc.; the concentration of the compatibilizer can be any point value or any two-point range between 0.3 and 2.2 parts, for example, it can be 0.5-2 parts, or 0.3, 0.5, 0.8, 1 part, 1.2 parts, 1.5 parts, 1.8 parts, 2 parts, 2.2 parts, etc.

[0010] Preferably, in the AS composite material, the mass percentage of AS resin is ≥48%.

[0011] More preferably, the mass percentage of AS resin in the AS composite material is 58-68%.

[0012] It should be noted that the test method for the mass content of acrylonitrile in the AS resin is as follows: the nitrogen content is determined by an elemental analyzer, and the mass content of acrylonitrile is further calculated by molecular weight.

[0013] In a preferred embodiment of the AS composite material of the present invention, the mass content of acrylonitrile in the AS resin is 27-40%.

[0014] For example, the mass content of acrylonitrile in the AS resin can be any point value or a range between any two points between 27% and 40%, such as 28-39.5%, 28-31%, 28-35%, 31-39.5%, 35-39.5%, etc., or 27%, 28%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, etc.

[0015] Preferably, the acrylonitrile content in the AS resin is 31-35% by mass.

[0016] The present invention has found that the mass content of acrylonitrile in AS resin affects its interaction with glass fiber, as well as its compatibility with phenolic resin and glycidyl ester. When the mass content of acrylonitrile in AS resin is further selected within the above-mentioned preferred range, the resulting composite material has better overall performance.

[0017] It should be noted that the present invention does not have any special requirements for the melt flow index of AS resin. For example, the melt flow index of the AS resin tested at 220°C / 10kg according to ISO 1133-1:2022-10 Plastics Thermoplastics Determination of Melt Mass Flow Rate (MFR) and Melt Volume Flow Rate (MVR) Part 1: Standard Methods can be 7-40 g / 10min.

[0018] It should be noted that the flowability test of the phenolic resin at 125℃ was conducted in accordance with GB / T 32688-2016 "Determination of Flow Distance of Plastic Phenolic Resin on Heated Glass Plate". Specifically, the sample was placed on a horizontal glass plate heated to 125±1℃ and kept at a constant temperature for approximately 3 minutes. Subsequently, the glass plate was tilted to a 60-degree angle within 5 seconds and maintained at 125℃ for 20 minutes. After removing the sample and cooling it to room temperature, the flowability was measured using vernier calipers.

[0019] For example, the flowability of the phenolic resin at 125°C can be any point value or a range between any two points between 22-52 mm, such as 24-50 mm, 24-33 mm, 24-40 mm, 33-40 mm, 33-50 mm, 40-50 mm, etc., or 22 mm, 25 mm, 28 mm, 30 mm, 32 mm, 35 mm, 38 mm, 40 mm, 42 mm, 45 mm, 48 mm, 50 mm, 52 mm, etc.

[0020] Preferably, the phenolic resin has a flowability of 33-40 mm at 125°C.

[0021] This invention has found that the flowability of phenolic resin at 125°C affects its ability to form an interpenetrating network structure with glycidyl ester, and also affects its compatibility with AS resin and glass fiber. When the flowability of phenolic resin at 125°C is further selected within the above range, the resulting composite material has higher flexural modulus and notched impact strength, and lower specific gravity.

[0022] As a preferred embodiment of the AS composite material of the present invention, the AS composite material comprises the following components in parts by weight: 65-75 parts AS resin, 20-30 parts glass fiber, 4-5 parts phenolic resin, 4-5 parts glycidyl ester, and 1-1.5 parts compatibilizer.

[0023] This invention has found that the mass fraction of components in AS composite materials affects the overall performance of the composite materials. When the mass fraction of components in the composite materials is further selected within the above-mentioned range, the resulting composite materials have higher flexural modulus and notched impact strength, and lower specific gravity.

[0024] In a preferred embodiment of the AS composite material of the present invention, the glycidyl ester includes at least one of aromatic glycidyl ester and triglycidyl isocyanurate.

[0025] Preferably, the glycidyl ester comprises an aromatic glycidyl ester.

[0026] This invention has found that aromatic glycidyl esters contain benzene ring functional groups. Compared with non-aromatic glycidyl esters, aromatic glycidyl esters have better compatibility with AS resins containing styrene units. Therefore, further selection of glycidyl esters, including aromatic glycidyl esters, can better improve the overall performance of composite materials.

[0027] More preferably, the aromatic glycidyl ester includes at least one of trimellitic acid triglycidyl ester, diglycidyl terephthalate, tris(ethylene oxide methyl) 1,2,4-benzenetricarboxylate, and tris(ethylene oxide methyl)benzene-1,3,5-tricarboxylate.

[0028] As a preferred embodiment of the AS composite material of the present invention, the acrylate copolymer includes at least one of polymethyl methacrylate-acrylic acid, ethylene-butyl acrylate copolymer, and ethylene-methacrylate-acrylate terpolymer.

[0029] It should be noted that this invention does not have specific requirements for the melt flow index of the acrylate copolymer. Exemplarily, the melt flow index of the acrylate copolymer, tested at 190°C / 2.16 kg according to ISO 1133-1:2022-10 Plastics Thermoplastics: Determination of Melt Mass Flow Rate (MFR) and Melt Volume Flow Rate (MVR) Part 1: Standard Methods, can be between 2.0 and 14.0 g / 10 min.

[0030] Preferably, the acrylate copolymer includes polymethyl methacrylate-acrylic acid.

[0031] The present invention has found that selecting the above-mentioned type of acrylate copolymer, especially the further preferred polymethyl methacrylate-acrylic acid copolymer, can better improve the compatibility between components, thereby effectively improving the overall performance of the composite material.

[0032] It should be noted that the present invention does not have any particular requirements on the average diameter of the glass fibers. For example, the average diameter of the glass fibers can be 8-13 μm.

[0033] As a preferred embodiment of the AS composite material of the present invention, the AS composite material further includes 0.1-1.2 parts of additives.

[0034] In a preferred embodiment of the AS composite material of the present invention, the additives include at least one of antioxidants and lubricants.

[0035] Preferably, the antioxidant includes hindered phenolic antioxidants.

[0036] For example, the hindered phenolic antioxidants include antioxidant 1010, antioxidant CHINOX 1076, etc.

[0037] Preferably, the lubricant includes stearic acid-based lubricants.

[0038] For example, the stearic acid-based lubricant includes stearamide, stearic acid, calcium stearate, etc.

[0039] In a second aspect, the present invention provides a method for preparing the biodegradable composition, the method comprising the following steps: After drying, the raw materials are weighed and mixed, then fed into a twin-screw extruder. The mixture undergoes melt extrusion, stranding, cooling, pelletizing, and drying to obtain the AS composite material.

[0040] In a preferred embodiment of the preparation method described in this invention, the temperature of the melt extrusion is 190-200°C.

[0041] In a third aspect, the present invention provides a component made of the AS composite material described herein.

[0042] As a preferred embodiment of the component described in this invention, the component includes at least one of home appliances, automotive interior and exterior trim, and office equipment.

[0043] For example, the home appliances include air conditioners, microwave ovens, TVs, etc.; the automotive interior and exterior trim includes dashboard systems, door panels, front and rear bumpers, air intake grilles, etc.; and the office equipment includes printers, copiers, scanners, etc.

[0044] Compared with the prior art, the beneficial effects of the present invention are as follows: This invention provides an AS composite material that, by selecting a specific type of compatibilizer, along with choosing specific proportions of components, and ensuring that the acrylonitrile content of the AS resin and the flowability of the phenolic resin at 125°C are within a certain range, results in an AS composite material that simultaneously possesses excellent flexural modulus and notched impact strength, while also having a low specific gravity. Therefore, it can be widely used in the manufacture of home appliances, automotive interior and exterior trim, and office equipment. Furthermore, the preparation method of the AS composite material provided by this invention is simple to operate and beneficial for practical production. Detailed Implementation

[0045] To better illustrate the purpose, technical solution, and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments.

[0046] Unless otherwise specified, the reagents, methods and equipment used in this invention are all conventional reagents, methods and equipment in the field.

[0047] AS Resin 1: Acrylonitrile content measured to be 31%, SAN KFA-180, Liaoning Kingfa Technology Co., Ltd. AS Resin 2: The measured mass content of acrylonitrile is 35%, SAN NX3400, Formosa Chemicals & Fibre (Ningbo) Co., Ltd. AS Resin 3: The measured mass content of acrylonitrile is 39.5%, Luran HH-12, INEOS Styrinthine. AS Resin 4: The measured mass content of acrylonitrile is 28%, SAN KFA-130L, Liaoning Kingfa Technology Co., Ltd. AS Resin 5: Acrylonitrile content measured to be 22%, SAN KFA-130B, Liaoning Kingfa Technology Co., Ltd. Glass fiber 1: average diameter 13μm, DCS13-3.0-109, Changzhou Tianma Group Co., Ltd.; Glass fiber 2: average diameter 7μm, ECS303-3-E, Chongqing International Composite Materials Co., Ltd.; Phenolic resin 1: The measured flowability at 125℃ was 33 mm, PF6233, Shengquan Group Co., Ltd. Phenolic resin 2: The measured flowability at 125℃ is 40 mm, PF-6318A, Shengquan Group Co., Ltd. Phenolic resin 3: The measured flowability at 125℃ is 24mm, PF6665, Shengquan Group Co., Ltd. Phenolic resin 4: The measured flowability at 125℃ is 50 mm, PF-6530A, Shengquan Group Co., Ltd. Phenolic resin 5: The measured flowability at 125℃ was 10 mm, PF6306, Shengquan Group Co., Ltd. Phenolic resin 6: The measured flowability at 125℃ is 58 mm, PF-6400A, Shengquan Group Co., Ltd. Glycidyl ester 1: Aromatic glycidyl ester, 1,2,4-benzenetricarboxylic acid tri(epoxyethylene methyl) ester, commercially available; Glycidyl ester 2: Aromatic glycidyl ester, diglycidyl terephthalate, commercially available; Glycidyl ester 3: Non-aromatic glycidyl ester, triglycidyl isocyanurate, commercially available; Oxyhexacyclobutane methacrylate, commercially available; Compatibilizer 1: Polymethyl methacrylate-acrylic acid, with a measured melt index of 4.2 g / 10 min at 190℃ / 2.16 kg, PMMA CM-207, LG Chem. Compatibilizer 2: Ethylene-butyl acrylate copolymer, with a measured melt index of 4.0 g / 10 min at 190℃ / 2.16 kg, 3427AC, DuPont, USA; Compatibilizer 3: Ethylene-methacrylic acid-acrylate terpolymer, with a measured melt index of 13.0 g / 10 min at 190℃ / 2.16 kg, AN4228C, Dow Chemical Company, USA; Compatibilizer 4: Styrene-maleic anhydride copolymer, with a measured melt index of 2.3 g / 10 min at 190℃ / 2.16 kg, SMA700, Shanghai Huawen Electronic New Materials Co., Ltd.; Antioxidant: A 1:1 mixture of antioxidant 1010 and antioxidant CHINOX 1076, commercially available; Lubricant: stearamide, commercially available.

[0048] Examples 1-14 and Comparative Examples 1-11 The present invention provides an AS composite material in the embodiments and comparative examples, wherein the component content (parts by weight) of the AS composite material is shown in Tables 1-3; Table 1 Table 2 Table 3 The preparation methods for the examples and comparative examples are as follows: After drying, the raw materials are weighed and added to a mixer for uniform mixing. Then, the mixture is fed into a twin-screw extruder, and the feed rate of the twin-screw extruder is adjusted to 50 kg / hour. After extrusion, stranding, cooling, pelletizing, and drying, AS composite material is obtained. The parameters of the twin-screw extruder are as follows: the temperature of each screw section from the feed port to the die head is 190℃, 190℃, 195℃, 195℃, 200℃, and 200℃, respectively; the screw speed is 300 rpm.

[0049] Example of effect The performance of the products prepared in the comparative examples of the present invention was verified by test items including the following aspects: 1. Flexural modulus test: The test standard refers to "ISO 178-2010 Plastics - Determination of Flexural Properties"; 2. Cantilever beam notched impact strength test: The test standard refers to "ISO 180-2000 Plastics - Determination of IZOD impact strength", and the notch type is Type A; 3. Specific gravity test: The test standard refers to "ISO 1183-1 Plastics - Non-foamed plastics - Determination of density - Part 1: Immersion method, liquid pyrometer method and titration method".

[0050] The test results are shown in Table 4. Table 4 As can be seen from Table 4, when the technical solution of the present invention is adopted, the obtained product has excellent modulus and strength, while having a low specific gravity; specifically, the flexural modulus of the obtained product is above 7854 MPa, and the notched impact strength of the cantilever beam is 7.5 kJ / m. 2 The specific gravity is above 1.35 g / cm³. 3 the following; As can be seen from Examples 1, 4-6 and Comparative Example 1, the mass content of acrylonitrile in AS resin will affect the product performance. When the mass content of acrylonitrile in AS resin in Comparative Example 1 is not within the range given in this invention, the flexural modulus of the obtained product decreases significantly. As can be seen from Examples 1, 8-10 and Comparative Examples 2-3, the flowability of phenolic resin at 125°C also affects the overall performance of the product. When the flowability of phenolic resin at 125°C in Comparative Example 2 is too low, the cantilever beam notched impact strength of the obtained product decreases significantly. When the flowability of phenolic resin at 125°C in Comparative Example 3 is too high, the flexural modulus of the obtained product decreases significantly. As can be seen from Examples 1, 13-14 and Comparative Example 4, the type of compatibilizer also affects the overall performance of the product. When the compatibilizer in Comparative Example 4 is not the acrylate copolymer of the present invention, the cantilever beam notched impact strength of the obtained product is significantly reduced. As can be seen from Examples 1, 11-12 and Comparative Example 5, the type of glycidyl ester also affects the performance of the product. When the product in Comparative Example 5 is not glycidyl ester, the flexural modulus and cantilever beam notched impact strength of the obtained product are significantly reduced. As can be seen from Examples 1-3 and Comparative Examples 6-8, the mass fraction of the components has a significant impact on the overall performance of the product. When the mass fraction of the components in Comparative Examples 6-8 is outside the range, the overall performance of the obtained product decreases significantly. As can be seen from Example 1 and Comparative Example 9, when phenolic resin and glycidyl ester are not added, increasing the amount of glass fiber can improve the flexural modulus to a certain extent, but the notched impact strength of the cantilever beam is not significantly improved, and the specific gravity of the product increases significantly. As can be seen from Example 1 and Comparative Example 10, when glycidyl ester is not added, but its amount is made up with phenolic resin, the flexural modulus and cantilever beam notched impact strength of the obtained product are significantly reduced. As can be seen from Example 1 and Comparative Example 11, when glycidyl ester is not added, but its amount is made up with phenolic resin, the flexural modulus and cantilever beam notched impact strength of the obtained product are significantly reduced.

[0051] Finally, it should be noted that the above embodiments are used to illustrate the technical solutions of the present invention and not to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. An AS composite material, characterized in that, The AS composite material comprises the following components in parts by weight: 58-82 parts AS resin, 18-42 parts glass fiber, 2-8 parts phenolic resin, 2-8 parts glycidyl ester, 0.3-2.2 parts compatibilizer; The mass content of acrylonitrile in the AS resin is ≥27%; The phenolic resin has a flowability of 22-52 mm at 125°C; The compatibilizer includes acrylate copolymers.

2. The AS composite material according to claim 1, characterized in that, The AS composite material comprises the following components in parts by weight: 65-75 parts AS resin, 20-30 parts glass fiber, 4-5 parts phenolic resin, 4-5 parts glycidyl ester, 1-1.5 parts compatibilizer.

3. The AS composite material according to claim 1, characterized in that, The acrylonitrile content in the AS resin is 27-40% by mass.

4. The AS composite material according to claim 1, characterized in that, The phenolic resin has a flowability of 30-43 mm at 125°C.

5. The AS composite material according to claim 1, characterized in that, The glycidyl ester includes at least one of aromatic glycidyl ester and triglycidyl isocyanurate; preferably, the aromatic glycidyl ester includes at least one of trimellitic acid triglycidyl ester, diglycidyl terephthalate, tris(ethylene oxide methyl) 1,2,4-benzenetricarboxylate, and tris(ethylene oxide methyl)benzene-1,3,5-tricarboxylate.

6. The AS composite material according to claim 1, characterized in that, The acrylate copolymers include at least one of polymethyl methacrylate-acrylic acid, ethylene-butyl acrylate copolymer, and ethylene-methacrylate-acrylate terpolymer.

7. The AS composite material according to claim 1, characterized in that, The AS composite material also includes 0.1-1.2 parts of additives.

8. The AS composite material according to claim 7, characterized in that, The additives include at least one of antioxidants and lubricants.

9. The method for preparing the AS composite material according to any one of claims 1-8, characterized in that, The preparation method includes the following steps: weighing the dried raw materials and mixing them, feeding them into a twin-screw extruder, and then performing melt extrusion, stranding, cooling, pelletizing, and drying to obtain the AS composite material.

10. A component, characterized in that, The component is made of the AS composite material as described in any one of claims 1-9.

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