Polyester composite material as well as preparation method and application thereof

Abstract

The invention discloses a polyester composite material as well as a preparation method and application thereof. The polyester composite material comprises the following components in parts by weight: 15-55 parts of polybutylene terephthalate, 15-55 parts of polyphenyl ether, 4-20 parts of a bromine-containing flame retardant, 0.07-3 parts of a titanium-containing inorganic component and 10-45 parts of glass fibers. The titanium-containing inorganic component comprises titanium powder and titanate in a mass ratio of 1: (0.2-4). According to the polyester composite material disclosed by the invention, the number of times of strip breakage during alloying production and extrusion is small, and continuous production of the polyester composite material is favorably realized.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, and more specifically, to a polyester composite material, its preparation method, and its application. Background Technology

[0002] Polybutylene terephthalate (PBT) is a polyester engineering plastic with high mechanical strength, primarily manifested in its toughness, fatigue resistance, and self-lubricating properties. Therefore, it is commonly used in the electronics, automotive, and machinery industries. Furthermore, PBT exhibits outstanding chemical resistance, heat resistance, and excellent electrical properties; however, it lacks flame retardancy and exhibits insufficient temperature resistance due to its low glass transition temperature. Polyphenylene ether (PPE) is a high-performance thermoplastic engineering plastic with good heat resistance and self-flame retardancy. When used together with PBT as a matrix resin, it can improve the flame retardancy and temperature resistance of PBT, making it suitable for applications such as cooling systems in humanoid robots and automotive parts. However, due to various reasons, during the alloying process, PBT and PPE are prone to breakage when extruded from the extruder die to the pelletizer, leading to interruptions in continuous production and requiring re-extrusion to resume production, resulting in resource waste.

[0003] Therefore, it is of great significance to develop a polyester composite material that can suppress the breakage phenomenon during alloying production extrusion. Summary of the Invention

[0004] The purpose of this invention is to overcome the shortcomings of the prior art and provide a polyester composite material, its preparation method, and its application.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows: In a first aspect, the present invention provides a polyester composite material comprising the following components in parts by weight: 15-55 parts polybutylene terephthalate (PBT), 15-55 parts polyphenylene ether (PPE), 4-20 parts bromine-containing flame retardant, 0.07-3 parts titanium-containing inorganic components, and 10-45 parts glass fiber. The titanium-containing inorganic components include titanium powder and titanate in a mass ratio of 1:(0.2-4).

[0006] In this invention, the addition of a specific proportion of titanium powder and titanate can promote the compatibility between PBT, PPE, brominated flame retardant and glass fiber, making the internal structure of the system more uniform, robust and stable. This suppresses the breakage phenomenon during the extrusion of polyester composite materials in alloy production, which is beneficial to the continuous production of polyester composite materials.

[0007] Preferably, the mass ratio of titanium powder to titanate is one or any two of the following: 1:0.2, 1:0.3, 1:0.5, 1:0.7, 1:1, 1:1.2, 1:1.5, 1:1.7, 1:2, 1:2.2, 1:2.5, 1:2.7, 1:3, 1:3.2, 1:3.5, 1:3.7, 1:4.

[0008] More preferably, the mass ratio of titanium powder to titanate is 1:(0.5-2).

[0009] Preferably, the titanium powder has an average particle size of 0.5-10 μm.

[0010] Preferably, the average particle size of the titanium powder is one or any two of the following: 0.5μm, 1μm, 2μm, 3μm, 4μm, 5μm, 6μm, 7μm, 8μm, 9μm, and 10μm.

[0011] More preferably, the titanium powder has an average particle size of 5-10 μm.

[0012] In this invention, the titanium powder is elemental titanium.

[0013] Preferably, the titanate includes at least one of calcium titanate, lead titanate, magnesium titanate, cerium titanate, lanthanum titanate, strontium titanate, zinc titanate, and barium titanate.

[0014] Preferably, the average particle size of the titanate is 0.1-20 μm.

[0015] Preferably, the average particle size of the titanate is one or any two of the following: 0.1 μm, 0.2 μm, 0.5 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 7 μm, 18 μm, 19 μm, and 20 μm.

[0016] More preferably, the titanate has an average particle size of 0.1-10 μm.

[0017] In this invention, the average particle size of the titanium powder and / or titanate is measured as follows: the titanium powder and / or titanate are subjected to particle size analysis test using a laser particle size analyzer - Mastersizer3000 according to the national standard GB / T 41949-2022, and the D50 particle size is taken as the average particle size of the titanium powder and / or titanate.

[0018] Preferably, the intrinsic viscosity of the polybutylene terephthalate (PBT) is 0.5-1.4 dl / g, specifically 0.5-1.2 dl / g.

[0019] Preferably, the intrinsic viscosity of the polybutylene terephthalate (PBT) is one or any two of the following values: 0.5 dl / g, 0.6 dl / g, 0.7 dl / g, 0.8 dl / g, 0.82 dl / g, 0.9 dl / g, 1 dl / g, 1.02 dl / g, 1.1 dl / g, 1.2 dl / g, 1.3 dl / g, and 1.4 dl / g.

[0020] More preferably, the intrinsic viscosity of the polybutylene terephthalate (PBT) is 0.8-1.2 dl / g, specifically 0.8-1.1 dl / g.

[0021] In this invention, the intrinsic viscosity of polybutylene terephthalate (PBT) is measured as follows: The intrinsic viscosity of PBT is measured according to GB / T 1632.1-2008. A 0.005 g / ml PBT solution is prepared using a phenol and tetrachloroethane mixture (volume ratio 3:2) as the solvent. The time it takes for the PBT solution to flow through a temperature Ubbelohde viscometer and the time it takes for the solvent (the phenol and tetrachloroethane mixture (volume ratio 3:2)) to flow through the temperature Ubbelohde viscometer are measured at 23°C. The intrinsic viscosity of PBT is then calculated using the formula.

[0022] Preferably, the polyphenylene oxide (PPE) has a shear viscosity of 200-600 Pa·s.

[0023] Preferably, the shear viscosity of the polyphenylene ether (PPE) is a range of one or any two of the following: 200 Pa·s, 250 Pa·s, 300 Pa·s, 350 Pa·s, 400 Pa·s, 450 Pa·s, 500 Pa·s, 550 Pa·s, and 600 Pa·s.

[0024] More preferably, the shear viscosity of the polyphenylene ether (PPE) is 400-600 Pa·s.

[0025] In this invention, the shear viscosity of the polyphenylene ether (PPE) is measured using a rheometer at a temperature of 280°C and a shear rate of 100 s. -1 The shear viscosity of polyphenylene oxide (PPE) was measured under the specified conditions.

[0026] Commonly used brominated flame retardants in this field can be used in this invention. For example, the brominated flame retardant is at least one of brominated epoxy polymer, brominated polycarbonate, and brominated polystyrene (BPS).

[0027] Preferably, the average length of the glass fiber is 2-6 mm.

[0028] Preferably, the average length of the glass fiber is a range of one or any two of 2mm, 3mm, 4mm, 5mm, 6mm, 7mm, and 8mm.

[0029] More preferably, the average length of the glass fiber is 2-4 mm.

[0030] Preferably, the glass fiber has an average diameter of 8-15 μm.

[0031] Preferably, the average diameter of the glass fiber is one or any two of the following: 8μm, 9μm, 10μm, 11μm, 12μm, 13μm, 14μm, and 15μm.

[0032] In this invention, the method for measuring the average length of the glass fiber is as follows: at least 150 glass fibers are selected, the length of the glass fibers is measured using an optical microscope, and the average value is calculated as the average length of the glass fiber.

[0033] Preferably, the polyester composite material further includes at least one of a synergistic flame retardant and a toughening agent.

[0034] More preferably, the synergistic flame retardant is present in parts by weight of 0.5-7 parts, specifically 1-5 parts.

[0035] More preferably, the synergistic flame retardant is in the range of one or both of the following weight parts: 0.5 parts, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, and 7 parts.

[0036] More preferably, the toughening agent is present in 0.5-8 parts by weight, specifically 0.5-4 parts.

[0037] More preferably, the toughening agent is in the range of one or both of the following weight parts: 0.5 parts, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, and 8 parts.

[0038] In this invention, commonly used synergistic flame retardants and toughening agents in the art can be used. For example, the synergistic flame retardants include, but are not limited to, at least one of antimony white (antimony trioxide), phosphazene, melamine cyanurate (MCA), aluminum diethylphosphonate (ADP), melamine polyphosphate (MPP), and phosphazene; and the toughening agents include, but are not limited to, at least one of ethylene-acrylate copolymer (EAA), ethylene-octene copolymer grafted glycidyl methacrylate (POE-g-GMA), and ethylene-methyl acrylate copolymer (EMA).

[0039] Preferably, in the polyester composite material, the weight parts of polybutylene terephthalate (PBT) are one or any two of the following: 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, and 55 parts; the weight parts of polyphenylene ether (PPE) are one or any two of the following: 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, and 55 parts; and the weight parts of the brominated flame retardant are 4 parts, 5 parts, 6 parts, 7 parts, 10 parts, 15 parts, and 16 parts. The weight of glass fiber is one or more of 10, 15, 20, 25, 30, 35, 40, and 45 parts, or any two of the weight ranges; the weight of titanium-containing inorganic components is one or more of 0.07, 0.08, 0.09, 0.1, 0.2, 0.5, 0.7, 0.8, 1, 1.2, 1.5, 1.7, 2, 2.2, 2.5, 2.7, and 3 parts, or any two of the weight ranges.

[0040] Preferably, the polyester composite material comprises the following components in parts by weight: 20-50 parts polybutylene terephthalate (PBT), 20-50 parts polyphenylene ether (PPE), 7-16 parts brominated flame retardant, and 0.1-1 parts... Contains titanium inorganic components and 15-40 parts glass fiber.

[0041] Preferably, based on the weight of the polyester composite material, the weight percentage of polybutylene terephthalate is ≥15%, specifically 17%-50%.

[0042] Secondly, the present invention provides a method for preparing a polyester composite material, comprising the following steps: The components are mixed, melt-extruded, and granulated to obtain the polyester composite material.

[0043] Preferably, during the melt extrusion, a screw extruder is used, with the screw extruder having a machine body temperature of 100-140°C in zone one, 150-190°C in zone two, 180-220°C in zone three, 200-240°C in zone four, 230-270°C in zone five, and a temperature of 250-300°C starting from zone six.

[0044] In this invention, the screw extruder is a single-screw extruder or a twin-screw extruder.

[0045] Thirdly, the present invention provides an application of polyester composite materials in automobiles and / or humanoid robots.

[0046] In this invention, the application of polyester composite materials in automobiles includes, but is not limited to, the application of polyester composite materials in at least one of the following: automotive lamp covers, seats, dashboard brackets, air conditioning systems, ventilation systems, interior parts, engine hoods, radiator grilles, etc.

[0047] In this invention, the application of polyester composite materials in humanoid robots includes, but is not limited to, the application of polyester composite materials in at least one of the humanoid robot's heat dissipation system, relay, sensor, etc., wherein the heat dissipation system includes, but is not limited to, a heat sink.

[0048] Compared with the prior art, the beneficial effects of the present invention are as follows: In this invention, the addition of a specific proportion of titanium powder and titanate can promote the compatibility between PBT, PPE, brominated flame retardant and glass fiber, making the internal structure of the system more uniform, robust and stable. This suppresses the breakage phenomenon during the extrusion of polyester composite materials in alloy production, which is beneficial to the continuous production of polyester composite materials. Detailed Implementation

[0049] 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.

[0050] The experimental methods in the following examples and comparative examples, where specific conditions are not specified, are generally performed under conventional conditions in the art or as recommended by the manufacturer; the raw materials and reagents used, unless otherwise specified, are all commercially available from the conventional market.

[0051] The reagents used in the various embodiments and comparative examples of this invention are as follows: Polybutylene terephthalate-1 (PBT-1), PBTGX112, Sinopec Yizheng Chemical Fiber Co., Ltd., intrinsic viscosity 0.82 dl / g; Polybutylene terephthalate-2 (PBT-2), PBTGX121, Sinopec Yizheng Chemical Fiber Co., Ltd., intrinsic viscosity 1.02 dl / g; Polybutylene terephthalate-3 (PBT-3), PBT GX111, Sinopec Yizheng Chemical Fiber Co., Ltd., intrinsic viscosity 0.6 dl / g; Polyphenylene oxide-1 (PPE-1), LXN040, Nantong Xingchen, shear viscosity 400 Pa·s; Polyphenylene oxide-2 (PPE-2), LXN045, Nantong Xingchen, shear viscosity 600 Pa·s; Polyphenylene oxide-3 (PPE-3), LXN035, Nantong Xingchen, shear viscosity 200 Pa·s; Brominated flame retardant, brominated epoxy polymer, F-2100H, Israel Dead Sea ICL; Titanium powder-1, with an average particle size of 5 μm, was obtained by grinding and crushing 300-mesh titanium powder (T819354, Shanghai Maclean) and then screening; Titanium powder-2, with an average particle size of 10 μm, was obtained by grinding and crushing 300-mesh titanium powder (T819354, Shanghai Maclean) and then screening; Titanium powder-3, with an average particle size of 0.5 μm, was obtained by grinding and crushing 300-mesh titanium powder (T819354, Shanghai Maclean) and then screening; Calcium titanate-1, with an average particle size of 10 μm, was obtained by grinding and crushing calcium titanate (C476697, Shanghai Aladdin) with a maximum particle size of 45 μm and then screening. Calcium titanate-2, with an average particle size of 0.1 μm, was obtained by grinding and crushing calcium titanate (C476697, Shanghai Aladdin) with a maximum particle size of 45 μm and then screening. Calcium titanate-3, with an average particle size of 20 μm, was obtained by grinding and crushing calcium titanate (C476697, Shanghai Aladdin) with a maximum particle size of 45 μm and then screening. Lead titanate with an average particle size of 10 μm was obtained by grinding and crushing lead titanate (L812620, Shanghai Maclean) with a maximum particle size of 45 μm and then screening it. Strontium titanate, with an average particle size of 10 μm, was obtained by grinding and crushing 200-mesh strontium titanate (PA05701, Guangdong Wengjiang Chemical Reagent) and then screening. Titanium trioxide with an average particle size of 10 μm was obtained by grinding and crushing 100-mesh titanium trioxide (T819037, Shanghai Maclean) and then screening. Synergistic flame retardant, antimony white (antimony trioxide), commercially available; Toughening agent, ethylene-octene copolymer grafted glycidyl methacrylate (POE-g-GMA), SOG-03, Jia Yi Rong; Glass fiber-1, ECS13-04-508A, China Jushi Co., Ltd., glass fiber with an average length of 4mm and an average diameter of 13μm. Glass fiber-2, glass fiber with an average length of 2 mm and an average diameter of 13 μm, was obtained by cutting and shredding glass fiber-1 (ECS13-04-508A, China Jushi Co., Ltd.) and screening. Glass fiber-3, ECS13-06-558, China Jushi Co., Ltd., glass fiber with an average length of 6mm and an average diameter of 13μm; In this invention, the intrinsic viscosity of polybutylene terephthalate (PBT) is measured as follows: The intrinsic viscosity of PBT is measured according to GB / T 1632.1-2008. A 0.005 g / ml PBT solution is prepared using a phenol and tetrachloroethane mixture (volume ratio 3:2) as the solvent. The time it takes for the PBT solution to flow through a temperature Ubbelohde viscometer and the time it takes for the solvent (the phenol and tetrachloroethane mixture (volume ratio 3:2)) to flow through the temperature Ubbelohde viscometer are measured at 23°C. The intrinsic viscosity of PBT is then calculated using the formula.

[0052] In this invention, the shear viscosity of the polyphenylene ether (PPE) is measured using a rheometer at a temperature of 280°C and a shear rate of 100 s. -1 The shear viscosity of polyphenylene oxide (PPE) was measured under the specified conditions.

[0053] In this invention, the average particle size of the titanium powder and / or titanate and / or titanium trioxide is measured as follows: the titanium powder and / or titanate are subjected to particle size analysis test using a laser particle size analyzer - Mastersizer3000 according to the national standard GB / T 41949-2022, and the D50 particle size is taken as the average particle size of the titanium powder and / or titanate and / or titanium trioxide.

[0054] In this invention, the method for measuring the average length of the glass fiber is as follows: at least 150 glass fibers are selected, the length of the glass fibers is measured using an optical microscope, and the average value is calculated as the average length of the glass fiber.

[0055] Examples 1-18 and Comparative Examples 1-3 Examples 1-18 and Comparative Examples 1-4 provide different polyester composite materials, differing only in the type and amount of each component. By weight, Examples 1-18 and Comparative Examples 1-4 comprise the components shown in Table 1. The preparation methods of the polyester composite materials of Examples 1-18 and Comparative Examples 1-4 include the following steps: The components are mixed and melt-extruded using a single-screw extruder at an extrusion frequency of 40 Hz, followed by granulation to obtain the polyester composite material. The temperature of the single screw extruder is 120°C in zone 1, 170°C in zone 2, 200°C in zone 3, 220°C in zone 4, 250°C in zone 5, and 280°C starting from zone 6. Table 1. Weight parts of each component in the polyester composite materials of Examples 1-18 Table 2 shows the weight parts of each component in the polyester composites of Comparative Examples 1-4. Performance testing The performance of the polyester composite materials in each embodiment and comparative example was tested, as follows: 1. Bar breakage test: According to Table 1-2, mix the components of each example or comparative example polyester composite material, take 20 kg, put it into a single screw extruder, and under the conditions of extrusion temperature of 270℃ and extrusion frequency of 40Hz, extrude from the extruder die to the pelletizer for alloying production. Record the number of times the strip breakage phenomenon occurs during the process, repeat the experiment 4 times, and take the average value; then, pelletize the polyester composite material through the pelletizer. 2. Tensile strength test: According to GB / T 1040.2-2006 standard, the polyester composite materials of each embodiment or comparative example were injection molded at an injection temperature of 260°C to form 1A type specimens with a thickness of 4 mm. The tensile strength of the polyester composite materials was measured at a speed of 10 mm / min, 23°C, and 50% RH. 3. Flame retardant performance test: The polyester composite materials of each embodiment or comparative example were injection molded at an injection temperature of 260°C to form a sample strip with a length of 125 mm, a width of 13 mm, and a thickness of 3 mm. The sample strip was then subjected to a vertical burning test according to the UL94 standard. The experimental results are shown in the table below: Table 3 Performance test results of polyester composite materials in each example and comparative example As shown in Table 3, the polyester composite material of the present invention can achieve a flame retardant rating of V-0 while ensuring flame retardancy and temperature resistance. Furthermore, it exhibits fewer instances of breakage during alloying extrusion, facilitating continuous production of the polyester composite material; specifically, the number of breakages in a 20kg batch of polyester composite material is ≤8. In addition, the polyester composite material of the present invention also possesses good tensile strength (≥105MPa).

[0056] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended 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. A polyester composite material, characterized in that, The components include the following parts by weight: 15-55 parts polybutylene terephthalate, 15-55 parts polyphenylene ether, 4-20 parts bromine-containing flame retardant, 0.07-3 parts titanium-containing inorganic components, 10-45 parts glass fiber; The titanium-containing inorganic components include titanium powder and titanate in a mass ratio of 1:(0.2-4).

2. The polyester composite material as described in claim 1, characterized in that, The mass ratio of titanium powder to titanate is 1:(0.5-2).

3. The polyester composite material as described in claim 1, characterized in that, The titanium powder has an average particle size of 5-10 μm.

4. The polyester composite material as described in claim 1, characterized in that, The titanate has an average particle size of 0.1-10 μm.

5. The polyester composite material as described in claim 1, characterized in that, Includes at least one of the following (1)-(2): (1) the intrinsic viscosity of the polybutylene terephthalate is 0.8-1.2 dl / g; (2) The shear viscosity of the polyphenylene ether is 400-600 Pa·s.

6. The polyester composite material as described in claim 1, characterized in that, The titanate includes at least one of calcium titanate, lead titanate, magnesium titanate, cerium titanate, lanthanum titanate, strontium titanate, zinc titanate, and barium titanate.

7. The polyester composite material as described in claim 1, characterized in that, The average length of the glass fiber is 2-4 mm.

8. The polyester composite material as described in claim 1, characterized in that, The polyester composite material also includes at least one of a synergistic flame retardant and a toughening agent.

9. A method for preparing a polyester composite material as described in any one of claims 1-8, characterized in that, The process includes the following steps: mixing the components, melt extrusion, and granulation to obtain the polyester composite material.

10. The use of a polyester composite material as described in any one of claims 1-8 in automobiles and / or humanoid robots.

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