Glass fiber reinforced polyetherimide black particles and preparation method thereof

Abstract

The present invention relates to the field of polymer materials technology and discloses glass fiber-reinforced polyetherimide black particles and a preparation method thereof. The glass fiber-reinforced polyetherimide black particles comprise the following components by weight: 60-100 parts polyetherimide, 1-40 parts glass fiber, 0.5-5 parts functional filler, 0.5-1.5 parts lubricant, and 0.1-1 part masterbatch. The preparation method of the functional filler comprises the following steps: A1. wet ball milling flake graphite and drying to obtain pretreated flake graphite; A2. wet ball milling the pretreated flake graphite, aluminum oxide, and tungsten carbide and drying to obtain the functional filler. This technical solution overcomes the problems of insufficient strength and poor processability of glass fiber-reinforced polyetherimide black particles in related technologies.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and in particular to glass fiber reinforced polyetherimide black particles and a preparation method thereof. Background Art

[0002] Polyetherimide ( Polyetherimide Polyetherimide (PEI) is a specialty engineering plastic with ether functional groups incorporated into the polyimide backbone. It exhibits excellent high-temperature resistance, insulation, flame retardancy, and chemical stability. Polyetherimide is primarily used in transportation, electrical and electronics, and machinery manufacturing. The conventional formula for preparing glass fiber (GF)-reinforced polyetherimide black granules consists of polyetherimide, glass fiber, and a dye. These granules are produced through melt extrusion and granulation in a twin-screw extruder.

[0003] Patent publication number CN101870815A discloses a method for melt extrusion of a thermotropic liquid crystal polymer and polyetherimide, which increases the melt flow rate and improves the material's processing performance. However, this method has the following drawbacks: the addition level of the thermotropic liquid crystal polymer is 15%, which is excessive and compromises the advantages of the substrate. The glass fiber-reinforced polyetherimide composite material obtained by adding 40 parts of GF to a PEI matrix has a tensile strength of 183 MPa and a flexural strength of 246 MPa. By comparison, the tensile strength of ULTEM™ 2410 (PEI+40GF) produced by Saudi Basic Industries Corporation (SABIC) is 180 MPa and the flexural strength is 241 MPa. Therefore, the strength of the glass fiber-reinforced polyetherimide composite material obtained by this patent is not significantly improved compared to ULTEM™ 2410.

[0004] The invention patent with publication number CN102010596B discloses a method for preparing modified glass fiber reinforced polyetherimide. The modified glass fiber improves the compatibility with the polyetherimide matrix, thereby improving the mechanical properties of the material. However, there are problems such as cumbersome glass fiber modification operations and serious pollution during the processing.

[0005] Therefore, it is necessary to prepare a glass fiber reinforced polyetherimide black particle with high strength to meet the growing practical application needs. Summary of the Invention

[0006] The present invention provides a glass fiber reinforced polyetherimide black particle and a preparation method thereof, which solves the problem of insufficient strength of the glass fiber reinforced polyetherimide black particle in the related art.

[0007] The technical solutions of the present invention are as follows:

[0008] The present invention provides a glass fiber reinforced polyetherimide black particle, comprising the following components in parts by weight: 60-100 parts of polyetherimide, 1-40 parts of glass fiber, 0.5-5 parts of functional filler, 0.5-1.5 parts of lubricant, and 0.1-1 part of masterbatch;

[0009] The preparation method of the functional filler comprises the following steps:

[0010] A1. Wet-milling the flake graphite and drying it to obtain pretreated flake graphite;

[0011] A2. Wet-milling the pretreated flake graphite, aluminum oxide, and tungsten carbide, and drying the mixture to obtain a functional filler.

[0012] The PEI used in the prior art is all imported ULTEM™ series products produced by Saudi Basic Industries Corporation (SABIC). The polyetherimide of the present invention is produced by China Energy Conservation Wanrun Co., Ltd. and has the advantage of low cost.

[0013] As a further technical solution, the glass fiber includes one or both of glass fibers having a flat cross section and glass fibers having a circular cross section.

[0014] As a further technical solution, the masterbatch includes a carrier-free carbon black masterbatch.

[0015] As a further technical solution, the carrier-free carbon black masterbatch contains 55 wt% carbon black and 45 wt% high-temperature resistant dispersant.

[0016] In the present invention, a carrier-free carbon black masterbatch is added to the formula of glass fiber reinforced polyetherimide. The high-temperature resistant dispersant in the masterbatch has a similar structure to the lubricant. In addition to dispersing the carbon black, it can also play a synergistic lubricating role with the lubricant, effectively improving the fluidity of the polyetherimide melt and improving the processability of the polyetherimide material.

[0017] As a further technical solution, the lubricant includes one or more of pentaerythritol tetrastearate, trimethylolpropane fatty acid ester, and polyethylene glycol fatty acid ester.

[0018] The lubricant can be a fluoroplastic or a fatty acid ester. Fluoroplastic lubricants can be, for example, polytetrafluoroethylene. Compared with fluoroplastic lubricants, fatty acid esters have the characteristics of high lubricity, environmental protection and biodegradability. They can reduce the friction between materials and between the materials and the surface of processing equipment, improve the fluidity of the polyetherimide melt, avoid adhesion of the melt to the equipment, improve the dispersibility of the glass fiber in the polyetherimide, prevent the glass fiber from being exposed, and improve the surface finish of the product. Among them, the fatty acid ester lubricant can be, for example, one or more of butyl stearate, monoglyceride of stearate, pentaerythritol tetrastearate, trimethylolpropane fatty acid ester, and polyethylene glycol fatty acid ester. In particular, when the fatty acid ester lubricant is pentaerythritol tetrastearate, trimethylolpropane fatty acid ester, or polyethylene glycol fatty acid ester, the lubricating effect is more prominent in the preparation process of glass fiber reinforced polyetherimide black particles.

[0019] As a further technical solution, the mass ratio of the glass fiber to the functional filler is 40-60:1.

[0020] As a further technical solution, when the glass fibers are glass fibers with a flat cross section and glass fibers with a circular cross section, the mass ratio of the glass fibers with a flat cross section to the glass fibers with a circular cross section is 4 to 7:1.

[0021] The existing technologies all adopt the method of adding additives or modifying the surface of glass fibers to increase the compatibility with the matrix. The performance is improved to a certain extent, but not significantly. The reason is that at high temperatures close to 400°C, additives or surface treatment agents are easily decomposed and become ineffective. Therefore, from the perspective of glass fiber appearance, the present invention selects glass fibers with circular cross sections and glass fibers with flat cross sections to compound. Since the flat glass fibers with cross sections similar to mica powder are significantly less subject to flow resistance than glass fibers with circular cross sections when flowing in polyetherimide resin, the melt flow rate is increased, the processability is improved, and the glass fibers are After compounding with glass fibers with circular cross-sections and functional fillers, the toughness of glass fiber reinforced polyetherimide is improved; the glass fibers with circular cross-sections serve as "reinforcers" for flat glass fibers and are oriented along the flow direction of the flat glass fibers. The orderly arranged and evenly dispersed glass fibers with circular cross-sections cooperate with the glass fibers with flat cross-sections to improve the strength and toughness of the glass fiber reinforced polyetherimide black particles; and when the mass ratio of glass fibers with flat cross-sections to glass fibers with circular cross-sections is 4~7:1, the synergistic effect reaches the best.

[0022] As a further technical solution, the mass ratio of the flake graphite, aluminum oxide and tungsten carbide is 3-5:1:1.

[0023] As a further technical solution, in step A1, the dispersion medium for the wet ball milling treatment includes one or more of methanol, ethanol, acetone, and N-methylpyrrolidone, and the rotation speed of the wet ball milling treatment is 160-280 rpm, and the time is 40-50 hours;

[0024] In step A2, the dispersion medium for the wet ball milling treatment includes one or both of a polyvinyl alcohol solution and a polyacrylamide solution, and the rotation speed of the wet ball milling treatment is 500-600 rpm, and the time is 15-20 h.

[0025] During wet ball milling, in step A1, when the flake graphite is pretreated, when the ball mill speed is low, the flaky structure of the flake graphite can be maintained and the deformation and damage of the lamellae can be reduced. In step A2, the ball mill speed is increased, the movement speed of the ball milling balls is accelerated, and the centrifugal force is increased. The higher speed can significantly improve the ball milling efficiency, accelerate the particle refinement speed, and cause local phase change and recombination of the powder.

[0026] As a further technical solution, in step A1 and step A2, the ball-to-material ratio during the wet ball milling treatment is independently 2~3:1, the ball milling balls are independently zirconia balls, and the zirconia balls are independently composed of 3mm diameter zirconia balls, 1mm diameter zirconia balls and 0.5mm diameter zirconia balls in a mass ratio of 1:3:1~3.

[0027] During ball milling, the zirconia balls are composed of 3mm diameter zirconia balls, 1mm diameter zirconia balls and 0.5mm diameter zirconia balls with a mass ratio of 1:3:1~3. Among them, the ball milling balls with smaller diameters can refine the powder and improve the uniformity of the powder. The ball milling balls with larger diameters have larger mass and kinetic energy and can generate stronger impact force during the ball milling process. The use of ball milling balls with different diameters for mixed ball milling can improve the ball milling composite effect of functional fillers.

[0028] The present invention also provides a method for preparing glass fiber reinforced polyetherimide black particles, which comprises the following steps:

[0029] After the polyetherimide is dried, it is mixed with the remaining components of the glass fiber reinforced polyetherimide black particles except the glass fiber for the first time, and then mixed with the glass fiber for extrusion granulation to obtain the glass fiber reinforced polyetherimide black particles.

[0030] As a further technical solution, the drying temperature is 120-150°C and the time is 4-6 hours;

[0031] The time of the first mixing is 3 to 5 minutes.

[0032] As a further technical solution, during the extrusion granulation, the temperature of the twin-screw extruder is set as follows: zone 1 temperature 340°C, zone 2 temperature 370°C, zone 3 temperature 380°C, zone 4 temperature 380°C, zone 5 temperature 390°C, zone 6 temperature 390°C, zone 7 temperature 390°C, zone 8 temperature 380°C, zone 9 temperature 380°C, and die head temperature 380°C.

[0033] The temperature setting of the twin-screw extruder is very important in the extrusion granulation process of polymer materials. The twin-screw extruder temperature set in the present invention can fully plasticize the polyetherimide. When mixed with other components, the material has excellent fluidity, is easy to transport, and ensures stable extrusion. The extruded glass fiber reinforced polyetherimide black particles have a smooth surface and few internal defects.

[0034] The working principle and beneficial effects of the present invention are:

[0035] In the present invention, polyetherimide is used as a matrix material to provide basic mechanical properties, and glass fiber can enhance the strength and rigidity of the material, effectively improving the mechanical properties of polyetherimide. When preparing the functional filler, flake graphite is wet-ball milled, the flake graphite is impacted and sheared, and after the flake graphite is peeled off, it is wet-ball milled with aluminum oxide and tungsten carbide. The particles rub and collide with each other, so that aluminum oxide and tungsten carbide can be evenly dispersed on the surface of the pretreated flake graphite, forming a functional filler composite system with special properties. The prepared functional filler and glass fiber jointly build a fiber network in the polyetherimide matrix and form riveting sites, thereby improving the strength of the glass fiber reinforced polyetherimide black particles and also improving the toughness of the glass fiber reinforced polyetherimide black particles. DETAILED DESCRIPTION

[0036] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0037] In the following examples and comparative examples, the polyetherimide model is VAT002, purchased from China Energy Conservation Wanrun Co., Ltd.

[0038] The model of glass fiber with a circular cross section is ECS13-4.5-510H;

[0039] The glass fiber with a flat cross section is model ECS301HP-3-M3, purchased from Chongqing International Composite Materials Co., Ltd.

[0040] The color masterbatch is a carrier-free carbon black masterbatch with a carbon black content of 55 wt% and a high-temperature resistant dispersant content of 45 wt%, purchased from Guangdong Jiucai New Materials Co., Ltd.

[0041] The particle size of flake graphite is 500 μm;

[0042] The particle size of aluminum oxide is 200 nm;

[0043] The particle size of tungsten carbide is 200 nm.

[0044] Example 1

[0045] Glass fiber reinforced polyetherimide black particles, comprising the following components in parts by weight: 60 parts of polyetherimide, 40 parts of glass fiber with a circular cross section, 1 part of functional filler, 0.5 parts of pentaerythritol tetrastearate, and 1 part of masterbatch;

[0046] The preparation method of the functional filler comprises the following steps:

[0047] A1. Place flake graphite and ethanol in a ball mill (ball-to-material ratio of 2:1, the ball milling balls are zirconia balls, and the zirconia balls are composed of 3 mm diameter zirconia balls, 1 mm diameter zirconia balls, and 0.5 mm diameter zirconia balls in a mass ratio of 1:3:1), wet ball milling at 160 rpm for 50 h, and drying to obtain pretreated flake graphite; the mass-to-volume ratio of flake graphite to ethanol is 1 g:5 mL;

[0048] A2. Place pretreated flake graphite, aluminum oxide, tungsten carbide, and a 3% (mass fraction) polyvinyl alcohol solution in a ball mill (ball-to-material ratio 2:1, using zirconia balls composed of 3 mm diameter, 1 mm diameter, and 0.5 mm diameter zirconia balls in a mass ratio of 1:3:1). Wet-mill at 500 rpm for 20 hours and dry to obtain a functional filler. The mass ratio of flake graphite, aluminum oxide, and tungsten carbide is 3:1:1; the mass-to-volume ratio of flake graphite to polyvinyl alcohol solution is 1 g:6 mL.

[0049] The preparation method of glass fiber reinforced polyetherimide black particles comprises the following steps:

[0050] The polyetherimide was placed in a forced air drying oven at 150° C. and dried for 4 hours, and mixed with the remaining components of the glass fiber reinforced polyetherimide black particles except the glass fiber with a circular cross section for 3 minutes to obtain a mixture;

[0051] The mixed material is placed in the main feeding hopper of a twin-screw extruder, and glass fibers with a circular cross section are placed in the side feeding port of the twin-screw extruder, and extruded into granules to obtain glass fiber reinforced polyetherimide black granules;

[0052] During extrusion granulation, the temperature of the twin-screw extruder is set as follows: zone 1 temperature 340°C, zone 2 temperature 370°C, zone 3 temperature 380°C, zone 4 temperature 380°C, zone 5 temperature 390°C, zone 6 temperature 390°C, zone 7 temperature 390°C, zone 8 temperature 380°C, zone 9 temperature 380°C, and die head temperature 380°C.

[0053] Example 2

[0054] Glass fiber reinforced polyetherimide black particles, comprising the following components in parts by weight: 60 parts of polyetherimide, 40 parts of glass fiber with a circular cross section, 1 part of functional filler, 1 part of pentaerythritol tetrastearate, and 1 part of masterbatch;

[0055] The preparation method of the functional filler comprises the following steps:

[0056] A1. Place flake graphite and ethanol in a ball mill (ball-to-material ratio of 3:1, the ball milling balls are zirconia balls, and the zirconia balls are composed of 3 mm diameter zirconia balls, 1 mm diameter zirconia balls, and 0.5 mm diameter zirconia balls in a mass ratio of 1:3:3), wet ball milling at 280 rpm for 40 h, and drying to obtain pretreated flake graphite; the mass volume ratio of flake graphite to ethanol is 1 g:5 mL;

[0057] A2. Place pretreated flake graphite, aluminum oxide, tungsten carbide, and a 3% (mass fraction) polyvinyl alcohol solution in a ball mill (ball-to-material ratio 3:1, using zirconia balls composed of 3 mm diameter, 1 mm diameter, and 0.5 mm diameter zirconia balls in a mass ratio of 1:3:3). Wet-mill at 600 rpm for 15 hours and dry to obtain a functional filler. The mass ratio of flake graphite, aluminum oxide, and tungsten carbide is 3:1:1; the mass-to-volume ratio of flake graphite to polyvinyl alcohol solution is 1 g:6 mL.

[0058] The preparation method of glass fiber reinforced polyetherimide black particles comprises the following steps:

[0059] The polyetherimide was placed in a forced air drying oven at 120° C. and dried for 6 hours, and mixed with the remaining components of the glass fiber reinforced polyetherimide black particles except the glass fiber with a circular cross section for 4 minutes to obtain a mixture;

[0060] The mixed material is placed in the main feeding hopper of a twin-screw extruder, and glass fibers with a circular cross section are placed in the side feeding port of the twin-screw extruder, and extruded into granules to obtain glass fiber reinforced polyetherimide black granules;

[0061] During extrusion granulation, the temperature of the twin-screw extruder is set as follows: zone 1 temperature 340°C, zone 2 temperature 370°C, zone 3 temperature 380°C, zone 4 temperature 380°C, zone 5 temperature 390°C, zone 6 temperature 390°C, zone 7 temperature 390°C, zone 8 temperature 380°C, zone 9 temperature 380°C, and die head temperature 380°C.

[0062] Example 3

[0063] Glass fiber reinforced polyetherimide black particles, comprising the following components in parts by weight: 60 parts of polyetherimide, 40 parts of glass fiber with a circular cross section, 1 part of functional filler, 1.5 parts of pentaerythritol tetrastearate, and 1 part of masterbatch;

[0064] The preparation method of the functional filler comprises the following steps:

[0065] A1. Place flake graphite and ethanol in a ball mill (ball-to-material ratio of 3:1, the ball milling balls are zirconia balls, and the zirconia balls are composed of 3 mm diameter zirconia balls, 1 mm diameter zirconia balls, and 0.5 mm diameter zirconia balls in a mass ratio of 1:3:2), wet ball mill at 250 rpm for 45 h, and dry to obtain pretreated flake graphite; the mass-to-volume ratio of flake graphite to ethanol is 1 g:5 mL;

[0066] A2. Place pretreated flake graphite, aluminum oxide, tungsten carbide, and a 3% (mass fraction) polyvinyl alcohol solution in a ball mill (ball-to-material ratio 3:1, using zirconia balls composed of 3 mm diameter, 1 mm diameter, and 0.5 mm diameter zirconia balls in a mass ratio of 1:3:2). Wet-mill at 500 rpm for 18 hours and dry to obtain a functional filler. The mass ratio of flake graphite, aluminum oxide, and tungsten carbide is 3:1:1; the mass-to-volume ratio of flake graphite to polyvinyl alcohol solution is 1 g:6 mL.

[0067] The preparation method of glass fiber reinforced polyetherimide black particles comprises the following steps:

[0068] The polyetherimide was placed in a forced air drying oven at 130° C. and dried for 5 hours, and mixed with the remaining components of the glass fiber reinforced polyetherimide black particles except the glass fiber with a circular cross section for 5 minutes to obtain a mixture;

[0069] The mixed material is placed in the main feeding hopper of a twin-screw extruder, and glass fibers with a circular cross section are placed in the side feeding port of the twin-screw extruder, and extruded into granules to obtain glass fiber reinforced polyetherimide black granules;

[0070] During extrusion granulation, the temperature of the twin-screw extruder is set as follows: zone 1 temperature 340°C, zone 2 temperature 370°C, zone 3 temperature 380°C, zone 4 temperature 380°C, zone 5 temperature 390°C, zone 6 temperature 390°C, zone 7 temperature 390°C, zone 8 temperature 380°C, zone 9 temperature 380°C, and die head temperature 380°C.

[0071] Example 4

[0072] The only difference between this embodiment and embodiment 3 is that the glass fiber with a circular cross section is replaced by a glass fiber with a flat cross section.

[0073] Example 5

[0074] The only difference between this embodiment and embodiment 3 is that eight-ninths of the mass of glass fibers with circular cross sections are replaced with an equal amount of glass fibers with flat cross sections.

[0075] Example 6

[0076] The only difference between this embodiment and embodiment 3 is that three-quarters of the mass of glass fibers with circular cross sections are replaced with an equal amount of glass fibers with flat cross sections.

[0077] Example 7

[0078] The only difference between this embodiment and embodiment 3 is that four-fifths of the mass of glass fibers with circular cross sections are replaced with an equal amount of glass fibers with flat cross sections.

[0079] Example 8

[0080] The only difference between this embodiment and embodiment 3 is that seven-eighths of the mass of glass fibers with circular cross-sections are replaced with an equal amount of glass fibers with flat cross-sections.

[0081] Example 9

[0082] The only difference between this embodiment and embodiment 3 is that the glass fiber reinforced polyetherimide black particles include the following components in parts by weight: 100 parts of polyetherimide, 1 part of glass fiber with a circular cross section, 5 parts of functional filler, 0.5 part of pentaerythritol tetrastearate, and 0.1 part of masterbatch; the mass ratio of flake graphite, aluminum oxide, and tungsten carbide is 5:1:1.

[0083] Example 10

[0084] The only difference between this embodiment and embodiment 3 is that the glass fiber reinforced polyetherimide black particles include the following components in parts by weight: 80 parts of polyetherimide, 30 parts of glass fiber with a circular cross section, 0.5 parts of functional filler, 1 part of pentaerythritol tetrastearate, and 1 part of masterbatch; the mass ratio of flake graphite, aluminum oxide, and tungsten carbide is 4:1:1.

[0085] Comparative Example 1

[0086] The difference between this comparative example and Example 1 is only that pentaerythritol tetrastearate and color masterbatch are not added.

[0087] Comparative Example 2

[0088] The difference between this comparative example and Example 1 is only that no color masterbatch is added.

[0089] Comparative Example 3

[0090] The only difference between this comparative example and Example 3 is that the glass fiber reinforced polyetherimide black particles include the following components in parts by weight: 60 parts of polyetherimide, 40 parts of glass fiber with a circular cross section, 0.6 parts of flake graphite, 0.2 parts of aluminum oxide, 0.2 parts of tungsten carbide, 1.5 parts of pentaerythritol tetrastearate, and 1 part of masterbatch.

[0091] Comparative Example 4

[0092] The only difference between this comparative example and Example 3 is that the preparation method of the functional filler comprises the following steps:

[0093] Flake graphite, aluminum oxide, tungsten carbide, and a 3% polyvinyl alcohol solution were placed in a ball mill (ball-to-material ratio of 3:1, the ball milling balls were zirconia balls, and the zirconia balls were composed of 3mm diameter zirconia balls, 1mm diameter zirconia balls, and 0.5mm diameter zirconia balls in a mass ratio of 1:3:2), and wet ball milled at 500 rpm for 18 hours and dried to obtain a functional filler; the mass ratio of flake graphite, aluminum oxide, and tungsten carbide was 3:1:1; the mass-to-volume ratio of flake graphite and polyvinyl alcohol solution was 1g:6mL.

[0094] Comparative Example 5

[0095] The only difference between this comparative example and Example 3 is that aluminum oxide is replaced by tungsten carbide.

[0096] Comparative Example 6

[0097] The only difference between this comparative example and Example 3 is that tungsten carbide is replaced by aluminum oxide.

[0098] Experimental example

[0099] The glass fiber reinforced polyetherimide black particles prepared in Examples 1 to 10 and Comparative Examples 1 to 6 were respectively subjected to performance tests according to the following performance test standards:

[0100] 1. Density: Tested in accordance with Method A of GB / T 1033.1-2008 "Plastics—Determination of density of non-foamed plastics—Part 1: Immersion method, liquid pycnometer method and titration method" at a temperature of 23°C. The result shall be rounded to two decimal places.

[0101] 2. Tensile strength and elongation at break: tested in accordance with GB / T 1040.2-2022 "Determination of tensile properties of plastics - Part 2: Test conditions for molded and extruded plastics", specimen type 1A specimen, test speed 50 mm / min;

[0102] 3. Bending strength: Tested in accordance with GB / T 9341-2008 "Determination of Flexural Properties of Plastics", specimen dimensions: length 80 mm, width 10 mm, thickness 4 mm; test speed 2 mm / min;

[0103] 4. Charpy notched impact strength: tested in accordance with GB / T 1043.1-2008 "Determination of impact properties of plastics - Part 1: Non-instrumented impact test", notch type: A-notch, specimen type: Type 1 specimen;

[0104] 5. Ash content: Tested in accordance with GB / T 9345-2008 "Plastics - Determination of ash content", test method: Method A;

[0105] 6. Melt flow rate: Tested in accordance with ASTM D1238 "Melt flow rate of thermoplastics by extrusion plastometer", the test conditions are 337℃ / 6.6kgf;

[0106] At the same time, the performance of the glass fiber reinforced polyetherimide black particles prepared in the present application was compared with that of Example 4 in the invention patent with publication number CN101870815A, the glass fiber reinforced polyetherimide product model ULTEM™ 2410 produced by Saudi Basic Industries Corporation, PEI-G40 produced by PRL of the United States, Edgetek™ PI-40GF / 000 BLACK produced by Avient, and OP-PEI 40GF produced by Oxford Polymers Co., Ltd. of the United States. The results are shown in Tables 1 and 2 below. “-” in the table indicates that the property was not tested.

[0107] Table 1 Performance test results

[0108]

[0109] Compared with CN101870815A-Example 4, ULTEM™ 2410, PEI-G40, Edgetek™ PI-40GF / 000BLACK, and OP-PEI 40GF, the glass fiber reinforced polyetherimide black particles prepared in Examples 1 to 4 of the present application have significantly improved properties such as strength and toughness, and have the advantage of low cost.

[0110] Compared with Comparative Examples 1-2, in Example 1, a masterbatch and a lubricant are added, and the masterbatch contains carbon black. In theory, the introduction of carbon black will reduce the melt flow rate of the material and deteriorate its processability. The present invention adds a carrier-free masterbatch, whose components contain a stearic acid-based high-temperature resistant dispersant, which has a similar structure to the lubricant in the formula. The two produce a synergistic lubrication effect, which makes up for the disadvantage of poor fluidity of carbon black itself, thereby improving processability.

[0111] According to the data of Examples 1 to 4, it can be found that as the lubricant content increases, the melt flow rate also increases, which can effectively improve production efficiency and improve the problem of surface floating fibers often occurring in glass fiber reinforced polyetherimide.

[0112] Compared with Example 3, the flat glass fiber in Example 4 has a rectangular structure because its cross-section is similar to that of mica powder. This structure will significantly reduce the flow resistance encountered by the flat fiber when flowing in the polyetherimide resin, thereby increasing the melt flow rate and improving the processability.

[0113] Compared with Comparative Examples 3 to 6, the tensile strength and elongation at break of the glass fiber reinforced polyetherimide black particles prepared in Examples 1 to 4 are higher, indicating that when polyetherimide is used as the matrix and the functional filler is prepared, the flake graphite is first wet-milled and then wet-milled with aluminum oxide and tungsten carbide. The obtained functional filler and glass fiber jointly improve the strength of the glass fiber reinforced polyetherimide black particles and also improve the toughness.

[0114] Table 2 Performance test results

[0115]

[0116] Compared with Examples 3 to 4, the elongation at break of the glass fiber reinforced polyetherimide black particles prepared in Examples 5 to 8 is higher, indicating that when the glass fibers are glass fibers with flat cross-sections and glass fibers with circular cross-sections, and are then compounded with functional fillers, the toughness of the glass fiber reinforced polyetherimide is improved. In addition, when the mass ratio of the flat glass fibers to the glass fibers with circular cross-sections in Examples 7 to 8 is 4 to 7:1, the toughness of the glass fiber reinforced polyetherimide is even better.

[0117] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A glass fiber reinforced polyetherimide black particle, characterized in that: The invention comprises the following components in parts by weight: 60-100 parts of polyetherimide, 1-40 parts of glass fiber, 0.5-5 parts of functional filler, 0.5-1.5 parts of lubricant, and 0.1-1 parts of masterbatch; The preparation method of the functional filler comprises the following steps: A1. Wet-milling the flake graphite and drying it to obtain pretreated flake graphite; A2, wet-milling the pretreated flake graphite, aluminum oxide, and tungsten carbide, and drying to obtain a functional filler; The color masterbatch includes a carrier-free carbon black masterbatch; The components of the carrier-free carbon black masterbatch include a stearic acid-based high-temperature resistant dispersant; The lubricant includes one or more of pentaerythritol tetrastearate, trimethylolpropane fatty acid ester, and polyethylene glycol fatty acid ester; The mass ratio of the flake graphite, aluminum oxide and tungsten carbide is 3-5:1:

1.

2. The glass fiber reinforced polyetherimide black particles according to claim 1, characterized in that: The glass fibers include one or both of glass fibers with a flat cross section and glass fibers with a round cross section.

3. The glass fiber reinforced polyetherimide black particles according to claim 1, characterized in that: The mass ratio of the glass fiber to the functional filler is 40-60:

1.

4. The glass fiber reinforced polyetherimide black particles according to claim 2, characterized in that: When the glass fibers are glass fibers with a flat cross section and glass fibers with a circular cross section, the mass ratio of the glass fibers with a flat cross section to the glass fibers with a circular cross section is 4 to 7:

1.

5. The glass fiber reinforced polyetherimide black particles according to claim 1, characterized in that: In step A1, the dispersion medium for the wet ball milling treatment includes one or more of methanol, ethanol, acetone, and N-methylpyrrolidone, and the rotation speed of the wet ball milling treatment is 160-280 rpm, and the time is 40-50 hours; In step A2, the dispersion medium for the wet ball milling treatment includes one or both of a polyvinyl alcohol solution and a polyacrylamide solution, and the rotation speed of the wet ball milling treatment is 500-600 rpm, and the time is 15-20 h.

6. A method for preparing glass fiber reinforced polyetherimide black particles, for preparing the glass fiber reinforced polyetherimide black particles according to any one of claims 1 to 5, characterized in that: The following steps are involved: After the polyetherimide is dried, it is mixed with the remaining components of the glass fiber reinforced polyetherimide black particles except the glass fiber for the first time, and then mixed with the glass fiber for extrusion granulation to obtain the glass fiber reinforced polyetherimide black particles.

7. The method for preparing glass fiber reinforced polyetherimide black particles according to claim 6, characterized in that: The drying process is carried out at a temperature of 120-150°C and a time of 4-6 hours; The time of the first mixing is 3 to 5 minutes.

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