Low-dielectric halogen-free flame-retardant nano-injection material, preparation method and application thereof

Abstract

The application provides a kind of low dielectric halogen-free flame-retardant nano injection molding material and its preparation method and application, the low dielectric halogen-free flame-retardant nano injection molding material includes polybutylene terephthalate, carboxylated polyphenyl ether, glass fiber, hollow glass microsphere, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide graft maleic anhydride, aluminum diethyl phosphinate, rare earth ion surface modified nano metal oxide, antioxidant, ultraviolet absorber, thermal stability agent and lubricant.The low dielectric halogen-free flame-retardant nano injection molding material provided by the application has higher mechanical properties, flame-retardant properties and metal bonding strength, lower dielectric constant and dielectric loss.

Description

Technical Field

[0001] This invention belongs to the field of nano-injection molding materials technology, specifically relating to a low-dielectric halogen-free flame-retardant nano-injection molding material, its preparation method, and its application. Background Technology

[0002] Polybutylene terephthalate (PBT) is a linear polymer with repeating ester groups in its molecule, formed by the condensation polymerization of terephthalic acid and butanediol. It is a milky white, translucent to opaque, semi-crystalline thermoplastic polyester with good flow properties, high heat resistance, easy coloring, fatigue resistance, self-lubrication, low coefficient of friction, and resistance to organic solvents. It can also form an "anchor effect" with metallic materials, making it suitable for nano-injection molding technology. However, its flame retardant properties are generally poor, and its impact strength and toughness are inadequate. Furthermore, its dielectric constant and dielectric loss are insufficient to meet the dielectric performance requirements of 5G technology.

[0003] CN111793335A discloses a low-dielectric nano-injection molding material, which comprises the following raw materials in parts by weight: 50-70 parts of polybutylene terephthalate (PBT), 20-50 parts of low-dielectric reinforcement, 2-6 parts of toughening agent, 1-4 parts of nucleating agent, 0.2-2 parts of dispersant, 0.2-2 parts of compatibilizer, 0.5-2 parts of antioxidant, and 0.5-2 parts of carbon black. The low-dielectric nano-injection molding material provided by this technical solution has low dielectric strength and loss, but low notched impact strength and poor toughness.

[0004] CN115637029A discloses a high-performance PBT material for nano-injection molding and its preparation method. The preparation method includes the following steps: mixing polybutylene terephthalate, dispersant, antioxidant, and ultra-low dielectric constant glass fiber; melting, mixing, and extruding using a twin-screw extruder; and obtaining the high-performance PBT material for nano-injection molding after cooling. The high-performance PBT material for nano-injection molding provided by this technical solution has both low dielectric constant and good mechanical properties, but its flame retardant properties are not improved.

[0005] CN108102311A discloses a low-dielectric PBT / PETG alloy nano-injection molding composite material, its preparation method, and its application. The raw materials for preparing the PBT / PETG alloy nano-injection molding composite material include 30-50 parts by weight of PBT resin, 30-50 parts by weight of PETG resin, 30-40 parts by weight of glass fiber, 0.2-0.8 parts by weight of antioxidant, 1-2 parts by weight of lubricant, 0.3-0.5 parts by weight of UV stabilizer, and 3-8 parts by weight of compatibilizer. The low-dielectric PBT / PETG alloy nano-injection molding composite material provided by this technical solution has good mechanical properties and low dielectric constant and low dielectric loss factor, but its flame retardant properties are not improved.

[0006] Although the aforementioned nano-injection molding materials have low dielectric constant and dielectric loss, they suffer from poor flame retardancy, low metal bonding strength, or poor mechanical properties, making it difficult to achieve a balance between these properties and meet the requirements for manufacturing 5G electronic products.

[0007] Therefore, there is a need to develop a nano-injection molding material that simultaneously possesses high mechanical and flame-retardant properties, low dielectric constant and dielectric loss, and high metal bonding strength. Summary of the Invention

[0008] To address the shortcomings of existing technologies, the present invention aims to provide a low-dielectric halogen-free flame-retardant nano-injection molding material, its preparation method, and its applications. The low-dielectric halogen-free flame-retardant nano-injection molding material simultaneously possesses high mechanical and flame-retardant properties, low dielectric constant and dielectric loss, and high metal bonding strength.

[0009] To achieve this objective, the present invention adopts the following technical solution:

[0010] In a first aspect, the present invention provides a low-dielectric halogen-free flame-retardant nano-injection molding material, wherein the low-dielectric halogen-free flame-retardant nano-injection molding material comprises polybutylene terephthalate, carboxylated polyphenylene ether, glass fiber, hollow glass microspheres, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide grafted maleic anhydride (DOPO-MAH), aluminum diethylphosphonate, rare earth ion surface-modified nano-metal oxides, antioxidants, ultraviolet absorbers, thermal stabilizers, and lubricants.

[0011] In this invention, "low dielectric" means a dielectric constant of 2.73 to 3.13 and a dielectric loss of 0.004 to 0.007 at a frequency of 2.5 GHz.

[0012] In this invention, the addition of carboxylated polyphenylene ether and glass fiber to polybutylene terephthalate (PET) imparts high strength and toughness to the low-dielectric halogen-free flame-retardant nano-injection molding material. The addition of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide grafted with maleic anhydride, diethylaluminum hypophosphite, and rare earth ion-modified nano-metal oxides synergistically enhances the flame retardancy of the low-dielectric halogen-free flame-retardant nano-injection molding material. Furthermore, the addition of carboxylated polyphenylene ether and hollow glass microspheres synergistically reduces the dielectric constant and dielectric loss of the low-dielectric halogen-free flame-retardant nano-injection molding material. Therefore, the low-dielectric halogen-free flame-retardant nano-injection molding material simultaneously possesses high mechanical and flame-retardant properties, as well as low dielectric constant and dielectric loss.

[0013] Preferably, the carboxylated polyphenylene ether is prepared by the following method:

[0014] (1) Vacuum-dried polyphenylene ether, n-butyllithium and solvent are mixed and reacted to obtain metal-lithiated polyphenylene ether.

[0015] (2) The lithium metal polyphenylene ether obtained in step (1), solid dry ice and n-hexane are mixed and reacted to obtain polyphenylene ether carboxylate.

[0016] (3) The polyphenylene ether carboxylate obtained in step (2), dilute hydrochloric acid and tetrahydrofuran are mixed and reacted to obtain the carboxylated polyphenylene ether.

[0017] In this invention, the carboxylated polyphenylene ether formed after carboxylation has carboxyl functional groups, which can chemically react with polybutylene terephthalate, glass fiber, hollow glass microspheres and DOPO-MAH, thereby improving the compatibility between the components, increasing the interaction, and improving the performance.

[0018] Preferably, the mass ratio of polyphenylene ether to n-butyllithium in step (1) is 10-15:1, such as 10.5:1, 11:1, 11.5:1, 12:1, 12.5:1, 13:1, 13.5:1, 14:1 or 14.5, etc.

[0019] Preferably, the mass ratio of n-butyllithium to solvent in step (1) is 1:640-800, such as 1:650, 1:670, 1:690, 1:710, 1:730, 1:750, 1:770 or 1:790.

[0020] Preferably, the solvent in step (1) includes toluene and tetrahydrofuran, wherein the volume ratio of toluene to tetrahydrofuran is 1:3-4, such as 1:3.1, 1:3.2, 1:3.3, 1:3.4, 1:3.5, 1:3.6, 1:3.7, 1:3.8 or 1:3.9, etc.

[0021] Preferably, the reaction in step (1) is carried out under nitrogen protection, the reaction temperature is 50-60℃ (e.g., 51℃, 52℃, 53℃, 54℃, 55℃, 56℃, 57℃, 58℃ or 59℃, etc.), and the reaction time is 18-22h (e.g., 18.5h, 19.5h, 20h, 20.5h, 21h or 21.5h, etc.).

[0022] Preferably, the mass ratio of the lithium metal polyphenylene ether to solid dry ice in step (2) is 1:1.2-1.8, for example, 1:1.25, 1:1.3, 1:1.35, 1:1.4, 1:1.45, 1:1.5, 1:1.55, 1:1.6, 1:1.65, 1:1.7 or 1:1.75, etc.

[0023] Preferably, the mass ratio of lithium metal-lithium polyphenylene ether to n-hexane in step (2) is 1:300-500, such as 1:320, 1:340, 1:360, 1:380, 1:400, 1:420, 1:460 or 1:480.

[0024] Preferably, the reaction temperature in step (2) is 30-40℃ (e.g., 31℃, 32℃, 33℃, 34℃, 35℃, 36℃, 37℃, 38℃ or 39℃, etc.), and the reaction time is 38-42h (e.g., 38.5h, 39h, 39.5h, 40h, 40.5h, 41h or 41.5h, etc.).

[0025] Preferably, the mass ratio of polyphenylene ether carboxylate to hydrochloric acid in step (3) is 1:1.8-2.2, such as 1:1.85, 1:1.9, 1:1.95, 1:2, 1:2.05, 1:2.1 or 1:2.15, etc.

[0026] Preferably, the mass percentage concentration of hydrochloric acid in the dilute hydrochloric acid in step (3) is 9-11%, such as 9.2%, 9.4%, 9.6%, 9.8%, 10%, 10.2%, 10.4%, 10.6%, or 10.8%.

[0027] Preferably, the mass ratio of polyphenylene ether carboxylate to tetrahydrofuran in step (3) is 1:300-400, such as 1:310, 1:320, 1:330, 1:340, 1:350, 1:360, 1:370, 1:380 or 1:390.

[0028] Preferably, the reaction temperature in step (3) is 45-55℃ (e.g., 46℃, 47℃, 48℃, 49℃, 50℃, 51℃, 52℃, 53℃ or 54℃, etc.), and the reaction time is 18-22h, e.g., 18.5h, 19.5h, 20h, 20.5h, 21h or 21.5h, etc.

[0029] Preferably, the glass fiber comprises glass fiber modified with a coupling agent.

[0030] In this invention, the coupling agent, after modifying the glass fiber, can improve the dispersion of the glass fiber in the resin matrix and the interaction with the isobutylene terephthalate.

[0031] Preferably, the hollow glass microspheres include coupling agent modified hollow glass microspheres.

[0032] In this invention, the coupling agent, after modifying the hollow glass microspheres, can improve the dispersibility of the hollow glass microspheres in the resin matrix and the interaction with the homobutylene terephthalate.

[0033] Preferably, the coupling agents in the coupling agent-modified glass fiber and the coupling agent-modified hollow glass microspheres each independently include any one or a combination of two or more of silane coupling agents, titanate coupling agents, aluminate coupling agents, or zirconate coupling agents.

[0034] Preferably, the silane coupling agent comprises any one or a combination of two or more of γ-aminopropyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidyl etheroxypropyltrimethoxysilane, γ-glycidyl etheroxypropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-ureapropyltriethoxysilane, N-aminoethyl-γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, N-(β-aminoethyl)-γ-aminopropyltriethoxysilane, polyaminoalkyltrialkoxysilane, or anilinemethyltrimethoxysilane.

[0035] Preferably, the titanate coupling agent comprises any one or a combination of two or more of the following: tris(dioctylphosphoyloxy)titanate, triisostearate titanate, isopropyl dioleoyloxy (dioctylphosphoyloxy)titanate, isopropyl tris(dioctylphosphoyloxy)titanate, isopropyl trioleoyloxy titanate, isopropyl tris(dioctylpyrophosphoyloxy)titanate, bis(dioctyloxypyrophosphate) ethylene titanate and triethanolamine chelate, bis(dioctyloxypyrophosphate) ethylene titanate or tetraisopropyl di(dioctylphosphite)titanate.

[0036] Preferably, the aluminate coupling agent includes any one or a combination of two or more of distearyloxyisopropyl aluminate, isopropoxydistearyloxyaluminate, trimethyl aluminate, triisopropyl aluminate, or tribenzyl aluminate.

[0037] Preferably, the zirconate coupling agent includes any one or a combination of two or more of alkoxytris(vinyl-ethoxy)zirconate, alkoxytris(p-aminophenoxy)zirconate, bis(diethyl citrate)dipropoxyzirconium chelate, or tetra(triethanolamine)zirconate.

[0038] Preferably, the rare earth ion surface-modified nano-metal oxide is prepared by the following method: rare earth salt and water are mixed to form a rare earth salt aqueous solution, nano-metal oxide is added, ultrasonically dispersed, and allowed to stand to obtain the rare earth ion surface-modified nano-metal oxide.

[0039] Preferably, the mass ratio of the rare earth salt to the nano metal oxide is 1:10-20, such as 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18 or 1:19.

[0040] Preferably, the process further includes a step of cleaning the nano-metal oxide before adding it.

[0041] Preferably, the nano-metal oxide includes any one or a combination of at least two of aluminum oxide, calcium oxide, iron oxide, titanium dioxide, manganese oxide, or magnesium oxide.

[0042] Preferably, the mass percentage concentration of rare earth salts in the rare earth salt aqueous solution is 0.8-1.2%, such as 0.85%, 0.9%, 0.95%, 1%, 1.05%, 1.1%, or 1.15%.

[0043] Preferably, the rare earth salt includes any one or a combination of at least two of zirconium salt, cobalt salt, lanthanum salt, praseodymium salt, samarium salt, europium salt, gadolinium salt, holmium salt, erbium salt, ytterbium salt, lutetium salt, scandium salt, indium salt, neodymium salt, cerium salt, yttrium salt, thulium salt, dysprosium salt, and terbium salt.

[0044] Preferably, the ultrasonic dispersion time is 1.5-2.5h, such as 1.6h, 1.7h, 1.8h, 1.9h, 2h, 2.1h, 2.2h, 2.3h or 2.4h.

[0045] Preferably, the settling time is 30-40 hours.

[0046] In this invention, rare earth ion surface modification can improve the dispersion of nano-metal oxides in the resin matrix and the interaction with polybutylene terephthalate.

[0047] Preferably, the low-dielectric halogen-free flame-retardant nano-injection molding material comprises the following components by weight: 70-90 parts of polybutylene terephthalate, 10-30 parts of carboxylated polyphenylene ether, 10-40 parts of glass fiber, 5-15 parts of hollow glass microspheres, 10-20 parts of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide grafted maleic anhydride, 5-10 parts of aluminum diethylphosphonate, 0.05-2.0 parts of rare earth ion surface-modified nano-metal oxides, 0.1-0.2 parts of antioxidant, 0.1-0.2 parts of ultraviolet absorber, 0.1-0.2 parts of thermal stabilizer, and 0.1-0.2 parts of lubricant.

[0048] The weight parts of the polybutylene terephthalate can be 72, 74, 76, 78, 80, 82, 84, 86, or 88 parts, etc.

[0049] The carboxylated polyphenylene ether can be in parts by weight of 13, 14, 16, 18, 20, 22, 24, 26, or 28, etc.

[0050] The weight percentage of the glass fiber can be 12, 15, 17, 20, 22, 25, 30, 32, 35, or 38 parts, etc.

[0051] The weight percentages of the hollow glass microspheres can be 6, 7, 8, 9, 10, 11, 12, 13, or 14 parts, etc.

[0052] The weight parts of the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide grafted maleic anhydride can be 11, 12, 13, 14, 15, 16, 17, 18 or 19 parts, etc.

[0053] The weight parts of the aluminum diethylphosphonate can be 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts, or 9.5 parts, etc.

[0054] The weight percentage of the rare earth ion-modified nano-metal oxide can be 0.1 parts, 0.3 parts, 0.5 parts, 0.7 parts, 1 part, 1.2 parts, 1.5 parts, or 1.8 parts, etc.

[0055] The antioxidant can be present in weight parts of 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, or 0.19, etc.

[0056] The weight percentage of the ultraviolet absorber can be 0.11 parts, 0.12 parts, 0.13 parts, 0.14 parts, 0.15 parts, 0.16 parts, 0.17 parts, 0.18 parts, or 0.19 parts, etc.

[0057] The stabilizer can be present in parts by weight of 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, or 0.19, etc.

[0058] The weight percentage of the lubricant can be 0.11 parts, 0.12 parts, 0.13 parts, 0.14 parts, 0.15 parts, 0.16 parts, 0.17 parts, 0.18 parts, or 0.19 parts, etc.

[0059] In this invention, if the mass fraction of carboxylated polyphenylene ether is too large, the processing performance of the resulting low-dielectric halogen-free flame-retardant nano-injection molding material will decrease; if the mass fraction of carboxylated polyphenylene ether is too small, it will be detrimental to reducing the dielectric constant, dielectric loss, and improving the flame-retardant performance. If the mass fraction of rare-earth ion surface-modified nano-metal oxide is too large, the mechanical properties of the resulting low-dielectric halogen-free flame-retardant nano-injection molding material will decrease; if the mass fraction of rare-earth ion surface-modified nano-metal oxide is too small, it will be detrimental to improving the flame-retardant performance of the material. If the mass fraction of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide grafted with maleic anhydride is too large, the mechanical properties of the resulting low-dielectric halogen-free flame-retardant nano-injection molding material will decrease; if the mass fraction of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide grafted with maleic anhydride is too small, it will be detrimental to improving the flame-retardant performance of the material.

[0060] In a second aspect, the present invention provides a method for preparing a low-dielectric halogen-free flame-retardant nano-injection molding material as described in the first aspect. The preparation method includes the following steps: mixing polybutylene terephthalate, carboxylated polyphenylene ether, glass fiber, hollow glass microspheres, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide grafted with maleic anhydride, aluminum diethylphosphonate, rare earth ion surface-modified nano-metal oxides, antioxidants, ultraviolet absorbers, thermal stabilizers, and lubricants, and extruding to obtain the low-dielectric halogen-free flame-retardant nano-injection molding material.

[0061] Preferably, the extrusion is performed using a twin-screw extruder.

[0062] Thirdly, the present invention provides an application of the low dielectric halogen-free flame-retardant nano-injection molding material as described in the first aspect in the preparation of electronic and electrical products.

[0063] Compared with the prior art, the present invention has the following beneficial effects:

[0064] In this invention, the low-dielectric halogen-free flame-retardant nano-injection molding material improves strength and toughness by adding carboxylated polyphenylene ether and glass fiber to polybutylene terephthalate. The addition of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide grafted with maleic anhydride, diethyl aluminum hypophosphite, and rare earth ion-modified nano-metal oxides synergistically enhances flame retardancy. Furthermore, the addition of carboxylated polyphenylene ether and hollow glass microspheres synergistically reduces dielectric constant and dielectric loss. This low-dielectric halogen-free flame-retardant nano-injection molding material simultaneously possesses high mechanical and flame-retardant properties, low dielectric constant and dielectric loss, and high metal bonding strength. Detailed Implementation

[0065] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0066] Example 1

[0067] This embodiment provides a low-dielectric halogen-free flame-retardant nano-injection molding material and its preparation method. The low-dielectric halogen-free flame-retardant nano-injection molding material comprises the following components by weight: 80 parts of polybutylene terephthalate (manufacturer: Lanxess, brand name: B1505), 20 parts of carboxylated polyphenylene ether, 20 parts of coupling agent modified glass fiber, 10 parts of coupling agent modified hollow glass microspheres, 11 parts of DOPO-MAH, 5 parts of aluminum diethylphosphinate, 0.6 parts of rare earth ion surface-modified nano-metal oxide, 0.1 parts of antioxidant (antioxidant 1010), 0.1 parts of ultraviolet absorber (UV326), 0.1 parts of thermal stabilizer (KM-503), and 0.1 parts of lubricant (PETS100).

[0068] The preparation method of the above-mentioned carboxylated polyphenylene ether is as follows:

[0069] Polyphenylene ether (manufacturer: Lanxing, grade LXR035) was vacuum dried at 100℃ for 24 hours, and then cooled to room temperature under vacuum. 6.4 g of n-butyllithium, 65 g of polyphenylene ether (manufacturer: Lanxing, grade LXR035), and 800 mL of a mixed solvent of toluene and tetrahydrofuran (toluene to tetrahydrofuran volume ratio of 1:4) were added to a 2 L three-necked round-bottom glass flask equipped with a stirrer, thermometer, and reflux condenser. The mixture was heated to 50℃ and stirred, and reacted completely for 20 h under a dry nitrogen atmosphere. After cooling to room temperature, the precipitate was collected by filtration, washed five times with a mixed solvent of water and ethanol, and finally dried under reduced pressure at 110℃ for 10 h. The product obtained was lithium metallized polyphenylene ether. 65g of lithium-ionized polyphenylene ether, 500mL of n-hexane, and 100g of solid dry ice were added to a 2L three-necked round-bottom glass flask equipped with a stirrer, thermometer, and reflux condenser. The mixture was heated to 35°C and stirred until fully reacted for 40 hours. A large amount of n-hexane was then added to precipitate the polyphenylene ether carboxylate. The precipitate was thoroughly washed with a mixture of ethanol and water and dried in a vacuum oven at 110°C for 2 days to remove the solvent, yielding the polyphenylene ether carboxylate. 100g of the polyphenylene ether carboxylate, 400mL of tetrahydrofuran, and 200g of 10% (w / w) dilute hydrochloric acid were added to a 2L three-necked round-bottom glass flask equipped with a stirrer, thermometer, and reflux condenser. The mixture was heated to 50°C and stirred until fully reacted for 20 hours. The precipitate was filtered and washed five times with distilled water and dried in a vacuum oven at 110°C for 2 days, yielding the carboxylated polyphenylene ether.

[0070] The preparation method of the above-mentioned coupling agent modified glass fiber is as follows:

[0071] First, 100g of glass fiber was vacuum dried at 110℃ for 5 hours, and then cooled to room temperature under vacuum. 8g of glass fiber was added to 200mL of toluene and ultrasonically dispersed at room temperature for 40min to obtain a uniform suspension. Then, 3.64g of γ-aminopropyltriethoxysilane was added to the suspension, ultrasonically mixed for 10min, and reacted in a 90℃ constant temperature bath for 7h. The reaction solution was centrifuged at 12000r / min at room temperature, washed three times with anhydrous ethanol, and vacuum dried for 8h to obtain the coupling agent modified glass fiber.

[0072] The preparation method of the above-mentioned coupling agent modified hollow glass microspheres is as follows:

[0073] First, 100g of hollow glass microspheres were vacuum dried at 110℃ for 5 hours, and then cooled to room temperature under vacuum. 8g of hollow glass microspheres were added to 200mL of toluene and ultrasonically dispersed at room temperature for 40min to obtain a uniform suspension. Then, 3.64g of γ-aminopropyltriethoxysilane was added to the suspension, ultrasonically mixed for 10min, and reacted in a 90℃ constant temperature bath for 7h. The reaction solution was centrifuged at 12000r / min at room temperature, washed three times with anhydrous ethanol, and vacuum dried for 8h to obtain the coupling agent modified hollow glass microspheres.

[0074] The preparation method of the above-mentioned DOPO-MAH is as follows:

[0075] 216.0 g (1.0 mol) of DOPO, 400.0 mL of toluene, and 400.0 mL of tetrahydrofuran were added to a 2 L three-necked round-bottom glass flask equipped with a stirrer, thermometer, and reflux condenser. The mixture was stirred under reflux for 1 hour. After the DOPO was completely dissolved, 98.0 g (1.0 mol) of MAH was added to the reactor in four portions over 1 hour. The reaction mixture was stirred under nitrogen for 24 hours and then kept under reflux to ensure the reaction was complete. After cooling to room temperature, the precipitate was collected by filtration, washed five times with a mixture of tetrahydrofuran and ethanol (1:1 volume ratio), and finally dried under reduced pressure at 120 °C for 10 hours to obtain the DOPO-MAH.

[0076] The preparation method of the above rare earth ion surface-modified nano-metal oxides is as follows:

[0077] 10g of nano-metal oxide (alumina) was added to deionized water, stirred, filtered, and then added to anhydrous ethanol, stirred, and allowed to stand for 20h. After filtration and drying, 10g of the washed nano-metal oxide (alumina) was added to 100g of 1% (w / w) thulium acetate deionized water solution, mixed, ultrasonically dispersed for 2h, allowed to stand for 36h, filtered, and vacuum dried to constant weight to obtain rare earth ion surface-modified nano-metal oxide.

[0078] The preparation method of the low-dielectric halogen-free flame-retardant nano-injection molding material is as follows: polybutylene terephthalate, carboxylated polyphenylene ether, coupling agent modified glass fiber, coupling agent modified hollow glass microspheres, DOPO-MAH, aluminum diethylphosphinate, rare earth ion surface modified nano metal oxides, antioxidants, ultraviolet absorbers, thermal stabilizers and lubricants are mixed and extruded in a twin-screw extruder at 250°C to obtain the low-dielectric halogen-free flame-retardant nano-injection molding material.

[0079] Example 2

[0080] This embodiment provides a low-dielectric halogen-free flame-retardant nano-injection molding material and its preparation method. The low-dielectric halogen-free flame-retardant nano-injection molding material comprises the following components by weight: 70 parts of polybutylene terephthalate (manufacturer: Lanxess, brand name: B1505), 30 parts of carboxylated polyphenylene ether, 10 parts of coupling agent modified glass fiber, 15 parts of coupling agent modified hollow glass microspheres, 10 parts of DOPO-MAH, 5 parts of aluminum diethylphosphinate, 0.05 parts of rare earth ion surface-modified nano-metal oxide, 0.1 parts of antioxidant (antioxidant 1010), 0.1 parts of ultraviolet absorber (UV326), 0.1 parts of thermal stabilizer (KM-503), and 0.1 parts of lubricant (PETS100).

[0081] The preparation method of the above-mentioned carboxylated polyphenylene ether is as follows:

[0082] Polyphenylene ether (manufacturer: Lanxing, grade LXR035) was vacuum dried at 100℃ for 24 hours, and then cooled to room temperature under vacuum. 6.4 g of n-butyllithium, 80 g of polyphenylene ether (manufacturer: Lanxing, grade LXR035) and 800 mL of a mixed solvent of toluene and tetrahydrofuran (toluene to tetrahydrofuran volume ratio of 1:3) were added to a 2 L three-necked round-bottom glass flask equipped with a stirrer, thermometer, and reflux condenser. The mixture was heated to 60℃ and stirred, and reacted completely for 18 hours under a dry nitrogen atmosphere. After cooling to room temperature, the precipitate was collected by filtration, washed five times with a mixed solvent of water and ethanol, and finally dried under reduced pressure at 110℃ for 10 hours to obtain the product, which was lithium metallized polyphenylene ether. 65g of lithium-ionized polyphenylene ether, 500mL of n-hexane, and 115g of solid dry ice were added to a 2L three-necked round-bottom glass flask equipped with a stirrer, thermometer, and reflux condenser. The mixture was heated to 40°C and stirred until fully reacted for 38 hours. A large amount of n-hexane was then added to precipitate the polyphenylene ether carboxylate. The precipitate was thoroughly washed with a mixture of ethanol and water and dried in a vacuum oven at 110°C for 2 days to remove the solvent, yielding the polyphenylene ether carboxylate. 100g of the polyphenylene ether carboxylate, 400mL of tetrahydrofuran, and 220g of 10% (w / w) dilute hydrochloric acid were added to a 2L three-necked round-bottom glass flask equipped with a stirrer, thermometer, and reflux condenser. The mixture was heated to 45°C and stirred until fully reacted for 22 hours. The precipitate was filtered and washed five times with distilled water and dried in a vacuum oven at 110°C for 2 days, yielding the carboxylated polyphenylene ether.

[0083] The preparation method of the above-mentioned coupling agent modified glass fiber is as follows:

[0084] First, 100g of glass fiber was vacuum dried at 100℃ for 4 hours, and then cooled to room temperature under vacuum. 8g of glass fiber was added to 200mL of toluene and ultrasonically dispersed at room temperature for 30min to obtain a uniform suspension. Then, 3.64g of tris(dioctylphosphono)titanate isopropyl ester was added to the suspension, ultrasonically mixed for 5min, and reacted in a 90℃ constant temperature bath for 6h. The reaction solution was centrifuged at 12000r / min at room temperature, washed three times with anhydrous ethanol, and vacuum dried for 8h to obtain the coupling agent modified glass fiber.

[0085] The preparation method of the above-mentioned coupling agent modified hollow glass microspheres is as follows:

[0086] First, 100g of hollow glass microspheres were vacuum dried at 100℃ for 4 hours, and then cooled to room temperature under vacuum. 8g of hollow glass microspheres were added to 200mL of toluene and ultrasonically dispersed at room temperature for 30min to obtain a uniform suspension. Then, 3.64g of tris(dioctylphosphoxy)titanate isopropyl ester was added to the suspension, ultrasonically mixed for 5min, and reacted in a 90℃ constant temperature bath for 6h. The reaction solution was centrifuged at 12000r / min at room temperature, washed 3 times with anhydrous ethanol, and vacuum dried for 8h to obtain the coupling agent modified hollow glass microspheres.

[0087] The preparation method of the above-mentioned DOPO-MAH is as follows:

[0088] 216.0 g (1.0 mol) of DOPO, 400.0 mL of toluene, and 400.0 mL of tetrahydrofuran were added to a 2 L three-necked round-bottom glass flask equipped with a stirrer, thermometer, and reflux condenser. The mixture was stirred under reflux for 1 hour. After the DOPO was completely dissolved, 98.0 g (1.0 mol) of MAH was added to the reactor in four portions over 1 hour. The reaction mixture was stirred under nitrogen for 24 hours and then kept under reflux to ensure the reaction was complete. After cooling to room temperature, the precipitate was collected by filtration, washed five times with a mixture of tetrahydrofuran and ethanol (1:1 volume ratio), and finally dried under reduced pressure at 120 °C for 10 hours to obtain the DOPO-MAH.

[0089] The preparation method of the above rare earth ion surface-modified nano-metal oxides is as follows:

[0090] 10g of nano-metal oxide (iron oxide) was added to deionized water, stirred, filtered, and then added to anhydrous ethanol, stirred, and allowed to stand for 20h, filtered, and dried. Then, 10g of the washed nano-metal oxide (iron oxide) was added to 100g of 1% (w / w) thulium acetate deionized water solution, mixed, ultrasonically dispersed for 2h, allowed to stand for 36h, filtered, and vacuum dried to constant weight to obtain rare earth ion surface modified nano-metal oxide.

[0091] The preparation method of the low-dielectric halogen-free flame-retardant nano-injection molding material is as follows: polybutylene terephthalate, carboxylated polyphenylene ether, coupling agent modified glass fiber, coupling agent modified hollow glass microspheres, DOPO-MAH, aluminum diethylphosphinate, rare earth ion surface-modified nano metal oxides, antioxidants, ultraviolet absorbers, thermal stabilizers and lubricants are mixed and extruded in a twin-screw extruder at 255°C to obtain the low-dielectric halogen-free flame-retardant nano-injection molding material.

[0092] Example 3

[0093] This embodiment provides a low-dielectric halogen-free flame-retardant nano-injection molding material and its preparation method. The low-dielectric halogen-free flame-retardant nano-injection molding material comprises the following components by weight: 90 parts of polybutylene terephthalate (manufacturer: Lanxess, brand name: B1505), 10 parts of carboxylated polyphenylene ether, 40 parts of coupling agent modified glass fiber, 5 parts of coupling agent modified hollow glass microspheres, 20 parts of DOPO-MAH, 10 parts of aluminum diethylphosphinate, 2 parts of rare earth ion surface-modified nano-metal oxides, 0.2 parts of antioxidant (antioxidant 1010), 0.2 parts of ultraviolet absorber (UV326), 0.2 parts of thermal stabilizer (KM-503), and 0.2 parts of lubricant (PETS100).

[0094] The preparation method of the above-mentioned carboxylated polyphenylene ether is as follows:

[0095] Polyphenylene ether (manufacturer: Lanxing, grade LXR035) was vacuum dried at 100℃ for 24 hours, and then cooled to room temperature under vacuum. 6.4 g of n-butyllithium, 65 g of polyphenylene ether (manufacturer: Lanxing, grade LXR035), and 800 mL of a mixed solvent of toluene and tetrahydrofuran (toluene to tetrahydrofuran volume ratio of 1:4) were added to a 2 L three-necked round-bottom glass flask equipped with a stirrer, thermometer, and reflux condenser. The mixture was heated to 50℃ and stirred, and reacted completely for 20 h under a dry nitrogen atmosphere. After cooling to room temperature, the precipitate was collected by filtration, washed five times with a mixed solvent of water and ethanol, and finally dried under reduced pressure at 110℃ for 10 h. The product obtained was lithium metallized polyphenylene ether. 65g of lithium-ionized polyphenylene ether, 500mL of n-hexane, and 100g of solid dry ice were added to a 2L three-necked round-bottom glass flask equipped with a stirrer, thermometer, and reflux condenser. The mixture was heated to 35°C and stirred until fully reacted for 40 hours. A large amount of n-hexane was then added to precipitate the polyphenylene ether carboxylate. The precipitate was thoroughly washed with a mixture of ethanol and water and dried in a vacuum oven at 110°C for 2 days to remove the solvent, yielding the polyphenylene ether carboxylate. 100g of the polyphenylene ether carboxylate, 400mL of tetrahydrofuran, and 200g of 10% (w / w) dilute hydrochloric acid were added to a 2L three-necked round-bottom glass flask equipped with a stirrer, thermometer, and reflux condenser. The mixture was heated to 50°C and stirred until fully reacted for 20 hours. The precipitate was filtered and washed five times with distilled water and dried in a vacuum oven at 110°C for 2 days, yielding the carboxylated polyphenylene ether.

[0096] The preparation method of the above-mentioned coupling agent modified glass fiber is as follows:

[0097] First, 100g of glass fiber was vacuum dried at 100℃ for 4 hours, and then cooled to room temperature under vacuum. 8g of glass fiber was added to 200mL of toluene and ultrasonically dispersed at room temperature for 30min to obtain a uniform suspension. Then, 3.64g of distearate isopropyl aluminate was added to the suspension, ultrasonically mixed for 5min, and reacted in a 90℃ constant temperature bath for 6h. The reaction solution was centrifuged at 12000r / min at room temperature, washed three times with anhydrous ethanol, and vacuum dried for 8h to obtain the coupling agent modified glass fiber.

[0098] The preparation method of the above-mentioned coupling agent modified hollow glass microspheres is as follows:

[0099] First, 100g of hollow glass microspheres were vacuum dried at 120℃ for 6 hours, and then cooled to room temperature under vacuum. 8g of hollow glass microspheres were added to 200mL of toluene and ultrasonically dispersed at room temperature for 30min to obtain a uniform suspension. Then, 3.64g of distearate isopropyl aluminate was added to the suspension, ultrasonically mixed for 10min, and reacted in a 90℃ constant temperature bath for 6h. The reaction solution was centrifuged at 12000r / min at room temperature, washed three times with anhydrous ethanol, and vacuum dried for 8h to obtain the coupling agent modified hollow glass microspheres.

[0100] The preparation method of the above-mentioned DOPO-MAH is as follows:

[0101] 216.0 g (1.0 mol) of DOPO, 400.0 mL of toluene, and 400.0 mL of tetrahydrofuran were added to a 2 L three-necked round-bottom glass flask equipped with a stirrer, thermometer, and reflux condenser. The mixture was stirred under reflux for 1 hour. After the DOPO was completely dissolved, 98.0 g (1.0 mol) of MAH was added to the reactor in four portions over 1 hour. The reaction mixture was stirred under nitrogen for 24 hours and then kept under reflux to ensure the reaction was complete. After cooling to room temperature, the precipitate was collected by filtration, washed five times with a mixture of tetrahydrofuran and ethanol (1:1 volume ratio), and finally dried under reduced pressure at 120 °C for 10 hours to obtain the DOPO-MAH.

[0102] The preparation method of the above rare earth ion surface-modified nano-metal oxides is as follows:

[0103] 10g of nano-metal oxide (titanium oxide) was added to deionized water, stirred, filtered, and then added to anhydrous ethanol, stirred, and allowed to stand for 20h, filtered, and dried. Then, 10g of the washed nano-metal oxide (titanium oxide) was added to 100g of 1% (w / w) thulium acetate deionized water solution, mixed, ultrasonically dispersed for 2h, allowed to stand for 36h, filtered, and vacuum dried to constant weight to obtain rare earth ion surface modified nano-metal oxide.

[0104] The preparation method of the low-dielectric halogen-free flame-retardant nano-injection molding material is as follows: polybutylene terephthalate, carboxylated polyphenylene ether, coupling agent modified glass fiber, coupling agent modified hollow glass microspheres, DOPO-MAH, aluminum diethylphosphinate, rare earth ion surface-modified nano metal oxides, antioxidants, ultraviolet absorbers, thermal stabilizers and lubricants are mixed and extruded in a twin-screw extruder at 255°C to obtain the low-dielectric halogen-free flame-retardant nano-injection molding material.

[0105] Example 4

[0106] This embodiment provides a low-dielectric halogen-free flame-retardant nano-injection molding material and its preparation method. The only difference between this embodiment and Example 1 is that the weight of carboxylated polyphenylene ether is adjusted to 35 parts, while the rest is the same as in Example 1.

[0107] Example 5

[0108] This embodiment provides a low-dielectric halogen-free flame-retardant nano-injection molding material and its preparation method. The only difference between this embodiment and Example 1 is that the weight of carboxylated polyphenylene ether is adjusted to 5 parts, while the rest is the same as Example 1.

[0109] Example 6

[0110] This embodiment provides a low-dielectric halogen-free flame-retardant nano-injection molding material and its preparation method. The only difference between this embodiment and Embodiment 1 is that the weight of the coupling agent-modified glass fiber is adjusted to 30 parts, while the rest is the same as Embodiment 1.

[0111] Comparative Example 1

[0112] This comparative example provides a low-dielectric halogen-free flame-retardant nano-injection molding material and its preparation method. The only difference between this material and Example 1 is that the low-dielectric halogen-free flame-retardant nano-injection molding material does not include coupling agent-modified glass fiber. Otherwise, it is the same as Example 1.

[0113] Comparative Example 2

[0114] This comparative example provides a low-dielectric halogen-free flame-retardant nano-injection molding material and its preparation method. The only difference between this and Example 1 is that the low-dielectric halogen-free flame-retardant nano-injection molding material does not include carboxylated polyphenylene ether, and the weight of the coupling agent-modified hollow glass microspheres is adjusted to 30 parts. Otherwise, it is the same as Example 1.

[0115] Comparative Example 3

[0116] This comparative example provides a low-dielectric halogen-free flame-retardant nano-injection molding material and its preparation method. The only difference between this and Example 1 is that the low-dielectric halogen-free flame-retardant nano-injection molding material does not include coupling agent-modified hollow glass microspheres, and the weight parts of carboxylated polyphenylene ether are adjusted to 30 parts. Otherwise, it is the same as Example 1.

[0117] Comparative Example 4

[0118] This comparative example provides a low-dielectric halogen-free flame-retardant nano-injection molding material and its preparation method. The only difference between this and Example 1 is that the low-dielectric halogen-free flame-retardant nano-injection molding material does not include rare earth ion surface-modified nano-metal oxides. The weight parts of DOPO-MAH are adjusted to 10.4 parts, and the weight parts of aluminum diethylphosphinic acid are adjusted to 5.2 parts. The rest is the same as in Example 1.

[0119] Comparative Example 5

[0120] This comparative example provides a low-dielectric halogen-free flame-retardant nano-injection molding material and its preparation method. The only difference between this example and Example 1 is that the low-dielectric halogen-free flame-retardant nano-injection molding material does not include DOPO-MAH, the weight of aluminum diethylphosphinic acid is adjusted to 15 parts, and the weight of rare earth ion surface-modified nano-metal oxide is adjusted to 1.6 parts. The rest is the same as in Example 1.

[0121] The following performance tests were performed on the low-dielectric halogen-free flame-retardant nano-injection molding materials provided in the examples and comparative examples.

[0122] (1) Tensile strength: Tested in accordance with ISO 527:2019.

[0123] (2) Room temperature notch impact: Tested according to ISO 180:2019.

[0124] (3) Dielectric constant: Tested according to IPC-TM-650.

[0125] (4) Dielectric loss: Tested according to IPC-TM-650.

[0126] (5) Flame retardant performance: Tested according to UL94, with a sample thickness of 0.8 mm.

[0127] (6) Shear strength of aluminum-plastic composite: Tested in accordance with ISO19095:2015.

[0128] (7) Melt index: Tested according to ISO 1133:2021.

[0129] The test results are shown in Table 1.

[0130] Table 1

[0131]

[0132]

[0133] According to the test results in Table 1, the tensile strength of the low-dielectric halogen-free flame-retardant nano-injection molding materials provided in Examples 1-6 is 85.1–135.6 MPa, and the notched impact strength of a simply supported beam is 6.2–15.1 kJ / m. 2 The dielectric constant is 2.73–3.13, the dielectric loss is 0.004–0.007, the flame retardant performance is V1–V0 (4.1s), and the aluminum-plastic bond shear strength is 23.1–33.5 MPa. This low-dielectric, halogen-free, flame-retardant nano-injection molding material simultaneously possesses high mechanical and flame-retardant properties, low dielectric constant and dielectric loss, and high metal bond strength.

[0134] Compared with Example 1, if the weight fraction of carboxylated polyphenylene ether is too large (Example 4), the notched impact strength and mass melt index of the simply supported beam decrease, and the flowability and processability of the low-dielectric halogen-free flame-retardant nano-injection molding material deteriorate; if the weight fraction of carboxylated polyphenylene ether is too small (Example 5), the dielectric constant and dielectric loss increase, and the dielectric properties deteriorate. This proves that the low-dielectric halogen-free flame-retardant nano-injection molding material prepared with the weight fraction of carboxylated polyphenylene ether within a specific range has better performance.

[0135] Compared with Example 1, if the low dielectric halogen-free flame-retardant nano-injection molding material does not include coupling agent-modified glass fiber (Comparative Example 1), the tensile strength, impact strength, and aluminum-plastic bond shear strength decrease.

[0136] Compared with Example 1, if the low-dielectric halogen-free flame-retardant nano-injection molding material does not include carboxylated polyphenylene ether (Comparative Example 2), the dielectric constant and dielectric loss increase, the dielectric properties deteriorate significantly, and the flame-retardant properties decrease. If the low-dielectric halogen-free flame-retardant nano-injection molding material does not include coupling agent-modified hollow glass microspheres (Comparative Example 3), the dielectric constant and dielectric loss increase, and the dielectric properties deteriorate significantly. This proves that the combination of carboxylated polyphenylene ether and hollow glass microspheres has a better effect on reducing the dielectric constant and dielectric loss.

[0137] Compared with Example 1, if the low-dielectric halogen-free flame-retardant nano-injection molding material does not include rare earth ion surface-modified nano-metal oxides (Comparative Example 4), the flame-retardant performance is significantly worse; if the low-dielectric halogen-free flame-retardant nano-injection molding material does not include DOPO-MAH (Comparative Example 5), the flame-retardant performance is significantly worse, proving that the combination of DOPO-MAH, diethylaluminum hypophosphite and rare earth ion surface-modified nano-metal oxides has better flame-retardant properties.

[0138] The applicant declares that this invention illustrates a low-dielectric halogen-free flame-retardant nano-injection molding material, its preparation method, and its application through the above embodiments. However, this invention is not limited to the above embodiments, meaning that this invention does not necessarily rely on the above embodiments for implementation. Those skilled in the art should understand that any improvements to this invention, equivalent substitutions of raw materials, additions of auxiliary components, and selection of specific methods, etc., all fall within the protection and disclosure scope of this invention.

Claims

1. A low-dielectric, halogen-free, flame-retardant nano-injection molding material, characterized in that, The low-dielectric halogen-free flame-retardant nano-injection molding material comprises the following components by weight: 70-90 parts polybutylene terephthalate, 10-30 parts carboxylated polyphenylene ether, 10-40 parts glass fiber, 5-15 parts hollow glass microspheres, 10-20 parts 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide grafted maleic anhydride, 5-10 parts aluminum diethylphosphonate, 0.05-2 parts rare earth ion surface-modified nano-metal oxides, 0.1-0.2 parts antioxidant, 0.1-0.2 parts ultraviolet absorber, 0.1-0.2 parts thermal stabilizer, and 0.1-0.2 parts lubricant.

2. The low-dielectric halogen-free flame-retardant nano-injection molding material according to claim 1, characterized in that, The carboxylated polyphenylene ether is prepared by the following method: (1) Vacuum-dried polyphenylene ether, n-butyllithium and solvent are mixed and reacted to obtain metal-lithiated polyphenylene ether; (2) The lithium metal polyphenylene ether obtained in step (1), solid dry ice and n-hexane are mixed and reacted to obtain polyphenylene ether carboxylate. (3) The polyphenylene ether carboxylate obtained in step (2), dilute hydrochloric acid and tetrahydrofuran are mixed and reacted to obtain the carboxylated polyphenylene ether; The mass ratio of polyphenylene ether to n-butyllithium in step (1) is 10-15:1; The mass ratio of n-butyllithium to solvent in step (1) is 1:640-800; The solvent in step (1) includes toluene and tetrahydrofuran, wherein the volume ratio of toluene to tetrahydrofuran is 1:3-4; The reaction described in step (1) is carried out under nitrogen protection at a temperature of 50-60℃ for a time of 18-22 h. In step (2), the mass ratio of lithium metal-lithium polyphenylene ether to solid dry ice is 1:1.2-1.8; In step (2), the mass ratio of lithium metal-lithium polyphenylene ether to n-hexane is 1:300-500; The reaction temperature in step (2) is 30-40℃, and the reaction time is 38-42 h; In step (3), the mass ratio of polyphenylene ether carboxylate to hydrochloric acid in dilute hydrochloric acid is 1:1.8-2.2; The mass percentage concentration of hydrochloric acid in the dilute hydrochloric acid in step (3) is 9-11%. The mass ratio of polyphenylene ether carboxylate to tetrahydrofuran in step (3) is 1:300-400; The reaction temperature in step (3) is 45-55℃, and the reaction time is 18-22 h.

3. The low-dielectric halogen-free flame-retardant nano-injection molding material according to claim 1 or 2, characterized in that, The glass fiber includes glass fiber modified with a coupling agent; The hollow glass microspheres include hollow glass microspheres modified with coupling agents.

4. The low-dielectric halogen-free flame-retardant nano-injection molding material according to claim 3, characterized in that, The coupling agents in the modified glass fibers and the modified hollow glass microspheres each independently include any one or a combination of two or more of the following: silane coupling agents, titanate coupling agents, aluminate coupling agents, or zirconate coupling agents. The silane coupling agent comprises any one or a combination of two or more of the following: γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-ureapropyltriethoxysilane, N-aminoethyl-γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, N-(β-aminoethyl)-γ-aminopropyltriethoxysilane, polyaminoalkyltrialkoxysilane, or anilinemethyltrimethoxysilane. The titanate coupling agent includes any one or a combination of two or more of the following: tris(dioctylphosphoyloxy)titanate, triisostearate titanate, isopropyl dioleoyloxy (dioctylphosphoyloxy)titanate, isopropyl tris(dioctylphosphoyloxy)titanate, isopropyl trioleoyloxy titanate, isopropyl tris(dioctylpyrophosphoyloxy)titanate, bis(dioctyloxypyrophosphate) ethylene titanate and triethanolamine, bis(dioctyloxypyrophosphate) ethylene titanate or tetraisopropyl di(dioctylphosphite) titanate. The aluminate coupling agent includes any one or a combination of two or more of the following: distearyloxyisopropyl aluminate, isopropoxydistearyloxyaluminate, trimethyl aluminate, triisopropyl aluminate, or tribenzyl aluminate. The zirconate coupling agent includes any one or a combination of two or more of alkoxytris(vinyl-ethoxy)zirconate, alkoxytris(p-aminophenoxy)zirconate, bis(diethyl citrate)dipropoxyzirconium chelate, or tetra(triethanolamine)zirconate.

5. The low-dielectric halogen-free flame-retardant nano-injection molding material according to claim 1, characterized in that, The rare earth ion-modified nano-metal oxide is prepared by the following method: rare earth salt and water are mixed to form a rare earth salt aqueous solution, nano-metal oxide is added, ultrasonically dispersed, and allowed to stand to obtain the rare earth ion-modified nano-metal oxide.

6. The low-dielectric halogen-free flame-retardant nano-injection molding material according to claim 5, characterized in that, The mass ratio of the rare earth salt to the nano metal oxide is 1:10-20; The process of adding nano-metal oxides also includes a step of cleaning the nano-metal oxides; The nano-metal oxides include any one or a combination of at least two of aluminum oxide, calcium oxide, iron oxide, titanium dioxide, manganese oxide, or magnesium oxide; The mass percentage concentration of rare earth salts in the rare earth salt aqueous solution is 0.8-1.2%; The rare earth salts include any one or a combination of at least two of the following: zirconium salts, cobalt salts, lanthanum salts, praseodymium salts, samarium salts, europium salts, gadolinium salts, holmium salts, erbium salts, ytterbium salts, lutetium salts, scandium salts, indium salts, neodymium salts, cerium salts, yttrium salts, thulium salts, dysprosium salts, and terbium salts. The ultrasonic dispersion time is 1.5-2.5 h; The settling time is 30-40 hours.

7. A method for preparing a low-dielectric halogen-free flame-retardant nano-injection molding material as described in any one of claims 1-6, characterized in that, The preparation method includes the following steps: mixing polybutylene terephthalate, carboxylated polyphenylene ether, glass fiber, hollow glass microspheres, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide grafted maleic anhydride, aluminum diethylphosphinate, rare earth ion surface-modified nano-metal oxides, antioxidants, ultraviolet absorbers, thermal stabilizers and lubricants, and extruding to obtain the low dielectric halogen-free flame-retardant nano-injection molding material.

8. The preparation method according to claim 7, characterized in that, The extrusion is performed using a twin-screw extruder.

9. The application of the low dielectric halogen-free flame-retardant nano-injection molding material according to any one of claims 1-6 in the preparation of electronic and electrical products.

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