Modified, ceramifiable, flame-retardant polyphenylene oxide insulating wire and cable material

Abstract

Disclosed in the present invention is a modified, ceramifiable, flame-retardant polyphenylene oxide insulating wire and cable material, which is prepared from the following starting materials in mass fractions: 15-20% of polyphenylene oxide, 10-20% of a SEBS thermoplastic elastomer, 4-8% of a polypropylene resin, 3-8% of a maleic anhydride grafted material, 5-20% of melamine cyanurate, 5-15% of aluminum diethyl phosphinate, 1-4% of 2,3-dimethyl-2,3-diphenylbutane, 10-30% of composite ceramic powder, and 1-4% of an antioxidant. The insulating wire and cable material of the present invention has outstanding electrical insulation, flowability and water resistance, good wear resistance and electrical performance, good dimensional stability, high heat resistance, good flame retardancy, self-extinguishing properties, and excellent ceramifiable properties upon high-temperature combustion, and still maintains excellent insulation performance after ceramization.

Description

A modified ceramicized flame-retardant polyphenylene ether insulated wire and cable material Technical Field

[0001] This invention belongs to the technical field of polyphenylene ether insulated wires and cables, specifically relating to a modified ceramicized flame-retardant polyphenylene ether insulated wire and cable material. Background Technology

[0002] There are many types of thermoplastic elastomers, mainly including styrene-based (TPS), olefin-based (TPO), cross-linked olefin-based (TPV), vinyl chloride-based (TPVC), and polyurethane-based (TPU). They possess characteristics such as high elasticity, high strength, low density, and ease of processing. They also exhibit good insulation, high and low temperature resistance, fatigue resistance, a pleasant feel, and no odor, making them the preferred material to replace PVC in the electronic wire industry. The application of halogen-free flame-retardant elastomers in wires and cables must meet certain requirements: hardness is generally 80-90A, flame retardancy meets VW-1 or FT-1 standards, good flow and molding properties, a smooth and fine surface, and mechanical properties such as tensile strength, tear strength, temperature resistance (80 / 90 / 105℃), heat distortion (121 / 150℃), thermal shock resistance, and migration meet standards.

[0003] Polyphenylene oxide (PPO) is a self-flame-retardant engineering plastic with an oxygen index of up to 29. Therefore, modifying elastomers with PPO and adding a halogen-free flame-retardant system can achieve high flame-retardant levels while maintaining high mechanical properties. With increasingly stringent environmental protection requirements both domestically and internationally, flexible PPO materials are an ideal environmentally friendly alternative to PVC.

[0004] Existing PPO insulated wires and cables on the market experience a decrease in insulation resistance when used in damp environments such as basements and garages due to moisture absorption by the insulation material. This sustained decrease in insulation resistance can lead to insulation breakdown, short circuits, and other safety hazards. Therefore, there is an urgent market need for an upgraded product: halogen-free, low-smoke, flame-retardant polyolefin insulated wires and cables suitable for use in damp environments.

[0005] Patent document CN114437494A discloses a TPE sheath material for charging cables and its preparation method. The raw materials include: 20-30 parts of hydrogenated styrene-butadiene block copolymer; 15-22 parts of polypropylene; 20-30 parts of plasticizer; 3-8 parts of ethylene-propylene copolymer; and 3-8 parts of anti-cracking agent. The anti-cracking agent is prepared from the following raw materials: 60-80 parts of end-functionalized hyperbranched polyphenylene ether; 20-40 parts of hydroxyl-terminated polysiloxane; and 3-5 parts of silane coupling agent. This document uses hydrogenated styrene-butadiene block copolymer and polypropylene together as the matrix, significantly improving the crack resistance of the cable sheath material.

[0006] Patent document CN113861658A discloses a scratch-resistant, halogen-free, flame-retardant elastomer, the raw materials of which include: 10-30 parts of polyphenylene ether resin; 10-40 parts of hydrogenated styrene-butadiene block copolymer; 10-30 parts of polypropylene resin; 5-15 parts of polyolefin elastomer; 10-40 parts of filler oil; 5-15 parts of polyamide elastomer; 10-25 parts of composite scratch-resistant agent; and 15-40 parts of flame retardant. The composite scratch-resistant agent is prepared by compounding silicone powder, maleic anhydride-grafted SEBS, and erucamide; the flame retardant is prepared by compounding melamine cyanurate and aluminum hypophosphite in a mass ratio of 2:3; the filler oil is paraffin-based white oil and / or naphthenic white oil; and the polyolefin elastomer is ethylene-propylene copolymer and / or ethylene-octene copolymer. However, the literature added a large amount of white oil, which not only easily precipitates out, causing a decline in material performance or poor appearance, but also reduces the flame retardancy of the material; in addition, the flame retardancy and fire resistance of the material still do not meet the requirements.

[0007] Patent document CN117362904A discloses a flame-retardant and aging-resistant styrene-based thermoplastic elastomer and its preparation method. The raw materials, by weight, are: 6-12 parts polyphenylene ether, 22-28 parts hydrogenated styrene-butadiene-styrene block copolymer, 14-20 parts polypropylene, 5-9 parts ethylene-octene copolymer, 9-12 parts white oil, and 25-35 parts microencapsulated flame retardant. The microencapsulated flame retardant consists of: 100 parts flame retardant, 5 parts cyanuric chloride... -15 parts, ethylenediamine 10-30 parts, antioxidant 6-15 parts, solvent 400 parts; flame retardant selected from one or more of the following: ammonium polyphosphate, aluminum hypophosphite, aluminum phosphonate, magnesium hydroxide, aluminum hydroxide, metal dihydroxide, melamine phosphate, melamine polyphosphate, melamine cyanurate, pentaerythritol, piperazine pyrophosphate, expandable graphite, zinc borate, graphene, transition metal disulfides, carbon nanotubes, halloysite, sepiolite, and kaolin, mixed in any proportion. However, this literature not only presents a complex microencapsulated flame retardant preparation process that increases production costs, but also adds a large amount of white oil, which is prone to precipitation, causing a decline in material performance or poor appearance, and reducing the flame retardancy of the material. Summary of the Invention

[0008] The purpose of this invention is to provide a modified ceramicized flame-retardant polyphenylene ether insulated wire and cable material to solve the problems of complex preparation process, high cost, and low upper temperature limit of thermal barrier coating in the prior art.

[0009] To achieve the above objectives, the technical solution of the present invention is as follows:

[0010] The present invention discloses a modified ceramic flame-retardant polyphenylene ether insulated wire and cable material, which is made from the following raw materials in the indicated mass fractions: 15%–20% polyphenylene ether resin, 10%–20% SEBS thermoplastic elastomer, 4%–8% polypropylene resin, 3%–8% maleic anhydride grafting material, 5%–20% melamine cyanurate, 5%–15% aluminum diethylphosphite, 1%–4% 2,3-dimethyl-2,3-diphenylbutane, 10%–30% compound ceramic powder, and 1%–4% antioxidant.

[0011] The polyphenylene oxide resin (PPO) has a melt index of 5–15 g / 10 min, a load deformation temperature ≥190℃, an embrittlement temperature ≤-170℃, and a density of 1.0–1.2 g / cm³. 3 For example: LXR035 and LXR040 produced by Shanxi Lanxing;

[0012] The SEBS thermoplastic elastomer is a hydrogenated styrene-butadiene block copolymer, wherein the styrene content is 25% to 33%, the viscosity is 2.0 to 3.0, and the styrene mass percentage is 31% to 35%; for example, 6151 produced by Taiwan Rubber Co., Ltd.

[0013] The polypropylene resin has a melt index of 2.5–4.0 g / 10 min and a flexural modulus of 1000–1500 kg / cm². 2 Homopolymer polypropylene or copolymer polypropylene; for example, T30S produced by Daqing Petrochemical.

[0014] The maleic anhydride grafting material is at least one of maleic anhydride-grafted polyethylene, maleic anhydride-grafted ethylene-octene copolymer, maleic anhydride-grafted SEBS, and maleic anhydride-grafted ethylene-propylene rubber, with a maleic anhydride grafting rate of 0.6% to 1.2%; preferably maleic anhydride-grafted SEBS, such as YS-1098-C produced by Anhui Dingshuo New Materials Co., Ltd.

[0015] The melamine cyanurate (MCA) has CAS number 37640-57-6, industrial grade MCA content ≥99.5%, and D50 particle size 2.5~3.5μm; the aluminum diethylphosphite (ADP) has CAS number 225789-38-8, effective content ≥98%, P content (24±1)%, and D98 particle size ≤20μm.

[0016] The compound ceramic powder is a mixture of any three of the following: glass powder, montmorillonite, nano alumina, nano magnesium oxide, ammonium polyphosphate, wollastonite, and sepiolite.

[0017] The antioxidant is composed of a primary antioxidant and a secondary antioxidant. The primary antioxidant is at least one of antioxidant 1010, antioxidant 1035 and / or antioxidant 1024. The secondary antioxidant is at least one of phosphite esters, thioester antioxidants (e.g., antioxidant 1035) and / or sulfur-containing hindered phenolic antioxidants (e.g., antioxidant 300).

[0018] The preparation method of the modified ceramicized flame-retardant polyphenylene ether insulated wire and cable material of the present invention includes the following steps: S1, mixing and stirring polyphenylene ether resin, SEBS thermoplastic elastomer, polypropylene resin and maleic anhydride graft material to form a first mixture; S2, mixing and stirring melamine cyanurate, aluminum diethyl phosphite and composite ceramic powder to form a second mixture; S3, mixing and stirring the first mixture, the second mixture and an antioxidant; S4, extruding and granulating using a twin-screw extruder, with the extruder set at a temperature of 200-260℃ and a speed of 350-450 rpm.

[0019] Preferably, the stirring rate in steps S1 and S2 is 1500–2500 rpm; and the stirring rate in step S3 is 150–600 rpm.

[0020] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0021] This invention employs polymer blending and grafting modification methods. Based on the blending modification of PPO and SEBS, polypropylene resin is introduced to improve the product's flowability. Maleic anhydride grafting material enhances the compatibility between inorganic materials and polymers, resulting in a significant improvement in the material's electrical and mechanical properties. The addition of phosphorus and nitrogen flame retardants such as MCA and ADP, as well as 2,3-dimethyl-2,3-diphenylbutane (L-K), gives the material good flame retardant properties. The introduction of compound ceramic powder significantly improves the material's crusting and ceramic-forming properties after combustion, thereby greatly enhancing its fire resistance.

[0022] Therefore, the modified ceramicized flame-retardant polyphenylene ether insulated wire and cable material of the present invention has outstanding electrical insulation, flowability, and water resistance; good wear resistance and electrical properties; good dimensional stability; high heat resistance, with a long-term operating temperature of up to 150℃; good flame retardancy and self-extinguishing properties; excellent high-temperature combustion ceramicization properties, and still has excellent insulation properties after ceramicization; low dielectric constant and dielectric loss, with negligible influence from temperature and humidity; non-toxic, halogen-free, low relative density, and excellent mechanical strength, stress relaxation resistance, creep resistance, and water vapor resistance. Detailed Implementation

[0023] Those skilled in the art should recognize that this embodiment is only used to illustrate the present invention and is not intended to limit the present invention. Any changes or modifications to the embodiment within the scope of the present invention are within the scope of the claims of the present invention.

[0024] The raw materials and proportions of the modified ceramicized flame-retardant polyphenylene ether insulated wire and cable materials of Examples 1-5 and Comparative Examples 1-2 are listed in Table 1. The preparation method includes the following steps: S1, polyphenylene ether resin, SEBS thermoplastic elastomer, polypropylene resin and maleic anhydride graft material are added to a high-speed mixer and stirred for 5 minutes at a speed of 2000 rpm to form a first mixture; S2, melamine cyanurate, aluminum diethylphosphite and compound ceramic powder are added to a high-speed mixer and mixed at high speed to 100°C at a speed of 2500 rpm to form a second mixture; S3, the first mixture, the second mixture and antioxidant are added to a high-speed mixer and mixed at a low speed of 500 rpm; S4, extrusion granulation is performed using a twin-screw extruder at a set temperature of 200-260°C and a speed of 400 rpm; finally, the particle size is made uniform by adjusting the speed of the pelletizer to obtain the modified ceramicized flame-retardant polyphenylene ether insulated wire and cable material.

[0025] Table 1. Raw materials and proportions for Examples 1-5 and Comparative Examples 1-2, in %wt.

[0026] Among them, PPO uses LXR035 and LXR040 produced by Shanxi Lanxing Company; SEBS thermoplastic elastomer uses 6151 produced by Taiwan Rubber Co., Ltd.; polypropylene resin uses T30S produced by Daqing Petrochemical; maleic anhydride grafted SEBS uses YS-1098-C produced by Anhui Dingshuo New Materials Co., Ltd., with a maleic anhydride grafting rate of 0.9%.

[0027] Comparative Example 1 is a comparative example of Example 1, the difference being that no tannin was added in Comparative Example 1.

[0028] Comparative Example 2 is a comparative example of Example 4, the difference being that no compound ceramic powder was added in Comparative Example 1, and the flame retardants were all melamine cyanurate and aluminum diethylphosphite.

[0029] Test Experiment Example

[0030] The materials from Examples 1-5 and Comparative Examples 1-2 were prepared by tableting and tested according to the test standards in Table 2.

[0031] Table 2 Performance test results of Examples 1-5 and Comparative Examples 1-2

[0032] As can be seen from Table 2, the properties listed in Examples 1 to 5 of the present invention all meet the requirements of the standard, and the oxygen index and ceramicization rate are significantly improved, exhibiting good flame retardant and fire-resistant properties.

[0033] Compared to Comparative Example 1, Example 1 incorporated tannin, resulting in better flame-retardant properties and effectively improving the safety and reliability of the cable. Compared to Comparative Example 2, Example 4 incorporated various ceramic powders, causing the cable to become ceramic after combustion. This allows the cable to continue operating normally for a period of time even when on fire, effectively improving its fire resistance and reliability.

Claims

1. A modified ceramic flame retardant polyphenylene ether insulation electrical wire cable material characterized by, It is made of the following raw materials with mass fraction: polyphenyl ether resin 15-20%, SEBS thermoplastic elastomer 10-20%, polypropylene resin 4-8%, maleic anhydride grafted material 3-8%, melamine cyanurate 5-20%, aluminum diethyl phosphinate 5-15%, 2,3-dimethyl-2,3-diphenylbutane 1-4%, compounded ceramic powder 10-30%, antioxidant 1-4%.

2. The modified ceramic flame retardant polyphenylene ether insulated electrical wire cable material of claim 1, wherein, The polyphenylene ether resin has a melt index of 5 to 15 g / 10 min, a load deflection temperature of ≥ 190°C, a brittle temperature of ≤ -170°C, and a density of 1.0 to 1.2 g / cm 3 .

3. The modified ceramic flame retardant polyphenylene ether insulated electrical wire cable material of claim 1, wherein, The SEBS thermoplastic elastomer is hydrogenated styrene-butadiene block copolymer, wherein the styrene content is 25-33%, and the viscosity is 2.0-3.0, and the mass percentage of styrene is 31-35%.

4. The modified ceramic flame retardant polyphenylene ether insulated electrical wire cable material of claim 1, wherein, The polypropylene resin has a melt index of 2.5 to 4.0 g / 10 min and a flexural modulus of 1000 to 1500 kg / cm 2 homopolymer polypropylene or copolymer polypropylene.

5. The modified ceramic flame retardant polyphenylene ether insulated electrical wire cable material of claim 1, wherein, The maleic anhydride grafted material is at least one of maleic anhydride grafted polyethylene, maleic anhydride grafted ethylene-octene copolymer, maleic anhydride grafted SEBS, and maleic anhydride grafted ethylene-propylene rubber, and the grafting rate of maleic anhydride is 0.6-1.2%.

6. The modified ceramic flame retardant polyphenylene ether insulated electrical wiring cable material of claim 1, wherein, The melamine cyanurate has a CAS number of 37640-57-6, an industrial grade MCA content of ≥99.5%, and a D50 particle size of 2.5-3.5 μm; the aluminum diethyl phosphinate has a CAS number of 225789-38-8, an effective content of ≥98%, a P content of (24±1)%, and a D98 particle size of ≤20 μm.

7. The modified ceramic flame retardant polyphenylene ether insulated electrical wiring cable material of claim 1, wherein, The compounded ceramic powder is a mixture of any three of glass powder, montmorillonite, nano-alumina, nano-magnesium oxide, ammonium polyphosphate, wollastonite, and sepiolite.

8. The modified ceramic flame retardant polyphenylene ether insulated electrical wiring cable material of claim 1, wherein, The antioxidant is composed of a primary antioxidant and a secondary antioxidant, the primary antioxidant is at least one of antioxidant 1010, antioxidant 1035, and / or antioxidant 1024; and the secondary antioxidant is at least one of phosphite ester, thioester antioxidant, and / or sulfur-containing hindered phenolic antioxidant.

9. The method of making a modified ceramic flame retardant polyphenylene ether insulation electrical wire and cable material according to any one of claims 1 to 8, characterized in that, It comprises the following steps: S1, mixing and stirring the polyphenyl ether resin, SEBS thermoplastic elastomer, polypropylene resin, and maleic anhydride grafted material uniformly to form a first mixture; S2, mixing and stirring the melamine cyanurate, aluminum diethyl phosphinate, and compounded ceramic powder uniformly to form a second mixture; S3, mixing and stirring the first mixture, the second mixture, and the antioxidant uniformly; and S4, using a double-screw extruder for extrusion granulation, wherein the extruder is set at a temperature of 200-260℃ and a rotation speed of 350-450 rpm.

10. The method of making a modified ceramic flame retardant polyphenylene ether insulated electrical wire cable material according to claim 9, characterized in that, The stirring speed in steps S1 and S2 is 1500-2500 rpm; and the stirring speed in step S3 is 150-600 rpm.

Images