Modified ceramic flame-retardant polyphenyl ether insulated wire and cable material

Abstract

The invention discloses a modified ceramic flame-retardant polyphenyl ether insulated wire and cable material which is prepared from the following raw materials in percentage by mass: 15%-20% of polyphenyl ether resin, 10%-20% of SEBS thermoplastic elastomer, 4%-8% of polypropylene resin, 3%-8% of maleic anhydride grafted material, 5%-20% of melamine cyanurate, 5%-15% of aluminum diethylhypophosphite, 1%-4% of 2, 3-dimethyl-2, 3-diphenyl butane, 10%-30% of compound ceramic powder and 1%-4% of antioxidant. The insulated wire and cable material disclosed by the invention has outstanding electrical insulativity, flowability and water resistance, relatively good wear resistance and electrical performance, good dimensional stability and relatively high heat resistance; the flame-retardant property is good, and the self-extinguishing property is realized; and the ceramic forming property after high-temperature combustion is excellent, and the ceramic still has excellent insulating property after being formed.

Description

Technical Field

[0001] The invention belongs to the technical field of polyphenylene ether insulated wires and cables, and in particular relates to a modified ceramic flame-retardant polyphenylene ether insulated wire and cable material. Background Art

[0002] There are many types of thermoplastic elastomers, mainly styrene (TPS), olefins (TPO), cross-linked olefins (TPV), vinyl chloride (TPVC), polyurethane (TPU), etc. They have the characteristics of high elasticity, high strength, low density, easy processing, etc. At the same time, they have good insulation, high and low temperature resistance, fatigue resistance, good hand feel, no odor, and have become the preferred material to replace PVC in the field of electronic wires. The application of halogen-free flame retardant elastomers in wires and cables must meet some requirements: the hardness is generally 80-90A, the flame retardancy meets the requirements of VW-1 or FT-1 traffic standards, good flow and molding performance, fine and smooth surface, tensile strength, tear strength, temperature resistance (80 / 90 / 105℃), heat deformation (121 / 150℃), hot and cold shock, migration and other mechanical properties meet the standards.

[0003] Polyphenylene ether (PPO) is a self-flame retardant engineering plastic with an oxygen index of up to 29. Therefore, by modifying elastomers with PPO and adding a halogen-free flame retardant system, a high flame retardant level can be achieved while maintaining high mechanical properties. With the increasing environmental protection requirements at home and abroad, flexible PPO materials are ideal environmentally friendly materials to replace PVC.

[0004] The PPO insulated wires and cables currently on the market will have their insulation resistance reduced when used in humid environments such as basements and garages due to moisture absorption by the insulation material; continued reduction in insulation resistance may lead to safety accidents such as insulation breakdown and line short circuits. Therefore, the market is in urgent need of an upgraded product of halogen-free, low-smoke, flame-retardant polyolefin insulated wires and cables for use in humid 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; 3-8 parts of anti-cracking agent; wherein the anti-cracking agent is made from the following raw materials: 60-80 parts of end-functionalized hyperbranched polyphenylene ether; 20-40 parts of terminal hydroxyl polysiloxane; 3-5 parts of silane coupling agent. The document uses hydrogenated styrene-butadiene block copolymer and polypropylene as the matrix, which significantly improves the anti-cracking performance 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 to 30 parts of polyphenylene ether resin; 10 to 40 parts of hydrogenated styrene-butadiene block copolymer; 10 to 30 parts of polypropylene resin; 5 to 15 parts of polyolefin elastomer; 10 to 40 parts of filler oil; 5 to 15 parts of polyamide elastomer; 10 to 25 parts of composite scratch-resistant agent; and 15 to 40 parts of flame retardant; wherein 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 cycloalkyl white oil; and the polyolefin elastomer is ethylene-propylene copolymer and / or ethylene-octene copolymer. However, a large amount of white oil is added in the document, which is not only easy to precipitate, resulting in a decrease in material performance or a 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 thermoplastic elastomer and its preparation method, wherein the raw materials are composed of 6-12 parts of polyphenylene ether, 22-28 parts of hydrogenated styrene-butadiene-styrene block copolymer, 14-20 parts of polypropylene, 5-9 parts of ethylene-octene copolymer, 9-12 parts of white oil, and 25-35 parts of microencapsulated flame retardant; the microencapsulated flame retardant is composed of 100 parts of flame retardant, 50 parts of cyanuric chloride, and 100 parts of cyanuric chloride. -15 parts, 10-30 parts of ethylenediamine, 6-15 parts of antioxidant, 400 parts of solvent; flame retardant is selected from ammonium polyphosphate, aluminum hypophosphite, aluminum phosphite, magnesium hydroxide, aluminum hydroxide, metal double hydroxide, melamine phosphate, melamine polyphosphate, melamine cyanurate, pentaerythritol, piperazine pyrophosphate, expandable graphite, zinc borate, graphene, transition metal disulfide, carbon nanotubes, halloysite, sepiolite, kaolin and one or more thereof are mixed in any proportion. However, in the document, not only the preparation process of microencapsulated flame retardant is complicated and increases the production cost, but also a large amount of white oil is added, which is easy to precipitate and causes the material performance to decline or the appearance to be poor, and reduces the flame retardancy of the material. Summary of the invention

[0008] The purpose of the present invention is to provide a modified ceramic 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 of high entropy alloy powder.

[0009] In order to achieve the above object, the technical solution of the present invention is:

[0010] The modified ceramic flame-retardant polyphenylene ether insulated wire and cable material of the present invention is prepared from the following raw materials in mass fraction: 15% to 20% of polyphenylene ether resin, 10% to 20% of SEBS thermoplastic elastomer, 4% to 8% of polypropylene resin, 3% to 8% of maleic anhydride grafted material, 5% to 20% of melamine cyanurate, 5% to 15% of diethyl aluminum hypophosphite, 1% to 4% of 2,3-dimethyl-2,3-diphenylbutane, 10% to 30% of compound ceramic powder, and 1% to 4% of antioxidant;

[0011] The polyphenylene ether resin (PPO for short) has a melt index of 5 to 15 g / 10 min, a load deformation temperature of ≥190° C., a brittle temperature of ≤-170° C., and a density of 1.0 to 1.2 g / cm 3 ; For example: LXR035 and LXR040 produced by Shanxi Bluestar;

[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 mass percentage of styrene is 31% to 35%; for example, 6151 produced by Taiwan Rubber Co., Ltd.;

[0013] 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 or copolymer polypropylene; for example, T30S produced by Daqing Petrochemical;

[0014] 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% 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 for short) has a CAS number of 37640-57-6, an industrial-grade MCA content of ≥99.5%, and a D50 particle size of 2.5 to 3.5 μm; the diethylaluminum hypophosphite (ADP for short) 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.

[0016] The composite ceramic powder is a mixture of any three of 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, wherein 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, thioester antioxidants (such as antioxidant 1035) and / or sulfur-containing hindered phenol antioxidants (such as antioxidant 300).

[0018] The preparation method of the modified ceramic flame-retardant polyphenylene ether insulated wire and cable material of the present invention comprises the following steps: S1, mixing polyphenylene ether resin, SEBS thermoplastic elastomer, polypropylene resin and maleic anhydride grafted material and stirring them uniformly to form a first mixture; S2, mixing melamine cyanurate, diethyl aluminum hypophosphite and compound ceramic powder and stirring them uniformly to form a second mixture; S3, mixing the first mixture, the second mixture and an antioxidant and stirring them uniformly; S4, using a twin-screw extruder for extrusion granulation, the extruder setting temperature is 200-260°C, and the rotation speed is 350-450rpm.

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

[0020] Compared with the prior art, the present invention has the following beneficial effects:

[0021] The present invention adopts the methods of polymer blending modification and grafting modification, and introduces polypropylene resin to improve product fluidity on the basis of PPO and SEBS blending modification; the maleic anhydride grafting material improves the compatibility between inorganic matter and polymer, so that the electrical properties and mechanical properties of the material are significantly improved; phosphorus nitrogen flame retardants such as MCA and ADP and 2,3-dimethyl-2,3-diphenylbutane (diphenylbutane) are added to make the material have good flame retardant properties; the introduction of compound ceramic powder greatly improves the crusting and porcelain-forming properties of the material after combustion, and can greatly improve the fire resistance of the material.

[0022] Therefore, the modified ceramic flame-retardant polyphenylene ether insulated wire and cable material of the present invention has outstanding electrical insulation, fluidity and water resistance, good wear resistance and electrical properties, good dimensional stability; high heat resistance, and the long-term use temperature can reach 150°C; good flame retardancy and self-extinguishing properties; excellent high-temperature combustion porcelain-forming properties, and still has excellent insulation properties after porcelain-forming; small dielectric constant and dielectric loss, and is minimally affected by temperature and humidity; non-toxic, halogen-free, low relative density, and has excellent mechanical strength, stress relaxation resistance, creep resistance, and water vapor resistance. DETAILED DESCRIPTION

[0023] Those skilled in the art should recognize that the present embodiment is only used to illustrate the present invention, and is not used 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 ceramic flame-retardant polyphenylene ether insulated wire and cable materials of Examples 1 to 5 and Comparative Examples 1 to 2 are listed in Table 1; the preparation method thereof comprises the following steps: S1, putting polyphenylene ether resin, SEBS thermoplastic elastomer, polypropylene resin and maleic anhydride grafted material into a high-speed mixer and stirring for 5 minutes, the mixer speed is 2000rpm, to form a first mixture; S2, putting melamine cyanurate, diethyl aluminum hypophosphite and compound ceramic powder into a high-speed mixer, mixing at high speed to 100°C, the mixer speed is 2500rpm, to form a second mixture; S3, putting the first mixture, the second mixture and the antioxidant into a high-speed mixer and mixing at a low speed, the speed is 500rpm; S4, using a twin-screw extruder for extrusion granulation, the extruder setting temperature is 200-260°C, the speed is 400rpm; finally, the particle size is made uniform by adjusting the pelletizer speed to obtain the modified ceramic flame-retardant polyphenylene ether insulated wire and cable material.

[0025] Table 1 Raw materials and proportions of Examples 1 to 5 and Comparative Examples 1 to 2, unit: %wt

[0026]

[0027] Among them, PPO uses LXR035 and LXR040 produced by Shanxi Bluestar Company; SEBS thermoplastic elastomer uses 6151 produced by Taiwan Rubber Corporation; polypropylene resin uses T30S produced by Daqing Petrochemical; maleic anhydride grafted SEBS uses YS-1098-C produced by Anhui Dingshuo New Materials Co., Ltd., and the maleic anhydride grafting rate is 0.9%.

[0028] Comparative Example 1 is a comparative example of Example 1, except that no linalool is added in Comparative Example 1.

[0029] Comparative Example 2 is a comparative example of Example 4, except that: in Comparative Example 1, no composite ceramic powder is added, and the flame retardants are all melamine cyanurate and diethyl aluminum hypophosphite.

[0030] Test experiment example

[0031] The materials of Examples 1 to 5 and Comparative Examples 1 to 2 were sampled by tableting and tested according to the test standards in Table 2.

[0032] Table 2 Performance test results of Examples 1 to 5 and Comparative Examples 1 to 2

[0033]

[0034]

[0035] It can be seen from Table 2 that the properties listed in Examples 1 to 5 of the present invention can all meet the requirements of the standard, the oxygen index and ceramicization rate indicators are significantly improved, and they have good flame retardancy and fire resistance.

[0036] Compared with comparative example 1, the addition of linalool in Example 1 makes the material have better flame retardant properties, which can effectively improve the safety and reliability of the cable. Compared with comparative example 2, the addition of multiple ceramic powders in Example 4 makes the material ceramicized after combustion, and the cable can still operate normally for a period of time when it is on fire, which can effectively improve the fire resistance reliability of the cable.

Claims

1. A modified ceramic flame-retardant polyphenylene ether insulated wire and cable material, characterized in that: The invention is made of the following raw materials in mass fraction: 15% to 20% of polyphenylene ether resin, 10% to 20% of SEBS thermoplastic elastomer, 4% to 8% of polypropylene resin, 3% to 8% of maleic anhydride grafted material, 5% to 20% of melamine cyanurate, 5% to 15% of diethyl aluminum hypophosphite, 1% to 4% of 2,3-dimethyl-2,3-diphenylbutane, 10% to 30% of compound ceramic powder and 1% to 4% of antioxidant.

2. The modified ceramic flame-retardant polyphenylene ether insulated wire and cable material according to claim 1, characterized in that: The polyphenylene ether resin has a melt index of 5 to 15 g / 10 min, a load deformation 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 wire and cable material according to claim 1, characterized in that: 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 mass percentage of styrene is 31% to 35%.

4. The modified ceramic flame-retardant polyphenylene ether insulated wire and cable material according to claim 1, characterized in that: 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 wire and cable material according to claim 1, characterized in that: 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% to 1.2%.

6. The modified ceramic flame-retardant polyphenylene ether insulated wire and cable material according to claim 1, characterized in that: 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 to 3.5 μm; the diethyl aluminum hypophosphite 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 wire and cable material according to claim 1, characterized in that: The composite ceramic powder is a mixture of any three of glass powder, montmorillonite, nano-alumina, nano-magnesia, ammonium polyphosphate, wollastonite and sepiolite.

8. The modified ceramic flame-retardant polyphenylene ether insulated wire and cable material according to claim 1, characterized in that: The antioxidant consists of a primary antioxidant and a secondary antioxidant, wherein 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, thioester antioxidants and / or sulfur-containing hindered phenol antioxidants.

9. The method for preparing the modified ceramic flame-retardant polyphenylene ether insulated wire and cable material according to any one of claims 1 to 8, characterized in that: The following steps are involved: S1, mix polyphenylene ether resin, SEBS thermoplastic elastomer, polypropylene resin and maleic anhydride grafted material and stir them evenly to form a first mixture; S2, mix melamine cyanurate, diethyl aluminum hypophosphite and compound ceramic powder and stir them evenly to form a second mixture; S3, mix the first mixture, the second mixture and an antioxidant and stir them evenly; S4, use a twin-screw extruder for extrusion granulation, and set the extruder temperature to 200-260°C and the rotation speed to 350-450rpm.

10. The method for preparing the modified ceramic flame-retardant polyphenylene ether insulated wire and cable material according to claim 9, characterized in that: The stirring rate in step S1 and step S2 is 1500-2500 rpm; the stirring rate in step S3 is 150-600 rpm.

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