125 DEG C thermoplastic low-smoke halogen-free polyolefin automobile cable material and preparation method thereof

Abstract

The invention relates to a 125 DEG C thermoplastic low-smoke halogen-free polyolefin automobile cable material and a preparation method thereof. 3 to 20 parts of polyethylene; 1-20 parts of a toughening agent; 3-15 parts of an elastomer; 1-10 parts of a compatilizer; 3 to 20 parts of an ethylene-vinyl acetate copolymer; 30 to 60 parts of a flame retardant; 0.3 to 20 parts of a synergistic flame retardant; 0.5 to 3 parts of an antioxidant; 0.1 to 1 part of a lubricant; and 0.3-1 part of a surface treating agent. Through synergistic cooperation of all the components, the product has better water resistance and processing fluidity; the thermal degradation of the product also has a slow release effect; the uniform mixing of the materials is promoted, and the risks of phase separation and recrystallization are avoided at high temperature, so that the thermal stability of the whole formula system at high temperature is ensured; the cabling process of the product is stable, decomposed air holes are not easy to appear, and the starting time of a client is prolonged.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of cable materials, and relates to a cable material, in particular to a 125 DEG C thermoplastic low-smoke halogen-free polyolefin automobile cable material and a preparation method thereof. BACKGROUND

[0002] The automobile wire cable material is mainly a low-halogen irradiation crosslinking material taking polyvinyl chloride as a base material. The polyvinyl chloride cable material has low price and good flame retardancy, but it usually contains halogen, which may pose a threat to human health. With the development of society and the progress of science, low-smoke halogen-free automobile wires gradually replace halogen-containing automobile wires.

[0003] The polyethylene system needs to be crosslinked to achieve a temperature resistance grade of above 125 DEG C, and the crosslinking methods commonly include peroxide chemical crosslinking, irradiation crosslinking and silane crosslinking. Each crosslinking method has advantages and disadvantages, or has high cost, or has large odor, or has an unstable process. The thermoplastic polypropylene cable material does not need irradiation, and has advantages such as not affecting recycling and the like, and has certain market demand.

[0004] A Chinese patent application No. 201510595174.1 discloses a preparation method and use of a 125 DEG C high-temperature-resistant thermoplastic low-smoke halogen-free flame-retardant polypropylene material for automobile wires. The thermoplastic low-smoke halogen-free flame-retardant polypropylene material mainly includes polypropylene, a compatibilizer, a phosphorus-nitrogen flame retardant, an inorganic flame retardant, a flame-retardant synergist, a lubricant and an antioxidant. Specifically, the thermoplastic polypropylene cable material is prepared by using a copolymerized polypropylene as a main raw material, maleic anhydride grafting as an elastomer segment and an aluminum hydroxide compound N-P synergistic flame retardant formula system. However, the thermoplastic low-smoke halogen-free flame-retardant polypropylene material has poor temperature resistance of the aluminum hydroxide flame retardant, and during the processing process, the material temperature is above 165 DEG C, so that decomposition occurs and pores are generated. The melting point of the block copolymerized polypropylene is 150-155 DEG C, and the temperature is too low, so that plasticization is poor, and thus the material cannot meet the long-term and short-term aging requirements of the ISO19642 standard. SUMMARY

[0005] In view of the shortcomings of the prior art, the application aims to provide a 125 DEG C thermoplastic low-smoke halogen-free polyolefin automobile cable material.

[0006] In order to achieve the above-mentioned purpose, the application provides a 125 DEG C thermoplastic low-smoke halogen-free polyolefin automobile cable material, which includes the following raw material components in parts by weight:

[0007]

[0008]

[0009] Optimally, the polypropylene is a mixture of one or two selected from PP-H and PP-B, with a melt index of 0.3-20 g / 10 min and a density of 0.90-0.91 g / cm³. 3 .

[0010] Optimally, the polyethylene is a mixture selected from one or more of HDPE, MDPE, LDPE and LLDPE, with a melt index of 0.05-20 g / 10 min and a density of 0.918-0.950 g / cm³. 3 .

[0011] Optimally, the toughening agent is a polyolefin elastomer (POE) with a melt index of 0.05-5 g / 10 min and a density of 0.86-0.90 g / cm³. 3 .

[0012] Ideally, the elastomer is a mixture of one or more components selected from ethylene propylene diene monomer (EPDM) rubber and ethylene propylene diene monomer (EPDM) rubber.

[0013] Optimally, the compatibilizer is a mixture of one or more components selected from PP-MAH, PE-MAH and POE-MAH, with a melt index of 0.2 to 6 g / min.

[0014] Optimally, the ethylene-vinyl acetate copolymer is an EVA resin with a VA content of 18%-45% or an EVM resin with a VA content of 50-70%.

[0015] Optimally, the flame retardant is chemically produced magnesium hydroxide with silane surface treatment, and its particle size range D50 is 0.8-2.0 μm;

[0016] The synergistic flame retardant is a mixture selected from one or more of glass powder, antimony trioxide, rare earth metal oxides, organosilicon, MCA, polyphenylene sulfide, and polyphenylene ether.

[0017] Optimally, the antioxidant is a mixture of one or more selected from antioxidant 1010, antioxidant 168, antioxidant 626, antioxidant BHT, antioxidant 1024, and antioxidant DLTP.

[0018] The lubricant is a silicone with a polysiloxane content of not less than 50%, or a mixture thereof with one or more of amides and stearates;

[0019] The surface treatment agent is silane 11-100.

[0020] Another object of the present invention is to provide a method for preparing the above-mentioned 125°C thermoplastic low-smoke halogen-free polyolefin automotive cable material, comprising the following steps:

[0021] (a) Weigh out the flame retardant and the synergistic flame retardant in the formulation amount, and spray them into the surface treatment agent in the formulation amount by spraying, and mix at high and low speeds for 3 to 10 minutes.

[0022] (b) Add the polypropylene, polyethylene, toughening agent, elastomer, compatibilizer, ethylene-vinyl acetate copolymer, antioxidant and lubricant in the formula amount, stir evenly, and then put them into an internal mixer for kneading and plasticizing. The discharge temperature is controlled at 175-190°C.

[0023] (c) The material after internal mixing is granulated by a granulation system and then vacuum packaged.

[0024] Due to the application of the above technical solutions, this invention has the following advantages compared with the prior art: The 125℃ thermoplastic low-smoke halogen-free polyolefin automotive cable material of this invention, through the synergistic cooperation of each component, makes the product have better water resistance and processing fluidity; the thermal degradation of the product also has a slow-release effect; it promotes uniform mixing of materials, and there is no risk of phase separation and recrystallization at high temperatures, thereby ensuring the thermal stability of the entire formulation system at high temperatures; the cable-making process of the product is stable, and it is not easy to produce decomposition pores, thus extending the customer's uptime. Detailed Implementation

[0025] This invention relates to a 125℃ thermoplastic low-smoke halogen-free polyolefin automotive cable material, characterized by comprising the following raw material components in parts by weight: 10-40 parts polypropylene; 3-20 parts polyethylene; 1-20 parts toughening agent; 3-15 parts elastomer; 1-10 parts compatibilizer; 3-20 parts ethylene-vinyl acetate copolymer; 30-60 parts flame retardant; 0.3-20 parts synergistic flame retardant; 0.5-3 parts antioxidant; 0.1-1 part lubricant; and 0.3-1 part surface treatment agent. Through the synergistic effect of these components, the product exhibits better water resistance and processing fluidity; it also has a slow-release effect on thermal degradation; it promotes uniform mixing of materials, eliminating the risk of phase separation and recrystallization at high temperatures, thus ensuring the thermal stability of the entire formulation system at high temperatures; the cable-making process is stable, less prone to decomposition pores, and can extend the customer's uptime.

[0026] The polypropylene is a mixture of one or two selected from PP-H and PP-B, with a melt index of 0.3-20 g / 10 min and a density of 0.90-0.91 g / cm³. 3 The polyethylene is a mixture selected from one or more of HDPE, MDPE, LDPE and LLDPE, with a melt index of 0.05-20 g / 10 min and a density of 0.918-0.950 g / cm³. 3The toughening agent is a polyolefin elastomer (POE) with a melt index of 0.05-5 g / 10 min and a density of 0.86-0.90 g / cm³. 3 The elastomer is a mixture selected from one or more of ethylene propylene diene monomer (EPDM) and ethylene propylene diene monomer (EPDM). The compatibilizer is a mixture selected from one or more of PP-MAH, PE-MAH, and POE-MAH, with a melt index of 0.2–6 g / min. The ethylene-vinyl acetate copolymer is EVA resin with a VA content of 18%–45% or EVM resin with a VA content of 50–70%. The flame retardant is chemically processed magnesium hydroxide with silane surface treatment, and its particle size range D50 is 0.8–2.0 μm; the synergistic flame retardant is a mixture selected from one or more of glass powder, antimony trioxide, rare earth metal oxides, organosilicon, MCA, polyphenylene sulfide, and polyphenylene ether. The antioxidant is a mixture selected from one or more of antioxidants 1010, antioxidant 168, antioxidant 626, antioxidant BHT, antioxidant 1024, and antioxidant DLTP; the lubricant is silicone with a polysiloxane content of not less than 50% (preferably 10,000g silicone), or a mixture thereof with one or more of amides and stearates; the surface treatment agent is Dow Corning Silane 11-100.

[0027] The preparation method of the above-mentioned 125℃ thermoplastic low-smoke halogen-free polyolefin automotive cable material includes the following steps: (a) weighing the flame retardant and the synergistic flame retardant in the formula amount, spraying the surface treatment agent in the formula amount by spraying, and mixing at high and low speeds for 3 to 10 minutes; (b) adding the polypropylene, polyethylene, toughening agent, elastomer, compatibilizer, ethylene-vinyl acetate copolymer, antioxidant and lubricant in the formula amount, stirring evenly, and then putting them into an internal mixer for kneading and plasticizing, with the discharge temperature controlled at 175 to 190℃; (c) granulating the material after internal mixing through a granulation system and vacuum packaging it.

[0028] The present invention will be further described in detail below with reference to specific embodiments, but the present invention is not limited to the following embodiments. The implementation conditions used in the embodiments can be further adjusted according to different requirements of specific use, and the implementation conditions not specified are conventional conditions in this industry.

[0029] Examples 1-5, Comparative Examples 1-6

[0030] Examples 1-5 and Comparative Examples 1-3 each provide a thermoplastic low-smoke halogen-free polyolefin automotive cable material at 125℃, and their performance is tested. See Table 1 for details (unit: kg).

[0031] Table 1. Formulation and performance of cable materials in Examples 1-5 and Comparative Examples 1-3.

[0032]

[0033]

[0034] Note: The ethylene-vinyl acetate copolymer used in Comparative Example 3 is not EVA45LX, but EVM 700XL (VA content > 45%). The test standards are as follows: density GB / T 1033.1-2008, oxygen index GB / T 2406-2009, tensile strength GB / T1040.1-2025, elongation at break GB / T 1040.1-2025, Shore D (Shore hardness) GB / T 2411-2008, after aging of the cable (150℃*240h) ISO 16942, winding test at -25℃ ISO 16942, flame retardancy at 45℃ ISO 16942.

[0035] The preparation method of the above-mentioned 125℃ thermoplastic low-smoke halogen-free polyolefin automotive cable material is as follows:

[0036] (a) Weigh out the amount of flame retardant and synergistic flame retardant in the formula, spray the amount of surface treatment agent in the formula by spraying, and mix at high and low speeds for 3 to 10 minutes (this range has little impact on the performance of the product, the same below).

[0037] (b) Add the formulated amounts of polypropylene, polyethylene, toughening agent, elastomer, compatibilizer, ethylene-vinyl acetate copolymer, antioxidant and lubricant, mix evenly, and then put into an internal mixer for kneading and plasticizing. The discharge temperature is controlled at 175-190℃.

[0038] (c) The material after internal mixing is granulated by a granulation system and then vacuum packaged.

[0039] The above embodiments are only for illustrating the technical concept and features of the present invention. Their purpose is to enable those skilled in the art to understand the content of the present invention and implement it accordingly. They should not be used to limit the scope of protection of the present invention. All equivalent changes or modifications made in accordance with the spirit and essence of the present invention should be covered within the scope of protection of the present invention.

Claims

1. A 125°C thermoplastic low smoke, halogen-free polyolefin automotive cable compound characterized in that, It comprises the following raw material components by weight: Polypropylene 10-40 parts; Polyethylene 3-20 parts; Toughening agent 1-20 parts; Elastomer 3-15 parts; Compatibilizer 1-10 parts; Ethylene-vinyl acetate copolymer 3-20 parts; Flame retardant 30-60 parts; Synergistic flame retardant 0.3-20 parts; Antioxidant 0.5-3 parts; Lubricant 0.1-1 part; Surface treatment agent 0.3-1 part.

2. The 125°C thermoplastic low smoke, zero halogen polyolefin automotive cable compound of claim 1, wherein: Said polypropylene is a mixture consisting of one or both of PP-H and PP-B, having a melt index of 0.3-20 g / 10 min, a density of 0.90-0.91 g / cm 3 .

3. The 125℃ thermoplastic low-smoke halogen-free polyolefin automotive cable material according to claim 1, characterized in that: The polyethylene is a mixture consisting of one or more selected from the group consisting of HDPE, MDPE, LDPE and LLDPE, having a melt index of 0.05-20 g / 10 min, a density of 0.918-0.950 g / cm 3 .

4. The 125℃ thermoplastic low-smoke halogen-free polyolefin automotive cable material according to claim 1, characterized in that: The toughening agent is a polyolefin elastomer POE having a melt index of 0.05-5 g / 10 min and a density of 0.86-0.90 g / cm 3 .

5. The 125℃ thermoplastic low-smoke halogen-free polyolefin automotive cable material according to claim 1, characterized in that: The elastomer is a mixture consisting of one or more selected from binary ethylene-propylene rubber and ternary ethylene-propylene rubber.

6. The 125℃ thermoplastic low-smoke halogen-free polyolefin automotive cable material according to claim 1, characterized in that: The compatibilizer is a mixture consisting of one or more selected from PP-MAH, PE-MAH and POE-MAH, and its melt index is 0.2-6 g / min.

7. The 125℃ thermoplastic low-smoke halogen-free polyolefin automotive cable material according to claim 1, characterized in that: The ethylene-vinyl acetate copolymer is an EVA resin with 18%-45% VA content or an EVM resin with 50-70% VA content.

8. The 125°C thermoplastic low smoke, zero halogen polyolefin automotive cable compound of claim 1, wherein: ###0002### The flame retardant is chemically prepared magnesium hydroxide with silane surface treatment, and its particle size range D50 is 0.8-2.0 μm; The synergistic flame retardant is a mixture consisting of one or more selected from glass powder, antimony trioxide, rare earth metal oxide, organosilicon, MCA, polyphenylene sulfide and polyphenyl ether.

9. The 125℃ thermoplastic low-smoke halogen-free polyolefin automotive cable material according to claim 1, characterized in that: The antioxidant is a mixture consisting of one or more selected from antioxidant 1010, antioxidant 168, antioxidant 626, antioxidant BHT antioxidant 1024 and antioxidant DLTP, The lubricant is silicone with a polysiloxane content of not less than 50%, or a mixture thereof with one or more of amides, stearate; The surface treatment agent is silane 11-100.

10. Process for the preparation of the 125°C thermoplastic low smoke halogen-free polyolefin automotive cable material according to any one of claims 1 to 9, characterized in that, It comprises the following steps: (a) Weigh the formula amount of the flame retardant and the synergistic flame retardant, and spray the formula amount of the surface treatment agent by spraying, and mix at high and low speed for 3-10 min; (b) After adding the formula amount of the polypropylene, polyethylene, toughening agent, elastomer, compatibilizer, ethylene-vinyl acetate copolymer, antioxidant and lubricant and stirring uniformly, put it into the internal mixer for kneading and plasticizing, and control the discharge temperature at 175-190℃; (c) Granulate the material after the end of the internal mixing through the granulation system, and vacuum package.

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