阅读说明：本技术 一种汽车线用耐热150℃辐照交联聚烯烃材料及其制备方法 (Heat-resistant 150 ℃ irradiation crosslinked polyolefin material for automobile wire and preparation method thereof ) 是由 袁宝 毛应涛 邓之俊 陆威 张坤 周玉梅 庄丽娜 章柏松 于 2019-09-23 设计创作，主要内容包括：本发明公开了一种汽车线用耐热150℃辐照交联聚烯烃材料,包括如下重量份数的组分：复合高密度聚乙烯树脂60-120份；接枝物树脂5-10份；阻燃剂30-45份；钙锌稳定剂1-3份；抗氧剂4-6份；分散剂0.5-1.5份；润滑剂0.5-1.0份；流变剂0.5-1.0份；交联敏化剂1-3份。复合高密度聚乙烯树脂包括三种熔融指数不同的高密度聚乙烯树脂。本发明采用了复合高密度聚乙烯树脂,可使高密度聚乙烯树脂形成“三峰”结构,克服使用单一树脂的缺陷,起到了互补的作用,同时采用了复合抗氧剂,从整体上提升汽车线用耐热150℃辐照交联聚烯烃材料的物理机械性能及加工工艺性能,使得本发明具有良好的力学性能、耐刮磨性、阻燃性,汽车线挤出放线速度快、气味低。(The invention discloses a heat-resistant 150 ℃ irradiation crosslinked polyolefin material for an automobile wire, which comprises the following components in parts by weight: 60-120 parts of composite high-density polyethylene resin; 5-10 parts of graft resin; 30-45 parts of a flame retardant; 1-3 parts of a calcium zinc stabilizer; 4-6 parts of an antioxidant; 0.5-1.5 parts of a dispersant; 0.5-1.0 part of lubricant; 0.5-1.0 part of rheological agent; 1-3 parts of a crosslinking sensitizer. The composite high-density polyethylene resin comprises three high-density polyethylene resins with different melt indexes. The composite high-density polyethylene resin is adopted, so that the high-density polyethylene resin can form a 'trimodal' structure, the defect of using single resin is overcome, a complementary effect is achieved, and meanwhile, the composite antioxidant is adopted, so that the physical and mechanical properties and the processing technological properties of the heat-resistant 150-DEG C irradiation crosslinked polyolefin material for the automobile wire are integrally improved, and the composite high-density polyethylene resin has good mechanical properties, scratch and abrasion resistance and flame retardance, and is high in automobile wire extrusion and paying-off speed and low in smell.)

1. The 150 ℃ radiation-resistant cross-linked polyolefin material for the automobile wire is characterized by comprising the following components in parts by weight:

the composite high-density polyethylene resin comprises a first high-density polyethylene resin with a melt index of 0.1-0.5g/10min, a second high-density polyethylene resin with a melt index of 4.0-8.0g/10min and a third high-density polyethylene resin with a melt index of 18.0-22.0g/10 min.

2. The automotive wire cross-linked polyolefin material resistant to 150 ℃ radiation according to claim 1, characterized in that: the mass ratio of the first high-density polyethylene resin, the second high-density polyethylene resin and the third high-density polyethylene resin is 5-8:1: 1.5-3.

3. The automotive wire cross-linked polyolefin material resistant to 150 ℃ radiation according to claim 1, characterized in that: the graft resin comprises maleic anhydride grafted polyethylene and maleic anhydride grafted ethylene-octene copolymer, and the mass ratio of the maleic anhydride grafted polyethylene to the maleic anhydride grafted ethylene-octene copolymer is 3-5: 1.

4. The automotive wire cross-linked polyolefin material resistant to 150 ℃ radiation according to claim 3, characterized in that: the melt index of the graft resin is 0.3-1.3g/10min, and the grafting rate is more than or equal to 0.8 percent.

5. The automotive wire cross-linked polyolefin material resistant to 150 ℃ radiation according to claim 1, characterized in that: the flame retardant comprises 20-30 parts by mass of a bromine additive type flame retardant and 10-15 parts by mass of an antimony-containing inorganic compound flame retardant.

6. The automotive wire cross-linked polyolefin material resistant to 150 ℃ radiation according to claim 1, characterized in that: the antioxidant is at least three selected from antioxidant 1010, antioxidant 1024, antioxidant DLTP, antioxidant XL-1 and antioxidant 412S.

7. The automotive wire cross-linked polyolefin material resistant to 150 ℃ radiation according to claim 1, characterized in that: the dispersing agent is ultra-high molecular weight polysiloxane master batch, and the content of polysiloxane in the dispersing agent is 30-70%; the rheological agent is a fluoropolymer processing aid, and the content of fluoropolymer is more than or equal to 80%.

8. The automotive wire cross-linked polyolefin material resistant to 150 ℃ radiation according to claim 1, characterized in that: the crosslinking sensitizer is one selected from triallyl isocyanurate, triallyl cyanate and trimethylolpropane trimethacrylate.

9. The automotive wire cross-linked polyolefin material resistant to 150 ℃ radiation according to claim 1, characterized in that: the lubricant is one or more selected from oxidized polyethylene wax, stearic acid, calcium stearate, magnesium stearate, zinc stearate and barium stearate.

10. A process for the preparation of a heat-resistant 150 ℃ radiation cross-linked polyolefin material for automotive lines according to any of claims 1 to 9, characterized in that it comprises the following steps:

the production method comprises the steps of producing by adopting a Swiss import BUSS line, mixing weighed composite high-density polyethylene resin, graft resin, flame retardant, calcium-zinc stabilizer, antioxidant, dispersant, lubricant, rheological agent and crosslinking sensitizer at high speed by adopting a high-speed mixer, discharging after mixing uniformly, feeding into a BUSS high-speed shearing machine, plasticizing, granulating by a single screw rod and drying to obtain the heat-resistant 150 ℃ irradiation crosslinking polyolefin material for the automobile line;

wherein the parameter of the high-speed mixer is 200-275rpm, when the temperature is raised to 90 ℃, the rotating speed of the high-speed mixer is adjusted to 400-450rpm, and the material is discharged at 120 ℃; BUSS host screw temperature: 180 plus or minus 10 ℃; temperature of the granulation screw: 170 +/-5 ℃; temperature of the granulator: 175 plus or minus 5 ℃; the variation amplitude of the rotation speed/torque of a screw of the main machine is 400 +/-50/50-70, the rotation speed/torque of a granulating screw is 50 +/-5/35-45, the rotation speed of a granulator is 650 +/-100, the temperature of the upper-stage material is 180 +/-5 ℃, and the pressure of a vacuum pump is 0.5-1.0 bar; the water spraying pressure is 0-2 bar.

Technical Field

The invention relates to a heat-resistant 150 ℃ irradiation crosslinked polyolefin material for an automobile wire and a preparation method thereof.

Background

Automobile manufacturing has become the backbone industry of national economy in China, driving the development of a large number of supporting industries. Automobile wires are important accessories in automobiles, and the development of the industry puts higher requirements on wire materials for manufacturing the automobile wires. Most of the existing automobile wire materials use polyvinyl chloride as a main resin component, and although polyvinyl chloride has good flame retardance and low price, the polyvinyl chloride can release hydrogen chloride and other toxic gases during combustion, has the defects of poor thermal stability, high smoke density during combustion and the like, and has great harm to the environment and personal safety.

At present, the development characteristics of the automobile wire are mainly thin-wall insulation, high reliability, excellent flame retardance, excellent electrical property and the like of the irradiation crosslinking polyolefin. The production method of the common polyolefin material for the automobile wire is to take polyolefin resin as a base material, add a flame retardant, an antioxidant, a crosslinking sensitizer and a processing aid, and process the mixture by a special mixing device, so that the basic requirements of automobile wire production can be met, but the phenomena of low yield, unstable process, backward equipment production capacity, low automobile wire extrusion and paying-off speed, large smell and the like exist. In recent years, the automobile industry is increasingly competitive, and more automobile industries improve the market competitiveness of branded automobiles by increasing the production efficiency and increasing the automobile configuration, so that the production efficiency is improved and the smell of an electric wire is reduced under the same condition of the matching materials of the automobile industry, so as to meet the increasingly competitive market competition.

Disclosure of Invention

Aiming at the defects in the prior art, the invention provides the low-odor 150 ℃ radiation-resistant cross-linked polyolefin material for the automobile wire, which has excellent performance, high paying-off speed, stable and advanced production process and low odor, and the preparation method thereof.

The invention aims to provide a heat-resistant 150 ℃ irradiation crosslinked polyolefin material for an automobile wire, which is characterized by comprising the following components in parts by weight:

the composite high-density polyethylene resin comprises a first high-density polyethylene resin with a melt index of 0.1-0.5g/10min, a second high-density polyethylene resin with a melt index of 4.0-8.0g/10min and a third high-density polyethylene resin with a melt index of 18.0-22.0g/10 min.

Specifically, the mass ratio of the first high-density polyethylene resin, the second high-density polyethylene resin and the third high-density polyethylene resin is 5-8:1: 1.5-3.

The first high-density polyethylene resin plays a key role in the tensile strength, hardness, aging and scraping performance of the heat-resistant 150 ℃ irradiation crosslinking polyolefin material for the automobile wire, the second high-density polyethylene resin can improve the impact strength and environmental stress cracking resistance of the heat-resistant 150 ℃ irradiation crosslinking polyolefin material for the automobile wire, and the third high-density polyethylene resin plays an important role in the fluidity and extrusion processing manufacturability of the heat-resistant 150 ℃ irradiation crosslinking polyolefin material for the automobile wire. The three kinds of high-density polyethylene resin are mixed for use, so that the high-density polyethylene resin can form a 'trimodal' structure, the physical and mechanical properties and the processing technological properties of the heat-resistant 150 ℃ irradiation crosslinking polyolefin material for the automobile line are integrally improved, and the defect of using single resin is overcome.

Specifically, the graft resin comprises maleic anhydride grafted polyethylene and a maleic anhydride grafted ethylene-octene copolymer, wherein the mass ratio of the maleic anhydride grafted polyethylene to the maleic anhydride grafted ethylene-octene copolymer is 3-5: 1.

Preferably, the melt index of the graft resin is 0.3-1.3g/10min, and the grafting rate is more than or equal to 0.8%.

Specifically, the flame retardant comprises a bromine-containing additive flame retardant and an antimony-containing inorganic compound flame retardant, wherein the mass fraction of the bromine-containing additive flame retardant is 20-30 parts, and the mass fraction of the antimony-containing inorganic compound flame retardant is 10-15 parts.

In the invention, the bromine additive flame retardant is decabromodiphenylethane, and the antimony-containing inorganic compound flame retardant is antimony trioxide.

Specifically, the antioxidant is at least three selected from antioxidant 1010, antioxidant 1024, antioxidant DLTP, antioxidant XL-1 and antioxidant 412S.

Preferably, the antioxidant is 1010, 1024 or XL-1, and the weight portion ratio of the antioxidant to the antioxidant is 1-3:1: 0.5-1.

Preferably, the antioxidant is 1010, 1024 or 412S, and the weight part ratio of the three is 1.2-3:1: 0.5-0.8.

Preferably, the antioxidant is 1010, DLTP and XL-1, and the feeding weight parts of the antioxidant, the DLTP and the XL-1 are 1-3:1: 0.5-1.

Preferably, the antioxidant is 1010, 1024, XL-1 or 412S, and the weight portion ratio of the four ingredients is 1-3:1:0.3-0.5: 0.5-1.

In the invention, the selection of the antioxidant plays a role in determining the aging performance of the heat-resistant 150 ℃ irradiation crosslinked polyolefin material for the automobile wire. For short-term aging (175 ℃ multiplied by 240h) specified by the ISO6722 standard, the traditional antioxidant 1010, the antioxidant 1024 and the like cannot effectively protect the material; for long-term aging (150 ℃ multiplied by 3000h) specified by the ISO6722 standard, if a traditional antioxidant is used, the addition amount of the antioxidant is greatly increased, which inevitably causes the problems of increased material cost, precipitation of the antioxidant in the using process of an automobile line, larger odor of the automobile line and the like, and influences the quality and the using safety of the automobile line. Meanwhile, if a single antioxidant is selected from the material, the aging performance and the discoloration of the automobile wire of the material in the production, processing, extrusion processing and use processes of the automobile wire cannot be protected no matter how much the antioxidant is added; in addition, copper-resistant oxidizers must be used due to the presence of metallic conductors in automotive wires. Therefore, a proper combination of multiple antioxidants must be selected in the heat-resistant 150 ℃ irradiation crosslinking polyolefin material for the automobile wire. The matching use of multiple antioxidants is that the imported auxiliary antioxidant with excellent performance is matched on the basis of the traditional antioxidant, the antioxidant XL-1 has excellent material discoloration resistance and copper oxidation resistance, and the antioxidant 412S has excellent performances such as low odor, low precipitation, long-term thermal processing stability and the like.

Specifically, the dispersing agent is an ultrahigh molecular weight polysiloxane master batch, and the content of polysiloxane in the dispersing agent is 30-70%; the rheological agent is a fluoropolymer processing aid, and the content of fluoropolymer is more than or equal to 80%. The use of the fluorine-containing polymer processing aid is beneficial to improving the problems of die residue accumulation and tape casting, rough automobile line surface and incapability of high-speed extrusion processing of the automobile line in the high-speed extrusion processing process of the radiation-crosslinked polyolefin material with the heat resistance of 150 ℃ for the automobile line, and can improve the extrusion processing speed of the automobile line.

Specifically, the crosslinking sensitizer is one selected from triallyl isocyanurate, triallyl cyanate and trimethylolpropane trimethacrylate.

Specifically, the lubricant is one or more selected from oxidized polyethylene wax, stearic acid, calcium stearate, magnesium stearate, zinc stearate and barium stearate.

The second purpose of the invention is to provide a preparation method of the heat-resistant 150 ℃ radiation cross-linked polyolefin material for the automobile line, which comprises the following steps:

the production method comprises the steps of producing by adopting a Swiss import BUSS line, mixing weighed composite high-density polyethylene resin, graft resin, flame retardant, calcium-zinc stabilizer, antioxidant, dispersant, lubricant, rheological agent and crosslinking sensitizer at high speed by adopting a high-speed mixer, discharging after mixing uniformly, feeding into a BUSS high-speed shearing machine, plasticizing, granulating by a single screw rod and drying to obtain the heat-resistant 150 ℃ irradiation crosslinking polyolefin material for the automobile line;

wherein the parameter of the high-speed mixer is 200-275rpm, when the temperature is raised to 90 ℃, the rotating speed of the high-speed mixer is adjusted to 400-450rpm, and the material is discharged at 120 ℃; BUSS host screw temperature: 180 plus or minus 10 ℃; temperature of the granulation screw: 170 +/-5 ℃; temperature of the granulator: 175 plus or minus 5 ℃; the variation amplitude of the rotation speed/torque of a screw of the main machine is 400 +/-50/50-70, the rotation speed/torque of a granulating screw is 50 +/-5/35-45, the rotation speed of a granulator is 650 +/-100, the temperature of the upper-stage material is 180 +/-5 ℃, and the pressure of a vacuum pump is 0.5-1.0 bar; the water spraying pressure is 0-2 bar.

Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages: the invention relates to a heat-resistant 150 ℃ irradiation crosslinking polyolefin material for an automobile wire, which adopts composite high-density polyethylene resin compounded by three high-density polyethylene resins, can enable the high-density polyethylene resin to form a 'trimodal' structure, overcomes the defect of using single resin, plays a complementary role, simultaneously adopts a composite antioxidant, and integrally improves the physical and mechanical properties and the processing technological properties of the heat-resistant 150 ℃ irradiation crosslinking polyolefin material for the automobile wire, so that the heat-resistant 150 ℃ irradiation crosslinking polyolefin material for the automobile wire has good mechanical properties, scratch and abrasion resistance and flame retardance, and has high automobile wire extrusion and paying-off speed and low smell.

Detailed Description

The following provides a detailed description of preferred embodiments of the invention.

The invention provides a heat-resistant 150 ℃ irradiation crosslinked polyolefin material for an automobile wire, which comprises the following components in parts by weight:

the composite high-density polyethylene resin comprises a first high-density polyethylene resin with a melt index of 0.1-0.5g/10min, a second high-density polyethylene resin with a melt index of 4.0-8.0g/10min and a third high-density polyethylene resin with a melt index of 18.0-22.0g/10 min. Wherein the first high-density polyethylene resin is Kataler petrochemical TR-144, the second high-density polyethylene resin is Mount mountain petrochemical DMDA-8008, and the third high-density polyethylene resin is Exxon Mobil HMA-016.

The mass ratio of the first high-density polyethylene resin, the second high-density polyethylene resin and the third high-density polyethylene resin is 5-8:1: 1.5-3.

The graft resin comprises maleic anhydride grafted polyethylene and maleic anhydride grafted ethylene-octene copolymer, and the mass ratio of the maleic anhydride grafted polyethylene to the maleic anhydride grafted ethylene-octene copolymer is 3-5: 1. Wherein the graft resin is JCP-1571A of Shanghai Tengyu polymer materials Co. The melt index of the graft resin is 0.3-1.3g/10min, and the grafting rate is more than or equal to 0.8 percent.

The flame retardant comprises 20-30 parts of bromine additive flame retardant and 10-15 parts of antimony-containing inorganic compound flame retardant.

In the invention, the bromine series additive flame retardant is decabromodiphenylethane, and the antimony-containing inorganic compound flame retardant is antimony trioxide.

The antioxidant is at least three selected from antioxidant 1010, antioxidant 1024, antioxidant DLTP, antioxidant XL-1 and antioxidant 412S, and the lubricant is one or more selected from oxidized polyethylene wax, stearic acid, calcium stearate, magnesium stearate, zinc stearate and barium stearate.

Preferably, the antioxidant is 1010, 1024 or XL-1, and the weight portion ratio of the three is 1-3:1: 0.5-1.

Preferably, the antioxidant is 1010, 1024 or 412S, and the weight portion ratio of the three is 1.2-3:1: 0.5-0.8.

Preferably, the antioxidant is 1010, DLTP and XL-1, and the feeding weight portion ratio of the antioxidant to the antioxidant is 1-3:1: 0.5-1.

Preferably, the antioxidant is 1010, 1024, XL-1 or 412S, and the weight portion ratio of the four ingredients is 1-3:1:0.3-0.5: 0.5-1.

The dispersing agent is ultra-high molecular weight polysiloxane master batch, and the content of polysiloxane in the dispersing agent is 30-70%; the rheological agent is a fluoropolymer processing aid, and the content of the fluoropolymer is more than or equal to 80 percent. Wherein the ultra-high molecular weight polysiloxane master batch is GENIOPLAST PelletS of Wacker company, and the fluorine-containing polymer processing aid is a Roux chemical PPA2300 MA.

The crosslinking sensitizer is one selected from triallyl isocyanurate, triallyl cyanate and trimethylolpropane trimethacrylate.

The invention provides a preparation method of the heat-resistant 150 ℃ irradiation crosslinked polyolefin material for the automobile line, which comprises the following steps:

the production method comprises the steps of producing by adopting a Swiss import BUSS line, mixing weighed composite high-density polyethylene resin, graft resin, flame retardant, calcium-zinc stabilizer, antioxidant, dispersant, lubricant, rheological agent and crosslinking sensitizer at high speed by adopting a high-speed mixer, discharging after mixing uniformly, feeding into a BUSS high-speed shearing machine, plasticizing, granulating by a single screw rod and drying to obtain the heat-resistant 150 ℃ irradiation crosslinking polyolefin material for the automobile line;

wherein the parameter of the high-speed mixer is 200-275rpm, when the temperature is raised to 90 ℃, the rotating speed of the high-speed mixer is adjusted to 400-450rpm, and the material is discharged at 120 ℃; BUSS host screw temperature: 180 plus or minus 10 ℃; temperature of the granulation screw: 170 +/-5 ℃; temperature of the granulator: 175 plus or minus 5 ℃; the variation amplitude of the rotation speed/torque of a screw of the main machine is 400 +/-50/50-70, the rotation speed/torque of a granulating screw is 50 +/-5/35-45, the rotation speed of a granulator is 650 +/-100, the temperature of the upper-stage material is 180 +/-5 ℃, and the pressure of a vacuum pump is 0.5-1.0 bar; the water spraying pressure is 0-2 bar.

The following provides a detailed description of preferred embodiments of the invention.