CN110591201B - Heat-resistant 150 ℃ irradiation crosslinked polyolefin material for automobile wire and preparation method thereof - Google Patents
Heat-resistant 150 ℃ irradiation crosslinked polyolefin material for automobile wire and preparation method thereof Download PDFInfo
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- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
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Abstract
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.
Description
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 Pellet S of Wacker company, and the fluorine-containing polymer processing aid is the Rogomeric 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.
Embodiment 1 provides a heat-resistant 150 ℃ radiation cross-linked polyolefin material for an automobile wire, which comprises the following components in parts by weight:
90 parts of composite high-density polyethylene resin; (the mass ratio of the first high-density polyethylene resin, the second high-density polyethylene resin and the third high-density polyethylene resin is 6.7:1:2.3, wherein the first high-density polyethylene resin is 60 parts, the second high-density polyethylene resin is 9 parts, and the third high-density polyethylene resin is 21 parts.)
7.5 parts of graft resin; (the mass ratio of the maleic anhydride grafted polyethylene to the maleic anhydride grafted ethylene-octene copolymer was 4:1, wherein 6 parts of maleic anhydride grafted polyethylene and 1.5 parts of maleic anhydride grafted ethylene-octene copolymer)
37.5 parts of a flame retardant; (decabromodiphenylethane 25 parts, antimony trioxide 12.5 parts)
2 parts of a calcium zinc stabilizer;
5 parts of an antioxidant; (the weight portion ratio of the antioxidant 1010 to the antioxidant 1024 to the antioxidant XL-1 is 2.5:1.5:1, wherein 2.5 portions of the antioxidant 1010, 1.5 portions of the antioxidant 1024 and 1 portion of the antioxidant XL-1)
1 part of a dispersant; (ultra-high molecular weight polysiloxane master batch, polysiloxane content 50%)
0.75 part of lubricant; (oxidized polyethylene wax)
0.75 part of rheological agent; (fluoropolymer processing aid, fluoropolymer content 90%)
And 2 parts of a crosslinking sensitizer. (triallyl isocyanurate)
A preparation method of a heat-resistant 150 ℃ irradiation crosslinking polyolefin material for an automobile wire 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.
Embodiment 2 provides a heat-resistant 150 ℃ irradiation crosslinked polyolefin material for an automobile wire, which has the same preparation method as that of embodiment 1, except that the raw material components are different, and the material comprises the following components in parts by weight:
60 parts of composite high-density polyethylene resin; (the mass ratio of the first high-density polyethylene resin, the second high-density polyethylene resin and the third high-density polyethylene resin is 6.7:1:2.3, wherein 40 parts of the first high-density polyethylene resin, 6 parts of the second high-density polyethylene resin and 14 parts of the third high-density polyethylene resin)
5 parts of graft resin; (the mass ratio of the maleic anhydride grafted polyethylene to the maleic anhydride grafted ethylene-octene copolymer was 4:1, wherein 4 parts of maleic anhydride grafted polyethylene and 1 part of maleic anhydride grafted ethylene-octene copolymer)
30 parts of a flame retardant; (decabromodiphenylethane 20 parts, antimony trioxide 10 parts)
1 part of calcium zinc stabilizer;
4 parts of an antioxidant; (the weight portion ratio of the antioxidant 1010 to the antioxidant 1024 to the antioxidant XL-1 is 2.5:1.5:1, wherein 2 portions of the antioxidant 1010 to 1.2 portions of the antioxidant 1024 to 0.8 portion of the antioxidant XL-1)
0.5 part of a dispersant; (ultra-high molecular weight polysiloxane master batch, polysiloxane content is 30%)
0.5 part of a lubricant; (polyethylene wax)
0.5 part of rheological agent; (fluoropolymer processing aid, fluoropolymer content 90%)
1 part of crosslinking sensitizer. (triallyl cyanate)
Embodiment 3 provides a heat-resistant 150 ℃ irradiation crosslinked polyolefin material for an automobile wire, which has the same preparation method as that of embodiment 1, except that the raw material components are different, and the material comprises the following components in parts by weight:
120 parts of composite high-density polyethylene resin; (the mass ratio of the first high-density polyethylene resin, the second high-density polyethylene resin and the third high-density polyethylene resin is 6.7:1:2.3, wherein 80 parts of the first high-density polyethylene resin, 12 parts of the second high-density polyethylene resin and 28 parts of the third high-density polyethylene resin)
10 parts of graft resin; (the mass ratio of the maleic anhydride grafted polyethylene to the maleic anhydride grafted ethylene-octene copolymer was 4:1, wherein 8 parts of maleic anhydride grafted polyethylene and 2 parts of maleic anhydride grafted ethylene-octene copolymer)
45 parts of a flame retardant; (decabromodiphenylethane 30 parts, antimony trioxide 15 parts)
3 parts of a calcium zinc stabilizer;
6 parts of an antioxidant; (the weight portion ratio of the antioxidant 1010 to the antioxidant 1024 to the antioxidant XL-1 is 2.5:1.5:1, wherein 3 portions of the antioxidant 1010, 1.8 portions of the antioxidant 1024 and 1.2 portions of the antioxidant XL-1)
1.5 parts of a dispersing agent; (ultra-high molecular weight polysiloxane master batch, polysiloxane content 70%)
1.0 part of a lubricant; (stearic acid)
1.0 part of rheological agent; (fluoropolymer processing aid, fluoropolymer content 80%)
3 parts of a crosslinking sensitizer. (trimethylolpropane trimethacrylate)
Example 4 provides a heat-resistant 150 ℃ radiation cross-linked polyolefin material for an automotive wire, which has the same formula components as example 1, and the same preparation method, except that: the weight part ratio of the first high-density polyethylene resin, the second high-density polyethylene resin and the third high-density polyethylene resin is different and is 5:1:1.5, wherein the weight part ratio of the first high-density polyethylene resin is 60 parts, the weight part ratio of the second high-density polyethylene resin is 12 parts, and the weight part ratio of the third high-density polyethylene resin is 18 parts.
Example 5 provides a heat-resistant 150 ℃ radiation cross-linked polyolefin material for an automotive wire, which has the same formula components as example 1, and the same preparation method, except that: the weight part ratio of the first high-density polyethylene resin, the second high-density polyethylene resin and the third high-density polyethylene resin is different and is 8:1:3, wherein the weight part ratio of the first high-density polyethylene resin to the second high-density polyethylene resin is 50 parts, the weight part ratio of the second high-density polyethylene resin to the third high-density polyethylene resin is 10 parts, and the weight part ratio of the third high-density polyethylene resin to the first high-density polyethylene resin is 30 parts.
Example 6 provides a heat-resistant 150 ℃ radiation cross-linked polyolefin material for an automotive wire, which has the same formulation components and the same preparation method as example 1, and the proportions of the parts by weight of the first high-density polyethylene resin, the second high-density polyethylene resin and the third high-density polyethylene resin are unchanged, except that: 60 parts of composite high-density polyethylene resin, wherein 40 parts of first high-density polyethylene resin, 6 parts of second high-density polyethylene resin and 14 parts of third high-density polyethylene resin.
Example 7 provides a heat-resistant 150 ℃ radiation cross-linked polyolefin material for an automotive wire, which has substantially the same formulation components and preparation method as example 1, and has the same proportions of the first high-density polyethylene resin, the second high-density polyethylene resin and the third high-density polyethylene resin in parts by weight, and is different from the following only in that: 120 parts of composite high-density polyethylene resin, wherein the composite high-density polyethylene resin comprises 80 parts of first high-density polyethylene resin, 12 parts of second high-density polyethylene resin and 28 parts of third high-density polyethylene resin.
Example 8 provides a heat-resistant 150 ℃ radiation cross-linked polyolefin material for an automotive wire, which has the same formula components as example 1, and the same preparation method, except that: the antioxidant comprises an antioxidant 1010, an antioxidant 1024 and an antioxidant 412S, and the feeding weight parts of the antioxidant 1010, the antioxidant 1024 and the antioxidant 412S are the same as those of the antioxidant 1 in example 1, wherein 2.5 parts of the antioxidant 1010, 1.5 parts of the antioxidant 1024 and 1 part of the antioxidant 412S are adopted.
Example 9 provides a heat-resistant 150 ℃ radiation cross-linked polyolefin material for automotive wire, which has substantially the same formulation components as in example 1, and the same preparation method, except that: the antioxidant is antioxidant 1010, antioxidant DLTP and antioxidant XL-1, and the feeding weight parts of the antioxidant 1010, the antioxidant DLTP and the antioxidant XL-1 are the same as those of the embodiment 1, wherein 2.5 parts of the antioxidant 1010, 1.5 parts of the antioxidant DLTP and 1 part of the antioxidant XL-1.
Example 10 provides a heat-resistant 150 ℃ radiation cross-linked polyolefin material for automotive wire, which has substantially the same formulation components as in example 1, and the same preparation method, except that: the antioxidant comprises 1010 antioxidant, 1024 antioxidant, XL-1 antioxidant and 412S antioxidant, and the weight portion ratio of the four ingredients is 2:1:0.4:0.6, wherein 2.5 portions of the antioxidant 1010, 1.25 portions of the antioxidant 1024, 0.5 portion of the antioxidant XL-1 antioxidant and 0.75 portion of the antioxidant 412S antioxidant.
Example 11 provides a heat-resistant 150 ℃ radiation cross-linked polyolefin material for automotive wire, which has substantially the same formulation components as in example 1, and which has the same preparation method, except that: 0.5 part of rheological agent.
Example 12 provides a heat-resistant 150 ℃ radiation cross-linked polyolefin material for automotive wire, which has substantially the same formulation components as in example 1, and which has the same preparation method except that: the rheological agent is 1.0 part.
Comparative example 1 provides a heat-resistant 150 ℃ radiation cross-linked polyolefin material for an automotive wire, which has substantially the same formulation components as in example 1, and completely the same preparation method, except that: the composite high-density polyethylene resin was not added, and only 90 parts of the first high-density polyethylene resin was added.
Comparative example 2 provides a heat-resistant 150 ℃ radiation cross-linked polyolefin material for an automotive wire, which has substantially the same formulation components as in example 1, and which has the same preparation method except that: 30 parts of composite high-density polyethylene resin is added, and the weight part ratio of the three is the same as that of the embodiment 1.
Comparative example 3 provides a heat-resistant 150 ℃ radiation cross-linked polyolefin material for an automotive wire, which has substantially the same formulation components as in example 1, and which has the same preparation method except that: 150 parts of composite high-density polyethylene resin is added.
Comparative example 4 provides a heat-resistant 150 ℃ radiation cross-linked polyolefin material for an automotive wire, which has substantially the same formulation components as in example 1, and which has exactly the same preparation method except for the following differences: the antioxidant is a single antioxidant, and 5 parts of antioxidant 1010 are added.
Comparative example 5 provides a heat-resistant 150 ℃ radiation cross-linked polyolefin material for an automotive wire, which has substantially the same formulation components as in example 1, and which has the same preparation method except that: the antioxidant is two compound antioxidants, wherein 3.1 parts of antioxidant 1010 and 1.9 parts of antioxidant 1024 are added.
Comparative example 6 provides a heat-resistant 150 ℃ radiation cross-linked polyolefin material for an automotive wire, which has substantially the same formulation components as in example 1 and completely the same preparation method, except that: no rheology agent was added.
Comparative example 7 provides a heat-resistant 150 ℃ radiation cross-linked polyolefin material for automotive wire, the formulation components of which are completely the same as in example 1, and the preparation method adopts a conventional process: the formula components are manually weighed and put into a high-speed mixer for mixing, and after being mixed for a certain time, the materials are fed into a double-screw extruder for melting, mixing and granulation.
TABLE 1 results of physical Property measurements of examples 1 to 9 (ref. QC/T730)
TABLE 2 results of physical Property test of examples 10 to 12 and comparative examples 1 to 7 (refer to QC/T730)
It can be seen from examples 1, 4-7 and comparative example 1 that the use of the high density polyethylene resin in combination has a significant effect on improving the low temperature winding performance, environmental resistance and chemical resistance of the material, and at the same time, the first high density polyethylene resin has a low melt index and a narrow molecular weight distribution, and the single use thereof results in a decrease in the unwinding speed and a poor doubling surface.
From examples 1 and 4-5, it can be seen that the combination of different proportions of the composite high density polyethylene resin has certain influence on the properties of the material: the increase of the third high density polyethylene resin content slightly reduces the mechanical property, hardness and wire releasing speed of the material, mainly because the third high density polyethylene resin has large melt index, low crystallinity and more short chains exist in the chain structure. The three high-density polyethylenes of the invention are all indispensable.
It can be seen from examples 1, 4-5 and comparative examples 2-3 that excessively reducing the amount of the composite high density polyethylene resin causes the flame retardant in the material to occupy too large a proportion, resulting in significant reduction in the mechanical properties and hardness of the material, too much flame retardant in the material prevents the polyethylene molecular chain segment from being transported, the low temperature winding property of the material and the low temperature winding property after thermal aging are deteriorated, the wire unwinding speed is greatly reduced, and the material cannot meet the requirements of the ISO6722 standard; the excessive increase of the amount of the composite high-density polyethylene resin reduces the proportion of the flame retardant in the material, so that the oxygen index of the material is obviously reduced, the flame-retardant property of the material is influenced, and the material cannot meet the use requirement of an automobile line.
From examples 1 and 6 to 7, it is known that when the addition ratio of the composite high density polyethylene resin in the material is decreased, the corresponding proportion of the flame retardant is increased, and the oxygen index is improved.
As can be seen from examples 1, 8-10 and comparative examples 4-5, the single antioxidant 1010 can not make the material meet the requirement of thermal aging, and the aged material has cracking phenomenon and can not meet the requirement of material use, mainly because the antioxidant 1010 has poor high temperature and thermal stability, and the material can not be effectively protected in the high temperature and long time aging process; the antioxidant compounded by the antioxidant 1010 and the antioxidant 1024 cannot meet the requirement of thermal aging of the material, and the aged material has a cracking phenomenon and cannot meet the requirement of the material; in the materials of the examples, three or four antioxidants are compounded, and the aging resistance tests of the materials all pass.
It is understood from examples 1, 11-12 and comparative example 6 that the absence of the added rheological agent results in a decrease in the paying-off speed and the accumulation of the residue at the paying-off die, mainly because the rheological agent can migrate to the surface of the wire when the material is extruded for paying-off, and the surface of the wire extruded at a high speed is protected at the die of the extruder. Due to the lack of rheological agent, the lubrication protection of the electric wire is lost when the electric wire is extruded from a die, the wire surface becomes rough, and the electric wire is sprayed in a 'flying chip' shape to form accumulated slag, so that the paying-off speed is reduced.
It can be seen from examples 1-12 and comparative example 7 that the productivity is greatly reduced by using the conventional twin-screw melt-kneading granulation method, the production efficiency is reduced and the stability and consistency of the product are reduced due to the manual operation method, and the material smell is increased due to the absence of an air extractor or the continuous production of an air extractor which is easily blocked during the twin-screw production process.
As can be seen from tables 1 and 2, the conventional internal mixer + twin screw production process used in comparative example 1, which did not employ the Swiss inlet BUSS line production process of the present invention, produced much less than the other examples and comparative examples employing the BUSS line.
In the comparative example 2, the contents of the dispersant and the lubricant are increased, and the corresponding paying-off speed is greatly reduced; in comparative example 3, increasing the content of flame retardant a, flame retardant B and crosslinking sensitizer resulted in an unpleasant odor in the corresponding product; in comparative example 4, the amount of antioxidant added was reduced and the corresponding product failed the air oven aging test.
In summary, it can be seen from the examples and comparative examples that the selection of the composite high-density resin can give consideration to the mechanical properties, wear resistance and low-temperature winding performance of the material, and the proper addition of the composite high-density resin has a great influence on the hardness, low-temperature winding performance, oxygen index and flame retardancy of the material. The selection and the compound use of the antioxidant have a key influence on the aging performance of the material, and are the key to whether the temperature resistance level of an automobile line can be reached. The use of the rheological agent improves the problem of slag accumulation of the high-speed extrusion die of the material, and improves the quality of the line surface of the automobile. The Swiss import BUSS production line is used, so that the production efficiency and stability of the material can be greatly improved, the smell of the material is improved, the smell and the use quality of the material can be optimized under the condition that no deodorant is used in the formula, and other bad smell and hidden danger of the quality of the material caused by the use of the deodorant are avoided.
According to the results in tables 1 and 2, the high linear speed, low odor and heat resistance 150 ℃ irradiation crosslinking polyolefin material for the automobile line produced by adopting the Swiss import BUSS line has good mechanical property, electrical property, excellent scratch resistance and flame retardance, high line opening speed, good extrusion surface, high efficiency and large yield, is suitable for the production of the automobile line with the requirements of high linear speed and low odor, does not generate harmful gas to the body or the environment basically, can completely meet the requirement of T4 in ISO6722, meets the ROHS and REACH standards in environmental protection performance, and can meet the use requirements of the automobile line in material performance and manufacturability tests. The preparation method of the high-speed low-odor heat-resistant 150 ℃ irradiation crosslinking polyolefin material for the automobile wire has high yield and stable process, the yield can reach 4 tons per hour, the preparation method is currently the first domestic manufacturer for producing the automobile wire harness material by using the imported BUSS wire, the process that the automobile cable material is produced by using the conventional internal mixer and the twin screw is broken through, the irradiation crosslinking polyolefin material for the automobile wire produced by the BUSS can realize the high-speed paying-off of customers, the current 0.35-0.5 square wire can realize the speed of 450 plus 550 meters/min, the production efficiency of a wire manufacturer is greatly improved, and the preparation method is a good material for the automobile wire in the future.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (6)
1. The 150 ℃ radiation-resistant cross-linked polyolefin material for the automobile wire is characterized by comprising 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 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;
the mass ratio of the first high-density polyethylene resin to the second high-density polyethylene resin to 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; 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 antioxidant is antioxidant 1010, antioxidant 1024 and antioxidant XL-1, or antioxidant 1010, antioxidant 1024 and antioxidant 412S, or antioxidant 1010, antioxidant DLTP and antioxidant XL-1, or antioxidant 1010, antioxidant 1024, antioxidant XL-1 and antioxidant 412S.
2. 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.
3. 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%.
4. 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.
5. 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.
6. A process for the preparation of a heat-resistant 150 ℃ radiation cross-linked polyolefin material for automotive lines according to any one of claims 1 to 5, 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.
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| CN117285768A (en) * | 2023-10-25 | 2023-12-26 | 苏州铂玛新材料有限公司 | Ultrathin-wall automobile wire polyolefin material and preparation method thereof |
| CN117511197B (en) * | 2024-01-05 | 2024-04-16 | 山东祥龙新材料股份有限公司 | Hydrolysis-resistant extrusion-moldable polyamide material and preparation method and application thereof |
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