CN108239330A - A kind of automotive line irradiated crosslinking low-smoke and halogen-free flame retardant material and preparation method thereof - Google Patents
A kind of automotive line irradiated crosslinking low-smoke and halogen-free flame retardant material and preparation method thereof Download PDFInfo
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- CN108239330A CN108239330A CN201611230225.1A CN201611230225A CN108239330A CN 108239330 A CN108239330 A CN 108239330A CN 201611230225 A CN201611230225 A CN 201611230225A CN 108239330 A CN108239330 A CN 108239330A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/123—Treatment by wave energy or particle radiation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- 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
- H01B3/441—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 from alkenes
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C08L2205/00—Polymer mixtures characterised by other features
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
- C08L2312/06—Crosslinking by radiation
Abstract
The present invention provides a kind of automotive line irradiated crosslinking low-smoke and halogen-free flame retardant material and preparation method thereof, which includes following raw material and parts by weight with irradiated crosslinking low-smoke and halogen-free flame retardant material：30 ~ 60 parts of substrate resin；10 ~ 25 parts of compatilizer；15 ~ 35 parts of fire retardant；5 ~ 10 parts of filler；0.75 ~ 1.35 part of antioxidant；2.5 ~ 5 parts of lubricant；1.5 ~ 2.5 parts of crosslinking sensitizer.The present invention is by adding in compatilizer, fire retardant and other auxiliary agents, substrate resin is modified, the automotive line of preparation is not only low with material density with irradiated crosslinking low-smoke and halogen-free flame retardant material, halogen-free environmental, fire-retardant and high abrasion excellent performance, all kinds of oil products of also resistance to automobile and corrosive liquid, it is resistant to chemical etching, resistance to ultralow temperature, mechanical performance is excellent, while has splendid production extrusion processability energy, can meet high-speed production demand.
Description
Technical field
The present invention relates to electric wire polymeric material field, specifically disclose a kind of low cigarette of automotive line cross-linking radiation without
Halogen flame-proof material and preparation method thereof.
Background technology
In recent years, the automobile industry of current All Around The World was still being grown rapidly, and China's domestic automobile industry is also closely followed
At the same time paces, high speed development are also higher and higher to the performance requirement of automobile items accessory etc..Orthodox car wire insulation
The raw material of layer is almost all pvc material.Although polyvinyl chloride has many advantages, such as that price is relatively low, easy to process, polychlorostyrene second
Alkene not only constrains its development, but also use occasion is restricted there are the shortcomings of decomposition temperature is low, high temperature resistance is poor.Row
The high speed development of industry certainly will can propose automobile linear higher requirement, high-low temperature resistant requirement, high scrape abrasion resistance energy, oil resistant and
All kinds of automobile liquid corrosions etc., while environment friendly non-halogen is also inevitable development trend；With the gradually hair of market new-energy automobile
Exhibition, the lightweight problem of conventional fuel oil automobile are also seeking more solutions；At present, in the market in confession can cross-linking radiation
Automobile electric wire insulating layer made of halogen-free anti-flaming polyolefin material, there are loss of properties on aging, resistance to scraped finish is poor, processing performance not
Well, the defects of extruded velocity is slow, while material density height is also unfavorable for energy saving requirement, it is difficult to it is 125 DEG C to meet temperature resistant grade
The requirement of car thin-wall electric wire.Therefore, it is above-mentioned there is an urgent need for developing a kind of high-low temperature resistant environmental-friendly halogen-free low-smoke flame retardant material solution
Problem.
Invention content
It is an object of the invention to overcome the defects of existing, a kind of automotive line irradiated crosslinking low-smoke and halogen-free flame retardant material is provided
And preparation method thereof, which has that material density is low, environment friendly non-halogen, high-wear resistance, all kinds of oil products of resistance to automobile and corrosion
Liquid, resistant to chemical etching, resistance to ultralow temperature, mechanical performance is excellent, good flame retardation effect.
In order to achieve the goal above, what the present invention was realized by including following technical scheme：A kind of automotive line is handed over irradiation
Join low-smoke halogen-free flame retardant material, including following raw material and parts by weight：30~60 parts of substrate resin；10~25 parts of compatilizer；It is fire-retardant
15~35 parts of agent；5~10 parts of filler；0.75~1.35 part of antioxidant；2.5~5 parts of lubricant；Crosslinking sensitizer 1.5~2.5
Part.
Preferably, automotive line irradiated crosslinking low-smoke and halogen-free flame retardant material, including following raw material and parts by weight：Base material
40-50 parts of resin；10~20 parts of compatilizer；25~30 parts of fire retardant；6~8 parts of filler；0.9~1.1 part of antioxidant；Lubrication
3~3.5 parts of agent；1.8~2.0 parts of crosslinking sensitizer.
Preferably, the substrate resin be selected from linear low density polyethylene, ethylene-butyl acrylate copolymer and ethylene-
It is one or more in propylene copolymer resins.
It is highly preferred that the substrate resin is selected from linear low density polyethylene, ethylene-butyl acrylate copolymer and second
The mixture of alkene-propylene copolymer resins.Wherein, with the total weight of substrate resin, linear low density polyethylene accounts for 50%~
66%；The mass percent that ethylene-butyl acrylate copolymer accounts for substrate resin is 17%~25%；Ethylene-propylene copolymer
The mass percent that resin accounts for substrate resin is 17%~30%.
It is highly preferred that the melt index of the linear low density polyethylene under 190 DEG C of load 2.16kg for 0.4~
2.5g/10min, density are 0.900~0.950g/cm3.It is further preferred that the melting of the linear low density polyethylene refers to
Number is 0.5~2.0g/10min under 190 DEG C of load 2.16kg, and density is 0.920~0.935g/cm3。
It is highly preferred that the ethylene-butyl acrylate copolymer melt index is 3.5- under 190 DEG C of load 2.16kg
4.5g/10min；Density is 0.90-1.00g/cm3, butyl acrylate content 25-28wt%.It is further preferred that the second
Alkene-butyl acrylate copolymer melt index is 4.0g/10min under 190 DEG C of load 2.16kg；Density is 0.926g/cm3,
Butyl acrylate content is 27wt%.
It is highly preferred that the melt index of the ethylene-propylene copolymer resin under 190 DEG C of load 2.16kg for 1.0~
The molar content of 4.0g/10min, wherein ethylene are 5%~35%.It is further preferred that the ethylene-propylene copolymer resin
Melt index under 190 DEG C of load 2.16kg for 2.0~3.5g/10min, wherein the molar content of ethylene for 10%~
25%.
Preferably, the compatilizer is selected from ethylene-octene copolymer grafted maleic anhydride copolymer and polycthylene grafted horse
Carry out one or both of acid anhydride copolymer.
It is highly preferred that the melt index of the ethylene-octene copolymer grafted maleic anhydride copolymer is in 190 DEG C of loads
It is 0.5~2.9g/10min under 2.16kg, grafting rate is in 0.5-1.0%.It is further preferred that the ethylene-octene copolymer
Grafted maleic anhydride copolymer, melt index is 0.8~2.5g/10min under the conditions of 190 DEG C of load 2.16kg, and grafting rate exists
0.8%.
It is highly preferred that the melt index of the Research of Grafting Malaic Anhydride Onto Polyethylene copolymer is under 190 DEG C of load 2.16kg
0.5~2.3g/10min, grafting rate is in 0.8-1.5%.It is further preferred that Research of Grafting Malaic Anhydride Onto Polyethylene copolymer is 190
Melt index is 1.0~1.9g/10min under the conditions of DEG C load 2.16kg, and grafting rate is 1.2%.
Preferably, the fire retardant is selected from Melamine Polyphosphate, high molecular weight ammonium polyphosphate and diethyl time
Any one or more in aluminum phosphate.
It is highly preferred that group of the fire retardant for both Melamine Polyphosphate and high molecular weight ammonium polyphosphate
It closes, and the mass ratio of Melamine Polyphosphate and high molecular weight ammonium polyphosphate is 3：1.It is further preferred that the height
The degree of polymerization of molecular weight polysaccharide ammonium phosphate is more than 1000.
Preferably, the filler is selected from one or both of ultrafine silicon dioxide powder and calcium carbonate silica gel master batch.
It is highly preferred that combination of the filler for ultrafine silicon dioxide powder and calcium carbonate silica gel master batch, and it is described super
The mass ratio of fineness silicon dioxide powder and the calcium carbonate silica gel master batch is 2:1.Wherein, the ultrafine silicon dioxide powder is flat
Equal grain size is 1.1 μm, and the calcium carbonate silica gel master batch is by nano-calcium carbonate and methyl vinyl silicone rubber with mass ratio 7：3 mixing
It is formulated, the nano-calcium carbonate average grain diameter is 700nm；Methyl vinyl silicone rubber molecular weight 45~800,000,
Contents of ethylene is 21~24%.
Preferably, the antioxidant is one or more in antioxidant 1010, irgasfos 168 and anti-oxidant DLTP.
It is highly preferred that the antioxidant is the combination of antioxidant 1010, irgasfos 168 and anti-oxidant DLTP three, and anti-
Oxygen agent 1010, irgasfos 168, anti-oxidant DLTP mass ratio be 12:2:1.
It is highly preferred that the antioxidant 1010 is four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythrites
Ester.
It is highly preferred that the irgasfos 168 is three (2,4- di-tert-butyl-phenyl) phosphite esters.
It is highly preferred that the anti-oxidant DLTP is the double lauryls of thio-2 acid.
Preferably, the lubricant is selected one or more in magnesium stearate, calcium stearate and polyethylene wax.
It is highly preferred that the lubricant is the combination of magnesium stearate, calcium stearate and polyethylene wax three, and stearic acid
Magnesium, calcium stearate, polyethylene wax mass ratio be 2:1:1.It is further preferred that the molecular weight of the polyethylene wax is 1000-
5000。
Preferably, the crosslinking sensitizer is iso-cyanuric acid triallyl ester.
The method of automotive line as described above with irradiated crosslinking low-smoke and halogen-free flame retardant material is prepared invention additionally discloses a kind of,
Include the following steps：
1) raw material is uniformly mixed according to proportioning through high-speed mixer；
2) raw material that step 1) mixes is placed in mixer and be kneaded, obtain bulk plastic cement semi-finished product；
3) the bulk plastic cement semi-finished product are placed in extruding pelletization in double screw extruder, prepare automotive line irradiation
Cross-linking low smoke halogen-free flame retardant material.
Preferably, the rotating speed of the high-speed mixer is 400~500 revs/min, incorporation time 2-4min.
Preferably, the temperature of the mixing is 155~165 DEG C, and the time of the mixing is 10~12min.
Preferably, the double screw extruder includes ten temperature sections, one to ten area's temperature is respectively 138-143 DEG C,
148-152℃、153-157℃、158-162℃、168-173℃、173-177℃、173-177℃、178-183℃、178-182
℃、168-173℃。
Invention additionally discloses a kind of automotive line irradiated crosslinking low-smoke and halogen-free flame retardant cable materials, are by vapour described above
Fare irradiated crosslinking low-smoke and halogen-free flame retardant material is obtained through Screw Extrusion and by irradiation crosslinking processes.
Preferably, irradiation crosslinking processes are 13~15Mrad using irradiation dose, in 200 DEG C of temperature, are loaded under 0.2MPa,
It is controlled in the range of 20%~50% by the hot extension value of 15min.
In conclusion the present invention provides a kind of automotive line irradiated crosslinking low-smoke and halogen-free flame retardant material and preparation method thereof, this
Advantageous effect of the invention：
The present invention is modified substrate resin, the automotive line of preparation by adding in compatilizer, fire retardant and other auxiliary agents
With irradiated crosslinking low-smoke and halogen-free flame retardant material not only have material density it is low, halogen-free environmental, fire-retardant and high abrasion excellent performance, also
All kinds of oil products of resistance to automobile and corrosive liquid, resistant to chemical etching, resistance to ultralow temperature, mechanical performance is excellent, while has splendid life
Produce extrusion processability energy, can meet high-speed production demand, cable extruded velocity up to 800m/min and more than, heatproof can be met
The performance requirement of 125 DEG C of automotive wire bundles.
Specific embodiment
Illustrate embodiments of the present invention below by way of particular specific embodiment, those skilled in the art can be by this explanation
Content disclosed by book understands other advantages and effect of the present invention easily.The present invention can also be by addition different specific
Embodiment is embodied or practiced, and the various details in this specification can also be based on different viewpoints and application, not carry on the back
Various modifications or alterations are carried out under spirit from the present invention.It should be noted that in the absence of conflict, following embodiment and reality
Applying the feature in example can be combined with each other.
Linear low density polyethylene employed in the embodiment of the present invention melts under the conditions of 190 DEG C of load 2.16kg to be referred to
Number is 0.5~2.0g/10min, and density is 0.920~0.935g/cm3.Ethylene-butyl acrylate copolymer is in 190 DEG C of loads
Melt index is 4.0g/10min, density 0.926g/cm under the conditions of 2.16kg3, butyl acrylate content 27wt.%.Second
Alkene-propylene copolymer resins melt index under the conditions of 190 DEG C of load 2.16kg is 2.0~3.5g/10min, wherein ethylene
Molar content is 10%~25%.Research of Grafting Malaic Anhydride Onto Polyethylene copolymer employed in embodiment is in 190 DEG C of loads
Melt index is 1.0~1.9g/10min under the conditions of 2.16kg, and grafting rate is 1.2%.Ethylene-octene employed in embodiment
Copolymer grafted copolymer-maleic anhydride, melt index is 0.8~2.5g/10min under the conditions of 190 DEG C of load 2.16kg, is connect
Branch rate is 0.8%.
Embodiment 1
A kind of automotive line irradiated crosslinking low-smoke and halogen-free flame retardant material, material component and proportioning are as follows：Substrate resin 30
Part；10 parts of compatilizer；15 parts of fire retardant；5 parts of filler；0.75 part of antioxidant；2.5 parts of lubricant；1.5 parts of sensitizer.
Wherein, with the total weight of substrate resin, linear low density polyethylene accounts for 66%；Ethylene-butyl acrylate is copolymerized
Object accounts for 17%；Ethylene-propylene copolymer resin accounts for 17%.
Compatilizer is Research of Grafting Malaic Anhydride Onto Polyethylene copolymer.
Fire retardant is Melamine Polyphosphate and high molecular weight ammonium polyphosphate combination, and melamine is more
The mass ratio of Quadrafos and high molecular weight ammonium polyphosphate is 3：1.
Combination of the filler for ultrafine silicon dioxide powder, two kinds of calcium carbonate silica gel master batch, and ultrafine silicon dioxide powder,
The mass ratio of calcium carbonate silica gel master batch is 2:1.
Antioxidant selects the combination of antioxidant 1010, irgasfos 168, anti-oxidant DLTP, and antioxidant 1010, antioxidant
168th, the mass ratio of anti-oxidant DLTP is 12:2:1.
Lubricant is composed of magnesium stearate, calcium stearate, polyethylene wax, and magnesium stearate, calcium stearate, polyethylene
The mass ratio of wax is 2:1:1, the MW ranging from 1000-5000 of polyethylene wax.
Preparation method includes the following steps：(1) by raw material according to proportioning through high-speed mixer with 400 revs/min of speed
Mixing 2 minutes is to uniform；(2) raw material mixed is placed in mixer and is kneaded 10 minutes at 155 DEG C of temperature, obtain bulk
Plastic cement semi-finished product.(3) by bulk plastic cement semi-finished product feed dual-screw-stem machine in extruding pelletization, grain length about 2~3mm, grain size about 2mm,
Up to the irradiated crosslinking low-smoke and halogen-free flame retardant material particles.The temperature setting of wherein specific screw extruder is：One area of machine barrel
It it is 140 DEG C, 2nd area of machine barrel is 150 DEG C, and 3rd area of machine barrel is 155 DEG C, and 4th area of machine barrel is 160 DEG C, and 5th area of machine barrel is 170 DEG C, machine barrel
6th area are 175 DEG C, and 7th area of machine barrel is 175 DEG C, and 8th area of machine barrel is 180 DEG C, and head and mold are respectively 180 DEG C and 170 DEG C.
Embodiment 2
A kind of automotive line irradiated crosslinking low-smoke and halogen-free flame retardant material, material component and proportioning are as follows：Substrate resin 40
Part；15 parts of compatilizer；25 parts of fire retardant；5 parts of filler；0.9 part of antioxidant；3 parts of lubricant；2 parts of sensitizer.
Wherein, with the total weight of substrate resin, linear low density polyethylene accounts for 50%；Ethylene-butyl acrylate is copolymerized
Object accounts for 25%；Ethylene-propylene copolymer resin accounts for 25%.
Compatilizer is ethylene-octene copolymer grafted maleic anhydride copolymer.
Fire retardant is Melamine Polyphosphate and high molecular weight ammonium polyphosphate combination, and melamine is more
The mass ratio of Quadrafos and high molecular weight ammonium polyphosphate is 3：1.
Combination of the filler for ultrafine silicon dioxide powder, two kinds of calcium carbonate silica gel master batch, and ultrafine silicon dioxide powder,
The mass ratio of calcium carbonate silica gel master batch is 2:1.
Antioxidant selects the combination of antioxidant 1010, irgasfos 168, anti-oxidant DLTP, and antioxidant 1010, antioxidant
168th, the mass ratio of anti-oxidant DLTP is 12:2:1.
Lubricant selects the combination of magnesium stearate, calcium stearate, polyethylene wax, and magnesium stearate, calcium stearate, polyethylene
The mass ratio of wax is 2:1:1.The MW of polyethylene wax ranging from 1000-5000.
Preparation method includes the following steps：(1) by raw material according to proportioning through high-speed mixer with 500 revs/min of speed
Mixing 3 minutes is to uniform；(2) raw material mixed is placed in mixer and is kneaded 11 minutes at 160 DEG C of temperature, obtain bulk
Plastic cement semi-finished product.(3) by bulk plastic cement semi-finished product feed dual-screw-stem machine in extruding pelletization, grain length about 2~3mm, grain size about 2mm,
Up to the irradiated crosslinking low-smoke and halogen-free flame retardant material particles.The temperature setting of wherein specific screw extruder is：One area of machine barrel
It it is 140 DEG C, 2nd area of machine barrel is 150 DEG C, and 3rd area of machine barrel is 155 DEG C, and 4th area of machine barrel is 160 DEG C, and 5th area of machine barrel is 170 DEG C, machine barrel
6th area are 175 DEG C, and 7th area of machine barrel is 175 DEG C, and 8th area of machine barrel is 180 DEG C, and head and mold are respectively 180 DEG C and 170 DEG C.
Embodiment 3
A kind of automotive line irradiated crosslinking low-smoke and halogen-free flame retardant material, material component and proportioning are as follows：Substrate resin 50
Part；15 parts of compatilizer；30 parts of fire retardant；8 parts of filler；1.1 parts of antioxidant；3.5 parts of lubricant；2 parts of sensitizer.
Wherein, with the total weight of substrate resin, linear low density polyethylene accounts for 50%；Ethylene-butyl acrylate is copolymerized
Object accounts for 30%；Ethylene-propylene copolymer resin accounts for 20%.
The compatilizer is ethylene-octene copolymer grafted maleic anhydride copolymer.
The fire retardant is Melamine Polyphosphate and high molecular weight ammonium polyphosphate combination, and melamine
The mass ratio of amine polyphosphate and high molecular weight ammonium polyphosphate is 3：1.
Combination of the filler for ultrafine silicon dioxide powder, two kinds of calcium carbonate silica gel master batch, and ultrafine titanium dioxide
Silica flour, calcium carbonate silica gel master batch mass ratio be 2:1.
The antioxidant selects the combination of antioxidant 1010, irgasfos 168, anti-oxidant DLTP, and antioxidant 1010, antioxygen
Agent 168, anti-oxidant DLTP mass ratio be 12:2:1.
The lubricant selects the combination of magnesium stearate, calcium stearate, polyethylene wax, and magnesium stearate, calcium stearate, poly-
The mass ratio of ethylene waxes is 2:1:1.The MW of the polyethylene wax ranging from 1000-5000.
Preparation method is the same as embodiment 2.
Embodiment 4
A kind of automotive line irradiated crosslinking low-smoke and halogen-free flame retardant material, material component and proportioning are as follows：Substrate resin 60
Part；25 parts of compatilizer；35 parts of fire retardant；10 parts of filler；1.35 parts of antioxidant；5 parts of lubricant；2.5 parts of sensitizer.
Wherein, with the total weight of substrate resin, linear low density polyethylene accounts for 75%；Ethylene-propylene copolymer resin
Account for 25%.
Compatilizer is ethylene-octene copolymer grafted maleic anhydride copolymer, Research of Grafting Malaic Anhydride Onto Polyethylene copolymer
Combination.Wherein, with the total weight of compatilizer, ethylene-octene copolymer grafted maleic anhydride copolymer accounts for 60%, and polyethylene connects
Branch copolymer-maleic anhydride accounts for 40%.
Fire retardant is Melamine Polyphosphate and high molecular weight ammonium polyphosphate combination, and melamine is more
The mass ratio of Quadrafos and high molecular weight ammonium polyphosphate is 3：1.
Combination of the filler for ultrafine silicon dioxide powder, two kinds of calcium carbonate silica gel master batch, and ultrafine silicon dioxide powder,
The mass ratio of calcium carbonate silica gel master batch is 2:1.
Antioxidant selects the combination of antioxidant 1010, irgasfos 168, anti-oxidant DLTP, and antioxidant 1010, antioxidant
168th, the mass ratio of anti-oxidant DLTP is 12:2:1.
Lubricant selects the combination of magnesium stearate, calcium stearate, polyethylene wax, and magnesium stearate, calcium stearate, polyethylene
The mass ratio of wax is 2:1:1.The MW of polyethylene wax ranging from 1000-5000.
Preparation method includes the following steps：(1) by raw material according to proportioning through high-speed mixer with 500 revs/min of speed
Mixing 4 minutes is to uniform；(2) raw material mixed is placed in mixer and is kneaded 12 minutes at 165 DEG C of temperature, obtain bulk
Plastic cement semi-finished product；(3) by bulk plastic cement semi-finished product feed dual-screw-stem machine in extruding pelletization, grain length about 2~3mm, grain size about 2mm,
Up to irradiated crosslinking low-smoke and halogen-free flame retardant material particles.The temperature setting of wherein specific screw extruder is：One area of machine barrel is 140
DEG C, 2nd area of machine barrel is 150 DEG C, and 3rd area of machine barrel is 155 DEG C, and 4th area of machine barrel is 160 DEG C, and 5th area of machine barrel is 170 DEG C, and 6th area of machine barrel is
175 DEG C, 7th area of machine barrel is 175 DEG C, and 8th area of machine barrel is 180 DEG C, and head and mold are respectively 180 DEG C and 170 DEG C.
Performance test
The cross-linking low smoke halogen-free flame retardant material of embodiment 1 to 4 is subjected to tabletting, the technique of tabletting is：Use vulcanizing press
Tabletting, pelletizing temperature are 175 DEG C, and preheating time is 10 minutes, and the dwell time is 5 minutes, uses different fixed gauge grid mold pressures
Piece, the thickness for obtaining tabletting are respectively 1mm, 2mm, 3mm, and length is 25mm, and width is 20mm.
To more than tabletting carry out radiation treatment technique be：The use of irradiation dose is 13~15Mrad, in 200 DEG C of temperature,
It loads under 0.2MPa, is controlled in the range of 20%~50% by the hot extension value of 15min.
The hot extension value of acquisition is tested in hot elongation test for the tabletting of 1mm thickness after radiation treatment in table 1；Low temperature rushes
It hits in brittle test and uses the tabletting of 2mm thickness, using 3mm thickness tablettings in oxygen index (OI) experiment, remaining uses 1mm thickness pressures
Piece.
The performance test results of table 1 automotive line irradiated crosslinking low-smoke and halogen-free flame retardant cable material
As it can be seen from table 1 automotive line has material with irradiated crosslinking low-smoke and halogen-free flame retardant cable material in embodiment 1 to 4
Matter density is low, environment friendly non-halogen；Especially there is high-wear resistance, all kinds of oil products of resistance to automobile and corrosive liquid, it is resistant to chemical etching, it is resistance to
Ultralow temperature, mechanical performance is excellent, good flame retardation effect, while has splendid production extrusion processability energy, can meet high-speed production
Demand；The performance requirement of 125 DEG C of automotive wire bundles of heatproof can be met.
The above, only presently preferred embodiments of the present invention, not to the present invention in any form with substantial limitation,
It should be pointed out that for those skilled in the art, under the premise of the method for the present invention is not departed from, can also make
Several improvement and supplement, these are improved and supplement also should be regarded as protection scope of the present invention.All those skilled in the art,
Without departing from the spirit and scope of the present invention, when made using disclosed above technology contents it is a little more
Dynamic, modification and the equivalent variations developed, are the equivalent embodiment of the present invention；Meanwhile all substantial technologicals pair according to the present invention
The variation, modification and evolution of any equivalent variations that above-described embodiment is made still fall within the range of technical scheme of the present invention
It is interior.
Claims (10)
1. a kind of automotive line irradiated crosslinking low-smoke and halogen-free flame retardant material, it is characterised in that：It includes following raw material and parts by weight：
2. automotive line as described in claim 1 irradiated crosslinking low-smoke and halogen-free flame retardant material, it is characterised in that：The substrate resin
One kind or more in linear low density polyethylene, ethylene-butyl acrylate copolymer and ethylene-propylene copolymer resin
Kind.
3. automotive line as described in claim 1 irradiated crosslinking low-smoke and halogen-free flame retardant material, it is characterised in that：The compatilizer choosing
From one or both of ethylene-octene copolymer grafted maleic anhydride copolymer and Research of Grafting Malaic Anhydride Onto Polyethylene copolymer.
4. automotive line as described in claim 1 irradiated crosslinking low-smoke and halogen-free flame retardant material, it is characterised in that：The fire retardant choosing
From one or more in Melamine Polyphosphate, high molecular weight ammonium polyphosphate and diethyl hypo-aluminum orthophosphate.
5. automotive line as described in claim 1 irradiated crosslinking low-smoke and halogen-free flame retardant material, it is characterised in that：The filler choosing
From one or both of ultrafine silicon dioxide powder and calcium carbonate silica gel master batch.
6. automotive line as described in claim 1 irradiated crosslinking low-smoke and halogen-free flame retardant material, it is characterised in that：The antioxidant choosing
From one or more in antioxidant 1010, irgasfos 168 and anti-oxidant DLTP.
7. automotive line as described in claim 1 irradiated crosslinking low-smoke and halogen-free flame retardant material, it is characterised in that：The lubricant choosing
With one or more in magnesium stearate, calcium stearate and polyethylene wax.
8. automotive line as described in claim 1 irradiated crosslinking low-smoke and halogen-free flame retardant material, it is characterised in that：The crosslinking sensitization
Agent is iso-cyanuric acid triallyl ester.
9. a kind of automotive line prepared as described in claim 1 to 8 any claim irradiated crosslinking low-smoke and halogen-free flame retardant material
Method, include the following steps：
1) raw material is uniformly mixed according to proportioning through high-speed mixer；
2) raw material that step 1) mixes is placed in mixer and be kneaded, obtain bulk plastic cement semi-finished product；
3) the bulk plastic cement semi-finished product are placed in extruding pelletization in double screw extruder, prepare automotive line cross-linking radiation
Low-smoke halogen-free flame retardant material.
10. a kind of automotive line irradiated crosslinking low-smoke and halogen-free flame retardant cable material is by any vapour of claim 1 to 8
Fare irradiated crosslinking low-smoke and halogen-free flame retardant material is obtained through Screw Extrusion and by irradiation crosslinking processes.
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| CN110818981A (en) * | 2019-10-29 | 2020-02-21 | 昆山勃盛电子有限公司 | Low-smoke flame-retardant cable material for locomotive and preparation method thereof |
| CN110903526A (en) * | 2019-11-18 | 2020-03-24 | 西安思后网络科技有限公司 | Crosslinked ethylene flame-retardant cable material and preparation method thereof |
| CN113087992A (en) * | 2021-04-08 | 2021-07-09 | 重庆丰驰实业有限公司 | Low-smoke halogen-free flame-retardant sheath material and preparation method thereof |
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| CN109320839B (en) * | 2018-09-11 | 2021-03-26 | 上海日之升科技有限公司 | Photodiffusion polypropylene composite material for LED |
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| CN114702747B (en) * | 2022-03-15 | 2023-09-26 | 金发科技股份有限公司 | High-temperature-resistant high-oxygen-aging polyolefin material and preparation method and application thereof |
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Address after: 201802 Shanghai City, Jiading District Nanxiang Town Yongle Village No. 271 Patentee after: Shanghai Kaibo cable special material Co., Ltd Address before: 201802 no.271 Yongle Village, Nanxiang Town, Jiading District, Shanghai Patentee before: SHANGHAI KAIBO SPECIAL CABLE FACTORY Co.,Ltd. |