CN106782787A - A kind of low smell automobile double wall heat draws of low VOC and preparation method - Google Patents

A kind of low smell automobile double wall heat draws of low VOC and preparation method Download PDF

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Publication number
CN106782787A
CN106782787A CN201611234293.5A CN201611234293A CN106782787A CN 106782787 A CN106782787 A CN 106782787A CN 201611234293 A CN201611234293 A CN 201611234293A CN 106782787 A CN106782787 A CN 106782787A
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parts
low
double wall
wall heat
mixture
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CN201611234293.5A
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Inventor
程炎波
刘军
曾志安
鲁雪莲
鲁尔军
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CHANGYUAN GROUP Ltd
CHANGYUAN ELECTRONIC (GROUP) Co Ltd
Changyuan Electronics (dongguan) Co Ltd
CYG Electronics Shanghai Co Ltd
Tianjin Changyuan Electronic Material Co Ltd
Original Assignee
CHANGYUAN GROUP Ltd
CHANGYUAN ELECTRONIC (GROUP) Co Ltd
Changyuan Electronics (dongguan) Co Ltd
CYG Electronics Shanghai Co Ltd
Tianjin Changyuan Electronic Material Co Ltd
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Priority to CN201611234293.5A priority Critical patent/CN106782787A/en
Publication of CN106782787A publication Critical patent/CN106782787A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/02—Disposition of insulation
    • H01B7/0208—Cables with several layers of insulating material
    • H01B7/0216—Two layers
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/02—Disposition of insulation
    • H01B7/0275—Disposition of insulation comprising one or more extruded layers of insulation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/28—Protection against damage caused by moisture, corrosion, chemical attack or weather
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/28—Protection against damage caused by moisture, corrosion, chemical attack or weather
    • H01B7/282—Preventing penetration of fluid, e.g. water or humidity, into conductor or cable
    • H01B7/2825—Preventing penetration of fluid, e.g. water or humidity, into conductor or cable using a water impermeable sheath
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/29—Protection against damage caused by extremes of temperature or by flame
    • H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R4/00—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation
    • H01R4/70—Insulation of connections
    • H01R4/72—Insulation of connections using a heat shrinking insulating sleeve
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/18—Applications used for pipes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/04—Thermoplastic elastomer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/062—HDPE
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/066—LDPE (radical process)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • C08L2312/06—Crosslinking by radiation

Abstract

A kind of low smell automobile double wall heat draws of low VOC, its inner wall material is modified dimer acid polyamide PUR, and its ring and ball softening point is 105 130 DEG C, 14000MPa.S/200 DEG C of viscosity 7000；Its external wall material is made up of following component in parts by weight：100 parts of vinylite, 10 40 parts of thermoplastic elastomer (TPE), 40 120 parts of fire retardant, 25 parts of compatilizer, 06 parts of color masterbatch, 25 parts of lubricant, 14 parts of antioxidant；5 30 parts of taste removal master batch；Described vinylite is two or more blend in following material：Low density polyethylene (LDPE)；LLDPE；Medium density polyethylene；High density polyethylene (HDPE)；Ethylene ethyl acrylate copolymer；Ethylene vinyl acetate copolymer；The thermoplastic elastomer (TPE) is one or two the mixture in following material：POE；Ethylene propylene diene rubber.The low low smell automobile double wall heat draws of VOC of the present invention, under use environment, the organic gas and smell of release are humble, meet requirement of the main engine plants for double wall heat draw.

Description

A kind of low smell automobile double wall heat draws of low VOC and preparation method
Technical field
Sealed with low VOC (volatile organics the present invention relates to a kind of sealing of automotive wire bundle, joint and Y connection Compound, volatile organic compounds) low smell double wall heat draw and preparation method thereof, belong to automobile cable seal With protection field.
Background technology
The public of attention with to(for) health and environmental problem, people increasingly weigh for automobile indoor air quality problems Depending on the pollution sources of automobile indoor air are mainly derived from the volatilizable composition of various plastic cement products, toluene, dimethylbenzene and aldehyde ketone Class etc., such excessive material of driver and crew's suction has poisoning, carcinogenic, teratogenesis harm.
Each main engine plants are gentle to in-car VOC (VOC, volatile organic compounds) Taste grade puts into effect associated test standards and requirement, management and control for VOC in vehicle room certainly will to each parts of automobile with Material carries out strict management and control to ensure that vehicle is tested by VOC.
Double wall heat draw is mainly used in automotive wire bundle sealing, joint and Y connection sealing, and use environment is in automobile With engine periphery, there is higher wanting for sealed insulation, lower temperature resistance, heat-resisting quantity, resistance to liquid, anti-flammability etc. Ask.Automotive wire bundle double wall heat draw is divided into two-layer, and outer wall is polyolefin material, and internal layer is that polyamide or polyolefin are heated Glue, the inside and outside layer material of double-wall pipe prepared by traditional handicraft all cannot be by VOC and smell level estimate.
The VOC sources of double wall heat draw are main by two aspects：The vistanex of ectonexine is with hot melt gum resin in synthesis During the monomer, solvent and the catalyst that remain；During extrusion processing and cross-linking radiation of the material under thermal field shearing field Catabolite.
Therefore, a kind of low smell automobile double wall heat draws of low VOC are researched and developed, is in fact the task of top priority.
The content of the invention
The technical problem to be solved in the present invention is：A kind of low smell automobile double wall heat draws of low VOC and preparation are provided Method, under use environment, the organic gas and smell of release are humble, meet requirement of the main engine plants for double wall heat draw.
In order to solve the above-mentioned technical problem, the present invention proposes following technical proposal：A kind of low smell automobile double wall heats of low VOC The draw, its inner wall material is modified dimer acid polyamide PUR, and its ring and ball softening point is 105-130 DEG C, viscosity 7000- 14000MPa.S/200℃；
Its external wall material is made up of following component in parts by weight：100 parts of vinylite, thermoplastic elastomer (TPE) 10-40 parts, fire retardant 40-120 parts, compatilizer 2-5 parts, color masterbatch 0-6 parts, lubricant 2-5 parts, antioxidant 1-4 parts；Taste removal is female 5-30 parts of grain；
Described vinylite is two or more blend in following material：Low density polyethylene (LDPE)；Linearly Low density polyethylene (LDPE)；Medium density polyethylene；High density polyethylene (HDPE)；Ethylene-ethyl acrylate copolymer；Ethylene-vinyl acetate Copolymer；
The thermoplastic elastomer (TPE) is one or two the mixture in following material：Ethylene-octene copolymer；Ternary EP rubbers；
The fire retardant is the mixture of one or more in following material：TDE；Antimony oxide；Hydrogen Aluminum oxide；Magnesium hydroxide；Hydrotalcite；Melamine cyanurate；Melamine polyphosphate；Aluminum diethylphosphinate；Nanometer Montmorillonite；
The compatilizer is random ethylene-vinyl acrylate-maleic anhydride terpolymer；
The color masterbatch is the mixture of the one or two kinds of in following material：Carbon black, low density polyethylene (LDPE) and toner Mixture；
The lubricant is the mixture of one or more in following substances：Tissuemat E；Stearic acid；Zinc stearate； Magnesium stearate；Calcium stearate；Oleamide；
The antioxidant is one or several the mixture in following material：(4- methyl -6- is special for 2,2'- thiobis Butylphenol)；Four [methyl-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters；2,6- di-t-butyls are to first Phenol；N, N'- bis- (betanaphthyl) p-phenylenediamine；Three (2,4- di-t-butyls) phenyl-phosphites；
The taste removal master batch is made up of base material and liquid steam stripping agent, and the base material is one or several in following material Mixture：4A molecular sieves；Zeolite；Nano-calcium carbonate；Concave convex rod scholar's clay；Sepiolite；Polyethylene foamed alcohol；The liquid vapour It is one or several the mixture in lower class material to propose agent：Water；Butanol；Glycol dimethyl ether；Glycol monoethyl ether.
In order to solve the above-mentioned technical problem, the present invention proposes following technical proposal：A kind of low smell automobile double wall heats of low VOC The preparation method of the draw, comprises the following steps：
Step 1：The preparation of outer wall masterbatch：
Each material is weighed by weight, but taste removal master batch weighs half, puts into resin, pellet successively in high speed mixer It is uniform with powder stirring；
Mixed material is carried out into melting extrusion in the parallel double-screw extruder with vacuum orifice, check rod is cooled down, Granulation, temperature setting is 90-170 DEG C, extruder is previous, two sections of temperature settings less than liquid steam stripping agent boiling point, vacuum for- 0.03~-0.1MPa；
The pellet that will be made stirs with second half taste removal master batch in high speed mixer；
Well mixed material carries out second time melting extrusion in the parallel double-screw extruder with vacuum orifice, leads Bar, cooling, granulation, drying, extrusion temperature is set to 90-170 DEG C, and extruder is previous, two sections of temperature settings are stripped less than liquid The boiling point of agent, vacuum is -0.03~-0.1MPa；
Step 2：It is prepared by double wall heat draw：
The modified dimer acid polyamide PUR of inner wall material processes 4h in 75 DEG C of cycling hot bellows before the use, uses 2% talcum powder is mixed with PUR；
External wall material and the modified dimer acid polyamide PUR of inner wall material exempt to adjust double wall heat draw co-extrusion die by being furnished with Two combination single screw extrusion machines on extrusion molding；
By Co 60 electron accelerator 50~160KGy crosslinkings with radiation, irradiation dose is 5-16M to the tubing；
Tubing after crosslinking with radiation expands 3~4 times on vacuum dilator, and expansion temperature is 130-180 DEG C.
Compared with prior art, the present invention has following beneficial effect：Automobile double-wall pipe of the present invention, its is volatilizable thing and liquid Body steam stripping agent formation azeotropic mixture discharges the purpose for having reached devolatilization, system via the passage that liquid steam stripping agent is formed from resin , according to German PV3900 oder levels testing standard, oder levels are below 2.0 for standby double-wall pipe product；According to masses PV3341TVOC testing standards, its result is less than 50 μ g/g；Sealed insulation ＞ 2 × 108Ω；Lower temperature resistance, 4h is cold at -40 DEG C Impact without cracking, without electric leakage；Resistance to ag(e)ing, 105 DEG C, 30000h, outward appearance is good, without electric leakage, sealed insulation ＞ 2 × 108Ω； Resistance to liquid, 23 DEG C, diesel oil immersion 30min, without electric leakage, sealed insulation ＞ 2 × 108Ω；Anti-flammability, surveys according to ISO6722 Examination, self-extinguishment in 30s.
Specific embodiment
A kind of low smell automobile double wall heat draws of low VOC, its inner wall material is modified dimer acid polyamide PUR, and its is global Method softening point is 105-130 DEG C, 7000-14000MPa.S/200 DEG C of viscosity.
Its external wall material is made up of following component in parts by weight：100 parts of vinylite, thermoplastic elastomer (TPE) 10-40 parts, fire retardant 40-120 parts, compatilizer 2-5 parts, color masterbatch 0-6 parts, lubricant 2-5 parts, antioxidant 1-4 parts；Taste removal is female 5-30 parts of grain.
Described vinylite is two or more blend in following material：Low density polyethylene (LDPE)；Linearly Low density polyethylene (LDPE)；Medium density polyethylene；High density polyethylene (HDPE)；Ethylene-ethyl acrylate copolymer；Ethylene-vinyl acetate Copolymer.
The thermoplastic elastomer (TPE) is one or two the mixture in following material：Ethylene-octene copolymer；Ternary EP rubbers.
The fire retardant is the mixture of one or more in following material：TDE；Antimony oxide；Hydrogen Aluminum oxide；Magnesium hydroxide；Hydrotalcite；Melamine cyanurate；Melamine polyphosphate；Aluminum diethylphosphinate；Nanometer Montmorillonite.
The compatilizer is random ethylene-vinyl acrylate-maleic anhydride terpolymer.
The color masterbatch is the mixture of the one or two kinds of in following material：Carbon black；Low density polyethylene (LDPE) and toner Mixture.
The lubricant is the mixture of one or more in following substances：Tissuemat E；Stearic acid；Zinc stearate； Magnesium stearate；Calcium stearate；Oleamide.
The antioxidant is one or several the mixture in following material：(4- methyl -6- is special for 2,2'- thiobis Butylphenol)；Four [methyl-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters；2,6- di-t-butyls are to first Phenol；N, N'- bis- (betanaphthyl) p-phenylenediamine；Three (2,4- di-t-butyls) phenyl-phosphites.
The taste removal master batch is made up of base material and liquid steam stripping agent.The base material is one or several in following material Mixture：4A molecular sieves；Zeolite；Nano-calcium carbonate；Concave convex rod scholar's clay；Sepiolite；Polyethylene foamed alcohol.
The liquid steam stripping agent is one or several the mixture in lower class material：Water；Butanol；Glycol dinitrate Ether；Glycol monoethyl ether.
The preparation method of the low smell automobile double wall heat draws of described low VOC, comprises the following steps：
Step 1：The preparation of outer wall masterbatch：
Each material is weighed by weight, but taste removal master batch weighs half, puts into resin, pellet successively in high speed mixer It is uniform with powder stirring；
Mixed material is carried out into melting extrusion in the parallel double-screw extruder with vacuum orifice, check rod is cooled down, Granulation, temperature setting is 90-170 DEG C, extruder is previous, two sections of temperature settings less than liquid steam stripping agent boiling point, vacuum for- 0.03~-0.1MPa；
The pellet that will be made stirs with second half taste removal master batch in high speed mixer；
Well mixed material carries out second time melting extrusion in the parallel double-screw extruder with vacuum orifice, leads Bar, cooling, granulation, drying, extrusion temperature is set to 90-170 DEG C, and extruder is previous, two sections of temperature settings are stripped less than liquid The boiling point of agent, vacuum is -0.03~-0.1MPa；
Step 2：It is prepared by double wall heat draw：
The modified dimer acid polyamide PUR of inner wall material processes 4h in 75 DEG C of cycling hot bellows before the use, uses 2% talcum powder is mixed with PUR；
Outer wall masterbatch and the modified dimer acid polyamide PUR of inner wall material exempt to adjust double wall heat draw coextrusion die by being furnished with Extrusion molding on two combination single screw extrusion machines of tool；
By Co 60 electron accelerator 50~160KGy crosslinkings with radiation, irradiation dose is 5-16M to the tubing；
Tubing after crosslinking with radiation expands 3~4 times on vacuum dilator, and expansion temperature is 130-180 DEG C.
Prepare embodiment 1：
Each component is weighed according to weight listed in Table.
Weigh each material (taste removal master batch weighs half) by weight, put into successively in high speed mixer resin, pellet and Powder stirring is uniform；
Mixed material is carried out into melting extrusion in the parallel double-screw extruder with vacuum orifice, check rod is cooled down, Granulation, one, two sections of temperature settings of extruder are 90 DEG C, and vacuum is -0.05MPa；
The pellet that will be made stirs with second half taste removal master batch in high speed mixer；Well mixed material is carried out Second time extrusion, granulation, drying, one, two sections of temperature settings of extruder are 90 DEG C, and vacuum is -0.05MPa.
Outer wall masterbatch is coextruded with inner surface heat melten gel, is crosslinked by co-60 radiation 100KGy through the tubing, irradiation dose It is 10M, the tubing after crosslinking with radiation expands 4 times at a temperature of 155 DEG C, prepares automotive line double wall heat draw.Performance is as follows：
Oder levels：According to popular company's odor detection standard PV 3900, placed in the baking oven that 80 ± 5 DEG C of test condition 2h, carries out smell test, oder levels 2.0 when being cooled to 60 DEG C；
TVOC (total volatile organism, Total Volatile Organic Compounds) is tested：According to masses PV3341TVOC testing standards, TVOC is 20 μ g/g；
Sealed insulation 5 × 108Ω；
Lower temperature resistance：4h cold shocks are without cracking at -40 DEG C, without electric leakage；
Resistance to ag(e)ing：105 DEG C, 30000h, outward appearance is good, without electric leakage, sealed insulation 6.3 × 108Ω；
Resistance to liquid；23 DEG C, diesel oil immersion 30min, without electric leakage, sealed insulation 2.9 × 108Ω；
Anti-flammability：Tested according to ISO6722, self-extinguishment in 30s.
Prepare embodiment 2
Each component is weighed according to weight listed in Table.
Weigh each material (taste removal master batch weighs half) by weight, put into resin successively in high speed mixer, pellet and Powder stirring is uniform；
Mixed material is carried out into melting extrusion in the parallel double-screw extruder with vacuum orifice, check rod is cooled down, Granulation, one, two sections of temperature settings of extruder are 90 DEG C, and vacuum is -0.05MPa；
The pellet that will be made stirs with second half taste removal master batch in high speed mixer；Well mixed material is carried out Second time extrusion, granulation, drying, one, two sections of temperature settings of extruder are 90 DEG C, and vacuum is -0.05MPa.
Outer wall masterbatch is coextruded with inner surface heat melten gel, is crosslinked by co-60 radiation 50KGy through the tubing, and irradiation dose is 5M, the tubing after crosslinking with radiation expands 4 times at a temperature of 155 DEG C, prepares automotive line double wall heat draw.Performance is as follows：
Oder levels：According to popular company's odor detection standard PV 3900, placed in the baking oven that 80 ± 5 DEG C of test condition 2h, carries out smell test, oder levels 3.0 when being cooled to 60 DEG C；
TVOC (total volatile organism, Total Volatile Organic Compounds) is tested：According to masses PV3341TVOC testing standards, TVOC is 34 μ g/g；
Sealed insulation：4.3×108Ω；
Lower temperature resistance：4h cold shocks are without cracking at 40 DEG C, without electric leakage；
Resistance to ag(e)ing：105 DEG C, 30000h, outward appearance is good, without electric leakage, sealed insulation 5.2 × 108Ω；
Resistance to liquid：23 DEG C, diesel oil immersion 30min, without electric leakage, sealed insulation 2.6 × 108Ω；
Anti-flammability：Tested according to ISO6722, self-extinguishment in 30s.
Prepare embodiment 3：
Each component is weighed according to weight listed in Table.
Weigh each material (taste removal master batch weighs half) by weight, put into resin successively in high speed mixer, pellet and Powder stirring is uniform；
Mixed material is carried out into melting extrusion in the parallel double-screw extruder with vacuum orifice, check rod is cooled down, Granulation, one, two sections of temperature settings of extruder are 90 DEG C, and vacuum is -0.05MPa；
The pellet that will be made stirs with second half taste removal master batch in high speed mixer；Well mixed material is carried out Second time extrusion, granulation, drying, one, two sections of temperature settings of extruder are 90 DEG C, and vacuum is -0.05MPa.
Outer wall masterbatch is coextruded with inner surface heat melten gel, is crosslinked by co-60 radiation 160KGy through the tubing, irradiation dose It is 16M, the tubing after crosslinking with radiation expands 4 times at a temperature of 155 DEG C, prepares automotive line double wall heat draw.Performance is as follows：
Oder levels：According to popular company's odor detection standard PV 3900, placed in the baking oven that 80 ± 5 DEG C of test condition 2h, carries out smell test, oder levels 2.5 when being cooled to 60 DEG C；
TVOC is tested：According to popular PV3341TVOC testing standards, TVOC is 28 μ g/g；
Sealed insulation：6.3×108Ω；
Lower temperature resistance：4h cold shocks are without cracking at 40 DEG C, without electric leakage；
Resistance to ag(e)ing：105 DEG C, 30000h, outward appearance is good, without electric leakage, sealed insulation 6.1 × 108Ω；
Resistance to liquid：23 DEG C, diesel oil immersion 30min, without electric leakage, sealed insulation 3.6 × 108Ω；
Anti-flammability：Tested according to ISO6722, self-extinguishment in 30s.
Prepare embodiment 4
Each component is weighed according to weight listed in Table.
Weigh each material (taste removal master batch weighs half) by weight, put into resin successively in high speed mixer, pellet and Powder stirring is uniform；Mixed material is carried out into melting extrusion in the parallel double-screw extruder with vacuum orifice, check rod, Cooling, granulation, one, two sections of temperature settings of extruder are 90 DEG C, and vacuum is -0.05MPa；The pellet that will be made is removed with second half Taste master batch stirs in high speed mixer；Well mixed material carries out second time extrusion, granulation, dries, extruder one, Two sections of temperature settings are 90 DEG C, and vacuum is -0.05MPa.Outer wall masterbatch is coextruded with inner surface heat melten gel, passes through through the tubing Co-60 radiation 80KGy is crosslinked, and irradiation dose is 8M, and the tubing after crosslinking with radiation expands 4 times at a temperature of 155 DEG C, prepares Automotive line double wall heat draw.Performance is as follows：
Oder levels：According to popular company's odor detection standard PV 3900, placed in the baking oven that 80 ± 5 DEG C of test condition 2h, carries out smell test, oder levels 2.0 when being cooled to 60 DEG C；
TVOC is tested：According to popular PV3341TVOC testing standards, TVOC is 10 μ g/g；
Sealed insulation：8×109Ω；
Lower temperature resistance：4h cold shocks are without cracking at -40 DEG C, without electric leakage；
Resistance to ag(e)ing：105 DEG C, 30000h, outward appearance is good, without electric leakage, sealed insulation 4.3 × 109Ω；
Resistance to liquid：23 DEG C, diesel oil immersion 30min, without electric leakage, sealed insulation 9.6 × 108Ω；
Anti-flammability：Tested according to ISO6722, self-extinguishment in 30s.
The present invention has following beneficial effect：Automobile double-wall pipe of the present invention, its is volatilizable, and thing is formed altogether with liquid steam stripping agent Boiling thing discharges to reach the purpose of devolatilization, the double-wall pipe product of preparation via the passage that liquid steam stripping agent is formed from resin According to German PV3900 oder levels testing standard, oder levels are below 2.0；According to popular PV3341TVOC testing standards, Its result is less than 50 μ g/g；According to RTM2583 standard testings, sealed insulation ＞ 2 × 108Ω；Surveyed according to RTM2574 standards Examination, at -40 DEG C 4h cold shocks without cracking, without electric leakage；Resistance to ag(e)ing, 105 DEG C, 30000h, outward appearance is good, and without electric leakage, sealing is exhausted Edge ＞ 2 × 108Ω；According to ISO 1817：2005 standard testing resistance to liquid, diesel oil soaks 30min (23 DEG C), without electric leakage, Sealed insulation ＞ 2 × 108Ω；Anti-flammability, tests, self-extinguishment in 30s according to ISO6722.

Claims (2)

1. low smell automobile double wall heat draws of a kind of low VOC, it is characterised in that its inner wall material is modified dimer acid polyamide hot melt Glue, its ring and ball softening point is 105-130 DEG C, 7000-14000MPa.S/200 DEG C of viscosity；
Its external wall material is made up of following component in parts by weight：100 parts of vinylite, thermoplastic elastomer (TPE) 10- 40 parts, fire retardant 40-120 parts, compatilizer 2-5 parts, color masterbatch 0-6 parts, lubricant 2-5 parts, antioxidant 1-4 parts；Taste removal master batch 5-30 parts；
Described vinylite is two or more blend in following material：Low density polyethylene (LDPE)；It is linear low close Degree polyethylene；Medium density polyethylene；High density polyethylene (HDPE)；Ethylene-ethyl acrylate copolymer；Ethylene-vinyl acetate copolymerization Thing；
The thermoplastic elastomer (TPE) is one or two the mixture in following material：Ethylene-octene copolymer；EPDM Rubber；
The fire retardant is the mixture of one or more in following material：TDE；Antimony oxide；Hydroxide Aluminium；Magnesium hydroxide；Hydrotalcite；Melamine cyanurate；Melamine polyphosphate；Aluminum diethylphosphinate；Nanometer is covered de- Soil；
The compatilizer is random ethylene-vinyl acrylate-maleic anhydride terpolymer；
The color masterbatch is the mixture of the one or two kinds of in following material：Carbon black, low density polyethylene (LDPE) and toner it is mixed Compound；
The lubricant is the mixture of one or more in following substances：Tissuemat E；Stearic acid；Zinc stearate；It is stearic Sour magnesium；Calcium stearate；Oleamide；
The antioxidant is one or several the mixture in following material：2,2'- thiobis (4- methyl -6- tertiary butyls Phenol)；Four [methyl-（3,5- di-tert-butyl-hydroxy phenyls）Propionic acid] pentaerythritol ester；BHT；N, N'- bis- (betanaphthyl) p-phenylenediamine；Three (2,4- di-t-butyls) phenyl-phosphites；
The taste removal master batch is made up of base material and liquid steam stripping agent, and the base material is the mixed of one or several in following material Compound：4A molecular sieves；Zeolite；Nano-calcium carbonate；Concave convex rod scholar's clay；Sepiolite；Polyethylene foamed alcohol；The liquid steam stripping agent It is one or several the mixture in lower class material：Water；Butanol；Glycol dimethyl ether；Glycol monoethyl ether.
2. a kind of preparation method of the low low smell automobile double wall heat draws of VOC as claimed in claim 1, it is characterised in that bag Include following steps：
Step 1：The preparation of outer wall masterbatch：
Each material is weighed by weight, but taste removal master batch weighs half, puts into resin, pellet and powder successively in high speed mixer Material stirs；
Mixed material is carried out into melting extrusion in the parallel double-screw extruder with vacuum orifice, check rod, cooling is made Grain, temperature setting is 90-170 DEG C, extruder is previous, two sections of temperature settings less than liquid steam stripping agent boiling point, vacuum for- 0.03~-0.1MPa；
The pellet that will be made stirs with second half taste removal master batch in high speed mixer；
Well mixed material carries out second time melting extrusion in the parallel double-screw extruder with vacuum orifice, check rod, Cooling, granulation, drying, extrusion temperature is set to 90-170 DEG C, and extruder is previous, two sections of temperature settings are less than liquid steam stripping agent Boiling point, vacuum is -0.03 ~ -0.1MPa；
Step 2：It is prepared by double wall heat draw：
The modified dimer acid polyamide PUR of inner wall material processes 4h in 75 DEG C of cycling hot bellows before the use, uses 2% talcum Powder is mixed with PUR；
External wall material and the modified dimer acid polyamide PUR of inner wall material exempt to adjust the two of double wall heat draw co-extrusion die by being furnished with Extrusion molding on platform combination single screw extrusion machine；
By Co 60 or electron accelerator 50 ~ 160KGy crosslinkings with radiation, irradiation dose is 5-16M to the tubing；
Tubing after crosslinking with radiation expands 3 ~ 4 times on vacuum dilator, and expansion temperature is 130-180 DEG C.
CN201611234293.5A 2016-12-28 2016-12-28 A kind of low smell automobile double wall heat draws of low VOC and preparation method Pending CN106782787A (en)

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CN108129734A (en) * 2018-01-08 2018-06-08 长园电子（东莞）有限公司 A kind of combustion gas protection of pipe fire retardant thermal shrinkage tube through walls and preparation method thereof
CN109021402A (en) * 2018-08-28 2018-12-18 安徽江淮汽车集团股份有限公司 A kind of polyolefin VOC modifier and preparation method thereof
CN109354812A (en) * 2018-10-16 2019-02-19 青岛新材料科技工业园发展有限公司 A kind of low VOC, low smell polystyrene type composite material and preparation method
CN109370005A (en) * 2018-10-08 2019-02-22 南京聚隆科技股份有限公司 One kind can silk-screen blow molding fretting map tool box and preparation method thereof
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CN109852076A (en) * 2017-11-30 2019-06-07 联泓(江苏)新材料研究院有限公司 A kind of low smell, modified thermoplastic elastomer material of low VOC and preparation method thereof
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CN110577695A (en) * 2018-06-07 2019-12-17 苏州市飞博冷热缩制品有限公司 material formula and manufacturing process of flame-retardant high-polymer heat-shrinkable high-voltage insulating sleeve
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CN107141572A (en) * 2017-07-06 2017-09-08 四川久远科技股份有限公司 A kind of low VOC automotive trims production material and preparation method thereof
CN109852076B (en) * 2017-11-30 2021-04-16 联泓(江苏)新材料研究院有限公司 Low-odor low-VOC modified thermoplastic elastomer material and preparation method thereof
CN109852076A (en) * 2017-11-30 2019-06-07 联泓(江苏)新材料研究院有限公司 A kind of low smell, modified thermoplastic elastomer material of low VOC and preparation method thereof
CN108129734A (en) * 2018-01-08 2018-06-08 长园电子（东莞）有限公司 A kind of combustion gas protection of pipe fire retardant thermal shrinkage tube through walls and preparation method thereof
CN110577695A (en) * 2018-06-07 2019-12-17 苏州市飞博冷热缩制品有限公司 material formula and manufacturing process of flame-retardant high-polymer heat-shrinkable high-voltage insulating sleeve
CN109021402A (en) * 2018-08-28 2018-12-18 安徽江淮汽车集团股份有限公司 A kind of polyolefin VOC modifier and preparation method thereof
CN109370005A (en) * 2018-10-08 2019-02-22 南京聚隆科技股份有限公司 One kind can silk-screen blow molding fretting map tool box and preparation method thereof
CN109354812A (en) * 2018-10-16 2019-02-19 青岛新材料科技工业园发展有限公司 A kind of low VOC, low smell polystyrene type composite material and preparation method
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CN109776930A (en) * 2018-12-06 2019-05-21 长园电子（东莞）有限公司 A kind of crosslinking with radiation halogen-free non-red-phosphorus flame-retardant heat-shrinkage material and preparation method thereof
CN110194861A (en) * 2018-12-20 2019-09-03 长园电子（东莞）有限公司 A kind of communications cable joint protective heat-shrink tube and preparation method thereof
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CN112778620A (en) * 2020-12-31 2021-05-11 长园电子（东莞）有限公司 Heat-shrinkable sleeve and preparation method thereof

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