CN113978076B - Heat-shrinkable material, preparation method and application thereof, and double-wall heat-shrinkable sleeve - Google Patents
Heat-shrinkable material, preparation method and application thereof, and double-wall heat-shrinkable sleeve Download PDFInfo
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- CN113978076B CN113978076B CN202110854465.3A CN202110854465A CN113978076B CN 113978076 B CN113978076 B CN 113978076B CN 202110854465 A CN202110854465 A CN 202110854465A CN 113978076 B CN113978076 B CN 113978076B
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- 239000002654 heat shrinkable material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000004831 Hot glue Substances 0.000 claims abstract description 77
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 69
- 229920001577 copolymer Polymers 0.000 claims abstract description 30
- -1 polyethylene Polymers 0.000 claims abstract description 27
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 23
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 23
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 17
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 17
- 150000003254 radicals Chemical class 0.000 claims abstract description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052802 copper Inorganic materials 0.000 claims abstract description 15
- 239000010949 copper Substances 0.000 claims abstract description 15
- 229920001971 elastomer Polymers 0.000 claims abstract description 15
- 239000000806 elastomer Substances 0.000 claims abstract description 15
- 239000004952 Polyamide Substances 0.000 claims abstract description 13
- 239000004698 Polyethylene Substances 0.000 claims abstract description 13
- 239000002250 absorbent Substances 0.000 claims abstract description 13
- 230000002745 absorbent Effects 0.000 claims abstract description 13
- 238000005336 cracking Methods 0.000 claims abstract description 13
- 239000003112 inhibitor Substances 0.000 claims abstract description 13
- 229920002647 polyamide Polymers 0.000 claims abstract description 13
- 229920000573 polyethylene Polymers 0.000 claims abstract description 13
- 239000000314 lubricant Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims description 15
- 238000004132 cross linking Methods 0.000 claims description 13
- 239000011265 semifinished product Substances 0.000 claims description 13
- 229920001684 low density polyethylene Polymers 0.000 claims description 12
- 239000004702 low-density polyethylene Substances 0.000 claims description 12
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229920002379 silicone rubber Polymers 0.000 claims description 8
- 239000004945 silicone rubber Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 238000007493 shaping process Methods 0.000 claims description 7
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 6
- DPWFWWRPRPJCFX-UHFFFAOYSA-L zinc pyridine sulfate Chemical compound S(=O)(=O)([O-])[O-].[Zn+2].N1=CC=CC=C1 DPWFWWRPRPJCFX-UHFFFAOYSA-L 0.000 claims description 6
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 5
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical group C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- 230000006353 environmental stress Effects 0.000 claims description 3
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 3
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- HCILJBJJZALOAL-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)-n'-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyl]propanehydrazide Chemical group CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 HCILJBJJZALOAL-UHFFFAOYSA-N 0.000 claims description 2
- ILWVABLRFKUOOO-UHFFFAOYSA-N [3-[2-(3,5-ditert-butyl-4-hydroxyphenyl)-2-methylpropanoyl]oxy-2,2-bis[[2-(3,5-ditert-butyl-4-hydroxyphenyl)-2-methylpropanoyl]oxymethyl]propyl] 2-(3,5-ditert-butyl-4-hydroxyphenyl)-2-methylpropanoate Chemical compound CC(C(=O)OCC(COC(C(C)(C1=CC(=C(C(=C1)C(C)(C)C)O)C(C)(C)C)C)=O)(COC(C(C)(C1=CC(=C(C(=C1)C(C)(C)C)O)C(C)(C)C)C)=O)COC(C(C)(C1=CC(=C(C(=C1)C(C)(C)C)O)C(C)(C)C)C)=O)(C)C1=CC(=C(C(=C1)C(C)(C)C)O)C(C)(C)C ILWVABLRFKUOOO-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 238000007789 sealing Methods 0.000 abstract description 9
- 238000003763 carbonization Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 238000004078 waterproofing Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 15
- 230000008569 process Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000005453 pelletization Methods 0.000 description 6
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000035882 stress Effects 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000006096 absorbing agent Substances 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 229920006225 ethylene-methyl acrylate Polymers 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000006386 memory function Effects 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D23/00—Producing tubular articles
- B29D23/001—Pipes; Pipe joints
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B1/00—Layered products having a non-planar shape
- B32B1/08—Tubular products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- 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
- C08L23/0853—Vinylacetate
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B17/00—Insulators or insulating bodies characterised by their form
- H01B17/56—Insulating bodies
- H01B17/58—Tubes, sleeves, beads, or bobbins through which the conductor passes
- H01B17/583—Grommets; Bushings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2597/00—Tubular articles, e.g. hoses, pipes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
- Insulating Bodies (AREA)
Abstract
The invention is applicable to the technical field of materials, and provides a heat-shrinkable material, a preparation method and application thereof, and a double-wall heat-shrinkable sleeve, comprising an outer layer master batch and a hot melt adhesive modified master batch; the outer layer masterbatch includes: 60-90 parts of polyethylene, 10-40 parts of ethylene-methacrylate copolymer, 4-10 parts of polyethylene octene copolymer elastomer, 0.5-3.0 parts of sensitizer, 0.5-1.5 parts of antioxidant and 0.5-2.0 parts of lubricant; the hot melt adhesive modified master batch comprises: 70-90 parts of ethylene-vinyl acetate copolymer hot melt adhesive, 10-30 parts of polyamide hot melt adhesive, 0.5-1.5 parts of copper inhibitor, 0.2-1.0 parts of free radical absorbent and 0.5-1.5 parts of antioxidant. The double-wall heat-shrinkable sleeve prepared by the invention has the characteristics of realizing rapid shrinkage at high temperature, no carbonization on the surface and no cracking during high-temperature baking shrinkage, solves the problem of poor transparency of the existing double-wall tube, and is suitable for sealing and waterproofing of multi-strand wire harnesses.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a heat-shrinkable material, a preparation method and application thereof, and a double-wall heat-shrinkable sleeve.
Background
The outer layer of the double-wall heat-shrinkable sleeve is made of irradiation crosslinking polyolefin material, has a heat-shrinkable memory function, and the inner layer is made of polyolefin or polyamide hot melt adhesive, so that a bonding sealing function is provided. The double-wall heat shrinkage tube has wide application in occasions needing electric protection, friction resistance protection and stress release. Moisture in automotive systems may enter the joint area directly or indirectly through capillary action between individual wires, resulting in corrosion of the wiring. An important function of double-walled pipes is to provide a moisture-tight seal for electrical connectors in automotive systems.
The double-wall pipe is arranged at the center of the electric joint area, and when the double-wall pipe is heated, the hot melt adhesive is melted and plays a role of tightly sealing the curled or welded parts of the electric wires and the wires through the thermal contraction of the sleeve. The installed double wall tube provides mechanical protection against bending, abrasion and penetration and electrical insulation. Conventional double-wall tubes have low production efficiency due to slow shrinkage speed and cannot provide enough shrinkage stress, so that the hot melt adhesive on the inner layer of the double-wall tube cannot fill the gaps of the multi-strand wire bundles through extrusion. In addition, if the parameter design of the hot melt adhesive is unreasonable, the situation that the hot melt adhesive cannot fill or overflow the multi-strand wire bundles can also occur. Second, for high shrinkage double wall tubing, cracking during shrinkage of the sleeve can occur if a stress concentration point occurs during the cutting process when a cutting unevenness occurs. The double-wall pipe sealing failure can be caused under the conditions, and hidden danger is avoided for the safety burying of an automobile system.
The prior art scheme can adopt the mode of increasing irradiation dose and improving crosslinking degree or improving shrinkage temperature to accelerate the shrinkage speed of the sleeve, and has the following defects: 1. the irradiation dose is too high, so that the hot melt adhesive is crosslinked and foamed, the fluidity is poor, cracking is more likely to occur in the shrinkage process, and a certain proportion of antioxidant is added to inhibit the hot melt adhesive from crosslinking in the conventional technical scheme, but the transparency of the pipe is seriously affected due to the too high addition proportion; in addition, cracking of the casing under high temperature shrinkage conditions may result. If the irradiation dose is too low, the shrinkage speed is slower, the production efficiency is seriously affected, and the shrinkage force is insufficient, so that the hot melt adhesive cannot be extruded and filled into the gaps of the multi-strand wire bundles. 2. If the shrinkage speed is accelerated by using an elevated temperature under the condition of low irradiation dose, the surface carbonization of the sleeve is caused by temperature difference resistance due to low crosslinking degree.
Therefore, the existing double-wall heat-shrinkable sleeve cannot simultaneously achieve the characteristics of quick shrinkage, high-power shrinkage, no cracking, high transparency and excellent filling tightness.
Disclosure of Invention
The embodiment of the invention aims to provide a heat-shrinkable material, which aims to solve the problems that the existing double-wall heat-shrinkable sleeve cannot realize the characteristics of quick shrinkage, high-power shrinkage, no cracking, high transparency and excellent filling tightness.
The embodiment of the invention is realized in such a way that the heat-shrinkable material comprises an outer layer master batch and a hot melt adhesive modified master batch;
the outer layer master batch comprises the following raw materials in parts by weight:
60-90 parts of polyethylene, 10-40 parts of ethylene-methacrylate copolymer, 4-10 parts of polyethylene octene copolymer elastomer, 0.5-3.0 parts of sensitizer, 0.5-1.5 parts of antioxidant and 0.5-2.0 parts of lubricant;
the hot melt adhesive modified master batch comprises the following raw materials in parts by weight:
70-90 parts of ethylene-vinyl acetate copolymer hot melt adhesive, 10-30 parts of polyamide hot melt adhesive, 0.5-1.5 parts of copper inhibitor, 0.2-1.0 parts of free radical absorbent and 0.5-1.5 parts of antioxidant.
Another object of the embodiment of the present invention is a method for preparing a heat shrinkable material, comprising:
uniformly mixing 60-90 parts of polyethylene, 10-40 parts of ethylene-methacrylate copolymer, 4-10 parts of polyethylene octene copolymer elastomer, 0.5-3.0 parts of sensitizer, 0.5-1.5 parts of antioxidant and 0.5-2.0 parts of lubricant, and extruding and granulating to obtain a skin master batch;
uniformly mixing 70-90 parts of ethylene-vinyl acetate copolymer hot melt adhesive, 10-30 parts of polyamide hot melt adhesive, 0.5-1.5 parts of copper inhibitor, 0.2-1.0 parts of free radical absorbent and 0.5-1.5 parts of antioxidant, and granulating under water and drying to obtain hot melt adhesive modified master batch;
and co-extruding the sheath master batch and the hot melt adhesive modified master batch by adopting a double-layer extruder, and performing irradiation crosslinking on the obtained semi-finished product, wherein the irradiation dose is 10-15Mrd, and the semi-finished product is obtained by expanding and cooling and shaping through internal and external pressure difference.
Another object of an embodiment of the present invention is the use of the heat shrinkable material in the preparation of a double-walled heat shrinkable sleeve.
Another object of an embodiment of the present invention is a double-wall heat-shrinkable sleeve prepared from the heat-shrinkable material.
According to the heat-shrinkable material provided by the embodiment of the invention, the polyethylene, ethylene-methyl acrylate copolymer is adopted as a main component to compound the polyethylene octene copolymer elastomer, the sensitizer, the antioxidant and the lubricant to obtain an outer-layer master batch, and the ethylene-vinyl acetate copolymer hot melt adhesive, the polyamide hot melt adhesive, the copper inhibitor, the free radical absorber and the antioxidant are adopted to compound to obtain a hot melt adhesive modified master batch, so that the double-wall heat-shrinkable sleeve prepared from the outer-layer master batch and the hot melt adhesive modified master batch has the excellent characteristics of being capable of realizing rapid shrinkage at high temperature, having no carbonization on the surface and having no cracking after high-temperature baking shrinkage, and the problem of poor transparency of the double-wall pipe in the prior art is solved; in addition, the invention has good fluidity in the shrinking process, and is suitable for sealing and waterproofing of the multi-strand wire harness.
Drawings
Fig. 1 is a graph of heat shrinkage provided by an embodiment of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The embodiment of the invention provides a heat-shrinkable material, which aims to solve the problems that the existing double-wall heat-shrinkable sleeve cannot simultaneously give consideration to the characteristics of quick shrinkage, high-time shrinkage, no cracking, high transparency and excellent filling tightness, and solves the problem that the transparency of a double-wall pipe is poor in the prior art by adopting the excellent characteristics that polyethylene, ethylene-methacrylate copolymer is adopted as a main component to compound polyethylene octene copolymerized elastomer, a sensitizer, an antioxidant and a lubricant to obtain an outer-layer master batch, and adopting ethylene-vinyl acetate copolymer hot melt adhesive, polyamide hot melt adhesive, a copper-resistant agent, a free radical absorbent and an antioxidant to compound to obtain a hot melt adhesive modified master batch; in addition, the invention has good fluidity in the shrinking process, and is suitable for sealing and waterproofing of the multi-strand wire harness.
In an embodiment of the invention, the heat-shrinkable material comprises an outer layer master batch and a hot melt adhesive modified master batch;
the outer layer master batch comprises the following raw materials in parts by weight:
60-90 parts of polyethylene, 10-40 parts of ethylene-methacrylate copolymer, 4-10 parts of polyethylene octene copolymer elastomer, 0.5-3.0 parts of sensitizer, 0.5-1.5 parts of antioxidant and 0.5-2.0 parts of lubricant;
the hot melt adhesive modified master batch comprises the following raw materials in parts by weight:
70-90 parts of ethylene-vinyl acetate copolymer hot melt adhesive, 10-30 parts of polyamide hot melt adhesive, 0.5-1.5 parts of copper inhibitor, 0.2-1.0 parts of free radical absorbent and 0.5-1.5 parts of antioxidant.
In the embodiment of the invention, the polyethylene is one or two of LDPE (low density polyethylene) or LLDPE (linear low density polyethylene) and is compounded in any proportion, the melting point is 105-115 ℃, the melt index (MFR) is 0.2-0.5g/10min, and the density is 0.91-0.94g/cm 3 。
In the examples of the present invention, the ethylene-methacrylate copolymer (EMMA) has an MMA content of 5-25%, a melt index (MFR) of 0.2-5g/10min, a melting point of 80-100deg.C, and an environmental stress crack resistance of > 300hr.
In the embodiment of the invention, the melt index (MFR) of the polyethylene octene copolymer elastomer (POE) is 0.1-3g/10min, and the density is 0.8-0.95g/cm3.
In the embodiment of the invention, the sensitizer is colorless transparent liquid and is formed by compounding one or more of trimethylolpropane trimethacrylate (TMPTMA), triallyl isocyanurate (TAIC) and triallyl cyanurate (TAC).
In the embodiment of the invention, the lubricant is one or a plurality of low molecular weight silicone rubber, polyethylene wax, zinc stearate and silicone master batch in any proportion.
In the embodiment of the invention, the low molecular weight silicone rubber is methyl vinyl silicone rubber, the molecular weight is 4.5X105-6.0X105, and the vinyl content is 0.01-0.25%.
In the embodiment of the invention, the EVA (ethylene-vinyl acetate copolymer) hot melt adhesive has a softening point of 90-100 ℃ and a rotational viscosity of 70000-100000 mPa.s (160 ℃ test).
In the embodiment of the invention, the PA (polyamide) hot melt adhesive has a softening point of 130-150 ℃ and a rotational viscosity of 50000mPa.s-70000mPa.s (160 ℃ test).
In the embodiment of the invention, the chemical structure of the copper inhibitor is N, N' -bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine, and the melting point is 210-250 ℃.
In the embodiment of the invention, the free radical absorbent is one or more of ammonium dihydrogen phosphate, zinc pyridine sulfate and lithium carbonate which are compounded in any proportion.
In the embodiment of the invention, the antioxidant is one or more of 3, 5-di-tert-butyl-4-hydroxyphenyl propionic acid octadecyl ester, tetra [ methyl- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, 2, 6-di-tert-butyl-p-cresol and 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tri-butyl-4-hydroxybenzyl) benzene, which are compounded in any proportion.
The embodiment of the invention also provides a preparation method of the heat-shrinkable material (double-wall heat-shrinkable sleeve), which comprises the following steps:
uniformly mixing 60-90 parts of polyethylene, 10-40 parts of ethylene-methacrylate copolymer, 4-10 parts of polyethylene octene copolymer elastomer, 0.5-3.0 parts of sensitizer, 0.5-1.5 parts of antioxidant and 0.5-2.0 parts of lubricant, and extruding and granulating to obtain a skin master batch;
uniformly mixing 70-90 parts of ethylene-vinyl acetate copolymer hot melt adhesive, 10-30 parts of polyamide hot melt adhesive, 0.5-1.5 parts of copper inhibitor, 0.2-1.0 parts of free radical absorbent and 0.5-1.5 parts of antioxidant, and granulating under water and drying to obtain hot melt adhesive modified master batch;
and co-extruding the sheath master batch and the hot melt adhesive modified master batch by adopting a double-layer extruder, and performing irradiation crosslinking, heating, expansion through internal and external pressure difference, cooling and shaping on the obtained semi-finished product to obtain the finished product.
The embodiment of the invention also provides an application of the heat-shrinkable material in preparing double-wall heat-shrinkable sleeves.
The embodiment of the invention also provides a double-wall heat-shrinkable sleeve, which is prepared from the heat-shrinkable material.
Examples of certain embodiments of the invention are given below and are not intended to limit the scope of the invention.
In addition, it should be noted that the numerical values set forth in the following examples are as precise as possible, but those skilled in the art will understand that each numerical value should be construed as a divisor rather than an absolute precise numerical value due to measurement errors and experimental operation problems that cannot be avoided. For example, due to errors in the weighing apparatus, it should be understood that the weight values of the respective raw materials for preparing the double-wall heat-shrinkable sleeve with respect to the respective embodiments may have an error of ±2% or ±1%.
Example 1
Weighing the outer layer master batch according to parts by weight: 70 parts of Low Density Polyethylene (LDPE), 30 parts of ethylene-methacrylate copolymer (EMMA), 5 parts of polyethylene octene copolymer elastomer (POE), 2 parts of trimethylolpropane trimethacrylate (TMPTMA), 0.8 part of 2, 6-di-tert-butyl-p-cresol, 0.5 part of zinc stearate and 1 part of methyl vinyl silicone rubber; taking a hot melt adhesive modified master batch: 80 parts of EVA hot melt adhesive, 20 parts of PA hot melt adhesive, 1 part of copper inhibitor, 1 part of zinc pyridine sulfate and 0.5 part of 2, 6-di-tert-butyl-p-cresol. The components of the outer layer master batch and the hot melt adhesive modified master batch are respectively and uniformly mixed by a high-speed mixer. And extruding and granulating the mixed outer layer master batch twice by using double screws, wherein the granulating temperature is 180 ℃. The mixed hot melt adhesive modified master batch is subjected to one-time underwater pelletization by a double screw, and the pelletization temperature is 180 ℃. The pelleting hot melt adhesive modified master batch is dried by a dryer at 60 ℃ for 12 hours. And co-extruding the outer layer master batch and the hot melt adhesive modified master batch by adopting a double-layer extruder to obtain an extruded semi-finished product. Then the irradiation crosslinking is carried out through an electron accelerator, and the irradiation dose is 12Mrd. And finally, heating the irradiated semi-finished product in an oil bath, expanding by using internal and external pressure difference, cooling and shaping to obtain the double-wall heat-shrinkable sleeve.
Example 2
Weighing the outer layer master batch according to parts by weight: 60 parts of Low Density Polyethylene (LDPE), 40 parts of ethylene-methacrylate copolymer (EMMA), 8 parts of polyethylene octene copolymer elastomer (POE), 0.5 part of triallyl isocyanurate (TAIC), 1.5 parts of 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tri-butyl-4-hydroxybenzyl) benzene, 1 part of zinc stearate and 1 part of silicone masterbatch; taking a hot melt adhesive modified master batch: 70 parts of EVA hot melt adhesive, 30 parts of PA hot melt adhesive, 1 part of copper inhibitor, 0.5 part of ammonium dihydrogen phosphate, 0.5 part of zinc pyridine sulfate and 0.5 part of 2, 6-di-tert-butyl-p-cresol. The components of the outer layer master batch and the hot melt adhesive modified master batch are respectively and uniformly mixed by a high-speed mixer. And extruding and granulating the mixed outer layer master batch twice by using double screws, wherein the granulating temperature is 180 ℃. The mixed hot melt adhesive modified master batch is subjected to one-time underwater pelletization by a double screw, and the pelletization temperature is 180 ℃. The pelleting hot melt adhesive modified master batch is dried by a dryer at 60 ℃ for 12 hours. And co-extruding the outer layer master batch and the hot melt adhesive modified master batch by adopting a double-layer extruder to obtain an extruded semi-finished product. Then the irradiation crosslinking is carried out through an electron accelerator, and the irradiation dose is 15Mrd. And finally, heating the irradiated semi-finished product in an oil bath, expanding by using internal and external pressure difference, cooling and shaping to obtain the double-wall heat-shrinkable sleeve.
Example 3
Weighing the outer layer master batch according to parts by weight: 90 parts of Low Density Polyethylene (LDPE), 10 parts of ethylene-methacrylate copolymer (EMMA), 10 parts of polyethylene octene copolymer elastomer (POE), 1 part of triallyl isocyanurate (TAIC), 2 parts of triallyl isocyanurate (TAC), 0.5 part of 2, 6-di-tert-butyl-p-cresol and 0.5 part of methyl vinyl silicone rubber; taking a hot melt adhesive modified master batch: 90 parts of EVA hot melt adhesive, 10 parts of PA hot melt adhesive, 0.5 part of copper inhibitor, 0.7 part of zinc pyridine sulfate and 1 part of pentaerythritol tetrakis [ methyl- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ]. The components of the outer layer master batch and the hot melt adhesive modified master batch are respectively and uniformly mixed by a high-speed mixer. And extruding and granulating the mixed outer layer master batch twice by using double screws, wherein the granulating temperature is 180 ℃. The mixed hot melt adhesive modified master batch is subjected to one-time underwater pelletization by a double screw, and the pelletization temperature is 180 ℃. The pelleting hot melt adhesive modified master batch is dried by a dryer at 60 ℃ for 12 hours. And co-extruding the outer layer master batch and the hot melt adhesive modified master batch by adopting a double-layer extruder to obtain an extruded semi-finished product. Then the irradiation crosslinking is carried out through an electron accelerator, and the irradiation dose is 10Mrd. And finally, heating the irradiated semi-finished product in an oil bath, expanding by using internal and external pressure difference, cooling and shaping to obtain the double-wall heat-shrinkable sleeve.
The double-wall heat-shrinkable sleeves prepared in examples 1-3 of the present invention were subjected to the relevant performance test, the test method and the test results are shown in table 1 (wherein the leakage test is a seal test of a double-wall tube sleeved with 2-to-2 PVC wires).
TABLE 1
In summary, as can be seen from table 1, in the embodiments 1-3 of the present invention, the transparent double-wall heat-shrinkable sleeve for a multi-strand wire harness is prepared by selecting low-density polyethylene with specific parameters, compounding with ethylene-methacrylate copolymer and modifying inner-layer hot melt adhesive, and the double-wall heat-shrinkable sleeve overcomes the problems of slow shrinkage speed, easy cracking during shrinkage at high temperature, easy carbonization at high temperature, poor transparency and the like in the prior art, and in addition, the double-wall heat-shrinkable sleeve has excellent low-temperature resistance, ageing resistance and oil resistance, and the product performance is far higher than the standard requirements.
In addition, in the early experiment process, the invention discovers that the selection of the ethylene-methacrylate copolymer and the ratio of the ethylene-methacrylate copolymer to the low-density polyethylene in the system can obviously influence the shrinkage speed and the high-temperature baking cracking resistance of the obtained double-wall heat-shrinkable sleeve, and the content of the free radical absorbent in the system can obviously influence the leakage current, particularly in comparative example 1.
In addition, in the early experiment process, the invention discovers that the selection of the ethylene-methyl acrylate copolymer and the ratio of the ethylene-methyl acrylate copolymer to the low-density polyethylene in the system can obviously influence the shrinkage speed and the high-temperature baking cracking resistance of the obtained double-wall heat-shrinkable sleeve, and the content of the free radical absorbent in the system can obviously influence the leakage current, and the specific comparison examples 1-8 are shown below.
Comparative example 1
On the basis of example 1, only the ethylene-methacrylate copolymer component was changed from 30 parts to 70 parts, and the other components and the process were identical.
Comparative example 2
On the basis of example 1, only the ethylene-methacrylate copolymer component was changed from 30 parts to 45 parts, and the other components and the process were identical.
Comparative example 3
On the basis of example 1, only the ethylene-methacrylate copolymer component was changed from 30 parts to 0 parts, and the other components and the process were identical.
Comparative example 4
Based on example 1, only the ethylene-methacrylate copolymer component was replaced with an ethylene-vinyl acetate copolymer, and the other components and the process were identical.
Comparative example 5
Based on example 1, the type of ethylene-methacrylate copolymer used was replaced, namely the ethylene-methacrylate copolymer used in comparative example 5 had a methyl methacrylate content of 2%, a melt index of 2-5g/10min, a melting point of 90-105℃and an environmental stress crack resistance of > 200hr.
Comparative example 6
On the basis of example 1, only the radical absorber zinc pyridine sulfate was removed, and the other components and the process were identical.
Comparative example 7
On the basis of example 1, the irradiation dose was replaced by 7Mrd only, and the other components and processes were identical.
Comparative example 8
On the basis of example 1, the irradiation dose was replaced by 18Mrd only, and the other components and processes were identical.
The shrinkage test was performed on the double-wall heat-shrinkable sleeves prepared in example 1 and comparative example 1 of the present invention, and the results of the obtained heat-shrinkable curves are shown in fig. 1; in addition, the double-wall heat-shrinkable sleeves prepared in comparative examples 1 to 8 of the present invention were subjected to the above-mentioned related performance tests, the test results of which are shown in Table 2 (wherein the leak test is a test of sealing properties of a double-wall tube with 2-by-2 PVC wires).
TABLE 2
In summary, as can be seen from comparative examples 1-3 in table 2, an increase in the ethylene-methacrylate copolymer content reduces the shrinkage rate of the double-wall pipe, and in combination with fig. 1, it can also be seen that an increase in the ethylene-methacrylate copolymer content leads to a significant increase in the temperature at which the sleeve is completely shrunk, and a decrease in the shrinkage rate, while an excessively low ethylene-methacrylate copolymer content in the system leads to cracking during high-temperature shrinkage, which makes the automobile safe and buried with serious hidden trouble; in addition, the removal of the radical absorber from the hot melt adhesive modified masterbatch in comparative example 5 resulted in excessive crosslinking of the hot melt adhesive at a certain irradiation dose, and poor flowability, resulting in poor sealing of the coated strands; moreover, in comparative examples 6-8, it can be seen that too low an irradiation dose would reduce the shrinkage stress of the sheath material sleeve, affect the shrinkage speed, and even fail to press the hot melt adhesive into the gaps of the multi-strand wire bundles to affect the sealability, but too high an irradiation dose would also cause too high crosslinking of the hot melt adhesive to affect the sealing effect.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (9)
1. A heat-shrinkable material, characterized in that the heat-shrinkable material comprises a sheath master batch and a hot melt adhesive modified master batch;
the sheath master batch comprises the following raw materials in parts by weight:
70-90 parts of polyethylene, 10-40 parts of ethylene-methacrylate copolymer, 4-10 parts of ethylene-octene copolymer elastomer, 0.5-3.0 parts of sensitizer, 0.5-1.5 parts of antioxidant and 0.5-2.0 parts of lubricant;
the hot melt adhesive modified master batch comprises the following raw materials in parts by weight:
70-90 parts of ethylene-vinyl acetate copolymer hot melt adhesive, 10-30 parts of polyamide hot melt adhesive, 0.5-1.5 parts of copper inhibitor, 0.2-1.0 parts of free radical absorbent and 0.5-1.5 parts of antioxidant; the free radical absorbent is one or more of ammonium dihydrogen phosphate, zinc pyridine sulfate and lithium carbonate in any proportion;
the content of methyl methacrylate in the ethylene-methacrylate copolymer is 5-25%, the melt index is 0.2-5g/10min, the melting point is 80-100 ℃, and the environmental stress cracking resistance is more than 300hr;
uniformly mixing 70-90 parts of polyethylene, 10-40 parts of ethylene-methacrylate copolymer, 4-10 parts of ethylene-octene copolymer elastomer, 0.5-3.0 parts of sensitizer, 0.5-1.5 parts of antioxidant and 0.5-2.0 parts of lubricant, extruding and granulating to obtain a skin master batch;
uniformly mixing 70-90 parts of ethylene-vinyl acetate copolymer hot melt adhesive, 10-30 parts of polyamide hot melt adhesive, 0.5-1.5 parts of copper inhibitor, 0.2-1.0 parts of free radical absorbent and 0.5-1.5 parts of antioxidant, and granulating under water and drying to obtain hot melt adhesive modified master batch;
and co-extruding the sheath master batch and the hot melt adhesive modified master batch by adopting a double-layer extruder, and performing irradiation crosslinking on the obtained semi-finished product, wherein the irradiation dose is 10-15Mrd, and the semi-finished product is obtained by expanding and cooling and shaping through internal and external pressure difference.
2. The heat shrinkable material of claim 1 wherein the polyethylene is one or both of low density polyethylene and linear low density polyethylene in any ratio, and has a melting pointAt 105-115 deg.C, melt index of 0.2-0.5g/10min, and density of 0.91-0.94g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The melt index of the ethylene octene copolymer elastomer is 0.1-3g/10min, and the density is 0.8-0.95g/cm 3 。
3. The heat-shrinkable material according to claim 1, wherein the sensitizer is one or more of trimethylolpropane trimethacrylate, triallyl isocyanurate, triallyl cyanurate, or a combination thereof in any proportion; the lubricant is one or more of low molecular weight silicone rubber, polyethylene wax, zinc stearate and silicone master batch in any proportion; the low molecular weight silicone rubber is methyl vinyl silicone rubber with molecular weight of 4.5X10 5 -6.0×10 5 The vinyl content is 0.01-0.25%.
4. The heat-shrinkable material according to claim 1, wherein the ethylene-vinyl acetate copolymer hot melt adhesive has a softening point of 90 ℃ to 100 ℃ and a rotational viscosity of 70000 mPa-s to 100000 mPa-s; the softening point of the polyamide hot melt adhesive is 130-150 ℃, and the rotational viscosity is 50000 mPas-70000 mPas.
5. The heat-shrinkable material according to claim 1, wherein the copper-resistant agent is N, N' -bis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionyl ] hydrazine, and the melting point is 210 ℃ to 250 ℃.
6. The heat-shrinkable material according to claim 1, wherein the antioxidant is one or more of stearyl 3, 5-di-t-butyl-4-hydroxyphenyl propionate, pentaerythritol tetrakis [ methyl- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], and 2, 6-di-t-butyl-p-cresol in any proportion.
7. The method of producing a heat shrinkable material according to claim 1, comprising:
uniformly mixing 70-90 parts of polyethylene, 10-40 parts of ethylene-methacrylate copolymer, 4-10 parts of ethylene-octene copolymer elastomer, 0.5-3.0 parts of sensitizer, 0.5-1.5 parts of antioxidant and 0.5-2.0 parts of lubricant, extruding and granulating to obtain a skin master batch;
uniformly mixing 70-90 parts of ethylene-vinyl acetate copolymer hot melt adhesive, 10-30 parts of polyamide hot melt adhesive, 0.5-1.5 parts of copper inhibitor, 0.2-1.0 parts of free radical absorbent and 0.5-1.5 parts of antioxidant, and granulating under water and drying to obtain hot melt adhesive modified master batch;
and co-extruding the sheath master batch and the hot melt adhesive modified master batch by adopting a double-layer extruder, and performing irradiation crosslinking on the obtained semi-finished product, wherein the irradiation dose is 10-15Mrd, and the semi-finished product is obtained by expanding and cooling and shaping through internal and external pressure difference.
8. Use of a heat-shrinkable material according to any of claims 1-6 for the preparation of a double-walled heat-shrinkable sleeve.
9. A double-wall heat-shrinkable sleeve, characterized in that it is produced from the heat-shrinkable material according to any one of claims 1 to 6.
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| CN107973972A (en) * | 2017-12-21 | 2018-05-01 | 上海长园电子材料有限公司 | A kind of puncture-resistant thermal contraction double-walled pipe and preparation method thereof |
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| CN107973972A (en) * | 2017-12-21 | 2018-05-01 | 上海长园电子材料有限公司 | A kind of puncture-resistant thermal contraction double-walled pipe and preparation method thereof |
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