CN104260423A - Outdoor anti-aging dual-wall heat-shrinkable tube and preparation method thereof - Google Patents
Outdoor anti-aging dual-wall heat-shrinkable tube and preparation method thereof Download PDFInfo
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- CN104260423A CN104260423A CN201410537245.8A CN201410537245A CN104260423A CN 104260423 A CN104260423 A CN 104260423A CN 201410537245 A CN201410537245 A CN 201410537245A CN 104260423 A CN104260423 A CN 104260423A
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- 230000003712 anti-aging effect Effects 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 21
- 239000004698 Polyethylene Substances 0.000 claims abstract description 20
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 20
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 16
- 239000003063 flame retardant Substances 0.000 claims abstract description 14
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 13
- 239000004611 light stabiliser Substances 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 7
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 7
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 7
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000314 lubricant Substances 0.000 claims abstract description 5
- 229920000098 polyolefin Polymers 0.000 claims abstract description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 25
- 238000001125 extrusion Methods 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 19
- 238000005469 granulation Methods 0.000 claims description 15
- 230000003179 granulation Effects 0.000 claims description 15
- 229920001577 copolymer Polymers 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- 229920005989 resin Polymers 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 13
- 238000007493 shaping process Methods 0.000 claims description 13
- 239000000155 melt Substances 0.000 claims description 11
- 239000006096 absorbing agent Substances 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- -1 Polyethylene Polymers 0.000 claims description 7
- 238000004132 cross linking Methods 0.000 claims description 7
- 238000005453 pelletization Methods 0.000 claims description 7
- 230000005855 radiation Effects 0.000 claims description 7
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 6
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 claims description 6
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical group [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 6
- 239000003094 microcapsule Substances 0.000 claims description 5
- 229920002379 silicone rubber Polymers 0.000 claims description 5
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- 238000004040 coloring Methods 0.000 claims description 4
- 230000003750 conditioning effect Effects 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004615 ingredient Substances 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 238000004513 sizing Methods 0.000 claims description 2
- 238000009413 insulation Methods 0.000 abstract description 3
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 abstract description 3
- 239000004831 Hot glue Substances 0.000 abstract 3
- 239000000654 additive Substances 0.000 abstract 1
- 239000003086 colorant Substances 0.000 abstract 1
- 239000005038 ethylene vinyl acetate Substances 0.000 abstract 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 13
- 239000002994 raw material Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 9
- 238000011069 regeneration method Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007888 film coating Substances 0.000 description 2
- 238000009501 film coating Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000008821 health effect Effects 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000007789 sealing 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
- B32B1/00—Layered products having a non-planar shape
- B32B1/08—Tubular products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
- B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
-
- 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
-
- 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
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (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
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- 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
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L9/00—Rigid pipes
- F16L9/18—Double-walled pipes; Multi-channel pipes or pipe assemblies
-
- 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
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/206—Insulating
-
- 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
- B32B2307/306—Resistant to heat
-
- 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
- B32B2307/306—Resistant to heat
- B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
-
- 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
- B32B2307/70—Other properties
- B32B2307/71—Resistive to light or to UV
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses an outdoor anti-aging dual-wall heat-shrinkable tube and a preparation method thereof. The dual-wall heat-shrinkable tube comprises a hot melt adhesive located on the inner layer and a heat shrinkage layer which is located on the outer layer and takes polyolefin as a main material. The dual-wall heat-shrinkable tube comprises components in parts by weight as follows: 10-50 parts of the hot melt adhesive, 30-60 parts of a polyethylene and/or ethylene-vinyl acetate copolymer, 10-40 parts of magnesium hydroxide and/or aluminum hydroxide and/or modified magnesium hydroxide and/or MCA (melamine cyanuric acid), 1-30 parts of a flame retardant, 0.1-5 parts of a light stabilizer and/or an ultraviolet absorber and 0-5 parts of additives, namely, an antioxidant, a lubricant, a colorant and a surface treating agent. The dual-wall heat-shrinkable tube has excellent properties such as the flame retardant property, the insulation property, the temperature resistance and the like; meanwhile, the heat shrinkage layer on the outer layer has anti-aging and ultraviolet-resistant functions; the hot melt adhesive on the inner layer has a self-repair function after special treatment; the preparation process is safe and environment-friendly.
Description
Technical field
The present invention relates to Material Field, particularly relate to anti-aging double wall heat Heat-Shrinkable Tubings of a kind of outdoor use and preparation method thereof.
Background technology
Double wall heat Heat-Shrinkable Tubings belongs to the high-end product in heat-shrinkable T bush, the outer crosslinked polyolefin materials adopting high-quality, the composite of a kind of high strength of internal layer PUR Compound Machining.Skin has insulation, the advantage such as anticorrosion, wear-resisting, and internal layer has the advantages such as low melting point, waterproof sealing and mechanical strain shock-absorbing capacity.
When heat-shrinkable T bush is applied to outdoor, double wall heat Heat-Shrinkable Tubings has certain advantage.For solar energy water heater pipe, existing solar energy water heater pipe crust is that employing plastics or stretched film are coated, use double-wall pipe to carry out coated to solar energy water heater pipe, there is the features such as easy to connect, strong adaptability, connection are reliable, good seal, good looking appearance, long service life.But the solar pipe coatings such as sleeve pipe conventional at present or stretched film do not do antiultraviolet pretreatment.And the pipeline connection of solar water heater outside water box uses under the environment that the day and night temperature that exposes to the sun and rain is large.Owing to being long-term used in open-air atmosphere, under being exposed to the large environment of the day and night temperature that exposes to the sun and rain, the a series of problem of easy generation, especially the ultraviolet in sunlight has degraded harmfulness to the solar energy water heater pipe such as conventional cannula or stretched film coating, it is aging that ultraviolet can accelerate heat-shrinkable T bush, shows as double wall heat Heat-Shrinkable Tubings skin material and come off, variable color, become fragile, the final function losing double wall heat Heat-Shrinkable Tubings.On the other hand, the self-regeneration under normal temperature and pressure conditions of the solar pipe such as conventional cannula or stretched film coating is poor, does not have self-regeneration function.
Therefore, develop a kind of anti-aging double wall heat Heat-Shrinkable Tubings being suitable for outdoor use effective utilization of resource is significant.
Summary of the invention
In order to overcome the weak point of the prior art of above-mentioned indication, the invention provides a kind ofly be suitable for that having of outdoor use is anti-aging, anti-ultraviolet function and double wall heat Heat-Shrinkable Tubings of environmental protection and preparation method thereof.
The anti-aging double wall heat Heat-Shrinkable Tubings of a kind of outdoor use, comprising the PUR that is positioned at internal layer and being positioned at outer field take polyolefin as the shrink wrap layer of major ingredient, and the component of described double wall heat Heat-Shrinkable Tubings is counted by weight:
PUR 10-50 part,
Polyethylene and/or vinyl-vinyl acetate copolymer 30-60 part,
Magnesium hydroxide and/or aluminium hydroxide and/or modified magnesium hydroxide and/or melamine lithate (MCA) 10-40 part,
Fire retardant 1-30 part,
Light stabilizer and/or UV absorbers 0.1-5 part,
Auxiliary agent 0-5 part, auxiliary agent is antioxidant, lubricant, colouring agent and surface conditioning agent.
Preferably, described UV absorbers adopts UV absorbers UV531.
The component of described PUR is counted by weight:
EVA vinyl acetate 7-35 part,
Tackifying resin 2-10 part,
PE wax 0.9-4.5 part,
Antioxidant 0.1-0.5 part.
Preferably, described fire retardant is red phosphorus or microcapsule red phosphorus or nitrogenated flame retardant.
In the present invention, preferably, described antioxidant is hindered phenol type antioxidant, especially can adopt antioxidant 1010, and lubricant is zinc stearate, and colouring agent is Masterbatch or toner, and surface conditioning agent is silicon rubber.
Preferably, the melt index of described vinyl-vinyl acetate copolymer is 1 ~ 5g/10min (190 DEG C), the weight content 17% ~ 20% of vinyl acetate.
The invention also discloses the preparation method of the anti-aging double wall heat Heat-Shrinkable Tubings of a kind of above-mentioned outdoor use, comprise the following steps:
S1, add in the airtight banbury run up by the auxiliary agent of the fire retardant of the magnesium hydroxide of the polyethylene of 30-60 weight portion and/or vinyl-vinyl acetate copolymer, 10-40 weight portion and/or aluminium hydroxide and/or modified magnesium hydroxide and/or melamine lithate (MCA), 1-30 weight portion, 0.1-5 weight portion light stabilizer and/or UV absorbers UV531,0-5 weight portion, prilling temperature controls within the scope of 95-150 DEG C;
S2, the mixture banbury in step S1 is mixing and after granulation at 100-140 DEG C, drop in single screw extrusion machine, extrude at 100-150 DEG C, pelletizing, air-cooled shaping;
S3, the material grain obtained in step S2 is become double wall casing with co-extrusion after PUR respectively melting, extrusion temperature controls within the scope of 85-150 DEG C;
S4, carry out radiation crosslinking modified by high-energy electron accelerator to the PUR of internal layer and outer field shrink wrap layer, by expansion device, double-wall pipe sizing is expanded.
Preferably, in step s 2, the mixture in banbury granulation process stands up number of times and controls at 3-8 time, and temperature controls within the scope of 95-150 DEG C.
Preferably, the thickness of extruding of the PUR of described internal layer is 0.01-5.0mm, and the thickness of extruding of outer field shrink wrap layer is 0.01-5.0mm.
Preferably, in step s 4 which, irradiation dose 5Mrad-20Mrad, hot extension value controls within the scope of 100-300%.
Compared with prior art, outdoor use of the present invention anti-aging double wall heat Heat-Shrinkable Tubings has the performances such as excellent fire-retardant, insulation, heatproof, outer shrink wrap layer with the addition of light stabilizer simultaneously, adopt with the airtight mixer mixing granulation run up, make outer shrink wrap layer have anti-aging, anti-ultraviolet function; On the other hand, the PUR of internal layer, through specially treated, has self-regeneration function, effectively improves service life, and is suitable for the double wall heat Heat-Shrinkable Tubings of outdoor use; Be cross-linked through electron accelerator irradiation after the extrusion molding of double wall heat Heat-Shrinkable Tubings raw material, replace Chemical Crosslinking Methods, effectively to avoid in operating process security incident to occur, and product environmental protection discarded after to human residential environment and Human health effects little; The cost of raw material is not high, is applicable to suitability for industrialized production.
Detailed description of the invention
For the ease of the understanding of those skilled in the art, below in conjunction with embodiment, the invention will be further described.
Embodiment one
First, the shrink wrap layer raw material of row parts by weight is taken off:
Polyethylene 30 parts,
Magnesium hydroxide 10 parts,
1 part, red phosphorus,
Light stabilizer 0.1 part,
Antioxidant 1010 0.5 part,
Zinc stearate 1 part,
Masterbatch 2 parts,
0.4 part, silicon rubber.
Added by said mixture in the airtight banbury run up mixing, temperature controls within the scope of 100-140 DEG C.Preferably, the mixture in banbury granulation process stands up number of times and controls at 3-8 time, and temperature controls within the scope of 95-150 DEG C, and each component disperses of material is good, and uniformity coefficient is high.The mixing mixture single screw extrusion machine obtained is extruded at 100-150 DEG C, pelletizing, air-cooled shaping, obtain the outer shrink wrap layer of double wall heat Heat-Shrinkable Tubings.
The second, take off the PUR raw material of row parts by weight:
EVA vinyl acetate 7 parts,
Tackifying resin 2 parts,
0.9 part, PE wax,
0.1 part, antioxidant;
First PE wax is melted, then adds EVA vinyl acetate, when EVA vinyl acetate melts substantially, add tackifying resin gradually, react 0.5-1.5h at 130-180 DEG C after, add antioxidant, then react 0.5-1h discharging, shaping, granulation and PUR.It can significantly reduce PUR cost; Improve product viscosity and softening point; Increase product adhesive strength, be easily uniformly dispersed.As double-wall pipe internal layer thermosol, there is self-regeneration function, be beneficial to and improve double-wall pipe mechanical property.
Then, material grain above-mentioned steps obtained becomes double wall casing with co-extrusion after PUR respectively melting, and extrusion temperature controls within the scope of 85-150 DEG C; The thickness of extruding of the PUR of described internal layer is 0.01-5.0mm, and the thickness of extruding of outer field shrink wrap layer is 0.01-5.0mm.
Finally, carry out cross-linking radiation, irradiation dose 5Mrad-20Mrad by high-energy electron accelerator to the PUR of internal layer and outer field shrink wrap layer, hot extension value controls within the scope of 100-300%; And by heating, internal diameter is expanded, obtain double wall heat Heat-Shrinkable Tubings.
Embodiment two
First, the shrink wrap layer raw material of row parts by weight is taken off:
Vinyl-vinyl acetate copolymer 35 parts,
20 parts, aluminium hydroxide,
Microcapsule red phosphorus 10 parts,
Light stabilizer 1 part,
Antioxidant 1010 1 part,
Zinc stearate 1.5 parts,
Masterbatch 1.5 parts,
1 part, silicon rubber;
Wherein
,the melt index of described vinyl-vinyl acetate copolymer is 1 ~ 5g/10min (190 DEG C), the weight content 17% ~ 20% of vinyl acetate.
Added by said mixture in the airtight banbury run up mixing, temperature controls within the scope of 100-140 DEG C.Preferably, the mixture in banbury granulation process stands up number of times and controls at 3-8 time, and temperature controls within the scope of 95-150 DEG C, and each component disperses of material is good, and uniformity coefficient is high.The mixing mixture single screw extrusion machine obtained is extruded at 100-150 DEG C, pelletizing, air-cooled shaping, obtain the outer shrink wrap layer of double wall heat Heat-Shrinkable Tubings.
The second, take off the PUR raw material of row parts by weight:
EVA vinyl acetate 21 parts,
Tackifying resin 6 parts,
2.7 parts, PE wax,
0.3 part, antioxidant;
First PE wax is melted, then adds EVA vinyl acetate, when EVA vinyl acetate melts substantially, add tackifying resin gradually, react 0.5-1.5h at 130-180 DEG C after, add antioxidant, then react 0.5-1h discharging, shaping, granulation and PUR.It can significantly reduce PUR cost; Improve product viscosity and softening point; Increase product adhesive strength, be easily uniformly dispersed.As double-wall pipe internal layer thermosol, there is self-regeneration function, be beneficial to and improve double-wall pipe mechanical property.
Then, material grain above-mentioned steps obtained becomes double wall casing with co-extrusion after PUR respectively melting, and extrusion temperature controls within the scope of 85-150 DEG C; The thickness of extruding of the PUR of described internal layer is 0.01-5.0mm, and the thickness of extruding of outer field shrink wrap layer is 0.01-5.0mm.
Finally, carry out cross-linking radiation, irradiation dose 5Mrad-20Mrad by high-energy electron accelerator to the PUR of internal layer and outer field shrink wrap layer, hot extension value controls within the scope of 100-300%; And by heating, internal diameter is expanded, obtain double wall heat Heat-Shrinkable Tubings.
Embodiment three
First, the shrink wrap layer raw material of row parts by weight is taken off:
Vinyl-vinyl acetate copolymer 40 parts,
Magnesium hydroxide 25 parts,
Microcapsule red phosphorus 10 parts,
Light stabilizer 5 parts,
Antioxidant 1010 1.5 parts,
Zinc stearate 0.5 part,
Masterbatch 2 parts,
1 part, silicon rubber;
Wherein, the melt index of described vinyl-vinyl acetate copolymer is 1 ~ 5g/10min (190 DEG C), the weight content 17% ~ 20% of vinyl acetate.
Added by said mixture in the airtight banbury run up mixing, temperature controls within the scope of 100-140 DEG C.Preferably, the mixture in banbury granulation process stands up number of times and controls at 3-8 time, and temperature controls within the scope of 95-150 DEG C, and each component disperses of material is good, and uniformity coefficient is high.The mixing mixture single screw extrusion machine obtained is extruded at 100-150 DEG C, pelletizing, air-cooled shaping, obtain the outer shrink wrap layer of double wall heat Heat-Shrinkable Tubings.
The second, take off the PUR raw material of row parts by weight:
EVA vinyl acetate 28 parts,
Tackifying resin 8 parts,
3.6 parts, PE wax,
0.4 part, antioxidant;
First PE wax is melted, then adds EVA vinyl acetate, when EVA vinyl acetate melts substantially, add tackifying resin gradually, react 0.5-1.5h at 130-180 DEG C after, add antioxidant, then react 0.5-1h discharging, shaping, granulation and PUR.It can significantly reduce PUR cost; Improve product viscosity and softening point; Increase product adhesive strength, be easily uniformly dispersed.As double-wall pipe internal layer thermosol, there is self-regeneration function, be beneficial to and improve double-wall pipe mechanical property.
Then, material grain above-mentioned steps obtained becomes double wall casing with co-extrusion after PUR respectively melting, and extrusion temperature controls within the scope of 85-150 DEG C; The thickness of extruding of the PUR of described internal layer is 0.01-3.0mm, and the thickness of extruding of outer field shrink wrap layer is 0.01-3.0mm.
Finally, carry out cross-linking radiation, irradiation dose 5Mrad-20Mrad by high-energy electron accelerator to the PUR of internal layer and outer field shrink wrap layer, hot extension value controls within the scope of 100-300%; And by heating, internal diameter is expanded, obtain double wall heat Heat-Shrinkable Tubings.
Embodiment four
First, the shrink wrap layer raw material of row parts by weight is taken off:
Vinyl-vinyl acetate copolymer 50 parts,
Modified magnesium hydroxide 40 parts,
Microcapsule red phosphorus 5 parts,
UV absorbers UV531 1 part;
Wherein, the melt index of described vinyl-vinyl acetate copolymer is 1 ~ 5g/10min (190 DEG C), the weight content 17% ~ 20% of vinyl acetate.
Added by said mixture in the airtight banbury run up mixing, temperature controls within the scope of 100-140 DEG C.Preferably, the mixture in banbury granulation process stands up number of times and controls at 3-8 time, and temperature controls within the scope of 95-150 DEG C, and each component disperses of material is good, and uniformity coefficient is high.The mixing mixture single screw extrusion machine obtained is extruded at 100-150 DEG C, pelletizing, air-cooled shaping, obtain the outer shrink wrap layer of double wall heat Heat-Shrinkable Tubings.
The second, take off the PUR raw material of row parts by weight:
EVA vinyl acetate 28 parts,
Tackifying resin 7 parts,
4.6 parts, PE wax,
0.4 part, antioxidant;
First PE wax is melted, then adds EVA vinyl acetate, when EVA vinyl acetate melts substantially, add tackifying resin gradually, react 0.5-1.5h at 130-180 DEG C after, add antioxidant, then react 0.5-1h discharging, shaping, granulation and PUR.It can significantly reduce PUR cost; Improve product viscosity and softening point; Increase product adhesive strength, be easily uniformly dispersed.As double-wall pipe internal layer thermosol, there is self-regeneration function, be beneficial to and improve double-wall pipe mechanical property.
Then, material grain above-mentioned steps obtained becomes double wall casing with co-extrusion after PUR respectively melting, and extrusion temperature controls within the scope of 85-150 DEG C; The thickness of extruding of the PUR of described internal layer is 0.01-3.0mm, and the thickness of extruding of outer field shrink wrap layer is 0.01-3.0mm.
Finally, carry out cross-linking radiation, irradiation dose 5Mrad-20Mrad by high-energy electron accelerator to the PUR of internal layer and outer field shrink wrap layer, hot extension value controls within the scope of 100-300%; And by heating, internal diameter is expanded, obtain double wall heat Heat-Shrinkable Tubings.
Embodiment five
First, the shrink wrap layer raw material of row parts by weight is taken off:
Polyethylene and vinyl-vinyl acetate copolymer 60 parts,
20 parts, aluminium hydroxide,
MCA fire retardant (melamine cyanurate) 40 parts
,
UV absorbers UV531 5 parts,
Antioxidant 1010 0.5 part,
Zinc stearate 0.5 part,
Masterbatch 3 parts,
Silicone 0.1 part;
Wherein, the melt index of described vinyl-vinyl acetate copolymer is 1 ~ 5g/10min (190 DEG C), the weight content 17% ~ 20% of vinyl acetate.
Added by said mixture in the airtight banbury run up mixing, temperature controls within the scope of 100-140 DEG C.Preferably, the mixture in banbury granulation process stands up number of times and controls at 3-8 time, and temperature controls within the scope of 95-150 DEG C, and each component disperses of material is good, and uniformity coefficient is high.The mixing mixture single screw extrusion machine obtained is extruded at 100-150 DEG C, pelletizing, air-cooled shaping, obtain the outer shrink wrap layer of double wall heat Heat-Shrinkable Tubings.
The second, take off the PUR raw material of row parts by weight:
EVA vinyl acetate 35 parts,
Tackifying resin 10 parts,
4.5 parts, PE wax,
0.5 part, antioxidant;
First PE wax is melted, then adds EVA vinyl acetate, when EVA vinyl acetate melts substantially, add tackifying resin gradually, react 0.5-1.5h at 130-180 DEG C after, add antioxidant, then react 0.5-1h discharging, shaping, granulation and PUR.It can significantly reduce PUR cost; Improve product viscosity and softening point; Increase product adhesive strength, be easily uniformly dispersed.As double-wall pipe internal layer thermosol, there is self-regeneration function, be beneficial to and improve double-wall pipe mechanical property.
Then, material grain above-mentioned steps obtained becomes double wall casing with co-extrusion after PUR respectively melting, and extrusion temperature controls within the scope of 85-150 DEG C; The thickness of extruding of the PUR of described internal layer is 0.01-3.0mm, and the thickness of extruding of outer field shrink wrap layer is 0.01-3.0mm.
Finally, carry out cross-linking radiation, irradiation dose 5Mrad-20Mrad by high-energy electron accelerator to the PUR of internal layer and outer field shrink wrap layer, hot extension value controls within the scope of 100-300%; And by heating, internal diameter is expanded, obtain double wall heat Heat-Shrinkable Tubings.
Double wall heat Heat-Shrinkable Tubings of the present invention is suitable for outdoor use, and use red phosphorus or micro-red phosphorus capsule as fire retardant, good flame retardation effect, sleeve pipe flame retardant rating reaches U.S. military project UL224 VW-1 standard; Not containing halogen, hydrogen halide and smog is not produced during product burning, human residential environment is affected little, meet European Union ROHS 2.0, meet European Union REACH environment protection control requirements, in outer shrink wrap layer, add light stabilizer, product can be adapted to expose to the sun and rain the large environment for use of day and night temperature, have anti-aging, prevention crust come off, variable color, the function that becomes fragile; Internal layer PUR, through becoming privileged process, has self-regeneration function.
Above content is in conjunction with concrete preferred embodiment further description made for the present invention, should not assert that specific embodiment of the invention is confined to above explanation.For those skilled in the art, without departing from the inventive concept of the premise, some simple deduction or replace can also be made, within the protection domain that the claim that all should be considered as being submitted to by the present invention is determined.
Claims (10)
1. the anti-aging double wall heat Heat-Shrinkable Tubings of outdoor use, comprising the PUR that is positioned at internal layer and being positioned at outer field take polyolefin as the shrink wrap layer of major ingredient, and the component of described double wall heat Heat-Shrinkable Tubings is counted by weight:
PUR 10-50 part,
Polyethylene and/or vinyl-vinyl acetate copolymer 30-60 part,
Magnesium hydroxide and/or aluminium hydroxide and/or modified magnesium hydroxide and/or melamine lithate (MCA) 10-40 part,
Fire retardant 1-30 part,
Light stabilizer and/or UV absorbers 0.1-5 part,
Auxiliary agent 0-5 part, auxiliary agent is antioxidant, lubricant, colouring agent and surface conditioning agent.
2. double wall heat Heat-Shrinkable Tubings according to claim 1, is characterized in that: described UV absorbers adopts UV absorbers UV531.
3. double wall heat Heat-Shrinkable Tubings according to claim 1, is characterized in that, the component of described PUR is counted by weight:
EVA vinyl acetate 7-35 part,
Tackifying resin 2-10 part,
PE wax 0.9-4.5 part,
Antioxidant 0.1-0.5 part.
4. double wall heat Heat-Shrinkable Tubings according to claim 1, is characterized in that: described fire retardant is red phosphorus or microcapsule red phosphorus or nitrogenated flame retardant.
5. double wall heat Heat-Shrinkable Tubings according to claim 1, is characterized in that: described antioxidant is 1010 antioxidant, and lubricant is zinc stearate, and colouring agent is Masterbatch or toner, and surface conditioning agent is silicon rubber or silicone.
6. double wall heat Heat-Shrinkable Tubings according to claim 1, is characterized in that: the weight content 17 ~ 20% of the vinyl acetate of described vinyl-vinyl acetate copolymer, and melt index is 1 ~ 5g/10min (190 DEG C)
.
7. a preparation method for the double wall heat Heat-Shrinkable Tubings according to any one of claim 1-6, is characterized in that, comprise the following steps:
S1, the auxiliary agent of the fire retardant of the magnesium hydroxide of the polyethylene of 30-60 weight portion and/or vinyl-vinyl acetate copolymer, 10-40 weight portion and/or aluminium hydroxide and/or modified magnesium hydroxide and/or melamine lithate (MCA), 1-30 weight portion, 0.1-5 weight portion light stabilizer and/or UV absorbers UV531,0-5 weight portion is added in the airtight banbury run up;
S2, the mixture banbury in step S1 is mixing and after granulation at 100-140 DEG C, drop in single screw extrusion machine, extrude at 100-150 DEG C, pelletizing, air-cooled shaping;
S3, the material grain obtained in step S2 is become double wall casing with co-extrusion after PUR respectively melting, extrusion temperature controls within the scope of 85-150 DEG C;
S4, carry out radiation crosslinking modified by high-energy electron accelerator to the PUR of internal layer and outer field shrink wrap layer, by expansion device, double-wall pipe sizing is expanded.
8. the preparation method of double wall heat Heat-Shrinkable Tubings according to claim 7, it is characterized in that: the PUR in described step S3 obtains through following step: PE wax is melted, add EVA vinyl acetate, tackifying resin is added again when EVA vinyl acetate melts, after said mixture reacts 0.5-1.5h at 130-180 DEG C, add antioxidant, through reaction 0.5-1h discharging, shaping, granulation and PUR.
9. the preparation method of double wall heat Heat-Shrinkable Tubings according to claim 7, is characterized in that: the thickness of extruding of the PUR of described internal layer is 0.01-5.0mm, and the thickness of extruding of outer field shrink wrap layer is 0.01-5.0mm.
10. the preparation method of double wall heat Heat-Shrinkable Tubings according to claim 7, is characterized in that: in step s 4 which, irradiation dose 5Mrad-20Mrad, and hot extension value controls within the scope of 100-300%.
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| CN104844889A (en) * | 2015-04-01 | 2015-08-19 | 无锡龙舜实业有限公司 | Double-wall heat-shrinkable tube |
| CN104845401A (en) * | 2015-05-06 | 2015-08-19 | 无锡龙舜实业有限公司 | Manufacturing process of dual wall heat-shrinkable tube |
| CN105038613A (en) * | 2015-07-31 | 2015-11-11 | 全椒海丰印刷包装有限公司 | Flame-retardant hot melt adhesive comprising red phosphorus |
| CN105885201A (en) * | 2016-06-15 | 2016-08-24 | 邱光南 | Self-repairing waterproof sealing double-wall pipe capable of achieving high-rate shrinkage |
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| CN104844889A (en) * | 2015-04-01 | 2015-08-19 | 无锡龙舜实业有限公司 | Double-wall heat-shrinkable tube |
| CN104845401A (en) * | 2015-05-06 | 2015-08-19 | 无锡龙舜实业有限公司 | Manufacturing process of dual wall heat-shrinkable tube |
| CN105038613A (en) * | 2015-07-31 | 2015-11-11 | 全椒海丰印刷包装有限公司 | Flame-retardant hot melt adhesive comprising red phosphorus |
| CN107501697A (en) * | 2016-06-14 | 2017-12-22 | 上海长园电子材料有限公司 | It is easy to long-term formula of thermal contraction double-walled pipe for storing and transporting and preparation method thereof |
| CN105885201A (en) * | 2016-06-15 | 2016-08-24 | 邱光南 | Self-repairing waterproof sealing double-wall pipe capable of achieving high-rate shrinkage |
| CN105885201B (en) * | 2016-06-15 | 2018-05-25 | 邱光南 | High magnification shrinks selfreparing waterproof sealing double-wall pipe |
| CN106221600A (en) * | 2016-08-17 | 2016-12-14 | 安徽兴源塑料包装有限公司 | A kind of thermal contraction gum cover |
| CN106318248A (en) * | 2016-08-17 | 2017-01-11 | 安徽兴源塑料包装有限公司 | Corrosion-resistant heat shrinkage rubber sleeve |
| CN106318259A (en) * | 2016-08-31 | 2017-01-11 | 安徽中科自动化股份有限公司 | Heat-shrinkable plastic sticker |
| CN108017825A (en) * | 2017-12-27 | 2018-05-11 | 上海长园电子材料有限公司 | A kind of ultra-thin high power shrinks heat-shrinkable T bush and preparation method thereof |
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Application publication date: 20150107 |