CN103642118B - Tube wall bubble-tight irradiation crosslinking halogen-free fire proofing and application during heat shrinkable - Google Patents
Tube wall bubble-tight irradiation crosslinking halogen-free fire proofing and application during heat shrinkable Download PDFInfo
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- CN103642118B CN103642118B CN201310709456.0A CN201310709456A CN103642118B CN 103642118 B CN103642118 B CN 103642118B CN 201310709456 A CN201310709456 A CN 201310709456A CN 103642118 B CN103642118 B CN 103642118B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
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- 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
- B29C61/00—Shaping by liberation of internal stresses; Making preforms having internal stresses; Apparatus therefor
- B29C61/02—Thermal shrinking
- B29C61/025—Thermal shrinking for the production of hollow or tubular articles
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- 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
- B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
- B29C71/04—After-treatment of articles without altering their shape; Apparatus therefor by wave energy or particle radiation, e.g. for curing or vulcanising preformed articles
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- 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
- F16L11/00—Hoses, i.e. flexible pipes
- F16L11/20—Double-walled hoses, i.e. two concentric hoses
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- 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
- F16L57/00—Protection of pipes or objects of similar shape against external or internal damage or wear
- F16L57/04—Protection of pipes or objects of similar shape against external or internal damage or wear against fire or other external sources of extreme heat
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- 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
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- 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
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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- 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
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- 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
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- 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
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Abstract
Tube wall bubble-tight irradiation crosslinking halogen-free fire proofing during the present invention open a kind of heat shrinkable, including: ethylene vinyl acetate copolymer 10 100 weight portion；Organosilicon polymer 0.5 10 weight portion；Antioxidant 0.1 10 weight portion；Wrapped up Phosphorus Fire Retardant 0.1 50 weight portion；Aluminium hydroxide and/or magnesium hydroxide and/or modified aluminium hydroxide and/or modified magnesium hydroxide 1 150 weight portion；High molecular APP (APP) 0 50 weight portion and/or phosphate ester flame retardants 0 50 weight portion and/or MCA (MCA) 0 50 weight portion and/or phosphinates 0 50 weight portion；Carbonate and/or phosphate and/or phosphide and/or calcinated argil and/or Kaolin and/or clay 0.1 100 weight portion.The present invention can be used for heat-shrinkable T bush etc., and flame retardant rating reaches U.S.'s UL224 VW 1 standard and without halogen.
Description
Technical field
The present invention relates to a kind of halogen-free flame-proof environmental protection material and application thereof, particularly relate to tube wall bubble-tight irradiation crosslinking halogen-free fire proofing and application during a kind of heat shrinkable.
Background technology
As far back as the seventies in last century, in succession develop various fire proofing both at home and abroad, but these fire proofing overwhelming majority are all halogen-containing, although there being certain flame retardant effect, but when fire occurs, the halogen-containing fire proofing of burning can produce toxic gas and smog, and this not only affects being smoothed out of disaster relief work, and lives and properties cause " disaster for the second time ".
Minority bittern-free flame-proof material then uses red phosphorus combustion inhibitor, red phosphorus combustion inhibitor shares with organophosphor nitrogen combustion inhibitor and aluminium hydroxide, magnesium hydroxide, there is good flame resistance, the advantage that consumption is few, cheap, material containing red phosphorus combustion inhibitor is when burning, although the amount of being fuming is more much smaller than halogen flame, toxicity is also much smaller than halogen flame, there is the problem that amount of smoke is big.
Aluminium hydroxide and magnesium hydroxide are a kind of filled-type fire retardants, discharge during by decomposes and combine water, absorb substantial amounts of latent heat, reduce synthetic material that it the is filled surface temperature in flame, there is the effect that suppression polymer decomposes and cools down produced fuel gas, decomposing the aluminium oxide generated and magnesium oxide is again good refractory material, also can help to improve the fire resistance of synthetic material, the steam that it is released simultaneously also can be as a kind of smoke suppressant.But aluminium hydroxide dehydration temperature is about 300 DEG C, the magnesium hydroxide decomposition temperature when being heated is 340-490 DEG C, when using aluminium hydroxide or magnesium hydroxide as the fire retardant of material contracting with heat, when shrinkage temperature when shrinking by spray gun or baking oven for heating is higher than the decomposition temperature of aluminium hydroxide or magnesium hydroxide, easily produce gas due to the decomposition of fire retardant, cannot discharge inside insulant owing to fire retardant decomposes the gas produced, last result is that insulant is being heated, when particularly high-temperature hot is shunk, the tube wall of insulant plays steep raising and rises, serious in cellular, lose insulating protection performance.
Therefore, tube wall bubble-tight bittern-free flame-proof material when developing a kind of environment amenable heat shrinkable, flame retardant rating can reach U.S. UL224 VW-1 and be very important.
Summary of the invention
The irradiation cross-linking flame-retardant material of tube wall bubble-tight low smoke and zero halogen when it is an object of the invention to provide a kind of heat shrinkable.
For achieving the above object, tube wall bubble-tight irradiation crosslinking halogen-free fire proofing during heat shrinkable provided by the present invention, including following compositions:
Vinyl-vinyl acetate copolymer 10-100 weight portion；
Ethylene-octene copolymer and/or ethylene-butene copolymer 0-30 weight portion；
Ethylene propylene monomer and/or ethylene propylene diene rubber and/or butadiene rubber and/or butadiene-styrene rubber 0-50 weight portion；
Polyethylene 0-30 weight portion；
Its Compatibilizing Technology 0-20 weight portion；
Organosilicon polymer 0.5-10 weight portion；
Wrapped up Phosphorus Fire Retardant 0.1-50 weight portion；
Antioxidant 0.1-10 weight portion；
Aluminium hydroxide and/or magnesium hydroxide and/or modified aluminium hydroxide and/or modified magnesium hydroxide 1-150 weight portion；
High molecular APP (APP) and/or phosphate ester flame retardants and/or MCA (MCA) 0.1-50 weight portion and/or melamine pyrophosphate (MPP) and/or phosphinates 0.1-50 weight portion;
Carbonate and/or phosphate and/or phosphide and/or calcinated argil and/or Kaolin and/or clay 0.1-100 weight portion；
Sensitizer 0-3 weight portion；
Lubricant 0-3 weight portion；
Color masterbatch 0-20 weight portion.
Preferably, described sensitizer is trimethylolpropane tris (methyl) acrylate or trimethylolpropane trimethacrylate or tetramethylol methane tetraacrylate or triallyl isocyanate or 1,3 butylene glycol dimethylacrylate.
Preferably, in described vinyl-vinyl acetate copolymer, the content of vinyl acetate accounts for 10-40% weight, and melt index is 0.5-6.0g/10min(190 DEG C).
Preferably, in described ethylene-octene copolymer, octene content accounts for 0-30% weight, and melt index is 0.5-5.0g/10min(190 DEG C).
Preferably, in described ethylene-butene copolymer, butene content accounts for 0-30% weight, and melt index is 0.5-5.0g/10min(190 DEG C).
Preferably, described polyethylene melt index is 0.5-6.0g/10min(190 DEG C).
Preferably, described Its Compatibilizing Technology be copolymer-maleic anhydride ethene improved-vinyl acetate copolymer or copolymer-maleic anhydride ethene improved-acrylate copolymer, copolymer level accounts for 0.5-15%, and melt index is 0.5-15.0g/10min(190 DEG C).
Preferably, the one or several during described organosilicon polymer is polydimethylsiloxane or silicone rubber or organic silicon fibre retardant.
Described carbonate is the one or several in magnesium carbonate, basic magnesium carbonate or calcium carbonate etc..
Described phosphate is the one in zinc phosphate or aluminum phosphate etc. or several.
Described phosphide is boron phosphide etc..
The mean diameter of described carbonate and/or phosphate and/or phosphide and/or calcinated argil and/or Kaolin and/or clay is less than 50 μm.
During heat shrinkable of the present invention, tube wall bubble-tight irradiation crosslinking halogen-free flame-retardant master batch can produce heat-shrinkable T bush or bus-bar protective sleeve, heat-shrink cable accessory, double-wall pipe, middle thick-walled pipe, is applied to heat-shrinkable T bush flame retardant rating and can reach U.S. UL224
VW-1 standard and without halogen and red phosphorus, environmentally friendly.
When as the raw material of heat-shrinkable T bush, during this heat shrinkable, tube wall bubble-tight cross-linking radiation environmental protection flame retardant heat-shrinkable T bush is made up of the bubble-tight irradiation crosslinking halogen-free fire proofing of tube wall during above-mentioned heat shrinkable, and its preparation method is:
First by the ethylene-ethyl acetate copolymer of 10～100 weight portions, 0～30 weight portion ethylene-octene copolymer and/or ethylene-butene copolymer, the ethylene propylene monomer of 0-50 weight portion and/or ethylene propylene diene rubber and/or butadiene rubber and/or butadiene-styrene rubber, the polyethylene of 0-100 weight portion, 0～20 parts by weight polymer compatilizers, 0.5～10 organosilicon polymer, 0.1～10 antioxidant of weight portion of weight portion, the Wrapped up Phosphorus Fire Retardant of 0.1-50 weight portion；The aluminium hydroxide of 1～150 weight portions and/or magnesium hydroxide and/or modified aluminium hydroxide and/or modified magnesium hydroxide flame retardant agent, the high molecular APP (APP) of 0-50 weight portion and/or phosphate ester flame retardants and/or MCA (MCA) and/or phosphinates;The carbonate of 0.1-100 weight portion and/or phosphate and/or phosphide and/or calcinated argil and/or Kaolin and/or clay, 0.1～3 lubricant, 0～3 sensitizers of weight portion of weight portion, the color masterbatch of 0-20 weight portion add in homogenizer, high-speed stirred 5-10 minute, temperature of charge controls in the range of 20 DEG C ~ 80 DEG C；
Then said mixture screw extruder is extruded at a temperature of 100-160 DEG C, wire drawing, air-cooled pelletizing；Also by said mixture banbury, hot cut pellet at a temperature of 100-160 DEG C；
Again by the pellet after above-mentioned pelletizing, at a temperature of 100-160 DEG C, extrude sleeve pipe by Screw Extrusion；
Then being 4-20Mrad by above-mentioned material through electron accelerator or cobalt-60 radiosterilize, irradiation dose, the sleeve pipe after irradiation expands 1-3 times with expansion device at a temperature of 100-180 DEG C；
Last cooling and shaping, obtains tube wall bubble-tight irradiation crosslinking halogen-free fire retardant thermal shrinkage sleeve pipe during heat shrinkable.
The present invention compared with prior art has the advantage that and effect:
(1) during heat shrinkable of the present invention, tube wall bubble-tight irradiation crosslinking halogen-free fire proofing has excellent flame retardant effect, and flame retardant rating can reach U.S. UL224
VW-1 flame retardant rating.Not halogen-containing flame retardant, it is to avoid tradition irradiation cross-linking flame-retardant material Han halogen when fire occurs, the halogen-containing material poisonous hydrogen halide of generation and smog, " secondary disaster " that lives and properties are caused during burning；
(2) tube wall bubble-tight irradiation crosslinking halogen-free fire proofing during heat shrinkable of the present invention, product does not produce poisonous flue gas when burning, efficiently solves magnesium hydroxide and problem that aluminium hydroxide fire retardant exists poor fire；It addition, the consumption of magnesium hydroxide fire proofing in the middle of and aluminium hydroxide is greatly reduced, when material contracting with heat heat shrinkable, tube wall is non-foaming, will not be formed at tube wall cellular, will not reduce the insulating properties of insulant.
(3) tube wall bubble-tight irradiation crosslinking halogen-free fire proofing during heat shrinkable of the present invention, when burning, the amount of being fuming is more much smaller than halogen flame, toxicity is also much smaller than halogen flame, owing to using Wrapped up Phosphorus Fire Retardant, being difficult to moisture absorption hydrolysis, safety is greatly improved.
(4) during heat shrinkable of the present invention, tube wall bubble-tight irradiation crosslinking halogen-free fire proofing is a kind of environmental protection close friend's product, materials processing, use, discarded after the least on the impact of ecological environment and human health；
(5) tube wall bubble-tight irradiation crosslinking halogen-free fire proofing of many uses during heat shrinkable of the present invention, may be used for preparing various thermal contraction components and parts, there is excellent fire-retardant, insulation, heat resistance, soft flexible, the field that the environmental requirements such as subway, aviation, electron trade, skyscraper, communal facility are strict can be widely used for；
(6) during heat shrinkable of the present invention, the preparation method of tube wall bubble-tight irradiation crosslinking halogen-free fire proofing is simple, and raw material is easy to get, cheap, it is adaptable to industrialized production.
Detailed description of the invention
By describing the technology contents of the present invention in detail, being realized purpose and effect, it is explained in detail below in conjunction with embodiment.
Irradiation crosslinking halogen-free fire proofing of the present invention can be as the raw material of heat-shrinkable T bush, and it is illustrated by embodiment 1, embodiment 2, embodiment 3, embodiment 4.
Embodiment 1
nullBy vinyl-vinyl acetate copolymer (EVA) 75 weight portion (wherein，The content of vinyl acetate accounts for 18% weight，Melt index is 3.0g/10min)、Ethylene-octene copolymer (POE) 10 weight portion is (wherein，The content of octene accounts for 20% weight，Melt index is 2.0g/10min)、Polyethylene 10 weight portion，Maleic anhydride modified vinyl-vinyl acetate copolymer 5 weight portion of Its Compatibilizing Technology is (wherein，The content of copolymer accounts for 8% weight，Melt index is 5.0g/10min)、Polydimethylsiloxane 3 weight portion、Flame retardant of magnesium hydroxide 15 weight portion、Wrapped up Phosphorus Fire Retardant 20 weight portion、Basic magnesium carbonate 45 weight portion,Antioxidant 3 weight portion、Lubricant stearic acid zinc 2 weight portion、Sensitizer trimethylolpropane trimethacrylate TMPTA
2 weight portions, color masterbatch 5 weight portion are sequentially added in homogenizer, high-speed stirred 5-10 minute, and temperature of charge controls in the range of 80 DEG C；Then said mixture double screw extruder is extruded at a temperature of 100-160 DEG C, wire drawing, air-cooled pelletizing；Again by the pellet after above-mentioned pelletizing, extruding sleeve pipe by Single screw extrusion at a temperature of 100-160 DEG C, then by above-mentioned material through electron accelerator irradiation or cobalt-60 radiosterilize, irradiation dose is 4-20Mrad；After sleeve pipe after irradiation expands 1-3 times with expansion device at a temperature of 100-180 DEG C, then cooling and shaping, finally obtain irradiation crosslinking halogen-free fire retardant thermal shrinkage sleeve pipe.
Being measured above-mentioned heat-shrinkable T bush product, result is as follows: shrinkage ratio is more than 2:1；Anti-flammability oxygen index (OI) ＞ 33, flame retardant rating UL224
VW-1；Use temperature range-55～125 DEG C；Hot strength >=10.4MPa；Elongation at break >=200%；Insulation voltage: 2500V, does not punctures；Thermal shock: 250 DEG C, 4 hours, flawless；Specific insulation >=1014Ω.cm;Environmental-protecting performance meets European Union's RoHS environmental protection standard and European Union REACH instruction, without halogen；During heat-shrink tube heat shrinkable, tube wall is non-foaming.
Embodiment 2
nullBy vinyl-vinyl acetate copolymer (EVA) 50 weight portion (wherein，The content of vinyl acetate accounts for 14% weight，Melt index is 2.0g/10min)、Ethylene-butene copolymer (POE) 40 weight portion is (wherein，The content of butylene accounts for 20% weight，Melt index is 2.0g/10min)，Maleic anhydride modified vinyl-acrylate copolymer 10 weight portion of Its Compatibilizing Technology is (wherein，The content of copolymer accounts for 2% weight，Melt index is 5.0g/10min)、Silicone rubber 5 weight portion、Ultra-fine magnesium hydroxide flame retardant 20 weight portion、Calcium carbonate 20 weight portion、Clay 20 weight portion、Phosphinate flame retardant 10 weight portion、Wrapped up Phosphorus Fire Retardant 10 weight portion、Antioxidant 2 weight portion、Lubricant stearic acid 3 weight portion、Sensitizer trimethylol-propane trimethacrylate TMPTA
2 weight portions, color masterbatch 5 weight portion are sequentially added in homogenizer, high-speed stirred 5-10 minute, and temperature of charge controls in the range of 80 DEG C；Then said mixture double screw extruder is extruded at a temperature of 100-160 DEG C, wire drawing, air-cooled pelletizing；Again by the pellet after above-mentioned pelletizing, extruding sleeve pipe by Single screw extrusion at a temperature of 100-160 DEG C, then by above-mentioned material through electron accelerator irradiation or cobalt-60 radiosterilize, irradiation dose is 4-20Mrad；After sleeve pipe after irradiation expands 1-3 times with expansion device at a temperature of 100-180 DEG C, then cooling and shaping, finally obtain crosslinked halogen-free irradiation crosslinking halogen-free fire retardant thermal shrinkage bus-bar protective sleeve.
Being measured above-mentioned pyrocondensation bus-bar protective sleeve product, result is as follows: shrinkage ratio is more than 2:1；Anti-flammability oxygen index (OI) ＞ 32, flame retardant rating UL224
VW-1；Use temperature range-55～125 DEG C；Hot strength >=10.4MPa；Elongation at break >=200%；Insulation voltage: 2500V, does not punctures；Specific insulation >=1014Ω.cm;Environmental-protecting performance meets European Union's RoHS environmental protection standard, without halogen；During pyrocondensation bus-bar protective sleeve heat shrinkable, tube wall is non-foaming.
Embodiment 3
nullBy vinyl-vinyl acetate copolymer (EVA) 70 weight portion (wherein，The content of vinyl acetate accounts for 40% weight，Melt index is 2.0g/10min)、Butadiene rubber 10 weight portion,Ethylene propylene diene rubber 10 weight portion，Maleic anhydride modified vinyl-vinyl acetate copolymer 10 weight portion of Its Compatibilizing Technology is (wherein，The content of copolymer accounts for 8% weight，Melt index is 5.0g/10min)、Organosilicon polymer 5 weight portion、Modified magnesium hydroxide flame retardant agent 25 weight portion、MCA (MCA) 15 weight portion、Wrapped up Phosphorus Fire Retardant 4 weight portion、Kaolin 10 weight portion、Zinc phosphate 25 weight portion、Antioxidant 4.5 weight portion、Magnesium stearate lubricant 3 weight portion、Sensitizer 1，3-butanediol dimethylacrylate 2 weight portion、Color masterbatch 5 weight portion puts into banbury successively，By the fervent pelletize at a temperature of 100-160 DEG C of said mixture banbury；Again by the pellet after above-mentioned pelletizing, extruding sleeve pipe by Single screw extrusion at a temperature of 100-160 DEG C, then by above-mentioned material through electron accelerator irradiation or cobalt-60 radiosterilize, irradiation dose is 4-20Mrad；After sleeve pipe after irradiation expands 1-3 times with expansion device at a temperature of 100-180 DEG C, then cooling and shaping, finally obtain irradiation crosslinking halogen-free fire retardant thermal shrinkage sleeve pipe.
Being measured above-mentioned heat-shrinkable T bush product, result is as follows: shrinkage ratio is more than 2:1；Anti-flammability oxygen index (OI) ＞ 32, flame retardant rating UL224
VW-1；Use temperature range-55～125 DEG C；Hot strength >=10.4MPa；Elongation at break >=200%；Insulation voltage: 2500V, does not punctures；Thermal shock: 250 DEG C, 4 hours, flawless；Specific insulation >=1014Ω.cm;Environmental-protecting performance meets European Union's RoHS environmental protection standard, without halogen；During heat-shrink tube heat shrinkable, tube wall is non-foaming.
Embodiment 4
By vinyl-vinyl acetate copolymer (EVA) 100 weight portion (wherein, the content of vinyl acetate accounts for 14% weight, melt index is 2.0g/10min), organosilicon polymer 2 weight portion, flame retardant of magnesium hydroxide 20 weight portion, encapsulated red phosphorus 20 weight portion, aluminium hydroxide 10 weight portion, calcinated argil 25 weight portion, antioxidant 4 weight portion, magnesium stearate lubricant 3 weight portion, color masterbatch 5 weight portion be sequentially added in homogenizer, high-speed stirred 5-10 minute, temperature of charge controls in the range of 80 DEG C；Then said mixture double screw extruder is extruded at a temperature of 100-160 DEG C, wire drawing, air-cooled pelletizing；Again by the pellet after above-mentioned pelletizing, extruding sleeve pipe by Single screw extrusion at a temperature of 100-160 DEG C, then by above-mentioned material through electron accelerator irradiation or cobalt-60 radiosterilize, irradiation dose is 4-20Mrad；After sleeve pipe after irradiation expands 1-3 times with expansion device at a temperature of 100-180 DEG C, then cooling and shaping, finally obtain cross-linking low-smoke halogen-free no red phosphorus irradiation crosslinking halogen-free fire retardant thermal shrinkage sleeve pipe.
Being measured above-mentioned heat-shrinkable T bush product, result is as follows: shrinkage ratio is more than 2:1；Anti-flammability oxygen index (OI) ＞ 38, flame retardant rating UL224
VW-1；Use temperature range-55～125 DEG C；Hot strength >=10.4MPa；Elongation at break >=200%；Insulation voltage: 2500V, does not punctures；Thermal shock: 250 DEG C, 4 hours, flawless；Specific insulation >=1014Ω.cm;Environmental-protecting performance meets European Union's RoHS environmental protection standard, without halogen；During heat-shrink tube heat shrinkable, tube wall is non-foaming.
In sum, the present invention compared with prior art has the advantage that and effect:
(1) during heat shrinkable of the present invention, tube wall bubble-tight irradiation crosslinking halogen-free fire proofing has excellent flame retardant effect, and flame retardant rating can reach U.S. UL224
VW-1 flame retardant rating.Not halogen-containing flame retardant, it is to avoid tradition irradiation cross-linking flame-retardant material Han halogen when fire occurs, the halogen-containing material poisonous hydrogen halide of generation and smog, " secondary disaster " that lives and properties are caused during burning；
(2) tube wall bubble-tight irradiation crosslinking halogen-free fire proofing during heat shrinkable of the present invention, product does not produce poisonous flue gas when burning, efficiently solves magnesium hydroxide and problem that aluminium hydroxide fire retardant exists poor fire；It addition, the consumption of magnesium hydroxide fire proofing in the middle of and aluminium hydroxide is greatly reduced, when material contracting with heat heat shrinkable, tube wall is non-foaming, will not be formed at tube wall cellular, will not reduce the insulating properties of insulant.
(3) tube wall bubble-tight irradiation crosslinking halogen-free fire proofing during heat shrinkable of the present invention, when burning, the amount of being fuming is more much smaller than halogen flame, toxicity is also much smaller than halogen flame, owing to using Wrapped up Phosphorus Fire Retardant, being difficult to moisture absorption hydrolysis, safety is greatly improved.
(4) during heat shrinkable of the present invention, tube wall bubble-tight irradiation crosslinking halogen-free fire proofing is a kind of environmental protection close friend's product, materials processing, use, discarded after the least on the impact of ecological environment and human health；
(5) during the heat shrinkable of the present invention, tube wall bubble-tight irradiation crosslinking halogen-free fire proofing is of many uses, may be used for preparing various thermal contraction components and parts, there is excellent fire-retardant, insulation, heat resistance, soft flexible, the field that the environmental requirements such as subway, aviation, electron trade, skyscraper, communal facility are strict can be widely used for；
(6) during heat shrinkable of the present invention, the preparation method of tube wall bubble-tight irradiation crosslinking halogen-free fire proofing is simple, and raw material is easy to get, cheap, it is adaptable to industrialized production.
Present invention can apply to heat-shrinkable T bush or bus-bar protective sleeve, heat-shrink cable accessory, double-wall pipe, middle thick-walled pipe, be applied to heat-shrinkable T bush flame retardant rating and can reach U.S.'s UL224 VW-1 standard and without halogen, environmentally friendly.
The invention is not limited in above-mentioned detailed description of the invention, those skilled in the art also can make multiple change accordingly, but any is equal to the present invention or similar change all should be contained within the scope of the claims.
Claims (14)
1. tube wall bubble-tight irradiation crosslinking halogen-free fire proofing during a heat shrinkable, it is characterised in that include following compositions: vinyl-vinyl acetate copolymer 10-100 weight portion；Ethylene-octene copolymer and/or ethylene-butene copolymer 0-30 weight portion；Ethylene propylene monomer and/or ethylene propylene diene rubber and/or butadiene rubber and/or butadiene-styrene rubber 0-50 weight portion；Polyethylene 0-30 weight portion；Its Compatibilizing Technology 0-20 weight portion；Organosilicon polymer 0.5-10 weight portion；Antioxidant 0.1-10 weight portion；Wrapped up Phosphorus Fire Retardant 0.1-50 weight portion；Ultrafine aluminium hydroxide and/or magnesium hydroxide 1-150 weight portion；High molecular APP (APP) and/or phosphate ester flame retardants and/or MCA (MCA) and/or phosphinates 0-50 weight portion；Carbonate and/or phosphate and/or phosphide and/or calcinated argil and/or Kaolin and/or clay 0.1-100 weight portion；Sensitizer 0-3 weight portion；Lubricant 0-3 weight portion；Color masterbatch 0-20 weight portion；Described carbonate is the one in magnesium carbonate, basic magnesium carbonate or calcium carbonate or several, and described phosphate is the one in zinc phosphate or aluminum phosphate or several.
2. tube wall bubble-tight irradiation crosslinking halogen-free fire proofing during heat shrinkable as claimed in claim 1, it is characterized in that: described sensitizer is trimethylolpropane tris (methyl) acrylate or tetramethylol methane tetraacrylate or triallyl isocyanate or 1,3 butylene glycol dimethylacrylate.
3. tube wall bubble-tight irradiation crosslinking halogen-free fire proofing during heat shrinkable as claimed in claim 1, it is characterised in that: in described vinyl-vinyl acetate copolymer, the content of vinyl acetate accounts for 10-40% weight, and melt index is 0.5-6.0g/10min.
4. tube wall bubble-tight irradiation crosslinking halogen-free fire proofing during heat shrinkable as claimed in claim 1, it is characterised in that: in described ethylene-octene copolymer, octene content accounts for 0-30% weight, and melt index is 0.5-5.0g/10min.
5. tube wall bubble-tight irradiation crosslinking halogen-free fire proofing during heat shrinkable as claimed in claim 1, it is characterised in that: in described ethylene-butene copolymer, butene content accounts for 0-30% weight, and melt index is 0.5-5.0g/10min.
6. tube wall bubble-tight irradiation crosslinking halogen-free fire proofing during heat shrinkable as claimed in claim 1, it is characterised in that: described polyethylene melt index is 0.5-6.0g/10min.
7. tube wall bubble-tight irradiation crosslinking halogen-free fire proofing during heat shrinkable as claimed in claim 1, it is characterized in that: described Its Compatibilizing Technology be copolymer-maleic anhydride ethene improved-vinyl acetate copolymer or copolymer-maleic anhydride ethene improved-acrylate copolymer, copolymer level accounts for 0.5-15%, and melt index is 0.5-15.0g/10min.
8. tube wall bubble-tight irradiation crosslinking halogen-free fire proofing during heat shrinkable as claimed in claim 1, it is characterised in that: described organosilicon polymer is the one or several in polydimethylsiloxane or silicone rubber or organic silicon fibre retardant.
9. tube wall bubble-tight irradiation crosslinking halogen-free fire proofing during heat shrinkable as claimed in claim 1, it is characterised in that: described phosphide is boron phosphide.
10. tube wall bubble-tight irradiation crosslinking halogen-free fire proofing during heat shrinkable as claimed in claim 1, it is characterised in that: the mean diameter of described carbonate and/or phosphate and/or phosphide and/or calcinated argil and/or Kaolin and/or clay is less than 50 μm.
Tube wall bubble-tight irradiation crosslinking halogen-free fire proofing during 11. heat shrinkable as claimed in claim 1, it is characterised in that: the mean diameter of described Wrapped up Phosphorus Fire Retardant is less than 50 μm, and phosphorus content is more than 80%.
Tube wall bubble-tight irradiation crosslinking halogen-free fire retardant thermal shrinkage sleeve pipe during 12. 1 kinds of heat shrinkable, it is characterised in that: this heat-shrinkable T bush by claim 1 to 11 during any one described heat shrinkable tube wall bubble-tight irradiation crosslinking halogen-free fire proofing make.
The preparation method of tube wall bubble-tight irradiation crosslinking halogen-free fire retardant thermal shrinkage sleeve pipe during 13. 1 kinds of heat shrinkable as claimed in claim 12, it is characterized in that comprising the steps: the vinyl-vinyl acetate copolymer first by 10～100 weight portions, the ethylene-octene copolymer of 0～30 weight portions and/or ethylene-butene copolymer, the ethylene propylene monomer of 0-50 weight portion and/or ethylene propylene diene rubber and/or butadiene rubber and/or butadiene-styrene rubber, the polyethylene of 0-30 weight portion, 0～20 parts by weight polymer compatilizers, the organosilicon polymer of 0.5～10 weight portions, the antioxidant of 0.1～10 weight portions, the Wrapped up Phosphorus Fire Retardant of 0.1-50 weight portion；The ultrafine aluminium hydroxide of 1～150 weight portions and/or magnesium hydroxide, the high molecular APP (APP) of 0-50 weight portion and/or phosphate ester flame retardants and/or MCA (MCA) and/or phosphinates；The carbonate of 0.1-100 weight portion and/or phosphate and/or phosphide and/or calcinated argil and/or Kaolin and/or clay, 0～3 lubricant, 0～3 sensitizers of weight portion of weight portion, the color masterbatch of 0-20 weight portion add in homogenizer, high-speed stirred 5-10 minute, temperature of charge controls in the range of 20 DEG C ~ 80 DEG C；Then the material screw extruder after above-mentioned stirring is extruded at a temperature of 100-160 DEG C, wire drawing, air-cooled pelletizing, or by the material banbury after above-mentioned stirring, hot cut pellet at a temperature of 100-160 DEG C；Again by the pellet after above-mentioned pelletizing, at a temperature of 100-160 DEG C, extrude sleeve pipe by Screw Extrusion；Then being 4-20Mrad by above-mentioned sleeve pipe through electron accelerator or cobalt-60 radiosterilize, irradiation dose, the sleeve pipe after irradiation expands 1-3 times with expansion device at a temperature of 100-180 DEG C；Last cooling and shaping, obtains tube wall bubble-tight irradiation crosslinking halogen-free fire retardant thermal shrinkage sleeve pipe during heat shrinkable.
Tube wall bubble-tight irradiation crosslinking halogen-free fire retardant thermal shrinkage double-wall pipe during 14. 1 kinds of heat shrinkable, it is characterized in that: the outer wall of this pyrocondensation double-wall pipe by claim 1 to 11 during any one described heat shrinkable tube wall bubble-tight irradiation crosslinking halogen-free fire proofing make, the inwall of this pyrocondensation double-wall pipe is hot melt adhesive layer.
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| CN104212047B (en) * | 2014-08-21 | 2016-04-27 | 江苏华侃核电器材科技有限公司 | Generation Ⅲ nuclear power station shrinkage stress materials in the tube and preparation method thereof |
| CN105017727A (en) * | 2015-08-11 | 2015-11-04 | 广州南车骏发电气有限公司 | Flame-retarded resin composition, winding of dry type transformer and manufacturing method of winding of dry type transformer |
| CN105801964B (en) * | 2016-04-07 | 2019-03-26 | 江苏德威新材料股份有限公司 | Security protection cable elastomer sheathing material and preparation method thereof |
| CN105949596A (en) * | 2016-05-25 | 2016-09-21 | 南通慧源塑胶有限公司 | High-strength high-temperature-resistant cable sheath material |
| CN106279951A (en) * | 2016-08-18 | 2017-01-04 | 苏州泰斯拓伟机电设备有限公司 | A kind of halogen-free non-red-phosphorus flame-retardant thermal shrinkable tube and preparation method thereof |
| CN106496753A (en) * | 2016-10-10 | 2017-03-15 | 杭州高新橡塑材料股份有限公司 | Cable for nuclear power station material and preparation method |
| 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 |
| CN110028730A (en) * | 2019-04-26 | 2019-07-19 | 江苏达胜热缩防护用品有限公司 | A kind of halogen-free flameproof pyrocondensation tubule and preparation method thereof |
| CN110669260A (en) * | 2019-10-28 | 2020-01-10 | 深圳市锦昊辉实业发展有限公司 | Preparation method of yellowing-resistant halogen-free flame retardant applied to LED lampshade |
| CN113611449A (en) * | 2021-09-13 | 2021-11-05 | 江苏亨通电力电缆有限公司 | B2Grade flame-retardant cable and preparation method and application thereof |
| CN114889226A (en) * | 2022-03-07 | 2022-08-12 | 上海先锋辐照制品厂有限公司 | High flame-retardant high-temperature-resistant composite heat-shrinkable tube for electric automobile |
| CN115746500B (en) * | 2022-11-16 | 2024-01-12 | 中广核俊尔(浙江)新材料有限公司 | Organosilicon modified PEEK heat shrinkage tube and preparation method thereof |
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| NO985318L (en) * | 1998-11-13 | 2000-05-15 | Borealis As | Polyolefin-based article with modified surface |
| KR20100025211A (en) * | 2008-08-27 | 2010-03-09 | 엘에스전선 주식회사 | Polypropylene-based flame-resistant resin composition for cable insulation material with superior mechanical properties |
| CN102766293B (en) * | 2011-08-16 | 2013-11-20 | 深圳市沃尔核材股份有限公司 | Radiation cross-linked low-smoke halogen-free red phosphorus-free flame retardant material and application thereof |
| CN202839168U (en) * | 2011-12-09 | 2013-03-27 | 深圳市沃尔核材股份有限公司 | Halogen and red phosphorus free flame retardant heat-shrinkable double-wall tube |
| CN102731895B (en) * | 2012-07-06 | 2014-06-18 | 深圳市沃尔核材股份有限公司 | 1E-grade K1 type halogen-free flame retardant material for nuclear power plants and application thereof |
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Address after: 518118 Vol Industrial Park, Lanjingbei Road, Pingshan New Area, Shenzhen City, Guangdong Province Patentee after: Shenzhen Woer Heat-shrinkable Material Co.,Ltd. Patentee after: SHENZHEN WOER SPECIAL CABLE Co.,Ltd. Patentee after: CHANGZHOU WOER HEAT-SHRINKABLE MATERIAL Co.,Ltd. Patentee after: LTK ELECTRIC WIRE (HUIZHOU) Ltd. Patentee after: HUIZHOU LTK ELECTRONIC CABLE Co.,Ltd. Address before: 518118 Vol Industrial Park, Lanjingbei Road, Pingshan New Area, Shenzhen City, Guangdong Province Patentee before: Shenzhen Woer Heat-shrinkable Material Co.,Ltd. Patentee before: SHENZHEN WOER SPECIAL CABLE Co.,Ltd. Patentee before: JINTAN WOER NEW MATERIAL Co.,Ltd. Patentee before: LTK ELECTRIC WIRE (HUIZHOU) Ltd. Patentee before: HUIZHOU LTK ELECTRONIC CABLE Co.,Ltd. |
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Effective date of registration: 20210622 Address after: 518118 Wool Industrial Park, Lanjing North Road, Longtian Street, Pingshan District, Shenzhen City, Guangdong Province Patentee after: Shenzhen Woer Heat-shrinkable Material Co.,Ltd. Patentee after: CHANGZHOU WOER HEAT-SHRINKABLE MATERIAL Co.,Ltd. Address before: 518118 Vol Industrial Park, Lanjingbei Road, Pingshan New Area, Shenzhen City, Guangdong Province Patentee before: Shenzhen Woer Heat-shrinkable Material Co.,Ltd. Patentee before: SHENZHEN WOER SPECIAL CABLE Co.,Ltd. Patentee before: CHANGZHOU WOER HEAT-SHRINKABLE MATERIAL Co.,Ltd. Patentee before: LTK ELECTRIC WIRE (HUIZHOU) Ltd. Patentee before: HUIZHOU LTK ELECTRONIC CABLE Co.,Ltd. |
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