CN109776930A - A kind of crosslinking with radiation halogen-free non-red-phosphorus flame-retardant heat-shrinkage material and preparation method thereof - Google Patents
A kind of crosslinking with radiation halogen-free non-red-phosphorus flame-retardant heat-shrinkage material and preparation method thereof Download PDFInfo
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Abstract
The present invention discloses a kind of crosslinking with radiation halogen-free non-red-phosphorus flame-retardant heat-shrinkage material, is grouped as by following groups based on parts by weight: 100 parts of polyolefin base material, 20-40 parts of alkyl phosphinate；40-80 parts of melamine cyanurate；20-80 parts of aluminium hydroxide；2-6 parts of compatilizer；1-2 parts of antioxidant；0.5-1 parts of lubricant；1-5 parts of Masterbatch.Crosslinking with radiation halogen-free non-red-phosphorus flame-retardant heat-shrinkage material of the present invention does not contain the poisonous and harmful substances such as halogen, red phosphorus and lead, mercury, cadmium, Cr VI, crosslinking can be realized using gamma-rays or high-energy electron irradiation, for manufacturing production crosslinking with radiation halogen-free non-red-phosphorus flame-retardant heat-shrinkage material and products thereof.
Description
Technical field
The present invention relates to a kind of crosslinking with radiation heat-shrinkage materials and preparation method thereof.
Background technique
Conventional halogen-free flame-retardant thermal shrinkage material is currently mainly used red phosphorus and does fire retardant, and good flame retardation effect can reach UL mark
The flame-retardancy requirements of quasi- V0 or VW-1 grade.But red phosphorus can release toxic, irritating hydrogen phosphide in burning, corrode people's
Skin and mucous membrane endanger the health of people；In addition red phosphorus can also the raw transport reaction of metallic copper, silver hair in photoinduced electron chip, make
At the failure of integrated circuit.For this purpose, Apple Inc. took the lead in proposing limitation red phosphorus combustion inhibitor in the product in the whole world in 2007 years
It uses, also actively limitation uses red phosphorus for supplier.
Therefore, it is necessary to develop halogen-free non-red-phosphorus flame-retardant heat-shrinkage material.
Summary of the invention
The technical problem to be solved in the present invention is that: overcome existing conventional halogen-free flame-retardant thermal shrinkage material material to contain red
The problem of poisonous and harmful substances such as phosphorus and lead, mercury, cadmium, Cr VI, provides a kind of crosslinking with radiation halogen-free non-red-phosphorus flame-retardant heat receipts
Compression material and preparation method thereof.
In order to solve the above-mentioned technical problem, the present invention proposes following technical scheme: a kind of crosslinking with radiation Halogen no red phosphorus resistance
Heat-shrinkage material is fired, is grouped as by following groups based on parts by weight:
The above technical solution is further limited in that: the polyolefin base material is one of following substance or a variety of
Mixture: polyethylene, ethylene-propylene copolymer, ethylene-octene copolymer, ethylene-vinyl acetate copolymer, ethylene-the third
E pioic acid methyl ester copolymer；
The melt index MI of the polyethylene is 0.1~10g/10min；
The ethylene contents of the ethylene-propylene copolymer are 50~70%, and propylene content is 30~50%, Mooney viscosity
(ML 1+4,125 DEG C) is 5-50；
The Mooney viscosity (ML 1+4,121 DEG C) of the ethylene-octene copolymer is 5-50；
The ethylene-vinyl acetate copolymer melt index MI be 1-6g/10min, vinyl acetate content be 10~
40%；
The ethylene-methyl acrylate copolymer melt index MI be 1-6g/10min, methyl acrylate content be 8~
30%.
The above technical solution is further limited in that: the polyolefin base material is by ethylene-vinyl acetate copolymer 90-95
Part, 5-10 parts of ethylene-octene copolymer compositions；The vinyl acetate content range of the ethylene-vinyl acetate copolymer is
10%-28%, MI are in 1~5.5g/10min；The ethylene-octene copolymer, Mooney viscosity range are 33 ± 5.
The above technical solution is further limited in that: the alkyl phosphinate structural formula are as follows: [R1R2P(O)O-]nMn+, R therein1And R2For the alkyl or aryl of C1~C6, M is metal.
The above technical solution is further limited in that: the melamine cyanurate is urinated by melamine and cyanogen
The salt of acid synthesis, structural formula C6H9N9O3, belong to nitrogen fire-retardant agent, average grain diameter is less than 4 μm.
The above technical solution is further limited in that: the aluminium hydroxide chemical formula is Al (OH)3, it is inorganic fire-retarded
Additive, average grain diameter is less than 4 μm.
The above technical solution is further limited in that: the compatilizer is the block copolymerization of maleic anhydride and polyolefin
One of object, graft copolymer or random copolymer or a variety of mixtures.
The above technical solution is further limited in that: the antioxidant is the mixed of one or more of following substance
Close object: four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol resins；N, N ' -1,6- inferior hexyl-bis- [3- (3,5-
Di-tert-butyl-hydroxy phenyl) propionamide]；Thiodipropionic acid bis-dodecanol ester；Phosphorous acid three (2,4- di-tert-butyl-phenyl)
Ester；P-isopropoxy-diphenylamine；4,4- bis- (alpha, alpha-dimethylbenzyl) diphenylamines；N, N- bis- (Isosorbide-5-Nitraes-dimethyl amyl group) are to benzene two
Amine；N, N- bis--betanaphthyl p-phenylenediamine；N- (1,3- dimethylbutyl) -4-aminodiphenylamine；2,2,4- trimethyls -1,2 two
Hydrogenated quinoline condensate.
The above technical solution is further limited in that: the lubricant is one or more of following substance
The mixture of substance: stearic acid, zinc stearate, calcium stearate, magnesium stearate, polyethylene wax.
In order to solve the above-mentioned technical problem, the present invention proposes following technical scheme: a kind of crosslinking with radiation Halogen no red phosphorus resistance
Fire the preparation method of heat-shrinkage material comprising following steps:
Step 1: weighing 100 parts of polyolefin base material, 20-40 parts of alkyl phosphinate, melamine cyanogen according to parts by weight
40-80 parts of lithate, 20-80 parts of aluminium hydroxide, 2-6 parts of compatilizer, 1-2 parts of antioxidant, 0.5-1 parts of lubricant, color masterbatch
1-5 parts of grain is sufficiently mixed uniformly at room temperature；
Step 2: the substance mixer that step 1 is uniformly mixed being kneaded in 130 DEG C of -150 DEG C of temperature ranges, squeezes out and makes
Grain；
Step 3: step 2 being kneaded to the substance uniformly obtained and uses double screw extruder in 130 DEG C of -200 DEG C of temperature after homogenizing
It spends and squeezes out water cooling bracing in section, pelletizing air-dries；
Step 4: above-mentioned material grain is extruded into tubulose at a temperature of with single screw extrusion machine at 130 DEG C -180 DEG C；
Step 5: aforementioned tubes being radiated through gamma-rays or electron ray, dose of radiation 8-18Mrad or 80-180KGY；
Step 6: and then aforementioned tubes caliber is expanded to 2-6 times at a temperature of 100-200 DEG C.
Compared with prior art, the invention has the following advantages: the fire-retardant heat of irradiation crosslinking halogen-free no red phosphorus of the present invention
Shrink-down material does not contain the poisonous and harmful substances such as halogen, red phosphorus and lead, mercury, cadmium, Cr VI, fire-retardant to be tried by VW-1
It tests, tensile strength is greater than 10.4MPa, and elongation at break is greater than 200%, can be tested by 224 safety of UL.
The present invention expands the type and application range for being heat-shrinked product, while also having opened up answering for conventional heat-shrinkage material
Use space.Aforementioned tubes performance is good, and preparation method is simple, is suitable for industrialized production.
Specific embodiment
The present invention proposes a kind of halogen-free non-red-phosphorus flame-retardant heat-shrinkage material, by following groups of groupings based on parts by weight
At:
The polyolefin base material is one of following substance or a variety of mixtures: polyethylene, ethylene-propylene copolymer
Object, ethylene-octene copolymer, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer.
The melt index MI of the polyethylene is 0.1~10g/10min.
The ethylene contents of the ethylene-propylene copolymer are 50~70%, and propylene content is 30~50%, Mooney viscosity
(ML 1+4,125 DEG C) is 5-50.
The Mooney viscosity (ML 1+4,121 DEG C) of the ethylene-octene copolymer is 5-50.
The ethylene-vinyl acetate copolymer melt index MI be 1-6g/10min, vinyl acetate content be 10~
40%.
The ethylene-methyl acrylate copolymer melt index MI be 1-6g/10min, methyl acrylate content be 8~
30%.
The optimal selection of the polyolefin base material is copolymerized by 90-95 parts of ethylene-vinyl acetate copolymer, ethylene-octene
5-10 parts of object compositions；The vinyl acetate content range of the ethylene-vinyl acetate copolymer is 10%-28%, MI 1~
5.5g/10min；The ethylene-octene copolymer, Mooney viscosity range are 33 ± 5.
The alkyl phosphinate structural formula are as follows: [R1R2P(O)O-]nMn+, R therein1And R2For the alkyl of C1~C6
(such as methyl, ethyl, n-propyl, isopropyl, normal-butyl, tert-butyl, n-pentyl) or aryl (such as phenyl), M are metal (examples
Such as zinc, calcium, aluminium).
The optimal selection of the alkyl phosphinate is one of following substance or a variety of mixtures: diethyl time phosphorus
Sour aluminium, Methylethyl hypo-aluminum orthophosphate.
The melamine cyanurate is the salt synthesized by melamine and cyanuric acid, structural formula C6H9N9O3, belong to
In nitrogen fire-retardant agent, average grain diameter is less than 4 μm.
The aluminium hydroxide chemical formula is Al (OH)3, it is inorganic fire-retarded additive, average grain diameter is less than 4 μm.
The compatilizer is one in the block copolymer, graft copolymer or random copolymer of maleic anhydride and polyolefin
Kind or a variety of mixtures.
The optimal selection of the compatilizer is the compounding of one or more of following substance: maleic anhydride and second
Alkene-acetate ethylene copolymer graft copolymer, maleic anhydride content 1-2.8%, vinyl acetate content 28%, MI >=
1g/10min；The random copolymer of maleic anhydride and ethylene-acrylic acid butylene copolymer, maleic anhydride content 1-3.5%, MI
≥2g/10min。
The antioxidant is the mixture of one or more of following substance: four [β-(3,5- di-t-butyl -4- hydroxyls
Base phenyl) propionic acid] pentaerythritol resin (antioxidant 1010)；N, N ' -1,6- inferior hexyl-bis- [3- (3,5- di-t-butyl -4- hydroxyls
Phenyl) propionamide]；The double lauryls (anti-oxidant DLTP) of thio-2 acid；Phosphorous acid three (2,4- di-tert-butyl-phenyl) ester；To different
Propoxyl group diphenylamines；4,4- bis- (alpha, alpha-dimethylbenzyl) diphenylamines；Bis- (Isosorbide-5-Nitrae-dimethyl amyl group) p-phenylenediamine of N, N-；N, N-
Two-betanaphthyl p-phenylenediamine；N- (1,3- dimethylbutyl) -4-aminodiphenylamine；2,2,4- trimethyl -1,2 dihydro quinolines
Quinoline condensate.
The optimal selection of the antioxidant is the compounding of one of following substance or two kinds: four [β-(3,5- bis- uncles
Butyl -4- hydroxy phenyl) propionic acid] pentaerythritol ester, β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester and
Dilauryl thiodipropionate；The mass ratio of compounding is 1:1.5.
The lubricant is one or more mixtures of following substance: stearic acid, zinc stearate, stearic acid
Calcium, magnesium stearate, polyethylene wax.
The preparation method of above-mentioned crosslinking with radiation halogen-free non-red-phosphorus flame-retardant heat-shrinkage material the following steps are included:
Step 1: weighing according to parts by weight: 100 parts of polyolefin base material, 20-40 parts of alkyl phosphinate, melamine cyanogen
40-80 parts of lithate, 20-80 parts of aluminium hydroxide, 2-6 parts of compatilizer, 1-2 parts of antioxidant, 0.5-1 parts of lubricant, color masterbatch
1-5 parts of grain, is sufficiently stirred at room temperature, is uniformly mixed；
Step 2: the substance mixer that step 1 is uniformly mixed being kneaded in 130-180 DEG C of temperature range, extruding pelletization；
Step 3: by step 2 be kneaded uniform substance after homogenizing with double screw extruder in 130-200 DEG C of temperature range
Interior extrusion water cooling bracing, pelletizing air-dry；
Step 4: above-mentioned material grain is extruded into tubulose at a temperature of with single screw extrusion machine at 130-180 DEG C；
Step 5: aforementioned tubes being radiated through gamma-rays or electron ray, dose of radiation 8-18Mrad (or 80-180KGY)；
Step 6: and then aforementioned tubes caliber is expanded to 2-6 times at a temperature of 130-180 DEG C.
Carry out the technical solution that the present invention is further explained below by preparation embodiment.
Prepare embodiment 1
Weigh according to parts by weight: 100 parts of polyolefin base material [takes ethylene-vinyl acetate copolymer (J5110, Yangba) 90
Part, 10 parts of ethylene-octene copolymer (POE8150, Tao Shi)]；
20 parts of alkyl phosphinate [takes 20 parts of aluminum diethylphosphinate (commercially available)]；
80 parts of melamine cyanurate (commercially available)
20 parts of aluminium hydroxide (commercially available)；
4 parts of compatilizer (take the random copolymer of maleic anhydride Yu ethylene-acrylic acid butylene copolymer, 4210, Arkema)；
1 part of antioxidant (take antioxidant 1010: anti-oxidant DLTP=1:1.5, commercially available)；
0.8 part of lubricant (taking zinc stearate, commercially available)；
1 part of Masterbatch (commercially available)；
It is sufficiently stirred, is uniformly mixed at room temperature.Uniformly mixed substance is mixed with mixer in 100 DEG C of temperature ranges
Refining, extruding pelletization.Water cooling bracing is squeezed out in 170 DEG C of temperature ranges with double screw extruder again, pelletizing air-dries.It is squeezed with single screw rod
Machine is extruded into tubulose at a temperature of 160 DEG C out.Aforementioned tubes are radiated through gamma-rays or electron ray, dose of radiation 8Mrad (or
80KGY).Aforementioned tubes caliber is expanded to 6 times at a temperature of 180 DEG C.
It measures as follows:
| Serial number | Performance | Unit | Measured value |
| 1 | Tensile strength | MPa | 13.2 |
| 2 | Elongation at break | % | 430 |
| 3 | Volume resistivity | Ω·m | 1.9×1015 |
| 4 | Anti-flammability | — | VW-1 passes through |
| 5 | Content of halogen | ppm | Cl:ND；Br:ND； |
| 6 | Red phosphorus content | ppm | ND |
| 7 | Lead content | ppm | ND |
| 8 | Mercury content | ppm | ND |
| 9 | Cadmium content | ppm | ND |
| 10 | Content of 6-valence Cr ions | ppm | ND |
Remarks: ND represents instrument inspection and does not measure
Prepare embodiment 2
Weigh according to parts by weight: 100 parts of polyolefin base material [takes ethylene-vinyl acetate copolymer (J4110, Yangba) 95
Part, 5 parts of ethylene-octene copolymer (POE8150, Tao Shi)]；
40 parts of alkyl phosphinic acid aluminium [takes 40 parts of ethylene methacrylic phosphinic acids aluminium (commercially available)]；
55 parts of melamine cyanurate (commercially available)；
60 parts of aluminium hydroxide (commercially available)；
6 parts of compatilizer (taking the graft copolymer of maleic anhydride and ethylene-vinyl acetate copolymer, MC328, the light of energy)；
2 parts of antioxidant (take antioxidant 1076: anti-oxidant DLTP=1:1.5, commercially available)；
1 part of lubricant (taking stearic acid, commercially available)；
5 parts of Masterbatch (commercially available)；
It is sufficiently stirred, is uniformly mixed at room temperature.Uniformly mixed substance is mixed with mixer in 150 DEG C of temperature ranges
Refining, extruding pelletization.Water cooling bracing is squeezed out in 150 DEG C of temperature ranges with double screw extruder again, pelletizing air-dries.It is squeezed with single screw rod
Machine is extruded into tubulose at a temperature of 180 DEG C out.Aforementioned tubes are radiated through gamma-rays or electron ray, dose of radiation 15Mrad
(or 150KGY).Aforementioned tubes caliber is expanded to 3 times at a temperature of 160 DEG C.
It measures as follows:
| Serial number | Performance | Unit | Measured value |
| 1 | Tensile strength | MPa | 12.7 |
| 2 | Elongation at break | % | 380 |
| 3 | Volume resistivity | Ω·m | 3.1×1014 |
| 4 | Anti-flammability | — | VW-1 passes through |
| 5 | Content of halogen | ppm | Cl:ND；Br:ND； |
| 6 | Red phosphorus content | ppm | ND |
| 6 | Red phosphorus content | ppm | ND |
| 7 | Lead content | ppm | ND |
| 8 | Mercury content | ppm | ND |
| 9 | Cadmium content | ppm | ND |
| 10 | Content of 6-valence Cr ions | ppm | ND |
Remarks: ND represents instrument inspection and does not measure
Prepare embodiment 3
Weigh according to parts by weight: 100 parts of polyolefin base material [takes ethylene-vinyl acetate copolymer (2803, Arkema) 95
Part, 5 parts of ethylene-octene copolymer (POE8150, Tao Shi)]；
30 parts of alkyl phosphinate [takes 30 parts of diethyl alkyl phosphinic acid aluminium (commercially available)]；
40 parts of melamine cyanurate (commercially available)；
80 parts of aluminium hydroxide (commercially available)；
2 parts of compatilizer (4210, Arkema)；
1.5 parts of antioxidant (take antioxidant 1010: anti-oxidant DLTP=1:1.5, commercially available)；
0.5 part of lubricant (taking polyethylene wax, commercially available)；
4 parts of Masterbatch (commercially available)；
It is sufficiently stirred, is uniformly mixed at room temperature.Uniformly mixed substance is mixed with mixer in 130 DEG C of temperature ranges
Refining, extruding pelletization.Water cooling bracing is squeezed out in 180 DEG C of temperature ranges with double screw extruder again, pelletizing air-dries.It is squeezed with single screw rod
Machine is extruded into tubulose at a temperature of 130 DEG C out.Aforementioned tubes are radiated through gamma-rays or electron ray, dose of radiation 16Mrad
(or 160KGY).Aforementioned tubes caliber is expanded to 2 times at a temperature of 150 DEG C.
It measures as follows:
| Serial number | Performance | Unit | Measured value |
| 1 | Tensile strength | MPa | 14.3 |
| 2 | Elongation at break | % | 301 |
| 3 | Volume resistivity | Ω·m | 7.2×1014 |
| 4 | Anti-flammability | — | VW-1 passes through |
| 5 | Content of halogen | ppm | Cl:ND；Br:ND； |
| 6 | Red phosphorus content | ppm | ND |
| 6 | Red phosphorus content | ppm | ND |
| 7 | Lead content | ppm | ND |
| 8 | Mercury content | ppm | ND |
| 9 | Cadmium content | ppm | ND |
| 10 | Content of 6-valence Cr ions | ppm | ND |
Remarks: ND represents instrument inspection and does not measure
Prepare embodiment 4
Weigh according to parts by weight: 100 parts of polyolefin base material [takes ethylene-vinyl acetate copolymer (2803, Arkema) 95
Part, 5 parts of ethylene-octene copolymer (POE8150, Tao Shi)]；
30 parts of alkyl-alkyl phosphinates (take aluminum diethylphosphinate: this aluminum phosphate=1:1 of Methylethyl, commercially available)；
40 parts of melamine cyanurate (commercially available)；
80 parts of aluminium hydroxide (commercially available)；
2 parts of compatilizer (4210, Arkema)；
1.5 parts of antioxidant (take antioxidant 1010: anti-oxidant DLTP=1:1.5, commercially available)；
1 part of lubricant (taking calcium stearate, commercially available)；
4 parts of Masterbatch (commercially available)；
It is sufficiently stirred, is uniformly mixed at room temperature.Uniformly mixed substance is mixed with mixer in 130 DEG C of temperature ranges
Refining, extruding pelletization.Water cooling bracing is squeezed out in 180 DEG C of temperature ranges with double screw extruder again, pelletizing air-dries.It is squeezed with single screw rod
Machine is extruded into tubulose at a temperature of 130 DEG C out.Aforementioned tubes are radiated through gamma-rays or electron ray, dose of radiation 16Mrad
(or 160KGY).Aforementioned tubes caliber is expanded to 2 times at a temperature of 150 DEG C.
It measures as follows:
| Serial number | Performance | Unit | Measured value |
| 1 | Tensile strength | MPa | 14.7 |
| 2 | Elongation at break | % | 315 |
| 3 | Volume resistivity | Ω·m | 6.8×1014 |
| 4 | Anti-flammability | — | VW-1 passes through |
| 5 | Content of halogen | ppm | Cl:ND；Br:ND； |
| 6 | Red phosphorus content | ppm | ND |
| 6 | Red phosphorus content | ppm | ND |
| 7 | Lead content | ppm | ND |
| 8 | Mercury content | ppm | ND |
| 9 | Cadmium content | ppm | ND |
| 10 | Content of 6-valence Cr ions | ppm | ND |
Remarks: ND represents instrument inspection and does not measure
Claims (10)
1. a kind of crosslinking with radiation halogen-free non-red-phosphorus flame-retardant heat-shrinkage material is grouped as by following groups based on parts by weight:
100 parts of polyolefin base material；
20-40 parts of alkyl phosphinate；
40-80 parts of melamine cyanurate；
20-80 parts of aluminium hydroxide；
2-6 parts of compatilizer；
1-2 parts of antioxidant；
0.5-1 parts of lubricant；
1-5 parts of Masterbatch.
2. the crosslinking with radiation halogen-free non-red-phosphorus flame-retardant heat-shrinkage material according to claim 1, it is characterised in that: described
Polyolefin base material is one of following substance or a variety of mixtures: polyethylene, ethylene-propylene copolymer, ethylene-octene are total
Polymers, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer；
The melt index MI of the polyethylene is 0.1~10g/10min；
The ethylene contents of the ethylene-propylene copolymer are 50~70%, and propylene content is 30~50%, Mooney viscosity (ML 1+4,
125 DEG C) it is 5-50；
The Mooney viscosity (ML 1+4,121 DEG C) of the ethylene-octene copolymer is 5-50；
The ethylene-vinyl acetate copolymer melt index MI is 1-6g/10min, and vinyl acetate content is 10~40%；
The ethylene-methyl acrylate copolymer melt index MI is 1-6g/10min, and methyl acrylate content is 8~30%.
3. crosslinking with radiation halogen-free non-red-phosphorus flame-retardant heat-shrinkage material according to claim 1 or 2, it is characterised in that: described
Polyolefin base material is made of 90-95 parts of ethylene-vinyl acetate copolymer, 5-10 parts of ethylene-octene copolymer；The ethylene-
The vinyl acetate content range of acetate ethylene copolymer is 10%-28%, and MI is in 1~5.5g/10min；The ethylene-octene
Copolymer, Mooney viscosity range are 33 ± 5.
4. crosslinking with radiation halogen-free non-red-phosphorus flame-retardant heat-shrinkage material according to claim 1, it is characterised in that: the alkane
Base phosphinates structural formula are as follows: [R1R2P(O)O-]n M n+, R therein1And R 2For the alkyl or aryl of C1 ~ C6, M is metal.
5. crosslinking with radiation halogen-free non-red-phosphorus flame-retardant heat-shrinkage material according to claim 1, it is characterised in that: described three
Poly cyanamid cyanurate is the salt synthesized by melamine and cyanuric acid, structural formula C6H9N9O3, belong to nitrogen fire-retardant agent,
Average grain diameter is less than 4 μm.
6. crosslinking with radiation halogen-free non-red-phosphorus flame-retardant heat-shrinkage material according to claim 1, it is characterised in that: the hydrogen
Aluminium oxide chemical formula is Al (OH)3, it is inorganic fire-retarded additive, average grain diameter is less than 4 μm.
7. the crosslinking with radiation halogen-free non-red-phosphorus flame-retardant heat-shrinkage material according to claim 1, it is characterised in that: the phase
Holding agent is one of block copolymer, graft copolymer or random copolymer of maleic anhydride and polyolefin or a variety of mixing
Object.
8. crosslinking with radiation halogen-free non-red-phosphorus flame-retardant heat-shrinkage material according to claim 1, it is characterised in that: the antioxygen
Agent is the mixture of one or more of following substance: four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] seasons penta
Four alcohol esters；N, N ' -1,6- inferior hexyl-bis- [3- (3,5- di-tert-butyl-hydroxy phenyl) propionamide]；Thio-2 acid double 12
Alcohol ester；Phosphorous acid three (2,4- di-tert-butyl-phenyl) ester；P-isopropoxy-diphenylamine；4,4- bis- (alpha, alpha-dimethylbenzyl) hexichol
Amine；Bis- (Isosorbide-5-Nitrae-dimethyl amyl group) p-phenylenediamine of N, N-；N, N- bis--betanaphthyl p-phenylenediamine；N- (1,3- dimethylbutyl)-N-
Diphenyl-para-phenylene diamine；2,2,4- trimethyl -1,2 dihyaroquinoline condensates.
9. crosslinking with radiation halogen-free non-red-phosphorus flame-retardant heat-shrinkage material according to claim 1, it is characterised in that: the processing
Lubricant is the mixture of one or more of following substance: stearic acid, calcium stearate, magnesium stearate, gathers zinc stearate
Ethylene waxes.
10. the preparation method of crosslinking with radiation halogen-free non-red-phosphorus flame-retardant heat-shrinkage material as described in claim 1, feature exist
In comprising following steps:
Step 1: weighing 100 parts of polyolefin base material, 20-40 parts of alkyl phosphinate, melamine cyanurea according to parts by weight
40-80 parts of hydrochlorate, 20-80 parts of aluminium hydroxide, 2-6 parts of compatilizer, 1-2 parts of antioxidant, 0.5-1 parts of lubricant, color masterbatch
1-5 parts of grain is sufficiently mixed uniformly at room temperature；
Step 2: the substance mixer that step 1 is uniformly mixed being kneaded in 130 DEG C of -150 DEG C of temperature ranges, squeezes out and makes
Grain；
Step 3: step 2 being kneaded to the substance uniformly obtained and uses double screw extruder in 130 DEG C of -200 DEG C of temperature after homogenizing
Water cooling bracing is squeezed out in section, pelletizing air-dries；
Step 4: above-mentioned material grain is extruded into tubulose at a temperature of with single screw extrusion machine at 130 DEG C -180 DEG C；
Step 5: aforementioned tubes being radiated through gamma-rays or electron ray, dose of radiation 8-18Mrad or 80-180 KGY；
Step 6: and then aforementioned tubes caliber is expanded to 2-6 times at a temperature of 100-200 DEG C.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112063037A (en) * | 2020-09-23 | 2020-12-11 | 上海长园电子材料有限公司 | Formula, preparation method and application of high-flame-retardant halogen-free phosphorus-free heat-shrinkable tube |
| CN112778620A (en) * | 2020-12-31 | 2021-05-11 | 长园电子（东莞）有限公司 | Heat-shrinkable sleeve and preparation method thereof |
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| CN112812416A (en) * | 2021-01-06 | 2021-05-18 | 长园电子（东莞）有限公司 | Semi-hard halogen-free red phosphorus-free flame-retardant heat-shrinkable tubing and preparation method thereof |
| CN116120653A (en) * | 2021-11-12 | 2023-05-16 | 南京喜悦科技股份有限公司 | Oil-resistant halogen-free red phosphorus-free flame-retardant polyolefin heat-shrinkable material and heat-shrinkable tube prepared from same |
| CN114133657A (en) * | 2021-12-31 | 2022-03-04 | 中广核高新核材科技（苏州）有限公司 | Preparation method of high-performance flame-retardant low-smoke halogen-free polyolefin cable material |
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Application publication date: 20190521 |