CN103194014B - Halogen-free flame-retardant polyolefin material - Google Patents
Halogen-free flame-retardant polyolefin material Download PDFInfo
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- CN103194014B CN103194014B CN201310118190.2A CN201310118190A CN103194014B CN 103194014 B CN103194014 B CN 103194014B CN 201310118190 A CN201310118190 A CN 201310118190A CN 103194014 B CN103194014 B CN 103194014B
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Abstract
The invention discloses a halogen-free flame-retardant polyolefin material without containing red phosphorus. The polyolefin material comprises the following components in parts by weight: 100 parts of polyolefin resin, 10 to 60 parts of powdery polyphenyl ether, 5 to 20 parts of phenoxy polyphosphazene, 0.3 to 2.0 parts of antioxidant and 0.5 to 1.5 parts of plastic processing lubricant. The polyolefin material can be used for preparing an insulating layer or a sheathing layer of a halogen-free fire-resistant wire without containing the red phosphorus, and other types of plastic elements. By irradiating the polyolefin material via natural radioactive rays and high-energy electron rays, the material crosslinking is realized, so that the physical and chemical properties of the polyolefin material are improved. Therefore, the polyolefin material disclosed by the invention can be used for preparing and producing the halogen-free flame-retardant radiation-crosslinking polyolefin material without containing the red phosphorus and the halogen-free flame-retardant thermal-shrinking material without containing the red phosphorus.
Description
Technical field
The present invention relates to a kind of halogen-free non-red-phosphorus flame-retardant polyolefine material, this material is not containing halogen, red phosphorus material, good flame resistance, can manufacture radiation crosslinking halogen-free non-red-phosphorus flame-retardant material by radiation crosslinking, and then manufacture Halogen no red phosphorus polyolefin flame-retardant heat-shrinkage material.
Background technology
Conventional flame retardant electric wire, cable (crosslinked or uncrosslinked) and flame-retardant heat-shrinkable material can generate more cigarette when burning, corrosive gases and some oncogene products (are as dioxin, the two cumarones of four bromos etc.), European Union, the U.S., the countries such as China or tissue are launched respectively relevant laws and regulations restriction or are forbidden in plastics containing halogen, the RoHS instruction that European Union passed through in 2003, " in electronics and IT products, the limitation of hazardous and noxious substances requires " of the Ministry of Information Industry of China promulgation in 2006 etc., halogen-free flameproof becomes electronics, the main development direction of electrical apparatus industry plastic material.
Bittern-free flame-proof material mainly uses red phosphorus to do fire retardant, good flame retardation effect at present, can reach the flame-retardancy requirements of state UL standard V0 or VW-1 grade.But red phosphorus can discharge poisonous, irritating phosphuret-(t)ed hydrogen when burning, corrode skin and the mucous membrane of people, the health of harm people; Red phosphorus also can metallic copper, the raw transport reaction of silver hair in photoinduced electron chip in addition, causes the inefficacy of integrated circuit.For this reason, Apple took the lead in proposing the use in the product of restriction red phosphorus combustion inhibitor in 2007 in the whole world, and its supplier also actively limits and uses red phosphorus, and exploitation halogen-free non-red-phosphorus flame-retardant material becomes a urgent problem.
Summary of the invention
The technical problem that will solve of the present invention is: overcome the problem that conventional flame retardant electric wire, cable (crosslinked or uncrosslinked), electronic apparatus associated plastic material and flame-retardant heat-shrinkable material contain the hazardous and noxious substances such as halogen and red phosphorus, a kind of halogen-free non-red-phosphorus flame-retardant polyolefine material and manufacture method thereof are provided, this material can be cross-linked by the mode of irradiation, and then manufactures radiation crosslinking halogen-free non-red-phosphorus flame-retardant polyolefine material and halogen-free non-red-phosphorus flame-retardant heat-shrinkage material.
In order to solve the problems of the technologies described above, the present invention proposes following technical scheme: a kind of halogen-free non-red-phosphorus flame-retardant polyolefine material, is made up of the component of following weight parts:
The further restriction of technique scheme is: described polyolefin resin is one or more the mixture in following material: polyethylene, ethylene-propylene copolymer, ethylene-octene copolymer, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer;
Above-mentioned poly melting index MI is 0.1 ~ 10g/10min;
The ethylene content of above-mentioned ethylene-propylene copolymer is 50 ~ 70%, and propylene content is 30 ~ 50%;
The mooney viscosity (ML 1+4,125 DEG C) of above-mentioned ethylene-octene copolymer is 5 ~ 50;
Above-mentioned ethylene-vinyl acetate copolymer melting index MI is 1 ~ 6g/10min, and vinyl acetate content is 14 ~ 40%;
Above-mentioned ethylene-methyl acrylate copolymer melting index MI is 1 ~ 6g/10min, and methyl acrylate content is 8 ~ 30%.
The further restriction of technique scheme is: described powdery polyphenylene oxide fusing point is 268 DEG C, and median size is 5 μm, and maximum particle diameter is 20 μm; Described powdery polyphenylene oxide, 5% decomposition temperature >350 DEG C.
The further restriction of technique scheme is: described oxidation inhibitor comprises Hinered phenols antioxidant and suffocated amine antioxidant, it is one or more the mixture in following material: four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol resin; N, N ＇-1,6-inferior hexyl-bis-[3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid amide]; The two lauryl alcohol ester of thio-2 acid; Tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester; P-isopropoxy-diphenylamine; 4,4 ,-bis-(alpha, alpha-dimethylbenzyl) pentanoic; Two (Isosorbide-5-Nitrae-dimethyl amyl group) Ursol D of N, N-; N, N-bis--betanaphthyl Ursol D; N-(1,3-dimethylbutyl)-4-aminodiphenylamine; 2,2,4-trimethylammonium-1,2 dihyaroquinoline polymer.
The further restriction of technique scheme is: described plastic working lubricant is one or more mixture of following material: stearic acid, Zinic stearas, calcium stearate, Magnesium Stearate, polyethylene wax.
In order to solve the problems of the technologies described above, the present invention proposes following technical scheme: a kind of manufacture method of described halogen-free non-red-phosphorus flame-retardant polyolefine material, and it comprises the following steps:
Step 1: take polyolefin resin 100 parts, powdery polyphenylene oxide 10-60 part, phenoxy group polyphosphonitrile 5-20 part, oxidation inhibitor 0.3-2.0 part, plastic working lubricant 0.5-1.5 part according to parts by weight, mix under the circumference of the high-speed rotation with high-speed mixer, put into Banbury mixer or twin screw compounder melting mixing that Heating temperature is set to 120-200 DEG C, making length is 2-4mm, and diameter is the cylindric plastic pellet of 3-5mm;
Step 2: by the plastic pellet of step 1 gained through the extrusion moulding of plastic extruding forming machine.
In order to solve the problems of the technologies described above, the present invention proposes following technical scheme: a kind of method of radiation crosslinking halogen-free non-red-phosphorus flame-retardant polyolefine material, is characterized in that comprising the following steps:
Step 1: take polyolefin resin 100 parts, powdery polyphenylene oxide 10-60 part, phenoxy group polyphosphonitrile 5-20 part, oxidation inhibitor 0.3-2.0 part, plastic working lubricant 0.5-1.5 part according to parts by weight, mix under the circumference of the high-speed rotation with high-speed mixer, put into Banbury mixer or twin screw compounder melting mixing that Heating temperature is set to 120-200 DEG C, making length is 2-4mm, and diameter is the cylindric plastic pellet of 3-5mm;
Step 2: by the plastic pellet of step 1 gained through the extrusion moulding of plastic extruding forming machine;
Step 3: by material high-energy electron accelerator shaping for step 2 with 5-20Mrad cross-linking radiation, or with radioelement cobalt Co60 release energetic ray with 50-200KGY cross-linking radiation, realize electric wire or cable outer layer to be cross-linked, obtain radiation crosslinking halogen-free non-red-phosphorus flame-retardant polyolefine material.
The further restriction of technique scheme is, described polyolefin resin is one or more the mixture in following material: polyethylene, ethylene-propylene copolymer, ethylene-octene copolymer, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer;
Above-mentioned poly melting index MI is 0.1 ~ 10g/10min;
The ethylene content of above-mentioned ethylene-propylene copolymer is 50 ~ 70%, and propylene content is 30 ~ 50%;
The mooney viscosity (ML 1+4,125 DEG C) of above-mentioned ethylene-octene copolymer is 5 ~ 50;
Above-mentioned ethylene-vinyl acetate copolymer melting index MI is 1 ~ 6g/10min, and vinyl acetate content is 14 ~ 40%;
Above-mentioned ethylene-methyl acrylate copolymer melting index MI is 1 ~ 6g/10min, and methyl acrylate content is 8 ~ 30%;
Described powdery polyphenylene oxide fusing point is 268 DEG C, and median size is 5 μm, and maximum particle diameter is 20 μm; Described powdery polyphenylene oxide, 5% decomposition temperature >350 DEG C;
Described oxidation inhibitor comprises Hinered phenols antioxidant and suffocated amine antioxidant, is one or more the mixture in following material: four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol resin; N, N ＇-1,6-inferior hexyl-bis-[3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid amide]; The two lauryl alcohol ester of thio-2 acid; Tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester; P-isopropoxy-diphenylamine; 4,4 ,-bis-(alpha, alpha-dimethylbenzyl) pentanoic; Two (Isosorbide-5-Nitrae-dimethyl amyl group) Ursol D of N, N-; N, N-bis--betanaphthyl Ursol D; N-(1,3-dimethylbutyl)-4-aminodiphenylamine; 2,2,4-trimethylammonium-1,2 dihyaroquinoline polymer;
Described plastic working lubricant is one or more mixture of following material: stearic acid, Zinic stearas, calcium stearate, Magnesium Stearate, polyethylene wax.
In order to solve the problems of the technologies described above, the present invention proposes following technical scheme: a kind of method of halogen-free non-red-phosphorus flame-retardant polyolefin heat-shrinkable material, is characterized in that comprising the following steps:
Step 1: take polyolefin resin 100 parts, powdery polyphenylene oxide 10-60 part, phenoxy group polyphosphonitrile 5-20 part, oxidation inhibitor 0.3-2.0 part, plastic working lubricant 0.5-1.5 part according to parts by weight, mix under the circumference of the high-speed rotation with high-speed mixer, put into Banbury mixer or twin screw compounder melting mixing that Heating temperature is set to 120-200 DEG C, making length is 2-4mm, and diameter is the cylindric plastic pellet of 3-5mm;
Step 2: by the plastic pellet of step 1 gained through the extrusion moulding of plastic extruding forming machine;
Step 3: by material high-energy electron accelerator shaping for step 2 with 5-20Mrad cross-linking radiation, or with radioelement cobalt Co
60the energetic ray of releasing, with 50-200KGY cross-linking radiation, realizes electric wire or cable outer layer and is cross-linked, obtain radiation crosslinking halogen-free non-red-phosphorus flame-retardant polyolefine material;
Step 4: by radiation crosslinking halogen-free non-red-phosphorus flame-retardant polyolefine material heat temperature raising, type of heating is warm air or glycerine, when material temperature reaches 110-200 DEG C, by mechanical force or air pressure or vacuum pressure official post material dilatating and deformable, distortion multiplying power is 2-5 times, by the quick cooling and shaping of material of distortion, obtain halogen-free non-red-phosphorus flame-retardant heat-shrinkage material.
The further restriction of technique scheme is, described polyolefin resin is one or more the mixture in following material: polyethylene, ethylene-propylene copolymer, ethylene-octene copolymer, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer;
Above-mentioned poly melting index MI is 0.1 ~ 10g/10min;
The ethylene content of above-mentioned ethylene-propylene copolymer is 50 ~ 70%, and propylene content is 30 ~ 50%;
The mooney viscosity (ML 1+4,125 DEG C) of above-mentioned ethylene-octene copolymer is 5 ~ 50;
Above-mentioned ethylene-vinyl acetate copolymer melting index MI is 1 ~ 6g/10min, and vinyl acetate content is 14 ~ 40%;
Above-mentioned ethylene-methyl acrylate copolymer melting index MI is 1 ~ 6g/10min, and methyl acrylate content is 8 ~ 30%;
Described powdery polyphenylene oxide fusing point is 268 DEG C, and median size is 5 μm, and maximum particle diameter is 20 μm; Described powdery polyphenylene oxide, 5% decomposition temperature >350 DEG C;
Described oxidation inhibitor comprises Hinered phenols antioxidant and suffocated amine antioxidant, is one or more the mixture in following material: four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol resin; N, N ＇-1,6-inferior hexyl-bis-[3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid amide]; The two lauryl alcohol ester of thio-2 acid; Tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester; P-isopropoxy-diphenylamine; 4,4 ,-bis-(alpha, alpha-dimethylbenzyl) pentanoic; Two (Isosorbide-5-Nitrae-dimethyl amyl group) Ursol D of N, N-; N, N-bis--betanaphthyl Ursol D; N-(1,3-dimethylbutyl)-4-aminodiphenylamine; 2,2,4-trimethylammonium-1,2 dihyaroquinoline polymer;
Described plastic working lubricant is one or more mixture of following material: stearic acid, Zinic stearas, calcium stearate, Magnesium Stearate, polyethylene wax.
The present invention has following beneficial effect: this material is not containing halogen, red phosphorus material, and good flame resistance, can radiation crosslinking, manufactures radiation crosslinking halogen-free non-red-phosphorus flame-retardant polyolefine material, and then manufactures Halogen no red phosphorus polyolefin flame-retardant heat-shrinkage material.
Embodiment
The present invention proposes a kind of halogen-free non-red-phosphorus flame-retardant polyolefine material, is made up of the component of following weight parts:
Described polyolefin resin is one or more the mixture in following material: the polythene derivatives such as polyethylene, ethylene-propylene copolymer, ethylene-octene copolymer, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer.
Above-mentioned poly melting index MI is 0.1 ~ 10g/10min.
The ethylene content of above-mentioned ethylene-propylene copolymer is 50 ~ 70%, and propylene content is 30 ~ 50%.
The mooney viscosity (ML 1+4,125 DEG C) of above-mentioned ethylene-octene copolymer is 5 ~ 50.
Above-mentioned ethylene-vinyl acetate copolymer melting index MI is 1 ~ 6g/10min, and vinyl acetate content is 14 ~ 40%.
Above-mentioned ethylene-methyl acrylate copolymer melting index MI is 1 ~ 6g/10min, and methyl acrylate content is 8 ~ 30%.
Described powdery polyphenylene oxide fusing point is 268 DEG C, and median size is 5 μm, and maximum particle diameter is 20 μm.Described powdery polyphenylene oxide, 5% decomposition temperature >350 DEG C.
Described oxidation inhibitor comprises Hinered phenols antioxidant and suffocated amine antioxidant, is the combination that is a kind of or wherein many kinds of substance in following material: four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol resin; N, N ＇-1,6-inferior hexyl-bis-[3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid amide]; The two lauryl alcohol ester of thio-2 acid; Tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester; P-isopropoxy-diphenylamine; 4,4 ,-bis-(alpha, alpha-dimethylbenzyl) pentanoic (KY-405); Two (Isosorbide-5-Nitrae-dimethyl amyl group) Ursol D (anti-aging agent 4030) of N, N-; N, N-bis--betanaphthyl Ursol D (antioxidant D NP); N-(1,3-dimethylbutyl)-4-aminodiphenylamine (antioxidant 4020); 2,2,4-trimethylammonium-1,2 dihyaroquinoline polymer (anti-aging agent RD).
Described plastic working lubricant is one or more mixture of following material: stearic acid, Zinic stearas, calcium stearate, Magnesium Stearate, polyethylene wax.
The present invention proposes a kind of manufacture method of halogen-free non-red-phosphorus flame-retardant polyolefine material, comprises the following steps:
Step 1: take polyolefin resin 100 parts, powdery polyphenylene oxide 10-60 part, phenoxy group polyphosphonitrile 5-20 part, oxidation inhibitor 0.3-2.0 part, plastic working lubricant 0.5-1.5 part according to parts by weight, mix under the circumference of the high-speed rotation with high-speed mixer, put into Banbury mixer or twin screw compounder melting mixing that Heating temperature is set to 120-200 DEG C, making length is 2-4mm, and diameter is the cylindric plastic pellet of 3-5mm;
Step 2: the structure and the shape that by the plastic pellet of step 1 gained through the extrusion moulding of plastic extruding forming machine are design.
The present invention proposes a kind of manufacture method of radiation crosslinking halogen-free non-red-phosphorus flame-retardant polyolefine material, comprises the following steps:
Step 1: take polyolefin resin 100 parts, powdery polyphenylene oxide 10-60 part, phenoxy group polyphosphonitrile 5-20 part, oxidation inhibitor 0.3-2.0 part, plastic working lubricant 0.5-1.5 part according to parts by weight, mix under the circumference of the high-speed rotation with high-speed mixer, put into Banbury mixer or twin screw compounder melting mixing that Heating temperature is set to 120-200 DEG C, making length is 2-4mm, and diameter is the cylindric plastic pellet of 3-5mm;
Step 2: the structure and the shape that by the plastic pellet of step 1 gained through the extrusion moulding of plastic extruding forming machine are design;
Step 3: by material high-energy electron accelerator shaping for step 2 with 5-20Mrad cross-linking radiation, or with radioelement cobalt Co
60the energetic ray of releasing, with 50-200KGY cross-linking radiation, realizes electric wire or cable outer layer and is cross-linked, obtain radiation crosslinking halogen-free non-red-phosphorus flame-retardant polyolefine material.
The present invention proposes a kind of manufacture method of halogen-free non-red-phosphorus flame-retardant polyolefin heat-shrinkable material, comprises the following steps:
Step 1: take polyolefin resin 100 parts, powdery polyphenylene oxide 10-60 part, phenoxy group polyphosphonitrile 5-20 part, oxidation inhibitor 0.3-2.0 part, plastic working lubricant 0.5-1.5 part according to parts by weight, mix under the circumference of the high-speed rotation with high-speed mixer, put into Banbury mixer or twin screw compounder melting mixing that Heating temperature is set to 120-200 DEG C, making length is 2-4mm, and diameter is the cylindric plastic pellet of 3-5mm;
Step 2: the structure and the shape that by the plastic pellet of step 1 gained through the extrusion moulding of plastic extruding forming machine are design;
Step 3: by material high-energy electron accelerator shaping for step 2 with 5-20Mrad cross-linking radiation, or with radioelement cobalt Co
60the energetic ray of releasing, with 50-200KGY cross-linking radiation, realizes electric wire or cable outer layer and is cross-linked, obtain radiation crosslinking halogen-free non-red-phosphorus flame-retardant polyolefine material;
Step 4: by radiation crosslinking halogen-free non-red-phosphorus flame-retardant polyolefine material heat temperature raising, type of heating is the medium such as warm air or glycerine, when material temperature reaches 110-200 DEG C, by mechanical force or air pressure or vacuum pressure official post material dilatating and deformable, distortion multiplying power is 2-5 times, by the quick cooling and shaping of material of distortion, obtain halogen-free non-red-phosphorus flame-retardant heat-shrinkage material.
preparation embodiment one
According to parts by weight, polyolefin resin, selects high density polyethylene(HDPE), takes 100 parts; Powdery polyphenylene oxide, takes 10 parts; Phenoxy group polyphosphonitrile, takes 20 parts; Oxidation inhibitor, selects four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol resin, takes 0.3 part; Plastic working lubricant, selects stearic acid, takes 0.5 part.
With Banbury mixer or twin screw compounder by abundant to said polyolefins resin, powdery polyphenylene oxide, phenoxy group polyphosphonitrile, oxidation inhibitor and plastic working lubricant melting mixing granulation.
By the above-mentioned master batch mixed, produce AWG18 line at conventional electric wire forcing machine, conductor is multiply tinned stranded wire (0.254mm × 16 piece), and thickness of insulating layer is 0.70mm, and the speed of extruding is 500m/min.
The performance of this insulation layer is as follows:
The halogen-free non-red-phosphorus flame-retardant polyolefine material of the present embodiment is used as the insulation layer of halogen-free flame-resistant electronic wire, except there is good insulativity, also there is good processibility, when extruding at a high speed production, wire surface is smooth, there will not be the too fast uncontrollable problem of screw rod shearing heat-dissipating, temperature rising.In addition, only have an appointment compared with 200%-300% with conventional halogen-free flame-retardant wire elongation at break, this material has good extensibility, can overcome conventional material deficiency in this regard.
preparation embodiment two
According to parts by weight, polyolefin resin, selects high density polyethylene(HDPE), takes 70 parts, also selects polyolefin elastomer (POE), takes 30 parts; Powdery polyphenylene oxide, takes 40 parts; Phenoxy group polyphosphonitrile, takes 18 parts; Oxidation inhibitor, selects four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol resin, takes 0.5 part; Plastic working lubricant, selects stearic acid, takes 0.7 part.
With Banbury mixer or twin screw compounder by abundant to said polyolefins resin, powdery polyphenylene oxide, phenoxy group polyphosphonitrile, oxidation inhibitor and plastic working lubricant melting mixing granulation.
By the above-mentioned master batch mixed, extrude at twice at double-deck electric wire forcing machine and produce AWG No. 12 lines, conductor is multiply tinned stranded wire (0.30mm × 52 piece), and thickness of insulating layer is 1.52mm, external sheath layer thickness is 0.76mm, and the speed of extruding is 400m/min.
By the double-deck electric wire high-energy electron accelerator of above-mentioned gained with 15Mrad, or with radioelement cobalt Co
60the energetic ray of releasing, with the energy irradiation of 150KGY, makes it be cross-linked, obtains radiation crosslinking halogen-free non-red-phosphorus flame-retardant polyolefine electric wire.
The performance of this insulation layer and external sheath layer is as follows:
The halogen-free non-red-phosphorus flame-retardant polyolefine material of the present embodiment is used as insulation layer and the external sheath layer of radiation crosslinking halogen-free flameproof photovoltaic electric wire, except there is good insulativity, also there is good processibility, when extruding at a high speed production, wire surface is smooth, there will not be the too fast uncontrollable problem of screw rod shearing heat-dissipating, temperature rising.In addition, only have an appointment compared with 200%-300% with conventional halogen-free flame-retardant wire elongation at break, this material has good extensibility, can conventional material deficiency in this regard.
preparation embodiment three
According to parts by weight, polyolefin resin, selects Low Density Polyethylene, takes 70 parts, selects ethylene-vinyl acetate copolymer, takes 30 parts; Powdery polyphenylene oxide, takes 50 parts; Phenoxy group polyphosphonitrile, takes 5 parts; Oxidation inhibitor, selects four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol resin, takes 2.0 parts; Plastic working lubricant, selects stearic acid, takes 1.5 parts.
With Banbury mixer or twin screw compounder by the described abundant melting mixing granulation of polyolefin resin, powdery polyphenylene oxide, phenoxy group polyphosphonitrile, oxidation inhibitor and plastic working lubricant of measuring in proportion.
By the above-mentioned master batch mixed, be extruded into circular pipe with common plastics single screw extrusion machine.
By the circular pipe high-energy electron accelerator of above-mentioned gained with 20Mrad, or with radioelement cobalt Co
60the energetic ray of releasing, with the energy irradiation of 200KGY, makes it be cross-linked, obtains radiation crosslinking halogen-free non-red-phosphorus flame-retardant polyolefine material.
Performance after this circular pipe radiation crosslinking is as follows:
The halogen-free non-red-phosphorus flame-retardant polyolefine material of the present embodiment is used as radiation crosslinking halogen-free non-red-phosphorus flame-retardant polyolefine sleeve pipe, except there is good insulativity, resistance toheat, also there is good processibility, when quick extrusion, sleeve surface is smooth, there will not be the too fast uncontrollable problem of screw rod shearing heat-dissipating, temperature rising.In addition, only have an appointment compared with 200%-300% with conventional halogen-free flameproof elongation at break, this material has good extensibility, can conventional material deficiency in this regard.
preparation embodiment four
According to parts by weight, polyolefin resin, selects Low Density Polyethylene, takes 70 parts, selects ethylene-methyl acrylate copolymer, takes 30 parts; Powdery polyphenylene oxide, takes 60 parts; Phenoxy group polyphosphonitrile, takes 15 parts; Oxidation inhibitor, selects N, and N ＇-1,6-inferior hexyl-bis-[3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid amide], takes 1.5 parts; Plastic working lubricant, selects stearic acid, takes 1.0 parts.
With Banbury mixer or twin screw compounder by the described abundant melting mixing granulation of polyolefin resin, powdery polyphenylene oxide, phenoxy group polyphosphonitrile, oxidation inhibitor and plastic working lubricant of measuring in proportion.
By the above-mentioned master batch mixed, be extruded into circular pipe with common plastics single screw extrusion machine.
By the circular pipe high-energy electron accelerator of above-mentioned gained with 10Mrad, or with radioelement cobalt Co
60the energetic ray of releasing, with the energy irradiation of 100KGY, makes it be cross-linked.
By the circular pipe heat temperature raising of radiation crosslinking, heating medium is glycerine, when temperature reaches 150 DEG C, vacuumize to the logical pressurized gas in tubing inside, outside, form inside and outside differential pressure and make tubing dilatating and deformable, distortion multiplying power is 3 times, by the quick cooling and shaping of material of distortion, obtains halogen-free non-red-phosphorus flame-retardant heat-shrinkable tube.
This heat-shrinkable tube performance is as follows:
The halogen-free non-red-phosphorus flame-retardant polyolefine material of the present embodiment is used as halogen-free non-red-phosphorus flame-retardant thermal contraction casing tube, except there is good insulativity, resistance toheat, also there is good processibility and heat shrinkability characteristic, when quick extrusion, sleeve surface is smooth, there will not be the too fast uncontrollable problem of screw rod shearing heat-dissipating, temperature rising.The most important thing is to overcome the deficiency that conventional halogen-free flame retardant heat shrinkable sheathing contains red phosphorus, the environmental requirement of Apple can be met.
Claims (1)
1. a halogen-free non-red-phosphorus flame-retardant polyolefine material, is made up of the component of following weight parts:
Polyolefin resin 100 parts;
Powdery polyphenylene oxide 10-60 part;
Phenoxy group polyphosphonitrile 5-20 part;
Oxidation inhibitor 0.3-2.0 part;
Plastic working lubricant 0.5-1.5 part;
Described polyolefin resin is one or more the mixture in following material: polyethylene, ethylene-propylene copolymer, ethylene-octene copolymer, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer;
Above-mentioned poly melting index MI is 0.1 ~ 10g/10min;
The ethylene content of above-mentioned ethylene-propylene copolymer is 50 ~ 70%, and propylene content is 30 ~ 50%;
The mooney viscosity (ML 1+4,125 DEG C) of above-mentioned ethylene-octene copolymer is 5 ~ 50;
Above-mentioned ethylene-vinyl acetate copolymer melting index MI is 1 ~ 6g/10min, and vinyl acetate content is 14 ~ 40%;
Above-mentioned ethylene-methyl acrylate copolymer melting index MI is 1 ~ 6g/10min, and methyl acrylate content is 8 ~ 30%;
Described powdery polyphenylene oxide fusing point is 268 DEG C, and median size is 5 μm, and maximum particle diameter is 20 μm; Described powdery polyphenylene oxide, 5% decomposition temperature >350 DEG C.
2. halogen-free non-red-phosphorus flame-retardant polyolefine material according to claim 1, it is characterized in that: described oxidation inhibitor comprises Hinered phenols antioxidant and suffocated amine antioxidant, it is one or more the mixture in following material: four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol resin; N, N ＇-1,6-inferior hexyl-bis-[3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid amide]; The two lauryl alcohol ester of thio-2 acid; Tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester; P-isopropoxy-diphenylamine; 4,4 ,-bis-(alpha, alpha-dimethylbenzyl) pentanoic; Two (Isosorbide-5-Nitrae-dimethyl amyl group) Ursol D of N, N-; N, N-bis--betanaphthyl Ursol D; N-(1,3-dimethylbutyl)-4-aminodiphenylamine; 2,2,4-trimethylammonium-1,2 dihyaroquinoline polymer.
3. halogen-free non-red-phosphorus flame-retardant polyolefine material according to claim 1, is characterized in that: described plastic working lubricant is one or more mixture of following material: stearic acid, Zinic stearas, calcium stearate, Magnesium Stearate, polyethylene wax.
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| CN106634647A (en) * | 2015-10-28 | 2017-05-10 | 阿特斯(中国)投资有限公司 | Solar photovoltaic flame-retardant type white EVA packaging glue film and flame-retardant type double-glass photovoltaic component |
| EP3663360A4 (en) * | 2017-08-03 | 2021-05-05 | Mitsubishi Engineering-Plastics Corporation | Resin composition and molded article |
| CN109705440A (en) * | 2018-01-30 | 2019-05-03 | 扬州辐照中心 | A kind of preparation method of halogen-free flameproof Special busbar connector box |
| CN109206711A (en) * | 2018-08-27 | 2019-01-15 | 芜湖市元奎新材料科技有限公司 | A kind of high voltage direct current cable cross-linkable polyethylene insulation material and preparation method thereof |
| CN111269266B (en) * | 2020-04-01 | 2021-11-16 | 吉林大学 | Cyano-containing aryl ether phosphazene type halogen-free flame retardant, preparation method and application in irradiation crosslinking cable insulation material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102093626A (en) * | 2010-12-20 | 2011-06-15 | 安徽中鼎密封件股份有限公司 | Non-halogen fire resistant low-temperature shrinkable and heat-shrinkable pipe material and preparation method thereof |
| CN102858873A (en) * | 2010-04-16 | 2013-01-02 | 住友电气工业株式会社 | Non-halogen flame-retardant resin composition, and electric wire and cable which are made using same |
-
2013
- 2013-04-08 CN CN201310118190.2A patent/CN103194014B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102858873A (en) * | 2010-04-16 | 2013-01-02 | 住友电气工业株式会社 | Non-halogen flame-retardant resin composition, and electric wire and cable which are made using same |
| CN102093626A (en) * | 2010-12-20 | 2011-06-15 | 安徽中鼎密封件股份有限公司 | Non-halogen fire resistant low-temperature shrinkable and heat-shrinkable pipe material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 芳氧基聚磷腈的合成及性能;王志锋等;《火炸药学报》;20100430;第33卷(第2期);61-64 * |
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