CN101649081B - Method for manufacturing halogen-free fire-retardant polyethylene material - Google Patents
Method for manufacturing halogen-free fire-retardant polyethylene material Download PDFInfo
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- CN101649081B CN101649081B CN2008100225226A CN200810022522A CN101649081B CN 101649081 B CN101649081 B CN 101649081B CN 2008100225226 A CN2008100225226 A CN 2008100225226A CN 200810022522 A CN200810022522 A CN 200810022522A CN 101649081 B CN101649081 B CN 101649081B
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Abstract
The invention provides a method for manufacturing a halogen-free fire-retardant polyethylene material. The material is prepared from the following materials in percentage by weight: 50 to 70 percent of polyolefin base material, 30 to 50 percent of halogen-free flame retardant, 0.2 to 0.5 percent of antioxidant and 0.5 to 1.5 percent of processing agent which are extruded and pelletized after being fused and mixed through a Booth kneader. Based on the mass of the base material, the base material comprises 50 to 70 percent of high-density polyethylene, 10 to 30 percent of linear low-density polyethylene, 5 to 20 percent of ethylene-octene copolymer elastomer and 5 to 20 percent of maleic anhydride grafting polyolefin elastomer; based on the mass of the halogen-free flame retardant, the halogen-free flame retardant comprises 70 to 90 percent of ammonium polyphosphate/pentaerythritol synthetical flame retardant, 5 to 20 percent of charcoal-formation promoting agent and 5 to 10 percent of zinc borate; and based on the mass of a complex flame retardant, the complex flame retardant comprises 65 to 85 percent of ammonium polyphosphate and 15 to 35 percent of pentaerythritol. The method ensures flame retardation and mechanical property of the material simultaneously.
Description
Technical field
The present invention relates to a kind of manufacture method of halogen-free fire-retardant polyethylene material, belong to the polymer new material technology field.
Background technology
The fire-retardant problem of cable in plastics cable is more and more important, the cable that uses in many modern facilities such as automobile, boats and ships, offshore production platform especially, and fire-retardant requirement is higher.But except several plastic cables such as tetrafluoroethylene, remaining plastics is fire-retardant hardly, all need pass through fire-retardantization processing.In order to improve the flame retardant properties of electric wire, general all the employing added halogenide and the antimonous oxide that contains halogen, and the amount of being fuming was big when the shortcoming of these fire retardants was burning, produced halogenide poisonous, that be harmful to, have strong corrosion.In order to reach the fire-retardant purpose of low-smoke low-toxicity, domestic and international many experts are devoted to the exploitation of low smoke and low halogen material.Bittern-free flame-proof material had obtained developing rapidly in recent years, all have corresponding product to realize suitability for industrialized production and application as the big Japanese ink company of the UCC company of Britain BP company, the U.S., Japan etc., they normally add aluminium hydroxide [Al (OH) in not halogen-containing cable material
3] or magnesium hydroxide [Mg (OH)
2] wait inorganic combustion inhibitor.Because Al (OH)
3Or Mg (OH)
2Need add 100%～120% (accounting for the base-material mass fraction) Deng inorganic combustion inhibitor and just reach certain fire-retardant requirement, the heavy addition of inorganic combustion inhibitor then reduces the mechanical property of material significantly.Studies show that the tensile strength of material, elongation at break, flexibility etc. are all with Mg (OH)
2Consumption increase and reduce gradually, especially under high addition, the mechanical property of material descends significantly.Another kind of halogen-free flame-retardant system is ammonium polyphosphate (APP) flame-retardant system, and the key of ammonium polyphosphate flame-retardant system is to improve the quality of expansion charcoal layer to greatest extent.Acid source is APP in this flame-retardant system, and it is with the effect in foaming source; The charcoal source is tetramethylolmethane (PER).In order to improve into the carbonaceous amount, one-tenth charcoal promotor (ZEO) and fire retarding synergist zinc borate in fire retardant, have been added.In order to reach certain flame retardant effect, need in polymkeric substance, add a certain amount of APP flame retardant of people.The interpolation of fire retardant increases the melt viscosity of polymkeric substance.Adding man-hour, if polymer malt viscosity is bigger, be difficult to make that blend mixes, flame retardant particle thoroughly is aggregated thing " wetting ", thereby cause material mechanical performance to descend significantly, flame retardant effect is undesirable.
Summary of the invention
The invention provides a kind of manufacture method of halogen-free fire-retardant polyethylene material, can reduce the fire retardant addition of flame-retardant system, when guaranteeing flame retardant effect, guarantee the mechanical property of material.
The manufacture method of halogen-free fire-retardant polyethylene material of the present invention is as follows: in mass, polyolefine with 50-70% is a base-material, the halogen-free flame retardants that adds 30-50%, 0.2-0.5% oxidation inhibitor and 0.5-1.5% processing aid, extruding pelletization obtains halogen-free fire-retardant polyethylene material after this kneader melting mixing of cloth; With the polyolefin base material quality is benchmark, and described polyolefin base material comprises the high density polyethylene(HDPE) (HDPE) of 50-70%, the linear low density polyethylene (LLDPE) of 10-30%, the ethylene-octene copolymer elastomerics (POE) of 5-20% and maleic anhydride grafted ethene-octene copolymer elastomerics (MAH-g-POE) of 5-20%; Quality with halogen-free flame retardants is a benchmark, and described halogen-free flame retardants comprises ammonium polyphosphate/tetramethylolmethane compound flame retardant of 70-90%, the one-tenth charcoal promotor zeolite (ZEO) of 5-20% and the fire retarding synergist zinc borate of 5-10%; Quality with ammonium polyphosphate/tetramethylolmethane compound flame retardant is a benchmark, and the ammonium polyphosphate in described ammonium polyphosphate/tetramethylolmethane compound flame retardant accounts for 65-85%, and tetramethylolmethane accounts for 15-35%.
Described oxidation inhibitor is selected from four, and [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010), (2,4 di-tert-butyl-phenyls) tris phosphite (oxidation inhibitor 168), the two octadecyl esters (oxidation inhibitor DSTP), 1 of thio-2 acid, 3,5-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl)-sym-triazine-2,4,6-(1H, 3H, 5H) triketone (antioxidant 3114) or two or more mixture.
Described processing aid is selected from polyethylene wax (softening temperature 〉=100 ℃), stearic acid and salt thereof, fluoropolymer additive, organosilicon, or two or more mixture.
Place stirrer for mixing even described base-material, oxidation inhibitor and processing aid, described halogen-free flame retardants places stirrer for mixing even, then described base-material is added this kneader pellet feeder of cloth, described halogen-free flame retardants is added this kneader powder feed device of cloth, simultaneously at the uniform velocity reinforced according to the above ratio, under following processing condition, melt extrude pelletizing after water cooling is air-dry then.The temperature of respectively distinguishing of kneader is set at: each distinguishes temperature: 1 district 160-170 ℃, and 2 district 180-190 ℃, 3 district 200-210 ℃, 4 district 200-210 ℃, 5 district 200-210 ℃, delivery area 200-210 ℃, 200-210 ℃ in die head district; Main-machine screw rotating speed 150-250rpm, conveying screw rod rotating speed 30-50rpm.
The present invention has adopted the APP flame-retardant system.The APP/PER compound flame retardant that this flame-retardant system comprises high density polyethylene(HDPE), linear low density polyethylene, ethylene-octene copolymer elastomerics, maleic anhydride grafted ethene-octene copolymer elastomerics, be made up of ammonium polyphosphate, tetramethylolmethane, one-tenth charcoal promotor (ZEO) and fire retarding synergist zinc borate, oxidation inhibitor, right amount of processing aids etc.By selecting rational prescription for use, this flame-retardant system had both guaranteed the flame retardant properties of material, reduced the addition of APP/PER compound flame retardant in matrix resin simultaneously again, had therefore reduced the mechanical property loss of bittern-free flame-proof material.
In order to improve high mixing uniformity of filling fire retardant material, make flame retardant particle thoroughly be aggregated thing " wetting " simultaneously, the present invention utilizes this kneader of cloth to carry out melt pelletization.In general, for continuous processing, should adopt the screw rod expressing technique.Common single screw extrusion machine shearing rate is very low, and mixing uniformity is very poor, does not reach the requirement of halogen-free flame-retardant cable.Twin screw extruder has higher shearing rate, but is difficult to process the high flame-proof material of filling.This kneader of cloth is the continuous thread of general single screw rod with 3 breach separately, on machine barrel, be equipped with the fixing pin of mediating usefulness in addition, during the screw rod rotation, make material carry out axially reciprocating and radial motion simultaneously, it is the comparatively ideal production unit of present halogen-free flameproof material, it has gentle shearing rate, the narrow residence time distributes, the of short duration mixing residence time, processing characteristic such as kneading effect efficiently, make fire retardant in system, be disperseed fully, improved the flame retardant effect of fire retardant effectively, reduced because the material mechanical performance that the fire retardant skewness causes worsens and flame-retarded efficiency is low, the Zero halogen flame resistance polyethylene protecting sleeve of optical cable of preparation gained has good flame retardancy and mechanical property, and the color and luster cleaning is attractive in appearance simultaneously.The use of compatilizer has simultaneously improved inorganic and shortcoming organic materials consistency difference, and preparation gained sheath material has the good mechanical performance.
The present invention has the following advantages:
1, adopts the ammonium polyphosphate flame-retardant system, reduced the addition of fire retardant, improved the mechanical property of fire retardant material.
2, adopt this kneader of cloth, improved the mixing of material in machine, in the flame retardant properties that guarantees fire retardant material, guaranteed the mechanical property of fire retardant material.
Product bittern-free flame-proof material of the present invention can be used as cable jacket, extrudes and be covered in the optical cable skin during production, plays the effect of protection optical cable.This kind halogen-free flameproof optical cable can be used for that Nuclear power plants, subway or light rail are overhead, power engineering, airport etc. be to the optical cable laying of the demanding national key construction project of fire safety, and public places such as other shipbuilding, mine, high building hotel, entertainment are also very big to halogen-free flameproof optical cable demand.
Description of drawings
Fig. 1 is the curve of magnesium hydroxide add-on to fire-retardant index influence
Fig. 2 is the influence curve of ammonium polyphosphate/tetramethylolmethane compound flame retardant (3:1) add-on to stretching and rupturing
Fig. 3 is that ammonium polyphosphate/tetramethylolmethane compound flame retardant (3:1) add-on is to fire retardant material oxygen index influence curve
Embodiment
Embodiment 1: take by weighing 50 parts of high density polyethylene(HDPE)s (MFR is at 0.05-1.0g/10min), 30 parts of linear low density polyethylenes (MFR is at 0.5-2.5g/10min), 10 parts on ethylene-octene copolymer elastomerics (MFR is at 1.5-4.5g/10min), maleic anhydride grafted ethene-(MFR is at 1.5-4.5g/10min for the octene copolymer elastomerics, percentage of grafting is at 0.5-2%) 10 parts, (1010) 0.2 parts of phenolic antioxidants, (5912) 0.5 parts of fluorine processing aids, place high-speed mixer to stir above-mentioned materials, it is standby to obtain base-material.Take by weighing 45.5 parts of ammonium polyphosphates, 24.5 parts of tetramethylolmethanes become charcoal promotor (ZEO) 20 parts, 10 parts of fire retarding synergist zinc borates.Place high-speed mixer to stir above-mentioned materials, obtain halogen-free flame retardants.With pellet and powder feed bucket that the base-material and the halogen-free flame retardants of gained places this kneader of cloth respectively, the charge weight ratio of setting pellet and powder is 70%/30%.The temperature of respectively distinguishing of this kneader of cloth is set at: 160 ℃ in 1 district, 180 ℃ in 2 districts, 200 ℃ in 3 districts, 200 ℃ in 4 districts, 200 ℃ in 5 districts, 200 ℃ of delivery areas, 200 ℃ in die head district; Main-machine screw rotating speed 150rpm, conveying screw rod rotating speed 30rpm.The material of extruding at last is air-dry pelletizing after water-cooled, obtains required halogen-free fire-retardant polyethylene material.
Embodiment 2: take by weighing 50 parts of high density polyethylene(HDPE)s (MFR is at 0.05-1.0g/10min), 30 parts of linear low density polyethylenes (MFR is at 0.5-2.5g/10min), 10 parts on ethylene-octene copolymer elastomerics (MFR is at 1.5-4.5g/10min), maleic anhydride grafted ethene-(MFR is at 1.5-4.5g/10min for the octene copolymer elastomerics, percentage of grafting is at 0.5-2%) 10 parts, (1010) 0.2 parts of phenolic antioxidants, (5912) 0.5 parts of fluorine processing aids, place high-speed mixer to stir above-mentioned materials, it is standby to obtain base-material.Take by weighing 45.5 parts of ammonium polyphosphates, 24.5 parts of tetramethylolmethanes become 20 parts of charcoal promotor, 10 parts of fire retarding synergist zinc borates.Place high-speed mixer to stir above-mentioned materials, obtain halogen-free flame retardants.With pellet and powder feed bucket that the base-material and the halogen-free flame retardants of gained places this kneader of cloth respectively, the charge weight ratio of setting pellet and powder is 60%/40%.The temperature of respectively distinguishing of this kneader of cloth is set at: 160 ℃ in 1 district, 180 ℃ in 2 districts, 200 ℃ in 3 districts, 200 ℃ in 4 districts, 200 ℃ in 5 districts, 200 ℃ of delivery areas, 200 ℃ in die head district; Main-machine screw rotating speed 150rpm, conveying screw rod rotating speed 30rpm.The material of extruding at last is air-dry pelletizing after water-cooled, obtains required halogen-free fire-retardant polyethylene material.
Embodiment 3: take by weighing 50 parts of high density polyethylene(HDPE)s (MFR is at 0.05-1.0g/10min), 30 parts of linear low density polyethylenes (MFR is at 0.5-2.5g/10min), 10 parts on ethylene-octene copolymer elastomerics (MFR is at 1.5-4.5g/10min), maleic anhydride grafted ethene-(MFR is at 1.5-4.5g/10min for the octene copolymer elastomerics, percentage of grafting is at 0.5-2%) 10 parts, (1010) 0.2 parts of phenolic antioxidants, (5912) 0.5 parts of fluorine processing aids, place high-speed mixer to stir above-mentioned materials, it is standby to obtain base-material.Take by weighing 45.5 parts of ammonium polyphosphates, 24.5 parts of tetramethylolmethanes become 20 parts of charcoal promotor, 10 parts of fire retarding synergist zinc borates.Place high-speed mixer to stir above-mentioned materials, obtain halogen-free flame retardants.With pellet and powder feed bucket that the base-material and the halogen-free flame retardants of gained places this kneader of cloth respectively, the charge weight ratio of setting pellet and powder is 50%/50%.The temperature of respectively distinguishing of this kneader of cloth is set at: 160 ℃ in 1 district, 180 ℃ in 2 districts, 200 ℃ in 3 districts, 200 ℃ in 4 districts, 200 ℃ in 5 districts, 200 ℃ of delivery areas, 200 ℃ in die head district; Main-machine screw rotating speed 150rpm, conveying screw rod rotating speed 30rpm.The material of extruding at last is air-dry pelletizing after water-cooled, obtains required halogen-free fire-retardant polyethylene material.
Embodiment 4: take by weighing 50 parts of high density polyethylene(HDPE)s (MFR is at 0.05-1.0g/10min), 30 parts of linear low density polyethylenes (MFR is at 0.5-2.5g/10min), 10 parts on ethylene-octene copolymer elastomerics (MFR is at 1.5-4.5g/10min), maleic anhydride grafted ethene-(MFR is at 1.5-4.5g/10min for the octene copolymer elastomerics, percentage of grafting is at 0.5-2%) 10 parts, (1010) 0.2 parts of phenolic antioxidants, (5912) 0.5 parts of fluorine processing aids, place high-speed mixer to stir above-mentioned materials, it is standby to obtain base-material.Take by weighing 52 parts of ammonium polyphosphates, 28 parts of tetramethylolmethanes become 15 parts of charcoal promotor, 5 parts of fire retarding synergist zinc borates.Place high-speed mixer to stir above-mentioned materials, obtain halogen-free flame retardants.With pellet and powder feed bucket that the base-material and the halogen-free flame retardants of gained places this kneader of cloth respectively, the charge weight ratio of setting pellet and powder is 60%/40%.The temperature of respectively distinguishing of this kneader of cloth is set at: 160 ℃ in 1 district, 180 ℃ in 2 districts, 200 ℃ in 3 districts, 200 ℃ in 4 districts, 200 ℃ in 5 districts, 200 ℃ of delivery areas, 200 ℃ in die head district; Main-machine screw rotating speed 150rpm, conveying screw rod rotating speed 30rpm.The material of extruding at last is air-dry pelletizing after water-cooled, obtains required halogen-free fire-retardant polyethylene material.
Embodiment 5: take by weighing 50 parts of high density polyethylene(HDPE)s (MFR is at 0.05-1.0g/10min), 30 parts of linear low density polyethylenes (MFR is at 0.5-2.5g/10min), 10 parts on POE elastomerics (MFR is at 1.5-4.5g/10min), maleic anhydride grafted ethene-(MFR is at 1.5-4.5g/10min for the octene copolymer elastomerics, percentage of grafting is at 0.5-2%) 10 parts, (1010) 0.2 parts of phenolic antioxidants, (5912) 0.5 parts of fluorine processing aids, place high-speed mixer to stir above-mentioned materials, it is standby to obtain base-material.Take by weighing 58.5 parts of ammonium polyphosphates, 31.5 parts of tetramethylolmethanes become 5 parts of charcoal promotor, 5 parts of fire retarding synergist zinc borates.Place high-speed mixer to stir above-mentioned materials, obtain halogen-free flame retardants.With pellet and powder feed bucket that the base-material and the halogen-free flame retardants of gained places this kneader of cloth respectively, the charge weight ratio of setting pellet and powder is 60%/40%.The temperature of respectively distinguishing of this kneader of cloth is set at: 160 ℃ in 1 district, 180 ℃ in 2 districts, 200 ℃ in 3 districts, 200 ℃ in 4 districts, 200 ℃ in 5 districts, 200 ℃ of delivery areas, 200 ℃ in die head district; Main-machine screw rotating speed 150rpm, conveying screw rod rotating speed 30rpm.The material of extruding at last is air-dry pelletizing after water-cooled, obtains required halogen-free fire-retardant polyethylene material.
Embodiment 6: take by weighing 50 parts of high density polyethylene(HDPE)s (MFR is at 0.05-1.0g/10min), 30 parts of linear low density polyethylenes (MFR is at 0.5-2.5g/10min), 10 parts on ethylene-octene copolymer elastomerics (MFR is at 1.5-4.5g/10min), maleic anhydride grafted ethene-(MFR is at 1.5-4.5g/10min for the octene copolymer elastomerics, percentage of grafting is at 0.5-2%) 10 parts, (1010) 0.2 parts of phenolic antioxidants, (5912) 0.5 parts of fluorine processing aids, place high-speed mixer to stir above-mentioned materials, it is standby to obtain base-material.Take by weighing 60 parts of ammonium polyphosphates, 20 parts of tetramethylolmethanes become 15 parts of charcoal promotor, 5 parts of fire retarding synergist zinc borates.Place high-speed mixer to stir above-mentioned materials, obtain halogen-free flame retardants.With pellet and powder feed bucket that the base-material and the halogen-free flame retardants of gained places this kneader of cloth respectively, the charge weight ratio of setting pellet and powder is 60%/40%.The temperature of respectively distinguishing of this kneader of cloth is set at: 160 ℃ in 1 district, 180 ℃ in 2 districts, 200 ℃ in 3 districts, 200 ℃ in 4 districts, 200 ℃ in 5 districts, 200 ℃ of delivery areas, 200 ℃ in die head district; Main-machine screw rotating speed 150rpm, conveying screw rod rotating speed 30rpm.The material of extruding at last is air-dry pelletizing after water-cooled, obtains required halogen-free fire-retardant polyethylene material.
Embodiment 7: take by weighing 50 parts of high density polyethylene(HDPE)s (MFR is at 0.05-1.0g/10min), 30 parts of linear low density polyethylenes (MFR is at 0.5-2.5g/10min), 10 parts on POE elastomerics (MFR is at 1.54.5g/10min), maleic anhydride grafted ethene-(MFR is at 1.5-4.5g/10min for the octene copolymer elastomerics, percentage of grafting is at 0.5-2%) 10 parts, (1010) 0.2 parts of phenolic antioxidants, (5912) 0.5 parts of fluorine processing aids, place high-speed mixer to stir above-mentioned materials, it is standby to obtain base-material.Take by weighing 68 parts of ammonium polyphosphates, 12 parts of tetramethylolmethanes become 5 parts of charcoal promotor, 5 parts of fire retarding synergist zinc borates.Place high-speed mixer to stir above-mentioned materials, obtain halogen-free flame retardants.With pellet and powder feed bucket that the base-material and the halogen-free flame retardants of gained places this kneader of cloth respectively, the charge weight ratio of setting pellet and powder is 60%/40%.The temperature of respectively distinguishing of this kneader of cloth is set at: 160 ℃ in 1 district, 180 ℃ in 2 districts, 200 ℃ in 3 districts, 200 ℃ in 4 districts, 200 ℃ in 5 districts, 200 ℃ of delivery areas, 200 ℃ in die head district; Main-machine screw rotating speed 150rpm, conveying screw rod rotating speed 30rpm.The material of extruding at last is air-dry pelletizing after water-cooled, obtains required halogen-free fire-retardant polyethylene material.
Embodiment 8: take by weighing 50 parts of high density polyethylene(HDPE)s (MFR is at 0.05-1.0g/10min), 30 parts of linear low density polyethylenes (MFR is at 0.5-2.5g/10min), 10 parts on ethylene-octene copolymer elastomerics (MFR is at 1.5-4.5g/10min), maleic anhydride grafted ethene-(MFR is at 1.5-4.5g/10min for the octene copolymer elastomerics, percentage of grafting is at 0.5-2%) 10 parts, (1010) 0.5 parts of phenolic antioxidants, (5912) 1.5 parts of fluorine processing aids, place high-speed mixer to stir above-mentioned materials, it is standby to obtain base-material.Take by weighing 60 parts of ammonium polyphosphates, 20 parts of tetramethylolmethanes become 15 parts of charcoal promotor, 5 parts of fire retarding synergist zinc borates.Place high-speed mixer to stir above-mentioned materials, obtain halogen-free flame retardants.With pellet and powder feed bucket that the base-material and the halogen-free flame retardants of gained places this kneader of cloth respectively, the charge weight ratio of setting pellet and powder is 60%/40%.The temperature of respectively distinguishing of this kneader of cloth is set at: 160 ℃ in 1 district, 180 ℃ in 2 districts, 200 ℃ in 3 districts, 200 ℃ in 4 districts, 200 ℃ in 5 districts, 200 ℃ of delivery areas, 200 ℃ in die head district; Main-machine screw rotating speed 150rpm, conveying screw rod rotating speed 30rpm.The material of extruding at last is air-dry pelletizing after water-cooled, obtains required halogen-free fire-retardant polyethylene material.
Embodiment 9: take by weighing 50 parts of high density polyethylene(HDPE)s (MFR is at 0.05-1.0g/10min), 30 parts of linear low density polyethylenes (MFR is at 0.5-2.5g/10min), 10 parts on ethylene-octene copolymer elastomerics (MFR is at 1.5-4.5g/10min), maleic anhydride grafted ethene-(MFR is at 1.54.5g/10min for the octene copolymer elastomerics, percentage of grafting is at 0.5-2%) 10 parts, (1010) 0.2 parts of phenolic antioxidants, (5912) 0.5 parts of fluorine processing aids, place high-speed mixer to stir above-mentioned materials, it is standby to obtain base-material.Take by weighing 60 parts of ammonium polyphosphates, 20 parts of tetramethylolmethanes become 15 parts of charcoal promotor, 5 parts of fire retarding synergist zinc borates.Place high-speed mixer to stir above-mentioned materials, obtain halogen-free flame retardants.With pellet and powder feed bucket that the base-material and the halogen-free flame retardants of gained places this kneader of cloth respectively, the charge weight ratio of setting pellet and powder is 60%/40%.The temperature of respectively distinguishing of this kneader of cloth is set at: 170 ℃ in 1 district, 190 ℃ in 2 districts, 210 ℃ in 3 districts, 210 ℃ in 4 districts, 210 ℃ in 5 districts, 210 ℃ of delivery areas, 210 ℃ in die head district; Main-machine screw rotating speed 150rpm, conveying screw rod rotating speed 30rpm.The material of extruding at last is air-dry pelletizing after water-cooled, obtains required halogen-free fire-retardant polyethylene material.
Embodiment 10: take by weighing 50 parts of high density polyethylene(HDPE)s (MFR is at 0.05-1.0g/10min), 30 parts of linear low density polyethylenes (MFR is at 0.5-2.5g/10min), 10 parts on ethylene-octene copolymer elastomerics (MFR is at 1.5-4.5g/10min), maleic anhydride grafted ethene-(MFR is at 1.5-4.5g/10min for the octene copolymer elastomerics, percentage of grafting is at 0.5-2%) 10 parts, (1010) 0.2 parts of phenolic antioxidants, (5912) 0.5 parts of fluorine processing aids, place high-speed mixer to stir above-mentioned materials, it is standby to obtain base-material.Take by weighing 60 parts of ammonium polyphosphates, 20 parts of tetramethylolmethanes become 15 parts of charcoal promotor, 5 parts of fire retarding synergist zinc borates.Place high-speed mixer to stir above-mentioned materials, obtain halogen-free flame retardants.With pellet and powder feed bucket that the base-material and the halogen-free flame retardants of gained places this kneader of cloth respectively, the charge weight ratio of setting pellet and powder is 60%/40%.The temperature of respectively distinguishing of this kneader of cloth is set at: 160 ℃ in 1 district, 180 ℃ in 2 districts, 200 ℃ in 3 districts, 200 ℃ in 4 districts, 200 ℃ in 5 districts, 200 ℃ of delivery areas, 200 ℃ in die head district; Main-machine screw rotating speed 250rpm, conveying screw rod rotating speed 50rpm.The material of extruding at last is air-dry pelletizing after water-cooled, obtains required halogen-free fire-retardant polyethylene material.
Embodiment 11: take by weighing 50 parts of high density polyethylene(HDPE)s (MFR is at 0.05-1.0g/10min), 30 parts of linear low density polyethylenes (MFR is at 0.5-2.5g/10min), 10 parts on ethylene-octene copolymer elastomerics (MFR is at 1.5-4.5g/10min), maleic anhydride grafted ethene-(MFR is at 1.5-4.5g/10min for the octene copolymer elastomerics, percentage of grafting is at 0.5-2%) 10 parts, (3114) 0.2 parts of phenolic antioxidants, (5912) 0.5 parts of fluorine processing aids, place high-speed mixer to stir above-mentioned materials, it is standby to obtain base-material.Take by weighing 60 parts of ammonium polyphosphates, 20 parts of tetramethylolmethanes become 15 parts of charcoal promotor, 5 parts of fire retarding synergist zinc borates.Place high-speed mixer to stir above-mentioned materials, obtain halogen-free flame retardants.With pellet and powder feed bucket that the base-material and the halogen-free flame retardants of gained places this kneader of cloth respectively, the charge weight ratio of setting pellet and powder is 60%/40%.The temperature of respectively distinguishing of this kneader of cloth is set at: 160 ℃ in 1 district, 180 ℃ in 2 districts, 200 ℃ in 3 districts, 200 ℃ in 4 districts, 200 ℃ in 5 districts, 200 ℃ of delivery areas, 200 ℃ in die head district; Main-machine screw rotating speed 250rpm, conveying screw rod rotating speed 50rpm.The material of extruding at last is air-dry pelletizing after water-cooled, obtains required halogen-free fire-retardant polyethylene material.
Embodiment 12: take by weighing 50 parts of high density polyethylene(HDPE)s (MFR is at 0.05-1.0g/10min), 30 parts of linear low density polyethylenes (MFR is at 0.5-2.5g/10min), 10 parts on ethylene-octene copolymer elastomerics (MFR is at 1.5-4.5g/10min), maleic anhydride grafted ethene-(MFR is at 1.5-4.5g/10min for the octene copolymer elastomerics, percentage of grafting is at 0.5-2%) 10 parts, (3114) 0.2 parts of phenolic antioxidants, 0.5 part of polyethylene wax (softening temperature 〉=100 ℃), place high-speed mixer to stir above-mentioned materials, it is standby to obtain base-material.Take by weighing 60 parts of ammonium polyphosphates, 20 parts of tetramethylolmethanes become 15 parts of charcoal promotor, 5 parts of fire retarding synergist zinc borates.Place high-speed mixer to stir above-mentioned materials, obtain halogen-free flame retardants.With pellet and powder feed bucket that the base-material and the halogen-free flame retardants of gained places this kneader of cloth respectively, the charge weight ratio of setting pellet and powder is 60%/40%.The temperature of respectively distinguishing of this kneader of cloth is set at: 160 ℃ in 1 district, 180 ℃ in 2 districts, 200 ℃ in 3 districts, 200 ℃ in 4 districts, 200 ℃ in 5 districts, 200 ℃ of delivery areas, 200 ℃ in die head district; Main-machine screw rotating speed 250rpm, conveying screw rod rotating speed 50rpm.The material of extruding at last is air-dry pelletizing after water-cooled, obtains required halogen-free fire-retardant polyethylene material.
Various binder resin proportionings are identical with various auxiliary agent proportionings, and processing units is this kneader of cloth, and fabrication process condition is also identical, and test one is to adopt Mg (OH)
2As main flame retardant, test two is to adopt ammonium polyphosphate as main flame retardant, investigates Mg (OH)
2The mechanical property of flame-retardant system and ammonium polyphosphate flame-retardant system of the present invention and flame retardant properties, concrete contrast test data see Table 1, Fig. 1, Fig. 2, Fig. 3.
Table 1 different hydro magnesium oxide addition is the fire retardant material data of mechanical of preparation down
Series 1 ammonium polyphosphate/tetramethylolmethane compound flame retardant add-on is to the influence of fire retardant material tensile strength
Series 2 ammonium polyphosphates/tetramethylolmethane compound flame retardant add-on is to the influence of fire retardant material elongation
Find out that from table 1 and Fig. 2 when the addition of magnesium hydroxide reached 100wt%, its tensile strength and elongation at break had only 13.8MPa and 220%; Oxygen index just reaches 26.0.But oxygen index just is being called flame-retardant materials more than 27 usually, so test-results shows that the flame retarding efficiency of magnesium hydroxide is lower, needs great addition could satisfy fire-retardant requirement.Can see that from Fig. 2 and Fig. 3 when the addition of ammonium polyphosphate/tetramethylolmethane (3:1) reached 30wt%, its tensile strength and elongation at break got final product 16.8MPa and 395%; Its oxygen index can reach 27.0.
2, according to prescription, processing units and the complete processing of embodiment one, test three.Prescription, processing units according to embodiment one are twin screw extruder, test four, and complete processing is as follows:
The temperature of respectively distinguishing of twin screw extruder is set at: 180 ℃ in 1 district, 190 ℃ in 2 districts, 210 ℃ in 3 districts, 210 ℃ in 4 districts, 210 ℃ in 5 districts, 200 ℃ in die head district; Screw speed 150rpm.The material of extruding at last is air-dry pelletizing after water-cooled, obtains required halogen-free fire-retardant polyethylene material.
The performance comparison of the fire retardant material that the different processing units same recipe of table 2 are prepared
As seen from Table 2, adopt this kneader of cloth to carry out the flame retardant properties of fire retardant material of melt pelletization and mechanical property more than adopting twin screw extruder to carry out the flame retardant properties and the good mechanical property of the fire retardant material of melt pelletization.
3, press the halogen-free fire-retardant polyethylene material of embodiment eight developments, every after testing index is shown in Table 3.
The The performance test results of table 3 Zero halogen flame resistance polyethylene protecting sleeve of optical cable
As seen from Table 3, the main performance index of this halogen-free fire-retardant polyethylene material reaches the standard YD/T1113-2001 of the Post and Telegraph Department.
Claims (4)
1. the manufacture method of a Zero halogen flame resistance polyethylene cable material, it is characterized in that: in mass, polyolefine with 50-70% is a base-material, the halogen-free flame retardants that adds 30-50%, 0.2-0.5% oxidation inhibitor and 0.5-1.5% processing aid, extruding pelletization obtains halogen-free fire-retardant polyethylene material after this kneader melting mixing of cloth; Described halogen-free flame retardants is ammonium polyphosphate/tetramethylolmethane compound flame retardant of 70-90%, the one-tenth charcoal promotor of 5-20% and the fire retarding synergist zinc borate of 5-10%; Quality with ammonium polyphosphate/tetramethylolmethane compound flame retardant is a benchmark, and the ammonium polyphosphate in described ammonium polyphosphate/tetramethylolmethane compound flame retardant accounts for 65-85%, and tetramethylolmethane accounts for 15-35%; Described polyolefin base material comprises the high density polyethylene(HDPE) of 50-70%, the linear low density polyethylene of 10-30%, the ethylene-octene copolymer elastomerics of 5-20% and maleic anhydride grafted ethene-octene copolymer elastomerics of 5-20%.
2. the manufacture method of halogen-free fire-retardant polyethylene material according to claim 1, it is characterized in that: described oxidation inhibitor is selected from four, and [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010), (2,4 di-tert-butyl-phenyls) tris phosphite (oxidation inhibitor 168), the two octadecyl esters (oxidation inhibitor DSTP), 1 of thio-2 acid, 3,5-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl)-sym-triazine-2,4,6-(1H, 3H, 5H) triketone (antioxidant 3114), or the mixture of described two or more oxidation inhibitor.
3. the manufacture method of halogen-free fire-retardant polyethylene material according to claim 1, it is characterized in that: described processing aid is selected from polyethylene wax, stearic acid and salt thereof, fluoropolymer additive, organosilicon, or the mixture of described two or more auxiliary agent.
4. the manufacture method of halogen-free fire-retardant polyethylene material according to claim 1, it is characterized in that: place stirrer for mixing even described base-material, oxidation inhibitor and processing aid, described halogen-free flame retardants places stirrer for mixing even, then described base-material is added this kneader pellet feeder of cloth, described halogen-free flame retardants is added this kneader powder feed device of cloth, simultaneously at the uniform velocity reinforced according to the above ratio, melt extrude pelletizing after water cooling is air-dry then.
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| US8691884B2 (en) | 2010-11-24 | 2014-04-08 | Tyco Electronics Corporation | Crosslinked flame retardant thermoplastic elastomer gels |
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| CN103183858A (en) * | 2011-12-29 | 2013-07-03 | 深圳市宏商材料科技股份有限公司 | Oil resistant type semihard flame retardation thermal contraction double layer sleeving and processing technology |
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| CN105602071B (en) * | 2016-03-21 | 2018-06-15 | 江苏德威新材料股份有限公司 | High temperature resistant irradiation halogen-free flameproof automobile strands and preparation method thereof |
| CN106504817A (en) * | 2016-11-24 | 2017-03-15 | 三峡大学 | A kind of flexible halogen-free flameproof fireproof cable and preparation method thereof |
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