CN101735601A - Heat and flame resistant nylon composite - Google Patents
Heat and flame resistant nylon composite Download PDFInfo
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Abstract
The invention relates to heat and flame resistant nylon composite belonging to the filed of the electrical and electronic material. The heat and flame resistant nylon composite is characterized by comprising phosphorus flame retardant, nitrogen flame retardant, inorganic synergist, filler and auxiliary agent facilitating the processing and stabilizing. Due to the synergistic effect of the phosphorus flame retardant, the nitrogen flame retardant and the inorganic synergist, the nylon has the flame resistance, mains the mechanical performance, the thermal performance and the electrical insulating performance and can pass the test of the glow wire at 850 DEG C, and the problems that the defect of the nylon product is increased and the mechanical performance and the electrical insulating performance of the nylon produce are decreased due to the large consumption of the phosphorus flame retardant are solved. The heat and flame resistant nylon composite has good flame resistance, mechanical performance, thermal performance and electrical insulating performance and is mainly applied to the electrical and electronic industry.
Description
Technical field
The present invention relates to a kind of heat and flame resistant nylon composite, more particularly, the present invention relates to a kind of high temperature resistant, halogen-free flameproof, can belong to a kind of electric industry macromolecular material by the nylon composite of 850 ℃ of glowing filaments tests.
Background technology
Nylon is owing to have outstanding advantage at aspects such as mechanical property, chemical property, thermal characteristicss, becomes output maximum in the five big general engineering plastic at present, kind is maximum, purposes is the widest, the base resin of high comprehensive performance.Along with developing rapidly of electric industry and other special industry, nylon is also more and more harsher as the environment for use that most widely used engineering plastics face, as high temperature, high humidity, high-voltage, high loading etc.Therefore, need under the prerequisite that keeps its strong mechanical performance, flame retardant properties, thermal characteristics, electrical property are further improved, and fire-retardant requirement transform to Halogen low toxicity aspect.
The halogen-free flame-retardant system that is used for nylon mainly contains red phosphorus, ammonium polyphosphate, poly melamine phosphate, melamine cyanurate, inorganic combustion inhibitor, phosphinates fire retardant etc.All there is limitation to a certain degree in these halogen-free flame retardantss.Though red phosphorus has advantages such as addition is few, of many uses, the easy moisture absorption of common red phosphorus is poor with the macromolecular material consistency, causes spontaneous combustion especially easily, can not actually use.Although adopt the micro encapsulation red phosphorus combustion inhibitor, reduced the activity of red phosphorus, solved consistency, red phosphorus content is about 85%, and the spontaneous combustion problem is not effectively solved, and dust pollution is serious.Characteristics such as ammonium polyphosphate has the phosphorus content height, and addition is few, but that its main drawback is a water absorbability is strong, and thermostability is not high.The poly melamine phosphate is the another kind of environment friendly flame retardant that is widely used in nylon, compares with ammonium polyphosphate, though improved its thermal stability, phosphorus content is lower, improves not obvious to flame retardant properties.It is fire-retardant that melamine cyanurate also is usually used in nylon, is characterized in low toxicity, no burn into to heat and UV stable, however with its fire-retardant nylon, molten drop severity during burning, relatively poor to the flame retardant resistance of glass fiber enhanced nylon, can't reach the UL94-V0 level.Inorganic combustion inhibitor (as magnesium hydroxide etc.) has advantages such as low toxicity, low corrosion and low cigarette, but when being used for nylon, taking off crystal water in the course of processing easily, thereby should not adopt.The various performances that the phosphinates fire retardant is used for fiberglass reinforced fire retardant nylon are relatively superior, but its price is common fire retardant 3-5 times.In actual applications, often add phosphorous and nitrogenous fire retardant simultaneously, utilize the synergy of nitrogen phosphorus fire retardant, further improve flame retardant properties.Along with the widespread use of flame retarded polymeric material in the electron trade, also more and more higher for the requirement of glowing filament test, common fire-resistant nylon composition is difficult to by 850 ℃ of glowing filament tests.
Summary of the invention
The purpose of this invention is to provide a kind of high temperature resistant, halogen-free flameproof, can be by the nylon composite of 850 ℃ of glowing filaments tests, to solve the problems referred to above that exist in the existing nylon Non-halogen Flame Retardant Technology.
The technical scheme that the present invention takes is as follows:
Heat and flame resistant nylon composite of the present invention is a kind ofly to contain nylon resin, phosphorus flame retardant, nitrogen flame retardant, inorganic synergist, filler and help processing and the nylon composite of the auxiliary agent of stabilization.
Above-mentioned nylon resin is meant the thermoplastic resin that does not have branching, the monomer of synthetic nylon is selected from aliphatics or aromatic diacid, as hexanodioic acid, nonane diacid, sebacic acid, neighbour (, to) phthalic acid etc. and aliphatics or aromatic diamine, as hexanediamine, nonamethylene diamine, neighbour (, to) phenylenediamine, neighbour (, to) xylylene diamines etc.Nylon resin makes by polycondensation or lactan ring-opening reaction, and the mass percentage content of above-mentioned nylon resin can be 40~77%.Above-mentioned phosphorus flame retardant is meant the composition of single or oligomeric phosphorus, phosphoric acid ester, ammonium phosphate, phosphonic acid ester, phosphinates, phosphite, pyrophosphate salt, phosphine oxide and phosphonitrile, or inorganic phosphate compound, as hypophosphite monohydrate boron, or the mineral flame retardants derivative, as the composition of aluminium hydroxide, magnesium hydroxide, hydrated calcium magnesium carbonate, molybdenum oxide, zinc oxide, magnesium oxide or other zinc salt magnesium salts.Above-mentioned phosphorus flame retardant is more preferably from phosphinates or diphosphinic acid salt.Above-mentioned nitrogen flame retardant is meant the compound that contains the nitrogen element, can be at least a in melamine cyanurate, trimeric cyanamide, boric acid trimeric cyanamide, oxalic acid trimeric cyanamide, melamine phosphate, melamine pyrophosphate, polyphosphoric acid trimeric cyanamide, trimeric cyanamide diamide, trimeric cyanamide monoamide and the guanidinesalt, guanidinesalt be meant at least a in Guanidinium carbonate, cyanuric acid guanidine, phosphoguanidine, guanidine sulfate, the boric acid guanidine.Above-mentioned nitrogen flame retardant is more preferably from the polyphosphoric acid trimeric cyanamide.These nitrogen flame retardants and phosphorus flame retardant cooperative flame retardant effectively reduce the usage quantity of phosphorus flame retardant, have also reduced the boundary defect of introducing because of inorganic synergist.Because it is fire-retardant cooperative flame retardant effect that nitrogen is arranged, the mass percentage content of above-mentioned phosphorus flame retardant can be 1~20%, preferred 5~15%.When the phosphorous flame-retardant agent content is lower than 5%, be difficult to make the flame retardant rating of nylon at following UL 94 V-0 of 1mm thickness.When the phosphorous flame-retardant agent content is higher than 15%, make the mechanical property and the decreasing insulating of the following nylon products of 1mm thickness bigger.The mass percentage content of nitrogen flame retardant can be 0.2~10% in the above-mentioned fire-resistant nylon composition, preferred 0.5~5%.When nitrogen flame retardant content is lower than 0.2% and when being higher than 10%, all can not mention effective cooperative flame retardant effect.In order to reach better flame retardant effect, in the above-mentioned fire-resistant nylon composition do not affect the mechanical properties, under the situation of thermal characteristics and insulating property, can also add a spot of inorganic synergist, these inorganic synergists are the metallic compounds that contain one of aerobic, nitrogen, three kinds of elements of sulphur at least.Preferred calcium, magnesium and zinc, more preferably zinc borate and zinc sulphide.The mass percentage content of above-mentioned inorganic synergist can be 0.5~5%, preferred 0.75~3.5%.When inorganic synergist content is 0.5~5%%, can be by 850 ℃ of glowing filament tests.Above-mentioned filler and strongthener are meant at least a in glass fibre, glass microballon, carbon fiber, aramid fiber, potassium titanate fiber, natural fiber, amorphous silicon, magnesiumcarbonate, barium sulfate, feldspar, mica, quartz, kaolin, titanium dioxide, wollastonite and the nano imvite, preferred glass fibers.The mass percentage content of above-mentioned filler and strongthener is 1~50%, preferred 10~40%.The above-mentioned auxiliary agent that helps processing with stabilization is meant at least a in stablizer, the lubricant etc., stablizer be the Resorcinol that is selected from fortified phenol, phosphite, Resorcinol, pentanoic, replacement, salicylate, at least a in 124 Triazole and the benzophenone, lubricant is to be selected from least a in the derivative of longer chain fatty acid, hard soap, long chain fatty acid ester or acid amides.
Compare with existing nylon flame-retardant system, beneficial effect of the present invention is to make nylon when obtaining flame retardant properties, and mechanical property, thermal characteristics and electrical insulation performance can also well be kept, and can be by 850 ℃ of glowing filament tests.And the present invention has also made full use of the cooperative flame retardant effect of phosphorus flame retardant, nitrogen flame retardant and inorganic synergist, has promoted the flame retardant properties of nylon greatly.Fire-resistant nylon composition of the present invention has good flame retardancy, mechanical property, thermal characteristics and insulating property, is mainly used in the electric industry.
Embodiment
Further specify the present invention below by embodiment, therefore do not limit the present invention among the described scope of embodiments.Wherein tensile strength is pressed ASTM D638-2008 standard test, shock strength is pressed ASTM D 256-2006 standard test, flame retardant rating is pressed the evaluation of UL 94-2009 vertical combustion testing standard, the glowing filament probe temperature is pressed IEC 60695 glowing filament testing standards mensuration, heat-drawn wire is pressed ASTM D648 standard test, and dielectric strength is pressed ASTM D149-1997 standard test.
Embodiment 1
The nylon 66 of the polyphosphoric acid trimeric cyanamide of 1312,1 kilogram of 2 kilograms of phosphinates fire retardant Exolit, 0.5 kilogram zinc sulphide, 20 kilograms of glass fibre and 76.5 kilograms melt extruded at 220~300 ℃ through twin screw extruder make the heat and flame resistant nylon pellet, again the heat and flame resistant nylon pellet is injection molded into mechanics, calorifics and flame-retardant standard batten through injection moulding machine at 220~300 ℃, by the standard test correlated performance, concrete data are listed in table 1.
Embodiment 2
The NYLON610 of the polyphosphoric acid trimeric cyanamide of 1240,4 kilograms of 2 kilograms of phosphinates fire retardant Exolit, 1 kilogram zinc borate, 30 kilograms of glass fibre and 63 kilograms melt extruded at 220~300 ℃ through twin screw extruder make the heat and flame resistant nylon pellet, again the heat and flame resistant nylon pellet is injection molded into mechanics, calorifics and flame-retardant standard batten through injection moulding machine at 220~300 ℃, by the standard test correlated performance, concrete data are listed in table 1.
Embodiment 3
The nylon 6T of 10 kilograms of ammonium phosphate, 5 kilograms melamine cyanurate, 0.5 kilogram magnesium sulfide, 30 kilograms of carbon fibers, 0.5 kilogram hindered phenol stabilizer and 54 kilograms melt extruded at 220~300 ℃ through twin screw extruder make the heat and flame resistant nylon pellet, again the heat and flame resistant nylon pellet is injection molded into mechanics, calorifics and flame-retardant standard batten through injection moulding machine at 220~300 ℃, by the standard test correlated performance, concrete data are listed in table 1.
Embodiment 4
The nylon 9 T of 12 kilograms of magnesium hydroxides, 5 kilograms polyphosphoric acid trimeric cyanamide, 1 kilogram sulfurated lime, 20 kilograms of glass fibre and 62 kilograms melt extruded at 220~300 ℃ through twin screw extruder make the heat and flame resistant nylon pellet, again the heat and flame resistant nylon pellet is injection molded into mechanics, calorifics and flame-retardant standard batten through injection moulding machine at 220~300 ℃, by the standard test correlated performance, concrete data are listed in table 1.
Embodiment 5
The PPTA of 7 kilograms of phosphine oxides, 4 kilograms trimeric cyanamide diamide, 1.5 kilograms zinc sulphide, 20 kilograms of aramid fibers, 0.6 kilogram 124 Triazole, 0.5 kilogram stearic acid and 66.9 kilograms melt extruded at 220~300 ℃ through twin screw extruder make the heat and flame resistant nylon pellet, again the heat and flame resistant nylon pellet is injection molded into mechanics, calorifics and flame-retardant standard batten through injection moulding machine at 220~300 ℃, by the standard test correlated performance, concrete data are listed in table 1.
Embodiment 6
The nylon 9 T of 8 kilograms of ammonium phosphate, 2 kilograms polyphosphoric acid trimeric cyanamide, 0.5 kilogram zinc sulphide, 20 kilograms of glass fibre and 69.5 kilograms melt extruded at 220~300 ℃ through twin screw extruder make the heat and flame resistant nylon pellet, again the heat and flame resistant nylon pellet is injection molded into mechanics, calorifics and flame-retardant standard batten through injection moulding machine at 220~300 ℃, by the standard test correlated performance, concrete data are listed in table 1.
Embodiment 7
The nylon 6T of the cyanuric acid guanidine of 1312,1 kilogram of 10 kilograms of phosphinates fire retardant Exolit, 2.5 kilograms zinc borate, 30 kilograms of glass fibre, 1 kilogram benzophenone and 55.5 kilograms melt extruded at 220~300 ℃ through twin screw extruder make the heat and flame resistant nylon pellet, again the heat and flame resistant nylon pellet is injection molded into mechanics, calorifics and flame-retardant standard batten through injection moulding machine at 220~300 ℃, by the standard test correlated performance, concrete data are listed in table 1.
Embodiment 8
The nylon 66 of 1 kilogram of red phosphorus master batch, 10 kilograms melamine pyrophosphate, 5 kilograms zinc sulphide, 39 kilograms of aramid fibers and 45 kilograms melt extruded at 220~300 ℃ through twin screw extruder make the heat and flame resistant nylon pellet, again the heat and flame resistant nylon pellet is injection molded into mechanics, calorifics and flame-retardant standard batten through injection moulding machine at 220~300 ℃, by the standard test correlated performance, concrete data are listed in table 1.
Embodiment 9
The nylon PPTA of the phosphonitrile of 1240,6 kilograms of 18 kilograms of phosphinates fire retardant Exolit, 1.5 kilograms magnesium sulfide, 30 kilograms of potassium titanate fibers and 44.5 kilograms melt extruded at 220~300 ℃ through twin screw extruder make the heat and flame resistant nylon pellet, again the heat and flame resistant nylon pellet is injection molded into mechanics, calorifics and flame-retardant standard batten through injection moulding machine at 220~300 ℃, by the standard test correlated performance, concrete data are listed in table 1.
Embodiment 10
The nylon 66 of 4 kilograms of ammonium pyrophosphates, 10 kilograms Guanidinium carbonate, 0.5 kilogram sulfurated lime, 20 kilograms of barium sulfate and 65.5 kilograms melt extruded at 220~300 ℃ through twin screw extruder make the heat and flame resistant nylon pellet, again the heat and flame resistant nylon pellet is injection molded into mechanics, calorifics and flame-retardant standard batten through injection moulding machine at 220~300 ℃, by the standard test correlated performance, concrete data are listed in table 1.
Embodiment 11
The nylon 6T of 8 kilograms of hydration borophosphoric acids, 4 kilograms magnesium hydroxide, 4 kilograms phosphoguanidine, 4.5 kilograms zinc sulphide, 25 kilograms of feldspars and 54.5 kilograms melt extruded at 220~300 ℃ through twin screw extruder make the heat and flame resistant nylon pellet, again the heat and flame resistant nylon pellet is injection molded into mechanics, calorifics and flame-retardant standard batten through injection moulding machine at 220~300 ℃, by the standard test correlated performance, concrete data are listed in table 1.
Embodiment 12
The nylon 66 of 20 kilograms of boric acid trimeric cyanamides, 0.2 kilogram phosphoguanidine, 5 kilograms zinc borate, 20 kilograms of kaolin, 2 kilograms of hindered phenol photostabilizers and 52.8 kilograms melt extruded at 220~300 ℃ through twin screw extruder make the heat and flame resistant nylon pellet, again the heat and flame resistant nylon pellet is injection molded into mechanics, calorifics and flame-retardant standard batten through injection moulding machine at 220~300 ℃, by the standard test correlated performance, concrete data are listed in table 1.
Embodiment 13
The nylon 6T of 11.2 kilograms of triaryl phosphates, 10 kilograms polyphosphoric acid trimeric cyanamide, 0.5 kilogram zinc sulphide, 1 kilogram of mica, 0.3 kilogram of hindered phenol photostabilizer and 77 kilograms melt extruded at 220~300 ℃ through twin screw extruder make the heat and flame resistant nylon pellet, again the heat and flame resistant nylon pellet is injection molded into mechanics, calorifics and flame-retardant standard batten through injection moulding machine at 220~300 ℃, by the standard test correlated performance, concrete data are listed in table 1.
Embodiment 14
The nylon 9 T of the polyphosphoric acid trimeric cyanamide of 1312,2.2 kilograms of 7 kilograms of phosphinates fire retardant Exolit, 0.5 kilogram zinc borate, 50 kilograms of carbon fibers, 0.3 kilogram of 124 Triazole and 40 kilograms melt extruded at 220~300 ℃ through twin screw extruder make the heat and flame resistant nylon pellet, again the heat and flame resistant nylon pellet is injection molded into mechanics, calorifics and flame-retardant standard batten through injection moulding machine at 220~300 ℃, by the standard test correlated performance, concrete data are listed in table 1.
Embodiment 15
The NYLON610 of 5 kilograms of ammonium phosphites, 5 kilograms melamine cyanurate, 3 kilograms zinc sulphide, 10 kilograms of glass microballons and 77 kilograms melt extruded at 220~300 ℃ through twin screw extruder make the heat and flame resistant nylon pellet, again the heat and flame resistant nylon pellet is injection molded into mechanics, calorifics and flame-retardant standard batten through injection moulding machine at 220~300 ℃, by the standard test correlated performance, concrete data are listed in table 1.
Embodiment 16
The nylon 9 T of 7 kilograms of phospho acid ammoniums, 3 kilograms of guanidine sulfates, 2 kilograms zinc borate, 15 kilograms of glass fibre and 73 kilograms melt extruded at 220~300 ℃ through twin screw extruder make the heat and flame resistant nylon pellet, again the heat and flame resistant nylon pellet is injection molded into mechanics, calorifics and flame-retardant standard batten through injection moulding machine at 220~300 ℃, by the standard test correlated performance, concrete data are listed in table 1.
Comparative example 1
The nylon 66 of the polyphosphoric acid trimeric cyanamide of 1312,1 kilogram of 2 kilograms of phosphinates fire retardant Exolit, 20 kilograms of glass fibre and 77 kilograms melt extruded at 220~300 ℃ through twin screw extruder make the heat and flame resistant nylon pellet, again the heat and flame resistant nylon pellet is injection molded into mechanics, calorifics and flame-retardant standard batten through injection moulding machine at 220~300 ℃, by the standard test correlated performance, concrete data are listed in table 1.
Comparative example 2
The NYLON610 of the polyphosphoric acid trimeric cyanamide of 1240,4 kilograms of 2 kilograms of phosphinates fire retardant Exolit, 30 kilograms of glass fibre and 64 kilograms melt extruded at 220~300 ℃ through twin screw extruder make the heat and flame resistant nylon pellet, again the heat and flame resistant nylon pellet is injection molded into mechanics, calorifics and flame-retardant standard batten through injection moulding machine at 220~300 ℃, by the standard test correlated performance, concrete data are listed in table 1.
The performance data of table 1 heat and flame resistant nylon composite
Embodiment | Tensile strength (MPa) | Shock strength (J/m) | Flame retardant rating (0.8mm is thick) | Dielectric strength (vol/mil) | 850 ℃ of glow wire ignition extinction times (s) | 1.8Mpa heat-drawn wire (℃) |
Embodiment 1 | ??155.12 | ??133.92 | ??V0 | ??530 | ??≤5 | ??215 |
Embodiment 2 | ??106.76 | ??152.28 | ??V0 | ??470 | ??≤5 | ??198 |
Embodiment 3 | ??170.54 | ??120.59 | ??V0 | ??400 | ??≤5 | ??280 |
Embodiment 4 | ??180.63 | ??108.46 | ??V0 | ??440 | ??≤5 | ??285 |
Embodiment 5 | ??2744.21 | ??1208.86 | ??V0 | ??545 | ??≤5 | ??320 |
Embodiment 6 | ??174.08 | ??113.72 | ??V0 | ??420 | ??≤5 | ??286 |
Embodiment 7 | ??175.52 | ??123.96 | ??V0 | ??410 | ??≤5 | ??276 |
Embodiment 8 | ??150.20 | ??114.20 | ??V0 | ??520 | ??≤5 | ??205 |
Embodiment 9 | ??2805.81 | ??1426.47 | ??V0 | ??520 | ??≤5 | ??330 |
Embodiment 10 | ??146.11 | ??119.16 | ??V0 | ??489 | ??≤5 | ??208 |
Embodiment 11 | ??173.65 | ??108.55 | ??V0 | ??415 | ??≤5 | ??275 |
Embodiment 12 | ??142.45 | ??129.57 | ??V0 | ??432 | ??≤5 | ??203 |
Embodiment 13 | ??180.78 | ??122.73 | ??V0 | ??423 | ??≤5 | ??287 |
Embodiment 14 | ??190.92 | ??135.41 | ??V0 | ??453 | ??≤5 | ??290 |
Embodiment 15 | ??114.32 | ??148.63 | ??V0 | ??465 | ??≤5 | ??195 |
Embodiment 16 | ??172.38 | ??121.46 | ??V0 | ??436 | ??≤5 | ??288 |
Embodiment | Tensile strength (MPa) | Shock strength (J/m) | Flame retardant rating (0.8mm is thick) | Dielectric strength (vol/mil) | 850 ℃ of glow wire ignition extinction times (s) | 1.8Mpa heat-drawn wire (℃) |
Comparative example 1 | ??152.79 | ??129.36 | ??V0 | ??536 | ??20 | ??210 |
Comparative example 2 | ??103.46 | ??157.34 | ??V0 | ??460 | ??22 | ??196 |
By last table data as can be known, beneficial effect of the present invention is to make nylon when obtaining flame retardant properties, and mechanical property, thermal characteristics and electrical insulation performance can also well be kept, and can be by 850 ℃ of glowing filament tests.
Claims (8)
1. heat and flame resistant nylon composite, it is characterized in that containing mass percentage content and be 40~77% nylon resin, mass percentage content is 1~20% phosphorus flame retardant, mass percentage content is 0.2~10% nitrogen flame retardant, mass percentage content is 0.5~5% inorganic synergist, mass percentage content be 1~50% filler and mass percentage content be 0.5~10% help processing auxiliary agent with stabilization, the described auxiliary agent that helps processing with stabilization is meant stablizer, at least a in the lubricant etc., stablizer is to be selected from fortified phenol, phosphite, Resorcinol, pentanoic, the Resorcinol that replaces, salicylate, at least a in 124 Triazole and the benzophenone, lubricant is to be selected from longer chain fatty acid, hard soap, at least a in the derivative of long chain fatty acid ester or acid amides.
2. heat and flame resistant nylon composite according to claim 1, it is characterized in that described phosphorus flame retardant can single or oligomeric phosphorus, at least a in phosphoric acid ester, ammonium phosphate, phosphonic acid ester, phosphinates, phosphite, pyrophosphate salt, phosphine oxide and the phosphonitrile.
3. heat and flame resistant nylon composite according to claim 1 is characterized in that described phosphorus flame retardant can be the composition of inorganic phosphate compound and mineral flame retardants derivative.
4. heat and flame resistant nylon composite according to claim 1 is characterized in that described phosphorus flame retardant can be any the composition in hypophosphite monohydrate boron and aluminium hydroxide, magnesium hydroxide, hydrated calcium magnesium carbonate, molybdenum oxide, zinc oxide, the magnesium oxide.
5. heat and flame resistant nylon composite according to claim 1 is characterized in that described nitrogen flame retardant can be at least a in melamine cyanurate, trimeric cyanamide, boric acid trimeric cyanamide, oxalic acid trimeric cyanamide, melamine phosphate, melamine pyrophosphate, polyphosphoric acid trimeric cyanamide, trimeric cyanamide diamide, trimeric cyanamide monoamide and the guanidinesalt.
6. heat and flame resistant nylon composite according to claim 1 is characterized in that described inorganic synergist is the metallic compound that contains one of aerobic, nitrogen, three kinds of elements of sulphur at least.
7. heat and flame resistant nylon composite according to claim 1 is characterized in that described inorganic synergist can be any in zinc borate, the zinc sulphide.
8. heat and flame resistant nylon composite according to claim 1 is characterized in that described filler and strongthener can be at least a in glass fibre, glass microballon, carbon fiber, aramid fiber, potassium titanate fiber, natural fiber, amorphous silicon, magnesiumcarbonate, barium sulfate, feldspar, mica, quartz, kaolin, titanium dioxide, wollastonite and the nano imvite.
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