CN101812231A - Halogen free flame retardant nylon 6 composite with high CTI value and preparation method thereof - Google Patents

Halogen free flame retardant nylon 6 composite with high CTI value and preparation method thereof Download PDF

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Publication number
CN101812231A
CN101812231A CN 201010151223 CN201010151223A CN101812231A CN 101812231 A CN101812231 A CN 101812231A CN 201010151223 CN201010151223 CN 201010151223 CN 201010151223 A CN201010151223 A CN 201010151223A CN 101812231 A CN101812231 A CN 101812231A
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China
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nylon
composite
cti value
flame retardant
fire
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CN 201010151223
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Chinese (zh)
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汪晓东
孙双月
武德珍
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北京化工大学
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Publication of CN101812231A publication Critical patent/CN101812231A/en

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Abstract

The invention discloses a halogen free flame retardant nylon 6 composite with high CTI value and a preparation method thereof. The composite comprises the following components by mass percent: 643.5-68.8wt.% of nylon, 10-12wt.% of fire retardant, 7-19wt.% of fire retardant synergetic inorganic packing, 8-12% wt.% of toughening agent, 1-3wt.% of bulking agent, 5-10% wt.% of enhance inorganic filler and 0.2-0.5wt.% of anti-oxygen which are prepared into the compound by a high speed premixing dispersing primary extrusion processing. The disclosed composite has as high as 550V CTI value and UL 94V-0 level excellent fire resistance; simultaneously, the polymer has good mechanical property by a comprehensive modified technique, wherein the tensile strength reaches 70.5Mpa, the bending strength reaches 90.7MPa and the impacting strength of a gap reaches 28.1kJ/m2. The invention solves the problem that the flaming resistant and high CTI value are difficult to satisfy simultaneously; the inventive 6 nylon compound is very suitable for preparing a low-pressure vacuum contactor, a transformer coil framework, a high-temperature resistant relay, a breaker, a high voltage electrical apparatus, a handle and a thin wall electronic and electrical appliance elements, and the like.

Description

Halogen free flame retardant nylon 6 composite of a kind of high CTI value and preparation method thereof
Technical field
The present invention relates to polymeric material field, be specifically related to a kind of high halogen free flame retardant nylon 6 composite of comparing electric trace index (CTI) value, be applicable to and make low-voltage vacuum contactor, transformer winding skeleton, high-temperature resistant relay, isolating switch, high-voltage appliance switch, handle, thin-walled electrical and electronic component etc., belong to the modification of nylon technical field.
Background technology
Nylon is being commonly called as of polymeric amide, is to contain amide group (high molecular polymer NHCO-) on the molecular backbone chain.Release so far in nineteen thirty-nine from Dupont (Du Pont) company, developed into maximum, the most widely used engineering plastics of kind in the world, ultimate production occupy the first place of world's engineering plastics.Principal item has: nylon 6, nylon 66, NYLON610, nylon 12, nylon 1010, nylon 43 etc., and wherein, nylon 6, nylon 66 are most widely used general, and the output maximum accounts for more than 90% of nylon output.Nylon 6 has very high mechanical strength, the fusing point height, excellent electric performance, wear resistance, chemical proofing, fine heat-resisting performance etc., therefore, be used as high performance material and be widely used in numerous areas such as automobile, mechanical means, electronic apparatus, chemical industry equipment, building, daily necessities, communications and transportation.But nylon 6 is inflammable, and exists circuit electric leakage, short circuit, electric arc, electrical spark etc. to cause the danger of fire, has limited its application in fields such as electronic apparatuss, and therefore, exploitation high electric insulation performance fire-retardant Nylon 6 is very necessary.
At present, the flame-retardant modified method of adding halogenated flame retardant that still adopts mostly of nylon 6, the general consumption of this flame-retardant system is less, the flame retarding efficiency height, can satisfy various flame retardant rating requirements, but halogen containing flame-retardant easily is decomposed into various ions and free radical under electric field and high temperature action, cause fire retardant to surface transport, cause that anti-electric trace voltinism can descend, and the amount of being fuming is big in combustion processes, and produce the acid gas of corrodibility, discharge carcinogens etc., have environmental protection hidden danger, do not meet the requirement that " some objectionable impurities instruction is used in restriction in electronic electric equipment " of generally acknowledging in the world reaches " waste electronic andelectrical equipment instruction ", so the exploitation halogen-free flame-retardant nylon 6 meets the development trend of halogen-free environment-friendly type flame-proof, has broad application prospects.English Patent GB2200913 report adopts red phosphorus flame-retardant master batch and Mg (OH) 2Composite adding in the nylon resin can obtain the well mixture of (UL 94 V-0 levels), CTI value 〉=400V of excellent combination property, flame retardant properties.German patent DE 3844224 is introduced, and adopts red phosphorus and maleic anhydride quasi-graft copolymer composite, has obtained all nylon composites preferably of flame retardant properties and electrical insulation capability.But red phosphorus combustion inhibitor band garnet itself has become its fatal weakness, has limited the application in many electronic apparatuss.Chinese patent CN101077928A report adds the material that phosphonium flame retardant and mineral flame retardants blend obtain in Nylon 66, have flame retardant properties and higher CTI value preferably.Chinese patent 101358033A discloses a kind of halogen-free anti-dripping fire-retardant master granule that is applicable to Nylon 6.This fire-retardant master granule is made up of melamine cyanurate, titanate coupling agent, resin, organic silica gel and salt of wormwood, drippage problem in the time of can improving the flame retardant properties of nylon 6 effectively and solve the burning of nylon 6 fire retardant materials, but do not announce the CTI value of nylon 6 fire retardant materials.Chinese patent CN1075728A discloses a kind of fire-resistant nylon composition.Be added with zn cpdss such as zinc borate, zinc oxide in the said composition, can prevent to produce highly toxic phosphorus hydrides and phosphorus oxidation compound, and the metal assembly corrosion to contacting with said composition, be a kind of have favorable mechanical performance, anti-electric-arc performance and thermoplastic flame-proof nylon composite extremely low to metal assembly corrodibility.
In order to obtain good flame retardant property, improve the mechanical property and the electrical insulation capability of material, to satisfy the new demand that field of electronics is used, suitable flame-retardant system and additive have obtained to have high CTI value by adopting in the present invention, environmental-protection flame-retardant modification of nylon 6 mixtures of high flame retardant, good mechanical performance and electrical property.
Summary of the invention
The objective of the invention is to, overcome the problems referred to above that prior art exists, and solve high flame retardant and high CTI value and be difficult to the difficult problem that satisfies simultaneously, and by matrix resin is carried out toughness reinforcing and enhancing modified, thereby provide non-halogen flame-retarding high performance nylon 6 composite of a kind of high CTI value and preparation method thereof.
To achieve these goals, in the technical scheme of the present invention, with the Nylon 6 is base material, add fire retardant and fire-retardant synergistic mineral filler and improve flame retardant properties and electrical insulation capability, toughner and enhancing mineral filler improve mechanical property, add the interaction between expanding material raising polar nylon and nonpolar toughner and each component.This mixture component and quality percentage composition thereof are: nylon 6 43.5~68.8wt.%, fire retardant 10~12wt.%, fire-retardant synergistic mineral filler 7~19wt.%, toughner 8~12wt.%, expanding material 1~3wt.%, enhancing mineral filler 5~10wt.%, oxidation inhibitor 0.2~0.5wt.%.
Wherein, described nylon 6 relative viscosities are 2.4~2.6PaS, good fluidity.
Described fire retardant is at least a in melamine cyanurate, melamine polyphosphate, melamine pyrophosphate, the ammonium polyphosphate.
Described fire-retardant synergistic mineral filler is at least a in magnesium hydroxide, aluminium hydroxide, zinc borate, zinc oxide, the methylethyl phospho acid magnesium, and coupling agent treatment is all passed through on its surface.Preferably adopt wet method that magnesium hydroxide, aluminium hydroxide, zinc borate, zinc oxide and methylethyl phospho acid magnesium are carried out pre-treatment with silane coupling agent or titanate coupling agent, strengthen its surface hydrophobicity, and then improvement and matrix resin and other compatibility between components.
Described toughner is MBS (MBS).This multipolymer is that to have with crosslinked polyhutadiene be that nuclear, polymethylmethacrylate are " nuclear-shell " structure latex particle of shell, is to form by emulsion polymerization prepared, and particle dia is controlled at 200~250 nanometers, and size distribution is even.The latex particle of this " nuclear-shell " structure can not change with the variation of processing conditions in the melt blending process, easily forms single discrete distribution in plastic substrate, has than the more excellent toughening effect of general elastic body toughening system.
Described expanding material is bisphenol A-type solid epoxy or poly bisphenol hydroxy ethers, and the epoxy equivalent (weight) of bisphenol A-type solid epoxy is 1750~2100 gram/equivalents, and the number-average molecular weight of poly bisphenol hydroxy ethers is 18,000.Epoxide group in these two kinds of expanding materials has very high reactive behavior, can form stable chemical bond with the amido reaction of nylon 6 molecule chain ends in the melt-processed process, and then make expanding material and nylon 6 can reach the compatible of molecular level.In addition, these two kinds of expanding materials all have thermodynamic compatibility with the housing polymethylmethacrylate of " nuclear-shell " structure MBS, therefore, add in these two kinds of expanding materials any one, all can effectively reduce the interfacial tension of " nuclear-shell " structure MBS and nylon-6 matrix body, improve itself and matrix phase interface cohesive force, can impel " nuclear-shell " structure MBS particle in matrix, to form single discrete distribution, thereby can greatly improve toughening effect.
Described enhancing mineral filler is wollastonite, the talcum powder through surface modification, a kind of in the organo montmorillonite.Needle-like or fibrous wollastonite ultrafine powder through surface modification are applied to nylon 6, owing to have certain length-to-diameter ratio, will be orientated along injection direction, can make matrix get to a certain degree enhancing.Contain many overlapping layers in the talcous lattice, when carrying out blend, be stripped from easily, have the enhanced effect with the nylon-6 matrix body.When organic polynite and nylon 6 melt blendings, but nylon 6 polymer intercalations enter between the silicate lamella, interlamellar spacing is enlarged, laminate structure is peeled off, be evenly dispersed in the nylon matrix with single sheet, then inorganics is equivalent to rigid rod-like molecules (the about 1 μ m of length and width is about thick 0.1nm), can play the effect of molecule toughener.
Described oxidation inhibitor is one or both the miscellany in four [β-(3,5-di-t-butyl-4-hydroxyl-phenyl) propionic acid] pentaerythritol ester (being antioxidant 1010), three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester (being oxidation inhibitor 168).
The preparation method of the halogen free flame retardant nylon 6 composite of high CTI value provided by the present invention is:
The first step, with nylon 6 thorough drying in 80 ℃ of electric heating constant temperature air dry ovens, fire retardant, fire-retardant synergistic mineral filler, toughner, expanding material, enhancing mineral filler be thorough drying in 70 ℃ vacuum drying oven respectively.
Second step according to above-mentioned mass percent, took by weighing nylon 6, fire retardant, fire-retardant synergistic mineral filler, toughner, expanding material, enhancing mineral filler and oxidation inhibitor, and will mix in all raw materials input mixing machines.
The 3rd step, the material that mixes is extruded the mixture melt by carrying out melt blending in the hopper adding twin screw extruder, screw speed is 160~180 rev/mins, and each section of barrel temperature is 220~235 ℃, and the head temperature out is 230~232 ℃.
The 4th step, the mixture melt tie rod extruded is immersed cold water tank internal cooling, and granulation on tablets press, sieve then, drying, finally obtain having the halogen free flame retardant nylon 6 composite of high CTI value.
Mixture disclosed by the invention has up to the CTI value of 550V and reaches the excellent flame retardancy of UL94 V-0 level; Make polymkeric substance possess the good mechanical performance by the comprehensively modifying technology simultaneously, wherein tensile strength reaches 70.5MPa, and flexural strength reaches 90.7MPa, and notched Izod impact strength reaches 28.1kJ/m2.The invention solves high flame retardant and high CTI value and be difficult to a satisfied simultaneously difficult problem, the nylon 6 composite of being invented is highly suitable for making low-voltage vacuum contactor, transformer winding skeleton, high-temperature resistant relay, isolating switch, high-voltage appliance switch, handle, thin-walled electrical and electronic component etc.
Advantage of the present invention is to adopt the halogen-free environment-friendly flame-proof agent, halogen-free flame-retardant system based on phosphorous nitrogenous compound carries out flame-retardant modified to Nylon 6, the material that uses prescription blend of the present invention to form not only has excellent flame-retardant, high CTI value, the good mechanical performance, and burning the time has advantages such as the amount of being fuming is little, toxicity is little, environmentally friendly.In addition, the preparation method of this mixture is simple, easy to process, easy handling, environment is not polluted.
Embodiment
Below be the embodiment that does according to the prescription that technical solution of the present invention provides, in order to further explanation the present invention.Below used nylon 6 relative viscosities be 2.4~2.6PaS, good fluidity, magnesium hydroxide, aluminium hydroxide, zinc borate, zinc oxide and methylethyl phospho acid magnesium carry out pre-treatment with silane coupling agent or titanate coupling agent.
Embodiment 1
Get Nylon 6, fire retardant, fire-retardant synergistic mineral filler, toughner, expanding material, enhancing mineral filler and oxidation inhibitor, all raw materials carried out blend by following composition and mass percent thereof:
Nylon 6 68.8
Melamine cyanurate 10
Zinc borate 7
" nuclear-shell " structure MBS 8
Bisphenol A-type solid epoxy 1
Organo montmorillonite 5
Antioxidant 1010 0.1
Oxidation inhibitor 168 0.1
To mix in above-mentioned all raw materials input mixing machines, adding in the twin screw extruder melt blending then extrudes, this extruder temperature distributes as follows, be respectively to head by feed zone: 220 ℃, 230 ℃, 233 ℃, 234 ℃, 235 ℃, 235 ℃, 233 ℃, 230 ℃, 230 ℃, 230 ℃, screw speed: 160~180 rev/mins, after material is extruded through water-cooled, pelletizing, sieve.With gained pellet thorough drying in 80 ℃ of vacuum drying ovens, on injection moulding machine, be injected into the standard testing batten again.The mechanical property of prepared mixture is pressed the ISO international standard and is measured, and flame retardant properties is tested by the U.S.'s UL94 of electrician association standard, and the CTI value is tested by GB4207, and the result is as shown in table 1.
Embodiment 2
Get Nylon 6, fire retardant, fire-retardant synergistic mineral filler, toughner, expanding material, enhancing mineral filler and oxidation inhibitor, all raw materials carried out blend by following composition and mass percent thereof:
Nylon 6 48.5
Melamine cyanurate 10
Magnesium hydroxide 12
Zinc borate 7
" nuclear-shell " structure MBS 12
Bisphenol A-type solid epoxy 2
Wollastonite 8
Antioxidant 1010 0.25
Oxidation inhibitor 168 0.25
To mix in above-mentioned all raw materials input mixing machines, adding in the twin screw extruder melt blending then extrudes, this extruder temperature distributes as follows, be respectively to head by feed zone: 220 ℃, 230 ℃, 233 ℃, 234 ℃, 235 ℃, 235 ℃, 233 ℃, 230 ℃, 230 ℃, 230 ℃, screw speed: 160~180 rev/mins, after material is extruded through water-cooled, pelletizing, sieve.With gained pellet thorough drying in 80 ℃ of vacuum drying ovens, on injection moulding machine, be injected into the standard testing batten again.The mechanical property of prepared mixture is pressed the ISO international standard and is measured, and flame retardant properties is tested by the U.S.'s UL94 of electrician association standard, and the CTI value is tested by GB4207, and the result is as shown in table 1.
Embodiment 3
Get Nylon 6, fire retardant, fire-retardant synergistic mineral filler, toughner, expanding material, enhancing mineral filler and oxidation inhibitor, all raw materials carried out blend by following composition and mass percent thereof:
Nylon 6 53.5
Melamine polyphosphate 10
Magnesium hydroxide 12
Zinc oxide 5
" nuclear-shell " structure MBS 12
Bisphenol A-type solid epoxy 2
Organo montmorillonite 5
Antioxidant 1010 0.25
Oxidation inhibitor 168 0.25
To mix in above-mentioned all raw materials input mixing machines, adding in the twin screw extruder melt blending then extrudes, this extruder temperature distributes as follows, be respectively to head by feed zone: 220 ℃, 230 ℃, 233 ℃, 234 ℃, 235 ℃, 235 ℃, 233 ℃, 230 ℃, 230 ℃, 230 ℃, screw speed: 160~180 rev/mins, after material is extruded through water-cooled, pelletizing, sieve.With gained pellet thorough drying in 80 ℃ of vacuum drying ovens, on injection moulding machine, be injected into the standard testing batten again.The mechanical property of prepared mixture is pressed the ISO international standard and is measured, and flame retardant properties is tested by the U.S.'s UL94 of electrician association standard, and the CTI value is tested by GB4207, and the result is as shown in table 1.
Embodiment 4
Get Nylon 6, fire retardant, fire-retardant synergistic mineral filler, toughner, expanding material, enhancing mineral filler and oxidation inhibitor, all raw materials carried out blend by following composition and mass percent thereof:
Nylon 6 46.5
Melamine cyanurate 10
Aluminium hydroxide 12
Zinc borate 6
" nuclear-shell " structure MBS 12
Poly bisphenol hydroxy ethers 3
Wollastonite 10
Antioxidant 1010 0.25
Oxidation inhibitor 168 0.25
To mix in above-mentioned all raw materials input mixing machines, adding in the twin screw extruder melt blending then extrudes, this extruder temperature distributes as follows, be respectively to head by feed zone: 220 ℃, 230 ℃, 233 ℃, 234 ℃, 235 ℃, 235 ℃, 233 ℃, 230 ℃, 230 ℃, 230 ℃, screw speed: 160~180 rev/mins, after material is extruded through water-cooled, pelletizing, sieve.With gained pellet thorough drying in 80 ℃ of vacuum drying ovens, on injection moulding machine, be injected into the standard testing batten again.The mechanical property of prepared mixture is pressed the ISO international standard and is measured, and flame retardant properties is tested by the U.S.'s UL94 of electrician association standard, and the CTI value is tested by GB4207, and the result is as shown in table 1.
Embodiment 5
Get Nylon 6, fire retardant, fire retarding synergist, toughner, expanding material, toughness reinforcing component and oxidation inhibitor, all raw materials carried out blend by following composition and mass percent thereof:
Nylon 6 53.5
Melamine cyanurate 8
Magnesium hydroxide 10
Methylethyl magnesium hypophosphite 6
" nuclear-shell " structure MBS 12
Bisphenol A-type solid epoxy 2
Talcum powder 8
Antioxidant 1010 0.25
Oxidation inhibitor 168 0.25
To mix in above-mentioned all raw materials input mixing machines, adding in the twin screw extruder melt blending then extrudes, this extruder temperature distributes as follows, be respectively to head by feed zone: 220 ℃, 230 ℃, 233 ℃, 234 ℃, 235 ℃, 235 ℃, 233 ℃, 230 ℃, 230 ℃, 230 ℃, screw speed: 160~180 rev/mins, after material is extruded through water-cooled, pelletizing, sieve.With gained pellet thorough drying in 80 ℃ of vacuum drying ovens, on injection moulding machine, be injected into the standard testing batten again.The mechanical property of prepared mixture is pressed the ISO international standard and is measured, and flame retardant properties is tested by the U.S.'s UL94 of electrician association standard, and the CTI value is tested by GB4207, and the result is as shown in table 1.
Embodiment 6
Get Nylon 6, fire retardant, fire-retardant synergistic mineral filler, toughner, expanding material, enhancing mineral filler and oxidation inhibitor, all raw materials carried out blend by following composition and mass percent thereof:
Nylon 6 58.5
Ammonium polyphosphate 4
Melamine cyanurate 8
Zinc borate 7
" nuclear-shell " structure MBS 12
Bisphenol A-type solid epoxy 2
Wollastonite 8
Antioxidant 1010 0.25
Oxidation inhibitor 168 0.25
To mix in above-mentioned all raw materials input mixing machines, adding in the twin screw extruder melt blending then extrudes, this extruder temperature distributes as follows, be respectively to head by feed zone: 220 ℃, 230 ℃, 233 ℃, 234 ℃, 235 ℃, 235 ℃, 233 ℃, 230 ℃, 230 ℃, 230 ℃, screw speed: 160~180 rev/mins, after material is extruded through water-cooled, pelletizing, sieve.With gained pellet thorough drying in 80 ℃ of vacuum drying ovens, on injection moulding machine, be injected into the standard testing batten again.The mechanical property of prepared mixture is pressed the ISO international standard and is measured, and flame retardant properties is tested by the U.S.'s UL94 of electrician association standard, and the CTI value is tested by GB4207, and the result is as shown in table 1.
Embodiment 7
Get Nylon 6, fire retardant, fire-retardant synergistic mineral filler, toughner, expanding material, enhancing mineral filler and oxidation inhibitor, all raw materials carried out blend by following composition and mass percent thereof:
Nylon 6 57.5
Ammonium polyphosphate 2
Melamine pyrophosphate 10
Zinc borate 7
Zinc oxide 4
" nuclear-shell " structure MBS 12
Bisphenol A-type solid epoxy 2
Organo montmorillonite 5
Antioxidant 1010 0.25
Oxidation inhibitor 168 0.25
To mix in above-mentioned all raw materials input mixing machines, adding in the twin screw extruder melt blending then extrudes, this extruder temperature distributes as follows, be respectively to head by feed zone: 220 ℃, 230 ℃, 233 ℃, 234 ℃, 235 ℃, 235 ℃, 233 ℃, 230 ℃, 230 ℃, 230 ℃, screw speed: 160~180 rev/mins, after material is extruded through water-cooled, pelletizing, sieve.With gained pellet thorough drying in 80 ℃ of vacuum drying ovens, on injection moulding machine, be injected into the standard testing batten again.The mechanical property of prepared mixture is pressed the ISO international standard and is measured, and flame retardant properties is tested by the U.S.'s UL94 of electrician association standard, and the CTI value is tested by GB4207, and the result is as shown in table 1.
Embodiment 8
Get Nylon 6, fire retardant, fire-retardant synergistic mineral filler, toughner, expanding material, enhancing mineral filler and oxidation inhibitor, all raw materials carried out blend by following composition and mass percent thereof:
Nylon 6 43.5
Ammonium polyphosphate 2
Melamine cyanurate 10
Magnesium hydroxide 12
Zinc borate 7
" nuclear-shell " structure MBS 12
Bisphenol A-type solid epoxy 2
Wollastonite 10
Antioxidant 1010 0.25
Oxidation inhibitor 168 0.25
To mix in above-mentioned all raw materials input mixing machines, adding in the twin screw extruder melt blending then extrudes, this extruder temperature distributes as follows, be respectively to head by feed zone: 220 ℃, 230 ℃, 233 ℃, 234 ℃, 235 ℃, 235 ℃, 233 ℃, 230 ℃, 230 ℃, 230 ℃, screw speed: 160~180 rev/mins, after material is extruded through water-cooled, pelletizing, sieve.With gained pellet thorough drying in 80 ℃ of vacuum drying ovens, on injection moulding machine, be injected into the standard testing batten again.The mechanical property of prepared mixture is pressed the ISO international standard and is measured, and flame retardant properties is tested by the U.S.'s UL94 of electrician association standard, and the CTI value is tested by GB4207, and the result is as shown in table 1.
Test event Testing standard Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7 Embodiment 8
Tensile strength (MPa) ??ISO??527 ??60.2 ??68.4 ??63.1 ??70.5 ??67.4 ??66.1 ??62.3 ??63.7
Elongation at break (%) ??ISO??527 ??39.6 ??28.6 ??32.4 ??22.8 ??26.3 ??31.6 ??36.9 ??19.6
Flexural strength (MPa) ??ISO??178 ??80.5 ??85.3 ??78.2 ??90.7 ??89.7 ??82.4 ??71.8 ??81.2
Socle girder notched Izod impact strength (kJ/m 2) ??ISO??180 ??27.9 ??21.8 ??27.6 ??16.9 ??17.1 ??21.5 ??28.1 ??15.0
Heat-drawn wire (℃, 0.45 MPa) ??GB1634 ??145 ??142 ??142 ??140 ??141 ??142 ??141 ??139
Vertical combustion grade (3.2mm) ??UL94 ??V-0 ??V-0 ??V-0 ??V-0 ??V-0 ??V-0 ??V-0 ??V-0
??CTI??(V) ??GB4207 ??500 ??525 ??500 ??525 ??550 ??525 ??500 ??550
The performance of the mixture for preparing among the table 1 embodiment 1-8
As can be seen from Table 1, the vertical combustion of the prepared material of all embodiment is tested all by UL94 V-0 level (3.2mm), CTI value 〉=500V, and have excellent mechanical property.Therefore, the invention solves high flame retardant (UL94 V-0 level) and high CTI value and be difficult to a satisfied simultaneously difficult problem, make this material not only have excellent flame-retardant but also have the excellent electric insulating energy.Harmful and noxious substances such as this mixture is not halogen-containing, heavy metal, the amount of being fuming is few in the combustion processes, toxicity is little, and is environmentally friendly, meets the RoHS and the WEEE instruction of European Union.Its preparation method has that complete processing is simple, easy to process, easy handling, to characteristics such as not pollution of environment, prepared constant product quality.This mixture is applicable to makes low-voltage vacuum contactor, transformer winding skeleton, high-temperature resistant relay, isolating switch, high-voltage appliance switch, handle, thin-walled electrical and electronic component etc.
Material name The trade mark Producer
Nylon 6 ??1013B Ube Co., Ltd.
" nuclear-shell " structure MBS (MBS) ??M600 Japan clock deep pool chemical industrial company
The bisphenol A-type solid epoxy ??7050 Wuxi blue star novel material company limited
The poly bisphenol hydroxy ethers Beijing chemical reagents corporation
Wollastonite ??G-1250F Liaoning celestial stone mining industry company limited
Organo montmorillonite ??PGV Beijing happy luxuriant specialization development in science and technology company limited
Talcum powder Blue powder company limited of Beijing section
Ammonium polyphosphate ??APP101R Hangzhou JLS Flame Retardants Chemical Co., Ltd.
Melamine cyanurate ??MC15 Hangzhou JLS Flame Retardants Chemical Co., Ltd.
Melamine polyphosphate ??PNA Hangzhou JLS Flame Retardants Chemical Co., Ltd.
Melamine pyrophosphate Shijiazhuang sky occasion Chemical Industry Science Co., Ltd
Magnesium hydroxide ??0012 Sea, Weifang magnesium chemical industry company limited
Material name The trade mark Producer
Aluminium hydroxide ??AH-Y Sea, Weifang magnesium chemical industry company limited
Zinc borate ??ZB-Y Sea, Weifang magnesium chemical industry company limited
Zinc oxide Sea, Weifang magnesium chemical industry company limited
The methylethyl magnesium hypophosphite Zibo is nation's chemical industry company limited all
Table 2 embodiment 1-8 raw materials used and the trade mark and producer

Claims (9)

1. the halogen free flame retardant nylon 6 composite of a high CTI value, it is characterized in that mixture component and quality percentage composition thereof are: nylon 643.5~68.8wt.%, fire retardant 10~12wt.%, fire-retardant synergistic mineral filler 7~19wt.%, toughner 8~12wt.%, expanding material 1~3wt.%, enhancing mineral filler 5~10wt.%, oxidation inhibitor 0.2~0.5wt.%.
2. the halogen free flame retardant nylon 6 composite of a kind of high CTI value according to claim 1 is characterized in that, described nylon 6 relative viscosities are 2.4~2.6PaS.
3. the halogen free flame retardant nylon 6 composite of a kind of high CTI value according to claim 1 is characterized in that, described fire retardant is at least a in melamine cyanurate, melamine polyphosphate, melamine pyrophosphate, the ammonium polyphosphate.
4. the halogen free flame retardant nylon 6 composite of a kind of high CTI value according to claim 1, it is characterized in that, described fire-retardant synergistic mineral filler is at least a in magnesium hydroxide, aluminium hydroxide, zinc borate, zinc oxide, the methylethyl phospho acid magnesium, and coupling agent treatment is all passed through on its surface.
5. the halogen free flame retardant nylon 6 composite of a kind of high CTI value according to claim 1, it is characterized in that, described toughner is MBS (MBS), and it is that nuclear, polymethylmethacrylate are " nuclear-shell " structure of shell that this multipolymer has with crosslinked polyhutadiene.
6. the halogen free flame retardant nylon 6 composite of a kind of high CTI value according to claim 1 is characterized in that, described expanding material is bisphenol A-type solid epoxy or poly bisphenol hydroxy ethers.
7. the halogen free flame retardant nylon 6 composite of a kind of high CTI value according to claim 1 is characterized in that, wollastonite, talcum powder that described enhancing mineral filler is a surface modification, a kind of in the organo montmorillonite.
8. the halogen free flame retardant nylon 6 composite of a kind of high CTI value according to claim 1, it is characterized in that, described oxidation inhibitor is four [β-(3,5-di-t-butyl-4-hydroxyl-phenyl) propionic acid] one or both miscellany in pentaerythritol ester (being antioxidant 1010), three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester (being oxidation inhibitor 168).
9. the preparation method of the halogen free flame retardant nylon 6 composite of a kind of high CTI value according to claim 1 is characterized in that, concrete method and step comprise:
The first step, with nylon 6 thorough drying in 80 ℃ of electric heating constant temperature air dry ovens, fire retardant, fire-retardant synergistic mineral filler, toughner, expanding material, enhancing mineral filler be thorough drying in 70 ℃ vacuum drying oven respectively;
Second step according to above-mentioned mass percent, took by weighing nylon 6, fire retardant, fire-retardant synergistic mineral filler, toughner, expanding material, enhancing mineral filler and oxidation inhibitor, and will mix in all raw materials input mixing machines;
The 3rd step, the material that mixes is extruded the mixture melt by carrying out melt blending in the hopper adding twin screw extruder, screw speed is 160~180 rev/mins, and each section of barrel temperature is 220~235 ℃, and the head temperature out is 230~232 ℃;
The 4th step, the mixture melt tie rod extruded is immersed cold water tank internal cooling, and granulation on tablets press, sieve then, drying, finally obtain having the halogen free flame retardant nylon 6 composite of high CTI value.
CN 201010151223 2010-04-16 2010-04-16 Halogen free flame retardant nylon 6 composite with high CTI value and preparation method thereof CN101812231A (en)

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Cited By (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102002218A (en) * 2010-11-24 2011-04-06 广东省石油化工研究院 Halogen-free compound flame retardant for glass fiber reinforced PBT (Polybutylene Terephthalate) material and preparation method thereof
CN102120879A (en) * 2011-02-19 2011-07-13 本松工程塑料(杭州)有限公司 High-temperature resistant and high-CTI (Comparative Tracing Index) flame-retardant polyamide composite material and preparation method thereof
CN102321367A (en) * 2011-09-07 2012-01-18 上海日之升新技术发展有限公司 High-CTI antistatic fire-retardance-enhanced PA6 composite material and preparation method thereof
CN102337022A (en) * 2011-05-31 2012-02-01 深圳市科聚新材料有限公司 Nylon material special for breakers and preparation method thereof
CN102391643A (en) * 2011-09-07 2012-03-28 上海日之升新技术发展有限公司 High temperate-resistant nanometer fire resistance-enhanced PA6 composite material and preparation method thereof
CN102399439A (en) * 2010-09-16 2012-04-04 佛山市顺德区威林工程塑料有限公司 High glow-wire ignition temperature halogen-free flame retardant PA66 material and preparation method thereof
CN102558850A (en) * 2011-12-13 2012-07-11 中国科学院宁波材料技术与工程研究所 Flame-retardant functional masterbatch special for nylon 6 and preparation method for masterbatch
CN102618026A (en) * 2012-04-25 2012-08-01 中国科学院宁波材料技术与工程研究所 Halogen-free and flame-retardant nylon master batch with high CTI (Comparative Tracking Index) value and preparation method thereof
CN102850787A (en) * 2012-04-27 2013-01-02 常熟市发东塑业有限公司 Halogen-free flame-retarding nylon composite material
CN102850789A (en) * 2012-04-27 2013-01-02 常熟市发东塑业有限公司 High-flame-retardance nylon composite material
CN102993625A (en) * 2012-11-19 2013-03-27 开滦能源化工股份有限公司 Halogen-free flame-retardant formaldehyde composite material with high CTI (comparative tracking index) and preparation method thereof
CN103013104A (en) * 2012-12-26 2013-04-03 上海金发科技发展有限公司 Halogen-free filling flame-retardant nylon 6 composite material and preparation method thereof
CN103131175A (en) * 2011-11-25 2013-06-05 上海日之升新技术发展有限公司 Low smoke halogen-free flame retardant reinforced nylon composite material and manufacture method
CN103319883A (en) * 2013-06-20 2013-09-25 吴江市董鑫塑料包装厂 High-strength high-toughness polyamide
CN103483811A (en) * 2013-09-27 2014-01-01 南京理工大学 Zirconate modified magnesium hydroxide synergistic flame-retardant composite material and preparation method thereof
CN103694695A (en) * 2013-12-19 2014-04-02 上海日之升新技术发展有限公司 Glass fiber reinforced halogen-free flame-retardant PA6 (Poly Amide 6)/PS (Poly Styrene) alloy material and preparation method thereof
CN103897387A (en) * 2014-03-13 2014-07-02 江苏康非特动力科技有限公司 High strength wearable polyamide composite material and preparation method thereof
CN103910999A (en) * 2014-04-02 2014-07-09 合肥杰事杰新材料股份有限公司 High-glowing nylon 6 composition and preparation method thereof
CN104151818A (en) * 2014-08-19 2014-11-19 南通瑞隆新材料有限公司 Preparation method of flame-retardant nylon PA6 modified engineering plastic
CN105315657A (en) * 2015-12-10 2016-02-10 重庆可益荧新材料有限公司 Composite polyamide flame-retardant material and preparation method thereof
CN105385155A (en) * 2015-12-31 2016-03-09 祥兴(福建)箱包集团有限公司 Nylon plastic bearing retainer for draw-bar box and preparation method of nylon plastic bearing retainer
CN104610735B (en) * 2015-01-29 2016-08-10 北京科方创业科技企业孵化器有限公司 A kind of preparation method of intumescent non-reinforcing halogen-free flame-retardant nylon 6
CN106633855A (en) * 2016-12-15 2017-05-10 苏州博云塑业有限公司 Nylon 66 composite material for office automation equipment and preparation method of nylon 66 composite material
CN106700514A (en) * 2015-08-27 2017-05-24 上海博怀化工有限公司 Fireproof and flame-resistant composite material used for locomotive bellows, and preparation method thereof
CN106751780A (en) * 2016-12-26 2017-05-31 东莞市佳乾新材料科技有限公司 For the daiamid composition and manufacture method of piezoelectric
CN106832906A (en) * 2017-03-02 2017-06-13 张家港市五湖新材料技术开发有限公司 A kind of high flame retardant nylon composite materials for 3D printing
CN109135277A (en) * 2018-08-28 2019-01-04 安徽江淮汽车集团股份有限公司 A kind of PA66 composite material and preparation method
CN109370207A (en) * 2018-10-24 2019-02-22 江苏亿超工程塑料有限公司 A kind of halogen-free flame-retardant polyamide material and preparation method thereof
CN109402764A (en) * 2018-09-12 2019-03-01 恒天中纤纺化无锡有限公司 A kind of high-strength flatness nylon staple 6 fibre and preparation method thereof
CN109957243A (en) * 2017-12-14 2019-07-02 凯赛(乌苏)生物材料有限公司 A kind of thermoplastic halogen-free flame retarding biology base PA56 and PA66 composite material and preparation method
CN110218442A (en) * 2019-06-25 2019-09-10 金旸(厦门)新材料科技有限公司 A kind of high flowing Heat conduction nylon composite material and its preparation method and application
CN110358290A (en) * 2019-06-27 2019-10-22 苍南县鑫洋新材料有限公司 A kind of nylon material of modification

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CN1510084A (en) * 2002-12-25 2004-07-07 北京化工大学 Method for preparing high strength super-toughened nylon alloy
CN101074317A (en) * 2007-06-25 2007-11-21 辽宁大学 Production of trimeric-cyanamide cyanurate fire-retardant nylon material

Cited By (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102399439A (en) * 2010-09-16 2012-04-04 佛山市顺德区威林工程塑料有限公司 High glow-wire ignition temperature halogen-free flame retardant PA66 material and preparation method thereof
CN102002218A (en) * 2010-11-24 2011-04-06 广东省石油化工研究院 Halogen-free compound flame retardant for glass fiber reinforced PBT (Polybutylene Terephthalate) material and preparation method thereof
CN102002218B (en) * 2010-11-24 2013-01-09 广东省石油化工研究院 Halogen-free compound flame retardant for glass fiber reinforced PBT (Polybutylene Terephthalate) material and preparation method thereof
CN102120879A (en) * 2011-02-19 2011-07-13 本松工程塑料(杭州)有限公司 High-temperature resistant and high-CTI (Comparative Tracing Index) flame-retardant polyamide composite material and preparation method thereof
CN102337022A (en) * 2011-05-31 2012-02-01 深圳市科聚新材料有限公司 Nylon material special for breakers and preparation method thereof
CN102321367A (en) * 2011-09-07 2012-01-18 上海日之升新技术发展有限公司 High-CTI antistatic fire-retardance-enhanced PA6 composite material and preparation method thereof
CN102391643A (en) * 2011-09-07 2012-03-28 上海日之升新技术发展有限公司 High temperate-resistant nanometer fire resistance-enhanced PA6 composite material and preparation method thereof
CN102391643B (en) * 2011-09-07 2014-04-09 上海日之升新技术发展有限公司 High temperate-resistant nanometer fire resistance-enhanced PA6 composite material and preparation method thereof
CN103131175A (en) * 2011-11-25 2013-06-05 上海日之升新技术发展有限公司 Low smoke halogen-free flame retardant reinforced nylon composite material and manufacture method
CN102558850A (en) * 2011-12-13 2012-07-11 中国科学院宁波材料技术与工程研究所 Flame-retardant functional masterbatch special for nylon 6 and preparation method for masterbatch
CN102618026A (en) * 2012-04-25 2012-08-01 中国科学院宁波材料技术与工程研究所 Halogen-free and flame-retardant nylon master batch with high CTI (Comparative Tracking Index) value and preparation method thereof
CN102850789A (en) * 2012-04-27 2013-01-02 常熟市发东塑业有限公司 High-flame-retardance nylon composite material
CN102850787A (en) * 2012-04-27 2013-01-02 常熟市发东塑业有限公司 Halogen-free flame-retarding nylon composite material
CN102993625A (en) * 2012-11-19 2013-03-27 开滦能源化工股份有限公司 Halogen-free flame-retardant formaldehyde composite material with high CTI (comparative tracking index) and preparation method thereof
CN102993625B (en) * 2012-11-19 2014-07-16 开滦能源化工股份有限公司 Halogen-free flame-retardant formaldehyde composite material with high CTI (comparative tracking index) and preparation method thereof
CN103013104A (en) * 2012-12-26 2013-04-03 上海金发科技发展有限公司 Halogen-free filling flame-retardant nylon 6 composite material and preparation method thereof
CN103013104B (en) * 2012-12-26 2015-06-24 上海金发科技发展有限公司 Halogen-free filling flame-retardant nylon 6 composite material and preparation method thereof
CN103319883A (en) * 2013-06-20 2013-09-25 吴江市董鑫塑料包装厂 High-strength high-toughness polyamide
CN103483811A (en) * 2013-09-27 2014-01-01 南京理工大学 Zirconate modified magnesium hydroxide synergistic flame-retardant composite material and preparation method thereof
CN103694695A (en) * 2013-12-19 2014-04-02 上海日之升新技术发展有限公司 Glass fiber reinforced halogen-free flame-retardant PA6 (Poly Amide 6)/PS (Poly Styrene) alloy material and preparation method thereof
CN103694695B (en) * 2013-12-19 2016-10-05 上海日之升新技术发展有限公司 A kind of fiber glass reinforced halogen-free flame retardant PA6/PS alloy material and preparation method thereof
CN103897387A (en) * 2014-03-13 2014-07-02 江苏康非特动力科技有限公司 High strength wearable polyamide composite material and preparation method thereof
CN103910999A (en) * 2014-04-02 2014-07-09 合肥杰事杰新材料股份有限公司 High-glowing nylon 6 composition and preparation method thereof
CN104151818A (en) * 2014-08-19 2014-11-19 南通瑞隆新材料有限公司 Preparation method of flame-retardant nylon PA6 modified engineering plastic
CN104610735B (en) * 2015-01-29 2016-08-10 北京科方创业科技企业孵化器有限公司 A kind of preparation method of intumescent non-reinforcing halogen-free flame-retardant nylon 6
CN106700514A (en) * 2015-08-27 2017-05-24 上海博怀化工有限公司 Fireproof and flame-resistant composite material used for locomotive bellows, and preparation method thereof
CN105315657A (en) * 2015-12-10 2016-02-10 重庆可益荧新材料有限公司 Composite polyamide flame-retardant material and preparation method thereof
CN105385155A (en) * 2015-12-31 2016-03-09 祥兴(福建)箱包集团有限公司 Nylon plastic bearing retainer for draw-bar box and preparation method of nylon plastic bearing retainer
CN106633855A (en) * 2016-12-15 2017-05-10 苏州博云塑业有限公司 Nylon 66 composite material for office automation equipment and preparation method of nylon 66 composite material
CN106751780A (en) * 2016-12-26 2017-05-31 东莞市佳乾新材料科技有限公司 For the daiamid composition and manufacture method of piezoelectric
CN106832906B (en) * 2017-03-02 2019-08-23 上海术博新材料技术有限公司 A kind of high flame retardant nylon composite materials for 3D printing
CN106832906A (en) * 2017-03-02 2017-06-13 张家港市五湖新材料技术开发有限公司 A kind of high flame retardant nylon composite materials for 3D printing
CN109957243A (en) * 2017-12-14 2019-07-02 凯赛(乌苏)生物材料有限公司 A kind of thermoplastic halogen-free flame retarding biology base PA56 and PA66 composite material and preparation method
CN109135277A (en) * 2018-08-28 2019-01-04 安徽江淮汽车集团股份有限公司 A kind of PA66 composite material and preparation method
CN109402764A (en) * 2018-09-12 2019-03-01 恒天中纤纺化无锡有限公司 A kind of high-strength flatness nylon staple 6 fibre and preparation method thereof
CN109370207A (en) * 2018-10-24 2019-02-22 江苏亿超工程塑料有限公司 A kind of halogen-free flame-retardant polyamide material and preparation method thereof
CN110218442A (en) * 2019-06-25 2019-09-10 金旸(厦门)新材料科技有限公司 A kind of high flowing Heat conduction nylon composite material and its preparation method and application
CN110358290A (en) * 2019-06-27 2019-10-22 苍南县鑫洋新材料有限公司 A kind of nylon material of modification

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