CN105907087A - Flame retardant nylon material and preparation method thereof - Google Patents

Flame retardant nylon material and preparation method thereof Download PDF

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Publication number
CN105907087A
CN105907087A CN201610377013.XA CN201610377013A CN105907087A CN 105907087 A CN105907087 A CN 105907087A CN 201610377013 A CN201610377013 A CN 201610377013A CN 105907087 A CN105907087 A CN 105907087A
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fire
parts
retardant
nylon material
nylon
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马志国
张保丰
李敏
陈帮军
陈小伟
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Huanghe Science and Technology College
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Huanghe Science and Technology College
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/92Measuring, controlling or regulating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/92704Temperature
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/002Physical properties
    • C08K2201/003Additives being defined by their diameter
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/02Flame or fire retardant/resistant
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/22Halogen free composition

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a flame retardant nylon material and a preparation method thereof. The flame retardant nylon material comprises the following raw materials by weight: 200-240 parts of nylon resin, 60-80 parts of a flame retardant, 0.5-3 parts of an antioxidant, 2-6 parts of a compatibilizer, and 1-5 parts of a coupling agent. According to the invention, zinc borate subjected to surfactant modification treatment is added into the material, an original hydrophilic surface of the zinc borate is converted into a hydrophobic surface because of adsorption of surfactant molecules, and the modified zinc borate cooperates with a compatilizer maleic anhydride grafted PE or maleic anhydride grafted PP to guarantee a good disperse state of the zinc borate molecules, thus maximumly playing a flame retardant role. Therefore, the flame retardant nylon material has an excellent flame retardant effect.

Description

A kind of fire-retardant nylon material and preparation method thereof
Technical field
The present invention relates to a kind of macromolecular material and preparation method thereof, especially relate to a kind of fire-retardant nylon material and system thereof Preparation Method.
Background technology
Nylon has excellent combination property, occupies critical role in engineering plastics field.But, excellent having each side While opposite sex energy, nylon material is the most inflammable, and especially electronics, electric equipment products in use cause temperature mistake because of fault During high or electrion, nylon easily causes burning and breaking out of fire.Therefore, the nylon that exploitation fire resistance is good is urgent and has Necessary.By flame-retardant modified, improve the anti-flammability of nylon material, and then promote that relevant industries product is to high-performance, high-quality side To development, there is important practical significance.The flame-retardant modified approach of the most common nylon has following three kinds: (1) directly adds resistance Combustion agent and nylon resin matrix composite.(2) on nylon polymer strand, modification has the group of fire retarding effect.(3) In nylon polymerization process, introduce flame-retardant monomer carry out copolymerized.In three of the above method, (1st) plants method due to operation side Method is simple, low cost and other advantages, is the main method of current fire-retardant nylon production;(2nd) kind method generally requires organic molten Agent is carried out, there is using and the problem such as recovery of a large amount of solvent;In composite prepared by (3rd) kind method, flame-retardant composition is equal Even dispersion in the base, simultaneously the most in the course of the polymerization process, only need to be through a polymerization forming, but operating condition is complicated, is not suitable for Industrialized production.But for method of modifying in (1st) in currently available technology, the fire retardant added often occurs at nylon Poor dispersion in resin matrix, flame retardant effect is the best, thus can affect the fire resistance of material.
The Chinese patent of Application No. 201510956985.X, discloses a kind of heat and flame resistant nylon tubing, its raw material bag Include: nylon 6, nylon 6, polymethyl hydrogen siloxane, epoxy resin, titanate coupling agent modified nano zine oxide, modified acicular silicon Lime stone, amination CNT, nano silicon, red phosphorus, melamine cyanurate salt, organic nano imvite, glass fibre, Magnesium borate crystal whisker, basic zinc carbonate nanofiber, ethylene propylene diene rubber, ethylene bis stearic acid amide, calcium pimelate, 1,5-pentanedicarboxylic acid. Zinc, silane coupler, aluminum diethylphosphinate, Lanthanum Stearate.The heat and flame resistant nylon tubing that this invention proposes, makes with it Nylon tube good combination property, service life is long.The Chinese patent of Application No. 201210197562.0, discloses a kind of fire-retardant Electric conduction nylon composite material, is made up of the raw material of following parts by weight: nylon 6 resin 200~230 parts;Nylon 12 resin 60~ 90 parts;Coupling agent 3~5 parts;Filler 60~100 parts;Fire retardant 50~90 parts;Antioxidant 1.0~2.0 parts;Conductive agent 30~45 Part;Reinforcing fiber 90~120 parts;Surface modifier 1.1~2.3 parts.The fire-retardant electric conduction nylon composite material that this invention provides Hot strength is big, bending strength big, Izod notched impact strength is more than 23kJ/m2, add conductive agent thus disappeared Destatic.But fire retardant poor dispersion in nylon resin matrix in above-mentioned patent, therefore flame retardant effect is the best.
Summary of the invention
In view of this, it is an object of the invention to for the deficiencies in the prior art, it is provided that a kind of fire-retardant nylon material and system thereof Preparation Method, after solving the fire retardant added in current fire-retardant nylon material, fire retardant dispersibility in nylon resin matrix Bad, that flame retardant effect is the best problem.
For reaching above-mentioned purpose, the present invention by the following technical solutions:
A kind of fire-retardant nylon material, including the raw material of following weight portion: nylon resin 200-240 part, fire retardant 60-80 part, anti- Oxygen agent 0.5-3 part, compatilizer 2-6 part, coupling agent 1-5 part.
Further, described nylon resin is nylon 6.
Further, described fire retardant is the compositions of boric acid modification zinc and hexaphenoxycyclotriphosphazene, and Firebrake ZB and The mass ratio of hexaphenoxycyclotriphosphazene is 1-3:1.
Further, the preparation method of described boric acid modification zinc is the surface work that Firebrake ZB puts into that mass concentration is 6~8% Property agent solution in heated and stirred 10~12h, sucking filtration, collecting filter cake is also washed with deionized 3~5 times, dries, and naturally cools to Room temperature, pulverizes, sieves, obtain boric acid modification zinc.
Further, described surfactant is cetyl benzenesulfonic acid sodium, trimethyl cetyl ammonium bromide and front three One in base octadecyl bromination ammonium.
Further, the one during described antioxidant is antioxidant 1010, anti-oxidant DLTP and irgasfos 168.
Further, the one during described compatilizer is maleic anhydride grafting PE and maleic anhydride graft PP.
Further, the one during described coupling agent is aluminate coupling agent and silane coupler.
Its preparation method, comprises the following steps:
(1) raw material mixed at high speed: nylon resin, fire retardant, antioxidant, compatilizer, coupling agent are put in high-speed mixer, Mixing and stirring, obtains compound;
(2) extruding pelletization: the compound obtained in step (1) is joined in double screw extruder, extruding pelletization, control double spiral shell The rotating speed of bar is 130-140r/min, extruder one to six district temperature be followed successively by 180-200 DEG C, 220-240 DEG C, 220-240 DEG C, 230-250 DEG C, 230-250 DEG C, 240-260 DEG C, head temperature is 240-250 DEG C, after water-cooled and product.
The invention has the beneficial effects as follows:
(1) Firebrake ZB is the non-halogen flame retardant of a kind of environment-friendly type, nontoxic, low aqueous solubility, high thermal stability, granularity are little, proportion The features such as little, good dispersion, are widely used in the fields such as plastics, rubber, coating as a kind of efficient flame-retarding agent.But Firebrake ZB As a kind of inorganic compound, add and be susceptible to reunite to nylon material so that Firebrake ZB molecule is in high-polymer molecular Dispersion effect the best, thus the impact flame retardant effect to high polymer.The present invention adds through surfactant-modified process After Firebrake ZB, Firebrake ZB is transferred to hydrophobic surface by original water-wetted surface because of absorption surface active agent molecule, with the present invention Compatilizer maleic anhydride grafting PE, maleic anhydride graft PP, both synergism, it is ensured that Firebrake ZB molecule presents good point Bulk state, serves fire retardation to the full extent, and therefore flame retardant effect is excellent.
(2) fire retardant to reach fire-retardant purpose and must consider from the following aspects: a reduces thing temperature of catching fire;B completely cuts off sky Gas;C catches activity HO greatly and stops flame spread.The fire-retardant nylon material of the present invention adds Firebrake ZB and six benzene oxygen Basic ring three phosphonitrile is as fire retardant, and both synergism, flame retardant effect is excellent.Firebrake ZB is that one does not fire inert inorganic chemical combination Thing, the water Han mass crystallization in its molecule, in the case of a high temperature, Firebrake ZB is heated thawing, on the one hand forms nonvolatile liquid glass Glass body covers at polymer surfaces, is a kind of well isolating membrane, it is possible to play fire-retardant from isolation air angle to nylon material Effect;On the other hand, in Firebrake ZB molecule, substantial amounts of water of crystallization is because of high-temperature evaporation, absorbs substantial amounts of heat, reduces nylon material The temperature of material, plays fire retardation from the angle reducing thing temperature of catching fire.Hexaphenoxycyclotriphosphazene is that a class is by phosphorus, nitrogen-atoms Alternately connect the organic-inorganic hybrid polymer of skeleton in the form of a ring, the nitrogen of high-load, phosphorus ignition-proof element, therefore have good Fire resistance;Under hexaphenoxycyclotriphosphazene high-temperature condition, decomposes goes out a large amount of epoxide and disproportionation products still will be released It is put in gas phase, it is possible to catch a large amount of activity greatly HO, decrease the generation of imflammable gas combustion reaction, decrease heat The release of amount, i.e. HPCP can stop flame spread angle to play fire retardation from catching activity HO greatly.Therefore this Bright middle interpolation Firebrake ZB and hexaphenoxycyclotriphosphazene are as fire retardant, and Firebrake ZB and the mass ratio of hexaphenoxycyclotriphosphazene For 1-3:1, two kinds of fire retardant reasonable mixture ratio, in use having played synergism, from realizing, fire-retardant three angle is complete Orientation plays fire retardation to nylon material, and therefore flame retardant effect is the most notable.
(3) preparation method of the present invention is simple, prepares raw material cheap and easy to get, is therefore suitable for large-scale promotion.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1
A kind of fire-retardant nylon material, including the raw material of following weight portion: nylon 6 200 parts, 40 parts of boric acid modification zinc, six phenoxy groups Ring three phosphonitrile 40 parts, antioxidant 1010 0.5 part, maleic anhydride grafting PE 6 parts, Silane coupling agent KH550 1 part.
Wherein, the preparation method of described boric acid modification zinc is the cetyl benzenesulfonic acid that Firebrake ZB puts into that mass concentration is 8% Heated and stirred 10h in sodium solution, sucking filtration, collect filter cake and be washed with deionized 3 times, drying, naturally cool to room temperature, powder Broken, cross 200 mesh sieves, obtain boric acid modification zinc.
Its preparation method, comprises the following steps:
(1) raw material mixed at high speed: nylon 6, boric acid modification zinc, hexaphenoxycyclotriphosphazene, antioxidant 1010, maleic anhydride are connect Branch PE, Silane coupling agent KH550 are put in high-speed mixer, and mixing and stirring obtains compound;
(2) extruding pelletization: the compound obtained in step (1) is joined in double screw extruder, extruding pelletization, control double spiral shell The rotating speed of bar is 130r/min, extruder one to six district temperature be followed successively by 180 DEG C, 220 DEG C, 2200 DEG C, 230 DEG C, 230 DEG C, 240 DEG C, head temperature is 240 DEG C, after water-cooled and product.
Embodiment 2
A kind of fire-retardant nylon material, including the raw material of following weight portion: nylon 6 240 parts, 40 parts of boric acid modification zinc, six phenoxy groups Ring three phosphonitrile 20 parts, anti-oxidant DLTP 3 parts, maleic anhydride graft PP 2 parts, silane coupler KH570 5 parts.
Wherein, the preparation method of described boric acid modification zinc is the cetyl benzenesulfonic acid that Firebrake ZB puts into that mass concentration is 6% Heated and stirred 12h in sodium solution, sucking filtration, collect filter cake and be washed with deionized 5 times, drying, naturally cool to room temperature, powder Broken, cross 300 mesh sieves, obtain boric acid modification zinc.
Its preparation method, comprises the following steps:
(1) raw material mixed at high speed: nylon 6, boric acid modification zinc, hexaphenoxycyclotriphosphazene, anti-oxidant DLTP, maleic anhydride are connect Branch PP, silane coupler KH570 put in high-speed mixer, and mixing and stirring obtains compound;
(2) extruding pelletization: the compound obtained in step (1) is joined in double screw extruder, extruding pelletization, control double spiral shell The rotating speed of bar is 140r/min, extruder one to six district temperature be followed successively by 200 DEG C, 240 DEG C, 240 DEG C, 250 DEG C, 250 DEG C, 260 DEG C, head temperature is 250 DEG C, after water-cooled and product.
Embodiment 3
A kind of fire-retardant nylon material, including the raw material of following weight portion: nylon 6 210 parts, 38.2 parts of boric acid modification zinc, six benzene oxygen Basic ring three phosphonitrile 31.8 parts, irgasfos 168 1 part, maleic anhydride grafting PE 5 parts, silane coupler KH560 2 parts.
Wherein, the preparation method of described boric acid modification zinc is the cetyl benzenesulfonic acid that Firebrake ZB puts into that mass concentration is 8% Heated and stirred 11h in sodium solution, sucking filtration, collect filter cake and be washed with deionized 4 times, drying, naturally cool to room temperature, powder Broken, cross 250 mesh sieves, obtain boric acid modification zinc.
Its preparation method, comprises the following steps:
(1) raw material mixed at high speed: nylon 6, boric acid modification zinc, hexaphenoxycyclotriphosphazene, irgasfos 168, maleic anhydride are connect Branch PE, silane coupler KH560 put in high-speed mixer, and mixing and stirring obtains compound;
(2) extruding pelletization: the compound obtained in step (1) is joined in double screw extruder, extruding pelletization, control double spiral shell The rotating speed of bar is 135r/min, extruder one to six district temperature be followed successively by 190 DEG C, 230 DEG C, 235 DEG C, 240 DEG C, 245 DEG C, 260 DEG C, head temperature is 245 DEG C, after water-cooled and product.
Embodiment 4
A kind of fire-retardant nylon material, including the raw material of following weight portion: nylon 6 230 parts, 37.9 parts of boric acid modification zinc, six benzene oxygen Basic ring three phosphonitrile 27.1 parts, antioxidant 1010 3 parts, maleic anhydride graft PP 3 parts, Silane coupling agent KH550 4 parts.
Wherein, the preparation method of described boric acid modification zinc is the cetyl benzenesulfonic acid that Firebrake ZB puts into that mass concentration is 7% Heated and stirred 12h in sodium solution, sucking filtration, collect filter cake and be washed with deionized 5 times, drying, naturally cool to room temperature, powder Broken, cross 280 mesh sieves, obtain boric acid modification zinc.
Its preparation method, comprises the following steps:
(1) raw material mixed at high speed: nylon 6, boric acid modification zinc, hexaphenoxycyclotriphosphazene, antioxidant 1010, maleic anhydride are connect Branch PP, Silane coupling agent KH550 are put in high-speed mixer, and mixing and stirring obtains compound;
(2) extruding pelletization: the compound obtained in step (1) is joined in double screw extruder, extruding pelletization, control double spiral shell The rotating speed of bar is 140r/min, extruder one to six district temperature be followed successively by 180 DEG C, 225 DEG C, 235 DEG C, 240 DEG C, 245 DEG C, 250 DEG C, head temperature is 250 DEG C, after water-cooled and product.
Embodiment 5
A kind of fire-retardant nylon material, including the raw material of following weight portion: nylon 6 220 parts, 42 parts of boric acid modification zinc, six phenoxy groups Ring three phosphonitrile 28 parts, irgasfos 168 1.8 parts, maleic anhydride graft PP 4 parts, aluminate coupling agent 3 parts.
Wherein, the preparation method of described boric acid modification zinc is the cetyl benzenesulfonic acid that Firebrake ZB puts into that mass concentration is 7% Heated and stirred 11h in sodium solution, sucking filtration, collect filter cake and be washed with deionized 5 times, drying, naturally cool to room temperature, powder Broken, cross 250 mesh sieves, obtain boric acid modification zinc.
Its preparation method, comprises the following steps:
(1) raw material mixed at high speed: nylon 6, boric acid modification zinc, hexaphenoxycyclotriphosphazene, irgasfos 168, maleic anhydride are connect Branch PP, aluminate coupling agent are put in high-speed mixer, and mixing and stirring obtains compound;
(2) extruding pelletization: the compound obtained in step (1) is joined in double screw extruder, extruding pelletization, control double spiral shell The rotating speed of bar is 140r/min, extruder one to six district temperature be followed successively by 190 DEG C, 230 DEG C, 235 DEG C, 240 DEG C, 245 DEG C, 250 DEG C, head temperature is 245 DEG C, after water-cooled and product.
Embodiment 6
A kind of fire-retardant nylon material, including the raw material of following weight portion: nylon 6 215 parts, 47.2 parts of boric acid modification zinc, six benzene oxygen Basic ring three phosphonitrile 27.8 parts, antioxidant 1010 2.3 parts, maleic anhydride grafting PE 5 parts, silane coupler KH570 5 parts.
Wherein, the preparation method of described boric acid modification zinc is the trimethyl cetyl that Firebrake ZB puts into that mass concentration is 8% Heated and stirred 11h in ammonium bromide solution, sucking filtration, collect filter cake and be washed with deionized 5 times, drying, naturally cool to room temperature, Pulverize, cross 250 mesh sieves, obtain boric acid modification zinc.
Its preparation method, comprises the following steps:
(1) raw material mixed at high speed: nylon 6, boric acid modification zinc, hexaphenoxycyclotriphosphazene, antioxidant 1010, maleic anhydride are connect Branch PE, silane coupler KH570 put in high-speed mixer, and mixing and stirring obtains compound;
(2) extruding pelletization: the compound obtained in step (1) is joined in double screw extruder, extruding pelletization, control double spiral shell The rotating speed of bar is 140r/min, extruder one to six district temperature be followed successively by 185 DEG C, 225 DEG C, 230 DEG C, 235 DEG C, 240 DEG C, 245 DEG C, head temperature is 250 DEG C, after water-cooled and product.
Embodiment 7
A kind of fire-retardant nylon material, including the raw material of following weight portion: nylon 6 225 parts, 39.3 parts of boric acid modification zinc, six benzene oxygen Basic ring three phosphonitrile 20.7 parts, anti-oxidant DLTP 2.7 parts, maleic anhydride graft PP 4 parts, Silane coupling agent KH550 2 parts.
Wherein, the preparation method of described boric acid modification zinc is the trimethyl cetyl that Firebrake ZB puts into that mass concentration is 7% Heated and stirred 10h in ammonium bromide solution, sucking filtration, collect filter cake and be washed with deionized 3 times, drying, naturally cool to room temperature, Pulverize, cross 260 mesh sieves, obtain boric acid modification zinc.
Its preparation method, comprises the following steps:
(1) raw material mixed at high speed: nylon 6, boric acid modification zinc, hexaphenoxycyclotriphosphazene, anti-oxidant DLTP, maleic anhydride are connect Branch PP, Silane coupling agent KH550 are put in high-speed mixer, and mixing and stirring obtains compound;
(2) extruding pelletization: the compound obtained in step (1) is joined in double screw extruder, extruding pelletization, control double spiral shell The rotating speed of bar is 130r/min, extruder one to six district temperature be followed successively by 180 DEG C, 225 DEG C, 230 DEG C, 230 DEG C, 245 DEG C, 250 DEG C, head temperature is 245 DEG C, after water-cooled and product.
Embodiment 8
A kind of fire-retardant nylon material, including the raw material of following weight portion: nylon 6 220 parts, 46.6 parts of boric acid modification zinc, six benzene oxygen Basic ring three phosphonitrile 23.4 parts, irgasfos 168 2 parts, triphenyl phosphite 1 part, maleic anhydride grafting PE 3 parts, Aluminate coupling Agent 3 parts.
Wherein, the preparation method of described boric acid modification zinc is the trimethyloctadecyl that Firebrake ZB puts into that mass concentration is 7% Heated and stirred 10h in ammonium bromide solution, sucking filtration, collect filter cake and be washed with deionized 5 times, drying, naturally cool to room temperature, Pulverize, cross 300 mesh sieves, obtain boric acid modification zinc.
Its preparation method, comprises the following steps:
(1) raw material mixed at high speed: by nylon 6, boric acid modification zinc, hexaphenoxycyclotriphosphazene, antioxygen irgasfos 168, maleic acid Acid anhydride grafting PE, aluminate coupling agent are put in high-speed mixer, and mixing and stirring obtains compound;
(2) extruding pelletization: the compound obtained in step (1) is joined in double screw extruder, extruding pelletization, control double spiral shell The rotating speed of bar is 135r/min, extruder one to six district temperature be followed successively by 190 DEG C, 230 DEG C, 235 DEG C, 240 DEG C, 245 DEG C, 250 DEG C, head temperature is 250 DEG C, after water-cooled and product.
Comparative example 1
Comparative example 1 is substantially the same manner as Example 5, and difference is in Firebrake ZB alternate embodiment 5 raw material by equal in quality Boric acid modification zinc, i.e. the raw material of comparative example 1 includes the raw material of following weight portion: nylon 6 220 parts, Firebrake ZB 42 parts, six benzene Epoxide ring three phosphonitrile 28 parts, irgasfos 168 1.8 parts, maleic anhydride graft PP 4 parts, aluminate coupling agent 3 parts, remaining is prepared Method is same as in Example 5.
Comparative example 2
Comparative example 2 is substantially the same manner as Example 5, and difference is by the boric acid modification zinc alternate embodiment 5 of equal in quality former Hexaphenoxycyclotriphosphazene in material, the i.e. raw material of comparative example 2 include the raw material of following weight portion: nylon 6 220 parts, modified boron Acid 70 parts of zinc, irgasfos 168 1.8 parts, maleic anhydride graft PP 4 parts, aluminate coupling agent 3 parts, remaining preparation method and reality Execute example 5 identical.
Comparative example 3
Comparative example 3 is substantially the same manner as Example 5, and difference is to substitute with the hexaphenoxycyclotriphosphazene of equal in quality to implement Boric acid modification zinc in example 5 raw material, the i.e. raw material of comparative example 2 include the raw material of following weight portion: nylon 6 220 parts, six benzene oxygen Basic ring three phosphonitrile 70 parts, irgasfos 168 1.8 parts, maleic anhydride graft PP 4 parts, aluminate coupling agent 3 parts, remaining preparation side Method is same as in Example 5.
Performance test
(1) tensile property test:
According to GB GB/T1040-92, the product preparing embodiment 1-8 and comparative example 1-3 is tested, in room temperature Under, product is carried out tensile property test.
(2) limiting oxygen index determination:
According to GB GB/ T2046-1993, the product preparing embodiment 1-8 and comparative example 1-3 carries out oxygen index (OI) survey Fixed.
(3) vertical combustion UL94 rank test:
The product using vertical combustion instrument to carry out preparing embodiment 1-8 and comparative example 1-3 according to UL94 standard hangs down Direct combustion burns performance test.
Above-mentioned every test result is shown in Table 1.
As shown in Table 1, when a kind of fire-retardant nylon material of the present invention, including the raw material of following weight portion: nylon 6 220 Part, 42 parts of boric acid modification zinc, hexaphenoxycyclotriphosphazene 28 parts, irgasfos 168 1.8 parts, maleic anhydride graft PP 4 parts, aluminum During acid esters coupling agent 3 parts, the product that the method provided according to the present invention prepares, its property indices is preferable, and stretching is strong Degree reaches 146 MPa, and oxygen index (OI) is up to 35%, and vertical combustion UL94 rank is V-0 level.
From embodiment 8 and table 1 result, when a kind of fire-retardant nylon material of the present invention adds irgasfos 168 and phosphorous During triphenyl phosphate ester, the fire-retardant nylon material prepared more aspect is more excellent, this is because triphenyl phosphite is not only one Planting the auxiliary antioxidant of function admirable, auxiliary antioxidant 168 is to reach to prevent the purpose of the material aging of the present invention;The opposing party Face, containing a large amount of P elements in triphenyl phosphite, can form phosphoric acid during heated combustion, phosphoric acid is condensed the poly-inclined phosphorus of generation further Acid vitreous body covering, the vitreous body synergism formed with mesoboric acid zinc of the present invention, enhance the fire resistance of the present invention.
From the embodiment of the present invention 5 and comparative example 1, Firebrake ZB is added directly to nylon material resistance without modification Combustion poor effect, and add the boric acid modification zinc after surfactant-modified process, the compatilizer in the collaborative present invention adds The maleic anhydride grafting PE, the maleic anhydride that add are grafted, both synergism, it is ensured that Firebrake ZB molecule presents good dispersed State, serves fire retardation to the full extent, and therefore flame retardant effect is excellent.
From the embodiment of the present invention 5, comparative example 2 and comparative example 3, a kind of fire-retardant nylon material of the present invention adds boron Acid zinc and hexaphenoxycyclotriphosphazene as fire retardant, both synergism, from reduction catch fire thing temperature, isolation air, seizure Activity HO greatly stops flame spread, and three angles are comprehensive to nylon material performance fire retardation, therefore flame retardant effect The most notable.
Finally illustrating, above example is only in order to illustrate technical scheme and unrestricted, and this area is common Other amendment or equivalents that technical scheme is made by technical staff, without departing from technical solution of the present invention Spirit and scope, all should contain in the middle of scope of the presently claimed invention.

Claims (9)

1. a fire-retardant nylon material, it is characterised in that include the raw material of following weight portion: nylon resin 200-240 part, fire-retardant Agent 60-80 part, antioxidant 0.5-3 part, compatilizer 2-6 part, coupling agent 1-5 part.
A kind of fire-retardant nylon material the most according to claim 1, it is characterised in that: described nylon resin is nylon 6.
A kind of fire-retardant nylon material the most according to claim 1, it is characterised in that: described fire retardant be boric acid modification zinc and The compositions of hexaphenoxycyclotriphosphazene, and the mass ratio of Firebrake ZB and hexaphenoxycyclotriphosphazene is 1-3:1.
A kind of fire-retardant nylon material the most according to claim 3, it is characterised in that the preparation method of described boric acid modification zinc For Firebrake ZB put into mass concentration be 6~8% surfactant solution in heated and stirred 10~12h, sucking filtration, collect filter cake also It is washed with deionized 3~5 times, dries, naturally cool to room temperature, pulverize, sieve, obtain boric acid modification zinc.
A kind of fire-retardant nylon material the most according to claim 4, it is characterised in that: described surfactant is cetyl One in benzene sulfonic acid sodium salt, trimethyl cetyl ammonium bromide and trimethyloctadecyl ammonium bromide.
A kind of fire-retardant nylon material the most according to claim 1, it is characterised in that: described antioxidant be antioxidant 1010, One in anti-oxidant DLTP and irgasfos 168.
A kind of fire-retardant nylon material the most according to claim 1, it is characterised in that: described compatilizer is maleic anhydride grafting One in PE and maleic anhydride graft PP.
A kind of fire-retardant nylon material the most according to claim 1, it is characterised in that: described coupling agent is aluminate coupling agent With the one in silane coupler.
The preparation method of a kind of fire-retardant nylon material the most according to claim 1, it is characterised in that comprise the following steps:
(1) raw material mixed at high speed: nylon resin, fire retardant, antioxidant, compatilizer, coupling agent are put in high-speed mixer, Mixing and stirring, obtains compound;
(2) extruding pelletization: the compound obtained in step (1) is joined in double screw extruder, extruding pelletization, control double spiral shell The rotating speed of bar is 130-140r/min, extruder one to six district temperature be followed successively by 180-200 DEG C, 220-240 DEG C, 220-240 DEG C, 230-250 DEG C, 230-250 DEG C, 240-260 DEG C, head temperature is 240-250 DEG C, after water-cooled and product.
CN201610377013.XA 2016-05-31 2016-05-31 Flame retardant nylon material and preparation method thereof Pending CN105907087A (en)

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CN107298854A (en) * 2017-08-30 2017-10-27 朱红艳 A kind of halogen-free environmental nylon fire proofing and preparation method thereof
CN112724676A (en) * 2020-12-17 2021-04-30 广州市高士实业有限公司 Ceramic room temperature curing silicone rubber and preparation method thereof
CN114806161A (en) * 2022-06-20 2022-07-29 台州俪盛塑料有限公司 Special super-tough nylon capable of being blown
US11401416B2 (en) 2017-10-17 2022-08-02 Celanese Sales Germany Gmbh Flame retardant polyamide composition
CN116396608A (en) * 2023-04-13 2023-07-07 清远市一丞阻燃材料有限公司 Fiber-reinforced halogen-free flame-retardant nylon composition and preparation method thereof

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CN104403228A (en) * 2014-11-20 2015-03-11 安徽渡江电缆集团有限公司 Modified polyvinyl chloride cable material with high cold resistance

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107298854A (en) * 2017-08-30 2017-10-27 朱红艳 A kind of halogen-free environmental nylon fire proofing and preparation method thereof
US11401416B2 (en) 2017-10-17 2022-08-02 Celanese Sales Germany Gmbh Flame retardant polyamide composition
US11981812B2 (en) 2017-10-17 2024-05-14 Celanese Sales Germany Gmbh Flame retardant polyamide composition
CN112724676A (en) * 2020-12-17 2021-04-30 广州市高士实业有限公司 Ceramic room temperature curing silicone rubber and preparation method thereof
CN112724676B (en) * 2020-12-17 2022-11-01 广州市高士实业有限公司 Ceramic room temperature curing silicone rubber and preparation method thereof
CN114806161A (en) * 2022-06-20 2022-07-29 台州俪盛塑料有限公司 Special super-tough nylon capable of being blown
CN116396608A (en) * 2023-04-13 2023-07-07 清远市一丞阻燃材料有限公司 Fiber-reinforced halogen-free flame-retardant nylon composition and preparation method thereof

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