CN104231622B - A kind of low precipitation flame-retardant polyamide composition and preparation method thereof - Google Patents

A kind of low precipitation flame-retardant polyamide composition and preparation method thereof Download PDF

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CN104231622B
CN104231622B CN201410526755.5A CN201410526755A CN104231622B CN 104231622 B CN104231622 B CN 104231622B CN 201410526755 A CN201410526755 A CN 201410526755A CN 104231622 B CN104231622 B CN 104231622B
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antioxidant
retardant
flame
nylon
fire
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CN104231622A (en
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黄慧
钟春重
张振文
陈原振
林柏齡
陈跃民
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JIANGSU JINLUN PLASTIC TECHNOLOGY CO., LTD.
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Jiangsu Ginar Plastic Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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  • Health & Medical Sciences (AREA)
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Abstract

The present invention relates to technical field of polymer materials, more particularly to a kind of low precipitation flame-retardant polyamide composition, include the raw material of following mass percent：Nylon resin 20 70%, main flame retardant 10 30%, fire retarding synergist 0 15%, alkali-free glass fiber 10 40%, antioxidant 0 1%, lubricant 0 2%, the nylon resin are the mixture of one or both of nylon66 fiber, nylon 6；The main flame retardant is bromide fire retardant；The fire retarding synergist is one or more kinds of mixtures of the compound of antimony trioxide parent particle, Firebrake ZB, silica and metal oxide；The lubricant is one kind in HMW polymolecularity lubricant, including Tissuemat E, modified PE wax, OP waxes and lignite wax.Daiamid composition produced by the present invention is not easy to migrate in hot humid environment or separates out, and the cost of material is low, and preparation method of the invention is simple, is advantageous to popularization and application.

Description

A kind of low precipitation flame-retardant polyamide composition and preparation method thereof
Technical field
The present invention relates to technical field of polymer materials, more particularly to a kind of low precipitation flame-retardant polyamide composition and its system Preparation Method.
Background technology
Bromine antimony composite flame-proof polyamide compoiste material has that anti-flammability is excellent, and flame retardant rating reaches UL94 V0 (0.4mm）, Good mechanical property and mechanical performance are kept simultaneously, processing characteristics is good, environmental protection, the excellent combination properties such as cost is cheap, There is leading position in present fire-retardant nylon in the market, the product demands such as electronic apparatus, low tension switch can be met.
Traditional bromine antimony composite flame-proof polyamide compoiste material on the market now, mainly with bromide fire retardant and three oxidations Two antimony powder bluk recombination Flameproof polyamides, because antimony oxide is as inorganic particle particle, have between nylon incompatible, lead Material injection is caused after placing a period of time, to have fire retardant precipitation into after product, cause product surface frosting phenomenon, particularly In the environment of high-temperature high-humidity, the frosting of product surface can be accelerated.This is mainly due to polyamide substrate resin as a kind of Crystalline material has exclusiveness, so causing the antimony oxide powder in resin to migrate, analyse from interiors of products to product surface Go out so that product surface forms one layer of bloom.Due to bromine antimony fire-retardant polyamide material mainly for the manufacture of terminal board, connector, The electric components such as DDR slots, these parts in use, generate heat so that product must is fulfilled for high temperature because circuit is present Environmental requirement.In high temperature environments, the mobility of polyamide molecule chain increases, and strand compliance enhancing, crystallinity improves, Due to crystallizing rejection so that therefore the migration of the antimony oxide in product also accelerates, in product surface shape in the short time Into substantial amounts of white powder precipitate, this precipitate understands the conductive metal material in polluted product, so as to influence the electrical of material Can, cause the metal material in product to be contaminated so as to cause product circuit conduction bad, have a strong impact on the usability of material Energy.Because precipitate is white creamy substance matter, product appearance is then also had a strong impact on for black product.
In addition to temperature, the humidity of environment separates out to antimony oxide in material also to have a significant impact, nylon main component It is polyamide, its amide groups-NHCO- polarizeds so that nylon has very strong water imbibition.After fire-retardant nylon water suction, hydrone It can enter in the space between polyamide molecule, to providing lubrication between intermolecular and each component, while have to other components Certain extraction so that what the antimony oxide component in material can be in a short time under the lubrication of hydrone and extraction The surface of product is moved to, influences the performance of material.In addition to antimony oxide, small-molecule substance and three oxidations in material Two antimony equally easily move to product surface by interiors of products in use, and the performance and outward appearance to product have larger shadow Ring.
Chinese patent 201110392827.2 discloses a kind of preparation method of high-strength high-toughness flame-retardant polyamide, with Based on the polyamide that 100 parts of parts by weight relative viscosities are 2.4-3.3, the TDE for adding 10-30 parts by weight is fire-retardant Agent, 3-10 parts by weight antimony oxide fire retardants, 0-5 parts by weight light stationary levels, 0.2-1 parts by weight heat stabilizers, 0.5-1 weight The mixture of part antioxidant composition, through twin-screw extrusion melting mixing, extrusion, cooling, drying, pelletizing, obtains high intensity and high ductility Property Flameproof polyamide.The TDE that the patent uses, the decomposition temperature of the fire retardant is 300 DEG C or so, and the material In twin-screw extrusion and injection moulding process, due to the presence of shear heat so that melt temperature exceedes this temperature, causes the bromine of part ten Diphenylethane resolves into small-molecule substance, and these decomposite the small-molecule substance that comes be readily migrate into product surface formed it is white Creamy substance matter, influences product appearance and use.Light stabilizer and heat stabilizer belong to small molecule auxiliary agent simultaneously, easily separate out.
The A of Chinese patent CN 101955657 A, CN 103421303 discloses a kind of green high fire-retardant enhancings of CTI The material of nylon 6, the main modified Pa 6 of the present invention, and PA66 processing temperatures are high compared with PA6, due to the temperature tolerance of phosphor nitrogen composite combustion inhibitor Can not be high so that phosphor nitrogen combustion inhibitor is easily thermally decomposed into small-molecule substance in process, so as to influence the resistance to height of material Warm high humidity separates out performance.The heat resistance of TDE fire retardant is relatively low described in the A of Chinese patent CN 102492290, Easily decomposed in process, cause to separate out and material xanthochromia.Similar patent also has CN 101503570A, 200610118566.X, the patents such as 200610028821.1,201110392827.8 are TDE and three oxidations two Antimony compositional flame-retardant nylon, described technique are also traditional handicraft, and specially treated is not done to the scattered of antimony oxide, so It is same in hot humid environment easily to separate out.Therefore, above mentioned problem is urgently to be resolved hurrily.
The content of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of low precipitation flame-retardant polyamide composition and its Preparation method, obtained daiamid composition is not easy to migrate in hot humid environment or separates out, and the cost of material is low, of the invention Preparation method is simple, is advantageous to popularization and application.
The present invention is achieved through the following technical solutions.
A kind of low precipitation flame-retardant polyamide composition, include the raw material of following mass percent：
Nylon resin 20-70%
Main flame retardant 10-30%
Fire retarding synergist 0-15%
Alkali-free glass fiber 10-40%
Antioxidant 0-1%
Lubricant 0-2%
Wherein, the nylon resin is the mixture of one or both of nylon66 fiber, nylon 6；The main flame retardant is Bromide fire retardant；The fire retarding synergist is antimony oxide powder, antimony trioxide parent particle, Firebrake ZB, silica and gold Belong to one or more kinds of mixtures of the compound of oxide；The lubricant is HMW polymolecularity lubricant, Including one kind in Tissuemat E, modified PE wax, OP waxes and lignite wax.
Preferably, the Firebrake ZB in fire retarding synergist is anhydrous zinc borate.
Preferably, a kind of low precipitation flame-retardant polyamide composition, the raw material of following mass percent is included：
Nylon resin 30-50%
Main flame retardant 10-30%
Fire retarding synergist 5-15%
Alkali-free glass fiber 10-40%
Antioxidant 0.1-0.5%
Lubricant 0.1-1%.
It is highly preferred that a kind of low precipitation flame-retardant polyamide composition, include the raw material of following mass percent：
Nylon resin 30-60%
Main flame retardant 15-25%
Fire retarding synergist 5-15%
Alkali-free glass fiber 15-30%
Antioxidant 0.2-0.5%
Lubricant 0.2-1%.
Wherein, the nylon resin is nylon66 fiber and nylon 6 using mass ratio as 0-60:0-20 mixture.Preferably, Buddhist nun The mass ratio of dragon 66 and nylon 6 is 30-50:5-15 mixture.Material its processability that nylon66 fiber and nylon 6 are formed after mixing Can be more superior, it can at relatively low temperature process, reduce material at high temperature and decompose precipitation.
Wherein, the bromide fire retardant is one kind in brominated Polystyrene, brominated polystyrene, brominated epoxy resin, The content of bromine is 66-75% in the bromide fire retardant.
Wherein, the carrier of the antimony trioxide parent particle is polyethylene（PE）, nylon 6, one kind in EVA, it is described fire-retardant Synergist is antimony trioxide parent particle, and the content of antimony oxide is equal in polyethylene, nylon 6, EVA carrier antimony trioxide parent particles For 85%, the content is mass percent, i.e., described polyethylene support antimony trioxide parent particle, EVA carriers antimony oxide are female The content of antimony oxide is 85% in grain, PA6 carrier antimony trioxide parent particles.It that is to say polyethylene support and three oxidations two Containing 85% antimony oxide in antimony master batch, contain 85% antimony oxide, PA6 in EVA carriers and antimony trioxide parent particle Contain 85% antimony oxide in carrier and antimony trioxide parent particle.
The present invention antimony trioxide parent particle preparation technology be：1）Score ratio weighs vector resin and three oxidations two by weight Antimony；2）Mixed in mixing tank；3）Well mixed raw material are added from the main spout of single screw rod, screw speed 200-500, Temperature is 100-220 DEG C, and antimony trioxide parent particle is made, and antimony trioxide parent particle has easily disperse energy by surface treatment. Nylon resin in the carrier of nylon 6 and formula of the present invention has good compatibility, and polyethylene and EVA carriers are advantageous to be lifted The toughness of material.
Wherein, the fire retarding synergist is silica and metal oxide using mass ratio as 0-15:0-10 compound, The metal oxide is magnesia or aluminum oxide.
Wherein, the fire retarding synergist be the compound of antimony trioxide parent particle and silica and metal oxide with Mass ratio is 0-15：0-10 mixture；Or, the fire retarding synergist is antimony trioxide parent particle and Firebrake ZB with mass ratio For 0-15：0-10 mixture；Or, the fire retarding synergist is antimony trioxide parent particle.
Wherein, the alkali-free glass fiber is the glass that single beam diameter is 7-14 μm.
Wherein, the antioxidant is primary antioxidant and auxiliary antioxidant using mass ratio as 4:1-1:4 mixture, main antioxygen Agent is Hinered phenols antioxidant or hexamethylene diamine kind antioxidant, and auxiliary antioxidant is phosphite ester kind antioxidant, thio esters antioxygen Agent.
It is preferred that primary antioxidant:The mass ratio of auxiliary antioxidant is 2:1-1:1.Antioxidant 1010 is that a kind of Hinered phenols resist Oxygen agent, action principle are capture free radicals, belong to primary antioxidant, anti-oxidant have effect to the long-term of polymer.Phosphorous acid esters Antioxidant, action principle are hydroperoxide decompositions, belong to auxiliary antioxidant, and very big work is played to polymer processing With, as in some material processings degrade jaundice, suppression yellowing Effect can be played；But there is no later stage antioxidant effect；It is main anti- Oxygen agent+auxiliary anti-oxidant is used in conjunction with producing cooperative effect, and both protection materials are not decomposed in energon process, and for a long time Ageing resistace improves.
A kind of preparation method of the flame-retardant polyamide composition of low precipitation, including following procedure of processing：
Step（1）Each raw material are weighed by weight percentage；
Step（2）By step（1）In the alkali-free glass fiber that weighs take out, then remaining raw material mix in mixing tank equal It is even；
Step（3）By step（2）In the raw material that is well mixed added from the main spout of twin-screw, by alkali-free glass fiber from double The glass fiber opening of screw rod adds, and the rotating speed of double screw extruder is 200-400 revs/min, and temperature is 200-300 DEG C, and low analysis is made The flame-retardant polyamide composition gone out.
Beneficial effects of the present invention are：
（1）Daiamid composition advantage produced by the present invention is that have excellent resistance to precipitation performance, and has excellent resistance Combustion property UL94V0, excellent mechanical property, can be extensively suitable for manufacture connector, terminal, DDR slots, thin-walled electronic building brick etc. Used in the environment of high-temperature high-humidity.
（2）The main flame retardant of the present invention is the outstanding brominated Polystyrene of heat endurance, in twin-screw extrusion process And decomposition is notheated in injection moulding process and is produced, while there is preferably compatibility with matrix resin, so material can also be kept Good mechanical property, simultaneously because having good compatibility between brominated Polystyrene and polyamide, so without analysis Go out.Brominated Polystyrene molecular weight distribution is narrower, and sub-prime amount is 1*104-5*104On the mobility of material without influence.
（3）One of fire retarding synergist of the present invention is antimony trioxide parent particle, and described antimony oxide purity is more than 99.9%, average grain diameter is 0.7 μm.Antimony oxide is previously prepared into antimony trioxide parent particle simultaneously.Antimony trioxide parent particle Carrier is polyethylene, nylon 6, EVA one kind.Antimony oxide is processed into master batch by Single screw extrusion, equivalent to by one Secondary scattered, the material enable antimony oxide during twin-screw melting extrusion disperses more fully, in the material scattered Evenly, the mechanical property and mechanical performance of material are had little to no effect, simultaneously because scattered abundant so that antimony oxide Flame retarding efficiency improve, so as to reduce the usage amount 5%-10% of antimony oxide, cost can be effectively reduced.Due to three oxidations The addition of two antimony is reduced, and antimony oxide content is reduced in material, can also reduce the precipitation of antimony oxide.In addition, Antimony trioxide parent particle does not have dust pollution, is advantageous to that environment is clean and tidy and workers ' health.
（4）The two of the fire retarding synergist of the present invention for silica and metal oxide compound, this silica and There is the compound of metal oxide whiteness to be more than 91%, have easily scattered sub- flaky nanometer structure, have good fire-retardant association Effect, synergistic effect.The structural formula of the compound of silica and metal oxide is (MxOy) n (SiO2) m, wherein, M=Al or Mg；X, y, m, n are natural number.
The compound of silica and metal oxide can be with 1 as fire retarding synergist:1 substitutes 50% three oxidations two Antimony, there is good anti-flammability, while also there is smoke suppressing effect.It is right and that flaky nanometer structure has lamella barriering effect The precipitation of the small molecular and powder of material has certain barriering effect, and for the infiltration of hydrone after the water suction of material Effect also functions to blocking effect, and this just can play certain decelerating effect to the precipitation of small molecule and powder.Titanium dioxide simultaneously The compound true qualities laminated structure of silicon and metal oxide, is hardly separated out in the material, so silica and metal oxygen The part antimony oxide of the compound substitution of compound can reduce precipitation.And the compound price of silica and metal oxide Lattice are cheap, can further reduce cost.The compound of silica and metal oxide is sub- nanostructured simultaneously, to material Effect on Mechanical Properties it is smaller.
（5）Glass of the present invention is alkali-free glass fiber, and glass filament diameter is 0.7-14 μm, and surface is by silane coupled Agent is handled, and has good interfacial combined function between polyamide substrate resin, when material is by external force, external force can pass through Good interface cohesion passes to glass, allows the glass of high rigidity to carry and consume external force, so as to reach the effect of activeness and quietness.
（6）Research at present on the resistance to precipitation of bromine antimony composite flame-proof polyamide is less, and this patent is by using heat resistance Outstanding brominated Polystyrene reduces material and produces small-molecule substance in process；It is fire-retardant with the antimony oxide of high dispersive Master batch enhancing powder body material is dispersed in matrix resin, while with partial obstruction function admirable and the dioxy without precipitation The compound of SiClx and metal oxide substitutes antimony oxide, reduces the migration and precipitation of small molecule and powder granule, together When can also effectively reduce material cost.
（7）The preparation method of the present invention compared with prior art, has the advantages that：
A. high dispersive antimony oxide fire-retardant master granule is used, is compared with traditional fire-retardant powder antimony oxide with following Advantage：The dispersive property of antimony oxide in the material is more preferable, and dispersion ratio is more uniform in matrix resin, can give full play to fire-retardant Property, so as to reduce the dosage of fire retardant, cost is effectively reduced, while less addition can effectively reduce antimony oxide Separate out.
B. had following as fire retarding synergist using the silica of sub- nano-sheet and the compound of metal oxide Advantage：
1）The compound of sub- nano-sheet silica and metal oxide can be with 1：1 substitutes 50% antimony oxide, energy Effectively reduce material cost；
2）The sub- flaky nanometer structure of the compound of silica and metal oxide, dispersive property is good in the material, energy Keep the good mechanical property of material；
3）The laminated structure of the compound of silica and metal oxide causes answering for silica and metal oxide Compound has certain blocking effect, has iris action to the small molecule in material and the precipitation of powder body material, reduces material Precipitation.
C. main flame retardant is used as brominated Polystyrene, and there is advantages below：
1）Molecular weight distribution is narrower, molecular mass 1*104-5*104, on the mobility of material without influence, due to molecular weight Greatly so without precipitation；
2）Brominated Polystyrene has resistance to elevated temperatures, will not resolve into the small molecule thing easily separated out in process Matter.
3）Brominated Polystyrene and nylon matrix resin have good compatibility, on the mechanical property of material without influence.
D. Flameproof polyamide provided by the invention has resistance to precipitation performance in outstanding hot and humid environment, inexpensive, good Good comprehensive mechanical property, fire resistance, processing characteristics and electrical property, it is widely used in electronics electricity in hot and humid environment Device product.
Embodiment
With reference to embodiment, the present invention is further illustrated.
Embodiment 1.
A kind of low precipitation flame-retardant polyamide composition of the present embodiment, include the raw material of following mass percent：
Nylon resin 41.4%, main flame retardant 21%, fire retarding synergist 7%, alkali-free glass fiber 30%, antioxidant 0.2%, lubricant 0.4%。
Wherein, the nylon resin is nylon66 fiber；The main flame retardant is brominated Polystyrene, in the bromide fire retardant The content of bromine is 68%；The fire retarding synergist is antimony oxide powder；The lubricant is Tissuemat E；The alkali-free glass Fibre is the glass that single beam diameter is 7 μm；The antioxidant is primary antioxidant and auxiliary antioxidant using mass ratio as 4:1 mixing Thing, primary antioxidant are Hinered phenols antioxidant, and auxiliary antioxidant is phosphite ester kind antioxidant.
Embodiment 2.
A kind of low precipitation flame-retardant polyamide composition of the present embodiment, include the raw material of following mass percent：
Nylon resin 41.4%, main flame retardant 21%, fire retarding synergist 7%, alkali-free glass fiber 30%, antioxidant 0.2%, lubricant 0.4%。
Wherein, the nylon resin is nylon 6；The main flame retardant is brominated polystyrene, in the bromide fire retardant The content of bromine is 68%；The fire retarding synergist is the carrier antimony trioxide parent particle of nylon 6, the load of the antimony trioxide parent particle The content of antimony oxide is 85% in body；The lubricant is modified PE wax；The alkali-free glass fiber is that single beam diameter is 8 μm Glass；The antioxidant is primary antioxidant and auxiliary antioxidant using mass ratio as 3:1 mixture, primary antioxidant are hindered phenol Kind antioxidant, auxiliary antioxidant are phosphite ester kind antioxidant.
Embodiment 3.
A kind of low precipitation flame-retardant polyamide composition of the present embodiment, include the raw material of following mass percent：
Nylon resin 41.4%, main flame retardant 21%, fire retarding synergist 7%, alkali-free glass fiber 30%, antioxidant 0.2%, lubricant 0.4%。
Wherein, the nylon resin is nylon66 fiber and nylon 6 using mass ratio as 50:15 mixture；The main flame retardant For brominated epoxy resin, the content of bromine is 68% in the bromide fire retardant；The fire retarding synergist is the EVA that mass ratio is 7% Carrier antimony trioxide parent particle, the content of antimony oxide is 85% in the EVA carriers antimony trioxide parent particle；The lubrication Agent is OP waxes；The alkali-free glass fiber is the glass that single beam diameter is 9 μm；The antioxidant be primary antioxidant and auxiliary antioxidant with Mass ratio is 2:1 mixture, primary antioxidant are Hinered phenols antioxidant, and auxiliary antioxidant is phosphite ester kind antioxidant.
Embodiment 4.
A kind of low precipitation flame-retardant polyamide composition of the present embodiment, include the raw material of following mass percent：
Nylon resin 41.4%, main flame retardant 21%, fire retarding synergist 7%, alkali-free glass fiber 30%, antioxidant 0.2%, lubricant 0.4%。
Wherein, the nylon resin is nylon66 fiber and nylon 6 using mass ratio as 30:5 mixture；The main flame retardant For brominated Polystyrene, the content of bromine is 68% in the bromide fire retardant；The fire retarding synergist is PE carrier antimony oxides Master batch, the content of antimony oxide is 85% in the PE carriers antimony trioxide parent particle；The lubricant is lignite wax.It is described Alkali-free glass fiber is the glass that single beam diameter is 10 μm；The antioxidant is primary antioxidant and auxiliary antioxidant using mass ratio as 1:1 Mixture, primary antioxidant is Hinered phenols antioxidant, and auxiliary antioxidant is phosphite ester kind antioxidant.
Embodiment 5.
A kind of low precipitation flame-retardant polyamide composition of the present embodiment, include the raw material of following mass percent：
Nylon resin 44.9%, main flame retardant 23%, fire retarding synergist 7.5%, alkali-free glass fiber 25%, antioxidant 0.2%, lubrication Agent 0.4%.
Wherein, the nylon resin is nylon66 fiber and nylon 6 using mass ratio as 40:10 mixture；The main flame retardant For brominated polystyrene, the content of bromine is 69% in the bromide fire retardant；The fire retarding synergist is that mass percent is 4% PA6 carriers antimony trioxide parent particle and the mixture of 3.5% silica and magnesia, wherein, silica and magnesia Mass ratio 10:5, the content of antimony oxide is 85% in the PA6 carriers antimony trioxide parent particle；The lubricant is poly- second Alkene wax；The alkali-free glass fiber is the glass that single beam diameter is 11 μm；The antioxidant is primary antioxidant and auxiliary antioxidant with matter Amount is than being 1:2 mixture, primary antioxidant are hexamethylene diamine kind antioxidant, and auxiliary antioxidant is monothioester kind antioxidant.
Embodiment 6.
A kind of low precipitation flame-retardant polyamide composition of the present embodiment, include the raw material of following mass percent：
Nylon resin 47.6%, main flame retardant 24%, fire retarding synergist 8%, alkali-free glass fiber 20%, antioxidant 0.2%, lubricant 0.4% 。
Wherein, the nylon resin is nylon66 fiber and nylon 6 using mass ratio as 50:10 mixture；The main flame retardant For brominated epoxy resin, the content of bromine is 70% in the bromide fire retardant；The fire retarding synergist is that mass percent is 4% PA6 carriers antimony trioxide parent particle and the mixture of 4% silica and aluminum oxide, wherein, the matter of silica and aluminum oxide Amount is than being 15:5, the content of antimony oxide is that 85% lubricant is modified PE in the carrier of the antimony trioxide parent particle Wax；The alkali-free glass fiber is the glass that single beam diameter is 12 μm；The antioxidant is primary antioxidant and auxiliary antioxidant with quality Than for 1:3 mixture, primary antioxidant are hexamethylene diamine kind antioxidant, and auxiliary antioxidant is monothioester kind antioxidant.
Embodiment 7.
A kind of low precipitation flame-retardant polyamide composition of the present embodiment, include the raw material of following mass percent：
Nylon resin 35%, main flame retardant 18%, fire retarding synergist 6%, alkali-free glass fiber 40%, antioxidant 0.4%, lubricant 0.6% 。
Wherein, the nylon resin is nylon66 fiber and nylon 6 using mass ratio as 30:10 mixture；The main flame retardant For brominated Polystyrene, the content of bromine is 71% in the bromide fire retardant；The fire retarding synergist is that mass percent is 3% The mixture of PA6 carriers antimony trioxide parent particle and the compound of 3% silica and magnesia, wherein, silica and oxygen The mass ratio for changing magnesium is 15:10, the content of antimony oxide is 85% in the PA6 carriers antimony trioxide parent particle；The lubrication Agent is OP waxes；The alkali-free glass fiber is the glass that single beam diameter is 13 μm；The antioxidant is primary antioxidant and auxiliary antioxidant Using mass ratio as 1:4 mixture, primary antioxidant are hexamethylene diamine kind antioxidant, and auxiliary antioxidant is phosphite ester kind antioxidant.
Embodiment 8.
A kind of low precipitation flame-retardant polyamide composition of the present embodiment, include the raw material of following mass percent：
Nylon resin 48.1%, main flame retardant 26%, fire retarding synergist 10%, alkali-free glass fiber 15%, antioxidant 0.4%, lubricant 0.5% 。
Wherein, the nylon resin is nylon66 fiber and nylon 6 using mass ratio as 35:15 mixture；The main flame retardant For brominated polystyrene, the content of bromine is 72% in the bromide fire retardant；The fire retarding synergist is that mass percent is 6% The mixture of PA6 carriers antimony trioxide parent particle and the compound of 4% silica and aluminum oxide, wherein, silica and oxygen The mass ratio for changing aluminium is 5:2, the content of antimony oxide is 85% in the PA6 carriers antimony trioxide parent particle；The lubricant For lignite wax；The alkali-free glass fiber is the glass that single beam diameter is 14 μm；The antioxidant is primary antioxidant and auxiliary antioxidant Using mass ratio as 2:1 mixture, primary antioxidant are Hinered phenols antioxidant, and auxiliary antioxidant is phosphite ester kind antioxidant.
Embodiment 9.
A kind of low precipitation flame-retardant polyamide composition of the present embodiment, include the raw material of following mass percent：
Nylon resin 44.8%, main flame retardant 30%, fire retarding synergist 14%, alkali-free glass fiber 10%, antioxidant 0.4%, lubricant 0.8% 。
Wherein, the nylon resin is nylon66 fiber；The main flame retardant is brominated epoxy resin, in the bromide fire retardant The content of bromine is 72%；The fire retarding synergist be the EVA carriers antimony trioxide parent particle that mass percent is 6% and 8% it is anhydrous The mixture of Firebrake ZB, the content of antimony oxide is 85% in the EVA carriers antimony trioxide parent particle；The lubricant is Tissuemat E；The alkali-free glass fiber is the glass that single beam diameter is 8 μm；The antioxidant is primary antioxidant and auxiliary antioxidant Using mass ratio as 2:1 mixture, primary antioxidant are hexamethylene diamine kind antioxidant, and auxiliary antioxidant is phosphite ester kind antioxidant.
Embodiment 10.
A kind of low precipitation flame-retardant polyamide composition of the present embodiment, include the raw material of following mass percent：
Nylon resin 53%, main flame retardant 27%, fire retarding synergist 8%, alkali-free glass fiber 11%, antioxidant 0.3%, lubricant 0.7% 。
Wherein, the nylon resin is nylon66 fiber and nylon 6 using mass ratio as 45:15 mixture；The main flame retardant For brominated Polystyrene, the content of bromine is 73% in the bromide fire retardant；The fire retarding synergist is the oxidation of EVA carriers three two Antimony master batch, the content of antimony oxide is 85% in the EVA carriers antimony trioxide parent particle；The lubricant is Tissuemat E； The alkali-free glass fiber is the glass that single beam diameter is 9 μm；The antioxidant be primary antioxidant and auxiliary antioxidant using mass ratio as 1:1 mixture, primary antioxidant are Hinered phenols antioxidant, and auxiliary antioxidant is monothioester kind antioxidant.
Embodiment 11.
A kind of low precipitation flame-retardant polyamide composition of the present embodiment, include the raw material of following mass percent：
Nylon resin 30%, main flame retardant 28%, fire retarding synergist 15%, alkali-free glass fiber 26%, antioxidant 0.5%, lubricant 0.5% 。
Wherein, the nylon resin is nylon66 fiber；The main flame retardant is brominated polystyrene, in the bromide fire retardant The content of bromine is 74%；The fire retarding synergist is 7% silica and the compound and 8% anhydrous boric acid of metal oxide Zinc, silica and metal oxide are using mass ratio as 15:10 compound, the metal oxide are magnesia or oxidation Aluminium；The lubricant is modified PE wax AC-540A；The alkali-free glass fiber is the glass that single beam diameter is 10 μm；The antioxidant It is primary antioxidant and auxiliary antioxidant using mass ratio as 3:1 mixture, primary antioxidant are Hinered phenols antioxidant, aid in antioxygen Agent is monothioester kind antioxidant.
Embodiment 12.
A kind of low precipitation flame-retardant polyamide composition of the present embodiment, include the raw material of following mass percent：
Nylon resin 50%, main flame retardant 20%, fire retarding synergist 8.5%, alkali-free glass fiber 21%, antioxidant 0.2%, lubricant 0.3% 。
Wherein, the nylon resin is nylon 6；The main flame retardant is brominated epoxy resin, in the bromide fire retardant The content of bromine is 75%；The fire retarding synergist is 6.5% anhydrous zinc borate and 2% PA6 carrier antimony trioxide parent particles；Institute It is OP waxes to state lubricant；The alkali-free glass fiber is the glass that single beam diameter is 12 μm；The antioxidant is primary antioxidant and auxiliary Antioxidant is using mass ratio as 3:1 mixture, primary antioxidant are hexamethylene diamine kind antioxidant, and auxiliary antioxidant resists for phosphorous acid esters Oxygen agent.
A kind of embodiment 1-12 of the flame-retardant polyamide composition of low precipitation composition of raw materials of the present invention is as follows：
　 Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6
Nylon resin 41.4 41.4 41.4 41.4 44.9 47.6
Alkali-free glass fiber 30 30 30 30 25 20
Bromide fire retardant 21 21 21 21 23 24
Antimony oxide powder 7 　 　 　 　 　
PA6 carrier antimony trioxide parent particles 　 7 　 　 4 4
EVA carrier antimony trioxide parent particles 　 　 7 　 　 　
PE carrier antimony trioxide parent particles 　 　 　 7 　 　
The compound of silica and magnesia 　 　 　 　 3.5
The compound of silica and aluminum oxide 4
Anhydrous zinc borate 　 　 　 　 　 　
Antioxidant 0.2 0.2 0.2 0.2 0.2 0.2
Lubricant 0.4 0.4 0.4 0.4 0.4 0.4
　 Embodiment 7 Embodiment 8 Embodiment 9 Embodiment 10 Embodiment 11 Embodiment 12
Nylon resin 35 48.1 44.8 53 30 50
Alkali-free glass fiber 40 15 10 11 26 21
Bromide fire retardant 18 26 30 27 28 20
Antimony oxide powder 　 　 　 　 　 　
PA6 carrier antimony trioxide parent particles 3 6 　 　 　 2　
EVA carrier antimony trioxide parent particles 　 　 6 8 　 　
PE carrier antimony trioxide parent particles 　 　 　 　 　 　
The compound of silica and magnesia 　3 　 　 　 7 　
The compound of silica and aluminum oxide 4
Anhydrous zinc borate 　 　 8 　 8 6.5　
Antioxidant 0.4 0.4 0.4 0.3 0.5 0.2
Lubricant 0.6 0.5 0.8 0.7 0.5 0.3
Twin-screw extrusion in a kind of embodiment 1-12 of the preparation method of the flame-retardant polyamide composition of low precipitation of the present invention The temperature of machine is：Temperature is 200-300 DEG C, and preferably 220-280 DEG C, the rotating speed of double screw extruder is 200-400 revs/min Clock, it is preferable that rotating speed is：240rpm.
The flame-retardant polyamide composition material index parameter of the obtained precipitations of embodiments of the invention 1-12 is as follows：
Tensile strength/psi Bending strength/Psi Impact strength/in-ft/lb Fire-retardant/0.8mm CTI/V Test piece separates out loss of weight/%
Embodiment 1 18075 26773 1.617 V0 250 1.250
Embodiment 2 19007 27477 2.125 V0 275 0.774
Embodiment 3 18870 27204 2.0 V0 275 0.770
Embodiment 4 18913 27084 1.95 V0 275 0.773
Embodiment 5 18157 26591 1.85 V0 300 0.733
Embodiment 6 17560 26025 1.50 V0 250 0.793
Embodiment 7 20094 29261 2.40 V0 325 0.715
Embodiment 8 15314 25872 1.30 V0 225 0.863
Embodiment 9 14006 22483 1.18 V0 200 0.980
Embodiment 10 14342 23495 1.22 V0 200 0.910
Embodiment 11 17428 25726 1.51 V0 200 0.815
Embodiment 12 17860 25875 1.45 V0 200 0.681
Embodiment described above, simply the present invention better embodiment, be not to limit the scope of the present invention, therefore The equivalent change or modification that all construction, feature and principles according to described in scope of the present invention patent are done, all should include this hair In bright patent claim.

Claims (7)

  1. A kind of 1. low precipitation flame-retardant polyamide composition, it is characterised in that：It is made up of the raw material of following mass percent：
    Nylon resin 20-70%
    Main flame retardant 10-30%
    Fire retarding synergist 0-15%
    Alkali-free glass fiber 10-40%
    Antioxidant 0-1%
    Lubricant 0-2%
    Wherein, the nylon resin is the mixture of one or both of nylon66 fiber, nylon 6；
    The main flame retardant is bromide fire retardant；
    The fire retarding synergist is antimony trioxide parent particle, and the carrier of the antimony trioxide parent particle is polyethylene, nylon 6, EVA In one kind, the content of antimony oxide is 85% in polyethylene, nylon 6, EVA carrier antimony trioxide parent particles, and described fire-retardant The mass percent of synergist is not 0；
    Or the fire retarding synergist is silica and metal oxide using mass ratio as 0-15:0-10 compound, the gold It is magnesia or aluminum oxide to belong to oxide, and the structural formula of the compound of the silica and metal oxide is (MxOy)n‧ (SiO2) m, wherein, M=Al or Mg；X, y, m, n are natural number；
    Or the fire retarding synergist is antimony trioxide parent particle:The mass ratio of the compound of silica and metal oxide is 0- 15:0-10 mixture；
    Or the fire retarding synergist is antimony trioxide parent particle：The mass ratio of Firebrake ZB is 0-15:0-10 mixture, and institute The mass ratio for stating antimony trioxide parent particle is not 0；
    The lubricant is in HMW polymolecularity lubricant, including Tissuemat E, modified PE wax, OP waxes and lignite wax It is a kind of.
  2. A kind of 2. low precipitation flame-retardant polyamide composition according to claim 1, it is characterised in that：Including following quality hundred Divide the raw material of ratio：
    Nylon resin 30-50%
    Main flame retardant 10-30%
    Fire retarding synergist 5-15%
    Alkali-free glass fiber 10-40%
    Antioxidant 0.1-0.5%
    Lubricant 0.1-1%.
  3. A kind of 3. low precipitation flame-retardant polyamide composition according to claim 1, it is characterised in that：The nylon resin is Nylon66 fiber and nylon 6 are using mass ratio as 0-60:0-20 mixture.
  4. A kind of 4. flame-retardant polyamide composition of low precipitation according to claim 1, it is characterised in that：The bromine system is fire-retardant Agent is brominated Polystyrene, one kind in brominated polystyrene, brominated epoxy resin, and the content of bromine is in the bromide fire retardant 66-75%。
  5. A kind of 5. flame-retardant polyamide composition of low precipitation according to claim 1, it is characterised in that：The alkali-free glass fiber It is the glass that single beam diameter is 7-14 μm.
  6. A kind of 6. flame-retardant polyamide composition of low precipitation according to claim 1, it is characterised in that：The antioxidant is Primary antioxidant and auxiliary antioxidant are using mass ratio as 4:1-1:4 mixture, primary antioxidant be Hinered phenols antioxidant or oneself two Amine antioxidants, auxiliary antioxidant are phosphite ester kind antioxidant and monothioester kind antioxidant.
  7. 7. a kind of preparation method of the flame-retardant polyamide composition of low precipitation as described in any one in claim 1-6, its It is characterised by：Including following procedure of processing：
    Step（1）Each raw material are weighed by weight percentage；
    Step（2）By step（1）In the alkali-free glass fiber that weighs take out, then remaining raw material is well mixed in mixing tank；
    Step（3）By step（2）In the raw material that is well mixed added from the main spout of twin-screw, then by alkali-free glass fiber from double The glass fiber opening of screw rod adds, and the rotating speed of double screw extruder is 200-400 revs/min, and temperature is 200-300 DEG C, and low analysis is made The flame-retardant polyamide composition gone out.
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CN105623256A (en) * 2016-03-04 2016-06-01 广西华锑科技有限公司 High-toughness antimony system compound flame retardant nylon material and preparation method thereof
CN106189221B (en) * 2016-08-05 2018-10-02 江苏晋伦塑料科技有限公司 A kind of halogen-free flame-retardant glass fiber enhancing nylon and its preparation method and application
CN107446349B (en) * 2017-07-05 2020-12-01 惠州市华聚塑化科技有限公司 Ultraviolet aging resistant flame-retardant nylon composite material and preparation method thereof
CN109021562B (en) * 2018-08-22 2020-11-06 浙江新力新材料股份有限公司 Efficient flame-retardant reinforced nylon composite material and preparation method thereof
CN109679338A (en) * 2018-12-23 2019-04-26 德力西电气有限公司 A kind of halogen-free flame-retardant polyamide alloy material of low precipitation and preparation method thereof
CN110982254B (en) * 2019-04-22 2022-02-11 江苏集萃先进高分子材料研究所有限公司 Flame-retardant fiber reinforced nylon 6 material and preparation method thereof
CN110229514A (en) * 2019-06-28 2019-09-13 江苏晋伦塑料科技有限公司 A kind of color inhibition fire-resistant polyamide composite and preparation method thereof
CN110724379A (en) * 2019-10-30 2020-01-24 南京聚隆科技股份有限公司 Flame-retardant nylon material for electronics and electrics and preparation method thereof
CN111574773A (en) * 2020-06-13 2020-08-25 厦门毅兴行塑胶原料有限公司 Flame-retardant master batch and preparation method thereof
CN111793334B (en) * 2020-08-18 2023-01-10 圆创享(苏州)新材料技术有限公司 PET film and preparation method thereof
CN112457664A (en) * 2020-11-05 2021-03-09 金发科技股份有限公司 Flame-retardant polyamide composite material and preparation method and application thereof
CN112795183B (en) * 2020-12-30 2023-02-21 上海普利特复合材料股份有限公司 High-strength, low-shrinkage and low-precipitation environment-friendly flame-retardant polyamide composition and preparation method thereof
CN114196196B (en) * 2021-12-27 2024-03-15 安徽星贝达新材料科技有限公司 Flame-retardant polyamide resin composition
CN114621583B (en) * 2022-04-12 2023-08-22 三一汽车制造有限公司 MC nylon material and preparation method thereof, guide ring, concrete piston and pumping system

Family Cites Families (3)

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Publication number Priority date Publication date Assignee Title
CN101205309B (en) * 2007-11-30 2010-10-27 上海锦湖日丽塑料有限公司 Antimony trioxide synergist
CN101250323B (en) * 2008-03-28 2010-07-14 浙江大学 Flame-proof smoke-inhibiting nylon 6 composite material
CN102229738B (en) * 2011-05-17 2013-05-01 威海联桥新材料科技股份有限公司 High glow-wire flame retardant reinforced PET/PA (polyethylene terephthalate/polyamide) alloy material and production method thereof

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