CN104231622A - Low-precipitate flame-retarded polyamide composition and preparation method thereof - Google Patents
Low-precipitate flame-retarded polyamide composition and preparation method thereof Download PDFInfo
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- 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
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Abstract
The invention relates to the technical field of a high polymer material and especially relates to a low-temperature flame-retarded polyamide composition, and the composition includes the raw materials based on the following mass percentage: 20-70% of nylon resin, 10-30% of main flame retardant, 0-15% of synergistic agent, 10-40% of alkali-free glass fiber, 0-1% of antioxidant, and 0-2% of lubricant, wherein the nylon resin is one of nylon 66 and nylon 6 or their mixture; the main flame retardant is a brominated flame retardant; the synergistic agent is selected from one of compounds of antimonous oxide master batch, zinc borate, silicon dioxide and metallic oxide or the mixture prepared by more than one compound; the lubricant is a lubricant with high molecular weight and dispersion and includes one of polyethylene wax, modified PE wax, OP wax and lignite wax. The polyamide composition isn't easily migrated or precipitated at high-temperature moisture conditions and low in material cost, the preparation method is simple and beneficial to popularization and application.
Description
Technical field
The present invention relates to technical field of polymer materials, particularly relate to a kind of low precipitation flame-retardant polyamide composition and preparation method thereof.
Background technology
It is excellent that bromine antimony composite flame-proof polyamide compoiste material has flame retardant resistance, flame retardant rating reaches UL94 V0 (0.4mm), keep good mechanical property and mechanical property simultaneously, processing characteristics is good, environmental protection, the excellent over-all properties such as with low cost, present fire-retardant nylon market has dominant position, can meet the product demand such as electronic apparatus, low-tension switch.
Now traditional on the market bromine antimony composite flame-proof polyamide compoiste material, mainly use bromide fire retardant and antimony sesquioxide powder volume recombination Flameproof polyamide, because antimonous oxide is as inorganic powder particle, and have incompatible between nylon, after causing material injection to become product, after placing for some time, have fire retardant to separate out, cause product surface frosting phenomenon, particularly under the environment of high-temperature high-humidity, the frosting on meeting expedite product surface.This mainly has exclusiveness due to polyamide substrate resin as a kind of crystalline material, so cause the antimonous oxide powder in resin to move from interiors of products to product surface, separate out, makes product surface form one deck bloom.Because bromine antimony fire-retardant polyamide material is mainly for the manufacture of electrical components such as terminal board, junctor, DDR slots, these parts in use, because circuit exists heating, make product must meet hot environment requirement.In high temperature environments, the mobility of polyamide molecule chain strengthens, molecular chain kindliness strengthens, degree of crystallinity improves, due to crystallization rejection, therefore the migration of the antimonous oxide in product is also accelerated, a large amount of white powder precipitates is formed at product surface in short period of time, conductive metal material in this precipitate meeting polluted product, thus affect the electrical property of material, cause the metallic substance in product to be polluted thus cause product circuit conduction bad, having a strong impact on the use properties of material.Because precipitate is white creamy substance matter, then also product appearance is had a strong impact on for black product.
Except temperature, the humidity of environment is separated out antimonous oxide in material and is also had a significant impact, and nylon main component is polymeric amide, and its amide group-NHCO-has polarity, makes nylon have very strong water-absorbent.After fire-retardant nylon water suction, water molecules can enter in the space between polyamide molecule, lubrication is provided between intermolecular and each component, to other components, there is certain extraction simultaneously, make the antimonous oxide component in material can move to the surface of product at short notice under the lubrication of water molecules and extraction, affect the use properties of material.Except antimonous oxide, the small-molecule substance in material is the same with antimonous oxide easily in use moves to product surface by interiors of products, has larger impact to the performance of product and outward appearance.
Chinese patent 201110392827.2 discloses a kind of preparation method of high-strength high-toughness flame-retardant polyamide, based on 100 parts of weight part relative viscosities polymeric amide that is 2.4-3.3, add the TDE fire retardant of 10-30 weight part, 3-10 weight part antimonous oxide fire retardant, 0-5 weight part light stationary level, 0.2-1 weight part thermo-stabilizer, the mixture of 0.5-1 weight part oxidation inhibitor composition, through twin-screw extrusion melting mixing, extrude, cool, dry, pelletizing, obtain high-strength high-toughness flame-retardant polyamide.The TDE that this patent adopts, the decomposition temperature of this fire retardant is about 300 DEG C, and this material is in twin-screw extrusion and injection moulding process, due to the existence of shear heat, melt temperature is made to exceed this temperature, cause part TDE to resolve into small-molecule substance, and the small-molecule substance that these decompose out is easily moving to product surface formation bloom shape material, affects product appearance and use.Photostabilizer and thermo-stabilizer belong to small molecules auxiliary agent simultaneously, easily separate out.
Chinese patent CN 101955657 A, CN 103421303 A discloses a kind of environmental protection height CTI flame-retardant reinforced nylon 6 material, the main modified Pa 6 of the present invention, and PA66 processing temperature comparatively PA6 is high, because the heat resistance of phosphor nitrogen composite combustion inhibitor is not high, make phosphor nitrogen combustion inhibitor easy decomposes in the course of processing become small-molecule substance, thus the high-temp resisting high-humidity resisting affecting material separate out performance.Described in Chinese patent CN 102492290 A, the resistance toheat of TDE fire retardant is on the low side, easily decomposes in the course of processing, causes separating out and material xanthochromia.Similar patent also has CN 101503570A, 200610118566.X, 200610028821.1,201110392827.8 be TDE and antimonous oxide compositional flame-retardant nylon etc. patent, described technique is also traditional technology, special processing is not done to the dispersion of antimonous oxide, easily separates out so same in hot humid environment.Therefore, the problems referred to above are urgently to be resolved hurrily.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, there is provided a kind of low precipitation flame-retardant polyamide composition and preparation method thereof, obtained daiamid composition is not easily migration or precipitation in hot humid environment, and the cost of material is low, preparation method of the present invention is simple, is conducive to applying.
The present invention is achieved through the following technical solutions.
A kind of low precipitation flame-retardant polyamide composition, comprises 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%
Oxidation inhibitor 0-1%
Lubricant 0-2%
Wherein, described nylon resin is one or both the mixture in nylon66 fiber, nylon 6; Described main flame retardant is bromide fire retardant; Described fire retarding synergist is one or more mixture of the mixture of antimonous oxide powder, antimony trioxide parent particle, zinc borate, silicon-dioxide and metal oxide; Described lubricant is high molecular polymolecularity lubricant, comprises the one in polyethylene wax, modified PE wax, OP wax and montanin wax.
Preferably, the zinc borate in fire retarding synergist is anhydrous zinc borate.
Preferably, a kind of low precipitation flame-retardant polyamide composition, comprises the raw material of following mass percent:
Nylon resin 30-50%
Main flame retardant 10-30%
Fire retarding synergist 5-15%
Alkali-free glass fiber 10-40%
Oxidation inhibitor 0.1-0.5%
Lubricant 0.1-1%.
More preferably, a kind of low precipitation flame-retardant polyamide composition, comprises 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%
Oxidation inhibitor 0.2-0.5%
Lubricant 0.2-1%.
Wherein, the mixture of described nylon resin to be nylon66 fiber and nylon 6 with mass ratio be 0-60:0-20.Preferably, the mass ratio of nylon66 fiber and nylon 6 is the mixture of 30-50:5-15.Its processing characteristics of material that nylon66 fiber and nylon 6 mix rear formation is more superior, can process at relatively low temperature, reduces material at high temperature and divides and parse.
Wherein, described bromide fire retardant is the one in brominated Polystyrene, brominated polystyrene, brominated epoxy resin, and in described bromide fire retardant, the content of bromine is 66-75%.
Wherein, the carrier of described antimony trioxide parent particle is the one in polyethylene (PE), nylon 6, EVA, described fire retarding synergist is antimony trioxide parent particle, in polyethylene, nylon 6, EVA carrier antimony trioxide parent particle, the content of antimonous oxide is 85%, this content is mass percent, and namely in described polyethylene support antimony trioxide parent particle, EVA carrier antimony trioxide parent particle, PA6 carrier antimony trioxide parent particle, the content of antimonous oxide is 85%.That is to say the antimonous oxide containing 85% in polyethylene support and antimony trioxide parent particle, containing the antimonous oxide of 85% in EVA carrier and antimony trioxide parent particle, containing the antimonous oxide of 85% in PA6 carrier and antimony trioxide parent particle.
Antimony trioxide parent particle preparation technology of the present invention is: 1) take vector resin and antimonous oxide by weight proportion by subtraction; 2) mix at mixing tank; 3) added by the main spout of the starting material mixed from singe screw, screw speed 200-500, temperature is 100-220 DEG C, and obtained antimony trioxide parent particle, antimony trioxide parent particle, through surface treatment, has easily disperse energy.Nylon 6 carrier of the present invention and the nylon resin in filling a prescription have good compatibility, and polyethylene and EVA carrier are conducive to the toughness promoting material.
Wherein, the mixture of described fire retarding synergist to be silicon-dioxide and metal oxide with mass ratio be 0-15:0-10, described metal oxide is magnesium oxide or aluminum oxide.
Wherein, described fire retarding synergist be the mixture of antimony trioxide parent particle and silicon-dioxide and metal oxide take mass ratio as the mixture of 0-15:0-10; Or, described fire retarding synergist be antimony trioxide parent particle and zinc borate take mass ratio as the mixture of 0-15:0-10; Or described fire retarding synergist is antimony trioxide parent particle.
Wherein, described alkali-free glass fiber to be single beam diameter the be glass of 7-14 μm.
Wherein, the mixture of described oxidation inhibitor to be primary antioxidant and auxiliary antioxidant with mass ratio be 4:1-1:4, primary antioxidant is Hinered phenols antioxidant or hexanediamine kind antioxidant, and auxiliary antioxidant is phosphite ester kind antioxidant, monothioester kind antioxidant.
Preferably, primary antioxidant: the mass ratio of auxiliary antioxidant is 2:1-1:1.Antioxidant 1010 is a kind of Hinered phenols antioxidant, and action principle catches free radical, belongs to primary antioxidant, has effect to the Long-term Anti oxidation of polymkeric substance.Phosphite ester kind antioxidant, action principle is hydroperoxide decomposition, belongs to auxiliary antioxidant, plays very large effect to polymer processing, as degraded jaundice in some material processing, can play suppression yellowing Effect; But there is no later stage antioxidant effect; Primary antioxidant+auxiliary anti-oxidant jointly use can produce synergistic effect both in the energon course of processing protecting materials do not decompose, and chronic anti-aging performance improves.
A preparation method for the flame-retardant polyamide composition of low precipitation, comprises following procedure of processing:
Step (1) takes each starting material by weight percentage;
The alkali-free glass fiber taken in step (1) takes out by step (2), is then mixed in mixing tank by all the other raw materials;
The main spout of the raw material mixed in step (2) from twin screw adds by step (3), the glass fiber opening of alkali-free glass fiber from twin screw is added, the rotating speed of twin screw extruder is 200-400 rev/min, and temperature is 200-300 DEG C, the flame-retardant polyamide composition of obtained low precipitation.
Beneficial effect of the present invention is:
(1) the daiamid composition advantage that the present invention obtains has excellent resistance to precipitation performance, and there is excellent flame retardant resistance UL94V0, excellent mechanical property, be applicable to manufacture junctor, terminal, DDR slot; thin-walled electronic package etc., can extensively use under the environment of high-temperature high-humidity.
(2) main flame retardant of the present invention is the outstanding brominated Polystyrene of thermostability, can not decomposes produce in the twin-screw extrusion course of processing and injection moulding process, simultaneously and matrix resin there is better compatibility, so material can also keep good mechanical property, simultaneously owing to there being good compatibility between brominated Polystyrene and polyamide resin, so without precipitation.Brominated Polystyrene molecular weight distribution is narrower, and point quality is 1*10
4-5*10
4on the mobility of material without impact.
(3) one of fire retarding synergist of the present invention is antimony trioxide parent particle, and described antimonous oxide purity is greater than 99.9%, and median size is 0.7 μm.The previously prepared one-tenth antimony trioxide parent particle of antimonous oxide simultaneously.The carrier of antimony trioxide parent particle is the one of polyethylene, nylon 6, EVA.Antimonous oxide is processed into master batch through Single screw extrusion, be equivalent to through once disperseing, the material enable melt extrudes antimonous oxide in process at twin screw and disperses more abundant, dispersion in the material evenly, the mechanical property of material and mechanical property are not almost affected, simultaneously owing to disperseing fully, to make the flame retarding efficiency of antimonous oxide improve, thus the usage quantity 5%-10% of antimonous oxide can be reduced, can cost be effectively reduced.Because the addition of antimonous oxide reduces, in material, antimonous oxide content reduces, and also can reduce the precipitation of antimonous oxide.In addition, antimony trioxide parent particle does not have dust pollution, is conducive to the clean and tidy and workers ' health of environment.
(4) two of fire retarding synergist of the present invention is the mixture of silicon-dioxide and metal oxide, the mixture of this silicon-dioxide and metal oxide has whiteness and is greater than 91%, there is the sub-flaky nanometer structure of easily dispersion, there is good fire-retardant synergistic, synergism.The structural formula of the mixture of silicon-dioxide and metal oxide is (MxOy) n (SiO2) m, wherein, M=Al or Mg; X, y, m, n are natural number.
The mixture of silicon-dioxide and metal oxide can substitute the antimonous oxide of 50% with 1:1 as fire retarding synergist, have good flame retardant resistance, also have smoke suppressing effect simultaneously.And that flaky nanometer structure has lamella barriering effect, to the small molecular of material and the precipitation of powder, there is certain barriering effect, and also blocking effect is played for the osmosis of water molecules after the water suction of material, this just can play certain decelerating effect to the precipitation of small molecules and powder.The mixture true qualities sheet structure of silicon-dioxide and metal oxide, separates out in the material hardly simultaneously, so the part antimonous oxide that the mixture of silicon-dioxide and metal oxide replaces can reduce precipitation.And the mixture of silicon-dioxide and metal oxide is cheap, can further reduce costs.The mixture of silicon-dioxide and metal oxide is sub-nanostructure simultaneously, less to the Effect on Mechanical Properties of material.
(5) glass of the present invention is alkali-free glass fiber, glass filament diameter is 0.7-14 μm, surface is through silane coupling agent process, and there is good interfacial combined function between polyamide substrate resin, when material is subject to external force, external force passes to glass by good interface cohesion, allows the glass of high rigidity carry and to consume external force, thus reaches the effect of activeness and quietness.
(6) less about the research of the resistance to precipitation of bromine antimony composite flame-proof polymeric amide at present, this patent produces small-molecule substance by using the outstanding brominated Polystyrene of heat resistance to reduce material in the course of processing; Dispersed in matrix resin of powder body material is strengthened with the antimonous oxide fire-retardant master granule of high dispersive, simultaneously by partial obstruction excellent property and without separate out silicon-dioxide and the mixture of metal oxide substitute antimonous oxide, reduce migration and the precipitation of small molecules and powder granule, can also material cost be effectively reduced simultaneously.
(7) preparation method of the present invention is compared with prior art, has following beneficial effect:
A. high dispersive antimonous oxide fire-retardant master granule is adopted, compare with traditional fire-retardant powder antimonous oxide and have the following advantages: antimonous oxide dispersing property is in the material better, disperse more even in matrix resin, flame retardant resistance can be given full play to, thus reduce the consumption of fire retardant, effectively reduce costs, less addition can effectively reduce the precipitation of antimonous oxide simultaneously.
B. adopt the mixture of the silicon-dioxide of sub-nano-sheet and metal oxide as fire retarding synergist, have the following advantages:
1) mixture of sub-nano-sheet silicon-dioxide and metal oxide can substitute the antimonous oxide of 50% with 1:1, effectively can reduce material cost;
2) the sub-flaky nanometer structure of the mixture of silicon-dioxide and metal oxide, dispersing property is good in the material, can keep the mechanical property that material is good;
3) sheet structure of the mixture of silicon-dioxide and metal oxide makes the mixture of silicon-dioxide and metal oxide have certain blocking effect, has iris action to the precipitation of the small molecules in material and powder body material, reduces the precipitation of material.
C. adopt main flame retardant to be brominated Polystyrene, have the following advantages:
1) molecular weight distribution is narrower, and molecular mass is 1*10
4-5*10
4, on the mobility of material without impact, because molecular weight is large so without precipitation;
2) brominated Polystyrene has resistance to elevated temperatures, can not resolve into the small-molecule substance of easily separating out in the course of processing.
3) brominated Polystyrene and nylon matrix resin have good compatibility, on the mechanical property of material without impact.
D. Flameproof polyamide provided by the invention has resistance to precipitation performance in outstanding hot and humid environment, and low cost, good comprehensive mechanical property, flame retardant properties, processing characteristics and electrical property, be widely used in electric equipment products in hot and humid environment.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated.
embodiment 1.
The low precipitation flame-retardant polyamide composition of one of the present embodiment, comprises the raw material of following mass percent:
Nylon resin 41.4%, main flame retardant 21%, fire retarding synergist 7%, alkali-free glass fiber 30%, oxidation inhibitor 0.2%, lubricant 0.4%.
Wherein, described nylon resin is nylon66 fiber; Described main flame retardant is brominated Polystyrene, and in described bromide fire retardant, the content of bromine is 68%; Described fire retarding synergist is antimonous oxide powder; Described lubricant is polyethylene wax; Described alkali-free glass fiber to be single beam diameter the be glass of 7 μm; The mixture of described oxidation inhibitor to be primary antioxidant and auxiliary antioxidant with mass ratio be 4:1, primary antioxidant is Hinered phenols antioxidant, and auxiliary antioxidant is phosphite ester kind antioxidant.
embodiment 2.
The low precipitation flame-retardant polyamide composition of one of the present embodiment, comprises the raw material of following mass percent:
Nylon resin 41.4%, main flame retardant 21%, fire retarding synergist 7%, alkali-free glass fiber 30%, oxidation inhibitor 0.2%, lubricant 0.4%.
Wherein, described nylon resin is nylon 6; Described main flame retardant is brominated polystyrene, and in described bromide fire retardant, the content of bromine is 68%; Described fire retarding synergist is nylon 6 carrier antimony trioxide parent particle, and in the carrier of described antimony trioxide parent particle, the content of antimonous oxide is 85%; Described lubricant is modified PE wax; Described alkali-free glass fiber to be single beam diameter the be glass of 8 μm; The mixture of described oxidation inhibitor to be primary antioxidant and auxiliary antioxidant with mass ratio be 3:1, primary antioxidant is Hinered phenols antioxidant, and auxiliary antioxidant is phosphite ester kind antioxidant.
embodiment 3.
The low precipitation flame-retardant polyamide composition of one of the present embodiment, comprises the raw material of following mass percent:
Nylon resin 41.4%, main flame retardant 21%, fire retarding synergist 7%, alkali-free glass fiber 30%, oxidation inhibitor 0.2%, lubricant 0.4%.
Wherein, the mixture of described nylon resin to be nylon66 fiber and nylon 6 with mass ratio be 50:15; Described main flame retardant is brominated epoxy resin, and in described bromide fire retardant, the content of bromine is 68%; Described fire retarding synergist to be mass ratio be 7% EVA carrier antimony trioxide parent particle, in described EVA carrier antimony trioxide parent particle, the content of antimonous oxide is 85%; Described lubricant is OP wax; Described alkali-free glass fiber to be single beam diameter the be glass of 9 μm; The mixture of described oxidation inhibitor to be primary antioxidant and auxiliary antioxidant with mass ratio be 2:1, primary antioxidant is Hinered phenols antioxidant, and auxiliary antioxidant is phosphite ester kind antioxidant.
embodiment 4.
The low precipitation flame-retardant polyamide composition of one of the present embodiment, comprises the raw material of following mass percent:
Nylon resin 41.4%, main flame retardant 21%, fire retarding synergist 7%, alkali-free glass fiber 30%, oxidation inhibitor 0.2%, lubricant 0.4%.
Wherein, the mixture of described nylon resin to be nylon66 fiber and nylon 6 with mass ratio be 30:5; Described main flame retardant is brominated Polystyrene, and in described bromide fire retardant, the content of bromine is 68%; Described fire retarding synergist is PE carrier antimony trioxide parent particle, and in described PE carrier antimony trioxide parent particle, the content of antimonous oxide is 85%; Described lubricant is montanin wax.Described alkali-free glass fiber to be single beam diameter the be glass of 10 μm; The mixture of described oxidation inhibitor to be primary antioxidant and auxiliary antioxidant with mass ratio be 1:1, primary antioxidant is Hinered phenols antioxidant, and auxiliary antioxidant is phosphite ester kind antioxidant.
embodiment 5.
The low precipitation flame-retardant polyamide composition of one of the present embodiment, comprises 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%, oxidation inhibitor 0.2%, lubricant 0.4%.
Wherein, the mixture of described nylon resin to be nylon66 fiber and nylon 6 with mass ratio be 40:10; Described main flame retardant is brominated polystyrene, and in described bromide fire retardant, the content of bromine is 69%; Described fire retarding synergist to be mass percent the be PA6 carrier antimony trioxide parent particle of 4% and the silicon-dioxide of 3.5% and magnesian mixture, wherein, silicon-dioxide and magnesian mass ratio 10:5, in described PA6 carrier antimony trioxide parent particle, the content of antimonous oxide is 85%; Described lubricant is polyethylene wax; Described alkali-free glass fiber to be single beam diameter the be glass of 11 μm; The mixture of described oxidation inhibitor to be primary antioxidant and auxiliary antioxidant with mass ratio be 1:2, primary antioxidant is hexanediamine kind antioxidant, and auxiliary antioxidant is monothioester kind antioxidant.
embodiment 6.
The low precipitation flame-retardant polyamide composition of one of the present embodiment, comprises the raw material of following mass percent:
Nylon resin 47.6%, main flame retardant 24%, fire retarding synergist 8%, alkali-free glass fiber 20%, oxidation inhibitor 0.2%, lubricant 0.4%.
Wherein, the mixture of described nylon resin to be nylon66 fiber and nylon 6 with mass ratio be 50:10; Described main flame retardant is brominated epoxy resin, and in described bromide fire retardant, the content of bromine is 70%; Described fire retarding synergist to be mass percent be 4% PA6 carrier antimony trioxide parent particle and the silicon-dioxide of 4% and the mixture of aluminum oxide, wherein, the mass ratio of silicon-dioxide and aluminum oxide is 15:5, in the carrier of described antimony trioxide parent particle antimonous oxide content for lubricant described in 85% be modified PE wax; Described alkali-free glass fiber to be single beam diameter the be glass of 12 μm; The mixture of described oxidation inhibitor to be primary antioxidant and auxiliary antioxidant with mass ratio be 1:3, primary antioxidant is hexanediamine kind antioxidant, and auxiliary antioxidant is monothioester kind antioxidant.
embodiment 7.
The low precipitation flame-retardant polyamide composition of one of the present embodiment, comprises the raw material of following mass percent:
Nylon resin 35%, main flame retardant 18%, fire retarding synergist 6%, alkali-free glass fiber 40%, oxidation inhibitor 0.4%, lubricant 0.6%.
Wherein, the mixture of described nylon resin to be nylon66 fiber and nylon 6 with mass ratio be 30:10; Described main flame retardant is brominated Polystyrene, and in described bromide fire retardant, the content of bromine is 71%; The mixture of described fire retarding synergist to be mass percent the be PA6 carrier antimony trioxide parent particle of 3% and the silicon-dioxide of 3% and magnesian mixture, wherein, silicon-dioxide and magnesian mass ratio are 15:10, and in described PA6 carrier antimony trioxide parent particle, the content of antimonous oxide is 85%; Described lubricant is OP wax; Described alkali-free glass fiber to be single beam diameter the be glass of 13 μm; The mixture of described oxidation inhibitor to be primary antioxidant and auxiliary antioxidant with mass ratio be 1:4, primary antioxidant is hexanediamine kind antioxidant, and auxiliary antioxidant is phosphite ester kind antioxidant.
embodiment 8.
The low precipitation flame-retardant polyamide composition of one of the present embodiment, comprises the raw material of following mass percent:
Nylon resin 48.1%, main flame retardant 26%, fire retarding synergist 10%, alkali-free glass fiber 15%, oxidation inhibitor 0.4%, lubricant 0.5%.
Wherein, the mixture of described nylon resin to be nylon66 fiber and nylon 6 with mass ratio be 35:15; Described main flame retardant is brominated polystyrene, and in described bromide fire retardant, the content of bromine is 72%; Described fire retarding synergist is mass percent is the PA6 carrier antimony trioxide parent particle of 6% and the mixture of the silicon-dioxide of 4% and the mixture of aluminum oxide, wherein, the mass ratio of silicon-dioxide and aluminum oxide is 5:2, and in described PA6 carrier antimony trioxide parent particle, the content of antimonous oxide is 85%; Described lubricant is montanin wax; Described alkali-free glass fiber to be single beam diameter the be glass of 14 μm; The mixture of described oxidation inhibitor to be primary antioxidant and auxiliary antioxidant with mass ratio be 2:1, primary antioxidant is Hinered phenols antioxidant, and auxiliary antioxidant is phosphite ester kind antioxidant.
embodiment 9.
The low precipitation flame-retardant polyamide composition of one of the present embodiment, comprises the raw material of following mass percent:
Nylon resin 44.8%, main flame retardant 30%, fire retarding synergist 14%, alkali-free glass fiber 10%, oxidation inhibitor 0.4%, lubricant 0.8%.
Wherein, described nylon resin is nylon66 fiber; Described main flame retardant is brominated epoxy resin, and in described bromide fire retardant, the content of bromine is 72%; The mixture of described fire retarding synergist to be mass percent the be EVA carrier antimony trioxide parent particle of 6% and the anhydrous zinc borate of 8%, in described EVA carrier antimony trioxide parent particle, the content of antimonous oxide is 85%; Described lubricant is polyethylene wax; Described alkali-free glass fiber to be single beam diameter the be glass of 8 μm; The mixture of described oxidation inhibitor to be primary antioxidant and auxiliary antioxidant with mass ratio be 2:1, primary antioxidant is hexanediamine kind antioxidant, and auxiliary antioxidant is phosphite ester kind antioxidant.
embodiment 10.
The low precipitation flame-retardant polyamide composition of one of the present embodiment, comprises the raw material of following mass percent:
Nylon resin 53%, main flame retardant 27%, fire retarding synergist 8%, alkali-free glass fiber 11%, oxidation inhibitor 0.3%, lubricant 0.7%.
Wherein, the mixture of described nylon resin to be nylon66 fiber and nylon 6 with mass ratio be 45:15; Described main flame retardant is brominated Polystyrene, and in described bromide fire retardant, the content of bromine is 73%; Described fire retarding synergist is EVA carrier antimony trioxide parent particle, and in described EVA carrier antimony trioxide parent particle, the content of antimonous oxide is 85%; Described lubricant is polyethylene wax; Described alkali-free glass fiber to be single beam diameter the be glass of 9 μm; The mixture of described oxidation inhibitor to be primary antioxidant and auxiliary antioxidant with mass ratio be 1:1, primary antioxidant is Hinered phenols antioxidant, and auxiliary antioxidant is monothioester kind antioxidant.
embodiment 11.
The low precipitation flame-retardant polyamide composition of one of the present embodiment, comprises the raw material of following mass percent:
Nylon resin 30%, main flame retardant 28%, fire retarding synergist 15%, alkali-free glass fiber 26%, oxidation inhibitor 0.5%, lubricant 0.5%.
Wherein, described nylon resin is nylon66 fiber; Described main flame retardant is brominated polystyrene, and in described bromide fire retardant, the content of bromine is 74%; Described fire retarding synergist is the anhydrous zinc borate of the silicon-dioxide of 7% and the mixture of metal oxide and 8%, and silicon-dioxide and metal oxide take mass ratio as the mixture of 15:10, and described metal oxide is magnesium oxide or aluminum oxide; Described lubricant is modified PE wax AC-540A; Described alkali-free glass fiber to be single beam diameter the be glass of 10 μm; The mixture of described oxidation inhibitor to be primary antioxidant and auxiliary antioxidant with mass ratio be 3:1, primary antioxidant is Hinered phenols antioxidant, and auxiliary antioxidant is monothioester kind antioxidant.
embodiment 12.
The low precipitation flame-retardant polyamide composition of one of the present embodiment, comprises the raw material of following mass percent:
Nylon resin 50%, main flame retardant 20%, fire retarding synergist 8.5%, alkali-free glass fiber 21%, oxidation inhibitor 0.2%, lubricant 0.3%.
Wherein, described nylon resin is nylon 6; Described main flame retardant is brominated epoxy resin, and in described bromide fire retardant, the content of bromine is 75%; Described fire retarding synergist is the anhydrous zinc borate of 6.5% and the PA6 carrier antimony trioxide parent particle of 2%; Described lubricant is OP wax; Described alkali-free glass fiber to be single beam diameter the be glass of 12 μm; The mixture of described oxidation inhibitor to be primary antioxidant and auxiliary antioxidant with mass ratio be 3:1, primary antioxidant is hexanediamine kind antioxidant, and auxiliary antioxidant is phosphite ester kind antioxidant.
The composition of raw materials of the embodiment 1-12 of the flame-retardant polyamide composition of a kind of low precipitation 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 |
| Antimonous oxide powder | 7 | |||||
| PA6 carrier antimony trioxide parent particle | 7 | 4 | 4 | |||
| EVA carrier antimony trioxide parent particle | 7 | |||||
| PE carrier antimony trioxide parent particle | 7 | |||||
| Silicon-dioxide and magnesian mixture | 3.5 | ? | ||||
| The mixture of silicon-dioxide and aluminum oxide | ? | ? | ? | ? | ? | 4 |
| Anhydrous zinc borate | ||||||
| Oxidation inhibitor | 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 |
| Antimonous oxide powder | ||||||
| PA6 carrier antimony trioxide parent particle | 3 | 6 | 2 | |||
| EVA carrier antimony trioxide parent particle | 6 | 8 | ||||
| PE carrier antimony trioxide parent particle | ||||||
| Silicon-dioxide and magnesian mixture | 3 | 7 | ||||
| The mixture of silicon-dioxide and aluminum oxide | ? | 4 | ? | ? | ? | ? |
| Anhydrous zinc borate | 8 | 8 | 6.5 | |||
| Oxidation inhibitor | 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 |
In the embodiment 1-12 of the preparation method of the flame-retardant polyamide composition of a kind of low precipitation of the present invention, the temperature of twin screw extruder is: temperature is 200-300 DEG C, be preferably 220-280 DEG C, the rotating speed of twin screw extruder is 200-400 rev/min, and preferably, rotating speed is: 240rpm.
The flame-retardant polyamide composition material index parameter of the precipitation that embodiments of the invention 1-12 obtains is as follows:
| ? | Tensile strength/psi | Flexural strength/Psi | Shock strength/in-ft/lb | Fire-retardant/0.8mm | CTI/V | Loss of weight/% is separated out in test piece |
| 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 |
The above embodiment, just better embodiment of the present invention, be not limit the scope of the present invention, therefore all equivalences done according to structure, feature and the principle described in the present patent application the scope of the claims change or modify, and all should comprise in patent claim of the present invention.
Claims (10)
1. a low precipitation flame-retardant polyamide composition, is characterized in that: the raw material comprising following mass percent:
Nylon resin 20-70%
Main flame retardant 10-30%
Fire retarding synergist 0-15%
Alkali-free glass fiber 10-40%
Oxidation inhibitor 0-1%
Lubricant 0-2%
Wherein, described nylon resin is one or both the mixture in nylon66 fiber, nylon 6; Described main flame retardant is bromide fire retardant; Described fire retarding synergist is one or more mixture of the mixture of antimonous oxide powder, antimony trioxide parent particle, zinc borate, silicon-dioxide and metal oxide; Described lubricant is high molecular polymolecularity lubricant, comprises the one in polyethylene wax, modified PE wax, OP wax and montanin wax.
2. the low precipitation flame-retardant polyamide composition of one according to claim 1, is characterized in that: the raw material comprising following mass percent:
Nylon resin 30-50%
Main flame retardant 10-30%
Fire retarding synergist 5-15%
Alkali-free glass fiber 10-40%
Oxidation inhibitor 0.1-0.5%
Lubricant 0.1-1%.
3. the low precipitation flame-retardant polyamide composition of one according to claim 1, is characterized in that: the mixture of described nylon resin to be nylon66 fiber and nylon 6 with mass ratio be 0-60:0-20.
4. the flame-retardant polyamide composition of a kind of low precipitation according to claim 1, it is characterized in that: described bromide fire retardant is the one in brominated Polystyrene, brominated polystyrene, brominated epoxy resin, in described bromide fire retardant, the content of bromine is 66-75%.
5. the flame-retardant polyamide composition of a kind of low precipitation according to claim 1, it is characterized in that: described fire retarding synergist is antimony trioxide parent particle, the carrier of described antimony trioxide parent particle is the one in polyethylene, nylon 6, EVA, and in polyethylene, nylon 6, EVA carrier antimony trioxide parent particle, the content of antimonous oxide is 85%.
6. the flame-retardant polyamide composition of a kind of low precipitation according to claim 1, is characterized in that: the mixture of described fire retarding synergist to be silicon-dioxide and metal oxide with mass ratio be 0-15:0-10, described metal oxide is magnesium oxide or aluminum oxide.
7. the flame-retardant polyamide composition of a kind of low precipitation according to claim 1, it is characterized in that: described fire retarding synergist is antimony trioxide parent particle: the mass ratio of the mixture of silicon-dioxide and metal oxide is the mixture of 0-15:0-10, or described fire retarding synergist is antimony trioxide parent particle: the mass ratio of zinc borate is the mixture of 0-15:0-10, or described fire retarding synergist is antimony trioxide parent particle.
8. the flame-retardant polyamide composition of a kind of low precipitation according to claim 1, is characterized in that: described alkali-free glass fiber to be single beam diameter the be glass of 7-14 μm.
9. the flame-retardant polyamide composition of a kind of low precipitation according to claim 1, it is characterized in that: the mixture of described oxidation inhibitor to be primary antioxidant and auxiliary antioxidant with mass ratio be 4:1-1:4, primary antioxidant is Hinered phenols antioxidant or hexanediamine kind antioxidant, and auxiliary antioxidant is phosphite ester kind antioxidant and monothioester kind antioxidant.
10. as the preparation method of the flame-retardant polyamide composition of a kind of low precipitation in claim 1-9 as described in any one, it is characterized in that: comprise following procedure of processing:
Step (1) takes each starting material by weight percentage;
The alkali-free glass fiber taken in step (1) takes out by step (2), is then mixed in mixing tank by all the other raw materials;
The main spout of the raw material mixed in step (2) from twin screw adds by step (3), then the glass fiber opening of alkali-free glass fiber from twin screw is added, the rotating speed of twin screw extruder is 200-400 rev/min, and temperature is 200-300 DEG C, the flame-retardant polyamide composition of obtained low precipitation.
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