CN103013105B - Conducting halogen-free flame-retardant PA6 (polyamide 6) composite material and preparation method thereof - Google Patents

Conducting halogen-free flame-retardant PA6 (polyamide 6) composite material and preparation method thereof Download PDF

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Publication number
CN103013105B
CN103013105B CN201210585604.8A CN201210585604A CN103013105B CN 103013105 B CN103013105 B CN 103013105B CN 201210585604 A CN201210585604 A CN 201210585604A CN 103013105 B CN103013105 B CN 103013105B
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halogen
graphene
conduction
matrix
free flameproof
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CN201210585604.8A
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CN103013105A (en
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陶国良
张发新
王维
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常州大学
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    • 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
    • B29C48/03Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/04Particle-shaped
    • 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
    • B29C48/36Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders

Abstract

The invention provides a conducting halogen-free flame-retardant PA6 (polyamide 6) composite material and a preparation method thereof, and overcomes the defects of low flame-retardant rate, high consumption of conducting filler, and poor dispersity in the PA6 material in the prior art. The composite material comprises the following components in parts by weight: 100 parts of PA6, 15-20 parts of flame retardant, 15-20 parts of conducting filler, 10-15 parts of toughener, 0.1-0.5 part of antioxidant and 0.3-0.5 part of anti-dripping agent. The preparation method comprises the following steps: proportionally and evenly mixing dried raw materials in a high-speed mixer; and adding the evenly mixed material into a hopper of the double screw extruder, carrying out high-temperature melt blending and extruding, cooling, airing and granulating. By adopting the compound flame-retardant system, the invention solves the problem of low flame-retardant efficiency in the single flame retardant, enhances the flame-retardant efficiency and lowers the cost; and by adopting the surface-modified conducting filler graphene, the invention overcomes the defects of high consumption of traditional conducting filler, poor dispersity and the like.

Description

Halogen-free flameproof PA6 matrix material of a kind of conduction and preparation method thereof
Technical field
The present invention relates to a kind of PA6 matrix material and preparation method thereof, halogen-free flameproof PA6 matrix material especially relating to a kind of conduction and preparation method thereof.
Background technology
PA6(polyamide 6 or nylon 6) be a kind of important engineering plastics, because it has good mechanical property, wear resistance, self lubricity, oil-proofness, many premium propertiess such as shock-resistant, be widely used in the fields such as automobile, machinery, electronics, instrument.
Along with the development of world economy and the department of use are to the requirement of material more Gao Gengxin, and the ratio of performance to price of PA6 and Other Engineering plastics is competed, the development priority of Polyamide Engineering Plastic is mainly the exploitation to existing kind, and the different purposes particularly for PA6 are carried out alloying, high performance, become more meticulous and customizations modification.The method of modification has filling-modified, blending and modifying, modification by copolymerization, nano-compound modified etc., and wherein blending and modifying is one of the most frequently used method.
But PA6 is as organic materials, and its combustibility is its obvious shortcoming, the combustionvelocity of PA6 in flame is fast, and thermal discharge is high, and what particularly produce during burning has flame molten drop in a large number, adds the danger of fire-propagation; At present also be confined to halogen system about PA6 fire-retardant fire-retardant, but halogenated flame retardant can generate a large amount of cigarettes when being heated or burn and corrosive gases causes personnel death; And some bromide fire retardants are as many bromobiphenyl ether, generate many Xiu Dai dioxin and many bromo furans at pyrolytic decomposition, above-mentioned substance has carcinogenesis.In this context, on February 13rd, 2003, European Union promulgated " RoHS instruction " and " WEEE instruction ", the toxicity of halogen flame and the arguement of environmental problem was pushed to a new high.Existing bittern-free flame-proof material flame retarding efficiency is not high, therefore develops the halogen-free flameproof PA6 of high comprehensive performance, has important and profound significance for expansion PA6 range of application and its added value of increase.
PA6 volume specific resistance is 10 14Ω about cm is a kind of insulating material, the functional composite material relevant to conductive characteristic can be prepared by the powder adding electroconductibility in the macromolecular material matrix of insulation, this respect has many correlation reports both at home and abroad, as added the matrix material of the preparation electroconductibility such as graphitized carbon black (CB), graphite or carbon nanotube in polyolefine, PA and polystyrene, but its conductive filler material consumption is large, bad dispersibility is very large to PA6 performance impact.
Summary of the invention
The technical problem to be solved in the present invention is: overcome the fire-retardant rate of halogen-free flameproof PA6 material of conducting electricity in prior art not high, and conductive filler material is large by doses, the deficiency of bad dispersibility, halogen-free flameproof PA6 matrix material providing a kind of conduction and preparation method thereof.
For solving the problems of the technologies described above the technical solution used in the present invention be: halogen-free flameproof PA6 matrix material of a kind of conduction and preparation method thereof, it is composed of the following components by weight:
As preferably, above-mentioned PA6 resin properties viscosity is 2.4 ~ 3.6dl/g.
As preferably, above-mentioned fire retardant is melamine cyanurate (MCA) with the compound of Resorcinol two [two (2,6-xylyl) phosphoric acid ester] (RXP) or be the compound of diethylphosphate aluminium (AlPi) and melamine phosphate (MPP); Wherein by mass, the composite ratio of MCA and RXP is the composite ratio of 2:1 ~ 3:1, AlPi and MPP is 2:1 ~ 2.5:1.
As preferably, described conductive filler material is the Graphene through tensio-active agent process, can improve the dispersiveness of Graphene in PA6, its treatment process is: the silane coupling agent KH570 taking 3% ~ 6% of Graphene quality, is dissolved in distilled water water, regulator solution PH to 4 ~ 5, with the aqueous solution of Graphene, under 80 ~ 90 DEG C of reaction conditionss, until Graphene forms obvious layering in the solution, suction filtration, dries the Graphene obtaining modification; The concentration of aqueous solution of wherein said Graphene is 0.4 ~ 0.6g/ml.
As preferably, described toughner is polyolefins grafting unsaturated acid or acid anhydrides, and its melting index is 2 ~ 27g/10min, and percentage of grafting is 0.8 ~ 1.2%.
As preferably, described toughner is POE graft glycidyl methacrylate (POE-g-GMA), HDPE grafted maleic anhydride (HDPE-g-MAH), POE grafted maleic anhydride (POE-g-GMA) etc.
As preferably, described anti-dripping agent is tetrafluoroethylene powder (PTFE).
As preferably, described oxidation inhibitor is mass ratio is four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters (antioxidant 1010) of 1:1 ~ 2:1 and the compound system of N, N '-two (2-naphthyl) Ursol D (DNP).
The preparation method of the halogen-free flameproof PA6 matrix material of above-mentioned conduction, step is as follows:
(1) by PA6 dry 5 ~ 6h at 110 ~ 120 DEG C of temperature; Toughner is dry 4 ~ 5h at 50 ~ 60 DEG C of temperature; By other components dry 4 ~ 5h at 80 DEG C ~ 100 DEG C temperature;
(2) dried PA6, conductive filler material, fire retardant, toughner, anti-dripping agent and oxidation inhibitor are mixed in proportion in high-speed mixer, stir 10 ~ 15min;
(3) material after mixing in step (2) is joined in the hopper of twin screw extruder, through high-temperature fusion blending extrusion, cooling, air-dry, granulation, the i.e. halogen-free flameproof PA6 matrix material of obtained conduction, the processing temperature of wherein said twin screw extruder is 190 ~ 235 DEG C, feeding machine rotating speed is 13 ~ 16Hz, and engine speed is 9 ~ 12Hz.
The halogen-free flameproof PA6 composite material process planning of the obtained conduction described in step (3) is that on injection moulding machine, be injection molded into the stretching of standard and impact batten, injection temperature is 235 ~ 245 DEG C by gained pellet again through 110 ~ 120 DEG C of forced air drying 4 ~ 5h; Its particle is pressed into sheet material by compression molding instrument, hot pressing temperature 230 ~ 240 DEG C, compacting gauge pressure 10MPa, hot pressing time 2 ~ 3min, cold pressing time 2min
The invention has the beneficial effects as follows:
(1) traditional halogenated flame retardant can generate a large amount of cigarettes when being heated or burn and corrosive gases causes personnel death, pollute the environment simultaneously, the present invention uses halogen-free flame retardants, greatly reduces material injury to human body when burning, and pollutes littlely to be conducive to environmental protection simultaneously.
(2) single fire retardant wants to reach desirable flame retardant effect, and the amount of required interpolation is comparatively large, and adopts two kinds and above kind of based flame retardant compound system not only can reach desirable flame retardant effect can also to reduce cost simultaneously.
(3) general filler is poor with the consistency of matrix resin, disperses bad, and Graphene through surface modification, can well improve the consistency of itself and resin, thus reduction filler is added the impact on material mechanical performance by the present invention.
Accompanying drawing explanation
Fig. 1 (a) is for using the PA6 matrix material section electron-microscope scanning figure of unmodified Graphene; The section electron-microscope scanning figure of the PA6 matrix material that Fig. 1 (b) is prepared for embodiment 1.
Embodiment:
Embodiment 1
First by PA6 forced air drying 6h at 110 DEG C, toughner is forced air drying 5h at 50 DEG C, and other components are forced air drying 4h at 100 DEG C, and wherein said PA6 resin properties viscosity is 3.6dl/g, the melting index of described toughner is 27g/10min, and percentage of grafting is 1.2%.。Once adding high-speed mixer according to PA6, fire retardant, toughner, conductive filler material, anti-dripping agent and oxidation inhibitor that the quality weighing provided in table 2 is dried in advance according to portion rate is pre-mixed evenly, stir 15min, obtain the material after mixing, then the processing temperature 190 ~ 235 DEG C of the forcing machine of twin screw is controlled, screw speed 10 ~ 15HZ, join in the hopper of twin screw extruder by the material after mixing, the processing temperature namely obtaining product concrete through high-temperature fusion blending extrusion, cooling, air-dry, granulation is as shown in table 1.Gained particle is again through 120 DEG C of forced air drying 4h, and injection moulding machine is injection molded into the stretching of standard and impacts batten, injection temperature is 235 ~ 245 DEG C; Its particle is pressed into sheet material by compression molding instrument, hot pressing temperature 230 DEG C, compacting gauge pressure 10MPa, hot pressing time 2min, cold pressing time 2min.
Wherein graphene surface modification method is: the silane coupling agent KH570 taking 6% of Graphene quality, be dissolved in distilled water water, adjustment is dissolved in PH to 5, mix with the aqueous solution (0.6g/ml) of Graphene, under 90 DEG C of reaction conditionss, until Graphene forms obvious layering in the solution, suction filtration, dries the Graphene obtaining modification.Fig. 1 (a) is by the present embodiment preparation method but its conductive filler material changes unmodified Graphene into, other component concentrations are constant, the section electron-microscope scanning figure of obtained PA6 matrix material, the section electron-microscope scanning figure of the conduction halogen-free flameproof PA6 matrix material that Fig. 1 (b) is prepared for the present embodiment; As can be seen from the figure the Graphene of surface modified mistake is compared unmodified Graphene and is disperseed in PA6 resin better, and also improves with the consistency of PA6.
Embodiment 2
First by PA6 forced air drying 5h at 120 DEG C, toughner is forced air drying 4h at 60 DEG C, and other components are forced air drying 5h at 80 DEG C, and described PA6 resin properties viscosity is 2.4dl/g, the melting index of described toughner is 24g/10min, and percentage of grafting is 0.8%.Once adding high-speed mixer according to PA6, fire retardant, toughner, conductive filler material, anti-dripping agent and oxidation inhibitor that the quality weighing provided in table 2 is dried in advance according to portion rate is pre-mixed evenly, stir 10min, obtain the material after mixing, then the processing temperature 190 ~ 235 DEG C of the forcing machine of twin screw is controlled, screw speed 10 ~ 15HZ, join in the hopper of twin screw extruder by the material after mixing, the processing temperature namely obtaining product concrete through high-temperature fusion blending extrusion, cooling, air-dry, granulation is as shown in table 1.Gained particle is again through 110 DEG C of forced air drying 4h, and injection moulding machine is injection molded into the stretching of standard and impacts batten, injection temperature is 235 ~ 245 DEG C; Its particle is pressed into sheet material by compression molding instrument, hot pressing temperature 240 DEG C, compacting gauge pressure 10MPa, hot pressing time 2min, cold pressing time 2min.
Wherein graphene surface modification method is: the silane coupling agent KH570 taking 3% of Graphene quality, be dissolved in distilled water water, adjustment is dissolved in PH to 4, mix with the aqueous solution (0.4g/ml) of Graphene, under 80 DEG C of reaction conditionss, until Graphene forms obvious layering in the solution, suction filtration, dries the Graphene obtaining modification.
Embodiment 3
First by PA6 forced air drying 6h at 115 DEG C, toughner is forced air drying 5h at 55 DEG C, and other components are forced air drying 4h at 100 DEG C, and described PA6 resin properties viscosity is 3.0dl/g, and the melting index of described toughner is 25g/10min, and percentage of grafting is 1.0%.Once adding high-speed mixer according to PA6, fire retardant, toughner, conductive filler material, anti-dripping agent and oxidation inhibitor that the quality weighing provided in table 2 is dried in advance according to portion rate is pre-mixed evenly, stir 15min, obtain the material after mixing, then the processing temperature 190 ~ 235 DEG C of the forcing machine of twin screw is controlled, screw speed 10 ~ 15HZ, join in the hopper of twin screw extruder by the material after mixing, the processing temperature namely obtaining product concrete through high-temperature fusion blending extrusion, cooling, air-dry, granulation is as shown in table 1.Gained particle is again through 120 DEG C of forced air drying 4h, and injection moulding machine is injection molded into the stretching of standard and impacts batten, injection temperature is 235 ~ 245 DEG C; Its particle is pressed into sheet material by compression molding instrument, hot pressing temperature 230 DEG C, compacting gauge pressure 10MPa, hot pressing time 3min, cold pressing time 2min.
Wherein graphene surface modification method is: the silane coupling agent KH570 taking 5% of Graphene quality, be dissolved in distilled water water, adjustment is dissolved in PH to 5, mix with the aqueous solution (0.5g/ml) of Graphene, under 85 DEG C of reaction conditionss, until Graphene forms obvious layering in the solution, suction filtration, dries the Graphene obtaining modification.
Embodiment 4
First by PA6 forced air drying 6h at 110 DEG C, toughner is forced air drying 5h at 50 DEG C, and other components are forced air drying 4h at 100 DEG C, and described PA6 resin properties viscosity is 2.8dl/g, and the melting index of described toughner is 27g/10min, and percentage of grafting is 0.8%.Once adding high-speed mixer according to PA6, fire retardant, toughner, conductive filler material, anti-dripping agent and oxidation inhibitor that the quality weighing provided in table 2 is dried in advance according to portion rate is pre-mixed evenly, stir 15min, obtain the material after mixing, then the processing temperature 220 ~ 240 DEG C of the forcing machine of twin screw is controlled, screw speed 10 ~ 15HZ, join in the hopper of twin screw extruder by the material after mixing, the processing temperature namely obtaining product concrete through high-temperature fusion blending extrusion, cooling, air-dry, granulation is as shown in table 1.Gained particle is again through 120 DEG C of forced air drying 4h, and injection moulding machine is injection molded into the stretching of standard and impacts batten, injection temperature is 235 ~ 245 DEG C; Above-mentioned particle is pressed into sheet material by compression molding instrument, hot pressing temperature 240 DEG C, compacting gauge pressure 10MPa, hot pressing time 3min, cold pressing time 2min.
Wherein graphene surface modification method is: the silane coupling agent KH570 taking 6% of Graphene quality, be dissolved in distilled water water, adjustment is dissolved in PH to 5, mix with the aqueous solution (0.6g/ml) of Graphene, under 90 DEG C of reaction conditionss, until Graphene forms obvious layering in the solution, suction filtration, dries the Graphene obtaining modification.
Embodiment 5
First by PA6 forced air drying 6h at 120 DEG C, toughner is forced air drying 5h at 60 DEG C, and other components are forced air drying 4h at 100 DEG C, and described PA6 resin properties viscosity is 3.2dl/g, and the melting index of described toughner is 25g/10min, and percentage of grafting is 1.2%.Once adding high-speed mixer according to PA6, fire retardant, toughner, conductive filler material, anti-dripping agent and oxidation inhibitor that the quality weighing provided in table 2 is dried in advance according to portion rate is pre-mixed evenly, stir 10min, obtain the material after mixing, then the processing temperature 190 ~ 235 DEG C of the forcing machine of twin screw is controlled, screw speed 9 ~ 16HZ, join in the hopper of twin screw extruder by the material after mixing, the processing temperature namely obtaining product concrete through high-temperature fusion blending extrusion, cooling, air-dry, granulation is as shown in table 1.Gained particle is again through 120 DEG C of forced air drying 5h, and injection moulding machine is injection molded into the stretching of standard and impacts batten, injection temperature is 235 ~ 245 DEG C; Above-mentioned particle is pressed into sheet material by compression molding instrument, hot pressing temperature 235 DEG C, compacting gauge pressure 10MPa, hot pressing time 3min, cold pressing time 2min.
Wherein graphene surface modification method is: the silane coupling agent KH570 taking 6% of Graphene quality, be dissolved in distilled water water, adjustment is dissolved in PH to 5, mix with the aqueous solution (0.6g/ml) of Graphene, under 90 DEG C of reaction conditionss, until Graphene forms obvious layering in the solution, suction filtration, dries the Graphene obtaining modification.
The test result of the properties of sample that table 3 prepares for specific embodiment 1 ~ 5.
Table 1 forcing machine machined parameters
Table 2 embodiment 1 ~ 5 material choice and consumption (counting by weight)
Table 3 test result
Mark: vertical combustion is mainly used in not combustionproperty plastics or film being measured under regulation burning things which may cause a fire disaster directly burns to plastics, and in order to judge the fire resistance rating of refractory materials, flame retardant rating is increased progressively to V-0 step by step by V-2, V-1.The typical thickness of sample has 0.8mm, 1.6mm, 3.2mm, and the thickness of sample is thinner, requires higher to the flame retardant properties of sample.
By the preparation method of embodiment 2, raw material and consumption are the component that provides of table 4 and parts by weight, the product obtained carries out testing vertical flammability (testing standard is with table 3) respectively, its result is as " vertical combustion " in table 4 hurdle, visible when consumption is identical, use the matrix material of compound system fire retardant than the good flame retardation effect using single fire-retardant composite material.
The single fire retardant of table 4 and compound flame retardant are on the impact (counting by weight) of the fire-retardant performance of matrix material

Claims (8)

1. a halogen-free flameproof PA6 matrix material for conduction, is characterized in that: it is composed of the following components by weight:
Described fire retardant is melamine cyanurate (MCA) with the compound of Resorcinol two [two (2,6-xylyl) phosphoric acid ester] (RXP) or be the compound of diethylphosphate aluminium (AlPi) and melamine phosphate (MPP); Wherein by mass, the composite ratio of MCA and RXP is the composite ratio of 2:1 ~ 3:1, AlPi and MPP is 2:1 ~ 2.5:1;
Described conductive filler material is silane coupler modified Graphene;
Four [β-(3 of described oxidation inhibitor to be mass ratio be 1:1 ~ 2:1,5-di-tert-butyl-hydroxy phenyl) propionic acid] compound system of pentaerythritol ester (antioxidant 1010) and N, N '-two (2-naphthyl) Ursol D (DNP).
2. the halogen-free flameproof PA6 matrix material of conduction according to claim 1, is characterized in that: described PA6 resin properties viscosity is 2.4 ~ 3.6dl/g.
3. the halogen-free flameproof PA6 matrix material of conduction according to claim 1, it is characterized in that: described conductive filler material is the Graphene through tensio-active agent process, its treatment process is: the silane coupling agent KH570 taking 3% ~ 6% of Graphene quality, be dissolved in distilled water water, regulator solution PH to 4 ~ 5, with the aqueous solution of Graphene, under 80 ~ 90 DEG C of reaction conditionss, until Graphene forms obvious layering in the solution, suction filtration, dries the Graphene obtaining modification; The concentration of aqueous solution of wherein said Graphene is 0.4 ~ 0.6g/ml.
4. the halogen-free flameproof PA6 matrix material of conduction according to claim 1, it is characterized in that: described toughner is polyolefins grafting unsaturated acid or acid anhydrides, its melting index is 2 ~ 27g/10min, and percentage of grafting is 0.8 ~ 1.2%.
5. the halogen-free flameproof PA6 matrix material of conduction according to claim 1, it is characterized in that: described toughner is POE graft glycidyl methacrylate (POE-g-GMA), HDPE grafted maleic anhydride (HDPE-g-MAH) or POE grafted maleic anhydride (POE-g-GMA).
6. the halogen-free flameproof PA6 matrix material of conduction according to claim 1, is characterized in that: described anti-dripping agent is tetrafluoroethylene powder (PTFE).
7. the preparation method of the halogen-free flameproof PA6 matrix material of the conduction according to any one of claim 1 ~ 6, is characterized in that: step is as follows:
(1) by PA6 dry 5 ~ 6h at 110 ~ 120 DEG C of temperature; Toughner is dry 4 ~ 5h at 50 ~ 60 DEG C of temperature; By other components dry 4 ~ 5h at 80 DEG C ~ 100 DEG C temperature;
(2) dried PA6, conductive filler material, fire retardant, toughner, anti-dripping agent and oxidation inhibitor are mixed in proportion in high-speed mixer, stir 10 ~ 15min;
(3) material after mixing in step (2) is joined in the hopper of twin screw extruder, through high-temperature fusion blending extrusion, cooling, air-dry, granulation, the i.e. halogen-free flameproof PA6 matrix material of obtained conduction, the processing temperature of wherein said twin screw extruder is 190 ~ 235 DEG C, feeding machine rotating speed is 13 ~ 16Hz, and engine speed is 9 ~ 12Hz.
8. the preparation method of the halogen-free flameproof PA6 matrix material of conduction according to claim 7, it is characterized in that: the halogen-free flameproof PA6 composite material process planning of the obtained conduction described in step (3) is again through 110 ~ 120 DEG C of forced air drying 4 ~ 5h by gained pellet, injection moulding machine is injection molded into the stretching of standard and impacts batten, injection temperature is 235 ~ 245 DEG C; Its particle is pressed into sheet material by compression molding instrument, hot pressing temperature 230 ~ 240 DEG C, compacting gauge pressure 10MPa, hot pressing time 2 ~ 3min, cold pressing time 2min.
CN201210585604.8A 2012-12-28 2012-12-28 Conducting halogen-free flame-retardant PA6 (polyamide 6) composite material and preparation method thereof CN103013105B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102206413A (en) * 2011-05-25 2011-10-05 佛山市顺德区高怡新塑料有限公司 Plastic-based composite material with electric conduction and electromagnetic shielding functions and preparation method thereof
CN102234422A (en) * 2011-05-06 2011-11-09 深圳市兴迪塑胶有限公司 Flame-retardant nylon resin composition and preparation method thereof
CN102516749A (en) * 2011-12-07 2012-06-27 深圳市科聚新材料有限公司 Polyamide halogen-free flame retardant master batch and preparation method thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100448115B1 (en) * 2000-11-30 2004-09-10 현대자동차주식회사 A polyamide resin composition
JP5394380B2 (en) * 2008-07-07 2014-01-22 協和化学工業株式会社 Flame retardant resin composition

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102234422A (en) * 2011-05-06 2011-11-09 深圳市兴迪塑胶有限公司 Flame-retardant nylon resin composition and preparation method thereof
CN102206413A (en) * 2011-05-25 2011-10-05 佛山市顺德区高怡新塑料有限公司 Plastic-based composite material with electric conduction and electromagnetic shielding functions and preparation method thereof
CN102516749A (en) * 2011-12-07 2012-06-27 深圳市科聚新材料有限公司 Polyamide halogen-free flame retardant master batch and preparation method thereof

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