CN103087518A - Glass-fiber-reinforced halogen-free flame-retardant nylon 46 composite material and preparation method thereof - Google Patents

Glass-fiber-reinforced halogen-free flame-retardant nylon 46 composite material and preparation method thereof Download PDF

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CN103087518A
CN103087518A CN2013100426828A CN201310042682A CN103087518A CN 103087518 A CN103087518 A CN 103087518A CN 2013100426828 A CN2013100426828 A CN 2013100426828A CN 201310042682 A CN201310042682 A CN 201310042682A CN 103087518 A CN103087518 A CN 103087518A
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glass fibre
retardant
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reingorced
flame retardant
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CN103087518B (en
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刘典典
冉进成
林晓丹
曾幸荣
赖学军
官炳桂
官炳荣
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HUIZHOU HUAJU PLASTICS TECHNOLOGY Co Ltd
South China University of Technology SCUT
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HUIZHOU HUAJU PLASTICS TECHNOLOGY Co Ltd
South China University of Technology SCUT
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00Making granules
    • B29B9/12Making granules characterised by structure or composition
    • B29B9/14Making granules characterised by structure or composition fibre-reinforced
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00Mixing; Kneading
    • B29B7/30Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/58Component parts, details or accessories; Auxiliary operations
    • B29B7/72Measuring, controlling or regulating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00Mixing; Kneading
    • B29B7/74Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
    • B29B7/7461Combinations of dissimilar mixers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00Mixing; Kneading
    • B29B7/80Component parts, details or accessories; Auxiliary operations
    • B29B7/88Adding charges, i.e. additives
    • B29B7/90Fillers or reinforcements, e.g. fibres
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00Making granules
    • B29B9/12Making granules characterised by structure or composition
    • 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/02Fibres or whiskers
    • C08K7/04Fibres or whiskers inorganic
    • C08K7/14Glass
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    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/08Ingredients agglomerated by treatment with a binding agent
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12Polyphenylene oxides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06Polyamides derived from polyamines and polycarboxylic acids
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00Fireproofing materials
    • C09K21/14Macromolecular materials
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00Mixing; Kneading
    • B29B7/30Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/46Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00Making granules
    • B29B9/02Making granules by dividing preformed material
    • B29B9/06Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K2003/026Phosphorus

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Abstract

The invention relates to a glass-fiber-reinforced halogen-free flame-retardant nylon 46 composite material and a preparation method thereof. The glass-fiber-reinforced halogen-free flame-retardant nylon 46 composite material is composed of, by weight: 38.9-63.9% of PA46 resin, 6-14% of a main flame retardant, 0.01-6% of an auxiliary flame retardant, 15-45% of glass fiber, and 3.1-5.1% of other auxiliary agents. The main flame retardant is microencapsulated red phosphorus masterbatch, and the auxiliary flame retardant is polyphenylene ether. The nylon 46 composite material has high flame retardant grade, excellent high-temperature resistance, and excellent mechanical properties. The material can be used in fields for preparing electrical and electronic product parts and automotive plastic parts with requirements on high-temperature resistance.

Description

A kind of glass fibre reingorced no-halogen flame-retardant nylon dragon 46 matrix materials and preparation method
Technical field
The present invention relates to polymeric material field, be specifically related to a kind of glass fibre reingorced no-halogen flame-retardant nylon dragon 46 matrix materials and preparation method thereof.
Background technology
Development along with society, the industries such as that increasing nylon engineering plastic is applied to is electric, automobile making, aerospace, the environment for use that nylon engineering plastic faces also can be more and more harsher, such as high temperature, high-voltage, high humidity, high loading etc., performance requriements to nylon engineering plastic is also higher, usually need under the condition that keeps its mechanical property, improve flame retardant properties or electrical property, therefore, the flame-retardant modified research of nylon engineering plastic is more and more received people's concern.In the face of more and more stricter safety and environmental requirement, and the industry such as electric, automobile making is to an urgent demand of Halogen, low toxicity, low-smoke and flame retardant material, after especially implementing RoHS Directive, countries in the world to bittern-free flame-proof material research pay much attention to.
Halogen-free flame retardants is main with phosphorus nitrogen at present.Wherein expansion type flame-retarding is the focus of studying at present, and it has gathered carbon source, acid source, three integral parts of source of the gas, and is obvious to the flame retardant effect of polymkeric substance.Be difficult to extensive popularization but, range of application large due to poor water resistance, the addition of its fire retardant be narrow.The phosphonium flame retardant that is applicable to nylon has red phosphorus, hypophosphite and response type phosphonium flame retardant etc.Available phosphorus content in red phosphorus is high, phosphorus compound than other when burning produces more Tripyrophosphoric acid, these phosphoric acid both can cover the nylon surface, can accelerate its dehydration carbonization at the nylon surface catalysis again, reduced the growing amount of combustiblematerials and the mass loss speed of superpolymer material.And the phosphoric acid that generates residues in the charcoal layer and the liquid film charcoal layer structure that form can separate volatile fuel, outside oxygen and inner superpolymer matrix.
Patent CN 101503568A discloses the polyamide thermoplastic compositions that a kind of red phosphorus flame-retardant strengthens.Its coating system is introduced thermoplastic polymer, played good interface compatible and " lubricate " act on, avoided encapsulated red phosphorus to be subjected to the destruction of high temperature, strong shearing action in the course of processing, improve greatly the flame retarding efficiency of red phosphorus, and be successfully applied to electrician, electronics, the industry such as electric.
Patent CN 102329507A discloses a kind of flame-proof glass fibre and has strengthened PA46 resin and preparation method.By adding take brominated flame retardant as main flame retardant and antimonous oxide carries out fire-retardant as the flame-retardant system of auxiliary flame retardant, adding the long fibre of alkali-free strengthens and makes a kind of flame retardant properties good (vertical combustion 1.6mm FV-0), outstanding mechanical property and stable on heating PA46 resin.PA46 resin 45-70% wherein, compatilizer 3-5%, main flame retardant 9-13%, auxiliary flame retardant 3-5%, the long fine 10-35% of alkali-free, auxiliary agent 1-3%.But the main flame retardant brominated flame retardant that adds is halogenated flame retardant, is unfavorable for safety and environmental protection.
Patent CN 102120879A discloses a kind of high temperature resistant, high CTI value flame-retardant polyamide composite material and preparation method.Adopted specific aromatic polyamide resin composition in this Material cladding system, preferred brominated Polystyrene is main flame retardant, take one or more of antimonous oxide, zinc borate and sodium antimoniate as synergistic flame retardant, and main flame retardant 8.0-20.0 part, synergistic flame retardant 2.0-15.0 part, the preferred compound proportion of main flame retardant and synergistic flame retardant is 1:1-6:1.Make matrix material and have good flame-retardance energy (vertical combustion 1.6mm FV-0), and heat-resisting ability is very excellent, CTI can reach 600V.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of glass fibre reingorced no-halogen flame-retardant nylon dragon 46 matrix materials and preparation method thereof, and this nylon 46 matrix material has excellent flame retardant properties and mechanical property.
The present invention adopts following technical scheme:
A kind of glass fibre reingorced no-halogen flame-retardant nylon dragon 46 matrix materials, composed of the following components by weight percentage:
PA46 resin 38.9-63.9%
Main flame retardant 6-14%
Auxiliary flame retardant 0.01-6%
Glass fibre 15-45%
Other auxiliary agents 3.1-5.1%;
Described main flame retardant is the red phosphorus master batch of micro encapsulation; Described auxiliary flame retardant is polyphenylene oxide.
The alkali-free long glass fibres of described glass fibre for crossing through coupling agent treatment.
Described auxiliary agent is selected from least a in oxidation inhibitor, compatilizer, lubricant and coupling agent.
Further, described oxidation inhibitor is phosphite ester kind antioxidant and amine antioxidants, and its component ratio is 1:1.
Described lubricant is pentaerythritol stearate.
Described compatilizer is at least a in styrene-ethylene/butylene-styrene block copolymer (SEBS) grafted maleic anhydride (SEBS-g-MAH), maleic anhydride grafted polystyrene (PS-g-MAH), polyphenylene oxide grafted maleic anhydride (PPO-MAH).
Described coupling agent is silane coupling agent.
A kind of glass fibre reingorced no-halogen flame-retardant nylon dragon 46 composite manufacture methods, preparation process is followed successively by:
Step 1, take various raw materials in above-described weight fraction ratio, and the various raw materials that take are carried out drying;
Step 2, with dried PA46 resin, main flame retardant, auxiliary flame retardant and other auxiliary agents as for mixing 15 ~ 20min in high-speed mixer, raw material is mixed;
Step 3, the mixed raw material of step 2 is joined the twin screw extruder hopper, add simultaneously the glass fibre extruding pelletization; The twin screw extruder processing condition are set to: screw slenderness ratio is 40, screw speed is 200 ~ 300r/min, twin screw one district's temperature is 280 ~ 285 ℃, and two district's temperature are 285 ~ 295 ℃, and three district's temperature are 285 ~ 295 ℃, four district's temperature are 290 ~ 300 ℃, five district's temperature are 295 ~ 310 ℃, and six district's temperature are 285 ~ 300 ℃, and seven district's temperature are 280 ~ 290 ℃, eight district's temperature are 275 ~ 280 ℃, 290 ~ 300 ℃ of head temperatures.
Further, the drying conditions of the described PA46 resin of step 1 is dry 8 ~ 12h under 100 ~ 110 ℃ of conditions.
The present invention has following excellent effect:
Glass fibre reingorced no-halogen flame-retardant nylon dragon 46 matrix materials of the present invention's preparation by adding composite halogen-free flame-retardant system, in the situation that addition is few, have not only obtained fabulous flame retardant properties, and have well preserved the original excellent properties of PA46; Increase simultaneously glass fibre and carry out modification, improved greatly mechanical property and the resistance toheat such as tensile strength, flexural strength of matrix material.
Embodiment
Following embodiment is detailed description of the present invention, but the present invention not only is confined to these embodiment.
The Stanyl that each embodiment PA46 resin used all adopts Dutch DSM engineering plastics companies to produce.
The red phosphorus master batch of micro encapsulation used is the agent of FRP-52 red phosphorus fire-retardant, and Qingyuan City daylight east becomes fire retardant material company limited to produce.
Each embodiment alkali-free long glass fibres used is selected the long fine ECT5301 of alkali-free, 11 microns of Fibre diameters.
Glass fibre reingorced no-halogen flame-retardant nylon dragon 46 composite manufacture methods in following each embodiment are followed successively by by step:
Step 1, the mark ratio takes various raw materials by weight, and the various raw materials that take are carried out drying, and wherein the drying conditions of PA46 resin is dry 8 ~ 12h under 100 ~ 110 ℃ of conditions;
Step 2, with dried PA46 resin, main flame retardant, auxiliary flame retardant and other auxiliary agents as for mixing 15 ~ 20min in high-speed mixer, raw material is mixed;
Step 3, the mixed raw material of step 2 is joined the twin screw extruder hopper, add simultaneously the glass fibre extruding pelletization; The twin screw extruder processing condition are set to: screw slenderness ratio is 40, screw speed is 200 ~ 300r/min, twin screw one district's temperature is 280 ~ 285 ℃, and two district's temperature are 285 ~ 295 ℃, and three district's temperature are 285 ~ 295 ℃, four district's temperature are 290 ~ 300 ℃, five district's temperature are 295 ~ 310 ℃, and six district's temperature are 285 ~ 300 ℃, and seven district's temperature are 280 ~ 290 ℃, eight district's temperature are 275 ~ 280 ℃, 290 ~ 300 ℃ of head temperatures.
According to above-mentioned preparation method, the weight percent formula is as shown in the table:
Each embodiment weight fraction formula of table 1
? Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7 Embodiment 8 Embodiment 9 Embodiment 10
PA46(%) 63.9 57.9 54.9 54.9 54.9 52.9 54.9 54.89 44.9 38.9
Red phosphorus master batch (%) 14 14 10 9 8 7 6 12 10 10
PPO(%) 4 4 2 3 4 5 6 0.01 2 2
Alkali-free long fine (%) 15 20 30 30 30 30 30 30 40 45
Oxidation inhibitor (%) 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4
Lubricant (%) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5
Compatilizer (%) 2 3 2 2 2 4 2 2 2 3
KH-550(%) 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2
Carry out the detection of tensile strength by the ASTM-D638 standard, specimen types is the I type, batten size (mm): (165 ± 2) * (12.70 ± 0.2) * (3.20 ± 0.2), draw speed are 50mm/min.
Flexural strength and modulus in flexure are tested by the ASTM-D790 standard, specimen size (mm): (127 ± 2) * (12.7 ± 0.2) * (3.20 ± 0.2), rate of bending are 13 mm/min.
Notched Izod impact strength is by testing by the ASTM-D256 standard, and specimen types is V breach type, specimen size (mm): 63.5 * (12.7 ± 0.2) * (3.2 ± 0.2); The breach type is V mouth class, breach residual thickness 10.16 mm.
Heat-drawn wire is tested by the ASTM-D648 standard, and load is 1.82Mpa, specimen size (mm): (127 ± 2) * (12.7 ± 0.2) * (3.20 ± 0.2); Maximum deformation quantity is 0.254mm.
Flame retardant properties is injection molded into standard burning testing bar by U.S.'s UL standard.
Table 2 sample properties
Figure 2013100426828100002DEST_PATH_IMAGE001
Can find out from embodiment 1-3 and 9-10, increase along with glass fiber content, it is very large that the mechanical property of matrix material promotes amplitude, as when the glass massfraction reaches 45%, the stretching of PA46 matrix material and flexural strength are respectively 184.6Mpa and 275.5Mpa, and heat-drawn wire reaches 286.1 ℃.Simultaneously, can find out from embodiment 1-2, after glass fiber content reduces, the matrix material that obtains flame retardant rating (1.6mm) V-0 level needs appropriateness to increase the addition of fire retardant, this is mainly because glass fiber content reduces, the content of matrix resin PA46 has increased, so must the appropriate addition that increases fire retardant.
Can find out from embodiment 3-8, in flame-retardant system, main flame retardant and auxiliary flame retardant have certain synergistic flame retardant effect.In embodiment 7, when main flame retardant and auxiliary flame retardant ratio are 1:1, not only can obtain flame retardant effect preferably, the tensile strength of matrix material, flexural strength, and the mechanical property of the aspect such as shock strength also better, heat-drawn wire also can reach 286.5 ℃ simultaneously.
The present invention is by selecting suitable halogen-free flame-retardant system and complete processing, overcome existing technological deficiency, make and add fine PA46 matrix material and can reach flame retardant effect preferably by adding a small amount of fire retardant with synergistic fire retardation, simultaneously, the glass fiber reinforced halogen-free flame-retardant PA46 matrix material of gained has kept its good mechanical property and original premium properties such as high temperature resistant.

Claims (9)

1. glass fibre reingorced no-halogen flame-retardant nylon dragon 46 matrix materials, is characterized in that, and are composed of the following components by weight percentage:
PA46 resin 38.9-63.9%,
Main flame retardant 6-14%,
Auxiliary flame retardant 0.01-6%,
Glass fibre 15-45%,
Other auxiliary agents 3.1-5.1%;
Described main flame retardant is micro encapsulation red phosphorus master batch; Described auxiliary flame retardant is polyphenylene oxide.
2. glass fibre reingorced no-halogen flame-retardant nylon dragon according to claim 1 46 matrix materials, is characterized in that: the alkali free glass fibre of described glass fibre for crossing through coupling agent treatment.
3. glass fibre reingorced no-halogen flame-retardant nylon according to claim 1 dragon 46 matrix materials is characterized in that: described other auxiliary agents are selected from least a in oxidation inhibitor, lubricant, compatilizer and coupling agent.
4. glass fibre reingorced no-halogen flame-retardant nylon according to claim 3 dragon 46 matrix materials, it is characterized in that: described oxidation inhibitor is phosphite ester kind antioxidant and amine antioxidants, its component ratio is 1:1.
5. glass fibre reingorced no-halogen flame-retardant nylon according to claim 3 dragon 46 matrix materials, it is characterized in that: described lubricant is pentaerythritol stearate.
6. glass fibre reingorced no-halogen flame-retardant nylon according to claim 3 dragon 46 matrix materials, it is characterized in that: described compatilizer is at least a in styrene-ethylene/butylene-styrene block copolymer (SEBS) grafted maleic anhydride (SEBS-g-MAH), maleic anhydride grafted polystyrene (PS-g-MAH), polyphenylene oxide grafted maleic anhydride (PPO-MAH).
7. glass fibre reingorced no-halogen flame-retardant nylon according to claim 3 dragon 46 matrix materials, it is characterized in that: described coupling agent is silane coupling agent.
8. glass fibre reingorced no-halogen flame-retardant nylon dragon as described in claim 1 to 7 any one 46 composite manufacture methods, is characterized in that, preparation process is followed successively by:
Step 1, take various raw materials in proportion, and the various raw materials that take are carried out drying;
Step 2, dried PA46 resin, main flame retardant, auxiliary flame retardant and other auxiliary agents are placed in high-speed mixer mix 15 ~ 20min, raw material is mixed;
Step 3, the mixed raw material of step 2 is joined the twin screw extruder hopper, glass fibre adds from the forcing machine stage casing, extruding pelletization; The twin screw extruder processing condition are set to: screw slenderness ratio is 40, screw speed is 200 ~ 300r/min, twin screw one district's temperature is 280 ~ 285 ℃, and two district's temperature are 290 ~ 295 ℃, and three district's temperature are 290 ~ 295 ℃, four district's temperature are 295 ~ 300 ℃, five district's temperature are 295 ~ 310 ℃, and six district's temperature are 290 ~ 300 ℃, and seven district's temperature are 280 ~ 290 ℃, eight district's temperature are 275 ~ 280 ℃, 290 ~ 300 ℃ of head temperatures.
9. glass fibre reingorced no-halogen flame-retardant nylon according to claim 8 dragon 46 composite manufacture methods, it is characterized in that: the drying conditions of the described PA46 resin of step 1 is dry 8 ~ 12h under 100 ~ 110 ℃ of conditions.
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CN104212162A (en) * 2013-05-30 2014-12-17 上海杰事杰新材料(集团)股份有限公司 Flame-retardation enhanced high-temperature resistance nylon composite material and preparation method thereof
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CN107325547A (en) * 2016-04-28 2017-11-07 深圳市德发高科技有限公司 A kind of fire-retardant reinforcing material of Halogen high-voltage isulation and preparation method thereof
CN107325546A (en) * 2016-04-28 2017-11-07 深圳市德发高科技有限公司 A kind of pressure-resistant flame-resistant insulation reinforcing material and preparation method thereof
CN106751776A (en) * 2016-12-09 2017-05-31 宜春学院 Composite of nano-nylon 6 and preparation method thereof
CN109852050A (en) * 2018-12-24 2019-06-07 余姚中国塑料城塑料研究院 A kind of glass fiber reinforcement low-smoke non-halogen flame-retardant PA66 material and preparation method thereof
CN112126223A (en) * 2019-06-25 2020-12-25 苏州和庚丽塑胶科技有限公司 Halogen-free flame-retardant polytetramethylene adipamide material and preparation method thereof

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