CN103087518B - 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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CN103087518B
CN103087518B CN201310042682.8A CN201310042682A CN103087518B CN 103087518 B CN103087518 B CN 103087518B CN 201310042682 A CN201310042682 A CN 201310042682A CN 103087518 B CN103087518 B CN 103087518B
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glass fibre
retardant
district
reingorced
flame retardant
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CN103087518A (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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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • B29B9/14—Making granules characterised by structure or composition fibre-reinforced
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/58—Component parts, details or accessories; Auxiliary operations
    • B29B7/72—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
    • B29B7/7461—Combinations of dissimilar mixers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/88—Adding charges, i.e. additives
    • B29B7/90—Fillers or reinforcements, e.g. fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion 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
    • B29C48/04—Particle-shaped
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions 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
    • C08L51/04—Compositions 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions 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
    • C08L51/06—Compositions 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions 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
    • C08L53/02—Compositions 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/14—Macromolecular materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K2003/026—Phosphorus

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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
Along with social development, 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., also higher to the performance requriements of nylon engineering plastic, usually need to keep, under the condition of its mechanical property, improving 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 an urgent demand of industry to Halogen, low toxicity, low-smoke and flame retardant material such as electric, automobile making, especially implement after 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, obvious to the flame retardant effect of polymkeric substance.But because poor water resistance, the addition of its fire retardant is large, range of application is narrow is difficult to extensive popularization.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, when burning, than other phosphorus compound, produce more Tripyrophosphoric acid, these phosphoric acid both can cover nylon surface, can accelerate its dehydration carbonization at nylon surface catalysis again, reduced the growing amount of combustiblematerials and the mass loss speed of superpolymer material.And the phosphoric acid generating residues in 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 coated system is introduced thermoplastic polymer, played good interface compatible and " lubricate " act on, avoided encapsulated red phosphorus in the course of processing, to be subject to the destruction of high temperature, strong shearing action, 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 the flame-retardant system that brominated flame retardant is auxiliary flame retardant as main flame retardant and antimonous oxide and carry out fire-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 adding 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.In this Material cladding system, adopted specific aromatic polyamide resin composition, preferably brominated Polystyrene is main flame retardant, one or more of antimonous oxide, zinc borate and sodium antimoniate of take are 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:
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 one 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 one 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 preparation method for glass fibre reingorced no-halogen flame-retardant nylon dragon 46 matrix materials, preparation process is followed successively by:
Step 1, in above-described weight fraction ratio, take various raw materials, and the various raw materials that take are dried;
Step 2, by 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 to twin screw extruder hopper, add glass fibre extruding pelletization simultaneously; 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 PA46 resin described in 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 prepared by the present invention, 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 glass fibre simultaneously 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 is not only confined to these embodiment.
The Stanyl that each embodiment PA46 resin used all adopts Dutch DSM engineering plastics company 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 Dong Cheng fire retardant material company limited produces.
Each embodiment alkali-free long glass fibres used is selected the long fine ECT5301 of alkali-free, 11 microns of Fibre diameters.
The preparation method of glass fibre reingorced no-halogen flame-retardant nylon dragon 46 matrix materials in following each embodiment, is followed successively by by step:
Step 1, mark ratio takes various raw materials by weight, and the various raw materials that take are dried, and wherein the drying conditions of PA46 resin is dry 8 ~ 12h under 100 ~ 110 ℃ of conditions;
Step 2, by 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 to twin screw extruder hopper, add glass fibre extruding pelletization simultaneously; 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, 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
By ASTM-D638 standard, carry out the detection of tensile strength, specimen types is I type, batten size (mm): (165 ± 2) * (12.70 ± 0.2) * (3.20 ± 0.2), draw speed is 50mm/min.
Flexural strength and modulus in flexure are tested by ASTM-D790 standard, specimen size (mm): (127 ± 2) * (12.7 ± 0.2) * (3.20 ± 0.2), rate of bending is 13 mm/min.
Notched Izod impact strength is by testing by ASTM-D256 standard, and specimen types is V breach type, specimen size (mm): 63.5 * (12.7 ± 0.2) * (3.2 ± 0.2); Breach type is V mouth class, breach residual thickness 10.16 mm.
Heat-drawn wire is tested by 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
From embodiment 1-3 and 9-10, can find out, increase along with glass fiber content, it is very large that the mechanical property of matrix material promotes amplitude, as when 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, from embodiment 1-2, can find out, 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.
From embodiment 3-8, can find out, 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 good flame retardant effect, the mechanical property of the aspects such as the tensile strength of matrix material, flexural strength and shock strength is also better, and 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, by adding a small amount of fire retardant with synergistic fire retardation, make to add fine PA46 matrix material and can reach good flame retardant effect, meanwhile, 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, 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 dragon according to claim 1 46 matrix materials, is characterized in that: other described auxiliary agents are selected from least one in oxidation inhibitor, lubricant, compatilizer and coupling agent.
4. glass fibre reingorced no-halogen flame-retardant nylon dragon according to claim 3 46 matrix materials, is characterized in that: described oxidation inhibitor is phosphite ester kind antioxidant and amine antioxidants, and its component ratio is 1:1.
5. glass fibre reingorced no-halogen flame-retardant nylon dragon according to claim 3 46 matrix materials, is characterized in that: described lubricant is pentaerythritol stearate.
6. glass fibre reingorced no-halogen flame-retardant nylon dragon according to claim 3 46 matrix materials, is characterized in that: described compatilizer is at least one 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 dragon according to claim 3 46 matrix materials, is characterized in that: described coupling agent is silane coupling agent.
8. a preparation method for the dragon of the glass fibre reingorced no-halogen flame-retardant nylon as described in claim 1 to 7 any one 46 matrix materials, 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 dried;
Step 2, dried PA46 resin, main flame retardant, auxiliary flame retardant and other auxiliary agents are placed in to high-speed mixer mix 15 ~ 20min, raw material is mixed;
Step 3, the mixed raw material of step 2 is joined to twin screw extruder hopper, glass fibre adds from forcing machine stage casing, extruding pelletization; 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. the preparation method of glass fibre reingorced no-halogen flame-retardant nylon dragon according to claim 8 46 matrix materials, is characterized in that: the drying conditions of the PA46 resin in the various raw materials described in step 1 is dry 8 ~ 12h under 100 ~ 110 ℃ of conditions.
CN201310042682.8A 2013-02-04 2013-02-04 Glass-fiber-reinforced halogen-free flame-retardant nylon 46 composite material and preparation method thereof Active CN103087518B (en)

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