CN104017363A - High-temperature-resistance flame-retardant glass fiber reinforced PA46/PA66 composite material and preparation method thereof - Google Patents

High-temperature-resistance flame-retardant glass fiber reinforced PA46/PA66 composite material and preparation method thereof Download PDF

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Publication number
CN104017363A
CN104017363A CN201410247649.3A CN201410247649A CN104017363A CN 104017363 A CN104017363 A CN 104017363A CN 201410247649 A CN201410247649 A CN 201410247649A CN 104017363 A CN104017363 A CN 104017363A
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glass fibre
nylon
heat
matrix
strengthens
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陆建华
蒋东升
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NINGBO EAGLE NEW MATERIAL Co Ltd
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NINGBO EAGLE NEW MATERIAL Co Ltd
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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
    • 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
    • B29C48/25Component 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
    • 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
    • B29C48/92Measuring, controlling or regulating
    • 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
    • C08K3/01Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/016Flame-proofing or flame-retarding additives
    • 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
    • C08K5/00Use of organic ingredients
    • C08K5/0008Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066Flame-proofing or flame-retarding additives
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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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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/08Copolymers of ethene
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    • 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
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    • 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
    • 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
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/92514Pressure
    • 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
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/9258Velocity
    • B29C2948/9259Angular velocity
    • 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
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/92609Dimensions
    • B29C2948/92619Diameter or circumference
    • 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
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/92609Dimensions
    • B29C2948/92638Length
    • 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
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/92704Temperature
    • CCHEMISTRY; METALLURGY
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    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/002Physical properties
    • C08K2201/003Additives being defined by their diameter
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    • C08K2201/004Additives being defined by their length
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    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/02Flame or fire retardant/resistant
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L2201/08Stabilised against heat, light or radiation or oxydation
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    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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    • C08L25/18Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen

Abstract

The invention relates to a high-temperature-resistance flame-retardant glass fiber reinforced PA46/PA66 composite material. The composite material is prepared from the following raw materials in percentage by mass: 5-15 percent of nylon 66, 19.4-66.8 percent of nylon 46, 8-20 percent of a compound flame retardant, 3-8 percent of a synergist, 15-30 percent of glass fiber, 2-6 percent of a flexibilizer, 0.1-0.6 percent of an antioxidant and 0.1-0.6 percent of a lubricant.According to the preparation method, the mechanical performance and the heat tolerance of the PA46/PA66 composite material can be greatly improved by means of the compounding effect of each functional adjuvant, the glowing filament ignition temperature can be increased, wherein a sample filament with thickness of 3.0mm can not be ignited when the temperature is over 800 DEG C, so that the product can be used for a long time in a high-temperature high-heat environment. Currently, the products can be successfully applied to production of binding posts, connectors, sockets, switches, electric appliance casings and the like.

Description

A kind of heat-resistant fireproof glass fibre strengthens PA46/PA66 matrix material and preparation method thereof
[technical field]
The present invention relates to polymer composite preparing technical field, more particularly, particularly a kind of heat-resistant fireproof glass fibre strengthens PA46/PA66 matrix material and preparation method thereof.
[background technology]
Polymeric amide 46 has the feature of electric property, fine heat-resisting performance and high tenacity, has higher surface and volume resistance, insulation strength.At high temperature still can keep high performance level, be applicable to electric material.But the flame retardant properties of polymeric amide 46 material own only has V-2 level and expensive, is limited in its large-scale application in field of electronics.PA66 resin has that physical strength is high, good toughness, antifatigue, have the advantages such as self lubricity, frictional coefficient are little, wear-resisting, heat-resisting, easy modification forming, and moderate, has good over-all properties and oneself is through being widely used.
How to widen the Application Areas of PA46, in conjunction with the PA46 principle similar with PA66 molecular structure, it is being kept on the basis of good mechanical property and thermal characteristics, make this Flame Retardancy can reach flame retardant properties V0 level (test bars thickness is 1.6mm), and glowing filament ignition temperature reaches 850 DEG C above nonflammable (test bars thickness 3mm), realize this material and use in fields such as terminal stud, junctor, sockets, become those skilled in the art's problem demanding prompt solution.
[summary of the invention]
The object of the present invention is to provide a kind of heat-resistant fireproof glass fibre to strengthen PA46/PA66 matrix material and preparation method thereof, it is being kept on the basis of good mechanical property and thermal characteristics, make this Flame Retardancy can reach flame retardant properties V0 level (test bars thickness is 1.6mm), and glowing filament ignition temperature reach 850 DEG C above nonflammable (test bars thickness 3mm).
For achieving the above object, the technical solution used in the present invention is:
One aspect of the present invention provides a kind of heat-resistant fireproof glass fibre to strengthen PA46/PA66 matrix material, and it is made up by mass percentage of following component:
The glass fibre of the compound flame redundant of the nylon 66 of 5%-15%, the nylon 46 of 19.4%-66.8%, 8%-20%, the synergist of 3%-8%, 15%-30%, toughner, the oxidation inhibitor of 0.1%-0.6% and the lubricant of 0.1%-0.6% of 2%-6%.
Further improve as the present invention, described nylon 46 is the aliphatics heat-resistant polyamide being formed by butanediamine and hexanodioic acid polycondensation, described nylon 66 by Ubbelohde viscosimetry survey relative viscosity be 2.4-3.2, Nylon 66 moisture content is less than 0.5%, preferably, relative viscosity is 2.5-2.8.
Further improve as the present invention, described compound flame redundant is that halogen-phosphorus is compound flame retardant, the weight proportion of described halogen and phosphorus system is 3: 2, halogen flame is any one or its multiple combination arbitrarily of brominated Polystyrene, TDE, brominated polystyrene, any one or its multiple combination arbitrarily of phosphorus flame retardant organic secondary phosphine acid salt, Tritolyl Phosphate, red phosphorus.
Further improve as the present invention, described synergist is auxiliary flame retardant and smoke suppressor, the weight proportion of described auxiliary flame retardant and smoke suppressor is 4: 1-2: 1, auxiliary flame retardant is any one or its combination of two kinds of antimonous oxide, zinc borate, and smoke suppressor is any one or its multiple combination arbitrarily of zinc oxide, manganese oxide, ferrocene.
Further improve as the present invention, described glass fibre is alkali-free short glass fiber, glass fiber diameter 9-13 μ m, and glass fibre length is 3.0mm/4.5mm.
Further improve as the present invention, described toughner is any one or its arbitrarily multiple combination in polyethylene octene copolymer elastomerics-copolymer-maleic anhydride (POE-g-MAH), terpolymer EP rubber-copolymer-maleic anhydride (EPDM-g-MAH), polystyrene-ethene-butylene-polystyrene-maleic anhydride multipolymer (SEBS-g-MAH).
Further improve as the present invention, described oxidation inhibitor is N, N '-hexylidene-1.6-bis-[(3,5-di-t-butyl-4-hydroxyphenyl) propionic acid amide] (1098), four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (1010), three (2,4-di-tert-butyl-phenyl) any one or its multiple combination arbitrarily in phosphorous acid ester (168), two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites (626).
Further improve as the present invention, described lubricant is: any one or its multiple combination arbitrarily in the two hard fatty acids acid amides of silicone, ethylene bis stearamide, calcium stearate, ethylene, oxidized polyethlene wax, montanin wax.
The present invention provides a kind of above-mentioned heat-resistant fireproof glass fibre to strengthen PA46/PA66 matrix material on the other hand, and it specifically comprises the following steps:
Step 1, nylon 66, nylon 46 resin are placed to dry 3-4 hour in the baking oven of 100 DEG C, made its water ratio be less than 5 ‰;
Step 2, by Nylon 66, nylon 46 resin, compound flame redundant, synergist, glass fibre, toughner, oxidation inhibitor, the lubricant respectively of each weight percentages of components in formula;
Step 3, Nylon 66, nylon 46 resin, toughner, oxidation inhibitor and lubricant are added in homogenizer and be uniformly mixed, obtain mixture A; Compound flame redundant and synergist are mixed in homogenizer, obtain mixture B;
Step 4, the length-to-diameter ratio of producing required twin screw extruder are 48: 1, configuration bilateral feeding, mixture A joins in twin screw extruder by main feeding, mixture B and glass fibre join in twin screw extruder by two side feedings respectively, the side feeding of send mixt B is positioned at Si district, carry the side feeding of glass to be positioned at SECTOR-SEVEN, after melting mixing, extrude tie rod, pelletizing, packaging.
Further improve as the present invention, the Temperature Setting interval of each section of temperature of described twin screw extruder from charging opening to head, the Temperature Setting 280-285 DEG C of the first five section, rear seven sections are 2265-250 DEG C, engine speed 600-800r/min, vacuum pressure is controlled at 0.06-0.08MPa.
Compared with prior art, the beneficial effect that the present invention obtains is:
The present invention passes through in conjunction with the PA46 principle similar with PA66 molecular structure, composite by PA46, PA66 and fire retardant, synergist, keeping on the basis of good mechanical property and thermal characteristics, make this Flame Retardancy can reach flame retardant properties V0 level (test bars thickness is 1.6mm), and glowing filament ignition temperature reach 850 DEG C above nonflammable (test bars thickness 3mm).This matrix material can meet the electric fittings that has high temperature requirement, and technique simple, convenient for production, meet suitability for industrialized production, market outlook are wide.
[brief description of the drawings]
Fig. 1 is the schema of heat-resistant fireproof fiberglass reinforced PA 46/PA66 composite material and preparation method thereof provided by the present invention.
[embodiment]
Below in conjunction with accompanying drawing 1, the present invention is described in more detail.
Embodiment 1:
First by dry 5kg rear Nylon 66 (relative viscosity 2.5, moisture content 1 ‰), 44.4kgPA46 resin, 0.2kg oxidation inhibitor 1098, 0.2kg irgasfos 168, 2kgPOE-g-MAH, 0.5kg oxidized polyethlene wax joins in the homogenizer on main drawing-in device and stirs, by 12kg brominated Polystyrene, 8kg organic secondary phosphine acid salt, 6kg antimonous oxide, 1.5kg zinc oxide joins in the homogenizer on 1# side drawing-in device and stirs, the mixture stirring is joined in the main feeding machine and 1# side feeding machine of twin screw extruder, 25kg short glass fiber is joined in the 2# side feeder of twin screw extruder, through twin screw extruder granulation, engine speed 600-800r/min, vacuum pressure is controlled at 0.06-0.08Mpa, engine speed 600-800r/mi n, vacuum pressure is controlled at 0.06-0.08MPa.
Embodiment 2:
First by dry 8kg rear Nylon 66 (relative viscosity 2.5, moisture content 1 ‰)), 44.4kgPA46 resin, 0.2kg antioxidant 1010, 0.2kg irgasfos 168, 2kgEPDM-g-MAH, the two hard fatty acids acid amides of 0.5kg ethylene join in the homogenizer on main drawing-in device and stir, by 12kg brominated Polystyrene, 8kg Tritolyl Phosphate, 3kg antimonous oxide, 1.5kg zinc oxide joins in the homogenizer on 1# side drawing-in device and stirs, the mixture stirring is joined in the main feeding machine and 1# side feeding machine of twin screw extruder, 25kg short glass fiber is joined in the 2# side feeder of twin screw extruder, through twin screw extruder granulation, engine speed 600-800r/min, vacuum pressure is controlled at 0.06-0.08MPa.Embodiment 3:
First by dry 10kg rear Nylon 66 (relative viscosity 2.5, moisture content 1 ‰)), 42.4kgPA46 resin, 0.2kg oxidation inhibitor 1098, 0.2kg irgasfos 168, 2kgSEBSM-g-MAH, 0.5kg montanin wax joins in the homogenizer on main drawing-in device, by 12kg TDE, 8kg organic secondary phosphine acid salt, 3kg antimonous oxide, 1.5kg manganese oxide joins in the homogenizer on 1# side drawing-in device, after stirring, join in the main feeding machine and 1# side feeding machine of twin screw extruder, 25kg short glass fiber is joined in the 2# side feeder of twin screw extruder, through twin screw extruder granulation, engine speed 600-800r/min, vacuum pressure is controlled at 0.06-0.08MPa.
Embodiment 4:
First by dry 8kg rear Nylon 66 (relative viscosity 2.5, moisture content 1 ‰)), 43kgPA46 resin, 0.2kg antioxidant 1010, 0.2kg irgasfos 168, 2kgEPDM-g-MAH, the two hard fatty acids acid amides of 0.5kg ethylene, 0.4kg calcium stearate joins in the homogenizer on main drawing-in device and stirs, by 12kg brominated Polystyrene, 8kg Tritolyl Phosphate, 2kg antimonous oxide, 2kg zinc borate, 1.5kg zinc oxide joins in the homogenizer on 1# side drawing-in device and stirs, the mixture stirring is joined in the main feeding machine and 1# side feeding machine of twin screw extruder, 25kg short glass fiber is joined in the 2# side feeder of twin screw extruder, through twin screw extruder granulation, engine speed 600-800r/min, vacuum pressure is controlled at 0.06-0.08MPa.
Embodiment 5:
First by dry 15kg rear Nylon 66 (relative viscosity 2.5, moisture content 1 ‰), 19.4kgPA46 resin, 0.3kg oxidation inhibitor 1098, 0.3kg irgasfos 168, 6kgPOE-g-MAH, 0.6kg oxidized polyethlene wax joins in the homogenizer on main drawing-in device and stirs, by 12kg brominated Polystyrene, 8kg Tritolyl Phosphate, 5kg antimonous oxide, 3kg zinc oxide joins in the homogenizer on 1# side drawing-in device and stirs, the mixture stirring is joined in the main feeding machine and 1# side feeding machine of twin screw extruder, 30kg short glass fiber is joined in the 2# side feeder of twin screw extruder, through twin screw extruder granulation, engine speed 600-800r/min, vacuum pressure is controlled at 0.06-0.08MPa.
Embodiment 6:
First by dry 5kg rear Nylon 66 (relative viscosity 2.5, moisture content 1 ‰)), 66.8kgPA46 resin, 0.1kg oxidation inhibitor 1098, 2kgSEBSM-g-MAH, 0.1kg montanin wax joins in the homogenizer on main drawing-in device, by 4kg TDE, 4kg organic secondary phosphine acid salt, 2kg antimonous oxide, 1kg manganese oxide joins in the homogenizer on 1# side drawing-in device, after stirring, join in the main feeding machine and 1# side feeding machine of twin screw extruder, 15kg short glass fiber is joined in the 2# side feeder of twin screw extruder, through twin screw extruder granulation, engine speed 600-800r/min, vacuum pressure is controlled at 0.06-0.08MPa.
Effect example 1
Mechanical mechanics property, thermal characteristics characterize: test according to iso standard; Flame retardant properties is tested according to UL94 standard.The heat-resistant fireproof glass fibre making of embodiment 1-6 is strengthened to PA46/PA66 matrix material and tests according to above-mentioned standard, the results are shown in Table 1 and table 2:
Table 1
Table 2
The above embodiment is only the preferred embodiments of the present invention, and is not the exhaustive of the feasible enforcement of the present invention.For persons skilled in the art, any apparent change of under the prerequisite that does not deviate from the principle of the invention and spirit, it having been done, within all should being contemplated as falling with claim protection domain of the present invention.

Claims (10)

1. heat-resistant fireproof glass fibre strengthens a PA46/PA66 matrix material, it is characterized in that: it is made up by mass percentage of following component:
The nylon 66,19 of 5%-15%, toughner, the oxidation inhibitor of 0.1%-0.6% and the lubricant of 0.1%-0.6% of the synergist of the nylon 46 of 8%-66.8%, the compound flame redundant of 8%-20%, 3%-8%, the glass fibre of 15%-30%, 2%-6%.
2. a kind of heat-resistant fireproof glass fibre according to claim 1 strengthens PA46/PA66 matrix material, it is characterized in that: described nylon 46 is the aliphatics heat-resistant polyamide being formed by butanediamine and hexanodioic acid polycondensation, described nylon 66 by Ubbelohde viscosimetry survey relative viscosity be 2.4-3.2, Nylon 66 moisture content is less than 0.5%, preferably, relative viscosity is 2.5-2.8.
3. a kind of heat-resistant fireproof glass fibre according to claim 1 strengthens PA46/PA66 matrix material, it is characterized in that: described compound flame redundant is that halogen-phosphorus is compound flame retardant, the weight proportion of described halogen and phosphorus system is 3: 2, halogen flame is any one or its multiple combination arbitrarily of brominated Polystyrene, TDE, brominated polystyrene, any one or its multiple combination arbitrarily of phosphorus flame retardant organic secondary phosphine acid salt, Tritolyl Phosphate, red phosphorus.
4. a kind of heat-resistant fireproof glass fibre according to claim 1 strengthens PA46/PA66 matrix material, it is characterized in that: described synergist is auxiliary flame retardant and smoke suppressor, the weight proportion of described auxiliary flame retardant and smoke suppressor is 4: 1-2: 1, auxiliary flame retardant is any one or its combination of two kinds of antimonous oxide, zinc borate, and smoke suppressor is any one or its multiple combination arbitrarily of zinc oxide, manganese oxide, ferrocene.
5. a kind of heat-resistant fireproof glass fibre according to claim 1 strengthens PA46/PA66 matrix material, it is characterized in that: described glass fibre is alkali-free short glass fiber, and glass fiber diameter 9-13 μ m, glass fibre length is 3.0mm/4.5mm.
6. a kind of heat-resistant fireproof glass fibre according to claim 1 strengthens PA46/PA66 matrix material, it is characterized in that: described toughner is any one or its multiple combination arbitrarily in polyethylene octene copolymer elastomerics-copolymer-maleic anhydride, terpolymer EP rubber-copolymer-maleic anhydride, polystyrene-ethene-butylene-polystyrene-maleic anhydride multipolymer.
7. a kind of heat-resistant fireproof glass fibre according to claim 1 strengthens PA46/PA66 matrix material, it is characterized in that: described oxidation inhibitor is: N, N '-hexylidene-1.6-bis-[(3,5-di-t-butyl-4-hydroxyphenyl) propionic acid amide], four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, three (2,4-di-tert-butyl-phenyl) any one or its multiple combination arbitrarily in phosphorous acid ester, two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites.
8. a kind of heat-resistant fireproof glass fibre according to claim 1 strengthens PA46/PA66 matrix material, it is characterized in that: described lubricant is: any one or its multiple combination arbitrarily in silicone, ethylene bis stearamide, calcium stearate, the two hard fatty acids acid amides of ethylene, oxidized polyethlene wax, montanin wax.
9. the preparation method who strengthens PA46/PA66 matrix material according to the heat-resistant fireproof glass fibre described in claim 1-8 any one, is characterized in that: it specifically comprises the following steps:
Step 1, nylon 66, nylon 46 resin are placed to dry 3-4 hour in the baking oven of 100 DEG C, made its water ratio be less than 5 ‰;
Step 2, by Nylon 66, nylon 46 resin, compound flame redundant, synergist, glass fibre, toughner, oxidation inhibitor, the lubricant respectively of each weight percentages of components in formula;
Step 3, Nylon 66, nylon 46 resin, toughner, oxidation inhibitor and lubricant are added in homogenizer and be uniformly mixed, obtain mixture A; Compound flame redundant and synergist are mixed in homogenizer, obtain mixture B;
Step 4, the length-to-diameter ratio of producing required twin screw extruder are 48: 1, configuration bilateral feeding, mixture A joins in twin screw extruder by main feeding, mixture B and glass fibre join in twin screw extruder by two side feedings respectively, carry the side feeding of mixture B to be positioned at Si district, carry the side feeding of glass to be positioned at SECTOR-SEVEN, after melting mixing, extrude tie rod, pelletizing, packaging.
10. a kind of heat-resistant fireproof glass fibre according to claim 9 strengthens the preparation method of PA46/PA66 matrix material, it is characterized in that: the Temperature Setting interval of each section of temperature of described twin screw extruder from charging opening to head, the Temperature Setting 280-285 DEG C of the first five section, rear seven sections are 2265-250 DEG C, engine speed 600-800r/min, vacuum pressure is controlled at 0.06-0.08MPa.
CN201410247649.3A 2014-06-06 2014-06-06 High-temperature-resistance flame-retardant glass fiber reinforced PA46/PA66 composite material and preparation method thereof Pending CN104017363A (en)

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CN104945893A (en) * 2015-07-31 2015-09-30 苏州新区特氟龙塑料制品厂 Modified polyamide with high safety for cables
CN105086178A (en) * 2015-07-28 2015-11-25 安徽丹凤集团桐城玻璃纤维有限公司 Preparation technology for glass fiber composite material with acid-base resistance
CN107474530A (en) * 2017-08-30 2017-12-15 朱红艳 A kind of ion colloidal sol reinforcement nylon fire proofing and preparation method thereof
CN107722622A (en) * 2017-11-17 2018-02-23 江门市荣龙新材料科技有限公司 A kind of high abrasion high-temperature resistant nylon 46 composite and preparation method thereof
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CN107936554A (en) * 2017-11-15 2018-04-20 惠州新彩工程塑料科技有限公司 A kind of modified nylon engineering plastics preparation method applied to automotive seat
CN107722622A (en) * 2017-11-17 2018-02-23 江门市荣龙新材料科技有限公司 A kind of high abrasion high-temperature resistant nylon 46 composite and preparation method thereof
CN107778856A (en) * 2017-11-17 2018-03-09 江门市荣龙新材料科技有限公司 Halogen-free flameproof high-temperature resistant nylon 46 composite and preparation method thereof
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