CN102964829B - Environment-friendly and flame-retardant glass fiber reinforced PA (polyamide) 66/PPO (polyphenylene oxide) alloy material with high CTI (comparative tracking index) value and high GWIT (glow-wire ignition temperature) value and preparation method thereof - Google Patents

Environment-friendly and flame-retardant glass fiber reinforced PA (polyamide) 66/PPO (polyphenylene oxide) alloy material with high CTI (comparative tracking index) value and high GWIT (glow-wire ignition temperature) value and preparation method thereof Download PDF

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CN102964829B
CN102964829B CN201210510322.1A CN201210510322A CN102964829B CN 102964829 B CN102964829 B CN 102964829B CN 201210510322 A CN201210510322 A CN 201210510322A CN 102964829 B CN102964829 B CN 102964829B
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flame
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CN102964829A (en
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郭建鹏
汤俊杰
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Shanghai Rizhisheng New Technology Development Co Ltd
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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
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    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/88—Adding charges, i.e. additives
    • B29B7/90—Fillers or reinforcements, e.g. fibres
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    • 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
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    • 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
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • 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
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    • 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
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means 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
    • B29C48/40—Means 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
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K3/2279—Oxides; Hydroxides of metals of antimony
    • C—CHEMISTRY; METALLURGY
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    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C—CHEMISTRY; METALLURGY
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    • C08K9/00—Use of pretreated ingredients
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    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
    • 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
    • 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
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    • C09K21/00—Fireproofing materials
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    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
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Abstract

The invention discloses an environment-friendly and flame-retardant glass fiber reinforced PA (polyamide) 66/PPO (polyphenylene oxide) alloy material with high CTI (comparative tracking index) value and high GWIT (glow-wire ignition temperature) value. The alloy material comprises the following raw components in percentage by weight: 23-41% of PA66, 22-41% of PPO, 6-20% of compound flame retardant, 3-15% of antimony trioxide, 20-30% of glass fiber, 2-10% of compatilizer, 0.1-1% of antioxidant and 0.1-1% of oxide, wherein the compound flame retardant comprises brominated polystyrene, magnesium hypophosphite and talcum powder. The invention also provides a preparation method of the alloy material. The alloy material has high GWIT value and CTI value and good flame retardant effect, is environment-friendly, has balanced overall performances and can be widely applied to such products in the field of electronics as low-voltage electronic capacitor shells, load break switches, carbon brush brackets and moulded case circuit breakers.

Description

A kind of high CTI value, high GWIT value environment-protection flame-proof fiberglass reinforced plastic PA66/PPO alloy material and preparation method thereof
Technical field
The present invention relates to technical field of alloy material, specifically, is a kind of high CTI value, high GWIT value environment-protection flame-proof fiberglass reinforced plastic PA66/PPO alloy material and preparation method thereof.
Background technology
Nylon (Nylon), Chinese name polymeric amide, English name Polyamide(is called for short PA), be on molecular backbone chain, contain recurring amide radical group-[NHCO]-thermoplastic resin general name.Its name is determined by the concrete carbonatoms of synthon, as: polycaprolactam (nylon 6, abbreviation PA6), polyhexamethylene adipamide (nylon 66, abbreviation PA66), poly-sebacic acid decamethylene diamine (nylon 1010, abbreviation PA1010), polyhexamethylene sebacamide (NYLON610 is called for short PA610), nylon 11 (nylon 11 is called for short PA11), poly-lauramide (nylon 12, abbreviation PA12), nylon 46 (nylon 46 is called for short PA46).PA degree of crystallinity is high, and fusing point is obvious; Surface hardness is large, abrasion performance, and frictional coefficient is little; There are self lubricity and noise reduction; Low-temperature performance is good, has certain thermotolerance (can use below 100 degree); Nontoxic, odorless, mildew and rot, have self-extinguishing, good weatherability, but dyeability is poor.
Polyphenylene oxide, English name Polyphenylene Oxide(is called for short PPO), be the resistant to elevated temperatures thermoplastic resin of a class, be one of the world's five large general engineering plastic.It has the advantages such as rigidity is large, thermotolerance is high, difficult combustion, intensity is higher, electrical property is good.In addition, polyphenylene oxide also has the advantages such as wear-resisting, nontoxic, anti-pollution.The specific inductivity of PPO and dielectric loss are one of minimum kinds in engineering plastics, are subject to hardly the impact of temperature, humidity, can be used for basic, normal, high frequency electric field field.The load deformation temperature of PPO can reach more than 190 ℃, and embrittlement temperature is-170 ℃.PPO material is as one of the world's five large general engineering plastic, and nontoxic, relative density is little, is density minimum in five large general engineering plastic, has good physical strength, creep resistance, and proof stress is lax, and fatigue resistance is high.
PA66/PPO alloy material combines the advantage of PA66 and PPO material, has excellent thermotolerance, good processibility, can sprayability etc.21 century electronics, electric, communication, household electrical appliances, electromechanical equipment are to high-performance microization development, and more and more higher to the requirement of flame-retardant PA 66/PPO alloy material, meanwhile, along with the understanding of the mankind to environmental protection, Green Product is subject to common concern.Therefore, flame-retardant PA 66/PPO alloy material developing direction is: performance function flame-retardant PA 66/PPO alloy material becomes main flow; The kind of environmental type flame-retardant PA 66/PPO alloy material and demand are more and more; The production of flame-retardant PA 66/PPO alloy material is to many variety series future development; The use of fire retardant is to diversification, compound development.Traditional bromide fire retardant can not meet the requirement of high standard product, the fire retardant compound system that some are traditional, for example glass fibre+TDE+antimonous oxide compound system, glass fibre+brominated Polystyrene+antimonous oxide compound system, the CTI value of these compound systems (comparative tracking index, relative discharge tracking index) and GWIT value (glow-wire ignition temperature, glow-wire ignition temperature) not high, be not suitable for the power utilization environment of high request.
Chinese patent literature application number 201210247335.4, in open day on October 17th, 2012, has announced a kind of flame-proof glass fibre reinforced plastic PA66/PPO alloy composite and preparation method thereof.This alloy composite comprises each component of following weight percent content: PA66 20-41%, PPO 20-41%, compatilizer 0-10%, compositional flame-retardant master batch 0-15%, glass fibre 20-40%, oxidation inhibitor 0.1-1%, lubrication dispersing agent 0.1-1%.Described compositional flame-retardant masterbatch comprises each component of following weight percent content: deironing red phosphorus master batch 50%, antimigration agent 25%, high CTI auxiliary agent 25%.The alloy composite of preparation has advantages of high CTI value, the low fire retardant property separated out, but have not been reported about integrating the alloy material of the advantages such as high GWIT value, high CTI value, environmental protection, over-all properties equilibrium.
Summary of the invention
The object of the invention is for deficiency of the prior art, a kind of high CTI value, high GWIT value environment-protection flame-proof fiberglass reinforced plastic PA66/PPO alloy material are provided.This alloy material glow wire temperature is higher, environmental protection, and over-all properties is balanced, is applicable to Low-voltage Electronic capacitor case, load break switch, carbon brush supports, the electronic applications such as breaker of plastic casing.
One object more of the present invention is that the preparation method of a kind of high CTI value, high GWIT value environment-protection flame-proof fiberglass reinforced plastic PA66/PPO alloy material is provided.
For achieving the above object, the technical scheme that the present invention takes is:
High CTI value, high GWIT value environment-protection flame-proof fiberglass reinforced plastic PA66/PPO alloy material, described alloy material comprises the feed composition of following weight percent content:
PA66 23%～41%，
PPO 22%～41%，
Compound flame redundant 6%～20%,
Antimonous oxide 3%～15%,
Glass fibre 20%～30%,
Compatilizer 2%～10%,
Oxidation inhibitor 0.1%～1%,
Oxide compound 0.1%～1%,
Described compound flame redundant is comprised of brominated Polystyrene, magnesium hypophosphite and talcum powder.
Described PA66 is polyhexamethylene adipamide, and the limiting viscosity of described PPO is 1.0 dl/g.
Described compound flame redundant is comprised of the feed composition of following weight percent content: brominated Polystyrene (being called for short BPS) 50%, magnesium hypophosphite 25%, talcum powder 25%.
Described glass fibre is the alkali free glass fibre that process through silane coupling agent on surface.
Described compatilizer is maleic anhydride graft PPO.
Described oxidation inhibitor is Hinered phenols antioxidant.
Described oxidation inhibitor is oxidation inhibitor 1330.
Described oxide compound is ferric oxide.
For realizing above-mentioned second object, the technical scheme that the present invention takes is:
A preparation method for high CTI value, high GWIT value environment-protection flame-proof fiberglass reinforced plastic PA66/PPO alloy material, comprises the steps:
(1) according to above-mentioned weight percent, take each raw material;
(2) the various raw materials that weigh up are put into high mixer, mix 2～5 minutes, discharging, then uses twin screw extruder extruding pelletization.
The processing temperature of described twin screw extruder is 240～260 ℃, and screw rod revolution is 30～40Hz.
Compared with prior art, the invention has the advantages that:
1, the present invention adopts BACN compound system, compares with traditional flame-retardant system, and in the situation that fire retardant percentage composition is identical, novel built system can make the GWIT value of material improve 50 ℃ to 100 ℃, can pass through 850 ℃ of glowing filaments;
2, can make the GWIT value of material obviously improve adding of glass fibre, compatilizer can improve the impact property of material, improves materials processing mobility, reduces frictional coefficient, improves slipping;
3, Hinered phenols antioxidant can improve alloy material in the antioxidant property of the course of processing and the ageing resistance in use procedure, adopts oxide compound as the auxiliary agent of carrying high CTI value;
4, the present invention is under specific processing conditions, and raw material is better dispersed, and the residence time is short, adopts and shears slightly weak combination, prevents that fire retardant from decomposing, thereby has guaranteed the steady quality of material; GWIT value and the CTI value of the alloy material preparing are higher, flame retardant effect is better, alloy material environmental protection, over-all properties is balanced, can be widely used in the product of the field of electronics such as Low-voltage Electronic capacitor case, load break switch, carbon brush supports, breaker of plastic casing.
Embodiment
Below embodiment provided by the invention is elaborated.
High CTI value of the present invention, high GWIT value environment-protection flame-proof fiberglass reinforced plastic PA66/PPO alloy material, described PA66 is commercially available polyhexamethylene adipamide; The limiting viscosity of described PPO is preferably 1.0 dl/g, can be also other value of 0.6～1.2 dl/g scope; Described compound flame redundant is comprised of brominated Polystyrene (being called for short BPS), magnesium hypophosphite and talcum powder, and weight percent content is preferably BPS 50%, magnesium hypophosphite 25%, talcum powder 25%, and this fire retardant can effectively improve the GWIT value of alloy material; Described glass fibre is preferably the alkali free glass fibre that process through silane coupling agent on surface, and glass fibre is added in silane coupling agent, and its surface is processed through silane coupling agent, and it can make the GWIT value of material obviously improve; Described compatilizer can improve the impact property of material, can be maleic anhydride grafted polystyrene, imide-modified vinylformic acid, maleic anhydride graft POE etc., is preferably maleic anhydride graft PPO; Described oxidation inhibitor is preferably the oxidation inhibitor 1330 in Hinered phenols antioxidant, can also be antioxidant 1010, antioxidant 300, thio-2 acid dibasic acid esters etc., all can block, suppress or delay polymkeric substance and be oxidized or autoxidation process, can improve the antioxidant property of alloy material in the course of processing and the ageing resistance in use procedure; Described oxide compound is as the auxiliary agent of carrying high CTI value, can be aluminum oxide, magnesium oxide etc., is preferably ferric oxide.
In the preparation process of PA66/PPO alloy material of the present invention, the various raw materials that weigh up are put into high mixer, mix 2～5 minutes, discharging, then uses twin screw extruder extruding pelletization; The processing temperature of described twin screw extruder is 240～260 ℃, and forcing machine comprises nine warm areas, wherein one section 240 ℃, and two sections 240 ℃, three sections 260 ℃, four sections 260 ℃, five sections 260 ℃, six sections 260 ℃, seven sections 260 ℃, eight sections 260 ℃, nine sections 240 ℃, screw rod revolution is 30～40Hz.
the preparation (one) of embodiment 1 PA66/PPO alloy material
The limiting viscosity of PPO is 1.0 dl/g, the raw material that compound flame redundant is BPS 50%, magnesium hypophosphite 25% and talcum powder 25% by weight percent content forms, glass fibre is the alkali free glass fibre that process through silane coupling agent on surface, compatilizer is maleic anhydride graft PPO, oxidation inhibitor is oxidation inhibitor 1330, and oxide compound is ferric oxide.
By following weight percent content, take each feed composition: PA66 23%, PPO 22%, compound flame redundant 20%, antimonous oxide 4%, glass fibre 20%, compatilizer 10%, oxidation inhibitor 0.1%, oxide compound 0.9%.Each raw material weighing up is put into high mixer, mix 2 minutes, discharging, then uses twin screw extruder extruding pelletization; The processing temperature of described twin screw extruder is 240～260 ℃, and forcing machine comprises nine warm areas, wherein one section 240 ℃, and two sections 240 ℃, three sections 260 ℃, four sections 260 ℃, five sections 260 ℃, six sections 260 ℃, seven sections 260 ℃, eight sections 260 ℃, nine sections 240 ℃, screw rod revolution is 30Hz.
the preparation (two) of embodiment 2 PA66/PPO alloy materials
The limiting viscosity of PPO is 0.6 dl/g, the raw material that compound flame redundant is BPS 50%, magnesium hypophosphite 25% and talcum powder 25% by weight percent content forms, glass fibre is the alkali free glass fibre that process through silane coupling agent on surface, compatilizer is maleic anhydride graft PPO, oxidation inhibitor is antioxidant 1010, and oxide compound is ferric oxide.
By following weight percent content, take each feed composition: PA66 41%, PPO 22%, compound flame redundant 6%, antimonous oxide 3%, glass fibre 20%, compatilizer 6%, oxidation inhibitor 1%, oxide compound 1%.Each raw material weighing up is put into high mixer, mix 5 minutes, discharging, then uses twin screw extruder extruding pelletization; The processing temperature of described twin screw extruder is 240～260 ℃, and forcing machine comprises nine warm areas, wherein one section 240 ℃, and two sections 240 ℃, three sections 260 ℃, four sections 260 ℃, five sections 260 ℃, six sections 260 ℃, seven sections 260 ℃, eight sections 260 ℃, nine sections 240 ℃, screw rod revolution is 35Hz.
the preparation (three) of embodiment 3 PA66/PPO alloy materials
The limiting viscosity of PPO is 1 dl/g, and the raw material that compound flame redundant is BPS 50%, magnesium hypophosphite 25% and talcum powder 25% by weight percent content forms, and compatilizer is maleic anhydride grafted polystyrene, and oxidation inhibitor is oxidation inhibitor 1330, and oxide compound is aluminum oxide.
By following weight percent content, take each feed composition: PA66 23%, PPO 23%, compound flame redundant 6%, antimonous oxide 15%, glass fibre 30%, compatilizer 2%, oxidation inhibitor 0.9%, oxide compound 0.1%.Each raw material weighing up is put into high mixer, mix 3 minutes, discharging, then uses twin screw extruder extruding pelletization; The processing temperature of described twin screw extruder is 240～260 ℃, and forcing machine comprises nine warm areas, wherein one section 240 ℃, and two sections 240 ℃, three sections 260 ℃, four sections 260 ℃, five sections 260 ℃, six sections 260 ℃, seven sections 260 ℃, eight sections 260 ℃, nine sections 240 ℃, screw rod revolution is 40Hz.
the preparation (four) of embodiment 4 PA66/PPO alloy materials
The limiting viscosity of PPO is 1 dl/g, the raw material that compound flame redundant is BPS 45%, magnesium hypophosphite 30% and talcum powder 25% by weight percent content forms, glass fibre is the alkali free glass fibre that process through silane coupling agent on surface, compatilizer is maleic anhydride graft PPO, oxidation inhibitor is oxidation inhibitor 1330, and oxide compound is ferric oxide.
By following weight percent content, take each feed composition: PA66 24%, PPO 30%, compound flame redundant 18%, antimonous oxide 4%, glass fibre 20%, compatilizer 3%, oxidation inhibitor 0.8%, oxide compound 0.2%.Each raw material weighing up is put into high mixer, mix 4 minutes, discharging, then uses twin screw extruder extruding pelletization; The processing temperature of described twin screw extruder is 240～260 ℃, and forcing machine comprises nine warm areas, wherein one section 240 ℃, and two sections 240 ℃, three sections 260 ℃, four sections 260 ℃, five sections 260 ℃, six sections 260 ℃, seven sections 260 ℃, eight sections 260 ℃, nine sections 240 ℃, screw rod revolution is 38Hz.
the preparation (five) of embodiment 5 PA66/PPO alloy materials
The limiting viscosity of PPO is 1.0 dl/g, the raw material that compound flame redundant is BPS 50%, magnesium hypophosphite 25% and talcum powder 25% by weight percent content forms, glass fibre is the alkali free glass fibre that process through silane coupling agent on surface, compatilizer is maleic anhydride graft PPO, oxidation inhibitor is antioxidant 300, and oxide compound is ferric oxide.
By following weight percent content, take each feed composition: PA66 23%, PPO 41%, compound flame redundant 7%, antimonous oxide 3%, glass fibre 23%, compatilizer 2%, oxidation inhibitor 0.5%, oxide compound 0.5%.Each raw material weighing up is put into high mixer, mix 5 minutes, discharging, then uses twin screw extruder extruding pelletization; The processing temperature of described twin screw extruder is 240～260 ℃, and forcing machine comprises nine warm areas, wherein one section 240 ℃, and two sections 240 ℃, three sections 260 ℃, four sections 260 ℃, five sections 260 ℃, six sections 260 ℃, seven sections 260 ℃, eight sections 260 ℃, nine sections 240 ℃, screw rod revolution is 30Hz.
the preparation (six) of embodiment 6 PA66/PPO alloy materials
The limiting viscosity of PPO is 1.0 dl/g, and the raw material that compound flame redundant is BPS 60%, magnesium hypophosphite 20% and talcum powder 20% by weight percent content forms, and compatilizer is imide-modified vinylformic acid, and oxidation inhibitor is oxidation inhibitor 1330, and oxide compound is magnesium oxide.
By following weight percent content, take each feed composition: PA66 30%, PPO 30%, compound flame redundant 6%, antimonous oxide 3%, glass fibre 25%, compatilizer 5%, oxidation inhibitor 0.7%, oxide compound 0.3%.Each raw material weighing up is put into high mixer, mix 4 minutes, discharging, then uses twin screw extruder extruding pelletization; The processing temperature of described twin screw extruder is 240～260 ℃, and forcing machine comprises nine warm areas, wherein one section 240 ℃, and two sections 240 ℃, three sections 260 ℃, four sections 260 ℃, five sections 260 ℃, six sections 260 ℃, seven sections 260 ℃, eight sections 260 ℃, nine sections 240 ℃, screw rod revolution is 40Hz.
the preparation (seven) of embodiment 7 PA66/PPO alloy materials
The limiting viscosity of PPO is 1.2 dl/g, the raw material that compound flame redundant is BPS 50%, magnesium hypophosphite 25% and talcum powder 25% by weight percent content forms, glass fibre is the alkali free glass fibre that process through silane coupling agent on surface, compatilizer is maleic anhydride graft PPO, oxidation inhibitor is oxidation inhibitor 1330, and oxide compound is ferric oxide.
By following weight percent content, take each feed composition: PA66 23%, PPO 22%, compound flame redundant 10%, antimonous oxide 9%, glass fibre 27%, compatilizer 8%, oxidation inhibitor 0.4%, oxide compound 0.6%.Each raw material weighing up is put into high mixer, mix 3 minutes, discharging, then uses twin screw extruder extruding pelletization; The processing temperature of described twin screw extruder is 240～260 ℃, and forcing machine comprises nine warm areas, wherein one section 240 ℃, and two sections 240 ℃, three sections 260 ℃, four sections 260 ℃, five sections 260 ℃, six sections 260 ℃, seven sections 260 ℃, eight sections 260 ℃, nine sections 240 ℃, screw rod revolution is 35Hz.
It should be noted that, glass fiber reinforced PA66/PPO alloy material that embodiment 1-7 is obtained carries out performance test, adopt ASTM standard, test result shows: the PA66/PPO alloy material of preparation has higher GWIT value and CTI value, and the flame retardant resistance of alloy material, tensile strength and flexural strength all meet the requirements.
embodiment 8～9 and comparative example 1～7
The limiting viscosity of PPO is 1.0 dl/g; The raw material that compound flame redundant is BPS 50%, magnesium hypophosphite 25% and talcum powder 25% by weight percent content forms; Common fire retardant can be triphenylphosphate, TDE, decabromodiphynly oxide, magnesium hydroxide, red phosphorus etc., and the present invention adopts TDE; Glass fibre is the alkali free glass fibre that process through silane coupling agent on surface; Compatilizer is maleic anhydride graft PPO; Oxidation inhibitor is oxidation inhibitor 1330; Oxide compound is ferric oxide.
By the weight percent content shown in table 1 (%), take each feed composition.Each raw material weighing up is put into high mixer, mix 5 minutes, discharging, then uses twin screw extruder extruding pelletization; The processing temperature of described twin screw extruder is 240～260 ℃, and forcing machine comprises nine warm areas, wherein one section 240 ℃, two sections 240 ℃, three sections 260 ℃, four sections 260 ℃, five sections 260 ℃, six sections 260 ℃, seven sections 260 ℃, eight sections 260 ℃, nine sections 240 ℃, screw host revolution is 35Hz, and feeding revolution is 13Hz.
Each composition of raw materials in table 1 embodiment 8～9 and comparative example 1～7
embodiment 10 performance tests
Adopt ASTM standard, the PA66/PPO alloy material that embodiment 8～9, comparative example 1～7 are prepared carries out performance test, and test result is as shown in table 2.
The performance test results of table 2 alloy material
Associative list 1 and table 2, as seen from the table, the present invention adopts BACN compound system, compares with traditional common fire retardant, and novel built fire retardant can effectively improve the GWIT value of material; Adding of alkali free glass fibre can make the GWIT value of alloy material obviously improve, and compatilizer can improve the impact property of material; Ferric oxide has considerable influence to carrying high CTI value.
GWIT value and the CTI value of alloy material of the present invention are higher, flame retardant effect is better, alloy material environmental protection, over-all properties is balanced, can be widely used in the product of the field of electronics such as Low-voltage Electronic capacitor case, load break switch, carbon brush supports, breaker of plastic casing.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, do not departing under the prerequisite of the inventive method; can also make some improvement and supplement, these improvement and supplement and also should be considered as protection scope of the present invention.

Claims (7)

1. high CTI value, high GWIT value environment-protection flame-proof fiberglass reinforced plastic PA66/PPO alloy material, is characterized in that, described alloy material comprises the feed composition of following weight percent content:
PA66 23%～41%，
PPO 22%～41%，
Compound flame redundant 6%～20%,
Antimonous oxide 3%～15%,
Glass fibre 20%～30%,
Compatilizer 2%～10%,
Oxidation inhibitor 0.1%～1%,
Oxide compound 0.1%～1%,
Described compound flame redundant is comprised of the feed composition of following weight percent content: brominated Polystyrene 50%, magnesium hypophosphite 25%, talcum powder 25%; Described glass fibre is the alkali free glass fibre that process through silane coupling agent on surface; Described oxide compound is ferric oxide.
2. high CTI value according to claim 1, high GWIT value environment-protection flame-proof fiberglass reinforced plastic PA66/PPO alloy material, is characterized in that, described PA66 is polyhexamethylene adipamide, and the limiting viscosity of described PPO is 1.0 dl/g.
3. high CTI value according to claim 1, high GWIT value environment-protection flame-proof fiberglass reinforced plastic PA66/PPO alloy material, is characterized in that, described compatilizer is maleic anhydride graft PPO.
4. high CTI value according to claim 1, high GWIT value environment-protection flame-proof fiberglass reinforced plastic PA66/PPO alloy material, is characterized in that, described oxidation inhibitor is Hinered phenols antioxidant.
5. high CTI value according to claim 4, high GWIT value environment-protection flame-proof fiberglass reinforced plastic PA66/PPO alloy material, is characterized in that, described oxidation inhibitor is oxidation inhibitor 1330.
6. a preparation method for high CTI value, high GWIT value environment-protection flame-proof fiberglass reinforced plastic PA66/PPO alloy material, is characterized in that, comprises the steps:
(1) according to weight percent claimed in claim 1, take each raw material;
(2) the various raw materials that weigh up are put into high mixer, mix 2～5 minutes, discharging, then uses twin screw extruder extruding pelletization.
7. preparation method according to claim 6, is characterized in that, the processing temperature of described twin screw extruder is 240～260 ℃, and screw rod revolution is 30～40Hz.
CN201210510322.1A 2012-12-04 2012-12-04 Environment-friendly and flame-retardant glass fiber reinforced PA (polyamide) 66/PPO (polyphenylene oxide) alloy material with high CTI (comparative tracking index) value and high GWIT (glow-wire ignition temperature) value and preparation method thereof Expired - Fee Related CN102964829B (en)

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