CN110698852B - Flame-retardant reinforced polyamide 6/polyphenyl ether composition and preparation method thereof - Google Patents

Flame-retardant reinforced polyamide 6/polyphenyl ether composition and preparation method thereof Download PDF

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CN110698852B
CN110698852B CN201911067885.6A CN201911067885A CN110698852B CN 110698852 B CN110698852 B CN 110698852B CN 201911067885 A CN201911067885 A CN 201911067885A CN 110698852 B CN110698852 B CN 110698852B
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CN110698852A (en
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王忠强
洪剑城
陈欣
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Guangdong Aldex New Material Co Ltd
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    • 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
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers

Abstract

The invention relates to a flame-retardant reinforced polyamide 6/polyphenyl ether composition and a preparation method thereof, wherein the flame-retardant reinforced polyamide 6/polyphenyl ether composition is prepared from the following raw materials: the low-viscosity polyamide 6 resin, the high-viscosity polyphenylene oxide resin, the low-viscosity polyphenylene oxide resin, the styrene-glycidyl methacrylate copolymer, toluene diisocyanate, hydrogenated styrene-isoprene copolymer grafted maleic anhydride, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, pentaerythritol zinc, a silane coupling agent, layered silicate, alkyl phosphinate, melamine polyphosphate and alkali-free glass fiber. The flame-retardant reinforced polyamide 6/polyphenyl ether composition has excellent mechanical property, processability and flame retardance, and can be applied to manufacturing of automobiles, electronic and electric elements and the like.

Description

Flame-retardant reinforced polyamide 6/polyphenyl ether composition and preparation method thereof
Technical Field
The invention relates to the field of materials, in particular to a flame-retardant reinforced polyamide 6/polyphenyl ether composition and a preparation method thereof.
Background
Polyamide 6(PA6) is a crystalline resin and is excellent in chemical resistance and processability, but has a large water absorption to cause a decrease in mechanical properties and a poor dimensional stability, while polyphenylene oxide (PPO) is an amorphous resin and has good mechanical properties and heat resistance but is poor in processability, chemical resistance and impact resistance. The polyamide 6 and the polyphenyl ether are prepared into the flame-retardant reinforced polyamide 6/polyphenyl ether composition, so that the defects of the polyamide 6 and the polyphenyl ether can be overcome, and the composition has the characteristics of high rigidity, small creep, high heat deformation temperature, good impact resistance and oil resistance and the like. From the microstructure, the flame-retardant reinforced polyamide 6/polyphenylene ether composition forms a sea-island structure, the polyamide 6 contributes to the composition with good solvent resistance, coating property and molding processability, and the polyphenylene ether contributes to the composition with good heat resistance, rigidity and dimensional stability. However, since crystalline PA6 and amorphous PPO are thermodynamically incompatible, resulting in too large a domain size of the dispersed phase of the blend and weak interfacial force, resulting in insufficient strength and toughness of the material, the key to the preparation of flame retardant reinforced polyamide 6/polyphenylene ether compositions lies in the compatibilization technique.
Because the dielectric constant of the polyphenyl ether is very low and hardly influenced by temperature and humidity, the polyphenyl ether can be widely used for producing electric products, particularly high-voltage-resistant and outdoor parts, such as various junction boxes used in the photovoltaic industry, line output transformers in color televisions and the like, and the polyphenyl ether is required to have excellent flame retardant property. With the release of environmental regulations such as the directive on scrap electronic and electrical equipment (WEEE) and the directive on limiting the use of certain harmful components in electronic and electrical equipment (ROHS) in the European Union, research and development of flame-retardant reinforced polyamide 6/polyphenylene oxide compositions meeting the international flame-retardant and environmental-protection requirements have become a research hotspot in the field of plastic modification.
Currently, some studies on toughening compatibilization and flame retardance of PA6/PPO systems are made in the prior art, such as: chinese patent CN102732003A discloses a flame-retardant glass fiber reinforced PA6/PPO alloy composition and a preparation method thereof, wherein the composition comprises the following components in percentage by weight: PA 620-41%, PPO 20-41%, compatilizer 0-10%, compound flame-retardant master batch 0-15%, glass fiber 20-40%, antioxidant 0.1-1%, lubricating dispersant 0.1-1%; chinese patent CN103146176A discloses a PPO/PA alloy modified compatibilizer and a PPO/PA alloy, wherein the compatibilizer is a graft copolymer of polyphenyl ether, glycidyl methacrylate and styrene, and the PPO/PA alloy using the compatibilizer comprises the following components in parts by weight: 50-59.5% of polyphenyl ether, 31.5-40.4% of nylon, 0.1-18% of compatibilizer and 0.1-0.5% of antioxidant; chinese patent CN108587108A discloses a high impact PPO/PA alloy material and a preparation method thereof, wherein the PPO/PA alloy material is composed of PPO resin, PA resin, a compatilizer, a flexibilizer and an antioxidant, and specifically comprises the following raw materials in parts by weight: 30-70 parts of PPO resin, 30-70 parts of PA resin, 3-10 parts of compatilizer, 5-15 parts of toughening agent and 0.1-1 part of antioxidant, wherein the compatilizer is PPO-g-MAH, and the toughening agent is SEBS-g-MAH; chinese patent CN108276758A discloses a high-filling PPO/PA alloy material with a good surface and a preparation method thereof, wherein the high-filling PPO/PA alloy material is composed of eight components of PPO resin, PA resin, PS resin, carbon fiber, a compatilizer, a toughening agent, a flow modifier and an antioxidant; according to the weight ratio: 10-50 parts of PPO resin, 10-60 parts of PA resin, 5-20 parts of PS resin, 20-40 parts of carbon fiber, 3-10 parts of compatilizer, 5-15 parts of toughening agent, 0.2-2 parts of flow modifier and 0.1-1 part of antioxidant, wherein the compatilizer is PPO-g-MAH, and the toughening agent is one or more of SEBS, SEBS-g-MAH and POE-g-MAH; chinese patent CN107236280A discloses a conductive heat-resistant PPO/PPA flame-retardant composition and a preparation method thereof, wherein the composition comprises the following components in percentage by mass: 10-40% of PPO; PPA 10-45%; 10-35% of a conductive agent; 3-8% of a compatilizer; 10-20% of a flame retardant; 0.3-0.8% of antioxidant, wherein the conductive agent is a mixture composed of graphene, conductive carbon black and carbon fibers, the compatilizer is at least one of PPO-g-MAH and SEBS-g-MAH, and the flame retardant is at least one of resorcinol-diphenyl diphosphate, melamine urate and triphenylphosphine; chinese patent CN109438959A discloses a flame-retardant heat-resistant PPO alloy, which is prepared from the following raw materials in parts by weight: 55-85 parts of PPO resin and 15-45 parts of PA6 resin, wherein the sum of the parts by weight of PPO and PA6 is 100 parts, 5-35 parts of compound powder, 10-16 parts of flame retardant, 10-16 parts of compatilizer and 0.4-1 part of antioxidant; chinese patent CN104962072A discloses a flame-retardant PPO/PA alloy, which comprises the following raw materials in parts by weight: 30-50 parts of PPO resin, 40-50 parts of PA resin, 3-5 parts of toughening agent, 2-4 parts of compatilizer and 12-18 parts of halogen-free flame retardant; chinese patent CN101302336A discloses a flame-retardant PPO/PA alloy and a preparation method thereof, wherein the flame-retardant PPO/PA alloy comprises the following components in parts by weight: 30-50% of PPO, 78-60% of PA10, 3-15% of toughening agent, 5-15% of composite flame retardant, 3-10% of compatilizer and 0.5-2% of other auxiliary agents; chinese patent CN103044895A discloses a high glow wire halogen-free flame-retardant reinforced PPO/PA alloy and a preparation method thereof, wherein the alloy comprises the following components in percentage by weight: PPO: 10-30%, PA: 10-50%, compatibilizer: 3-10%, phosphorus flame retardant: 5-15%, intumescent flame retardant: 2-10%, smoke suppressant: 0.2-3%, alkali-free glass fiber: 10-40%, toughening agent: 2-10%, char-forming agent: 0.2-2%, antioxidant 0.2-0.5%, lubricant 0.2-1.0%; chinese patent CN103421245A discloses an enhanced halogen-free flame-retardant PP/PPO alloy and a preparation method thereof, belonging to the technical field of high polymer materials, wherein the alloy comprises the following raw materials in parts by weight: the anti-corrosion coating comprises, by weight, 70-90 parts of PP, 50-80 parts of PPO, 10-18 parts of magnesium borate whisker, 8-12 parts of ammonium polyphosphate, 6-10 parts of melamine phosphate, 5-8 parts of magnesium hydroxide whisker, 5-20 parts of a compatilizer, 1-2 parts of an antioxidant and 0.5-1.4 parts of a lubricant.
Disclosure of Invention
Based on the above, the invention aims to provide a flame-retardant reinforced polyamide 6/polyphenyl ether composition with excellent mechanical property, processability and flame retardance, which can be applied to manufacturing of automobiles, electronic and electric appliance components and the like.
In order to achieve the purpose, the invention adopts the following scheme:
the flame-retardant reinforced polyamide 6/polyphenyl ether composition is prepared from the following raw materials in parts by weight:
60-80 parts of low-viscosity polyamide 6 resin (PA6),
10-20 parts of high-viscosity polyphenylene oxide resin (PPO),
10-20 parts of low-viscosity polyphenylene oxide (PPO),
the sum of the parts by weight of the low-viscosity polyamide 6 resin, the high-viscosity polyphenyl ether resin and the low-viscosity polyphenyl ether resin is 100 parts,
Figure BDA0002259973250000031
the intrinsic viscosity of the low-viscosity polyamide 6 resin is 1.01-1.33 dL/g; the intrinsic viscosity of the high-viscosity polyphenyl ether resin is 0.45-0.51 dL/g; the intrinsic viscosity of the low-viscosity polyphenyl ether resin is 0.33-0.37 dL/g;
the silane coupling agent is at least one of gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, gamma-aminopropylmethyldiethoxysilane and aniline methyltriethoxysilane;
the layered silicate is at least one of montmorillonite, kaolin, hydrotalcite and sepiolite;
the alkyl phosphinate is at least one of aluminum diethyl phosphinate, zinc diethyl phosphinate, calcium diethyl phosphinate, magnesium diethyl phosphinate, aluminum dipropyl phosphinate, aluminum isobutyl phosphinate, aluminum methyl ethyl phosphinate and aluminum phenyl phosphinate;
the melamine polyphosphate is at least one of melamine aluminum polyphosphate, melamine zinc polyphosphate and melamine magnesium polyphosphate.
In some embodiments, the flame retardant reinforced polyamide 6/polyphenylene ether composition is prepared from the following raw materials in parts by weight:
64-76 parts of low-viscosity polyamide 6 resin (PA6),
12-18 parts of high-viscosity polyphenylene oxide resin (PPO),
12-18 parts of low-viscosity polyphenylene oxide (PPO),
the sum of the parts by weight of the low-viscosity polyamide 6 resin, the high-viscosity polyphenyl ether resin and the low-viscosity polyphenyl ether resin is 100 parts,
Figure BDA0002259973250000041
in some of the embodiments, the flame retardant reinforced polyamide 6/polyphenylene ether composition is further preferably prepared from the following raw materials in parts by weight:
68-72 parts of low-viscosity polyamide 6 resin (PA6),
14-16 parts of high-viscosity polyphenylene oxide resin (PPO),
14-16 parts of low-viscosity polyphenylene oxide (PPO),
the sum of the parts by weight of the low-viscosity polyamide 6 resin, the high-viscosity polyphenyl ether resin and the low-viscosity polyphenyl ether resin is 100 parts,
Figure BDA0002259973250000042
Figure BDA0002259973250000051
in some embodiments, the mass fraction of the glycidyl methacrylate in the copolymer of styrene and glycidyl methacrylate is 2 to 4 wt%.
In some of the embodiments, the maleic anhydride grafting ratio of the hydrogenated styrene-isoprene copolymer grafted maleic anhydride is 0.8 to 1.5 wt%.
In some of these embodiments, the alkali-free glass fibers have a length of 2 to 4mm and a diameter of 9 to 11 μm.
In some of these embodiments, the silane coupling agent is at least one of gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane; the phyllosilicate is montmorillonite; the alkyl phosphinate is aluminum diethyl phosphinate; the melamine polyphosphate is melamine aluminum polyphosphate.
Another object of the present invention is to provide a method for preparing a flame retardant reinforced polyamide 6/polyphenylene ether composition.
The preparation method of the flame-retardant reinforced polyamide 6/polyphenyl ether composition comprises the following steps:
(1) drying the low-viscosity polyamide 6 resin at the temperature of 110-140 ℃ for 4-8 hours, drying the high-viscosity polyphenylene ether resin and the low-viscosity polyphenylene ether resin at the temperature of 80-110 ℃ for 4-8 hours, cooling, and adding the cooled low-viscosity polyamide 6 resin, the high-viscosity polyphenylene ether resin, the low-viscosity polyphenylene ether resin, the N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, pentaerythritol zinc, a silane coupling agent, a layered silicate, an alkyl phosphinate and melamine polyphosphate into a stirrer for mixing;
(2) adding the styrene-glycidyl methacrylate copolymer, toluene diisocyanate, hydrogenated styrene-isoprene copolymer grafted maleic anhydride and alkali-free glass fiber into another stirrer for mixing;
(3) adding the mixed material obtained in the step (1) into a parallel double-screw extruder through a feeder, adding the mixed material obtained in the step (2) into the parallel double-screw extruder (totally eight zones) (for example, a fourth zone) in the lateral direction (for example, the fourth zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature of the first zone is 245-265 ℃, the temperature of the second zone is 250-270 ℃, the temperature of the third zone is 250-270 ℃, the temperature of the fourth zone is 255-275 ℃, the temperature of the fifth zone is 255-275 ℃, the temperature of the sixth zone is 250-270 ℃, the temperature of the seventh zone is 250-270 ℃, the temperature of the eighth zone is 250-270 ℃, the temperature of the die head is 250-270 ℃, and the rotating speed of the screw is 200-600 rpm.
In some embodiments, in the step (1), the low-viscosity polyamide 6 resin is dried at a temperature of 120-130 ℃ for 4-6 hours, and the high-viscosity polyphenylene ether resin and the low-viscosity polyphenylene ether resin are dried at a temperature of 90-100 ℃ for 4-6 hours; the process parameters in the step (3) comprise: the temperature of the first zone is 250-260 ℃, the temperature of the second zone is 255-265 ℃, the temperature of the third zone is 255-265 ℃, the temperature of the fourth zone is 260-270 ℃, the temperature of the fifth zone is 260-270 ℃, the temperature of the sixth zone is 255-265 ℃, the temperature of the seventh zone is 255-265 ℃, the temperature of the eighth zone is 255-265 ℃, the temperature of the die head is 255-265 ℃ and the rotation speed of the screw is 300-500 rpm.
In some of these embodiments, the screw shape of the parallel twin screw extruder is a single thread; the ratio L/D of the length L of the screw to the diameter D of the screw is 35 to 50; the screw is provided with more than 1 (including 1) meshing block area and more than 1 (including 1) reverse thread area.
In some of these embodiments, the ratio L/D of the length L of the screw to the diameter D of the screw is 35 to 45; and 2 meshing block areas and 1 reverse thread area are arranged on the screw rod.
In some embodiments, in step (1) and/or step (2), the stirrer is a high-speed stirrer with a rotation speed of 500-.
The principle of the flame-retardant reinforced polyamide 6/polyphenyl ether composition is as follows:
in order to solve the defects of poor compatibility, processability and flame retardant property of PA6 and PPO in the flame-retardant reinforced polyamide 6/polyphenylene oxide composition, the invention improves the compatibility between PA6 and PPO by adding a copolymer of styrene and glycidyl methacrylate, toluene diisocyanate and hydrogenated styrene-isoprene copolymer grafted maleic anhydride, simultaneously improves the notch impact strength of the PA6/PPO composition by the hydrogenated styrene-isoprene copolymer grafted maleic anhydride, ensures the mechanical property of the PA6/PPO composition by adding high-viscosity polyphenylene oxide resin, ensures the processability of the PA6/PPO composition by adding low-viscosity polyphenylene oxide resin and low-viscosity polyamide 6 resin, improves the flame retardant property of the PA6/PPO composition by compounding pentaerythritol zinc, phyllosilicate, alkyl phosphinate and melamine polyphosphate, meanwhile, alkali-free glass fiber is used for improving the mechanical property of the PA6/PPO composition.
The styrene-glycidyl methacrylate copolymer, the toluene diisocyanate and the hydrogenated styrene-isoprene copolymer grafted maleic anhydride adopted by the invention can effectively improve the interfacial adhesion between PA6 and PPO and improve the compatibility between the PA6 and the PPO. The styrene structural unit in the copolymer of styrene and glycidyl methacrylate has good compatibility with PPO, and the epoxy group of glycidyl methacrylate can react with the terminal amino group of PA6 and the terminal hydroxyl group of PPO, so that the compatibility between PA6 and PPO is improved; the isocyanate group of the toluene diisocyanate can react with the terminal amino group and the terminal carboxyl group of PA6 and the terminal hydroxyl group of PPO, so that the compatibility between PA6 and PPO is improved; the styrene structural unit in the hydrogenated styrene-isoprene copolymer grafted maleic anhydride has good compatibility with PPO, and the anhydride group of the maleic anhydride can react with the terminal amino group of PA6 and the terminal hydroxyl group of PPO, so that the compatibility between PA6 and PPO is improved. In addition, styrene and glycidyl methacrylate copolymer, toluene diisocyanate, hydrogenated styrene-isoprene copolymer grafted maleic anhydride can react with a silane coupling agent, so that the interfacial bonding force and compatibility of pentaerythritol zinc, phyllosilicate, alkyl phosphinate and melamine polyphosphate with polyamide resin and polyphenylene oxide resin are improved, and the influence of the interfacial bonding force and compatibility on the mechanical property of the PA6/PPO composition is reduced.
The melting point of N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide adopted by the invention is 272 ℃, the boiling point is more than 360 ℃, the thermal stability in the blending process of PA6 and PPO is better, the amide group can react with the end group of PA6 resin to improve the compatibility, and the hindered piperidyl can provide the antioxidation and improve the dyeing property of the copolymer.
The bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate adopted by the invention has the melting point of 239 ℃ and the thermal decomposition temperature of over 350 ℃, has good heat resistance and hydrolysis resistance, can provide excellent color stability and melt stability for the blending process of PA6 and PPO, can prevent thermal degradation of PA6 and PPO in the high-temperature process, inhibits thermo-oxidative discoloration caused by long time, and also provides nitrogen for nitrogenOxide (NO)x) Color stability in gas environment, and prevention of discoloration of fumigant.
The pentaerythritol zinc adopted by the invention has the functions of lubrication and thermal stabilization, and simultaneously, when the pentaerythritol zinc is used as a thermal stabilizer alone, compared with a common zinc-containing compound (such as zinc oxide), the zinc-containing compound can effectively reduce the occurrence probability of zinc burning in the blending process.
The invention adopts silane coupling agents, preferably gamma-aminopropyltriethoxysilane and gamma-aminopropyltrimethoxysilane, which all contain amino, and the auxiliary agents can react with the end group of polyamide resin, styrene and glycidyl methacrylate copolymer, toluene diisocyanate and hydrogenated styrene-isoprene copolymer grafted maleic anhydride, so as to further improve the interfacial bonding force and compatibility of pentaerythritol zinc, phyllosilicate, alkyl phosphinate and melamine polyphosphate with polyamide resin and polyphenylene oxide resin, reduce the influence of the interfacial bonding force and compatibility on the mechanical properties of the PA6/PPO composition, improve the interfacial bonding force and compatibility of alkali-free glass fiber with polyphenylene oxide resin and polyamide resin, and improve the mechanical properties of the PPO/PA6 composition.
The flame retardant phyllosilicate, the alkyl phosphinate, the melamine polyphosphate and the pentaerythritol zinc can form a synergistic effect with one another. The phyllosilicate and the pentaerythritol zinc can promote the surface of the material to form carbon, a carbonization layer is added, the carbon layer structure is compact and hard, good heat and gas resistance and insulation effects are exerted, the phyllosilicate and the pentaerythritol zinc have the capability of capturing free radicals at high temperature, the thermal degradation of a polymer matrix is inhibited, the free radicals generated during combustion are reduced, and the degradation rate and the heat release rate of the polymer are reduced; the alkyl phosphinate mainly plays a role in inhibiting flame in a gas phase, and the melamine polyphosphate plays a role in diluting fuel and a solid-phase phosphorus layer barrier, so that the phosphorus-nitrogen synergistic enhancement flame retardant effect between the alkyl phosphinate and the melamine polyphosphate is obvious.
The length and diameter of the alkali-free glass fibers have a great influence on the mechanical properties and appearance of the PA6/PPO composition. The longer the alkali-free glass fiber is, the higher the tensile property of the resin composite material is, and the possibility of exposing the glass fiber is increased; the smaller the diameter of the alkali-free glass fiber, the higher the tensile strength, but the higher the cost of its manufacture, and the more coupling agent required per unit area. Therefore, the selection of proper length and diameter of the alkali-free glass fiber is important for preparing PA6/PPO composition with excellent performance and high cost performance. The alkali-free glass fiber is preferably 2-4 mm long and 9-11 μm in diameter, so that the PPO/PA6 composition has better mechanical property and higher cost performance.
Compared with the prior art, the invention has the following beneficial effects:
aiming at the defects of poor compatibility, processability and flame retardant property of PA6 and PPO in the existing flame-retardant reinforced polyamide 6/polyphenyl ether composition, the compatibility between PA6 and PPO is improved by adding a copolymer of styrene and glycidyl methacrylate, toluene diisocyanate and hydrogenated styrene-isoprene copolymer grafted maleic anhydride, the toughness of the flame-retardant reinforced polyamide 6/polyphenyl ether composition is improved by the hydrogenated styrene-isoprene copolymer grafted maleic anhydride, and meanwhile, the mechanical property and the processability of the flame-retardant reinforced polyamide 6/polyphenyl ether composition are ensured by compounding high-viscosity and low-viscosity polyphenyl ether resin and low-viscosity polyamide 6 resin, and the mechanical property of the flame-retardant reinforced polyamide 6/polyphenyl ether composition is ensured by alkali-free glass fiber, n, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate and pentaerythritol zinc are compounded to improve the yellowing phenomenon and the thermal stability in the blending processing process of the flame-retardant reinforced polyamide 6/polyphenyl ether composition, pentaerythritol zinc, layered silicate, alkyl phosphinate and melamine polyphosphate are compounded to improve the flame-retardant property of the PA6/PPO composition, and the raw material components are mutually matched to ensure that the prepared flame-retardant reinforced polyamide 6/polyphenyl ether composition has excellent mechanical property, processing property and flame-retardant property, and can be applied to manufacturing automobiles, electronic and electric appliance elements and the like.
The preparation method of the flame-retardant reinforced polyamide 6/polyphenyl ether composition provided by the invention has the advantages of simple process, easiness in control and low requirement on equipment, and the used equipment is general polymer processing equipment, so that the investment is low, and the industrial production is facilitated.
Drawings
FIG. 1 is a flow chart of a process for preparing a flame retardant reinforced polyamide 6/polyphenylene ether composition according to an embodiment of the present invention.
Detailed Description
In order to further understand the features and technical means of the present invention and achieve the specific objects and functions, the advantages and spirit of the present invention are further illustrated by the following embodiments.
The reaction mechanism of the flame-retardant reinforced polyamide 6/polyphenylene ether composition according to an embodiment of the present invention is as follows (see fig. 1 for a flow chart of the preparation process):
Figure BDA0002259973250000091
mechanism of reaction
As can be seen from the reaction formula, the epoxy group of the copolymer of styrene and glycidyl methacrylate can chemically react with the terminal amino group of PA6 and the terminal hydroxyl group of PPO, so that the compatibility between PA6 and PPO is improved; the isocyanate group of the toluene diisocyanate can react with the terminal amino group and the terminal carboxyl group of PA6 and the terminal hydroxyl group of PPO, so that the compatibility between PA6 and PPO is improved; anhydride groups in the hydrogenated styrene-isoprene copolymer grafted maleic anhydride can react with terminal amino groups of PA6 and terminal hydroxyl groups of PPO, so that the compatibility between PA6 and PPO is improved.
The examples of the invention and the comparative examples used the following raw materials:
low-viscosity polyamide 6 resin with the intrinsic viscosity of 1.17dL/g, and is selected from Shanyang Ba Ling petrochemical company, Hunan;
low-viscosity polyamide 6 resin with the intrinsic viscosity of 1.05dL/g and selected from Hunan Yueyangba Ling petrochemical company Limited;
low-viscosity polyamide 6 resin with the intrinsic viscosity of 0.97dL/g, and is selected from Shanyang Ba Ling petrochemical company, Hunan;
high viscosity polyphenylene ether resin with intrinsic viscosity of 0.48dL/g, selected from Nantong star synthetic materials GmbH;
high viscosity polyphenylene ether resin with intrinsic viscosity of 0.46dL/g, selected from Nantong star synthetic materials GmbH;
high viscosity polyphenylene ether resin with intrinsic viscosity of 0.55dL/g, selected from Nantong star synthetic materials GmbH;
low viscosity polyphenylene ether resin with intrinsic viscosity of 0.35dL/g, selected from Nantong star synthetic materials GmbH;
low viscosity polyphenylene ether resin with intrinsic viscosity of 0.34dL/g, selected from Nantong star synthetic materials GmbH;
low viscosity polyphenylene ether resin with intrinsic viscosity of 0.28dL/g, selected from Nantong star synthetic materials GmbH;
a copolymer of styrene and glycidyl methacrylate, the mass fraction of Glycidyl Methacrylate (GMA) being 3% by weight, selected from sigma aldrich trade ltd;
toluene diisocyanate selected from the group consisting of national pharmaceutical group chemical agents;
the hydrogenated styrene-isoprene copolymer was grafted with maleic anhydride, the maleic anhydride grafting ratio was 1.2 wt%, and was selected from the group consisting of the company clony, japan;
n, N' -bis (2,2,6, 6-tetramethyl-4-piperidinyl) -1, 3-benzenedicarboxamide, selected from Toxongitai chemical Co., Ltd;
bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate selected from Shanghai Yaozao Fine chemical Co., Ltd;
pentaerythritol zinc selected from Zhaoqing Sendeli chemical industry Co., Ltd;
gamma-aminopropyltriethoxysilane selected from Hubei Wuda organosilicon New materials GmbH;
gamma-aminopropyltrimethoxysilane selected from the group consisting of Hubei Wuda Silicone New materials GmbH;
montmorillonite selected from Zhejiang Fenghong New materials GmbH;
aluminum diethylphosphinate selected from Jiangsu Risk New materials, Inc.;
melamine aluminium polyphosphate, selected from fine chemical research and design institute of Sichuan province;
alkali-free glass fibers selected from the group consisting of China megalithic corporation, 3mm in length, and 10 μm in diameter;
hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride, selected from Shenyangtotong plastics Co.
The present invention will be described in detail with reference to specific examples.
Example 1:
the flame-retardant reinforced polyamide 6/polyphenylene ether composition is prepared from the following raw materials in parts by weight:
60 parts of low-viscosity polyamide 6 resin (the intrinsic viscosity is 1.17dL/g),
20 parts of high-viscosity polyphenylene ether resin (the intrinsic viscosity is 0.48dL/g),
20 parts of low-viscosity polyphenylene ether resin (the intrinsic viscosity is 0.35dL/g),
the sum of the parts by weight of the low-viscosity polyamide 6 resin, the high-viscosity polyphenyl ether resin and the low-viscosity polyphenyl ether resin is 100 parts,
Figure BDA0002259973250000111
the preparation method of the flame-retardant reinforced polyamide 6/polyphenyl ether composition comprises the following steps:
(1) drying the low-viscosity polyamide 6 resin at the temperature of 110 ℃ for 8 hours, drying the high-viscosity polyphenylene ether resin and the low-viscosity polyphenylene ether resin at the temperature of 80 ℃ for 8 hours, cooling, and adding the cooled low-viscosity polyamide 6 resin, the cooled high-viscosity polyphenylene ether resin, the cooled low-viscosity polyphenylene ether resin, the cooled N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, pentaerythritol zinc, gamma-aminopropyltriethoxysilane, montmorillonite, aluminum diethylphosphinate and melamine polyphosphate into a high-speed stirrer (the rotating speed is 1000 revolutions per minute) for mixing;
(2) adding the styrene-glycidyl methacrylate copolymer, toluene diisocyanate, hydrogenated styrene-isoprene copolymer grafted maleic anhydride and alkali-free glass fiber into another high-speed stirrer (the rotating speed is 1000 rpm) for mixing;
(3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into the side direction (the fourth zone) of the parallel double-screw extruder (total eight zones) for melt extrusion and granulation, wherein the process parameters are as follows: the temperature in the first zone was 245 ℃, the temperature in the second zone was 250 ℃, the temperature in the third zone was 250 ℃, the temperature in the fourth zone was 255 ℃, the temperature in the fifth zone was 255 ℃, the temperature in the sixth zone was 250 ℃, the temperature in the seventh zone was 250 ℃, the temperature in the eighth zone was 250 ℃, the temperature of the die head was 250 ℃ and the screw speed was 200 rpm.
The screw of the parallel double-screw extruder is in a single-thread shape, the ratio L/D of the length L and the diameter D of the screw is 35, and the screw is provided with 2 meshing block areas and 1 back-thread area.
Example 2:
the flame-retardant reinforced polyamide 6/polyphenylene ether composition is prepared from the following raw materials in parts by weight:
80 parts of low-viscosity polyamide 6 resin (the intrinsic viscosity is 1.05dL/g),
10 parts of high-viscosity polyphenylene ether resin (the intrinsic viscosity is 0.46dL/g),
10 parts of low-viscosity polyphenylene ether resin (the intrinsic viscosity is 0.34dL/g),
the sum of the parts by weight of the low-viscosity polyamide 6 resin, the high-viscosity polyphenyl ether resin and the low-viscosity polyphenyl ether resin is 100 parts,
Figure BDA0002259973250000121
the preparation method of the flame-retardant reinforced polyamide 6/polyphenyl ether composition comprises the following steps:
(1) drying the low-viscosity polyamide 6 resin at the temperature of 140 ℃ for 4 hours, drying the high-viscosity polyphenylene ether resin and the low-viscosity polyphenylene ether resin at the temperature of 110 ℃ for 4 hours, cooling, and adding the cooled low-viscosity polyamide 6 resin, the cooled high-viscosity polyphenylene ether resin, the cooled low-viscosity polyphenylene ether resin, the cooled N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, pentaerythritol zinc, gamma-aminopropyltrimethoxysilane, montmorillonite, aluminum diethylphosphinate and melamine aluminum polyphosphate into a high-speed stirrer (the rotating speed is 1000 revolutions per minute) for mixing;
(2) adding the styrene-glycidyl methacrylate copolymer, toluene diisocyanate, hydrogenated styrene-isoprene copolymer grafted maleic anhydride and alkali-free glass fiber into another high-speed stirrer (the rotating speed is 1000 rpm) for mixing;
(3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into the side direction (the fourth zone) of the parallel double-screw extruder (total eight zones) for melt extrusion and granulation, wherein the process parameters are as follows: the temperature in the first zone was 265 deg.C, the temperature in the second zone was 270 deg.C, the temperature in the third zone was 270 deg.C, the temperature in the fourth zone was 275 deg.C, the temperature in the fifth zone was 275 deg.C, the temperature in the sixth zone was 270 deg.C, the temperature in the seventh zone was 270 deg.C, the temperature in the eighth zone was 270 deg.C, the temperature in the die head was 270 deg.C, and the screw speed was 600 rpm.
The screw of the parallel double-screw extruder is in a single-thread shape, the ratio L/D of the length L and the diameter D of the screw is 50, and the screw is provided with 2 meshing block areas and 1 back-thread area.
Example 3:
the flame-retardant reinforced polyamide 6/polyphenylene ether composition is prepared from the following raw materials in parts by weight:
64 parts of low-viscosity polyamide 6 resin (the intrinsic viscosity is 1.17dL/g),
18 parts of high-viscosity polyphenylene ether resin (the intrinsic viscosity is 0.48dL/g),
18 parts of low-viscosity polyphenylene ether resin (the intrinsic viscosity is 0.35dL/g),
the sum of the parts by weight of the low-viscosity polyamide 6 resin, the high-viscosity polyphenyl ether resin and the low-viscosity polyphenyl ether resin is 100 parts,
Figure BDA0002259973250000131
Figure BDA0002259973250000141
the preparation method of the flame-retardant reinforced polyamide 6/polyphenyl ether composition comprises the following steps:
(1) drying the low-viscosity polyamide 6 resin at the temperature of 120 ℃ for 6 hours, drying the high-viscosity polyphenylene ether resin and the low-viscosity polyphenylene ether resin at the temperature of 90 ℃ for 6 hours, cooling, and adding the cooled low-viscosity polyamide 6 resin, the cooled high-viscosity polyphenylene ether resin, the cooled low-viscosity polyphenylene ether resin, the cooled N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, pentaerythritol zinc, gamma-aminopropyltriethoxysilane, montmorillonite, aluminum diethylphosphinate and melamine polyphosphate into a high-speed stirrer (the rotating speed is 1000 revolutions per minute) for mixing;
(2) adding the styrene-glycidyl methacrylate copolymer, toluene diisocyanate, hydrogenated styrene-isoprene copolymer grafted maleic anhydride and alkali-free glass fiber into another high-speed stirrer (the rotating speed is 1000 rpm) for mixing;
(3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into the side direction (the fourth zone) of the parallel double-screw extruder (total eight zones) for melt extrusion and granulation, wherein the process parameters are as follows: the temperature in the first zone was 250 deg.C, the temperature in the second zone was 255 deg.C, the temperature in the third zone was 255 deg.C, the temperature in the fourth zone was 260 deg.C, the temperature in the fifth zone was 260 deg.C, the temperature in the sixth zone was 255 deg.C, the temperature in the seventh zone was 255 deg.C, the temperature in the eighth zone was 255 deg.C, the temperature in the die head was 255 deg.C, and the screw speed was 300 rpm.
The screw of the parallel double-screw extruder is in a single-thread shape, the ratio L/D of the length L and the diameter D of the screw is 35, and the screw is provided with 2 meshing block areas and 1 back-thread area.
Example 4:
the flame-retardant reinforced polyamide 6/polyphenylene ether composition is prepared from the following raw materials in parts by weight:
76 parts of low-viscosity polyamide 6 resin (the intrinsic viscosity is 1.17dL/g),
12 parts of high-viscosity polyphenylene ether resin (the intrinsic viscosity is 0.48dL/g),
12 parts of low-viscosity polyphenylene ether resin (the intrinsic viscosity is 0.35dL/g),
the sum of the parts by weight of the low-viscosity polyamide 6 resin, the high-viscosity polyphenyl ether resin and the low-viscosity polyphenyl ether resin is 100 parts,
Figure BDA0002259973250000151
the preparation method of the flame-retardant reinforced polyamide 6/polyphenyl ether composition comprises the following steps:
(1) drying the low-viscosity polyamide 6 resin at 130 ℃ for 4 hours, drying the high-viscosity polyphenylene ether resin and the low-viscosity polyphenylene ether resin at 100 ℃ for 4 hours, cooling, and adding the cooled low-viscosity polyamide 6 resin, the cooled high-viscosity polyphenylene ether resin, the cooled low-viscosity polyphenylene ether resin, the cooled N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, pentaerythritol zinc, gamma-aminopropyltriethoxysilane, montmorillonite, aluminum diethylphosphinate and melamine polyphosphate into a high-speed stirrer (the rotating speed is 1000 revolutions per minute) for mixing;
(2) adding the styrene-glycidyl methacrylate copolymer, toluene diisocyanate, hydrogenated styrene-isoprene copolymer grafted maleic anhydride and alkali-free glass fiber into another high-speed stirrer (the rotating speed is 1000 rpm) for mixing;
(3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into the side direction (the fourth zone) of the parallel double-screw extruder (total eight zones) for melt extrusion and granulation, wherein the process parameters are as follows: the temperature in the first zone was 260 ℃, the temperature in the second zone was 265 ℃, the temperature in the third zone was 265 ℃, the temperature in the fourth zone was 270 ℃, the temperature in the fifth zone was 270 ℃, the temperature in the sixth zone was 265 ℃, the temperature in the seventh zone was 265 ℃, the temperature in the eighth zone was 265 ℃, the temperature in the die head was 265 ℃ and the screw speed was 500 rpm.
The screw of the parallel double-screw extruder is in a single-thread shape, the ratio L/D of the length L and the diameter D of the screw is 45, and the screw is provided with 2 meshing block areas and 1 reverse-thread area.
Example 5:
the flame-retardant reinforced polyamide 6/polyphenylene ether composition is prepared from the following raw materials in parts by weight:
68 parts of low-viscosity polyamide 6 resin (the intrinsic viscosity is 1.17dL/g),
16 parts of high-viscosity polyphenylene ether resin (the intrinsic viscosity is 0.48dL/g),
16 parts of low-viscosity polyphenylene ether resin (the intrinsic viscosity is 0.35dL/g),
the sum of the parts by weight of the low-viscosity polyamide 6 resin, the high-viscosity polyphenyl ether resin and the low-viscosity polyphenyl ether resin is 100 parts,
Figure BDA0002259973250000161
the preparation method of the flame-retardant reinforced polyamide 6/polyphenyl ether composition comprises the following steps:
(1) drying the low-viscosity polyamide 6 resin at 125 ℃ for 5 hours, drying the high-viscosity polyphenylene ether resin and the low-viscosity polyphenylene ether resin at 95 ℃ for 5 hours, cooling, and adding the cooled low-viscosity polyamide 6 resin, the cooled high-viscosity polyphenylene ether resin, the cooled low-viscosity polyphenylene ether resin, the cooled N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, pentaerythritol zinc, gamma-aminopropyltriethoxysilane, montmorillonite, aluminum diethylphosphinate and melamine polyphosphate into a high-speed stirrer (the rotating speed is 1000 revolutions per minute) for mixing;
(2) adding the styrene-glycidyl methacrylate copolymer, toluene diisocyanate, hydrogenated styrene-isoprene copolymer grafted maleic anhydride and alkali-free glass fiber into another high-speed stirrer (the rotating speed is 1000 rpm) for mixing;
(3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into the side direction (the fourth zone) of the parallel double-screw extruder (total eight zones) for melt extrusion and granulation, wherein the process parameters are as follows: the temperature in the first zone was 255 ℃, the temperature in the second zone was 260 ℃, the temperature in the third zone was 260 ℃, the temperature in the fourth zone was 265 ℃, the temperature in the fifth zone was 265 ℃, the temperature in the sixth zone was 260 ℃, the temperature in the seventh zone was 260 ℃, the temperature in the eighth zone was 260 ℃, the temperature in the die head was 260 ℃ and the screw speed was 400 rpm.
The screw of the parallel double-screw extruder is in a single-thread shape, the ratio L/D of the length L and the diameter D of the screw is 40, and the screw is provided with 2 meshing block areas and 1 back-thread area.
Example 6:
the flame-retardant reinforced polyamide 6/polyphenylene ether composition is prepared from the following raw materials in parts by weight:
72 parts of low-viscosity polyamide 6 resin (the intrinsic viscosity is 1.17dL/g),
14 parts of high-viscosity polyphenyl ether resin (the intrinsic viscosity is 0.48dL/g),
14 parts of low-viscosity polyphenylene ether resin (the intrinsic viscosity is 0.35dL/g),
the sum of the parts by weight of the low-viscosity polyamide 6 resin, the high-viscosity polyphenyl ether resin and the low-viscosity polyphenyl ether resin is 100 parts,
Figure BDA0002259973250000171
the preparation method of the flame-retardant reinforced polyamide 6/polyphenyl ether composition comprises the following steps:
(1) drying the low-viscosity polyamide 6 resin at 125 ℃ for 5 hours, drying the high-viscosity polyphenylene ether resin and the low-viscosity polyphenylene ether resin at 95 ℃ for 5 hours, cooling, and adding the cooled low-viscosity polyamide 6 resin, the cooled high-viscosity polyphenylene ether resin, the cooled low-viscosity polyphenylene ether resin, the cooled N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, pentaerythritol zinc, gamma-aminopropyltriethoxysilane, montmorillonite, aluminum diethylphosphinate and melamine polyphosphate into a high-speed stirrer (the rotating speed is 1000 revolutions per minute) for mixing;
(2) adding the styrene-glycidyl methacrylate copolymer, toluene diisocyanate, hydrogenated styrene-isoprene copolymer grafted maleic anhydride and alkali-free glass fiber into another high-speed stirrer (the rotating speed is 1000 rpm) for mixing;
(3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into the side direction (the fourth zone) of the parallel double-screw extruder (total eight zones) for melt extrusion and granulation, wherein the process parameters are as follows: the temperature in the first zone was 255 ℃, the temperature in the second zone was 260 ℃, the temperature in the third zone was 260 ℃, the temperature in the fourth zone was 265 ℃, the temperature in the fifth zone was 265 ℃, the temperature in the sixth zone was 260 ℃, the temperature in the seventh zone was 260 ℃, the temperature in the eighth zone was 260 ℃, the temperature in the die head was 260 ℃ and the screw speed was 400 rpm.
The screw of the parallel double-screw extruder is in a single-thread shape, the ratio L/D of the length L and the diameter D of the screw is 40, and the screw is provided with 2 meshing block areas and 1 back-thread area.
Example 7:
the flame-retardant reinforced polyamide 6/polyphenylene ether composition is prepared from the following raw materials in parts by weight:
70 parts of low-viscosity polyamide 6 resin (the intrinsic viscosity is 1.17dL/g),
15 parts of high-viscosity polyphenyl ether resin (the intrinsic viscosity is 0.48dL/g),
15 parts of low-viscosity polyphenyl ether resin (the intrinsic viscosity is 0.35dL/g),
the sum of the parts by weight of the low-viscosity polyamide 6 resin, the high-viscosity polyphenyl ether resin and the low-viscosity polyphenyl ether resin is 100 parts,
Figure BDA0002259973250000181
Figure BDA0002259973250000191
the preparation method of the flame-retardant reinforced polyamide 6/polyphenyl ether composition comprises the following steps:
(1) drying the low-viscosity polyamide 6 resin at 125 ℃ for 5 hours, drying the high-viscosity polyphenylene ether resin and the low-viscosity polyphenylene ether resin at 95 ℃ for 5 hours, cooling, and adding the cooled low-viscosity polyamide 6 resin, the cooled high-viscosity polyphenylene ether resin, the cooled low-viscosity polyphenylene ether resin, the cooled N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, pentaerythritol zinc, gamma-aminopropyltriethoxysilane, montmorillonite, aluminum diethylphosphinate and melamine polyphosphate into a high-speed stirrer (the rotating speed is 1000 revolutions per minute) for mixing;
(2) adding the styrene-glycidyl methacrylate copolymer, toluene diisocyanate, hydrogenated styrene-isoprene copolymer grafted maleic anhydride and alkali-free glass fiber into another high-speed stirrer (the rotating speed is 1000 rpm) for mixing;
(3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into the side direction (the fourth zone) of the parallel double-screw extruder (total eight zones) for melt extrusion and granulation, wherein the process parameters are as follows: the temperature in the first zone was 255 ℃, the temperature in the second zone was 260 ℃, the temperature in the third zone was 260 ℃, the temperature in the fourth zone was 265 ℃, the temperature in the fifth zone was 265 ℃, the temperature in the sixth zone was 260 ℃, the temperature in the seventh zone was 260 ℃, the temperature in the eighth zone was 260 ℃, the temperature in the die head was 260 ℃ and the screw speed was 400 rpm.
The screw of the parallel double-screw extruder is in a single-thread shape, the ratio L/D of the length L and the diameter D of the screw is 40, and the screw is provided with 2 meshing block areas and 1 back-thread area.
Example 8:
the flame-retardant reinforced polyamide 6/polyphenyl ether composition is prepared from the following raw materials in parts by weight:
70 parts of low-viscosity polyamide 6 resin (the intrinsic viscosity is 1.17dL/g),
15 parts of high-viscosity polyphenyl ether resin (the intrinsic viscosity is 0.48dL/g),
15 parts of low-viscosity polyphenyl ether resin (the intrinsic viscosity is 0.35dL/g),
the sum of the parts by weight of the low-viscosity polyamide 6 resin, the high-viscosity polyphenyl ether resin and the low-viscosity polyphenyl ether resin is 100 parts,
Figure BDA0002259973250000201
the preparation method of the flame-retardant reinforced polyamide 6/polyphenyl ether composition comprises the following steps:
(1) drying the low-viscosity polyamide 6 resin at 125 ℃ for 5 hours, drying the high-viscosity polyphenylene ether resin and the low-viscosity polyphenylene ether resin at 95 ℃ for 5 hours, cooling, and adding the cooled low-viscosity polyamide 6 resin, the cooled high-viscosity polyphenylene ether resin, the cooled low-viscosity polyphenylene ether resin, the cooled N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, pentaerythritol zinc, gamma-aminopropyltriethoxysilane, montmorillonite, aluminum diethylphosphinate and melamine polyphosphate aluminum zinc into a high-speed stirrer (the rotating speed is 1000 revolutions per minute) for mixing;
(2) adding the styrene-glycidyl methacrylate copolymer, toluene diisocyanate, hydrogenated styrene-isoprene copolymer grafted maleic anhydride and alkali-free glass fiber into another high-speed stirrer (the rotating speed is 1000 rpm) for mixing;
(3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into the side direction (the fourth zone) of the parallel double-screw extruder (total eight zones) for melt extrusion and granulation, wherein the process parameters are as follows: the temperature in the first zone was 255 ℃, the temperature in the second zone was 260 ℃, the temperature in the third zone was 260 ℃, the temperature in the fourth zone was 265 ℃, the temperature in the fifth zone was 265 ℃, the temperature in the sixth zone was 260 ℃, the temperature in the seventh zone was 260 ℃, the temperature in the eighth zone was 260 ℃, the temperature in the die head was 260 ℃ and the screw speed was 400 rpm.
The shape of a screw of the parallel double-screw extruder is double-thread, the ratio L/D of the length L and the diameter D of the screw is 40, and the screw is provided with 2 meshing block areas and 1 back-thread area.
Comparative example 1:
the flame-retardant reinforced polyamide 6/polyphenyl ether composition is prepared from the following raw materials in parts by weight:
70 parts of low-viscosity polyamide 6 resin (the intrinsic viscosity is 1.17dL/g),
15 parts of high-viscosity polyphenyl ether resin (the intrinsic viscosity is 0.55dL/g),
15 parts of low-viscosity polyphenyl ether resin (the intrinsic viscosity is 0.35dL/g),
the sum of the parts by weight of the low-viscosity polyamide 6 resin, the high-viscosity polyphenyl ether resin and the low-viscosity polyphenyl ether resin is 100 parts,
Figure BDA0002259973250000211
the preparation method of the flame-retardant reinforced polyamide 6/polyphenyl ether composition comprises the following steps:
(1) drying the low-viscosity polyamide 6 resin at 125 ℃ for 5 hours, drying the high-viscosity polyphenylene ether resin and the low-viscosity polyphenylene ether resin at 95 ℃ for 5 hours, cooling, and adding the cooled low-viscosity polyamide 6 resin, the cooled high-viscosity polyphenylene ether resin, the cooled low-viscosity polyphenylene ether resin, the cooled N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, pentaerythritol zinc, gamma-aminopropyltriethoxysilane, montmorillonite, aluminum diethylphosphinate and melamine polyphosphate aluminum zinc into a high-speed stirrer (the rotating speed is 1000 revolutions per minute) for mixing;
(2) adding the styrene-glycidyl methacrylate copolymer, toluene diisocyanate, hydrogenated styrene-isoprene copolymer grafted maleic anhydride and alkali-free glass fiber into another high-speed stirrer (the rotating speed is 1000 rpm) for mixing;
(3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into the side direction (the fourth zone) of the parallel double-screw extruder (total eight zones) for melt extrusion and granulation, wherein the process parameters are as follows: the temperature in the first zone was 255 ℃, the temperature in the second zone was 260 ℃, the temperature in the third zone was 260 ℃, the temperature in the fourth zone was 265 ℃, the temperature in the fifth zone was 265 ℃, the temperature in the sixth zone was 260 ℃, the temperature in the seventh zone was 260 ℃, the temperature in the eighth zone was 260 ℃, the temperature in the die head was 260 ℃ and the screw speed was 400 rpm.
The screw of the parallel double-screw extruder is in a single-thread shape, the ratio L/D of the length L and the diameter D of the screw is 40, and the screw is provided with 2 meshing block areas and 1 back-thread area.
Comparative example 2:
the flame-retardant reinforced polyamide 6/polyphenyl ether composition is prepared from the following raw materials in parts by weight:
70 parts of low-viscosity polyamide 6 resin (with the intrinsic viscosity of 0.97dL/g),
15 parts of high-viscosity polyphenyl ether resin (the intrinsic viscosity is 0.48dL/g),
15 parts of low-viscosity polyphenylene ether resin (the intrinsic viscosity is 0.28dL/g),
the sum of the parts by weight of the low-viscosity polyamide 6 resin, the high-viscosity polyphenyl ether resin and the low-viscosity polyphenyl ether resin is 100 parts,
Figure BDA0002259973250000221
the preparation method of the flame-retardant reinforced polyamide 6/polyphenyl ether composition comprises the following steps:
(1) drying the low-viscosity polyamide 6 resin at 125 ℃ for 5 hours, drying the high-viscosity polyphenylene ether resin and the low-viscosity polyphenylene ether resin at 95 ℃ for 5 hours, cooling, and adding the cooled low-viscosity polyamide 6 resin, the cooled high-viscosity polyphenylene ether resin, the cooled low-viscosity polyphenylene ether resin, the cooled N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, pentaerythritol zinc, gamma-aminopropyltriethoxysilane, montmorillonite, aluminum diethylphosphinate and melamine polyphosphate into a high-speed stirrer (the rotating speed is 1000 revolutions per minute) for mixing;
(2) adding the styrene-glycidyl methacrylate copolymer, toluene diisocyanate, hydrogenated styrene-isoprene copolymer grafted maleic anhydride and alkali-free glass fiber into another high-speed stirrer (the rotating speed is 1000 rpm) for mixing;
(3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into the side direction (the fourth zone) of the parallel double-screw extruder (total eight zones) for melt extrusion and granulation, wherein the process parameters are as follows: the temperature in the first zone was 255 ℃, the temperature in the second zone was 260 ℃, the temperature in the third zone was 260 ℃, the temperature in the fourth zone was 265 ℃, the temperature in the fifth zone was 265 ℃, the temperature in the sixth zone was 260 ℃, the temperature in the seventh zone was 260 ℃, the temperature in the eighth zone was 260 ℃, the temperature in the die head was 260 ℃ and the screw speed was 400 rpm.
The screw of the parallel double-screw extruder is in a single-thread shape, the ratio L/D of the length L and the diameter D of the screw is 40, and the screw is provided with 2 meshing block areas and 1 back-thread area.
Comparative example 3:
the flame-retardant reinforced polyamide 6/polyphenyl ether composition is prepared from the following raw materials in parts by weight:
70 parts of low-viscosity polyamide 6 resin (the intrinsic viscosity is 1.17dL/g),
15 parts of high-viscosity polyphenyl ether resin (the intrinsic viscosity is 0.48dL/g),
15 parts of low-viscosity polyphenyl ether resin (the intrinsic viscosity is 0.35dL/g),
the sum of the parts by weight of the low-viscosity polyamide 6 resin, the high-viscosity polyphenyl ether resin and the low-viscosity polyphenyl ether resin is 100 parts,
0.2 portion of N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide,
0.2 part of bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate,
0.2 part of pentaerythritol zinc.
The preparation method of the flame-retardant reinforced polyamide 6/polyphenyl ether composition comprises the following steps:
(1) drying the low-viscosity polyamide 6 resin at 125 ℃ for 5 hours, drying the high-viscosity polyphenylene ether resin and the low-viscosity polyphenylene ether resin at 95 ℃ for 5 hours, cooling, and adding the cooled low-viscosity polyamide 6 resin, the cooled high-viscosity polyphenylene ether resin, the cooled low-viscosity polyphenylene ether resin, the cooled N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate and pentaerythritol zinc into a high-speed stirrer (the rotating speed is 1000 revolutions per minute) for mixing;
(2) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder for melt extrusion and granulation, wherein the process parameters are as follows: the temperature in the first zone was 255 ℃, the temperature in the second zone was 260 ℃, the temperature in the third zone was 260 ℃, the temperature in the fourth zone was 265 ℃, the temperature in the fifth zone was 265 ℃, the temperature in the sixth zone was 260 ℃, the temperature in the seventh zone was 260 ℃, the temperature in the eighth zone was 260 ℃, the temperature in the die head was 260 ℃ and the screw speed was 400 rpm.
The screw of the parallel double-screw extruder is in a single-thread shape, the ratio L/D of the length L and the diameter D of the screw is 40, and the screw is provided with 2 meshing block areas and 1 back-thread area.
Comparative example 4:
the flame-retardant reinforced polyamide 6/polyphenyl ether composition is prepared from the following raw materials in parts by weight:
70 parts of low-viscosity polyamide 6 resin (the intrinsic viscosity is 1.17dL/g),
15 parts of high-viscosity polyphenyl ether resin (the intrinsic viscosity is 0.48dL/g),
15 parts of low-viscosity polyphenyl ether resin (the intrinsic viscosity is 0.35dL/g),
the sum of the parts by weight of the low-viscosity polyamide 6 resin, the high-viscosity polyphenyl ether resin and the low-viscosity polyphenyl ether resin is 100 parts,
Figure BDA0002259973250000241
the preparation method of the flame-retardant reinforced polyamide 6/polyphenyl ether composition comprises the following steps:
(1) drying the low-viscosity polyamide 6 resin at 125 ℃ for 5 hours, drying the high-viscosity polyphenylene ether resin and the low-viscosity polyphenylene ether resin at 95 ℃ for 5 hours, cooling, and adding the cooled low-viscosity polyamide 6 resin, the cooled high-viscosity polyphenylene ether resin, the cooled low-viscosity polyphenylene ether resin, the cooled N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, pentaerythritol zinc, gamma-aminopropyltriethoxysilane, montmorillonite, aluminum diethylphosphinate and melamine polyphosphate into a high-speed stirrer (the rotating speed is 1000 revolutions per minute) for mixing;
(2) adding the styrene-glycidyl methacrylate copolymer, toluene diisocyanate, hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride and alkali-free glass fiber into another high-speed stirrer (the rotating speed is 1000 rpm) for mixing;
(3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into the side direction (the fourth zone) of the parallel double-screw extruder (total eight zones) for melt extrusion and granulation, wherein the process parameters are as follows: the temperature in the first zone was 255 ℃, the temperature in the second zone was 260 ℃, the temperature in the third zone was 260 ℃, the temperature in the fourth zone was 265 ℃, the temperature in the fifth zone was 265 ℃, the temperature in the sixth zone was 260 ℃, the temperature in the seventh zone was 260 ℃, the temperature in the eighth zone was 260 ℃, the temperature in the die head was 260 ℃ and the screw speed was 400 rpm.
The screw of the parallel double-screw extruder is in a single-thread shape, the ratio L/D of the length L and the diameter D of the screw is 40, and the screw is provided with 2 meshing block areas and 1 back-thread area.
The following is a list of raw material compositions of examples and comparative examples (table 1).
TABLE 1 summary of the composition parts by weight of the raw materials of the examples and comparative examples
Figure BDA0002259973250000251
Figure BDA0002259973250000261
Remarking: a, the intrinsic viscosity of the high-viscosity PPO is 0.55 dL/g; b, the intrinsic viscosity of the low-viscosity PA6 is 0.97dL/g, and the intrinsic viscosity of the low-viscosity PPO is 0.28 dL/g; c, replacing SEPS-g-MAH with SEBS-g-MAH; and d, changing the screw structure.
The amounts of N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide, bis (2, 6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphate and pentaerythritol zinc used in the above examples and comparative examples were 0.2 parts.
The flame-retardant reinforced polyamide 6/polyphenylene ether compositions prepared in the above examples and comparative examples were subjected to the following performance tests:
tensile property: testing according to GB/T1040-2006 standard, wherein the stretching speed is 50 mm/min;
impact properties: according to the test of GB/T1843-2008 standard, the thickness of the sample strip is 4 mm;
melt index: testing according to GB/T3682-2000 standard, wherein the testing temperature is 280 ℃, and the load is 5 kg;
flame retardant property: the sample thickness was 1/16 inches (i.e., 1.6mm) as tested by UL 94-2006 standard;
the results of the performance tests are shown in table 2.
TABLE 2 Properties of the flame-retardant reinforced Polyamide 6/polyphenylene ether compositions of the examples and comparative examples
Figure BDA0002259973250000262
Figure BDA0002259973250000271
In examples 1 to 7, the addition amounts of the low-viscosity polyamide 6 resin, the high-viscosity polyphenylene ether resin, the low-viscosity polyphenylene ether resin, SG, TDI, SEPS-g-MAH and the alkali-free glass fiber were adjusted, and it can be seen from the table that as the addition amounts of the low-viscosity polyamide 6 resin and the alkali-free glass fiber decrease (or the addition amount of the polyphenylene ether resin increases), the tensile strength and the melt index thereof tend to decrease, and the notch impact strength tends to increase, mainly because PA6 belongs to a crystalline plastic, the substrate itself thereof has higher tensile strength and better fluidity, and the alkali-free glass fiber plays a role of reinforcing the resin, while PPO belongs to an amorphous plastic, the substrate itself has not high tensile strength, and the main chain thereof has rigid benzene rings and poor fluidity. Meanwhile, the addition amounts of SG, TDI and SEPS-g-MAH are increased, so that the compatibility between two phases of PA6 and PPO can be effectively improved, and the tensile strength and the notch impact strength of PA6/PPO are improved, but the tensile strength is influenced on the contrary due to excessive addition of SG, TDI and SEPS-g-MAH. The flame retardant property is improved along with the increase of the addition amount of the gamma-aminopropyltriethoxysilane, the montmorillonite, the aluminum diethylphosphinate and the melamine aluminum zinc polyphosphate. By comparison, the overall performance of example 7 is best.
Example 7 compared with example 8, the screw shape of the parallel twin-screw extruder of example 8 is double screw thread, the screw shape of the parallel twin-screw extruder of example 7 is single screw thread, and the comparison shows that the screw parameters of the parallel twin-screw extruder described in example 7 are adopted, so that the prepared flame-retardant reinforced polyamide 6/polyphenylene ether composition has better tensile strength, notch impact strength, melt index and flame retardant property.
Compared with the comparative example 1, the high-viscosity polyphenyl ether resin with the intrinsic viscosity of 0.55dL/g is used in the comparative example 1, the high-viscosity polyphenyl ether resin with the intrinsic viscosity of 0.48dL/g is used in the example 7, the fluidity of the high-viscosity polyphenyl ether resin is greatly reduced along with the increase of the intrinsic viscosity of the polyphenyl ether resin, and when the intrinsic viscosity of the polyphenyl ether resin is 0.55dL/g, the melt index of the flame-retardant reinforced polyamide 6/polyphenyl ether composition is only 12g/10min, and the processability is poor; example 7 in comparison with comparative example 2, comparative example 2 used a low-tack polyamide 6 resin having an intrinsic viscosity of 0.97dL/g and a low-tack polyphenylene ether resin having an intrinsic viscosity of 0.28dL/g, whereas example 7 used a low-tack polyamide 6 resin having an intrinsic viscosity of 1.17dL/g and a low-tack polyphenylene ether resin having an intrinsic viscosity of 0.35dL/g, the tensile strength and the notched impact strength of the flame retardant reinforced polyamide 6/polyphenylene ether composition prepared in comparative example 2 decreased as the intrinsic viscosities of the polyamide 6 resin and the polyphenylene ether resin decreased, and the tensile strength and the notched impact strength of the flame retardant reinforced polyamide 6/polyphenylene ether composition were lower than those of example 7; example 7 compared with comparative example 3, comparative example 3 has no addition of SG, TDI and SEPS-g-MAH, and has poor compatibility of PA6 and PPO, so that the tensile strength and the notch impact strength of the prepared flame-retardant reinforced polyamide 6/polyphenylene ether composition are far lower than those of example 7, and comparative example 3 has no addition of gamma-aminopropyltriethoxysilane, montmorillonite, aluminum diethylphosphinate and melamine aluminum polyphosphate, has the flame retardant property of UL 94HB (1.6mm), has the flame retardant property of lower than that of example 7, and has no addition of alkali-free glass fiber, and has the tensile strength of only 58 MPa; example 7 in comparison to comparative example 4, which used SEBS-g-MAH in comparative example 4 and SEPS-g-MAH in example 7, the tensile strength and notched impact strength of the flame retardant reinforced polyamide 6/polyphenylene ether composition prepared in example 7 was higher than that of comparative example 4.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (9)

1. The flame-retardant reinforced polyamide 6/polyphenyl ether composition is characterized by being prepared from the following raw materials in parts by weight:
68-72 parts of low-viscosity polyamide 6 resin,
14-16 parts of high-viscosity polyphenyl ether resin,
14-16 parts of low-viscosity polyphenyl ether resin,
the sum of the parts by weight of the low-viscosity polyamide 6 resin, the high-viscosity polyphenyl ether resin and the low-viscosity polyphenyl ether resin is 100 parts,
Figure FDA0003460699860000011
the intrinsic viscosity of the low-viscosity polyamide 6 resin is 1.01-1.33 dL/g; the intrinsic viscosity of the high-viscosity polyphenyl ether resin is 0.45-0.51 dL/g; the intrinsic viscosity of the low-viscosity polyphenyl ether resin is 0.33-0.37 dL/g;
the silane coupling agent is at least one of gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, gamma-aminopropylmethyldiethoxysilane and aniline methyltriethoxysilane;
the layered silicate is at least one of montmorillonite, kaolin, hydrotalcite and sepiolite;
the alkyl phosphinate is at least one of aluminum diethyl phosphinate, zinc diethyl phosphinate, calcium diethyl phosphinate, magnesium diethyl phosphinate, aluminum dipropyl phosphinate, aluminum isobutyl phosphinate, aluminum methyl ethyl phosphinate and aluminum phenyl phosphinate;
the melamine polyphosphate is at least one of melamine aluminum polyphosphate, melamine zinc polyphosphate and melamine magnesium polyphosphate;
the preparation method of the flame-retardant reinforced polyamide 6/polyphenyl ether composition comprises the following steps:
(1) drying the low-viscosity polyamide 6 resin at the temperature of 110-140 ℃ for 4-8 hours, drying the high-viscosity polyphenylene ether resin and the low-viscosity polyphenylene ether resin at the temperature of 80-110 ℃ for 4-8 hours, cooling, and adding the cooled low-viscosity polyamide 6 resin, the high-viscosity polyphenylene ether resin, the low-viscosity polyphenylene ether resin, the N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, pentaerythritol zinc, a silane coupling agent, a layered silicate, an alkyl phosphinate and melamine polyphosphate into a stirrer for mixing;
(2) adding the styrene-glycidyl methacrylate copolymer, toluene diisocyanate, hydrogenated styrene-isoprene copolymer grafted maleic anhydride and alkali-free glass fiber into another stirrer for mixing;
(3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into the parallel double-screw extruder in the lateral direction, performing melt extrusion, and granulating, wherein the process parameters comprise: the temperature of the first zone is 245-265 ℃, the temperature of the second zone is 250-270 ℃, the temperature of the third zone is 250-270 ℃, the temperature of the fourth zone is 255-275 ℃, the temperature of the fifth zone is 255-275 ℃, the temperature of the sixth zone is 250-270 ℃, the temperature of the seventh zone is 250-270 ℃, the temperature of the eighth zone is 250-270 ℃, the temperature of the die head is 250-270 ℃, and the rotation speed of the screw is 200-600 rpm;
the screw shape of the parallel double-screw extruder is a single thread; the ratio L/D of the length L of the screw to the diameter D of the screw is 35 to 50; the screw is provided with more than 1 meshing block area and more than 1 reverse thread area.
2. The flame-retardant reinforced polyamide 6/polyphenylene ether composition according to claim 1, which is prepared from the following raw materials in parts by weight:
70 parts of low-viscosity polyamide 6 resin,
15 parts of high-viscosity polyphenyl ether resin,
15 parts of low-viscosity polyphenyl ether resin,
the sum of the parts by weight of the low-viscosity polyamide 6 resin, the high-viscosity polyphenyl ether resin and the low-viscosity polyphenyl ether resin is 100 parts,
Figure FDA0003460699860000021
Figure FDA0003460699860000031
3. the flame-retardant reinforced polyamide 6/polyphenylene ether composition according to claim 1 or 2, wherein the mass fraction of glycidyl methacrylate in the copolymer of styrene and glycidyl methacrylate is 2 to 4 wt%; and/or the presence of a catalyst in the reaction mixture,
the maleic anhydride grafting rate of the hydrogenated styrene-isoprene copolymer grafted maleic anhydride is 0.8-1.5 wt%.
4. The flame retardant reinforced polyamide 6/polyphenylene ether composition according to claim 1 or 2, wherein the alkali-free glass fiber has a length of 2 to 4mm and a diameter of 9 to 11 μm.
5. The flame retardant reinforced polyamide 6/polyphenylene ether composition according to claim 1 or 2, wherein the silane coupling agent is at least one of γ -aminopropyltriethoxysilane, γ -aminopropyltrimethoxysilane; the phyllosilicate is montmorillonite; the alkyl phosphinate is aluminum diethyl phosphinate; the melamine polyphosphate is melamine aluminum polyphosphate.
6. A process for the preparation of a flame retardant reinforced polyamide 6/polyphenylene ether composition according to any of claims 1 to 5, comprising the steps of:
(1) drying the low-viscosity polyamide 6 resin at the temperature of 110-140 ℃ for 4-8 hours, drying the high-viscosity polyphenylene ether resin and the low-viscosity polyphenylene ether resin at the temperature of 80-110 ℃ for 4-8 hours, cooling, and adding the cooled low-viscosity polyamide 6 resin, the high-viscosity polyphenylene ether resin, the low-viscosity polyphenylene ether resin, the N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, pentaerythritol zinc, a silane coupling agent, a layered silicate, an alkyl phosphinate and melamine polyphosphate into a stirrer for mixing;
(2) adding the styrene-glycidyl methacrylate copolymer, toluene diisocyanate, hydrogenated styrene-isoprene copolymer grafted maleic anhydride and alkali-free glass fiber into another stirrer for mixing;
(3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into the parallel double-screw extruder in the lateral direction, performing melt extrusion, and granulating, wherein the process parameters comprise: the temperature of the first zone is 245-265 ℃, the temperature of the second zone is 250-270 ℃, the temperature of the third zone is 250-270 ℃, the temperature of the fourth zone is 255-275 ℃, the temperature of the fifth zone is 255-275 ℃, the temperature of the sixth zone is 250-270 ℃, the temperature of the seventh zone is 250-270 ℃, the temperature of the eighth zone is 250-270 ℃, the temperature of the die head is 250-270 ℃, and the rotation speed of the screw is 200-600 rpm;
the screw shape of the parallel double-screw extruder is a single thread; the ratio L/D of the length L of the screw to the diameter D of the screw is 35 to 50; the screw is provided with more than 1 meshing block area and more than 1 reverse thread area.
7. The preparation method according to claim 6, wherein in the step (1), the low-viscosity polyamide 6 resin is dried at a temperature of 120 to 130 ℃ for 4 to 6 hours, and the high-viscosity polyphenylene ether resin and the low-viscosity polyphenylene ether resin are dried at a temperature of 90 to 100 ℃ for 4 to 6 hours; the process parameters in the step (3) comprise: the temperature of the first zone is 250-260 ℃, the temperature of the second zone is 255-265 ℃, the temperature of the third zone is 255-265 ℃, the temperature of the fourth zone is 260-270 ℃, the temperature of the fifth zone is 260-270 ℃, the temperature of the sixth zone is 255-265 ℃, the temperature of the seventh zone is 255-265 ℃, the temperature of the eighth zone is 255-265 ℃, the temperature of the die head is 255-265 ℃ and the rotation speed of the screw is 300-500 rpm.
8. The method according to claim 6, wherein the ratio L/D of the screw length L to the diameter D is 35 to 45; and 2 meshing block areas and 1 reverse thread area are arranged on the screw rod.
9. The method according to claim 6 or 7, wherein in step (1) and/or step (2), the stirrer is a high-speed stirrer with a rotation speed of 500 and 1500 rpm.
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