CN110724374A - Flame-retardant polyphenyl ether/polyamide 66 composition and preparation method thereof - Google Patents
Flame-retardant polyphenyl ether/polyamide 66 composition and preparation method thereof Download PDFInfo
- Publication number
- CN110724374A CN110724374A CN201911019181.1A CN201911019181A CN110724374A CN 110724374 A CN110724374 A CN 110724374A CN 201911019181 A CN201911019181 A CN 201911019181A CN 110724374 A CN110724374 A CN 110724374A
- Authority
- CN
- China
- Prior art keywords
- temperature
- zone
- polyamide
- viscosity
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
-
- 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
- C08L2205/02—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
- C08L2205/05—Polymer mixtures characterised by other features containing polymer components which can react with one another
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a flame-retardant polyphenyl ether/polyamide 66 composition and a preparation method thereof, wherein the flame-retardant polyphenyl ether/polyamide 66 composition is prepared from the following raw materials: high-viscosity polyphenyl ether resin, low-viscosity polyamide 66 resin, 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 and melamine polyphosphate. The flame-retardant polyphenyl ether/polyamide 66 composition has excellent mechanical property, processability and flame retardance, and can be applied to electronic and electric products, high-voltage-resistant and outdoor parts and the like.
Description
Technical Field
The invention relates to the field of materials, in particular to a flame-retardant polyphenyl ether/polyamide 66 composition and a preparation method thereof.
Background
The polyphenylene oxide (PPO) has good mechanical property, heat resistance and chemical stability, can be continuously used at the temperature of-160-190 ℃, and is the most excellent material for resisting creep property of thermoplastic engineering plastics. Polyamide 66(PA66) is a crystalline resin and is excellent in chemical resistance and processability, but its mechanical properties are reduced and its dimensional stability is poor due to its large water absorption. In order to improve the processability and solvent resistance of PPO, PPO/PA66 compositions can be prepared by blending polyphenylene oxide with polyamide 66. However, since amorphous PPO and crystalline PA66 are thermodynamically incompatible, the dispersed phase domain size of the blend is too large, the interfacial force is weak, and the material strength and toughness are insufficient, which will lose the use value. Therefore, toughening compatibilization of PPO/PA66 systems appears to be of paramount importance.
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 restriction of the use of certain harmful components in electronic and electrical equipment (ROHS) in the European Union, research and development of flame retardant polyphenylene ether/polyamide 66 compositions meeting the international flame retardant and environmental protection requirements have become a research hotspot in the field of plastic modification.
At present, some researches on toughening, compatibilization and flame retardance of PPO/PA66 systems are carried out in the prior art, such as: chinese patent CN102863776A discloses a PPO/PA66 synthetic plastic, which comprises the following components in percentage by weight: 25-35% of polyphenyl ether, 25-35% of nylon 66, 15-20% of carbon fiber, 8-12% of carbon black, 5-10% of compatilizer, 5-10% of toughening agent and 0.5-1.5% of auxiliary agent, wherein the compatilizer is PPO-g-MAH, and the toughening agent is SEBS-g-MAH; chinese patent CN101875776A discloses a high-strength PPO/PA66 alloy material and a preparation method thereof, wherein the high-strength PPO/PA66 alloy material comprises the following components in percentage by weight: 20-40% of polyphenyl ether resin; 20-40% of nylon 66 resin; 5-10% of a compatilizer; 5-10% of a toughening agent; 5-15% of glass fiber; 5-15% of glass beads; 5-15% of mica powder; 0.2 to 0.4 percent of antioxidant; 0.5-1% of other auxiliary agents, wherein the compatilizer is PPO-g-MAH, and the flexibilizer is SEBS-g-MAH; chinese patent CN109181298A discloses a high-flow PPO/PA66 resin composition, which comprises the following components in parts by weight: 10-50 parts of PPO resin; 30-70 parts of PA66 resin; 2-5 parts of a self-made compatilizer; 6-13 parts of a toughening agent; 10-20 parts of PPO/HIPS master batch; 0.1 to 0.3 weight portion of antioxidant; 0.2-0.5 part of lubricant, wherein the self-made compatilizer is PPO-g-MAH; 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 is characterized by comprising 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, 10-60% of PA, 3-15% of toughening agent, 5-15% of composite flame retardant, 3-10% of compatilizer and 0.5-2% of other auxiliary agents.
Disclosure of Invention
Based on the above, the invention aims to provide a flame-retardant polyphenyl ether/polyamide 66 composition with excellent mechanical property, processability and flame retardance, which can be applied to electronic and electric products, high-voltage-resistant and outdoor-used parts and the like.
In order to achieve the purpose, the invention adopts the following scheme:
the flame-retardant polyphenyl ether/polyamide 66 composition is prepared from the following raw materials in parts by weight:
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 intrinsic viscosity of the low-viscosity polyamide 66 resin is 1.27-1.57 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 polyphenylene ether/polyamide 66 composition is prepared from the following raw materials in parts by weight:
in some of the examples, the flame retardant polyphenylene ether/polyamide 66 composition is further preferably prepared from the following raw materials in parts by weight:
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 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.
It is another object of the present invention to provide a method for preparing a flame retardant polyphenylene ether/polyamide 66 composition.
The preparation method of the flame-retardant polyphenyl ether/polyamide 66 composition comprises the following steps of:
(1) drying the high-viscosity polyphenyl ether resin and the low-viscosity polyphenyl ether resin at the temperature of 80-110 ℃ for 4-8 hours, drying the low-viscosity polyamide 66 resin at the temperature of 110-140 ℃ for 4-8 hours, cooling, and adding the cooled high-viscosity polyphenyl ether resin, the cooled low-viscosity polyamide 66 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 and hydrogenated styrene-isoprene copolymer grafted maleic anhydride 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 265-285 ℃, the temperature of the second zone is 270-290 ℃, the temperature of the third zone is 270-290 ℃, the temperature of the fourth zone is 275-295 ℃, the temperature of the fifth zone is 275-295 ℃, the temperature of the sixth zone is 270-290 ℃, the temperature of the seventh zone is 270-290 ℃, the temperature of the eighth zone is 270-290 ℃, the temperature of the die head is 270-290 ℃, and the rotating speed of the screw is 200-600 rpm.
In some embodiments, in the step (1), 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, and the low-viscosity polyamide 66 resin is dried at a temperature of 120-130 ℃ for 4-6 hours; the process parameters in the step (3) comprise: the temperature of the first zone is 270-280 ℃, the temperature of the second zone is 275-285 ℃, the temperature of the third zone is 275-285 ℃, the temperature of the fourth zone is 280-290 ℃, the temperature of the fifth zone is 280-290 ℃, the temperature of the sixth zone is 275-285 ℃, the temperature of the seventh zone is 275-285 ℃, the temperature of the eighth zone is 275-285 ℃, the temperature of the die head is 275-285 ℃ and the rotating 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 polyphenylene ether/polyamide 66 composition of the invention is as follows:
in order to overcome the defects of poor compatibility, processing performance and flame retardant performance of PPO and PA66 in the flame retardant polyphenyl ether/polyamide 66 composition, the invention improves the compatibility between PPO and PA66 by adding styrene and glycidyl methacrylate copolymer, toluene diisocyanate and hydrogenated styrene-isoprene copolymer grafted maleic anhydride, meanwhile, the hydrogenated styrene-isoprene copolymer grafted maleic anhydride can improve the notch impact strength of the PPO/PA66 composition, the mechanical property of the PPO/PA66 composition is ensured by adding high-viscosity polyphenyl ether resin, the processing property of the PPO/PA66 composition is ensured by adding low-viscosity polyphenyl ether resin and low-viscosity polyamide 66 resin, and the flame retardant property of the PPO/PA66 composition is improved by compounding pentaerythritol zinc, phyllosilicate, alkyl phosphinate and melamine polyphosphate.
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 two phases of PPO and PA66 and improve the compatibility between the two phases. The styrene structural unit in the copolymer of the styrene and the glycidyl methacrylate has good compatibility with the PPO, and the epoxy group of the glycidyl methacrylate can react with the terminal hydroxyl of the PPO and the terminal amino of PA66, so that the compatibility between the PPO and PA66 is improved; the isocyanate group of the toluene diisocyanate can react with the terminal hydroxyl group of the PPO and the terminal amino group and the terminal carboxyl group of the PA66, so that the compatibility between the PPO and the PA66 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 hydroxyl of the PPO and the terminal amino of PA66, so that the compatibility between the PPO and PA66 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 polyphenylene oxide resin and polyamide resin are improved, and the influence of the interfacial bonding force and compatibility on the mechanical properties of the PPO/PA66 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 is better in the blending process of PPO and PA66, the amide group can react with the end group of PA66 resin to improve the compatibility, and the hindered piperidyl group 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 PPO and PA66, can prevent the thermal degradation of PPO and PA66 in the high-temperature process, inhibits the thermal oxidative discoloration caused by long time, and also provides a Nitrogen Oxide (NO) for the preparation of the compoundx) 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 polyphenylene oxide resin and polyamide resin, and reduce the influence of the interfacial bonding force and compatibility on the mechanical property of the PPO/PA66 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.
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 PPO and PA66 in the existing flame retardant polyphenyl ether/polyamide 66 composition, the compatibility between PPO and PA66 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 polyphenyl ether/polyamide 66 composition is improved by hydrogenated styrene-isoprene copolymer grafted maleic anhydride, the mechanical property and the processability of the flame retardant polyphenyl ether/polyamide 66 composition are ensured by compounding high-viscosity and low-viscosity polyphenyl ether resin and low-viscosity polyamide 66 resin, and N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1 is compounded, 3-benzenedicarboxamide, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate and pentaerythritol zinc improve the yellowing phenomenon and the thermal stability of the flame-retardant polyphenyl ether/polyamide 66 composition in the blending processing process, pentaerythritol zinc, phyllosilicate, alkyl phosphinate and melamine polyphosphate are compounded to improve the flame retardant property of the PPO/PA66 composition, and the obtained flame-retardant polyphenyl ether/polyamide 66 composition has excellent mechanical property, processing property and flame retardant property due to the mutual matching of the raw material components, and can be applied to electronic and electric products, high-pressure-resistant and outdoor-used parts and the like.
The preparation method of the flame-retardant polyphenyl ether/polyamide 66 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 polyphenylene ether/polyamide 66 composition in accordance with one 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 polyphenylene ether/polyamide 66 composition according to an embodiment of the invention is as follows (see FIG. 1 for a flow chart of the preparation process):
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 hydroxyl of PPO and the terminal amino of PA66, so that the compatibility between PPO and PA66 is improved; the isocyanate group of the toluene diisocyanate can react with the terminal hydroxyl group of the PPO, the terminal amino group and the terminal carboxyl group of the PA66, so that the compatibility between the PPO and the PA66 is improved; anhydride groups in the hydrogenated styrene-isoprene copolymer grafted maleic anhydride can react with terminal hydroxyl groups of PPO and terminal amino groups of PA66, so that the compatibility between PPO and PA66 is improved.
The examples of the invention and the comparative examples used the following raw materials:
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;
low viscosity polyamide 66 resin with intrinsic viscosity of 1.42dL/g, selected from Henan Shenma Nylon chemical industry Limited responsibility company;
low viscosity polyamide 66 resin with intrinsic viscosity of 1.33dL/g, selected from Henan Shenma Nylon chemical industry Limited responsibility company;
low viscosity polyamide 66 resin with intrinsic viscosity of 1.1dL/g, selected from Henan Shenma nylon chemical industry Limited responsibility company;
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;
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 polyphenyl ether/polyamide 66 composition is prepared from the following raw materials in parts by weight:
the preparation method of the flame-retardant polyphenyl ether/polyamide 66 composition comprises the following steps:
(1) drying the high-viscosity polyphenyl ether resin and the low-viscosity polyphenyl ether resin at the temperature of 80 ℃ for 8 hours, drying the low-viscosity polyamide 66 resin at the temperature of 110 ℃ for 8 hours, cooling, and adding the cooled high-viscosity polyphenyl ether resin, the cooled low-viscosity polyamide 66 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 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 and hydrogenated styrene-isoprene copolymer grafted maleic anhydride 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 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 polyphenyl ether/polyamide 66 composition is prepared from the following raw materials in parts by weight:
the preparation method of the flame-retardant polyphenyl ether/polyamide 66 composition comprises the following steps:
(1) drying the high-viscosity polyphenyl ether resin and the low-viscosity polyphenyl ether resin at the temperature of 110 ℃ for 4 hours, drying the low-viscosity polyamide 66 resin at the temperature of 140 ℃ for 4 hours, cooling, and adding the cooled high-viscosity polyphenyl ether resin, the cooled low-viscosity polyamide 66 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 and hydrogenated styrene-isoprene copolymer grafted maleic anhydride 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 285 deg.C, the temperature in the second zone was 290 deg.C, the temperature in the third zone was 290 deg.C, the temperature in the fourth zone was 295 deg.C, the temperature in the fifth zone was 295 deg.C, the temperature in the sixth zone was 290 deg.C, the temperature in the seventh zone was 290 deg.C, the temperature in the eighth zone was 290 deg.C, the temperature in the die head was 290 deg.C, and.
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 polyphenyl ether/polyamide 66 composition is prepared from the following raw materials in parts by weight:
the preparation method of the flame-retardant polyphenyl ether/polyamide 66 composition comprises the following steps:
(1) drying the high-viscosity polyphenyl ether resin and the low-viscosity polyphenyl ether resin at the temperature of 90 ℃ for 6 hours, drying the low-viscosity polyamide 66 resin at the temperature of 120 ℃ for 6 hours, cooling, and adding the cooled high-viscosity polyphenyl ether resin, the cooled low-viscosity polyamide 66 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 and hydrogenated styrene-isoprene copolymer grafted maleic anhydride 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 270 ℃, the temperature in the second zone was 275 ℃, the temperature in the third zone was 275 ℃, the temperature in the fourth zone was 280 ℃, the temperature in the fifth zone was 280 ℃, the temperature in the sixth zone was 275 ℃, the temperature in the seventh zone was 275 ℃, the temperature in the eighth zone was 275 ℃, the temperature in the die head was 275 ℃ 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 polyphenyl ether/polyamide 66 composition is prepared from the following raw materials in parts by weight:
the preparation method of the flame-retardant polyphenyl ether/polyamide 66 composition comprises the following steps:
(1) drying the high-viscosity polyphenyl ether resin and the low-viscosity polyphenyl ether resin at the temperature of 100 ℃ for 4 hours, drying the low-viscosity polyamide 66 resin at the temperature of 130 ℃ for 4 hours, cooling, and adding the cooled high-viscosity polyphenyl ether resin, the cooled low-viscosity polyamide 66 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 and hydrogenated styrene-isoprene copolymer grafted maleic anhydride 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 of the first zone is 280 ℃, the temperature of the second zone is 285 ℃, the temperature of the third zone is 285 ℃, the temperature of the fourth zone is 290 ℃, the temperature of the fifth zone is 290 ℃, the temperature of the sixth zone is 285 ℃, the temperature of the seventh zone is 285 ℃, the temperature of the eighth zone is 285 ℃, the temperature of the die head is 285 ℃ and the rotating speed of the screw is 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 polyphenyl ether/polyamide 66 composition is prepared from the following raw materials in parts by weight:
the preparation method of the flame-retardant polyphenyl ether/polyamide 66 composition comprises the following steps:
(1) drying the high-viscosity polyphenyl ether resin and the low-viscosity polyphenyl ether resin at the temperature of 95 ℃ for 5 hours, drying the low-viscosity polyamide 66 resin at the temperature of 125 ℃ for 5 hours, cooling, and adding the cooled high-viscosity polyphenyl ether resin, the cooled low-viscosity polyamide 66 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 and hydrogenated styrene-isoprene copolymer grafted maleic anhydride 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 of the first zone was 275 deg.C, the temperature of the second zone was 280 deg.C, the temperature of the third zone was 280 deg.C, the temperature of the fourth zone was 285 deg.C, the temperature of the fifth zone was 285 deg.C, the temperature of the sixth zone was 280 deg.C, the temperature of the seventh zone was 280 deg.C, the temperature of the eighth zone was 280 deg.C, the temperature of the die head was 280 deg.C, and.
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 polyphenyl ether/polyamide 66 composition is prepared from the following raw materials in parts by weight:
the preparation method of the flame-retardant polyphenyl ether/polyamide 66 composition comprises the following steps:
(1) drying the high-viscosity polyphenyl ether resin and the low-viscosity polyphenyl ether resin at the temperature of 95 ℃ for 5 hours, drying the low-viscosity polyamide 66 resin at the temperature of 125 ℃ for 5 hours, cooling, and adding the cooled high-viscosity polyphenyl ether resin, the cooled low-viscosity polyamide 66 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 and hydrogenated styrene-isoprene copolymer grafted maleic anhydride 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 of the first zone was 275 deg.C, the temperature of the second zone was 280 deg.C, the temperature of the third zone was 280 deg.C, the temperature of the fourth zone was 285 deg.C, the temperature of the fifth zone was 285 deg.C, the temperature of the sixth zone was 280 deg.C, the temperature of the seventh zone was 280 deg.C, the temperature of the eighth zone was 280 deg.C, the temperature of the die head was 280 deg.C, and.
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 polyphenyl ether/polyamide 66 composition is prepared from the following raw materials in parts by weight:
the preparation method of the flame-retardant polyphenyl ether/polyamide 66 composition comprises the following steps:
(1) drying the high-viscosity polyphenyl ether resin and the low-viscosity polyphenyl ether resin at the temperature of 95 ℃ for 5 hours, drying the low-viscosity polyamide 66 resin at the temperature of 125 ℃ for 5 hours, cooling, and adding the cooled high-viscosity polyphenyl ether resin, the cooled low-viscosity polyamide 66 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 and hydrogenated styrene-isoprene copolymer grafted maleic anhydride 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 of the first zone was 275 deg.C, the temperature of the second zone was 280 deg.C, the temperature of the third zone was 280 deg.C, the temperature of the fourth zone was 285 deg.C, the temperature of the fifth zone was 285 deg.C, the temperature of the sixth zone was 280 deg.C, the temperature of the seventh zone was 280 deg.C, the temperature of the eighth zone was 280 deg.C, the temperature of the die head was 280 deg.C, and.
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 polyphenyl ether/polyamide 66 composition is prepared from the following raw materials in parts by weight:
the preparation method of the flame-retardant polyphenyl ether/polyamide 66 composition comprises the following steps:
(1) drying the high-viscosity polyphenyl ether resin and the low-viscosity polyphenyl ether resin at the temperature of 95 ℃ for 5 hours, drying the low-viscosity polyamide 66 resin at the temperature of 125 ℃ for 5 hours, cooling, and adding the cooled high-viscosity polyphenyl ether resin, the cooled low-viscosity polyamide 66 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 and hydrogenated styrene-isoprene copolymer grafted maleic anhydride 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 of the first zone was 275 deg.C, the temperature of the second zone was 280 deg.C, the temperature of the third zone was 280 deg.C, the temperature of the fourth zone was 285 deg.C, the temperature of the fifth zone was 285 deg.C, the temperature of the sixth zone was 280 deg.C, the temperature of the seventh zone was 280 deg.C, the temperature of the eighth zone was 280 deg.C, the temperature of the die head was 280 deg.C, and.
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 polyphenyl ether/polyamide 66 composition is prepared from the following raw materials in parts by weight:
the preparation method of the flame-retardant polyphenyl ether/polyamide 66 composition comprises the following steps:
(1) drying the high-viscosity polyphenyl ether resin and the low-viscosity polyphenyl ether resin at the temperature of 95 ℃ for 5 hours, drying the low-viscosity polyamide 66 resin at the temperature of 125 ℃ for 5 hours, cooling, and adding the cooled high-viscosity polyphenyl ether resin, the cooled low-viscosity polyamide 66 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 and hydrogenated styrene-isoprene copolymer grafted maleic anhydride 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 of the first zone was 275 deg.C, the temperature of the second zone was 280 deg.C, the temperature of the third zone was 280 deg.C, the temperature of the fourth zone was 285 deg.C, the temperature of the fifth zone was 285 deg.C, the temperature of the sixth zone was 280 deg.C, the temperature of the seventh zone was 280 deg.C, the temperature of the eighth zone was 280 deg.C, the temperature of the die head was 280 deg.C, and.
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 polyphenyl ether/polyamide 66 composition is prepared from the following raw materials in parts by weight:
the preparation method of the flame-retardant polyphenyl ether/polyamide 66 composition comprises the following steps:
(1) drying the high-viscosity polyphenyl ether resin and the low-viscosity polyphenyl ether resin at the temperature of 95 ℃ for 5 hours, drying the low-viscosity polyamide 66 resin at the temperature of 125 ℃ for 5 hours, cooling, and adding the cooled high-viscosity polyphenyl ether resin, the cooled low-viscosity polyamide 66 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 and hydrogenated styrene-isoprene copolymer grafted maleic anhydride 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 of the first zone was 275 deg.C, the temperature of the second zone was 280 deg.C, the temperature of the third zone was 280 deg.C, the temperature of the fourth zone was 285 deg.C, the temperature of the fifth zone was 285 deg.C, the temperature of the sixth zone was 280 deg.C, the temperature of the seventh zone was 280 deg.C, the temperature of the eighth zone was 280 deg.C, the temperature of the die head was 280 deg.C, and.
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 polyphenyl ether/polyamide 66 composition is prepared from the following raw materials in parts by weight:
the preparation method of the flame-retardant polyphenyl ether/polyamide 66 composition comprises the following steps:
(1) drying the high-viscosity polyphenyl ether resin and the low-viscosity polyphenyl ether resin at the temperature of 95 ℃ for 5 hours, drying the low-viscosity polyamide 66 resin at the temperature of 125 ℃ for 5 hours, cooling, and adding the cooled high-viscosity polyphenyl ether resin, the cooled low-viscosity polyamide 66 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 of the first zone was 275 deg.C, the temperature of the second zone was 280 deg.C, the temperature of the third zone was 280 deg.C, the temperature of the fourth zone was 285 deg.C, the temperature of the fifth zone was 285 deg.C, the temperature of the sixth zone was 280 deg.C, the temperature of the seventh zone was 280 deg.C, the temperature of the eighth zone was 280 deg.C, the temperature of the die head was 280 deg.C, and.
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 polyphenyl ether/polyamide 66 composition is prepared from the following raw materials in parts by weight:
the preparation method of the flame-retardant polyphenyl ether/polyamide 66 composition comprises the following steps:
(1) drying the high-viscosity polyphenyl ether resin and the low-viscosity polyphenyl ether resin at the temperature of 95 ℃ for 5 hours, drying the low-viscosity polyamide 66 resin at the temperature of 125 ℃ for 5 hours, cooling, and adding the cooled high-viscosity polyphenyl ether resin, the cooled low-viscosity polyamide 66 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 and hydrogenated styrene-butadiene-styrene copolymer grafted maleic anhydride into another high-speed stirrer (the rotating speed is 1000 revolutions per minute) 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 of the first zone was 275 deg.C, the temperature of the second zone was 280 deg.C, the temperature of the third zone was 280 deg.C, the temperature of the fourth zone was 285 deg.C, the temperature of the fifth zone was 285 deg.C, the temperature of the sixth zone was 280 deg.C, the temperature of the seventh zone was 280 deg.C, the temperature of the eighth zone was 280 deg.C, the temperature of the die head was 280 deg.C, and.
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
Remarking: a, the intrinsic viscosity of the high-viscosity PPO is 0.55 dL/g; b, the intrinsic viscosity of the low-viscosity PPO is 0.28dL/g, and the intrinsic viscosity of the low-viscosity PA66 is 1.1 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 polyphenylene ether/polyamide 66 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 flame retardant polyphenylene ether/polyamide 66 compositions of examples and comparative examples
In examples 1 to 7, the addition amounts of the high-viscosity polyphenylene ether resin, the low-viscosity polyamide 66 resin, SG, TDI, and SEPS-g-MAH were adjusted, and it can be seen from the table that as the addition amount of the low-viscosity polyamide 66 resin decreases (or the addition amount of the polyphenylene ether resin increases), the tensile strength and the melt index thereof decrease, and the notch impact strength thereof decreases after increasing, mainly because PA66 is a crystalline plastic, the tensile strength of the base material itself is high and the fluidity thereof is good, and PPO is an amorphous plastic, the tensile strength of the base material itself is not high, and the fluidity thereof is poor because the base material itself has rigid benzene rings in the main chain. Meanwhile, the addition amounts of SG, TDI and SEPS-g-MAH are increased, so that the compatibility between two phases of PPO and PA66 can be effectively improved, and the tensile strength and the notch impact strength of PPO/PA66 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-aminopropyl trimethoxy silane, the montmorillonite, the aluminum diethyl phosphinate 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 by comparison, it can be found that the tensile strength, notch impact strength, melt index and flame retardant property of the flame retardant polyphenylene ether/polyamide 66 composition prepared by adopting the screw parameters of the parallel twin-screw extruder described in example 7 are better.
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 fluidity of the high-viscosity polyphenyl ether resin with the intrinsic viscosity of 0.48dL/g 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 polyphenyl ether/polyamide 66 composition is only 7g/10min, so that the processing requirement cannot be met; example 7 in comparison with comparative example 2, comparative example 2 used a low-tack polyphenylene ether resin having an intrinsic viscosity of 0.28dL/g and a low-tack polyamide 66 resin having an intrinsic viscosity of 1.1dL/g, whereas example 7 used a low-tack polyphenylene ether resin having an intrinsic viscosity of 0.35dL/g and a low-tack polyamide 66 resin having an intrinsic viscosity of 1.42dL/g, the tensile strength and the notched impact strength of the flame retardant polyphenylene ether/polyamide 66 composition prepared in comparative example 2 decreased as the intrinsic viscosities of the polyphenylene ether resin and the polyamide 66 resin decreased, and the tensile strength and the notched impact strength of the flame retardant polyphenylene ether/polyamide 66 composition prepared in comparative example 2 were lower than those of example 7; example 7 in comparison with comparative example 3, which had no addition of SG, TDI and SEPS-g-MAH, had poor compatibility of PPO and PA66, and thus produced a flame retardant polyphenylene ether/polyamide 66 composition having tensile strength and notched impact strength much lower than those of example 7, and comparative example 3, which had no addition of gamma-aminopropyltrimethoxysilane, montmorillonite, aluminum diethylphosphinate and melamine aluminum zinc polyphosphate, had flame retardant properties UL 94 HB (1.6mm) and lower flame retardant properties than those of example 7; 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 polyphenylene ether/polyamide 66 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 (10)
1. The flame-retardant polyphenyl ether/polyamide 66 composition is characterized by being prepared from the following raw materials in parts by weight:
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 intrinsic viscosity of the low-viscosity polyamide 66 resin is 1.27-1.57 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.
2. The flame-retardant polyphenylene ether/polyamide 66 composition as claimed in claim 1, which is prepared from the following raw materials in parts by weight:
3. the flame retardant polyphenylene ether/polyamide 66 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%.
4. The flame retardant polyphenylene ether/polyamide 66 composition according to claim 1 or 2, wherein the maleic anhydride graft ratio in the hydrogenated styrene-isoprene copolymer grafted maleic anhydride is 0.8 to 1.5 wt%.
5. The flame retardant polyphenylene ether/polyamide 66 composition of claim 1 or 2, wherein 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.
6. A method for preparing a flame retardant polyphenylene ether/polyamide 66 composition according to any of claims 1 to 5, comprising the steps of:
(1) drying the high-viscosity polyphenyl ether resin and the low-viscosity polyphenyl ether resin at the temperature of 80-110 ℃ for 4-8 hours, drying the low-viscosity polyamide 66 resin at the temperature of 110-140 ℃ for 4-8 hours, cooling, and adding the cooled high-viscosity polyphenyl ether resin, the cooled low-viscosity polyamide 66 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 and hydrogenated styrene-isoprene copolymer grafted maleic anhydride 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 265-285 ℃, the temperature of the second zone is 270-290 ℃, the temperature of the third zone is 270-290 ℃, the temperature of the fourth zone is 275-295 ℃, the temperature of the fifth zone is 275-295 ℃, the temperature of the sixth zone is 270-290 ℃, the temperature of the seventh zone is 270-290 ℃, the temperature of the eighth zone is 270-290 ℃, the temperature of the die head is 270-290 ℃, and the rotating speed of the screw is 200-600 rpm.
7. The preparation method according to claim 6, wherein in the step (1), 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, and the low-viscosity polyamide 66 resin is dried at a temperature of 120-130 ℃ for 4-6 hours; the process parameters in the step (3) comprise: the temperature of the first zone is 270-280 ℃, the temperature of the second zone is 275-285 ℃, the temperature of the third zone is 275-285 ℃, the temperature of the fourth zone is 280-290 ℃, the temperature of the fifth zone is 280-290 ℃, the temperature of the sixth zone is 275-285 ℃, the temperature of the seventh zone is 275-285 ℃, the temperature of the eighth zone is 275-285 ℃, the temperature of the die head is 275-285 ℃ and the rotating speed of the screw is 300-500 rpm.
8. The production method according to claim 6 or 7, wherein the screw shape of the parallel twin-screw extruder is a single-screw 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.
9. The method according to claim 8, 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.
10. 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911019181.1A CN110724374B (en) | 2019-10-24 | 2019-10-24 | Flame-retardant polyphenyl ether/polyamide 66 composition and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911019181.1A CN110724374B (en) | 2019-10-24 | 2019-10-24 | Flame-retardant polyphenyl ether/polyamide 66 composition and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110724374A true CN110724374A (en) | 2020-01-24 |
| CN110724374B CN110724374B (en) | 2022-03-25 |
Family
ID=69221985
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911019181.1A Active CN110724374B (en) | 2019-10-24 | 2019-10-24 | Flame-retardant polyphenyl ether/polyamide 66 composition and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110724374B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114716818A (en) * | 2021-01-04 | 2022-07-08 | 上海凯赛生物技术股份有限公司 | Polyamide/polyphenyl ether resin composition and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0270796A1 (en) * | 1986-10-23 | 1988-06-15 | Mitsubishi Petrochemical Co., Ltd. | Process for the preparation of Polyphenylene ether-polyamide resin compositions |
| CN102876002A (en) * | 2011-07-11 | 2013-01-16 | 苍南县慧丰塑料有限公司 | Rapid molding high heat-resistant polyamide-polyphenyl ether alloy and preparation method thereof |
| CN103160107A (en) * | 2011-12-09 | 2013-06-19 | 上海杰事杰新材料(集团)股份有限公司 | Polyphenylene oxide/polyamide 6 blend alloy as well as preparation method and application for same |
| CN106316790A (en) * | 2016-08-18 | 2017-01-11 | 河源市鑫达科技有限公司 | Process for synthesizing zinc pentaerythritol in heat stabilizer |
| CN106479174A (en) * | 2016-11-08 | 2017-03-08 | 广东中塑新材料有限公司 | Fire-retardant enhancing copolyamide 6T composite and preparation method thereof |
| CN106519665A (en) * | 2016-11-08 | 2017-03-22 | 广东中塑新材料有限公司 | Flame-retardant reinforced polyamide composite material and preparation method thereof |
| CN106832915A (en) * | 2017-01-09 | 2017-06-13 | 广东中塑新材料有限公司 | High heat conductive insulating polyamide 6 T composites and preparation method thereof |
| CN106867245A (en) * | 2015-12-09 | 2017-06-20 | 旭化成株式会社 | The manufacture method of thermoplastic resin composition, products formed and products formed |
-
2019
- 2019-10-24 CN CN201911019181.1A patent/CN110724374B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0270796A1 (en) * | 1986-10-23 | 1988-06-15 | Mitsubishi Petrochemical Co., Ltd. | Process for the preparation of Polyphenylene ether-polyamide resin compositions |
| CN102876002A (en) * | 2011-07-11 | 2013-01-16 | 苍南县慧丰塑料有限公司 | Rapid molding high heat-resistant polyamide-polyphenyl ether alloy and preparation method thereof |
| CN103160107A (en) * | 2011-12-09 | 2013-06-19 | 上海杰事杰新材料(集团)股份有限公司 | Polyphenylene oxide/polyamide 6 blend alloy as well as preparation method and application for same |
| CN106867245A (en) * | 2015-12-09 | 2017-06-20 | 旭化成株式会社 | The manufacture method of thermoplastic resin composition, products formed and products formed |
| CN106316790A (en) * | 2016-08-18 | 2017-01-11 | 河源市鑫达科技有限公司 | Process for synthesizing zinc pentaerythritol in heat stabilizer |
| CN106479174A (en) * | 2016-11-08 | 2017-03-08 | 广东中塑新材料有限公司 | Fire-retardant enhancing copolyamide 6T composite and preparation method thereof |
| CN106519665A (en) * | 2016-11-08 | 2017-03-22 | 广东中塑新材料有限公司 | Flame-retardant reinforced polyamide composite material and preparation method thereof |
| CN106832915A (en) * | 2017-01-09 | 2017-06-13 | 广东中塑新材料有限公司 | High heat conductive insulating polyamide 6 T composites and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114716818A (en) * | 2021-01-04 | 2022-07-08 | 上海凯赛生物技术股份有限公司 | Polyamide/polyphenyl ether resin composition and preparation method thereof |
| CN114716818B (en) * | 2021-01-04 | 2023-12-08 | 上海凯赛生物技术股份有限公司 | Polyamide/polyphenyl ether resin composition and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110724374B (en) | 2022-03-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110791049B (en) | Flame-retardant reinforced polyphenyl ether/high impact polystyrene composition and preparation method thereof | |
| CN110643167B (en) | Flame-retardant reinforced polyphenyl ether/polyamide 66 composition and preparation method thereof | |
| CN110698852B (en) | Flame-retardant reinforced polyamide 6/polyphenyl ether composition and preparation method thereof | |
| CN103740025A (en) | Glass fiber reinforced inflaming retarding AES (Acrylonitrile-Ethylene propylene diene monomer-Styrene) composite material and preparation method thereof | |
| CN110669332B (en) | Flame-retardant polyamide 6/polyphenyl ether composition and preparation method thereof | |
| CN110776729B (en) | Flame-retardant polyphenyl ether/high impact polystyrene composition and preparation method thereof | |
| CN102492290B (en) | Preparation method for high-strength high-toughness flame-retardant polyamide | |
| CN101486824B (en) | Preparation of low temperature resistant environment friendly flame-retardant high impact resistance polystyrene composition | |
| CN110724374B (en) | Flame-retardant polyphenyl ether/polyamide 66 composition and preparation method thereof | |
| CN110698839B (en) | High dielectric constant polyphenyl ether/high impact polystyrene composition and preparation method thereof | |
| CN104693793A (en) | Flame-retardant reinforced nylon composite material and preparation method thereof | |
| CN110628202B (en) | High dielectric constant polyphenylene ether/polyamide 66 composition and preparation method thereof | |
| CN101864137B (en) | High impact-resistance anti-smoldering polystyrene resin composite and preparation method thereof | |
| CN110591332B (en) | Polyphenylene ether/polyamide 66 composition and method for making same | |
| CN110655787B (en) | Conductive polyphenylene ether/polyamide 66 composition and preparation method thereof | |
| CN113045892B (en) | Flame-retardant nylon 66 material and preparation method thereof | |
| CN110760177B (en) | Conductive polyphenyl ether/high impact polystyrene composition and preparation method thereof | |
| CN110643175B (en) | High dielectric constant polyamide 6/polyphenyl ether composition and preparation method thereof | |
| CN110684347B (en) | Conductive polyamide 6/polyphenyl ether composition and preparation method thereof | |
| CN102070886A (en) | PBT (polybutylene terephthalate)/PC (polycarbonate) alloy material with high CTI (comparative tracking index) value and high flame retardance and preparation method thereof | |
| CN110819095B (en) | Polyphenyl ether/high impact polystyrene composition and preparation method thereof | |
| CN110684346B (en) | Polyamide 6/polyphenyl ether composition and preparation method thereof | |
| CN112552677A (en) | Modified nylon 66 composition and preparation method thereof | |
| CN111875963A (en) | Low-linear expansion coefficient polyphenylene sulfide/nylon 6 composite material and preparation method thereof | |
| CN104725792A (en) | Low-smoke inorganic flame-retardant PET/ABS (polyethylene terephthalate/acrylonitrile-butadiene-styrene) alloy and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |