CN113930003A - MPPO material, mineral filling master batch and preparation method thereof - Google Patents

MPPO material, mineral filling master batch and preparation method thereof Download PDF

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CN113930003A
CN113930003A CN202111474191.1A CN202111474191A CN113930003A CN 113930003 A CN113930003 A CN 113930003A CN 202111474191 A CN202111474191 A CN 202111474191A CN 113930003 A CN113930003 A CN 113930003A
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CN113930003B (en
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衣晓良
房晓勇
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Hisense Visual Technology Co Ltd
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • 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
    • C08L71/126—Polyphenylene oxides modified by chemical after-treatment
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract

The invention provides an MPPO material, a mineral filling master batch and a preparation method thereof. The mineral filling master batch comprises, by weight, 16-32 parts of calcium carbonate mixture, 48-64 parts of modified talcum powder and 20 parts of polyethylene polymer base material. Wherein the calcium carbonate mixture comprises 15 to 20 parts by weight of calcium carbonate with the particle size of 0.5 to 2 mu m, 8 to 12 parts by weight of calcium carbonate with the particle size of 4 to 6 mu m and 70 to 75 parts by weight of calcium carbonate with the particle size of 25 to 35 mu m; the modified talcum powder comprises the following components in parts by weight (4-6): 1 talcum powder and surface treating agent, wherein the grain diameter of the talcum powder is 15-25 mu m. The MPPO material takes the mineral filled master batch as a raw material, so the MPPO material has the advantages of low shrinkage, high impact resistance and high fluidity, can be used for forming a product by sharing a mold with the existing PC/ABS or HIPS, and is particularly suitable for manufacturing large-size parts.

Description

MPPO material, mineral filling master batch and preparation method thereof
Technical Field
The invention relates to the technical field of composite materials, and particularly relates to an MPPO material, a mineral filling master batch and a preparation method thereof.
Background
Polyphenylene Oxide (PPO) is the fifth engineering plastic after polycarbonate PC, polyformaldehyde POM, polyamide PA, thermoplastic polyester PBT and PET, and has the advantages of high rigidity, high heat resistance, flame retardancy, wear resistance, pollution resistance, high strength, excellent electrical property and the like. Most of PPO in the market is used after being modified, and the modified polyphenyl ether is generally called MPPO.
With the understanding of human beings on environmental protection and the development of electronic and electric products towards high-performance miniaturization, the requirements on the flame-retardant MPPO material are higher and higher. The requirements for the MPPO material are now: high impact strength, good heat resistance, high flame retardant property and good fluidity. However, the low shrinkage, high fluidity and high impact resistance of the conventional MPPO materials are difficult to be simultaneously achieved.
Disclosure of Invention
The invention aims to provide a mineral filling master batch and a preparation method thereof, and the MPPO material prepared from the mineral filling master batch is adopted to solve the problems in the prior art.
In order to solve the technical problems, the invention provides a mineral filling master batch which comprises 16-32 parts by weight of calcium carbonate mixture, 48-64 parts by weight of modified talcum powder and 20 parts by weight of polyethylene polymer base stock; wherein the calcium carbonate mixture comprises 15-20 parts by weight of small-particle-size calcium carbonate with the particle size of 0.5-2 mu m, 8-12 parts by weight of medium-particle-size calcium carbonate with the particle size of 4-6 mu m and 70-75 parts by weight of large-particle-size calcium carbonate with the particle size of 25-35 mu m; the small particle size calcium carbonate, the medium particle size calcium carbonate and the large particle size calcium carbonate are all spherical;
the modified talcum powder comprises the following components in parts by weight (4-6): 1 talcum powder and a surface treating agent, wherein the particle size of the talcum powder is 15-25 mu m.
In one embodiment, the surface treatment agent is a siloxane-maleic anhydride copolymer.
In one embodiment, the surface treatment agent is synthesized from unsaturated siloxane, Maleic Anhydride (MA), dimethyl Azodiisobutyrate (AIBME), and isopropyl mercaptan in a ratio of 20:10:7: 2.
In one embodiment, in the calcium carbonate mixture, the surfaces of the small particle size calcium carbonate, the medium particle size calcium carbonate and the large particle size calcium carbonate are coated with a resin layer, and the resin layer is formed by performing a plasma surface treatment on the calcium carbonate mixture.
The invention also provides a preparation method of the mineral filling master batch, which comprises the following steps:
weighing 15-20 parts of small-particle-size calcium carbonate with the particle size of 0.5-2 microns, 8-12 parts of medium-particle-size calcium carbonate with the particle size of 4-6 microns and 70-75 parts of large-particle-size calcium carbonate with the particle size of 25-35 microns according to parts by weight, and uniformly mixing to obtain a calcium carbonate mixture;
weighing the following components in parts by weight (4-6): 1, uniformly mixing the talcum powder and the surface treating agent, and standing for 18-30 hours to obtain modified talcum powder; wherein the particle size of the talcum powder is 15-25 μm;
weighing 16-32 parts of the calcium carbonate mixture, 48-64 parts of the modified talcum powder and 20 parts of polyethylene polymer base material, uniformly mixing, and extruding and granulating by using a double-screw extruder to obtain the mineral filling master batch.
In one embodiment, the surface treatment agent is a siloxane-maleic anhydride copolymer.
In one embodiment, before the step of weighing 16 to 32 parts of the calcium carbonate mixture, 48 to 64 parts of the modified talc powder and 20 parts of the polyethylene polymer base material, and uniformly mixing, the method further comprises the following steps:
and drying the calcium carbonate mixture, placing the dried calcium carbonate mixture in a plasma generating device, vacuumizing, introducing ethylene, keeping constant pressure, starting the plasma generating device, and treating for 0.5-1 h.
The invention also provides an MPPO material, which comprises the following components in parts by weight:
40-65 parts of polyphenyl ether, 15-30 parts of high impact polystyrene, 8-12 parts of the mineral filling master batch, 3-10 parts of a toughening agent, 10-16 parts of a phosphorus flame retardant, 0.2-0.4 part of polytetrafluoroethylene, 1.6-2.4 parts of a dispersing agent and 0.1-0.5 part of an antioxidant;
wherein the intrinsic viscosity of the polyphenyl ether is 35-38dl/g, the content of volatile matters is less than 0.45%, the content of copper is less than 5ppm, and the melt index (300 ℃,10 kg) is more than or equal to 20g/10 min.
In one embodiment, the high impact polystyrene has a melt index (200 ℃, 5kg) of not less than 8.5g/10min, an impact strength of more than 110J/m, and a flexural strength of more than 2000 MPa.
In one embodiment, the toughening agent comprises at least one of styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene-butylene-styrene block copolymer (SEBS), acrylate core-shell copolymer (ACR), low molecular weight random copolymer of styrene-acrylonitrile (EMI), styrene-isoprene-styrene (SIS);
the phosphorus flame retardant comprises at least one of bisphenol A bis (diphenyl phosphate) (BDP), resorcinol bis (diphenyl phosphate) (RDP), triphenyl phosphate (TPP), 1, 3-phenylene tetrakis (2, 6-dimethylphenyl) phosphate (RDX), polyphosphazene flame retardant and bis-p-dihydroxybenzene (diphenyl phosphate) (HDP);
the antioxidant is at least one of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010), n-octadecyl beta- (-4-hydroxy-3, 5-di-tert-butylphenyl) propionate (antioxidant 1076), tris (2, 4-di-tert-butylphenyl) phosphite (antioxidant 168), 3, 9-bis (2, 4-di-tert-butylphenoxy) -2,4,8, 10-tetraoxo-3, 9-diphosphabicyclo [5.5] undecane (antioxidant 126);
the dispersant comprises at least one of Chlorinated Polyethylene (CPE), Low Density Polyethylene (LDPE), ethylene-vinyl acetate copolymer (EVA) and ethylene-octene copolymer (POE).
According to the technical scheme, the invention has the advantages and positive effects that:
the talcum powder in the mineral filling master batch can reduce the shrinkage of an MPPO material system, the molding shrinkage is close to that of a PC/ABS material, and calcium carbonate with different particle sizes is uniformly dispersed between the talcum powder and a high-molecular chain segment of the MPPO material to play a role of a plasticizer. And the selection of different particle sizes in the calcium carbonate mixture conforms to the cumulative distribution equation under tight packing, and has the minimum melt shear viscosity. And after the talcum powder is treated by the surface treating agent, the dispersity is improved, so that the problem of mineral thickening of the material is reduced, and the viscosity of the MPPO material is effectively reduced.
The MPPO material takes the mineral filling master batch as a raw material, so the MPPO material has the advantages of low shrinkage, high impact resistance and high fluidity, can be used for forming a product by sharing a mold with the existing PC/ABS or HIPS, and is particularly suitable for manufacturing large-size workpieces.
Drawings
FIG. 1 is a flow chart of the process for preparing mineral filled masterbatches of the present invention.
Detailed Description
Exemplary embodiments that embody features and advantages of the invention are described in detail below in the specification. It is to be understood that the invention is capable of other embodiments and that various changes in form and details may be made therein without departing from the scope of the invention and the description and drawings are to be regarded as illustrative in nature and not as restrictive.
For further explanation of the principles and construction of the present invention, reference will now be made in detail to the preferred embodiments of the present invention, which are illustrated in the accompanying drawings.
Currently, conventional polycarbonate and acrylonitrile-butadiene-styrene copolymers and blends (PC/ABS) and High Impact Polystyrene (HIPS) are often used for housings for liquid crystal televisions, laser televisions, and the like. Among them, the halogen-free flame retardant material is only PC/ABS solution for the requirements of halogen-free flame retardant in some specific markets. However, the price of flame retardant PC/ABS is high, so halogen-free and low cost modified polyphenylene ether (MPPO) is considered to be the most likely solution.
However, the existing injection molded parts of the MPPO are often smaller-sized parts such as an electronic control box, an electric glue box and the like, and the MPPO is not found in the rear shell of a larger-sized television. Moreover, when the MPPO is molded in the existing HIPS or PC/ABS mold, the problems of larger size shrinkage, poorer fluidity, poorer impact performance, larger size shrinkage and the like exist.
The invention provides a high-impact-resistance, high-flow and low-shrinkage MPPO material, a mineral filling master batch for preparing the MPPO material and a preparation method of the mineral filling master batch.
The mineral filled masterbatch is described in detail below.
The mineral filling master batch comprises, by weight, 16-32 parts of calcium carbonate mixture, 48-64 parts of modified talcum powder and 20 parts of polyethylene polymer base material.
The calcium carbonate mixture comprises 15-20 parts by weight of small-particle-size calcium carbonate with the particle size of 0.5-2 mu m, 8-12 parts by weight of medium-particle-size calcium carbonate with the particle size of 4-6 mu m and 70-75 parts by weight of large-particle-size calcium carbonate with the particle size of 25-35 mu m.
Specifically, the small particle size calcium carbonate, the medium particle size calcium carbonate and the large particle size calcium carbonate are all spherical.
Among them, if one of the calcium carbonates is used alone, that is, the small-particle calcium carbonate, the medium-particle calcium carbonate or the large-particle calcium carbonate is used alone, the calcium carbonates are easy to agglomerate to form loose secondary particles due to the large electrostatic charge adsorption force, which is not beneficial to the reduction of viscosity. And the particle size of calcium carbonate in the calcium carbonate mixture is selected to meet the requirement of the mixture with close packing accumulation distribution, so that the viscosity of the MPPO material is reduced.
Furthermore, in the calcium carbonate mixture, the surfaces of the small-particle-size calcium carbonate, the medium-particle-size calcium carbonate and the large-particle-size calcium carbonate are also coated with resin layers. Specifically, the calcium carbonate mixture is subjected to plasma surface treatment by using a radio frequency plasma generating device, so that the surface of the calcium carbonate mixture is coated with a thin resin layer.
In this example, the resin layer is a polyethylene layer. The method can be realized by introducing ethylene in the plasma surface treatment process.
The modified talcum powder comprises the following components in parts by weight (4-6): 1 talc powder and a surface treatment agent.
The particle size of the talcum powder is 15-25 μm. In this example, the talc powder is in the form of a flake.
Under the action of water or air, the talcum powder can form active functional groups such as Si-O-, OH-, Si-OH and the like on the surface.
The surface treating agent is siloxane-maleic anhydride copolymer, and its packageIncluding Si2+and-O-. Wherein, Si2+and-O-is used as an anchoring group to interact with active groups on the surface of the talcum powder, so that the dispersion of the talcum powder is facilitated.
Wherein the surface treating agent is obtained by synthesizing unsaturated siloxane, Maleic Anhydride (MA), dimethyl Azodiisobutyrate (AIBME) and isopropyl mercaptan in a ratio of 20:10:7: 2.
The preparation method comprises the following steps:
weighing unsaturated siloxane, Maleic Anhydride (MA), dimethyl Azodiisobutyrate (AIBME) and isopropyl mercaptan according to the ratio of 20:10:7:2 in parts by weight, gradually adding the weighed unsaturated siloxane, Maleic Anhydride (MA), dimethyl Azodiisobutyrate (AIBME) and isopropyl mercaptan into a flask, heating the mixture in a water bath at the temperature of 80 ℃, and finishing the reaction for 3 hours to obtain the surface treating agent.
The reaction formula for the preparation of the surface treating agent is as follows:
Figure BDA0003391675500000051
the polyethylene polymer base material is used for forming the mineral filling master batch.
Referring to fig. 1, the preparation method of the mineral-filled masterbatch includes the following steps:
s1, weighing 15-20 parts by weight of small-particle-size calcium carbonate with the particle size of 0.5-2 microns, 8-12 parts by weight of medium-particle-size calcium carbonate with the particle size of 4-6 microns and 70-75 parts by weight of large-particle-size calcium carbonate with the particle size of 25-35 microns, and uniformly mixing to obtain a calcium carbonate mixture.
S2, weighing the following components in parts by weight (4-6): 1, uniformly mixing the talcum powder and the surface treating agent, and standing for 18-30 h to obtain the modified talcum powder. Wherein the particle size of the talcum powder is 15-25 μm. The surface treating agent is siloxane-maleic anhydride copolymer.
Specifically, the talcum powder and the surface treating agent are stirred and mixed in a low mixing pot, and the mixture is kept still for 18 to 30 hours after stirring is finished, so that the modified talcum powder is obtained.
S3, weighing 16-32 parts of the calcium carbonate mixture, 48-64 parts of modified talcum powder and 20 parts of polyethylene polymer base material, uniformly mixing, and performing extrusion granulation by using a double-screw extruder to obtain the mineral filling master batch.
Specifically, the calcium carbonate mixture, the modified talc powder and the polyethylene polymer base material were mixed in a high-speed mixer at 180r/min for 2 min.
The processing temperature of the double-screw extruder is 180-200 ℃, the extruder comprises seven temperature zones, wherein one temperature zone is 180 ℃, the second temperature zone is 185 ℃, the third temperature zone is 200 ℃, the fourth temperature zone is 200 ℃, the fifth temperature zone is 190 ℃, the sixth temperature zone is 195 ℃, the seventh temperature zone is 195 ℃, and the screw rotating speed is 350 r/min.
Before step S3, that is, before mixing the calcium carbonate mixture with the modified talc powder and the polyethylene polymer base, the method further comprises the steps of:
and drying the calcium carbonate mixture, placing the dried calcium carbonate mixture in a plasma generating device, vacuumizing, introducing ethylene, keeping constant pressure, starting the plasma generating device, and treating for 0.5-1 h to obtain the calcium carbonate mixture with the surface coated with the resin layer.
Specifically, the calcium carbonate mixture was dried in a vacuum forced air drying oven at 100 ± 5 ℃. And placing the dried calcium carbonate mixture in a plasma generating device, vacuumizing, introducing ethylene, keeping constant pressure, starting the plasma generating device, and treating for 30min to obtain the calcium carbonate mixture with the surface coated with the resin layer.
The mineral filling master batch in the embodiment takes the talcum powder as a main filler and the calcium carbonate mixture as an auxiliary filler, so that the low shrinkage rate and the high fluidity of the MPPO material are ensured when the mineral filling master batch is used for preparing the MPPO material.
Example one
The mineral filling master batch comprises 16 parts by weight of calcium carbonate mixture, 64 parts by weight of modified talcum powder and 20 parts by weight of polyethylene polymer base stock.
Wherein the calcium carbonate mixture comprises 15 parts by weight of small-particle-size calcium carbonate having a particle size of 0.5 μm, 10 parts by weight of medium-particle-size calcium carbonate having a particle size of 4 μm, and 75 parts by weight of large-particle-size calcium carbonate having a particle size of 35 μm.
The modified talcum powder comprises the following components in parts by weight: 1 talc powder and a surface treatment agent.
Example two
The mineral filling master batch comprises 32 parts by weight of calcium carbonate mixture, 48 parts by weight of modified talcum powder and 20 parts by weight of polyethylene polymer base material.
Wherein the calcium carbonate mixture comprises 20 parts by weight of small-particle-size calcium carbonate having a particle size of 2 μm, 8 parts by weight of medium-particle-size calcium carbonate having a particle size of 6 μm, and 72 parts by weight of large-particle-size calcium carbonate having a particle size of 25 μm.
The modified talcum powder comprises the following components in parts by weight: 1 talc powder and a surface treatment agent.
EXAMPLE III
The mineral filling master batch comprises 25 parts by weight of calcium carbonate mixture, 55 parts by weight of modified talcum powder and 20 parts by weight of polyethylene polymer base material.
Wherein the calcium carbonate mixture comprises 18 parts by weight of small-particle-size calcium carbonate having a particle size of 1 μm, 10 parts by weight of medium-particle-size calcium carbonate having a particle size of 5 μm, and 72 parts by weight of large-particle-size calcium carbonate having a particle size of 30 μm.
The modified talcum powder comprises the following components in parts by weight: 1 talc powder and a surface treatment agent.
Example four
The mineral filling master batch comprises 20 parts by weight of calcium carbonate mixture, 60 parts by weight of modified talcum powder and 20 parts by weight of polyethylene polymer base material.
Wherein the calcium carbonate mixture comprises 18 parts by weight of small-particle-size calcium carbonate having a particle size of 1.5 μm, 12 parts by weight of medium-particle-size calcium carbonate having a particle size of 4.5 μm, and 70 parts by weight of large-particle-size calcium carbonate having a particle size of 32 μm.
The modified talcum powder comprises the following components in parts by weight of 5.5: 1 talc powder and a surface treatment agent.
The invention also provides the MPPO material, which has the advantages of low shrinkage, high impact resistance and high fluidity, can be used for forming products by sharing a mold with the existing PC/ABS or HIPS, and is particularly suitable for manufacturing large-size parts.
Specifically, the MPPO material comprises, by weight, 40-65 parts of polyphenyl ether, 15-30 parts of high impact polystyrene, 8-12 parts of mineral filling master batches, 3-10 parts of toughening agents, 10-16 parts of phosphorus flame retardants, 0.2-0.4 part of polytetrafluoroethylene, 1.6-2.4 parts of dispersing agents and 0.1-0.5 part of antioxidants.
Wherein the intrinsic viscosity of the polyphenylene oxide (PPO) is 35-38dl/g, the content of volatile matters is less than 0.45%, the content of copper is less than 5ppm, and the melt index (300 ℃,10 kg) is more than or equal to 20g/10 min. The PPO has smaller intrinsic viscosity and larger molecular weight distribution, so that the PPO has higher fluidity.
High Impact Polystyrene (HIPS) has the characteristics of high fluidity and high impact resistance. Specifically, the melt index (200 ℃, 5kg) of the high impact polystyrene is more than or equal to 8.5g/10min, the impact strength is more than 110J/m, and the bending strength is more than 2000 Mpa.
The toughening agent comprises at least one of styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene-butylene-styrene block copolymer (SEBS), acrylate core-shell copolymer (ACR), styrene-acrylonitrile low molecular weight random copolymer (EMI) and styrene-isoprene-styrene (SIS). That is, the toughening agent may be any one of the above, may be a mixture of any two of the above, and may be a mixture of any three or other amounts.
The phosphorus flame retardant comprises at least one of bisphenol A bis (diphenyl phosphate) (BDP), resorcinol bis (diphenyl phosphate) (RDP), triphenyl phosphate (TPP), 1, 3-phenylene tetrakis (2, 6-dimethylphenyl) phosphate (RDX), polyphosphazene flame retardant and bis-p-dihydroxybenzene (diphenyl phosphate) (HDP). None of the above flame retardants contain halogen. The phosphorus-based flame retardant may be any one of the above, may be a mixture of any two of the above, and may be a mixture of any three or other amounts.
Polytetrafluoroethylene (PTFE) has the characteristics of corrosion resistance, aging resistance, impact resistance, and high temperature resistance.
The antioxidant is at least one of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010), n-octadecyl beta- (-4-hydroxy-3, 5-di-tert-butylphenyl) propionate (antioxidant 1076), tris (2, 4-di-tert-butylphenyl) phosphite (antioxidant 168), 3, 9-bis (2, 4-di-tert-butylphenoxy) -2,4,8, 10-tetraoxo-3, 9-diphosphabicyclo [5.5] undecane (antioxidant 126). That is, the toughening agent may be any one of the above, may be a mixture of any two of the above, may be a mixture of any three of the above, or the like.
The dispersant comprises at least one of Chlorinated Polyethylene (CPE), Low Density Polyethylene (LDPE), ethylene-vinyl acetate copolymer (EVA) and ethylene-octene copolymer (POE).
The MPPO material in the application has the following principles of low shrinkage, high fluidity and high impact resistance:
the PPO and the HIPS enable the MPPO material to have high impact resistance, and the impact resistance is further improved by adding the toughening agent.
The addition of the talcum powder in the mineral filling master batch reduces the shrinkage rate of an MPPO material system, the molding shrinkage rate is close to that of a PC/ABS material, and calcium carbonate with different particle sizes is uniformly dispersed among the talcum powder, high-molecular chain segments of PPO and HIPS to play a role of a plasticizer. And the selection of different particle sizes in the calcium carbonate mixture conforms to the cumulative distribution equation under tight packing, and has the minimum melt shear viscosity.
The addition modes of large-particle-size non-spherical filling and small-particle-size spherical filling in the calcium carbonate mixture and the modified talcum powder can effectively reduce the entanglement of a high-molecular chain segment. The problem of viscosity increase of the MPPO system caused by addition of mineral filling can be effectively reduced.
In addition, after the talcum powder is treated by the surface treating agent, the dispersity is improved, so that the problem of mineral thickening of the material is solved, and the viscosity of the MPPO material is effectively reduced.
Further, after the surface treatment, the surface of the calcium carbonate mixture is coated with a resin layer, specifically a polyethylene film. The polyethylene film has excellent compatibility with the dispersing agent, and can effectively disperse particles of the calcium carbonate mixture, so that the calcium carbonate mixture can be used as a plasticizer of the whole system.
The inventors of the present application realized the effects of low shrinkage, high fluidity and high impact resistance of the MPPO material by strictly designing the contents of the respective components, which are described below through the respective examples. In each example, the mineral filler masterbatch of example three was used as a raw material.
EXAMPLE five
The MPPO material comprises, by weight, 40 parts of polyphenyl ether, 30 parts of high impact polystyrene, 12 parts of mineral filling master batch, 10 parts of toughening agent, 16 parts of phosphorus flame retardant, 0.4 part of PTFE, 2.4 parts of dispersing agent and 0.1 part of antioxidant.
The preparation method of the MPPO material in this embodiment includes the following steps:
weighing the raw materials in the embodiment, putting the raw materials into a high-speed mixer, and mixing for 2min at a speed of 300r/min to obtain a mixture. And extruding and granulating the mixture by a double-screw extruder to obtain the MPPO material. The processing temperature of the double-screw extruder is 225-255 ℃, the extruder comprises seven temperature zones, wherein the temperature of one zone is 230 ℃, the temperature of the second zone is 245 ℃, the temperature of the third zone is 255 ℃, the temperature of the fourth zone is 255 ℃, the temperature of the fifth zone is 255 ℃, the temperature of the sixth zone is 245 ℃, the temperature of the seventh zone is 235 ℃, and the rotation speed of the screw is 550 r/min.
EXAMPLE six
The MPPO material comprises, by weight, 40 parts of polyphenyl ether, 30 parts of high impact polystyrene, 11 parts of mineral filling master batch, 8 parts of toughening agent, 14 parts of phosphorus flame retardant, 0.4 part of PTFE, 2 parts of dispersing agent and 0.5 part of antioxidant.
The preparation method of the MPPO material in this embodiment includes the following steps:
weighing the raw materials in the embodiment, putting the raw materials into a high-speed mixer, and mixing for 2min at a speed of 300r/min to obtain a mixture. And extruding and granulating the mixture by a double-screw extruder to obtain the MPPO material. The processing temperature of the double-screw extruder is 225-255 ℃, the extruder comprises seven temperature zones, wherein the temperature of one zone is 230 ℃, the temperature of the second zone is 245 ℃, the temperature of the third zone is 255 ℃, the temperature of the fourth zone is 255 ℃, the temperature of the fifth zone is 255 ℃, the temperature of the sixth zone is 245 ℃, the temperature of the seventh zone is 235 ℃, and the rotation speed of the screw is 550 r/min.
EXAMPLE seven
The MPPO material comprises, by weight, 50 parts of polyphenyl ether, 20 parts of high impact polystyrene, 12 parts of mineral filling master batch, 5 parts of toughening agent, 13 parts of phosphorus flame retardant, 0.3 part of PTFE, 2.1 parts of dispersing agent and 0.2 part of antioxidant.
The preparation method of the MPPO material in this embodiment includes the following steps:
weighing the raw materials in the embodiment, putting the raw materials into a high-speed mixer, and mixing for 2min at a speed of 300r/min to obtain a mixture. And extruding and granulating the mixture by a double-screw extruder to obtain the MPPO material. The processing temperature of the double-screw extruder is 225-255 ℃, the extruder comprises seven temperature zones, wherein the temperature of one zone is 230 ℃, the temperature of the second zone is 245 ℃, the temperature of the third zone is 255 ℃, the temperature of the fourth zone is 255 ℃, the temperature of the fifth zone is 255 ℃, the temperature of the sixth zone is 245 ℃, the temperature of the seventh zone is 235 ℃, and the rotation speed of the screw is 550 r/min.
Example eight
The MPPO material comprises, by weight, 50 parts of polyphenyl ether, 20 parts of high impact polystyrene, 10 parts of mineral filling master batch, 5 parts of toughening agent, 13 parts of phosphorus flame retardant, 0.3 part of PTFE, 1.9 parts of dispersing agent and 0.4 part of antioxidant.
The preparation method of the MPPO material in this embodiment includes the following steps:
weighing the raw materials in the embodiment, putting the raw materials into a high-speed mixer, and mixing for 2min at a speed of 300r/min to obtain a mixture. And extruding and granulating the mixture by a double-screw extruder to obtain the MPPO material. The processing temperature of the double-screw extruder is 225-255 ℃, the extruder comprises seven temperature zones, wherein the temperature of one zone is 230 ℃, the temperature of the second zone is 245 ℃, the temperature of the third zone is 255 ℃, the temperature of the fourth zone is 255 ℃, the temperature of the fifth zone is 255 ℃, the temperature of the sixth zone is 245 ℃, the temperature of the seventh zone is 235 ℃, and the rotation speed of the screw is 550 r/min.
Example nine
The MPPO material comprises 65 parts of polyphenyl ether, 15 parts of high impact polystyrene, 8 parts of mineral filling master batch, 3 parts of toughening agent, 10 parts of phosphorus flame retardant, 0.2 part of PTFE, 1.6 parts of dispersing agent and 0.5 part of antioxidant in parts by weight.
The preparation method of the MPPO material in this embodiment includes the following steps:
weighing the raw materials in the embodiment, putting the raw materials into a high-speed mixer, and mixing for 2min at a speed of 300r/min to obtain a mixture. And extruding and granulating the mixture by a double-screw extruder to obtain the MPPO material. The processing temperature of the double-screw extruder is 225-255 ℃, the extruder comprises seven temperature zones, wherein the temperature of one zone is 230 ℃, the temperature of the second zone is 245 ℃, the temperature of the third zone is 255 ℃, the temperature of the fourth zone is 255 ℃, the temperature of the fifth zone is 255 ℃, the temperature of the sixth zone is 245 ℃, the temperature of the seventh zone is 235 ℃, and the rotation speed of the screw is 550 r/min.
Example ten
The MPPO material comprises 65 parts of polyphenyl ether, 15 parts of high impact polystyrene, 9 parts of mineral filling master batch, 5 parts of toughening agent, 10 parts of phosphorus flame retardant, 0.2 part of PTFE, 1.8 parts of dispersing agent and 0.3 part of antioxidant in parts by weight.
The preparation method of the MPPO material in this embodiment includes the following steps:
weighing the raw materials in the embodiment, putting the raw materials into a high-speed mixer, and mixing for 2min at a speed of 300r/min to obtain a mixture. And extruding and granulating the mixture by a double-screw extruder to obtain the MPPO material. The processing temperature of the double-screw extruder is 225-255 ℃, the extruder comprises seven temperature zones, wherein the temperature of one zone is 230 ℃, the temperature of the second zone is 245 ℃, the temperature of the third zone is 255 ℃, the temperature of the fourth zone is 255 ℃, the temperature of the fifth zone is 255 ℃, the temperature of the sixth zone is 245 ℃, the temperature of the seventh zone is 235 ℃, and the rotation speed of the screw is 550 r/min.
Comparative example 1
The MPPO material comprises 65 parts of polyphenyl ether, 15 parts of high impact polystyrene, 8 parts of talcum powder, 5 parts of toughening agent, 10 parts of phosphorus flame retardant, 0.2 part of PTFE and 0.5 part of antioxidant in parts by weight.
The preparation method of the MPPO material in this embodiment includes the following steps:
weighing the raw materials in the embodiment, putting the raw materials into a high-speed mixer, and mixing for 2min at a speed of 300r/min to obtain a mixture. And extruding and granulating the mixture by a double-screw extruder to obtain the MPPO material. The processing temperature of the double-screw extruder is 225-255 ℃, the extruder comprises seven temperature zones, wherein the temperature of one zone is 230 ℃, the temperature of the second zone is 245 ℃, the temperature of the third zone is 255 ℃, the temperature of the fourth zone is 255 ℃, the temperature of the fifth zone is 255 ℃, the temperature of the sixth zone is 245 ℃, the temperature of the seventh zone is 235 ℃, and the rotation speed of the screw is 550 r/min.
Comparative example 2
The MPPO material comprises 65 parts of polyphenyl ether, 15 parts of high impact polystyrene, 5 parts of toughening agent, 10 parts of phosphorus flame retardant, 0.2 part of PTFE and 0.5 part of antioxidant in parts by weight.
The preparation method of the MPPO material in this embodiment includes the following steps:
weighing the raw materials in the embodiment, putting the raw materials into a high-speed mixer, and mixing for 2min at a speed of 300r/min to obtain a mixture. And extruding and granulating the mixture by a double-screw extruder to obtain the MPPO material. The processing temperature of the double-screw extruder is 225-255 ℃, the extruder comprises seven temperature zones, wherein the temperature of one zone is 230 ℃, the temperature of the second zone is 245 ℃, the temperature of the third zone is 255 ℃, the temperature of the fourth zone is 255 ℃, the temperature of the fifth zone is 255 ℃, the temperature of the sixth zone is 245 ℃, the temperature of the seventh zone is 235 ℃, and the rotation speed of the screw is 550 r/min.
The MPPO materials of examples 5-10 and the MPPO materials of comparative examples 1-2 were subjected to performance tests, and the performances are shown in Table 1.
Wherein the melt fingers are tested according to a test standard ASTM 1238 and are tested at a temperature of 280 ℃ and a load of 5kg, the tensile strength is tested according to a test standard ASTM D638, the flexural strength and the flexural modulus are tested according to a test standard ASTM D790, and the notched Izod/J.m.-1The test is carried out according to the test standard ASTM D256, the heat distortion temperature is tested according to the test standard ASTM D648, the flame retardant performance is tested according to the test standard UL941.6 mm, and the size of the injection-molded 55 rear shell and the appearance of the high-low temperature impact rear shell are tested according to the enterprise standard.
TABLE 1 Properties of MPPO materials
Figure BDA0003391675500000121
As can be seen from the above table, in comparative example 2, the size of the television rear shell is smaller than the standard by about 1.3mm without adding mineral fillers, which affects the product assembly. Comparative example 1 after adding a certain proportion of talcum powder, although the size of the back shell basically meets the requirements, the material has overall performance, lower impact strength and poorer fluidity, the problem of cracking occurs when the high and low temperature impact of the whole machine is tested, the appearance of an injection molded part with poorer fluidity has defects, and partial screw holes have the defect of being not full.
The MPPO material of mineral filling master batch is added in the embodiment 5-10, and the final product has good material flowability and no gas mark defect in appearance on the premise of ensuring the size. And no defects are generated after the reliability test.
According to the technical scheme, the invention has the advantages and positive effects that:
the talcum powder in the mineral filling master batch can reduce the shrinkage of an MPPO material system, the molding shrinkage is close to that of a PC/ABS material, and calcium carbonate with different particle sizes is uniformly dispersed between the talcum powder and a high-molecular chain segment of the MPPO material to play a role of a plasticizer. And the selection of different particle sizes in the calcium carbonate mixture conforms to the cumulative distribution equation under tight packing, and has the minimum melt shear viscosity. And after the talcum powder is treated by the surface treating agent, the dispersity is improved, so that the problem of mineral thickening of the material is reduced, and the viscosity of the MPPO material is effectively reduced.
The MPPO material takes the mineral filling master batch as a raw material, so the MPPO material has the advantages of low shrinkage, high impact resistance and high fluidity, can be used for forming a product by sharing a mold with the existing PC/ABS or HIPS, and is particularly suitable for manufacturing large-size workpieces.
While the present invention has been described with reference to several exemplary embodiments, it is understood that the terminology used is intended to be in the nature of words of description and illustration, rather than of limitation. As the present invention may be embodied in several forms without departing from the spirit or essential characteristics thereof, it should also be understood that the above-described embodiments are not limited by any of the details of the foregoing description, but rather should be construed broadly within its spirit and scope as defined in the appended claims, and therefore all changes and modifications that fall within the meets and bounds of the claims, or equivalences of such meets and bounds are therefore intended to be embraced by the appended claims.

Claims (10)

1. A mineral filling master batch is characterized by comprising 16-32 parts by weight of calcium carbonate mixture, 48-64 parts by weight of modified talcum powder and 20 parts by weight of polyethylene polymer base stock;
wherein the calcium carbonate mixture comprises 15-20 parts by weight of small-particle-size calcium carbonate with the particle size of 0.5-2 mu m, 8-12 parts by weight of medium-particle-size calcium carbonate with the particle size of 4-6 mu m and 70-75 parts by weight of large-particle-size calcium carbonate with the particle size of 25-35 mu m; the small particle size calcium carbonate, the medium particle size calcium carbonate and the large particle size calcium carbonate are all spherical;
the modified talcum powder comprises the following components in parts by weight (4-6): 1 talcum powder and a surface treating agent, wherein the particle size of the talcum powder is 15-25 mu m.
2. The mineral-filled masterbatch of claim 1, wherein the surface treatment agent is a siloxane-maleic anhydride copolymer.
3. The mineral-filled masterbatch of claim 2, wherein the surface treatment agent is obtained by synthesis of unsaturated siloxane, Maleic Anhydride (MA), dimethyl Azodiisobutyrate (AIBME), and isopropyl mercaptan in a ratio of 20:10:7: 2.
4. The mineral-filled masterbatch according to claim 1, wherein the calcium carbonate mixture is formed by surface-treating the calcium carbonate mixture with plasma, and the surfaces of the small-particle-size calcium carbonate, the medium-particle-size calcium carbonate and the large-particle-size calcium carbonate are coated with a resin layer.
5. The preparation method of the mineral filling master batch is characterized by comprising the following steps:
weighing 15-20 parts of small-particle-size calcium carbonate with the particle size of 0.5-2 microns, 8-12 parts of medium-particle-size calcium carbonate with the particle size of 4-6 microns and 70-75 parts of large-particle-size calcium carbonate with the particle size of 25-35 microns according to parts by weight, and uniformly mixing to obtain a calcium carbonate mixture;
weighing the following components in parts by weight (4-6): 1, uniformly mixing the talcum powder and the surface treating agent, and standing for 18-30 hours to obtain modified talcum powder; wherein the particle size of the talcum powder is 15-25 μm;
weighing 16-32 parts of the calcium carbonate mixture, 48-64 parts of the modified talcum powder and 20 parts of polyethylene polymer base material, uniformly mixing, and extruding and granulating by using a double-screw extruder to obtain the mineral filling master batch.
6. The method of preparing a mineral-filled masterbatch according to claim 5 wherein the surface treatment agent is a siloxane-maleic anhydride copolymer.
7. The preparation method of the mineral-filled masterbatch according to claim 5, wherein the method further comprises the following steps before the step of weighing 16-32 parts of the calcium carbonate mixture, 48-64 parts of the modified talc powder and 20 parts of the polyethylene polymer base material, and uniformly mixing:
and drying the calcium carbonate mixture, placing the dried calcium carbonate mixture in a plasma generating device, vacuumizing, introducing ethylene, keeping constant pressure, starting the plasma generating device, and treating for 0.5-1 h.
8. The MPPO material is characterized by comprising the following components in parts by weight:
40-65 parts of polyphenyl ether, 15-30 parts of high impact polystyrene, 8-12 parts of the mineral filled master batch as claimed in any one of claims 1-7, 3-10 parts of a toughening agent, 10-16 parts of a phosphorus flame retardant, 0.2-0.4 part of polytetrafluoroethylene, 1.6-2.4 parts of a dispersing agent and 0.1-0.5 part of an antioxidant;
wherein the intrinsic viscosity of the polyphenyl ether is 35-38dl/g, the content of volatile matters is less than 0.45%, the content of copper is less than 5ppm, and the melt index (300 ℃,10 kg) is more than or equal to 20g/10 min.
9. The MPPO material of claim 8, wherein the high impact polystyrene has a melt index (200 ℃, 5kg) of 8.5g/10min or more, an impact strength of 110J/m, and a flexural strength of 2000MPa or more.
10. The MPPO material of claim 8, wherein the toughening agent includes at least one of styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene-butylene-styrene block copolymer (SEBS), acrylate core-shell copolymer (ACR), low molecular weight random copolymer of styrene-acrylonitrile (EMI), styrene-isoprene-styrene (SIS);
the phosphorus flame retardant comprises at least one of bisphenol A bis (diphenyl phosphate) (BDP), resorcinol bis (diphenyl phosphate) (RDP), triphenyl phosphate (TPP), 1, 3-phenylene tetrakis (2, 6-dimethylphenyl) phosphate (RDX), polyphosphazene flame retardant and bis-p-dihydroxybenzene (diphenyl phosphate) (HDP);
the antioxidant is at least one of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010), n-octadecyl beta- (-4-hydroxy-3, 5-di-tert-butylphenyl) propionate (antioxidant 1076), tris (2, 4-di-tert-butylphenyl) phosphite (antioxidant 168), 3, 9-bis (2, 4-di-tert-butylphenoxy) -2,4,8, 10-tetraoxo-3, 9-diphosphabicyclo [5.5] undecane (antioxidant 126);
the dispersant comprises at least one of Chlorinated Polyethylene (CPE), Low Density Polyethylene (LDPE), ethylene-vinyl acetate copolymer (EVA) and ethylene-octene copolymer (POE).
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