CN111019319A - PPE material for mobile phone charger shell and preparation method thereof - Google Patents
PPE material for mobile phone charger shell and preparation method thereof Download PDFInfo
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- CN111019319A CN111019319A CN201911365793.6A CN201911365793A CN111019319A CN 111019319 A CN111019319 A CN 111019319A CN 201911365793 A CN201911365793 A CN 201911365793A CN 111019319 A CN111019319 A CN 111019319A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
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Abstract
The invention discloses a PPE material for a mobile phone charger shell and a preparation method thereof. The PPE composite material is prepared by adopting a PPE/HIPS/SEBS ternary blend as a basic material, adding a compatibilizer, a flame retardant, a flame-retardant synergist, an organic silicon lubricant and an antioxidant, and performing extrusion granulation by a double-screw extruder. According to the invention, the alkylated hypophosphite flame retardant is adopted, and the nano zinc oxide is added as the flame-retardant synergist, so that a high-efficiency flame-retardant effect is obtained under the condition of low total addition amount of the flame retardant. By fully utilizing the high strength, high wear resistance and high heat resistance of the PPE and the flexibility and easy processability of the HIPS and the SEBS and regulating and controlling the adding proportion of the PPE, the HIPS and the SEBS, the prepared PPE composite material has the characteristics of flame retardance, wear resistance, heat resistance, high strength, easy processing and the like, and can be applied to materials such as mobile phone charger shells and the like.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a PPE material for a mobile phone charger shell and a preparation method thereof.
Background
In recent years, the rapid development of mobile communication enables the mobile phone and the accessories thereof to obtain wide application space. The mobile phone charger, as a daily necessary mobile phone accessory product, has the characteristics of long service time and frequent use in use, so the requirements on the performance of the mobile phone charger are higher and higher. The current mobile phone charger shell material mainly adopts resins such as PC, ABS, PC/ABS, HIPS and the like, but the materials still have some defects: such as poor flame retardancy, insufficient heat resistance, low strength, and difficulty in processing and molding.
Polyphenylene Ether (PPE) material is one of five general engineering plastics, not only has certain intrinsic flame retardance, but also has the advantages of good heat resistance, high strength, high rigidity, excellent electrical property, wear resistance, no toxicity, pollution resistance and the like, so that the PPE material is widely applied to the fields of traffic, spaceflight, electronic and electric appliances and the like. But the processing temperature of the polyphenyl ether material is very high, the injection molding temperature is more than or equal to 300 ℃, and the internal stress of the injection molding product is very large, so that the problems of cracking and the like are easily caused; on the other hand, polyphenylene ether materials are more brittle and the addition of a toughening agent tends to increase their flammability. The above problems lead to limitations in their applications. Therefore, polyphenylene oxide materials are used in the electronic field, such as the housing materials of electronic products like mobile phone chargers, relays, connectors, etc., and must be blended and modified for use.
Disclosure of Invention
In order to meet the requirements of electronic products which are developed at a high speed, particularly higher and more excellent service performance of products such as mobile phone chargers and the like, the invention provides a PPE material for mobile phone charger shells and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the PPE material for the shell of the mobile phone charger comprises the following raw materials in parts by weight: 100 parts of PPE (polyphenylene ether), 5-100 parts of HIPS (high impact polystyrene), 10-100 parts of SEBS (styrene-ethylene-butadiene-styrene), 1.2-10 parts of a compatibilizer, 5-80 parts of a flame retardant, 0.3-10 parts of a flame retardant synergist, 0.5-8 parts of a lubricant and 0.1-2 parts of an antioxidant.
Further, the specific gravity of the PPE is 1.06g/cm3The bulk density is 0.40 to 0.52g/cm3The particle size is 200 to 400 μm, the glass transition temperature (Tg) is 214 ℃, and the solution viscosity (0.5g/dl-PPE in CHCl)3And 30 ℃ C. is 0.34 to 0.52 dl/g.
Preferably, the PPE is S201A manufactured by Asahi Kasei corporation, Japan, and its solution viscosity (0.5g/dl-PPE inCHCl)3At 30 deg.C, 0.52dl/g, and volatile matter less than or equal to 0.3%.
Furthermore, the SEBS is a styrene-butadiene-styrene block copolymer with a linear structure, the molecular weight of the SEBS is 5-40 ten thousand, the tensile strength is more than or equal to 5MPa, the Shore hardness is 30-75A, and the melt index is 1.0-12.0 g/10min (190 ℃/2.16 KG).
Further, the compatibilizer is SEBS (SEBS-g-MAH) grafted by maleic anhydride, wherein the grafting ratio of the MAH is 0.3% -2.2%.
Further, the flame retardant is a phosphorus-containing flame retardant selected from hypophosphite, pyrophosphate, polyphosphate or phosphate.
Further, the flame retardant synergist is a nano metal oxide selected from nano zinc oxide, nano calcium oxide or nano silicon oxide.
Further, the lubricant is an organosilicon compound selected from silane, silicone oil or silicone.
Further, the antioxidant is a high temperature resistant antioxidant selected from antioxidant 330, antioxidant 412S, antioxidant 445, antioxidant 626 or antioxidant 627A.
The preparation method of the PPE material for the mobile phone charger shell comprises the steps of sequentially adding PPE, HIPS, SEBS, a compatibilizer, a flame retardant synergist, a lubricant and an antioxidant into a mixer, mixing at a high speed for 3-5 min, and then performing melt extrusion granulation at 230-310 ℃ through a double-screw extruder to obtain the PPE material for the mobile phone charger shell.
Further, the length-diameter ratio L/D of the double-screw extruder is 35-56.
The base material adopted by the invention is a ternary blend of PPE, HIPS and SEBS, and the high strength, high wear resistance and high heat resistance of the PPE and the flexibility and easy processability of the HIPS and the SEBS are fully utilized. And the compatibility of each component of the blend is improved by adding a compatibilizer SEBS-g-MAH. By regulating and controlling the addition proportion of the PPE, the HIPS and the SEBS, the composite material obtains the optimal balance of hardness, strength, toughness, wear resistance, heat resistance, flame retardance and easy processability.
By introducing the HIPS and the SEBS with low melting points, the critical eutectic temperature of the HIPS and the SEBS and the PPE is only 260 ℃, and the blend can be extruded and processed at the temperature of 260 ℃ and 270 ℃. The processing temperature is greatly reduced compared to the extrusion processing temperature (300-.
The flame retardant adopted by the invention is powdery phosphinate, such as organic phosphides like ZDP and ADP, and the like, not only has good compatibility with base material resin and high flame retardance, but also avoids the problem that common liquid flame retardants like RDP and BDP are easy to separate out. By adding the flame-retardant synergist, the nano-ZNO can form a flame-retardant synergistic effect with ZDP and ADP, so that the high-efficiency flame-retardant effect is achieved.
The antioxidant adopted by the invention is the high-temperature-resistant antioxidant 330, and the volatilization and decomposition of the antioxidant in the processing process caused by poor heat resistance are avoided by utilizing the high melting point (more than or equal to 242 ℃) and the high thermal decomposition temperature (more than or equal to 300 ℃), so that the antioxidant durability is maintained.
The invention adopts the PPE/HIPS/SEBS ternary blend as the basic material, fully utilizes the high strength, high wear resistance and high heat resistance of the PPE and the flexibility and easy processability of the HIPS and the SEBS, and enables the composite material to obtain the optimal balance of hardness, tensile strength, wear resistance, heat resistance, flame retardance and easy processability by regulating and controlling the adding proportion of the PPE, the HIPS and the SEBS.
The flame retardant adopted by the invention is mainly a solid hypophosphite substance, and is matched with the added flame-retardant synergist of nano zinc oxide, so that a high-efficiency flame-retardant effect is obtained under the condition of low total addition amount.
Detailed Description
The invention relates to a PPE material for a mobile phone charger shell and a preparation method thereof, which are characterized in that the preparation method comprises the following components (based on 100 parts of PPE resin) in parts by weight: sequentially adding 100 parts of PPE, 0-100 parts of HIPS, 0-100 parts of SEBS, 0-10 parts of a compatibilizer, 5-80 parts of a flame retardant, 0-10 parts of a flame retardant synergist, 0.5-8 parts of an organic silicon lubricant and 0.1-2 parts of an antioxidant into a mixer, mixing at a high speed for 3-5 min, and performing melt extrusion granulation at 230-310 ℃ through a double-screw extruder to obtain the PPE material for the mobile phone charger shell.
The PPE used in the present invention was a white powder having a specific gravity of 1.06g/cm3The bulk density is 0.40 to 0.52g/cm3A particle size of 200 to 400 μm, a glass transition temperature (Tg, measured by DSC) of 214 ℃, and a solution viscosity (0.5g/dl-PPEin CHCl)3And 30 ℃ C. is 0.34 to 0.52 dl/g. A preferred PPE is S201A manufactured by Asahi Kasei corporation, Japan, and has a solution viscosity (0.5g/dl-PPE in CHCl3At 30 deg.C, 0.52dl/g, and volatile matter less than or equal to 0.3%.
The HIPS adopted by the invention is a raiserHigh impact polystyrene resin manufactured by Zibasf corporation, having a 466F brand, a melt index of 4.0g/10min (230 ℃/2.16KG), and a specific gravity of 1.05g/cm3Rockwell hardness of 70, water absorption of less than or equal to 0.1 percent, tensile strength of 30MPa, bending strength of 45MPa, thermal deformation temperature (0.45MPa) of 92 ℃, impact strength (23 ℃) of 130KJ/m of simply supported beam2Impact strength of simply supported beam notch (23 ℃) is 11KJ/m2。
The SEBS adopted by the invention is a styrene-butadiene-styrene block copolymer with a linear structure, the molecular weight of the SEBS is 5-40 ten thousand, the tensile strength is more than or equal to 5MPa, the Shore hardness is 30-75A, and the melt index is 1.0-12.0 g/10min (190 ℃/2.16 KG). A preferred SEBS is a clear, granular SEBS from Kentum, USA, with a G1643 trade name, an S/B ratio of 18/82, a Shore hardness of 52A, a molecular weight of 12 ten thousand, a tensile strength of 8.5MPa, and a melt index of 5.5G/10min (190 ℃/2.16 KG).
The compatibilizer adopted by the invention is SEBS (SEBS-g-MAH) grafted by maleic anhydride, wherein the grafting ratio of the MAH is 0.3-2.2%. A preferred SEBS-g-MAH, available under the trademark FG1901 from the United states Keteng company, has a linear molecular structure, an S/B ratio of 30/70, a molecular weight of 13 ten thousand, a Shore hardness of 75 + -3A, a tensile strength of 11.2MPa, an elongation at break of 722%, a grafting yield of 1.8% and a melt index of 2.6g/10min (190 ℃/2.16 KG).
The flame retardant used in the invention is a phosphorus-containing flame retardant, such as a phosphide such as hypophosphite, pyrophosphate, polyphosphate or phosphate. Preferred phosphorus-containing flame retardants are alkylated phosphinate salts, such as organic phosphonates like Zinc Diethylphosphinate (ZDP) and Aluminum Diethylphosphinate (ADP), which are white free-flowing powders in appearance. Wherein, the phosphorus content (w/w) of ZDP is 19.5-21.0%, the zinc content (w/w) is 20.5-22.0%, the content of effective substances is more than or equal to 99.9%, and the decomposition temperature is more than or equal to 350 ℃; the phosphorus content (w/w) of ADP is 23-24%, the particle distribution D50 is 10-20 μm, and the bulk density is 250-400 kg/m3The decomposition temperature is more than or equal to 350 ℃.
The flame-retardant synergist adopted by the invention is a nano-scale metal oxide, such as nano-zinc oxide, nano-calcium oxide, nano-silicon oxide and the like. The preferable flame-retardant synergist is nano zinc oxide, the appearance of the flame-retardant synergist is white amorphous powder, the melting point is 1975 ℃, the average particle size is 10-20 nm, the purity is more than or equal to 99.9 percent, and the drying loss is less than or equal to 0.3 percent.
The lubricant used in the present invention is an organosilicon compound such as silane, silicone oil or silicone. Preferred lubricants are silicone lubricants, such as silicone masterbatches or silicone powders.
The antioxidant adopted by the invention is a high-temperature-resistant antioxidant, such as 330, 412S, 445, 626 or 627A. The preferable antioxidant is antioxidant 330, is white crystalline powder in appearance, is insoluble in water, and has a purity of not less than 99.5%, a melting point of not less than 242 ℃, a thermal decomposition temperature of not less than 300 ℃ and a gray level of not more than 0.1%.
The length-diameter ratio L/D of the double-screw extruder adopted by the invention is 35-56. The L/D of the preferred double-screw extruder is 48-52.
The following examples further illustrate the present invention but are not to be construed as limiting the invention. Modifications or substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit and scope of the invention. The experimental methods and reagents of the formulations not specified in the examples are in accordance with the conventional conditions in the art.
The raw material grades and physical properties used in the following examples and comparative examples of the present invention are shown in table 1 below:
TABLE 1
The PPE materials for the housing of the mobile phone charger prepared in the following examples and comparative examples were tested for hardness by using shore durometer (shore D table), and the number of the PPE material was read when the PPE material was pressed for 1 second. The mechanical property is tested on an electronic tensile machine according to the GB/T2951.11-2008 standard, and the selected tensile speed is 50 mm/min; the impact strength thereof is divided intoRespectively testing the impact strength of the simply supported beam and the impact strength of the simple supported beam gap with the unit of KJ/m2. The test method for stress cracking resistance comprises the steps of injecting the material into a charger product, standing for 5000 hours, and observing whether the charger product cracks or not. The flame retardance of the flame-retardant alloy is tested by a UL94 vertical combustion method, and the size standard of a sample strip is as follows: length/width/thickness 125mm/12.5mm/3.2 mm. The thermal aging performance adopts GB/T2951.2 standard, and according to the test conditions of 125 ℃ temperature resistance level of the material: aging at 158 ℃ for 168 hours, wherein the change rate of the tensile strength is less than or equal to +/-25%. The method for testing the precipitation resistance comprises the following steps: the material is placed in an oven with the humidity of 80 ℃/80 ℃ for 7 days continuously, then is taken out and cooled to the room temperature, and the surface of the material is observed whether the precipitation phenomenon exists.
The following examples and comparative examples were prepared by injection molding using samples for testing, and the injection molding temperatures used for the respective groups of samples were determined by referring to the injection molding temperature intervals in Table 3.
The formulations and compositions of examples 1 to 4 of the present invention and comparative examples 5 to 9 are shown in Table 2:
TABLE 2
The test results and performance indexes of the above examples 1 to 4 and comparative examples 5 to 9 of the present invention are shown in table 3:
TABLE 3
As can be seen from the above table, in examples 1 to 4, a PPE material for a mobile phone charger case is prepared by using a ternary blend of PPE, HIPS and SEBS as a base material, adding SEBS-g-MAH as a compatibilizer, using an organic phosphide ZDP or ADP as a flame retardant, and using nano ZNO as a flame retardant synergist. The results of the tests of examples 1-4 in Table 3 show that: the prepared PPE composite material has vertical burning UL94 reaching V-0 level, obviously improved toughness and stress cracking resistance, no assistant micromolecule separation, greatly reduced injection molding temperature and excellent comprehensive performance.
Comparative example 5, to which HIPS and SEBS resins were not added, had poor impact resistance, the material product exhibited cracking after 5000 hours of standing, and the injection molding temperature was as high as 305 ℃. Comparative examples 1 and 2, comparative examples 6 and 7, to which the same flame retardant was added but the flame retardant synergist nano ZNO was not added, were slightly less flame retardant, UL94 vertical burning was V-1 grade; in contrast, in comparative examples 8 and 9 containing a higher amount of liquid flame retardant RDP or BDP, UL94 vertical burning was only V-2 level, and flame retardant precipitation occurred after the constant temperature and humidity test.
The embodiment shows that the PPE material for the mobile phone charger shell, prepared by the invention, has the characteristics of high strength, impact resistance, good heat resistance, excellent flame retardance and easiness in processing.
While specific embodiments of the invention have been disclosed, the invention is not limited thereto, and any local variations in the formulations and processes therein are contemplated as falling within the scope of the invention.
Claims (10)
1. The PPE material for the shell of the mobile phone charger is characterized in that: the raw materials comprise the following components in parts by weight: 100 parts of PPE, 5-100 parts of HIPS, 10-100 parts of SEBS, 1.2-10 parts of a compatibilizer, 5-80 parts of a flame retardant, 0.3-10 parts of a flame retardant synergist, 0.5-8 parts of a lubricant and 0.1-2 parts of an antioxidant.
2. The PPE material for mobile phone charger case according to claim 1, wherein: the specific gravity of the PPE is 1.06g/cm3The bulk density is 0.40 to 0.52g/cm3The particle size is 200-400 mu m, the glass transition temperature (Tg) is 214 ℃, and the solution viscosity (0.5g/dl-PPE in CHCl)3And 30 ℃ C. is 0.34 to 0.52 dl/g.
3. The PPE material for mobile phone charger case according to claim 1, wherein: the SEBS is a styrene-butadiene-styrene block copolymer with a linear structure, the molecular weight of the SEBS is 5-40 ten thousand, the tensile strength is more than or equal to 5MPa, the Shore hardness is 30-75A, and the melt index is 1.0-12.0 g/10min (190 ℃/2.16 KG).
4. The PPE material for mobile phone charger case according to claim 1, wherein: the compatibilizer is SEBS (SEBS-g-MAH) grafted by maleic anhydride, wherein the grafting ratio of the MAH is 0.3-2.2%.
5. The PPE material for mobile phone charger case according to claim 1, wherein: the flame retardant is a phosphorus-containing flame retardant and is selected from hypophosphite, pyrophosphate, polyphosphate or phosphate.
6. The PPE material for mobile phone charger case according to claim 1, wherein: the flame-retardant synergist is a nano metal oxide selected from nano zinc oxide, nano calcium oxide or nano silicon oxide.
7. The PPE material for mobile phone charger case according to claim 1, wherein: the lubricant is an organosilicon compound selected from silane, silicone oil or silicone.
8. The PPE material for mobile phone charger case according to claim 1, wherein: the antioxidant is a high-temperature-resistant antioxidant and is selected from antioxidant 330, antioxidant 412S, antioxidant 445, antioxidant 626 or antioxidant 627A.
9. The method for preparing PPE material for mobile phone charger shell as claimed in claim 1, wherein: sequentially adding PPE, HIPS, SEBS, a compatibilizer, a flame retardant synergist, a lubricant and an antioxidant into a mixer, mixing at a high speed for 3-5 min, and performing melt extrusion granulation at 230-310 ℃ through a double-screw extruder to obtain the PPE material for the mobile phone charger shell.
10. The method of claim 9, wherein: the length-diameter ratio L/D of the double-screw extruder is 35-56.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112063131A (en) * | 2020-09-23 | 2020-12-11 | 柳州塑友科技有限公司 | PPE/PBT composite material for new energy automobile cooling fan and preparation method |
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| CN102477189A (en) * | 2010-11-30 | 2012-05-30 | 深圳市亚塑科技有限公司 | High-fluidity environmental protection halogen-free flame-retardant HIPS composite material and its preparation method |
| US20150183991A1 (en) * | 2013-11-20 | 2015-07-02 | Asahi Kasei Chemicals Corporation | Flame-retardant thermoplastic resin composition and molded article of the same |
| CN110144109A (en) * | 2019-05-31 | 2019-08-20 | 上海奇彩塑胶原料有限公司 | A kind of weather-proof high CTI halogen-free flameproof PPO/HIPS composite material and preparation method |
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| CN102477189A (en) * | 2010-11-30 | 2012-05-30 | 深圳市亚塑科技有限公司 | High-fluidity environmental protection halogen-free flame-retardant HIPS composite material and its preparation method |
| US20150183991A1 (en) * | 2013-11-20 | 2015-07-02 | Asahi Kasei Chemicals Corporation | Flame-retardant thermoplastic resin composition and molded article of the same |
| CN110144109A (en) * | 2019-05-31 | 2019-08-20 | 上海奇彩塑胶原料有限公司 | A kind of weather-proof high CTI halogen-free flameproof PPO/HIPS composite material and preparation method |
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| CN112063131A (en) * | 2020-09-23 | 2020-12-11 | 柳州塑友科技有限公司 | PPE/PBT composite material for new energy automobile cooling fan and preparation method |
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