CN102964821A - Flame-retardant glass fiber reinforced PA6 (polyamide 6)/PPO (P-Polyphenylene Oxide) alloy material and preparation method thereof - Google Patents
Flame-retardant glass fiber reinforced PA6 (polyamide 6)/PPO (P-Polyphenylene Oxide) alloy material and preparation method thereof Download PDFInfo
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K3/20—Oxides; Hydroxides
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- C08K3/34—Silicon-containing compounds
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- C08K7/00—Use of ingredients characterised by shape
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- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
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- 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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- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- C09K21/00—Fireproofing materials
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Abstract
The invention relates to a flame-retardant glass fiber reinforced PA6 (polyamide 6)/PPO (P-Polyphenylene Oxide) alloy material and a preparation method thereof. The alloy material comprises the following components by weight percent: 23-41% of PA6, 22-41% of PPO, 6-20% of compound type flame retardant, 3-15% of antimonous oxide, 20-30% of glass fiber, 2-10% of compatilizer, 0.1-1% of antioxidant and 0.1-1% of oxidizing material. The raw materials are put into a high mixing machine to be mixed for 2-5min and then are discharged, and then a doubles-screw extruder is used for extruding and pelletizing so as to obtain the flame-retardant glass fiber reinforced PA6/PPO alloy material. Compared with the prior art, the flame-retardant glass fiber reinforced PA6/PPO alloy material has the advantages that being high in temperature of a glowing filament, environment-friendly, balanced in comprehensive properties, high in CTI (Comparative Tracking lndex) and GWIT (Glow-Wire Flammability Index), and the like.
Description
Technical field
The present invention relates to a kind of PA6/PPO alloy material, especially relate to a kind of high CTI value, high GWIT value environment-protection flame-proof fiberglass enhancing PA6/PPO alloy material and preparation method thereof.
Background technology
Nylon (Nylon), the Chinese name polymeric amide, English name Polyamide, be contain on the molecular backbone chain recurring amide radical group-[NHCO]-the thermoplastic resin general name.Its name is decided by the concrete carbonatoms of synthon, such as: nylon-6,66,1010,610. its degree of crystallinity are high, fusing point is obvious; Surface hardness is large, abrasion performance, frictional coefficient are little, self lubricity and noise reduction are arranged.Low-temperature performance is good, and certain thermotolerance (can use below 100 degree) is arranged.Nontoxic, odorless, mildew and rot self-extinguishing, good weatherability are arranged, but dyeability are poor.PPO is one of the world's five large general engineering plastic.It has that rigidity is large, thermotolerance is high, difficult combustion, intensity be than advantages such as high electrical performance are good.In addition, polyphenylene oxide also has the advantages such as wear-resisting, nontoxic, anti-pollution.The specific inductivity of PPO and dielectric loss are one of minimum kind in engineering plastics, are subjected to hardly the impact of temperature, humidity, can be used for basic, normal, high frequency electric field field.The load deformation temperature of PPO can reach more than 190 ℃, and embrittlement temperature is-170 ℃.The PPO material is as one of the world's five large general engineering plastic, and nontoxic, relative density is little, is density minimum in the five large general engineering plastic, has good physical strength, creep resistance, and proof stress is lax, and fatigue resistance is high.The polypropylene molecule formula: (C3H6) n is a kind of thermoplastic resin that is made by propylene polymerization.Be divided into three kinds of isotatic polypropylene (isotaeticpolyprolene), Atactic Polypropelene (atactic polypropylene) and syndiotactic polypropylenes (syndiotaticpolypropylene) by the methyl arrangement position.Nontoxic, tasteless, density is little, and intensity, rigidity, hardness thermotolerance all are better than low pressure polyethylene, can use about 100 ℃.Have good electrical property and high-frequency insulation and be not subjected to humidity effect.Be suitable for making common mechanical part, corrosion-resistant part and insulating part.The organic solvents such as common acid, alkali work hardly to it, can be used for tableware.The PA6/PPO alloy material combines the advantage of bi-material.21 century, electric appliance communication electromechanical equipment was to the high-performance micro development, and more and more higher to the requirement of flame-proof PA 6/PPO alloy material, simultaneously, along with the understanding of the mankind to environmental protection, Green Product is subject to common concern.Therefore, flame-proof PA 6/PPO alloy material developing direction is; Performance function flame-proof PA 6/PPO alloy material becomes main flow; The kind of environmental type flame-proof PA 6/PPO alloy material and demand are more and more; The production of flame-proof PA 6/PPO alloy material is to many variety series future development; The use diversification of fire retardant, compound development.Some traditional modes are (GF+ TDE+antimonous oxide) compound system, (GF+ brominated Polystyrene+antimonous oxide) compound system, but the CTI value of these compound systems and GWIT value are not high, are not suitable for the power utilization environment of high request.This material is applicable to Low-voltage Electronic capacitor case, load break switch, carbon brush supports, breaker of plastic casing.
Summary of the invention
Purpose of the present invention is exactly to provide a kind of glow wire temperature higher for the defective that overcomes above-mentioned prior art existence, environmental protection, and the high CTI value of over-all properties equilibrium, high GWIT value environment-protection flame-proof fiberglass strengthen PA6/PPO alloy material and preparation method thereof.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of flame-proof glass fibre strengthens the PA6/PPO alloy material, comprises following component and weight percentage: PA6 23-41%, PPO 22-41%, compound flame redundant 6-20%, antimonous oxide 3-15%, glass fibre 20-30%, compatilizer 2-10%, oxidation inhibitor 0.1-1%, oxide compound 0.1-1%.
Described PA6 is commercially available polyamide 6.
The limiting viscosity of described PPO is 1.0dl/g.
Described compound flame redundant is 50% BPS, 25% magnesium hypophosphite and 25% composite the obtaining of talcum powder by mass percent.
Described for glass fibre be the alkali free glass fibre that process through silane coupling agent on the surface.
Described compatilizer is commercially available maleic anhydride graft PPO.
Described oxidation inhibitor is Hinered phenols antioxidant, selects oxidation inhibitor 1330.
Described oxide compound is ferric oxide.
Flame-proof glass fibre strengthens the preparation method of PA6/PPO alloy material, take by weighing raw material by weight ratio after, above-mentioned raw materials is put into high-speed mixer and mixing 2-5 minute discharging, use again the twin screw extruder extruding pelletization, namely obtain flame-proof glass fibre and strengthen the PA6/PPO alloy material.
The extrusion temperature of described twin screw extruder is 220-240 ℃, and the screw rod revolution is at 300-400rpm.
Compared with prior art, the present invention adopts the novel flame-retardant compound system, compares with traditional flame-retardant system, and in the identical situation of fire retardant percentage composition, the novel built system can make the glowing filament of material improve 50 to 100 ℃, can pass through 850 ℃ of glowing filaments.Simultaneously, the adding of glass fibre also makes the glowing filament of material significantly improve, adding compatilizer is be used to the impact property of improving material, oxidation inhibitor is that a kind of Hinered phenols antioxidant can improve composition in the antioxidant property of the course of processing and the ageing resistance in the use procedure, adopt ferric oxide as improving the CTI auxiliary agent, it is mobile to improve materials processing, reduce frictional coefficient, improve slipping, adopt dispersiveness better under specific processing conditions, the residence time is short, shears slightly weak combination, prevent that fire retardant from decomposing, thereby guaranteed the steady quality of material.
Advantage of the present invention is that to have a glow wire temperature (GWIT) higher, has creepage trace index higher (CTI), environmental protection, and over-all properties is balanced, can be widely used in the Low-voltage Electronic capacitor case, load break switch, carbon brush supports, breaker of plastic casing.
Embodiment
The present invention is described in detail below in conjunction with specific embodiment.
Comparative Examples 1-5 and embodiment 1-2
The formula for raw stock of Comparative Examples 1-5 and embodiment 1-2 is as follows, all percentage composition meter by weight:
Said components was put into high-speed mixer and mixing 2-5 minute in proportion, and then discharging uses the screw extrusion press extruding pelletization, and processing temperature is at 220-240 ℃, and the screw rod revolution is at 300-400rpm.
According to the sample that Comparative Examples 1-5 and embodiment 1-2 make, carry out the performance test contrast, adopt the ASTM standard.
The test performance contrast is as shown in the table:
To have a glow wire temperature (GWIT) higher for sample of the present invention as can be seen from the above table, has creepage trace index higher (CTI), environmental protection, over-all properties is balanced, is widely used in the Low-voltage Electronic capacitor case, load break switch, carbon brush supports, breaker of plastic casing.
Embodiment 3
A kind of high CTI value, high GWIT value environment-protection flame-proof fiberglass strengthen the preparation method of PA6/PPO alloy material, the method is as follows: take by weighing by weight ratio raw material: PA6 23%, PPO 22%, compound flame redundant 20%, antimonous oxide 4.3%, glass fibre 20%, commercially available maleic anhydride graft PPO 10%, oxidation inhibitor (1330) 0.1%, ferric oxide 0.6%; Put into high-speed mixer and mixing 2 minutes, then discharging uses the twin screw extruder extruding pelletization, and processing temperature is at 240 ℃, and the screw rod revolution is at 300rpm.
Described compound flame redundant, composite voluntarily by my company, mixed by three kinds of components, its mass percent is BPS:50%; Magnesium hypophosphite: 25%; Talcum powder: 25%.
Embodiment 4
A kind of high CTI value, high GWIT value environment-protection flame-proof fiberglass strengthen the preparation method of PA6/PPO alloy material, the method is as follows: take by weighing by weight ratio raw material: PA646%, PPO 20%, compound flame redundant 6%, antimonous oxide 3%, glass fibre 21%, commercially available maleic anhydride graft PPO 2%, oxidation inhibitor (1330) 1%, ferric oxide 1%; Put into high-speed mixer and mixing 5 minutes, then discharging uses the twin screw extruder extruding pelletization, and processing temperature is at 240 ℃, and the screw rod revolution is at 400rpm.
Described compound flame redundant, composite voluntarily by my company, mixed by three kinds of components, its mass percent is BPS:50%; Magnesium hypophosphite: 25%; Talcum powder: 25%.
Described glass fibre is alkali free glass fibre, and glass fibre is added in the silane coupling agent, and its surface is processed through silane coupling agent.
Embodiment 5
A kind of high CTI value, high GWIT value environment-protection flame-proof fiberglass strengthen the preparation method of PA6/PPO alloy material, the method is as follows: take by weighing by weight ratio raw material: PA625%, PPO 41%, compound flame redundant 6%, antimonous oxide 5%, glass fibre 20%, commercially available maleic anhydride graft PPO 2%, oxidation inhibitor (1330) 0.5%, ferric oxide 0.5%; Put into high-speed mixer and mixing 3 minutes, then discharging uses the twin screw extruder extruding pelletization, and processing temperature is at 240 ℃, and the screw rod revolution is at 350rpm.
Described compound flame redundant, composite voluntarily by my company, mixed by three kinds of components, its mass percent is BPS:50%; Magnesium hypophosphite: 25%; Talcum powder: 25%.
Embodiment 6
A kind of high CTI value, high GWIT value environment-protection flame-proof fiberglass strengthen the preparation method of PA6/PPO alloy material, the method is as follows: take by weighing by weight ratio raw material: PA641%, PPO 22%, compound flame redundant 6%, antimonous oxide 6.5%, glass fibre 20%, commercially available maleic anhydride graft PPO 3%, oxidation inhibitor (1330) 0.8%, ferric oxide 0.7%; Put into high-speed mixer and mixing 2 minutes, then discharging uses the twin screw extruder extruding pelletization, and processing temperature is at 220 ℃, and the screw rod revolution is at 380rpm.
Described compound flame redundant, composite voluntarily by my company, mixed by three kinds of components, its mass percent is BPS:50%; Magnesium hypophosphite: 25%; Talcum powder: 25%.
Embodiment 7
A kind of high CTI value, high GWIT value environment-protection flame-proof fiberglass strengthen the preparation method of PA6/PPO alloy material, the method is as follows: take by weighing by weight ratio raw material: PA625%, PPO 25%, compound flame redundant 10%, antimonous oxide 15%, glass fibre 20%, commercially available maleic anhydride graft PPO 3%, oxidation inhibitor (1330) 1%, ferric oxide 1%; Put into high-speed mixer and mixing 5 minutes, then discharging uses the twin screw extruder extruding pelletization, and processing temperature is at 220 ℃, and the screw rod revolution is at 380rpm.
Described compound flame redundant, composite voluntarily by my company, mixed by three kinds of components, its mass percent is BPS:50%; Magnesium hypophosphite: 25%; Talcum powder: 25%.
Claims (10)
1. a flame-proof glass fibre strengthens the PA6/PPO alloy material, it is characterized in that, this alloy material comprises following component and weight percentage: PA6 23-41%, PPO 22-41%, compound flame redundant 6-20%, antimonous oxide 3-15%, glass fibre 20-30%, compatilizer 2-10%, oxidation inhibitor 0.1-1%, oxide compound 0.1-1%.
2. a kind of flame-proof glass fibre according to claim 1 strengthens the PA6/PPO alloy material, it is characterized in that described PA6 is commercially available polyamide 6.
3. a kind of flame-proof glass fibre according to claim 1 strengthens the PA6/PPO alloy material, it is characterized in that the limiting viscosity of described PPO is 1.0dl/g.
4. a kind of flame-proof glass fibre according to claim 1 strengthens the PA6/PPO alloy material, it is characterized in that, described compound flame redundant is 50% BPS, 25% magnesium hypophosphite and 25% composite the obtaining of talcum powder by mass percent.
5. a kind of flame-proof glass fibre according to claim 1 strengthens the PA6/PPO alloy material, it is characterized in that, described for glass fibre be surperficial alkali free glass fibre through the silane coupling agent processing.
6. a kind of flame-proof glass fibre according to claim 1 strengthens the PA6/PPO alloy material, it is characterized in that described compatilizer is commercially available maleic anhydride graft PPO.
7. a kind of flame-proof glass fibre according to claim 1 strengthens the PA6/PPO alloy material, it is characterized in that described oxidation inhibitor is Hinered phenols antioxidant, selects oxidation inhibitor 1330.
8. a kind of flame-proof glass fibre according to claim 1 strengthens the PA6/PPO alloy material, it is characterized in that described oxide compound is ferric oxide.
9. strengthen the preparation method of PA6/PPO alloy material such as each described flame-proof glass fibre among the claim 1-8, it is characterized in that, the method is after taking by weighing raw material by weight ratio, above-mentioned raw materials is put into high-speed mixer and mixing 2-5 minute discharging, use again the twin screw extruder extruding pelletization, namely obtain flame-proof glass fibre and strengthen the PA6/PPO alloy material.
10. a kind of flame-proof glass fibre according to claim 9 strengthens the preparation method of PA6/PPO alloy material, it is characterized in that the extrusion temperature of described twin screw extruder is 220-240 ℃, and the screw rod revolution is at 300-400rpm.
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| CN113717518A (en) * | 2021-09-22 | 2021-11-30 | 宁波华腾首研新材料有限公司 | Laser-markable halogen-free flame-retardant glass fiber reinforced alloy material and preparation method thereof |
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| CN102040827A (en) * | 2009-10-22 | 2011-05-04 | 上海日之升新技术发展有限公司 | Environmentally-friendly flame-retardant reinforced PA66 composite material of high glowing filament and preparation method thereof |
| CN102575100A (en) * | 2009-09-14 | 2012-07-11 | 三菱瓦斯化学株式会社 | Flame-retardant polyamide resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102575100A (en) * | 2009-09-14 | 2012-07-11 | 三菱瓦斯化学株式会社 | Flame-retardant polyamide resin composition |
| CN102040827A (en) * | 2009-10-22 | 2011-05-04 | 上海日之升新技术发展有限公司 | Environmentally-friendly flame-retardant reinforced PA66 composite material of high glowing filament and preparation method thereof |
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| CN113717518A (en) * | 2021-09-22 | 2021-11-30 | 宁波华腾首研新材料有限公司 | Laser-markable halogen-free flame-retardant glass fiber reinforced alloy material and preparation method thereof |
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