CN104672817A - Flame retardant enhanced PET material having high glowing filament temperature and preparation method of material - Google Patents
Flame retardant enhanced PET material having high glowing filament temperature and preparation method of material Download PDFInfo
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- CN104672817A CN104672817A CN201310636943.9A CN201310636943A CN104672817A CN 104672817 A CN104672817 A CN 104672817A CN 201310636943 A CN201310636943 A CN 201310636943A CN 104672817 A CN104672817 A CN 104672817A
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Abstract
The invention belongs to the technical field of high polymer materials and relates to a flame retardant enhanced PET material having a high glowing filament temperature and a preparation method of the material. The material is prepared from the following components in parts by weight: 45-72 parts of PET, 10-30 parts of glass fibers, 0.3-0.6 part of lubricant, 0.3-0.6 part of antioxidant, 0.2-0.7 part of nucleating agent, 15-20 parts of flame retardant and 3-5 parts of flexibilizer. The material has the characteristics of high strength, good flame retardancy, high glowing filament temperature, high temperature resistance, easy molding and the like, and has a wide application prospect in the household appliance industry.
Description
Technical field
The invention belongs to technical field of polymer materials, relate to a kind of flame-retardant strengthening polythylene terephthalate (PET) material with high glow wire temperature and preparation method thereof.
Background technology
Polyethylene terephthalate (PET) is a kind of engineering plastics of excellent combination property.PET has excellent mechanical property, rigidity is high, hardness is large, good toughness, shock-resistant, rub resistance, resistance to creep.Chemical resistant properties is good, is dissolved in cresols, the vitriol oil, oil of mirbane, Tricholroacetic Acid, chlorophenol, is insoluble to the features such as methyl alcohol, ethanol, acetone, alkane.Itself becomes various bottle mainly through blowing, as container, and is spun into the application such as fiber.Apply in electronic apparatus and automotive industry as its alternative nylon of engineering plastics and polybutylene terephthalate.
The fire-retardant document of current PET is more, but great majority are only considered single fire-retardant and do not reached the requirement of high glow wire temperature by adjustment fire retardant contamination, make it apply in electrical apparatus industry and are restricted.
Current PET material is applied more and more extensive in household electric appliances, especially as household electrical appliances motor housing.Because motor can produce a large amount of heat in the process of running up.Long contact time can make its outward appearance Yin Wendu too high and spontaneous combustion produces fire, brings the disaster being difficult to add to broad masses of the people.Carry out flame-retardant modified simply by fire retardant to PET at present, can only simply prevent material at the combustion problem at single short period of time burning things which may cause a fire disaster place, the spontaneous combustion problems under it can not be prevented to be in high enthusiasm condition for a long time., add after fire retardant meanwhile, after forming materials toughness especially the toughness of thin-walled material be difficult to be guaranteed.
Summary of the invention
The object of the invention is to develop a kind of flame-retardant strengthening polythylene terephthalate (PET) material with high glow wire temperature, its resistance to higher glow wire temperature performance can ensure its not spontaneous combustion under long-time high temperature, and its shaping after especially thin-wall product shaping after still have good toughness.
For achieving the above object, the present invention is by the following technical solutions:
The present invention carries out enhancing modified by glass and nucleator to PET, makes it have good intensity and higher modulus.It is made to reach the flame retardant effect of FV-0 level by the interpolation of fire retardant.The selection of fire retardant simultaneously and the adjustment of content can make it have high glow wire temperature.
There is a flame-retardant strengthening polythylene terephthalate (PET) material for high glow wire temperature, be made up of the component comprising following weight part:
The temperature of described high glow-wire is not less than 960 DEG C.
Described auxiliary agent comprises: lubricant 0.3-0.6 part, oxidation inhibitor 0.3-0.6 part and nucleator 0.2-0.7 part.
Described glass fibre is continuous glass fibre, and diameter is 10-15 μm, is preferably 10-12 μm.
Described lubricant be selected from stearyl alcohol, silicone or pentaerythritol stearate (PETS) one or more.
Described oxidation inhibitor is selected from four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester] one or more in pentaerythritol ester (antioxidant 1010), β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid positive octadecanol ester (antioxidant 1076) or the long-acting stablizer of hindered phenol and the composite oxidation inhibitor P262 of phosphite process stabilizer.
Described nucleator be selected from the ionomer of saturated carboxylic acid sodium salt or ethylene/methacrylic acid one or more.
Described fire retardant comprise in the mixture of TDE and antimonous oxide or red phosphorus one or more, wherein the weight ratio of TDE and antimonous oxide is (3:1) ~ (3:2).
Described toughner is ethylene-acrylate-glycidyl acrylate terpolymer.
An above-mentioned preparation method with the flame-retardant strengthening polythylene terephthalate (PET) material of high glow wire temperature, comprises the following steps:
(1) by said ratio, polyethylene terephthalate 45-72 part is taken, auxiliary agent 0.8-1.9 part, fire retardant 15-20 part, toughner 3-5 part, through high mixer mixing at a high speed;
(2) pour the mixture that step (1) is mixed to get into twin-screw extrusion owner spout, then 10-30 part glass fibre is added entrance by rear end glass add, obtain product through the pelletizing of screw extrusion press tie rod.
The mixing condition of described high mixer is rotating speed is 800-1000rpm, and normal temperature mixing time is 3-6min.
The extrusion temperature of described dual-screw-stem machine is 260-280 DEG C.
Compared with prior art, the present invention has following beneficial effect:
The invention provides a kind of flame-retardant strengthening polythylene terephthalate (PET) material with high glow wire temperature, this material is by fiberglass reinforced PET, reduce PET Tc by the interpolation of nucleator simultaneously, accelerate its crystallization velocity, PET is made to have high strength and modulus, improve its heat-drawn wire and Vicat softening point simultaneously, make it have good resistance to elevated temperatures.
The present invention by adjustment flame retardant combination kind and content, thus reaches have high glow wire temperature while it has fire-retardant condition, and it is less on material property impact, maintains material rigidity originally and modulus.The interpolation of toughner, but make its toughness have lifting by a relatively large margin, and thin-wall product has good toughness under the constant prerequisite of rigidity.Make PET material safety in utilization in household electric appliances higher.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated.
All according to ASTM standard testing to the testing standard of product in following examples.
Embodiment 1
(1) by 45 parts of PET, 0.3 part of silicone, 0.1 part of antioxidant 1010,0.2 part of antioxidant 1076, the ionomer of 0.2 part of nucleator ethylene/methacrylic acid, 20 parts of red phosphorus, 5 parts of toughner ethylene-acrylate-glycidyl acrylate terpolymers, use high mixer high-speed mixing, rotating speed is 800rpm, normal temperature, and mixing time is 6min;
(2) compound that step (1) is mixed to get is poured into Screw Extrusion owner spout, again 30 parts of continuous glass fibres (diameter is 12 μm) are added entrance by rear end glass to add, control extruder temperature at 260-280 DEG C, mixture can be obtained the flame-retardant strengthening polythylene terephthalate (PET) material of product high glow wire temperature through the pelletizing of twin screw extruder tie rod, the test of product correlated performance is in table 1.
Embodiment 2
(1) by 72 parts of PET, 0.3 part of lubricant PETS, 0.2 part of antioxidant 1010,0.4 part of antioxidant 1076,0.5 part of nucleator saturated carboxylic acid sodium salt, 10 parts of TDE and 5 parts of antimonous oxides (weight ratio of TDE and antimonous oxide is 2:1), 3 parts of ethylene-acrylate-glycidyl acrylate high mixer high-speed mixing, rotating speed is 1000rpm, normal temperature, mixing time is 3min;
(2) compound that step (1) is mixed to get is poured into Screw Extrusion owner spout, again 10 parts of continuous glass fibres (diameter is 12 μm) are added entrance by rear end glass to add, control extruder temperature at 260-280 DEG C, mixture can be obtained the flame-retardant strengthening polythylene terephthalate (PET) material of product high glow wire temperature through the pelletizing of twin screw extruder tie rod.
Embodiment 3
(1) by 60 parts of PET, 0.3 part of stearyl alcohol, 0.5 part of oxidation inhibitor P262,0.7 part of saturated carboxylic acid sodium salt, 20 parts of red phosphorus, 5 parts of ethylene-acrylate-glycidyl acrylate high mixer high-speed mixing, rotating speed is 800rpm, normal temperature, and mixing time is 6min;
(2) compound that step (1) is mixed to get is poured into Screw Extrusion owner spout, again 15 parts of continuous glass fibres (diameter is 12 μm) are added entrance by rear end glass to add, control extruder temperature at 260-280 DEG C, mixture can be obtained the flame-retardant strengthening polythylene terephthalate (PET) material of high glow wire temperature through the pelletizing of twin screw extruder tie rod.
Embodiment 4
(1) by 60 parts of PET, 0.4 part of silicone, 0.2 part of antioxidant 1010,0.2 part of antioxidant 1076, the ionomer of 0.5 part of ethylene/methacrylic acid, 12 parts of TDE and 4 parts of antimonous oxides (weight ratio of TDE and antimonous oxide is 3:1), 4 parts of ethylene-acrylate-glycidyl acrylate high mixer high-speed mixing, rotating speed is 900rpm, normal temperature, and mixing time is 5min;
(2) compound that step (1) is mixed to get is poured into Screw Extrusion owner spout, again 20 parts of continuous glass fibres (diameter is 15 μm) are added entrance by rear end glass to add, control extruder temperature at 260-280 DEG C, mixture can be obtained the flame-retardant strengthening polythylene terephthalate (PET) material of product high glow wire temperature through the pelletizing of twin screw extruder tie rod.
Embodiment 5
(1) by 50 parts of PET, 0.4 part of silicone, 0.4 part of antioxidant 1076, the ionomer of 0.5 part of ethylene/methacrylic acid, 15 parts of red phosphorus, 5 parts of ethylene-acrylate-glycidyl acrylate high mixer high-speed mixing, rotating speed is 1000rpm, normal temperature, and mixing time is 6min;
(2) compound that step (1) is mixed to get is poured into Screw Extrusion owner spout, again 30 parts of continuous glass fibres (diameter is 13 μm) are added entrance by rear end glass to add, control extruder temperature at 260-280 DEG C, mixture can be obtained product through the pelletizing of twin screw extruder tie rod, and the test of product correlated performance is in table 1.
Embodiment 6
(1) by 60 parts of PET, 0.6 part of stearyl alcohol, 0.3 part of antioxidant 1076, the ionomer of 0.5 part of ethylene/methacrylic acid, 12 parts of TDE and 8 parts of antimonous oxides (weight ratio of TDE and antimonous oxide is 3:2), 5 parts of ethylene-acrylate-glycidyl acrylate high mixer high-speed mixing, rotating speed is 800rpm, normal temperature, mixing time is 4min;
(2) compound that step (1) is mixed to get is poured into Screw Extrusion owner spout, again 15 parts of continuous glass fibres (diameter is 10 μm) are added entrance by rear end glass to add, control extruder temperature at 260-280 DEG C, mixture can be obtained product through the pelletizing of twin screw extruder tie rod.The test of product correlated performance is in table 1.
Table 1
| Embodiment | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Tensile strength MPa | 135 | 89 | 102 | 120 | 130 | 105 |
| Flexural strength MPa | 223 | 195 | 209 | 215 | 226 | 205 |
| Modulus in flexure MPa | 9500 | 6620 | 7250 | 8600 | 9602 | 7300 |
| Simply supported beam notched Izod impact strength KJ/m 2 | 15.6 | 10.7 | 14.3 | 12.8 | 16.0 | 15.0 |
| Flame retardant resistance | FV-0 | FV-0 | FV-0 | FV-0 | FV-0 | FV-0 |
| Heat-drawn wire | 213 | 228 | 210 | 220 | 227 | 218 |
| Glow wire temperature (2mm, 960 DEG C) | Pass through | Pass through | Pass through | Pass through | Pass through | Pass through |
Can be found out by table 1, the above embodiment of the present invention provides a kind of flame-retardant strengthening polythylene terephthalate (PET) material with high glow wire temperature, this material is by fiberglass reinforced PET, reduce PET Tc by adding nucleator simultaneously, accelerate its crystallization velocity, make PET have high strength and modulus, improve its heat-drawn wire and Vicat softening point simultaneously, make it have good resistance to elevated temperatures.By high addition fire retardant, make it have higher glow wire temperature, the interpolation of toughner, but make its toughness have lifting by a relatively large margin; thin-wall product has good toughness under the constant prerequisite of rigidity, makes PET material safety in utilization in household electric appliances higher.
Above-mentioned is can understand and apply the invention for ease of those skilled in the art to the description of embodiment.Person skilled in the art obviously easily can make various amendment to these embodiments, and General Principle described herein is applied in other embodiments and need not through performing creative labour.Therefore, the invention is not restricted to embodiment here, those skilled in the art, according to announcement of the present invention, do not depart from improvement that scope makes and amendment all should within protection scope of the present invention.
Claims (10)
1. there is a flame-retardant strengthening polythylene terephthalate (PET) material for high glow wire temperature, it is characterized in that: be made up of the component comprising following weight part:
2. the flame-retardant strengthening polythylene terephthalate (PET) material with high glow wire temperature according to claim 1, is characterized in that: described high glow wire temperature is for being not less than 960 DEG C.
3. the flame-retardant strengthening polythylene terephthalate (PET) material with high glow wire temperature according to claim 1, is characterized in that: described auxiliary agent comprises: lubricant 0.3-0.6 part, oxidation inhibitor 0.3-0.6 part and nucleator 0.2-0.7 part.
4. the flame-retardant strengthening polythylene terephthalate (PET) material with high glow wire temperature according to claim 3, is characterized in that: described lubricant be selected from stearyl alcohol, silicone or pentaerythritol stearate one or more.
5. the flame-retardant strengthening polythylene terephthalate (PET) material with high glow wire temperature according to claim 3, it is characterized in that: described oxidation inhibitor is selected from four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester] one or more in pentaerythritol ester, β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid or oxidation inhibitor P262.
6. the flame-retardant strengthening polythylene terephthalate (PET) material with high glow wire temperature according to claim 3, is characterized in that: described nucleator be selected from the ionomer of saturated carboxylic acid sodium salt or ethylene/methacrylic acid one or more.
7. the flame-retardant strengthening polythylene terephthalate (PET) material with high glow wire temperature according to claim 1, is characterized in that: described glass fibre is continuous glass fibre, and diameter is 10-15 μm, is preferably 10-12 μm.
8. the flame-retardant strengthening polythylene terephthalate (PET) material with high glow wire temperature according to claim 1, it is characterized in that: described fire retardant comprise in the mixture of TDE and antimonous oxide or red phosphorus one or more, wherein the weight ratio of TDE and antimonous oxide is (3:1) ~ (3:2);
Or described toughner is ethylene-acrylate-glycidyl acrylate terpolymer.
9. an arbitrary described preparation method with the flame-retardant strengthening polythylene terephthalate (PET) material of high glow wire temperature in claim 1-8, is characterized in that: comprise the following steps:
(1) by proportioning according to claim 1, polyethylene terephthalate 45-72 part is taken, auxiliary agent 0.8-1.9 part, fire retardant 15-20 part, toughner 3-5 part, through high mixer mixing at a high speed;
(2) pour the mixture that step (1) is mixed to get into twin-screw extrusion owner spout, then 10-30 part glass fibre is added entrance by rear end glass add, obtain product through the pelletizing of screw extrusion press tie rod.
10. preparation method according to claim 9, is characterized in that: the mixing condition of described high mixer is rotating speed is 800-1000rpm, and normal temperature mixing time is 3-6min;
Or the extrusion temperature of described dual-screw-stem machine is 260-280 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
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| CN105111696A (en) * | 2015-09-01 | 2015-12-02 | 深圳市兴邦盛塑胶原料有限公司 | Flame-retardant reinforced PET (polyethylene terephthalate) composition and preparation method thereof |
| CN111393807A (en) * | 2020-03-13 | 2020-07-10 | 杭州金州高分子科技有限公司 | High-strength V0 flame-retardant PET composite modified material |
| CN114213812A (en) * | 2021-11-15 | 2022-03-22 | 佛山市鑫塑新材料科技有限公司 | PET flame-retardant material and preparation method thereof |
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Cited By (3)
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| CN111393807A (en) * | 2020-03-13 | 2020-07-10 | 杭州金州高分子科技有限公司 | High-strength V0 flame-retardant PET composite modified material |
| CN114213812A (en) * | 2021-11-15 | 2022-03-22 | 佛山市鑫塑新材料科技有限公司 | PET flame-retardant material and preparation method thereof |
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Application publication date: 20150603 |