CN104371253A - High performance flame retardant material - Google Patents
High performance flame retardant material Download PDFInfo
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- CN104371253A CN104371253A CN201310346741.0A CN201310346741A CN104371253A CN 104371253 A CN104371253 A CN 104371253A CN 201310346741 A CN201310346741 A CN 201310346741A CN 104371253 A CN104371253 A CN 104371253A
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Abstract
The invention provides a high performance flame retardant material. The material is characterized by being composed of the following components in parts by weight: 40 to 70 parts of ABS resin, 10 to 20 parts of PBT resin, 10 to 20 parts of alkali-free glass fiber with a diameter of 10-20 [mu]m, 2 to 3 parts of reinforcing agent, 5 to 10 parts of phosphorus flame retardant, 5 to 10 parts of nitrogen flame retardant, 3 to 5 parts of silicon synergist, 3 to 5 parts of compatibilizer, and 2 to 3 parts of antioxidant. A phosphorus flame retardant and a nitrogen flame retardant or a phosphorous flame retardant and a silicon flame retardant are used together so as to improve the flame retardant efficiency and comprehensive performance of a halogen-free flame retardant ABS material. Moreover, the released toxic gas amount during the burning process is reduced, and thus the provided high performance flame retardant material is a low-smoke material with little toxicity. The prepared PBT/ABS composite material has the advantages of smooth surface, good luster and color, high performance, and easiness for processing.
Description
Technical field
The invention belongs to composite processing field, be specifically related to a kind of high-performance flame-retardant material.
Background technology
ABS resin is the blend of acrylonitrile-butadiene-styrene copolymer or vinyl cyanide/cinnamic multipolymer and styrene/butadiene copolymers, it is the graft copolymer of divinyl and the mixture of acrylonitritrile-styrene resin, wherein vinyl cyanide accounts for 15%-35%, divinyl accounts for 5%-30%, and vinylbenzene accounts for 40-60%.Along with the change of three kinds of component proportionss, the physical and mechanical properties of ABS resin changes thereupon.ABS resin is that a kind of intensity is high, good toughness, heat-resisting, low temperature resistant, chemical resistance corrosion, physical strength and electric property are excellent, is easy to thermoplastics type's macromolecular material of machine-shaping.The fields such as ABS is widely used in automobile, electronic apparatus, building materials, packaging, sports goods, machinery instrument industry.Along with domestic ABS resin is in the increase of the industry annual requirements such as automobile, electronic apparatus, building materials, the demand of flame-proof ABS increases year by year.
For a long time, the fire-retardant main employing of ABS be halide-containing, wherein the bromide fire retardant flame retardant effect such as decabromodiphenyl oxide, tetrabromo-bisphenol, eight bromo ether is best, particularly when them and antimonous oxide coupling, can make the flame retardant properties that ABS reaches excellent.Because difficulty combustion polymkeric substance (PVC) and chlorinatedpolyethylene (CPE) and ABS have good consistency and high chlorinity, be thus also a kind of fire retardant of ABS, and small molecules fire retardant can be reduced the mechanics of ABS is lost.But these halide-containings can produce a large amount of toxic gases in burning, the ABS that PVC, CPE are fire-retardant in addition also also exists poor heat stability, the easily shortcoming such as decomposition, difficult processing.Thus under the situation that the non-halogen cry of fire retardant material is day by day surging, domestic and international investigator starts to attempt one after another all kinds of halogen-free flame retardants is applied to ABS, to obtaining the halogen-free flame retardant ABS product of low toxicity, few cigarette, high-efficiency environment friendly green.
At present, the halogen-free flame-retardant system of ABS resin and alloy thereof comprises phosphorous, nitrogen, silicon flame-retardant system and inorganic fire-retarded system.Aluminium hydroxide and magnesium hydroxide are the two kinds of inorganic combustion inhibitors commonly used the most, because of have nontoxic, press down cigarette, the advantage such as cheap and be widely used in the flame-retardant modified of ABS, but the flame retarding efficiency of inorganic powdered filler is lower, addition reaches more than 40% and just likely reaches UL94V-0 flame retardant rating, inorganic combustion inhibitor and ABS poor compatibility in addition, high amount of inorganic filler makes the mechanical properties decrease of material in ABS resin serious, and outward appearance and processing characteristics sharply worsen.
In phosphorous flame-retardant system, triphenyl and derivative thereof are widely used in polymkeric substance because flame retarding efficiency is higher, but, when TPP is applied to ABS without the obvious fire retardation of generation.This mainly due in ABS structure without oxygen-containing functional group, when being unfavorable for that phosphonium flame retardant burns formed charing film; Be on the other hand then because the volatilization temperature of TPP is lower than the processing temperature of ABS, cause TPP and volatilize in the ABS course of processing and ooze out, the flame retardant effect of expection cannot be reached.For above-mentioned reason, the phosphorus flame retardant selecting thermostability higher and introduce the flame retarding efficiency that synergist can improve ABS effectively in phosphorus flame retardant.
PBT resin is a kind of crystalline polymer, has excellent mechanical property, electrical property and other physical and chemical performance, especially good fluidity, is easy to processing, is widely used in automobile, electronic enterprises.But, for some products that product size stability is very high, surface requirements is strict, need to add ABS resin and glass fibre regulates.As everyone knows, ABS has good elasticity, is a kind of non-crystalline polymer, and the polymkeric substance of these two kinds of different crystal forms be made well compatible, is all generally add a certain amount of compatilizer.How can solve consistency and surfacing sex chromosome mosaicism, performance is high, anti-impact is strong, realizes good flame retardant effect, is the technical problem to be solved in the present invention simultaneously.
Summary of the invention
The invention provides a kind of high-performance flame-retardant material, it is characterized in that, each component is as follows according to weight distribution ratio: ABS resin 40-70 part; PBT resin 10-20 part; Diameter is alkali free glass fibre 10-20 part of 10-20 μm; Toughener 2-3 part; Phosphorus flame retardant 5-10 part; Nitrogenated flame retardant 5-10 part; Silicon system synergist 3-5 part; Expanding material 3-5 part; Oxidation inhibitor 2-3 part.
Above-mentioned a kind of high-performance flame-retardant material, is characterized in that, described toughener is the mixture of barium sulfate, talcous one or both.
Above-mentioned a kind of high-performance flame-retardant material, is characterized in that, described phosphorus flame retardant comprises any one in phosphoric acid salt, poly-phosphate, pyrophosphate salt.
Above-mentioned a kind of high-performance flame-retardant material, is characterized in that, described nitrogenated flame retardant comprises any one in trimeric cyanamide, melamine cyanurate, Dyhard RU 100 and guanidinesalt thereof.
Above-mentioned a kind of high-performance flame-retardant material, is characterized in that contained expanding material is any one in maleic anhydride grafted polystyrene, maleic anhydride grafted ABS, glycidyl methacrylate graft SBS, Maleic anhydride-containg polyethylene, maleic anhydride graft rubber.
Above-mentioned a kind of high-performance flame-retardant material, is characterized in that contained silicon system synergist is any one in silane, dimethyl siloxane, methylphenyl siloxane, silicone resin, polysilsesquioxane (POSS).
Above-mentioned a kind of high-performance flame-retardant material, is characterized in that, described oxidation inhibitor is antioxidant 1010 or antioxidant 1076.
The beneficial effect of the invention:
The flame-retardant ABS compound material that theres is provided in the present invention adopts phosphorus system and nitrogen system synergistic flame-retardant system or phosphorus system and silicon-series five-retardant is collaborative uses, the flame retarding efficiency of halogen-free flame retardant ABS material can be improved on the one hand, promote the comprehensive mechanical property of halogen-free flame-retardant ABS compound material; And the poisonous gas discharged in minimizing combustion processes, the few poison of low cigarette.The PBT/ABS matrix material that the present invention obtains, has excellent surface, and good luster, performance is good, easily processes.
Embodiment
embodiment 1
Be that alkali free glass fibre 10 parts, 2 parts, the barium sulfate of 10-20 μm joins high-speed mixer batch mixing by ABS resin 60 parts, PBT resin 10 parts, diameter, join melt blending in twin screw extruder after mud conjunction evenly to extrude, and to control extruder temperature scope be 180 DEG C, screw speed is 400r/min, and melt pressure is 1.5MPa; Vacuum tightness is-0.04MPa, is cooled to normal temperature after extruding through tank, by dicing machine granulation, then gained pellet is put into baking oven, and temperature range is 80 DEG C, dry 3 hours, obtains modified ABS particle; Take quantitative sodium phosphate 5 parts, trimeric cyanamide 5 parts, 3 parts, silane, maleic anhydride grafted polystyrene 3 parts, antioxidant 1010 2 parts successively, above component and the ABS particle that adds conductive material are joined in high speed mixing smelting machine, mix, then join in twin screw extruder and extrude, extrusion temperature scope is 220 DEG C, screw speed is 400r/min, and melt pressure is 1.5MPa; Vacuum tightness is-0.04MPa, extrudes material strip and is cooled to normal temperature by circulating water channel, enters dicing machine granulation after Hairdryer drying.The LOI of the ABS material of the phosphorus system cooperative flame retardant of gained is 26.6%, UL94 vertical combustion rank is V-0.
embodiment 2
Be that alkali free glass fibre 10 parts, the talcum powder 2 parts of 10-20 μm joins high-speed mixer batch mixing by ABS resin 60 parts, PBT resin 10 parts, diameter, join melt blending in twin screw extruder after mud conjunction evenly to extrude, and to control extruder temperature scope be 200 DEG C, screw speed is 500r/min, and melt pressure is 2.0MPa; Vacuum tightness is-0.04MPa, is cooled to normal temperature after extruding through tank, by dicing machine granulation, then gained pellet is put into baking oven, and temperature range is 80 DEG C, dry 3 hours, obtains modified ABS particle; Take quantitative sodium polyphosphate 5 parts, melamine cyanurate 5 parts, dimethyl siloxane 3 parts, maleic anhydride grafted ABS 3 parts, antioxidant 1010 2 parts successively, above component and the ABS particle that adds conductive material are joined in high speed mixing smelting machine, mix, then join in twin screw extruder and extrude, extrusion temperature scope is 200 DEG C, screw speed is 500r/min, and melt pressure is 2.0MPa; Vacuum tightness is-0.04MPa, extrudes material strip and is cooled to normal temperature by circulating water channel, enters dicing machine granulation after Hairdryer drying.The LOI of the ABS material of the phosphorus system cooperative flame retardant of gained is 26.4%, UL94 vertical combustion rank is V-0.
embodiment 3
Be that alkali free glass fibre 10 parts, 2 parts, the barium sulfate of 10-20 μm joins high-speed mixer batch mixing by ABS resin 60 parts, PBT resin 10 parts, diameter, join melt blending in twin screw extruder after mud conjunction evenly to extrude, and to control extruder temperature scope be 220 DEG C, screw speed is 600r/min, and melt pressure is 1.5MPa; Vacuum tightness is-0.04MPa, is cooled to normal temperature after extruding through tank, by dicing machine granulation, then gained pellet is put into baking oven, and temperature range is 90 DEG C, dry 3 hours, obtains modified ABS particle; Take quantitative trisodium phosphate 5 parts, Dyhard RU 100 5 parts, methylphenyl siloxane 3 parts, glycidyl methacrylate graft SBS 3 parts, antioxidant 1010 2 parts successively, above component and the ABS particle that adds conductive material are joined in high speed mixing smelting machine, mix, then join in twin screw extruder and extrude, extrusion temperature scope is 220 DEG C, screw speed is 600r/min, and melt pressure is 1.5MPa; Vacuum tightness is-0.04MPa, extrudes material strip and is cooled to normal temperature by circulating water channel, enters dicing machine granulation after Hairdryer drying.The LOI of the ABS material of the phosphorus system cooperative flame retardant of gained is 26.7%, UL94 vertical combustion rank is V-0.
In a kind of high-performance flame-retardant material of the present invention, each component and parts by weight thereof are in table 1, and corresponding physicals is in table 2.A kind of high-performance flame-retardant material prepared by embodiment is injection molded into the standard batten of test by standard size, its physicals is respectively by China's national standard and U.S. UL standard testing.Wherein ABS resin is German BASF GP22.
Tensile strength GB1040
Elongation at break GB1040
Izod notched Izod impact strength GB1843
Flexural strength GB9341
Incendivity UL94
LOI GB/T 2406-93
the concrete formula of phosphorus system synergistic flame-proof ABS corresponding in table 1 reference examples and embodiment
the mechanical property of table 2 embodiment flame-proof ABS and reference examples ABS sample and flame retardant properties
| Performance | Embodiment 1 | Embodiment 2 | Embodiment 3 | Reference examples |
| Tensile strength/MPa | 40.6 | 38.7 | 38. 4 | 44.1 |
| Tensile modulus/GPa | 2.14 | 2.51 | 2.42 | 26 |
| Elongation/% | 6 | 5 | 5 | 7 |
| Notched Izod impact strength/KJ/m 2 | 4.5 | 4.3 | 4.4 | 8.2 |
| Flexural strength/MPa | 63.2 | 62.4 | 61.1 | 65.1 |
| Modulus in flexure/GPa | 45 | 4.22 | 45 | 4.11 |
| Flame retardant rating/3.2mm | V-0 | V-0 | V-0 | NR |
| Oxygen index (LOI)/% | 26.6 | 26.4 | 26.7 | 18 |
Claims (7)
1. a high-performance flame-retardant material, is characterized in that, each component is as follows according to weight distribution ratio:
aBS resin 40-70 part;
pBT resin 10-20 part;
Diameter is alkali free glass fibre 10-20 part of 10-20 μm;
Toughener 2-3 part;
phosphorus flame retardant 5-10 part;
nitrogenated flame retardant 5-10 part;
Silicon system synergist 3-5 part
expanding material 3-5 part;
Oxidation inhibitor 2-3 part.
2. a kind of high-performance flame-retardant material according to claim 1, is characterized in that, described toughener is the mixture of barium sulfate, talcous one or both.
3. a kind of high-performance flame-retardant material according to claim 1, is characterized in that, described phosphorus flame retardant comprises any one in phosphoric acid salt, poly-phosphate, pyrophosphate salt.
4. a kind of high-performance flame-retardant material according to claim 1, is characterized in that, described nitrogenated flame retardant comprises any one in trimeric cyanamide, melamine cyanurate, Dyhard RU 100 and guanidinesalt thereof.
5. a kind of high-performance flame-retardant material according to claim 1, is characterized in that contained expanding material is any one in maleic anhydride grafted polystyrene, maleic anhydride grafted ABS, glycidyl methacrylate graft SBS, Maleic anhydride-containg polyethylene, maleic anhydride graft rubber.
6. a kind of high-performance flame-retardant material according to claim 1, is characterized in that contained silicon system synergist is any one in silane, dimethyl siloxane, methylphenyl siloxane, silicone resin, polysilsesquioxane (POSS).
7. a kind of high-performance flame-retardant material according to claim 1, is characterized in that, described oxidation inhibitor is antioxidant 1010 or antioxidant 1076.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310346741.0A CN104371253A (en) | 2013-08-12 | 2013-08-12 | High performance flame retardant material |
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| CN201310346741.0A CN104371253A (en) | 2013-08-12 | 2013-08-12 | High performance flame retardant material |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107474510A (en) * | 2017-08-29 | 2017-12-15 | 华南理工大学 | High fluidity high rigidity halogen-free flame retardant PC/ABS mixtures and preparation method thereof |
| CN108102284A (en) * | 2018-02-01 | 2018-06-01 | 浙江马新材料有限公司 | A kind of glazed flame-retardant heat-resistant antifriction ABS plastic |
| CN109554954A (en) * | 2019-01-22 | 2019-04-02 | 重庆纤维研究设计院股份有限公司 | High flame retardant glass fiber material and preparation method thereof |
-
2013
- 2013-08-12 CN CN201310346741.0A patent/CN104371253A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107474510A (en) * | 2017-08-29 | 2017-12-15 | 华南理工大学 | High fluidity high rigidity halogen-free flame retardant PC/ABS mixtures and preparation method thereof |
| CN108102284A (en) * | 2018-02-01 | 2018-06-01 | 浙江马新材料有限公司 | A kind of glazed flame-retardant heat-resistant antifriction ABS plastic |
| CN109554954A (en) * | 2019-01-22 | 2019-04-02 | 重庆纤维研究设计院股份有限公司 | High flame retardant glass fiber material and preparation method thereof |
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Application publication date: 20150225 |