CN102604246A - Efficient-inflame-retardance styrene resin composition - Google Patents
Efficient-inflame-retardance styrene resin composition Download PDFInfo
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Abstract
The invention relates to an efficient-inflame-retardance styrene resin composition, comprising the following components in parts by weight: 100 parts of styrene resin, 5-18 parts of halogen flame retardants, 1-5 parts of antimony flame retardants, 1-6 parts of metal halide, 1-6 parts of inorganic substances containing silicon, 0.1-0.5 part of anti-drip agent, 0.3-0.5 part of antioxidant, 0.1-0.5 part of light stabilizer and 0.5-2.0 parts of lubricating agents. The composition greatly enhances inflaming retarding efficiency, can reduce the additive amount of the halogen and antimony flame retardants, and solves the problems that the carbon forming efficiency of the conventional inflame-retardance styrene resin is low, and the conventional inflame-retardance styrene resin only depends on a gas phase to retard inflaming. The efficient-inflame-retardance styrene resin provided by the invention has the advantages of being good in inflame retardance performance, high in thermal stability, good in heat resistance and low in cost, thus having a wide application prospect.
Description
Technical field
The present invention relates to a kind of flame-retardant modified resin combination, more specifically, relate to a kind of styrene resin composite of highly effective flame-retardant.
Background technology
Styrene resin is widely used in fields such as electronics, Communication Equipment, automotive industry, household electrical appliance, office equipment, electric product; Belong to inflammable macromolecular material; When being used to have the products such as various electronic apparatuss of fire-retardant requirement; Need carry out flame-retardant modified, to satisfy the request for utilization of fire safety.
But owing to lack oxy radical; The combustion of the styrene resin poor ability of charring, so phosphorus system, the fire retardant that silicon system relies on the condensed phase fire retardant mechanism is very low to its flame retarding efficiency; Also Just because of this, the halogen-free flameproof styrene resin of preparation high flame resistance still is a difficult problem.At present, the flame-retardant system that styrene resin is the most commonly used is halogenated flame retardant and Antimony Trioxide: 99.5Min synergistic system, realizes flame retardant resistance through the fire-retardant mechanism of gas phase.Total institute is known, and halogen antimony flame-retardant system can produce a large amount of toxic gases when burning, and smoke density is also very big, is unfavorable for fire disaster escaping.Halogen antimony fire retardant belongs to Nonrenewable resources, hold at high price, particularly weisspiessglanz in recent years price continue to skyrocket and be unfavorable for cost degradation scale operation.In addition owing to added a large amount of halogenated flame retardants, can be to the weathering resistance of styrene resin, thermostability and all can produce bigger negative impact to mould.
How to improve the one-tenth charcoal ability of styrene resin, improving flame retarding efficiency is a problem demanding prompt solution.Proton can be provided, and the Lewis acid of accepting electronics can change the Thermal Decomposition Mechanism of some polymkeric substance, makes polymkeric substance generation dehydrogenation reaction, produces unsaturated link(age), thereby further causes crosslinked and charing, the final purpose that realizes improving into the charcoal ability.Yet only use lewis acidic effect to produce the charcoal layer, its thermostability is relatively poor, under the high temperature thermal oxidation condition, oxidative degradation can take place, and can cause worsening flame retardant properties.
Therefore, the invention provides a kind of new technical scheme, further improved the thermostability of charcoal layer, thereby have more excellence flame retardant resistance efficiently.
Summary of the invention
The object of the invention is exactly a kind of low cost to be provided, the styrene resin composite of high flame retardant efficient in order to overcome one-tenth charcoal ability that above-mentioned existing styrene resin flame-retarded technology exists, the low defective of flame retarding efficiency.
The object of the invention can be realized through following technical scheme:
The present invention relates to a kind of styrene resin composite of highly effective flame-retardant, said composition comprises following component and weight part content:
Styrene resin 100;
Halogenated flame retardant 5-18;
Sb system fire retardant 1-5;
Metal halide 1-6;
Siliceous inorganics 1-6;
Anti-dripping agent 0.1-0.5;
Oxidation inhibitor 0.3-0.5;
Photostabilizer 0.1-0.5;
Lubricant 0.5-2.0.
Preferably, described styrene resin is selected from one or more the mixing in acrylonitrile-butadiene-styrene copolymer, acrylonitrile-butadiene-Yodo Sol GH 28, MBS, vinyl cyanide-terpolymer EP rubber-styrol copolymer, acrylonitrile-chlorianted polyethylene-styrene terpolymer, high-impact polystyrene, K glue, general purpose polystyrene, acrylonitritrile-styrene resin, copolymer of methyl methacrylatestyrene, the vinyl cyanide-α-Jia Jibenyixigongjuwu.
Preferably, said halogenated flame retardant is selected from one or more the mixing in chlorinatedpolyethylene, two (hexachlorocyclopentadiene) cyclooctane, clorafin, tetrabromo-bisphenol, TDE, three (bromophenyl) triazine, bromination epoxy, decabromodiphenyl oxide, hexabromocyclododecane, PHT4, hexabromobenzene, octabromodiphenyl ether, Brominated Polystyrene, brominated polycarbonate oligopolymer, bromination phenoxy resin, the tribromo-benzene based phosphates; Said Sb system fire retardant is a kind of in Antimony Trioxide: 99.5Min, antimony peroxide or the sodium antimonate.
Preferably, described metal halide is the muriate or the bromide of magnesium, aluminium, potassium, sodium, calcium, tin, lead, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, tungsten, mercury, yttrium, zirconium, niobium or molybdenum.
Preferably, described metal halide is one or both the mixing in the muriate of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, tungsten, mercury, yttrium, zirconium, niobium or molybdenum.
Preferably, the particle diameter of described metal halide is 0.1-10 μ m.
Preferably, described siliceous inorganics is one or both the mixture in elemental silicon, silicon oxide, silit, silicon chlorides, silicon fluoride, silicate or the silicofluoride.
Preferably, said elemental silicon is Pure Silicon Metal, silicon single crystal or polysilicon.
Preferably, said silicate is the silicate of sodium, magnesium, potassium, calcium, aluminium or ammonium.
Preferably, said silicofluoride is the silicofluoride of sodium, magnesium, potassium, calcium, aluminium or ammonium.
Preferably, the particle diameter of described siliceous inorganics is 0.1-10 μ m.
Preferably, described anti-dripping agent is that molecular weight is 2,000,000-5,000,000 tetrafluoroethylene.
Preferably, described oxidation inhibitor is one or both the mixture of Irganox 1010, Irganox 1076 or Irganox 168.
Preferably, said photostabilizer is one or more the mixture in 2-dihydroxy benaophenonel, salicylate class, phosphorous acid diphenyl ester, triphenyl phosphite, the hydroxybenzotriazole; Said lubricant is one or more the mixture in silicone oil, white mineral oil, fatty acid amide, pentaerythritol tetrastearate, barium stearate, Magnesium Stearate, Zinic stearas, paraffin, polyethylene wax, ethylene bis stearic acid amide, Injecatable EVA Copolymer, the ethylene-acrylic acid copolymer.
Preferably; Described styrene resin composite also comprises mineral filler, and said mineral filler is one or more the mixing in talcum powder, lime carbonate, aluminum oxide, kaolin, Attapulgite, hydrotalcite, mica, polynite, zeyssatite, wollastonite, spun glass, charcoal fiber, glass microballon or the graphite.
Preferably; Described styrene resin composite also comprises compatilizer, and said compatilizer is selected from one or more the mixing in styrene-maleic anhydride copolymer, acrylonitrile-styrene-glycidyl methacrylate copolymer, acrylonitrile-butadiene-styrene (ABS) grafted maleic anhydride, acrylonitrile-butadiene-styrene (ABS) graft glycidyl methacrylate, acrylonitrile-styrene grafted maleic anhydride, acrylonitrile-styrene grafting methylacrylic acid or the ethylene-methyl acrylate copolymer graft glycidyl methacrylate.
Preferably, in said styrene resin 100 weight parts, the content of said compatilizer is the 1-5 weight part.
The present invention has improved flame retarding efficiency through the cooperative flame retardant of metal halide and siliceous inorganics, and reduces the addition of halogen antimony fire retardant, has reduced cost, thereby has had broad application prospects.
Embodiment
Below in conjunction with specific embodiment the present invention is elaborated.Following examples will help those skilled in the art further to understand the present invention, but not limit the present invention in any form.Should be pointed out that to those skilled in the art, under the prerequisite that does not break away from the present invention's design, can also make some distortion and improvement.These all belong to protection scope of the present invention.
The preparation method of the styrene resin of highly effective flame-retardant is following:
Get the raw materials ready by proportioning, the styrene resin of getting ready, halogenated flame retardant, Sb system fire retardant, metal halide, siliceous inorganics, anti-dripping agent, oxidation inhibitor, lubricant and photostabilizer are stirred uniform mixing through high-speed mixer; At last, the said mixture accurate measurement is sent in the forcing machine, in the shearing of twin screw, carried, mixing fully fusing is compound down, extrude through head again, and tie rod, pelletizing, drying is packaged as finished product at last.
The length-to-diameter ratio of twin screw extruder screw rod is 40, and front-end temperature is 180-190 ℃, and the stage casing temperature is 200-220 ℃, and the head extrusion temperature is 210 ℃, and screw speed is 100 rev/mins.
The flame retardant styrene resin of each embodiment and Comparative Examples preparation is injection molded into the mechanical property and the flame retardant properties of various standard Mechanics Performance Testing resins by the ASTM standard, and physicals and testing method are as shown in table 1.
Table 1
| Physicals | Testing method |
| Tensile strength (50mm/min) | ASTM?D638 |
| Melting index (200 ℃, 5kg) | ASTM?D1238 |
| Heat-drawn wire (1.82MPa) | ASTM?D648 |
| IZOD notched Izod impact strength (3.2mm) | ASTM?D256 |
| Incendivity (vertical combustion 3.2mm/1.6mm) | UL?94 |
Embodiment 1
Present embodiment relates to a kind of styrene resin composite, and its component and content are:
Wherein
Styrene resin is strange beautiful PA747 resin;
Halogenated flame retardant is DRCP;
Sb system fire retardant is an Antimony Trioxide: 99.5Min;
Metal halide is CuCl
2
Siliceous inorganics is a Pure Silicon Metal;
Anti-dripping agent is the PTFE of 2,000,000 molecular weight;
Photostabilizer is the 2-dihydroxy benaophenonel;
Oxidation inhibitor is Irganox 1010, Ciba;
Lubricant is PETS.
Embodiment 2
Present embodiment relates to a kind of styrene resin composite, and its component and content are:
Wherein
Styrene resin is strange beautiful PA747 resin;
Halogenated flame retardant is a tetrabromo-bisphenol;
Sb system fire retardant is an Antimony Trioxide: 99.5Min;
Metal halide is CuBr
2
Siliceous inorganics is a silit;
Anti-dripping agent is the PTFE of 2,500,000 molecular weight;
Photostabilizer is a salicylate;
Oxidation inhibitor is Irganox 1076, Ciba;
Lubricant is a silicone oil.
Embodiment 3
Present embodiment relates to a kind of styrene resin composite, and its component and content are:
Wherein
Styrene resin is strange beautiful PA747 resin;
Halogenated flame retardant is the bromination epoxy;
Sb system fire retardant is an antimony peroxide;
Metal halide is NiCl;
Siliceous inorganics is a polysilicon;
Anti-dripping agent is the PTFE of 3,000,000 molecular weight;
Photostabilizer is the phosphorous acid diphenyl ester;
Oxidation inhibitor is Irganox 168, Ciba;
Lubricant is a fatty acid amide.
Embodiment 4
Present embodiment relates to a kind of styrene resin composite, and its component and content are:
Wherein
Styrene resin is a beautiful ASAXC190 resin of Shanghai Jin Hu day;
Halogenated flame retardant is a chlorinatedpolyethylene;
Sb system fire retardant is an antimony peroxide;
Metal halide is FeCl
3
Siliceous inorganics is a silicon tetrafluoride;
Anti-dripping agent is the PTFE of 3,500,000 molecular weight;
Photostabilizer is a triphenyl phosphite;
Oxidation inhibitor is Irganox 1010 and Irganox 1076, Ciba;
Lubricant is a paraffin.
Embodiment 5
Present embodiment relates to a kind of styrene resin composite, and its component and content are:
Wherein
Styrene resin is a beautiful HIPS425 resin of Shanghai Jin Hu day;
Halogenated flame retardant is FR245;
Sb system fire retardant is an antimony peroxide;
Metal halide is MgBr
2
Siliceous inorganics is a silicon single crystal;
Anti-dripping agent is the PTFE of 4,000,000 molecular weight;
Photostabilizer is a hydroxybenzotriazole;
Oxidation inhibitor is Irganox 1010 and Irganox 168, Ciba;
Lubricant is an ethylene-acrylic acid copolymer.
Embodiment 6
Present embodiment relates to a kind of styrene resin composite, and its component and content are:
Wherein
Styrene resin is a beautiful SAN360 resin of Shanghai Jin Hu day;
Halogenated flame retardant is a decabromodiphenyl oxide;
Sb system fire retardant is a sodium antimonate;
Metal halide is MgCl
2
Siliceous inorganics is a silicon oxide;
Anti-dripping agent is the PTFE of 4,500,000 molecular weight;
Photostabilizer is 2-dihydroxy benaophenonel and phosphorous acid diphenyl ester;
Oxidation inhibitor is Irganox 1076 and Irganox 168, Ciba;
Lubricant is an Injecatable EVA Copolymer.
Embodiment 7
Present embodiment relates to a kind of styrene resin composite, and its component and content are:
Wherein
Styrene resin is a beautiful ABS745 resin of Shanghai Jin Hu day;
Halogenated flame retardant is the tribromo-benzene based phosphates;
Sb system fire retardant is a sodium antimonate;
Metal halide is ZnCl
2
Siliceous inorganics is a water glass;
Anti-dripping agent is the PTFE of 5,000,000 molecular weight;
Photostabilizer is triphenyl phosphite and hydroxybenzotriazole;
Oxidation inhibitor is Irganox 1010, Ciba;
Lubricant is a Magnesium Stearate.
Comparative Examples 1
Present embodiment relates to a kind of styrene resin composite, and its component and content are:
Wherein
Styrene resin is strange beautiful PA747 resin;
Halogenated flame retardant is FR245;
Sb system fire retardant is a weisspiessglanz;
Anti-dripping agent is the PTFE of 3,000,000 molecular weight;
Photostabilizer is Tinuvins UVP, Ciba;
Oxidation inhibitor is B900, Ciba;
Lubricant is a Magnesium Stearate.
Comparative Examples 2
Present embodiment relates to a kind of styrene resin composite, and its component and content are:
Wherein
Styrene resin is a beautiful HIPS425 resin of Shanghai Jin Hu day;
Halogenated flame retardant is FR245;
Sb system fire retardant is a weisspiessglanz;
Anti-dripping agent is the PTFE of 3,000,000 molecular weight;
Photostabilizer is Tinuvins UVP, Ciba;
Oxidation inhibitor is B900, Ciba;
Lubricant is a Magnesium Stearate.
Table 2
The physical property measurement result of embodiment 1-7 and Comparative Examples 1-2 is as shown in table 2; Embodiment 1～7 and Comparative Examples 1～2 test result show; Cooperative flame retardant through metal halide and siliceous inorganics can improve flame retarding efficiency; Reduce the addition of halogen antimony fire retardant, reduced cost, improve the purpose of heat-drawn wire.
Claims (17)
1. the styrene resin composite of a highly effective flame-retardant is characterized in that, comprises following component and parts by weight:
Styrene resin 100;
Halogenated flame retardant 5-18;
Sb system fire retardant 1-5;
Metal halide 1-6;
Siliceous inorganics 1-6;
Anti-dripping agent 0.1-0.5;
Oxidation inhibitor 0.3-0.5;
Photostabilizer 0.1-0.5;
Lubricant 0.5-2.0.
2. the styrene resin composite of highly effective flame-retardant according to claim 1; It is characterized in that described styrene resin is selected from one or more the mixing in acrylonitrile-butadiene-styrene copolymer, acrylonitrile-butadiene-Yodo Sol GH 28, MBS, vinyl cyanide-terpolymer EP rubber-styrol copolymer, acrylonitrile-chlorianted polyethylene-styrene terpolymer, high-impact polystyrene, K glue, general purpose polystyrene, acrylonitritrile-styrene resin, copolymer of methyl methacrylatestyrene, the vinyl cyanide-α-Jia Jibenyixigongjuwu.
3. the styrene resin composite of highly effective flame-retardant according to claim 1; It is characterized in that said halogenated flame retardant is selected from one or more the mixing in chlorinatedpolyethylene, two (hexachlorocyclopentadiene) cyclooctane, clorafin, tetrabromo-bisphenol, TDE, three (bromophenyl) triazine, bromination epoxy, decabromodiphenyl oxide, hexabromocyclododecane, PHT4, hexabromobenzene, octabromodiphenyl ether, Brominated Polystyrene, brominated polycarbonate oligopolymer, bromination phenoxy resin, the tribromo-benzene based phosphates; Said Sb system fire retardant is a kind of in Antimony Trioxide: 99.5Min, antimony peroxide or the sodium antimonate.
4. the styrene resin composite of highly effective flame-retardant according to claim 1; It is characterized in that described metal halide is the muriate or the bromide of magnesium, aluminium, potassium, sodium, calcium, tin, lead, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, tungsten, mercury, yttrium, zirconium, niobium or molybdenum.
5. the styrene resin composite of highly effective flame-retardant according to claim 4; It is characterized in that described metal halide is one or both the mixing in the muriate of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, tungsten, mercury, yttrium, zirconium, niobium or molybdenum.
6. the styrene resin composite of highly effective flame-retardant according to claim 4 is characterized in that, the particle diameter of described metal halide is 0.1-10 μ m.
7. the styrene resin composite of highly effective flame-retardant according to claim 1 is characterized in that, described siliceous inorganics is one or both the mixture in elemental silicon, silicon oxide, silit, silicon chlorides, silicon fluoride, silicate or the silicofluoride.
8. the styrene resin composite of highly effective flame-retardant according to claim 7 is characterized in that, said elemental silicon is Pure Silicon Metal, silicon single crystal or polysilicon.
9. the styrene resin composite of highly effective flame-retardant according to claim 7 is characterized in that, said silicate is the silicate of sodium, magnesium, potassium, calcium, aluminium or ammonium.
10. the styrene resin composite of highly effective flame-retardant according to claim 7 is characterized in that, said silicofluoride is the silicofluoride of sodium, magnesium, potassium, calcium, aluminium or ammonium.
11. the styrene resin composite of highly effective flame-retardant according to claim 7 is characterized in that, the particle diameter of described siliceous inorganics is 0.1-10 μ m.
12. the styrene resin composite of highly effective flame-retardant according to claim 1 is characterized in that, described anti-dripping agent is that molecular weight is 2,000,000-5,000,000 tetrafluoroethylene.
13. the styrene resin composite of highly effective flame-retardant according to claim 1 is characterized in that, described oxidation inhibitor is one or both the mixture of Irganox 1010, Irganox 1076 or Irganox 168.
14. the styrene resin composite of highly effective flame-retardant according to claim 1; It is characterized in that said photostabilizer is one or more the mixture in 2-dihydroxy benaophenonel, salicylate class, phosphorous acid diphenyl ester, triphenyl phosphite, the hydroxybenzotriazole; Said lubricant is one or more the mixture in silicone oil, white mineral oil, fatty acid amide, pentaerythritol tetrastearate, barium stearate, Magnesium Stearate, Zinic stearas, paraffin, polyethylene wax, ethylene bis stearic acid amide, Injecatable EVA Copolymer, the ethylene-acrylic acid copolymer.
15. the styrene resin composite of highly effective flame-retardant according to claim 1; It is characterized in that; Described styrene resin composite also comprises mineral filler, and said mineral filler is one or more the mixing in talcum powder, lime carbonate, aluminum oxide, kaolin, Attapulgite, hydrotalcite, mica, polynite, zeyssatite, wollastonite, spun glass, charcoal fiber, glass microballon or the graphite.
16. the styrene resin composite of highly effective flame-retardant according to claim 1; It is characterized in that; Described styrene resin composite also comprises compatilizer, and said compatilizer is selected from one or more the mixing in styrene-maleic anhydride copolymer, acrylonitrile-styrene-glycidyl methacrylate copolymer, acrylonitrile-butadiene-styrene (ABS) grafted maleic anhydride, acrylonitrile-butadiene-styrene (ABS) graft glycidyl methacrylate, acrylonitrile-styrene grafted maleic anhydride, acrylonitrile-styrene grafting methylacrylic acid or the ethylene-methyl acrylate copolymer graft glycidyl methacrylate.
17. the styrene resin composite of highly effective flame-retardant according to claim 16 is characterized in that, in said styrene resin 100 weight parts, the content of said compatilizer is the 1-5 weight part.
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