CN103788614A - Halogen-free flame retardant super-tough type polycarbonate material - Google Patents
Halogen-free flame retardant super-tough type polycarbonate material Download PDFInfo
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- CN103788614A CN103788614A CN201410016958.XA CN201410016958A CN103788614A CN 103788614 A CN103788614 A CN 103788614A CN 201410016958 A CN201410016958 A CN 201410016958A CN 103788614 A CN103788614 A CN 103788614A
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Abstract
The invention discloses a halogen-free flame retardant super-tough type polycarbonate material. The halogen-free flame retardant super-tough type polycarbonate material is characterized by comprising the following components in parts by weight: 100 parts of the polycarbonate, 0.1-2 parts of the sulfonate series flame retardant, 0.02-0.5 part of the polymethylphenyl silicone, 0.1-5 parts of the polytetrafluoroethylene type anti-dropping agent, 0-5 parts of the methyl methacrylate copolymer, 0-5 parts of the methyl methacrylate butadiene-styrene copolymer, 3-10 parts of the siloxane-acrylic copolymer, 0.1-1 part of the lubricant, 0.1-1 part of the anti-oxidant and 1 part of the toner. The halogen-free flame retardant super-tough type polycarbonate material has the advantage of high toughness.
Description
Technical field:
The present invention relates to technical field of polymer materials, be specifically related to a kind of halogen-free and flame-retardant polycarbonate material with higher toughness.
Background technology:
The shortcomings such as polycarbonate (PC) material has excellent performance, but PC unrelieved stress is high, stress cracking, low to breach anti-impact force easily occurs, impact processing injection moulding, have therefore limited its purposes.In addition (oxygen index is 21%～24% to the flame retardant resistance of polycarbonate (PC), flame retardant properties reaches uL94V-2 level) although be better than common thermoplastic polymer (as polyethylene, polypropylene etc.), but still be difficult to meet the requirement of some Application Areas to flame retardant properties, for example much be applied in electronic apparatus, and interior architecture and household product, generally material is had to fire-retardant requirement (960 ℃ of V-0/3.2mm or glowing filaments), but existing PC cannot meet the requirement of this series products, therefore must carry out fire-retardant and toughening modifying to PC.
Generally, can reach flame-retardant modified object by adding fire retardant or introduce the elements such as bromine, phosphorus, silicon in polymkeric substance in polymkeric substance building-up process.PC has tetrabromo-bisphenol (TBBPA), the poly-dibromobenzene aether (PDBPO) of decabromodiphynly oxide (DBDPO), ten tetrabromo two phenoxy group benzene (DBDPOB) etc. with fire retardant at present.The existence in the toxicity of the halogenated flame retardants such as polybromodiphenyl ether and environmental problem of European countries and the U.S. such as Germany is disputed on, and the corrosive gases producing when halogenated flame retardant cracking easily causes the malfunctioning of electronic electric equipment key part, therefore, non-halogen or low halogen, press down cigarette, low toxicity, high efficiency, multi-functional Composite and become the focus of fire retardant exploitation and Applied research fields.
-as the fire retardant mechanism of fire retardant can be divided into: 1, gas phase is fire-retardant, is suppressed at the free radical that plays chain propagation in combustion reactions; 2, condensed phase is fire-retardant, in solid phase, stops the thermolysis of polymkeric substance and stops polymkeric substance to discharge inflammable gas; 3, interrupt heat exchange, the heat producing by polymkeric substance is taken away and is not fed back on polymkeric substance, makes no longer last decomposition of polymkeric substance.
Summary of the invention:
The object of the present invention is to provide a kind of halogen-free and flame-retardant polycarbonate material with higher toughness.
Above-mentioned purpose of the present invention is achieved by following scheme:
The super tough type polycarbonate material of a kind of halogen-free flameproof, it is characterized in that: the super tough type polycarbonate material of described halogen-free flameproof comprises polycarbonate, the agent of sulfonate fire-retardant, PSI, tetrafluoroethylene class anti-dripping agent, ethylene methyl acrylate copolymer, MMB methyl methacrylate butadiene-styrol copolymer, siloxanes acrylic copolymer, lubricant, oxidation inhibitor and toner, and the component of its parts by weight is:
Polycarbonate: 100 parts;
Sulfonate fire-retardant agent: 0.1～2 part;
PSI: 0.02～0.5 part;
Tetrafluoroethylene class anti-dripping agent: 0.1～5 part;
Ethylene methyl acrylate copolymer: 0～5 part;
MMB methyl methacrylate butadiene-styrol copolymer: 0～5 part;
Siloxanes acrylic copolymer: 3～10 parts;
Lubricant: 0.1～1 part;
Oxidation inhibitor: 0.1～1 part;
Toner: 1 part.
The super tough type polycarbonate material of halogen-free flameproof according to claim 1, is characterized in that: the agent of described sulfonate fire-retardant is one or more the mixture in potassium phenylsulphonyl benzene sulfonate, perfluoro butyl potassium sulfonate and 2,4,5-trichlorobenzene sodium sulfonate.
The super tough type polycarbonate material of halogen-free flameproof according to claim 1, is characterized in that: the silicon rubber that described siloxanes acrylic copolymer is a kind of nucleocapsid structure, its core is that siloxanes shell is acrylic copolymer.
The super tough type polycarbonate material of halogen-free flameproof according to claim 1, is characterized in that: described lubricant is fatty acid or metal soap or ester class or amides lubricant.
The super tough type polycarbonate material of halogen-free flameproof according to claim 1, is characterized in that: described tetrafluoroethylene class anti-dripping agent is polymer fluoro-resin, as tetrafluoroethylene class anti-dripping agent.
The super tough type polycarbonate material of halogen-free flameproof according to claim 1, is characterized in that: described oxidation inhibitor is elected one or more in antioxidant 1010, irgasfos 168, antioxidant 1076, oxidation inhibitor B215, antioxidant 2246 or antioxidant 264 as.
Sulfonate fire retardant of the present invention has following function: when burning, it can accelerate the one-tenth charcoal speed of PC, promotes polymer molecule crosslinked.Although the dosage that sulfonate fire retardant of the present invention uses is less, flame retarding efficiency is high, not only can be in the specific preparation technology of product of the present invention good be scattered in whole system, realizes the stable of flame retardant properties.The present invention is also by adding a small amount of PSI and sulfonate fire retardant to carry out composite raising flame retarding efficiency, and the consumption of PSI can make the thick batten flame retardant resistance of 1.6mm reach UL-94V-0 level while being the 0.02%--0.3% of formula total amount.In addition, in order to eliminate burning drippage, also added anti-dripping agent, realized the high quality combination of flame-retardant system, made material there is good flame retardant resistance and resistance to impact shock.
Halogen-free flame-proof toughening system of the present invention also has another one effect, interaction between sulfonate fire retardant, siloxanes acrylic copolymer and PC wherein mainly contains three: first, sulfonate fire retardant at high temperature can promote the isomerization of PC, and discharges the incombustible substance such as CO2 and H2O; Isomerization energy improves the crosslinked of PC and becomes charcoal speed, forms carbon-coating on PC surface, and obstruct PC contacts with airborne oxygen, stops the generation of oxidizing reaction, thereby reaches extinguishing of material; CO2 and the water discharging on the one hand can barrier material and the contacting of oxygen in air, and has the effect that reduces temperature simultaneously, burns thereby stop; The second, sulfonate fire retardant and toughened with silicon rubber agent produce synergy, have promoted the shear yielding of PC, have further improved the toughening effect of modification PC; The 3rd, in burning, siloxanes toughner can move to rapidly PC surface, forms the charcoal protective layer of high flame retardant; Between PC and toughened with silicon rubber agent, form crosslinking structure, form the protective layer of high flame retardant, thereby PC is produced to fire retardation, further improved the flame retardant effect of modification PC simultaneously.
Toughened system of the present invention adopts EMA, MBS and silastic copolymer system, three kinds of toughened systems play respectively different toughening effects, make product all there is excellent shock resistance at low temperature and high temperature, the nucleocapsid structure that wherein silastic copolymer has, for core-shell structure toughening mechanism, realized the mutual supplement with each other's advantages of toughner, toughening effect is good, has improved consistency, the dispersiveness of toughner.Acrylic polymer has the feature good with polycarbonate resin consistency, and functional group and resin reaction produce good interface bonding, have improved shock strength.
Above-mentioned supplementary material is dry mixed according to certain proportioning, fully mixes in rear input twin screw extruder and melt extrudes, and the cooling and pelletizing by tank, finally obtains the super tough type polycarbonate alloy material of halogen-free flameproof.
Wherein the control of double-screw extruder screw temperature is 200-260 ℃, 50～80 ℃ of pelletizing water-cooled temperature.
Embodiment:
Below in conjunction with specific embodiment, the present invention is done further and described, but specific embodiment does not do any restriction to the present invention.
Embodiment 1:
Polycarbonate (PC): 100 parts
Perfluoro butyl potassium sulfonate (PPFBS): 0.1 part
PSI: 0.02 part
Tetrafluoroethylene class anti-dripping agent: 0.1 part
Ethylene methyl acrylate copolymer (EMA): 1 part
MMB methyl methacrylate butadiene-styrol copolymer (MBS): 1 part
Siloxanes acrylic copolymer (METABLEN-S2030): 5 parts
Tetramethylolmethane stearate fire-resistant lubricants (PETS): 0.4 part
Oxidation inhibitor: 0.4 part.
Toner: 1 part.
Embodiment 2:
Polycarbonate (PC): 100 parts
Perfluoro butyl potassium sulfonate (PPFBS): 1 part
PSI: 0.5 part
Tetrafluoroethylene class anti-dripping agent: 0.1 part
Ethylene methyl acrylate copolymer (EMA): 1 part
MMB methyl methacrylate butadiene-styrol copolymer (MBS): 1 part
Siloxanes acrylic copolymer (METABLEN-S2030): 5 parts
Tetramethylolmethane stearate fire-resistant lubricants (PETS): 0.4 part
Oxidation inhibitor: 0.4 part.
Toner: 1 part.
Embodiment 3:
Polycarbonate (PC): 100 parts
Perfluoro butyl potassium sulfonate (PPFBS): 0.5 part
Ethylene methyl acrylate copolymer (EMA): 2 parts
MMB methyl methacrylate butadiene-styrol copolymer (MBS): 2 parts
Siloxanes acrylic copolymer: 5 parts
Tetramethylolmethane stearate fire-resistant lubricants (PETS): 0.4 part
Oxidation inhibitor: 0.4 part.
Toner: 1 part.
Embodiment 4:
Polycarbonate (PC): 100 parts
Perfluoro butyl potassium sulfonate (PPFBS): 0.5 part
PSI: 0.05 part
Tetrafluoroethylene class anti-dripping agent: 0.1 part
Ethylene methyl acrylate copolymer (EMA): 2 parts
MMB methyl methacrylate butadiene-styrol copolymer (MBS): 2 parts
Tetramethylolmethane stearate fire-resistant lubricants (PETS): 0.4 part
Oxidation inhibitor: 0.4 part.
Toner: 1 part.
Comparative example:
100 parts of polycarbonate resins;
0.4 part of tetramethylolmethane stearate fire-resistant lubricants (PETS);
Oxidation inhibitor: 0.4 part.
Toner: 1 part.
The material of being produced by above-described embodiment 1 to embodiment 4 and comparative example has the technical indicator shown in following table after tested:
As can be seen from the above table, 1. flame retardant resistance, toughness, the tensile strength of the modification PC of embodiment 1 and 2 preparations are all relatively good; 2. use flame retardant effect, mechanical property and the thermotolerance of the PC that fire retardant of the present invention and toughner makes better;
This specific embodiment is only explanation of the invention; it is not limitation of the present invention; those skilled in the art are reading after this specification sheets and can make to the present embodiment the modification that there is no creative contribution as required, but as long as within the scope of claim of the present invention, are all subject to the protection of patent law.
Claims (6)
1. the super tough type polycarbonate material of halogen-free flameproof, it is characterized in that: the super tough type polycarbonate material of described halogen-free flameproof comprises polycarbonate, the agent of sulfonate fire-retardant, PSI, tetrafluoroethylene class anti-dripping agent, ethylene methyl acrylate copolymer, MMB methyl methacrylate butadiene-styrol copolymer, siloxanes acrylic copolymer, lubricant, oxidation inhibitor and toner, and the component of its parts by weight is:
Polycarbonate: 100 parts;
Sulfonate fire-retardant agent: 0.1～2 part;
PSI: 0.02～0.5 part;
Tetrafluoroethylene class anti-dripping agent: 0.1～5 part;
Ethylene methyl acrylate copolymer: 0～5 part;
MMB methyl methacrylate butadiene-styrol copolymer: 0～5 part;
Siloxanes acrylic copolymer: 3～10 parts;
Lubricant: 0.1～1 part;
Oxidation inhibitor: 0.1～1 part;
Toner: 1 part.
2. the super tough type polycarbonate material of halogen-free flameproof according to claim 1, is characterized in that: the agent of described sulfonate fire-retardant is one or more the mixture in potassium phenylsulphonyl benzene sulfonate, perfluoro butyl potassium sulfonate and 2,4,5-trichlorobenzene sodium sulfonate.
3. the super tough type polycarbonate material of halogen-free flameproof according to claim 1, is characterized in that: the silicon rubber that described siloxanes acrylic copolymer is a kind of nucleocapsid structure, its core is that siloxanes shell is acrylic copolymer.
4. the super tough type polycarbonate material of halogen-free flameproof according to claim 1, is characterized in that: described lubricant is fatty acid or metal soap or ester class or amides lubricant.
5. the super tough type polycarbonate material of halogen-free flameproof according to claim 1, is characterized in that: described tetrafluoroethylene class anti-dripping agent is polymer fluoro-resin, as tetrafluoroethylene class anti-dripping agent.
6. the super tough type polycarbonate material of halogen-free flameproof according to claim 1, is characterized in that: described oxidation inhibitor is elected one or more in antioxidant 1010, irgasfos 168, antioxidant 1076, oxidation inhibitor B215, antioxidant 2246 or antioxidant 264 as.
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| CN201410016958.XA CN103788614A (en) | 2014-01-14 | 2014-01-14 | Halogen-free flame retardant super-tough type polycarbonate material |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109575560A (en) * | 2018-11-30 | 2019-04-05 | 中广核俊尔新材料有限公司 | A kind of resistance to toluene, heat-resisting, fire retardation PC material and its preparation process |
| CN109666281A (en) * | 2018-12-28 | 2019-04-23 | 四川中物材料股份有限公司 | High transparency film halogen-free flameproof, which can scald, is moulded into type makrolon material and its preparation method |
| CN110835460A (en) * | 2018-08-17 | 2020-02-25 | 汉达精密电子(昆山)有限公司 | High-temperature-resistant halogen-free flame-retardant polycarbonate material and product thereof |
| JP2020139141A (en) * | 2019-12-04 | 2020-09-03 | 住化ポリカーボネート株式会社 | Aromatic polycarbonate resin composition and optic molding |
| CN113817307A (en) * | 2021-11-11 | 2021-12-21 | 上海品诚创奇新材料科技有限公司 | Low-temperature low-smoke halogen-free flame-retardant PC material composition and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110835460A (en) * | 2018-08-17 | 2020-02-25 | 汉达精密电子(昆山)有限公司 | High-temperature-resistant halogen-free flame-retardant polycarbonate material and product thereof |
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| CN113817307A (en) * | 2021-11-11 | 2021-12-21 | 上海品诚创奇新材料科技有限公司 | Low-temperature low-smoke halogen-free flame-retardant PC material composition and preparation method thereof |
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Application publication date: 20140514 |