CN103224690A - Low-smoke density plastic composition and its preparation method and use - Google Patents
Low-smoke density plastic composition and its preparation method and use Download PDFInfo
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- CN103224690A CN103224690A CN2012105924149A CN201210592414A CN103224690A CN 103224690 A CN103224690 A CN 103224690A CN 2012105924149 A CN2012105924149 A CN 2012105924149A CN 201210592414 A CN201210592414 A CN 201210592414A CN 103224690 A CN103224690 A CN 103224690A
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Abstract
The invention discloses a low-smoke density plastic composition and its preparation method and use. The low-smoke density plastic composition comprises a smoke-inhibition agent. The smoke-inhibition agent comprises at least one inorganic sulfur-containing compound containing sulfur atoms having positive four or more valences, and the at least one inorganic sulfur-containing compound is not a nonmetal sulfate or a nonmetal bisulfate. In combustion, the low-smoke density plastic composition has low smoke density and has a low carbon monoxide release ratio. The inorganic sulfur-containing compound as the smoke-inhibition agent is used for preparation of low-smoke density plastic. A lot of experiments prove that the at least one smoke-inhibition agent can produce obvious effects of inhibiting smoke and reducing a CO ratio, is not limited by a plastic system, can be used for different types of plastics, and has a wider use range than that of the existing smoke-inhibition agent.
Description
Technical field
The present invention relates to field of polymer technology, particularly plastics composite of a kind of low smoke density and its production and application.
Background technology
Harm during the plastics burning derives from the thermal radiation that flame brings on the one hand, and poisonous, the harmful product that generates when coming from burning on the other hand is especially because the condensed-nuclei aromatics class material that incomplete oxidation generated.At the latter, when burning to plastics, the researchist presses down that the research of cigarette low toxicity is existing extensively to be carried out.At dissimilar thermoplasticss, the cigarette low toxicity scheme that presses down of report mainly contains at present: 1. use the scheme of a large amount of oxyhydroxide fillings at polyolefine, its principle is to generate water after oxyhydroxide is heated, and has dilution, adsorption, thereby reduces smoke density; 2. at PVC and alloy thereof, use magnesium-yttrium-transition metal compound such as ammonium octamolybdate etc., its principle is the decomposition approach that changes alkene, reduces its annulation, reduces condensed-nuclei aromatics output; 3 at urethane employing melamine cyanurate, and the generation of promotes oxidn product carbonic acid gas reduces incomplete oxidation or the like.But the application system that presses down fumicants of prior art is limited, and can not play the effect that reduces smoke density and the generation of less toxic gas at the plastics of whole or most of type simultaneously.
Summary of the invention
Goal of the invention of the present invention is in order to overcome the deficiencies in the prior art, a kind of plastics composite of low smoke density to be provided, and the plastics composite of this low smoke density smoke density when burning is low, and the ratio of carbon monoxide is reduced in the gas that discharges of burning.
Another object of the present invention is to provide the preparation method of the plastics composite of described low smoke density.
Another object of the present invention is to provide sulfocompound as pressing down the application of fumicants in the low smoke density engineering plastics of preparation.
Above-mentioned purpose of the present invention is achieved by following technical solution:
A kind of plastics composite of low smoke density comprises in the described plastics composite and presses down fumicants, and the described fumicants that presses down comprises at least a inorganic sulfocompound that contains the above sulphur atom of positive tetravalence, and described but fumicants is not nonmetallic vitriol or hydrosulfate.
As mentioned above, prior art presses down fumicants by adding often in order to obtain the lower plastics composite of smoke density in plastic formula, and therefore the still existing fumicants that presses down often can only be used to exist and be limited to specific system generation effect.The contriver finds, when suitable sulfocompound is added into the plastics composite that obtains in the plastic formula, the smoke density that produces when burning significantly descends, simultaneously, the also decrease to some degree of content of content of harmful gas, particularly CO in the gas that burning discharges.Therefore plastic compound of the present invention is lower to HUMAN HEALTH degree of damage when burning, has increased user's safety.Among the present invention, described sulfocompound can be to use as pressing down fumicants separately, also can mix with other non-sulfocompounds as pressing down fumicants and use.
In the common inorganic sulfocompound that contains the above sulphur atom of positive tetravalence, the valency of sulphur atom generally shows as positive tetravalence or positive sexavalence; Wherein, described inorganic sulfocompound is metal sulfate, metal bisulfite salt, sulphite or hydrosulphite.
The contriver is through experiment discovery repeatedly, and the fumicants that presses down of the present invention can play oxygenizement in combustion processes, make combustion processes more abundant, can reduce the generation of this incomplete oxidation thing of condensed-nuclei aromatics and carbon monoxide.
Wherein, described inorganic sulfocompound is in nitrogen atmosphere, and under the condition of the heat-up rate of 20 ℃/min, the TGA1% decomposition temperature is greater than 235 ℃ inorganic sulfocompound.Inorganic sulfocompound in this scope also possesses good processing properties, in the preparation process of low smoke density plastics composite, phenomenons such as foaming or gas line can not occur, and it also has the effect of better reduction smoke density and CO content.
Wherein, the described fumicants that presses down is made up of separately inorganic sulfocompound, and described inorganic sulfocompound is sodium sulfate, vitriolate of tartar, Tai-Ace S 150, sal epsom, sodium pyrosulfate, sal enixum, S-WAT, potassium sulfite, aluminium sulfite, magnesium sulfite, sodium bisulfite or Potassium hydrogen sulfite.
Wherein, the plastics composite of described low smoke density, the consumption of described sulfocompound are to account for 1 ~ 50% of plastics composite gross weight.
Wherein, the plastics composite of described low smoke density, the consumption of described sulfocompound are to account for 5 ~ 35% of plastics composite gross weight.
Wherein, the plastics composite of described low smoke density, the plastics in the described plastics composite are thermosetting resin or thermoplastics.
Described thermosetting resin includes but not limited to Resins, epoxy, urethane, unsaturated polyester resin;
Described thermoplastics includes but not limited to polymeric amide, polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate or acrylonitrile-butadiene-styrene copolymer.
The preparation method of the plastics composite of described low smoke density when described plastics are thermoplastics, extruding blend stage adding inorganic sulfocompound, extrude and obtains plastics composite;
When described plastics are thermosetting resin, when plastics need be cured, add inorganic sulfocompound, and then be cured, obtain plastics composite.
Sulfocompound is as pressing down the application of fumicants in the low smoke density plastics of preparation.
The plastics composite of described low smoke density can be applied to the various occasions that the plastics composite flame retardant properties had high request.
Compared with prior art, the present invention has following beneficial effect:
The plastics composite of a kind of low smoke density of the present invention, the plastics composite of this low smoke density smoke density when burning is low, and the ratio of carbon monoxide is reduced in the gas of burning release.The invention provides sulfocompound as pressing down the application of fumicants in the low smoke density plastics of preparation, through experimental results demonstrate of contriver, the multiple fumicants that presses down provided by the invention all can produce the effect that significantly presses down cigarette and reduce the CO ratio, and be not subjected to the restriction of plastics system, can be applied in the plastics of number of different types, have wider range of application than the at present known fumicants that presses down.
Embodiment
Be described further below in conjunction with of plastics composite, preparation method and the application thereof of some embodiments the low smoke density of the present invention.Specific embodiment is for further describing the present invention, non-limiting protection scope of the present invention.
Embodiments of the invention adopt following raw material:
Used mineral sulfates, inorganic hydrosulfate, sulphite, hydrosulphite is the analytical pure product that Guangzhou Chemical Reagent Factory is produced among the embodiment.
Epoxy-resin systems: the quadrol that the bisphenol A type epoxy resin E-44 of Ba Ling petrochemical industry and BASF are produced;
Polyurethane system: the polymethylene multi-phenenyl isocyanate WANNATE PM-700 of the magnificent urethane in the Jiangsu Jia Feng chemistry PEG1000 of limited-liability company and Yantai ten thousand company limited production;
Polycarbonate: the PCTRIREX3030PJ of LG chemistry;
Polystyrene: the PH-888G of Qimei Industry Co., Ltd.;
Acrylonitrile-butadiene-styrene copolymer: the D-150 of the tall petro-chemical corporation of Taiwan state
PBT TH6100 Xinjiang Lanshan Tunhe Polyester Co., Ltd;
PET FC-01-68 Foshan FSPG Hi-Tech. Shares Co., Ltd.;
The refreshing horse nylon of polymeric amide: PA66EPR27 chemical industry company limited;
TDE, stibium trioxide, triphenylphosphate are commercially available product.
The composition properties testing method:
Sulfide in the thermoplastics adds when the twin screw blend is extruded, and the sulfide of thermosetting resin adds before curing.The experiment the smoke density of surveying according to the GB/T8627-2007 standard implementation, sample size is 25mm * 25mm * 6mm; The experiment the taper calorimeter of surveying according to the GB/T16172-2007 standard implementation, sample size is 100mm * 100mm * 3mm, irradiation energy is 50kw/m
2Carbon monoxide content, carbon dioxide content are measured by the taper calorimeter.
Below be illustrated in the mode of specific embodiment, described raw material is weight part.
The preparation of plastics composite is carried out as follows among the embodiment 1 ~ 7:
Described thermoset specimen preparation is in container to be added resin and solidifying agent, presses down fumicants, mixes through high-speed stirring, injects specific sheet metal die, and part kind sample is through the gained that is heating and curing.
The preparation of described thermoplastic sample be with resin with but fumicants mixes, through twin screw extruder extruding pelletization under this resin treatment temperature, be injection molded into the specified size print with injection moulding machine.
Embodiment 1 low smoke density Resins, epoxy
In the ratio in the table 1, preparation embodiment 1 described low smoke density Resins, epoxy.
Table 1
Embodiment 2 low smoke density urethane
In the ratio in the table 2, preparation embodiment 2 described low smoke density urethane.
Table 2
Embodiment 3 low smoke density polycarbonate
In the ratio in the table 3, preparation embodiment 3 described low smoke density polycarbonate.
Table 3
Embodiment 4 low smoke density polystyrene
In the ratio in the table 4, preparation embodiment 4 described low smoke density polystyrene.
Table 4
Embodiment 5 low smoke density ABS
In the ratio in the table 5, preparation embodiment 5 described low smoke density ABS.
Table 5
Embodiment 6 low smoke density PET
In the ratio in the table 6, preparation embodiment 6 described low smoke density PET.
Table 6
Embodiment 7 low smoke density PBT
In the ratio in the table 7, preparation embodiment 7 described low smoke density PBT.
Table 7
From embodiment 1 ~ 7 as can be seen, the multiple inorganic sulfocompound that the invention provides all can produce the effect that significantly presses down cigarette and reduce CO content in the combustion gases as pressing down fumicants, thereby reduce the toxicity of plastics composite in combustion processes, safer to the people, and be not subjected to the restriction of plastics system, can be applied in the plastics of number of different types, have wider range of application than the at present known fumicants that presses down.
The fumicants that presses down of the present invention can satisfy the needs that plastics composite prepares, and in preparation process, phenomenons such as foaming, gas line do not occur, and its effect that presses down cigarette and reduction obnoxious flavour content is remarkable.
Embodiment 8 low smoke density flame-retardant plastic compositions
With resin with press down fumicants, fire retardant mixes, and through twin screw extruder extruding pelletization under this resin treatment temperature, is injection molded into the specified size print with injection moulding machine.
The above only is embodiments of the invention; be not so limit claim of the present invention; every equivalent structure or equivalent flow process conversion that utilizes description of the present invention to do; or directly or indirectly be used in other relevant technical fields, all in like manner be included in the scope of patent protection of the present invention.
Claims (10)
1. the plastics composite of a low smoke density, it is characterized in that, comprise in the described plastics composite and press down fumicants, the described fumicants that presses down comprises at least a inorganic sulfocompound that contains the above sulphur atom of positive tetravalence, and described but fumicants is not nonmetallic vitriol or hydrosulfate.
2. hang down the plastics composite of smoke density according to claim 1, it is characterized in that described inorganic sulfocompound is metal sulfate, metal bisulfite salt, sulphite or hydrosulphite.
3. hang down the plastics composite of smoke density as claimed in claim 1 or 2, it is characterized in that in nitrogen atmosphere, under the condition of the heat-up rate of 20 ℃/min, the TGA1% decomposition temperature of described inorganic sulfocompound is greater than 235 ℃.
4. hang down the plastics composite of smoke density as claimed in claim 1 or 2, it is characterized in that described inorganic sulfocompound is sodium sulfate, vitriolate of tartar, Tai-Ace S 150, sal epsom, sodium pyrosulfate, sal enixum, S-WAT, potassium sulfite, aluminium sulfite, magnesium sulfite, sodium bisulfite or Potassium hydrogen sulfite.
5. the plastics composite of low smoke density as claimed in claim 1 or 2 is characterized in that, the consumption of described inorganic sulfocompound is to account for 1 ~ 50% of plastics composite gross weight.
6. the plastics composite of low smoke density as claimed in claim 1 or 2 is characterized in that, the consumption of described inorganic sulfocompound is to account for 5 ~ 35% of plastics composite gross weight.
7. hang down the plastics composite of smoke density as claimed in claim 1 or 2, it is characterized in that the plastics in the described plastics composite are thermosetting resin or thermoplastics.
8. as the plastics composite of low smoke density as described in the claim 7, it is characterized in that the plastics in the described plastics composite are Resins, epoxy, urethane, unsaturated polyester resin, polymeric amide, polystyrene, polycarbonate or polyethylene terephthalate, polybutylene terephthalate or acrylonitrile-butadiene-styrene copolymer.
9. the preparation method of the plastics composite of any described low smoke density of claim in the claim 1 ~ 8 is characterized in that, when described plastics are thermoplastics, extruding blend stage adding inorganic sulfocompound, extrude and obtains plastics composite;
When described plastics are thermosetting resin, before plastics need be cured, add inorganic sulfocompound, and then be cured, obtain plastics composite.
10. the described inorganic sulfocompound of any claim of claim 1 ~ 8 is as pressing down the application of fumicants in the low smoke density plastics of preparation.
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| US4371655A (en) * | 1981-12-30 | 1983-02-01 | The B. F. Goodrich Company | Polymer compositions containing sulfate glasses or glass-ceramics |
| NZ206811A (en) * | 1983-01-18 | 1987-03-31 | Ici Plc | Olefin polymer containing filler and processing aid |
| CN1307611A (en) * | 1998-06-26 | 2001-08-08 | 拜尔公司 | Flame resistant polycarbonate/ABS plastic molding materials |
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| CN101457010A (en) * | 2007-12-11 | 2009-06-17 | 天津德昊超微新材料有限公司 | Low smoke halogen-free flame retardant ABS resin |
| CN101875745A (en) * | 2010-03-30 | 2010-11-03 | 金发科技股份有限公司 | Flame-retardant styrene polymer compound containing smoke inhibitor and preparation method thereof |
| CN101885871A (en) * | 2010-07-21 | 2010-11-17 | 天津工业大学 | Fire-retardant cellulose reinforced plastic composite material and preparation method thereof |
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2012
- 2012-12-29 CN CN2012105924149A patent/CN103224690A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4371655A (en) * | 1981-12-30 | 1983-02-01 | The B. F. Goodrich Company | Polymer compositions containing sulfate glasses or glass-ceramics |
| NZ206811A (en) * | 1983-01-18 | 1987-03-31 | Ici Plc | Olefin polymer containing filler and processing aid |
| CN1307611A (en) * | 1998-06-26 | 2001-08-08 | 拜尔公司 | Flame resistant polycarbonate/ABS plastic molding materials |
| US20020013393A1 (en) * | 1999-08-03 | 2002-01-31 | Menachem Lewin | Flame retardation of polymeric compositions |
| CN101457010A (en) * | 2007-12-11 | 2009-06-17 | 天津德昊超微新材料有限公司 | Low smoke halogen-free flame retardant ABS resin |
| CN101875745A (en) * | 2010-03-30 | 2010-11-03 | 金发科技股份有限公司 | Flame-retardant styrene polymer compound containing smoke inhibitor and preparation method thereof |
| CN101885871A (en) * | 2010-07-21 | 2010-11-17 | 天津工业大学 | Fire-retardant cellulose reinforced plastic composite material and preparation method thereof |
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| 李斌: "《聚氯乙烯PVC的抑烟与阻燃》", 31 May 2000 * |
| 田春明等: "低熔点硫酸盐对软质PVC的阻燃与消烟性能研究", 《中国塑料》 * |
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