CN102942728A - Antistatic halogen-free fire retardation ultra-high molecule weight polyethylene material and preparation method thereof - Google Patents
Antistatic halogen-free fire retardation ultra-high molecule weight polyethylene material and preparation method thereof Download PDFInfo
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Abstract
The present invention discloses an antistatic halogen-free fire retardation ultra-high molecule weight polyethylene material, which comprises, by weight, 100 parts of ultra-high molecule weight polyethylene, 5-40 parts of expanded graphite, 5-20 parts of a synergistic fire retardation agent, 0.1-2 parts of a coupling agent, 0.1-10 parts of a flowing modifier, 0.1-1 part of a nucleating agent, 0.1-1 part of an antioxidant, and 0.1-5 parts of an antistatic agent. According to the present invention, the large particle size (general tens or even hundreds of mum) expanded graphite is added to the ultra-high molecule weight polyethylene material, such that the disadvantage of fire retardation effect reduction due to non-uniform dispersion of the halogen fire retardation agent and the traditional halogen-free fire retardation agent in the ultra-high molecule weight polyethylene substrate is solved; and the graphite itself is a good electric conduction material, such that surface electric resistance and volume electric resistance of the material can be significantly reduced so as to solve disadvantages of the halogen fire retardation agent and the traditional halogen-free fire retardation agent in the ultra-high molecule weight polyethylene, wherein the disadvantages comprise that the halogen fire retardation agent and the traditional halogen-free fire retardation agent can not concurrently have an antistatic performance and a fire retardation performance.
Description
Technical field
The present invention relates to a kind of superhigh molecular weight polyethylene material, or rather, is a kind of antistatic halogen-free flame-retardant ultra-high molecular weight polyvinyl material and preparation method.
Background technology
Superhigh molecular weight polyethylene material is because it has good performance, such as its good abrasion resistance, resistance to chemical corrosion, low-friction coefficient, low temperature impact strength is high, can reach 50 years work-ing life etc.In recent years, be widely used in mine, power plant, oil, chemical industry, machinery, shipbuilding, instrument, train EMUs etc. to high-impact, high abrasion, the field that particular requirement is arranged such as anticorrosive.But since its flame retardant properties is poor, resistivity is high etc. drawbacks limit ultrahigh molecular weight polyethylene(UHMWPE) in requirements at the higher level, more specifically occasion (such as the heavy duty service in colliery, oil transportation etc.) is used.
Expansible black lead (Expandable Graphite is abbreviated as EG) is a kind of physical expansion type halogen-free flame retardants, it be by natural graphite through the oxidation of molecule edge, intercalation processing, then wash, filter, make after the drying.When EG is heated to high temperature rapidly, can expand hundreds of times along the carbon direction of principal axis of crystalline texture.Graphite after the expansion becomes very low " worm " shape of density by original flakey, has formed a thermal insulation, oxygen barrier layer.EG plays following effect in fire-retardant process: form tough and tensile charcoal layer in Polymer Surface, combustiblematerials and thermal source are separated; In the expansion process, a large amount of heat absorption reduced the temperature of system; In the expansion process, the acid ion in the release jacket coating promotes the dehydration carbonization, thereby and can be in conjunction with the middle chain-breaking reaction of free radical of burning generation.The fire retardant compound uses such as EG and phosphorus-nitrogen compound, metal oxide can produce synergy, add just can reach fire-retardant purpose on a small quantity.
The expansible black lead that adds in the antistatic halogen-free flame-retardant ultra-high molecular weight polyvinyl material is not only a kind of efficient halogen-free flame retardants, and because expansible black lead itself is a kind of good electro-conductive material, be aided with surface resistivity and volume resistance that graphitized carbon black can significantly reduce material, make material have concurrently antistatic and the halogen-free flameproof performance.Expansible black lead is because its special synusia structure and the characteristics of high abrasion, when being added in of expansible black lead improved antistatic, the flame retardant properties of material, not only can not destroy intensity and the wear resistance of material, and the over-all properties of material is improved.Anti-static halogen-free flame-retardant type superhigh molecular weight polyethylene material can be widely used in the fields such as mine, oil, chemical industry, electronics, shipbuilding, track traffic.
Summary of the invention
The present invention solves the existing technical problem of prior art, thereby a kind of antistatic halogen-free flame-retardant ultra-high molecular weight polyvinyl material and preparation method are provided.
Above-mentioned technical problem of the present invention is mainly solved by following technical proposals:
A kind of antistatic halogen-free flame-retardant ultra-high molecular weight polyvinyl material, according to parts by weight, comprise: 100 parts of ultrahigh molecular weight polyethylene(UHMWPE)s, 5～40 parts of expansible black leads, 5～20 parts of synergistic flame retardants, 0.1～2 part of coupling agent, 0.1～10 part of flow ability modifying agent, 0.1～1 part of nucleator, 0.1～1 part in oxidation inhibitor, 0.1～5 part in static inhibitor, wherein, described ultrahigh molecular weight polyethylene(UHMWPE) is that viscosity-average molecular weight is 1,000,000～8,000,000 ultrahigh molecular weight polyethylene(UHMWPE), the granularity of described expansible black lead is 20～300 orders, described synergistic flame retardant is that phosphorus nitrogen is at least a in expansibility flame-proof agent or the inorganic combustion inhibitor, described coupling agent is silane coupling agent, titanate coupling agent, at least a in the aluminate coupling agent, described flow ability modifying agent is fluoropolymer additive (such as the PPA of Minnesota Mining and Manufacturing Company), at least a in the silicone-based lubricant (such as the MB50 of Dow corning company), described nucleator is fumed silica, silicon-dioxide, at least a in the stearate, described oxidation inhibitor is Hinered phenols antioxidant (such as antioxidant 1010), sulfur-bearing oxidation inhibitor (such as oxidation inhibitor DSTP), at least a in the phosphite ester kind antioxidant (such as irgasfos 168), described static inhibitor is graphitized carbon black.
As preferred embodiment of the present invention, described phosphorus nitrogen is that the expansibility flame-proof agent comprises ammonium polyphosphate, trimeric cyanamide and tetramethylolmethane, according to parts by weight, the ratio of ammonium polyphosphate, trimeric cyanamide and tetramethylolmethane is 8 ︰, 3 ︰ 5, and described inorganic combustion inhibitor is at least a in aluminium hydroxide, magnesium hydroxide and the antimonous oxide.
The invention also discloses a kind of antistatic halogen-free flame-retardant ultra-high molecular weight polyvinyl material preparation method, comprise following steps:
1) described flow ability modifying agent, nucleator, oxidation inhibitor and static inhibitor and described ultrahigh molecular weight polyethylene(UHMWPE) are mixed;
2) described expansible black lead, synergistic flame retardant is for subsequent use after with described coupling agent treatment;
3) with step 2) in the fire retardant crossed through coupling agent treatment mix with the material that step 1) makes;
4) the raw material of step 3) gained by extruding or the method for compression moulding makes the antistatic halogen-free flame-retardant ultra-high molecular weight polyvinyl material.
Compared with prior art, the inventive method has the following advantages:
1, the present invention is different from halogen fire retardant and traditional halogen-free flame retardants, for the ultrahigh molecular weight polyethylene(UHMWPE) melt without flowability, traditional powdery flame retardent can't homodisperse characteristics, add the expansible black lead of granularity large (being generally dozens or even hundreds of micron) in matrix material.Solved that to have halogen fire retardant and traditional halogen-free flame retardants to disperse inhomogeneous in the ultrahigh molecular weight polyethylene(UHMWPE) matrix, reduced the shortcoming of the flame retardant effect of fire retardant.
2, the expansible black lead that adds of the present invention is to be made by the crystalline flake graphite intercalation processing, the macromole coating that intercalation is formed by the C-C key of horizontal direction.Expansible black lead itself is a kind of good electro-conductive material, is aided with surface resistivity and volume resistance that graphitized carbon black can significantly reduce material, makes material have concurrently antistatic and the halogen-free flameproof performance.
3, the antistatic halogen-free flame-retardant ultra-high molecular weight polyvinyl material of the present invention's preparation, when improving static resistance and flame retardant properties, because its special synusia structure and high abrasion of expansible black lead makes material can also keep the mechanical property of material excellence in the good wear resistance of maintenance.
Embodiment
The below is described in detail the preferred embodiments of the present invention, thereby so that advantages and features of the invention can be easier to be it will be appreciated by those skilled in the art that protection scope of the present invention is made more explicit defining.
Embodiment 1
By weight, with the ultrahigh molecular weight polyethylene(UHMWPE) of 100 parts of viscosity-average molecular weights 8,000,000, the granularity that 5 parts of titanate coupling agents were processed is 80 purpose expansible black leads, 0.3 a part antioxidant 1010 mixes, 1 part of nucleator Zinic stearas, 0.5 part of flow ability modifying agent PPA, 1 part of graphitized carbon black.Then with mixture with compression molding method at 220 ℃, 20MPa(MPa: melting compacting under condition MPa).The material properties of preparation sees Table 1.
Embodiment 2
By weight, with the ultrahigh molecular weight polyethylene(UHMWPE) of 100 parts of viscosity-average molecular weights 8,000,000, the granularity that 10 parts of titanate coupling agents were processed is 80 purpose expansible black leads, 0.3 a part antioxidant 1010 mixes, 1 part of nucleator Zinic stearas, 0.5 part of flow ability modifying agent PPA, 1 part of graphitized carbon black.Then with mixture with compression molding method melting compacting under 220 ℃, the condition of 20MPa.The material properties of preparation sees Table 1.
Embodiment 3
By weight, with the ultrahigh molecular weight polyethylene(UHMWPE) of 100 parts of viscosity-average molecular weights 8,000,000, the granularity that 20 parts of titanate coupling agents were processed is 80 purpose expansible black leads, 0.3 a part antioxidant 1010 mixes, 1 part of nucleator Zinic stearas, 0.5 part of flow ability modifying agent PPA, 1 part of graphitized carbon black.Then with mixture with compression molding method melting compacting under 220 ℃, the condition of 20MPa.The material properties of preparation sees Table 1.
Embodiment 4
By weight, ultrahigh molecular weight polyethylene(UHMWPE) with 100 parts of viscosity-average molecular weights 8,000,000, the granularity that 40 parts of titanate coupling agents were processed is 80 purpose expansible black leads, 0.3 a part antioxidant 1010 mixes, 1 part of nucleator Zinic stearas, 0.5 part flow ability modifying agent PPA, 1 part of graphitized carbon black then with mixture with compression molding method melting compacting under 220 ℃, the condition of 20MPa.The material properties of preparation sees Table 1.
Embodiment 5
By weight, ultrahigh molecular weight polyethylene(UHMWPE) with 100 parts of viscosity-average molecular weights 8,000,000, the granularity that 10 parts of titanate coupling agents were processed is 80 purpose expansible black leads, 5 parts of phosphorus nitrogen are the expansibility flame-proof agent, 0.3 a part antioxidant 1010 mixes, 1 part of nucleator Zinic stearas, 0.5 part of flow ability modifying agent PPA, 1 part of graphitized carbon black then with mixture with compression molding method melting compacting under 220 ℃, the condition of 20MPa.The material properties of preparation sees Table 1.
Embodiment 6
By weight, ultrahigh molecular weight polyethylene(UHMWPE) with 100 parts of viscosity-average molecular weights 8,000,000, the granularity that 10 parts of titanate coupling agents were processed is 80 purpose expansible black leads, 10 parts of phosphorus nitrogen are the expansibility flame-proof agent, 0.3 a part antioxidant 1010 mixes, 1 part of nucleator Zinic stearas, 0.5 part of flow ability modifying agent PPA, 1 part of graphitized carbon black then with mixture with compression molding method melting compacting under 220 ℃, the condition of 20MPa.The material properties of preparation sees Table 1.
Embodiment 7
By weight, ultrahigh molecular weight polyethylene(UHMWPE) with 100 parts of viscosity-average molecular weights 8,000,000, the granularity that 10 parts of titanate coupling agents were processed is 80 purpose expansible black leads, 20 parts of phosphorus nitrogen are the expansibility flame-proof agent, 0.3 a part antioxidant 1010 mixes, 1 part of nucleator Zinic stearas, 0.5 part of flow ability modifying agent PPA, 1 part of graphitized carbon black then with mixture with compression molding method melting compacting under 220 ℃, the condition of 20MPa.The material properties of preparation sees Table 1.
Embodiment 8
By weight, ultrahigh molecular weight polyethylene(UHMWPE) with 100 parts of viscosity-average molecular weights 8,000,000, the granularity that 10 parts of titanate coupling agents were processed is 80 purpose expansible black leads, 5 parts of inorganic combustion inhibitor aluminium hydroxides, 0.3 a part antioxidant 1010 mixes, 1 part of nucleator Zinic stearas, 0.5 part of flow ability modifying agent PPA, 1 part of graphitized carbon black then with mixture with compression molding method melting compacting under 220 ℃, the condition of 20MPa.The material properties of preparation sees Table 1.
Embodiment 9
By weight, ultrahigh molecular weight polyethylene(UHMWPE) with 100 parts of viscosity-average molecular weights 8,000,000, the granularity that 10 parts of titanate coupling agents were processed is 80 purpose expansible black leads, 5 parts of inorganic combustion inhibitor aluminium hydroxides, 5 parts of phosphorus nitrogen are the expansibility flame-proof agent, and 0.3 part of antioxidant 1010 mixes, 1 part of nucleator Zinic stearas, 0.5 part flow ability modifying agent PPA, 1 part of graphitized carbon black then with mixture with compression molding method melting compacting under 220 ℃, the condition of 20MPa.The material properties of preparation sees Table 1.
Table 1
As can be seen from Table 1, adopted the index parameter of the independent flame-retardant ultra-high molecular weight polyvinyl of expansible black lead very excellent.
The present invention is different from traditional halogen-free flame retardants, adopts the independent flame-retardant ultra-high molecular weight polyvinyl of expansible black lead and add respectively the inorganic combustion inhibitor cooperative flame retardants such as metal hydroxides such as phosphorus-nitrogen expanding fire retardant and aluminium hydroxide to reach different effects.When phosphorus-nitrogen expanding fire retardant and expansible black lead acting in conjunction, phosphorus nitrogen is that the expansibility flame-proof agent can further promote into charcoal enhancing flame retardant effect.When the inorganic combustion inhibitors such as aluminium hydroxide and expansible black lead acting in conjunction, can absorb a large amount of heat during the metal hydroxides decomposes, and it is dispersed in and plays a part charcoal layer that skeleton makes generation in the carburization zone and have intensity preferably to play the effect of cooperative flame retardant.
The granularity of expansible black lead is larger, is added in the material matrix still that the form with itself exists, and has remedied the ultrahigh molecular weight polyethylene(UHMWPE) melt without flowability, and additive is difficult to finely dispersed shortcoming in material matrix.The fire retardant mechanism of expansible black lead be the intercalator that coats between the graphite molecular layer of plane after being heated with graphite carbon atom generation redox reaction, emit a large amount of gases and it expanded rapidly form foamed char stable, heat insulation oxygen barrier.Granularity just because of expansible black lead is large, so more the stable flame-retardant effect is better for its charcoal layer that forms behind expanded by heating.
It is limited that common static inhibitor descends the surface resistivity of ultrahigh molecular weight polyethylene(UHMWPE), and add a large amount of inorganic conductive materials the surface resistivity of ultrahigh molecular weight polyethylene(UHMWPE) descended obviously, but cause simultaneously the workability of material and mechanical property sharply to worsen.The fire retardant expansible black lead that adds among the present invention itself is a kind of good electro-conductive material, in the situation that be aided with a small amount of graphitized carbon black, just can form conductive network in the ultrahigh molecular weight polyethylene(UHMWPE) system, significantly reduces surface resistivity and the volume resistance of material.
Below only with an embodiment mentality of designing of the present invention is described, in the situation that system allows, the present invention can expand to simultaneously external more functional module, thereby expands to greatest extent its function.
The above be the specific embodiment of the present invention only, but protection scope of the present invention is not limited to this, and any variation or replacement of expecting without creative work all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain that claims were limited.
Claims (4)
1. antistatic halogen-free flame-retardant ultra-high molecular weight polyvinyl material, according to parts by weight, by 100 parts of ultrahigh molecular weight polyethylene(UHMWPE)s, 5～40 parts of expansible black leads, 5～20 parts of synergistic flame retardants, 0.1～2 part of coupling agent, 0.1～10 part of flow ability modifying agent, 0.1～1 part of nucleator, 0.1～1 part in oxidation inhibitor, 0.1～5 part of composition of static inhibitor, wherein, described ultrahigh molecular weight polyethylene(UHMWPE) is that viscosity-average molecular weight is 1,000,000～8,000,000 ultrahigh molecular weight polyethylene(UHMWPE), the granularity of described expansible black lead is 20～300 orders, described synergistic flame retardant is that phosphorus nitrogen is at least a in expansibility flame-proof agent or the inorganic combustion inhibitor, described coupling agent is silane coupling agent, titanate coupling agent, at least a in the aluminate coupling agent, described flow ability modifying agent is fluoropolymer additive, at least a in the silicone-based lubricant, described nucleator is fumed silica, silicon-dioxide, at least a in the stearate, described oxidation inhibitor is Hinered phenols antioxidant, sulfur-bearing oxidation inhibitor, at least a in the phosphite ester kind antioxidant, described static inhibitor is graphitized carbon black.
2. antistatic halogen-free flame-retardant ultra-high molecular weight polyvinyl material according to claim 1, it is characterized in that, described phosphorus nitrogen is that the expansibility flame-proof agent comprises ammonium polyphosphate, trimeric cyanamide and tetramethylolmethane, according to parts by weight, the ratio of ammonium polyphosphate, trimeric cyanamide and tetramethylolmethane is 8:3:5, and described inorganic combustion inhibitor is at least a in aluminium hydroxide, magnesium hydroxide and the antimonous oxide.
3. an antistatic halogen-free flame-retardant ultra-high molecular weight polyvinyl material preparation method as described in claim 1 comprises following steps: 1) described flow ability modifying agent, nucleator, oxidation inhibitor and static inhibitor and described ultrahigh molecular weight polyethylene(UHMWPE) are mixed; 2) described expansible black lead, synergistic flame retardant is for subsequent use after with described coupling agent treatment; 3) with step 2) in the fire retardant crossed through coupling agent treatment mix with the material that step 1) makes; 4) the raw material of step 3) gained by extruding or the method for compression moulding makes the antistatic halogen-free flame-retardant ultra-high molecular weight polyvinyl material.
4. antistatic halogen-free flame-retardant ultra-high molecular weight polyvinyl material preparation method according to claim 3, it is characterized in that, described phosphorus nitrogen is that the expansibility flame-proof agent comprises trimeric cyanamide, ammonium polyphosphate and tetramethylolmethane, according to parts by weight, the ratio of ammonium polyphosphate, trimeric cyanamide and tetramethylolmethane is 8:3:5, and described inorganic combustion inhibitor is at least a in aluminium hydroxide, magnesium hydroxide and the antimonous oxide.
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| CN103756089A (en) * | 2013-12-27 | 2014-04-30 | 上海至正道化高分子材料有限公司 | Halogen-free flame retardant insulating material for photovoltaic cables |
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| CN116041823A (en) * | 2022-12-29 | 2023-05-02 | 金旸（厦门）新材料科技有限公司 | Halogen-free intumescent flame-retardant antistatic thermoplastic elastomer composite foaming material and preparation method thereof |
| CN116041823B (en) * | 2022-12-29 | 2023-11-03 | 金旸（厦门）新材料科技有限公司 | Halogen-free intumescent flame-retardant antistatic thermoplastic elastomer composite foaming material and preparation method thereof |
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