CN101775170A - Method for preparing material special for anti-static halogen-free flame-retardant ultra-high molecular weight polyethylene pipe - Google Patents
Method for preparing material special for anti-static halogen-free flame-retardant ultra-high molecular weight polyethylene pipe Download PDFInfo
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Abstract
The invention discloses a method for preparing a material special for an anti-static halogen-free flame-retardant ultra-high molecular weight polyethylene pipe. The method comprises the following steps: uniformly mixing 100 weight parts of ultra-high molecular weight polyethylene, 5 to 15 weight parts of conductive material, 1 to 15 weight parts of ammonium polyphosphate, 0.1 to 10 parts of polyorganosiloxane, 1 to 10 weight parts of nanometer flame retardant, 1 to 10 weight parts of polymer interface adhesive, 1 to 10 weight parts of dispersant and 0.5 to 4 weight parts of antioxidant; and extruding the mixture with a single screw extruder to mold the pipe, wherein the extrusion-melt temperature is controlled to between 180 and 250 DEG C. The method enhances antistatic behavior and fire resistance and keeps peculiar excellent mechanical property of the ultra-high molecular weight polyethylene. The pipe has tensile strength more than 25MPa, elongation at break more than 400 percent; and when impacted, a cantilever beam cannot be broken.
Description
Technical field:
The invention belongs to technical field of polymer, relate to a kind of preparation method of anti-static halogen-free flame-retardant ultra-high molecular weight polyethylene pipe PP Pipe Compound.
Background technology:
The colliery presses for the high-performance type material of halogen-free flame-proof antistatic.For many years, accident such as great gas explosion perplexs the coal in China industry for a long time under the coal mine, mainly be because coal mine gas pipe etc. adopts steel pipe or cast iron pipe always, exists deadly defects such as heavy, perishable, the easy fouling of quality, maintenance expense height, carrying and installation difficulty.Adopted Glass Steel Tube and polyvinyl chloride (PVC) pipe although develop into the part mine afterwards, these two kinds of materials still exist many shortcomings.For example the Glass Steel Tube quality is heavy, easily aging, uses maintenance inconvenient; Pvc pipe is subjected to the easily aging embrittlement of pressure-bearing, poor toughness, causes the generation of down-hole accident easily.And the antistatic halogen-free flame-retardant ultra-high molecular weight polyvinyl of mechanical property excellence (UHMWPE) tubing can remedy these shortcoming deficiencies, and it also has the advantage that density is light, cost is low simultaneously, is that ideal improves equivalent material.
Ultrahigh molecular weight polyethylene(UHMWPE) is a viscosity-average molecular weight greater than 1,500,000 polyethylene (PE), is a kind of novel thermoplastic engineering plastics, and its high molecular weight, the segmented structure of highly twining are given its excellent mechanical property.The shock resistance of ultrahigh molecular weight polyethylene(UHMWPE) occupies first of the plastics, and is low temperature resistant, still can keep toughness at-80 ℃, corrosion-resistant, wear-resistant and self-lubricating property is excellent.This material obtains research and application at high-technology fields such as petrochemical complex, technics of metallurgy mineral dressing, biomedicine, microelectron-mechanical, oceanographic engineerings.The mine is the industry of ultrahigh molecular weight polyethylene(UHMWPE) alkene raw material consumption maximum.
At the flame-retardant modified of ultrahigh molecular weight polyethylene(UHMWPE) mainly is that the fire-retardant and halogen-free flameproof two big classes of halogen are arranged.Though there is halogen fire retardant can effectively improve the flame retardant resistance of ultrahigh molecular weight polyethylene(UHMWPE), but it is incompatible with the ultrahigh molecular weight polyethylene(UHMWPE) matrix of high melt viscosity, in the extrusion moulding process, separate out easily and accumulate in tube surfaces and stop up extrusion neck ring mold, also can produce toxic gas during burning.Tradition is not obvious to the flame retardant effect of ultrahigh molecular weight polyethylene(UHMWPE), can't cooperate ultrahigh molecular weight polyethylene(UHMWPE) to form one deck under the situation of being heated and can completely cut off the bulk porous charcoal layer barrier that heat transmits effectively.While is bad with the consistency of ultrahigh molecular weight polyethylene(UHMWPE), also phase-splitting is separated out in material surface easily.
In addition, the flame-retardant modified and applied research of ultrahigh molecular weight polyethylene(UHMWPE) not only will be considered fire-retardant problem, and must will take into account big addition fire retardant to flowability, the mechanical property that has been difficult to the ultrahigh molecular weight polyethylene(UHMWPE) of the processing problem that descends significantly itself.
Summary of the invention:
The preparation method who the purpose of this invention is to provide a kind of anti-static halogen-free flame-retardant ultra-high molecular weight polyethylene pipe PP Pipe Compound, the ultrahigh molecular weight polyethylene tubing of this method preparation, when improving static resistance and flame retardant resistance, also keep the distinctive excellent mechanical property of ultrahigh molecular weight polyethylene(UHMWPE), the tensile strength that is tubing is greater than 25MPa, elongation at break is greater than 400%, and cantilever beam impact strength is continuous.
The inventive method is achieved through the following technical solutions.The preparation method of a kind of anti-static halogen-free flame-retardant ultra-high molecular weight polyethylene pipe PP Pipe Compound of the present invention, be by weight, 100 portions of ultrahigh molecular weight polyethylene(UHMWPE)s, 5～15 parts of electro-conductive materials, 1～15 part of ammonium polyphosphate, 0.1～10 part of polysiloxane, 1～10 part of nano-meter flame retardants, 1～10 portion of polymer interface bridge stick, 1～8 part of dispersion agent and 0.5～4 part of oxidation inhibitor high-speed mixing is even, then mixture is used single screw extrusion machine extrusion moulding tubing, the temperature of mixture melt is controlled at 180 ℃～250 ℃ when extruding.
Described ultrahigh molecular weight polyethylene(UHMWPE) is that viscosity-average molecular weight is 1,500,000～6,000,000 ultrahigh molecular weight polyethylene(UHMWPE).
Described electro-conductive material is selected from one or more the mixture in carbon black, graphite and the copper powder.
Described ammonium polyphosphate is that crystalline structure is the ammonium polyphosphate of II type.
Described polysiloxane is selected from one or more the mixture in polydimethylsiloxane, PSI and linear siloxane-acetylene multipolymer.
Described nano-meter flame retardants is selected from one or more the mixture in silicon-dioxide, talcum powder and the magnesium hydroxide, and the particle diameter of described nano-meter flame retardants is 10～100 nanometers.
Described polymer interface bridge stick is selected from one or more the mixture in polyethylene and maleic anhydride graft copolymer, polyethylene and acrylic acid graft copolymer and polyethylene and the acrylamide grafted copolymer.
Described dispersion agent be selected from polyethylene wax, paraffin, silicone oil or and white oil in one or more mixture.
Described oxidation inhibitor is antioxidant 2246 or antioxidant 1010.
The present invention is different from traditional halogen-free expanded flame-retardant agent, adopt nano-meter flame retardants to assist phosphorus system and siloxane-based fire retardant ultrahigh molecular weight polyethylene(UHMWPE), nanoparticle is well dispersed in and plays a part skeleton in the charring layer, make the charring layer of generation have rigidity and intensity preferably, sealing process is played in hole and crack in the newborn charcoal, reduce charcoal slabbing line and groove, improve the quality of charcoal layer.
Nano-meter flame retardants has the special flame retardant properties that is different from common fire retardant aspect following three.The one, heterogeneous restraining effect, along with reducing of particle diameter, the increase of specific surface area, fire-retardant particle increases with the extraneous area that contacts, the free radical that produces for reaction zone provides the compound " place " that carry out more, has reduced free radical effectively, has reached the purpose that suppresses chain reaction.The 2nd, the homogeneous phase restraining effect is meant that abundant dispersive nano-meter flame retardants evenly decomposes, gasifies, produces radical in flame, enters gas phase, and the radical with the combustionmaterial generation fully acts on and the termination reaction chain at short notice.The 3rd, the heat absorption extinguishing mechanism because the more common sized particles of nano particle is low, can absorbs a large amount of heat energy at the fire initial stage and the combustion reactions chain can not be continued and put out a fire.
Static inhibitor can only make the surface resistivity of ultrahigh molecular weight polyethylene(UHMWPE) slightly descend, and adds a large amount of inorganic conductive materials the surface resistivity of ultrahigh molecular weight polyethylene(UHMWPE) is descended obviously, but cause the workability and the mechanical property rapid deterioration of material simultaneously.The present invention adopts polymkeric substance bridge stick increase-volume ultrahigh molecular weight polyethylene(UHMWPE) electro-conductive material system, the ultrahigh molecular weight polyethylene(UHMWPE) matrix is combined firmly with the electro-conductive material interface, under the situation of only adding a small amount of electro-conductive material, just can in the ultrahigh molecular weight polyethylene(UHMWPE) matrix, form two conductive networks.
Compared with prior art, the inventive method has the following advantages:
1, the present invention is different from halogen fire retardant, traditional halogen-free expanded flame-retardant agent, adopt nano-meter flame retardants to assist phosphorus system and siloxane-based fire retardant ultrahigh molecular weight polyethylene(UHMWPE), nanoparticle is well dispersed in and plays a part skeleton in the charring layer, make the charring layer of generation have rigidity and intensity preferably, sealing process is played in hole and crack in the newborn charcoal.Solved halogen fire retardant is arranged, the ultrahigh molecular weight polyethylene(UHMWPE) matrix of traditional halogen-free expanded flame-retardant agent and high melt viscosity is incompatible, in the extrusion moulding process, separate out easily to accumulate in tube surfaces and stop up problems such as extrusion neck ring mold.
2, the present invention adopts polymkeric substance bridge stick increase-volume ultrahigh molecular weight polyethylene(UHMWPE)/electro-conductive material system, the ultrahigh molecular weight polyethylene(UHMWPE) matrix is combined firmly with the electro-conductive material interface, under the situation of only adding a small amount of electro-conductive material, just can in the ultrahigh molecular weight polyethylene(UHMWPE) matrix, form two conductive networks.
3, the ultrahigh molecular weight polyethylene tubing of the present invention's preparation, when improving static resistance and flame retardant resistance, also keep the distinctive excellent mechanical property of ultrahigh molecular weight polyethylene(UHMWPE), promptly the tensile strength of tubing is greater than 25MPa, elongation at break is greater than 400%, and cantilever beam impact strength is continuous.
Embodiment:
Below in conjunction with specific embodiment the present invention is illustrated, but embodiment is not a limitation of the present invention.
Embodiment 1
By weight, 100 portions of viscosity-average molecular weight 1,500,000 ultrahigh molecular weight polyethylene(UHMWPE)s, 5 parts of carbon blacks, 10 parts of ammonium polyphosphates, 5 parts of polydimethyl phenyl siloxanes, 6 parts of nano-sized magnesium hydroxides, 2 parts of polyethylene and acrylic acid graft copolymer, 1 part of silicone oil and 0.5 part of antioxidant 2246 high-speed mixing is even, then mixture is used single screw extrusion machine extrusion moulding tubing, the melt extrusion temperature is controlled at 180 ℃.Every performance index of tubing see Table 1.
Embodiment 2
By weight, 100 portions of viscosity-average molecular weight 1,500,000 ultrahigh molecular weight polyethylene(UHMWPE)s, 2 parts of carbon blacks, 9 parts of graphite, 8 parts of ammonium polyphosphates, 2 parts of linear siloxane-acetylene multipolymers, 4 parts of nano-sized magnesium hydroxides, 8 parts of polyethylene and acrylic acid graft copolymer, 1 part of silicone oil, 5 parts of polyethylene waxs and 1.5 parts of antioxidant 2246 high-speed mixing are even, then mixture is used single screw extrusion machine extrusion moulding tubing, the melt extrusion temperature is controlled at 190 ℃.Every performance index of tubing see Table 1.
Embodiment 3
By weight, 100 portions of viscosity-average molecular weight 1,500,000 ultrahigh molecular weight polyethylene(UHMWPE)s, 1 part of carbon black, 5 parts of copper powders, 15 parts of ammonium polyphosphates, 0.1 part of linear siloxane-acetylene multipolymer, 1 part of nano silicon, 1 part of polyethylene and acrylic acid graft copolymer, 1 part of silicone oil and 1.5 parts of antioxidant 2246 high-speed mixing are even, then mixture is used single screw extrusion machine extrusion moulding tubing, the melt extrusion temperature is controlled at 190 ℃.Every performance index of tubing see Table 1.
Embodiment 4
By weight, 100 portions of viscosity-average molecular weight 2,500,000 ultrahigh molecular weight polyethylene(UHMWPE)s, 6 parts of carbon blacks, 5 parts of ammonium polyphosphates, 8 parts of polydimethylsiloxanes, 10 parts of nanomete talc powders, 5 parts of polyethylene and maleic anhydride graft copolymer, 1 part of white oil, 4 parts of paraffin and 1.5 parts of antioxidant 1010 high-speed mixing are even, then mixture is used single screw extrusion machine extrusion moulding tubing, the melt extrusion temperature is controlled at 200 ℃.Every performance index of tubing see Table 1.
Embodiment 5
By weight, 100 portions of viscosity-average molecular weight 2,500,000 ultrahigh molecular weight polyethylene(UHMWPE)s, 15 parts of graphite, 1 part of ammonium polyphosphate, 10 parts of PSIs, 2 parts of nano silicons, 10 parts of polyethylene and maleic anhydride graft copolymer, 8 parts of polyethylene waxs and 2.5 parts of antioxidant 1010 high-speed mixing are even, then mixture is used single screw extrusion machine extrusion moulding tubing, the melt extrusion temperature is controlled at 220 ℃.Every performance index of tubing see Table 1.
Embodiment 6
By weight, 100 portions of viscosity-average molecular weight 3,500,000 ultrahigh molecular weight polyethylene(UHMWPE)s, 4 parts of carbon blacks, 7 parts of graphite, 6 parts of ammonium polyphosphates, 3 parts of PSIs, 1 part of nano silicon, 5 parts of polyethylene and acrylamide grafted copolymer, 5 parts of paraffin and 3.5 parts of antioxidant 2246 high-speed mixing are even, then mixture is used single screw extrusion machine extrusion moulding tubing, the melt extrusion temperature is controlled at 230 ℃.Every performance index of tubing see Table 1.
Embodiment 7
By weight, 100 portions of viscosity-average molecular weight 3,500,000 ultrahigh molecular weight polyethylene(UHMWPE)s, 7 parts of carbon blacks, 3 parts of ammonium polyphosphates, 5 parts of polydimethyl phenyl siloxanes, 6 parts of nano-sized magnesium hydroxides, 8 parts of polyethylene and acrylic acid graft copolymer, 5 parts of polyethylene waxs and 3.5 parts of antioxidant 1010 high-speed mixing are even, then mixture is used single screw extrusion machine extrusion moulding tubing, the melt extrusion temperature is controlled at 230 ℃.Every performance index of tubing see Table 1.
Embodiment 8
By weight, 100 portions of viscosity-average molecular weight 4,000,000 ultrahigh molecular weight polyethylene(UHMWPE)s, 4 parts of carbon blacks, 3 parts of graphite, 5 parts of ammonium polyphosphates, 3 parts of polydimethyl phenyl siloxanes, 1 part of nano silicon, 5 parts of nano talcum powder, 5 parts of polyethylene and acrylic acid graft copolymer, 7 parts of polyethylene waxs and 4 parts of antioxidant 1010 high-speed mixing are even, then mixture is used single screw extrusion machine extrusion moulding tubing, the melt extrusion temperature is controlled at 240 ℃.Every performance index of tubing see Table 1.
Embodiment 9
By weight, 100 portions of viscosity-average molecular weight 5,000,000 ultrahigh molecular weight polyethylene(UHMWPE)s, 5 parts of carbon blacks, 1 part of copper powder, 6 parts of ammonium polyphosphates, 5 parts of polydimethyl phenyl siloxanes, 5 parts of nano talcum powder, 8 parts of polyethylene and acrylic acid graft copolymer, 8 parts of polyethylene waxs and 4 parts of antioxidant 1010 high-speed mixing are even, then mixture is used single screw extrusion machine extrusion moulding tubing, the melt extrusion temperature is controlled at 240 ℃.Every performance index of tubing see Table 1.
Embodiment 10
By weight, 100 portions of viscosity-average molecular weight 6,000,000 ultrahigh molecular weight polyethylene(UHMWPE)s, 5 parts of carbon blacks, 1 part of copper powder, 7 parts of ammonium polyphosphates, 5 parts of polydimethyl phenyl siloxanes, 2 parts of nano silicons, 5 parts of polyethylene and acrylic acid graft copolymer, 5 parts of polyethylene waxs and 4 parts of antioxidant 1010 high-speed mixing are even, then mixture is used single screw extrusion machine extrusion moulding tubing, the melt extrusion temperature is controlled at 250 ℃.Every performance index of tubing see Table 1.
Claims (9)
1. the preparation method of an anti-static halogen-free flame-retardant ultra-high molecular weight polyethylene pipe PP Pipe Compound, it is characterized in that, this method by weight, 100 portions of ultrahigh molecular weight polyethylene(UHMWPE)s, 5～25 parts of electro-conductive materials, 4～20 parts of ammonium polyphosphates, 0.1～10 part of polysiloxane, 1～20 part of nano-meter flame retardants, 1～10 portion of polymer interface bridge stick, 1～10 part of dispersion agent and 0.5～5 part of oxidation inhibitor are mixed, then mixture is used single screw extrusion machine extrusion moulding tubing, the mixture melt temperature is controlled at 180～250 ℃ when extruding.
2. preparation method according to claim 1 is characterized in that, described ultrahigh molecular weight polyethylene(UHMWPE) is that viscosity-average molecular weight is 1,500,000～6,000,000 ultrahigh molecular weight polyethylene(UHMWPE).
3. preparation method according to claim 1 is characterized in that, described electro-conductive material is selected from one or more the mixture in carbon black, graphite and the copper powder.
4. preparation method according to claim 1 is characterized in that, described ammonium polyphosphate is that crystalline structure is the ammonium polyphosphate of II type.
5. preparation method according to claim 1 is characterized in that, described polysiloxane is selected from one or more the mixture in polydimethylsiloxane, PSI and linear siloxane-acetylene multipolymer.
6. preparation method according to claim 1 is characterized in that, described nano-meter flame retardants is selected from one or more the mixture in silicon-dioxide, talcum powder and the magnesium hydroxide, and the particle diameter of described nano-meter flame retardants is 10～100 nanometers.
7. preparation method according to claim 1, it is characterized in that described polymer interface bridge stick is selected from one or more the mixture in polyethylene and maleic anhydride graft copolymer, polyethylene and acrylic acid graft copolymer and polyethylene and the acrylamide grafted copolymer.
8. preparation method according to claim 1 is characterized in that, described dispersion agent is selected from one or more the mixture in polyethylene wax, paraffin, silicone oil and the white oil.
9. according to the described preparation method of claim 1, it is characterized in that described oxidation inhibitor is antioxidant 2246 or antioxidant 1010.
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