CN101724197A - PP/PA composite material used for corrugated pipe and preparation method thereof - Google Patents
PP/PA composite material used for corrugated pipe and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a PP/PA composite material used for a corrugated pipe, which is prepared by processing polypropylene, nylon, compatilizer, toughening agent, filling master batch, light stabilizer, heat stabilizer and processing aid. The PP/PA composite material is prepared by feeding the components into mixing equipment according to a proportion, and melting, mixing, scattering, extruding and granulating the components at the temperature of between 210 and 280 DEG C. The PP/PA composite material not only has higher toughness, excellent high impact resistance and bending property and extremely good high temperature resistance, but also are excellent in the aspects of surface gloss, abrasion resistance, chemical corrosion resistance, electric insulation and the like, and solves the defect problems of insufficient heat resistance of the conventional PP corrugated pipe, over-high price of the PA corrugated pipe; and in addition, a preparation method for the PP/PA composite material is simple and meets the requirement of industrialized production.
Description
Technical field
The present invention relates to a kind of PP/PA matrix material and preparation method thereof, specifically, relate to a kind of PP/PA matrix material that is used for corrugated tube and preparation method thereof, belong to technical field of composite materials.
Background technology
Corrugated tube is a kind of cylinder-shaped thin wall elastic shell with transverse wave, has the function of aspects such as conversion, compensation, connection and energy storage.With respect to the tubing that same material is made, corrugated tube has light weight, attractive in appearance, durable and advantages such as cost is low, good springiness, therefore is used widely in fields such as petrochemical industry, instrument, space flight, chemical industry, electric power, cement, metallurgy.In use, make the corrugated tube opening end fix, sealed end is in free state, during work in inside or the effect lower edge pipe of external pressure vertically or radial variations, the effects such as connection that play damping, keep particular device.
The material of preparation corrugated tube mainly contains metal and plastics at present.Wherein, metallic substance commonly used has stainless steel, brass, berylliumbronze and tinbronze etc., and plastic material has polypropylene (PP), polyethylene (PE), nylon (PA) and polyvinyl chloride (PVC) etc.The corrugated tube that different materials is made all has difference on performance and Application Areas.Have very high bending fatigue strength and solidity to corrosion such as stainless material, welding property is good, the corrugated tube made from it is through being usually used in connecting petroleum storage tank and petroleum pipe line, to attract the relative displacement between petroleum storage tank that earthquake or setting of ground etc. cause and the pipeline, improve the external force resistance ability of system.The berylliumbronze corrugated tube has very little sluggishness and retarded elasticity, and very high resilience stability, corrosion-resistant, nonmagnetic is used in the high-precision metrical instrument more.Plastics (PA, PE, PP, PVC) corrugated tube is commonly used for cable shoe (as telecommunications, railway, motorway, tunnel, telecommunication cable, broadcast TV line protective casing), underground cable pipe, agricultural irrigation pipe, vent-pipe and hydraulic pipe etc.; wherein with the most use with PVC, HDPE, account for 80% of plastic ripple tube material.PP and PA corrugated tube are usually used in thermal characteristics is had on the equipment of requirement, such as some automotive wire bundles, mechanical wire harness etc.But the characteristic that is limited to material itself, every kind of corrugated tube all has the relative merits of oneself, thermotolerance as the PVC material is not good, and the corrugated tube that PP or PE material are made is more a little bit poorer than the corrugated tube mechanical property that PA makes, but is being better than the PA corrugated tube aspect product stability and the water-absorbent.If PA and PP are made the Composite Preparation corrugated tube, can overcome the shortcoming separately of PP, PA material on the one hand, cost is significantly reduced, have good cost performance, but do not see related products and technology report at present.
Summary of the invention
The purpose of this invention is to provide a kind of PP/PA matrix material that is used for corrugated tube and preparation method thereof,, fill a hole in the market to overcome the above-mentioned defective of existing in prior technology.
For achieving the above object, the technical solution used in the present invention is as follows:
The PP/PA matrix material that is used for corrugated tube of the present invention, the weight percent that it is formed and each is formed is as follows:
Polypropylene (PP) 47%～80%
Nylon (PA) 3%～40%
Compatilizer 5%～20%
Toughner 1%～40%
Filler parent granule 0～10%
Photostabilizer 0.1～1%
Thermo-stabilizer 0.2～1.5%
Processing aid 0.2～1.5%
Above-mentioned each proportioning sum of forming is 100%; Wherein: the melt flow index (MFR) of polypropylene under 230 ℃/2.16kg test condition is less than 5g/10min; The melt flow index (MFR) of nylon under 270 ℃/2.16kg test condition is less than 15g/10min; Described filler parent granule is that the processing aid by the thermo-stabilizer of the mineral filler of the polyolefin resin of 15wt%～58.5wt%, 40wt%～80wt%, 0.2wt%～0.5wt% and 0.2wt%～0.5wt% carries out extruding pelletization and forms.
Described nylon can be selected from one or more the mixture in nylon 6, nylon 66, Ni Long11, nylon 12, NYLON610 and the nylon 612.
Described compatilizer is preferably by polypropylene, polyolefin elastomer POE or the terpolymer EP rubber (EPDM) of maleic anhydride, vinylformic acid, methacrylic acid or glycidyl methacrylate modification.
The mixture of one or more among described toughner preferably polyethylene (PE), polyolefin elastomer POE, terpolymer EP rubber (EPDM), thermoplastic polyolefin elastomer TPO, styrene analog thermoplastic elastomer TPE, dynamic vulcanization thermoplastic elastomer TPV and the thermoplastic elastomer SEBS.
Preferably the melt flow index (MFR) under 230 ℃/2.16kg test condition is less than the polyvinyl resin of 5g/10min for polyolefin resin in the described filler parent granule, and the preferred median size of described mineral filler is one or more the mixture in 0.1～10 micron talcum powder, barium sulfate, lime carbonate, pure aluminium silicate whisker, Magnesium Silicate q-agent whisker, magnesium sulfate crystal whisker and the calcium sulfate crystal whiskers.
Described photostabilizer can be selected from one or more the mixture in Whitfield's ointment lipid, benzophenone, benzotriazole category, triazines, the fine class of replacement propylene, Oxamides, organic nickel compounds and the hindered amine light stabilizer.
Described thermo-stabilizer can be selected from the mixture class of phenols, amine, phosphorous acid esters, half Hinered phenols, acryl functional group and monothioester and one or more the mixture in the calixarene kind thermo-stabilizer.
Described processing aid can be selected from one or more the mixture in low molecule ester class, metallic soap class, stearic acid complex ester class and the amides processing aid.
The preparation method who is used for the PP/PA matrix material of corrugated tube of the present invention comprises the steps:
A) preparation of filler parent granule
Polyolefin resin, mineral filler are pre-mixed, add thermo-stabilizer and processing aid again, melt pelletization in mixing facilities then, processing temperature is 140～250 ℃;
B) preparation of matrix material
Polypropylene, nylon, compatilizer, toughner, filler parent granule, photostabilizer, thermo-stabilizer and processing aid are added in the mixing facilities by proportioning, carry out melting mixing at 210～280 ℃ and disperse extruding pelletization.
Described mixing facilities can be single screw extrusion machine, twin screw extruder, Banbury mixer, mill or screw rod number greater than 2 multiple screw extruder, and preferred length-to-diameter ratio is 36～46: 1 twin screw extruder.
Compared with prior art, product of the present invention not only has very high toughness, good high-impact performance and bending property, splendid resistance to elevated temperatures, and excellent in the performance of aspects such as surface luster, rub resistance, resistance to chemical attack, electric insulating quality, solved defect problems such as existing P P corrugated tube resistance toheat deficiency, the selling at exorbitant prices of PA corrugated tube; In addition, the preparation technology of product of the present invention is simple, meets the suitability for industrialized production requirement.
Embodiment
Is doing further in detail of how realizing, explanation clearly and completely below in conjunction with specific embodiment to the present invention, and listed embodiment only gives further instruction to the present invention, and is not thereby limiting the invention.The melt flow index (MFR) of polypropylene under 230 ℃/2.16kg test condition used among the embodiment is less than 5g/10min; The melt flow index (MFR) of used nylon under 270 ℃/2.16kg test condition is less than 15g/10min; Described photostabilizer can be selected from one or more the mixture in Whitfield's ointment lipid, benzophenone, benzotriazole category, triazines, the fine class of replacement propylene, Oxamides, organic nickel compounds and the hindered amine light stabilizer; Described thermo-stabilizer can be selected from the mixture class of phenols, amine, phosphorous acid esters, half Hinered phenols, acryl functional group and monothioester and one or more the mixture in the calixarene kind thermo-stabilizer; Described processing aid can be selected from one or more the mixture in low molecule ester class, metallic soap class, stearic acid complex ester class and the amides processing aid.
Embodiment 1
A) preparation of filler parent granule
With melt flow index is that the mixture of 27 kilograms of the polypropylene powders of 1.2g/10min, emboliform mineral filler-lime carbonate that median size is 3 microns and pure aluminium silicate whisker is pre-mixed evenly for 30 kilograms, add 0.2 kilogram thermo-stabilizer Irganox 1010 and 0.2 kilogram processing aid again, carry out melt pelletization then in twin screw extruder, processing temperature is 140～250 ℃;
B) preparation of matrix material
It is in 40: 1 the twin screw extruder that the compatilizer-maleic anhydride inoculated polypropylene (PP-g-MAH) of 6,10 kilograms of 60 kilograms of polypropylene, 25 kilograms of nylon, 5 kilograms of toughner-EPDM, 2 kilograms of filler parent granules, 0.2 kilogram of photostabilizer, 0.2 kilogram of thermo-stabilizer and 0.3 kilogram of processing aid are added length-to-diameter ratio, carrying out melting mixing at 245 ℃ disperses, extruding pelletization promptly gets PP/PA matrix material of the present invention.
The prepared PP/PA matrix material of present embodiment has very high toughness, good impact resistance and higher heat-drawn wire, and have surface of good gloss, good resistance to chemical attack, ultraviolet resistance is aging and scratch-resistant performance, electrical insulation properties is greater than 200M Ω, and specific performance is shown in Table 1:
The PP/PA performance of composites data of table 1 present embodiment
Embodiment 2
It is in 40: 1 the twin screw extruder that the compatilizer-maleic anhydride graft POE (POE-g-MAH) of 6,5 kilograms of 60 kilograms of polypropylene, 25 kilograms of nylon, 5 kilograms of toughner-POE, 0.2 kilogram of photostabilizer, 0.2 kilogram of thermo-stabilizer and 0.3 kilogram of processing aid are added length-to-diameter ratio, carrying out melting mixing at 245 ℃ disperses, extruding pelletization promptly gets PP/PA matrix material of the present invention.
The prepared PP/PA matrix material of present embodiment has very high toughness, good impact resistance and higher heat-drawn wire, and have surface of good gloss, good resistance to chemical attack, ultraviolet resistance is aging and scratch-resistant performance, electrical insulation properties is greater than 400M Ω, and specific performance is shown in Table 2:
The PP/PA performance of composites data of table 2 present embodiment
Embodiment 3
A) preparation of filler parent granule
With melt flow index is that the mixture of 27 kilograms of the polyethylene of 0.8g/10min, emboliform mineral filler-barium sulfate that median size is 1 micron and calcium sulfate crystal whiskers is pre-mixed evenly for 30 kilograms, add 0.2 kilogram thermo-stabilizer Irganox 1010 and 0.2 kilogram processing aid again, carry out melt pelletization then in twin screw extruder, processing temperature is 140～250 ℃;
B) preparation of matrix material
It is in 40: 1 the twin screw extruder that the compatilizer-maleic anhydride graft POE (POE-g-MAH) of 6,5 kilograms of 60 kilograms of polypropylene, 25 kilograms of nylon, 5 kilograms of toughner-TPV, 2 kilograms of filler parent granules, 0.2 kilogram of photostabilizer, 0.2 kilogram of thermo-stabilizer and 0.5 kilogram of processing aid are added length-to-diameter ratio, carrying out melting mixing at 245 ℃ disperses, extruding pelletization promptly gets PP/PA matrix material of the present invention.
The prepared PP/PA matrix material of present embodiment has very high toughness, good impact resistance and higher heat-drawn wire, and have surface of good gloss, good resistance to chemical attack, ultraviolet resistance is aging and scratch-resistant performance, electrical insulation properties is greater than 200M Ω, and specific performance is shown in Table 3:
The PP/PA performance of composites data of table 3 present embodiment
Embodiment 4
It is in 40: 1 the twin screw extruder that the compatilizer-maleic anhydride graft EPDM (EPDM-g-MAH) of 6,5 kilograms of 60 kilograms of polypropylene, 25 kilograms of nylon, 5 kilograms of toughner-TPO, 0.2 kilogram of photostabilizer, 0.2 kilogram of thermo-stabilizer and 0.3 kilogram of processing aid are added length-to-diameter ratio, carrying out melting mixing at 245 ℃ disperses, extruding pelletization promptly gets PP/PA matrix material of the present invention.
The prepared PP/PA matrix material of present embodiment has very high toughness, good impact resistance and higher heat-drawn wire, and have surface of good gloss, good resistance to chemical attack, ultraviolet resistance is aging and scratch-resistant performance, electrical insulation properties is greater than 200M Ω, and specific performance is shown in Table 4:
The PP/PA performance of composites data of table 4 present embodiment
Embodiment 5
It is in 40: 1 the twin screw extruder that the compatilizer-maleic anhydride graft EPDM (EPDM-g-MAH) of 6,5 kilograms of 60 kilograms of polypropylene, 25 kilograms of nylon, 5 kilograms of toughner-TPE, 0.2 kilogram of photostabilizer, 0.2 kilogram of thermo-stabilizer and 0.3 kilogram of processing aid are added length-to-diameter ratio, carrying out melting mixing at 245 ℃ disperses, extruding pelletization promptly gets PP/PA matrix material of the present invention.
The prepared PP/PA matrix material of present embodiment has very high toughness, good impact resistance and higher heat-drawn wire, and have surface of good gloss, good resistance to chemical attack, ultraviolet resistance is aging and scratch-resistant performance, electrical insulation properties is greater than 200M Ω, and specific performance is shown in Table 5:
The PP/PA performance of composites data of table 5 present embodiment
Embodiment 6
It is in 40: 1 the twin screw extruder that the mixture of compatilizer-maleic anhydride graft POE (POE-g-MAH), 3 kilograms of toughner-2 kilogram EPDM of 6,5 kilograms of 60 kilograms of polypropylene, 25 kilograms of nylon and 1 kilogram of SEBS, 0.2 kilogram of photostabilizer, 0.2 kilogram of thermo-stabilizer and 0.3 kilogram of processing aid are added length-to-diameter ratio, carrying out melting mixing at 245 ℃ disperses, extruding pelletization promptly gets PP/PA matrix material of the present invention.
The prepared PP/PA matrix material of present embodiment has very high toughness, good impact resistance and higher heat-drawn wire, and have surface of good gloss, good resistance to chemical attack, ultraviolet resistance is aging and scratch-resistant performance, electrical insulation properties is greater than 700M Ω, and specific performance is shown in Table 6:
The PP/PA performance of composites data of table 6 present embodiment
Claims (10)
1. a PP/PA matrix material that is used for corrugated tube is characterized in that, the weight percent that it is formed and each is formed is as follows:
Polypropylene (PP) 47%～80%
Nylon (PA) 3%～40%
Compatilizer 5%～20%
Toughner 1%～40%
Filler parent granule 0～10%
Photostabilizer 0.1～1%
Thermo-stabilizer 0.2～1.5%
Processing aid 0.2～1.5%
Above-mentioned each proportioning sum of forming is 100%; Wherein: the melt flow index (MFR) of polypropylene under 230 ℃/2.16kg test condition is less than 5g/10min; The melt flow index (MFR) of nylon under 270 ℃/2.16kg test condition is less than 15g/10min; Described filler parent granule is that the processing aid by the thermo-stabilizer of the mineral filler of the polyolefin resin of 15wt%～58.5wt%, 40wt%～80wt%, 0.2wt%～0.5wt% and 0.2wt%～0.5wt% carries out extruding pelletization and forms.
2. the PP/PA matrix material that is used for corrugated tube according to claim 1 is characterized in that: described nylon is selected from one or more the mixture in nylon 6, nylon 66, Ni Long11, nylon 12, NYLON610 and the nylon 612.
3. the PP/PA matrix material that is used for corrugated tube according to claim 1 is characterized in that: described compatilizer is by the polypropylene of maleic anhydride, vinylformic acid, methacrylic acid or glycidyl methacrylate modification, polyolefin elastomer POE or terpolymer EP rubber (EPDM).
4. the PP/PA matrix material that is used for corrugated tube according to claim 1 is characterized in that: described toughner is selected from one or more the mixture among polyethylene (PE), polyolefin elastomer POE, terpolymer EP rubber (EPDM), thermoplastic polyolefin elastomer TPO, styrene analog thermoplastic elastomer TPE, dynamic vulcanization thermoplastic elastomer TPV and the thermoplastic elastomer SEBS.
5. the PP/PA matrix material that is used for corrugated tube according to claim 1, it is characterized in that: the polyolefin resin in the described filler parent granule be melt flow index (MFR) under 230 ℃/2.16kg test condition less than the polyvinyl resin of 5g/10min, mineral filler is that to be selected from median size be one or more mixture in 0.1～10 micron talcum powder, barium sulfate, lime carbonate, pure aluminium silicate whisker, Magnesium Silicate q-agent whisker, magnesium sulfate crystal whisker and the calcium sulfate crystal whiskers.
6. the PP/PA matrix material that is used for corrugated tube according to claim 1 is characterized in that: described photostabilizer is selected from one or more the mixture in Whitfield's ointment lipid, benzophenone, benzotriazole category, triazines, the fine class of replacement propylene, Oxamides, organic nickel compounds and the hindered amine light stabilizer.
7. the PP/PA matrix material that is used for corrugated tube according to claim 1 is characterized in that: described thermo-stabilizer is selected from the mixture class of phenols, amine, phosphorous acid esters, half Hinered phenols, acryl functional group and monothioester and one or more the mixture in the calixarene kind thermo-stabilizer.
8. the PP/PA matrix material that is used for corrugated tube according to claim 1 is characterized in that: described processing aid is selected from one or more the mixture in low molecule ester class, metallic soap class, stearic acid complex ester class and the amides processing aid.
9. the described preparation method who is used for the PP/PA matrix material of corrugated tube of claim 1 is characterized in that described method comprises the steps:
A) preparation of filler parent granule
Polyolefin resin, mineral filler are pre-mixed, add thermo-stabilizer and processing aid again, melt pelletization in mixing facilities then, processing temperature is 140～250 ℃;
B) preparation of matrix material
Polypropylene, nylon, compatilizer, toughner, filler parent granule, photostabilizer, thermo-stabilizer and processing aid are added in the mixing facilities by proportioning, carry out melting mixing at 210～280 ℃ and disperse extruding pelletization;
Described mixing facilities is single screw extrusion machine, twin screw extruder, Banbury mixer, mill or screw rod number greater than 2 multiple screw extruder.
10. the preparation method who is used for the PP/PA matrix material of corrugated tube according to claim 9 is characterized in that: described mixing facilities is that length-to-diameter ratio is 36～46: 1 twin screw extruder.
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2009
- 2009-11-05 CN CN200910198364A patent/CN101724197A/en active Pending
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