CN111320817A - Special material for outer layer of flame-retardant, antistatic, wear-resistant and rat-bite-proof power pipeline and preparation method thereof - Google Patents
Special material for outer layer of flame-retardant, antistatic, wear-resistant and rat-bite-proof power pipeline and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a special material for an outer layer of a flame-retardant, antistatic, wear-resistant and rat-bite-proof power pipeline and a preparation method thereof. Mainly plays the roles of flame retardance, static resistance, scraping resistance and rat bite resistance. The special material comprises the following components in parts by weight: 100 parts of polypropylene, 1-6 parts of ethylene-vinyl acetate copolymer, 1-6 parts of ethylene propylene diene monomer, 5-20 parts of unsaturated carboxylic acid graft copolymer of polyolefin elastomer, 5-10 parts of ultrahigh molecular weight polyethylene, 3-10 parts of phosphogypsum whisker, 6-10 parts of decabromodiphenylethane, 1-2 parts of nano antimony trioxide, 0.2-0.6% of silane coupling agent, 1-6 parts of dicumyl peroxide, 1-6 parts of conductive graphite, 6-10 parts of nonanoic acid vanillimide, 0.4-0.6 part of antioxidant 1,1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 0.4-0.6 part of anti-aging agent 2-mercaptobenzimidazole and 0.4-0.6 part of calcium stearate. The special material for the outer layer pipe of the electric double-wall pipeline has the advantages of good flame retardant property, good antistatic property, high notch impact strength, scratch resistance, rat bite resistance, easiness in processing, recyclability and the like.
Description
Technical Field
The invention relates to the technical field of polymer composite materials, and particularly relates to a preparation method and application of a special material for an outer layer of a flame-retardant antistatic high-notch impact strength polypropylene pipeline.
Background
Power pipes are commonly used for construction and are typically made of modified Polyethylene (PE), epoxy resin, or chlorinated polyvinyl chloride (CPVC) resin. However, PE pipes have the disadvantage of low mechanical strength, epoxy resins (EP) have the disadvantage of poor weather resistance and brittleness, and chlorinated polyvinyl chloride (CPVC) has the disadvantages of high price, difficult processing and the like. The power pipeline needs to be guaranteed to be used in trenchless construction, when the power pipeline encounters an obstacle with high hardness and clear edges and corners, the power pipeline can be protected from being scratched to cause damage and cracking, and the characteristics of static electricity resistance, flame retardance and scratch resistance are guaranteed. Modified polypropylene (PP) pipes are currently being developed, but conventional PP pipes generally lack flame retardant, antistatic and rat bite resistant effects. Patent CN 205388192U adopts the two parts of spaces separated by the double-layer corrugated pipe to respectively place the substances (aluminum sulfate solution and sodium bicarbonate solution) for foam fire extinguishing to achieve the flame retardant effect, but the scheme greatly increases the weight of the pipeline. Patent CN 106751261A adopts CPVC and auxiliary agents ACR-61, MBS and HSt to achieve the balance of flame retardance and performanceAnd (5) effect. However, this solution has the disadvantage of expensive raw materials. Patent CN 205051312U discloses a modified polypropylene double-wall corrugated pipe for buried high-voltage power cable, which is made of polypropylene resin added with mineral particle scratch-resistant agent, but lacks antistatic, flame-retardant and rat-bite-resistant properties, and does not disclose the kind and addition ratio of the mineral scratch-resistant agent. Patent CN 103668987A discloses a preparation method of flame-retardant PP non-woven fabric, which is characterized in that decabromodiphenylethane 6-12 percent and Sb are added2O3The 2% -4% flame retardant property reaches the B2 effect, but far from the V-0 grade. The patent CN 101880420B discloses a flame-retardant polypropylene compound without surface precipitation and a preparation method thereof, melamine cyanurate and phosphinate are used as main flame retardants and flame-retardant synergists, the total addition of the flame-retardant synergists reaches 20%, so that the flame-retardant grade of a PP material reaches V-0, and traditionally, a brominated flame retardant and Sb are selected2O3The addition amount of the compounded flame-retardant PP reaches V-0 level is more than 15%, so that the mechanical property of the material is poor. Patent CN 105315557B discloses an antistatic PP modified material and a preparation method thereof, wherein 5-15 parts of carbon black with the particle size of 10-50nm and carbon fiber with the monofilament diameter of 50-100nm are mixed according to the weight ratio of 1.4-2.2: the antistatic agent of the mixture consisting of the components 1 achieves the antistatic effect, but after the carbon fiber is added into PP, the material can generate a candle wick effect when being burnt, and the flame retardance can be damaged. Patent CN 105330965B discloses PP plastic with ardealite as filler and a preparation method thereof, wherein 10-30 parts of ardealite is adopted as antistatic agent and added into PP, but the mechanical property of the material is obviously reduced, and particularly, the notch impact strength is only 2KJ/m2And the material is not beneficial to further application. Therefore, the invention needs to invent a PP material for the outer pipe of the pipeline, which has the advantages of flame retardance, static resistance, wear resistance, rat bite resistance and excellent mechanical property.
Disclosure of Invention
The invention aims to provide a preparation method and application of an outer pipe of a polypropylene pipeline, which is flame-retardant, antistatic, rat-bite-proof, high in notch impact strength, wear-resistant and capable of overcoming the defects that the flame retardant property, the antistatic property, the notch impact property and the scratch resistance of the existing polypropylene pipeline cannot be considered at the same time.
The technical problem to be solved by the invention is realized by adopting the following technical scheme.
The invention provides a flame-retardant, antistatic, wear-resistant and rat-bite-proof special material for an outer layer of a power pipeline, which comprises the following components in parts by weight: 100 parts of polypropylene, 1-6 parts of ethylene-vinyl acetate copolymer, 1-6 parts of ethylene propylene diene monomer, 5-20 parts of unsaturated carboxylic acid graft copolymer of polyolefin elastomer, 5-10 parts of ultrahigh molecular weight polyethylene, 3-10 parts of phosphogypsum whisker, 6-10 parts of decabromodiphenylethane, 1-2 parts of nano antimony trioxide, 0.2-0.6% of silane coupling agent, 1-6 parts of dicumyl peroxide, 1-6 parts of conductive graphite, 6-10 parts of nonanoic acid vanillimide, 0.4-0.6 part of antioxidant 1,1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 0.4-0.6 part of anti-aging agent 2-mercaptobenzimidazole and 0.4-0.6 part of calcium stearate.
The invention also provides a flame-retardant, antistatic, wear-resistant and rat-bite-proof special material for the outer layer of the power pipeline and a preparation method thereof, wherein the preparation method comprises the following steps:
mixing the preparation raw materials into uniform materials according to the proportion, then extruding and granulating the uniformly mixed materials by a double screw rod added with a micro-nano laminated stretching device,
preferably, the extrusion molding temperature is 230 ℃, the temperatures of the sections of the screw extruder from the feeding port to the feed port of the micro-nano laminated drawing device are respectively 90 ℃, 160 ℃, 210 ℃, 230 ℃, 225 ℃, and the rotating speed of the main machine is 200 and 400 revolutions per minute. The temperature of each section from the feed inlet to the discharge outlet of the micro-nano laminated stretching device is 230 ℃.
The invention also provides application of the flame-retardant antistatic high-notch impact strength scratch-resistant polypropylene pipeline outer pipe material.
The invention has the beneficial effects that:
the invention provides a special material for an outer layer of a flame-retardant, antistatic, wear-resistant and rat-bite-proof power pipeline, a preparation method and application thereof, the preparation raw materials of the special material for the outer layer of the flame-retardant, antistatic, wear-resistant and rat-bite-proof power pipeline are coordinated and matched, and simultaneously, a micro-nano laminated stretching device is adopted to orient an impact modifier and conductive graphite, so that the prepared material has the advantages that the flame retardant used in a conventional formula is reduced by 5% at least, the flame retardant property reaches V-0 level, the antistatic agent used is reduced by 50% at least, meanwhile, the material has excellent properties of rat-bite resistance, high notch impact strength, low temperature resistance, high strength, aging resistance and the like, and the product has the advantages of low processing energy consumption, rec.
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In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
Fig. 1 is a planar view of a micro-nano laminated stretching device according to an embodiment of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The special material for the outer layer of the flame-retardant, antistatic, wear-resistant and rat-bite-proof power pipeline, the preparation method thereof and the application thereof provided by the embodiment of the invention are specifically explained below.
The embodiment of the invention provides a flame-retardant, antistatic, wear-resistant and rat-bite-proof special material for an outer layer of an electric power pipeline and a preparation method thereof, wherein the preparation raw materials comprise the following components in parts by weight:
100 parts of polypropylene, 1-6 parts of ethylene-vinyl acetate copolymer, 1-6 parts of ethylene propylene diene monomer, 5-20 parts of unsaturated carboxylic acid graft copolymer of polyolefin elastomer, 5-10 parts of ultrahigh molecular weight polyethylene, 3-10 parts of phosphogypsum whisker, 6-10 parts of decabromodiphenylethane, 1-2 parts of nano antimony trioxide, 0.2-0.6% of silane coupling agent, 1-6 parts of dicumyl peroxide, 6-10 parts of vanillic amide nonanoate, 1-6 parts of conductive graphite, 0.4-0.6 part of antioxidant 1,1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 0.4-0.6 part of anti-aging agent 2-mercaptobenzimidazole, 0.6-0.6 part of light stabilizer GW-9440.4 and 0.4-0.6 part of calcium stearate.
Further, the preparation raw materials of the flame-retardant, antistatic, wear-resistant, rat-bite-proof and high-notch impact strength polypropylene material comprise the following components in parts by weight:
100 parts of polypropylene, 1-3 parts of ethylene-vinyl acetate copolymer, 1-3 parts of ethylene propylene diene monomer, 5-10 parts of unsaturated carboxylic acid graft copolymer of polyolefin elastomer, 8-10 parts of ultrahigh molecular weight polyethylene, 5-10 parts of phosphogypsum whisker, 6-8 parts of decabromodiphenylethane, 1-2 parts of nano antimony trioxide, 0.4-0.6% of silane coupling agent, 2-6 parts of dicumyl peroxide, 6-10 parts of nonanoic acid vanillimide, 2-6 parts of conductive graphite, 0.4-0.5 part of antioxidant 1,1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 0.4-0.5 part of anti-aging agent 2-mercaptobenzimidazole, and 0.5-0.5 part of light stabilizer GW-9440.4, 0.4-0.5 part of calcium stearate.
Furthermore, the modified polypropylene composite material comprises the following raw materials in parts by weight:
100 parts of polypropylene, 1 part of ethylene-vinyl acetate copolymer, 1 part of ethylene propylene diene monomer, 10 parts of unsaturated carboxylic acid graft copolymer of polyolefin elastomer, 10 parts of ultrahigh molecular weight polyethylene, 10 parts of phosphogypsum whisker, 8 parts of decabromodiphenylethane, 2 parts of nano antimony trioxide, 0.4-0.6 part of silane coupling agent, 2-6 parts of dicumyl peroxide, 6 parts of vanillic nonanoate, 6 parts of conductive graphite, 0.4-0.5 part of antioxidant 1,1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 0.4-0.5 part of anti-aging agent 2-mercaptobenzimidazole, 0.78-0.5 part of light stabilizer GW-9440.4, and 0.4-0.5 part of calcium stearate.
The modified polypropylene composite material provided by the embodiment of the invention has the characteristics of flame retardance, static resistance and high notch impact strength, takes the main raw materials of polypropylene, unsaturated carboxylic acid graft copolymer of polyolefin elastomer, ultrahigh molecular weight polyethylene, phosphogypsum whisker, decabromodiphenylethane and nano antimony trioxide as auxiliary materials, introduces conductive graphite with barrier and heat insulation into the raw materials, can change a toughness assisting toughening agent and other raw materials with synergistic improvement functions, and has the advantages of flame retardance, static resistance, high notch impact strength, scratch resistance and the like through scientific and reasonable proportioning, and the product has the advantages of low processing energy consumption, recyclability and the like.
In some embodiments, the polypropylene has a melt index of 0.29 to 0.3g/10min of a co-polypropylene having a designation of 4220 or 4101; the ethylene-vinyl acetate copolymer has the Vinyl Acetate (VA) content of 8-10% and the melt index of 0.6-0.9g/10min, and the trade mark is V4110F; the ethylene propylene diene monomer is Mooney viscosity of 38-52 and the grade of 4045; the weight average molecular weight of the ultra-high molecular weight polyethylene is 500-700 ten thousand, and the mark number is 4170; the silane coupling agent is methacryloxy functional group silane with the trade name of KH-570; the dicumyl peroxide is manufactured and sold by akoma (orthodox) chemical limited; the antioxidant is 1,1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane; the anti-aging agent is 2-mercaptobenzimidazole.
The modified silane coupling agent treatment can obviously improve and reduce the agglomeration of powder, improve the compatibility with a base material and further improve the notch impact strength of the material. The orientation of the conductive graphite in the micro-nano laminated stretching device can obviously improve the flame retardant and antistatic effects of the material. The orientation of the toughening agent in a micro-nano laminated drawing device can obviously improve the tensile strength of the material. The ultra-high molecular weight polyethylene and the conductive graphite are used together to improve the scratch resistance of the material synergistically.
In some embodiments, the synergistic flame retardant and the synergistic antistatic agent comprise conductive graphite.
The fire retardant decabromodiphenylethane is prepared by the following method:
mixing decabromodiphenylethane with ethanol solution of methacryloxy functional group silane, reacting to obtain methacryloxy functional group silane modified decabromodiphenylethane,
preferably, the decabromodiphenyl ethane is obtained by drying decabromodiphenyl ethane for 6-10 hours at 80-100 ℃ in vacuum,
more preferably, the mass ratio of the decabromodiphenylethane to the methacryloxy-functional silane is 100: 1-200: 1,
more preferably, the reaction conditions are: the temperature is 60-80 deg.C, the time is 4-6h, and the pressure is 7.38-30 MPa. (ii) a
The preparation method of the synergistic flame retardant antimony trioxide refers to the preparation method of decabromodiphenylethane.
In the preparation raw materials of the modified polypropylene composite material provided by the embodiment of the invention, the introduction of the synergistic flame retardant and antistatic agent flake graphite can obviously improve the flame retardance, the antistatic property, the surface hardness, the rigidity and the bending strength of a plastic product, reduce the molding shrinkage rate and increase the dimensional stability, and when the flame retardant reaches the flame retardant V-0 level, the addition amount of the flame retardant is reduced by at least 20 percent, and the addition amount of the antistatic agent is reduced by at least 50 percent.
In some embodiments, the toughening agent includes at least one of an unsaturated carboxylic acid graft copolymer of a polyolefin elastomer, a maleic anhydride grafted ethylene-octene copolymer, a maleic anhydride grafted ethylene-propylene-diene rubber, and a maleic anhydride grafted hydrogenated styrene-butadiene block copolymer.
The unsaturated carboxylic acid graft copolymer of the toughening agent polyolefin elastomer is prepared by the following method:
adding butynedioic acid, polyolefin elastomer (POE) and dicumyl peroxide (DCP) into a double-screw extruder in proportion, and carrying out melt extrusion to obtain an unsaturated carboxylic acid graft copolymer of the polyolefin elastomer;
preferably, the mass ratio of butynedioic acid, polyolefin elastomer (POE) and dicumyl peroxide (DCP) is 1: 100: 0.1-3: 100: 0.3;
preferably, the temperatures of the sections of the screw extruder from the feeding port of the twin-screw extruder to the twin-screw extrusion die head are respectively 90 ℃, 160 ℃, 210 ℃, 230 ℃, 225 ℃ and the rotation speed of the main machine is 200 and 400 revolutions per minute.
In the preparation raw materials of the modified polypropylene composite material provided by the embodiment of the invention, the toughening agent is introduced, and the modified polypropylene added with the powder such as the phosphogypsum whisker is easy to crack and quickly expand when bearing external force, so that the material is cracked and is not fatigue-resistant, and the service performance of the material is reduced. Therefore, the toughening agent is introduced into the preparation raw materials, so that the brittleness of the modified polypropylene composite material is reduced, the toughness is increased, and the bearing strength is improved.
In some embodiments, the preparation raw materials further comprise phosphogypsum whiskers, and the addition of the phosphogypsum whiskers increases the antistatic property of the material and improves the rigidity and the dimensional stability of the material.
In some embodiments, the starting materials for the preparation further comprise a silane coupling agent, dicumyl peroxide, 1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 2-mercaptobenzimidazole, GW-944, and calcium stearate.
In the preparation raw materials of the modified polypropylene composite material provided by the embodiment of the invention, 1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 2-mercaptobenzimidazole and GW-944 are introduced, so that the weather resistance of the material is improved and the service life of the material is prolonged.
In the preparation raw materials of the modified polypropylene composite material provided by the embodiment of the invention, calcium stearate is introduced to improve the processing performance of the material.
The embodiment of the invention also provides a special material for the outer layer of the flame-retardant, antistatic, wear-resistant and rat-bite-proof power pipeline and a preparation method thereof, wherein the preparation method comprises the following steps:
weighing various materials according to the proportion of the components in the formula, mixing all the materials in a mixer for 2 minutes, extruding and granulating the uniformly mixed materials by a double screw with a micro-nano laminated stretching device,
preferably, the extrusion molding temperature is 200 ℃, the temperatures of the sections of the screw extruder from the feeding port to the feed port of the micro-nano laminated drawing device are respectively 90 ℃, 160 ℃, 210 ℃, 230 ℃, 225 ℃, and the main machine rotating speed is 200 and 400 revolutions per minute. The temperature of each section from the feed inlet to the discharge outlet of the micro-nano laminated stretching device is 230 ℃.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The special material for the outer layer of the flame-retardant, antistatic, wear-resistant and rat-bite-proof power pipeline and the preparation method thereof comprise the following steps:
preparing conductive flake graphite, comprising the following steps:
a. flake graphite was pretreated with a fluidized bed type jet mill. 25kg of flake graphite was fed into the pulverization chamber by a screw feeder, and then high-speed injection of high-pressure air into the pulverization chamber was achieved by a supersonic nozzle. Air consumption of 3m3And/min. The flake graphite is accelerated in a supersonic jet flow and then repeatedly impacted and collided at a nozzle, and finally the conductive flake graphite with the size of 1-3 mu m is obtained.
b. 20g of graphite flakes were dried in an oven at 90 ℃ under vacuum for 8 hours. This was then mixed homogeneously with 2g of methacryloxy functional silane and 4g of ethanol, acetic acid was added dropwise thereto so that the solution had a pH of between 4 and 6, after which it was poured into a reactor and the mixture was then treated at 60 ℃ for 4 hours with constant stirring to obtain methacryloxy functional silane-modified graphite flakes.
An unsaturated carboxylic acid graft copolymer for preparing a polyolefin elastomer comprising the steps of:
mixing butynedioic acid, polyolefin elastomer (POE), dicumyl peroxide (DCP) according to the mass fraction of 100: 2: 0.2 into a double-screw extruder, and carrying out melt extrusion to obtain the unsaturated carboxylic acid graft copolymer of the polyolefin elastomer. The temperature of each section of the screw extruder from the feeding port of the double-screw extruder to the double-screw extrusion die head is respectively 90 ℃, 130 ℃, 180 ℃, 190 ℃, 185 ℃ and the rotating speed of the main machine is 300 revolutions per minute.
The special material for the outer layer of the flame-retardant, antistatic, wear-resistant and rat-bite-proof power pipeline and the preparation method thereof comprise the following steps:
100Kg of polypropylene, 1Kg of ethylene-vinyl acetate copolymer, 1Kg of ethylene propylene diene monomer, 10Kg of unsaturated carboxylic acid graft copolymer of polyolefin elastomer, 10Kg of ultrahigh molecular weight polyethylene, 10Kg of phosphogypsum whisker, 8Kg of decabromodiphenylethane, 2Kg of nano antimony trioxide, 0.5Kg of silane coupling agent, 2Kg of dicumyl peroxide, 6Kg of nonanoic acid vanillylamide, 6Kg of conductive graphite, 0.5Kg of 1,1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 0.5Kg of 2-mercaptobenzimidazole, 0.5Kg of light stabilizer GW-944 and 0.5Kg of calcium stearate are mixed uniformly in a mixer.
Then, the uniformly mixed materials are extruded and granulated by a double screw with a micro-nano laminated stretching device, the extrusion molding temperature is 230 ℃, the temperature of each section of a screw extruder from a feeding port to a feeding port of the micro-nano laminated stretching device is 90 ℃, 160 ℃, 210 ℃, 230 ℃, 225 ℃, and the rotating speed of a main machine is 300 revolutions per minute. And the temperature of each section from the feed inlet to the discharge outlet of the micro-nano laminated stretching device is 230 ℃, and then the product is prepared by cooling, granulating, drying and packaging.
Example 2
The preparation process of the unsaturated carboxylic acid graft copolymer of the ultra-zero treatment octadecyl ammonium chloride modified montmorillonite, the ultra-zero carbon dioxide flake graphite and the polyolefin elastomer used in the embodiment 2 of the invention is the same as that in the embodiment 1.
The special material for the outer layer of the flame-retardant, antistatic, wear-resistant and rat-bite-proof power pipeline and the preparation method thereof comprise the following steps:
100Kg of polypropylene, 6Kg of ethylene-vinyl acetate copolymer, 6Kg of ethylene propylene diene monomer, 20Kg of unsaturated carboxylic acid graft copolymer of polyolefin elastomer, 8Kg of ultrahigh molecular weight polyethylene, 10Kg of phosphogypsum whisker, 9Kg of decabromodiphenylethane, 3Kg of nano antimony trioxide, 1Kg of silane coupling agent, 6Kg of dicumyl peroxide, 6Kg of vanillylamide nonanoate, 6Kg of conductive graphite, 0.6Kg of 1,1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 0.6Kg of 2-mercaptobenzimidazole, 0.6Kg of light stabilizer GW-944 and 0.5Kg of calcium stearate are mixed uniformly in a mixer.
Then, the uniformly mixed materials are extruded and granulated by a double screw with a micro-nano laminated stretching device, the extrusion molding temperature is 230 ℃, the temperature of each section of a screw extruder from a feeding port to a feeding port of the micro-nano laminated stretching device is 90 ℃, 160 ℃, 210 ℃, 230 ℃, 225 ℃, and the rotating speed of a main machine is 300 revolutions per minute. And the temperature of each section from the feed inlet to the discharge outlet of the micro-nano laminated stretching device is 230 ℃, and then the product is prepared by cooling, granulating, drying and packaging.
Example 3
The procedure for preparing the unsaturated carboxylic acid graft copolymer of conductive graphite flakes and polyolefin elastomer used in example 3 of the present invention was the same as in example 1.
The special material for the outer layer of the flame-retardant, antistatic, wear-resistant and rat-bite-proof power pipeline and the preparation method thereof comprise the following steps:
100Kg of polypropylene, 1Kg of ethylene-vinyl acetate copolymer, 1Kg of ethylene propylene diene monomer, 5Kg of unsaturated carboxylic acid graft copolymer of polyolefin elastomer, 5Kg of ultrahigh molecular weight polyethylene, 3Kg of phosphogypsum whisker, 6Kg of decabromodiphenylethane, 2Kg of nano antimony trioxide, 0.2Kg of silane coupling agent, 1Kg of dicumyl peroxide, 10Kg of nonanoic acid vanillylamide, 1Kg of conductive graphite, 0.4Kg of 1,1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 0.4Kg of 2-mercaptobenzimidazole, 0.4Kg of light stabilizer GW-944 and 0.5Kg of calcium stearate are mixed uniformly in a mixer.
Then, the uniformly mixed materials are extruded and granulated by a double screw with a micro-nano laminated stretching device, the extrusion molding temperature is 230 ℃, the temperature of each section of a screw extruder from a feeding port to a feeding port of the micro-nano laminated stretching device is 90 ℃, 160 ℃, 210 ℃, 230 ℃, 225 ℃, and the rotating speed of a main machine is 300 revolutions per minute. And the temperature of each section from the feed inlet to the discharge outlet of the micro-nano laminated stretching device is 230 ℃, and then the product is prepared by cooling, granulating, drying and packaging.
Comparative example 1
The special material for the outer layer of the flame-retardant, antistatic, wear-resistant and rat-bite-proof power pipeline and the preparation method thereof comprise the following steps:
the material composition and the production process are the same as those of the embodiment 1, and the difference from the embodiment 1 is only that: conductive flake graphite.
Comparative example 2
The material composition and the production process are the same as those of the embodiment 1, and the difference from the embodiment 1 is only that: conductive flake graphite and phosphogypsum whisker.
Comparative example 3
Material composition example 1 was the same, differing from example 1 only in that: a double-screw extruder in the processing technology is not provided with a micro-nano laminated stretching device.
Comparative example 4
The only difference from example 1 is that: conductive flake graphite and phosphogypsum whiskers are not added, 12Kg of decabromodiphenylethane is added, and 4Kg of antimony trioxide is added. A double-screw extruder in the processing technology is not provided with a micro-nano laminated stretching device.
Test results
Table 1 shows the results of the property measurements of the modified polypropylene composites of examples 1 to 3 of the present invention and comparative examples 1 to 4.
TABLE 1 test results
| Test items | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| Flame retardant rating | V-0 | V-0 | V-1 | HB | HB40 | HB | V-0 |
| Surface resistivity omega | 2.3×106 | 2.0×106 | 7.6×107 | 9.7×107 | 9.9×109 | 4.6×107 | 2.1×1010 |
| Tensile strength MPa | 26.6 | 24.5 | 28.6 | 27.2 | 29.3 | 26.1 | 27.1 |
| Notched impact strength (23 ℃ C.) KJ/m2 | 23.1 | 26.8 | 22.5 | 23.3 | 26.7 | 19.1 | 22.3 |
| Low temperature notched impact strength (-20 ℃ C.) KJ/m2 | 2.3 | 2.7 | 2.1 | 2.4 | 2.4 | 2.2 | 2.3 |
As can be seen from table 1 above, the modified polypropylene composite prepared in example 1 of the present invention is compared with the modified polypropylene composite in comparative example 1, and it can be seen that: in 5 aspects of flame retardant grade, surface resistivity, tensile strength, notch impact strength (23 ℃) and low-temperature notch impact strength (-20 ℃), the numerical values of the modified polypropylene composite material in the embodiment 1 of the invention are all higher than the corresponding numerical values in the comparative example 1, and particularly in the aspects of flame retardant grade and surface resistivity, the scratch resistance agent used in the conventional formula is reduced by at least 30%, meanwhile, the material has excellent performances of high flame retardant grade, low surface resistivity, high notch impact strength, low-temperature use and the like, and the product has the advantages of low processing energy consumption, recyclability and the like, which also shows that: the modified polypropylene composite material provided by the embodiment of the invention has flame retardant, antistatic, rat bite preventing and impact resistant properties which can completely meet the use requirements of PP for pipelines, so that the modified polypropylene composite material is suitable for being used as a special material for outer pipes of electric double-wall pipelines.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (10)
1. The special material for the outer layer of the flame-retardant, antistatic, wear-resistant and rat-bite-resistant power pipeline is characterized by comprising the following components in parts by weight:
100 parts of polypropylene;
1-6 parts of ethylene-vinyl acetate copolymer;
1-6 parts of ethylene propylene diene monomer;
5-20 parts of unsaturated carboxylic acid graft copolymer of polyolefin elastomer;
5-10 parts of ultrahigh molecular weight polyethylene;
3-10 parts of phosphogypsum whiskers;
6-9 parts of decabromodiphenylethane;
2-3 parts of nano antimony trioxide;
1-6 parts of conductive graphite;
6-10 parts of nonanoic vanilloylamine,
0.2 to 1.0 percent of silane coupling agent;
1-6 parts of dicumyl peroxide,
0.4-0.6 part of antioxidant 1,1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane;
0.4-0.6 part of anti-aging agent 2-mercaptobenzimidazole;
0.4-0.6 part of calcium stearate.
2. The special material for the outer layer of the flame-retardant, antistatic, wear-resistant and rodent-resistant power pipeline as claimed in claim 1, wherein the polypropylene has a melt index of 0.29-0.3g/10min, is a copolymerized polypropylene with a trademark of 4220 or 4101, and is produced and sold by Yanshan petrochemical industry; the ethylene-vinyl acetate copolymer has the Vinyl Acetate (VA) content of 8-10% and the melt index of 0.6-0.9g/10min, and is sold by Yangzibasfu with the trade name V4110F;
the ethylene propylene diene monomer is Mooney viscosity of 38-52, the mark thereof is 4045, and is produced and sold by Jilin petrochemical industry;
the weight-average molecular weight of the ultra-high molecular weight polyethylene is 500-700 ten thousand, the mark number of the ultra-high molecular weight polyethylene is 4170, and the ultra-high molecular weight polyethylene is produced and sold by Takona;
the nonanoic vanilloylamine is produced and sold by a natural perfume oil factory of flowers in the Qingyuan region of Jian city;
the silane coupling agent is methacryloxy functional group silane with the trade name of KH-570, and is produced and sold by Nanjing to the front chemical industry Co.Ltd;
the dicumyl peroxide is manufactured and sold by akoma (orthodox) chemical limited;
the antioxidant 1,1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane is produced and sold by Tianmen Ganchang chemical Co., Ltd;
the anti-aging agent 2-mercaptobenzimidazole is produced and sold by Shanghai Signal chemical Co., Ltd;
calcium stearate and calcium stearate are produced and sold by Zichuan Ruifeng plastic additive factories.
3. The special material for the outer layer of the flame-retardant, antistatic, wear-resistant and rat-bite-proof power pipeline as claimed in claim 1, wherein the phosphogypsum whisker is prepared by the following method:
mixing the dried phosphogypsum whisker with an ethanol solution of methacryloxy functional group silane, and reacting to obtain the methacryloxy functional group silane modified phosphogypsum whisker, wherein the phosphogypsum whisker is preferably obtained by drying the phosphogypsum whisker at 80-100 ℃ for 6-10 hours in vacuum, more preferably, the size of the phosphogypsum whisker is 1-5 mu m, and the mass ratio of the phosphogypsum whisker to the methacryloxy functional group silane is 100: 1-200: 1, more preferably, the reaction conditions are: the temperature is 60-80 ℃ and the time is 4-6 h.
4. The special material for the outer layer of the flame-retardant, antistatic, wear-resistant and rat-bite-proof power pipeline as claimed in claim 1, wherein the decabromodiphenylethane is prepared by the following method:
mixing decabromodiphenylethane with an ethanol solution of methacryloxy functional group silane, and reacting to obtain methacryloxy functional group silane modified decabromodiphenylethane, wherein the decabromodiphenylethane is preferably obtained by drying decabromodiphenylethane at 80-100 ℃ for 6-10 hours in vacuum, and more preferably, the mass ratio of the decabromodiphenylethane to the methacryloxy functional group silane is 100: 1-200: 1, more preferably, the reaction conditions are: the temperature is 60-80 ℃ and the time is 4-6 h.
5. The special material for the outer layer of the flame-retardant, antistatic, wear-resistant and rat-bite-proof power pipeline as claimed in claim 1, wherein the antimony trioxide is prepared by the following method:
mixing antimony trioxide with an ethanol solution of methacryloxy functional group silane, and reacting to obtain methacryloxy functional group silane modified antimony trioxide, preferably, the antimony trioxide is obtained by drying the antimony trioxide at 80-100 ℃ for 6-10 hours in vacuum, more preferably, the mass ratio of the antimony trioxide to the methacryloxy functional group silane is 100: 1-200: more preferably, the supercritical reaction conditions are as follows: the temperature is 60-80 ℃ and the time is 4-6 h.
6. The special material for the outer layer of the flame-retardant, antistatic, wear-resistant and rat-bite-proof power pipeline as claimed in claim 1, wherein the conductive graphite is prepared by the following method:
mixing conductive graphite with an ethanol solution of methacryloxy functional silane, and performing supercritical reaction to obtain methacryloxy functional silane modified conductive graphite, preferably, the conductive graphite is obtained by drying the conductive graphite at 80-100 ℃ for 6-10 hours in vacuum, more preferably, the mass ratio of the conductive graphite to the methacryloxy functional silane is 100: 1-200: 1, more preferably, the reaction conditions are: the temperature is 40-60 deg.C, the time is 4-6h, and the pressure is 7.38-30 MPa.
7. The special material for the outer layer of the flame-retardant, antistatic, wear-resistant and rat-bite-proof power pipeline as claimed in claim 1, wherein the unsaturated carboxylic acid graft copolymer of the polyolefin elastomer is prepared by the following method:
adding butynedioic acid, polyolefin elastomer (POE) and dicumyl peroxide (DCP) into a double-screw extruder in proportion, and carrying out melt extrusion to obtain an unsaturated carboxylic acid graft copolymer of the polyolefin elastomer, wherein the preferred mass ratio of the butynedioic acid to the polyolefin elastomer (POE) to the dicumyl peroxide (DCP) is 1: 100: 0.1-3: 100: 0.3, preferably, the temperatures of the sections of the screw extruder from the feeding port of the twin-screw extruder to the twin-screw extrusion die head are respectively 90 ℃, 160 ℃, 210 ℃, 230 ℃, 225 ℃, and the main machine rotating speed is 200 and 400 revolutions per minute.
8. The special material for the outer layer of the flame-retardant, antistatic, wear-resistant and rat-bite-proof power pipeline as claimed in claim 7, wherein the polyolefin elastomer has a melt index of 0.5g/10min and a trademark of 8180, and is manufactured and sold by the Dow chemical industry.
9. The preparation method of the special material for the outer layer of the flame-retardant, antistatic, wear-resistant and rat-bite-proof power pipeline according to any one of claims 1 to 8 is characterized by comprising the following steps of:
mixing the preparation raw materials into uniform materials according to the proportion, and then extruding and granulating the uniformly mixed materials by a double screw rod with a micro-nano laminated stretching device, wherein preferably, the extrusion molding temperature is 230 ℃, the temperature of each section of a screw extruder from a feeding port to a feeding port of the micro-nano laminated stretching device is 90 ℃, 160 ℃, 210 ℃, 230 ℃ and 225 ℃, and the rotating speed of a main machine is 200-400 revolutions per minute. The temperature of each section from the feed inlet to the discharge outlet of the micro-nano laminated stretching device is 230 ℃.
10. Use of a flame-retardant, antistatic, wear-resistant and rat-bite-resistant power pipeline outer layer special material according to any one of claims 1 to 9 or the flame-retardant, antistatic, wear-resistant and rat-bite-resistant power pipeline outer layer special material prepared by the preparation method according to claim 9 in manufacturing a square power double-wall pipeline outer layer pipe.
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