CN117534894B - Antistatic flame-retardant polyethylene composite material and preparation method and application thereof - Google Patents
Antistatic flame-retardant polyethylene composite material and preparation method and application thereof Download PDFInfo
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- CN117534894B CN117534894B CN202410032085.5A CN202410032085A CN117534894B CN 117534894 B CN117534894 B CN 117534894B CN 202410032085 A CN202410032085 A CN 202410032085A CN 117534894 B CN117534894 B CN 117534894B
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 79
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 65
- -1 polyethylene Polymers 0.000 title claims abstract description 59
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 56
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 239000004114 Ammonium polyphosphate Substances 0.000 claims abstract description 36
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims abstract description 36
- 229920001276 ammonium polyphosphate Polymers 0.000 claims abstract description 36
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 32
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 31
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 31
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 30
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 30
- 239000003963 antioxidant agent Substances 0.000 claims description 13
- 230000003078 antioxidant effect Effects 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000002216 antistatic agent Substances 0.000 claims description 10
- 239000007822 coupling agent Substances 0.000 claims description 10
- 239000000314 lubricant Substances 0.000 claims description 10
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- 238000005065 mining Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229920001903 high density polyethylene Polymers 0.000 claims description 5
- 239000004700 high-density polyethylene Substances 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 4
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 4
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 4
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 claims description 2
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 2
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 11
- 230000002195 synergetic effect Effects 0.000 abstract description 9
- 229920000642 polymer Polymers 0.000 abstract description 5
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 5
- 238000000354 decomposition reaction Methods 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 15
- 239000000463 material Substances 0.000 description 10
- 230000018044 dehydration Effects 0.000 description 8
- 238000006297 dehydration reaction Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 5
- 239000000347 magnesium hydroxide Substances 0.000 description 5
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000779 smoke Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000002955 isolation Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 2
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 239000012796 inorganic flame retardant Substances 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical group [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- JQYOCVPEXWBLGO-UHFFFAOYSA-N [N].[Si].[P] Chemical compound [N].[Si].[P] JQYOCVPEXWBLGO-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
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- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229960003753 nitric oxide Drugs 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
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Abstract
The invention discloses an antistatic flame-retardant polyethylene composite material, and a preparation method and application thereof, and belongs to the technical field of modified polyethylene composite materials. The invention takes two components of ammonium polyphosphate and nano montmorillonite as main flame retardants, and aluminum hydroxide and magnesium oxide as auxiliary flame retardants, thus playing a role of synergistic flame retardance. The magnesium oxide can not only enhance the thermal decomposition resistance of the polymer, but also lighten the decomposition effect of the acid flame retardant on the polyethylene and improve the flame retardant effect of the flame retardant. The finally prepared antistatic flame-retardant polyethylene composite material has good flame retardant property, good mechanical property and good application prospect.
Description
Technical Field
The invention belongs to the technical field of modified polyethylene composite materials, and particularly relates to an antistatic flame-retardant polyethylene composite material, and a preparation method and application thereof.
Background
In the current society, the polymer material has penetrated into various aspects of clothing, food, living, running and the like of people, is widely applied to the fields of building, medical treatment, automobiles and the like, and is indispensible from human life. The common material of the pipe in the mineral exploitation field, namely the polyolefin material, is very easy to burn, a large amount of heat can be released in the burning process and thick smoke is generated, and meanwhile, the generated molten drops are easy to ignite other objects, so that great hidden danger is brought to personnel and engineering safety. In addition, polyolefin belongs to a high-insulation material, and under the conditions of friction, extrusion and the like, static electricity is easily generated and accumulated, so that static electricity induction, electric shock and product production barriers are often caused, and even fire and explosion accidents can be caused in severe cases, and the production and use safety is directly influenced.
Polyethylene is nontoxic, odorless, low-temperature resistant, capable of being subjected to corrosion of most acid and alkali, has very stable physical and chemical properties, is commonly used in the fields of building, aerospace, power cables, household life, electrical appliances, and the like, but has an oxygen index of only 17.4, is extremely easy to burn in air, has high burning speed, releases a large amount of smoke and heat, and is easy to generate molten drops, so that the polyethylene material used alone has a certain fire risk.
Many researches prove that the probability of fire disaster caused by the flame retardant treatment can be fundamentally reduced by carrying out the flame retardant treatment on the polyethylene, compared with the pure polyethylene, the flame retardant treatment is difficult to burn on the polyethylene material, the flame propagation speed after burning is reduced, and the fire disaster safety in practical application is obviously improved. In order to make the polyethylene have certain flame retardant property, adding the flame retardant in the processing process is a simple and effective method. Flame retardants can be broadly divided into three categories: halogen flame retardants, inorganic flame retardants, and intumescent flame retardants. Among them, halogen-based flame retardants have been used for the earliest time. The flame retardant has high flame retardant efficiency, can achieve better flame retardant effect by only adding a small amount into the composite material, has moderate price, multiple varieties and wide application range, and is a traditional flame retardant. However, it has serious drawbacks, such as that the smoke generated during the flame-retardant process is large, and toxic gases such as hydrogen halide are released, and the brominated flame retardant also generates toxic and carcinogenic dioxin, which seriously threatens the health of human bodies and the safety of the environment. Therefore, the field of polyethylene flame retardance is gradually developed towards the directions of no halogen, low smoke and low toxicity. In the prior art, inorganic flame retardants such as phosphorus-containing flame retardants and nitrogen-containing flame retardants are adopted to improve the flame retardant property of polyethylene to a certain extent, but the use requirements of mining pipes with high fire resistance and antistatic requirements still cannot be met. Moreover, the prior art mostly improves the fire resistance of polyethylene by adding a large amount of flame retardant, which is inevitably accompanied by a decrease in the mechanical properties of polyethylene. Therefore, development of a flame-retardant antistatic mining polyethylene composite material is urgently needed to meet the rapid development requirement of the mining pipe industry.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an antistatic flame-retardant polyethylene composite material, a preparation method and application thereof, wherein the antistatic flame-retardant polyethylene composite material has the advantages of wide raw material sources, low energy consumption and low production cost, has good flame-retardant and antistatic properties, can meet the use requirements of mining pipes, and has good application prospects.
The aim of the invention is achieved by the following technical scheme.
In a first aspect, the invention provides an antistatic flame-retardant polyethylene composite material, which comprises the following components in parts by weight:
60-80 parts of polyethylene, 10-20 parts of ethylene-vinyl acetate copolymer, 5-12 parts of ammonium polyphosphate, 5-12 parts of nano montmorillonite, 3-8 parts of aluminum hydroxide, 2-6 parts of magnesium oxide, 3-8 parts of antistatic agent, 1-5 parts of coupling agent, 1-3 parts of lubricant and 1-3 parts of antioxidant.
The invention takes the ethylene-vinyl acetate copolymer (EVA) as the toughening filler of the polyethylene, not only can improve the mechanical property of the polyethylene, but also can improve the compatibility of the polyethylene and inorganic powder, save the addition of compatilizer, reduce the cost and further improve the mechanical property of the composite material. According to the invention, ammonium polyphosphate (APP) and nano montmorillonite are used as main flame retardants, and aluminum hydroxide and magnesium oxide are used as auxiliary flame retardants, so that a synergistic effect can be achieved. Ammonium polyphosphate belongs to inorganic phosphorus-nitrogen flame retardants, phosphoric acid, metaphosphoric acid and active free radicals are generated during thermal decomposition, the active free radicals can capture active free radicals generated by polymer combustion to terminate chain reaction, and the phosphoric acid and metaphosphoric acid can be attached to the surface of a polyethylene matrix to isolate oxygen and have the function of dehydration and char formation. The nano montmorillonite is silicate material, and can generate oxygen-insulating heat-insulating protective layer containing-Si-O-and-Si-C-when burning. The ammonium polyphosphate and the nano montmorillonite can play a role in synergistic flame retardance of phosphorus-silicon-nitrogen.
Meanwhile, when aluminum hydroxide is decomposed by heating, a large amount of heat is absorbed by dehydration, so that the ignition time of the material is delayed; the concentration of oxygen can be diluted by the water vapor released by dehydration, so that the degradation of materials is reduced; finally, al generated by decomposing aluminum hydroxide 2 O 3 Can form a protective layer together with charring matters generated by burning the surface of the resin, and has the functions of isolation and flame retardance. The aluminum hydroxide is selected as the metal hydroxide flame retardant, because the aluminum hydroxide has lower dehydration temperature (the dehydration temperature of the aluminum hydroxide is 200-300 ℃ and the dehydration temperature of the magnesium hydroxide is 350-500 ℃) than the magnesium hydroxide, and the aluminum hydroxide is used as the metal hydroxide flame retardantCan more effectively prevent the occurrence of fire and generate Al in advance 2 O 3 Can play a role of isolation and flame retardance together with ammonium polyphosphate and montmorillonite. However, ammonium polyphosphate generally has problems of moisture absorption and migration and precipitation during processing, and acidic substances such as phosphoric acid are generated even when exposed to high temperature for a long period of time. In order to solve the above problems, the stability of the ammonium polyphosphate flame retardant and the flame retardancy of the composite material can be improved by adding magnesium oxide to the raw material. Compared with oxides such as alumina, the magnesium oxide has stronger water absorption, and meanwhile, the water absorption is lower than that of calcium oxide, so that the magnesium oxide can be prevented from excessively absorbing moisture in the air. Therefore, the magnesium oxide can adsorb the water vapor released by the material in the processing process, and prevent the phenomenon of moisture absorption and migration of ammonium polyphosphate. Meanwhile, the magnesium oxide has excellent thermal stabilization effect, and can enhance the thermal decomposition resistance of the polymer; in addition, acidic micromolecules decomposed in the high-temperature processing process of the flame retardant react with magnesium oxide preferentially, so that the decomposition effect of acidic substances on polyethylene can be reduced.
The polyethylene is at least one of high-density polyethylene and linear low-density polyethylene.
The density of the high-density polyethylene is 0.94-0.95 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or the linear low density polyethylene has a density of 0.90 to 0.93g/cm 3 。
The antistatic agent is at least one of carbon black, carbon nano tube and graphene.
The coupling agent is at least one of KH-550, KH-560, KH-570 and KH-590.
The lubricant is at least one of ethylene bis-stearamide, stearate, oleamide and erucamide.
The antioxidant is at least one of antioxidant 1010, antioxidant 168 and antioxidant DSTP.
Further, the antistatic flame-retardant polyethylene composite material comprises the following components in parts by weight: 70 parts of polyethylene, 15 parts of ethylene-vinyl acetate copolymer, 8 parts of ammonium polyphosphate, 8 parts of nano montmorillonite, 4 parts of aluminum hydroxide, 4 parts of magnesium oxide, 4 parts of antistatic agent, 4 parts of coupling agent, 2 parts of lubricant and 2 parts of antioxidant.
In a second aspect of the present invention, there is provided a method for preparing the antistatic flame retardant polyethylene composite material, comprising the steps of:
weighing polyethylene, ethylene-vinyl acetate copolymer, antistatic agent, coupling agent, lubricant and antioxidant according to parts by weight, uniformly mixing by using a high-speed stirrer, and adding into a double-screw extruder through a main feeding port; uniformly mixing ammonium polyphosphate, nano montmorillonite, aluminum hydroxide and magnesium oxide, adding the mixture into a double-screw extruder through a side feeding port, and then extruding and granulating to obtain the antistatic flame-retardant polyethylene composite material; wherein, the high-speed stirrer is mixed for 5 to 20 minutes at the temperature of 60 to 80 ℃ and the rotating speed of 600 to 1200 r/min;
in the extrusion granulation process, parameters of the double-screw extruder are as follows: 160-170 ℃ in the first area, 170-175 ℃ in the second area, 175-185 ℃ in the third area, 185-200 ℃ in the fourth area, 185-200 ℃ in the fifth area, 170-185 ℃ in the head die and 60-200 r/min in the screw rotating speed.
In a third aspect of the invention, the invention provides an application of the antistatic flame-retardant polyethylene composite material, wherein the antistatic flame-retardant polyethylene composite material is used for preparing mining pipes.
The invention has the beneficial effects that:
(1) The material has wide sources, low production cost, simple production process and excellent flame-retardant and antistatic properties.
(2) The invention takes two components of ammonium polyphosphate and nano montmorillonite as main flame retardant, and aluminum hydroxide and magnesium oxide are taken as a third component together, thus playing a role of synergistic flame retardance. The ammonium polyphosphate and the nano montmorillonite can play a role in synergistic flame retardance of phosphorus, silicon and nitrogen, and Al generated by decomposing aluminum hydroxide 2 O 3 Can play a role of isolating and flame-retarding barrier together with ammonium polyphosphate and montmorillonite. The magnesium oxide can not only enhance the thermal decomposition resistance of the polymer, but also lighten the decomposition effect of acidic substances on the polyethylene and improve the flame retardant effect of the flame retardant.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The formulation (unit: parts by weight) of the examples provided by the invention is shown in table 1 below:
wherein, except for the other description, the raw material components in the examples and comparative examples in Table 1 are identical in kind selection, and the components are specifically:
the polyethylene is high density polyethylene with the density of 0.94-0.95 g/cm 3 ；
The antistatic agent is graphene;
the coupling agent is KH-550;
the lubricant is ethylene bis-stearamide;
the antioxidant is a compound antioxidant with the mass ratio of the antioxidant 1010 to the antioxidant 168 being 1:1.
Comparative example 1
The components and the proportions are basically the same as those of the embodiment 3, except that the components and the proportions of the ammonium polyphosphate, the nano montmorillonite, the aluminum hydroxide and the magnesium oxide are respectively 0 part, 12 parts, 6 parts and 6 parts.
Comparative example 2
The components and the proportions are basically the same as those of the embodiment 3, except that the components and the proportions of ammonium polyphosphate, nano montmorillonite, aluminum hydroxide and magnesium oxide are respectively 12 parts, 0 part, 6 parts and 6 parts.
Comparative example 3
The components and the proportions are basically the same as those of the embodiment 3, except that the components and the proportions of ammonium polyphosphate, nano montmorillonite, aluminum hydroxide and magnesium oxide are respectively 12 parts, 0 part and 0 part.
Comparative example 4
The components and the proportions are basically the same as those of the embodiment 3, except that 9 parts of ammonium polyphosphate, 9 parts of nano montmorillonite, 0 part of aluminum hydroxide and 6 parts of magnesium oxide are respectively adopted.
Comparative example 5
The components and the proportions are basically the same as those of the embodiment 3, except that 9 parts of ammonium polyphosphate, 9 parts of nano montmorillonite, 6 parts of aluminum hydroxide and 0 part of magnesium oxide are respectively adopted.
Comparative example 6
The components and the proportions are basically the same as those of the embodiment 3, except that the ammonium polyphosphate, the nano montmorillonite, the aluminum hydroxide and the magnesium oxide are respectively 20 parts, 8 parts, 4 parts and 4 parts.
Comparative example 7
The components and the proportions are basically the same as those of the embodiment 3, except that the components and the proportions of the ammonium polyphosphate, the nano montmorillonite, the aluminum hydroxide and the magnesium oxide are respectively 2 parts, 8 parts, 4 parts and 4 parts.
Comparative example 8
The composition and the proportions thereof were substantially the same as in example 3 except that 4 parts of aluminum hydroxide was replaced with 4 parts of magnesium hydroxide.
The raw material components in examples 1-9 and comparative examples 1-8 were prepared as follows:
weighing polyethylene, ethylene-vinyl acetate copolymer, antistatic agent, coupling agent, lubricant and antioxidant according to parts by weight, uniformly mixing by using a high-speed stirrer, and adding into a double-screw extruder through a main feeding port; uniformly mixing ammonium polyphosphate, nano montmorillonite, aluminum hydroxide and magnesium oxide, adding the mixture into a double-screw extruder through a side feeding port, and then extruding and granulating to obtain the antistatic flame-retardant polyethylene composite material; wherein, the high-speed stirrer is mixed for 8min at the temperature of 60 ℃ and the rotating speed of 700 r/min;
in the extrusion granulation process, parameters of the double-screw extruder are as follows: the rotation speed of the screw is 100r/min at 165 ℃ in the first region, 170 ℃ in the second region, 180 ℃ in the third region, 190 ℃ in the fourth region, 190 ℃ in the fifth region and 175 ℃ in the head die.
The antistatic flame retardant polyethylene composite materials prepared in examples 1 to 9 and comparative examples 1 to 8 were subjected to the test of the relevant performance indexes, and the test results are shown in tables 2 to 3 below;
it can be seen from comparative examples 1 to 8 and examples 1 to 9 that: by taking two components of ammonium polyphosphate and nano montmorillonite as main flame retardants, aluminum hydroxide and magnesium oxide as auxiliary flame retardants: the ammonium polyphosphate and the nano montmorillonite can play a role in synergistic flame retardance of phosphorus, silicon and nitrogen, and aluminum hydroxide absorbs a large amount of heat due to dehydration when being heated and decomposed, so that Al is generated in advance 2 O 3 Can play a role of isolation and flame retardance together with ammonium polyphosphate and montmorillonite. The magnesium oxide can not only enhance the thermal decomposition resistance of the polymer, but also prevent the moisture absorption phenomenon of ammonium polyphosphate. The addition of the components not only solves the technical problem of the reduction of mechanical properties of the polyethylene composition caused by the addition of the flame retardant, but also improves the flame retardant effect of the flame retardant, and has good application prospect.
Specifically, it can be seen from comparative examples 1 to 5 and example 3 that: the ammonium polyphosphate is used as an inorganic phosphorus-nitrogen flame retardant and plays a synergistic flame retardant effect of phosphorus, silicon and nitrogen with the nano montmorillonite. Aluminum hydroxide delays the ignition time of the material, and Al is generated 2 O 3 Can play a role of isolating and flame retarding together with ammonium polyphosphate, montmorillonite and magnesia. The magnesium oxide can lighten the decomposition effect of acidic substances on polyethylene, prevent the flame retardants such as ammonium polyphosphate and the like from absorbing moisture and deteriorating, and strengthen the stability of a matrix. The ammonium polyphosphate, the nano montmorillonite, the aluminum hydroxide and the magnesium oxide together play a role in improving the flame retardant grade and the oxygen index.
It can be seen from comparative examples 6 to 7 and example 3 that: the addition of the flame retardant is not as good as the addition of a large amount of flame retardant, which is not only unfavorable for the improvement of flame retardant property, but also can lead to the reduction of mechanical property of the composite material due to the poor compatibility of the flame retardant as inorganic filler and matrix resin.
As can be seen from comparative example 8 and examples 1 to 9: after the aluminum hydroxide is replaced by the magnesium hydroxide, the magnesium hydroxide has a flame retardant hysteresis effect due to higher dehydration temperature, and is unfavorable for constructing a synergistic flame retardant system with ammonium polyphosphate and montmorillonite.
In conclusion, the invention takes two components of ammonium polyphosphate and nano montmorillonite as main flame retardants, and takes aluminum hydroxide and magnesium oxide as a third component together to play a role of synergistic flame retardance. The flame retardant property of the polyethylene composite material is improved to the maximum extent, and simultaneously, the good mechanical property is maintained.
While the invention has been described in detail in the foregoing general description and specific examples, it will be apparent to those skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (10)
1. The antistatic flame-retardant polyethylene composite material is characterized by comprising the following components in parts by weight:
60-80 parts of polyethylene, 10-20 parts of ethylene-vinyl acetate copolymer, 5-12 parts of ammonium polyphosphate, 5-12 parts of nano montmorillonite, 3-8 parts of aluminum hydroxide, 2-6 parts of magnesium oxide, 3-8 parts of antistatic agent, 1-5 parts of coupling agent, 1-3 parts of lubricant and 1-3 parts of antioxidant.
2. The antistatic flame retardant polyethylene composite according to claim 1, wherein said polyethylene is at least one of high density polyethylene, linear low density polyethylene.
3. An antistatic flame retardant polyethylene composite material as claimed in claim 2, characterized in thatCharacterized in that the density of the high-density polyethylene is 0.94-0.95 g/cm 3 ；
And/or the linear low density polyethylene has a density of 0.90 to 0.93g/cm 3 。
4. The antistatic flame retardant polyethylene composite material according to claim 1, wherein said antistatic agent is at least one of carbon black, carbon nanotubes, graphene.
5. The antistatic flame retardant polyethylene composite according to claim 1, wherein said coupling agent is at least one of KH-550, KH-560, KH-570, KH-590.
6. The antistatic flame retardant polyethylene composite according to claim 1, wherein said lubricant is at least one of ethylene bisstearamide, stearate, oleamide, erucamide.
7. The antistatic flame retardant polyethylene composite material according to claim 1, wherein said antioxidant is at least one of antioxidant 1010, antioxidant 168, antioxidant DSTP.
8. The antistatic flame retardant polyethylene composite material according to claim 1, comprising the following components in parts by weight: 70 parts of polyethylene, 15 parts of ethylene-vinyl acetate copolymer, 8 parts of ammonium polyphosphate, 8 parts of nano montmorillonite, 4 parts of aluminum hydroxide, 4 parts of magnesium oxide, 4 parts of antistatic agent, 4 parts of coupling agent, 2 parts of lubricant and 2 parts of antioxidant.
9. The method for preparing the antistatic flame retardant polyethylene composite material according to claim 1, comprising the steps of:
weighing polyethylene, ethylene-vinyl acetate copolymer, antistatic agent, coupling agent, lubricant and antioxidant according to parts by weight, uniformly mixing by using a high-speed stirrer, and adding into a double-screw extruder through a main feeding port; uniformly mixing ammonium polyphosphate, nano montmorillonite, aluminum hydroxide and magnesium oxide, adding the mixture into a double-screw extruder through a side feeding port, and then extruding and granulating to obtain the antistatic flame-retardant polyethylene composite material; wherein, the high-speed stirrer is mixed for 5 to 20 minutes at the temperature of 60 to 80 ℃ and the rotating speed of 600 to 1200 r/min;
in the extrusion granulation process, parameters of the double-screw extruder are as follows: 160-170 ℃ in the first area, 170-175 ℃ in the second area, 175-185 ℃ in the third area, 185-200 ℃ in the fourth area, 185-200 ℃ in the fifth area, 170-185 ℃ in the head die and 60-200 r/min in the screw rotating speed.
10. Use of an antistatic flame retardant polyethylene composite according to any of claims 1-8 for the preparation of mining pipes.
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