CN103087380A - Microencapsulation red phosphorus fire retardation antistatic polyethylene pipe composition - Google Patents
Microencapsulation red phosphorus fire retardation antistatic polyethylene pipe composition Download PDFInfo
- Publication number
- CN103087380A CN103087380A CN2011103322573A CN201110332257A CN103087380A CN 103087380 A CN103087380 A CN 103087380A CN 2011103322573 A CN2011103322573 A CN 2011103322573A CN 201110332257 A CN201110332257 A CN 201110332257A CN 103087380 A CN103087380 A CN 103087380A
- Authority
- CN
- China
- Prior art keywords
- red phosphorus
- composition
- micro encapsulation
- polyethylene
- fire retardation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 42
- 239000000203 mixture Substances 0.000 title claims abstract description 41
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 40
- -1 polyethylene Polymers 0.000 title claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 42
- 239000007822 coupling agent Substances 0.000 claims abstract description 13
- 239000006229 carbon black Substances 0.000 claims abstract description 12
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 4
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 4
- 239000003063 flame retardant Substances 0.000 claims description 64
- 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 claims description 45
- 238000005538 encapsulation Methods 0.000 claims description 32
- 239000011248 coating agent Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 13
- 229920001903 high density polyethylene Polymers 0.000 claims description 10
- 239000004700 high-density polyethylene Substances 0.000 claims description 10
- 239000003112 inhibitor Substances 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 7
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 5
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 150000004645 aluminates Chemical class 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 3
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 3
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 3
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims 1
- 229920003023 plastic Polymers 0.000 abstract description 11
- 239000004033 plastic Substances 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 10
- 238000001125 extrusion Methods 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- LXWPJAGZRHTAOO-UHFFFAOYSA-N [Sb].[Br] Chemical compound [Sb].[Br] LXWPJAGZRHTAOO-UHFFFAOYSA-N 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000002270 dispersing agent Substances 0.000 abstract 1
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 abstract 1
- 229920013716 polyethylene resin Polymers 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 13
- 238000012360 testing method Methods 0.000 description 7
- 238000005065 mining Methods 0.000 description 6
- 239000003245 coal Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 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 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 229920003193 cis-1,4-polybutadiene polymer Polymers 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000003211 malignant effect Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 238000005464 sample preparation method Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical group [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a microencapsulation red phosphorus fire retardation antistatic polyethylene pipe composition, and belongs to the technical field of plastic processing. The composition comprises the following raw materials, by weight, 45-60 parts of a polyethylene resin, 30 parts of an electric conduction carbon black master batch, 6-10 parts of microencapsulation red phosphorus, 6-10 parts of a melamine isocyanurate, 1.0-3.0 parts of a coupling agent, 0.1-0.3 part of an antioxidant, and 1.0-3.0 parts of a dispersing agent. With the present invention, the problem of not good fire retardation effect during fire retardation of polyethylene through single microencapsulation red phosphorus is solved; a synergetic fire retardation agent MCA is added so as to reduce the amount of the red phosphorus and improve a fire retardation effect of the composition; the microencapsulation red phosphorus fire retardation antistatic polyethylene pipe composition is an environmental protection type material, and has characteristics of good extrusion processability and good mechanical property; and compared with the bromine-antimony fire retardation system, the composition has characteristics of low raw material cost, low density, good economic benefits, and good market application prospects.
Description
Technical field
The present invention relates to a kind of antistatic polyethylene pipe material composition of micro encapsulation red phosphorus flame-retardant, belong to technical field of plastic.
Background technology
Polyvinyl piping materials has the advantages such as inexpensive light weight, easy for installation, environmental protection, adds the promotion of national policy, is widely used in every field.Wherein, mineral polyethylene piping materials is except the physical and mechanical properties that should possess general plastic pipe, and the particular requirement that also should satisfy the colliery namely must have static resistance and self-extinguishing, and products of combustion must not have toxicity.Polyethylene is a kind of organic polymer material, and its volume specific resistance is very high, is 10
16-20Ω/cm will produce static through friction, and be gathered in frosting, and therefore possible initiation fire and gas explosion must be carried out antistatic modified to the polyvinyl resin of producing mining pipes.At present method of modifying commonly used is for to add graphitized carbon black in polyethylene, and the processing technology comparative maturity, and the concentration of graphitized carbon black reaches 6% when above, and the surface resistivity of the polyvinyl piping materials of production just can reach 10
6Below Ω, can satisfy the requirement of mining drainage gas pipe.The overwhelming majority in plastics is flammable at present, and is difficult for putting out, and the accident that causes because of the plastics burning has become a serious social concern.According to U.S. 1973 statistics, in the U.S., catch fire event 2,000,000 times of plastics approximately occurs every year; Japan's nineteen ninety-five statistics is because of plastics approximately 10,000 people of the casualties of catching fire; China's plastics malignant event that catches fire also happens occasionally.Therefore give high polymeric fire-retardant, to preventing fire spread and expansion, have very important significance.
China starts late to the research of fire retardant, static inhibitor, but development is very rapid.Mandatory national coal mine under the unified-allocation system whole use flame-retardant and anti-static travelling belts, safety net, ventilating duct, the cable etc. from January, 1991 emphasized of the former Chinese coal Department of Industry; The Ministry of Public Security, former the Ministry of Domestic Trade, former China National Textile Council have just issued " about actively promoting the use of flame-retardant textile and strengthening the notice of Production﹠Operations Management work " April nineteen ninety-five jointly; In society, increasing people produces keen interest to the application of flame-retardant and anti-static material, and these are all that research and development and the application of flame-retardant and anti-static material plays great pushing effect.
The fire retardant of high molecular polymer has a variety of, in the majority with halogen-containing, phosphorus, nitrogen, magnesium and aluminium, only add a large amount of phosphorous, boron, magnesium, aluminium fire retardant just can play fire retardation, but can have a strong impact on physical and mechanical properties and the electric property of superpolymer in superpolymer; Halogen-containing flame retardant is take organism as main, and this based flame retardant consumption is few, and is less, comparatively commonly used on the physical and mechanical properties impact of superpolymer.But due in recent years, bromide fire retardant and antimonous oxide price more and more higher makes the raw materials cost increasing degree of producing polythene mining tubing very large, seriously restricted the application of mining pipes.The smog that produces in fire-retardant process due to bromide fire retardant in addition also has certain toxicity, and along with the enhancing of social environment consciousness, its application also is subject to certain restrictions.So replacing in the urgent need to a kind of not only environmental protection but also the new fire retardant that can reduce fire-retardant cost aspect mining polyethylene anti-flaming.Phosphorus flame retardant is halogen-free flame retardants the earliest, is broadly divided into red phosphorus, ammonium polyphosphate, ammonium phosphate and phosphorus-nitrogen expansion type fire retardant.In order to control the release of phosphuret-(t)ed hydrogen, the technological development of micro encapsulation red phosphorus is very active.Material (capsule material) according to encapsulated red phosphorus can be divided into inorganic, organic and inorganic-three kinds of methods of organic composite coating.The inorganic coating material comprises aluminium hydroxide, magnesium hydroxide, zinc hydroxide etc.; The organic coating material comprises resol, melamine resin, furfuryl alcohol resin, aniline resin, epoxy resin etc.; The inorganic-organic hybrid coating material is first to coat one deck inorganic layer on red phosphorus, then coats one deck organic layer, and this method is the comparatively desirable method of present red phosphorus surface modification, and domestic research and comparison is active.
Micro encapsulation red phosphorus is mainly used in the fire-retardant and coating of various plastics, rubber, the fire-retardant finish of timber, such as: be used for the fire-retardant of the thermoplastic resins such as PE, EVA, PBT, PET, PP, PC, PA, also can be used for the fire-retardant of the thermosetting resin such as epoxy, phenolic aldehyde, unsaturated polyester and cis-1,4-polybutadiene rubber and ethylene-propylene rubber(EPR).At present, large usage quantity in non-halogen flame-retardant cable is desirable halogen-free flame-retardant cable fire retardant.But micro encapsulation red phosphorus does not generally use separately in polyethylene, because its flame retardant effect does not reach V-0 level (UL-94 standard) requirement.Micro encapsulation red phosphorus and magnesium hydroxide are compound excellent for the PE flame retardant effect, are easy to by the requirement of V-0 level, and both have significant synergistic effect.The red phosphorus consumption is 5-9 part, and the aluminium hydroxide consumption has good flame retardant effect when reaching more than 60 parts.Yet the Physical Mechanical loss of energy that the filler component of high consumption like this makes tubing in polythene mining tubing totally, even extruding pipe material is also without any use value.
Summary of the invention
Not enough according to prior art, technical problem to be solved by this invention is: the antistatic polyethylene pipe material composition that a kind of micro encapsulation red phosphorus flame-retardant is provided, solve the not good problem of the independent flame-proof polyethylene flame retardant effect of micro encapsulation red phosphorus, this flame-retardant system and antistatic master batch compound use can obtain having the pipe composition of excellent flame retardant properties, antistatic property and excellent mechanical performances.
The technical solution adopted for the present invention to solve the technical problems is: a kind of antistatic polyethylene pipe material composition of micro encapsulation red phosphorus flame-retardant is provided, it is characterized in that being comprised of the raw material of following parts by weight:
Polyvinyl resin: 45-60 part;
Graphitized carbon black masterbatch: 30 parts;
Micro encapsulation red phosphorus: 6-10 part;
Trimeric cyanamide isocyanurate: 6-10 part;
Coupling agent: 1.0-3.0 part;
Oxidation inhibitor: 0.1-0.3 part;
Dispersion agent: 1.0-3.0 part.
Described polyvinyl resin is the composition of high density polyethylene(HDPE) or high density polyethylene(HDPE) and linear low density polyethylene.
The carbon black concentration of described graphitized carbon black masterbatch is 20%, and vector resin is the composition of polyethylene or polyethylene and ethylene vinyl acetate (EVA) or ethylene-octene copolymer (POE).
Described micro encapsulation red phosphorus is the micro encapsulation red phosphorus of inorganic coating material, organic coating material or inorganic-organic hybrid coating material for coating base material.
Wherein the trimeric cyanamide isocyanurate is high nitrogen combustion inhibitor, and molecular formula is C
9H
9N
9O
3, molecular weight 255.2, white nontoxic powder, density 1.5-1.7.Trimeric cyanamide isocyanurate (being called for short MCA), stable below 300 ℃, decompose more than 600 ℃, have concurrently fire-retardant and multifunctional assistant lubricity.
Described dispersion agent is polyethylene wax, preferred polymeric type polyethylene wax.
Described oxidation inhibitor is that phosphoric acid ester and suffocated amine antioxidant mix use, preferably both mixes by the weight ratio of 1: 1.Phosphoric acid ester and suffocated amine antioxidant are selected plastic working industry various components used usually.
Described coupling agent is titanate coupling agent or aluminate coupling agent.
The antistatic polyethylene pipe material composition of micro encapsulation red phosphorus flame-retardant provided by the present invention, said composition has solved the not good problem of the independent flame-proof polyethylene flame retardant effect of micro encapsulation red phosphorus, this flame-retardant system and antistatic master batch compound use, can obtain having the pipe composition of excellent flame retardant properties, antistatic property and excellent mechanical performances, the performance of polyethylene extrusion tubing satisfies the index request of MT558.1-2006 (" plastic pipe for coal mine material part 1: polyvinyl piping materials ").
The antistatic polyethylene pipe material composition of red phosphorus flame-retardant, adopting micro encapsulation red phosphorus is main flame retardant, trimeric cyanamide isocyanurate (MCA) is synergistic fire retardant, and test shows, adopts MCA and micro encapsulation red phosphorus to act synergistically according to a certain percentage, not only can improve the flame retardant properties of composition, and because amount of flame-retardant agent is less, compare with bromine antimony flame-retardant system, material has not only kept physical and mechanical properties preferably, and cost is lower, and meets environmental requirement.
This invention first with polyethylene, graphitized carbon black masterbatch (concentration is 20%), micro encapsulation red phosphorus, MCA, coupling agent, dispersion agent and oxidation inhibitor weighing by a certain percentage, adds in high-speed mixer mixing time 10-15 minute.Add length-to-diameter ratio greater than extruding pelletization in 30 parallel double-screw extruder the material that mixes, extrusion temperature 150-200 ℃, material is polythene tube composition of the present invention after 60-80 ℃ of drying.
The antistatic polyethylene pipe material composition of micro encapsulation red phosphorus flame-retardant of the present invention can reach following physical index, and flame retardant properties reaches the requirement of UL-94 standard V-0 level, surface resistivity≤1.0 * 10
6Ω, tensile strength 〉=18.0MPa, elongation at break 〉=350%.Said composition has the good processing characteristics of extruding, and the flame-retardant and anti-static tubing high comprehensive performance of extrusion satisfies the requirement of the industry standard MT558.1-2006 of Ministry of Coal Industry.
The invention has the beneficial effects as follows:
1, solve the not good problem of the independent flame-proof polyethylene flame retardant effect of micro encapsulation red phosphorus, by adding synergistic fire retardant MCA, reduced the consumption of red phosphorus, improved the flame retardant effect of composition.
2, the antistatic polyethylene pipe material composition of micro encapsulation red phosphorus flame-retardant is a kind of ep-type material, has good processing characteristics and the good physical and mechanical properties extruded.
3, compare with bromine antimony flame-retardant system, the raw materials cost of said composition is low, and density is low, has good economic benefit and market application foreground.
Embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1～3
Table 1 is the embodiment of the present invention and Comparative Examples
| Raw material | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative Examples 4 | Comparative Examples 5 |
| High density polyethylene(HDPE) | 53.2 | 54.2 | 43.2 | 100 | 100 |
| Linear low density polyethylene | 10 | ||||
| 20% graphitized carbon black masterbatch | 30 | 30 | 30 | 30 | 30 |
| Micro encapsulation red phosphorus | 6 | 7 | 9 | 12 | 14 |
| MCA | 8 | 10 | 6 | ||
| Dispersion agent | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
| Titanate coupling agent | 1.0 | 1.0 | 1.0 | 1.0 | |
| Aluminate coupling agent | 1.0 | ||||
| Antioxidant 1010 | 0.15 | 0.15 | 0.15 | 0.15 | 0.15 |
| Irgasfos 168 | 0.15 | 0.15 | 0.15 | 0.15 | 0.15 |
The sample preparation methods of embodiment and comparative example:
First with polyethylene, graphitized carbon black masterbatch (concentration is 20%), micro encapsulation red phosphorus, MCA, coupling agent, dispersion agent and oxidation inhibitor weighing by a certain percentage, add in high-speed mixer mixing time 10-15 minute.Add length-to-diameter ratio greater than extruding pelletization in 30 parallel double-screw extruder the material that mixes, extrusion temperature 150-200 ℃, material is polythene tube composition of the present invention after 60-80 ℃ of drying.
The material of the above-mentioned embodiment of mixing and comparative example is hacked compressing tablet on the press of 180 ℃, print preheating 5 minutes on two rollers of 180 ℃, then pressurize 5 minutes is cooled to room temperature, and print is made the standard batten with impact mill, carry out performance test, the results are shown in Table 2.
Table 2 is the performance test results of embodiment and Comparative Examples
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 |
| Flame retardant properties | V-0 | V-0 | V-0 | V-2 | V-1 | V-0 |
| Oxygen index, % | 25.8 | 26.4 | 25.6 | 21.2 | 22.7 | 25.8 |
| Tensile strength, MPa | 20.5 | 19.8 | 19.2 | 19.8 | 19.7 | 18.8 |
| Elongation at break, % | 426 | 455 | 439 | 506 | 489 | 375 |
| Density, g/cm 3 | 1.08 | 1.07 | 1.08 | 1.04 | 1.05 | 1.18 |
| Surface resistivity, Ω | 3.0×10 5 | 5.7×10 5 | 2.1×10 5 | 7.8×10 4 | 1.2×10 5 | 2.6×10 4 |
Can find out from the performance test of table 2, compare with Comparative Examples 2 with comparative example 1, the present composition has higher oxygen index, and flame retardant properties all can reach the requirement of V-0 level, and surface resistivity reaches≤and 1.0 * 10
6The requirement of Ω; Compare with Comparative Examples 3, present composition density is less, and tensile strength and elongation at break are higher, and flame retardant properties is substantially suitable, but this invention composition does not have the flameless combustion phenomenon.Can find out by contrast, the present composition has good over-all properties, and property indices satisfies the standard-required of MT558.1, can be applied in the drainage gas pipe of colliery.
This invention composition is used for tube extrusion, the tubing surfaces externally and internally of extruding is smooth smooth, flawless, decomposition variable color line or obvious groove, depression, impurity and cut, pipe performance is qualified through national coal winning machinery quality supervision and test Spot detection, and the detected result of the flame retardant properties of tubing, physicals and conductivity sees Table respectively 3, table 4 and table 5.
Table 3 is the alcohol blast burner combustionproperty
Table 4 is physical property test
| Interventions Requested | Standard value | Measured value | Whether qualified |
| Flattening test | Leakless | Leakless | Qualified |
| Tensile strength, MPa | ≥9.0 | 19.9 | Qualified |
| Elongation at break, % | ≥300 | 432 | Qualified |
| The test drop impact | Leakless is without destroying | Leakless is without destroying | Qualified |
| Hydro-test | Ne-leakage is without destroying | Ne-leakage is without destroying | Qualified |
Table 5 is the conductivity test
| Interventions Requested | Standard value | Measured value | Whether qualified |
| Internal surface resistance mean value, Ω | ≤1.0×10 6 | 2.6×10 5 | Qualified |
| Outside surface resistance mean value, Ω | ≤1.0×10 6 | 3.4×10 5 | Qualified |
Claims (7)
1. the antistatic polyethylene pipe material composition of a micro encapsulation red phosphorus flame-retardant is characterized in that being comprised of the raw material of following parts by weight:
Polyvinyl resin: 45-60 part;
Graphitized carbon black masterbatch: 30 parts;
Micro encapsulation red phosphorus: 6-10 part;
Trimeric cyanamide isocyanurate: 6-10 part;
Coupling agent: 1.0-3.0 part;
Oxidation inhibitor: 0.1-0.3 part;
Dispersion agent: 1.0-3.0 part.
2. the antistatic polyethylene pipe material composition of micro encapsulation red phosphorus flame-retardant according to claim 1, is characterized in that described polyvinyl resin is the composition of high density polyethylene(HDPE) or high density polyethylene(HDPE) and linear low density polyethylene.
3. the antistatic polyethylene pipe material composition of micro encapsulation red phosphorus flame-retardant according to claim 1, the carbon black concentration that it is characterized in that described graphitized carbon black masterbatch is 20%, and vector resin is the composition of polyethylene or polyethylene and ethylene vinyl acetate or ethylene-octene copolymer.
4. the antistatic polyethylene pipe material composition of micro encapsulation red phosphorus flame-retardant according to claim 1, is characterized in that described micro encapsulation red phosphorus is the micro encapsulation red phosphorus of inorganic coating material, organic coating material or inorganic-organic hybrid coating material for coating base material.
5. the antistatic polyethylene pipe material composition of micro encapsulation red phosphorus flame-retardant according to claim 1, is characterized in that described dispersion agent is polyethylene wax, preferred polymeric type polyethylene wax.
6. the antistatic polyethylene pipe material composition of micro encapsulation red phosphorus flame-retardant according to claim 1, is characterized in that described oxidation inhibitor is that phosphoric acid ester and suffocated amine antioxidant mix use, preferably both mixes by the weight ratio of 1: 1.
7. the antistatic polyethylene pipe material composition of micro encapsulation red phosphorus flame-retardant according to claim 1, is characterized in that described coupling agent is titanate coupling agent or aluminate coupling agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110332257.3A CN103087380B (en) | 2011-10-27 | 2011-10-27 | The antistatic polyethylene pipe material composition that microencapsulated powder oil is fire-retardant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110332257.3A CN103087380B (en) | 2011-10-27 | 2011-10-27 | The antistatic polyethylene pipe material composition that microencapsulated powder oil is fire-retardant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103087380A true CN103087380A (en) | 2013-05-08 |
| CN103087380B CN103087380B (en) | 2015-09-23 |
Family
ID=48200536
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110332257.3A Expired - Fee Related CN103087380B (en) | 2011-10-27 | 2011-10-27 | The antistatic polyethylene pipe material composition that microencapsulated powder oil is fire-retardant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103087380B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106633344A (en) * | 2016-11-30 | 2017-05-10 | 山东东方新材料有限公司 | Antistatic functional masterbatch, production process thereof, and production process of polyethylene pipes |
| CN109616245A (en) * | 2018-12-25 | 2019-04-12 | 西安双盛电线电缆有限责任公司 | Photovoltaic cable and its preparation process |
| CN109776919A (en) * | 2019-01-23 | 2019-05-21 | 保定华月胶带有限公司 | Non-halogen flame-proof ethylene thickener plasticizing process |
| CN110951137A (en) * | 2019-11-26 | 2020-04-03 | 湖北祥源新材科技股份有限公司 | Flame-retardant antistatic irradiation crosslinked polyethylene colored foam and preparation method thereof |
| CN111635571A (en) * | 2020-06-03 | 2020-09-08 | 杭州联通管业有限公司 | Flame-retardant polyethylene communication pipe and preparation method thereof |
| CN113321823A (en) * | 2021-06-25 | 2021-08-31 | 山东东宏管业股份有限公司 | Polyethylene red phosphorus flame-retardant master batch and preparation method and application thereof |
| CN114933750A (en) * | 2022-03-02 | 2022-08-23 | 上海上塑控股（集团）有限公司 | HDPE flame-retardant pipe for building drainage |
| CN116836590A (en) * | 2022-03-25 | 2023-10-03 | 国家能源投资集团有限责任公司 | Coated crosslinked polyethylene composition, crosslinkable polyethylene blend and composite article |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101153094A (en) * | 2007-09-05 | 2008-04-02 | 山东方大工程有限责任公司 | Material special for polythene beam tube and method of producing the same |
| CN101402754A (en) * | 2008-11-10 | 2009-04-08 | 杨积位 | Flame-proof antistatic master material and production method thereof |
| CN101456962A (en) * | 2008-12-29 | 2009-06-17 | 黄华昌 | High-content red phosphorus flame-retardant master batch |
-
2011
- 2011-10-27 CN CN201110332257.3A patent/CN103087380B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101153094A (en) * | 2007-09-05 | 2008-04-02 | 山东方大工程有限责任公司 | Material special for polythene beam tube and method of producing the same |
| CN101402754A (en) * | 2008-11-10 | 2009-04-08 | 杨积位 | Flame-proof antistatic master material and production method thereof |
| CN101456962A (en) * | 2008-12-29 | 2009-06-17 | 黄华昌 | High-content red phosphorus flame-retardant master batch |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106633344A (en) * | 2016-11-30 | 2017-05-10 | 山东东方新材料有限公司 | Antistatic functional masterbatch, production process thereof, and production process of polyethylene pipes |
| CN109616245A (en) * | 2018-12-25 | 2019-04-12 | 西安双盛电线电缆有限责任公司 | Photovoltaic cable and its preparation process |
| CN109776919A (en) * | 2019-01-23 | 2019-05-21 | 保定华月胶带有限公司 | Non-halogen flame-proof ethylene thickener plasticizing process |
| CN110951137A (en) * | 2019-11-26 | 2020-04-03 | 湖北祥源新材科技股份有限公司 | Flame-retardant antistatic irradiation crosslinked polyethylene colored foam and preparation method thereof |
| CN111635571A (en) * | 2020-06-03 | 2020-09-08 | 杭州联通管业有限公司 | Flame-retardant polyethylene communication pipe and preparation method thereof |
| CN111635571B (en) * | 2020-06-03 | 2023-03-03 | 杭州联通管业有限公司 | Flame-retardant polyethylene communication pipe and preparation method thereof |
| CN113321823A (en) * | 2021-06-25 | 2021-08-31 | 山东东宏管业股份有限公司 | Polyethylene red phosphorus flame-retardant master batch and preparation method and application thereof |
| CN114933750A (en) * | 2022-03-02 | 2022-08-23 | 上海上塑控股（集团）有限公司 | HDPE flame-retardant pipe for building drainage |
| CN116836590A (en) * | 2022-03-25 | 2023-10-03 | 国家能源投资集团有限责任公司 | Coated crosslinked polyethylene composition, crosslinkable polyethylene blend and composite article |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103087380B (en) | 2015-09-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103087380B (en) | The antistatic polyethylene pipe material composition that microencapsulated powder oil is fire-retardant | |
| CN102617915B (en) | Anti-mildew halogen-free flame-retardant smoke-suppression wood-plastic composite material and preparation method thereof | |
| CN101260228B (en) | Method for preparing natural fiber/polylactic acid composite material with anti-flaming function | |
| CN102993537A (en) | Weather-proof flame retardation antistatic crosslinking polyethylene tubing, preparation method and application | |
| CN103030879A (en) | Environment-friendly flame retardance permanent antistatic polypropylene material and preparation method of environment-friendly flame retardance permanent antistatic polypropylene material | |
| CN101402754B (en) | Flame-proof antistatic master material and production method thereof | |
| CN101469129A (en) | Flame-retardant antistatic reinforced nylon 6 composition and preparation | |
| CN102964667B (en) | Halogen-free flame-retardant polyethylene composite material and preparation method thereof | |
| CN1962746A (en) | Expansion type flame-proof smoke-suppressing soft polyvinyl chloride composition and its preparation method | |
| CN102352087B (en) | Antistatic flame-retardant acrylonitrile butadiene styrene (ABS) rubber material and preparation method thereof | |
| CN106700525B (en) | A kind of HI high impact halogen-free flameproof POK/PA alloy material | |
| CN108410160A (en) | A kind of fire-retardant TPU cable jacket materials and preparation method thereof with electro-magnetic screen function | |
| CN103013081B (en) | High temperature resistant scratch resistant halogen-free flame retardant polycarbonate film | |
| CN101429302A (en) | Halogen free flame-proof composite material of polythene and preparation method thereof | |
| CN104140598A (en) | Halogen-free flame-retardance anti-static polypropylene composite material and preparation methods thereof | |
| CN103059443A (en) | Polyvinyl chloride wire and cable material with good flame resistance | |
| CN102875953B (en) | Halogen-free flame retardant ABS (Acrylonitrile Butadiene StyreneAcrylonitrile Butadiene Styrene) material | |
| CN102924884A (en) | PBT (polybutylece terephthalate) composite and preparation method thereof | |
| CN103172920A (en) | Environment-friendly flame-retardant anti-static polyethylene mining tube | |
| CN108102359A (en) | A kind of environmentally protective, high-performance, high CTI flame-retardant reinforced nylon materials and preparation method thereof | |
| CN107189324A (en) | A kind of electronic engineering cable elastomer sheathing material and preparation method thereof | |
| CN108070198A (en) | A kind of flame-retardant and anti-static polyformaldehyde composite material and preparation method thereof | |
| CN103059447A (en) | Environment-friendly flame retardant polyvinyl chloride wire and cable material | |
| CN102816405B (en) | Low-smoke halogen-free flame-retardant thermoplastic elastomer and preparation method thereof | |
| CN103613913B (en) | A kind of Halogen-free flame-retardant thermoplastic polyester elastomer material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Microencapsulation red phosphorus fire retardation antistatic polyethylene pipe composition Effective date of registration: 20171218 Granted publication date: 20150923 Pledgee: Qi Shang bank, Limited by Share Ltd, Binzhou branch Pledgor: SHANDONG YUANYANG PLASTIC INDUSTRIAL CO., LTD. Registration number: 2017370000198 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20190605 Granted publication date: 20150923 Pledgee: Qi Shang bank, Limited by Share Ltd, Binzhou branch Pledgor: SHANDONG YUANYANG PLASTIC INDUSTRIAL CO., LTD. Registration number: 2017370000198 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Microencapsulation red phosphorus fire retardation antistatic polyethylene pipe composition Effective date of registration: 20190610 Granted publication date: 20150923 Pledgee: Qi Shang bank, Limited by Share Ltd, Binzhou branch Pledgor: SHANDONG YUANYANG PLASTIC INDUSTRIAL CO., LTD. Registration number: 2019370000124 |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150923 Termination date: 20191027 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20201105 Granted publication date: 20150923 Pledgee: Qi Shang bank Limited by Share Ltd. Binzhou branch Pledgor: SHANDONG YUANYANG PLASTIC INDUSTRIAL Co.,Ltd. Registration number: 2019370000124 |