CN116554584A - Flame-retardant PE communication pipe and preparation method thereof - Google Patents
Flame-retardant PE communication pipe and preparation method thereof Download PDFInfo
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- CN116554584A CN116554584A CN202310694150.6A CN202310694150A CN116554584A CN 116554584 A CN116554584 A CN 116554584A CN 202310694150 A CN202310694150 A CN 202310694150A CN 116554584 A CN116554584 A CN 116554584A
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 121
- 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 120
- 238000004891 communication Methods 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000004698 Polyethylene Substances 0.000 claims abstract description 116
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 56
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 20
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 20
- 229920013716 polyethylene resin Polymers 0.000 claims abstract description 18
- 230000002195 synergetic effect Effects 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000000314 lubricant Substances 0.000 claims abstract description 9
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 8
- 229920001002 functional polymer Polymers 0.000 claims abstract description 3
- 239000002861 polymer material Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 54
- 239000000203 mixture Substances 0.000 claims description 41
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical group [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 claims description 29
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 24
- 229920005989 resin Polymers 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000001788 mono and diglycerides of fatty acids Substances 0.000 claims description 14
- 229940075507 glyceryl monostearate Drugs 0.000 claims description 12
- 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 11
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 11
- 229920002627 poly(phosphazenes) Polymers 0.000 claims description 11
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000007493 shaping process Methods 0.000 claims description 9
- 238000004513 sizing Methods 0.000 claims description 9
- 239000003381 stabilizer Substances 0.000 claims description 9
- 229920001684 low density polyethylene Polymers 0.000 claims description 7
- 239000004702 low-density polyethylene Substances 0.000 claims description 7
- 229920001179 medium density polyethylene Polymers 0.000 claims description 7
- 239000004701 medium-density polyethylene Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 5
- IZHVBANLECCAGF-UHFFFAOYSA-N 2-hydroxy-3-(octadecanoyloxy)propyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)COC(=O)CCCCCCCCCCCCCCCCC IZHVBANLECCAGF-UHFFFAOYSA-N 0.000 claims description 4
- WZUNUACWCJJERC-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CC)(CO)CO WZUNUACWCJJERC-UHFFFAOYSA-N 0.000 claims description 2
- YFHKLSPMRRWLKI-UHFFFAOYSA-N 2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenyl)sulfanyl-6-methylphenol Chemical compound CC(C)(C)C1=C(O)C(C)=CC(SC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 YFHKLSPMRRWLKI-UHFFFAOYSA-N 0.000 claims description 2
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- 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 2
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 2
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 2
- 229940074045 glyceryl distearate Drugs 0.000 claims description 2
- 229920001903 high density polyethylene Polymers 0.000 claims description 2
- 239000004700 high-density polyethylene Substances 0.000 claims description 2
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 2
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004209 oxidized polyethylene wax Substances 0.000 claims description 2
- 235000013873 oxidized polyethylene wax Nutrition 0.000 claims description 2
- 229940059574 pentaerithrityl Drugs 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 abstract description 100
- -1 polyethylene Polymers 0.000 abstract description 59
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 17
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 14
- 239000005051 trimethylchlorosilane Substances 0.000 description 10
- 238000001125 extrusion Methods 0.000 description 7
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000008234 soft water Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004605 External Lubricant Substances 0.000 description 1
- 239000004610 Internal Lubricant Substances 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000002262 irrigation Effects 0.000 description 1
- 238000003973 irrigation Methods 0.000 description 1
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/328—Phosphates of heavy metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/20—Controlling water pollution; Waste water treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of polyethylene pipes, in particular to a flame-retardant PE communication pipe and a preparation method thereof, wherein the flame-retardant PE communication pipe comprises the following raw materials in parts by weight: 80-100 parts of polyethylene resin, 10-30 parts of functional master batch, 1-3 parts of compatilizer, 0.5-2 parts of antioxidant, 2-5 parts of lubricant and 0.1-1 part of heat stabilizer, wherein the functional master batch is prepared from functional polymer material, flame retardant and synergistic flame retardant. The aim is that: the PE communication pipe has good flame retardant property and mechanical property, and can adapt to different environments.
Description
Technical Field
The invention relates to the technical field of polyethylene pipes, in particular to a flame-retardant PE communication pipe and a preparation method thereof.
Background
Polyethylene (PE) refers to a polymer formed by polymerizing ethylene monomers in a free radical way, is one of the most general plastics with the largest yield, is a thermoplastic plastic with light weight, no toxicity, better mechanical strength, excellent electrical insulation and chemical corrosion resistance, is convenient to form and process, and is widely applied to the industries of wires and cables, chemical industry, food, packaging, machinery, electronic communication, home decoration, civil engineering and construction and the like. PE (polyethylene) pipe is one of the most common pipes, has the advantages of low-temperature impact resistance, chemical corrosion resistance, wear resistance and the like, and is widely applied to water supply, water discharge, heat supply, fuel gas supply, agricultural irrigation, hydraulic engineering, communication, cables and various industrial devices.
The PE communication pipe is widely used for sheath pipeline systems of outdoor communication cables and optical cables, comprises a local relay pipeline, a feeder pipeline, a distribution pipeline, a special network pipeline and a special specified length communication pipeline, has strong applicability, is suitable for penetrating and releasing various cables such as cables, wires and the like, is suitable for penetrating, conducting, isolating and protecting urban communication optical cables, low-voltage cables, cable television networks, multimedia transmission network line sheath pipes and indoor wires and cables of buildings, and therefore the flame retardant performance of the PE communication pipe is particularly important.
At present, when a PE communication tube is prepared, a flame retardant is generally added, and the flame retardant can be classified into two types of halogen flame retardance and halogen-free flame retardance, wherein the halogen flame retardance has small addition amount and high flame retardance, but a large amount of toxic smoke is volatilized during combustion, so that secondary disasters are caused, and the environmental protection problem also exists. The halogen-free flame retardant material has various choices and different flame retardant formulas, and achieves different flame retardant effects, for example, the common hydrated hydroxide has overlarge addition amount, and the processability and part of mechanical properties are affected. The PE communication tube has various application environments, and the flame retardant property of the conventional PE communication tube needs to be improved in order to adapt to the application requirements which are continuously improved at present.
Disclosure of Invention
Therefore, the invention aims to provide a flame-retardant PE communication pipe and a preparation method thereof, so that the PE communication pipe has good flame-retardant performance and mechanical performance and can adapt to different environments.
The invention solves the technical problems by the following technical means:
a flame-retardant PE communication tube comprises the following raw materials in parts by weight: 80-100 parts of polyethylene resin, 10-30 parts of functional master batch, 1-3 parts of compatilizer, 0.5-2 parts of antioxidant, 2-5 parts of lubricant and 0.1-1 part of heat stabilizer, wherein the functional master batch is prepared from functional polymer material, flame retardant and synergistic flame retardant.
The communication pipe prepared from the polyethylene has good flame retardant property and mechanical property by adding the flame retardant functional master batch into the polyethylene, and can adapt to various environments; and the processing performance of the polyethylene and the functional master batch in the preparation process can be improved by adding the processing aid.
Preferably, the polyethylene resin is one or a combination of a plurality of high-density polyethylene, medium-density polyethylene, low-density polyethylene and linear low-density polyethylene.
Further preferably, the polyethylene resin is a mixture of low density polyethylene and medium density polyethylene, and the mass ratio of the low density polyethylene to the medium density polyethylene is 1:0.35. The melt index of the low-density polyethylene is 3-40 g/10min, and the melt index of the medium-density polyethylene is 0.1-35g/10min.
Preferably, the compatilizer is one or a combination of more than one of PE-g-ST, PP-g-ST, ABS-g-MAH, PE-g-MAH and PP-g-MAH.
Further preferably, the compatibilizer is PE-g-MAH. The maleic anhydride grafted polyethylene is used as a compatilizer, so that the interfacial bonding capability of the functional master batch and polyethylene resin can be improved, and the dispersion uniformity of the functional master batch in the polyethylene can be improved.
Preferably, the antioxidant is one or a combination of more of antioxidant 1010, antioxidant 168, antioxidant 736 and antioxidant AT-10.
Further preferably, the antioxidant is a mixture of antioxidant 168 and antioxidant AT-10, and the mass ratio of antioxidant 168 to antioxidant AT-10 is 1:1.
Preferably, the lubricant is one or a combination of several of stearic acid, oxidized polyethylene wax, glyceryl monostearate, glyceryl distearate or pentaerythritol monostearate; the heat stabilizer is an environment-friendly calcium-zinc stabilizer.
Further preferably, the lubricant is polyethylene wax and glyceryl monostearate, wherein the polyethylene wax is used as an external lubricant, the glyceryl monostearate is used as an internal lubricant, and the mass ratio of the polyethylene wax to the glyceryl monostearate is 1:1.
Preferably, the functional master batch comprises the following raw materials in parts by weight: 30-50 parts of EVA resin, 3-8 parts of flame retardant, 1-3 parts of synergistic flame retardant and 0.1-1 part of dispersing agent.
Further preferably, the flame retardant is a modified zirconium phosphate.
In this scheme, the preparation of the modified zirconium phosphate comprises the following steps:
preparing alpha-zirconium phosphate into nano zirconium phosphate by ball milling, dispersing the nano zirconium phosphate in water, slowly adding an ethylamine aqueous solution, and slowly stirring to form a suspension for later use; slowly adding trimethylchlorosilane into the nano zirconium phosphate suspension, slowly stirring for 2-5h at 30-40 ℃, washing, suction filtering and drying after stirring is completed, and obtaining the modified zirconium phosphate.
Zirconium phosphate can be used as a flame retardant material, the dispersion performance of zirconium phosphate can be improved by preparing nano zirconium phosphate, pre-supported zirconium phosphate can be obtained by the action of ethylamine, trimethylchlorosilane is added into the pre-supported zirconium phosphate and reacts, and trimethylchlorosilane intercalation modified zirconium phosphate can be obtained, so that the dispersion performance of zirconium phosphate, the combination performance with polymers and the flame retardant performance are improved, the polymers can be catalyzed to crosslink into carbon during combustion, a barrier is formed, the transmission of combustible gas, oxygen and heat is blocked, and the flame retardant efficiency can be improved by combining with a synergistic flame retardant, a denser carbon layer is formed, and the flame retardant effect is improved.
Further preferably, the synergistic flame retardant is one or a combination of more of ammonium polyphosphate, pentaerythritol, phenoxy polyphosphazene and melamine phosphate; in this embodiment, the synergistic flame retardant is preferably a phenoxy polyphosphazene.
The phenoxy polyphosphazene is used as a synergistic flame retardant, has low volatility and high temperature stability, can absorb more heat when the polymer burns, and further enhances the flame retardant effect of the PE pipe.
Further preferably, the dispersing agent is polyethylene wax, which can improve the dispersibility of the flame retardant and the synergistic flame retardant in the EVA resin, and is beneficial to the subsequent dispersion in the polyethylene resin.
Preferably, the preparation of the functional master batch comprises the following steps:
B1. placing EVA resin in a mixer, uniformly stirring, heating to 90-120 ℃, continuously stirring for 3-5min, adding a flame retardant, a synergistic flame retardant and a dispersing agent, and continuously stirring for 2-4min to obtain a premix;
B2. and (3) transferring the mixture into a screw extruder, extruding and granulating to obtain the functional master batch.
The EVA resin has good chemical stability, ageing resistance, ozone resistance, water resistance, corrosion resistance, vibration resistance, heat preservation, processability, environmental stress cracking resistance and large filler tolerance, and the flame retardant and the synergistic flame retardant are firstly dispersed in the EVA resin, so that the flame retardant property of the EVA resin is increased on the basis of not changing the property of the EVA resin, and the flame retardant master batch is formed, and when the flame retardant master batch is added into polyethylene, the light stability and the mechanical property of the polyethylene can be improved, and the flame retardant property of the polyethylene can also be improved.
The application also discloses a preparation method of the flame-retardant PE communication tube, which comprises the following steps:
A1. adding polyethylene resin and functional master batch into a mixer, uniformly stirring, heating to 130-150 ℃, adding a compatilizer, continuously stirring for 3-5min, adding an antioxidant, a lubricant and a heat stabilizer, and uniformly stirring to obtain a mixture;
A2. transferring the mixture into a screw extruder, extruding and granulating to obtain a flame-retardant PE master batch;
A3. and transferring the flame-retardant PE master batch into a forming machine, extruding, sizing, traction, cooling and shaping to obtain the flame-retardant PE communication pipe.
By firstly melt-blending the polyethylene resin and the functional master batch and then adding the compatilizer, the compatibility of the EVA resin and the polyethylene and the dispersibility of the flame retardant in the polyethylene can be improved and the processing rheological property and the mechanical property of the polyethylene can be improved when the functional master batch is blended with the modified polyethylene; and then, an antioxidant, a lubricant and a heat stabilizer are added, so that the polyethylene pipe has good oxidation resistance, and meanwhile, the processing condition of the polyethylene pipe is wider.
Preferably, in the step A2, the melting temperature of the screw extruder is 160-200 ℃ and the rotating speed is 250-350r/min.
The invention adopting the scheme has the following beneficial effects:
1. by adding the functional master batch into the polyethylene, the flame retardant property of the polyethylene can be improved, the mechanical property of the polyethylene can be improved, and the excellent flame retardant effect can be achieved under the condition of less addition;
2. the PE pipe prepared by the method has good mechanical property and flame retardant property, can be used as a communication pipe, can adapt to various environments when being used as the communication pipe, and can be used as other pipes, such as a wiring pipe, a cable protection pipe and the like.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments.
Example 1 preparation of flame retardant PE communication tube
In this example, low density polyethylene and medium density polyethylene were used as the polyethylene, and Saint sabic 1905UMS was used as the low density polyethylene, and the melt index was 5g/10min. The medium density polyethylene used was Korean SK DX800 with a melt index of 0.64g/10min. EVA adopts Yangzibaschiff V6110M, and the melt index is 5.6-6.4g/10min.
Preparation of modified zirconium phosphate
Preparing 10 parts by mass of alpha-zirconium phosphate into nano zirconium phosphate by ball milling, dispersing the nano zirconium phosphate in 30 parts by mass of soft water, slowly adding 13 parts by mass of ethylamine aqueous solution, and slowly stirring to form a suspension for later use; slowly adding 16.8 parts by mass of trimethylchlorosilane into the nano zirconium phosphate suspension, slowly stirring for 2-5 hours at the temperature of 30-40 ℃, washing with soft water for 3-5 times after stirring is completed, carrying out suction filtration, and drying at the temperature of 80 ℃ to obtain trimethylchlorosilane modified zirconium phosphate.
Preparation of functional masterbatch
Placing 30 parts by mass of EVA resin into a mixer, uniformly stirring, heating to 90-120 ℃, continuously stirring for 3min, adding 3 parts by mass of trimethylchlorosilane modified zirconium phosphate, 1 part by mass of phenoxy polyphosphazene and 0.1 part by mass of polyethylene wax, and continuously stirring for 2-4min to obtain a premix;
B2. and (3) transferring the mixture into a screw extruder, extruding and granulating to obtain the functional master batch.
Preparation of polyethylene pipe
A1. Putting 80 parts by mass of polyethylene resin and 10 parts by mass of functional master batch into a mixer, uniformly stirring, heating to 130-150 ℃, adding 1 part by mass of PE-g-MAH, continuously stirring for 3min, adding 0.5 part by mass of a mixture of antioxidant 168 and antioxidant AT-10 in a mass ratio of 1:1, 2 parts by mass of a mixture of polyethylene wax and glyceryl monostearate in a mass ratio of 1:1 and 0.1 part by mass of an environment-friendly calcium-zinc stabilizer, and uniformly stirring to obtain a mixture;
A2. transferring the mixture into a screw extruder for extrusion, setting the temperature of a first area of a machine barrel to be 160-180 ℃, the temperature of a second area to be 170-190 ℃, the temperature of a third area to be 180-200 ℃, the temperature of a fourth area to be 190-200 ℃, the screw speed of the extruder to be 250-350r/min, and granulating to obtain a flame-retardant PE master batch;
A3. and transferring the flame-retardant PE master batch into a forming machine, extruding, sizing, traction, cooling and shaping to obtain the flame-retardant PE communication pipe.
Example 2 preparation of flame retardant PE communication tube
In this example, the raw materials of polyethylene and EVA resin were the same as in example 1, and the flame retardant used the trimethylchlorosilane-modified zirconium phosphate prepared in example 1.
Preparation of functional masterbatch
Placing 40 parts by mass of EVA resin into a mixer, uniformly stirring, heating to 90-120 ℃, continuously stirring for 4min, adding 6.5 parts by mass of trimethylchlorosilane modified zirconium phosphate, 2 parts by mass of phenoxy polyphosphazene and 0.5 part by mass of polyethylene wax, and continuously stirring for 2-4min to obtain a premix;
B2. and (3) transferring the mixture into a screw extruder, extruding and granulating to obtain the functional master batch.
Preparation of polyethylene pipe
A1. Putting 90 parts by mass of polyethylene resin and 20 parts by mass of functional master batch into a mixer, uniformly stirring, heating to 130-150 ℃, adding 2 parts by mass of PE-g-MAH, continuously stirring for 3min, adding 1 part by mass of a mixture of antioxidant 168 and antioxidant AT-10 in a mass ratio of 1:1, 3 parts by mass of a mixture of polyethylene wax and glyceryl monostearate in a mass ratio of 1:1 and 0.45 part by mass of an environment-friendly calcium-zinc stabilizer, and uniformly stirring to obtain a mixture;
A2. transferring the mixture into a screw extruder for extrusion, setting the temperature of a first area of a machine barrel to be 160-180 ℃, the temperature of a second area to be 170-190 ℃, the temperature of a third area to be 180-200 ℃, the temperature of a fourth area to be 190-200 ℃, the screw speed of the extruder to be 250-350r/min, and granulating to obtain a flame-retardant PE master batch;
A3. and transferring the flame-retardant PE master batch into a forming machine, extruding, sizing, traction, cooling and shaping to obtain the flame-retardant PE communication pipe.
Example 3 preparation of flame retardant PE communication tube three
In this example, the raw materials of polyethylene and EVA resin were the same as in example 1, and the flame retardant used the trimethylchlorosilane-modified zirconium phosphate prepared in example 1.
Preparation of functional masterbatch
Placing 50 parts by mass of EVA resin into a mixer, uniformly stirring, heating to 90-120 ℃, continuously stirring for 5min, adding 8 parts by mass of trimethylchlorosilane modified zirconium phosphate, 3 parts by mass of phenoxy polyphosphazene and 1 part by mass of polyethylene wax, and continuously stirring for 2-4min to obtain a premix;
B2. and (3) transferring the mixture into a screw extruder, extruding and granulating to obtain the functional master batch.
Preparation of polyethylene pipe
A1. Adding 100 parts by mass of polyethylene resin and 30 parts by mass of functional master batch into a mixer, uniformly stirring, heating to 130-150 ℃, adding 3 parts by mass of PE-g-MAH, continuously stirring for 3min, adding 2 parts by mass of a mixture of antioxidant 168 and antioxidant AT-10 in a mass ratio of 1:1, 5 parts by mass of a mixture of polyethylene wax and glyceryl monostearate in a mass ratio of 1:1 and 1 part by mass of an environment-friendly calcium-zinc stabilizer, and uniformly stirring to obtain a mixture;
A2. transferring the mixture into a screw extruder for extrusion, setting the temperature of a first area of a machine barrel to be 160-180 ℃, the temperature of a second area to be 170-190 ℃, the temperature of a third area to be 180-200 ℃, the temperature of a fourth area to be 190-200 ℃, the screw speed of the extruder to be 250-350r/min, and granulating to obtain a flame-retardant PE master batch;
A3. and transferring the flame-retardant PE master batch into a forming machine, extruding, sizing, traction, cooling and shaping to obtain the flame-retardant PE communication pipe.
Example 4 (comparative example 1), preparation of flame retardant PE communication tube four
In this example, the raw materials of polyethylene and EVA resin were the same as in example 1, and the trimethylchlorosilane-modified zirconium phosphate prepared in example 1 was used as the flame retardant, without using a synergistic flame retardant.
Preparation of functional masterbatch
Placing 40 parts by mass of EVA resin into a mixer, uniformly stirring, heating to 90-120 ℃, continuously stirring for 4min, adding 6.5 parts by mass of trimethylchlorosilane modified zirconium phosphate and 0.5 part by mass of polyethylene wax, and continuously stirring for 2-4min to obtain a premix;
B2. and (3) transferring the mixture into a screw extruder, extruding and granulating to obtain the functional master batch.
Preparation of polyethylene pipe
A1. Putting 90 parts by mass of polyethylene resin and 20 parts by mass of functional master batch into a mixer, uniformly stirring, heating to 130-150 ℃, adding 2 parts by mass of PE-g-MAH, continuously stirring for 3min, adding 1 part by mass of a mixture of antioxidant 168 and antioxidant AT-10 in a mass ratio of 1:1, 3 parts by mass of a mixture of polyethylene wax and glyceryl monostearate in a mass ratio of 1:1 and 0.45 part by mass of an environment-friendly calcium-zinc stabilizer, and uniformly stirring to obtain a mixture;
A2. transferring the mixture into a screw extruder for extrusion, setting the temperature of a first area of a machine barrel to be 160-180 ℃, the temperature of a second area to be 170-190 ℃, the temperature of a third area to be 180-200 ℃, the temperature of a fourth area to be 190-200 ℃, the screw speed of the extruder to be 250-350r/min, and granulating to obtain a flame-retardant PE master batch;
A3. and transferring the flame-retardant PE master batch into a forming machine, extruding, sizing, traction, cooling and shaping to obtain the flame-retardant PE communication pipe.
Example 5 (comparative example 2), preparation of flame retardant PE communication tube five
In this example, the raw materials of polyethylene and EVA resin were the same as in example 1, and phenoxypolyphosphazene was used as a flame retardant.
Preparation of functional masterbatch
Placing 40 parts by mass of EVA resin into a mixer, uniformly stirring, heating to 90-120 ℃, continuously stirring for 4min, adding 2 parts by mass of phenoxy polyphosphazene and 0.5 part by mass of polyethylene wax, and continuously stirring for 2-4min to obtain a premix;
B2. and (3) transferring the mixture into a screw extruder, extruding and granulating to obtain the functional master batch.
Preparation of polyethylene pipe
A1. Putting 90 parts by mass of polyethylene resin and 20 parts by mass of functional master batch into a mixer, uniformly stirring, heating to 130-150 ℃, adding 2 parts by mass of PE-g-MAH, continuously stirring for 3min, adding 1 part by mass of a mixture of antioxidant 168 and antioxidant AT-10 in a mass ratio of 1:1, 3 parts by mass of a mixture of polyethylene wax and glyceryl monostearate in a mass ratio of 1:1 and 0.45 part by mass of an environment-friendly calcium-zinc stabilizer, and uniformly stirring to obtain a mixture;
A2. transferring the mixture into a screw extruder for extrusion, setting the temperature of a first area of a machine barrel to be 160-180 ℃, the temperature of a second area to be 170-190 ℃, the temperature of a third area to be 180-200 ℃, the temperature of a fourth area to be 190-200 ℃, the screw speed of the extruder to be 250-350r/min, and granulating to obtain a flame-retardant PE master batch;
A3. and transferring the flame-retardant PE master batch into a forming machine, extruding, sizing, traction, cooling and shaping to obtain the flame-retardant PE communication pipe.
Example 6 (comparative example 3), preparation of flame retardant PE communication tube six
In this example, the raw materials of the polyethylene were the same as in example 1, and the flame retardant was trimethylchlorosilane-modified zirconium phosphate prepared in example 1.
Preparation of polyethylene pipe
A1. Putting 90 parts by mass of polyethylene resin into a mixer, uniformly stirring, heating to 130-150 ℃, adding 2 parts by mass of PE-g-MAH, continuously stirring for 3min, adding 6.5 parts by mass of trimethylchlorosilane modified zirconium phosphate, 2 parts by mass of phenoxy polyphosphazene, 1 part by mass of a mixture of antioxidant 168 and antioxidant AT-10 in a mass ratio of 1:1, 3 parts by mass of a mixture of polyethylene wax and glyceryl monostearate in a mass ratio of 1:1 and 0.45 part by mass of an environment-friendly calcium-zinc stabilizer, and uniformly stirring to obtain a mixture;
A2. transferring the mixture into a screw extruder for extrusion, setting the temperature of a first area of a machine barrel to be 160-180 ℃, the temperature of a second area to be 170-190 ℃, the temperature of a third area to be 180-200 ℃, the temperature of a fourth area to be 190-200 ℃, the screw speed of the extruder to be 250-350r/min, and granulating to obtain a flame-retardant PE master batch;
A3. and transferring the flame-retardant PE master batch into a forming machine, extruding, sizing, traction, cooling and shaping to obtain the flame-retardant PE communication pipe.
Example 7 (comparative example 4), preparation of flame retardant PE communication tube seven
In this example, the raw materials of polyethylene were the same as in example 1, and the flame retardant was nano zirconium phosphate.
Preparation of polyethylene pipe
A1. Putting 90 parts by mass of polyethylene resin into a mixer, uniformly stirring, heating to 130-150 ℃, adding 2 parts by mass of PE-g-MAH, continuously stirring for 3min, adding 6.5 parts by mass of nano zirconium phosphate, 1 part by mass of a mixture of antioxidant 168 and antioxidant AT-10 in a mass ratio of 1:1, 3 parts by mass of a mixture of polyethylene wax and glyceryl monostearate in a mass ratio of 1:1 and 0.45 part by mass of an environment-friendly calcium-zinc stabilizer, and uniformly stirring to obtain a mixture;
A2. transferring the mixture into a screw extruder for extrusion, setting the temperature of a first area of a machine barrel to be 160-180 ℃, the temperature of a second area to be 170-190 ℃, the temperature of a third area to be 180-200 ℃, the temperature of a fourth area to be 190-200 ℃, the screw speed of the extruder to be 250-350r/min, and granulating to obtain a flame-retardant PE master batch;
A3. and transferring the flame-retardant PE master batch into a forming machine, extruding, sizing, traction, cooling and shaping to obtain the flame-retardant PE communication pipe.
Physical properties of the polyethylene pipes prepared in examples 1 to 7 were tested, including tensile strength, elongation at break, vertical burn, limiting oxygen index and oxidation induction time; the tensile strength is tested by GB/T1040, the vertical combustion is tested by UL94 standard, the limiting oxygen index is tested by GB/T2406-2008, and the standard of the sample in the test process meets the corresponding test requirement; the test 5 sets of data were averaged and the test results are shown in table 1:
as can be seen from the data in Table 1, the polyethylene pipes prepared in examples 1-3 have good flame retardant properties and mechanical properties, and the overall properties are better in example 1.
From the data in table 1, it is understood that in example 4, the addition of phenoxy polyphosphazene as a flame retardant is better in flame retardant performance than in example 5, the addition of trimethylchlorosilane-modified zirconium phosphate as a flame retardant is better in limiting oxygen index, and the addition of trimethylchlorosilane-modified zirconium phosphate as a flame retardant and the addition of phenoxy polyphosphazene as a synergistic flame retardant are higher in limiting oxygen index and longer in oxidation induction time than the addition of trimethylchlorosilane-modified zirconium phosphate alone as a flame retardant.
As can be seen from the data in table 1, in examples 6 and 7, the EVA resin was added and prepared into functional master batches with flame retardant and synergistic flame retardant, which can improve tensile strength and elongation at break of polyethylene pipe, and the addition of trimethylchlorosilane-modified zirconium phosphate as flame retardant gave better flame retardant effect than the addition of nano zirconium phosphate as flame retardant.
The flame-retardant PE communication pipe and the preparation method thereof are described in detail. The description of the specific embodiments is only intended to aid in understanding the method of the present invention and its core ideas. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.
What needs to be specifically stated is: the specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
The above examples are provided for better understanding of the present invention, and are not limited to the preferred embodiments, but are not limited to the content and scope of the present invention, and any product which is the same or similar to the present invention obtained by any person who is in the light of the present invention or combines the present invention with other features of the prior art falls within the scope of the present invention.
Claims (10)
1. The flame-retardant PE communication pipe is characterized by comprising the following raw materials in parts by weight: 80-100 parts of polyethylene resin, 10-30 parts of functional master batch, 1-3 parts of compatilizer, 0.5-2 parts of antioxidant, 2-5 parts of lubricant and 0.1-1 part of heat stabilizer, wherein the functional master batch is prepared from functional polymer material, flame retardant and synergistic flame retardant.
2. The flame retardant PE communication pipe of claim 1 wherein the polyethylene resin is one or a combination of a plurality of high density polyethylene, medium density polyethylene, low density polyethylene, linear low density polyethylene.
3. The flame-retardant PE communication pipe according to claim 1, wherein the compatilizer is one or a combination of a plurality of PE-g-ST, PP-g-ST, ABS-g-MAH, PE-g-MAH and PP-g-MAH.
4. The flame retardant PE communication pipe of claim 1 wherein the antioxidant is one or a combination of several of antioxidant 1010, antioxidant 168, antioxidant 736, antioxidant AT-10.
5. The flame-retardant PE communication pipe according to claim 1, wherein the lubricant is one or a combination of several of stearic acid, oxidized polyethylene wax, glyceryl monostearate, glyceryl distearate or pentaerythritol monostearate; the heat stabilizer is an environment-friendly calcium-zinc stabilizer.
6. The flame-retardant PE communication pipe according to claim 1, wherein the functional master batch comprises the following raw materials in parts by weight: 30-50 parts of EVA resin, 3-8 parts of flame retardant, 1-3 parts of synergistic flame retardant and 0.1-1 part of dispersing agent.
7. The flame retardant PE communication pipe of claim 6, wherein the preparation of the functional masterbatch comprises the steps of:
B1. placing EVA resin in a mixer, uniformly stirring, heating to 90-120 ℃, continuously stirring for 3-5min, adding a flame retardant, a synergistic flame retardant and a dispersing agent, and continuously stirring for 2-4min to obtain a premix;
B2. and (3) transferring the mixture into a screw extruder, extruding and granulating to obtain the functional master batch.
8. The flame-retardant PE communication pipe of claim 6 wherein the flame retardant is a modified zirconium phosphate and the synergistic flame retardant is one or a combination of more of ammonium polyphosphate, pentaerythritol, phenoxy polyphosphazene and melamine phosphate.
9. A method of preparing a flame retardant PE communication pipe according to any of claims 1-8, comprising the steps of:
A1. adding polyethylene resin and functional master batch into a mixer, uniformly stirring, heating to 130-150 ℃, adding a compatilizer, continuously stirring for 3-5min, adding an antioxidant, a lubricant and a heat stabilizer, and uniformly stirring to obtain a mixture;
A2. transferring the mixture into a screw extruder, extruding and granulating to obtain a flame-retardant PE master batch;
A3. and transferring the flame-retardant PE master batch into a forming machine, extruding, sizing, traction, cooling and shaping to obtain the flame-retardant PE communication pipe.
10. The method for preparing a flame-retardant PE communication pipe according to claim 9, wherein in the step A2, the melting temperature of the screw extruder is 160-200 ℃ and the rotating speed is 250-350r/min.
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