CN116656027A - PE cable sheath material with good flame retardant effect and preparation method thereof - Google Patents
PE cable sheath material with good flame retardant effect and preparation method thereof Download PDFInfo
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- CN116656027A CN116656027A CN202310663061.5A CN202310663061A CN116656027A CN 116656027 A CN116656027 A CN 116656027A CN 202310663061 A CN202310663061 A CN 202310663061A CN 116656027 A CN116656027 A CN 116656027A
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- Prior art keywords
- flame retardant
- cable sheath
- sheath material
- retardant effect
- parts
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 79
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000000463 material Substances 0.000 title claims abstract description 51
- 230000000694 effects Effects 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000945 filler Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 14
- 239000011347 resin Substances 0.000 claims abstract description 13
- 229920005989 resin Polymers 0.000 claims abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 239000003381 stabilizer Substances 0.000 claims abstract description 10
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 239000000314 lubricant Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000004698 Polyethylene Substances 0.000 claims description 60
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 28
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 14
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 12
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 9
- -1 polyethylene Polymers 0.000 claims description 9
- 229920000573 polyethylene Polymers 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- DYPJJAAKPQKWTM-UHFFFAOYSA-N 2-chloropropane-1,3-diol Chemical compound OCC(Cl)CO DYPJJAAKPQKWTM-UHFFFAOYSA-N 0.000 claims description 7
- GPXCORHXFPYJEH-UHFFFAOYSA-N 3-[[3-aminopropyl(dimethyl)silyl]oxy-dimethylsilyl]propan-1-amine Chemical compound NCCC[Si](C)(C)O[Si](C)(C)CCCN GPXCORHXFPYJEH-UHFFFAOYSA-N 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 7
- KKIMETYRXLWWSD-UHFFFAOYSA-N n-methylhex-5-en-1-amine Chemical compound CNCCCCC=C KKIMETYRXLWWSD-UHFFFAOYSA-N 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000012188 paraffin wax Substances 0.000 claims description 6
- 238000007792 addition Methods 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- WOAZEKPXTXCPFZ-UHFFFAOYSA-N dimethyl(phenyl)azanium;chloride Chemical compound Cl.CN(C)C1=CC=CC=C1 WOAZEKPXTXCPFZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 4
- 239000000347 magnesium hydroxide Substances 0.000 claims description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 4
- 239000012074 organic phase Substances 0.000 claims description 4
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000008187 granular material Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 239000001993 wax Substances 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 238000004381 surface treatment Methods 0.000 claims description 2
- 239000003957 anion exchange resin Substances 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 8
- 231100000331 toxic Toxicity 0.000 abstract description 5
- 230000002588 toxic effect Effects 0.000 abstract description 5
- 230000002045 lasting effect Effects 0.000 abstract description 4
- 230000007246 mechanism Effects 0.000 abstract description 4
- 238000013508 migration Methods 0.000 abstract description 4
- 230000005012 migration Effects 0.000 abstract description 4
- 239000004480 active ingredient Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000004132 cross linking Methods 0.000 abstract description 3
- 229910052736 halogen Inorganic materials 0.000 abstract description 3
- 150000002367 halogens Chemical class 0.000 abstract description 3
- 239000000155 melt Substances 0.000 abstract description 3
- 230000001737 promoting effect Effects 0.000 abstract description 3
- 238000002485 combustion reaction Methods 0.000 description 6
- 239000004342 Benzoyl peroxide Substances 0.000 description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical group [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000779 smoke Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000005292 vacuum distillation Methods 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000032683 aging Effects 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 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
- 241000894006 Bacteria Species 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 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
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65742—Esters of oxyacids of phosphorus non-condensed with carbocyclic rings or heterocyclic rings or ring systems
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- 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
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
-
- 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
- Y02A30/00—Adapting or protecting infrastructure or their operation
- Y02A30/14—Extreme weather resilient electric power supply systems, e.g. strengthening power lines or underground power cables
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Insulated Conductors (AREA)
Abstract
The invention discloses a PE cable sheath material with good flame retardant effect and a preparation method thereof, belonging to the technical field of cable materials, and comprising the following raw materials in parts by weight: 100 parts of PE resin, 8-12 parts of composite filler, 6-9 parts of flame retardant, 5-8 parts of lubricant, 0.3-0.5 part of stabilizer and 0.2-0.3 part of initiator. According to the invention, the synthetic flame retardant is added into the PE cable material, and the flame retardant has multiple flame retardant mechanisms and does not contain toxic halogen components, thus the PE cable material belongs to a high-efficiency and safe flame retardant; the flame retardant contains a plurality of unsaturated carbon-carbon double bonds, can participate in the crosslinking process of PE molecular chains in the melt blending process of the flame retardant and the PE matrix, and plays a role in promoting the formation of a crosslinked network structure, so that the mechanical strength, the wear resistance and the water resistance of PE materials are improved, the migration resistance and the exudation resistance of active ingredients are improved, and the lasting stability of the flame retardant effect is improved.
Description
Technical Field
The invention belongs to the technical field of cable materials, and particularly relates to a PE cable sheath material with a good flame retardant effect and a preparation method thereof.
Background
PE (polyethylene) materials have the performances of chemical corrosion resistance, easiness in processing and forming, excellent insulating property and the like, do not contain halogen atoms, and do not generate toxic smoke when being burnt, so that the PE (polyethylene) materials are often used for preparing wire and cable sheath materials, but are easy to burn and poor in flame retardance, and therefore, the research on how to obtain PE cables with excellent flame retardance is of great significance.
The prior art discloses a flame-retardant polyethylene cable material and a preparation method thereof, for example, the China patent with publication number of CN106336562A discloses a flame-retardant polyethylene cable material and a preparation method thereof, wherein the low-density and modified low-density polyethylene material is used as a resin matrix, magnesium hydroxide, aluminum hydroxide, zinc borate, red phosphorus and other materials are used as a compound flame retardant, and a compatilizer, silicone master batch, carbon black and other materials are used for enabling the resin matrix to be well compatible with the compound flame retardant, the obtained polyethylene cable material has flame retardant performance of V0 grade in vertical combustion and better electrical property, however, the contained red phosphorus and other materials may decompose to generate extremely toxic phosphide, black smoke and pungent gas in the combustion process, the requirements of cable safety cannot be met, and the red phosphorus, zinc borate and the like are added into the polyethylene in an additive manner, so that the defects of easy migration and exudation exist, and the durability of the flame-retardant effect needs to be further improved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a PE cable sheath material with good flame retardant effect and a preparation method thereof.
The aim of the invention can be achieved by the following technical scheme:
the PE cable sheath material with good flame retardant effect comprises the following raw materials in parts by weight: 100 parts of PE resin, 8-12 parts of composite filler, 6-9 parts of flame retardant, 5-8 parts of lubricant, 0.3-0.5 part of stabilizer and 0.2-0.3 part of initiator;
the preparation method of the PE cable sheath material comprises the following steps:
placing PE resin, composite filler, flame retardant, lubricant and stabilizer into a high-speed mixing stirrer for high-speed mixing at a rotating speed of 1500r/min for 15-20min to obtain premix;
placing the premix and the initiator into an internal mixer for banburying plasticization (banburying temperature is 175 ℃ and banburying plasticization is 18-20 min), then carrying out secondary plasticization extrusion by a double screw extruder, and drawing into strips for air-cooling and granulating to obtain the PE cable sheath material.
Further, the composite filler is obtained by surface treatment of magnesium hydroxide and silicon dioxide according to a mass ratio of 2:1.
Further, the lubricant is one or more of polyethylene wax, chlorinated paraffin and paraffin wax.
Further, the stabilizer is a calcium-zinc stabilizer.
Further, the initiator is benzoyl peroxide.
Further, the flame retardant is prepared by the steps of:
s1, adding N-methyl-5-hexene-1-amine, triethylamine and tetrahydrofuran into a dry three-neck flask, placing the flask into an ice bath, stirring and mixing, slowly dripping 2-chloro-1, 3-propanediol into the flask through a constant pressure dropping funnel under stirring when the temperature of the system is stabilized at 0-2 ℃, reacting for 3 hours under normal temperature after the dripping is finished, filtering to remove salt, and removing the tetrahydrofuran through reduced pressure rotary evaporation to obtain an intermediate 1; n-methyl-5-hexen-1-amine, sodium bicarbonate and 2-chloro-1, 3-propanediol in an amount ratio of 0.1mol:10.1g:0.1mol;
under the action of triethylamine, nucleophilic substitution reaction is carried out on-NH-on N-methyl-5-hexene-1-amine molecule and-Cl on 2-chloro-1, 3-propanediol molecule to obtain an intermediate 1, and the process is as follows:
s2, continuously introducing nitrogen into a three-neck flask with a stirrer, a thermometer and a condenser tube for 10min (replacing air in the flask), adding phosphorus oxychloride, dioxane and N, N-dimethylaniline (acid binding agent), stirring and dissolving uniformly, then dropwise adding a dioxane solution of the intermediate 1, controlling the reaction temperature to be not higher than 40 ℃ in the dropwise adding process, heating to 100 ℃ after the dropwise adding process is completed, preserving heat for reaction for 12h, cooling to below 30 ℃, removing generated N, N-dimethylaniline hydrochloride by suction filtration, removing dioxane from filtrate by reduced pressure distillation, washing twice with distilled water, separating a lower organic phase, then adding ethyl acetate, drying and suction filtration with anhydrous magnesium sulfate, and removing ethyl acetate by reduced pressure distillation of filtrate to obtain the intermediate 2; the dosage ratio of phosphorus oxychloride, N-dimethylaniline and the intermediate 1 is 15.3g:24.2g:18.7g;
under the action of N, N-dimethylaniline, phosphorus oxychloride and two-OH groups on the intermediate 1 molecule undergo substitution and cyclization reactions to obtain an intermediate 2, wherein the process is as follows:
s3, adding the intermediate 2 and acetonitrile into a three-neck flask with a stirring device, stirring uniformly, then adding methyl iodide, stirring at room temperature for reaction for 16 hours, stopping the reaction, concentrating under reduced pressure (removing most of acetonitrile), adding deionized water, exchanging by anion (Cl-) exchange resin, concentrating under reduced pressure, and obtaining an intermediate 3; the ratio of the amount of intermediate 2 to the amount of methyl iodide is 26.8g to 20.8g;
alkylation reaction is carried out on tertiary amine on the intermediate 2 and methyl iodide to obtain a quaternization product, namely an intermediate 3, and the reaction process is as follows:
s4, adding dichloromethane into a four-neck flask, introducing nitrogen, continuously removing air in the flask for 10min, adding an intermediate 3 and triethylamine, stirring and uniformly mixing, dropwise adding 1, 3-bis (3-aminopropyl) tetramethyl disiloxane by adopting a constant pressure funnel, reacting for 4h at normal temperature after the dropwise addition is finished, removing generated triethylamine hydrochloride by suction filtration after the reaction is finished, and distilling filtrate under reduced pressure to obtain a flame retardant; the ratio of the amounts of intermediate 3, triethylamine and 1, 3-bis (3-aminopropyl) tetramethyldisiloxane was 35.3g:10.1g:12.5g;
-Cl on intermediate 3 molecule and-NH on 1, 3-bis (3-aminopropyl) tetramethyl disiloxane molecule 2 Nucleophilic substitution reaction is carried out to obtain an initial product, and the reaction process is as follows:
from the molecular structure, the flame retardant has a phosphate group, a nitrogen-containing group and a-Si-O-Si-chain segment, wherein the phosphate group and the nitrogen-containing group respectively belong to P-series and N-series flame retardant components, have different flame retardant mechanisms, and are directly connected with each other, so that the flame retardant belongs to P-N synergistic flame retardant components; the Si-O-Si-belongs to an organic silicon halogen-free flame retardant component, is also a char-forming smoke suppressant, can play a synergistic effect with the P-N flame retardant component, and can suppress smoke while being flame-retardant, so that the obtained flame retardant has various flame retardant mechanisms, does not contain toxic halogen components, and is a high-efficiency and safe flame retardant; the phosphate group is in a six-membered ring form, the stability is high, and a single flame retardant molecule contains a plurality of phosphate esters and N-containing groups, so that the flame retardant activity density is high;
in addition, the flame retardant molecule contains a plurality of unsaturated carbon-carbon double bonds, and under the action of an initiator, the flame retardant molecule can participate in the crosslinking process of PE molecular chains in the melt blending process of the flame retardant molecule and PE matrix, so that the effect of promoting the formation of a crosslinked network structure is achieved, on one hand, the generation of the crosslinked network structure can improve the mechanical strength, the wear resistance and the water resistance of PE materials; on the other hand, the flame retardant can act with the PE matrix in a chemical crosslinking mode, so that the anchoring degree of the flame retardant component on the PE matrix in the PE material is improved, and compared with a direct adding mode, the migration resistance and exudation resistance of the effective component can be improved, and the lasting stability of the flame retardant effect is improved;
furthermore, the flame retardant disclosed by the invention also contains quaternary ammonium salt groups on molecules, and the quaternary ammonium salt belongs to a safe and nontoxic antibacterial active ingredient, so that the antibacterial performance of the PE material can be improved to a certain extent, the corrosion of the cable sheath to bacteria, mold and other microorganisms can be improved, and the use safety can be improved.
The invention has the beneficial effects that:
according to the invention, the synthetic flame retardant is added into the PE cable material, and the flame retardant has multiple flame retardant mechanisms and does not contain toxic halogen components, thus the PE cable material belongs to a high-efficiency and safe flame retardant; the flame retardant contains a plurality of unsaturated carbon-carbon double bonds, can participate in the crosslinking process of PE molecular chains in the melt blending process of the flame retardant and the PE matrix, and plays a role in promoting the formation of a crosslinked network structure, so that the mechanical strength, the wear resistance and the water resistance of PE materials are improved, the migration resistance and the exudation resistance of active ingredients are improved, and the lasting stability of the flame retardant effect is improved; the PE cable material with good flame retardant effect is obtained, and has very important application value in the fields of high temperature and flame retardance.
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. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Preparing composite filler:
uniformly mixing 8g of magnesium hydroxide and 4g of silicon dioxide to obtain a filler for standby; 33.2g of silane coupling agent KH550 was dissolved in 350mL of ethanol aqueous solution (volume fraction 60%), stirred at room temperature on a magnetic stirrer for 10min, then 10g of filler was added to the mixed solution, the temperature was raised to 80 ℃, the reaction was refluxed for 1h, centrifugally separated, washed 3 times with ethanol aqueous solution, finally the product was dried in a vacuum oven at 60℃for 5h, and ground to obtain a composite filler.
Example 2
Preparing a flame retardant:
s1, adding 11.3g of N-methyl-5-hexene-1-amine, 10.1g of triethylamine and tetrahydrofuran into a dry three-neck flask, placing the flask into an ice bath, stirring and mixing, slowly dripping 11g of 2-chloro-1, 3-propanediol into the flask through a constant pressure dropping funnel under stirring when the temperature of the system is stabilized at 0-2 ℃, reacting for 3 hours under normal temperature after the dripping is finished, filtering to remove salt, and removing the tetrahydrofuran through reduced pressure rotary evaporation to obtain an intermediate 1;
s2, continuously introducing nitrogen into a three-neck flask with a stirrer, a thermometer and a condenser tube for 10min (replacing air in the flask), adding 15.3g phosphorus oxychloride, 100mL dioxane and 24.2g N, N-dimethylaniline (acid binding agent), stirring and dissolving uniformly, then dropwise adding 50mL dioxane solution containing 18.7g intermediate 1, controlling the reaction temperature to be not higher than 40 ℃, heating to 100 ℃ after the dropwise adding, preserving heat for reaction for 12h, cooling to below 30 ℃, filtering to remove the generated N, N-dimethylaniline hydrochloride, removing the dioxane from the filtrate by vacuum distillation, washing twice with distilled water, separating out a lower organic phase, then adding ethyl acetate, drying by anhydrous magnesium sulfate, and removing the ethyl acetate from the filtrate by vacuum distillation to obtain intermediate 2;
s3, adding 26.8g of intermediate 2 and 120mL of acetonitrile into a three-neck flask with a stirring device, stirring uniformly, adding 20.8g of methyl iodide, stirring at room temperature for 16h, stopping the reaction, concentrating under reduced pressure (removing most of acetonitrile), adding 100mL of deionized water, exchanging by anion (Cl-) exchange resin, concentrating under reduced pressure, and obtaining an intermediate 3;
s4, adding 100mL of dichloromethane into a four-necked flask, introducing nitrogen, continuously adding 10min (removing air in the flask), adding 35.3g of intermediate 3 and 10.1g of triethylamine, stirring and uniformly mixing, dropwise adding 12.5g of 1, 3-bis (3-aminopropyl) tetramethyl disiloxane by adopting a constant pressure funnel, reacting for 4h under normal temperature after the dropwise addition is finished, removing generated triethylamine hydrochloride by suction filtration after the reaction is finished, and distilling filtrate under reduced pressure to obtain the flame retardant.
Example 3
Preparing a flame retardant:
s1, adding 22.6g of N-methyl-5-hexene-1-amine, 20.2g of triethylamine and tetrahydrofuran into a dry three-neck flask, placing the flask into an ice bath, stirring and mixing, slowly dripping 22g of 2-chloro-1, 3-propanediol into the flask through a constant pressure dropping funnel under stirring when the temperature of the system is stabilized at 0-2 ℃, reacting for 3 hours under normal temperature after the dripping is finished, filtering to remove salt, and removing the tetrahydrofuran through reduced pressure rotary evaporation to obtain an intermediate 1;
s2, continuously introducing nitrogen into a three-neck flask with a stirrer, a thermometer and a condenser tube for 10min (replacing air in the flask), adding 30.6g of phosphorus oxychloride, 180mL of dioxane and 48.4g of N, N-dimethylaniline (acid binding agent), stirring and dissolving uniformly, then dropwise adding 50mL of dioxane solution containing 37.4g of intermediate 1, controlling the reaction temperature to be not higher than 40 ℃ in the dropwise adding process, heating to 100 ℃ after the dropwise adding, preserving heat for reaction for 12h, cooling to below 30 ℃, filtering to remove generated N, N-dimethylaniline hydrochloride, removing dioxane from filtrate by vacuum distillation, washing twice with distilled water, separating out a lower organic phase, adding ethyl acetate, drying by anhydrous magnesium sulfate, and removing ethyl acetate from filtrate by vacuum distillation to obtain intermediate 2;
s3, adding 53.6g of intermediate 2 and 200mL of acetonitrile into a three-neck flask with a stirring device, stirring uniformly, adding 41.6g of methyl iodide, stirring at room temperature for 16h, stopping the reaction, concentrating under reduced pressure (removing most of acetonitrile), adding 180mL of deionized water, exchanging by anion (Cl-) exchange resin, concentrating under reduced pressure, and obtaining an intermediate 3;
s4, adding 200mL of dichloromethane into a four-necked flask, introducing nitrogen, continuously removing air in the flask for 10min, adding 70.6g of intermediate 3, 20.2g of triethylamine and dichloromethane, stirring and uniformly mixing, dropwise adding 25g of 1, 3-bis (3-aminopropyl) tetramethyl disiloxane by adopting a constant pressure funnel, reacting for 4h under normal temperature after the dropwise addition is finished, removing generated triethylamine hydrochloride by suction filtration after the reaction is finished, and distilling filtrate under reduced pressure to obtain the flame retardant.
Example 4
Preparing PE cable sheath material:
putting 1kg of PE resin, 80g of the composite filler prepared in the embodiment 1, 60g of the flame retardant prepared in the embodiment 2, 50g of polyethylene wax and 3g of calcium zinc stabilizer into a high-speed mixing stirrer for high-speed mixing at a rotating speed of 1500r/min for 15min to obtain a premix;
placing the premix and 2g of benzoyl peroxide into an internal mixer for internal mixing and plasticizing (the internal mixing temperature is 175 ℃ and the internal mixing and plasticizing is 18 min), then carrying out secondary plasticizing extrusion by a double-screw extruder, and drawing into strips for air-cooling and granulating to obtain the PE cable sheath material.
Example 5
Preparing PE cable sheath material:
1kg of PE resin, 100g of the composite filler prepared in the embodiment 1, 75g of the flame retardant prepared in the embodiment 3, 65g of chlorinated paraffin and 4g of calcium zinc stabilizer are placed into a high-speed mixing stirrer to be mixed at a high speed, the rotating speed is 1500r/min, and the mixing time is 18min, so as to obtain a premix;
placing the premix and 2.5g of benzoyl peroxide into an internal mixer for internal mixing and plasticizing (the internal mixing temperature is 175 ℃ and the internal mixing and plasticizing is 19 min), then carrying out secondary plasticizing extrusion by a double-screw extruder, and bracing and air-cooling to form granules to obtain the PE cable sheath material.
Example 6
Preparing PE cable sheath material:
1kg of PE resin, 120g of the composite filler prepared in the embodiment 1, 90g of the flame retardant prepared in the embodiment 2, 80g of paraffin and 5g of calcium zinc stabilizer are placed into a high-speed mixing stirrer to be mixed at a high speed, the rotating speed is 1500r/min, and the mixing time is 20min, so as to obtain premix;
placing the premix and 3g of benzoyl peroxide into an internal mixer for internal mixing and plasticizing (the internal mixing temperature is 175 ℃ and the internal mixing and plasticizing time is 20 minutes), and then performing secondary plasticizing extrusion through a double-screw extruder, and stretching and air-cooling to form granules to obtain the PE cable sheath material.
Comparative example
The flame retardant in example 4 was changed to a nitrogen-phosphorus flame retardant (HF-900A halogen-free flame retardant manufactured by Kang Nuode Co.) of the same quality, and the remaining raw materials and the preparation process were unchanged to obtain PE materials.
The PE materials obtained in examples 4 to 6 and comparative examples were processed and cut into test samples, and the following performance tests were performed:
mechanical properties: tensile strength and elongation at break were tested according to GB/T2951.11-2008; tear resistance was tested according to GB/T33594-2017;
flame retardancy: oxygen index was tested according to GB/T2406.2-2009; the single vertical combustion is tested according to GB/T18380-2008, and after hot air aging is carried out at 100 ℃ for 240 hours, the single vertical combustion test is continued;
the results are shown in the following table:
| example 4 | Example 5 | Example 6 | Comparative example | |
| Tensile Strength/MPa | 13.6 | 13.8 | 14.1 | 11.9 |
| Elongation at break/% | 238 | 230 | 223 | 242 |
| Tear strength/N.mm -1 | 25.4 | 25.7 | 26.0 | 24.1 |
| Oxygen index/% | 37.6 | 37.9 | 38.2 | 34.9 |
| Single vertical combustion (initial) | By passing through | By passing through | By passing through | By passing through |
| Single vertical combustion (after aging) | By passing through | By passing through | By passing through | Not pass through |
As can be seen from the data in the table, the PE cable material obtained by the invention has safe, efficient and durable flame retardant property and mechanical property meeting the requirements; according to the data of the comparative example, the flame retardant can not only improve the flame retardant property of the PE cable, but also promote the generation of a PE matrix crosslinked network structure, thereby improving the mechanical strength and the flame retardant lasting stability of PE.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (9)
1. The PE cable sheath material with good flame retardant effect is characterized by comprising the following raw materials in parts by weight: 100 parts of PE resin, 8-12 parts of composite filler, 6-9 parts of flame retardant, 5-8 parts of lubricant, 0.3-0.5 part of stabilizer and 0.2-0.3 part of initiator;
wherein the flame retardant is prepared by the following steps:
s1, adding N-methyl-5-hexene-1-amine, triethylamine and tetrahydrofuran into a dry three-neck flask, placing the flask into an ice bath, stirring and mixing, slowly dripping 2-chloro-1, 3-propanediol into the flask through a constant pressure dropping funnel under stirring when the temperature of the system is stabilized at 0-2 ℃, reacting for 3 hours under normal temperature after the dripping is finished, filtering to remove salt, and removing the tetrahydrofuran through reduced pressure rotary evaporation to obtain an intermediate 1;
s2, continuously introducing nitrogen into a three-neck flask for 10min, adding phosphorus oxychloride, dioxane and N, N-dimethylaniline, stirring and dissolving uniformly, then dropwise adding a dioxane solution of the intermediate 1, controlling the reaction temperature to be not higher than 40 ℃ in the dropwise adding process, heating to 100 ℃ after the dropwise adding process is finished, preserving heat for reaction for 12h, cooling to below 30 ℃, and performing aftertreatment to obtain an intermediate 2;
s3, adding the intermediate 2 and acetonitrile into a three-neck flask with a stirring device, stirring uniformly, then adding methyl iodide, stirring at room temperature for reaction for 16 hours, stopping the reaction, concentrating under reduced pressure, adding deionized water, exchanging by anion exchange resin, concentrating under reduced pressure, and obtaining an intermediate 3;
s4, adding dichloromethane into a four-neck flask, introducing nitrogen, continuously adding intermediate 3 and triethylamine after 10min, stirring and uniformly mixing, dropwise adding 1, 3-bis (3-aminopropyl) tetramethyl disiloxane by adopting a constant pressure funnel, reacting for 4h under normal temperature after the dropwise addition is completed, removing generated triethylamine hydrochloride by suction filtration after the reaction is completed, and distilling filtrate under reduced pressure to obtain the flame retardant.
2. The PE cable sheath material with good flame retardant effect according to claim 1, wherein the dosage ratio of N-methyl-5-hexene-1-amine, sodium bicarbonate and 2-chloro-1, 3-propanediol in the step S1 is 0.1mol:10.1g:0.1mol.
3. The PE cable sheath material with good flame retardant effect according to claim 1, wherein the post-treatment process in the step S2 is as follows: removing generated N, N-dimethylaniline hydrochloride by suction filtration, removing dioxane from the filtrate by reduced pressure distillation, washing twice by distilled water, separating out a lower organic phase, then adding ethyl acetate, drying by anhydrous magnesium sulfate, suction-filtering, and removing the ethyl acetate by reduced pressure distillation of the filtrate.
4. The PE cable sheath material with good flame retardant effect according to claim 1, wherein the dosage ratio of phosphorus oxychloride, N-dimethylaniline and intermediate 1 in the step S2 is 15.3g:24.2g:18.7g.
5. The PE cable sheath material with good flame retardant effect according to claim 1, wherein the ratio of the amount of the intermediate 2 to the amount of methyl iodide in the step S3 is 26.8g to 20.8g.
6. The PE cable sheath material with good flame retardant effect according to claim 1, wherein the ratio of the amount of the intermediate 3, triethylamine and 1, 3-bis (3-aminopropyl) tetramethyldisiloxane in the step S4 is 35.3g:10.1g:12.5g.
7. The PE cable sheath material with good flame retardant effect according to claim 1, wherein the composite filler is obtained by surface treatment of magnesium hydroxide and silicon dioxide according to a mass ratio of 2:1.
8. The PE cable sheath material with good flame retardant effect according to claim 1, wherein the lubricant is one or more of polyethylene wax, chlorinated paraffin and paraffin.
9. The preparation method of the PE cable sheath material with good flame retardant effect as claimed in claim 1, which is characterized by comprising the following steps:
placing PE resin, composite filler, flame retardant, lubricant and stabilizer into a high-speed mixing stirrer for high-speed mixing to obtain premix;
placing the premix and the initiator into an internal mixer for banburying and plasticizing, then carrying out secondary plasticizing extrusion through a double-screw extruder, and bracing and air-cooling to form granules to obtain the PE cable sheath material.
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| CN117659564A (en) * | 2023-11-24 | 2024-03-08 | 广州银塑阻燃新材料股份有限公司 | High-temperature-resistant PP halogen-free flame retardant master batch and preparation method thereof |
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| CN103387589A (en) * | 2013-07-31 | 2013-11-13 | 中国科学技术大学 | Phosphor-nitrogen containing silane A, phosphite ester halogen-free flame retardant containing nitrogen phosphor silicon and preparation method of phosphite ester halogen-free flame retardant |
| CN114974705A (en) * | 2022-06-16 | 2022-08-30 | 安徽蒙特尔电缆集团有限公司 | Fireproof cable |
| CN115746432A (en) * | 2022-11-13 | 2023-03-07 | 深圳市宝御顺实业有限公司 | Environment-friendly regenerated flame-retardant plastic and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103387589A (en) * | 2013-07-31 | 2013-11-13 | 中国科学技术大学 | Phosphor-nitrogen containing silane A, phosphite ester halogen-free flame retardant containing nitrogen phosphor silicon and preparation method of phosphite ester halogen-free flame retardant |
| CN114974705A (en) * | 2022-06-16 | 2022-08-30 | 安徽蒙特尔电缆集团有限公司 | Fireproof cable |
| CN115746432A (en) * | 2022-11-13 | 2023-03-07 | 深圳市宝御顺实业有限公司 | Environment-friendly regenerated flame-retardant plastic and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117659564A (en) * | 2023-11-24 | 2024-03-08 | 广州银塑阻燃新材料股份有限公司 | High-temperature-resistant PP halogen-free flame retardant master batch and preparation method thereof |
| CN117659564B (en) * | 2023-11-24 | 2024-05-03 | 广州银塑阻燃新材料股份有限公司 | High-temperature-resistant PP halogen-free flame retardant master batch and preparation method thereof |
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