CN116253947B - Halogen-free low-smoke flame-retardant polyolefin sheath material and preparation process thereof - Google Patents
Halogen-free low-smoke flame-retardant polyolefin sheath material and preparation process thereof Download PDFInfo
- Publication number
- CN116253947B CN116253947B CN202310413407.6A CN202310413407A CN116253947B CN 116253947 B CN116253947 B CN 116253947B CN 202310413407 A CN202310413407 A CN 202310413407A CN 116253947 B CN116253947 B CN 116253947B
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- parts
- halogen
- sheath material
- polyolefin sheath
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 127
- 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 94
- 239000000463 material Substances 0.000 title claims abstract description 54
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000000779 smoke Substances 0.000 title claims abstract description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229920001577 copolymer Polymers 0.000 claims abstract description 36
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims abstract description 31
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 19
- QWDQYHPOSSHSAW-UHFFFAOYSA-N 1-isocyanatooctadecane Chemical compound CCCCCCCCCCCCCCCCCCN=C=O QWDQYHPOSSHSAW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920001971 elastomer Polymers 0.000 claims abstract description 12
- 239000000806 elastomer Substances 0.000 claims abstract description 12
- 229920001903 high density polyethylene Polymers 0.000 claims abstract description 12
- 239000004700 high-density polyethylene Substances 0.000 claims abstract description 12
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000000314 lubricant Substances 0.000 claims abstract description 5
- 150000001451 organic peroxides Chemical class 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 22
- 125000000129 anionic group Chemical group 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 18
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 15
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 15
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 15
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 14
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 12
- 229910044991 metal oxide Inorganic materials 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 10
- 150000004706 metal oxides Chemical class 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 8
- 244000028419 Styrax benzoin Species 0.000 claims description 7
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 7
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 7
- 229960002130 benzoin Drugs 0.000 claims description 7
- 235000019382 gum benzoic Nutrition 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 6
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 claims description 6
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 230000001678 irradiating effect Effects 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- 238000012545 processing Methods 0.000 abstract description 16
- 230000008569 process Effects 0.000 abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 abstract description 6
- 239000001301 oxygen Substances 0.000 abstract description 6
- -1 polyethylene Polymers 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 239000010410 layer Substances 0.000 description 8
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229920013716 polyethylene resin Polymers 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000013307 optical fiber Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000012650 click reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920006124 polyolefin elastomer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- PNGBYKXZVCIZRN-UHFFFAOYSA-M sodium;hexadecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCCS([O-])(=O)=O PNGBYKXZVCIZRN-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
-
- 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
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
-
- 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
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/02—Heterophasic composition
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of flame-retardant polyolefin sheath materials, in particular to a halogen-free low-smoke flame-retardant polyolefin sheath material and a preparation process thereof. The method comprises the following steps: step 1: preparing a halogen-free flame retardant; step 2: preparation of flame retardant synergist: dispersing montmorillonite in N, N-dimethylformamide, and modifying with octadecyl isocyanate to obtain flame retardant synergist; step 3: ethylene-octene copolymer elastomer, high-density polyethylene, ethylene-octene copolymer grafted maleic anhydride copolymer, halogen-free flame retardant, flame retardant synergist, lubricant and organic peroxide are stirred, mixed, kneaded and extruded to pelletize to obtain the polyolefin sheath material. The prepared polyolefin sheath material can still maintain excellent mechanical properties under the condition of high oxygen index, and has high presentation speed and easy processing and forming in the cable processing process.
Description
Technical Field
The invention relates to the technical field of flame-retardant polyolefin sheath materials, in particular to a halogen-free low-smoke flame-retardant polyolefin sheath material and a preparation process thereof.
Background
In recent years, the high-speed development of the communication industry makes the demand of the optical cable rise, and the research of the protective layer sheath material of the optical cable is greatly promoted. Because some optical fiber cables are paved underground or in pipelines and some optical fiber cables are paved indoors or outdoors of high buildings, the sheath material is required to have excellent mechanical properties, and fireproof and flame-retardant properties are also required to adapt to different application environments.
Currently, to improve the safety of electrical equipment and devices, sheathing materials have been developed toward low smoke and zero halogen. Polyvinyl chloride and other materials have been gradually replaced by polyethylene and other polyolefin materials due to the generation of a large amount of smoke. However, in polyolefin sheath materials such as polyethylene, either inorganic materials such as aluminum hydroxide are used to improve the flame retardancy of the polyolefin sheath materials or intumescent flame retardants having both flame retardancy and plasticization functions are used to achieve a flame retardant free of halogenation. Inorganic filler is used in the super halogen-free low-smoke flame-retardant sheath material disclosed in CN201610176191.6, and an intumescent flame retardant is used in the preparation process of the synergistic intumescent flame-retardant polyolefin elastomer cable material disclosed in CN 2016102072239.5; in both patents, in order to ensure flame retardant performance, a large amount of flame retardant is introduced, and the problems of compatibility and dispersibility caused by higher content exist, so that the mechanical properties of the polyolefin sheath material such as strength, toughness, deformability and the like are reduced, and the linear speed is slow in the cable processing process.
Therefore, the preparation of the halogen-free low-smoke flame-retardant polyolefin sheath material has important value.
Disclosure of Invention
The invention aims to provide a halogen-free low-smoke flame-retardant polyolefin sheath material and a preparation process thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
a preparation process of a halogen-free low-smoke flame-retardant polyolefin sheath material comprises the following steps:
step 1: preparation of halogen-free flame retardant:
(1) Mixing ammonium polyphosphate and pentaerythritol in proportion, and modifying by using oligosiloxane to obtain an intumescent flame retardant;
(2) Modifying the intumescent flame retardant by using 3-mercaptopropionic acid to obtain an anionic intumescent flame retardant;
(3) Dispersing the layered double metal oxide in deionized water by ultrasonic, adding an anionic intumescent flame retardant, stirring, filtering and drying to obtain a halogen-free flame retardant;
step 2: preparation of flame retardant synergist: dispersing montmorillonite in N, N-dimethylformamide, and modifying with octadecyl isocyanate to obtain flame retardant synergist;
step 3: ethylene-octene copolymer elastomer, high-density polyethylene, ethylene-octene copolymer grafted maleic anhydride copolymer, halogen-free flame retardant, flame retardant synergist, lubricant and organic peroxide are put into a high-speed stirrer, stirred and mixed, and transferred to a pressurized internal mixer; and mixing by a double-screw extruder, extruding by a single-screw extruder to pelletize by a pelleting machine, and obtaining the polyolefin sheath material.
Further, the polyolefin sheath material comprises the following raw materials: 30-32 parts of ethylene-octene copolymer elastomer, 14-18 parts of high-density polyethylene, 12-15 parts of ethylene-octene copolymer grafted maleic anhydride copolymer, 23-25 parts of halogen-free flame retardant, 12-15 parts of flame retardant synergist, 1-2 parts of lubricant and 0.2-0.5 part of organic peroxide.
Further, the preparation method of the halogen-free flame retardant comprises the following specific steps:
(1) Mixing ammonium polyphosphate and pentaerythritol in proportion, adding the mixture into an oligosiloxane solution, stirring the mixture for 3 to 4 hours at a temperature of between 40 and 50 ℃, and carrying out suction filtration and drying to obtain an intumescent flame retardant;
(2) Dispersing an intumescent flame retardant into N, N-dimethylformamide, adding 3-mercaptopropionic acid and benzoin dimethyl ether, and at room temperature, under the wavelength of 365nm, the strength is 120-150W/cm 2 Irradiating with ultraviolet light for 5-10 minutes, filtering, washing and drying to obtain the anionic intumescent flame retardant;
(3) And (3) ultrasonically dispersing the layered double metal oxide in deionized water to obtain a dispersion liquid with the concentration of 4-6 g/L, adding the anionic intumescent flame retardant, stirring, filtering and drying to obtain the halogen-free flame retardant.
Further, the intumescent flame retardant comprises ammonium polyphosphate, pentaerythritol and oligosiloxane in a mass ratio of 0.75:0.25 (1.5-2);
the raw materials of the anionic intumescent flame retardant comprise: 100 parts of N, N-dimethylformamide, 20-24 parts of intumescent flame retardant, 22-25 parts of 3-mercaptopropionic acid and 2-3 parts of benzoin dimethyl ether;
in the halogen-free flame retardant, the mass ratio of the layered bimetallic oxide to the anionic intumescent flame retardant is (2.5-3): 2-2.5.
Further, the preparation process of the oligosiloxane comprises the following steps: sequentially adding methyltrimethoxysilane, methylvinyldimethoxysilane, vinyltrimethoxysilane and ethanol into a reaction kettle, uniformly stirring, adding hydrochloric acid, heating to 60-70 ℃, dropwise adding deionized water, stirring for 4-5 hours, and performing rotary evaporation to obtain the oligosiloxane.
Further, in the oligosiloxane, the mass ratio of methyltrimethoxysilane, methylvinyldimethoxysilane and vinyltrimethoxysilane is 1:5:2.
Further, the specific preparation process of the flame retardant synergist comprises the following steps: dispersing montmorillonite in N, N-dimethylformamide, adding octadecyl isocyanate and dibutyl tin dilaurate, heating to 80-90 ℃, stirring for reacting for 2-3 hours, washing and drying to obtain the flame retardant synergist.
Further, the raw materials of the flame retardant synergist comprise: 100 parts of N, N-dimethylformamide, 6-9 parts of montmorillonite and 4-6 parts of octadecyl isocyanate.
Further, in the step 3, the processing temperature of the high-speed stirrer is 120-130 ℃; the processing temperature of the double-screw extruder is as follows: 100-120 ℃ of conveying section, 125-140 ℃ of melting section, 140-155 ℃ of mixing section, 150-160 ℃ of exhaust section, 150-160 ℃ of homogenizing section and 165-175 ℃ of machine head; the processing temperature of the single screw extruder is as follows: the first area is 125-140 ℃, the second area is 125-140 ℃, the third area is 125-140 ℃, and the machine head is 145-150 ℃, and the machine head is cooled by cyclone.
Further, the polyolefin sheath material is prepared by a preparation process of the halogen-free low-smoke flame-retardant polyolefin sheath material.
The beneficial effects in the scheme are as follows:
(1) In the scheme, the prepared polyolefin sheath material has good insulating property, flame retardance and low smoke performance, and is halogen-free, green and pollution-free; and under the condition of high oxygen index, the cable can still keep excellent mechanical properties, has higher presentation speed in the process of processing the cable, and is easy to process and form.
(2) In the scheme, through the optimal design of the formula, an ethylene-octene copolymer elastomer, high-density polyethylene and an ethylene-octene copolymer grafted maleic anhydride copolymer are used as matrix resin; preparing an intumescent flame retardant, and then anionizing to modify the layered bimetallic oxide to obtain a halogen-free flame retardant serving as a main flame retardant; then octadecyl isocyanate modified montmorillonite is used as a synergist, so that the problems of mechanical property and processing property degradation caused by high-performance flame retardance are solved.
Wherein, the thermoplastic resin of the polyolefin sheath material adopts ethylene-octene copolymer elastomer, high-density polyethylene and ethylene-octene copolymer grafted maleic anhydride copolymer, which effectively ensures the processability of the sheath material and the compatibility with inorganic materials, thereby improving the mechanical property of the polyolefin sheath material.
The halogen-free flame retardant is an intumescent flame retardant based on ammonium polyphosphate and pentaerythritol, and is modified in an oligosiloxane solution to obtain the intumescent flame retardant; enhancing the compatibility with the base resin, improving the mechanical property and improving the flame retardance and smoke suppression. Specifically: the oligosiloxane is obtained by hydrolysis and self-polymerization of methyltrimethoxysilane, methylvinyldimethoxysilane and vinyltrimethoxysilane, has good thermal stability and can assist in enhancing flame retardance; firstly, the flexible silica bond is contained, so that the tensile strength of the polyolefin sheath material can be improved. Secondly, the self-curing coating has low-temperature self-curing performance, can coat the surfaces of ammonium polyphosphate and pentaerythritol, has good compatibility between vinyl and polyolefin, effectively improves the dispersibility, and simultaneously, because the oligosiloxane can generate silicon dioxide in the pyrolysis process, the compactness of a carbon layer is effectively improved, the flame retardance is increased, and the smoke suppression rate is reduced.
Then modifying the intumescent flame retardant by using mercaptopropionic acid, and grafting carboxyl by using a click reaction of vinyl-mercapto to obtain an anionic intumescent flame retardant; and the halogen-free flame retardant is obtained by compounding the flame retardant with the layered bimetallic oxide under the action of static electricity. Specifically: the layered double metal oxide has extremely strong thermal stability, gas barrier property and mechanical property, and the introduction of the layered double metal oxide effectively enhances the property of the polyolefin material. However, the hydroxyl groups are arranged on the laminate, the crystal water is arranged between the layers, the compatibility with polyolefin is poor, and the rest of the anionic intumescent flame retardant is compounded, so that the compatibility of the anionic intumescent flame retardant in polyethylene resin can be effectively enhanced, and the mechanical property is improved.
The flame retardant synergist is prepared from octadecyl isocyanate modified montmorillonite, wherein the montmorillonite is a silicate sheet layer with good thermal stability, compressive strength and expansibility, the silicate sheet layer effectively promotes the formation of an expanded carbon layer, the stability of the carbon layer is increased, severe combustion is inhibited, carbamate generated when the octadecyl isocyanate is modified with montmorillonite can be decomposed to generate isocyanate and alcohol in the initial pyrolysis process, and isocyanate groups can generate a structure similar to polyimide with maleic anhydride in matrix resin, so that the carbon residue rate and the density of the carbon layer are enhanced, and the flame retardance and smoke suppression performance are effectively enhanced. Meanwhile, the octadecyl isocyanate is modified, so that the lipophilicity of the material can be enhanced, the dispersibility in polyethylene resin can be enhanced, and the aggregation of the material is inhibited; meanwhile, the long chain is introduced, so that intercalation of montmorillonite is enhanced, heterogeneous nucleation of polyethylene resin is enhanced, and tensile strength of polyolefin sheath material is enhanced.
In conclusion, the optimized design of the polyolefin sheath material effectively increases the acting force between polymer molecules and between an organic phase and an inorganic phase, reduces intermolecular shedding and increases the interpenetration between polymer molecules; thereby ensuring the high flame retardance of the polyolefin sheath material and simultaneously ensuring the mechanical property.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but 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.
In the following embodiments, parts are mass units, 1 part is 100g; the ethylene-octene copolymer elastomer is ceramic 9507; the high density polyethylene is music day chemistry 2600F; the ethylene-octene copolymer grafted maleic anhydride copolymer is Exxon PO-1020; the polymerization degree of the ammonium polyphosphate is more than 1000, and the ammonium polyphosphate is purchased from the Tianyuan synthetic chemical plant in Jinhua city; the CAS number of pentaerythritol is 115-77-5, and the CAS number of octadecyl isocyanate is 2877-26-1, which are all commercially available; the CAS number of the sodium montmorillonite is 1318-93-0, and the specific surface area is 240m 2 /g, purchased from Shanghai source leaves.
In addition, the preparation process of the layered double metal oxide comprises the following steps: adding 0.06g of nickel nitrate, 0.05g of ferric sulfate and 0.6g of urea into 60g of deionized water in sequence, stirring uniformly, placing into a reaction kettle, sealing, reacting for 10 hours at 120 ℃, cooling, washing, drying, placing into a high-temperature furnace, and calcining for 4 hours at 400 ℃ to obtain the layered double metal oxide.
The preparation process of the oligosiloxane comprises the following steps: 10 parts of methyltrimethoxysilane, 50 parts of methylvinyldimethoxysilane, 20 parts of vinyltrimethoxysilane and 100 parts of ethanol are sequentially added into a reaction kettle, uniformly stirred, 2 parts of hydrochloric acid is added, the temperature is raised to 65 ℃,50 parts of deionized water is dropwise added, stirring is carried out for 4 hours at 500rpm, and the solvent is removed by rotary evaporation, so that the oligosiloxane is obtained.
Example 1: step 1: preparation of halogen-free flame retardant:
(1) Mixing 0.75 part of ammonium polyphosphate and 0.25 part of pentaerythritol in proportion, adding the mixture into an oligosiloxane ethanol solution with the concentration of 18 percent (the oligosiloxane content is 1.8 parts), stirring the mixture for 3 hours at 45 ℃, and carrying out suction filtration and drying to obtain an intumescent flame retardant;
(2) Dispersing 22 parts of intumescent flame retardant in 100 parts of N, N-dimethylformamide, adding 22 parts of 3-mercaptopropionic acid and 2 parts of benzoin dimethyl ether, and maintaining the strength of 125W/cm at a wavelength of 365nm at room temperature 2 Irradiating for 8 minutes under ultraviolet light, filtering, washing and drying to obtain the anionic intumescent flame retardant;
(3) And (3) ultrasonically dispersing 5 parts of layered double metal oxide in deionized water to obtain a dispersion liquid with the concentration of 5g/L, adding 4.5 parts of anionic intumescent flame retardant, stirring, filtering and drying to obtain the halogen-free flame retardant.
Step 2: preparation of flame retardant synergist: 8 parts of sodium montmorillonite is dispersed in 100 parts of N, N-dimethylformamide, 5 parts of octadecylisocyanate and 0.2 part of dibutyltin dilaurate are added, the temperature is raised to 80 ℃, the mixture is stirred for 3 hours, and the mixture is washed and dried to obtain the flame retardant synergist.
Step 3: 30 parts of ethylene-octene copolymer elastomer, 16 parts of high-density polyethylene, 14 parts of ethylene-octene copolymer grafted maleic anhydride copolymer, 24 parts of halogen-free flame retardant, 14 parts of flame retardant synergist, 2 parts of polyethylene wax and 0.3 part of dibenzoyl peroxide are put into a high-speed stirrer and stirred and mixed for 10 minutes at 120 ℃; putting the materials into a high-speed mixer, mixing and stirring, and transferring the materials to a pressurized internal mixer; and then mixing by a double-screw extruder, extruding by a single-screw extruder to a granulator for granulation, wherein the processing temperature of the double-screw extruder is as follows: conveying section 110 ℃, melting section 130 ℃, mixing section 145 ℃, exhaust section 155 ℃, homogenizing section 160 ℃ and machine head 170 ℃; the processing temperature of the single screw extruder is as follows: the polyolefin sheath material is obtained by cyclone cooling at 125 ℃ in the first zone, 130 ℃ in the second zone, 140 ℃ in the third zone and 145 ℃ in the machine head.
Example 2: step 1: preparation of halogen-free flame retardant:
(1) Mixing 0.75 part of ammonium polyphosphate and 0.25 part of pentaerythritol in proportion, adding the mixture into an oligosiloxane ethanol solution with the concentration of 15 percent (the oligosiloxane content is 1.5 parts), stirring the mixture for 3 hours at 45 ℃, and carrying out suction filtration and drying to obtain an intumescent flame retardant;
(2) Dispersing 20 parts of intumescent flame retardant in 100 parts of N, N-dimethylformamide, adding 22 parts of 3-mercaptopropionic acid and benzoin dimethyl ether, and maintaining the strength of 125W/cm at 365nm at room temperature 2 Irradiating for 8 minutes under ultraviolet light, filtering, washing and drying to obtain the anionic intumescent flame retardant;
(3) And (3) ultrasonically dispersing 5 parts of layered double metal oxide in deionized water to obtain a dispersion liquid with the concentration of 4g/L, adding 5 parts of anionic intumescent flame retardant, stirring, filtering and drying to obtain the halogen-free flame retardant.
Step 2: preparation of flame retardant synergist: 6 parts of sodium montmorillonite is dispersed in 100 parts of N, N-dimethylformamide, 4 parts of octadecylisocyanate and 0.2 part of dibutyltin dilaurate are added, the temperature is raised to 80 ℃, the mixture is stirred for 3 hours, and the mixture is washed and dried to obtain the flame retardant synergist.
Step 3: 30 parts of ethylene-octene copolymer elastomer, 14 parts of high-density polyethylene, 12 parts of ethylene-octene copolymer grafted maleic anhydride copolymer, 25 parts of halogen-free flame retardant, 15 parts of flame retardant synergist, 2 parts of polyethylene wax and 0.3 part of dibenzoyl peroxide are put into a high-speed stirrer and stirred and mixed for 10 minutes at 120 ℃; putting the materials into a high-speed mixer, mixing and stirring, and transferring the materials to a pressurized internal mixer; and then mixing by a double-screw extruder, extruding by a single-screw extruder to a granulator for granulation, wherein the processing temperature of the double-screw extruder is as follows: conveying section 110 ℃, melting section 130 ℃, mixing section 145 ℃, exhaust section 155 ℃, homogenizing section 160 ℃ and machine head 170 ℃; the processing temperature of the single screw extruder is as follows: the polyolefin sheath material is obtained by cyclone cooling at 125 ℃ in the first zone, 130 ℃ in the second zone, 140 ℃ in the third zone and 145 ℃ in the machine head.
Example 3: step 1: preparation of halogen-free flame retardant:
(1) Mixing 0.75 part of ammonium polyphosphate and 0.25 part of pentaerythritol in proportion, adding the mixture into an oligosiloxane ethanol solution with the concentration of 20 percent (the oligosiloxane content is 2 parts), stirring the mixture for 3 hours at 45 ℃, and carrying out suction filtration and drying to obtain an intumescent flame retardant;
(2) 24 parts of intumescent flame retardant are dispersed in 100 parts of N, N-dimethylformamide, 25 parts of 3-mercaptopropionic acid and benzoin dimethyl ether are added, and the strength is 125W/cm at room temperature and at a wavelength of 365nm 2 Irradiating for 8 minutes under ultraviolet light, filtering, washing and drying to obtain the anionic intumescent flame retardant;
(3) And (3) ultrasonically dispersing 6 parts of layered double metal oxide in deionized water to obtain a dispersion liquid with the concentration of 6g/L, adding 4 parts of anionic intumescent flame retardant, stirring, filtering and drying to obtain the halogen-free flame retardant.
Step 2: preparation of flame retardant synergist: 9 parts of sodium montmorillonite is dispersed in 100 parts of N, N-dimethylformamide, 6 parts of octadecylisocyanate and 0.2 part of dibutyltin dilaurate are added, the temperature is raised to 80 ℃, the mixture is stirred for 3 hours, and the mixture is washed and dried to obtain the flame retardant synergist.
Step 3: adding 32 parts of ethylene-octene copolymer elastomer, 18 parts of high-density polyethylene, 15 parts of ethylene-octene copolymer grafted maleic anhydride copolymer, 23 parts of halogen-free flame retardant, 12 parts of flame retardant synergist, 2 parts of polyethylene wax and 0.3 part of dibenzoyl peroxide into a high-speed stirrer, and stirring and mixing for 10 minutes at 120 ℃; putting the materials into a high-speed mixer, mixing and stirring, and transferring the materials to a pressurized internal mixer; and then mixing by a double-screw extruder, extruding by a single-screw extruder to a granulator for granulation, wherein the processing temperature of the double-screw extruder is as follows: conveying section 110 ℃, melting section 130 ℃, mixing section 145 ℃, exhaust section 155 ℃, homogenizing section 160 ℃ and machine head 170 ℃; the processing temperature of the single screw extruder is as follows: the polyolefin sheath material is obtained by cyclone cooling at 125 ℃ in the first zone, 130 ℃ in the second zone, 140 ℃ in the third zone and 145 ℃ in the machine head.
Comparative example 1: ammonium polyphosphate, pentaerythritol and a bimetallic oxide were directly used as intumescent flame retardants, the rest being the same as in example 1;
specifically: mixing and drying 0.75 part of ammonium polyphosphate, 0.25 part of pentaerythritol and 5 parts of lamellar bimetallic oxide to obtain the halogen-free flame retardant.
Comparative example 2: the modification with 3-mercaptopropionic acid was omitted and the rest was the same as in example 1;
specifically: (1) Mixing 0.75 part of ammonium polyphosphate and 0.25 part of pentaerythritol in proportion, adding the mixture into an oligosiloxane ethanol solution with the concentration of 18 percent (the oligosiloxane content is 1.8 parts), stirring the mixture for 3 hours at 45 ℃, and carrying out suction filtration and drying to obtain an intumescent flame retardant;
(2) And (3) uniformly mixing 22 parts of intumescent flame retardant with 5 parts of lamellar bimetallic oxide to obtain the halogen-free flame retardant.
Comparative example 3: flame retardant synergist was not introduced, and the rest was the same as in example 1;
specifically: 30 parts of ethylene-octene copolymer elastomer, 16 parts of high-density polyethylene, 14 parts of ethylene-octene copolymer grafted maleic anhydride copolymer, 38 parts of halogen-free flame retardant, 2 parts of polyethylene wax and 0.3 part of dibenzoyl peroxide are put into a high-speed stirrer and stirred and mixed for 10 minutes at 120 ℃; putting the materials into a high-speed mixer, mixing and stirring, and transferring the materials to a pressurized internal mixer; and then mixing by a double-screw extruder, extruding by a single-screw extruder to a granulator for granulation, wherein the processing temperature of the double-screw extruder is as follows: conveying section 110 ℃, melting section 130 ℃, mixing section 145 ℃, exhaust section 155 ℃, homogenizing section 160 ℃ and machine head 170 ℃; the processing temperature of the single screw extruder is as follows: the polyolefin sheath material is obtained by cyclone cooling at 125 ℃ in the first zone, 130 ℃ in the second zone, 140 ℃ in the third zone and 145 ℃ in the machine head.
Comparative example 4: montmorillonite was directly added without modification, and the rest was the same as in example 1.
Comparative example 5: sodium cetyl sulfonate modified montmorillonite was used, the remainder being the same as in example 1;
specifically: 8 parts of sodium montmorillonite is dispersed in 100 parts of deionized water, 5 parts of sodium hexadecyl sulfonate is added, stirring is carried out for 3 hours, and the flame retardant synergist is obtained after filtration and drying.
Experiment: the polyolefin sheath material prepared in the scheme is injection molded into a spline, and the mechanical property and the flame retardant property are tested. Taking 75X 4X 1mm 3 Is used for the spline of (B) and is based on GB/T1040.3-2006, a universal test is usedThe tensile strength was measured at a tensile rate of 50mm/min at 25℃in an inspection machine. 80X 10X 4mm is taken 3 Using an oxygen index meter, the oxygen concentration was adjusted to maintain the minimum oxygen content required for combustion for 50mm, using GB/T2406-2009 as a standard. Taking 75X 1mm 3 And (3) using a smoke density tester to test under the flameless condition by taking GB/T8323-87 as a standard to obtain the smoke density. The specific table is shown below:
the data indicate that: in the scheme, the halogen-free flame retardant containing the layered double hydroxide metal oxide is prepared, and the organically modified montmorillonite is synergistically contained to form the compound flame retardant, so that the flame retardance and the low smoke performance are effectively improved, and meanwhile, the high mechanical property is effectively ensured. As in example 1, the limiting oxygen index was 35.6% and the tensile strength was as high as 18MPa.
Comparison of the comparative example with example 1 shows that: in comparative example 1, since polysiloxane and anion modification are not used, compatibility and dispersibility are lowered, and flame retardance and mechanical properties are lowered; in comparative example 2, since the anionic modification is not used, the dispersibility of the layered double hydroxide metal oxide is lowered, so that the performance is lowered; in comparative example 3, since the flame retardant synergist was not introduced, no synergistic effect was generated, so that the flame retardant property was lowered; in comparative example 4, since montmorillonite was not modified, compatibility was lowered, and performance was lowered; in comparative example 5, since the montmorillonite modified with the isocyanate group-containing substance was not used, the compactness of the carbon layer was lowered, so that the flame retardant property was lowered. The above comparative examples demonstrate that: the modification of the oligosiloxane can effectively reduce the smoke density and improve the flame retardance and the mechanical property; the halogen-free flame retardant and the synergist have synergistic effect, and compared with other substances, the hexadecyl isocyanate modified montmorillonite has better performance than other substances due to the similar polyimide structure formed in the pyrolysis process.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (2)
1. A preparation process of a halogen-free low-smoke flame-retardant polyolefin sheath material is characterized by comprising the following steps of: the method comprises the following steps:
step 1: preparation of halogen-free flame retardant:
(1) Mixing ammonium polyphosphate and pentaerythritol in proportion, adding the mixture into the oligosiloxane solution, stirring the mixture for 3 to 4 hours at a temperature of between 40 and 50 ℃, and carrying out suction filtration and drying to obtain an intumescent flame retardant;
(2) Dispersing the intumescent flame retardant in N, N-dimethylformamide, adding 3-mercaptopropionic acid and benzoin dimethyl ether, and at room temperature, under the wavelength of 365nm, the strength is 120-150W/cm 2 Irradiating with ultraviolet light for 5-10 min, filtering, washing and drying to obtain anionic intumescent flame retardant;
(3) Ultrasonically dispersing the layered double metal oxide in deionized water to obtain a dispersion liquid with the concentration of 4-6 g/L, adding an anionic intumescent flame retardant, stirring, filtering and drying to obtain a halogen-free flame retardant;
step 2: preparation of flame retardant synergist: dispersing montmorillonite in N, N-dimethylformamide, adding octadecylisocyanate and dibutyltin dilaurate, heating to 80-90 ℃, stirring for reacting for 2-3 hours, washing and drying to obtain a flame-retardant synergist;
step 3: ethylene-octene copolymer elastomer, high-density polyethylene, ethylene-octene copolymer grafted maleic anhydride copolymer, halogen-free flame retardant, flame retardant synergist, lubricant and organic peroxide are stirred, mixed, kneaded, extruded and granulated to obtain polyolefin sheath material;
the polyolefin sheath material comprises the following raw materials: 30-32 parts of ethylene-octene copolymer elastomer, 14-18 parts of high-density polyethylene, 12-15 parts of ethylene-octene copolymer grafted maleic anhydride copolymer, 23-25 parts of halogen-free flame retardant, 12-15 parts of flame retardant synergist, 1-2 parts of lubricant and 0.2-0.5 part of organic peroxide;
the intumescent flame retardant comprises ammonium polyphosphate, pentaerythritol and oligosiloxane with the mass ratio of (1.5-2) being 0.75:0.25;
the raw materials of the anionic intumescent flame retardant comprise: 100 parts of N, N-dimethylformamide, 20-24 parts of intumescent flame retardant, 22-25 parts of 3-mercaptopropionic acid and 2-3 parts of benzoin dimethyl ether;
in the halogen-free flame retardant, the mass ratio of the layered bimetallic oxide to the anionic intumescent flame retardant is (2.5-3) (2-2.5);
the flame retardant synergist comprises the following raw materials: 100 parts of N, N-dimethylformamide, 6-9 parts of montmorillonite and 4-6 parts of octadecyl isocyanate according to weight fraction;
the preparation process of the oligosiloxane comprises the following steps: sequentially adding methyltrimethoxysilane, methylvinyldimethoxysilane, vinyltrimethoxysilane and ethanol into a reaction kettle, uniformly stirring, adding hydrochloric acid, heating to 60-70 ℃, dropwise adding deionized water, stirring for 4-5 hours, and performing rotary evaporation to obtain oligosiloxane; in the oligosiloxane, the mass ratio of the methyltrimethoxysilane to the methylvinyldimethoxysilane to the vinyltrimethoxysilane is 1:5:2.
2. The polyolefin sheath material prepared by the preparation process of the halogen-free low-smoke flame retardant polyolefin sheath material according to claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310049593 | 2023-02-01 | ||
| CN202310049593X | 2023-02-01 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116253947A CN116253947A (en) | 2023-06-13 |
| CN116253947B true CN116253947B (en) | 2023-10-27 |
Family
ID=86688166
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310413407.6A Active CN116253947B (en) | 2023-02-01 | 2023-04-18 | Halogen-free low-smoke flame-retardant polyolefin sheath material and preparation process thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116253947B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117777621A (en) * | 2023-12-28 | 2024-03-29 | 广东金榜塑料包装有限公司 | Modified PVC plastic particle |
| CN117986745B (en) * | 2024-02-22 | 2024-07-30 | 江苏馨德高分子材料股份有限公司 | LDHs-based synergistic flame-retardant cable insulation material and preparation process thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101280086A (en) * | 2008-05-09 | 2008-10-08 | 浙江工业大学 | Special material for environment-friendly flame-proof polypropylene and preparation thereof |
| CN101293984A (en) * | 2007-04-28 | 2008-10-29 | 中国石油化工股份有限公司 | Expanded carbon flame-proof polypropelene composition and preparation method thereof |
| CN102321274A (en) * | 2011-06-21 | 2012-01-18 | 浙江工业大学 | A kind of hydrotalcite-ammonium polyphosphate halogen-free flame retardants and preparation method thereof |
| CN103333403A (en) * | 2013-07-01 | 2013-10-02 | 北京化工大学 | Halogen-free intumescent flame retardant polyolefine cable sheath material and preparation method thereof |
| CN103467832A (en) * | 2013-06-03 | 2013-12-25 | 公安部四川消防研究所 | Low temperature-resistant flexible crosslinkable halogen-free flame retardant cable material and preparation method thereof |
| CN104530519A (en) * | 2014-11-21 | 2015-04-22 | 哈尔滨理工大学 | Halogen-free low-smoke fire-resistant cable material, and preparation method thereof |
| CN113549269A (en) * | 2021-07-29 | 2021-10-26 | 河南大学 | Application of nickel cobaltate as flame-retardant synergist |
-
2023
- 2023-04-18 CN CN202310413407.6A patent/CN116253947B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101293984A (en) * | 2007-04-28 | 2008-10-29 | 中国石油化工股份有限公司 | Expanded carbon flame-proof polypropelene composition and preparation method thereof |
| CN101280086A (en) * | 2008-05-09 | 2008-10-08 | 浙江工业大学 | Special material for environment-friendly flame-proof polypropylene and preparation thereof |
| CN102321274A (en) * | 2011-06-21 | 2012-01-18 | 浙江工业大学 | A kind of hydrotalcite-ammonium polyphosphate halogen-free flame retardants and preparation method thereof |
| CN103467832A (en) * | 2013-06-03 | 2013-12-25 | 公安部四川消防研究所 | Low temperature-resistant flexible crosslinkable halogen-free flame retardant cable material and preparation method thereof |
| CN103333403A (en) * | 2013-07-01 | 2013-10-02 | 北京化工大学 | Halogen-free intumescent flame retardant polyolefine cable sheath material and preparation method thereof |
| CN104530519A (en) * | 2014-11-21 | 2015-04-22 | 哈尔滨理工大学 | Halogen-free low-smoke fire-resistant cable material, and preparation method thereof |
| CN113549269A (en) * | 2021-07-29 | 2021-10-26 | 河南大学 | Application of nickel cobaltate as flame-retardant synergist |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116253947A (en) | 2023-06-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN116253947B (en) | Halogen-free low-smoke flame-retardant polyolefin sheath material and preparation process thereof | |
| CN113956572B (en) | Flame-retardant polyolefin composition and preparation method thereof | |
| CN104774372B (en) | A kind of high performance cable flame-proof material and preparation method thereof | |
| CN102952316A (en) | Halogen-free inflaming retarding insulating material of nuclear cable and cable insulating layer as well as preparation method and application thereof | |
| CN113292777B (en) | Fireproof flame-retardant sheath material, and preparation method and application thereof | |
| CN109369958B (en) | Preparation method and application of organically modified zirconium phosphate | |
| CN110776690A (en) | 105 ℃ B1-grade irradiation crosslinking halogen-free low-smoke flame-retardant polyolefin elastomer insulating material and preparation method thereof | |
| CN114133657A (en) | Preparation method of high-performance flame-retardant low-smoke halogen-free polyolefin cable material | |
| CN117362979B (en) | Halogen-free flame-retardant PPO composite material and preparation method thereof | |
| CN112812420B (en) | Low-smoke halogen-free cable material containing functional compatilizer and preparation thereof | |
| CN103694549A (en) | Low-temperature-resistant oil-resistant halogen-free flame-retardant crosslinking cable sheath material and preparation method thereof | |
| CN113956588A (en) | Anti-aging flame-retardant PVC material, preparation method and application thereof in wires or cables | |
| CN117844141A (en) | Compression-resistant wear-resistant cable material and preparation method thereof | |
| CN113861550A (en) | B1-grade ultraviolet light crosslinking low-smoke halogen-free flame-retardant cable material and preparation method thereof | |
| CN117004127A (en) | Chitosan-based high-flame-retardance MPP pipe and preparation method thereof | |
| CN115073845A (en) | Flexible crosslinked ethylene-tetrafluoroethylene copolymer insulated light wire cable | |
| CN111393771B (en) | PVC flame-retardant plastic particle for wires and cables and preparation process thereof | |
| CN113717456A (en) | Preparation method of low-smoke halogen-free elevator cable material | |
| CN109438955B (en) | High-toughness and high-flame-retardant PBT/PC composite material and preparation method thereof | |
| CN112898493B (en) | Flame-retardant power cable protection pipe and production process thereof | |
| CN113980351B (en) | Preparation method of modified magnesium hydroxide flame retardant and application of modified magnesium hydroxide flame retardant in low-smoke halogen-free cable material | |
| CN117089153B (en) | Environment-friendly modified PVC material | |
| CN118652550A (en) | Ceramic halogen-free flame-retardant organic silica gel material and preparation method thereof | |
| CN117645764B (en) | High-temperature-resistant PVC pipe and manufacturing process thereof | |
| CN117659564B (en) | High-temperature-resistant PP halogen-free flame retardant master batch and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |