CN116535766A - B1-grade low-smoke halogen-free flame retardant composition and preparation method and application thereof - Google Patents
B1-grade low-smoke halogen-free flame retardant composition and preparation method and application thereof Download PDFInfo
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- CN116535766A CN116535766A CN202310470988.7A CN202310470988A CN116535766A CN 116535766 A CN116535766 A CN 116535766A CN 202310470988 A CN202310470988 A CN 202310470988A CN 116535766 A CN116535766 A CN 116535766A
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- Prior art keywords
- flame retardant
- retardant composition
- grade low
- calcium oxide
- smoke halogen
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 78
- 239000000779 smoke Substances 0.000 title claims abstract description 58
- 239000000203 mixture Substances 0.000 title claims abstract description 56
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000000463 material Substances 0.000 claims abstract description 31
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000292 calcium oxide Substances 0.000 claims abstract description 30
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 24
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012796 inorganic flame retardant Substances 0.000 claims abstract description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 5
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 21
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical group [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 18
- 239000000347 magnesium hydroxide Substances 0.000 claims description 18
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 18
- -1 polyethylene Polymers 0.000 claims description 18
- 239000004698 Polyethylene Substances 0.000 claims description 14
- 239000003963 antioxidant agent Substances 0.000 claims description 14
- 229920000573 polyethylene Polymers 0.000 claims description 14
- 229920013716 polyethylene resin Polymers 0.000 claims description 14
- 230000003078 antioxidant effect Effects 0.000 claims description 10
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 9
- 229920001577 copolymer Polymers 0.000 claims description 8
- 239000000314 lubricant Substances 0.000 claims description 8
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 3
- 239000008116 calcium stearate Substances 0.000 claims description 3
- 235000013539 calcium stearate Nutrition 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 229920002545 silicone oil Polymers 0.000 claims description 2
- 150000007970 thio esters Chemical class 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims 9
- 150000002367 halogens Chemical class 0.000 claims 9
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052799 carbon Inorganic materials 0.000 abstract description 7
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 229920000098 polyolefin Polymers 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 16
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 7
- 229920000092 linear low density polyethylene Polymers 0.000 description 7
- 239000004707 linear low-density polyethylene Substances 0.000 description 7
- 239000000155 melt Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DMHHYBUEZRZGDK-UHFFFAOYSA-N 2-(3,5-ditert-butyl-4-hydroxyphenyl)propanamide Chemical compound NC(=O)C(C)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 DMHHYBUEZRZGDK-UHFFFAOYSA-N 0.000 description 1
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 1
- FLZYQMOKBVFXJS-UHFFFAOYSA-N 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoic acid Chemical compound CC1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O FLZYQMOKBVFXJS-UHFFFAOYSA-N 0.000 description 1
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 1
- 239000003508 Dilauryl thiodipropionate Substances 0.000 description 1
- 239000002656 Distearyl thiodipropionate Substances 0.000 description 1
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- GYOZZWNPRKAISG-UHFFFAOYSA-N P(O)(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C(O)(C(CO)(CO)CO)C1=CC(=C(C(=C1)C(C)(C)C)C)C(C)(C)C)C(C)(C)C)C Chemical compound P(O)(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C(O)(C(CO)(CO)CO)C1=CC(=C(C(=C1)C(C)(C)C)C)C(C)(C)C)C(C)(C)C)C GYOZZWNPRKAISG-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Substances CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- 238000002479 acid--base titration Methods 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 description 1
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
- 235000019305 distearyl thiodipropionate Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- QYVZEPLDLPYECM-XUTLUUPISA-N octadecyl (e)-3-(3,4-dihydroxyphenyl)prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)\C=C\C1=CC=C(O)C(O)=C1 QYVZEPLDLPYECM-XUTLUUPISA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
-
- 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
- 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
- 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)
- 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 provides a B1-level low-smoke halogen-free flame retardant composition, and a preparation method and application thereof. The B1-grade low-smoke halogen-free flame retardant composition comprises the following components in parts by weight: 60-120 parts of polyolefin resin; 3-8 parts of compatilizer; 160-230 parts of inorganic flame retardant; 0.5 to 3 parts of calcium oxide; 0.5 to 1.5 portions of dehydrogenation catalyst; 0-4 parts of processing aid; wherein the dehydrogenation catalyst is a palladium alumina catalyst; the D50 of the calcium oxide is 4-10 mu m. The composition is added with a dehydrogenation catalyst, and the dehydrogenation catalyst can dehydrogenate the polyolefin substrate into carbon in a heating process, so that the substrate forms a stable and efficient carbon layer; meanwhile, the dehydrogenation catalyst is compounded with calcium oxide, so that the heat release of the sheath material can be effectively reduced, the flame retardant property of the material is improved, the tensile strength of the prepared material is not lower than 10MPa, the elongation at break is not lower than 160%, and the B1-level flame retardant is met.
Description
Technical Field
The invention relates to the technical field of cable sheath materials, in particular to a B1-level low-smoke halogen-free flame-retardant composition, a preparation method and application thereof.
Background
The traditional low-smoke halogen-free flame-retardant sheath material adopts a composition of polyethylene, ethylene-vinyl acetate copolymer and ethylene-octene copolymer as a resin base material, and adopts environment-friendly metal hydroxide such as magnesium hydroxide and aluminum hydroxide as a flame retardant to prepare a modified polymer material with low-smoke halogen-free flame-retardant property, and is mainly applied to densely populated places such as airports, stations, rail transit, large buildings and the like.
Along with the increasing importance of the national fire protection safety of buildings, the fire protection requirements of densely populated places are also higher, and cables with the combustion performance not lower than B1 level, such as cables, refuge layers, exposed wires of refuge rooms, underground buildings with long-term people retention and the like which are arranged in high-rise buildings with the electric fire protection design specifications of civil buildings of more than 100 meters and less than 250 meters, are selected. Compared with GB/T19666 and GB/T17651, the GB/T31247B 1-level flame retardant has higher requirements on heat release and smoke release performance of the sheath material, and the traditional sheath material is harder to meet the requirements.
According to the GB/T32129-2015 halogen-free flame-retardant cable material for the electric wires and cables, the tensile strength is more than or equal to 10.0MPa, the elongation at break is more than or equal to 160%, but the materials meeting the standards of GB/T31247B 1 grade flame-retardant and GB/T32129-2015 low-smoke halogen-free materials in the prior art are fewer, the application of the materials can be limited, and the flame retardant is generally required to be compounded or to be cooperated with a flame retardant synergist to meet the requirements.
Disclosure of Invention
The invention aims to overcome at least one defect in the prior art, and provides a B1-grade low-smoke halogen-free flame-retardant composition, wherein the B1-grade low-smoke halogen-free flame-retardant composition meets the B1-grade flame retardance, has better tensile strength and elongation at break, and meets the GB/T32129-2015 low-smoke halogen-free material standard.
The invention further aims at providing a preparation method of the B1-grade low-smoke halogen-free flame retardant composition.
The invention further aims to provide an application of the B1-grade low-smoke halogen-free flame retardant composition in preparing a cable sheath material.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the B1-grade low-smoke halogen-free flame retardant composition comprises the following components in parts by weight:
wherein the dehydrogenation catalyst is a palladium alumina catalyst; the D50 of the calcium oxide is 4-10 mu m.
The inventor finds out through a large number of experiments that a small amount of palladium alumina is added into a polyolefin resin system as a dehydrogenation catalyst, so that the polyolefin resin can be dehydrogenated into carbon in a heating process, and a stable and efficient carbon layer is formed on a base material; meanwhile, the dehydrogenation catalyst is compounded with the inorganic flame retardant, so that the heat release of the sheath material can be effectively reduced, and the flame retardant property of the material can be improved; in addition, a proper amount of calcium oxide is added into the system, the inorganic flame retardant releases water in the heating process, the water can react with the calcium oxide to generate calcium hydroxide, a small amount of milky calcium hydroxide can form a membranous structure on the surface of the material, and the dehydrogenation catalyst and the calcium oxide are synergistic to increase the flame retardant property.
Further, the compatilizer is polyethylene grafted maleic anhydride.
The inorganic flame retardant related to the invention can be magnesium hydroxide or magnesium hydroxide surface-treated by a silane coupling agent, wherein the mass ratio of the magnesium hydroxide in the magnesium hydroxide surface-treated by the silane coupling agent to the silane coupling agent is 95-100:1, the invention is not limited thereto.
The magnesium hydroxide subjected to surface treatment can be sold in the market or made in a self-made way.
Specifically, the self-making method comprises the following steps: in a high-speed mixer, heating magnesium hydroxide, and proportionally adding 3-aminopropyl triethoxy silane, mixing at high speed for coating.
Further, the D50 of the calcium oxide is 5-8 mu m.
The polyolefin resin according to the present invention may be selected according to the prior art. For example, but not limited to, the polyolefin resin is one or both of polyethylene resin, ethylene-octene copolymer, or ethylene-vinyl acetate copolymer.
Further, the polyolefin resin has a melt index of 0.5 to 5g/10min as measured according to GB/T3682-2000 at 190℃and 2.16 kg.
Further, the polyethylene resin is a linear low density polyethylene.
Further, the polyethylene resin is synthesized by adopting a metallocene catalyst system.
Further, the comonomer of the polyethylene resin is 1-hexene.
Further, the polyethylene resin has a density of 0.925 to 0.936g/cm 3 。
Further, the polyethylene resin has a melt index of 1 to 3.5g/10min at 190 ℃ under 2.16 kg.
Further, the mass ratio of the linear low-density polyethylene resin, the ethylene-octene copolymer and the ethylene-vinyl acetate copolymer in the polypropylene resin ranges from 0.5 to 4.5: (2.5-4.5): 1.
specifically, 25-45 parts of linear low-density polyethylene resin; 25-45 parts of ethylene-octene copolymer; 10-30 parts of ethylene-vinyl acetate copolymer. With the use amount, the mechanical property of the prepared low-smoke halogen-free flame retardant composition is better.
Further, the melt index of the polyethylene resin is measured in GB/T3682-2000.
Further, the comonomer of the polyethylene grafted maleic anhydride is 1-hexene.
Further, the polyethylene density of the grafting base of the polyethylene grafted with the maleic anhydride is 0.92 to 0.940g/cm 3 。
Further, the maleic anhydride grafting rate of the polyethylene grafted maleic anhydride is more than or equal to 0.8%. The grafting rate of maleic anhydride is too low, the effect is not obvious, the compatibility of inorganic substances and organic substances of the material is poor, and the mechanical property of the material is affected.
The method for measuring the maleic anhydride grafting ratio of the polyethylene grafted maleic anhydride can be a conventional method, for example, an acid-base titration method.
Further, the maleic anhydride monomer residue in the polyethylene grafted maleic anhydride is not more than 0.5 per mill.
Further, the melt index of the ethylene-octene copolymer is 0.5-5 g/10min under the condition of 190 ℃ and 2.16 kg.
Further, the melt index of the polyethylene resin is measured in GB/T3682-2000.
Further, the melt index of the ethylene-vinyl acetate copolymer is 0.5-3 g/10min under the condition of 190 ℃ and 2.16 kg.
Further, the melt index of the polyethylene resin is measured in GB/T3682-2000.
Further, in the ethylene-vinyl acetate copolymer, the vinyl acetate content is 18 to 30%.
Further, the processing aid is an antioxidant and/or a lubricant.
The invention can select common antioxidant according to the prior art. Further, the antioxidant is one or more of hindered phenols, phosphite antioxidants or thioester antioxidants.
Specifically, the hindered phenol antioxidant is one or more of N, N' -hexamethylenebis (3, 5-di-tert-butyl-4-hydroxy-phenyl-propionamide (Irganox 1098), tetra [1093,5-di-tert-butyl-4-hydroxy-phenyl) -propionic acid ] pentaerythritol ester (Irganox 1010), triethylene glycol bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) -propionic acid ester (Iragnox 259), beta- (4-hydroxy-3, 5-di-tert-butylphenyl) propionic acid N-octadecyl ester (Iragno 1076) or spiro ethylene glycol bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) -propionic acid ester ] (ADK AO-80).
The phosphite antioxidant is one or more of 2, 4-di-tert-butylphenol (Irganox 168), bis (2, 6-di-tert-butyl-4-tolyl) pentaerythritol phosphite (PEP-36) or 627A.
One or more of the thioether antioxidants of distearyl thiodipropionate, dilauryl thiodipropionate or pentaerythritol dodecyl thiopropyl ester.
The present invention may be carried out using conventional lubricants according to the prior art. Further, the lubricant is one or more of calcium stearate, polyethylene wax, silicone oil or silicone master batch.
The invention also provides a preparation method of the B1-grade low-smoke halogen-free flame retardant composition, which comprises the following steps:
the polyolefin resin, the compatilizer, the inorganic flame retardant, the calcium oxide, the dehydrogenation catalyst and the processing aid are proportionally put into an internal mixer for mixing, cooling, discharging and granulating to obtain the B1-level low-smoke halogen-free flame retardant composition.
Further, the temperature of the internal mixer is 145-160 ℃.
Further, the banburying time is not less than 10min.
The invention also protects the application of the B1-level low-smoke halogen-free flame retardant composition in preparing cable sheath materials.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a B1-level low-smoke halogen-free flame-retardant composition, which promotes polyolefin base material dehydrogenation to form carbon by adding a dehydrogenation catalyst into a polyolefin resin system, so as to form a stable and efficient carbon layer; meanwhile, the dehydrogenation catalyst is compounded with the magnesium hydroxide flame retardant, so that the heat release of the sheath material can be effectively reduced, and the flame retardant property of the material can be improved; in addition, a small amount of milky calcium hydroxide is generated in the reaction process of the calcium oxide, a membranous structure is formed on the surface of the material, and the flame retardant effect is improved. The tensile strength of the B1-level low-smoke halogen-free flame-retardant composition is not lower than 10MPa, the elongation at break is not lower than 160%, the GB/T32129-2015 standard is met, and meanwhile the composition meets the B1-level flame retardance.
Detailed Description
Technical solutions in the embodiments of the present invention will be clearly and completely described below, but the embodiments of the present invention are not limited thereto.
The reagents, methods and apparatus employed in the present invention, unless otherwise specified, are all conventional in the art.
The following examples and comparative examples were prepared from the following raw materials:
polyolefin resin:
polyethylene resin 1: linear low density polyethylene resin, LLDPE 3527, comonomer 1-hexene, melt flow rate of 2.16kg at 190℃3.5g/10min, density 0.927g/10cm 3 ；
Polyethylene resin 2: linear low density polyethylene resin, LLDPE M2735, comonomer 1-butene, melt flow rate of 2.16kg at 190℃2g/10min, density 0.930g/10cm 3 ；
Ethylene-octene copolymer: POE 58750, melt index at 190 ℃,2.16kg, is 5g/10min;
ethylene-vinyl acetate copolymer: escorene Ultra UL00328, melt index at 190℃under 2.16kg of 3g/10min, vinyl acetate content of 28%;
and (3) a compatilizer:
polyethylene grafted maleic anhydride 1: the grafting rate of maleic anhydride is 0.9%, and the residual maleic anhydride is 0.5 per mill;
polyethylene grafted maleic anhydride 2: the grafting rate of maleic anhydride is 0.7%, and the residual maleic anhydride is 0.5 per mill;
inorganic flame retardant:
magnesium hydroxide 1: magnesium hydroxide surface-treated with a silane coupling agent;
self-making in a laboratory; magnesium hydroxide with the brand of F5 of Shandong Aifuler company is adopted; the preparation method comprises the steps of heating magnesium hydroxide to 60 ℃ in a high-speed mixer, wherein the mass ratio of the magnesium hydroxide to the 3-aminopropyl triethoxy silane is 99:1 adding 3-aminopropyl triethoxysilane; mixing at high speed for 30 minutes, wherein the coating rate is 99.5%;
magnesium hydroxide 2: f5, magnesium hydroxide available from eastern eiffel company under the trade designation F5.
Calcium oxide 1: d50 is 3 μm, commercially available;
calcium oxide 2: d50 is 4 μm, commercially available;
calcium oxide 3: d50 is 5 μm, commercially available;
calcium oxide 4: d50 is 8 μm, commercially available;
calcium oxide 5: d50 is 10 μm, commercially available;
calcium oxide 6: d50 is 11 μm, commercially available;
dehydrogenation catalyst: palladium alumina catalyst, RH-33T, available from liaoning haitai technology development limited;
dehydrogenation catalyst: platinum alumina catalyst, available from Shaanxi Kogyo;
an antioxidant: the antioxidant 1010 and the antioxidant 168 are combined, and the mass ratio of the antioxidant to the antioxidant 168 is 3:1, basiff, germany;
and (3) a lubricant: calcium stearate, commercially available. The same antioxidants and lubricants were used in parallel experiments for each of the examples and comparative examples of the present invention.
The present invention will be described in detail with reference to examples.
The following examples and comparative examples each prepared a B1 grade low smoke halogen free flame retardant composition by weighing the components in the weight ratios of tables 1 to 2; the method comprises the following specific steps:
the preparation method comprises the steps of putting polyethylene resin, polyethylene grafted maleic anhydride, ethylene-octene copolymer, ethylene-vinyl acetate copolymer, magnesium hydroxide, calcium oxide, dehydrogenation catalyst, antioxidant and lubricant into an internal mixer in proportion for mixing until the mixing temperature is 145-160 ℃, and cooling water is required to be introduced into the internal mixer for not less than 10 minutes. And (3) discharging, putting the discharged material into a single-screw granulator for granulation, wherein the granulating mode is air-cooled die face granulating.
Examples 1 to 12 and comparative examples 1 to 9
TABLE 1 amounts of the components (parts by weight) of the B1 stage Low smoke halogen free flame retardant compositions of examples 1-12
TABLE 2 comparative examples 1 to 9 the amounts (parts by weight) of the respective components in the B1 grade low smoke halogen-free flame retardant compositions
Performance testing
The B1-grade low smoke halogen-free flame retardant compositions prepared in examples 1 to 12 and comparative examples 1 to 9 are pressed into tablets on a flat vulcanizing machine at 180 ℃ for 10min, the pressure is 15Mpa, the thickness of a sample is 1mm, and the conventional performance is tested after the sample is placed at room temperature for 16 h; the cable and the cable material are measured according to the test method of GB/T32129-2015 low smoke halogen-free material standard and GB 31247-2014B1 flame retardant grade standard. Wherein, the tensile strength is more than or equal to 10MPa in GB/T32129-2015 standard to reach the standard; the elongation at break is more than or equal to 160 percent, which is up to the standard, and the larger the effect is, the better the effect is under the condition of meeting the standard. In GB 31247-2014B1 flame retardance, the specified heat release peak value is less than or equal to 30KW, the total heat release amount is less than or equal to 15MJ, and the smoke generation peak value is less than or equal to 0.25m 2 Per second, the total amount of produced tobacco is less than or equal to 50m 2 And/s is the passing test. The test results are shown in Table 3.
Table 3 test results of the B1 grade low smoke halogen free flame retardant compositions of the examples and comparative examples
As can be seen from Table 3, the B1-grade low-smoke halogen-free flame-retardant composition prepared by the invention has good comprehensive performance, not only meets GB/T31247B 1-grade flame retardance, but also meets GB/T32129-2015 low-smoke halogen-free material standards, and the prepared B1-grade low-smoke halogen-free flame-retardant composition has tensile strength not lower than 10MPa and elongation at break not lower than 160 percent, and meets B1-grade flame retardance.
As can be seen from examples 1 to 4, when the D50 of calcium oxide in the B1-stage low-smoke halogen-free flame retardant composition is 5-8 mu m, the prepared B1-stage low-smoke halogen-free flame retardant composition has better comprehensive performance, has tensile strength not lower than 13MPa and elongation at break not lower than 205 percent, and meets the B1-stage flame retardance.
As can be seen from comparing example 1 with example 5, when the comonomer of the linear polyethylene resin is 1-hexene, the mechanical properties of the prepared low smoke halogen-free flame retardant composition are better under the condition of meeting B1 grade flame retardance, the tensile strength is 11MPa, and the elongation at break is 185%.
As can be seen from comparison of example 4 and example 10, when the grafting ratio of maleic anhydride of the selected polyethylene grafted maleic anhydride is greater than or equal to 0.8%, the prepared low smoke halogen-free flame retardant composition has better mechanical properties under the condition of meeting the B1-level flame retardance, and has 12MPa of tensile strength and 195% of elongation at break.
As can be seen from a comparison of example 4 and example 11, the mechanical properties of the prepared low smoke halogen-free flame retardant composition are better when the halogen-free flame retardant is subjected to surface treatment.
As can be seen from comparative example 1, when the amount of calcium oxide is too small, the prepared B1-grade low-smoke halogen-free flame retardant composition has good mechanical properties, but cannot meet the B1-grade flame retardance, and because the amount of calcium oxide is too small, the composition has a film-shaped structure formed by reaction with moisture, so that the flame retardant property of the composition is poor, and cannot meet the B1-grade flame retardance.
As can be seen from comparative example 2, when the amount of calcium oxide is too much, the elongation at break of the prepared B1-stage low-smoke halogen-free flame retardant composition is reduced to be only 157%, and the requirement cannot be met, because the excessive amount of added calcium oxide causes the calcium oxide to react with maleic anhydride grafts in the resin matrix, so that the B1-stage low-smoke halogen-free flame retardant composition is obviously reduced mechanically, and the calcium oxide reacts with magnesium hydroxide in the combustion process and is mutually consumed, so that the B1-stage flame retardant cannot be met.
As can be seen from comparative example 3, when the amount of the dehydrogenation catalyst is small, the prepared B1-grade low-smoke halogen-free flame retardant composition has good mechanical properties, but cannot meet the B1-grade flame retardant, because the amount of the dehydrogenation catalyst is too small, the polyolefin substrate cannot be dehydrogenated to form a stable and efficient carbon layer, so that the flame retardant property of the composition is poor, and the B1-grade flame retardant cannot be met.
As can be seen from comparative example 4, when the amount of the dehydrogenation catalyst is too much, the tensile strength of the prepared B1-grade low-smoke halogen-free flame retardant composition is reduced, and the tensile strength of the prepared B1-grade low-smoke halogen-free flame retardant composition is only 9.5MPa, because the dehydrogenation agent is difficult to disperse in the high-filling powder flame retardant system, so that agglomerated points appear, and the mechanical properties of the materials are greatly damaged by the agglomerated points.
As can be seen from comparative example 5, when the D50 of calcium oxide is too small and is 3 μm, the tensile strength and the elongation at break of the prepared B1-grade low-smoke halogen-free flame retardant composition cannot meet the requirements, the tensile strength is only 9.4MPa, and the elongation at break is only 155%.
As can be seen from comparative example 6, when the D50 of calcium oxide is too large and is 11 μm, the tensile strength and elongation at break of the prepared B1-grade low-smoke halogen-free flame retardant composition are both obviously reduced, the tensile strength is only 8MPa, and the elongation at break is only 150%.
As can be seen from comparative example 7, when platinum alumina is used as a dehydrogenation catalyst, the prepared B1-grade low-smoke halogen-free flame retardant composition has poor flame retardant property and cannot meet the B1-grade flame retardant.
As can be seen from comparative example 8, when calcium oxide is not added, the prepared B1-grade low-smoke halogen-free flame retardant composition has poor flame retardant property and cannot meet the B1-grade flame retardant.
As can be seen from comparative example 9, when the dehydrogenation catalyst is not added, the prepared B1-grade low-smoke halogen-free flame retardant composition has poor flame retardant property and cannot meet the B1-grade flame retardance.
It is to be understood that the above examples of the present invention are provided by way of illustration only and not by way of limitation of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (10)
1. The B1-grade low-smoke halogen-free flame-retardant composition is characterized by comprising the following components in parts by weight:
wherein the dehydrogenation catalyst is a palladium alumina catalyst; the D50 of the calcium oxide is 4-10 mu m.
2. The B1 grade low smoke zero halogen flame retardant composition of claim 1 wherein the calcium oxide has a D50 of 5 to 8 μm.
3. The B1 grade low smoke zero halogen flame retardant composition of claim 1 wherein said inorganic flame retardant is magnesium hydroxide.
4. The B1 grade low smoke zero halogen flame retardant composition of claim 1 wherein the polyolefin resin is one or both of polyethylene resin, ethylene-octene copolymer or ethylene-vinyl acetate copolymer.
5. The B1 grade low smoke zero halogen flame retardant composition of claim 1 wherein said compatibilizer is polyethylene grafted maleic anhydride.
6. The B1 grade low smoke zero halogen flame retardant composition of claim 1 wherein said processing aid is an antioxidant and/or lubricant.
7. The B1 grade low smoke zero halogen flame retardant composition of claim 6, wherein the antioxidant is one or more of hindered phenols, phosphites or thioesters.
8. The B1 grade low smoke zero halogen flame retardant composition of claim 6, wherein the lubricant is one or more of calcium stearate, polyethylene wax, silicone oil or silicone masterbatch.
9. The method for preparing a B1-stage low smoke zero halogen flame retardant composition according to any one of claims 1 to 8, comprising the steps of:
the polyolefin resin, the compatilizer, the inorganic flame retardant, the calcium oxide, the dehydrogenation catalyst and the processing aid are proportionally put into an internal mixer for mixing, cooling, discharging and granulating to obtain the B1-level low-smoke halogen-free flame retardant composition.
10. Use of a B1 grade low smoke zero halogen flame retardant composition according to any one of claims 1 to 8 in the preparation of a cable sheath material.
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