CN114058109A - Halogen-free flame-retardant polyolefin sheath material and preparation method and application thereof - Google Patents
Halogen-free flame-retardant polyolefin sheath material and preparation method and application thereof Download PDFInfo
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- CN114058109A CN114058109A CN202111444290.5A CN202111444290A CN114058109A CN 114058109 A CN114058109 A CN 114058109A CN 202111444290 A CN202111444290 A CN 202111444290A CN 114058109 A CN114058109 A CN 114058109A
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 119
- 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 102
- 239000000463 material Substances 0.000 title claims abstract description 72
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910000077 silane Inorganic materials 0.000 claims abstract description 27
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 18
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 18
- 229920002725 thermoplastic elastomer Polymers 0.000 claims abstract description 18
- 239000004712 Metallocene polyethylene (PE-MC) Substances 0.000 claims abstract description 16
- 229920002545 silicone oil Polymers 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 24
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims description 16
- 239000003963 antioxidant agent Substances 0.000 claims description 15
- 230000003078 antioxidant effect Effects 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 15
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 14
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 13
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 13
- 239000000347 magnesium hydroxide Substances 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- -1 compatilizer Polymers 0.000 claims description 7
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 claims description 5
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 2
- 229920005989 resin Polymers 0.000 abstract description 12
- 239000011347 resin Substances 0.000 abstract description 12
- 239000011159 matrix material Substances 0.000 abstract description 8
- 238000005336 cracking Methods 0.000 abstract description 7
- 238000011049 filling Methods 0.000 abstract description 3
- 238000004381 surface treatment Methods 0.000 abstract description 3
- 238000005461 lubrication Methods 0.000 abstract description 2
- 239000000843 powder Substances 0.000 abstract description 2
- 239000000945 filler Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000779 smoke Substances 0.000 description 9
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 230000006353 environmental stress Effects 0.000 description 4
- 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 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical class O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000004595 color masterbatch Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens 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
- 229920001526 metallocene linear low density polyethylene Polymers 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002113 nanodiamond Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- FWMUJAIKEJWSSY-UHFFFAOYSA-N sulfur dichloride Chemical compound ClSCl FWMUJAIKEJWSSY-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization 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
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
-
- 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
- C08K2003/2217—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
- 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
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
-
- 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
- C08L2207/04—Thermoplastic elastomer
Abstract
The invention provides a halogen-free flame-retardant polyolefin sheath material and a preparation method and application thereof; the halogen-free flame-retardant polyolefin sheath material comprises a combination of ethylene-vinyl acetate copolymer, metallocene polyethylene, thermoplastic elastomer, flame retardant, compatilizer, silane and silicone oil in a specific part; three resin matrixes are selected to be matched with each other, so that the filling capacity of the powder can be effectively improved; meanwhile, silane surface treatment flame retardant is used, and the compatilizer and the silicone oil in specific parts are matched to enhance the internal lubrication of the material, so that the flame retardant can be better fused in the resin matrix, and further the halogen-free flame-retardant polyolefin sheath material can have excellent flame retardant property under the condition of low addition of the flame retardant, and the problem of cracking resistance reduction caused by excessive addition of the filler is avoided.
Description
Technical Field
The invention belongs to the technical field of cables, and particularly relates to a halogen-free flame-retardant polyolefin sheath material and a preparation method and application thereof.
Background
The electric wire and the cable are indispensable important components of a power system and play an irreplaceable role in daily life, business and industrial fields. In recent years, with the national improvement of fire-retardant and fire-proof standards and the improvement of safety awareness of the whole people, the improvement of fire-fighting and fire-proof capabilities of electric wires and cables has become an important research direction. The halogen-containing flame-retardant cable material can emit a large amount of smoke and corrosive gas during combustion, so that escape routes of personnel in closed occasions are blocked and are gradually eliminated; halogen-free low-smoke flame-retardant cables are widely applied to some key projects, such as places of subways, shopping malls, railway stations, airports and the like, and are gradually hot spots of current research.
CN111117054A discloses a low-smoke halogen-free flame-retardant B1-grade polyolefin cable sheath material and a preparation method thereof, wherein the cable sheath material comprises the following raw materials in parts by weight: 60-80 parts of EVA resin, 10-20 parts of linear low-density polyethylene, 1-3 parts of maleic anhydride grafted linear low-density polyethylene, 3-5 parts of modified halloysite nanotube, 40-60 parts of modified magnesium hydroxide, 3-5 parts of polyphosphate flame retardant, 0.1-0.2 part of antioxidant and 0.5-1 part of lubricant. The cable sheath material prepared by the invention has the characteristics of low smoke and good flame-retardant and fireproof performance, can meet the requirement of B1-grade flame-retardant performance, and has excellent mechanical properties and wide application range. CN107418013A discloses an oil-resistant cable sheath material, which comprises raw rubber, butadiene rubber, chloroprene rubber, NBR1965, paraffin, PVC, coumarone, nano-diamond, pottery clay, barite powder, sulfur dichloride, asphalt, dimethyl silicone oil, dibutyl phthalate, a silane coupling agent A-151, a reinforcing filler, a softening agent, a TMTD accelerator, an anti-aging agent, an active agent and a vulcanization accelerator. The cable sheath material disclosed by the invention has the advantages of excellent oil resistance, long service life and good wear-resistant and heat-resistant properties. CN102585428A discloses a flexible halogen-free flame-retardant polyphenyl ether wire and cable sheath material and a preparation method thereof; comprises the following raw materials in percentage by weight: 10-30% of polyphenyl ether resin; 15-35% of styrene elastomer; 5-10% of polyolefin; 8-15% of a plasticizer; 3-8% of a compatilizer; 15-25% of a main flame retardant; 2-8% of a synergistic flame retardant; 2-8% of a smoke suppressant; 0.5-1% of a lubricant; 0.5-1% of antioxidant; 2-3% of color master batch. The cable sheath material has good mechanical property, softness, flame retardant property, heat resistance and processability.
However, in order to obtain higher flame retardant performance, the cable sheath material provided by the prior art is added with a large amount of flame retardant additives in the formula, so that the impact resistance and processability of the finally obtained product are affected, the processing is difficult, and the cable sheath material is very easy to crack during use.
Therefore, the development of a halogen-free flame retardant polyolefin sheath material with excellent flame retardant property and impact resistance is a technical problem to be solved urgently in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a halogen-free flame-retardant polyolefin sheath material, and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a halogen-free flame-retardant polyolefin sheath material, which comprises the following components in parts by weight:
while the ethylene-vinyl acetate copolymer may be present in an amount of 2 parts by weight, 4 parts by weight, 6 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 14 parts by weight, 16 parts by weight, 18 parts by weight, 20 parts by weight, 22 parts by weight, 24 parts by weight, 26 parts by weight, or 28 parts by weight, and specific points therebetween, the present invention is not exhaustive of the specific points included in the range for brevity and clarity.
The metallocene polyethylene may be 2 parts by weight, 4 parts by weight, 6 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 14 parts by weight, 16 parts by weight, or 18 parts by weight, and specific values therebetween, are not exhaustive and are included for brevity.
The thermoplastic elastomer may be 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, or 9 parts by weight, and specific values therebetween are not exhaustive, and the invention is not limited to the specific values included in the ranges for brevity and clarity.
The flame retardant may be 10 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight, 80 parts by weight, or 90 parts by weight, and specific points therebetween, the present invention is not exhaustive of the specific points included in the ranges for brevity and clarity.
The compatibilizing agent may be present in an amount of 1.5, 2, 2.5, 3, 3.5, 4, or 4.5 parts by weight, and the ranges therebetween are not exhaustive, as is the case for brevity and clarity.
The silane may be present in an amount of 0.2 parts by weight, 0.3 parts by weight, 0.4 parts by weight, 0.5 parts by weight, 0.6 parts by weight, 0.7 parts by weight, 0.8 parts by weight, or 0.9 parts by weight, and the specific values therebetween, limited to space and for the sake of brevity, are not exhaustive and are not intended to include the specific values within the stated ranges.
The silicone oil may be 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, or 4.5 parts by weight, and specific points therebetween, not to be construed as limiting the disclosure and for brevity, the invention is not exhaustive of the specific points included in the recited ranges.
The halogen-free flame-retardant polyolefin sheath material provided by the invention comprises the combination of ethylene-vinyl acetate copolymer, metallocene polyethylene, thermoplastic elastomer, flame retardant, compatilizer, silane and silicone oil in a specific part; firstly, selecting specific parts of ethylene-vinyl acetate copolymer (EVA), metallocene polyethylene (MLLDPE) and thermoplastic elastomer (POE) to be mutually matched as a resin matrix, wherein the filling capacity of the resin matrix is stronger, meanwhile, silane surface treatment flame retardant is used, and compatilizer is matched, so that the flame retardant is better fused in a formula system, an intangible bridge formed between the flame retardant and resin shows higher catalytic efficiency, and further the material has excellent flame retardant performance under the condition of lower addition amount of the flame retardant, and meanwhile, the problem that the cracking resistance of the material is obviously reduced due to the large addition amount of the flame retardant is avoided; and secondly, the silicone oil with a specific part is added, so that the internal lubrication of the material can be enhanced, the extrusion performance and speed of the product are improved, and precipitation is prevented.
Preferably, the thermoplastic elastomer comprises POE material.
Preferably, the flame retardant comprises a combination of magnesium hydroxide, aluminum hydroxide and a nitrogen-based flame retardant.
As the preferable technical scheme of the invention, the combination of aluminum hydroxide, magnesium hydroxide and nitrogen flame retardant is selected as the flame retardant, and the nitrogen flame retardant is used for catalyzing and promoting the combustion and crusting of the powdery magnesium hydroxide and aluminum hydroxide, so that the prepared halogen-free flame-retardant polyolefin sheath material has higher flame retardant performance.
Preferably, the amount of the magnesium hydroxide in the halogen-free flame-retardant polyolefin sheathing compound is 1 to 50 parts by weight, for example, 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, or 45 parts by weight, and specific values therebetween are not exhaustive, and for brevity, the specific values included in the range are not limited thereto.
Preferably, the amount of the aluminum hydroxide in the halogen-free flame-retardant polyolefin sheathing compound is 1 to 50 parts by weight, for example, 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, or 45 parts by weight, and specific values therebetween are not exhaustive, and for brevity, the specific values included in the range are not limited thereto.
Preferably, the amount of the nitrogen-based flame retardant in the halogen-free flame retardant polyolefin sheathing compound is 1 to 5 parts by weight, for example, 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, or 45 parts by weight, and specific values therebetween are not exhaustive, and for brevity, the invention is not limited to the specific values included in the ranges.
Preferably, the nitrogen-based flame retardant comprises melamine and/or melamine cyanurate.
Preferably, the compatibilizer comprises maleic anhydride grafted polyethylene.
Preferably, the silane comprises silane 172.
Preferably, the halogen-free flame-retardant polyolefin sheathing compound also comprises an antioxidant.
Preferably, the antioxidant is contained in the halogen-free flame retardant polyolefin sheathing compound in an amount of 0.1 to 1 part by weight, for example, 0.2 part by weight, 0.3 part by weight, 0.4 part by weight, 0.5 part by weight, 0.6 part by weight, 0.7 part by weight, 0.8 part by weight, or 0.9 part by weight, and specific values therebetween are not exhaustive, and for brevity, the specific values included in the range are not limited to the space and are not exhaustive.
In a second aspect, the present invention provides a preparation method of the halogen-free flame retardant polyolefin sheathing compound according to the first aspect, wherein the preparation method comprises the following steps:
(1) mixing a flame retardant and silane to obtain a mixture;
(2) and (2) mixing part of the mixture obtained in the step (1), ethylene-vinyl acetate copolymer, metallocene polyethylene, thermoplastic elastomer, compatilizer, silicone oil and optionally antioxidant for the first time, adding the rest of the mixture obtained in the step (1), and mixing again to obtain the halogen-free flame-retardant polyolefin sheath material.
In the invention, the flame retardant and silane are mixed firstly, and the silane is used for modifying the flame retardant, so that the compatibility of the flame retardant and a matrix is improved, and a mixture is obtained; and then mixing the obtained mixture with a matrix and other auxiliary agents twice, wherein the first mixing is beneficial to pre-dispersion of the resin matrix and the mixture, the silane in the mixture is utilized to promote the micro-crosslinking effect of the resin substrate, the flame retardant property and the thermal shock resistance of the product are greatly improved in a micro-crosslinking state, the secondary mixing is utilized to fully mix the resin substrate and the mixture, the complete plasticizing effect is achieved, and the aging resistance and the shock resistance of the halogen-free flame-retardant polyolefin sheath material are further improved.
Preferably, the mixing of step (1) is carried out in a high-speed mixer.
Preferably, the mixing time in step (1) is 1-5 min, such as 1.5min, 2min, 2.5min, 3min, 3.5min, 4min or 4.5min, and the specific points between the above points are limited by space and for brevity, the invention is not exhaustive of the specific points included in the range.
Preferably, the temperature of the mixing in the step (1) is 90-110 ℃, such as 92 ℃, 94 ℃, 96 ℃, 98 ℃, 100 ℃, 102 ℃, 104 ℃, 106 ℃ or 108 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the range.
Preferably, the temperature of the first mixing in step (2) is 40-60 ℃, for example, 42 ℃, 44 ℃, 46 ℃, 48 ℃, 50 ℃, 52 ℃, 54 ℃, 56 ℃ or 58 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the range.
Preferably, the first mixing time in step (2) is 20-40 min, such as 22min, 24min, 26min, 28min, 30min, 32min, 34min, 36min or 38min, and the specific values therebetween are limited by space and for brevity, the invention is not exhaustive of the specific values included in the range.
Preferably, the mixing time in step (2) is 30-60 min, such as 33min, 36min, 39min, 42min, 45min, 48min, 51min, 54min or 57min, and the specific values therebetween are limited by space and for brevity, the invention is not exhaustive.
Preferably, the remixing temperature in step (2) is 160-180 ℃, for example, 162 ℃, 164 ℃, 166 ℃, 168 ℃, 170 ℃, 172 ℃, 174 ℃, 176 ℃ or 178 ℃, and the specific values therebetween are limited by space and for brevity, and the invention is not exhaustive.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) mixing a flame retardant and silane at 90-110 ℃ for 1-5 min to obtain a mixture;
(2) mixing part of the mixture obtained in the step (1), ethylene-vinyl acetate copolymer, metallocene polyethylene, thermoplastic elastomer, compatilizer, silicone oil and optionally antioxidant for 20-40 min at 40-60 ℃, adding the rest of the mixture obtained in the step (1), mixing for 30-60 min at 160-180 ℃ again, and obtaining the halogen-free flame-retardant polyolefin sheath material.
In a third aspect, the present invention provides a halogen-free flame retardant polyolefin sheath material as described in the first aspect, which is applied in a cable.
Compared with the prior art, the invention has the following beneficial effects:
(1) the halogen-free flame-retardant polyolefin sheath material provided by the invention comprises the combination of ethylene-vinyl acetate copolymer, metallocene polyethylene, thermoplastic elastomer, flame retardant, compatilizer, silane and silicone oil in a specific part; the composite matrix with stronger powder filling capacity is obtained by selecting three matrixes to match with each other, and meanwhile, the silane surface treatment flame retardant is used, and the compatilizer is matched, so that the flame retardant can be better fused in a formula system, an invisible bridge is formed between the flame retardant and resin, and higher catalytic efficiency is shown, and further, the material has excellent flame retardant property under the condition of lower addition amount of the flame retardant, and meanwhile, the problem that the cracking resistance of the material is obviously reduced due to the large addition amount of the flame retardant is avoided; specifically, the smoke density (with flame) test of the halogen-free flame-retardant polyolefin sheath material is 72-88, the tensile strength is 11-13.2 MPa, and the environmental stress cracking resistance test is 91-98 h.
(2) The preparation method of the halogen-free flame-retardant polyolefin sheath material provided by the invention adopts two-step mixing, is beneficial to the full fusion between the flame retardant and the resin matrix, and further improves the flame retardant property and the mechanical property of the halogen-free flame-retardant polyolefin sheath material.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The halogen-free flame-retardant polyolefin sheath material comprises the following components in parts by weight:
the ethylene-vinyl acetate copolymer provided in this example was derived from (taiwan plastics industry, 7470M), the metallocene polyethylene was derived from (EXCEED ), the thermoplastic elastomer was derived from (sabic, 5070D), the silane was silane 172, the antioxidant was antioxidant 1010, and the maleic anhydride grafted polyethylene was derived from (korea koreda plastics, W1H, from guan);
the preparation method comprises the following steps:
(1) mixing magnesium hydroxide, aluminum hydroxide, nitrogen system and silane at 100 ℃ for 2.5min to obtain a mixture;
(2) and (2) mixing part of the mixture obtained in the step (1), ethylene-vinyl acetate copolymer, metallocene polyethylene, thermoplastic elastomer, compatilizer, silicone oil and optionally antioxidant for the first time at 50 ℃ for 30min, adding the rest of the mixture obtained in the step (1) and mixing for another 40min at 170 ℃ to obtain the halogen-free flame-retardant polyolefin sheath material.
Example 2
The halogen-free flame-retardant polyolefin sheath material comprises the following components in parts by weight:
the ethylene-vinyl acetate copolymer provided in this example was derived from (taiwan plastics industry, 7470M), the metallocene polyethylene was derived from (EXCEED ), the thermoplastic elastomer was derived from (sabic, 5070D), the silane was silane 172, the antioxidant was antioxidant 1010, and the maleic anhydride grafted polyethylene was derived from (korea koreda plastics, W1H, from guan);
the preparation method comprises the following steps:
(1) mixing magnesium hydroxide, aluminum hydroxide, nitrogen system and silane at 110 ℃ for 1min to obtain a mixture;
(2) and (2) mixing part of the mixture obtained in the step (1), ethylene-vinyl acetate copolymer, metallocene polyethylene, thermoplastic elastomer, compatilizer, silicone oil and optionally antioxidant for 40min at 40 ℃, adding the rest of the mixture obtained in the step (1), mixing for 30min again at 180 ℃ to obtain the halogen-free flame-retardant polyolefin sheath material.
Example 3
The halogen-free flame-retardant polyolefin sheath material comprises the following components in parts by weight:
the ethylene-vinyl acetate copolymer provided in this example was derived from (taiwan plastics industry, 7470M), the metallocene polyethylene was derived from (EXCEED ), the thermoplastic elastomer was derived from (sabic, 5070D), the silane was silane 172, the antioxidant was antioxidant 1010, and the maleic anhydride grafted polyethylene was derived from (korea koreda plastics, W1H, from guan);
the preparation method comprises the following steps:
(1) mixing magnesium hydroxide, aluminum hydroxide, nitrogen system and silane at 90 ℃ for 5min to obtain a mixture;
(2) and (2) mixing part of the mixture obtained in the step (1), ethylene-vinyl acetate copolymer, metallocene polyethylene, thermoplastic elastomer, compatilizer, silicone oil and optionally antioxidant for 20min at 60 ℃, adding the rest of the mixture obtained in the step (1) and mixing for 40min at 160 ℃ again to obtain the halogen-free flame-retardant polyolefin sheath material.
Example 4
The halogen-free flame-retardant polyolefin sheath material is different from the material in the embodiment 1 only in that magnesium hydroxide is not added, the adding amount of aluminum hydroxide is 50 parts by weight, and other components, the using amount and the preparation method are the same as those in the embodiment 1.
Example 5
The halogen-free flame-retardant polyolefin sheath material is different from the material in the embodiment 1 only in that aluminum hydroxide is not added, the addition amount of magnesium hydroxide is 50 parts by weight, and other components, the use amount and the preparation method are the same as those in the embodiment 1.
Example 6
A halogen-free flame-retardant polyolefin sheath material is different from the material in the embodiment 1 only in that a nitrogen-based flame retardant is not added, the addition amount of magnesium hydroxide is 26.25 parts by weight, the addition amount of aluminum hydroxide is 26.25 parts by weight, and other components, the use amounts and the preparation method are the same as those in the embodiment 1.
Comparative example 1
The halogen-free flame-retardant polyolefin sheath material is different from the material in the embodiment 1 in that the ethylene-vinyl acetate copolymer is not added, the mass ratio of other components is kept unchanged, and the preparation method is also the same as the embodiment 1.
Comparative example 2
A halogen-free flame-retardant polyolefin sheath material, which is different from the material in the embodiment 1 in that metallocene polyethylene is not added, the mass ratio of other components is kept unchanged, and the preparation method is also the same as the embodiment 1.
Comparative example 3
A halogen-free flame-retardant polyolefin sheathing compound, which is different from the material in example 1 in that no thermoplastic elastomer is added, the mass ratio of other components is kept unchanged, and the preparation method is also the same as that in example 1.
Comparative example 4
A halogen-free flame-retardant polyolefin sheath material is different from the material in the embodiment 1 in that silane is not added, the mass ratio of other components is kept unchanged, and the preparation method is also the same as the embodiment 1.
Comparative example 5
The halogen-free flame-retardant polyolefin sheath material is different from the material in the embodiment 1 in that no silicone oil is added, the mass ratio of other components is kept unchanged, and the preparation method is also the same as the embodiment 1.
And (3) performance testing:
(1) smoke density: testing according to a testing method provided by GB/T8323-1987;
(2) tensile strength: testing according to the testing method provided by GBT 528-2009;
(3) environmental stress cracking resistance: the test was carried out according to the test method provided in GB/T2951.41-2008.
The halogen-free flame-retardant polyolefin sheath materials provided in examples 1 to 6 and comparative examples 1 to 5 were tested according to the above test method, and the test results are shown in table 1:
TABLE 1
As can be seen from the data in table 1:
the halogen-free flame-retardant polyolefin sheath material provided by the invention has excellent flame retardant property and mechanical property; specifically, the smoke density (with flame) test of the halogen-free flame retardant polyolefin sheath material obtained in the examples 1 to 6 is 72 to 88, the tensile strength is 11 to 13.2MPa, and the environmental stress cracking resistance test is 91 to 98 hours.
Comparing example 1 with comparative examples 1 to 3, it can be found that the smoke density (with flame) of the halogen-free flame retardant polyolefin sheath material obtained without adding ethylene-vinyl acetate copolymer (comparative example 1), the halogen-free flame retardant polyolefin sheath material obtained without adding metallocene polyethylene (comparative example 2), and the halogen-free flame retardant polyolefin sheath material obtained without adding thermoplastic elastomer (comparative example 3) is reduced, the tensile strength is reduced, and the environmental stress cracking resistance time is also reduced, which proves that the halogen-free flame retardant polyolefin sheath material with excellent mechanical properties and flame retardancy cannot be obtained by any of the three substrates.
Further comparing the examples 1 and 4 to 6, it can be found that the use of magnesium hydroxide, aluminum hydroxide and nitrogen flame retardant in combination is more helpful to improve the flame retardant property of the polyolefin sheath material.
The applicant states that the present invention is illustrated by the above examples to provide a halogen-free flame retardant polyolefin sheathing compound, a preparation method and applications thereof, but the present invention is not limited to the above examples, i.e. it is not meant that the present invention must be implemented by the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The halogen-free flame-retardant polyolefin sheath material is characterized by comprising the following components in parts by weight:
2. the halogen-free flame retardant polyolefin sheathing compound according to claim 1, wherein the thermoplastic elastomer comprises a POE material.
3. The halogen-free flame-retardant polyolefin sheathing compound according to claim 1 or 2, wherein the flame retardant comprises a combination of magnesium hydroxide, aluminum hydroxide and a nitrogen-based flame retardant;
preferably, the content of the magnesium hydroxide in the halogen-free flame-retardant polyolefin sheath material is 1-50 parts by weight;
preferably, the content of the aluminum hydroxide in the halogen-free flame-retardant polyolefin sheath material is 1-50 parts by weight;
preferably, the content of the nitrogen-based flame retardant in the halogen-free flame-retardant polyolefin sheath material is 1-5 parts by weight;
preferably, the nitrogen-based flame retardant comprises melamine and/or melamine cyanurate.
4. The halogen-free flame retardant polyolefin sheathing compound according to any one of claims 1 to 3, wherein the compatibilizer comprises maleic anhydride grafted polyethylene;
preferably, the silane comprises silane 172.
5. The halogen-free flame retardant polyolefin sheathing compound according to any one of claims 1 to 4, wherein the halogen-free flame retardant polyolefin sheathing compound further comprises an antioxidant;
preferably, the content of the antioxidant in the halogen-free flame-retardant polyolefin sheathing compound is 0.1-1 part by weight.
6. The preparation method of the halogen-free flame retardant polyolefin sheathing compound as claimed in any one of claims 1 to 5, wherein the preparation method comprises the following steps:
(1) mixing a flame retardant and silane to obtain a mixture;
(2) and (2) mixing part of the mixture obtained in the step (1), ethylene-vinyl acetate copolymer, metallocene polyethylene, thermoplastic elastomer, compatilizer, silicone oil and optionally antioxidant for the first time, adding the rest of the mixture obtained in the step (1), and mixing again to obtain the halogen-free flame-retardant polyolefin sheath material.
7. The method of claim 6, wherein the mixing of step (1) is performed in a high-speed mixer;
preferably, the mixing time in the step (1) is 1-5 min;
preferably, the mixing temperature in the step (1) is 90-110 ℃.
8. The preparation method according to claim 6 or 7, wherein the temperature of the first mixing in the step (2) is 40-60 ℃;
preferably, the time for the first mixing in the step (3) is 20-40 min.
9. The method according to any one of claims 6 to 8, wherein the mixing time in the step (2) is 30 to 60 min;
preferably, the temperature for re-mixing in the step (2) is 160-180 ℃.
10. Use of the halogen-free flame-retardant polyolefin sheath material according to any one of claims 1 to 5 in cables.
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