CN116199959A - Flame-retardant polyethylene sheath material and preparation method thereof - Google Patents
Flame-retardant polyethylene sheath material and preparation method thereof Download PDFInfo
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- CN116199959A CN116199959A CN202211534652.4A CN202211534652A CN116199959A CN 116199959 A CN116199959 A CN 116199959A CN 202211534652 A CN202211534652 A CN 202211534652A CN 116199959 A CN116199959 A CN 116199959A
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- flame retardant
- flame
- retardant polyethylene
- sheath material
- resin
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 105
- 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 90
- 239000000463 material Substances 0.000 title claims abstract description 64
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 51
- -1 polyethylene Polymers 0.000 title claims abstract description 51
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title description 8
- 229920005989 resin Polymers 0.000 claims abstract description 37
- 239000011347 resin Substances 0.000 claims abstract description 37
- 239000000779 smoke Substances 0.000 claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 230000001629 suppression Effects 0.000 claims abstract description 15
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 13
- 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 13
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 11
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 11
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 11
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 11
- 229920000092 linear low density polyethylene Polymers 0.000 claims abstract description 10
- 239000004707 linear low-density polyethylene Substances 0.000 claims abstract description 10
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920001903 high density polyethylene Polymers 0.000 claims abstract description 9
- 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 abstract description 8
- 239000004700 high-density polyethylene Substances 0.000 claims abstract description 7
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 claims abstract description 7
- 239000000155 melt Substances 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 15
- 238000001125 extrusion Methods 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 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 description 6
- 238000000265 homogenisation Methods 0.000 claims description 6
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 6
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims 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 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 239000003610 charcoal Substances 0.000 claims description 3
- 230000006835 compression Effects 0.000 claims description 3
- 238000007906 compression Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000008187 granular material Substances 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 claims description 2
- 239000011230 binding agent Substances 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 14
- 238000002485 combustion reaction Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000007480 spreading Effects 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000010561 standard procedure 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
- C08L23/06—Polyethene
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
-
- 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
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
-
- 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
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- 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 discloses a flame-retardant polyethylene sheath material, which comprises the following components in percentage by weight: 46-50% of a resin base comprising 8-12% of a HDPE resin, 30-34% of a ULDPE resin and 5.0-7.0% of a maleic anhydride grafted LLDPE;44% -48% of halogen-free flame retardant, wherein the halogen-free flame retardant comprises 29% -33% of superfine magnesium hydroxide flame retardant, 7% -11% of superfine aluminum hydroxide flame retardant and 5% -7% of melamine cyanurate flame retardant; 2.5 to 3.5 percent of smoke suppression and carbon forming agent and 2.5 to 3.5 percent of processing aid.
Description
Technical Field
The invention belongs to the technical field of plastics, and particularly relates to a flame-retardant polyethylene sheath material and a preparation method thereof.
Background
Because of the need to maintain good mechanical properties, the addition amount of the flame retardant in the flame-retardant polyethylene sheath material is usually low, so a flame-retardant system of halogen, antimony or aluminum, magnesium and red phosphorus with good flame-retardant effect is generally adopted. However, the flame retardant systems have the defect of higher smoke density, and cannot meet the application occasions with high requirements on light transmittance.
In view of the foregoing, it is necessary to provide a flame retardant polyethylene sheath material and a preparation method thereof, which have the advantages of excellent mechanical properties, good process performance, small smoke density and the like, and meanwhile, the optical cable can meet the flame retardant requirement of single vertical combustion.
Disclosure of Invention
The invention aims at: at least one defect in the prior art is overcome, and the flame-retardant polyethylene sheath material and the preparation method thereof are provided, which have the advantages of excellent mechanical property, good technological property, small smoke density and the like, and simultaneously, the optical cable can meet the flame-retardant requirement of single vertical combustion.
In order to achieve the above object, the present invention provides a flame retardant polyethylene sheathing compound comprising, in weight percent:
46-50% of a resin binder comprising 8% -12% hdpe resin, 30% -34% uldpe resin and 5.0% -7.0% maleic anhydride grafted LLDPE;
44% -48% of halogen-free flame retardant, wherein the halogen-free flame retardant comprises 29% -33% of superfine magnesium hydroxide flame retardant, 7% -11% of superfine aluminum hydroxide flame retardant and 5% -7% of melamine cyanurate flame retardant;
2.5 to 3.5 percent of smoke suppression char forming agent and 2.5 to 3.5 percent of processing aid.
According to one embodiment of the flame retardant polyethylene sheathing compound of the present invention, the HDPE resin has a density of 0.945±0.02g/cm 3 The melt flow rate is 0.6-0.8g/10min.
According to one embodiment of the flame retardant polyethylene sheathing compound of the present invention, the ULDPE resin density is 0.905 ± 0.02g/cm 3 The melt flow rate is 3.0-3.5g/10min.
According to one embodiment of the flame retardant polyethylene sheathing compound of the present invention, the maleic anhydride grafted LLDPE has a grafting ratio of 0.8 to 1.0% and a melt flow rate of 0.8 to 1.2g/10min.
According to one embodiment of the flame-retardant polyethylene sheath material, the superfine magnesium hydroxide adopts a chemical synthesis method, the purity is more than or equal to 99.5 percent, and the particle size of D97 is less than or equal to 5.0um.
According to one embodiment of the flame retardant polyethylene sheath material, the purity of the superfine aluminum hydroxide is more than or equal to 99.5 percent, the D50 particle size is 1.5-2.2um, and the D97 particle size is less than or equal to 7.0um.
According to one embodiment of the flame retardant polyethylene sheath material, the purity of melamine urate is more than or equal to 98%, and the D50 particle size is 1.0-2.0um.
According to one embodiment of the flame-retardant polyethylene sheath material, the smoke suppression and char formation agent is nano montmorillonite, the whiteness is not less than 88, and the D50 particle size is not more than 10um.
According to one embodiment of the flame retardant polyethylene sheathing compound of the present invention, the processing aid comprises 0.18-0.22% antioxidant 1010, 0.18-0.22% antioxidant DLTP, 0.70-0.90% silicone masterbatch, 0.35-0.45% polyethylene wax, 0.35-0.45% silane coupling agent and 0.9% -1.1% carbon black.
In order to achieve the above object, the present invention also provides a method for preparing a flame retardant polyethylene sheath material, comprising the steps of:
1) And (3) batching: weighing the components of the flame-retardant polyethylene sheath material according to parts by weight, wherein the weighing precision of the resin base material and the flame retardant is +/-0.1 kg, and the weighing precision of the smoke suppression charring agent and the processing aid is +/-0.01 kg;
2) Feeding: the feeding sequence is as follows: firstly, adding a halogen-free flame retardant, then adding a resin base material, and finally, adding a smoke suppression and charcoal forming agent and other processing aids;
3) Banburying: mixing the materials in an internal mixer for 12-15min, and turning the materials at 100deg.C, 125deg.C and 135deg.C for one time;
4) Feeding: conveying the melt after banburying to a conical forced feeder, and allowing the melt to enter a double-screw extruder through forced feeding;
5) Extrusion: plasticizing the melt by a double-screw extruder, and then extruding and granulating by a single screw, wherein the screw speed of the double-screw extruder is 250-350rpm, and the temperature of the double-screw extruder is set as follows: the temperature setting range of the single screw is 110 ℃ to 140 ℃ in the compression section 100 ℃ to 115 ℃ and the homogenization section 120 ℃ to 135 DEG C
6) Granulating: the granules are packaged after air cooling, vibration sieving and homogenization.
Compared with the prior art, the flame-retardant polyethylene sheath material and the preparation method thereof have the following advantages: the flame-retardant polyethylene sheath material has the smoke density obviously lower than that of common flame-retardant polyethylene; the oxygen index and single flame-retardant effect of the flame-retardant polyethylene sheath material are obviously better than those of the common flame-retardant polyethylene material.
In the flame-retardant polyethylene sheath material, the resin base material is grafted with LLDPE by maleic anhydride, and the HDPE resin has excellent high-speed extrusion performance, so that the extrusion surface of the material can be improved; the ULDPE resin has excellent processability, and can obviously reduce current during processing in a flame-retardant formula system; therefore, the resin base material can ensure the technological performance and mechanical performance of the product. The superfine magnesium hydroxide and aluminum hydroxide flame retardant is beneficial to the base material to obtain good flame retardance, and the mechanical property and the processing property of the base material are reserved to the maximum extent; the melamine cyanurate is a halogen-free environment-friendly nitrogen high-efficiency flame retardant, has the advantages of good flame retardant effect, small heat release amount, small smoke generation amount and the like, and can remarkably reduce the heat release amount during combustion and reduce the heat spreading, thereby achieving the flame retardant effect; the nano montmorillonite is an excellent smoke suppression charcoal forming agent, a compact and hard shell layer can be formed on the surface of a material during combustion, heat transfer during combustion can be effectively reduced, the material is isolated from oxygen, a good flame retardant effect is achieved, and smoke can be wrapped inside the material by the shell layer, so that the effect of reducing smoke density is achieved. The flame retardants cooperate in use, and have ideal synergistic flame retardance.
Through reasonable resin base material selection and mutual combination of various halogen-free flame retardants, the flame-retardant polyethylene sheath material has good flame-retardant effect, mechanical property and processing extrusion property.
Detailed Description
In order to make the objects, technical solutions and technical effects of the present invention more clear, the present invention will be described in further detail with reference to the following specific embodiments. It should be understood that the detailed description is presented herein for purposes of illustration only and is not intended to limit the invention.
The invention provides a flame-retardant polyethylene sheath material, which comprises the following components in percentage by weight:
46-50% of a resin base comprising 8-12% of a HDPE resin, 30-34% of a ULDPE resin and 5.0-7.0% of a maleic anhydride grafted LLDPE;
44% -48% of halogen-free flame retardant, wherein the halogen-free flame retardant comprises 29% -33% of superfine magnesium hydroxide flame retardant, 7% -11% of superfine aluminum hydroxide flame retardant and 5% -7% of melamine cyanurate flame retardant; and
2.5 to 3.5 percent of smoke suppression char forming agent and 2.5 to 3.5 percent of processing aid.
Specifically, in one embodiment of the invention, the HDPE resin has a density of 0.945.+ -. 0.02g/cm 3 The melt flow rate is 0.6-0.8g/10min. ULDPE resin density of 0.905.+ -. 0.02g/cm 3 The melt flow rate is 3.0-3.5g/10min. The grafting rate of the maleic anhydride grafted LLDPE is 0.8-1.0%, and the melt flow rate is 0.8-1.2g/10min.
Specifically, in one embodiment of the invention, the superfine magnesium hydroxide adopts a chemical synthesis method, the purity is more than or equal to 99.5 percent, and the D97 particle size is less than or equal to 5.0um. The purity of the superfine aluminum hydroxide is more than or equal to 99.5 percent, the particle size of D50 is 1.5-2.2um, and the particle size of D97 is less than or equal to 7.0um. The purity of the melamine cyanurate is more than or equal to 98 percent, and the particle size of D50 is 1.0-2.0um.
Specifically, in one embodiment of the invention, the smoke suppression and char formation agent is nano montmorillonite, the whiteness is not less than 88, and the D50 particle size is not more than 10um. The processing aid contains 0.18-0.22% of antioxidant 1010, 0.18-0.22% of antioxidant DLTP, 0.70-0.90% of silicone master batch, 0.35-0.45% of polyethylene wax, 0.35-0.45% of silane coupling agent and 0.9-1.1% of carbon black.
The present invention will be described in detail with reference to examples.
Example 1
The preparation of the flame retardant polyethylene sheathing compound of the present invention will be described in as detail as possible in combination with the respective components and the corresponding contents in example 1.
1. Proportioning materials
The 48% resin base material is: 9% HDPE-3364, 33% ULDPE-4607GC and 6% maleic anhydride grafted LLDPE;46% flame retardant is: 32% of superfine magnesium hydroxide flame retardant, 8% of superfine aluminum hydroxide flame retardant and 6% of melamine cyanurate; 3.0% of smoke suppression and char formation agent is nano montmorillonite; 3.0% of processing aid is: 0.2% antioxidant 1010, 0.2% antioxidant DLTP, 0.8% silicone masterbatch, 0.4% polyethylene wax, 0.4% silane coupling agent, and 1.0% carbon black.
The weighing precision of the resin base material, the flame retardant and the smoke suppression and charring agent is +/-0.1 kg, and the weighing precision of the auxiliary agent is +/-0.01 kg.
2. Feeding: the feeding sequence is that firstly, a flame retardant is added, then a resin base material is added, and finally, a smoke suppression and carbon formation agent and other processing aids are added;
3. banburying for 12-15min, wherein the temperature of the melt is 155-160 ℃, and the material is turned once at 100 ℃, 125 ℃ and 135 ℃ in the middle;
4. feeding: conveying the melt after banburying to a conical forced feeder, and allowing the melt to enter a double-screw extruder through forced feeding;
5. extrusion: plasticizing the melt by a double-screw extruder, and then extruding and granulating by a single screw, wherein the screw speed of the double-screw extruder is 250-350rpm, and the temperature of the double-screw extruder is set as follows: the temperature setting range of the single screw is 110-140 ℃ in the compression section 100-115 ℃ and the homogenization section 120-135 ℃;
6. granulating: the granules are packaged after air cooling, vibration sieving and homogenization.
Examples 2 to 4
Examples 2-4 were substantially the same as example 1 except that the specific components and amounts of examples 2-4 were different from example 1, as specifically shown in Table 1.
Comparative example 1
Comparative example 1 and example 1 are substantially identical except for the following two points: 1) Because of the selection difference of the resin base materials, the common flame-retardant polyethylene is mainly used for the cable outer sheath with larger outer diameter, the extrusion speed is low, and a part of LLDPE-FB2230 with small melt fingers and good cracking resistance is generally added into the resin base materials. 2) The flame-retardant system is different in selection, and adopts a flame-retardant system of magnesium hydroxide, aluminum hydroxide and coated red phosphorus, and the flame-retardant system has higher flame-retardant efficiency, but has large smoke quantity during combustion and very low light transmittance of a cable.
The components and contents of each of examples 1 to 4 and comparative example 1 are shown in Table 1.
TABLE 1 Each component and proportion of examples 1-4 and comparative example 1
The performance of examples 1-4 and comparative example 1 was tested according to the national standard method, and the test results are shown in Table 2.
Table 2 performance tests for examples 1-4 and comparative example 1
Product extrusion process performance verification
Extruder model: SJ65 x 25 (screw diameter 65mm, aspect ratio 25:1), equipment manufacturer: tin-free south electrician machinery Co., ltd; the die selects a tube extruding die, the type of the test machine optical cable is a direct protection optical cable, the outer diameter of the optical cable is 5.0+/-0.2 mm, and the extruding temperature is set as follows: 140-150-155-160-165-170-170, the starting speed is 20m/min, the fluctuation range of the optical cable wire diameter is 5.0+/-0.1 mm, the extrusion surface is smooth and fine, the wire diameter is gradually accelerated to 40m/min, the stability of the wire diameter is good during acceleration, the speed reaching 40m/min is continuously observed, the fluctuation range of the wire diameter is 4.92-5.02mm, the extrusion surface is smooth, and the process test is qualified.
Single vertical combustion performance verification
According to the national standard GB/T18380-2008, the single vertical combustion performance of the product is tested, the distance between the lower edge of the upper bracket and the starting point of the carbonization part is more than 50mm, the lower starting point of the carbonization part is not more than 540mm, the actual measurement result shows that the product is extinguished immediately after leaving fire, and the product is judged to be qualified.
Compared with the prior art, the flame-retardant polyethylene sheath material and the preparation method thereof are basically consistent with the common flame-retardant polyethylene product in technical performance and physical performance, but have the following advantages:
the flame-retardant polyethylene sheath material has the smoke density obviously lower than that of common flame-retardant polyethylene; the oxygen index and single flame-retardant effect of the flame-retardant polyethylene sheath material are obviously better than those of the common flame-retardant polyethylene material.
In the flame-retardant polyethylene sheath material, the resin base material is grafted with LLDPE by maleic anhydride, and the HDPE resin has excellent high-speed extrusion performance, so that the extrusion surface of the material can be improved; the ULDPE resin has excellent processability, and can obviously reduce current during processing in a flame-retardant formula system; therefore, the resin base material can ensure the technological performance and mechanical performance of the product. The superfine magnesium hydroxide and aluminum hydroxide flame retardant is beneficial to the base material to obtain good flame retardance, and the mechanical property and the processing property of the base material are reserved to the maximum extent; the melamine cyanurate is a halogen-free environment-friendly nitrogen high-efficiency flame retardant, has the advantages of good flame retardant effect, small heat release amount, small smoke generation amount and the like, and can remarkably reduce the heat release amount during combustion and reduce the heat spreading, thereby achieving the flame retardant effect; the nano montmorillonite is an excellent char forming agent, a compact and hard shell layer can be formed on the surface of a material during combustion, heat transfer during combustion can be effectively reduced, the material is isolated from oxygen, a good flame retardant effect is achieved, and meanwhile smoke can be wrapped inside the material by the shell layer, so that the effect of reducing smoke density is achieved. The flame retardants cooperate in use, and have ideal synergistic flame retardance.
Through reasonable resin base material selection and mutual combination of various halogen-free flame retardants, the flame-retardant polyethylene sheath material has good flame-retardant effect, mechanical property and processing extrusion property.
The present invention is also capable of suitable alterations and modifications in the above-described embodiments, in light of the above principles. Therefore, the invention is not limited to the specific embodiments disclosed and described above, but some modifications and changes of the invention should be also included in the scope of the claims of the invention. In addition, although specific terms are used in the present specification, these terms are for convenience of description only and do not limit the present invention in any way.
Claims (10)
1. The flame-retardant polyethylene sheath material is characterized by comprising the following components in percentage by weight:
46-50% of a resin binder comprising 8% -12% hdpe resin, 30% -34% uldpe resin and 5.0% -7.0% maleic anhydride grafted LLDPE;
44% -48% of halogen-free flame retardant, wherein the halogen-free flame retardant comprises 29% -33% of superfine magnesium hydroxide flame retardant, 7% -11% of superfine aluminum hydroxide flame retardant and 5% -7% of melamine cyanurate; and
2.5 to 3.5 percent of smoke suppression char forming agent and 2.5 to 3.5 percent of processing aid.
2. The flame retardant polyethylene sheathing compound of claim 1, wherein the HDPE resin has a density of 0.945 ± 0.02g/cm 3 The melt flow rate is 0.6-0.8g/10min.
3. The flame retardant polyethylene sheathing compound of claim 1, wherein the ULDPE resin density is 0.905 ± 0.02g/cm 3 The melt flow rate is 3.0-3.5g/10min.
4. The flame retardant polyethylene sheathing compound of claim 1, wherein the maleic anhydride grafted LLDPE has a grafting ratio of 0.8-1.0% and a melt flow rate of 0.8-1.2g/10min.
5. The flame retardant polyethylene sheath material according to claim 1, wherein the superfine magnesium hydroxide has a purity of 99.5% or more and a D97 particle size of 5.0 μm or less.
6. The flame retardant polyethylene sheath material according to claim 1, wherein the purity of the superfine aluminum hydroxide is more than or equal to 99.5%, the D50 particle size is 1.5-2.2um, and the D97 particle size is less than or equal to 7.0um.
7. The flame retardant polyethylene sheath material according to claim 1, wherein the melamine urate has a purity of not less than 98% and a D50 particle size of 1.0-2.0um.
8. The flame retardant polyethylene sheath material according to claim 1, wherein the smoke suppression and char formation agent is nano montmorillonite, the whiteness is not less than 88, and the D50 particle size is not more than 10um.
9. The flame retardant polyethylene sheathing compound of claim 1, wherein the processing aid comprises 0.18-0.22% antioxidant 1010, 0.18-0.22% antioxidant DLTP, 0.70-0.90% silicone masterbatch, 0.35-0.45% polyethylene wax, 0.35-0.45% silane coupling agent, and 0.9% -1.1% carbon black.
10. A method of preparing a flame retardant polyethylene sheathing compound according to any one of claims 1 to 9, wherein the method comprises the steps of:
1) And (3) batching: weighing the components of the flame-retardant polyethylene sheath material according to parts by weight, wherein the weighing precision of the resin base material and the halogen-free flame retardant is +/-0.1 kg, and the weighing precision of the smoke suppression and char formation agent and the processing aid is +/-0.01 kg;
2) Feeding: the feeding sequence is as follows: firstly, adding a halogen-free flame retardant, then adding a resin base material, and finally, adding a smoke suppression and charcoal forming agent and other processing aids;
3) Banburying: the banburying time is 12-15min, the temperature of the melt is 155-160 ℃, and the material is turned once at 100 ℃, 125 ℃ and 135 ℃ in the middle;
4) Feeding: conveying the melt after banburying to a conical forced feeder, and allowing the melt to enter a double-screw extruder through forced feeding;
5) Extrusion: plasticizing the melt by a double-screw extruder, and then extruding and granulating by a single screw, wherein the screw speed of the double-screw extruder is 250-350rpm, and the temperature of the double-screw extruder is set as follows: the temperature setting range of the single screw is 110-140 ℃ in the compression section 100-115 ℃ and the homogenization section 120-135 ℃;
6) Granulating: the granules are packaged after air cooling, vibration sieving and homogenization.
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