CN114685880A - Self-crosslinking polyolefin material and preparation method and application thereof - Google Patents
Self-crosslinking polyolefin material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 83
- 238000004132 cross linking Methods 0.000 title claims abstract description 32
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000004698 Polyethylene Substances 0.000 claims abstract description 12
- -1 polyethylene Polymers 0.000 claims abstract description 12
- 229920000573 polyethylene Polymers 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 10
- 239000012745 toughening agent Substances 0.000 claims abstract description 10
- 238000011049 filling Methods 0.000 claims abstract description 9
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 8
- 239000000779 smoke Substances 0.000 claims abstract description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 5
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 4
- 238000012360 testing method Methods 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 230000008878 coupling Effects 0.000 claims description 5
- 238000010168 coupling process Methods 0.000 claims description 5
- 238000005859 coupling reaction Methods 0.000 claims description 5
- 238000010008 shearing Methods 0.000 claims description 5
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- 229920001971 elastomer Polymers 0.000 claims description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 4
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 4
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical group CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- 239000008187 granular material Substances 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 238000004806 packaging method and process Methods 0.000 claims description 3
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 229920002943 EPDM rubber Polymers 0.000 claims description 2
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims description 2
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 2
- QYMGIIIPAFAFRX-UHFFFAOYSA-N butyl prop-2-enoate;ethene Chemical compound C=C.CCCCOC(=O)C=C QYMGIIIPAFAFRX-UHFFFAOYSA-N 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 239000000806 elastomer Substances 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- 229920006245 ethylene-butyl acrylate Polymers 0.000 claims description 2
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 claims description 2
- 229920006225 ethylene-methyl acrylate Polymers 0.000 claims description 2
- 239000004700 high-density polyethylene Substances 0.000 claims description 2
- 229920004889 linear high-density polyethylene Polymers 0.000 claims description 2
- 229920001684 low density polyethylene Polymers 0.000 claims description 2
- 239000004702 low-density polyethylene Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 1
- 239000007822 coupling agent Substances 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 239000011256 inorganic filler Substances 0.000 claims 1
- 229910003475 inorganic filler Inorganic materials 0.000 claims 1
- 238000004643 material aging Methods 0.000 claims 1
- 229910000077 silane Inorganic materials 0.000 claims 1
- 239000000454 talc Substances 0.000 claims 1
- 229910052623 talc Inorganic materials 0.000 claims 1
- 230000006750 UV protection Effects 0.000 abstract description 8
- 239000003963 antioxidant agent Substances 0.000 abstract description 6
- 230000003078 antioxidant effect Effects 0.000 abstract description 6
- 238000010292 electrical insulation Methods 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 28
- 239000000203 mixture Substances 0.000 description 10
- 238000009472 formulation Methods 0.000 description 8
- 229910052724 xenon Inorganic materials 0.000 description 8
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 8
- 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 description 5
- 239000003063 flame retardant Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 229910008051 Si-OH Inorganic materials 0.000 description 3
- 229910006358 Si—OH Inorganic materials 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 230000004224 protection Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- NNNLYDWXTKOQQX-UHFFFAOYSA-N 1,1-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical compound C=CC(=O)OC(CC)(OC(=O)C=C)OC(=O)C=C NNNLYDWXTKOQQX-UHFFFAOYSA-N 0.000 description 1
- SSADPHQCUURWSW-UHFFFAOYSA-N 3,9-bis(2,6-ditert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C)=CC(C(C)(C)C)=C1OP1OCC2(COP(OC=3C(=CC(C)=CC=3C(C)(C)C)C(C)(C)C)OC2)CO1 SSADPHQCUURWSW-UHFFFAOYSA-N 0.000 description 1
- 101100344720 Caenorhabditis elegans mdh-1 gene Proteins 0.000 description 1
- 101000680091 Homo sapiens Transmembrane protein 54 Proteins 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 101000709029 Toxoplasma gondii Rhomboid-like protease 5 Proteins 0.000 description 1
- 102100022241 Transmembrane protein 54 Human genes 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 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 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 238000012946 outsourcing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007858 starting material Substances 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 atoms other than carbon or hydrogen
- C08L23/0853—Ethene vinyl acetate copolymers
-
- 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
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- 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
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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)
- Organic Insulating Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a self-crosslinking polyolefin material and a preparation method and application thereof, wherein the crosslinking polyolefin material comprises a low-smoke halogen-free material A and a material B in parts by weight, wherein the low-smoke halogen-free material A accounts for 60-90 parts, and the material B accounts for 5-20 parts; the low-smoke halogen-free material A comprises the following components in parts by weight: 0-10 parts of polyethylene; 20-40 parts of a toughening agent; 80-120 parts of inorganic filling powder; 3-10 parts of a compatibilizer; 1-5 parts of an auxiliary crosslinking agent; 1-5 parts of an antioxidant; 1-5 parts of a processing aid; the material B comprises the following components in parts by weight: 10-30 parts of polyethylene; 30-50 parts of a toughening agent; 1-5 parts of silane coupling agent. The self-crosslinking polyolefin material provided by the invention can be self-crosslinked without additional irradiation, and has excellent mechanical properties, electrical insulation properties, ultraviolet resistance and other properties.
Description
Technical Field
The invention relates to the technical field of wire and cable materials, in particular to a self-crosslinking polyolefin material and a preparation method and application thereof.
Background
Since the oil crisis happened in the world in the last 70 th century, the solar photovoltaic power generation technology has attracted great attention in western developed countries, and governments of various countries make policies from the perspective of environmental protection and energy sustainable development strategies to encourage and support the solar photovoltaic power generation technology. Photovoltaic cables in photovoltaic systems are used as important electrical parts, and working environments are often severe, such as high and low temperatures, ultraviolet irradiation, ozone and the like. By combining the above factors, the photovoltaic cable material is required to have the characteristics of high and low temperature resistance, ultraviolet irradiation resistance, high flame retardant property, low combustion smoke generation amount and the like.
In order to meet the use requirements of materials of photovoltaic cables, after the materials are extruded into finished cables by cable plants, outsourcing irradiation is needed, high-energy electron beam irradiation is adopted, and crosslinking is carried out by adopting free radicals.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a self-crosslinking polyolefin material and a preparation method thereof. The self-crosslinking polyolefin material provided by the invention does not need to be irradiated outside, and can be crosslinked after being placed for a period of time after being extruded by a downstream cable plant, so that the obtained photovoltaic cable has strong mechanical property, electrical insulation property and ultraviolet resistance, good flame retardance, capability of meeting actual requirements and environmental friendliness.
The method is realized by the following technical scheme:
a self-crosslinking polyolefin material comprises, by weight, 60-90 parts of a low-smoke halogen-free material A and 5-20 parts of a material B;
the low-smoke halogen-free material A comprises the following components in parts by weight:
the material B comprises the following components in parts by weight:
10-30 parts of polyethylene
30-50 parts of toughening agent
1-5 parts of silane coupling agent.
Further, the polyethylene is at least one of linear low density polyethylene, high density polyethylene and low density polyethylene.
Further, the density of the polyethylene is 0.88-0.96g/cm3The melt index at 190 ℃ under 2.16Kg test conditions is between 0.1 and 5g/10min, the melt index of the polyethylene being determined according to the standard ISO 1133-1-2011.
Further, the toughening agent is one or more of ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, thermoplastic elastomer, thermoplastic polyurethane elastomer rubber, ethylene methyl acrylate copolymer, ethylene butyl acrylate or ethylene propylene diene monomer rubber.
Further, the density of the toughening agent is 0.92-1.3g/cm3The melt index under the test conditions of 190 ℃ and 2.16Kg is 1-30g/10min, and the melt index of the toughening agent is determined according to the standard ISO 1133-1-2011. If the density is too low, a reduction in the tensile strength of the material may result, and if the melt index is too high, a reduction in the elongation at break may result.
Further, the particle size D50 of the inorganic filling powder is 0.1-10um, and the inorganic filling powder is selected from at least one of magnesium hydroxide, aluminum hydroxide, calcium carbonate, talcum powder, melamine phosphate, barium sulfate or high clay.
Further, the compatibilizer is at least one of maleic anhydride graft or EXA type toughening agent, and the maleic anhydride graft is preferably one or more of POE-g-MAH, LLDPE-g-MAH or EVA-g-MAH.
Further, the auxiliary crosslinking agent is one or more of triallyl isocyanurate, trihydromethyl propane triacrylate or trimethylolpropane trimethacrylate. If the content of the auxiliary crosslinking agent is too high, excessive crosslinking is caused, the tensile strength is too high, the elongation at break is too low, the thermal elongation test effect is poor, and even if the fracture occurs, the thermal elongation test cannot be carried out. If the content of the auxiliary crosslinking agent is too low, self-crosslinking cannot be realized, the mechanical properties of the material after aging are adversely affected, and brittle fracture occurs after aging.
Further, the antioxidant includes, but is not limited to, one or more of antioxidant 1010, antioxidant 445, antioxidant 1076, antioxidant 168, antioxidant 1079, antioxidant 1035, RIANOX, DSTDP, or PEP-36.
Further, the processing aid is selected from at least one of fluorine compounds, polyethylene wax, silicone or stearic acid compounds.
Further, the silane coupling agent is vinyltrimethoxysilane or vinyltriethoxysilane.
The invention also provides a preparation method of the self-crosslinking polyolefin material, which comprises the following steps:
s1: weighing the components according to the proportion; selecting an intermittent multi-field coupling weak shearing mode, and plasticizing and granulating the components except the inorganic filling powder in the material A to obtain a granulation material; plasticizing and granulating the obtained granulated material and inorganic filling powder to obtain a material A, drying the material A, vacuumizing and packaging for later use;
s2: blending, granulating and drying each component of the material B through a double-screw extruder to obtain a material B;
s3: and mixing the material A and the material B according to the proportion to obtain the self-crosslinking polyolefin material.
Further, the intermittent multi-field coupling weak shearing mode is a single screw extrusion mode with a screw compression ratio of 1-2 after mixing by an internal mixer; the technological conditions are that the banburying rotor is 30-100r/min, and the banburying temperature is 80-180 ℃; the single screw rotating speed is 50-200rpm, and the temperature is 100-300 ℃.
The invention also provides application of the self-crosslinking polyolefin material in preparation of photovoltaic cables.
Compared with the prior art, the invention has the beneficial effects that:
through the combination of the formula of the material A and the formula of the material B, the prepared self-crosslinking polyolefin material does not need to be irradiated outside, water molecules in the air enter the material after extrusion molding in a downstream cable plant and are placed for a period of time to generate-Si-OH, and then the-Si-OH and the-Si-OH are dehydrated to comprehensively form a crosslinking network, so that self-crosslinking is realized, the obtained photovoltaic cable is good in mechanical property and strong in ultraviolet resistance, and the electric insulating property and the flame retardant property can meet the actual requirements.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
< preparation of examples and comparative examples >
The raw materials used in the examples of the present invention and the comparative examples are commercially available, but are not limited to these materials:
polyethylene: linear low density polyethylene having a density of 0.918g/cm3The melt index at 190 ℃ under the test condition of 2.16kg is 5g/10min, and the trade mark LLDPE is 1C7A and is purchased from China petrochemical;
a toughening agent: ethylene-vinyl acetate copolymer with a density of 0.96g/cm3The melt index under the test condition of 190 ℃ and 2.16kg is 2g/10min, and the mark is EVA 2020, which is purchased from raisin;
compatibilizer: EVA-G-MAH with a melt index of 3G/10min at 190 deg.C under 2.16kg test, brand G75B, available from Jinfa science and technology, Inc.;
magnesium hydroxide: d50 is 2-4 μm, and is available from Liaoning Yingkou under the trade designation MDH-1;
aluminum hydroxide A: d50 is 2-6 μm, and is available from Medium aluminum group under the designation ATH-1;
aluminum hydroxide B: d50 is 16-20 μm, and is available from Medium aluminum group under the designation ATH-2;
calcium carbonate: d50 is 2-6 μm, brand CAC-1, and is purchased from Jiangxi Guangyuan chemical industry;
melamine phosphate, D50 is 2-6 μm, trade name MPP-1, purchased from Changxing chemical;
auxiliary crosslinking agent: triallyl isocyanurate, brand TAIC, available from the coleson chemical industry;
antioxidant: commercially available, the commercial starting materials used in the parallel experiments were the same;
processing aid: silicone masterbatches, brand SISE-50, available from Changxing chemical industry.
Silane coupling agent: vinyltrimethoxysilane, designation G-172, available from Silicones technologies;
the preparation methods of examples 1 to 11 and comparative examples 6 to 9 of the present invention are as follows:
s1: weighing the components according to the mixture ratio in the formula tables 1, 2 and 4; selecting an intermittent multi-field coupling weak shearing mode, and plasticizing and granulating the components except the inorganic filling powder in the material A to obtain a granulation material; plasticizing and granulating the obtained granulated material and inorganic filling powder to obtain a material A, drying the material A, vacuumizing and packaging for later use;
s2: blending, granulating and drying each component of the material B through a double-screw extruder to obtain a material B;
s3: and mixing the material A and the material B according to the proportion to prepare the cable, and carrying out subsequent performance test.
Wherein, the intermittent multi-field coupling weak shearing mode is a single screw extrusion mode with a screw compression ratio of 1-2 after mixing by an internal mixer; the technological conditions are that the banburying rotor is 30-100r/min, and the banburying temperature is 80-180 ℃; the single screw rotating speed is 50-200rpm, and the temperature is 100-300 ℃.
Preparation of comparative examples 1 to 5:
the formulation of example 1 was used and the preparation was similar to that of the examples except that the materials A and B were prepared and then vacuum packed without separate drying.
In the present specification, the term "part(s)" means "part(s) by weight" unless otherwise specified.
< test standards >
The performance test standards of the examples of the present invention and the comparative examples are as follows:
tensile strength: testing according to GB/T1040.3-2006 standard;
elongation at break: testing according to GB/T1040.3-2006 standard;
hot extension of the finished cable: testing at 200 ℃ and 0.2MPa according to GB/T2951.21-2008 standard, and if the thermal extension data of the finished cable is overlarge and even breaks occur, indicating that the crosslinking is insufficient or does not occur;
single vertical burn test: testing according to a GB/T18380 single vertical combustion method;
electrical insulation properties: testing according to GB/T3048.5-2007 standard, requiring soaking water at 90 ℃ for a long time, and testing that the insulation resistance constant is still above 2M omega Km to be qualified after 720 h;
ultraviolet resistance: according to ISO 4892-2: and (3) testing 2003 standard conditions, wherein after the xenon lamp is aged for 720h, the tensile strength is still more than 10MPa, the elongation at break is still more than 150%, and compared with the xenon lamp before the xenon lamp is aged, the change rate of the tensile strength and the elongation at break is less than 30%, so that the xenon lamp is qualified.
TABLE 1 EXAMPLES 1-8 formulations
In examples 1 to 8, 70 parts of each material A and 15 parts of each material B were used.
TABLE 2 formulations of examples 9-10
| Components | Example 9 | Example 10 |
| A material (in parts) | 60 | 90 |
| B material (in parts) | 5 | 20 |
Note: the formulations of the A and B batches in examples 9 and 10 were the same as in example 1.
TABLE 3 results of the Performance test of examples 1 to 10
According to the results, the photovoltaic finished product cable prepared by adopting a proper production process has uniform and non-pregel points on the surface in the required component dosage ratio; the obtained finished cable is qualified after being placed naturally and subjected to thermal extension and can be effectively crosslinked, and the mechanical property, the electrical insulation property and the ultraviolet resistance of the finished cable can meet the requirements.
TABLE 4 comparative examples 1-7 formulations
TABLE 5 COMPARATIVE EXAMPLES 8-9 FORMULATIONS
| Components | Comparative example 8 | Comparative example 9 |
| Material A (parts) | 96 | 75 |
| B material (in parts) | 4 | 25 |
Note: the formulations of the A and B formulations in comparative examples 8 and 9 were the same as in example 1.
TABLE 6 Performance test results for comparative examples 1-9
From the above results, in the specific preparation methods of comparative examples 1 to 5, since the material a and the material B were not dried and vacuum-sealed, the pre-gel condition appeared on the surface of the finished cable during the extrusion process, and the degree of cross-linking was not uniform in different parts, which resulted in the unstable thermal extension test, failing to pass the test, the poor insulation performance and elongation at break, and failing to pass the single vertical combustion.
Comparative examples 6 and 7 compared with example 1, in comparative example 6, too much crosslinking agent was used, which resulted in a large decrease in elongation at break of comparative example 6 and elongation at break after 720h xenon lamp aging, and deterioration in insulation electrical properties, and comparative example 6 broke and failed the single vertical burning test in the test of thermal extension of the finished cable, and further, comparative example 6 was extruded, the surface of the finished cable was not smooth, and more gel points appeared; in comparative example 7, the use amount of the auxiliary crosslinking agent is too small, so that the elongation at break of comparative example 7 and the elongation at break after the xenon lamp is aged for 720h are greatly reduced, and the single vertical burning test cannot be passed, which indicates that the ultraviolet resistance and the flame retardant property of comparative example 7 are poor, and the fracture of comparative example 7 occurs during the thermal extension of the finished cable.
Compared with example 1, in comparative examples 8 and 9, the use amount of the material A is too much in comparative example 8, so that the mechanical property, the electrical insulation property, the ultraviolet resistance and the flame retardant property of comparative example 8 cannot meet the requirements, and in comparative example 9, the use amount of the material B is too much in comparative example 9, so that the electrical insulation property, the ultraviolet resistance and the flame retardant property of comparative example 9 are also greatly reduced, so that the comparative example 9 cannot meet the use requirements.
Example 11
The self-crosslinking polyolefin material of the formulation of example 1 was prepared into a cable, with the results: the tensile strength is 11MPa, the elongation at break is 170%, the thermal extension of the finished cable is 50% under the test conditions of 200 ℃ and 0.2MPa, the insulation resistance constant is 3M omega Km after the cable is soaked in water for 720h at the temperature of 90 ℃, the tensile strength is 12MPa after the xenon lamp is aged for 720h, the elongation at break is 160% after the xenon lamp is aged for 720h, and the cable can be vertically combusted through a single cable.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The self-crosslinking polyolefin material is characterized by comprising 60-90 parts of low-smoke halogen-free material A and 5-20 parts of material B by weight;
the low-smoke halogen-free material A comprises the following components in parts by weight:
the material B comprises the following components in parts by weight:
10-30 parts of polyethylene
30-50 parts of toughening agent
1-5 parts of silane coupling agent.
2. The self-crosslinking polyolefin material of claim 1, wherein the polyethylene is at least one of linear low density polyethylene, high density polyethylene, and low density polyethylene.
3. The self-crosslinking polyolefin material according to claim 1, wherein the polyethylene has a density of 0.88 to 0.96g/cm3The melt index under the test conditions of 190 ℃ and 2.16Kg is 0.1-5g/10 min.
4. The self-crosslinking polyolefin material of claim 1, wherein the toughening agent is one or more of an ethylene-vinyl acetate copolymer, an ethylene-ethyl acrylate copolymer, a thermoplastic elastomer, a thermoplastic polyurethane elastomer rubber, an ethylene methyl acrylate copolymer, an ethylene butyl acrylate, or an ethylene propylene diene monomer rubber.
5. The self-crosslinking polyolefin material according to claim 1, wherein the inorganic filler powder has a particle size D50 of 0.1-10um, and is at least one selected from magnesium hydroxide, aluminum hydroxide, calcium carbonate, talc, melamine phosphate, barium sulfate, and high clay.
6. The self-crosslinking polyolefin material of claim 1, wherein the processing aid is at least one of a fluorine-based compound, a polyethylene wax, a silicone, or a stearic-based compound.
7. The self-crosslinking polyolefin material according to claim 1, wherein the silane-based coupling agent is vinyltrimethoxysilane or vinyltriethoxysilane.
8. The self-crosslinking polyolefin material of claim 1, wherein the co-crosslinking agent is one or more of triallyl isocyanurate, trihydromethylpropane triacrylate, or trimethylolpropane trimethacrylate.
9. A process for the preparation of a self-crosslinking polyolefin material according to any one of claims 1 to 8, characterized in that it comprises the following steps:
s1: weighing the components according to the proportion; selecting an intermittent multi-field coupling weak shearing mode, and plasticizing and granulating the components except the inorganic filling powder in the material A to obtain a granulation material; plasticizing and granulating the obtained granulated material and inorganic filling powder to obtain a material A, vacuumizing the material A and packaging for later use;
s2: blending, granulating and drying each component of the material B through a double-screw extruder to obtain a material B;
s3: and mixing the material A and the material B according to the proportion to obtain the self-crosslinking polyolefin material.
10. Use of the self-crosslinking polyolefin material according to any one of claims 1 to 8 for the preparation of photovoltaic cables.
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Cited By (1)
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