CN117285769A - Reversible crosslinked polyethylene cable material and preparation method thereof - Google Patents
Reversible crosslinked polyethylene cable material and preparation method thereof Download PDFInfo
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- CN117285769A CN117285769A CN202210684782.XA CN202210684782A CN117285769A CN 117285769 A CN117285769 A CN 117285769A CN 202210684782 A CN202210684782 A CN 202210684782A CN 117285769 A CN117285769 A CN 117285769A
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- Prior art keywords
- cable material
- polyethylene
- reaction area
- coupling agent
- antioxidant
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- 239000000463 material Substances 0.000 title claims abstract description 131
- 229920003020 cross-linked polyethylene Polymers 0.000 title claims abstract description 61
- 239000004703 cross-linked polyethylene Substances 0.000 title claims abstract description 61
- 230000002441 reversible effect Effects 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title abstract description 17
- -1 polyethylene copolymer Polymers 0.000 claims abstract description 67
- 239000004698 Polyethylene Substances 0.000 claims abstract description 62
- 229920000573 polyethylene Polymers 0.000 claims abstract description 62
- 239000007822 coupling agent Substances 0.000 claims abstract description 48
- DHEJIZSVHGOKMJ-UHFFFAOYSA-N 2-ethenylbenzaldehyde Chemical compound C=CC1=CC=CC=C1C=O DHEJIZSVHGOKMJ-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 30
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000005977 Ethylene Substances 0.000 claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 229920000768 polyamine Polymers 0.000 claims abstract description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 52
- 229920001684 low density polyethylene Polymers 0.000 claims description 48
- 239000004702 low-density polyethylene Substances 0.000 claims description 48
- 230000003078 antioxidant effect Effects 0.000 claims description 46
- 239000000203 mixture Substances 0.000 claims description 42
- 238000002156 mixing Methods 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 22
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000001072 heteroaryl group Chemical group 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- 238000011282 treatment Methods 0.000 claims description 5
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 4
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 claims description 4
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000003107 substituted aryl group Chemical group 0.000 claims description 3
- 238000012545 processing Methods 0.000 abstract description 17
- 238000006243 chemical reaction Methods 0.000 description 152
- 230000000052 comparative effect Effects 0.000 description 28
- 239000003999 initiator Substances 0.000 description 27
- 238000001035 drying Methods 0.000 description 14
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 14
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 13
- 238000001816 cooling Methods 0.000 description 13
- 235000012438 extruded product Nutrition 0.000 description 13
- 239000008187 granular material Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 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 12
- 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 12
- 125000003172 aldehyde group Chemical group 0.000 description 11
- 229920001577 copolymer Polymers 0.000 description 11
- 238000004132 cross linking Methods 0.000 description 11
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 11
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 11
- 238000012216 screening Methods 0.000 description 11
- 238000002347 injection Methods 0.000 description 10
- 239000007924 injection Substances 0.000 description 10
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical group CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 239000003431 cross linking reagent Substances 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 150000002978 peroxides Chemical class 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- HGXJDMCMYLEZMJ-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2,2-dimethylpropaneperoxoate Chemical group CC(C)(C)OOOC(=O)C(C)(C)C HGXJDMCMYLEZMJ-UHFFFAOYSA-N 0.000 description 2
- CATOVPRCMWIZLR-UHFFFAOYSA-N 3-ethenylbenzaldehyde Chemical compound C=CC1=CC=CC(C=O)=C1 CATOVPRCMWIZLR-UHFFFAOYSA-N 0.000 description 2
- UASMMGZSYVCUBZ-UHFFFAOYSA-N 4-ethenyl-2-methylbenzaldehyde Chemical compound CC1=CC(C=C)=CC=C1C=O UASMMGZSYVCUBZ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920013716 polyethylene resin Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical group CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 229920006249 styrenic copolymer Polymers 0.000 description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical group NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical group NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 description 1
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 1
- MGLZGLAFFOMWPB-UHFFFAOYSA-N 2-chloro-1,4-phenylenediamine Chemical group NC1=CC=C(N)C(Cl)=C1 MGLZGLAFFOMWPB-UHFFFAOYSA-N 0.000 description 1
- OBCSAIDCZQSFQH-UHFFFAOYSA-N 2-methyl-1,4-phenylenediamine Chemical group CC1=CC(N)=CC=C1N OBCSAIDCZQSFQH-UHFFFAOYSA-N 0.000 description 1
- HCILJBJJZALOAL-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)-n'-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyl]propanehydrazide Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 HCILJBJJZALOAL-UHFFFAOYSA-N 0.000 description 1
- XYFRHHAYSXIKGH-UHFFFAOYSA-N 3-(5-methoxy-2-methoxycarbonyl-1h-indol-3-yl)prop-2-enoic acid Chemical group C1=C(OC)C=C2C(C=CC(O)=O)=C(C(=O)OC)NC2=C1 XYFRHHAYSXIKGH-UHFFFAOYSA-N 0.000 description 1
- QBFNGLBSVFKILI-UHFFFAOYSA-N 4-ethenylbenzaldehyde Chemical compound C=CC1=CC=C(C=O)C=C1 QBFNGLBSVFKILI-UHFFFAOYSA-N 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000012772 electrical insulation material Substances 0.000 description 1
- 125000003916 ethylene diamine group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- HPFYHMPQLQBFLL-UHFFFAOYSA-N hexane pyrrole-2,5-dione Chemical compound CCCCCC.O=C1NC(=O)C=C1 HPFYHMPQLQBFLL-UHFFFAOYSA-N 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000000561 purinyl group Chemical group N1=C(N=C2N=CNC2=C1)* 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/34—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an aldehydo radical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/29—Protection against damage caused by extremes of temperature or by flame
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/29—Protection against damage caused by extremes of temperature or by flame
- H01B7/292—Protection against damage caused by extremes of temperature or by flame using material resistant to heat
-
- 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
- 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
Landscapes
- 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)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a reversible crosslinked polyethylene cable material and a preparation method thereof. The raw materials of the reversible crosslinked polyethylene cable material comprise polyethylene copolymer and coupling agent; the polyethylene copolymer is obtained by copolymerizing a polymerization monomer; the polymerized monomer comprises ethylene, vinyl benzaldehyde and/or vinyl benzaldehyde derivative; the coupling agent is selected from the group consisting of primary polyamine compounds. The reversible crosslinked polyethylene cable material has the advantages of excellent heat resistance and wide processing window.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and relates to a reversible crosslinked polyethylene cable material and a preparation method thereof.
Background
Polyethylene has good insulation, easy processing, low temperature resistance and aging resistance, is an excellent electrical insulation material, but also has the defects of low temperature resistance level, poor creep resistance and the like. After the polyethylene is crosslinked, the molecular structure of the polyethylene is changed into a three-dimensional network structure from a two-dimensional structure, the electric performance, heat resistance, physical strength and the like of the polyethylene can be improved to a great extent, and the application range of the polyethylene is widened.
The traditional polyethylene crosslinking mode mainly comprises peroxide crosslinking, radiation crosslinking, silane crosslinking and the like, but the crosslinking modes belong to irreversible crosslinking, so that precious thermoplasticity is lost, and the cable material cannot be reprocessed and recycled.
Dynamic covalent bonds refer to covalent bonds capable of realizing reversible cleavage/bonding after being subjected to specific stimuli (such as heat, light and pH), and thus the polymer crosslinked network formed can realize topological rearrangement under the external action. It has been reported that a reversibly crosslinked polyolefin is obtained by DA reaction, for example, patent CN111072858A reports a polyethylene resin having cyclopentadienyl groups as side groups, the polymerized monomers of which comprise ethylene and an alpha-olefin having cyclopentadienyl groups, wherein the resulting polyethylene resin has a reversibly crosslinked network structure by DA reaction between the cyclopentadienyl groups on the alpha-olefin monomer, and the resin undergoes a reverse reaction upon heating to 160℃or higher to crosslink the polyethylene, thereby imparting thermoplasticity to the material. In addition, patent WO2019024633A1 reports a styrenic copolymer with reversible crosslinks, which is obtained by reacting a styrenic copolymer with furanyl groups with a polyfunctional maleimide derivative via DA, and also provides the use of the copolymer in a cable material, wherein the reversible crosslinks of the copolymer can be broken at high temperature, so that the cable material has secondary processability and can be reused.
However, in many current occasions, the current transmission capacity per unit section area is large, the heat quantity is high, the long-term working temperature of the conductor is high, so that higher requirements are put on the heat resistance grade of the insulating material, the heat resistance of the DA-type reversible crosslinked polyethylene cable material is poor, and the viscosity of the cable material is suddenly reduced during the decrosslinking, so that the application of the cable material in a working environment with higher temperature is limited to a certain extent.
Disclosure of Invention
The invention provides a reversible crosslinked polyethylene cable material, which has the advantages of excellent heat resistance and wide processing window.
The invention also provides a preparation method of the reversible crosslinked polyethylene cable material, and the reversible crosslinked polyethylene cable material with excellent heat resistance and wide processing window can be simply and rapidly prepared by the method.
The first aspect of the invention provides a reversible cross-linked polyethylene cable material, wherein the cable material comprises polyethylene copolymer and coupling agent;
the polymerized monomer comprises ethylene, vinyl benzaldehyde and/or vinyl benzaldehyde derivative;
the coupling agent is selected from the group consisting of primary polyamine compounds.
A reversibly crosslinked polyethylene cable material as described above wherein the coupling agent is selected from the group consisting of compounds of formula (I):
H 2 N-R 1 -NH 2 formula (I)
In the formula (I), R 1 Selected from C1-C12 alkyl, C6-C12 substituted or unsubstituted aryl or C6-C12 substituted or unsubstituted heteroaryl;
wherein the substituents in the substituted aryl or substituted heteroaryl are selected from C1-C3 alkyl or halogen.
The reversible crosslinked polyethylene cable material as described above, wherein R 1 A linear alkyl group selected from C2 or C3.
The reversible cross-linked polyethylene cable material as described above, wherein the derivative of vinyl benzaldehyde is selected from vinyl benzaldehyde compounds having at least one C1-C6 alkyl substituent on the benzene ring.
The reversible cross-linked polyethylene cable material is characterized in that the mass ratio of the polyethylene copolymer to the coupling agent is 100 (1-20).
The reversible cross-linked polyethylene cable material comprises 70% -93% of ethylene units and 5% -29% of vinyl benzaldehyde units and/or vinyl benzaldehyde derivative units according to the molar content.
A reversibly crosslinked polyethylene cable material as described above wherein the polyethylene copolymer is a low density polyethylene copolymer.
The reversible crosslinked polyethylene cable material comprises the following raw materials, wherein the raw materials of the cable material further comprise an antioxidant;
the mass ratio of the polyethylene copolymer, the coupling agent and the antioxidant is 100: (2-15): (0.3 to 0.7).
The second aspect of the invention provides a method for preparing the reversible cross-linked polyethylene cable material, which comprises the following steps: mixing the raw materials of the cable materials to obtain a mixture; and extruding the mixture to obtain the reversible crosslinked polyethylene cable material.
The preparation method as described above, wherein the temperature of the extrusion treatment is 190-230 ℃.
The implementation of the invention has at least the following beneficial effects:
1. according to the invention, the polyethylene cable material with an imine bond covalent cross-linked network structure is obtained through the reaction of aldehyde groups on the side chains of the polyethylene copolymer and amino groups in the coupling agent, and the cable material has excellent heat resistance.
2. When the polyethylene cable material is subjected to crosslinking, the viscosity of the cable material is slowly reduced, so that the processing window temperature and the processing stability of the cable material are greatly widened, and the processing process is simpler and easier to control.
3. According to the preparation method of the reversible crosslinked polyethylene cable material, the reversible crosslinked polyethylene cable material with excellent heat resistance and wide processing window can be obtained by simply mixing and extruding the cable material raw materials, and the method has the advantages of simplicity and easiness in operation.
Drawings
FIG. 1 is a graph showing the IR spectrum of cable materials of example 1, comparative example 2 and comparative example 3;
FIG. 2 is a graph showing IR spectrum comparison of cable materials of example 1 and comparative example 4.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The first aspect of the invention provides a reversible crosslinked polyethylene cable material, wherein the raw materials of the cable material comprise polyethylene copolymer and coupling agent; the polyethylene copolymer is obtained by copolymerizing polymerization monomers, wherein the polymerization monomers comprise ethylene, and vinyl benzaldehyde and/or vinyl benzaldehyde derivatives; the coupling agent is selected from the group consisting of primary polyamine compounds.
Wherein the polymerized monomer comprises ethylene, and at least one of vinyl benzaldehyde and a vinyl benzaldehyde derivative in addition to ethylene.
The substitution position of the vinyl group on the benzaldehyde is not particularly limited in the present invention, and may be, for example, o-vinylbenzaldehyde, m-vinylbenzaldehyde, p-vinylbenzaldehyde or the like. Wherein, the derivative of vinyl benzaldehyde refers to a compound with alkyl substituent groups connected on benzene rings of vinyl benzaldehyde.
The lateral group of the polyethylene copolymer contains aldehyde (-CHO), the coupling agent is a multi-primary amine compound, and the coupling agent contains at least two amino (-NH) 2 ) The aldehyde group and the amino group are subjected to Schiff base reaction, so that the reversible crosslinked polyethylene with a dynamic imine bond crosslinked network can be obtained.
Although the polyethylene cable material of the dissociative dynamic covalent cross-linked network represented by the D-A reaction can be reprocessed, the problems of narrow processing window and sudden viscosity drop during the decrosslinking exist, and the application and processing difficulty of the polyethylene cable material under the high-temperature environment are limited. The reversible crosslinked polyethylene cable material has a dynamic imine bond crosslinked network, has good heat resistance, and the viscosity of the cable material gradually decreases along with the temperature rise during the decrosslinking, so that the processing process is simple and easy to control.
In the invention, the copolymerization process of the polymerization monomer is a free radical polymerization process, and a peroxide initiator can be added in the copolymerization reaction to initiate the polymerization reaction. In order to control the molecular weight of the polyethylene copolymer obtained by copolymerization, it is also necessary to add a small amount of a molecular weight regulator to the polymerization system, and the molecular weight regulator may be selected from molecular weight regulators commonly used in the art, including but not limited to propylene, butene or propane, etc., preferably propylene. The molecular weight regulator is added in an amount of 0 to 5000ppm, preferably 1000 to 3000ppm.
In a specific embodiment, the coupling agent is selected from compounds of formula (I):
H 2 N-R 1 -NH 2 formula (I)
In the formula (I), R 1 Selected from C1-C12 alkyl, C6-C12 substituted or unsubstituted aryl or C6-C12 substituted or unsubstituted heteroaryl;
wherein the substituents in the substituted aryl or substituted heteroaryl are selected from C1-C3 alkyl or halogen.
Specifically, the C1-C12 alkyl group may be a straight-chain alkyl group or a branched-chain alkyl group having 1 to 12 carbon atoms, including but not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, sec-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, etc. The C1-C6 alkyl group may be a straight chain alkyl group or a branched alkyl group having 1 to 6 carbon atoms, including but not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, sec-butyl, n-pentyl, n-hexyl, etc. The C1-C3 alkyl group may be a straight-chain alkyl group or a branched alkyl group having 1 to 3 carbon atoms, for example, methyl, ethyl, n-propyl, isopropyl, etc.
Except in the specific case, "aryl" refers to an unsaturated, aromatic, monocyclic or polycyclic fused or covalently linked substituent; "heteroaryl" refers to an aryl group containing 1 to 4 heteroatoms, typically nitrogen, oxygen, sulfur.
Aryl groups of C6 to C12 include, but are not limited to, phenyl, naphthyl, biphenyl, and the like; heteroaryl groups of C6 to C12 include, but are not limited to, pyrrolyl, pyridyl, pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, pyrimidinyl, purinyl, indolyl, and the like.
Further, R in formula (I) 1 A linear alkyl group selected from C2 or C3, i.e. ethyl or n-propyl.
In a specific embodiment, the derivative of vinylbenzaldehyde is selected from vinylbenzaldehyde compounds having at least one C1-C6 alkyl substitution on the benzene ring. Further, the C1-C6 alkyl-substituted vinylbenzaldehyde compound is preferably a methyl-substituted vinylbenzaldehyde compound.
In a specific embodiment, the mass ratio of the polyethylene copolymer to the coupling agent in the raw materials of the cable material is 100: (1-20).
In a specific embodiment, the polyethylene copolymer comprises, in terms of molar content, from 70% to 93% of ethylene units and from 5% to 29% of vinylbenzaldehyde units and/or vinylbenzaldehyde derivative units. Wherein the polyethylene copolymer comprises 5% -29% of vinyl benzaldehyde units and/or vinyl benzaldehyde derivative units, the molar content of the vinyl benzaldehyde units in the polyethylene copolymer is 5% -29%, the molar content of the vinyl benzaldehyde derivative units in the polyethylene copolymer is 5% -29%, and the sum of the molar contents of the vinyl benzaldehyde units and the vinyl benzaldehyde derivative units in the polyethylene copolymer is 5% -29%. Specifically, the molar content of the ethylene unit, the vinylbenzaldehyde and the derivative unit in the copolymer can be determined by infrared spectroscopy, for example, the molar content of the aldehyde group in the copolymer can be determined by infrared spectroscopy, and the content of the vinylbenzaldehyde and the derivative unit can be determined by the molar content of the aldehyde group.
The polyethylene copolymer of the invention is preferably a low density polyethylene copolymer, also known as high pressure polyethylene, having a density of 0.91g/cm 3 ～0.93g/cm 3 The cable has the advantages of excellent electrical insulation performance, good mechanical performance, excellent cost performance, low cost and the like.
In a specific embodiment, the low density polyethylene copolymer of the present invention may be prepared using the following preparation method:
adding a polymerization monomer into a high-pressure polyethylene reactor, and carrying out a first-stage polymerization reaction on the polymerization monomer at 280-300 ℃ to obtain a first polymerization product; carrying out a second-stage polymerization reaction on the first polymerization product at 285-295 ℃ to obtain a second polymerization product; the second polymerization product is subjected to a third-stage polymerization reaction at 280-290 ℃ to obtain a third polymerization product; and (3) carrying out a fourth-stage polymerization reaction on the third polymerization product at 270-285 ℃ to obtain the polyethylene copolymer.
The four polymerization reactions in the four different stages are all initiated by organic peroxide, and the organic peroxide is injected into the four stages by an injection pump to respectively initiate four-stage polymerization reactions.
The method further comprises the step of preheating the polymerized monomer before the polymerized monomer is added into the reactor, wherein the temperature of the polymerized monomer after preheating is preferably 160-170 ℃, and more preferably 165 ℃.
The raw materials of the cable material also comprise the antioxidant, and the crosslinked polyolefin is easy to age when being applied to the cable material insulating material, so that the crosslinking property, the mechanical property and the thermal stability of the cable material are poor, and the oxidation aging of the oxide can be delayed by adding the antioxidant.
The antioxidant of the present invention is preferably at least one selected from hindered phenol antioxidants and phosphorous acid antioxidants. Among them, hindered phenolic antioxidants include, but are not limited to, mono-hindered phenols, poly-hindered phenols such as dibutyl hydroxy toluene BHT, antioxidant 1024, antioxidant 3114, antioxidant 1010, antioxidant 1330; phosphorous acid antioxidants refer to phosphite antioxidants including, but not limited to, non-phenolic phosphite antioxidants, low-phenolic phosphite antioxidants, such as antioxidant 168.
Further, the mass ratio of the polyethylene copolymer, the coupling agent and the antioxidant is 100: (2-15): (0.3 to 0.7). For example, in one specific embodiment, 80000ppm of coupling agent and 4000ppm of antioxidant are added to each kilogram of polyethylene copolymer, wherein the mass of coupling agent and antioxidant expressed in ppm is the weight percent of the mass of the polyethylene copolymer, then in the above embodiment the mass ratio of polyethylene copolymer, coupling agent to antioxidant is 100:8:0.4.
the second aspect of the present invention provides a method for preparing the reversible crosslinked polyethylene cable material, which comprises the following steps: mixing the raw materials of the cable materials to obtain a mixture; extruding the mixture to obtain the reversible cross-linked polyethylene cable material.
Firstly, mixing all components of the cable material in a mixer to obtain a mixture; and then the mixture is sent to an extruder for mixing and then is extruded.
After extrusion, the process of cooling, granulating and drying the extrudate is also included, and the reversible crosslinked polyethylene cable material of the invention can be obtained.
The mixer of the present invention may be a high speed mixer, and the extruder includes, but is not limited to, a single screw extruder or a twin screw extruder.
Further, the mixing of the cable materials can be accomplished at 0-50 ℃.
Further, the temperature of the extrusion treatment is 190-230 ℃. At the temperature, the extrusion treatment not only completes the molding process of the polyethylene cable material, but also promotes the reaction of aldehyde groups in the polyethylene copolymer and amino groups in the coupling agent, and completes the covalent crosslinking process of the polyethylene copolymer through imine bonds.
The reversible crosslinked polyethylene cable material and the preparation method thereof provided by the invention are further described in detail below with reference to specific examples.
In the following examples, unless otherwise indicated, all the materials used were prepared by commercially available methods or by conventional methods, and experimental methods without specifying the specific conditions were conventional and well known in the art.
Example 1
The preparation method of the reversible crosslinked polyethylene cable material comprises the following steps:
1) Adopting a tubular high-pressure polyethylene reactor with four reaction areas as a reaction device, wherein the temperatures of the first reaction area, the second reaction area, the third reaction area and the fourth reaction area are 295 ℃, 285 ℃, 275 ℃ and 285 ℃ respectively, the reactor pressure is 285Mpa, ethylene and 2-vinyl benzaldehyde are respectively introduced into the reactor at the flow rates of 50t/h and 2.95t/h for preheating, the reaction temperature of the preheated materials reaches 165 ℃, the materials sequentially pass through the first reaction area, the second reaction area, the third reaction area and the fourth reaction area, a molecular weight regulator is introduced into the inlet of the first reaction area at the flow rate of 100kg/h, an initiator is respectively injected into the first reaction area, the second reaction area, the third reaction area and the fourth reaction area at four points through an injection pump, the total amount of the initiator is 0.17t/h, 4-stage polymerization reaction is initiated, and the low-density polyethylene copolymer is prepared, wherein the aldehyde group content in the copolymer is 6.31%;
wherein the initiator is di-tert-butyl peroxide and the molecular weight regulator is propylene.
2) Adding the low-density polyethylene copolymer prepared in the step 1), a coupling agent and an antioxidant into a high-speed mixer, and uniformly mixing the components at a high speed to obtain a mixture. Extruding the mixture by a 35-type double-screw extruder (Long Keya Nanjing mechanical company) at 200 ℃, cooling the extruded product by circulating water, granulating by a granulator, drying granules, and screening to obtain a reversible crosslinked polyethylene cable material;
wherein the coupling agent is ethylenediamine, the antioxidant is a mixture obtained by mixing hindered phenol antioxidant 1010 and phosphite antioxidant 168 according to a mass ratio of 2:1; the coupling agent was added in an amount of 80000ppm per kg of the low density polyethylene copolymer and the antioxidant was added in an amount of 4000ppm per kg of the low density polyethylene copolymer.
Example 2
The preparation method of the reversible crosslinked polyethylene cable material comprises the following steps:
1) The method comprises the steps of adopting a tubular high-pressure polyethylene reactor with four reaction areas as a reaction device, wherein the temperatures of the first reaction area, the second reaction area, the third reaction area and the fourth reaction area are respectively 300 ℃, 297 ℃, 290 ℃, 280 ℃, the reactor pressure is set to 285Mpa, ethylene and 3-vinyl benzaldehyde are respectively introduced into the reactor at the flow rates of 50t/h and 4.51t/h for preheating, the reaction temperature of the preheated materials reaches 165 ℃, the materials sequentially pass through the first reaction area, the second reaction area, the third reaction area and the fourth reaction area, simultaneously, a molecular weight regulator is introduced into the inlet of the first reaction area at the flow rate of 150kg/h, an initiator is respectively injected into the first reaction area, the second reaction area, the third reaction area and the fourth reaction area at four points through an injection pump, the total amount of the initiator is 0.20t/h, and 4-stage polymerization reaction is initiated, so that the low-density polyethylene copolymer is prepared, wherein the aldehyde group content in the copolymer is 11.45%;
wherein the initiator is tert-butyl peroxyacetate and the molecular weight regulator is propylene.
2) Adding the low-density polyethylene copolymer prepared in the step 1), a coupling agent and an antioxidant into a high-speed mixer, and uniformly mixing the components at a high speed to obtain a mixture. Extruding the mixture by a 35-type double-screw extruder (Long Keya Nanjing mechanical company) at 200 ℃, cooling the extruded product by circulating water, granulating by a granulator, drying granules, and screening to obtain a reversible crosslinked polyethylene cable material;
wherein the coupling agent is propylene diamine, the antioxidant is a mixture obtained by mixing hindered phenol antioxidant 1010 and phosphite antioxidant 168 according to a mass ratio of 1:1; the coupling agent is added in an amount of 90000ppm per kg of the low-density polyethylene copolymer, and the antioxidant is added in an amount of 5000ppm per kg of the low-density polyethylene copolymer.
Example 3
The preparation method of the reversible crosslinked polyethylene cable material comprises the following steps:
1) The method comprises the steps of adopting a tubular high-pressure polyethylene reactor with four reaction areas as a reaction device, wherein the temperatures of the first reaction area, the second reaction area, the third reaction area and the fourth reaction area are respectively 300 ℃, 295 ℃, 290 ℃ and 285 ℃, the reactor pressure is set to 290Mpa, ethylene and 2-vinyl benzaldehyde are respectively introduced into the reactor at the flow rates of 50t/h and 2.43t/h for preheating, the reaction temperature of the preheated materials reaches 165 ℃, the materials sequentially pass through the first reaction area, the second reaction area, the third reaction area and the fourth reaction area, simultaneously, a molecular weight regulator is introduced into the inlet of the first reaction area at the flow rate of 150kg/h, an initiator is respectively injected into the first reaction area, the second reaction area, the third reaction area and the fourth reaction area at four points through an injection pump, the total amount of the initiator is 0.18t/h, and 4-stage polymerization is initiated, so that the low-density polyethylene copolymer is prepared, wherein the aldehyde group content in the copolymer is 5.79mol%;
wherein the initiator is tert-butyl peroxypivalate and the molecular weight regulator is propylene.
2) Adding the low-density polyethylene copolymer prepared in the step 1), a coupling agent and an antioxidant into a high-speed mixer, and uniformly mixing the components at a high speed to obtain a mixture. Extruding the mixture by a 35-type double-screw extruder (Long Keya Nanjing mechanical company) at 200 ℃, cooling the extruded product by circulating water, granulating by a granulator, drying granules, and screening to obtain a reversible crosslinked polyethylene cable material;
wherein the coupling agent is 1, 2-propylene diamine, the antioxidant is a mixture obtained by mixing hindered phenol antioxidant 1010 and phosphite antioxidant 168 according to the mass ratio of 2:0.5; the amount of the coupling agent added is 60000ppm per kg of the low density polyethylene copolymer, and the amount of the antioxidant added is 4500ppm per kg of the polyethylene.
Example 4
The preparation method of the reversible crosslinked polyethylene cable material comprises the following steps:
1) The method comprises the steps of adopting a tubular high-pressure polyethylene reactor with four reaction areas as a reaction device, wherein the temperatures of the first reaction area, the second reaction area, the third reaction area and the fourth reaction area are respectively 300 ℃, 295 ℃, 290 ℃ and 285 ℃, the reactor pressure is set to 285Mpa, ethylene and 2-vinyl benzaldehyde are respectively introduced into the reactor at the flow rates of 50t/h and 2.43t/h for preheating, the reaction temperature of the preheated materials reaches 165 ℃, the materials sequentially pass through the first reaction area, the second reaction area, the third reaction area and the fourth reaction area, simultaneously, a molecular weight regulator is introduced into the inlet of the first reaction area at the flow rate of 50kg/h, an initiator is respectively injected into the first reaction area, the second reaction area, the third reaction area and the fourth reaction area at four points through an injection pump, the total amount of initiator addition is 0.20t/h, and 4-stage polymerization reaction is initiated, so that the low-density polyethylene copolymer is prepared, wherein the aldehyde group content in the copolymer is 10.65%;
wherein the initiator is di-tert-butyl peroxide and the molecular weight regulator is propylene.
2) Adding a coupling agent and an antioxidant into the low-density polyethylene copolymer prepared in the step 1), mixing uniformly at a high speed, and mixing the components uniformly at a high speed to obtain a mixture. Extruding the mixture by a 35-type double-screw extruder (Long Keya Nanjing mechanical company) at 200 ℃, cooling the extruded product by circulating water, granulating by a granulator, drying granules, and screening to obtain a reversible crosslinked polyethylene cable material;
wherein the coupling agent is 1, 3-propylene diamine, the antioxidant is hindered phenol antioxidant 1010 and phosphite antioxidant 168 according to the mass ratio of 1:1 mixing the obtained mixture; the coupling agent is added in an amount of 70000ppm per kg of the low-density polyethylene copolymer, and the antioxidant is added in an amount of 4000ppm per kg of the low-density polyethylene copolymer.
Example 5
The reversible crosslinked polyethylene cable material obtained in example 4 is added into a 35-type double screw extruder (Long Keya Nanjing mechanical company) again for melting, the temperature of the melting section of the extruder is 200 ℃, the melt is extruded at 200 ℃, the extruded product is cooled and pelletized through a circulating water bath, and then the final product is obtained after drying and screening.
Example 6
The reversible crosslinked polyethylene cable material obtained in example 5 is added into a 35-type double screw extruder (Long Keya Nanjing mechanical company) again for melting, the temperature of the melting section of the extruder is 200 ℃, the melt is extruded at 200 ℃, the extruded product is cooled and pelletized through a circulating water bath, and then the final product is obtained after drying and screening.
Example 7
The preparation method of the reversible crosslinked polyethylene cable material comprises the following steps:
1) The method comprises the steps of adopting a tubular high-pressure polyethylene reactor with four reaction areas as a reaction device, wherein the temperatures of the first reaction area, the second reaction area, the third reaction area and the fourth reaction area are 296 ℃, 287 ℃, 285 ℃ and 280 ℃, the reactor pressure is set to 285Mpa, ethylene and 2-methyl-4-vinylbenzaldehyde are respectively introduced into the reactor at the flow rates of 50t/h and 3.24t/h for preheating, the reaction temperature of the preheated materials reaches 165 ℃, the materials sequentially pass through the first reaction area, the second reaction area, the third reaction area and the fourth reaction area, simultaneously, a molecular weight regulator is introduced into the inlet of the first reaction area at the flow rate of 110kg/h, an initiator is respectively injected into the first reaction area, the second reaction area, the third reaction area and the fourth reaction area at four points through an injection pump, the total amount of the initiator is 0.18t/h, and 4-stage polymerization reaction is initiated, so that the low-density polyethylene copolymer is prepared, and the aldehyde content in the copolymer is 10.34mol%;
wherein the initiator is di-tert-butyl peroxide and the molecular weight regulator is propylene.
2) Adding the low-density polyethylene copolymer prepared in the step 1), a coupling agent and an antioxidant into a high-speed mixer, and uniformly mixing the components at a high speed to obtain a mixture. Extruding the mixture by a 35-type double-screw extruder (Long Keya Nanjing mechanical company) at 200 ℃, cooling the extruded product by circulating water, granulating by a granulator, drying granules, and screening to obtain a reversible crosslinked polyethylene cable material;
wherein the coupling agent is p-phenylenediamine, the antioxidant is a mixture obtained by mixing hindered phenol antioxidant 1010 and phosphite antioxidant 168 according to a mass ratio of 2:1; the coupling agent was added in an amount of 90000ppm per kg of the low-density polyethylene copolymer and the antioxidant was added in an amount of 4500ppm per kg of the low-density polyethylene copolymer.
Example 8
The preparation method of the reversible crosslinked polyethylene cable material comprises the following steps:
1) Adopting a tubular high-pressure polyethylene reactor with four reaction areas as a reaction device, wherein the temperatures of the first reaction area, the second reaction area, the third reaction area and the fourth reaction area are 295 ℃, 288 ℃, 287 ℃, 275 ℃ and 285Mpa respectively, introducing ethylene and 2-methyl-4-vinylbenzaldehyde into the reactor at the flow rates of 50t/h and 4.86t/h respectively for preheating, enabling the reaction temperature of the preheated materials to reach 165 ℃, enabling the materials to sequentially pass through the first reaction area, the second reaction area, the third reaction area and the fourth reaction area, introducing a molecular weight regulator at the inlet of the first reaction area at the flow rate of 150kg/h, respectively injecting an initiator into the first reaction area, the second reaction area, the third reaction area and the fourth reaction area at four points through an injection pump, and initiating 4-stage polymerization reaction by the total amount of 0.20t/h to obtain the low-density polyethylene copolymer, wherein the aldehyde content in the copolymer is 14.51mol%;
wherein the initiator is tert-butyl peroxypivalate and the molecular weight regulator is propylene.
2) Adding the low-density polyethylene copolymer prepared in the step 1), a coupling agent and an antioxidant into a high-speed mixer, and uniformly mixing the components at a high speed to obtain a mixture. Extruding the mixture by a 35-type double-screw extruder (Long Keya Nanjing mechanical company) at 200 ℃, cooling the extruded product by circulating water, granulating by a granulator, drying granules, and screening to obtain a reversible crosslinked polyethylene cable material;
wherein the coupling agent is 2-methyl p-phenylenediamine and the antioxidant is a mixture obtained by mixing hindered phenol antioxidant 1010 and phosphite antioxidant 168 according to a mass ratio of 2:1; the coupling agent is added in an amount of 110000ppm per kg of the low-density polyethylene copolymer, and the antioxidant is added in an amount of 5000ppm per kg of the low-density polyethylene copolymer.
Example 9
The preparation method of the reversible crosslinked polyethylene cable material comprises the following steps:
1) Adopting a tubular high-pressure polyethylene reactor with four reaction areas as a reaction device, wherein the temperatures of the first reaction area, the second reaction area, the third reaction area and the fourth reaction area are 298 ℃, 288 ℃, 287 ℃, 275 ℃, the reactor pressure is set to 285Mpa, ethylene and 2-vinylbenzaldehyde are respectively introduced into the reactor at the flow rates of 50t/h and 4.12t/h for preheating, the reaction temperature of the preheated materials reaches 165 ℃, the materials sequentially pass through the first reaction area, the second reaction area, the third reaction area and the fourth reaction area, simultaneously, a molecular weight regulator is introduced into the inlet of the first reaction area at the flow rate of 130kg/h, an initiator is respectively injected into the first reaction area, the second reaction area, the third reaction area and the fourth reaction area at four points through an injection pump, the total amount of the initiator is 0.18t/h, 4-stage polymerization reaction is initiated, and the low-density polyethylene copolymer is prepared, wherein the aldehyde group content in the copolymer is 12.17mol%;
wherein the initiator is di-tert-butyl peroxide and the molecular weight regulator is propylene.
2) Adding the low-density polyethylene copolymer prepared in the step 1), a coupling agent and an antioxidant into a high-speed mixer, and uniformly mixing the components at a high speed to obtain a mixture. Extruding the mixture by a 35-type double-screw extruder (Long Keya Nanjing mechanical company) at 200 ℃, cooling the extruded product by circulating water, granulating by a granulator, drying granules, and screening to obtain a reversible crosslinked polyethylene cable material;
wherein the coupling agent is 2-chloro-p-phenylenediamine and the antioxidant is a mixture obtained by mixing hindered phenol antioxidant 1010 and phosphite antioxidant 168 according to a mass ratio of 2:1; the coupling agent was added in an amount of 75000ppm per kg of the low density polyethylene copolymer and the antioxidant was added in an amount of 7000ppm per kg of the low density polyethylene copolymer.
Comparative example 1
1) The method comprises the steps of adopting a tubular high-pressure polyethylene reactor with four reaction areas as a reaction device, wherein the temperatures of the first reaction area, the second reaction area, the third reaction area and the fourth reaction area are 295 ℃, 285 ℃ and 275 ℃ respectively, the reactor pressure is set to 285Mpa, ethylene is introduced into the reactor at the flow rate of 50t/h for preheating, the reaction temperature of the preheated materials reaches 165 ℃, the materials sequentially pass through the first reaction area, the second reaction area, the third reaction area and the fourth reaction area, a molecular weight regulator is introduced at the inlet of the first reaction area at the flow rate of 100kg/h, an initiator is respectively injected into the first reaction area, the second reaction area, the third reaction area and the fourth reaction area at four points through an injection pump, the total addition amount of the initiator is 0.17t/h, and 4-section polymerization reaction is initiated, so that low-density polyethylene is prepared;
wherein the initiator is di-tert-butyl peroxide and the molecular weight regulator is propylene.
2) And (3) uniformly mixing the low-density polyethylene prepared in the step (1) with an antioxidant in a high-speed mixer at a high speed to obtain a mixture. Extruding the mixture by a 35-type double-screw extruder (Long Keya Nanjing mechanical company) at 200 ℃, cooling the extruded product by circulating water, granulating by a granulator, drying granules, and sieving to obtain polyethylene;
wherein the antioxidant is a mixture obtained by mixing hindered phenol antioxidant 1010 and phosphite antioxidant 168 according to a mass ratio of 2:1; the amount of antioxidant added was 4000ppm per kg of low density polyethylene.
Comparative example 2
1) Step 1) of this comparative example corresponds to step 1) of example 1;
2) Adding the low-density polyethylene copolymer prepared in the step 1) and an antioxidant into a high-speed mixer, and uniformly mixing the components at a high speed to obtain a mixture. Extruding the mixture by a 35-type double-screw extruder (Long Keya Nanjing mechanical company) at 200 ℃, cooling the extruded product by circulating water, granulating by a granulator, drying and screening the granules to obtain the 2-vinyl benzaldehyde grafted modified polyethylene;
wherein the antioxidant is a mixture obtained by mixing hindered phenol antioxidant 1010 and phosphite antioxidant 168 according to a mass ratio of 2:1; the amount of antioxidant added was 4000ppm per kg of polyethylene.
Comparative example 3
1) Step 1) of this comparative example corresponds to step 1) of comparative example 1;
2) Adding the low-density polyethylene prepared in the step 1) and an antioxidant into a high-speed mixer, and uniformly mixing the components at a high speed to obtain a mixture. Extruding the mixture by a 35-type double-screw extruder (Long Keya Nanjing mechanical company) at 200 ℃, cooling the extruded product by circulating water, granulating by a granulator, drying and sieving the granules to obtain polyethylene granules;
wherein the antioxidant is a mixture obtained by mixing hindered phenol antioxidant 1010 and phosphite antioxidant 168 according to a mass ratio of 2:1; the amount of antioxidant added was 4000ppm per kg of low density polyethylene.
3) Mixing the polyethylene granules prepared in the step 2) with a peroxide crosslinking agent, and obtaining a crosslinked polyethylene cable material through post-absorption, cooling and packaging;
wherein the peroxide crosslinking agent is di-tert-butyl peroxide, and the peroxide crosslinking agent is added in an amount of 80000ppm per kilogram of polyethylene pellets.
Comparative example 4
The preparation method of the reversible crosslinked polyethylene cable material of the comparative example comprises the following steps:
1) Adopting a tubular high-pressure polyethylene reactor with four reaction areas as a reaction device, wherein the temperatures of the first reaction area, the second reaction area, the third reaction area and the fourth reaction area are 295 ℃ and 285 ℃ and 275 ℃ respectively, the reactor pressure is set to 285MPa, ethylene and 6-furan-1-hexene are introduced into the reactor at the flow rates of 50t/h and 2.95t/h respectively for preheating, the reaction temperature of the preheated materials reaches 165 ℃, the materials sequentially pass through the first reaction area, the second reaction area, the third reaction area and the fourth reaction area, simultaneously, a molecular weight regulator is introduced into the inlet of the first reaction area at the flow rate of 100kg/h, an initiator is respectively injected into the first reaction area, the second reaction area, the third reaction area and the fourth reaction area at four points through an injection pump, the total addition amount of the initiator is 0.17t/h, and 4-stage polymerization reaction is initiated, so that the low-density polyethylene copolymer is prepared;
wherein the initiator is di-tert-butyl peroxide and the molecular weight regulator is propylene.
2) Adding the low-density polyethylene copolymer, the coupling agent and the antioxidant in the step 1) into a high-speed mixer, and uniformly mixing the components at a high speed to obtain a mixture. Extruding the mixture by a 35-type double-screw extruder (Long Keya Nanjing mechanical company) at 200 ℃, cooling the extruded product by circulating water, granulating by a granulator, drying granules, and screening to obtain a reversible crosslinked polyethylene cable material;
wherein the coupling agent is 1, 6-bis (maleimide) hexane, and the antioxidant is a mixture obtained by mixing hindered phenol antioxidant 1010 and phosphite antioxidant 168 according to a mass ratio of 2:1; the coupling agent was added in an amount of 80000ppm per kg of the low density polyethylene copolymer and the antioxidant was added in an amount of 4000ppm per kg of the low density polyethylene copolymer.
Test example 1
The cable materials of example 1, comparative example 2, comparative example 3 and comparative example 4 were subjected to infrared spectrum testing by the following methods: the sample was pressed into a sheet of 2mm or less in thickness at a temperature of not lower than the melting temperature, and the characteristic peaks of the sample were analyzed by fourier transform infrared spectroscopy (FT-IR).
FIG. 1 is a graph showing the IR spectrum of cable materials of example 1, comparative example 2 and comparative example 3; FIG. 2 is a graph showing IR spectrum comparison of cable materials of example 1 and comparative example 4.
Comparative example 1 is an uncrosslinked low-density polyethylene cable material, comparative example 2 is a low-density polyethylene copolymer cable material prepared from ethylene and vinylbenzaldehyde, comparative example 3 is an irreversibly crosslinked low-density polyethylene cable material, and example 1 is an imine-bond reversibly crosslinked low-density polyethylene copolymer cable material prepared from ethylene and vinylbenzaldehyde. As can be seen from FIG. 1, the cable material of comparative example 2 was at 1725cm -1 An aldehyde group absorption peak appears, indicating that vinyl benzaldehyde is polymerized onto the polyethylene chain; the cable material of example 1 was used at 1627cm -1 The c=n bond absorption peak appears, indicating that the cable material of example 1 contains an imine bond covalent cross-linked network.
Example 4 was a reversible crosslinked polyethylene cable material prepared with DA reaction, as can be seen in FIG. 2, the cable material of comparative example 4 was at 1197cm -1 In-plane bending vibration absorption peaks of the cyclic molecules appear, indicating the formation of the cyclic structure.
Test example 2
The cable compositions obtained in the above examples and comparative examples were tested for the following parameters:
1. solution flow rate (MFR): measured according to GB/T3682.1-2018 at 190℃under a load of 2.16 kg.
2. Density: according to GB/T1033.2.
3. Tensile strength: according to GB/T1040.3-2006.
4. Elongation at break: according to GB/T1040.3-2006.
5. Vicat softening temperature: according to GB/T1633-2000.
6. Dielectric constant: according to GB/T1409-2006.
7. Dielectric loss tangent: according to GB/T1409-2006.
The test results of the above parameters are shown in table 1.
TABLE 1
1) The tensile strength, elongation at break, vicat softening temperature were significantly improved for examples 1-9 compared to the low density polyethylene prepared in comparative example 1. The low density polyethylene (comparative example 3) of examples 1-9 with pre-buried cross-linking agent has better properties than comparative example 3, and especially the dielectric constant and dielectric loss tangent of the cable material are significantly reduced compared with comparative example 3 in examples 1-9 due to the reduced complicated process steps of pre-buried cross-linking agent.
2) As can be seen from a comparison of examples 4, 5 and 6, the cable material of the present invention has substantially unchanged material properties after a plurality of processing treatments, which is advantageous from the thermoreversible crosslinking function of the cable material of the present invention, and the crosslinked structure of the cable material can be stably recovered after repeated processing, which is completely different from the permanent crosslinked network formed by the conventional crosslinked polyethylene, thereby imparting excellent thermoplastic properties to the crosslinked polymer.
3) The cable materials of examples 1 to 9 of the present invention all have higher vicat softening temperatures than comparative examples 1 to 4, thus demonstrating that the cable materials of the present invention have excellent heat resistance.
In addition, due to the characteristic of association type dynamic covalent bonds, even above the Vicat softening temperature, the low-density polyethylene copolymer in the cable material still has a cross-linked structure, so that the melt viscosity of the material is slowly reduced, and the processing temperature window and the processing stability are greatly widened. The thermal reversible crosslinked polyethylene prepared by the invention completely meets the use requirement of high-voltage polyethylene cable materials.
In conclusion, the cable material has the remarkable characteristics of high-temperature (during processing) decrosslinking, easiness in processing, low-temperature (after molding) crosslinking formation and excellent performances during melt processing.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. The reversible crosslinked polyethylene cable material is characterized in that the cable material comprises polyethylene copolymer and coupling agent;
the polyethylene copolymer is obtained by copolymerizing a polymerization monomer; the polymerized monomer comprises ethylene, vinyl benzaldehyde and/or vinyl benzaldehyde derivative;
the coupling agent is selected from the group consisting of primary polyamine compounds.
2. The reversibly crosslinked polyethylene cable material according to claim 1, wherein the coupling agent is selected from the group consisting of compounds of formula (I):
H 2 N-R 1 -NH 2 formula (I)
In the formula (I), R 1 Selected from C1-C12 alkyl, C6-C12 substituted or unsubstituted aryl or C6-C12 substituted or unsubstituted heteroaryl;
wherein the substituents in the substituted aryl or substituted heteroaryl are selected from C1-C3 alkyl or halogen.
3. The reversibly crosslinked polyethylene cable material according to claim 2, wherein R 1 A linear alkyl group selected from C2 or C3.
4. A reversibly crosslinked polyethylene cable material according to any of claims 1-3 wherein said derivative of vinyl benzaldehyde is selected from vinyl benzaldehyde compounds having at least one C1-C6 alkyl substitution on the benzene ring.
5. The reversible crosslinked polyethylene cable material according to any of claims 1-4, wherein the mass ratio of the polyethylene copolymer to the coupling agent is 100 (1-20).
6. The reversible cross-linked polyethylene cable material of any one of claims 1-5 wherein said polyethylene copolymer comprises, in terms of molar content, from 70% to 93% of ethylene units and from 5% to 29% of vinyl benzaldehyde units and/or vinyl benzaldehyde derivative units.
7. The reversible cross-linked polyethylene cable material of any one of claims 1-6 wherein said polyethylene copolymer is a low density polyethylene copolymer.
8. The reversible cross-linked polyethylene cable material of any one of claims 1-7 wherein the cable material raw material further comprises an antioxidant;
the mass ratio of the polyethylene copolymer, the coupling agent and the antioxidant is 100: (2-15): (0.3 to 0.7).
9. A method of preparing a reversible cross-linked polyethylene cable material according to any one of claims 1-8, comprising: mixing the raw materials of the cable materials to obtain a mixture; and extruding the mixture to obtain the reversible crosslinked polyethylene cable material.
10. The method according to claim 9, wherein the extrusion treatment is carried out at a temperature of 190 to 230 ℃.
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| CN202210684782.XA CN117285769A (en) | 2022-06-17 | 2022-06-17 | Reversible crosslinked polyethylene cable material and preparation method thereof |
| PCT/CN2022/135845 WO2023240938A1 (en) | 2022-06-17 | 2022-12-01 | Reversibly crosslinked polyethylene cable material and preparation method therefor |
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| CN107353473B (en) * | 2017-07-07 | 2020-07-14 | 天津科技大学 | Small molecular compound filled high-pressure crosslinked polyethylene cable material and preparation method thereof |
| CN113185796A (en) * | 2021-05-17 | 2021-07-30 | 江苏北化新橡新材料科技有限公司 | 125 ℃ halogen-free flame-retardant cable material capable of self-crosslinking at room temperature and preparation method thereof |
| CN113896998B (en) * | 2021-10-12 | 2022-09-16 | 浙江大学 | Preparation method of polyolefin thermoplastic elastomer based on dynamic crosslinking modification |
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