CN113563528B - Application of aromatic olefin grafted modified polypropylene as insulating material and insulating material - Google Patents
Application of aromatic olefin grafted modified polypropylene as insulating material and insulating material Download PDFInfo
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- CN113563528B CN113563528B CN202011195775.0A CN202011195775A CN113563528B CN 113563528 B CN113563528 B CN 113563528B CN 202011195775 A CN202011195775 A CN 202011195775A CN 113563528 B CN113563528 B CN 113563528B
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- China
- Prior art keywords
- polypropylene
- use according
- aromatic olefin
- modified polypropylene
- substituted
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- -1 aromatic olefin Chemical class 0.000 title claims abstract description 306
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 196
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 195
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000011810 insulating material Substances 0.000 title claims abstract description 43
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 64
- 238000006243 chemical reaction Methods 0.000 claims description 83
- 229920001577 copolymer Polymers 0.000 claims description 52
- 238000000034 method Methods 0.000 claims description 41
- 229920005606 polypropylene copolymer Polymers 0.000 claims description 39
- 239000000178 monomer Substances 0.000 claims description 36
- 230000015556 catabolic process Effects 0.000 claims description 35
- 239000003999 initiator Substances 0.000 claims description 25
- 229910052736 halogen Inorganic materials 0.000 claims description 24
- 150000002367 halogens Chemical class 0.000 claims description 24
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 23
- 150000003254 radicals Chemical class 0.000 claims description 23
- 125000000217 alkyl group Chemical group 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 22
- 125000003545 alkoxy group Chemical group 0.000 claims description 21
- 239000012774 insulation material Substances 0.000 claims description 19
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 18
- 239000005977 Ethylene Substances 0.000 claims description 18
- 238000009413 insulation Methods 0.000 claims description 18
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 15
- 239000002270 dispersing agent Substances 0.000 claims description 15
- 239000008096 xylene Substances 0.000 claims description 15
- 229910019142 PO4 Inorganic materials 0.000 claims description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 14
- 239000010452 phosphate Substances 0.000 claims description 14
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000011261 inert gas Substances 0.000 claims description 12
- 239000000155 melt Substances 0.000 claims description 12
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 11
- 150000001412 amines Chemical class 0.000 claims description 10
- 150000002148 esters Chemical class 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 9
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 9
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 9
- 239000011541 reaction mixture Substances 0.000 claims description 9
- 230000008961 swelling Effects 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000004711 α-olefin Substances 0.000 claims description 5
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 claims description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 4
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 claims description 4
- KXYAVSFOJVUIHT-UHFFFAOYSA-N 2-vinylnaphthalene Chemical compound C1=CC=CC2=CC(C=C)=CC=C21 KXYAVSFOJVUIHT-UHFFFAOYSA-N 0.000 claims description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 4
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 4
- 150000002978 peroxides Chemical group 0.000 claims description 4
- 239000007790 solid phase Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 3
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 3
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 claims description 2
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 claims description 2
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 claims description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims description 2
- SHZIWNPUGXLXDT-UHFFFAOYSA-N caproic acid ethyl ester Natural products CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 claims description 2
- BLCKNMAZFRMCJJ-UHFFFAOYSA-N cyclohexyl cyclohexyloxycarbonyloxy carbonate Chemical compound C1CCCCC1OC(=O)OOC(=O)OC1CCCCC1 BLCKNMAZFRMCJJ-UHFFFAOYSA-N 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 claims description 2
- 150000003440 styrenes Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 42
- 239000000047 product Substances 0.000 description 38
- 239000000843 powder Substances 0.000 description 30
- 229910052757 nitrogen Inorganic materials 0.000 description 22
- 239000011159 matrix material Substances 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 11
- 238000001816 cooling Methods 0.000 description 11
- 238000005259 measurement Methods 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- 238000010907 mechanical stirring Methods 0.000 description 10
- 238000010926 purge Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 230000018109 developmental process Effects 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 5
- 125000004185 ester group Chemical group 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 229920005604 random copolymer Polymers 0.000 description 5
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000005684 electric field Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 description 3
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 229920001384 propylene homopolymer Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229920003020 cross-linked polyethylene Polymers 0.000 description 2
- 239000004703 cross-linked polyethylene Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 102220040412 rs587778307 Human genes 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 230000002522 swelling effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 2
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- YKTNISGZEGZHIS-UHFFFAOYSA-N 2-$l^{1}-oxidanyloxy-2-methylpropane Chemical group CC(C)(C)O[O] YKTNISGZEGZHIS-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 241000196322 Marchantia Species 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
- C08F255/04—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms on to ethene-propene copolymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/442—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from aromatic vinyl compounds
-
- 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
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention belongs to the field of new materials, and relates to an application of aromatic olefin grafted modified polypropylene as an insulating material and the insulating material. The aromatic olefin grafted modified polypropylene comprises a structural unit derived from copolymerized polypropylene and a structural unit derived from a styrene monomer; the content of the structural unit which is derived from the styrene monomer and is in a grafted state in the aromatic olefin grafted modified polypropylene is 0.5 to 14 weight percent based on the weight of the aromatic olefin grafted modified polypropylene. The aromatic olefin grafted modified polypropylene used in the invention can give consideration to mechanical performance and electrical performance at higher working temperature, is suitable for working conditions of high temperature and high running field intensity, and is an ideal insulating material.
Description
Technical Field
The invention belongs to the field of new materials, and particularly relates to an application of aromatic olefin grafted modified polypropylene as an insulating material and an insulating material containing the aromatic olefin grafted modified polypropylene.
Background
The insulating material is the foundation and guarantee of the development of electrical products, and plays an important role in the development of the motor and the electrical industry. The development and progress of insulating materials depend on the development of high polymer materials and directly restrict and influence the development and progress of electrical products. With the rapid development of the power industry, the power grid system advances towards higher voltage levels and larger power transmission capacity, and higher requirements are put on the performance of insulating materials. The main insulating material of the high-voltage direct-current cable in operation at present is crosslinked polyethylene. The maximum long-term use temperature is 70 ℃. The manner of increasing the insulation thickness alone has only proved to be of little consequence if higher voltage levels and higher service temperatures are to be met. There is therefore an urgent need to develop new electrical equipment insulation materials to accommodate the use requirements at higher operating temperatures and field strengths.
The operating temperature is an important indicator of the dc cable insulation. In the normal operation process of the direct-current cable, the temperature of the core wire conductor can be increased due to the thermal effect of the conductor resistance under the condition of larger conveying current because the core wire conductor has resistance. The electrical properties (including volume resistivity, breakdown field strength, aging characteristics and the like) of the polymer insulating material serving as the direct-current cable insulating layer are closely related to the temperature of an operation environment, and the high temperature can cause the electrical properties of the polymer insulating material to be drastically reduced, so that the operation performance and the service life of the direct-current cable are reduced, and the improvement of the operation temperature of the direct-current cable insulating material has important significance for improving the conveying capacity of the direct-current cable.
The improvement of the operating temperature of the DC cable insulation material needs to be considered from two aspects: (1) The running temperature of the matrix of the DC cable insulating material is improved, so that the material is ensured to still maintain certain mechanical properties at high temperature, and the structural changes such as softening, melting and the like are avoided; (2) The electrical performance of the direct current cable insulation material under the action of high temperature and high electric field is improved, and the temperature characteristic of the electrical performance of the polymer insulation material is improved, so that the direct current cable insulation material can still maintain equivalent electrical performance at higher operating temperature.
The direct-current volume resistivity is also an important performance parameter of the cable insulation material, and directly reflects the insulation performance of the material. The higher resistivity of the insulating material means that the cable insulation has higher resistance, has smaller leakage current when the cable is in normal operation, and reduces the loss of electric energy transmission. On the other hand, injection and accumulation of space charge has been an important problem affecting the normal operation of the cable. The higher resistivity means that the number of carriers in the insulator is lower, so that the injection and accumulation of charges in the normal operation process of the cable can be reduced, the distortion of an electric field in the insulator caused by space charges is reduced, the operation reliability of the cable is improved, and the service life of the cable is prolonged.
The volume resistivity of the cable insulation material is related to both temperature and electric field strength. As the temperature and electric field strength increase, the volume resistivity decreases significantly. At present, with the improvement of the voltage class and the conveying capacity of a cable system, only the cable is insulated and thickened in order to ensure that the insulation level is not reduced. But this not only increases the amount and cost of the insulating material, but also weakens the heat dissipation capacity thereof due to the thickening of the insulation, so that the resistivity is further reduced and the insulation level is improved to a limited extent. Therefore, the problem can be fundamentally solved only by increasing the volume resistivity of the insulating material.
Some methods of increasing resistivity are disclosed in the prior art, but are mostly developed around crosslinked polyethylene. Polypropylene has better electrical insulation properties and a higher melting point than polyethylene, however, polypropylene cannot be used directly as an insulation material due to its poor mechanical properties, especially at low temperatures. Therefore, there are few solutions in the prior art for improving polypropylene to achieve integrated regulation of electrical, mechanical and thermal properties. If a novel modified polypropylene material with obvious insulating property regulating and controlling capability and mechanical property and thermal property can be developed, and the novel modified polypropylene material is applied to engineering practical application, a novel insulating material branch field is developed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides an application of aromatic olefin grafted modified polypropylene as an insulating material, wherein the aromatic olefin grafted modified polypropylene can give consideration to mechanical properties and electrical properties at a higher working temperature, is suitable for working conditions of high temperature and high operating field intensity, and is an ideal insulating material.
The invention provides an application of aromatic olefin grafted modified polypropylene as an insulating material, wherein the aromatic olefin grafted modified polypropylene comprises a structural unit derived from copolymerized polypropylene and a structural unit derived from a styrene monomer; the content of the structural unit derived from the styrene monomer in the grafted state in the aromatic olefin graft modified polypropylene is 0.5 to 14wt%, preferably 1 to 7.5wt%, more preferably 1.5 to 5wt%, based on the weight of the aromatic olefin graft modified polypropylene.
According to the invention, the insulation material is preferably a cable insulation material; further preferred is a dc cable insulation. More specifically, the insulating material is a cable insulating layer material.
The aromatic olefin grafted modified polypropylene used in the invention can be directly used as a base material of an insulating material without blending other polymers.
In the present invention, the "structural unit" means that it is a part of the aromatic olefin-grafted modified polypropylene, and the form thereof is not limited. In particular, "structural units derived from a copolymerized polypropylene" refers to products formed from the copolymerized polypropylene, including both "radical" forms and "polymeric" forms. "structural units derived from styrenic monomers" refers to products formed from styrenic monomers that include both "radical" forms, as well as "monomer" forms, as well as "polymer" forms. The "structural units" may be repeating units or may be non-repeating independent units.
In the present invention, the structural unit derived from a styrenic monomer "in a grafted state" means a structural unit derived from a styrenic monomer which forms a covalent bond (grafting) with a copolymer polypropylene.
In the present invention, the meaning of "comonomer" of the polypropylene copolymer is known to the person skilled in the art and refers to a monomer copolymerized with propylene.
According to the present invention, the aromatic olefin graft-modified polypropylene is preferably produced by grafting reaction of a copolymer polypropylene and a styrenic monomer, preferably by solid phase grafting reaction. The grafting reaction of the present invention is a radical polymerization reaction, and thus, the "in a grafted state" means a state in which a reactant forms a connection with another reactant after radical polymerization. The connection includes both direct and indirect connections.
During the grafting reaction, the styrenic monomer may polymerize to form a certain amount of ungrafted polymer. The term "aromatic olefin graft modified polypropylene" in the present invention includes both a product (crude product) directly obtained by grafting a copolymer polypropylene and a styrene monomer, and an aromatic olefin graft modified polypropylene purified product obtained by further purifying the product.
According to the present invention, preferably, the aromatic olefin graft-modified polypropylene has at least one of the following characteristics: the melt flow rate under a load of 2.16kg at 230℃is 0.01 to 30g/10min, preferably 0.05 to 20g/10min, more preferably 0.1 to 10g/10min, still more preferably 0.2 to 8g/10min, still more preferably 0.2 to 5g/10min; the flexural modulus is 10 to 1250MPa, preferably 20 to 1000MPa, more preferably 50 to 600MPa; the elongation at break is more than or equal to 200 percent, preferably more than or equal to 300 percent; the tensile strength is more than 5MPa, preferably 10-40 MPa.
According to the present invention, preferably, the aromatic olefin graft-modified polypropylene has at least one of the following characteristics:
The working temperature of the aromatic olefin grafted modified polypropylene is more than or equal to 90 ℃, preferably 90-160 ℃;
the breakdown field strength E g of the aromatic olefin grafted modified polypropylene at 90 ℃ is more than or equal to 200kV/mm, preferably 200-800 kV/mm;
-the rate of change of the breakdown field strength Δe/E of the aromatic olefin graft modified polypropylene divided by the breakdown field strength E of the copolymer polypropylene at 90 ℃ is greater than 1.5%, preferably from 1.6% to 40%, more preferably from 5% to 30%, even more preferably from 10% to 20%, of the difference Δe between the breakdown field strength E g of the aromatic olefin graft modified polypropylene at 90 ℃ and the breakdown field strength E of the copolymer polypropylene at 90 ℃;
-the aromatic olefin grafted modified polypropylene has a direct volume resistivity ρ vg≥1.0×1013 Ω -m, preferably 1.5x10 13Ω·m～1.0×1020 Ω -m, at 90 ℃ at a field strength of 15 kV/mm;
-the ratio ρ vg/ρv of the direct current volume resistivity ρ vg of the aromatic olefin graft modified polypropylene at 90 ℃,15 kV/mm field strength to the direct current volume resistivity ρ v of the co-polypropylene at 90 ℃,15 kV/mm field strength is greater than 1, preferably from 1.5 to 50, more preferably from 2 to 20, even more preferably from 3 to 10;
-said aromatic olefin grafted modified polypropylene has a dielectric constant at 90 ℃, 50Hz of more than 2.0, preferably between 2.1 and 2.5.
According to the present invention, the copolymerized polypropylene (base polypropylene in the present invention) is a propylene copolymer containing ethylene or higher α -olefin or a mixture thereof. Specifically, the comonomer of the copolymerized polypropylene is selected from at least one of C 2-C8 alpha-olefins other than propylene. The alpha-olefins of C 2-C8 other than propylene include, but are not limited to: at least one of ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene and 1-octene, preferably ethylene and/or 1-butene, further preferably the copolymerized polypropylene consists of propylene and ethylene.
The copolymer polypropylene of the present invention may be a heterophasic propylene copolymer. The heterophasic propylene copolymer may contain a propylene homopolymer or propylene random copolymer matrix component (1), and a further propylene copolymer component (2) dispersed therein. In propylene random copolymers, the comonomer is randomly distributed in the backbone of the propylene polymer. Preferably, the copolymerized polypropylene of the present invention is a heterophasic propylene copolymer prepared in situ (in situ) in the reactor by existing processes.
According to a preferred embodiment, the heterophasic propylene copolymer comprises a propylene homopolymer matrix or random copolymer matrix (1), and dispersed therein a propylene copolymer component (2) comprising one or more ethylene or higher alpha-olefin comonomers. The heterophasic propylene copolymer may be of islands-in-the-sea or bicontinuous structure.
Two heterophasic propylene copolymers are known in the art, heterophasic propylene copolymers containing a propylene random copolymer as matrix phase or heterophasic propylene copolymers containing a propylene homopolymer as matrix phase. The random copolymer matrix (1) is a copolymer formed by the random distribution of comonomer moieties on the polymer chain, in other words, consisting of an alternating sequence of two monomer units of random length (comprising a single molecule). Preferably the comonomer in the matrix (1) is selected from ethylene or butene. It is particularly preferred that the comonomer in the matrix (1) is ethylene.
Preferably, the propylene copolymer (2) dispersed in the homo-or copolymer matrix (1) of the heterophasic propylene copolymer is substantially amorphous. The term "substantially amorphous" means herein that the propylene copolymer (2) has a lower crystallinity than the homopolymer or copolymer matrix (1).
According to the invention, the copolymer polypropylene has, in addition to the above-mentioned compositional features, at least one of the following features: the comonomer content is 0.5 to 40mol%, preferably 0.5 to 30mol%, preferably 4 to 25wt%, more preferably 4 to 22wt%; the xylene solubles content is 2 to 80wt%, preferably 18 to 75wt%, further preferably 30 to 70wt%, more preferably 30 to 67wt%; the comonomer content in the solubles is 10 to 70wt%, preferably 10 to 50wt%, more preferably 20 to 35wt%; the intrinsic viscosity ratio of the soluble substance to the polypropylene is 0.3 to 5, preferably 0.5 to 3, more preferably 0.8 to 1.3.
According to the present invention, preferably, the copolymerized polypropylene has at least one of the following characteristics: the melt flow rate under a load of 2.16kg at 230℃is 0.01 to 60g/10min, preferably 0.05 to 35g/10min, more preferably 0.5 to 15g/10min, still more preferably 0.5 to 8g/10min; the melting temperature Tm is 100℃or higher, preferably 110 to 180℃and more preferably 110 to 170℃and still more preferably 120 to 166 ℃. The weight average molecular weight is preferably 20X 10 4～60×104 g/mol. The base polypropylene having a high Tm has satisfactory impact strength and flexibility at both low and high temperatures, and in addition, the aromatic olefin graft modified polypropylene of the present invention has an advantage of being able to withstand higher working temperatures when using the base polypropylene having a high Tm. The polypropylene copolymer of the present invention is preferably a porous particulate or powdery resin.
According to the present invention, preferably, the copolymerized polypropylene further has at least one of the following characteristics: the flexural modulus is 10 to 1000MPa, preferably 50 to 600MPa; the elongation at break is more than or equal to 200 percent, and the elongation at break is more than or equal to 300 percent. Preferably, the tensile strength of the copolymer polypropylene is greater than 5MPa, preferably from 10 to 40MPa.
The polypropylene copolymer of the present invention may include, but is not limited to, any commercially available polypropylene powder suitable for the present invention, such as NS06, SPF179, etc. of chinese petrochemical, marchantia, and may also be produced by the polymerization processes described in chinese patents CN1081683, CN1108315, CN1228096, CN1281380, CN1132865C, CN102020733a, etc. Common polymerization processes include the Spheripol process from Basell, the Hypol process from Sanjing, the Borstar PP process from Borealis, the Unipol process from DOW chemical, the Innovene gas phase process from INEOS (original BP-Amoco), and the like.
The styrene monomer can be any monomer styrene compound capable of being polymerized by free radicals, and can be at least one selected from the monomer with the structure shown in the formula I, the monomer with the structure shown in the formula II and the monomer with the structure shown in the formula III;
In formula I, R 1、R2、R3 are each independently selected from H, substituted or unsubstituted C 1-C6 alkyl; R 4-R8 is each independently selected from H, halogen, hydroxy, amino, phosphate, sulfonate, substituted or unsubstituted C 1-C12 alkyl, substituted or unsubstituted C 3-C12 cycloalkyl, substituted or unsubstituted C 1-C12 alkoxy, an ester group of a substituted or unsubstituted C 1-C12, an amine group of a substituted or unsubstituted C 1-C12, the substituted group being selected from the group consisting of halogen, hydroxy, amino, phosphate, sulfonate, alkyl of C 1-C12, cycloalkyl of C 3-C12, Alkoxy of C 1-C12, ester of C 1-C12, amine of C 1-C12; Preferably, R 1、R2、R3 is each independently selected from H, substituted or unsubstituted C 1-C3 alkyl, R 4-R8 is each independently selected from H, halogen, hydroxy, amino, substituted or unsubstituted C 1-C6 alkyl, An alkoxy group of C 1-C6 substituted or unsubstituted;
in formula II, R 1、R2、R3 are each independently selected from H, substituted or unsubstituted C 1-C6 alkyl; R 4-R10 is each independently selected from H, halogen, hydroxy, amino, phosphate, sulfonate, substituted or unsubstituted C 1-C12 alkyl, substituted or unsubstituted C 3-C12 cycloalkyl, substituted or unsubstituted C 1-C12 alkoxy, an ester group of a substituted or unsubstituted C 1-C12, an amine group of a substituted or unsubstituted C 1-C12, the substituted group being selected from the group consisting of halogen, hydroxy, amino, phosphate, sulfonate, alkyl of C 1-C12, cycloalkyl of C 3-C12, Alkoxy of C 1-C12, ester of C 1-C12, amine of C 1-C12; Preferably, R 1、R2、R3 is each independently selected from H, substituted or unsubstituted C 1-C3 alkyl, R 4-R10 is each independently selected from H, halogen, hydroxy, amino, substituted or unsubstituted C 1-C6 alkyl, A substituted or unsubstituted alkoxy group of C 1-C6 selected from halogen, hydroxy, amino, alkyl of C 1-C6, alkoxy of C 1-C6;
In formula III, R 1'、R2'、R3' are each independently selected from H, substituted or unsubstituted alkyl of C 1-C6; R 4'-R10' are each independently selected from H, halogen, hydroxy, amino, phosphate, sulfonate, substituted or unsubstituted C 1-C12 alkyl, substituted or unsubstituted C 3-C12 cycloalkyl, substituted or unsubstituted C 1-C12 alkoxy, an ester group of a substituted or unsubstituted C 1-C12, an amine group of a substituted or unsubstituted C 1-C12, the substituted group being selected from the group consisting of halogen, hydroxy, amino, phosphate, sulfonate, alkyl of C 1-C12, cycloalkyl of C 3-C12, Alkoxy of C 1-C12, ester of C 1-C12, amine of C 1-C12; preferably, R 1'、R2'、R3 'is each independently selected from H, substituted or unsubstituted C 1-C3 alkyl, R 4'-R10' is each independently selected from H, halogen, hydroxy, amino, substituted or unsubstituted C 1-C6 alkyl, A substituted or unsubstituted alkoxy group of C 1-C6, said substituted group selected from halogen, hydroxy, amino, alkyl of C 1-C6, alkoxy of C 1-C6.
Preferably, the styrenic monomer may be selected from at least one of styrene, α -methylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, mono-or poly-substituted styrene, mono-or poly-substituted α -methylstyrene, mono-or poly-substituted 1-vinylnaphthalene, and mono-or poly-substituted 2-vinylnaphthalene; the substituted group is preferably at least one selected from halogen, hydroxy, amino, phosphate, sulfonate, C 1-C8 straight chain alkyl or cycloalkyl, C 3-C8 branched or cyclic alkoxy, C 1-C6 straight chain alkoxy, C 3-C8 branched or cyclic alkoxy, C 1-C8 straight chain ester group, C 3-C8 branched or cyclic ester group, C 1-C8 straight chain amine group, and C 3-C8 branched or cyclic amine group.
More preferably, the styrenic monomer is selected from at least one of styrene, alpha-methylstyrene, 2-methylstyrene, 3-methylstyrene and 4-methylstyrene.
The aromatic olefin grafted modified polypropylene can be prepared from copolymerized polypropylene and styrene monomers through a solid-phase grafting reaction, and specifically can be prepared by a method comprising the following steps: and (3) in the presence of inert gas, carrying out grafting reaction on a reaction mixture comprising the copolymerized polypropylene and the styrene monomer to obtain the aromatic olefin grafting modified polypropylene.
The grafting reaction of the present invention can be carried out by referring to various methods conventional in the art, and is preferably a solid phase grafting reaction. For example, active grafting sites are formed on the polypropylene copolymer in the presence of the grafting styrenic monomer, or the polypropylene copolymer is first formed with active grafting sites and then treated with the grafting monomer. The grafting sites may be formed by treatment with a free radical initiator or by treatment with high energy ionizing radiation or microwaves. The free radicals in the polymer, which are generated as a result of the chemical or radiation treatment, form grafting sites on the polymer and initiate the polymerization of the monomers at these sites.
Preferably, the grafting sites are initiated by a free radical initiator and the grafting reaction is further carried out. In this case, the reaction mixture further comprises a free radical initiator; further preferably, the radical initiator is selected from peroxide-based radical initiators and/or azo-based radical initiators.
Wherein the peroxide radical initiator is preferably at least one selected from dibenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, lauroyl peroxide, t-butyl peroxybenzoate, diisopropyl peroxydicarbonate, t-butyl peroxy2-ethylhexanoate and dicyclohexyl peroxydicarbonate; the azo-based free radical initiator is preferably azobisisobutyronitrile and/or azobisisoheptonitrile.
More preferably, the grafting sites are initiated by peroxide-based free radical initiators and the grafting reaction is further carried out.
Furthermore, the grafting reaction of the present invention can also be carried out by the methods described in CN106543369A, CN104499281A, CN102108112A, CN109251270A, CN1884326a and CN 101492517B.
The amount of each component used in the grafting reaction of the present invention is not particularly limited on the premise of satisfying the above-mentioned product characteristics, and specifically, the mass ratio of the radical initiator to the styrene monomer may be 0.1 to 10:100, preferably 0.5 to 5:100. The mass ratio of the styrene-based monomer to the copolymerized polypropylene may be 0.5 to 16:100, preferably 1 to 12:100, and more preferably 2 to 10:100.
The technological conditions of the grafting reaction are not particularly limited either, and specifically, the temperature of the grafting reaction may be 30 to 130 ℃, preferably 60 to 120 ℃; the time may be 0.5 to 10 hours, preferably 1 to 5 hours.
In the present invention, the "reaction mixture" includes all materials added to the grafting reaction system, and the materials may be added at one time or at different stages of the reaction.
The reaction mixture of the present invention may also include a dispersant, preferably water or an aqueous solution of sodium chloride. The mass amount of the dispersing agent is preferably 50-300% of the mass of the polypropylene copolymer.
The reaction mixture of the present invention may further comprise an interfacial agent which is an organic solvent having a swelling effect on polyolefin, preferably at least one of the following organic solvents having a swelling effect on copolymerized polypropylene: ether solvents, ketone solvents, aromatic hydrocarbon solvents, and alkane solvents; more preferably at least one of the following organic solvents: chlorobenzene, polychlorinated benzene, alkane or cycloalkane with more than C 6, benzene, C 1-C4 alkyl substituted benzene, C 2-C6 aliphatic ether, C 3-C6 aliphatic ketone, decalin; further preferred is at least one of the following organic solvents: benzene, toluene, xylene, chlorobenzene, tetrahydrofuran, diethyl ether, acetone, hexane, cyclohexane, decalin, heptane. The mass content of the interfacial agent is preferably 1 to 30% by mass, more preferably 10 to 25% by mass, of the polypropylene copolymer.
The reaction mixture of the present invention may further comprise an organic solvent, preferably at least one of C 2-C5 alcohols, C 2-C4 ethers and C 3-C5 ketones, more preferably at least one of C 2-C4 alcohols, C 2-C3 ethers and C 3-C5 ketones, and most preferably at least one of ethanol, diethyl ether and acetone, as a solvent for dissolving the solid free radical initiator. The mass content of the organic solvent is preferably 1 to 35% of the mass of the polypropylene copolymer.
In the preparation method of the aromatic olefin grafted modified polypropylene, the limitation of the styrene monomer and the copolymerized polypropylene is the same as the previous one, and the description thereof is omitted.
According to the invention, the preparation method of the aromatic olefin grafted modified polypropylene can be selected from one of the following modes:
in one mode, the preparation method comprises the following steps:
a. placing the polypropylene copolymer in a closed reactor for inert gas replacement;
b. adding a free radical initiator and a styrene monomer into the closed reactor, and stirring and mixing;
c. optionally adding an interfacial agent, and optionally swelling the reaction system;
d. optionally adding a dispersing agent, heating the reaction system to a grafting reaction temperature, and carrying out grafting reaction;
e. After the reaction is finished, the aromatic olefin graft modified polypropylene is obtained by optionally filtering (in the case of using an aqueous dispersing agent) and drying.
More specifically, the preparation method comprises the following steps:
a. placing the polypropylene copolymer in a closed reactor for inert gas replacement;
b. Dissolving a free radical initiator in a styrene monomer to prepare a solution, adding the solution into a closed reactor filled with polypropylene copolymer, and stirring and mixing;
c. Adding 0-30 parts of interfacial agent, and optionally swelling the reaction system at 20-60 ℃ for 0-24 hours;
d. Adding 0-300 parts of dispersing agent, heating the system to the grafting polymerization temperature of 30-130 ℃ and reacting for 0.5-10 hours;
e. After the reaction is finished, the aromatic olefin graft modified polypropylene is obtained by optionally filtering (in the case of using an aqueous dispersing agent) and drying.
In a second mode, the preparation method includes the following steps:
a. placing the polypropylene copolymer in a closed reactor for inert gas replacement;
b. Mixing an organic solvent and a free radical initiator, and adding the mixture into the closed reactor;
c. removing the organic solvent;
d. Adding a styrenic monomer, optionally adding an interfacial agent, and optionally swelling the reaction system;
e. optionally adding a dispersing agent, heating the reaction system to a grafting reaction temperature, and carrying out grafting reaction;
f. After the reaction is finished, the aromatic olefin graft modified polypropylene is obtained by optionally filtering (in the case of using an aqueous dispersing agent) and drying.
More specifically, the preparation method comprises the following steps:
a. placing the polypropylene copolymer in a closed reactor for inert gas replacement;
b. mixing an organic solvent and a free radical initiator to prepare a solution, and adding the solution into a closed reactor filled with the polypropylene copolymer;
c. purging with an inert gas or removing the organic solvent by vacuum;
d. adding styrene monomer, adding 0-30 parts of interfacial agent, and optionally swelling the reaction system at 20-60 ℃ for 0-24 hours;
e. adding 0-300 parts of dispersing agent, heating the system to the grafting polymerization temperature of 30-130 ℃ and reacting for 0.5-10 hours;
f. After the reaction is finished, the aromatic olefin graft modified polypropylene is obtained by optionally filtering (in the case of using an aqueous dispersing agent) and drying.
According to the process of the invention, if volatile components are present in the system after the end of the reaction, the process of the invention preferably comprises a step of devolatilization, which can be carried out by any conventional method, including vacuum extraction or the use of stripping agents at the end of the grafting process. Suitable stripping agents include, but are not limited to, inert gases.
As described above, the "aromatic olefin graft modified polypropylene" of the present invention includes both a product (crude product) directly obtained by graft reaction of a copolymer polypropylene and a styrene-based monomer and a pure product of an aromatic olefin graft modified polypropylene obtained by further purifying the product, and therefore, the preparation method of the present invention may optionally include a step of purifying the crude product. The purification may be carried out by various methods conventional in the art, such as extraction.
The grafting efficiency of the grafting reaction is not particularly limited, but the higher grafting efficiency is more beneficial to obtaining the aromatic olefin grafting modified polypropylene material with the required performance through one-step grafting reaction. Therefore, the grafting efficiency of the grafting reaction is preferably controlled to be 30 to 100%, more preferably 35 to 80%. The concept of grafting efficiency is well known to the person skilled in the art and refers to the amount of styrene grafted on/total amount of styrene fed in the reaction.
The inert gas of the present invention may be various inert gases commonly used in the art, including but not limited to nitrogen, argon.
The invention also provides an insulating material containing the aromatic olefin grafted modified polypropylene, wherein the aromatic olefin grafted modified polypropylene is the aromatic olefin grafted modified polypropylene; the aromatic olefin graft modified polypropylene used in the present invention may be directly used as a base material of an insulating material or directly used as an insulating material, and the aromatic olefin graft modified polypropylene may be contained in an amount of 20 to 100wt%, preferably 40 to 100wt%, more preferably 60 to 100wt%, still more preferably 80 to 100wt%, still more preferably 90 to 100wt%, based on the weight of the insulating material. The aromatic olefin graft-modified polypropylene may be contained in an amount of 20wt％、25wt％、30wt％、35wt％、40wt％、45wt％、50wt％、55wt％、60wt％、65wt％、70wt％、75wt％、80wt％、85wt％、90wt％、91wt％、92wt％、93wt％、94wt％、95wt％、96wt％、97wt％、98wt％、99wt％、100wt％.
According to the invention, the insulation material is preferably a cable insulation material; further preferred is a dc cable insulation. More specifically, the insulating material is a cable insulating layer material.
The aromatic olefin grafted modified polypropylene material can give consideration to mechanical properties and electrical properties at a higher working temperature, and is suitable for working conditions of high temperature and high running field intensity. In addition, compared with the material added with the small molecular additive, the aromatic olefin grafted modified polypropylene material avoids performance degradation caused by small molecular migration, and therefore has better stability.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
In the following examples and comparative examples:
1. determination of comonomer content in the Co-Polypropylene:
comonomer content was determined by quantitative Fourier Transform Infrared (FTIR) spectroscopy. The correlation of the determined comonomer content is calibrated by quantitative Nuclear Magnetic Resonance (NMR) spectroscopy. The calibration method based on the results obtained by quantitative 13 C-NMR spectroscopy is performed according to the conventional methods in the art.
2. Determination of xylene solubles content in the copolymer polypropylene, comonomer content in the solubles, and intrinsic viscosity ratio of the solubles/copolymer polypropylene:
The test was performed by means of CRYST-EX equipment from Polymer Char. Dissolving with trichlorobenzene solvent at 150deg.C, maintaining the temperature for 90min, sampling, cooling to 35deg.C, maintaining the temperature for 70min, and sampling.
3. Measurement of the weight average molecular weight of the copolymer polypropylene:
The sample was dissolved in 1,2, 4-trichlorobenzene by using PL-GPC 220 type gel permeation chromatography (Polymer Laboratory) under high temperature GPC measurement, and the concentration was 1.0mg/ml. The test temperature was 150℃and the solution flow rate was 1.0ml/min. The molecular weight of polystyrene is used as an internal reference to make a standard curve, and the molecular weight and molecular weight distribution of the sample are calculated according to the outflow time.
4. Determination of melt flow Rate MFR:
The measurement was carried out by using a CEAST model 7026 melt index apparatus at 230℃under a load of 2.16kg according to the method specified in GB/T3682-2018.
5. Determination of melting temperature Tm:
The melting process and crystallization process of the material were analyzed using a differential scanning calorimeter. The specific operation is as follows: under the protection of nitrogen, 5-10 mg of samples are measured by adopting a three-stage temperature rise and fall measuring method from 20 ℃ to 200 ℃, and the melting and crystallization processes of the materials are reflected by the change of heat flow, so that the melting temperature Tm is calculated.
6. Determination of grafting efficiency GE, parameter M1:
2-4 g of the grafted product is put into a Soxhlet extractor, extracted for 24 hours by ethyl acetate, unreacted monomers and homopolymers thereof are removed, and the pure grafted product is obtained, dried and weighed, and parameters M1 and grafting efficiency GE are calculated.
The parameter M1 represents the content of structural units derived from styrene monomers in the aromatic olefin grafting modified polypropylene material, and in the invention, the calculation formulas of M1 and GE are as follows:
In the above formula, w 0 is the mass of the PP matrix; w 1 is the mass of grafted product drawn forward; w 2 is the mass of the grafted product after extraction; w 3 is the mass of styrene added.
7. Measurement of the direct-current volume resistivity:
The measurement was carried out according to the method specified in GB/T1410-2006.
8. Determination of breakdown field strength:
The measurement was performed according to the method specified in GB/T1408-2006.
9. Determination of tensile Strength:
the measurement was carried out according to the method specified in GB/T1040.2-2006.
10. Determination of flexural modulus:
The measurement was carried out according to the method specified in GB/T9341-2008.
11. Determination of elongation at break:
The measurement was carried out according to the method specified in GB/T1040-2006.
12. Measurement of dielectric constant and dielectric loss tangent:
The measurement was carried out according to the method specified in GB/T1409-2006.
The raw materials used in the examples are described in table a below.
Table A
* Copolymer polypropylene 1: the polypropylene copolymer used in example 1.
* Copolymer polypropylene 2: the polypropylene copolymer used in example 2.
* Copolymer polypropylene 3: the polypropylene copolymer used in example 3.
* Copolymer polypropylene 4: the polypropylene copolymer used in example 4.
* Copolymer polypropylene 5: the polypropylene copolymer used in example 5.
* Copolymer polypropylene 6: the polypropylene copolymer used in example 6.
Example 1
Selecting basic copolymerized polypropylene powder with the following characteristics: the comonomer ethylene content is 18.1wt%, the xylene solubles content is 48.7wt%, the comonomer content in the solubles is 31.9wt%, the intrinsic viscosity ratio of the solubles/the copolymerized polypropylene is 0.89, the weight average molecular weight is 34.3X10 4 g/mol, the MFR under the load of 2.16kg at 230 ℃ is 1.21g/10min, the Tm=143.4 ℃, the breakdown field strength (90 ℃) is 236kV/mm, the direct current volume resistivity (90 ℃ and 15 kV/mm) is 1.16E13 Ω.m, and the fine powder smaller than 40 meshes is sieved and removed. 2.0kg of the basic polypropylene copolymer powder is weighed and added into a 10L reaction kettle with mechanical stirring, a reaction system is closed, and nitrogen is replaced for deoxidization. 2g of dibenzoyl peroxide and 100g of styrene are added, stirred and mixed for 60min, swelled for 4 hours at 40 ℃, heated to 95 ℃ and reacted for 4 hours. After the reaction is finished, nitrogen purging and cooling are carried out, and a polypropylene-g-styrene material product C1 is obtained. The resulting product was tested for various performance parameters and the results are shown in table 1.
Example 2
Selecting basic copolymerized polypropylene powder with the following characteristics: the comonomer ethylene content is 14.7wt%, the xylene solubles content is 41.7wt%, the comonomer content in the solubles is 34.5wt%, the intrinsic viscosity ratio of the solubles/the copolymerized polypropylene is 0.91, the weight average molecular weight is 36.6X10 4 g/mol, the MFR under the load of 2.16kg at 230 ℃ is 1.54g/10min, the Tm=164.9 ℃, the breakdown field strength (90 ℃) is 248kV/mm, the direct current volume resistivity (90 ℃ and 15 kV/mm) is 7.25E12 Ω.m, and the fine powder smaller than 40 meshes is sieved and removed. 2.0kg of the basic polypropylene copolymer powder is weighed and added into a 10L reaction kettle with mechanical stirring, a reaction system is closed, and nitrogen is replaced for deoxidization. 2.8g of lauroyl peroxide and 150g of styrene are added, stirred and mixed for 60min, swelled for 2 hours at 60 ℃, heated to 90 ℃ and reacted for 4 hours. After the reaction is finished, nitrogen purging and cooling are carried out, and a polypropylene-g-styrene material product C2 is obtained. The resulting product was tested for various performance parameters and the results are shown in table 1.
Example 3
Selecting basic copolymerized polypropylene powder with the following characteristics: the comonomer ethylene content is 20.1wt%, the xylene solubles content is 66.1wt%, the comonomer content in the solubles is 29.5wt%, the intrinsic viscosity ratio of the solubles/the copolymerized polypropylene is 1.23, the weight average molecular weight is 53.8X10 4 g/mol, the MFR under the load of 2.16kg at 230 ℃ is 0.51g/10min, the Tm=142.5 ℃, the breakdown field strength (90 ℃) is 176kV/mm, the direct current volume resistivity (90 ℃ and 15 kV/mm) is 5.63E12 Ω.m, and the fine powder smaller than 40 meshes is sieved and removed. 2.0kg of the basic polypropylene copolymer powder is weighed and added into a 10L reaction kettle with mechanical stirring, a reaction system is closed, and nitrogen is replaced for deoxidization. 1.5g lauroyl peroxide and 50g styrene were added, and the mixture was stirred and mixed for 60 minutes, swollen for 2 hours at 60℃and heated to 85℃for 4 hours. After the reaction is finished, nitrogen purging and cooling are carried out, and a polypropylene-g-styrene material product C3 is obtained. The resulting product was tested for various performance parameters and the results are shown in table 1.
Example 4
Selecting basic copolymerized polypropylene powder with the following characteristics: the comonomer ethylene content is 9.3wt%, the xylene solubles content is 21.0wt%, the comonomer content in the solubles is 35.4wt%, the intrinsic viscosity ratio of the solubles/the copolymerized polypropylene is 1.68, the weight average molecular weight is 30.4 multiplied by 10 4 g/mol, the MFR under the load of 2.16kg at 230 ℃ is 5.69g/10min, the Tm= 163.0 ℃, the breakdown field strength (90 ℃) is 288kV/mm, the direct current volume resistivity (90 ℃ and 15 kV/mm) is 1.32E13 Ω.m, and the fine powder smaller than 40 meshes is sieved and removed. 2.0kg of the basic polypropylene copolymer powder is weighed and added into a 10L reaction kettle with mechanical stirring, a reaction system is closed, and nitrogen is replaced for deoxidization. 7.0g of tert-butyl peroxy (2-ethylhexanoate) and 200g of styrene were added, stirred and mixed for 60min, swollen for 1 hour at 60 ℃, heated to 90 ℃ and reacted for 4 hours. After the reaction is finished, nitrogen purging and cooling are carried out, and a polypropylene-g-styrene material product C4 is obtained. The resulting product was tested for various performance parameters and the results are shown in table 1.
Example 5
Selecting basic copolymerized polypropylene powder with the following characteristics: comonomer ethylene content 4.8wt%, xylene solubles content 19.2wt%, comonomer content 17.6wt% in the solubles, solubles/copolymerized polypropylene intrinsic viscosity ratio 1.04, weight average molecular weight 29.2X10 4 g/mol, MFR at 230 ℃,2.16kg load 5.37g/10min, tm=163.3deg.C, breakdown field strength (90 ℃) 322kV/mm, direct current volume resistivity (90 ℃,15 kV/mm) 1.36E13 Ω·m, and sieving to remove fines less than 40 mesh. 2.0kg of the basic polypropylene copolymer powder is weighed and added into a 10L reaction kettle with mechanical stirring, a reaction system is closed, and nitrogen is replaced for deoxidization. 4.0g of dibenzoyl peroxide is dissolved in 100g of acetone, the obtained acetone solution is added into a reaction system, the temperature is raised to 40 ℃, nitrogen is purged for 30min to remove acetone, 100g of p-methylstyrene is added, stirring and mixing are carried out for 30min, swelling is carried out at 60 ℃ for 1 hour, the temperature is raised to 100 ℃, and the reaction is carried out for 1 hour. After the reaction is finished, nitrogen purging and cooling are carried out, and a polypropylene-g-p-methylstyrene material product C5 is obtained. The resulting product was tested for various performance parameters and the results are shown in table 1.
Example 6
Selecting basic copolymerized polypropylene powder with the following characteristics: the comonomer ethylene content is 12.6wt%, the xylene solubles content is 30.6wt%, the comonomer content in the solubles is 43.6wt%, the intrinsic viscosity ratio of the solubles/the copolymerized polypropylene is 1.84, the weight average molecular weight is 27.1 multiplied by 10 4 g/mol, the MFR under the load of 2.16kg at 230 ℃ is 8.46g/10min, the Tm=162.0 ℃, the breakdown field strength (90 ℃) is 261kV/mm, the direct current volume resistivity (90 ℃ and 15 kV/mm) is 9E12 Ω & m, and the fine powder smaller than 40 meshes is sieved and removed. 2.0kg of the basic polypropylene copolymer powder is weighed and added into a 10L reaction kettle with mechanical stirring, a reaction system is closed, and nitrogen is replaced for deoxidization. 3.0g of dibenzoyl peroxide is dissolved in 100g of styrene and 100g of toluene as an interfacial agent to form a solution, the solution is stirred and mixed for 30min, swelling is carried out for 0.5 hour at 60 ℃, 4kg of dispersant water is added, the temperature is raised to 110 ℃, and the reaction is carried out for 0.5 hour. After the reaction is finished, cooling, filtering to remove dispersant water, and vacuum drying for 10 hours at 70 ℃ to obtain a polypropylene-g-styrene material product C6. The resulting product was tested for various performance parameters and the results are shown in table 1.
Example 7
2.0Kg of the base polypropylene copolymer powder of example 1 was weighed and added to a 10L reaction kettle with mechanical stirring, the reaction system was closed, and oxygen was removed by nitrogen substitution. 0.6g of dibenzoyl peroxide and 30g of styrene are added, stirred and mixed for 60min, swelled for 4 hours at 40 ℃, heated to 95 ℃ and reacted for 4 hours. After the reaction is finished, nitrogen purging and cooling are carried out, and a polypropylene-g-styrene material product C7 is obtained. The resulting product was tested for various performance parameters and the results are shown in table 1.
Example 8
2.0Kg of the base polypropylene copolymer powder of example 1 was weighed and added to a 10L reaction kettle with mechanical stirring, the reaction system was closed, and oxygen was removed by nitrogen substitution. 4g of dibenzoyl peroxide and 200g of styrene are added, stirred and mixed for 60min, swelled for 4 hours at 40 ℃, heated to 95 ℃ and reacted for 4 hours. After the reaction is finished, nitrogen purging and cooling are carried out, and a polypropylene-g-styrene material product C8 is obtained. The resulting product was tested for various performance parameters and the results are shown in table 1.
Comparative example 1
Weighing and sieving to remove T30S powder with the fine powder less than 40 meshes (the breakdown field strength (90 ℃) is 347kV/mm, the direct-current volume resistivity (90 ℃ and 15 kV/mm) is 1.18E13 Ω & m), 2.0kg, adding into a 10L reaction kettle with mechanical stirring, sealing the reaction system, and removing oxygen by nitrogen replacement. 2g of dibenzoyl peroxide and 100g of styrene are added, stirred and mixed for 60min, swelled for 4 hours at 40 ℃, heated to 95 ℃ and reacted for 4 hours. After the reaction is finished, nitrogen purging and cooling are carried out, and a polypropylene-g-styrene material product D1 is obtained. The resulting product was tested for various performance parameters and the results are shown in table 1.
Comparative example 2
Selecting basic copolymerized polypropylene powder with the following characteristics: the comonomer ethylene content is 18.1wt%, the xylene solubles content is 48.7wt%, the comonomer content in the solubles is 31.9wt%, the intrinsic viscosity ratio of the solubles/the copolymerized polypropylene is 0.89, the weight average molecular weight is 34.3X10 4 g/mol, the MFR under the load of 2.16kg at 230 ℃ is 1.21g/10min, the Tm=143.4 ℃, the breakdown field strength (90 ℃) is 236kV/mm, the direct current volume resistivity (90 ℃ and 15 kV/mm) is 1.16E13 Ω.m, and the fine powder smaller than 40 meshes is sieved and removed. 2.0kg of the basic polypropylene copolymer powder is weighed and added into a 10L reaction kettle with mechanical stirring, a reaction system is closed, and nitrogen is replaced for deoxidization. 12g of dibenzoyl peroxide and 600g of styrene are added, stirred and mixed for 60min, swelled for 4 hours at 40 ℃, heated to 95 ℃ and reacted for 4 hours. After the reaction is finished, nitrogen purging and cooling are carried out, and a polypropylene-g-styrene material product D2 is obtained. The resulting product was tested for various performance parameters and the results are shown in table 1.
Comparative example 3
Selecting basic copolymerized polypropylene powder with the following characteristics: the comonomer ethylene content is 18.1wt%, the xylene solubles content is 48.7wt%, the comonomer content in the solubles is 31.9wt%, the intrinsic viscosity ratio of the solubles/the copolymerized polypropylene is 0.89, the weight average molecular weight is 34.3X10 4 g/mol, the MFR under the load of 2.16kg at 230 ℃ is 1.21g/10min, the Tm=143.4 ℃, the breakdown field strength (90 ℃) is 236kV/mm, the direct current volume resistivity (90 ℃ and 15 kV/mm) is 1.16E13 Ω.m, and the fine powder smaller than 40 meshes is sieved and removed. 2.0kg of the above base polypropylene powder was weighed, mixed with 100g of polystyrene GPPS-123, and mixed using a screw extruder to obtain a blend D3. The resulting product was tested for various performance parameters and the results are shown in table 1.
As can be seen from the data of comparative example 1 and comparative example 1, the flexural modulus of the obtained polypropylene-g-styrene material product is too high and the mechanical properties of the material are poor to meet the processing requirements of the insulating material by adopting the T30S powder as the basic powder.
As can be seen from the data of comparative examples 1 and 2, an excessively high addition amount of styrene monomer (an excessively high M1 value) can lead to a significant decrease in the elongation at break of the resulting polypropylene-g-styrene material product, affecting the mechanical properties of the material, and a decrease in the breakdown field strength and volume resistivity of the material, affecting the electrical properties of the material.
As can be seen from comparing the data of example 1 and comparative example 3, the mode of blending polystyrene instead causes the breakdown field strength and volume resistivity of the material to be greatly reduced, which greatly affects the electrical properties of the material.
From the data in table 1, it can be seen that the great decrease of flexural modulus makes the aromatic olefin grafted modified polypropylene material of the present invention have good mechanical properties, and the breakdown field strength of the grafted product is improved compared with the copolymer polypropylene without grafted styrene monomer, which indicates that the aromatic olefin grafted modified polypropylene material of the present invention has good electrical properties.
In addition, as can be seen from the dielectric constant and dielectric loss data, the graft modification does not affect the dielectric constant and dielectric loss of the material, and the material of the invention meets the necessary conditions for insulation.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Claims (73)
1. The use of an aromatic olefin graft modified polypropylene as an insulating material, characterized in that the aromatic olefin graft modified polypropylene comprises structural units derived from a copolymer polypropylene and structural units derived from a styrenic monomer; based on the weight of the aromatic olefin grafted modified polypropylene, the content of the structural unit which is derived from the styrene monomer and is in a grafted state in the aromatic olefin grafted modified polypropylene is 0.5-14 wt%; the copolymer polypropylene has the following characteristics: the comonomer content is 0.5 to 40mol%; the content of xylene solubles is 2-80 wt%; the content of comonomer in the soluble matters is 10-70 wt%; the intrinsic viscosity ratio of the soluble matters to the polypropylene is 0.3-5;
the aromatic olefin grafted modified polypropylene has the following characteristics:
the working temperature of the aromatic olefin grafted modified polypropylene is more than or equal to 90 ℃;
The breakdown field strength E g of the aromatic olefin grafted modified polypropylene at 90 ℃ is more than or equal to 200kV/mm;
-the difference Δe between the breakdown field strength E g of the aromatic olefin graft modified polypropylene at 90 ℃ and the breakdown field strength E of the co-polypropylene at 90 ℃ divided by the breakdown field strength E of the co-polypropylene at 90 ℃ has a breakdown field strength change rate Δe/E of greater than 1.5%;
-the dc volume resistivity ρ vg≥1.0×1013 Ω·m of the aromatic olefin grafted modified polypropylene at 90 ℃, 15kV/mm field strength;
-the ratio ρ vg/ρv of the direct current volume resistivity ρ vg of the aromatic olefin grafted modified polypropylene at 90 ℃,15 kV/mm field strength to the direct current volume resistivity ρ v of the co-polypropylene at 90 ℃,15 kV/mm field strength is greater than 1;
-the aromatic olefin grafted modified polypropylene has a dielectric constant at 90 ℃,50Hz of more than 2.0;
the styrene monomer is at least one selected from a monomer with a structure shown in a formula I, a monomer with a structure shown in a formula II and a monomer with a structure shown in a formula III;
In formula I, R 1、R2、R3 are each independently selected from H, substituted or unsubstituted C 1-C6 alkyl; r 4-R8 is each independently selected from H, halogen, hydroxy, amino, phosphate, sulfonate, substituted or unsubstituted alkyl of C 1-C12, substituted or unsubstituted cycloalkyl of C 3-C12, substituted or unsubstituted alkoxy of C 1-C12, substituted or unsubstituted ester of C 1-C12, substituted or unsubstituted amine of C 1-C12, the substituted group being selected from halogen, hydroxy, amino, phosphate, sulfonate, alkyl of C 1-C12, cycloalkyl of C 3-C12, alkoxy of C 1-C12, ester of C 1-C12, amine of C 1-C12;
In formula II, R 1、R2、R3 are each independently selected from H, substituted or unsubstituted C 1-C6 alkyl; r 4-R10 is each independently selected from H, halogen, hydroxy, amino, phosphate, sulfonate, substituted or unsubstituted alkyl of C 1-C12, substituted or unsubstituted cycloalkyl of C 3-C12, substituted or unsubstituted alkoxy of C 1-C12, substituted or unsubstituted ester of C 1-C12, substituted or unsubstituted amine of C 1-C12, the substituted group being selected from halogen, hydroxy, amino, phosphate, sulfonate, alkyl of C 1-C12, cycloalkyl of C 3-C12, alkoxy of C 1-C12, ester of C 1-C12, amine of C 1-C12;
In formula III, R 1'、R2'、R3' are each independently selected from H, substituted or unsubstituted alkyl of C 1-C6; r 4'-R10' is each independently selected from H, halogen, hydroxy, amino, phosphate, sulfonate, substituted or unsubstituted alkyl of C 1-C12, substituted or unsubstituted cycloalkyl of C 3-C12, substituted or unsubstituted alkoxy of C 1-C12, substituted or unsubstituted ester of C 1-C12, substituted or unsubstituted amine of C 1-C12, said substituted groups being selected from halogen, hydroxy, amino, phosphate, sulfonate, alkyl of C 1-C12, cycloalkyl of C 3-C12, alkoxy of C 1-C12, ester of C 1-C12, amine of C 1-C12.
2. Use according to claim 1, wherein the content of structural units derived from styrenic monomers in the grafted state in the aromatic olefin graft modified polypropylene is from 1 to 7.5 wt.%, based on the weight of the aromatic olefin graft modified polypropylene.
3. Use according to claim 1, wherein the content of structural units derived from styrenic monomers in the grafted state in the aromatic olefin graft modified polypropylene is from 1.5 to 5 wt.%, based on the weight of the aromatic olefin graft modified polypropylene.
4. The use according to claim 1, wherein the insulation material is cable insulation material.
5. The use according to claim 4, wherein the insulation material is a dc cable insulation material.
6. The use according to claim 4, wherein the insulation material is a cable insulation material.
7. Use according to any one of claims 1-6, wherein the aromatic olefin graft modified polypropylene has at least one of the following characteristics: the melt flow rate under the load of 2.16kg at 230 ℃ is 0.01-30 g/10min; the flexural modulus is 10-1250 MPa; the elongation at break is more than or equal to 200%; the tensile strength is more than 5MPa.
8. The use according to claim 7, wherein the melt flow rate of the aromatic olefin graft modified polypropylene at 230 ℃ under a load of 2.16kg is 0.05 to 20g/10min.
9. The use according to claim 8, wherein the melt flow rate of the aromatic olefin graft modified polypropylene at 230 ℃ under a load of 2.16kg is 0.1 to 10g/10min.
10. The use according to claim 9, wherein the melt flow rate of the aromatic olefin graft modified polypropylene at 230 ℃, under a load of 2.16kg is 0.2-8 g/10min.
11. Use according to claim 10, wherein the melt flow rate of the aromatic olefin grafted modified polypropylene at 230 ℃, under a load of 2.16kg is between 0.2 and 5g/10min.
12. The use according to claim 7, wherein the aromatic olefin-grafted modified polypropylene has a flexural modulus of 20 to 1000MPa.
13. Use according to claim 12, wherein the aromatic olefin grafted modified polypropylene has a flexural modulus of 50 to 600MPa.
14. The process according to claim 7, wherein the aromatic olefin-grafted modified polypropylene has an elongation at break of not less than 300%.
15. The use according to claim 7, wherein the aromatic olefin-grafted modified polypropylene has a tensile strength of 10 to 40MPa.
16. Use according to claim 1, wherein the operating temperature of the aromatic olefin grafted modified polypropylene is between 90 and 160 ℃.
17. The use according to claim 1, wherein the aromatic olefin graft modified polypropylene has a breakdown field strength E g at 90 ℃ of 200 to 800kV/mm.
18. The use according to claim 1, wherein the aromatic olefin graft modified polypropylene has a breakdown field strength E g at 90 ℃ and the copolymer polypropylene has a breakdown field strength E difference Δe at 90 ℃ divided by the copolymer polypropylene has a breakdown field strength E change rate Δe/E of 1.6% to 40%.
19. The use according to claim 18, wherein the aromatic olefin graft modified polypropylene has a breakdown field strength E g at 90 ℃ and the copolymer polypropylene has a breakdown field strength E difference Δe at 90 ℃ divided by the copolymer polypropylene has a breakdown field strength E change rate Δe/E of 5% to 30%.
20. The use according to claim 19, wherein the aromatic olefin graft modified polypropylene has a breakdown field strength E g at 90 ℃ and the copolymer polypropylene has a breakdown field strength E difference Δe at 90 ℃ divided by the copolymer polypropylene has a breakdown field strength E change rate Δe/E of 10% to 20%.
21. Use according to claim 1, wherein the aromatic olefin graft modified polypropylene has a direct current volume resistivity ρ vg of 1.5x10 13Ω·m～1.0×1020 Ω -m at 90 ℃, 15kV/mm field strength.
22. Use according to claim 1, wherein the ratio ρ vg/ρv of the dc volume resistivity ρ vg of the aromatic olefin graft modified polypropylene at 90 ℃,15 kV/mm field strength to the dc volume resistivity ρ v of the co-polypropylene at 90 ℃,15 kV/mm field strength is 1.5-50.
23. Use according to claim 22, wherein the ratio ρ vg/ρv of the dc volume resistivity ρ vg of the aromatic olefin graft modified polypropylene at 90 ℃, 15kV/mm field strength to the dc volume resistivity ρ v of the co-polypropylene at 90 ℃, 15kV/mm field strength is 2-20.
24. Use according to claim 23, wherein the ratio ρ vg/ρv of the dc volume resistivity ρ vg of the aromatic olefin graft modified polypropylene at 90 ℃, 15kV/mm field strength to the dc volume resistivity ρ v of the co-polypropylene at 90 ℃, 15kV/mm field strength is 3-10.
25. The use according to claim 1, wherein the aromatic olefin graft modified polypropylene has a dielectric constant of 2.1 to 2.5 at 90 ℃ and 50Hz.
26. Use according to any of claims 1-6, wherein the co-polypropylene has at least one of the following characteristics: the comonomer content is 0.5 to 30mol%; the content of xylene solubles is 18-75wt%; the content of comonomer in the soluble matters is 10-50wt%; the intrinsic viscosity ratio of the soluble matters to the polypropylene is 0.5-3.
27. Use according to claim 26, wherein the comonomer content of the copolypropylene is 4 to 25wt%.
28. Use according to claim 27, wherein the comonomer content of the copolypropylene is 4 to 22wt%.
29. Use according to claim 26, wherein the copolymer polypropylene has a xylene solubles content of 30 to 70wt%.
30. Use according to claim 29, wherein the copolymer polypropylene has a xylene solubles content of 30 to 67wt%.
31. Use according to claim 26, wherein the comonomer content in the solubles of the copolypropylene is 20 to 35wt%.
32. Use according to claim 26, wherein the ratio of the intrinsic viscosity of the soluble fraction of the copolymerized polypropylene to the polypropylene is between 0.8 and 1.3.
33. Use according to any of claims 1-6, wherein the co-polypropylene has at least one of the following characteristics: the melt flow rate under the load of 2.16kg at 230 ℃ is 0.01-60 g/10min; the melting temperature Tm is above 100 ℃; the weight average molecular weight was 20X 10 4～60×104 g/mol.
34. Use according to claim 33, wherein the melt flow rate of the copolymer polypropylene at 230 ℃, under a load of 2.16kg is between 0.05 and 35g/10min.
35. Use according to claim 34, wherein the melt flow rate of the copolymer polypropylene at 230 ℃, under a load of 2.16kg is between 0.5 and 15g/10min.
36. Use according to claim 35, wherein the melt flow rate of the copolymer polypropylene at 230 ℃, under a load of 2.16kg is between 0.5 and 8g/10min.
37. Use according to claim 33, wherein the copolymer polypropylene has a melting temperature Tm of 110-180 ℃.
38. Use according to claim 37, wherein the melt temperature Tm of the copolypropylene is 110-170 ℃.
39. Use according to claim 38, wherein the copolymer polypropylene has a melting temperature Tm of 120-170 ℃.
40. The use according to claim 39, wherein the polypropylene copolymer has a melting temperature Tm of 120-166 ℃.
41. Use according to any of claims 1-6, wherein the comonomer of the co-polypropylene is selected from at least one of the alpha-olefins of C 2-C8 other than propylene.
42. The process according to claim 41, wherein the comonomer of the polypropylene copolymer is selected from at least one of ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene and 1-octene.
43. The process according to claim 42, wherein the comonomer of the polypropylene copolymer is ethylene and/or 1-butene.
44. The process according to claim 43, wherein the polypropylene copolymer consists of propylene and ethylene.
45. The use of claim 1, wherein in formula I, R 1、R2、R3 is each independently selected from H, substituted or unsubstituted C 1-C3 alkyl, R 4-R8 is each independently selected from H, halogen, hydroxy, amino, substituted or unsubstituted C 1-C6 alkyl, substituted or unsubstituted C 1-C6 alkoxy.
46. The use according to claim 1, wherein in formula II R 1、R2、R3 is each independently selected from H, substituted or unsubstituted C 1-C3 alkyl, R 4-R10 is each independently selected from H, halogen, hydroxy, amino, substituted or unsubstituted C 1-C6 alkyl, substituted or unsubstituted C 1-C6 alkoxy, said substituted group being selected from halogen, hydroxy, amino, C 1-C6 alkyl, C 1-C6 alkoxy.
47. The use according to claim 1, wherein in formula III R 1'、R2'、R3 'are each independently selected from H, substituted or unsubstituted C 1-C3 alkyl, R 4'-R10' are each independently selected from H, halogen, hydroxy, amino, substituted or unsubstituted C 1-C6 alkyl, substituted or unsubstituted C 1-C6 alkoxy, said substituted group being selected from halogen, hydroxy, amino, C 1-C6 alkyl, C 1-C6 alkoxy.
48. The use according to claim 1, wherein the styrenic monomer is selected from at least one of styrene, alpha-methylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, mono-or poly-substituted styrene, mono-or poly-substituted alpha-methylstyrene, mono-or poly-substituted 1-vinylnaphthalene, and mono-or poly-substituted 2-vinylnaphthalene.
49. The method of claim 48, wherein the substituted group is at least one selected from the group consisting of halogen, hydroxy, amino, phosphate, sulfonate, C 1-C8 straight chain alkyl, C 3-C8 branched chain alkyl or cycloalkyl, C 1-C6 straight chain alkoxy, C 3-C8 branched or cyclic alkoxy, C 1-C8 straight chain ester, C 3-C8 branched or cyclic ester, C 1-C8 straight chain amine, and C 3-C8 branched or cyclic amine.
50. The method of claim 48, wherein the styrenic monomer is selected from at least one of styrene, alpha-methylstyrene, 2-methylstyrene, 3-methylstyrene and 4-methylstyrene.
51. The use according to any one of claims 1 to 6, wherein the aromatic olefin graft modified polypropylene is prepared from a copolymer polypropylene and a styrenic monomer by a solid phase grafting reaction.
52. The use according to claim 51, wherein the process for preparing the aromatic olefin graft modified polypropylene comprises: and (3) in the presence of inert gas, carrying out grafting reaction on a reaction mixture comprising the copolymerized polypropylene and the styrene monomer to obtain the aromatic olefin grafting modified polypropylene.
53. The method of claim 52, wherein the reaction mixture further comprises a free radical initiator.
54. The process according to claim 53, wherein the free-radical initiator is selected from peroxide-based free-radical initiators and/or azo-based free-radical initiators.
55. The use according to claim 54, wherein the peroxide-based free radical initiator is selected from at least one of dibenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, lauroyl peroxide, t-butyl peroxybenzoate, diisopropyl peroxydicarbonate, t-butyl peroxy (2-ethylhexanoate) and dicyclohexyl peroxydicarbonate; the azo free radical initiator is azo diisobutyronitrile and/or azo diisoheptonitrile.
56. The process according to claim 53, wherein the mass ratio of the free-radical initiator to the styrene monomer is from 0.1 to 10:100.
57. The process according to claim 56, wherein the mass ratio of the free radical initiator to the styrene monomer is from 0.5 to 5:100.
58. The use according to claim 52, wherein the mass ratio of the styrenic monomer to the co-polypropylene is from 0.5 to 16:100.
59. The use according to claim 58, wherein the mass ratio of the styrenic monomer to the co-polypropylene is 1-12:100.
60. The process according to claim 59, wherein the mass ratio of the styrene monomer to the polypropylene copolymer is 2-10:100.
61. The use according to claim 52, wherein the grafting reaction is carried out at a temperature of 30 to 130 ℃; the time is 0.5-10 h.
62. The process according to claim 61, wherein the grafting reaction is carried out at a temperature of 60 to 120℃for a period of 1 to 5 hours.
63. The use of any one of claims 52-62, wherein the reaction mixture further comprises at least one of the following components: the mass content of the dispersing agent is 50-300% of the mass of the polypropylene copolymer, the mass content of the interfacial agent is 1-30% of the mass of the polypropylene copolymer, and the mass content of the organic solvent is 1-35% of the mass of the polypropylene copolymer.
64. The use of claim 60, wherein the method of preparation comprises the steps of:
a. placing the polypropylene copolymer in a closed reactor for inert gas replacement;
b. adding a free radical initiator and a styrene monomer into the closed reactor, and stirring and mixing;
c. optionally adding an interfacial agent, and optionally swelling the reaction system;
d. optionally adding a dispersing agent, heating the reaction system to a grafting reaction temperature, and carrying out grafting reaction;
e. And after the reaction is finished, optionally filtering and drying to obtain the aromatic olefin grafted modified polypropylene.
65. The use of claim 60, wherein the method of preparation comprises the steps of:
a. placing the polypropylene copolymer in a closed reactor for inert gas replacement;
b. Mixing an organic solvent and a free radical initiator, and adding the mixture into the closed reactor;
c. removing the organic solvent;
d. Adding a styrenic monomer, optionally adding an interfacial agent, and optionally swelling the reaction system;
e. optionally adding a dispersing agent, heating the reaction system to a grafting reaction temperature, and carrying out grafting reaction;
f. And after the reaction is finished, optionally filtering and drying to obtain the aromatic olefin grafted modified polypropylene.
66. An insulating material comprising an aromatic olefin graft modified polypropylene, characterized in that the aromatic olefin graft modified polypropylene is the aromatic olefin graft modified polypropylene according to any one of claims 1 to 65; the aromatic olefin grafted modified polypropylene is contained in an amount of 20 to 99wt% based on the weight of the insulating material.
67. The insulation of claim 66, wherein the aromatic olefin grafted modified polypropylene comprises from 40 to 99 weight percent, based on the weight of the insulation.
68. The insulation of claim 67, wherein the aromatic olefin graft modified polypropylene is present in an amount of 60-99wt% based on the weight of the insulation.
69. The insulation of claim 68, wherein the aromatic olefin grafted modified polypropylene comprises from 80 to 99 weight percent, based on the weight of the insulation.
70. The insulation of claim 69, wherein the aromatic-olefin graft modified polypropylene is present in an amount of from 90 to 99 weight percent, based on the weight of the insulation.
71. The insulating material of claim 66, wherein the insulating material is a cable insulating material.
72. The insulating material of claim 71, wherein the insulating material is a dc cable insulating material.
73. The insulating material of claim 71, wherein the insulating material is a cable insulation material.
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| CN116063785B (en) * | 2021-10-30 | 2024-08-20 | 中国石油化工股份有限公司 | Electric insulation thermoplastic composite material containing aromatic olefin grafted modified polypropylene, and preparation method and application thereof |
| WO2023130848A1 (en) * | 2022-01-06 | 2023-07-13 | 中国石油化工股份有限公司 | Biaxially oriented polypropylene dielectric film, modified polypropylene material and use thereof |
| CN115651129A (en) * | 2022-11-11 | 2023-01-31 | 国网辽宁省电力有限公司电力科学研究院 | Insulating material, preparation method and application |
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| DE1420341B2 (en) * | 1958-11-05 | 1971-02-04 | The Dow Chemical Co., Midland, Mich (V.St.A.) | Process for the production of graft polymers |
| IL99498A0 (en) * | 1990-10-05 | 1992-08-18 | Himont Inc | Blends of graft copolymers of propylene polymer material and of olefinic rubber material |
| CN1293111C (en) * | 2004-06-30 | 2007-01-03 | 中国科学院化学研究所 | Process for preparing polypropylene graft copolymer |
| CN101492517B (en) * | 2009-02-20 | 2011-03-16 | 北京化工大学 | Method of preparing polypropylene graft polymer |
| CN104072708A (en) * | 2014-07-03 | 2014-10-01 | 青岛方达化工有限公司 | Copolymer flame retardant and preparation method thereof |
| JP6563316B2 (en) * | 2014-11-28 | 2019-08-21 | 日本エイアンドエル株式会社 | Graft copolymer |
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| CN107312128A (en) * | 2016-04-27 | 2017-11-03 | 中国科学院化学研究所 | Polyolefin graft copolymer and preparation method thereof |
| CN106317334B (en) * | 2016-08-19 | 2019-01-22 | 中国科学院化学研究所 | Graft-modified ultra-high molecular weight ultra-fine propylene polymer and its solid-phase grafting method |
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