CN113563528A - Application of aromatic olefin graft modified polypropylene as insulating material and insulating material - Google Patents
Application of aromatic olefin graft modified polypropylene as insulating material and insulating material Download PDFInfo
- Publication number
- CN113563528A CN113563528A CN202011195775.0A CN202011195775A CN113563528A CN 113563528 A CN113563528 A CN 113563528A CN 202011195775 A CN202011195775 A CN 202011195775A CN 113563528 A CN113563528 A CN 113563528A
- Authority
- CN
- China
- Prior art keywords
- substituted
- polypropylene
- unsubstituted
- modified polypropylene
- aromatic olefin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 aromatic olefin Chemical class 0.000 title claims abstract description 243
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 172
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 171
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000011810 insulating material Substances 0.000 title claims abstract description 38
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000000463 material Substances 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims description 77
- 239000000178 monomer Substances 0.000 claims description 32
- 150000003254 radicals Chemical class 0.000 claims description 30
- 229920001577 copolymer Polymers 0.000 claims description 26
- 230000015556 catabolic process Effects 0.000 claims description 24
- 229910052736 halogen Inorganic materials 0.000 claims description 24
- 150000002367 halogens Chemical class 0.000 claims description 24
- 239000003999 initiator Substances 0.000 claims description 24
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical group CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 23
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 18
- 239000005977 Ethylene Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000012774 insulation material Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 18
- 239000002270 dispersing agent Substances 0.000 claims description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 16
- 238000009413 insulation Methods 0.000 claims description 16
- 230000008961 swelling Effects 0.000 claims description 16
- 229910019142 PO4 Inorganic materials 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 239000003960 organic solvent Substances 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
- 238000003756 stirring Methods 0.000 claims description 13
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 claims description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 12
- 239000011261 inert gas Substances 0.000 claims description 12
- 239000008096 xylene Substances 0.000 claims description 12
- 125000003277 amino group Chemical group 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
- 238000002360 preparation method Methods 0.000 claims description 9
- 239000011541 reaction mixture Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 6
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 6
- 238000007334 copolymerization reaction Methods 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 6
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 claims description 5
- 150000002978 peroxides Chemical group 0.000 claims description 5
- 239000000126 substance 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
- 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 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 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
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 125000004185 ester group Chemical group 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 4
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 claims description 4
- 239000007790 solid phase Substances 0.000 claims description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 4
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims description 3
- KXYAVSFOJVUIHT-UHFFFAOYSA-N 2-vinylnaphthalene Chemical class C1=CC=CC2=CC(C=C)=CC=C21 KXYAVSFOJVUIHT-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
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- SHZIWNPUGXLXDT-UHFFFAOYSA-N caproic acid ethyl ester Natural products CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 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
- 125000004191 (C1-C6) alkoxy group Chemical group 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
- 125000003545 alkoxy group Chemical group 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
- 239000002131 composite material Substances 0.000 claims 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 44
- 239000000843 powder Substances 0.000 description 41
- 239000000047 product Substances 0.000 description 37
- 238000000034 method Methods 0.000 description 26
- 229910052757 nitrogen Inorganic materials 0.000 description 22
- 229920005606 polypropylene copolymer Polymers 0.000 description 13
- 239000011159 matrix material Substances 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 11
- 238000005303 weighing Methods 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 238000010907 mechanical stirring Methods 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 238000007789 sealing Methods 0.000 description 8
- 238000007873 sieving Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000011161 development Methods 0.000 description 7
- 230000018109 developmental process Effects 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 229920005604 random copolymer Polymers 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 230000005684 electric field Effects 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 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
- 239000004020 conductor Substances 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 229920001384 propylene homopolymer Polymers 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000012360 testing method Methods 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
- 238000005481 NMR spectroscopy Methods 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
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001816 cooling 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
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000010559 graft polymerization reaction Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 230000006872 improvement Effects 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
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000012264 purified product Substances 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
- 150000003384 small molecules Chemical class 0.000 description 2
- 230000002522 swelling effect Effects 0.000 description 2
- 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
- 239000004698 Polyethylene Substances 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
- 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
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 125000004855 decalinyl group Chemical group C1(CCCC2CCCCC12)* 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009826 distribution Methods 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
- 150000002170 ethers Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 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
- 238000004519 manufacturing process Methods 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
- 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
- 230000005855 radiation Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material 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
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 application of aromatic olefin graft modified polypropylene as an insulating material and the insulating material. The aromatic olefin graft 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 styrene monomer and is in a grafting state in the aromatic olefin graft modified polypropylene is 0.5-14 wt% based on the weight of the aromatic olefin graft modified polypropylene. The aromatic olefin graft modified polypropylene used in the invention can give consideration to both mechanical property and electrical property at a higher working temperature, is suitable for working conditions of high temperature and high operating field intensity, and is an ideal insulating material.
Description
Technical Field
The invention belongs to the field of new materials, and particularly relates to application of aromatic olefin graft modified polypropylene as an insulating material, and the insulating material containing the aromatic olefin graft 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 motors and the electrical industry. The development and progress of insulating materials are dependent on the development of high molecular 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 moves towards higher voltage level and larger electric energy transmission capacity, and higher requirements are put forward on the performance of the insulating material. The main insulating material of the high-voltage direct-current cable in operation at present is crosslinked polyethylene. The maximum long-term service temperature is 70 ℃. Increasing the thickness of the insulation alone has been less effective in meeting higher voltage ratings and higher operating temperatures. Therefore, the development of novel insulating materials for electrical equipment is urgently needed to meet the use requirements at higher operating temperature and field strength.
The operating temperature is an important indicator of the insulation material of the direct current cable. During normal operation of the direct current cable, because the core conductor has resistance, the temperature of the core conductor rises due to the thermal effect of the conductor resistance under a large transmission current. The electrical properties (including volume resistivity, breakdown field strength, aging characteristic and the like) of the polymer insulating material serving as the insulating layer of the direct current cable are closely related to the temperature of the operating environment, and the electrical properties of the polymer insulating material are rapidly reduced due to high temperature, so that the operating performance and the service life of the direct current cable are reduced, and therefore, the improvement of the operating temperature of the insulating material of the direct current cable has important significance for improving the transmission capacity of the direct current cable.
Increasing the operating temperature of dc cable insulation requires two considerations: (1) the operating temperature of the DC cable insulating material matrix is increased, so that the material still keeps certain mechanical properties at high temperature without structural changes such as softening, melting and the like; (2) the electric performance of the direct current cable insulating material under the action of high temperature and high electric field is improved, and the temperature characteristic of the electric performance of the polymer insulating material is improved, so that the direct current cable insulating material can still maintain the equivalent electric 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, and has smaller leakage current when the cable normally runs, thereby reducing the loss of electric energy transmission. On the other hand, space charge injection and accumulation are always 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 electric field distortion 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 is related to both temperature and electric field strength. The volume resistivity decreases significantly with increasing temperature and electric field strength. At present, with the improvement of the voltage grade and the transmission capacity of a cable system, in order to ensure that the insulation level is not reduced, the insulation of the cable is only thickened. However, this not only increases the amount and cost of the insulating material, but also weakens the heat dissipation capability due to the thickening of the insulation, so that the resistivity is further reduced and the increase of the insulation level is limited. Therefore, the problem can be solved fundamentally only by increasing the volume resistivity of the insulating material.
Some methods of increasing resistivity are disclosed in the prior art, but most are carried out around crosslinked polyethylene. Polypropylene has better electrical insulation properties and a higher melting point than polyethylene, however, polypropylene cannot be directly used as an insulation material due to its poor mechanical properties, and is brittle especially at low temperatures. Therefore, there is no proposal in the prior art for improving polypropylene to achieve comprehensive regulation and control of electrical properties, mechanical properties and thermal properties. If a novel modified polypropylene material which has obvious insulating property regulation and control capability, can give consideration to mechanical property and thermal property and is attached to practical application of engineering can be developed, a new insulating material branch field is developed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the application of the aromatic olefin graft modified polypropylene as the insulating material, wherein the aromatic olefin graft modified polypropylene can take mechanical property and electrical property into consideration at 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 graft modified polypropylene as an insulating material, wherein the aromatic olefin graft modified polypropylene comprises a structural unit derived from copolymerized polypropylene and a structural unit derived from styrene monomer; the content of the structural units derived from styrene monomers and in a grafted state in the aromatic olefin graft-modified polypropylene is 0.5-14 wt%, preferably 1-7.5 wt%, and more preferably 1.5-5 wt%, 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 preferably a dc cable insulation. More specifically, the insulation material is a cable insulation material.
The aromatic olefin graft 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 graft-modified polypropylene, and the form thereof is not limited. Specifically, "structural units derived from a co-polypropylene" refers to products formed from a co-polypropylene, including both in "radical" form and "polymer" form. "structural units derived from styrenic monomers" refers to products formed from styrenic monomers, including both in "radical" form and "monomer" form, as well as "polymer" form. The "structural unit" may be a repeating unit or a non-repeating independent unit.
In the present invention, the structural units derived from a styrenic monomer "in the grafted state" refer to structural units derived from a styrenic monomer that form a covalent link (graft) with the copolymerized polypropylene.
In the present invention, the term "comonomer" of the copolymerized polypropylene is known to those skilled in the art, and means a monomer copolymerized with propylene.
According to the present invention, preferably, the aromatic olefin graft-modified polypropylene is prepared by a graft reaction, preferably a solid phase graft reaction, of a copolymer polypropylene and a styrene monomer. The grafting reaction of the present invention is a radical polymerization reaction, and thus, the term "in a grafted state" means a state in which a reactant is polymerized by a radical and then forms a bond with another reactant. The connection includes both a direct connection and an indirect connection.
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 graft-reacting a copolymerized polypropylene and a styrene-based monomer, and a purified product of the aromatic olefin graft-modified polypropylene 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 the load of 2.16kg at 230 ℃ is 0.01-30 g/10min, preferably 0.05-20 g/10min, further preferably 0.1-10 g/10min, more preferably 0.2-8 g/10min, and further preferably 0.2-5 g/10 min; the flexural modulus is 10-1250 MPa, preferably 20-1000 MPa, and more preferably 50-600 MPa; the elongation at break is more than or equal to 200 percent, and preferably the elongation at break is 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 graft modified polypropylene is more than or equal to 90 ℃, and preferably 90-160 ℃;
the breakdown field strength E of the aromatic olefin graft-modified polypropylene at 90 ℃gThe voltage is more than or equal to 200kV/mm, and preferably 200-800 kV/mm;
the breakdown field strength E of the aromatic olefin graft-modified polypropylene at 90 ℃gThe change rate of breakdown field intensity delta E/E obtained by dividing the difference delta E of the breakdown field intensity E of the copolymerized polypropylene at 90 ℃ by the breakdown field intensity E of the copolymerized polypropylene at 90 ℃ is more than 1.5%, preferably 1.6-40%, more preferably 5-30%, and further preferably 10-20%;
-the direct volume resistivity p of the aromatic olefin graft-modified polypropylene at 90 ℃ and 15kV/mm field strengthvg≥1.0×1013Ω · m, preferably 1.5 × 1013Ω·m～1.0×1020Ω·m；
-said aromatic olefin is connected toDC volume resistivity rho of branch modified polypropylene at 90 ℃ and 15kV/mm field intensityvgThe direct current volume resistivity rho of the copolymerized polypropylene at 90 ℃ and 15kV/mm field intensityvRatio of (p)vg/ρvMore than 1, preferably 1.5 to 50, more preferably 2 to 20, and further preferably 3 to 10;
-the aromatic olefin graft modified polypropylene has a dielectric constant of greater than 2.0, preferably 2.1 to 2.5 at 90 ℃ and 50 Hz.
According to the present invention, the copolymerized polypropylene (base polypropylene in the present invention) is a propylene copolymer containing ethylene or higher alpha-olefin or a mixture thereof. In particular, the comonomer of the copolymerized polypropylene is selected from C other than propylene2-C8At least one of alpha-olefins (b) of (a). Said C other than propylene2-C8The α -olefins of (a) 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, and further preferably, the copolymerized polypropylene is composed of propylene and ethylene.
The copolymeric polypropylene of the present invention may be a heterophasic propylene copolymer. The heterophasic propylene copolymer may contain a propylene homopolymer or a propylene random copolymer matrix component (1) and dispersed therein another propylene copolymer component (2). In the propylene random copolymer, the comonomer is randomly distributed in the main chain of the propylene polymer. Preferably, the co-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 a 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 sea-island structure or bicontinuous structure.
Two heterophasic propylene copolymers are known in the art, a heterophasic propylene copolymer containing a propylene random copolymer as matrix phase or a heterophasic propylene copolymer containing a propylene homopolymer as matrix phase. The random copolymer matrix (1) is a copolymer in which the comonomer moieties are randomly distributed 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 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 present invention, in addition to the above-mentioned compositional features, the copolymerized polypropylene has at least one of the following features: the content of the comonomer is 0.5 to 40 mol%, preferably 0.5 to 30 mol%, preferably 4 to 25 wt%, and more preferably 4 to 22 wt%; the xylene soluble content is 2 to 80 wt%, preferably 18 to 75 wt%, more preferably 30 to 70 wt%, and still more preferably 30 to 67 wt%; the content of the comonomer in the soluble substance is 10-70 wt%, preferably 10-50 wt%, more preferably 20-35 wt%; the intrinsic viscosity ratio of the soluble matter to the polypropylene is 0.3 to 5, preferably 0.5 to 3, and 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 the load of 2.16kg at 230 ℃ is 0.01-60 g/10min, preferably 0.05-35 g/10min, further preferably 0.5-15 g/10min, and more preferably 0.5-8 g/10 min; the melting temperature Tm is 100 ℃ or higher, preferably 110 to 180 ℃, more preferably 110 to 170 ℃, still more preferably 120 to 170 ℃, and still more preferably 120 to 166 ℃. The weight average molecular weight is preferably 20X 104～60×104g/mol. The base polypropylene having a high Tm has satisfactory impact strength and flexibility at both low and high temperatures, and in addition, when the base polypropylene having a high Tm is used, the aromatic olefin graft-modified polypropylene of the present invention has an advantage of being able to withstand a higher working temperature. The copolymerized polypropylene of the present invention is preferably a porous granular or powdery resin.
According to the present invention, preferably, the copolymerized polypropylene further has at least one of the following features: the flexural modulus is 10-1000 MPa, preferably 50-600 MPa; the elongation at break is more than or equal to 200 percent, and the preferred elongation at break is more than or equal to 300 percent. Preferably, the tensile strength of the copolymerized polypropylene is more than 5MPa, and preferably 10-40 MPa.
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 in the martian petrochemical industry, SPF179 in the zipru petrochemical industry in the china, and the like, and may also be produced by the polymerization processes described in chinese patents CN1081683, CN1108315, CN1228096, CN1281380, CN1132865C, CN102020733A, and the like. Common polymerization processes include the Spheripol process from Basell, the Hypol process from Mitsui oil chemical, 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 selected from at least one of 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 the formula I, R1、R2、R3Each independently selected from H, substituted or unsubstituted C1-C6Alkyl groups of (a); r4-R8Each independently selected from H, halogen, hydroxyl, amino, phosphate, sulfonic acid, substituted or unsubstituted C1-C12Alkyl, substituted or unsubstituted C3-C12Cycloalkyl, substituted or unsubstituted C1-C12Alkoxy, substituted or unsubstituted C1-C12Ester group of (1), substituted or unsubstituted C1-C12The substituted group is selected from halogen, hydroxyl, amino, phosphate, sulfonic group, C1-C12Alkyl of (C)3-C12Cycloalkyl of, C1-C12Alkoxy group of (C)1-C12Ester group of (1), C1-C12An amine group of (a); preferably, R1、R2、R3Each independently selected from H, substituted or unsubstituted C1-C3Alkyl of R4-R8Each independently selected from H, halogen, hydroxy, amino, substituted or unsubstituted C1-C6Alkyl, substituted or unsubstituted C1-C6Alkoxy group of (a);
in the formula II, R1、R2、R3Each independently selected from H, substituted or unsubstituted C1-C6Alkyl groups of (a); r4-R10Each independently selected from H, halogen, hydroxyl, amino, phosphate, sulfonic acid, substituted or unsubstituted C1-C12Alkyl, substituted or unsubstituted C3-C12Cycloalkyl, substituted or unsubstituted C1-C12Alkoxy, substituted or unsubstituted C1-C12Ester group of (1), substituted or unsubstituted C1-C12The substituted group is selected from halogen, hydroxyl, amino, phosphate, sulfonic group, C1-C12Alkyl of (C)3-C12Cycloalkyl of, C1-C12Alkoxy group of (C)1-C12Ester group of (1), C1-C12An amine group of (a); preferably, R1、R2、R3Each independently selected from H, substituted or unsubstituted C1-C3Alkyl of R4-R10Each independently selected from H, halogen, hydroxy, amino, substituted or unsubstituted C1-C6Alkyl, substituted or unsubstituted C1-C6The substituted radical is selected from halogen, hydroxyl, amino, C1-C6Alkyl of (C)1-C6Alkoxy group of (a);
in the formula III, R1’、R2’、R3' each is independently selected from H, substituted or unsubstituted C1-C6Alkyl groups of (a); r4’-R10' each is independently selected from H, halogen, hydroxyl, amino, phosphate, sulfonate, substituted or unsubstituted C1-C12Alkyl, substituted or unsubstituted C3-C12Cycloalkyl, substituted or unsubstituted C1-C12Alkoxy, substituted or unsubstituted C1-C12Ester group of (1), substituted or unsubstituted C1-C12The substituted group is selected from halogen, hydroxyl, amino, phosphate, sulfonic group, C1-C12Alkyl of (C)3-C12Cycloalkyl of, C1-C12Alkoxy group of (C)1-C12Ester group of (1), C1-C12An amine group of (a); preferably, R1’、R2’、R3' each is independently selected from H, substituted or unsubstituted C1-C3Alkyl of R4’-R10' each is independently selected from H, halogen, hydroxy, amino, substituted or unsubstituted C1-C6Alkyl, substituted or unsubstituted C1-C6The substituted radical is selected from halogen, hydroxyl, amino, C1-C6Alkyl of (C)1-C6Alkoxy group of (2).
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 selected from the group consisting of halogen, hydroxy, amino, phosphate, sulfonate, C1-C8Straight chain alkyl group of (1), C3-C8Is branched chain ofAlkyl or cycloalkyl, C1-C6Linear alkoxy of (2), C3-C8Branched or cyclic alkoxy of (A), C1-C8Linear ester group of (1), C3-C8A branched or cyclic ester group of1-C8And C is a linear amino group3-C8At least one of a branched amine group or a cyclic amine group.
More preferably, the styrenic monomer is selected from at least one of styrene, α -methylstyrene, 2-methylstyrene, 3-methylstyrene and 4-methylstyrene.
The aromatic olefin graft modified polypropylene can be prepared by the solid-phase graft reaction of copolymerized polypropylene and styrene monomers, and specifically can be prepared by the method comprising the following steps: and (2) carrying out grafting reaction on the reaction mixture comprising the copolymerized polypropylene and the styrene monomer in the presence of inert gas to obtain the aromatic olefin graft modified polypropylene.
The grafting reaction of the present invention can be carried out by various methods which are conventional in the art, and is preferably a solid phase grafting reaction. For example, the active grafting site may be formed on the copolymerized polypropylene in the presence of the styrene-based monomer for grafting, or the active grafting site may be formed on the copolymerized polypropylene first and then treated with the monomer for grafting. The grafting sites may be formed by treatment with a free radical initiator, or by high energy ionizing radiation or microwave treatment. The free radicals produced in the polymer 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-based radical initiator is preferably at least one selected from the group consisting 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 radical initiator is preferably azobisisobutyronitrile and/or azobisisoheptonitrile.
More preferably, the grafting sites are initiated by a peroxide-based free radical initiator and the grafting reaction proceeds further.
In addition, 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.
On the premise of meeting the product characteristics, the dosage of each component in the grafting reaction is not particularly limited, and specifically, the mass ratio of the radical initiator to the styrene monomer can be 0.1-10: 100, and preferably 0.5-5: 100. The mass ratio of the styrene 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 invention also has no special limitation on the technical conditions of the grafting reaction, and specifically, the temperature of the grafting reaction can be 30-130 ℃, and preferably 60-120 ℃; the time can 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, which is preferably water or an aqueous solution of sodium chloride. The mass usage amount of the dispersing agent is preferably 50-300% of the mass of the copolymerized polypropylene.
The reaction mixture of the present invention may further comprise an interfacial agent, wherein the interfacial agent is an organic solvent having a swelling effect on polyolefin, and preferably at least one of the following organic solvents having a swelling effect on polypropylene copolymer: ether solvents, ketone solvents, aromatic hydrocarbon solvents, and alkane solvents; more preferably at least one of the following organic solvents: chlorobenzene, polychlorinated benzene, C6The above alkane or cycloalkaneHydrocarbons, benzene, C1-C4Alkyl substituted benzene, C2-C6Fatty ethers, C3-C6Aliphatic ketones, decalins; further preferred is at least one of the following organic solvents: benzene, toluene, xylene, chlorobenzene, tetrahydrofuran, diethyl ether, acetone, hexane, cyclohexane, decahydronaphthalene, heptane. The mass content of the interfacial agent is preferably 1-30% of the mass of the copolymerized polypropylene, and more preferably 10-25%.
The reaction mixture according to the invention may also comprise an organic solvent, preferably comprising C, as solvent for dissolving the solid free-radical initiator2-C5Alcohols, C2-C4Ethers and C3-C5At least one of ketones, more preferably C2-C4Alcohols, C2-C3Ethers and C3-C5At least one ketone, and most preferably at least one of ethanol, diethyl ether and acetone. The mass content of the organic solvent is preferably 1-35% of the mass of the copolymerized polypropylene.
In the preparation method of the aromatic olefin graft-modified polypropylene of the present invention, the definitions of the styrene monomer and the copolymerized polypropylene are the same as those described above, and thus, the details are not repeated herein.
According to the present invention, the preparation method of the aromatic olefin graft-modified polypropylene can be selected from one of the following ways:
in a first aspect, the preparation method comprises the steps of:
a. placing the copolymerization polypropylene 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 dispersant, heating the reaction system to the grafting reaction temperature, and carrying out grafting reaction;
e. after the reaction is finished, optionally filtering (in the case of using an aqueous phase dispersant), and drying to obtain the aromatic olefin graft modified polypropylene.
More specifically, the preparation method comprises the following steps:
a. placing the copolymerization polypropylene 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 the polypropylene copolymer, and stirring and mixing;
c. adding 0-30 parts of an 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 graft polymerization temperature of 30-130 ℃, and reacting for 0.5-10 hours;
e. after the reaction is finished, optionally filtering (in the case of using an aqueous phase dispersant), and drying to obtain the aromatic olefin graft modified polypropylene.
In a second mode, the preparation method comprises the following steps:
a. placing the copolymerization polypropylene 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 styrene monomer, optionally adding an interfacial agent, and optionally swelling the reaction system;
e. optionally adding a dispersant, heating the reaction system to the grafting reaction temperature, and carrying out grafting reaction;
f. after the reaction is finished, optionally filtering (in the case of using an aqueous phase dispersant), and drying to obtain the aromatic olefin graft modified polypropylene.
More specifically, the preparation method comprises the following steps:
a. placing the copolymerization polypropylene 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. inert gas purging 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 graft polymerization temperature of 30-130 ℃, and reacting for 0.5-10 hours;
f. after the reaction is finished, optionally filtering (in the case of using an aqueous phase dispersant), and drying to obtain the aromatic olefin graft modified polypropylene.
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 a stripping agent 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) obtained directly by graft-reacting a copolymerized polypropylene and a styrene-based monomer and a purified product of the aromatic olefin graft-modified polypropylene obtained by further purifying the product, and therefore, the production process of the present invention optionally includes 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 favorable for obtaining the aromatic olefin graft 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%, and more preferably 35 to 80%. The concept of grafting efficiency is well known to those skilled in the art and refers to the amount of styrene grafted per total amount of styrene charged to the reaction.
The inert gas of the present invention may be any of 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 graft modified polypropylene, wherein the aromatic olefin graft modified polypropylene is the aromatic olefin graft modified polypropylene; the aromatic olefin graft-modified polypropylene used in the present invention may be used directly as a base material for an insulating material or directly as an insulating material, and the content of the aromatic olefin graft-modified polypropylene may be 20 to 100% by weight, preferably 40 to 100% by weight, more preferably 60 to 100% by weight, further preferably 80 to 100% by weight, and still further preferably 90 to 100% by weight, based on the weight of the insulating material. The content of the aromatic olefin graft-modified polypropylene may be specifically 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 91 wt%, 92 wt%, 93 wt%, 94 wt%, 95 wt%, 96 wt%, 97 wt%, 98 wt%, 99 wt%, 100 wt%, based on the weight of the insulating material.
According to the invention, the insulation material is preferably a cable insulation material; further preferably a dc cable insulation. More specifically, the insulation material is a cable insulation material.
The aromatic olefin graft modified polypropylene material can give consideration to mechanical property and electrical property at higher working temperature, and is suitable for working conditions of high temperature and high operating field intensity. In addition, compared with the material added with the small molecule additive, the aromatic olefin graft modified polypropylene material avoids performance reduction caused by small molecule 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 in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
In the following examples and comparative examples:
1. determination of comonomer content in the copolymerized Polypropylene:
comonomer content was determined by quantitative Fourier Transform Infrared (FTIR) spectroscopy. By quantitative Nuclear Magnetic Resonance (NMR) lightThe spectra were calibrated for correlation with the determined comonomer content. The basis weight13The calibration method for the results obtained by C-NMR spectroscopy was carried out according to a conventional method in the art.
2. Determination of xylene soluble content in the copolymerized polypropylene, comonomer content in the soluble and intrinsic viscosity ratio of the soluble/copolymerized polypropylene:
the test was carried out using a CRYST-EX instrument from Polymer Char corporation. Heating to 150 deg.C with trichlorobenzene solvent, dissolving, holding at constant temperature for 90min, sampling, testing, cooling to 35 deg.C, holding at constant temperature for 70min, and sampling.
3. Determination of weight average molecular weight of the copolymerized Polypropylene:
the measurement was carried out by high temperature GPC using PL-GPC 220 type gel permeation chromatography of Polymer Laboratory, and the sample was dissolved in 1,2, 4-trichlorobenzene at a concentration of 1.0 mg/ml. The test temperature was 150 ℃ and the solution flow rate was 1.0 ml/min. A standard curve is established by taking the molecular weight of the polystyrene as an internal reference, and the molecular weight distribution of the sample are calculated according to the outflow time.
4. Determination of the melt flow Rate MFR:
measured at 230 ℃ under a load of 2.16kg using a melt index apparatus of type 7026 from CEAST, according to the method specified in GB/T3682-2018.
5. Determination of the melting temperature Tm:
the melting process and the crystallization process of the material were analyzed by a differential scanning calorimeter. The specific operation is as follows: under the protection of nitrogen, 5-10 mg of a sample is measured from 20 ℃ to 200 ℃ by a three-stage temperature rise and fall measuring method, and the melting and crystallization processes of the material are reflected by the change of heat flow, so that the melting temperature Tm is calculated.
6. Determination of the grafting efficiency GE, parameter M1:
and (2) putting 2-4 g of the grafting product into a Soxhlet extractor, extracting with ethyl acetate for 24 hours, removing unreacted monomers and homopolymers thereof to obtain a pure grafting product, drying and weighing, and calculating a parameter M1 and a grafting efficiency GE.
The parameter M1 represents the content of structural units derived from styrenic monomers in the aromatic olefin graft-modified polypropylene material, and in the present invention, the calculation formulas of M1 and GE are as follows:
in the above formula, w0Is the mass of the PP matrix; w is a1Is the mass of the grafted product before extraction; w is a2Is the mass of the grafted product after extraction; w is a3Is the mass of styrene added.
7. Measurement of 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 carried out according to the method defined in GB/T1408-2006.
9. Determination of tensile Strength:
the measurement was carried out according to the method defined 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 defined in GB/T1040-.
12. Determination of dielectric constant and dielectric loss tangent:
the measurement was carried out according to the method defined in GB/T1409-.
The starting materials used in the examples are described in table a below.
TABLE A
Copolymerized polypropylene 1: the copolymer polypropylene used in example 1.
Copolymerized polypropylene 2: the copolymer polypropylene used in example 2.
Copolymerized polypropylene 3: the copolymer polypropylene used in example 3.
Copolymerized polypropylene 4: the copolymer polypropylene used in example 4.
Copolymerized polypropylene 5: the copolymer polypropylene used in example 5.
Copolymerized polypropylene 6: the copolymer polypropylene used in example 6.
Example 1
Selecting basic copolymerized polypropylene powder with the following characteristics: comonomer ethylene content 18.1 wt%, xylene solubles content 48.7 wt%, comonomer content in solubles 31.9 wt%, solubles/polypropylene intrinsic viscosity ratio 0.89, weight average molecular weight 34.3X 104g/mol, MFR of 1.21g/10min at 230 ℃ under a load of 2.16kg, Tm of 143.4 ℃, breakdown field strength (90 ℃) of 236kV/mm, and direct current volume resistivity (90 ℃, 15kV/mm) of 1.16E 13. omega. m, and fine powder of less than 40 mesh was removed by sieving. Weighing 2.0kg of the basic polypropylene copolymer powder, adding the powder into a 10L reaction kettle with mechanical stirring, sealing the reaction system, and removing oxygen by nitrogen replacement. Adding 2g of dibenzoyl peroxide and 100g of styrene, stirring and mixing for 60min, swelling for 4 hours at 40 ℃, heating to 95 ℃, and reacting for 4 hours. After the reaction is finished, nitrogen is blown and cooled to obtain a polypropylene-g-styrene material product C1. The product obtained 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: comonomer ethylene content 14.7 wt%, xylene solubles content 41.7 wt%, comonomer content in solubles 34.5 wt%, solubles/polypropylene intrinsic viscosity ratio 0.91, weight average molecular weight 36.6X 104g/mol at 230 ℃ under a load of 2.16kgThe MFR of (1.54 g/10 min), Tm of 164.9 ℃, the breakdown field strength (90 ℃) of 248kV/mm, and the direct current volume resistivity (90 ℃, 15kV/mm) of 7.25E 12. omega. m, and the fine powder of less than 40 mesh was removed by sieving. Weighing 2.0kg of the basic polypropylene copolymer powder, adding the powder into a 10L reaction kettle with mechanical stirring, sealing the reaction system, and removing oxygen by nitrogen replacement. Adding 2.8g of lauroyl peroxide and 150g of styrene, stirring and mixing for 60min, swelling for 2 hours at 60 ℃, heating to 90 ℃, and reacting for 4 hours. After the reaction is finished, nitrogen is blown and cooled to obtain a polypropylene-g-styrene material product C2. The product obtained 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: comonomer ethylene content 20.1 wt%, xylene solubles content 66.1 wt%, comonomer content in solubles 29.5 wt%, solubles/polypropylene intrinsic viscosity ratio 1.23, weight average molecular weight 53.8X 104g/mol, MFR of 0.51g/10min at 230 ℃ under a load of 2.16kg, Tm of 142.5 ℃, breakdown field strength (90 ℃) of 176kV/mm, and direct current volume resistivity (90 ℃, 15kV/mm) of 5.63E 12. omega. m, and fine powder of less than 40 mesh was removed by sieving. Weighing 2.0kg of the basic polypropylene copolymer powder, adding the powder into a 10L reaction kettle with mechanical stirring, sealing the reaction system, and removing oxygen by nitrogen replacement. Adding 1.5g of lauroyl peroxide and 50g of styrene, stirring and mixing for 60min, swelling at 60 ℃ for 2 hours, heating to 85 ℃, and reacting for 4 hours. After the reaction is finished, nitrogen is blown and cooled to obtain a polypropylene-g-styrene material product C3. The product obtained 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: comonomer ethylene content 9.3 wt%, xylene solubles content 21.0 wt%, comonomer content in solubles 35.4 wt%, solubles/polypropylene intrinsic viscosity ratio 1.68, weight average molecular weight 30.4X 104g/mol, MFR of 5.69g/10min at 230 ℃ under a load of 2.16kg, Tm of 163.0 ℃, breakdown field strength (90 ℃) of 288kV/mm, DC volume resistivity (90 ℃, 15kV/mm)At 1.32E 13. omega. m, and fine powder of less than 40 mesh was removed by sieving. Weighing 2.0kg of the basic polypropylene copolymer powder, adding the powder into a 10L reaction kettle with mechanical stirring, sealing the reaction system, and removing oxygen by nitrogen replacement. Adding 7.0g of tert-butyl peroxy (2-ethylhexanoate) and 200g of styrene, stirring and mixing for 60min, swelling for 1 hour at 60 ℃, heating to 90 ℃, and reacting for 4 hours. After the reaction is finished, nitrogen is blown and cooled to obtain a polypropylene-g-styrene material product C4. The product obtained 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 4.8 wt%, xylene solubles content 19.2 wt%, comonomer content in solubles 17.6 wt%, solubles/polypropylene intrinsic viscosity ratio 1.04, weight average molecular weight 29.2X 104g/mol, MFR of 5.37g/10min at 230 ℃ under a load of 2.16kg, Tm of 163.3 ℃, breakdown field strength (90 ℃) of 322kV/mm, and direct current volume resistivity (90 ℃, 15kV/mm) of 1.36E 13. omega. m, and fine powder of less than 40 mesh was removed by sieving. Weighing 2.0kg of the basic polypropylene copolymer powder, adding the powder into a 10L reaction kettle with mechanical stirring, sealing the reaction system, and removing oxygen by nitrogen replacement. Dissolving 4.0g of dibenzoyl peroxide in 100g of acetone, adding the obtained acetone solution into a reaction system, heating to 40 ℃, purging with nitrogen for 30min to remove acetone, adding 100g of p-methylstyrene, stirring and mixing for 30min, swelling at 60 ℃ for 1 hour, heating to 100 ℃, and reacting for 1 hour. After the reaction is finished, nitrogen is blown and cooled to obtain a polypropylene-g-p-methylstyrene material product C5. The product obtained 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: comonomer ethylene content 12.6 wt%, xylene solubles content 30.6 wt%, comonomer content in solubles 43.6 wt%, solubles/polypropylene intrinsic viscosity ratio 1.84, weight average molecular weight 27.1X 104g/mol, MFR of 8.46g/10min at 230 ℃ under a load of 2.16kg, Tm of 162.0 ℃, breakdown field strength (90℃)) 261kV/mm, and a direct current volume resistivity (90 ℃, 15kV/mm) of 9E 12. omega. m, and fine powder of less than 40 mesh was removed by sieving. Weighing 2.0kg of the basic polypropylene copolymer powder, adding the powder into a 10L reaction kettle with mechanical stirring, sealing the reaction system, and removing oxygen by nitrogen replacement. Dissolving 3.0g of dibenzoyl peroxide in 100g of styrene and 100g of interfacial agent toluene to form a solution, stirring and mixing the solution for 30min, swelling at 60 ℃ for 0.5 h, adding 4kg of dispersant water, heating to 110 ℃, and reacting for 0.5 h. After the reaction is finished, cooling, filtering to remove the dispersant water, and vacuum drying at 70 ℃ for 10 hours to obtain a polypropylene-g-styrene material product C6. The product obtained was tested for various performance parameters and the results are shown in table 1.
Example 7
2.0kg of the basic polypropylene copolymer powder obtained in example 1 was weighed, and the obtained powder was put into a 10L reactor equipped with a mechanical stirrer, and the reaction system was closed and deoxygenated by nitrogen displacement. Adding 0.6g of dibenzoyl peroxide and 30g of styrene, stirring and mixing for 60min, swelling for 4 hours at 40 ℃, heating to 95 ℃, and reacting for 4 hours. After the reaction is finished, nitrogen is blown and cooled to obtain a polypropylene-g-styrene material product C7. The product obtained was tested for various performance parameters and the results are shown in table 1.
Example 8
2.0kg of the basic polypropylene copolymer powder obtained in example 1 was weighed, and the obtained powder was put into a 10L reactor equipped with a mechanical stirrer, and the reaction system was closed and deoxygenated by nitrogen displacement. Adding 4g of dibenzoyl peroxide and 200g of styrene, stirring and mixing for 60min, swelling for 4 hours at 40 ℃, heating to 95 ℃, and reacting for 4 hours. After the reaction is finished, nitrogen is blown and cooled to obtain a polypropylene-g-styrene material product C8. The product obtained was tested for various performance parameters and the results are shown in table 1.
Comparative example 1
Weighing T30S powder (breakdown field strength (90 ℃) is 347kV/mm, direct current volume resistivity (90 ℃, 15kV/mm) is 1.18E13 omega.m) which is sieved to remove fine powder smaller than 40 meshes, adding 2.0kg of the powder into a 10L reaction kettle with mechanical stirring, sealing the reaction system, and removing oxygen by nitrogen replacement. Adding 2g of dibenzoyl peroxide and 100g of styrene, stirring and mixing for 60min, swelling for 4 hours at 40 ℃, heating to 95 ℃, and reacting for 4 hours. After the reaction is finished, nitrogen is blown and cooled to obtain a polypropylene-g-styrene material product D1. The product obtained 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: comonomer ethylene content 18.1 wt%, xylene solubles content 48.7 wt%, comonomer content in solubles 31.9 wt%, solubles/polypropylene intrinsic viscosity ratio 0.89, weight average molecular weight 34.3X 104g/mol, MFR of 1.21g/10min at 230 ℃ under a load of 2.16kg, Tm of 143.4 ℃, breakdown field strength (90 ℃) of 236kV/mm, and direct current volume resistivity (90 ℃, 15kV/mm) of 1.16E 13. omega. m, and fine powder of less than 40 mesh was removed by sieving. Weighing 2.0kg of the basic polypropylene copolymer powder, adding the powder into a 10L reaction kettle with mechanical stirring, sealing the reaction system, and removing oxygen by nitrogen replacement. Adding 12g of dibenzoyl peroxide and 600g of styrene, stirring and mixing for 60min, swelling for 4 hours at 40 ℃, heating to 95 ℃, and reacting for 4 hours. After the reaction is finished, nitrogen is blown and cooled to obtain a polypropylene-g-styrene material product D2. The product obtained 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: comonomer ethylene content 18.1 wt%, xylene solubles content 48.7 wt%, comonomer content in solubles 31.9 wt%, solubles/polypropylene intrinsic viscosity ratio 0.89, weight average molecular weight 34.3X 104g/mol, MFR of 1.21g/10min at 230 ℃ under a load of 2.16kg, Tm of 143.4 ℃, breakdown field strength (90 ℃) of 236kV/mm, and direct current volume resistivity (90 ℃, 15kV/mm) of 1.16E 13. omega. m, and fine powder of less than 40 mesh was removed by sieving. 2.0kg of the above-mentioned basic copolymerized polypropylene powder was weighed and mixed with 100g of polystyrene GPPS-123, and mixed by a screw extruder to obtain a blend D3. The product obtained was tested for various performance parameters and the results are shown in table 1.
Comparing the data of example 1 and comparative example 1, it can be seen that the flexural modulus of the polypropylene-g-styrene material product obtained by using the powder of T30S as the base powder is too high, the mechanical properties of the material are poor, and the processing requirements of the insulating material can not be met.
Comparing the data of example 1 and comparative example 2, it can be seen that the excessive addition of styrene monomer (excessive M1 value) can cause the elongation at break of the obtained polypropylene-g-styrene material product to be greatly reduced, thus affecting the mechanical properties of the material, and the breakdown field strength and the volume resistivity of the material to be reduced, thus affecting the electrical properties of the material.
Comparing the data of example 1 and comparative example 3 shows that the mode of blending polystyrene leads to the great reduction of the breakdown field strength and the volume resistivity of the material, and the electrical property of the material is greatly influenced.
In summary, it can be seen from the data in table 1 that the aromatic olefin graft modified polypropylene material of the present invention has good mechanical properties due to the large reduction of the flexural modulus, and the breakdown field strength of the graft product is increased compared to the copolymerized polypropylene without grafted styrene monomer, which indicates that the aromatic olefin graft modified polypropylene material of the present invention has good electrical properties at the same time.
Furthermore, 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 present invention meets the necessary requirements for insulation.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not 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 described embodiments.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Claims (20)
1. 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 copolymerized polypropylene and structural units derived from a styrenic monomer; the content of the structural units derived from styrene monomers and in a grafted state in the aromatic olefin graft-modified polypropylene is 0.5-14 wt%, preferably 1-7.5 wt%, and more preferably 1.5-5 wt%, based on the weight of the aromatic olefin graft-modified polypropylene.
2. Use according to claim 1, wherein the insulation material is a cable insulation material; preferably a dc cable insulation.
3. Use according to claim 2, wherein the insulation material is a cable insulation material.
4. Use according to any one of claims 1 to 3, 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, preferably 0.05-20 g/10min, further preferably 0.1-10 g/10min, more preferably 0.2-8 g/10min, and further preferably 0.2-5 g/10 min; the flexural modulus is 10-1250 MPa, preferably 20-1000 MPa, and more preferably 50-600 MPa; the elongation at break is more than or equal to 200 percent, and preferably the elongation at break is more than or equal to 300 percent; the tensile strength is more than 5MPa, preferably 10-40 MPa.
5. Use according to any one of claims 1 to 3, wherein the aromatic olefin graft-modified polypropylene has at least one of the following characteristics:
the working temperature of the aromatic olefin graft modified polypropylene is more than or equal to 90 ℃, and preferably 90-160 ℃;
the breakdown field strength E of the aromatic olefin graft-modified polypropylene at 90 ℃gThe voltage is more than or equal to 200kV/mm, and preferably 200-800 kV/mm;
the breakdown field strength E of the aromatic olefin graft-modified polypropylene at 90 ℃gThe change rate of breakdown field intensity delta E/E obtained by dividing the difference delta E of the breakdown field intensity E of the copolymerized polypropylene at 90 ℃ by the breakdown field intensity E of the copolymerized polypropylene at 90 ℃ is more than 1.5%, preferably 1.6-40%, more preferably 5-30%, and further preferably 10-20%;
-the direct volume resistivity p of the aromatic olefin graft-modified polypropylene at 90 ℃ and 15kV/mm field strengthvg≥1.0×1013Ω · m, preferably 1.5 × 1013Ω·m～1.0×1020Ω·m；
-the direct volume resistivity p of the aromatic olefin graft-modified polypropylene at 90 ℃ and 15kV/mm field strengthvgThe direct current volume resistivity rho of the copolymerized polypropylene at 90 ℃ and 15kV/mm field intensityvRatio of (p)vg/ρvMore than 1, preferably 1.5 to 50, more preferably 2 to 20, and further preferably 3 to 10;
-the aromatic olefin graft modified polypropylene has a dielectric constant of greater than 2.0, preferably 2.1 to 2.5 at 90 ℃ and 50 Hz.
6. Use according to any one of claims 1 to 3, wherein the co-polypropylene has at least one of the following characteristics: the content of the comonomer is 0.5 to 40 mol%, preferably 0.5 to 30 mol%, preferably 4 to 25 wt%, and more preferably 4 to 22 wt%; the xylene soluble content is 2 to 80 wt%, preferably 18 to 75 wt%, more preferably 30 to 70 wt%, and still more preferably 30 to 67 wt%; the content of the comonomer in the soluble substance is 10-70 wt%, preferably 10-50 wt%, more preferably 20-35 wt%; the intrinsic viscosity ratio of the soluble matter to the polypropylene is 0.3 to 5, preferably 0.5 to 3, and more preferably 0.8 to 1.3.
7. Use according to any one of claims 1 to 3, 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, preferably 0.05-35 g/10min, further preferably 0.5-15 g/10min, and more preferably 0.5-8 g/10 min; the melting temperature Tm is more than 100 ℃, preferably 110-180 ℃, more preferably 110-170 ℃, further preferably 120-170 ℃, and further preferably 120-166 ℃; weight average molecular weight of 20X 104～60×104g/mol。
8. Use according to any one of claims 1 to 3, wherein the comonomer of the copolymeric polypropylene is selected from C other than propylene2-C8At least one of alpha-olefins of (a); preferably, the comonomer of the copolymerized polypropylene is selected from at least one of ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene and 1-octene; further preferably, the comonomer of the copolymerized polypropylene is ethylene and/or 1-butene; further preferably, the co-polypropylene consists of propylene and ethylene.
9. The use according to any one of claims 1 to 3, wherein the styrenic monomer is selected from at least one of a monomer having a structure represented by formula I, a monomer having a structure represented by formula II, and a monomer having a structure represented by formula III;
in the formula I, R1、R2、R3Each independently selected from H, substituted or unsubstituted C1-C6Alkyl groups of (a); r4-R8Each independently selected from H, halogen, hydroxyl, amino, phosphate, sulfonic acid, substituted or unsubstituted C1-C12Alkyl, substituted or unsubstituted C3-C12A cycloalkyl group of,Substituted or unsubstituted C1-C12Alkoxy, substituted or unsubstituted C1-C12Ester group of (1), substituted or unsubstituted C1-C12The substituted group is selected from halogen, hydroxyl, amino, phosphate, sulfonic group, C1-C12Alkyl of (C)3-C12Cycloalkyl of, C1-C12Alkoxy group of (C)1-C12Ester group of (1), C1-C12An amine group of (a); preferably, R1、R2、R3Each independently selected from H, substituted or unsubstituted C1-C3Alkyl of R4-R8Each independently selected from H, halogen, hydroxy, amino, substituted or unsubstituted C1-C6Alkyl, substituted or unsubstituted C1-C6Alkoxy group of (a);
in the formula II, R1、R2、R3Each independently selected from H, substituted or unsubstituted C1-C6Alkyl groups of (a); r4-R10Each independently selected from H, halogen, hydroxyl, amino, phosphate, sulfonic acid, substituted or unsubstituted C1-C12Alkyl, substituted or unsubstituted C3-C12Cycloalkyl, substituted or unsubstituted C1-C12Alkoxy, substituted or unsubstituted C1-C12Ester group of (1), substituted or unsubstituted C1-C12The substituted group is selected from halogen, hydroxyl, amino, phosphate, sulfonic group, C1-C12Alkyl of (C)3-C12Cycloalkyl of, C1-C12Alkoxy group of (C)1-C12Ester group of (1), C1-C12An amine group of (a); preferably, R1、R2、R3Each independently selected from H, substituted or unsubstituted C1-C3Alkyl of R4-R10Each independently selected from H, halogen, hydroxy, amino, substituted or unsubstituted C1-C6Alkyl, substituted or unsubstituted C1-C6The substituted radical is selected from halogen, hydroxyl, amino, C1-C6Alkyl of (C)1-C6Alkoxy group of (a);
in the formula III, R1’、R2’、R3' each is independently selected from H, substituted or unsubstituted C1-C6Alkyl groups of (a); r4’-R10' each is independently selected from H, halogen, hydroxyl, amino, phosphate, sulfonate, substituted or unsubstituted C1-C12Alkyl, substituted or unsubstituted C3-C12Cycloalkyl, substituted or unsubstituted C1-C12Alkoxy, substituted or unsubstituted C1-C12Ester group of (1), substituted or unsubstituted C1-C12The substituted group is selected from halogen, hydroxyl, amino, phosphate, sulfonic group, C1-C12Alkyl of (C)3-C12Cycloalkyl of, C1-C12Alkoxy group of (C)1-C12Ester group of (1), C1-C12An amine group of (a); preferably, R1’、R2’、R3' each is independently selected from H, substituted or unsubstituted C1-C3Alkyl of R4’-R10' each is independently selected from H, halogen, hydroxy, amino, substituted or unsubstituted C1-C6Alkyl, substituted or unsubstituted C1-C6The substituted radical is selected from halogen, hydroxyl, amino, C1-C6Alkyl of (C)1-C6Alkoxy group of (a);
preferably, the styrenic monomer is selected from the group consisting of styrene, alpha-methylstyrene, 1-vinylnaphthalene, 2-at least one of 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; the substituted group is preferably selected from the group consisting of halogen, hydroxy, amino, phosphate, sulfonate, C1-C8Straight chain alkyl group of (1), C3-C8Branched alkyl or cycloalkyl of, C1-C6Linear alkoxy of (2), C3-C8Branched or cyclic alkoxy of (A), C1-C8Linear ester group of (1), C3-C8A branched or cyclic ester group of1-C8And C is a linear amino group3-C8At least one of a branched amine group or a cyclic amine group of (a);
more preferably, the styrenic monomer is selected from at least one of styrene, α -methylstyrene, 2-methylstyrene, 3-methylstyrene and 4-methylstyrene.
10. The use according to any one of claims 1 to 3, wherein the aromatic olefin graft-modified polypropylene is prepared by solid phase grafting reaction of a copolymerized polypropylene and a styrene monomer.
11. The use according to claim 10, wherein the preparation method of the aromatic olefin graft-modified polypropylene comprises: and (2) carrying out grafting reaction on the reaction mixture comprising the copolymerized polypropylene and the styrene monomer in the presence of inert gas to obtain the aromatic olefin graft modified polypropylene.
12. Use according to claim 11, wherein the reaction mixture further comprises a free radical initiator;
preferably, the radical initiator is selected from peroxide-based radical initiators and/or azo-based radical initiators;
the peroxide-based radical initiator is preferably at least one selected from the group consisting 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 radical initiator is preferably azobisisobutyronitrile and/or azobisisoheptonitrile.
13. Use according to claim 12, wherein the mass ratio of the radical initiator to the styrenic monomer is 0.1 to 10:100, preferably 0.5 to 5: 100.
14. The use according to claim 11, wherein the mass ratio of the styrene monomer to the copolymerized polypropylene is 0.5-16: 100, preferably 1-12: 100, and more preferably 2-10: 100.
15. Use according to claim 11, wherein the temperature of the grafting reaction is between 30 and 130 ℃, preferably between 60 and 120 ℃; the time is 0.5 to 10 hours, preferably 1 to 5 hours.
16. Use according to any one of claims 11 to 15, wherein the reaction mixture further comprises at least one of the following components: the modified polypropylene composite material comprises a dispersing agent, an interface agent and an organic solvent, wherein the mass content of the dispersing agent is 50-300% of the mass of the copolymerized polypropylene, the mass content of the interface agent is 1-30% of the mass of the copolymerized polypropylene, and the mass content of the organic solvent is 1-35% of the mass of the copolymerized polypropylene.
17. Use according to claim 16, wherein the preparation method comprises the following steps:
a. placing the copolymerization polypropylene 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 dispersant, heating the reaction system to the grafting reaction temperature, and carrying out grafting reaction;
e. and after the reaction is finished, optionally filtering and drying to obtain the aromatic olefin graft modified polypropylene.
18. Use according to claim 16, wherein the preparation method comprises the following steps:
a. placing the copolymerization polypropylene 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 styrene monomer, optionally adding an interfacial agent, and optionally swelling the reaction system;
e. optionally adding a dispersant, heating the reaction system to the grafting reaction temperature, and carrying out grafting reaction;
f. and after the reaction is finished, optionally filtering and drying to obtain the aromatic olefin graft modified polypropylene.
19. An insulating material comprising an aromatic olefin graft-modified polypropylene, wherein the aromatic olefin graft-modified polypropylene is the aromatic olefin graft-modified polypropylene according to any one of claims 1 to 18; the content of the aromatic olefin graft-modified polypropylene is 20 to 100 wt%, preferably 40 to 100 wt%, more preferably 60 to 100 wt%, further preferably 80 to 100 wt%, and further preferably 90 to 100 wt%, based on the weight of the insulating material.
20. An insulation material as claimed in claim 19, wherein the insulation material is cable insulation; preferably a dc cable insulation;
preferably, the insulation material is a cable insulation layer material.
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| CN116063785A (en) * | 2021-10-30 | 2023-05-05 | 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 |
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| 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 |
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