CN113563527A - Graft modified polypropylene material and preparation method and application thereof - Google Patents
Graft modified polypropylene material and preparation method and application thereof Download PDFInfo
- Publication number
- CN113563527A CN113563527A CN202011195771.2A CN202011195771A CN113563527A CN 113563527 A CN113563527 A CN 113563527A CN 202011195771 A CN202011195771 A CN 202011195771A CN 113563527 A CN113563527 A CN 113563527A
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- China
- Prior art keywords
- acrylate
- graft
- modified polypropylene
- polypropylene
- meth
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- Granted
Links
- -1 polypropylene Polymers 0.000 title claims abstract description 198
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 191
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 190
- 239000000463 material Substances 0.000 title claims abstract description 102
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 111
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 87
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000000126 substance Substances 0.000 claims abstract description 20
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000008096 xylene Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims description 81
- 150000003254 radicals Chemical class 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 26
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical group CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 25
- 239000003999 initiator Substances 0.000 claims description 24
- 230000015556 catabolic process Effects 0.000 claims description 22
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 21
- 239000005977 Ethylene Substances 0.000 claims description 21
- 239000002270 dispersing agent Substances 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 14
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 13
- 239000011261 inert gas Substances 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 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 10
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 10
- 239000011541 reaction mixture Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000000155 melt Substances 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 7
- 230000008961 swelling Effects 0.000 claims description 7
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 claims description 6
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 6
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 6
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 6
- 238000007334 copolymerization reaction Methods 0.000 claims description 6
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 150000002978 peroxides Chemical group 0.000 claims description 5
- 239000004711 α-olefin Substances 0.000 claims description 5
- 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
- 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
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 3
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 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
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 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
- 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
- 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
- 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
- 239000002195 soluble material Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 42
- 239000000047 product Substances 0.000 description 42
- 239000000843 powder Substances 0.000 description 41
- 229920001577 copolymer Polymers 0.000 description 27
- 229910052757 nitrogen Inorganic materials 0.000 description 21
- 229920005606 polypropylene copolymer Polymers 0.000 description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 11
- 239000011159 matrix material Substances 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 239000011810 insulating material Substances 0.000 description 10
- 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
- 238000009413 insulation Methods 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
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 229920005604 random copolymer Polymers 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 238000000605 extraction Methods 0.000 description 4
- 239000002105 nanoparticle Substances 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
- 230000008901 benefit Effects 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
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 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
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920001384 propylene homopolymer Polymers 0.000 description 3
- 238000012360 testing method Methods 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
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 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
- 150000001555 benzenes Chemical class 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
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 238000010559 graft polymerization reaction Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 102220040412 rs587778307 Human genes 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 230000002522 swelling effect Effects 0.000 description 2
- 238000001291 vacuum drying Methods 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
- 239000004593 Epoxy Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes 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
- 230000005540 biological transmission Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 125000004855 decalinyl group Chemical group C1(CCCC2CCCCC12)* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004870 electrical engineering 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
- 239000012774 insulation material Substances 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 229920002454 poly(glycidyl methacrylate) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 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
- 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
- 229920002554 vinyl polymer Polymers 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
Landscapes
- 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 polymers, and relates to a graft modified polypropylene material, and a preparation method and application thereof. The graft-modified polypropylene material comprises structural units derived from copolymerized polypropylene and structural units derived from an acrylate monomer and optionally an acrylic monomer; based on the weight of the graft modified polypropylene material, the graft modified polypropylene material contains 0.3-7 wt% of structural units which are derived from acrylate monomers and optional acrylic monomers and are in a graft state; the copolymerized polypropylene has the following characteristics: the content of the comonomer is 0.5-40 mol%; the content of xylene soluble substances is 2-80 wt%. The grafted modified polypropylene material of the invention can give consideration to both mechanical property and electrical property at higher working temperature.
Description
Technical Field
The invention belongs to the field of polymers, and particularly relates to a graft modified polypropylene material, a preparation method of the graft modified polypropylene material, the graft modified polypropylene material prepared by the preparation method, and application of the graft modified polypropylene material.
Background
The high molecular polymer material has excellent electrical insulating property and low manufacturing cost, and is widely applied as an insulating material of power equipment in the field of electrical engineering and the power industry. Among them, the simple-structured polymer plastic insulating materials represented by polyethylene are widely used, and the cross-linked polyethylene, copolymer polyolefin and rubber materials developed on the basis of the simple-structured polymer plastic insulating materials are widely used for insulation of motors and transformers, insulation of lines and insulation of circuit breakers. The vinyl polymer insulating material has better mechanical property and thermal property, excellent electrical insulating property and lower price, and is a mature insulating material developed in engineering.
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. With this trend, the conventional polyethylene-based insulation has failed to meet higher long-term operating temperatures and electric fields (the maximum long-term service temperature of the currently shipped crosslinked polyethylene insulation is 70 ℃). 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.
Polypropylene material, as a simple-structured polymer plastic, has all the advantages of polyethylene material. Compared with polyethylene, polypropylene has better electrical insulation performance and higher melting point, and is expected to adapt to more severe working environment as an insulation material. However, polypropylene has slightly inferior mechanical properties to polyethylene, is brittle especially at low temperatures, and cannot be used directly as an insulating material. Therefore, for polypropylene materials, it is necessary to modify the materials to achieve comprehensive control of electrical, mechanical and thermal properties, so as to maintain good insulation performance at higher temperature and electric field.
A great deal of literature and data show that the modification by doping the nano particles in the polypropylene material is an effective way for improving the electrical insulation performance. However, in the actual preparation, the difficulty that the doping behavior of the nanoparticles is difficult to control is encountered, so that the problem that the nanoparticles are easy to agglomerate and the insulating property is reduced is caused, and the wide application of the nanoparticles in the actual engineering is limited.
Therefore, a novel modified polypropylene material which has obvious insulating property regulation and control capability, can give consideration to mechanical property and thermal property, has stable performance and convenient preparation and is suitable for practical application of engineering needs to be searched.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a novel graft modified polypropylene material which 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.
A first aspect of the present invention provides a graft-modified polypropylene material comprising structural units derived from a copolypropylene and structural units derived from an acrylate monomer and optionally an acrylic monomer; based on the weight of the graft modified polypropylene material, the content of structural units derived from acrylate monomers and optional acrylic monomers in a grafted state in the graft modified polypropylene material is 0.3-7 wt%, preferably 0.8-5 wt%;
the copolymerized polypropylene has the following characteristics: the content of the comonomer is 0.5 to 40 mol%, preferably 0.5 to 30 mol%, and more preferably 4 to 25 mol%; the content of xylene soluble substances is 2-80 wt%; the content of the comonomer in the soluble substance is 10-70 wt%; the ratio of the soluble substance to the polypropylene is 0.3 to 5.
In the present invention, the "structural unit" means that it is a part of the graft-modified polypropylene material, 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 acrylate monomers and optionally acrylic monomers" refers to products formed from acrylate monomers or to mixtures of products formed from acrylate monomers and products formed from acrylic monomers, including both in "radical" and "monomer" form, as well as in "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 the acrylate monomer and the optional acrylic monomer "in the grafted state" refer to the structural units derived from the acrylate monomer and the optional acrylic monomer which form a covalent bond (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 graft modified polypropylene material is prepared by a graft reaction, preferably a solid phase graft reaction, of a copolymer polypropylene and an acrylate monomer and optionally an acrylic 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 acrylate monomer and optional acrylic monomer may polymerize with each other or with each other to form a quantity of ungrafted polymer. The term "graft-modified polypropylene material" in the present invention includes both a product (crude product) directly obtained by graft-reacting a copolymer polypropylene with an acrylic monomer and optionally an acrylic monomer, and a graft-modified polypropylene pure product obtained by further purifying the product.
According to the present invention, preferably, the graft-modified polypropylene material 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, and more preferably 0.2-8 g/10 min; the flexural modulus is 10-1100 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 graft-modified polypropylene material has at least one of the following characteristics:
the working temperature of the grafted modified polypropylene material is more than or equal to 90 ℃, and preferably 90-160 ℃;
-said connectionBreakdown field intensity E of branch modified polypropylene material at 90 DEG CgThe voltage is more than or equal to 180kV/mm, and preferably 180-800 kV/mm;
-the breakdown field strength E of the graft-modified polypropylene material 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 2%, preferably 2.5-50%, more preferably 4-35%, and further preferably 5-25%;
-the direct volume resistivity p of the graft-modified polypropylene material at 90 ℃ at a field strength of 15kV/mmvg≥1.0×1013Ω · m, preferably 1.5 × 1013Ω·m～1.0×1020Ω·m；
-the direct volume resistivity p of the graft-modified polypropylene material at 90 ℃ at a field strength of 15kV/mmvgThe direct current volume resistivity rho of the copolymerized polypropylene at 90 ℃ and 15kV/mm field intensityvRatio of (p)vg/ρvMore than 1.5, preferably 1.8-30, more preferably 2-10, and further preferably 2.5-6;
-the dielectric constant of the graft-modified polypropylene material at 90 ℃ and 50Hz is greater than or equal to 2.0, preferably 2.0-2.5.
The acrylate monomer can be any monomer acrylate compound capable of polymerizing through free radicals, and can be at least one of monomers with the structure shown in the formula I;
wherein R is1、R2、R3Each independently selected from H, C1-C6Straight chain alkyl, C3-C6A branched alkyl group; r4Selected from the following substituted or unsubstituted groups: c1-C20Straight chain alkyl, C3-C20Branched alkyl radical, C3-C12Cycloalkyl radical, C3-C12Epoxyalkyl, C3-C12Epoxy resinAn alkyl group, the substituted group being selected from at least one of halogen, amino and hydroxyl.
Preferably, the acrylate-based monomer is at least one selected from the group consisting of methyl (meth) acrylate, sec-butyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, isooctyl (meth) acrylate, dodecyl (meth) acrylate, cocooleate, octadecyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, and glycidyl (meth) acrylate.
The acrylic monomer of the present invention may be any monomer acrylic compound capable of undergoing radical polymerization, and may be at least one selected from monomers having a structure represented by formula II;
wherein R is1、R2、R3Each independently selected from H, C1-C6Straight chain alkyl, C3-C6A branched alkyl group.
Preferably, the acrylic monomer is selected from at least one of acrylic acid, methacrylic acid, and 2-ethacrylic acid.
In the invention C3-C12By epoxyalkylalkyl is meant an epoxyalkyl-substituted alkyl group having 3 to 12 carbon atoms, for example, an oxiranylmethyl group.
In the present invention, the structural unit derived from the acrylic monomer may be absent or present together with the structural unit derived from the acrylate monomer, and preferably, the molar ratio of the structural unit derived from the acrylate monomer to the structural unit derived from the acrylic monomer is 1:0 to 2, preferably 1:0.125 to 1.
According to the present invention, the polypropylene copolymer (the base polypropylene in the present invention) is a propylene copolymer containing ethylene or a higher alpha-olefinA polymer 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 comonomer content is 4-25 wt%, preferably 4-22 wt%; the xylene soluble content is 18 to 75 wt%, preferably 30 to 70 wt%, more preferably 30 to 67 wt%; the content of the comonomer in the soluble substance is 10-50 wt%, preferably 20-35 wt%; the intrinsic viscosity ratio of the soluble material to the copolymerized polypropylene is 0.5 to 3, preferably 0.8 to 1.3.
According to the present invention, preferably, the copolymerized polypropylene further has at least one of the following features: the melt flow rate under a load of 2.16kg at 230 ℃ is 0.01 to 60g/10min, preferably 0.05 to 35g/10min, and more preferably 0.5 to 15g/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 graft-modified polypropylene of the present invention has an advantage of being able to withstand higher working temperatures. 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 graft modified polypropylene material can be prepared by a method comprising the following steps: and carrying out solid-phase grafting reaction on a reaction mixture comprising the copolymerized polypropylene and an acrylate monomer and an optional acrylic monomer in the presence of inert gas to obtain the graft modified polypropylene material.
The second aspect of the present invention provides a preparation method of a graft-modified polypropylene material, comprising: in the presence of inert gas, carrying out grafting reaction on a reaction mixture comprising copolymerized polypropylene, an acrylate monomer and an optional acrylic monomer to obtain a graft modified polypropylene material;
wherein the comonomer content of the copolymerized polypropylene is 0.5-40 mol%, preferably 0.5-30 mol%, and more preferably 4-25 mol%; the content of xylene soluble substances is 2-80 wt%; the content of the comonomer in the soluble substance is 10-70 wt%; the characteristic viscosity ratio of the soluble substance to the polypropylene is 0.3-5; the conditions of the grafting reaction are such that: the graft modified polypropylene material contains 0.3-7 wt%, preferably 0.8-5 wt% of structural units derived from acrylate monomers and optional acrylic monomers and in a grafted state, based on the weight of the graft modified polypropylene material.
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 reactive grafting sites may be formed on the polypropylene copolymer in the presence of the grafting acrylate monomer and optionally the acrylic monomer, or the reactive grafting sites may be formed on the polypropylene copolymer first followed by treatment with the grafting monomer. 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 amount of each component used in the grafting reaction is not particularly limited, and specifically, the ratio of the mass of the radical initiator to the total mass of the acrylate monomer and the optional acrylic monomer may be 0.1 to 10:100, and preferably 0.5 to 5: 100. The ratio of the total mass of the acrylate monomer and the optional acrylic monomer to the mass of the copolymerized polypropylene is 0.1-10: 100, preferably 0.5-8: 100, and more preferably 0.8-7: 100. The molar ratio of the acrylate monomer to the acrylic monomer is 1: 0-2, and preferably 1: 0.125-1.
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, C6Alkane or cycloalkane, benzene, C, or both1-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 graft modified polypropylene material of the present invention, the definitions of the acrylate monomer and the polypropylene copolymer are the same as those described above, and are not repeated herein.
According to the present invention, the preparation method of the graft-modified polypropylene material 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, an acrylate monomer and an optional acrylic 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 dispersing agent) and drying to obtain the graft modified polypropylene material.
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 an acrylate monomer and an optional acrylic 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 dispersing agent) and drying to obtain the graft modified polypropylene material.
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 an acrylate monomer and an optional acrylic 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 dispersing agent) and drying to obtain the graft modified polypropylene material.
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 an acrylate monomer and optionally an acrylic monomer, adding 0-30 parts of an 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 dispersing agent) and drying to obtain the graft modified polypropylene material.
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 "graft-modified polypropylene material" of the present invention includes both a product (crude product) directly obtained by graft-reacting a copolymerized polypropylene with an acrylic monomer and optionally an acrylic monomer, and a graft-modified polypropylene pure product obtained by further purifying the product, and therefore, the production 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 favorable for obtaining the 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 total amount of acrylate monomer and optional acrylic monomer grafted on per total amount of acrylate monomer and optional acrylic monomer reacted charge.
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 third aspect of the present invention provides a graft-modified polypropylene material obtained by the above-mentioned production method.
The fourth aspect of the present invention provides the use of the above graft-modified polypropylene material. For example as an insulating material.
The 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 micromolecule additive, the grafted modified polypropylene material avoids performance reduction caused by micromolecule 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. Calibration of the correlation of the determined comonomer content by quantitative Nuclear Magnetic Resonance (NMR) spectroscopy. 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 acrylate monomers and optionally acrylic monomers in the 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 the added acrylate monomer and optionally the acrylic monomer.
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 2.5g of dibenzoyl peroxide and 80g of glycidyl methacrylate, stirring and mixing for 30min, heating to 90 ℃, and reacting for 4 hours. After the reaction is finished, nitrogen is blown and cooled to obtain a polypropylene-g-glycidyl methacrylate 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%, solubles comonomer content 34.5 wt%, solubles/copolypropylene intrinsic viscosity ratio 0.91, weightAverage molecular weight of 36.6X 104g/mol, MFR of 1.54g/10min at 230 ℃ under a load of 2.16kg, Tm of 164.9 ℃, breakdown field strength (90 ℃) of 248kV/mm, and direct current volume resistivity (90 ℃, 15kV/mm) of 7.25E 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 1.2g of dibenzoyl peroxide and 40g of glycidyl methacrylate, stirring and mixing for 30min, heating to 95 ℃, and reacting for 4 hours. After the reaction is finished, nitrogen is blown and cooled to obtain a polypropylene-g-glycidyl methacrylate 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. 3.5g of dibenzoyl peroxide and 125g of glycidyl methacrylate are added, stirred and mixed for 30min, the temperature is raised to 90 ℃, and the reaction is carried out for 4 hours. After the reaction is finished, nitrogen is blown and cooled to obtain a polypropylene-g-glycidyl methacrylate 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%, and solubles/copolymerized polypropylene intrinsic viscosity ratio1.68, 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, and direct current volume resistivity (90 ℃, 15kV/mm) of 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 2.8g of tert-butyl peroxy (2-ethylhexanoate) and 100g of methyl methacrylate, stirring and mixing for 30min, heating to 95 ℃, adding 3.0kg of dispersant deionized water at 95 ℃, and reacting for 4 hours. After the reaction is finished, filtering to remove the dispersant water, vacuum-drying for 10 hours at 70 ℃, cooling and cooling to obtain a polypropylene-g-methyl methacrylate 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 1.3g of dibenzoyl peroxide in 70g of acetone, adding the obtained acetone solution into a reaction system, heating to 40 ℃, purging with nitrogen for 30min to remove acetone, adding 50g of butyl acrylate, stirring and mixing for 30min, heating to 100 ℃, and reacting for 1 hour. After the reaction is finished, nitrogen is blown and cooled to obtain a polypropylene-g-butyl acrylate material product C5.
The product obtained was tested for various performance parameters and the results are shown in table 1.
Example 6
Is selected to have the followingThe basic copolymerized polypropylene powder is characterized in that: 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 ℃) of 261kV/mm, and 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. 0.8g of lauroyl peroxide is dissolved in 30g of methyl methacrylate and 40g of interfacial agent toluene to form a solution, the solution is stirred and mixed for 30min, the temperature is raised to 85 ℃, 4kg of dispersant water at 85 ℃ is added, and the reaction is carried out for 1.5 hours. And after the reaction is finished, cooling, filtering to remove the dispersant water, and performing vacuum drying at 70 ℃ for 10 hours to obtain a polypropylene-g-methyl methacrylate 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 5.0g of dibenzoyl peroxide and 180g of glycidyl methacrylate, stirring and mixing for 30min, swelling for 1 hour at 40 ℃, heating to 90 ℃, and reacting for 4 hours. After the reaction is finished, nitrogen is blown and cooled to obtain a polypropylene-g-glycidyl methacrylate 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 1.5g of dibenzoyl peroxide, 40g of methyl acrylate and 10g of acrylic acid, stirring and mixing for 30min, heating to 90 ℃, and reacting for 4 hours. After the reaction is finished, nitrogen is blown and cooled to obtain a polypropylene-g-methyl acrylate/acrylic acid material product C8.
The product obtained was tested for various performance parameters and the results are shown in table 1.
Comparative example 1
Weighing 2.0kg of 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 the powder into a 10L reaction kettle with mechanical stirring, sealing the reaction system, and removing oxygen by nitrogen replacement. Adding 2.5g of dibenzoyl peroxide and 80g of glycidyl methacrylate, stirring and mixing for 60min, heating to 90 ℃, and reacting for 4 hours. After the reaction is finished, nitrogen is blown and cooled to obtain a polypropylene-g-glycidyl methacrylate 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. 6g of dibenzoyl peroxide and 225g of glycidyl methacrylate are added, stirred and mixed for 60min, the temperature is raised to 90 ℃, and the reaction is carried out for 4 hours. After the reaction is finished, nitrogen is used for blowing, cooling and obtaining a polypropylene-g-glycidyl methacrylate 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: the comonomer ethylene content was 18.1 wt%,xylene solubles content 48.7 wt.%, comonomer content in solubles 31.9 wt.%, solubles/copolymerized 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. 500g of the above-mentioned basic copolymerized polypropylene powder was weighed and mixed with 20g of polyglycidyl methacrylate, 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 polypropylene-g-acrylate material product obtained by using the powder T30S as the base powder has too high flexural modulus and poor mechanical properties, and cannot meet the processing requirements of insulating materials.
Comparing the data of example 1 and comparative example 2, it can be seen that too high of the addition amount of the acrylate monomer (too high of M1 value) can result in the decrease of the breakdown field strength and the volume resistivity of the obtained polypropylene-g-acrylate material product, and the electrical property of the product is influenced.
Comparing the data of example 1 and comparative example 3 shows that the mode of blending the acrylate polymer can cause the breakdown field strength and the volume resistivity of the product to be greatly reduced, and the electrical property of the product is greatly influenced.
In summary, it can be seen from the data in table 1 that the great reduction of the flexural modulus enables the graft modified polypropylene material of the present invention to have good mechanical properties, and the breakdown field strength of the grafted product is increased compared to the polypropylene copolymer without grafted acrylate monomer and optional acrylic monomer, which indicates that the 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 (24)
1. A graft-modified polypropylene material, characterised in that the graft-modified polypropylene material comprises structural units derived from a copolymerised polypropylene and structural units derived from an acrylate monomer and optionally an acrylic monomer; based on the weight of the graft modified polypropylene material, the content of structural units derived from acrylate monomers and optional acrylic monomers in a grafted state in the graft modified polypropylene material is 0.3-7 wt%, preferably 0.8-5 wt%;
the copolymerized polypropylene has the following characteristics: the content of the comonomer is 0.5-40 mol%, preferably 0.5-30 mol%; the content of xylene soluble substances is 2-80 wt%; the content of the comonomer in the soluble substance is 10-70 wt%; the ratio of the soluble substance to the polypropylene is 0.3 to 5.
2. The graft-modified polypropylene material of claim 1, wherein the graft-modified polypropylene material 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, and more preferably 0.2-8 g/10 min; the flexural modulus is 10-1100 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.
3. The graft-modified polypropylene material of claim 1, wherein the graft-modified polypropylene material has at least one of the following characteristics:
the working temperature of the grafted modified polypropylene material is more than or equal to 90 ℃, and preferably 90-160 ℃;
-the breakdown field strength E of the graft-modified polypropylene material at 90 ℃gThe voltage is more than or equal to 180kV/mm, and preferably 180-800 kV/mm;
-the breakdown field strength E of the graft-modified polypropylene material 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 2%, preferably 2.5-50%, more preferably 4-35%, and further preferably 5-25%;
-the direct volume resistivity p of the graft-modified polypropylene material at 90 ℃ at a field strength of 15kV/mmvg≥1.0×1013Ω · m, preferably 1.5 × 1013Ω·m～1.0×1020Ω·m；
-the direct volume resistivity p of the graft-modified polypropylene material at 90 ℃ at a field strength of 15kV/mmvgThe direct current volume resistivity rho of the copolymerized polypropylene at 90 ℃ and 15kV/mm field intensityvRatio of (p)vg/ρvMore than 1.5, preferably 1.8-30, more preferably 2-10, and further preferably 2.5-6;
-the dielectric constant of the graft-modified polypropylene material at 90 ℃ and 50Hz is greater than or equal to 2.0, preferably 2.0-2.5.
4. The graft-modified polypropylene material according to claim 1, wherein the acrylate monomer is at least one selected from monomers having a structure represented by formula I;
wherein R is1、R2、R3Each independently selected from H, C1-C6Straight chain alkyl, C3-C6A branched alkyl group; r4Selected from the following substituted or unsubstituted groups: c1-C20Straight chain alkyl, C3-C20Branched alkyl radical, C3-C12Cycloalkyl radical, C3-C12Epoxyalkyl, C3-C12An epoxyalkyl group, said substituted group being selected from at least one of halogen, amino and hydroxyl;
preferably, the acrylate-based monomer is at least one selected from the group consisting of methyl (meth) acrylate, sec-butyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, isooctyl (meth) acrylate, dodecyl (meth) acrylate, cocooleate, octadecyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, and glycidyl (meth) acrylate.
5. The graft-modified polypropylene material according to claim 1, wherein the acrylic monomer is at least one selected from monomers having a structure represented by formula II;
wherein R is1、R2、R3Each independently selected from H, C1-C6Straight chain alkyl, C3-C6A branched alkyl group;
preferably, the acrylic monomer is selected from at least one of acrylic acid, methacrylic acid, and 2-ethacrylic acid.
6. The graft-modified polypropylene material according to claim 1, wherein the molar ratio of the structural units derived from the acrylate monomer to the structural units derived from the acrylic monomer is 1:0 to 2, preferably 1:0.125 to 1.
7. The graft-modified polypropylene material according to any one of claims 1 to 6, wherein the comonomer of the co-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.
8. The graft modified polypropylene material of any one of claims 1 to 6, wherein the co-polypropylene has at least one of the following characteristics: the comonomer content is 4-25 wt%, preferably 4-22 wt%; the xylene soluble content is 18 to 75 wt%, preferably 30 to 70 wt%, more preferably 30 to 67 wt%; the content of the comonomer in the soluble substance is 10-50 wt%, preferably 20-35 wt%; the intrinsic viscosity ratio of the soluble material to the copolymerized polypropylene is 0.5 to 3, preferably 0.8 to 1.3.
9. The graft modified polypropylene material of any one of claims 1 to 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, preferably 0.05-35 g/10min, and further preferably 0.5-15 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。
10. The graft-modified polypropylene material according to any one of claims 1 to 6, wherein the graft-modified polypropylene material is prepared by a solid phase grafting reaction of a co-polypropylene with an acrylate monomer and optionally an acrylic monomer.
11. A preparation method of a graft modified polypropylene material comprises the following steps: in the presence of inert gas, carrying out grafting reaction on a reaction mixture comprising copolymerized polypropylene, an acrylate monomer and an optional acrylic monomer to obtain a graft modified polypropylene material;
wherein the comonomer content of the copolymerized polypropylene is 0.5-40 mol%, preferably 0.5-30 mol%; the content of xylene soluble substances is 2-80 wt%; the content of the comonomer in the soluble substance is 10-70 wt%; the characteristic viscosity ratio of the soluble substance to the polypropylene is 0.3-5; the conditions of the grafting reaction are such that: the graft modified polypropylene material contains 0.3-7 wt%, preferably 0.8-5 wt% of structural units derived from acrylate monomers and optional acrylic monomers and in a grafted state, based on the weight of the graft modified polypropylene material.
12. The method of 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. The production method according to claim 12, wherein the ratio of the mass of the radical initiator to the total mass of the acrylate-based monomer and the optional acrylic-based monomer is 0.1 to 10:100, preferably 0.5 to 5: 100.
14. The production method according to claim 11, wherein the ratio of the total mass of the acrylate monomer and the optional acrylic monomer to the mass of the copolymerized polypropylene is 0.1 to 10:100, preferably 0.5 to 8:100, and more preferably 0.8 to 7: 100.
15. The preparation method according to claim 11, wherein the molar ratio of the acrylate monomer to the acrylic monomer is 1: 0-2, preferably 1: 0.125-1.
16. The preparation method according to claim 11, wherein the temperature of the grafting reaction is 30 to 130 ℃, preferably 60 to 120 ℃; the time is 0.5 to 10 hours, preferably 1 to 5 hours.
17. The method of any one of claims 11-16, wherein the reaction mixture further comprises at least one of: 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.
18. The method of manufacturing of claim 17, wherein the method of manufacturing comprises the steps of:
a. placing the copolymerization polypropylene in a closed reactor for inert gas replacement;
b. adding a free radical initiator, an acrylate monomer and an optional acrylic 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 graft modified polypropylene material.
19. The method of manufacturing of claim 17, wherein the method of manufacturing comprises the steps of:
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 an acrylate monomer and an optional acrylic 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 graft modified polypropylene material.
20. The production method according to any one of claims 11 to 16, wherein the acrylate monomer is at least one selected from monomers having a structure represented by formula I;
wherein R is1、R2、R3Each independently selected from H, C1-C6Straight chain alkyl, C3-C6A branched alkyl group; r4Selected from the following substituted or unsubstituted groups: c1-C20Straight chain alkyl, C3-C20Branched alkyl radical, C3-C12Cycloalkyl radical, C3-C12Epoxyalkyl radical、C3-C12An epoxyalkyl group, said substituted group being selected from at least one of halogen, amino and hydroxyl;
preferably, the acrylate-based monomer is at least one selected from the group consisting of methyl (meth) acrylate, sec-butyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, isooctyl (meth) acrylate, dodecyl (meth) acrylate, cocooleate, octadecyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, and glycidyl (meth) acrylate.
21. The production method according to any one of claims 11 to 16, wherein the acrylic monomer is at least one selected from monomers having a structure represented by formula II;
wherein R is1、R2、R3Each independently selected from H, C1-C6Straight chain alkyl, C3-C6A branched alkyl group;
preferably, the acrylic monomer is selected from at least one of acrylic acid, methacrylic acid, and 2-ethacrylic acid.
22. The production method according to any one of claims 11 to 16, wherein the comonomer of the copolymerized 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;
and/or the presence of a gas in the gas,
the copolymerized polypropylene has at least one of the following characteristics: the comonomer content is 4-25 wt%, preferably 4-22 wt%; the xylene soluble content is 18 to 75 wt%, preferably 30 to 70 wt%, more preferably 30 to 67 wt%; the content of the comonomer in the soluble substance is 10-50 wt%, preferably 20-35 wt%; the intrinsic viscosity ratio of the soluble substance to the copolymerized polypropylene is 0.5-3, preferably 0.8-1.3;
and/or the presence of a gas in the gas,
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, and further preferably 0.5-15 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。
23. A graft-modified polypropylene material produced by the production method according to any one of claims 11 to 22.
24. Use of a graft-modified polypropylene material according to any one of claims 1 to 10 and 23.
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