CN113563523A - Polypropylene graft containing anhydride group and preparation method and application thereof - Google Patents
Polypropylene graft containing anhydride group and preparation method and application thereof Download PDFInfo
- Publication number
- CN113563523A CN113563523A CN202011190917.4A CN202011190917A CN113563523A CN 113563523 A CN113563523 A CN 113563523A CN 202011190917 A CN202011190917 A CN 202011190917A CN 113563523 A CN113563523 A CN 113563523A
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- China
- Prior art keywords
- substituted
- unsubstituted
- group
- polypropylene
- anhydride
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- Pending
Links
- -1 Polypropylene Polymers 0.000 title claims abstract description 232
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 212
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 211
- 150000008064 anhydrides Chemical group 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 115
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 51
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 42
- 125000004018 acid anhydride group Chemical group 0.000 claims abstract description 35
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims description 80
- 150000003254 radicals Chemical class 0.000 claims description 47
- 229910052736 halogen Inorganic materials 0.000 claims description 42
- 150000002367 halogens Chemical class 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 33
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 29
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 28
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 28
- 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 23
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 claims description 21
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 21
- 239000005977 Ethylene Substances 0.000 claims description 21
- 239000000126 substance Substances 0.000 claims description 21
- 229920005606 polypropylene copolymer Polymers 0.000 claims description 19
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 18
- 229910019142 PO4 Inorganic materials 0.000 claims description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 18
- 239000010452 phosphate Substances 0.000 claims description 18
- 239000008096 xylene Substances 0.000 claims description 18
- 239000002270 dispersing agent Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 125000000623 heterocyclic group Chemical group 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 14
- 230000008961 swelling Effects 0.000 claims description 14
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 239000011261 inert gas Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 11
- 239000011541 reaction mixture Substances 0.000 claims description 10
- 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
- 125000003277 amino group Chemical group 0.000 claims description 9
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 9
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 9
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 7
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000001914 filtration 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
- 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
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 6
- 238000007334 copolymerization reaction Methods 0.000 claims description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 6
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 239000004711 α-olefin Substances 0.000 claims description 6
- 150000002978 peroxides Chemical group 0.000 claims description 5
- 239000007790 solid phase 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
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 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
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 3
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 3
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims description 3
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims description 3
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims description 3
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- 125000003860 C1-C20 alkoxy group Chemical group 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
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000003118 aryl 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- JEVCWSUVFOYBFI-UHFFFAOYSA-N cyanyl Chemical compound N#[C] JEVCWSUVFOYBFI-UHFFFAOYSA-N 0.000 claims description 3
- 125000004185 ester group Chemical group 0.000 claims description 3
- 125000005670 ethenylalkyl group Chemical group 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
- 125000002883 imidazolyl group Chemical group 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000002757 morpholinyl group Chemical group 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- 125000005968 oxazolinyl group Chemical group 0.000 claims description 3
- 125000005936 piperidyl group Chemical group 0.000 claims description 3
- 125000000561 purinyl group Chemical group N1=C(N=C2N=CNC2=C1)* 0.000 claims description 3
- 125000003373 pyrazinyl group Chemical group 0.000 claims description 3
- 125000004076 pyridyl group Chemical group 0.000 claims description 3
- 239000002195 soluble material Substances 0.000 claims description 3
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- 125000000335 thiazolyl 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
- 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
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 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
- 125000003226 pyrazolyl group Chemical group 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 40
- 239000000843 powder Substances 0.000 description 39
- 239000000047 product Substances 0.000 description 39
- 229920001577 copolymer Polymers 0.000 description 27
- 239000000463 material Substances 0.000 description 24
- 229910052757 nitrogen Inorganic materials 0.000 description 20
- 239000000243 solution Substances 0.000 description 15
- 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 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 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
- 230000000052 comparative effect Effects 0.000 description 7
- 238000009413 insulation Methods 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 5
- 229920000573 polyethylene Polymers 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
- 238000000605 extraction Methods 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000012360 testing method Methods 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
- 229920001384 propylene homopolymer Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001555 benzenes Chemical class 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
- 238000011161 development 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
- 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
- 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
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 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
- 238000006073 displacement reaction Methods 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
- 239000007789 gas Substances 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
- 239000002861 polymer material Substances 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
- 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
- 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
- 238000001291 vacuum drying Methods 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
Abstract
The invention belongs to the field of polymers, and relates to an anhydride group-containing polypropylene graft and a preparation method and application thereof. The polypropylene graft containing an acid anhydride group comprises a structural unit derived from copolymerized polypropylene, a structural unit derived from a maleic anhydride monomer and a structural unit derived from an alkenyl-containing polymerized monomer; the content of structural units derived from an acid anhydride monomer and an alkenyl-containing polymerized monomer and in a grafted state in the acid anhydride group-containing polypropylene graft is 0.1 to 5 wt% based on the weight of the acid anhydride group-containing polypropylene graft; and the content of structural units derived from anhydride monomers and in a grafted state in the polypropylene graft containing anhydride groups is 0.05-2 wt%. The polypropylene graft containing the anhydride group 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 an anhydride group-containing polypropylene graft, a preparation method of the anhydride group-containing polypropylene graft, the anhydride group-containing polypropylene graft prepared by the preparation method, and application of the anhydride group-containing polypropylene graft.
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 polypropylene graft containing an anhydride group, 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 strength.
The first aspect of the present invention provides an acid anhydride group-containing polypropylene graft comprising a structural unit derived from a copolymerized polypropylene, a structural unit derived from an acid anhydride monomer, and a structural unit derived from an alkenyl-containing polymerized monomer; the content of the structural units derived from the acid anhydride monomer and the alkenyl-containing polymerized monomer in a grafted state in the acid anhydride group-containing polypropylene graft is 0.1 to 5 wt%, preferably 0.4 to 3 wt%, based on the weight of the acid anhydride group-containing polypropylene graft; and the content of the structural unit which is derived from the anhydride monomer and is in a grafting state in the polypropylene graft containing the anhydride group is 0.05-2 wt%, preferably 0.2-0.7 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.
According to the invention, preferably, the anhydride is chosen from anhydrides having at least one olefinic unsaturation. More preferably, the anhydride is selected from maleic anhydride and/or itaconic anhydride. Further preferably, the anhydride is maleic anhydride.
According to a preferred embodiment of the present invention, there is provided an acid anhydride group-containing polypropylene graft comprising a structural unit derived from a copolymerized polypropylene, a structural unit derived from a maleic anhydride monomer, and a structural unit derived from an olefin-containing polymeric monomer; the content of the structural units derived from the maleic anhydride monomer and the alkenyl group-containing polymerized monomer in a grafted state in the polypropylene graft containing the acid anhydride group is 0.1 to 5 wt%, preferably 0.4 to 3 wt%, based on the weight of the polypropylene graft containing the acid anhydride group; and the content of the structural unit which is derived from the maleic anhydride monomer and is in a grafting state in the polypropylene graft containing the anhydride group is 0.05-2 wt%, preferably 0.2-0.7 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 polypropylene graft containing an acid anhydride group, and its form 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 (maleic) anhydride monomers" refers to the products formed from (maleic) anhydride, including both in "radical" form and in "monomer" form, as well as in "polymer" form. "structural units derived from an alkenyl-containing polymeric monomer" refers to the product formed from an alkenyl-containing polymeric monomer, including both in the "radical" form and in the "monomer" form, as well as in the "polymer" form. The "structural unit" may be a repeating unit or a non-repeating independent unit.
In the present invention, the structural unit derived from (maleic) anhydride monomer "in a grafted state" means a structural unit derived from (maleic) anhydride monomer which forms a covalent bond (graft) with the copolymerized polypropylene. Structural units derived from an alkenyl-containing polymeric monomer "in the grafted state" refer to structural units derived from an alkenyl-containing polymeric monomer that form a covalent link (graft) with the co-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 polypropylene graft containing an acid anhydride group is prepared by a graft reaction, preferably a solid phase graft reaction, of a copolymerized polypropylene, a (maleic) anhydride monomer and an alkenyl-containing polymerized 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 (maleic) anhydride monomer and the alkenyl-containing polymeric monomer may polymerize with each other or with each other to form a certain amount of ungrafted polymer. The term "polypropylene graft containing an acid anhydride group" in the present invention includes both a product (crude product) directly obtained by graft-reacting a copolymerized polypropylene, a (maleic) anhydride monomer and an alkenyl-containing polymerized monomer, and a graft-modified polypropylene pure product obtained by further purifying the product.
According to the present invention, preferably, the polypropylene graft containing an acid anhydride group 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 10-1050 MPa, preferably 20-1000 MPa, and more preferably 50-500 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 polypropylene graft containing the anhydride group is more than 5MPa, and preferably 10-40 MPa.
According to the present invention, preferably, the polypropylene graft containing an acid anhydride group has at least one of the following characteristics:
the working temperature of the polypropylene graft containing the anhydride group is more than or equal to 90 ℃, and preferably 90-160 ℃;
the breakdown field strength E of the polypropylene graft containing anhydride groups at 90 ℃gThe voltage is more than or equal to 210kV/mm, and preferably 210-800 kV/mm;
the breakdown field strength E of the polypropylene graft containing anhydride groups 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 1.8 percent, preferably 2 to 50 percent, more preferably 5 to 35 percent, and further preferably 8 to 28 percent;
-the direct volume resistivity p of the polypropylene graft containing anhydride groups at 90 ℃ at a field strength of 15kV/mmvg≥1.5×1013Ω · m, preferably 1.5 × 1013Ω·m～1.0×1020Ω·m；
-the direct volume resistivity p of the polypropylene graft containing anhydride groups 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 2, preferably 2.1 to 40, more preferably 2.3 to 20, and further preferably 2.5 to 10;
-the polypropylene graft containing anhydride groups has a dielectric constant of more than 2.0, preferably 2.1 to 2.5 at 90 ℃ and 50 Hz.
The alkenyl-containing polymeric monomer of the present invention is preferably at least one selected from monomers having a structure represented by formula 1,
in the formula 1, R1、R2、R3Each independently selected from H, substituted or unsubstituted alkyl; r4Selected from substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryl, substituted or unsubstituted ester group, substituted or unsubstituted carboxyl, substituted or unsubstituted cycloalkyl or heterocyclic group, cyano.
Preferably, R1、R2、R3Each independently selected from H, substituted or unsubstituted C1-C6Alkyl, more preferablyOptionally, R1、R2、R3Each independently selected from H, substituted or unsubstituted C1-C3An alkyl group; r4Selected from substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted C1-C20Alkoxy, substituted or unsubstituted C6-C20Aryl, substituted or unsubstituted C1-C20Ester group, substituted or unsubstituted C1-C20Carboxy, substituted or unsubstituted C3-C20Cycloalkyl or heterocyclic radical, cyano radical, the said substituted radicals being halogen, hydroxy, amino, C1-C6Alkyl radical, C3-C6A cycloalkyl group; preferably, R4Selected from substituted or unsubstituted C1-C12Alkyl, substituted or unsubstituted C1-C18Alkoxy, substituted or unsubstituted C6-C12Aryl, substituted or unsubstituted C1-C12Ester group, substituted or unsubstituted C1-C12Carboxy, substituted or unsubstituted C3-C12Cycloalkyl or heterocyclyl, cyano, said substituted radicals being halogen, C1-C6Alkyl radical, C3-C6A cycloalkyl group; more preferably, R4Selected from substituted or unsubstituted C1-C6Alkyl, substituted or unsubstituted C1-C12Alkoxy, substituted or unsubstituted C6-C8Aryl, substituted or unsubstituted C1-C6Ester group, substituted or unsubstituted C1-C6Carboxy, substituted or unsubstituted C3-C6Cycloalkyl or heterocyclyl, cyano. Particularly preferably, the heterocyclic group is selected from the group consisting of imidazolyl, pyrazolyl, carbazolyl, pyrrolidinonyl, pyridyl, piperidyl, caprolactam group, pyrazinyl, thiazolyl, purinyl, morpholinyl, oxazolinyl.
More preferably, R1、R2、R3Each independently selected from H, substituted or unsubstituted C1-C6An alkyl group;
R4selected from the group consisting of a group represented by formula 2, a group represented by formula 3, and a group represented by formula 4A group represented by formula 5, a combination of a group represented by formula 5 and a group represented by formula 6, a heterocyclic group;
in the formula 2, 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, 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 3, 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, 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 4, 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, 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);
in the formula 5, RmSelected from substituted or unsubstitutedThe following 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.
Further preferably, the alkenyl-containing polymeric monomer is selected from at least one of vinyl acetate, styrene, α -methylstyrene, (meth) acrylic acid esters, vinyl alkyl ethers, vinyl pyrrolidone, vinyl pyridine, vinyl imidazole, and acrylonitrile; the (meth) acrylate is preferably at least one of methyl (meth) acrylate, ethyl (meth) acrylate, and glycidyl (meth) acrylate. Preferably, the alkenyl-containing polymeric monomer is selected from vinyl acetate, styrene, alpha-methylstyrene. Further preferably, the alkenyl-containing polymeric monomer is styrene.
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.
According to the present invention, it is preferable that the mole ratio of the structural unit derived from the (maleic) anhydride monomer to the structural unit derived from the olefin-containing polymerized monomer in the acid anhydride group-containing polypropylene graft is 1: 1-20, preferably 1: 1 to 10.
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%, and the preferable content is 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 ratio of the intrinsic viscosity of the soluble material to the intrinsic viscosity of the 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. A melting temperature Tm of 100 ℃ or higher, preferably 110 to 180 ℃, furtherPreferably 110 to 170 ℃, more preferably 120 to 170 ℃, and even 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 polypropylene graft containing an acid anhydride group of the present invention can be prepared by a method comprising the steps of: and (2) carrying out solid-phase grafting reaction on a reaction mixture comprising polypropylene copolymer, maleic anhydride monomer and alkenyl-containing polymerized monomer in the presence of inert gas to obtain the polypropylene graft containing anhydride groups.
The second aspect of the present invention provides a method for preparing an acid anhydride group-containing polypropylene graft, comprising: in the presence of inert gas, carrying out grafting reaction on a reaction mixture comprising polypropylene copolymer, anhydride monomer and alkenyl-containing polymerized monomer to obtain the polypropylene graft containing anhydride groups;
wherein the grafting reaction conditions are such that: the content of the structural units derived from the acid anhydride monomer and the alkenyl-containing polymerized monomer in a grafted state in the acid anhydride group-containing polypropylene graft is 0.1 to 5 wt%, preferably 0.4 to 3 wt%, based on the weight of the acid anhydride group-containing polypropylene graft; and the content of the structural unit which is derived from the anhydride monomer and is in a grafting state in the polypropylene graft containing the anhydride group is 0.05-2 wt%, preferably 0.2-0.7 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.
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 polypropylene copolymer in the presence of the (maleic) anhydride for grafting and the alkenyl group-containing polymerizable monomer, or the active grafting site may be formed on the polypropylene copolymer 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 satisfying the above 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 (maleic) anhydride monomer and the alkenyl group-containing polymeric monomer is 0.1 to 10:100, preferably 0.5 to 5: 100. The mass ratio of the total mass of the (maleic) anhydride monomer and the alkenyl-containing polymerized monomer to the copolymerized polypropylene is 0.1-8: 100, preferably 0.3-5: 100. The mass amount of the (maleic) anhydride monomer may be 5 to 100 wt%, preferably 10 to 100 wt% of the mass amount of the alkenyl group-containing polymer monomer.
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 polypropylene graft containing an acid anhydride group according to the present invention, the definitions of the olefin-containing polymeric monomer, the acid anhydride and the copolymerized polypropylene are the same as those described above, and thus, the detailed description thereof is omitted.
According to the invention, preferably, the conditions of the grafting reaction are such that: the mole ratio of the structural unit derived from the acid anhydride monomer to the structural unit derived from the olefin-containing polymerized monomer in the acid anhydride group-containing polypropylene graft is 1: 1-20, preferably 1: 1 to 10.
According to the present invention, the preparation method of the polypropylene graft containing an acid anhydride group may be selected from one of the following manners:
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 anhydride monomer and an alkenyl-containing polymerization 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 polypropylene graft containing an acid anhydride group.
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 anhydride monomer and an alkenyl-containing polymerization 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 polypropylene graft containing an acid anhydride group.
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 anhydride monomer and an alkenyl-containing polymeric 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 polypropylene graft containing an acid anhydride group.
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 anhydride monomer and an alkenyl-containing polymerized 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 dispersant) and drying to obtain the polypropylene graft containing an acid anhydride group.
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 "polypropylene graft containing an acid anhydride group" of the present invention includes both a product (crude product) directly obtained by graft-reacting a copolymerized polypropylene with an acid anhydride monomer and an alkenyl group-containing polymeric 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 invention has no special limitation on the grafting efficiency of the grafting reaction, but the higher grafting efficiency is more beneficial to obtain the polypropylene graft containing the anhydride group with the required performance through one-step grafting reaction. Therefore, the grafting efficiency of the grafting reaction is preferably controlled to be 20 to 100%, and more preferably 25 to 80%. The concept of grafting efficiency is well known to those skilled in the art and refers to the total amount of anhydride monomer and alkenyl-containing polymeric monomer grafted on per total amount of anhydride monomer and alkenyl-containing polymeric monomer reacted.
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 an acid anhydride group-containing polypropylene graft obtained by the above-mentioned production method.
The fourth aspect of the present invention provides the use of the above-mentioned polypropylene graft containing an acid anhydride group. For example as an insulating material.
The polypropylene graft containing the anhydride group can give consideration to both 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 polypropylene graft containing the anhydride group avoids the performance reduction caused by the small molecule migration, thereby having 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. The correlation of the determined comonomer content was calibrated 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, parameter M2:
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 parameters M1, M2 and a grafting efficiency GE.
The mass content of maleic anhydride,% was measured and calculated according to the method described in the literature (Zhangguangping, polypropylene solid phase graft maleic anhydride in spiral band reactor, Chinese plastics, Vol.2.16, 2002, No. 2, 69-71)MAH. The parameter M1 represents the structural units derived from maleic anhydride monomers and olefin-containing polymeric monomers in the grafted state in the anhydride group-containing polypropylene graftContent (c); the parameter M2 represents the content of structural units derived from maleic anhydride monomer and in the grafted state in the anhydride group-containing polypropylene graft. In the present invention, the calculation formulas of M1, M2 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 total mass of the maleic anhydride monomer and the alkenyl group-containing polymerized monomer; is based onMAHIs the mass content of maleic anhydride.
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 a solution of 1.3g of dibenzoyl peroxide, 10g of maleic anhydride and 40g of styrene, stirring and mixing for 30min, swelling for 2 hours 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-styrene/maleic anhydride material product C1. Testing the product for various propertiesThe energy parameters and 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, 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 a solution of 0.6g of dibenzoyl peroxide, 5g of maleic anhydride and 22g of styrene, stirring and mixing for 30min, swelling for 3 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/maleic anhydride 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 a solution of 2.6g of dibenzoyl peroxide, 12g of maleic anhydride and 88g of styrene, stirring and mixing for 30min, swelling for 2 hours 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-styrene/maleic anhydride material product C3. The product obtained was tested for various performance parameters and the results are given in Table 1As shown.
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, 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. A solution of 5.0g of tert-butyl peroxy (2-ethylhexanoate), 25g of maleic anhydride, 50g of vinyl acetate and 100g of toluene was added, stirred and mixed for 30min, the temperature was raised to 95 ℃ and the reaction was carried out for 4 hours. After the reaction is finished, nitrogen is blown and cooled to obtain a polypropylene-g-vinyl acetate/maleic anhydride 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. Adding a solution of 0.6g of dibenzoyl peroxide, 10g of maleic anhydride, 11g of styrene and 50g of toluene, stirring and mixing for 30min, swelling for 2h at 50 ℃, heating to 100 ℃, and reacting for 1 hour. After the reaction is finished, nitrogen is blown and cooled to obtain a polypropylene-g-styrene/maleic anhydride material product C5. The product obtained was tested for various performance parameters and the results are given in Table 1Shown in the figure.
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 ℃) 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. Dissolving 2g of lauroyl peroxide and 20g of maleic anhydride in 150g of acetone, adding the obtained acetone solution into a reaction system, heating to 50 ℃, purging with nitrogen for 30min to remove acetone, dropwise adding 60g of alpha-methyl styrene into a reaction kettle, stirring and mixing the solution for 30min, swelling at 40 ℃ for 2h, heating to 85 ℃, adding 4kg of dispersant water at 85 ℃, and reacting for 2 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-alpha-methylstyrene/maleic anhydride 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 4.0g of dibenzoyl peroxide, 30g of maleic anhydride and 120g of styrene solution, stirring and mixing for 30min, swelling for 2 hours 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-styrene/maleic anhydride product C7. 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 a solution of 1.3g of dibenzoyl peroxide, 10g of maleic anhydride and 40g of styrene, stirring and mixing for 60min, swelling for 2 hours 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-styrene/maleic anhydride 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 5g of dibenzoyl peroxide, 40g of maleic anhydride and 160g of styrene solution, stirring and mixing for 60min, swelling for 2 hours 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-styrene/maleic anhydride 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. Weighing 2000g of the basic polypropylene copolymer powder and 50g of styreneThe/maleic anhydride copolymer was mixed and mixed using a screw extruder to give 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-styrene/maleic anhydride material product obtained by using the powder of 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 a maleic anhydride monomer/alkenyl group-containing polymeric monomer addition (too high a value of M1) can result in a decrease in breakdown field strength and volume resistivity of the resulting polypropylene-g-styrene/maleic anhydride material product, which can affect the electrical properties of the product.
Comparing the data of example 1 and comparative example 3 shows that the mode of blending the styrene/maleic anhydride copolymer 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 leads the polypropylene graft containing the anhydride group of the present invention to have good mechanical properties, and the breakdown field strength of the graft product is improved compared with the polypropylene copolymer without grafting the maleic anhydride/the alkenyl-containing polymeric monomer, which indicates that the polypropylene graft containing the anhydride group 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 (29)
1. An anhydride group-containing polypropylene graft, characterized in that the anhydride group-containing polypropylene graft comprises a structural unit derived from a copolymerized polypropylene, a structural unit derived from an anhydride monomer, and a structural unit derived from an alkenyl-containing polymerized monomer; the content of the structural units derived from the acid anhydride monomer and the alkenyl-containing polymerized monomer in a grafted state in the acid anhydride group-containing polypropylene graft is 0.1 to 5 wt%, preferably 0.4 to 3 wt%, based on the weight of the acid anhydride group-containing polypropylene graft; and the content of the structural unit which is derived from the anhydride monomer and is in a grafting state in the polypropylene graft containing the anhydride group is 0.05-2 wt%, preferably 0.2-0.7 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 anhydride group-containing polypropylene graft of claim 1, wherein the anhydride group-containing polypropylene graft 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 10-1050 MPa, preferably 20-1000 MPa, and more preferably 50-500 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 anhydride group-containing polypropylene graft of claim 1, wherein the anhydride group-containing polypropylene graft has at least one of the following characteristics:
the working temperature of the polypropylene graft containing the anhydride group is more than or equal to 90 ℃, and preferably 90-160 ℃;
the breakdown field strength E of the polypropylene graft containing anhydride groups at 90 ℃gThe voltage is more than or equal to 210kV/mm, and preferably 210-800 kV/mm;
the breakdown field strength E of the polypropylene graft containing anhydride groups 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 1.8 percent, preferably 2 to 50 percent, more preferably 5 to 35 percent, and further preferably 8 to 28 percent;
-the direct volume resistivity p of the polypropylene graft containing anhydride groups at 90 ℃ at a field strength of 15kV/mmvg≥1.5×1013Ω · m, preferably 1.5 × 1013Ω·m～1.0×1020Ω·m；
-the direct volume resistivity p of the polypropylene graft containing anhydride groups 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 2, preferably 2.1 to 40, more preferably 2.3 to 20, and further preferably 2.5 to 10;
-the polypropylene graft containing anhydride groups has a dielectric constant of more than 2.0, preferably 2.1 to 2.5 at 90 ℃ and 50 Hz.
4. The anhydride group-containing polypropylene graft according to any one of claims 1 to 3, wherein 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 material to the copolymerized polypropylene is 0.5 to 3, preferably 0.8 to 1.3.
5. The anhydride group-containing polypropylene graft according to any one of claims 1 to 3, wherein 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。
6. The anhydride group-containing polypropylene graft according to any one of claims 1 to 3, 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.
7. The anhydride group-containing polypropylene graft according to any one of claims 1 to 3, wherein the alkenyl-containing polymerizable monomer is at least one selected from monomers having a structure represented by formula 1,
in the formula 1, R1、R2、R3Each independently selected from H, substituted or unsubstituted alkyl; r4Selected from substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryl, substituted or unsubstituted ester group, substituted or unsubstituted carboxyl, substituted or unsubstituted cycloalkyl or heterocyclic group, cyano;
preferably, R1、R2、R3Each independently selected from H, substituted or unsubstituted C1-C6Alkyl, more preferably, R1、R2、R3Each independently selected from H, substituted or unsubstituted C1-C3An alkyl group; preferably, R4Selected from substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted C1-C20Alkoxy, substituted or unsubstituted C6-C20Aryl, substituted or unsubstituted C1-C20Ester group, substituted or unsubstituted C1-C20Carboxy, substituted or unsubstituted C3-C20Cycloalkyl or heterocyclic radical, cyano radical, the said substituted radicals being halogen, hydroxy, amino, C1-C6Alkyl radical, C3-C6A cycloalkyl group; further preferably, R4Selected from substituted or unsubstituted C1-C12Alkyl, substituted or unsubstituted C1-C18Alkoxy, substituted or unsubstituted C6-C12Aryl, substituted or unsubstituted C1-C12Ester group, substituted or unsubstituted C1-C12Carboxy, substituted or unsubstituted C3-C12Cycloalkyl or heterocyclyl, cyano, said substituted radicals being halogen, C1-C6Alkyl radical, C3-C6A cycloalkyl group; more preferably, R4Selected from substituted or unsubstituted C1-C6Alkyl, substituted or unsubstituted C1-C12Alkoxy, substituted or unsubstituted C6-C8Aryl, substituted or unsubstituted C1-C6Ester group, substituted or unsubstituted C1-C6Carboxy, substituted or unsubstituted C3-C6Cycloalkyl or heterocyclyl, cyano; preferably, the heterocyclic group is selected from the group consisting of imidazolyl, pyrazolyl,Carbazolyl, pyrrolidinonyl, pyridyl, piperidyl, caprolactam base, pyrazinyl, thiazolyl, purinyl, morpholinyl, oxazolinyl.
8. The anhydride group-containing polypropylene graft according to claim 7, wherein R1、R2、R3Each independently selected from H, substituted or unsubstituted C1-C6An alkyl group;
R4a heterocyclic group selected from the group consisting of a group represented by formula 2, a group represented by formula 3, a group represented by formula 4, a group represented by formula 5, a combination of a group represented by formula 5 and a group represented by formula 6;
in the formula 2, 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, 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 3, 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, 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 4, 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, R4’-R10' each independently of the otherIs selected from H, halogen, hydroxyl, 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 5, RmSelected 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.
9. The anhydride group-containing polypropylene graft according to claim 8, wherein the alkenyl-containing polymeric monomer is at least one selected from the group consisting of vinyl acetate, styrene, α -methylstyrene, (meth) acrylate, vinyl alkyl ether, vinyl pyrrolidone, vinyl pyridine, vinyl imidazole and acrylonitrile; the (meth) acrylate is preferably at least one of methyl (meth) acrylate, ethyl (meth) acrylate, and glycidyl (meth) acrylate; preferably, the alkenyl-containing polymeric monomer is selected from vinyl acetate, styrene, alpha-methylstyrene; further preferably, the alkenyl-containing polymeric monomer is styrene.
10. The anhydride group-containing polypropylene graft according to any one of claims 1 to 3, wherein the anhydride group-containing polypropylene graft has a molar ratio of the structural unit derived from the anhydride monomer to the structural unit derived from the alkenyl-containing polymeric monomer of 1: 1-20, preferably 1: 1 to 10.
11. The anhydride group-containing polypropylene graft according to any one of claims 1 to 3, wherein the anhydride is selected from the group consisting of anhydrides having at least one olefinic unsaturation; preferably, the anhydride is selected from maleic anhydride and/or itaconic anhydride; further preferably, the anhydride is maleic anhydride.
12. The anhydride group-containing polypropylene graft according to any one of claims 1 to 3, wherein the anhydride group-containing polypropylene graft is prepared by a solid phase graft reaction of a copolymerized polypropylene, an anhydride monomer and an alkenyl-containing polymerized monomer.
13. A method for preparing an anhydride group-containing polypropylene graft, comprising: in the presence of inert gas, carrying out grafting reaction on a reaction mixture comprising polypropylene copolymer, anhydride monomer and alkenyl-containing polymerized monomer to obtain the polypropylene graft containing anhydride groups;
wherein the grafting reaction conditions are such that: the content of the structural units derived from the acid anhydride monomer and the alkenyl-containing polymerized monomer in a grafted state in the acid anhydride group-containing polypropylene graft is 0.1 to 5 wt%, preferably 0.4 to 3 wt%, based on the weight of the acid anhydride group-containing polypropylene graft; and the content of the structural unit which is derived from the anhydride monomer and is in a grafting state in the polypropylene graft containing the anhydride group is 0.05-2 wt%, preferably 0.2-0.7 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.
14. The production method according to claim 13, wherein the conditions of the grafting reaction are such that: the mole ratio of the structural unit derived from the acid anhydride monomer to the structural unit derived from the olefin-containing polymerized monomer in the acid anhydride group-containing polypropylene graft is 1: 1-20, preferably 1: 1 to 10.
15. The method of claim 13, wherein the anhydride is selected from anhydrides having at least one olefinic unsaturation; preferably, the anhydride is selected from maleic anhydride and itaconic anhydride; further preferably, the anhydride is maleic anhydride.
16. The production method according to claim 13, wherein 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 material to the copolymerized polypropylene is 0.5 to 3, preferably 0.8 to 1.3.
17. The production method according to claim 13, wherein 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 ℃, more preferably 120-170 ℃, and more preferably 120-166 ℃; weight average molecular weight of 20X 104～60×104g/mol。
18. The method of claim 13, wherein the comonomer of the co-polypropylene is selected from the group consisting of 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.
19. The production method according to claim 13, wherein the alkenyl-containing polymeric monomer is at least one selected from monomers having a structure represented by formula 1,
in the formula 1, R1、R2、R3Each independently selected from H, substituted or unsubstituted alkyl; r4Selected from substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryl, substituted or unsubstituted ester group, substituted or unsubstituted carboxyl, substituted or unsubstituted cycloalkyl or heterocyclic group, cyano;
preferably, R1、R2、R3Each independently selected from H, substituted or unsubstituted C1-C6Alkyl, preferably, R1、R2、R3Each independently selected from H, substituted or unsubstituted C1-C3An alkyl group; r4Selected from substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted C1-C20Alkoxy, substituted or unsubstituted C6-C20Aryl, substituted or unsubstituted C1-C20Ester group, substituted or unsubstituted C1-C20Carboxy, substituted or unsubstituted C3-C20Cycloalkyl or heterocyclic radical, cyano radical, the said substituted radicals being halogen, hydroxy, amino, C1-C6Alkyl radical, C3-C6A cycloalkyl group; preferably, R4Selected from substituted or unsubstituted C1-C12Alkyl, substituted or unsubstituted C1-C18Alkoxy, substituted or unsubstituted C6-C12Aryl, substituted or unsubstituted C1-C12Ester group, substituted or unsubstituted C1-C12Carboxy, substituted or unsubstituted C3-C12Cycloalkyl or heterocyclyl, cyano, said substituted radicals being halogen, C1-C6Alkyl radical, C3-C6A cycloalkyl group; more preferably, R4Selected from substituted or unsubstituted C1-C6Alkyl, substituted or unsubstituted C1-C12Alkoxy, substituted or unsubstituted C6-C8Aryl, substituted or unsubstituted C1-C6Ester group, substituted or unsubstituted C1-C6Carboxy, substituted or unsubstituted C3-C6Cycloalkyl or heterocyclyl, cyano; preferably, the heterocyclic group is selected from the group consisting of imidazolyl, pyrazolyl, carbazolyl, pyrrolidinonyl, pyridyl, piperidyl, caprolactam group, pyrazinyl, thiazolyl, purinyl, morpholinyl, oxazolinyl.
20. The method of claim 19, wherein R1、R2、R3Each independently selected from H, substituted or unsubstituted C1-C6An alkyl group;
R4a heterocyclic group selected from the group consisting of a group represented by formula 2, a group represented by formula 3, a group represented by formula 4, a group represented by formula 5, a combination of a group represented by formula 5 and a group represented by formula 6;
in the formula 2, 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, 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 3, 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, 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 4, 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 notSubstituted 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, 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);
in the formula 5, RmSelected 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 alkenyl-containing polymeric monomer is selected from at least one of vinyl acetate, styrene, α -methylstyrene, (meth) acrylate, vinyl alkyl ether, vinyl pyrrolidone, vinyl pyridine, vinyl imidazole, and acrylonitrile; the (meth) acrylate is preferably at least one of methyl (meth) acrylate, ethyl (meth) acrylate, and glycidyl (meth) acrylate; preferably, the alkenyl-containing polymeric monomer is selected from vinyl acetate, styrene, alpha-methylstyrene; further preferably, the alkenyl-containing polymeric monomer is styrene.
21. The method of any one of claims 13-20, 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.
22. The production method according to claim 21, wherein a ratio of the mass of the radical initiator to the total mass of the acid anhydride monomer and the alkenyl group-containing polymerized monomer is 0.1 to 10:100, preferably 0.5 to 5: 100.
23. The production method according to any one of claims 13 to 20, wherein the mass ratio of the total mass of the acid anhydride monomer and the alkenyl group-containing polymerized monomer to the copolymerized polypropylene is 0.1 to 8:100, preferably 0.3 to 5: 100.
24. The method of any one of claims 13 to 20, 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.
25. The method of any one of claims 13-20, 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.
26. The method of manufacturing of claim 25, 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 anhydride monomer and an alkenyl-containing polymerization 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 and drying to obtain the polypropylene graft containing the anhydride group.
27. The method of manufacturing of claim 25, 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 anhydride monomer and an alkenyl-containing polymeric 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 and drying to obtain the polypropylene graft containing the anhydride group.
28. An acid anhydride group-containing polypropylene graft obtained by the production method according to any one of claims 13 to 27.
29. Use of an anhydride group-containing polypropylene graft according to any one of claims 1 to 12 and 29.
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