CN115197355B - Ethylene/butadiene copolymer with high breakdown voltage and preparation method thereof - Google Patents
Ethylene/butadiene copolymer with high breakdown voltage and preparation method thereof Download PDFInfo
- Publication number
- CN115197355B CN115197355B CN202211031837.3A CN202211031837A CN115197355B CN 115197355 B CN115197355 B CN 115197355B CN 202211031837 A CN202211031837 A CN 202211031837A CN 115197355 B CN115197355 B CN 115197355B
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- China
- Prior art keywords
- ethylene
- copolymer
- butadiene
- carbon atoms
- borate
- Prior art date
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims abstract description 224
- 229920001577 copolymer Polymers 0.000 title claims abstract description 195
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 175
- 239000005977 Ethylene Substances 0.000 title claims abstract description 175
- 230000015556 catabolic process Effects 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- -1 salt compound Chemical class 0.000 claims abstract description 89
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 64
- 239000003054 catalyst Substances 0.000 claims abstract description 43
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 36
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 34
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- 239000012429 reaction media Substances 0.000 claims abstract description 23
- 238000002844 melting Methods 0.000 claims abstract description 16
- 230000008018 melting Effects 0.000 claims abstract description 16
- 238000002425 crystallisation Methods 0.000 claims abstract description 8
- 230000008025 crystallization Effects 0.000 claims abstract description 8
- 230000000977 initiatory effect Effects 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 81
- 239000000243 solution Substances 0.000 claims description 55
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 49
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 21
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 18
- 125000001931 aliphatic group Chemical group 0.000 claims description 15
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 claims description 14
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 14
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 13
- 150000001768 cations Chemical class 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 10
- 125000003342 alkenyl group Chemical group 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 125000003282 alkyl amino group Chemical group 0.000 claims description 9
- 150000001450 anions Chemical class 0.000 claims description 9
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 230000003197 catalytic effect Effects 0.000 claims description 9
- 125000000262 haloalkenyl group Chemical group 0.000 claims description 9
- 125000001188 haloalkyl group Chemical group 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- 125000001769 aryl amino group Chemical group 0.000 claims description 8
- 150000004758 branched silanes Chemical group 0.000 claims description 8
- 238000009826 distribution Methods 0.000 claims description 8
- 229910052684 Cerium Inorganic materials 0.000 claims description 7
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 7
- 229910052691 Erbium Inorganic materials 0.000 claims description 7
- 229910052693 Europium Inorganic materials 0.000 claims description 7
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 7
- 229910052689 Holmium Inorganic materials 0.000 claims description 7
- 229910052765 Lutetium Inorganic materials 0.000 claims description 7
- 229910052779 Neodymium Inorganic materials 0.000 claims description 7
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 7
- 229910052772 Samarium Inorganic materials 0.000 claims description 7
- 229910052771 Terbium Inorganic materials 0.000 claims description 7
- 229910052775 Thulium Inorganic materials 0.000 claims description 7
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 7
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 7
- HPYNZHMRTTWQTB-UHFFFAOYSA-N dimethylpyridine Natural products CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 claims description 7
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 7
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 7
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 7
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 7
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 7
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 7
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 7
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 7
- 229910052706 scandium Inorganic materials 0.000 claims description 7
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 7
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052727 yttrium Inorganic materials 0.000 claims description 7
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 6
- 150000001502 aryl halides Chemical class 0.000 claims description 6
- 125000001626 borono group Chemical group [H]OB([*])O[H] 0.000 claims description 6
- 150000004757 linear silanes Chemical class 0.000 claims description 6
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 claims description 6
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 6
- OJJVPGJEBAZOIF-UHFFFAOYSA-N (2,3,4,5-tetrafluorophenoxy)boronic acid Chemical compound OB(O)OC1=CC(F)=C(F)C(F)=C1F OJJVPGJEBAZOIF-UHFFFAOYSA-N 0.000 claims description 5
- JWZGJDATMFMKIO-UHFFFAOYSA-N (2,3,4-trifluorophenoxy)boronic acid Chemical compound OB(O)OC1=CC=C(F)C(F)=C1F JWZGJDATMFMKIO-UHFFFAOYSA-N 0.000 claims description 5
- LCIOIBLOWNIOOF-UHFFFAOYSA-N (2,3-difluorophenoxy)boronic acid Chemical compound OB(O)OC1=CC=CC(F)=C1F LCIOIBLOWNIOOF-UHFFFAOYSA-N 0.000 claims description 5
- LKWLQPNRJQQVEB-UHFFFAOYSA-N (2,3-dimethylphenoxy)boronic acid Chemical compound CC1=CC=CC(OB(O)O)=C1C LKWLQPNRJQQVEB-UHFFFAOYSA-N 0.000 claims description 5
- HTGQCLJTWPSFNL-UHFFFAOYSA-N (2-methylphenoxy)boronic acid Chemical compound CC1=CC=CC=C1OB(O)O HTGQCLJTWPSFNL-UHFFFAOYSA-N 0.000 claims description 5
- PHBVXHIVWULVNF-UHFFFAOYSA-N (4-fluorophenoxy)boronic acid Chemical compound OB(O)OC1=CC=C(F)C=C1 PHBVXHIVWULVNF-UHFFFAOYSA-N 0.000 claims description 5
- GWUXLTRGPPIDJA-UHFFFAOYSA-N (4-methylphenyl)alumane Chemical compound CC1=CC=C([AlH2])C=C1 GWUXLTRGPPIDJA-UHFFFAOYSA-N 0.000 claims description 5
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 5
- 150000001924 cycloalkanes Chemical class 0.000 claims description 5
- OTACYDLCOLOKPA-UHFFFAOYSA-N dibenzyl(ethyl)alumane Chemical compound C=1C=CC=CC=1C[Al](CC)CC1=CC=CC=C1 OTACYDLCOLOKPA-UHFFFAOYSA-N 0.000 claims description 5
- 150000008040 ionic compounds Chemical class 0.000 claims description 5
- 150000003254 radicals Chemical class 0.000 claims description 5
- MCWWHQMTJNSXPX-UHFFFAOYSA-N tribenzylalumane Chemical compound C=1C=CC=CC=1C[Al](CC=1C=CC=CC=1)CC1=CC=CC=C1 MCWWHQMTJNSXPX-UHFFFAOYSA-N 0.000 claims description 5
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 claims description 5
- ZIYNWDQDHKSRCE-UHFFFAOYSA-N tricyclohexylalumane Chemical compound C1CCCCC1[Al](C1CCCCC1)C1CCCCC1 ZIYNWDQDHKSRCE-UHFFFAOYSA-N 0.000 claims description 5
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 5
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 claims description 5
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 5
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 5
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 claims description 5
- JOJQVUCWSDRWJE-UHFFFAOYSA-N tripentylalumane Chemical compound CCCCC[Al](CCCCC)CCCCC JOJQVUCWSDRWJE-UHFFFAOYSA-N 0.000 claims description 5
- JQPMDTQDAXRDGS-UHFFFAOYSA-N triphenylalumane Chemical compound C1=CC=CC=C1[Al](C=1C=CC=CC=1)C1=CC=CC=C1 JQPMDTQDAXRDGS-UHFFFAOYSA-N 0.000 claims description 5
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 claims description 5
- WSITXTIRYQMZHM-UHFFFAOYSA-N tris(4-methylphenyl)alumane Chemical compound C1=CC(C)=CC=C1[Al](C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WSITXTIRYQMZHM-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- ANEFWEBMQHRDLH-UHFFFAOYSA-N tris(2,3,4,5,6-pentafluorophenyl) borate Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1OB(OC=1C(=C(F)C(F)=C(F)C=1F)F)OC1=C(F)C(F)=C(F)C(F)=C1F ANEFWEBMQHRDLH-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- OJOSABWCUVCSTQ-UHFFFAOYSA-N cyclohepta-2,4,6-trienylium Chemical compound C1=CC=C[CH+]=C[CH]1 OJOSABWCUVCSTQ-UHFFFAOYSA-N 0.000 claims description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 100
- 238000006243 chemical reaction Methods 0.000 description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 20
- 239000000178 monomer Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000001514 detection method Methods 0.000 description 8
- 229920001971 elastomer Polymers 0.000 description 8
- 239000005060 rubber Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 229920001721 polyimide Polymers 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000007983 Tris buffer Substances 0.000 description 4
- 229920003020 cross-linked polyethylene Polymers 0.000 description 4
- 239000004703 cross-linked polyethylene Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920006030 multiblock copolymer Polymers 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000004224 protection Effects 0.000 description 3
- 229920005604 random copolymer Polymers 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229920000028 Gradient copolymer Polymers 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 230000037048 polymerization activity Effects 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- 101000734334 Arabidopsis thaliana Protein disulfide isomerase-like 1-1 Proteins 0.000 description 1
- 101000609815 Caenorhabditis elegans Protein disulfide-isomerase 1 Proteins 0.000 description 1
- 101000609840 Caenorhabditis elegans Protein disulfide-isomerase 2 Proteins 0.000 description 1
- 101100135890 Caenorhabditis elegans pdi-6 gene Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention provides an ethylene/butadiene copolymer, which consists of an ethylene structural unit and a butadiene structural unit; the content of ethylene structural units is not less than 65mol%, and the content of trans-1, 4-structural units in butadiene structural units is not less than 10mol%; the melting point of the crystallization sequence in the copolymer is 100-140 ℃; the ethylene/butadiene copolymer has a high breakdown voltage; the breakdown field intensity of the ethylene/butadiene copolymer is 260-370 mm/KV. The invention also provides a corresponding preparation method, which comprises the steps of initiating polymerization reaction of ethylene, 1, 3-butadiene and a catalyst system in a reaction medium to obtain an ethylene/butadiene binary copolymer; the catalyst system comprises an organoboron salt compound, an organoaluminum compound, and a rare earth metal complex; the rare earth metal complex has a general formula shown in a structure of a formula (I).
Description
Technical Field
The invention belongs to the technical field of ethylene/butadiene copolymer materials, relates to an ethylene/butadiene copolymer and a preparation method thereof, and particularly relates to an ethylene/butadiene copolymer with high breakdown voltage and a preparation method thereof.
Background
The second largest ethylene producing country in the world is second to the united states, and the shale gas revolution provides a large amount of cheap ethane as ethylene cracking raw material for ethylene industry, which causes serious impact to the traditional ethylene industry of China which takes naphtha as cracking raw material. Meanwhile, the polyethylene industry, as a major downstream industry of the ethylene industry, faces the dilemma that the profitability is lowered although the yield is increased year by year, and thus it is important to increase the competitiveness of the ethylene industry by increasing the additional value of ethylene.
Ethylene and butadiene are copolymerized, and with the change of the feeding proportion of the two monomers, the novel plastic reinforced rubber and the plastic containing unsaturated double bond functional groups and other materials with different series of properties can be prepared theoretically. The ethylene homopolymer is plastic and the cis-polybutadiene is rubber. The polyethylene molecular chain has large flexibility, strong crystallization capability, higher modulus and strength, good toughness and tear resistance; butadiene rubber molecular chain is extremely compliant, excellent in elasticity and cold resistance, but low in tensile and tear strength. The polyethylene sequence is introduced into the rubber, so that the double bond content in the rubber is reduced, the ageing resistance and ultraviolet resistance of the rubber are improved, the rubber can be enhanced, and the application field of the rubber is further widened. Unsaturated carbon-carbon double bonds are introduced into the polyolefin chain and can be used as reactive functional groups, thereby providing convenience for preparing high-performance and functional polyolefin through chemical conversion. Thus, ethylene/conjugated diene copolymerization has attracted research interest since the invention of Ziegler-Natta catalysts.
The crosslinked polyethylene has good electrical properties, large insulation resistance, low dielectric loss tangent and high breakdown field strength (generally, the breakdown field strength is about 260 mm/KV). The material has a three-dimensional reticular macromolecular structure, good mechanical property and environmental stress cracking resistance, and the long-term working temperature of the material can reach 90 ℃. At present, the crosslinked polyethylene is mainly prepared into the special crosslinked polyethylene for the cable insulating material by the methods of chemical crosslinking, silane crosslinking, irradiation crosslinking, ultraviolet crosslinking and the like through the low-density polyethylene. Low density polyethylene is usually prepared from ethylene by radical polymerization under high pressure, and its heat resistance is not high, but in practice, the case of high cable heating with the increase of the distance of power transmission limits the application of crosslinked polyethylene in power transmission.
In the prior art, the rubber is prepared by ethylene/butadiene copolymerization, so that the ethylene content of the prepared copolymer cannot be excessively high, and crystalline polyethylene sequences are not present or only polyethylene segments with short sequence lengths are present. Therefore, materials with high breakdown field strength have not been prepared previously by ethylene-butadiene copolymerization.
Therefore, how to further improve the performance of the ethylene/butadiene copolymer, and solve the above limitations of the ethylene/butadiene copolymer in application at present, so that the ethylene/butadiene copolymer becomes a low dielectric constant material with very good development prospect, and has become one of the focuses of great attention of many researchers in the industry.
Disclosure of Invention
In view of the above, the present invention provides an ethylene/butadiene copolymer and a preparation method thereof, and in particular, an ethylene/butadiene copolymer with high breakdown voltage. The ethylene/butadiene copolymer provided by the invention can be crosslinked to obtain a material with low dielectric constant, and has higher breakdown voltage.
The invention provides an ethylene/butadiene copolymer, which consists of an ethylene structural unit and a butadiene structural unit;
wherein the content of ethylene structural units is not less than 65mol%, and the content of trans-1, 4-structural units in butadiene structural units is not less than 10mol%;
the melting point of the crystallization sequence in the copolymer is 100-140 ℃;
the ethylene/butadiene copolymers include ethylene/butadiene copolymers having a high breakdown voltage;
the breakdown field intensity of the ethylene/butadiene copolymer is 260-370 mm/KV.
Preferably, the content of ethylene structural units in the copolymer is not less than 75mol%;
the content of trans-1, 4-structural units in butadiene structural units in the copolymer is not less than 20mol%;
the melting point of the crystalline sequence in the copolymer is 105-135 ℃.
Preferably, the ethylene/butadiene copolymer is an ethylene/butadiene copolymer containing crystalline sequences;
The copolymer is prepared from ethylene and 1, 3-butadiene under the action of a catalytic system.
Preferably, the copolymer has a molecular weight distribution of not more than 8;
the number average molecular weight of the copolymer is 10000-500000.
Preferably, the catalyst system comprises an organoboron salt compound, an organoaluminum compound, and a rare earth metal complex;
the rare earth metal complex has a general formula shown in a structure of a formula (I):
wherein M is selected from one of scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium;
R 1 、R 2 and R is 3 Each independently selected from the group consisting of a hydrogen atom, an alkyl or haloalkyl group containing from 1 to 10 carbon atoms, an alkenyl or haloalkenyl group containing from 2 to 20 carbon atoms, an aralkyl or haloaralkyl group containing from 6 to 20 carbon atoms, a silyl group containing from 1 to 14 carbon atoms;
X 1 and X 2 Each independently selected from the group consisting of hydrogen, a linear or branched aliphatic or cycloaliphatic radical having from 1 to 20 carbon atoms, phenyl, a linear or branched alkyl or cycloaliphatic or aromatic substituted phenyl having from 1 to 20 carbon atoms, a linear or branched alkoxy having from 1 to 20 carbon atoms, a linear or branched alkylamino having from 1 to 20 carbon atoms, a linear or branched arylamino having from 1 to 20 carbon atoms, a linear or branched silane group having from 1 to 20 carbon atoms, a borono, an allyl derivative, and a halogen;
L is selected from one of tetrahydrofuran, ethylene glycol dimethyl ether and pyridine;
w is an integer of 0 to 3.
The invention also provides a preparation method of the ethylene/butadiene copolymer, which comprises the following steps:
1) Initiating polymerization reaction of ethylene, 1, 3-butadiene and a catalyst system in a reaction medium to obtain an ethylene/butadiene binary copolymer;
the catalyst system comprises an organoboron salt compound, an organoaluminum compound, and a rare earth metal complex;
the rare earth metal complex has a general formula shown in a structure of a formula (I):
wherein M is selected from one of scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium;
R 1 、R 2 and R is 3 Each independently selected from the group consisting of a hydrogen atom, an alkyl or haloalkyl group containing from 1 to 10 carbon atoms, an alkenyl or haloalkenyl group containing from 2 to 20 carbon atoms, an aralkyl or haloaralkyl group containing from 6 to 20 carbon atoms, a silyl group containing from 1 to 14 carbon atoms;
X 1 and X 2 Each independently selected from the group consisting of hydrogen, a linear or branched aliphatic or cycloaliphatic radical having from 1 to 20 carbon atoms, phenyl, a linear or branched alkyl or cycloaliphatic or aromatic substituted phenyl having from 1 to 20 carbon atoms, a linear or branched alkoxy having from 1 to 20 carbon atoms, a linear or branched alkylamino having from 1 to 20 carbon atoms, a linear or branched arylamino having from 1 to 20 carbon atoms, a linear or branched silane group having from 1 to 20 carbon atoms, a borono, an allyl derivative, and a halogen;
L is selected from one of tetrahydrofuran, ethylene glycol dimethyl ether and pyridine;
w is an integer of 0 to 3.
Preferably, the organoboron salt compound comprises an ionic compound formed from an organoboron anion and a cation, and/or an organoboron compound;
the organoboron anions include one or more of tetraphenyl borate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetrakis (tolyl) borate, tetrakis (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [ tris (pentafluorophenyl) borate, phenyl ] borate, and undecahydride-7, 8-dicarbaundecaborate;
the cation includes carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptatrienyl cation or ferrocenium cation containing transition metal;
the organoboron compound comprises B (C 6 F 5 ) 3 ；
The organoaluminum compound includes one or more of trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisopropylaluminum, triisobutylaluminum, tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum, triphenylaluminum, tri-p-tolylaluminum, tribenzylaluminum, ethyldibenzylaluminum and ethyldi (p-tolylaluminum;
The organoboron salt compound is specifically an organoboron salt compound solution.
Preferably, the molar ratio of the organoboron salt compound to the rare earth metal complex is (1-10):
(10～1)；
the molar ratio of the organic aluminum compound to the rare earth metal complex is (2-300): 1, a step of;
the ethylene pressure is 1-50 atmospheres.
Preferably, the reaction medium comprises one or more of aliphatic saturated hydrocarbons, aromatic hydrocarbons, aryl halides and cycloalkanes;
the concentration of the 1, 3-butadiene in the reaction medium is lower than 2mol/L;
the temperature of the polymerization reaction is-20-150 ℃.
Preferably, the step 1) specifically includes:
1) Mixing 1, 3-butadiene, a part of organic aluminum compound solution and a reaction medium, and introducing ethylene to obtain a polymerization reaction system;
2) Mixing the rare earth metal complex solution, the other part of organic aluminum compound, organic boron salt compound and reaction medium again to obtain catalyst solution, heating the catalyst solution in the polymerization reaction system obtained in the above steps, increasing the pressure of ethylene, and carrying out polymerization reaction to obtain the ethylene/butadiene binary copolymer.
The invention provides an ethylene/butadiene copolymer, which consists of an ethylene structural unit and a butadiene structural unit; wherein the content of ethylene structural units is not less than 65mol%, and the content of trans-1, 4-structural units in butadiene structural units is not less than 10mol%; the melting point of the crystallization sequence in the copolymer is 100-140 ℃; the ethylene/butadiene copolymers include ethylene/butadiene copolymers having a high breakdown voltage; the breakdown field intensity of the ethylene/butadiene copolymer is 260-370 mm/KV. Compared with the prior art, the invention aims at the limitation of the prior ethylene/butadiene copolymer in performance, and particularly the defect that the ethylene/butadiene copolymer is difficult to apply in the environment of high breakdown field strength. The invention creatively obtains the ethylene/butadiene copolymer with specific composition and structure and high breakdown voltage, the breakdown field strength of the binary copolymer is between 260 and 370mm/KV, the content of ethylene structural units in the copolymer is not less than 65mol percent, the content of trans-1, 4-structure in the butadiene structural units is not less than 10mol percent, and more importantly, the melting point of a crystallization sequence in the copolymer is between 100 and 140 ℃. The present invention provides a binary copolymer of ethylene and 1, 3-butadiene, which is a random copolymer or a multiblock copolymer containing 1, 3-butadiene monomer units and ethylene monomer units, has a higher content of ethylene, and has crystalline polyethylene segments with longer sequence lengths. The copolymer can be crosslinked to obtain a material with low dielectric constant, has higher breakdown voltage, and is a novel plastic material which is not reported in the prior art such as patents, documents and the like.
The invention also provides a preparation method of the copolymer, and particularly, the ethylene/butadiene copolymer is obtained by copolymerizing ethylene and butadiene monomers through a catalytic system composed of amidino rare earth metal complex with a specific structure, an organoboron compound and aluminum alkyl. The invention adopts two monomers of ethylene and 1, 3-butadiene with very different polymerization mechanisms and polymerization activities, and can obtain high catalytic activities on ethylene and 1, 3-butadiene monomers by adjusting the catalyst structure and changing the polymerization process.
The ethylene-butadiene provided by the invention has a lower dielectric constant, can be used in an environment with higher breakdown field strength, is a low dielectric constant material with a very development prospect, solves the application limitation of the existing ethylene-butadiene copolymer, and greatly widens the application depth and breadth of the ethylene-butadiene copolymer.
Experimental results show that the breakdown voltage of the ethylene/butadiene copolymer provided by the invention can reach 370mm/KV.
Drawings
FIG. 1 is a sample of a copolymer prepared in example 1 of the present invention 1 H NMR spectrum;
FIG. 2 is a sample of the copolymer prepared in example 6 of the present invention 1 H NMR spectrum;
FIG. 3 is a sample of the copolymer prepared in example 6 of the present invention 13 C NMR spectrum;
FIG. 4 is a graph showing the mechanical properties of a copolymer sample prepared in example 7 of the present invention;
FIG. 5 is a graph showing the mechanical properties of a copolymer sample prepared in example 8 of the present invention;
FIG. 6 is a graph showing breakdown voltage test of a copolymer sample prepared in example 9 of the present invention.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention and are not limiting of the invention claims.
All the raw materials of the present invention are not particularly limited in their sources, and may be purchased on the market or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the present invention are not particularly limited in terms of purity, and the present invention preferably employs analytically pure or conventional purity requirements in the field of ethylene/butadiene copolymer production.
The expression of the substituents is not particularly limited in the present invention, and all of them are well known to those skilled in the art, and those skilled in the art can correctly understand the meaning based on the general knowledge.
All raw materials of the invention, the brands or abbreviations of which belong to the conventional brands or abbreviations in the field of the related application are clear and definite, and the person skilled in the art can purchase from the market or prepare by the conventional method according to the brands, abbreviations and the corresponding application.
The invention provides an ethylene/butadiene copolymer, which is characterized in that the copolymer consists of an ethylene structural unit and a butadiene structural unit;
wherein the content of ethylene structural units is not less than 65mol%, and the content of trans-1, 4-structural units in butadiene structural units is not less than 10mol%;
the melting point of the crystallization sequence in the copolymer is 100-140 ℃;
the ethylene/butadiene copolymers include ethylene/butadiene copolymers having a high breakdown voltage;
the breakdown field intensity of the ethylene/butadiene copolymer is 260-370 mm/KV.
In the present invention, the melting point of the crystalline sequence in the copolymer is 100 to 140℃and may be 105 to 135℃and preferably 110 to 130℃and more preferably 115 to 125 ℃.
In the present invention, the ethylene/butadiene copolymer has a breakdown field strength of 260 to 370mm/KV, which may be 280 to 350mm/KV, preferably 300 to 330mm/KV.
In the present invention, the content of the ethylene structural unit in the copolymer is preferably not less than 75mol%, more preferably not less than 80mol%. Specifically, the main chain of the copolymer preferably contains ethylene units, and the content of the ethylene units is preferably greater than 65mol% of the entire copolymer, more preferably greater than 68mol% of the entire copolymer, and most preferably 70 to 93mol% of the entire copolymer, more preferably 72 to 91mol%, more preferably 70 to 89mol%, more preferably 72 to 87mol%, more preferably 74 to 85mol%, and most preferably 80mol%.
In the present invention, the content of trans 1, 4-structural units in the butadiene structural unit in the copolymer is preferably not less than 20mol%, more preferably not less than 30mol%.
In the present invention, the content of trans-1, 4-structural units in the ethylene structural unit+butadiene structural unit is 100mol% or less.
In the present invention, the melting point of the crystalline sequence in the copolymer is preferably 105 to 135 ℃, more preferably 110 to 130 ℃, and still more preferably 115 to 125 ℃.
In the present invention, the copolymer backbone comprises ethylene units and 1, 3-butadiene units; the content of the 1, 3-butadiene structural unit is 10-35 mol%; the content of the ethylene structural unit is 65-90 mol%.
Wherein the 1, 3-butadiene unit content is preferably more than 10mol% and less than 35mol% of the whole of the copolymer, more preferably more than 12mol% and less than 32mol% of the whole of the copolymer, and most preferably more than 15mol% and less than 30mol% of the whole of the copolymer.
Wherein the 1,3 butadiene structural unit content in the copolymer is preferably higher than 15mol%.
Wherein the content of trans 1,4 butadiene structural units in the copolymer is preferably higher than 10mol%.
The main chain of the copolymer preferably further contains ethylene units, and the content of the ethylene units is preferably 65mol% or more, more preferably 68mol% or more, and most preferably 70 to 93mol%, more preferably 72 to 91mol%, more preferably 70 to 89mol%, more preferably 72 to 87mol%, more preferably 74 to 85mol%, and more preferably 80mol% of the entire copolymer.
In the present invention, the ethylene/butadiene copolymer is preferably an ethylene/butadiene copolymer containing a crystalline sequence.
In the present invention, the copolymer is preferably prepared from ethylene and 1, 3-butadiene under the action of a catalytic system.
In the present invention, the molecular weight distribution of the copolymer is preferably not higher than 8, more preferably not higher than 6, and still more preferably not higher than 4. Specifically, the ratio may be 1 to 8, more preferably 1 to 5, and most preferably 1 to 3.
In the present invention, the number average molecular weight of the copolymer is preferably 10000 to 500000, more preferably 100000 ～ 400000, and still more preferably 200000 ～ 300000.
In the present invention, the catalyst system preferably comprises an organoboron salt compound, an organoaluminum compound, and a rare earth metal complex.
In the present invention, the rare earth metal complex preferably has a general formula represented by the structure of formula (I):
in the present invention, M is preferably one selected from scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium.
In the present invention, R 1 、R 2 And R is 3 Each independently is preferably selected from the group consisting of a hydrogen atom, an alkyl or haloalkyl group having 1 to 10 carbon atoms, an alkenyl or haloalkenyl group having 2 to 20 carbon atoms, an aralkyl or haloaralkyl group having 6 to 20 carbon atoms, a silyl group having 1 to 14 carbon atoms, more preferably selected from the group consisting of a hydrogen atom, an alkyl or haloalkyl group having 3 to 8 carbon atoms, an alkenyl or haloalkenyl group having 6 to 16 carbon atoms, an aralkyl or haloaralkyl group having 9 to 17 carbon atoms, a silyl group having 4 to 10 carbon atoms, more preferably selected from the group consisting of a hydrogen atom, an alkyl or haloalkyl group having 5 to 6 carbon atoms, an alkenyl or haloalkenyl group having 10 to 12 carbon atoms, an aralkyl or haloaralkyl group having 11 to 14 carbon atoms, and a silyl group having 6 to 8 carbon atoms.
In the present invention, X 1 And X 2 Each independently is preferably selected from the group consisting of hydrogen, a linear or branched aliphatic or cycloaliphatic group having 1 to 20 carbon atoms, phenyl, a linear or branched alkyl or cycloaliphatic or aromatic group substituted phenyl having 1 to 20 carbon atoms, a linear or branched alkoxy having 1 to 20 carbon atoms, a linear or branched alkylamino having 1 to 20 carbon atoms, a linear or branched arylamine having 1 to 20 carbon atoms, a linear or branched silane group having 1 to 20 carbon atoms, borohydrides, allyl and allyl derivatives, halogens, more preferably selected from the group consisting of hydrogen, a linear or branched aliphatic or cycloaliphatic group having 5 to 16 carbon atoms, phenyl, a linear or branched alkyl or cycloaliphatic or aromatic group substituted phenyl having 5 to 16 carbon atoms, a linear or branched alkoxy having 5 to 16 carbon atoms Straight-chain or branched alkylamino, straight-chain or branched arylamino, straight-chain or branched silane groups, borohydrides, allyl and allyl derivatives, halogens, more preferably selected from hydrogen, straight-chain or branched aliphatic or alicyclic groups, phenyl, straight-chain or branched alkyl or cyclic aliphatic or aromatic group substituted phenyl, straight-chain or branched alkoxy, straight-chain or branched alkylamino, straight-chain or branched arylamino, straight-chain or branched silane groups, borohydrides, allyl and allyl derivatives, halogen.
In the present invention, the L is one selected from tetrahydrofuran, ethylene glycol dimethyl ether and pyridine.
In the present invention, w is preferably an integer of 0 to 3, more preferably 0, 1, 2 or 3.
The invention is a complete and refined whole technical proposal, better ensures the structure of the ethylene/butadiene copolymer, further improves the breakdown voltage of the ethylene/butadiene copolymer, and the ethylene/butadiene copolymer preferably has the following structure:
An ethylene/butadiene copolymer having a high breakdown voltage, which copolymer is composed of an ethylene structural unit and a butadiene structural unit, wherein the ethylene structural unit contains not less than 65mol%, the butadiene structural unit contains not less than 10mol% of trans-1, 4-structural unit, and the melting point of the crystalline sequence in the copolymer is between 100 and 140 ℃.
Specifically, the breakdown field intensity of the copolymer is 260-370 mm/KV.
Specifically, the content of ethylene structural units in the copolymer is not less than 75mol%.
Specifically, the copolymer backbone comprises ethylene units and 1, 3-butadiene units; the content of the 1, 3-butadiene structural unit is 10-35 mol%; the content of the ethylene structural unit is 65-90 mol%.
Specifically, the content of trans-1, 4-structural units in the butadiene structural units in the copolymer is not less than 20mol%.
Specifically, the melting point of the crystalline sequence in the copolymer is between 105 and 135 ℃.
Specifically, the molecular weight of the copolymer is between 10000 and 500000.
Specifically, the molecular weight distribution of the copolymer is not higher than 8.
Further, the invention provides a binary copolymer with high breakdown field strength, and the monomers for preparing the binary copolymer comprise: ethylene and 1, 3-butadiene, the binary copolymer being a random copolymer or a multiblock copolymer;
Specifically, the copolymer backbone comprises ethylene units and 1, 3-butadiene units; the content of the 1, 3-butadiene structural unit is 10-35 mol%; the content of the ethylene structural unit is 65-90 mol%.
Specifically, the 1, 3-butadiene unit content is preferably more than 10mol% and less than 35mol% of the entire binary copolymer, more preferably more than 12mol% and less than 32mol% of the entire binary copolymer, and most preferably more than 15mol% and less than 30mol% of the entire binary copolymer.
In particular, the content of 1,3 butadiene structural units in the copolymer is preferably greater than 15mol%,
in particular, the content of trans 1,4 butadiene structural units in the copolymer is preferably higher than 10mol%.
Specifically, the main chain of the copolymer preferably further contains ethylene units, and the content of the ethylene units is preferably more than 65mol% of the entire copolymer, more preferably more than 68mol% of the entire copolymer, most preferably 70 to 95mol% of the entire copolymer, more preferably 72 to 88mol%, more preferably 70 to 86mol%, more preferably 72 to 84mol%, more preferably 74 to 82mol%, and most preferably 80mol%.
In particular, the crystalline sequences in the copolymer have a melting point of between 105 and 135 ℃, more preferably between 110 ℃ and 130 ℃, more preferably between 115 ℃ and 125 ℃, most preferably 125 ℃.
Specifically, the number average molecular weight of the binary copolymer is preferably 10000-500000, more preferably 50000-400000, and even more preferably 100000 ～ 400000; the molecular weight distribution of the copolymer is preferably between 1 and 8, more preferably between 1 and 5, most preferably between 1 and 3.
The invention also provides a preparation method of the ethylene/butadiene copolymer, which comprises the following steps:
1) Initiating polymerization reaction of ethylene, 1, 3-butadiene and a catalyst system in a reaction medium to obtain an ethylene/butadiene binary copolymer;
the catalyst system comprises an organoboron salt compound, an organoaluminum compound, and a rare earth metal complex;
the rare earth metal complex has a general formula shown in a structure of a formula (I):
wherein M is selected from one of scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium;
R 1 、R 2 and R is 3 Each independently selected from the group consisting of a hydrogen atom, an alkyl or haloalkyl group containing from 1 to 10 carbon atoms, an alkenyl or haloalkenyl group containing from 2 to 20 carbon atoms, an aralkyl or haloaralkyl group containing from 6 to 20 carbon atoms, a silyl group containing from 1 to 14 carbon atoms;
X 1 And X 2 Each independently selected from the group consisting of hydrogen, a linear or branched aliphatic or cycloaliphatic radical having from 1 to 20 carbon atoms, phenyl, a linear or branched alkyl or cycloaliphatic or aromatic substituted phenyl having from 1 to 20 carbon atoms, a linear or branched alkoxy having from 1 to 20 carbon atoms, a linear or branched alkylamino having from 1 to 20 carbon atoms, a linear or branched arylamino having from 1 to 20 carbon atoms, a linear or branched silane group having from 1 to 20 carbon atoms, a borono, an allyl derivative, and a halogen;
l is selected from one of tetrahydrofuran, ethylene glycol dimethyl ether and pyridine;
w is an integer of 0 to 3.
In the present invention, the structure, substituent and corresponding preferred principle of the rare earth metal complex in the preparation method are in one-to-one correspondence with the structure, substituent and corresponding preferred principle of the rare earth metal complex in the ethylene/butadiene copolymer, and are preferably not described in detail herein.
In the present invention, the organoboron salt compound preferably includes an ionic compound formed from an organoboron anion and a cation, and/or an organoboron compound, more preferably includes an ionic compound formed from an organoboron anion and a cation, or an organoboron compound.
In the present invention, the organoboron anion preferably includes one or more of tetraphenyl borate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetrakis (tolyl) borate, tetrakis (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [ tris (pentafluorophenyl) borate, phenyl ] borate and undecano-7, 8-dicarbaundecano, more preferably tetraphenyl borate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetrakis (tolyl) borate, tetrakis (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [ tris (pentafluorophenyl) borate, phenyl ] borate or undecano-7, 8-dicarbaundecano.
In the present invention, the cation preferably includes a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptatrienyl cation or a ferrocenium cation containing a transition metal.
In the present invention, the organoboron compound preferably includes B (C6F 5) 3 。
In the present invention, the organoaluminum compound preferably includes one or more of trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisopropylaluminum, triisobutylaluminum, tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum, triphenylaluminum, tri-p-tolylaluminum, tribenzylaluminum, ethyldibenzylaluminum and ethyldi (p-tolylaluminum, more preferably trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisopropylaluminum, triisobutylaluminum, tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum, triphenylaluminum, tri-p-tolylaluminum, tribenzylaluminum, ethyldibenzylaluminum or ethyldi (p-tolylaluminum.
In the present invention, the organoboron salt compound is particularly preferably an organoboron salt compound solution.
In the present invention, the molar ratio of the organoboron salt compound to the rare earth metal complex is preferably (1 to 10): (10 to 1), more preferably (3 to 8): (10 to 1), more preferably (5 to 6): (10 to 1), more preferably (1 to 10): (8-3), more preferably (1-10): (6-5).
In the present invention, the molar ratio of the organoaluminum compound to the rare earth metal complex is preferably (2 to 300): 1, more preferably (20 to 200): 1, more preferably (50 to 100): 1.
In the present invention, the pressure of the ethylene is preferably 1 to 50 atmospheres, more preferably 10 to 40 atmospheres, and still more preferably 20 to 30 atmospheres.
In the present invention, the reaction medium preferably includes one or more of aliphatic saturated hydrocarbons, aromatic hydrocarbons, aryl halides and cycloalkanes, more preferably aliphatic saturated hydrocarbons, aromatic hydrocarbons, aryl halides or cycloalkanes.
In the present invention, the concentration of the 1, 3-butadiene in the reaction medium is preferably less than 2mol/L, more preferably less than 1.5mol/L, and still more preferably less than 1.2mol/L.
In the present invention, the temperature of the polymerization reaction is preferably-20 to 150 ℃, more preferably 0 to 100 ℃, and still more preferably 20 to 50 ℃.
In the present invention, the step 1) is specifically preferably:
1) Mixing 1, 3-butadiene, a part of organic aluminum compound solution and a reaction medium, and introducing ethylene to obtain a polymerization reaction system;
2) Mixing the rare earth metal complex solution, the other part of organic aluminum compound, organic boron salt compound and reaction medium again to obtain catalyst solution, heating the catalyst solution in the polymerization reaction system obtained in the above steps, increasing the pressure of ethylene, and carrying out polymerization reaction to obtain the ethylene/butadiene binary copolymer.
The invention is a complete and refined whole technical proposal, better ensures the structure of the ethylene/butadiene copolymer, further improves the breakdown voltage of the ethylene/butadiene copolymer, and the preparation method of the ethylene/butadiene copolymer preferably comprises the following steps:
the preparation method of the binary copolymer comprises the following steps:
ethylene and butadiene are subjected to polymerization reaction in a reaction medium under a catalytic system to obtain a binary copolymer;
the catalytic system comprises: an organoboron salt compound, an organoaluminum compound, and a rare earth metal complex.
Specifically, the concentration of butadiene in the reaction system is not higher than 2mol/L, and the pressure of ethylene is not higher than 50bar.
Specifically, the reaction medium is selected from one or more of aliphatic saturated hydrocarbon, aromatic hydrocarbon, aryl halide and cycloparaffin.
The rare earth metal complex has the structure of formula I:
m in the formula I is selected from one of scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium;
R 1 、R 2 and R is 3 Independently selected from the group consisting of a hydrogen atom, an alkyl or haloalkyl group containing from 1 to 10 carbon atoms, an alkenyl or haloalkenyl group containing from 2 to 20 carbon atoms, an aralkyl or haloaralkyl group containing from 6 to 20 carbon atoms, a silyl group containing from 1 to 14 carbon atoms;
X 1 And X is 2 X is a monoanionic ligand 1 And X 2 Independently selected from hydrogen, a linear or branched aliphatic or cycloaliphatic radical having from 1 to 20 carbon atoms, phenyl, a linear or branched alkyl or cycloaliphatic or aromatic substituted phenyl having from 1 to 20 carbon atoms, a linear or branched alkoxy having from 1 to 20 carbon atoms, a linear or branched alkylamino having from 1 to 20 carbon atoms, a linear or branched arylamino having from 1 to 20 carbon atoms, a linear or branched silane group having from 1 to 20 carbon atoms, a borono, an allyl derivative or halogen;
l is neutral Lewis base selected from one of tetrahydrofuran, ethylene glycol dimethyl ether and pyridine;
w is an integer of 0 to 3.
Specifically, the rare earth metal complex is preferably one of formulas 1 to 8:
the source of the rare earth metal complex is not particularly limited and can be prepared according to methods well known to those skilled in the art, for example, by synthesis according to the methods disclosed in J.Am.chem.Soc.2004,126,30,9182-9183.
In particular, the organoboron compound is preferably an ionic compound formed from an organoboron anion and a cation; the organoboron anion is preferably selected from tetraphenylborates ([ BPh) 4 ] - ) Tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) borate ([ B (C) 6 F 5 ) 4 ] - ) Tetrakis (tetrafluoromethylphenyl) borate, tetrakis (tolyl) borate, tetrakis (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [ tris (pentafluorophenyl) boratePhenyl group]Borate or undecahydride-7, 8-dicarbaundecaborate; the cation is preferably selected from carbonium cations, oxonium cations, ammonium cations, phosphonium cations, cycloheptatrienyl cations or ferrocenium cations containing transition metals; the carbonium cation preferably comprises a trisubstituted carbonium cation such as a triphenylcarbonium cation ([ Ph ] 3 C] + ) And a tris (substituted phenyl) carbonium cation, and a tris (substituted phenyl) carbonium cation such as a tris (tolyl) carbonium cation; the ammonium cations preferably include trialkylammonium cations such as trimethylammonium cations, triethylammonium cations ([ NEt ] 3 H] + ) Tripropylammonium cation and tributylammonium cation; n, N-dialkylanilinium cations such as N, N-dimethylanilinium cation ([ PhNMe) 2 H] + ) N, N-diethylanilinium cations and N, N-2,4, 6-pentamethylphenylammonium cations; dialkylammonium cations such as diisopropylammonium cation and dicyclohexylammonium cation; the phosphonium cations preferably include triarylphosphonium cations such as triphenylphosphine, tri (tolyl) phosphonium or tri (xylyl) phosphonium cations.
In particular, the organoboron salt compound is preferably selected from [ Ph ] in particular 3 C][B(C 6 F 5 ) 4 ]、[PhNMe 2 H][BPh 4 ]、[NEt 3 H][BPh 4 ]Or [ PhNMe ] 2 H][B(C 6 F 5 ) 4 ]The method comprises the steps of carrying out a first treatment on the surface of the Organoboron compounds having the same function as organoboron salt compounds, e.g. B (C) 6 F 5 ) 3 。
In particular, the organoaluminum compound is preferably selected from trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisopropylaluminum, triisobutylaluminum, tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum, triphenylaluminum, tri-p-tolylaluminum, tribenzylaluminum, ethyldibenzylaluminum or ethyldi (p-tolylaluminum).
Specifically, the organoaluminum compound is preferably dissolved in a solvent, preferably toluene.
Specifically, the catalyst system preferably further comprises a solvent; the solvent is preferably selected from toluene.
Specifically, the concentration of the 1, 3-butadiene in the polymerization system is preferably less than 2mol/L, more preferably 0.05 to 2mol/L, still more preferably 0.05 to 1.0mol/L, and most preferably 0.1 to 0.8mol/L.
The amount of the catalyst system used in the present invention is not particularly limited, and a person skilled in the art may select a proper amount of catalyst system according to the amount of catalyst used in the polymerization of monomers known in the art, and may ensure that the polymerization reaction proceeds according to the actual situation.
Specifically, the molar ratio of the organoboron salt compound to the rare earth metal complex is preferably (1 to 10): (10 to 1), more preferably (2 to 8): (8-2), most preferably (3-6): (6-3); in an embodiment of the present invention, the molar ratio of the organoboron salt compound to the rare earth metal complex is preferably (0.5 to 10): 1, more preferably (1 to 8): 1, still more preferably (2 to 6): 1, and most preferably 1:1.
Specifically, the molar ratio of the organoaluminum compound to the rare earth metal complex is preferably (2 to 300): 1, more preferably (5 to 250): 1, more preferably (5 to 200): 1, more preferably (5 to 150): 1, more preferably (5 to 120): 1, most preferably (5 to 60): 1.
specifically, the polymerization reaction temperature is preferably-20 to 150 ℃, more preferably-10 to 120 ℃, more preferably 10 to 90 ℃, more preferably 20 to 80 ℃, more preferably 30 to 60 ℃, and most preferably 40 to 50 ℃.
Specifically, the pressure of ethylene during the reaction is preferably 1 to 50 atmospheres, more preferably 1 to 45 atmospheres, and still more preferably 1 to 30 atmospheres.
Specifically, the polymerization reaction time of the present invention is not particularly limited, and is selected according to the amount of the catalyst and the size of the reaction system. Wherein the polymerization reaction is carried out by a batch kettle, and the reaction time is 1 minute to 10 hours; if the polymerization is carried out in a continuous kettle, the reaction time is 1 to 10 days.
Specifically, the reaction medium is preferably one or more selected from aliphatic saturated hydrocarbons, aromatic hydrocarbons, aryl halides and cycloalkanes, more preferably one or more selected from hexane, cyclohexane, benzene, toluene, xylene, chlorobenzene, dichlorobenzene and bromobenzene.
The amount of the reaction medium used in the present invention is not particularly limited, and a person skilled in the art may select a suitable amount of the reaction medium according to the actual situation to ensure that the polymerization reaction can be performed.
Specifically, the method of polymerization preferably comprises:
a saturated solution containing a rare earth metal complex, an organoaluminum compound and an organoboron salt compound (the solvent in the solution is the above-mentioned reaction medium) is added to a polymerization reaction system of a solution of 1, 3-butadiene (the solvent in the solution is the above-mentioned reaction medium), and ethylene gas is introduced.
Specifically, the polymerization method may preferably include:
mixing rare earth metal complex, organic aluminum compound and organic boron salt compound with ethylene and 1, 3-butadiene monomer to initiate polymerization. In the present invention, ethylene is preferably continuously fed at a constant pressure during the polymerization reaction.
Specifically, the method of polymerization may preferably further include:
Specifically, it is preferable to terminate the reaction by adding a methanolic hydrochloric acid solution after the completion of the polymerization reaction.
Specifically, after the polymerization reaction is terminated, preferably adding ethanol, separating the prepared copolymer, and drying; the drying method is preferably vacuum drying; the drying temperature is preferably 30 to 50 ℃, more preferably 35 to 45 ℃, and most preferably 40 ℃.
The present invention provides an ethylene/butadiene copolymer having a high breakdown voltage and a method for preparing the same. The high breakdown voltage ethylene/butadiene copolymer with specific composition and structure has breakdown field strength of 260-370 mm/KV, butadiene structure unit content of not lower than 65mol%, trans-1, 4-structure content of not lower than 10mol%, and especially the melting point of the crystallization sequence in the copolymer of 100-140 deg.c. The present invention provides a binary copolymer of ethylene and 1, 3-butadiene, which is a random copolymer or a multiblock copolymer containing 1, 3-butadiene monomer units and ethylene monomer units, has a higher content of ethylene, and has crystalline polyethylene segments with longer sequence lengths. The copolymer can be crosslinked to obtain a material with low dielectric constant, has higher breakdown voltage, and is a novel plastic material which is not reported in the prior art such as patents, documents and the like.
The invention also provides a preparation method of the copolymer, and particularly, the ethylene/butadiene copolymer is obtained by copolymerizing ethylene and butadiene monomers through a catalytic system composed of amidino rare earth metal complex with a specific structure, an organoboron compound and aluminum alkyl. The invention adopts two monomers of ethylene and 1, 3-butadiene with very different polymerization mechanisms and polymerization activities, and can obtain high catalytic activities on ethylene and 1, 3-butadiene monomers by adjusting the catalyst structure and changing the polymerization process.
The ethylene-butadiene provided by the invention has a lower dielectric constant, can be used in an environment with higher breakdown field strength, is a low dielectric constant material with a very development prospect, solves the application limitation of the existing ethylene-butadiene copolymer, and greatly widens the application depth and breadth of the ethylene-butadiene copolymer.
Experimental results show that the breakdown voltage of the ethylene/butadiene copolymer provided by the invention can reach 370mm/KV.
For further explanation of the present invention, an ethylene/butadiene copolymer and a method for preparing the same are described in detail with reference to examples, but it should be understood that these examples are carried out based on the technical scheme of the present invention, and detailed embodiments and specific operation procedures are given only for further explanation of the features and advantages of the present invention, not limitation of the claims of the present invention, and the scope of protection of the present invention is not limited to the examples described below.
The source of the raw materials in the following examples is not particularly limited, and may be prepared by a preparation method well known to those skilled in the art or commercially available.
The complexes used in the following examples of the invention were prepared according to the methods disclosed in J.Am.chem.Soc.2004,126,30, 9182-9183.
Example 1
In a glove box, 30mL of a toluene solution of 0.5mol/L butadiene was added to a 75mL glass pressure-resistant bottle, and Al was added thereto i Bu 3 (150. Mu.L, 75. Mu. Mol,0.5mol/L toluene solvent). Then, the pressure-resistant bottle was capped, the glove box was taken out, and 1.0atm of ethylene was introduced under stirring to saturate it in toluene, thereby forming a polymerization reaction system.
In a glove box, a complex of the structure of formula 1 (13.7 mg, 15. Mu. Mol), al i Bu 3 (60. Mu.L, 30. Mu. Mol,0.5mol/L toluene solvent) and triphenylcarbonium tetrakis (pentafluorophenyl) borate [ Ph ] 3 C][B(C 6 F 5 ) 4 ](14.4 mg, 15. Mu. Mol) was dissolved in 2mL of toluene to prepare a catalyst solution. Thereafter, the catalyst solution was taken out of the glove box and rapidly added to the above polymerization reaction system at 40℃to initiate polymerization, after which the ethylene pressure was rapidly adjusted to 4.0atm. After 2 hours of reaction, the reaction was terminated by adding 20mL of methanolic hydrochloric acid solution. The copolymer was then isolated by increasing the amount of ethanol and dried under vacuum at 40℃until the weight of the polymer was unchanged.
The copolymer prepared in example 1 of the present invention was subjected to nuclear magnetic resonance hydrogen spectrum detection, and the detection result is shown in FIG. 1.
FIG. 1 is a sample of a copolymer prepared in example 1 of the present invention 1 H NMR spectrum.
Example 2
In a glove box, 30mL of a toluene solution of 0.2mol/L butadiene was added to a 75mL glass pressure-resistant bottle, and Al was added thereto i Bu 3 (150. Mu.L, 75. Mu. Mol,0.5mol/L toluene solvent). Then, the pressure-resistant bottle was capped, the glove box was taken out, and 1.0atm of ethylene was introduced under stirring to saturate it in toluene, thereby forming a polymerization reaction system.
In a glove box, a complex of the structure of formula 2 (15.1 mg, 15. Mu. Mol), al i Bu 3 (60. Mu.L, 30. Mu. Mol,0.5mol/L toluene solvent) andtriphenylcarbonium tetrakis (pentafluorophenyl) borate [ Ph ] 3 C][B(C 6 F 5 ) 4 ](14.4 mg, 15. Mu. Mol) was dissolved in 2mL of toluene to prepare a catalyst solution. Thereafter, the catalyst solution was taken out of the glove box and rapidly added to the above polymerization reaction system at 40℃to initiate polymerization, after which the ethylene pressure was rapidly adjusted to 4.0atm. After 2 hours of reaction, the reaction was terminated by adding 20mL of methanolic hydrochloric acid solution. The copolymer was then isolated by increasing the amount of ethanol and dried under vacuum at 40℃until the weight of the polymer was unchanged.
Example 3
In a glove box, 30mL of a toluene solution of 0.1mol/L butadiene was added to a 75mL glass pressure-resistant bottle, and Al was added thereto i Bu 3 (150. Mu.L, 75. Mu. Mol,0.5mol/L toluene solvent). Then, the pressure-resistant bottle was capped, the glove box was taken out, and 1.0atm of ethylene was introduced under stirring to saturate it in toluene, thereby forming a polymerization reaction system.
In a glove box, a complex of the structure of formula 3 (13.8 mg, 15. Mu. Mol), al i Bu 3 (60. Mu.L, 30. Mu. Mol,0.5mol/L toluene solvent) and triphenylcarbonium tetrakis (pentafluorophenyl) borate [ Ph ] 3 C][B(C 6 F 5 ) 4 ](14.4 mg, 15. Mu. Mol) was dissolved in 2mL of toluene to prepare a catalyst solution. Thereafter, the catalyst solution was taken out of the glove box and rapidly added to the above polymerization reaction system at 40℃to initiate polymerization, after which the ethylene pressure was rapidly adjusted to 4.0atm. After 2 hours of reaction, the reaction was terminated by adding 20mL of methanolic hydrochloric acid solution. The copolymer was then isolated by increasing the amount of ethanol and dried under vacuum at 40℃until the weight of the polymer was unchanged.
Example 4
In a glove box, 30mL of a toluene solution of 0.2mol/L butadiene was added to a 75mL glass pressure-resistant bottle, and Al was added thereto i Bu 3 (90. Mu.L, 45. Mu. Mol,0.5mol/L toluene solvent). Then, the pressure-resistant bottle was capped, the glove box was taken out, and 1.0atm of ethylene was introduced under stirring to saturate it in toluene, thereby forming a polymerization reaction system.
In a glove box, a complex of the structure of formula 4 (14.5 mg, 15. Mu. Mol), al i Bu 3 (60. Mu.L, 30. Mu. Mol,0.5mol/L toluene solvent) and triphenylcarbonium tetrakis (pentafluorophenyl) borate [ Ph ] 3 C][B(C 6 F 5 ) 4 ](14.4 mg, 15. Mu. Mol) was dissolved in 2mL of toluene to prepare a catalyst solution. Thereafter, the catalyst solution was taken out of the glove box and rapidly added to the above polymerization reaction system at 40℃to initiate polymerization, after which the ethylene pressure was rapidly adjusted to 4.0atm. After 2 hours of reaction, the reaction was terminated by adding 20mL of methanolic hydrochloric acid solution. The copolymer was then isolated by increasing the amount of ethanol and dried under vacuum at 40℃until the weight of the polymer was unchanged.
Example 5
In a glove box, 30mL of a toluene solution of 0.2mol/L butadiene was added to a 75mL glass pressure-resistant bottle, and Al was added thereto i Bu 3 (90. Mu.L, 45. Mu. Mol,0.5mol/L toluene solvent). Then, the pressure-resistant bottle was capped, the glove box was taken out, and 1.0atm of ethylene was introduced under stirring to saturate it in toluene, thereby forming a polymerization reaction system.
In a glove box, a complex of the structure of formula 5 (14.7 mg, 15. Mu. Mol), al i Bu 3 (60. Mu.L, 30. Mu. Mol,0.5mol/L toluene solvent) and triphenylcarbonium tetrakis (pentafluorophenyl) borate [ Ph ] 3 C][B(C 6 F 5 ) 4 ](14.4 mg, 15. Mu. Mol) was dissolved in 2mL of toluene to prepare a catalyst solution. Thereafter, the catalyst solution was taken out of the glove box and rapidly added to the above polymerization reaction system at 40℃to initiate polymerization, after which the ethylene pressure was rapidly adjusted to 4.0atm. After 6 hours of reaction, the reaction was terminated by adding 20mL of methanolic hydrochloric acid solution. The copolymer was then isolated by increasing the amount of ethanol and dried under vacuum at 40℃until the weight of the polymer was unchanged.
Example 6
1.5L of toluene, 1, 3-butadiene (1.57 mol,85 g) and Al were added to a 5L stainless steel reactor thoroughly purged with nitrogen i Bu 3 (1.04 g,5.25 mmol) was charged with 1.0atm ethylene under vigorous stirringThe saturated state is reached in toluene solution, and a polymerization reaction system is formed.
In a glove box, a complex of the structure of formula 6 (0.35 g,0.375 mmol), al i Bu 3 (0.75 mmol,0.15 g) and triphenylcarbonium tetrakis (pentafluorophenyl) borate [ Ph ] 3 C][B(C 6 F 5 ) 4 ](0.36 g,0.375 mmol) was dissolved in 30mL of toluene to prepare a catalyst solution. Thereafter, the catalyst solution was taken out of the glove box and rapidly added to the above polymerization reaction system at 40℃to initiate polymerization, after which the ethylene pressure was rapidly adjusted to 10.0atm. The method comprises the steps of carrying out a first treatment on the surface of the After 3 hours of reaction, 500mL of methanolic hydrochloric acid solution was immediately added to terminate the reaction. The copolymer was then isolated by increasing the amount of ethanol and dried under vacuum at 40℃until the weight of the polymer was unchanged.
The copolymer prepared in example 6 of the present invention was subjected to nmr hydrogen spectrum detection, the detection result is shown in fig. 2, and the copolymer prepared in example 6 of the present invention was subjected to nmr carbon spectrum detection, the detection result is shown in fig. 3.
FIG. 2 is a sample of the copolymer prepared in example 6 of the present invention 1 H NMR spectrum.
FIG. 3 is a sample of the copolymer prepared in example 6 of the present invention 13 C NMR spectrum.
Example 7
1.5L of toluene, 1, 3-butadiene (0.83 mol,45 g) and Al were added to a 5L stainless steel reactor sufficiently purged with nitrogen i Bu 3 (1.04 g,5.25 mmol) was charged with 1.0atm of ethylene under vigorous stirring to bring it to a saturated state in toluene solution, thereby forming a polymerization reaction system.
In a glove box, a complex of the structure of formula 7 (0.37 g,0.375 mmol), al i Bu 3 (0.75 mmol,0.15 g) and triphenylcarbonium tetrakis (pentafluorophenyl) borate [ Ph ] 3 C][B(C 6 F 5 ) 4 ](0.36 g,0.375 mmol) was dissolved in 30mL of toluene to prepare a catalyst solution. Thereafter, the catalyst solution was taken out of the glove box and rapidly added to the above polymerization reaction system at 40℃to initiate polymerization, after which the ethylene pressure was rapidly adjusted to 10.0atm. The method comprises the steps of carrying out a first treatment on the surface of theAfter 5 hours of reaction, 500mL of methanolic hydrochloric acid solution was immediately added to terminate the reaction. The copolymer was then isolated by increasing the amount of ethanol and dried under vacuum at 40℃until the weight of the polymer was unchanged.
Example 8
1.5L of toluene, 1, 3-butadiene (0.26 mol,14 g) and Al were added to a 5L stainless steel reactor sufficiently purged with nitrogen i Bu 3 (1.04 g,5.25 mmol) was charged with 1.0atm of ethylene under vigorous stirring to bring it to a saturated state in toluene solution, thereby forming a polymerization reaction system.
In a glove box, a complex of the structure of formula 8 (0.36 g,0.375 mmol), al i Bu 3 (0.75 mmol,0.15 g) and triphenylcarbonium tetrakis (pentafluorophenyl) borate [ Ph ] 3 C][B(C 6 F 5 ) 4 ](0.36 g,0.375 mmol) was dissolved in 30mL of toluene to prepare a catalyst solution. Thereafter, the catalyst solution was taken out of the glove box and rapidly added to the above polymerization reaction system at 40℃to initiate polymerization, after which the ethylene pressure was rapidly adjusted to 10.0atm. The method comprises the steps of carrying out a first treatment on the surface of the After 7.3 hours of reaction, 500mL of methanolic hydrochloric acid solution was immediately added to terminate the reaction. The copolymer was then isolated by increasing the amount of ethanol and dried under vacuum at 40℃until the weight of the polymer was unchanged.
Example 9
1.5L of toluene, 1, 3-butadiene (0.26 mol,14 g) and Al were added to a 5L stainless steel reactor sufficiently purged with nitrogen i Bu 3 (0.52 g,2.63 mmol) was charged with 1.0atm of ethylene under vigorous stirring to bring it to a saturated state in toluene solution, thereby forming a polymerization reaction system.
In a glove box, a complex of the structure of formula 8 (0.36 g,0.375 mmol), al i Bu 3 (0.75 mmol,0.15 g) and triphenylcarbonium tetrakis (pentafluorophenyl) borate [ Ph ] 3 C][B(C 6 F 5 ) 4 ](0.36 g,0.375 mmol) was dissolved in 30mL of toluene to prepare a catalyst solution. Thereafter, the catalyst solution was taken out of the glove box and rapidly introduced into the above polymerization reaction system at 40℃to initiate polymerization, after which the ethylene pressure was rapidly adjusted to 10.0atm. The method comprises the steps of carrying out a first treatment on the surface of the After 6 hours of reaction, 500mL of methanolic hydrochloric acid solution was immediately added to terminate the reaction. The copolymer was then isolated by increasing the amount of ethanol and dried under vacuum at 40℃until the weight of the polymer was unchanged.
Determination of the ethylene/butadiene copolymer composition
The ethylene (E) and 1, 3-Butadiene (BD) contents of the copolymer are determined according to the content in C 6 D 2 Cl 4 Copolymers measured at 110℃in the middle 1 The H NMR spectrum was calculated using the following formula:
f E ＝(I (1.21-1.79) -1.5*I 5.20 )/(I (1.21-1.79) +2*I (5.50-6.00) -0.5*I I5.20 )＊100％；
f BD ＝1-f E ；
thermal performance measurement of ethylene/butadiene copolymer
Copolymer glass transition temperature (T) g ) And determination of melting point (Tm): the glass transition temperature and melting point of the copolymer were determined by Differential Scanning Calorimetry (DSC) using a Metrehler TOPEM.
Determination of the molecular weight and molecular weight distribution of ethylene/butadiene copolymers
Copolymer number average molecular weight (M n ) And determination of molecular weight distribution (PDI): number average molecular weight (M) of copolymer n ) And molecular weight distribution (PDI) by Gel Permeation Chromatography (GPC) with polystyrene as standard at 150deg.C with C 6 H 6 Cl 3 For mobile phase determination.
Ethylene/butadiene copolymer breakdown voltage test
1) Cutting three polyimide films with the thickness of 150 mu m according to the length-width ratio of 20 multiplied by 20cm, and wiping the polyimide films by using deionized water, ethanol and deionized water in sequence to ensure the surface cleaning of the films. One polyimide film is selected, and a circular hole is formed at a radius of 2 cm.
2) 0.1884g of the ethylene/butadiene copolymer obtained in example 9 was selected, placed in the pores of an open-pore polyimide film and placed on a polyimide film having a thickness of 150 μm, and heated together in a press vulcanizer at 160℃for 10 minutes;
3) After confirming that the gradient copolymer is melted, a complete polyimide film with the length of 20 multiplied by 20cm is covered, and the gradient copolymer powder is subjected to membrane combination and air discharge at the temperature of 160 ℃ under the pressure of 10MPa for 3 seconds, wherein the air discharge times are 10 times.
4) And (3) carrying out hot pressing on the ethylene/butadiene copolymer powder film at 160 ℃ for 10min under the pressure of 20 MPa. After the completion, the rapid cooling treatment of the prepared film sample is completed in a circulating water cooling mode, so that the sample reaches the room temperature.
5) And taking out the ethylene/butadiene copolymer film after hot pressing, and annealing for 30 minutes.
6) The test specimens were subjected to a breakdown test. The breakdown test was performed using a copper ball-and-plate electrode with a ball electrode diameter of 25mm. In order to prevent flashover during the test, the ball plate electrode is used for clamping the sample and is placed in the Kramary No. 25 transformer oil for insulation protection. When the breakdown experiment is carried out on the sample, a continuous boosting mode is adopted, and the boosting rate is 1kV/mm until the breakdown of the sample occurs. Each set of breakdown experiments was repeated 6 times and the results are shown in fig. 4, where the breakdown voltage strength of the samples was 302KV/mm.
FIG. 4 is a graph showing the mechanical properties of a copolymer sample prepared in example 7 of the present invention.
The copolymers prepared in examples 1 to 5 of the present invention were subjected to performance test.
The results of the detection of the copolymers prepared in examples 1 to 5 are shown in Table 1.
TABLE 1 results of Performance test of the copolymers prepared in examples 1 to 5 of the present invention
| entry | BD/g | w t /％ | t/h | yield/g | conv. BD /％ | f E /％ | T g /T m /℃ | M n /kDa | PDI |
| 1 | 0.73 | 2.83 | 2 | 1.44 | 86.17 | 71.24 | -84.62/125.25 | 18.29 | 1.93 |
| 2 | 0.32 | 1.22 | 2 | 1.04 | 42.22 | 92.87 | -/130.18 | 40.51 | 2.56 |
| 3 | 0.15 | 0.56 | 2 | 1.32 | 36.21 | 97.88 | -/127.64 | 44.17 | 3.57 |
| 4 | 0.44 | 1.69 | 2 | 0.54 | 44.59 | 77.29 | -/121.46 | 83.64 | 2.17 |
| 5 | 0.44 | 1.69 | 6 | 6.49 | 70.63 | 97.47 | -/131.50 | 430.15 | 2.44 |
The copolymers prepared in examples 6 to 9 of the present invention were subjected to performance test.
The results of the detection of the copolymers prepared in examples 6 to 9 are shown in Table 2.
TABLE 2 results of Performance test of the copolymers prepared in examples 6 to 9 of the present invention
| entry | BD/g | w t /％ | t/h | yield/g | conv. BD /％ | f E /％ | T g /T m /℃ | M n (kDa) | PDI |
| 6 | 85.38 | 6 | 5 | 143.89 | 79.17 | 68.52 | -97.85/124.61 | 22.91 | 2.66 |
| 7 | 44.73 | 3 | 7.3 | 126.64 | 81.99 | 82.55 | -/129.02 | 23.93 | 2.94 |
| 8 | 13.32 | 1 | 3 | 81.75 | 80.19 | 92.77 | -/125.31 | 22.38 | 2.71 |
| 9 | 13.70 | 1 | 3 | 90.51 | 80.03 | 93.33 | -/124.67 | 93.19 | 1.34 |
Referring to fig. 5, fig. 5 is a graph showing mechanical properties of a copolymer sample prepared in example 8 of the present invention.
Referring to fig. 6, fig. 6 is a graph showing breakdown voltage test of a copolymer sample prepared in example 9 of the present invention.
The foregoing has outlined rather broadly the principles and embodiments of the present invention in order that the detailed description of a method and system of preparing an ethylene/butadiene copolymer having a high breakdown voltage may be better understood, and in order that the detailed description may be better understood, and in order that the present invention may be put into practice by anyone skilled in the art, including by making and using any devices or systems, and in any combination. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims. The scope of the patent protection is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal language of the claims.
Claims (10)
1. An ethylene/butadiene copolymer, characterized in that the copolymer consists of ethylene structural units and butadiene structural units;
wherein the content of ethylene structural units is not less than 65mol%, and the content of trans-1, 4-structural units in butadiene structural units is not less than 10mol%;
the melting point of the crystallization sequence in the copolymer is 100-140 ℃;
the ethylene/butadiene copolymer is an ethylene/butadiene copolymer having a high breakdown voltage;
the breakdown field intensity of the ethylene/butadiene copolymer is 260-370 mm/KV;
the copolymer is prepared from ethylene and 1, 3-butadiene under the action of a catalytic system;
the catalyst system comprises an organoboron salt compound, an organoaluminum compound, and a rare earth metal complex;
the rare earth metal complex has a general formula shown in a structure of a formula (I):
wherein M is selected from one of scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium;
R 1 、R 2 and R is 3 Each independently selected from the group consisting of a hydrogen atom, an alkyl or haloalkyl group containing from 1 to 10 carbon atoms, an alkenyl or haloalkenyl group containing from 2 to 20 carbon atoms, an aralkyl or haloaralkyl group containing from 6 to 20 carbon atoms, a silyl group containing from 1 to 14 carbon atoms;
X 1 And X 2 Each independently selected from the group consisting of hydrogen, a linear or branched aliphatic or cycloaliphatic radical having from 1 to 20 carbon atoms, phenyl, a linear or branched alkyl or cycloaliphatic or aromatic substituted phenyl having from 1 to 20 carbon atoms, a linear or branched alkoxy having from 1 to 20 carbon atoms, a linear or branched alkylamino having from 1 to 20 carbon atoms, a linear or branched arylamino having from 1 to 20 carbon atoms, a linear or branched silane group having from 1 to 20 carbon atoms, a borono, an allyl derivative, and a halogen;
l is selected from one of tetrahydrofuran, ethylene glycol dimethyl ether and pyridine;
w is an integer of 0 to 3.
2. The ethylene/butadiene copolymer according to claim 1, characterized in that the content of ethylene structural units in the copolymer is not less than 75mol%.
3. The ethylene/butadiene copolymer according to claim 1, wherein the content of trans 1, 4-structural units in the butadiene structural units in the copolymer is not less than 20mol%;
the melting point of the crystalline sequence in the copolymer is 105-135 ℃.
4. The ethylene/butadiene copolymer of claim 1, wherein the ethylene/butadiene copolymer is an ethylene/butadiene copolymer containing crystalline sequences.
5. The ethylene/butadiene binary copolymer according to claim 1, characterized in that the molecular weight distribution of the copolymer is not higher than 8;
the number average molecular weight of the copolymer is 10000-500000.
6. A process for the preparation of an ethylene/butadiene copolymer as claimed in any one of claims 1 to 5, comprising the steps of:
1) Initiating polymerization reaction of ethylene, 1, 3-butadiene and a catalyst system in a reaction medium to obtain an ethylene/butadiene binary copolymer;
the catalyst system comprises an organoboron salt compound, an organoaluminum compound, and a rare earth metal complex;
the rare earth metal complex has a general formula shown in a structure of a formula (I):
wherein M is selected from one of scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium;
R 1 、R 2 and R is 3 Each independently selected from the group consisting of a hydrogen atom, an alkyl or haloalkyl group containing from 1 to 10 carbon atoms, an alkenyl or haloalkenyl group containing from 2 to 20 carbon atoms, an aralkyl or haloaralkyl group containing from 6 to 20 carbon atoms, a silyl group containing from 1 to 14 carbon atoms;
X 1 and X 2 Each independently selected from hydrogen, 1-20A linear or branched aliphatic or cycloaliphatic group having from 1 to 20 carbon atoms, a phenyl group, a linear or branched alkyl or cycloaliphatic or aromatic substituted phenyl group having from 1 to 20 carbon atoms, a linear or branched alkoxy group having from 1 to 20 carbon atoms, a linear or branched alkylamino group having from 1 to 20 carbon atoms, a linear or branched arylamino group having from 1 to 20 carbon atoms, a linear or branched silyl group having from 1 to 20 carbon atoms, a borono, an allyl group, an allyl derivative, and a halogen;
L is selected from one of tetrahydrofuran, ethylene glycol dimethyl ether and pyridine;
w is an integer of 0 to 3.
7. The method of preparing according to claim 6, wherein the organoboron salt compound comprises an ionic compound formed from an organoboron anion and a cation, and/or an organoboron compound;
the organoboron anions include one or more of tetraphenyl borate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetrakis (tolyl) borate, tetrakis (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [ tris (pentafluorophenyl) borate, phenyl ] borate, and undecahydride-7, 8-dicarbaundecaborate;
the cation includes carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptatrienyl cation or ferrocenium cation containing transition metal;
the organoboron compound comprises B (C 6 F 5 ) 3 ；
The organoaluminum compound includes one or more of trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisopropylaluminum, triisobutylaluminum, tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum, triphenylaluminum, tri-p-tolylaluminum, tribenzylaluminum, ethyldibenzylaluminum and ethyldi (p-tolylaluminum;
The organoboron salt compound is specifically an organoboron salt compound solution.
8. The method according to claim 6, wherein the molar ratio of the organoboron salt compound to the rare earth metal complex is (1 to 10): (10-1);
the molar ratio of the organic aluminum compound to the rare earth metal complex is (2-300): 1, a step of;
the ethylene pressure is 1-50 atmospheres.
9. The method of claim 6, wherein the reaction medium comprises one or more of aliphatic saturated hydrocarbons, aromatic hydrocarbons, aryl halides, and cycloalkanes;
the concentration of the 1, 3-butadiene in the reaction medium is lower than 2mol/L;
the temperature of the polymerization reaction is-20-150 ℃.
10. The method according to claim 6, wherein the step 1) specifically comprises:
1) Mixing 1, 3-butadiene, a part of organic aluminum compound solution and a reaction medium, and introducing ethylene to obtain a polymerization reaction system;
2) Mixing the rare earth metal complex solution, the other part of organic aluminum compound, organic boron salt compound and reaction medium again to obtain catalyst solution, heating the catalyst solution in the polymerization reaction system obtained in the above steps, increasing the pressure of ethylene, and carrying out polymerization reaction to obtain the ethylene/butadiene binary copolymer.
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| US4057681A (en) * | 1975-06-06 | 1977-11-08 | Exxon Research & Engineering Co. | Process for homogeneously polymerized high unsaturation C4-C10 isoolefin conjugated diene copolymers |
| CN106574150A (en) * | 2014-09-18 | 2017-04-19 | 三菱树脂株式会社 | Photocrosslinkable transparent adhesive material, transparent adhesive material layered body, and layered body for constituting optical device |
| CN112029017A (en) * | 2019-06-03 | 2020-12-04 | 中国石油天然气股份有限公司 | Bridged metallocene rare earth metal compound and application thereof in olefin copolymerization |
| CN113307901A (en) * | 2021-06-09 | 2021-08-27 | 中国科学院长春应用化学研究所 | Preparation method of ethylene-isoprene random copolymer, rubber composition and rubber product |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4057681A (en) * | 1975-06-06 | 1977-11-08 | Exxon Research & Engineering Co. | Process for homogeneously polymerized high unsaturation C4-C10 isoolefin conjugated diene copolymers |
| CN106574150A (en) * | 2014-09-18 | 2017-04-19 | 三菱树脂株式会社 | Photocrosslinkable transparent adhesive material, transparent adhesive material layered body, and layered body for constituting optical device |
| CN112029017A (en) * | 2019-06-03 | 2020-12-04 | 中国石油天然气股份有限公司 | Bridged metallocene rare earth metal compound and application thereof in olefin copolymerization |
| CN113307901A (en) * | 2021-06-09 | 2021-08-27 | 中国科学院长春应用化学研究所 | Preparation method of ethylene-isoprene random copolymer, rubber composition and rubber product |
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