CN113087826B - External electron donor composition, olefin polymerization catalyst and application thereof, and polyolefin and preparation method thereof - Google Patents
External electron donor composition, olefin polymerization catalyst and application thereof, and polyolefin and preparation method thereof Download PDFInfo
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- CN113087826B CN113087826B CN202110426658.9A CN202110426658A CN113087826B CN 113087826 B CN113087826 B CN 113087826B CN 202110426658 A CN202110426658 A CN 202110426658A CN 113087826 B CN113087826 B CN 113087826B
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- Prior art keywords
- electron donor
- external electron
- compound
- olefin polymerization
- titanium
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- 150000001336 alkenes Chemical class 0.000 title claims abstract description 64
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000000203 mixture Substances 0.000 title claims abstract description 46
- 239000002685 polymerization catalyst Substances 0.000 title claims abstract description 38
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 193
- -1 polypropylene Polymers 0.000 claims abstract description 78
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 37
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 27
- 239000001257 hydrogen Substances 0.000 claims abstract description 27
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 44
- 239000010936 titanium Substances 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 31
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 29
- 229910052749 magnesium Inorganic materials 0.000 claims description 28
- 239000011777 magnesium Substances 0.000 claims description 28
- 229910052719 titanium Inorganic materials 0.000 claims description 28
- 239000003054 catalyst Substances 0.000 claims description 23
- 239000007787 solid Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 15
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 claims description 14
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 14
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 12
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 11
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 11
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 11
- MQHNKCZKNAJROC-UHFFFAOYSA-N dipropyl phthalate Chemical compound CCCOC(=O)C1=CC=CC=C1C(=O)OCCC MQHNKCZKNAJROC-UHFFFAOYSA-N 0.000 claims description 10
- 150000002431 hydrogen Chemical class 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 8
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 8
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 6
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 4
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 4
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 3
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 claims description 2
- JMMZCWZIJXAGKW-UHFFFAOYSA-N 2M2P Natural products CCC=C(C)C JMMZCWZIJXAGKW-UHFFFAOYSA-N 0.000 claims description 2
- WWUVJRULCWHUSA-UHFFFAOYSA-N 2MP Natural products CCCC(C)=C WWUVJRULCWHUSA-UHFFFAOYSA-N 0.000 claims description 2
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 claims description 2
- QWDBCIAVABMJPP-UHFFFAOYSA-N Diisopropyl phthalate Chemical compound CC(C)OC(=O)C1=CC=CC=C1C(=O)OC(C)C QWDBCIAVABMJPP-UHFFFAOYSA-N 0.000 claims description 2
- RYCNBIYTZSGSPI-UHFFFAOYSA-N ditert-butyl benzene-1,2-dicarboxylate Chemical compound CC(C)(C)OC(=O)C1=CC=CC=C1C(=O)OC(C)(C)C RYCNBIYTZSGSPI-UHFFFAOYSA-N 0.000 claims description 2
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 claims description 2
- 229910001623 magnesium bromide Inorganic materials 0.000 claims description 2
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 claims description 2
- 229910001641 magnesium iodide Inorganic materials 0.000 claims description 2
- ITNVWQNWHXEMNS-UHFFFAOYSA-N methanolate;titanium(4+) Chemical compound [Ti+4].[O-]C.[O-]C.[O-]C.[O-]C ITNVWQNWHXEMNS-UHFFFAOYSA-N 0.000 claims description 2
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pent-2-ene Chemical compound CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 claims description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 2
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 claims description 2
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 claims description 2
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 claims 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 claims 1
- RTAKQLTYPVIOBZ-UHFFFAOYSA-N tritert-butylalumane Chemical compound CC(C)(C)[Al](C(C)(C)C)C(C)(C)C RTAKQLTYPVIOBZ-UHFFFAOYSA-N 0.000 claims 1
- 239000004743 Polypropylene Substances 0.000 abstract description 45
- 229920001155 polypropylene Polymers 0.000 abstract description 45
- 238000009826 distribution Methods 0.000 abstract description 34
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 17
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 230000035945 sensitivity Effects 0.000 abstract description 4
- 239000002245 particle Substances 0.000 description 22
- 239000000843 powder Substances 0.000 description 22
- 229920000642 polymer Polymers 0.000 description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 11
- 239000000155 melt Substances 0.000 description 11
- 238000011056 performance test Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 229940126062 Compound A Drugs 0.000 description 9
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 8
- 239000002612 dispersion medium Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- 125000005843 halogen group Chemical group 0.000 description 7
- HTDQSWDEWGSAMN-UHFFFAOYSA-N 1-bromo-2-methoxybenzene Chemical compound COC1=CC=CC=C1Br HTDQSWDEWGSAMN-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 150000004795 grignard reagents Chemical class 0.000 description 5
- 229910000077 silane Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- 239000007818 Grignard reagent Substances 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 3
- 238000000518 rheometry Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VUIUOSKXGNEORM-UHFFFAOYSA-N 1-bromo-2-methoxy-3-methylbenzene Chemical compound COC1=C(C)C=CC=C1Br VUIUOSKXGNEORM-UHFFFAOYSA-N 0.000 description 2
- RMYVECCGQUCNMZ-UHFFFAOYSA-N 1-bromo-2-methoxy-3-propan-2-ylbenzene Chemical compound COC1=C(Br)C=CC=C1C(C)C RMYVECCGQUCNMZ-UHFFFAOYSA-N 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical group C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 description 2
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 2
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- 125000003107 substituted aryl group Chemical group 0.000 description 2
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- BEAAMQFNOLIIDG-UHFFFAOYSA-N 2-cyanobutanedioic acid Chemical compound OC(=O)CC(C#N)C(O)=O BEAAMQFNOLIIDG-UHFFFAOYSA-N 0.000 description 1
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- ZWINORFLMHROGF-UHFFFAOYSA-N 9,9-bis(methoxymethyl)fluorene Chemical compound C1=CC=C2C(COC)(COC)C3=CC=CC=C3C2=C1 ZWINORFLMHROGF-UHFFFAOYSA-N 0.000 description 1
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- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
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- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 150000002680 magnesium Chemical class 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
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- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
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- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
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- 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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention relates to the field of olefin polymerization, and discloses an external electron donor composition, an olefin polymerization catalyst and application thereof, and polyolefin and a preparation method thereof. The external electron donor composition contains a first external electron donor compound and a second external electron donor compound, wherein the first external electron donor compound is at least one selected from compounds having a structure shown in a formula I:
the second external electron donor compound has a structure represented by formula II:
Description
Technical Field
The invention relates to the field of olefin polymerization, in particular to an external electron donor composition, an olefin polymerization catalyst and application thereof, and polyolefin and a preparation method thereof.
Background
The relative molecular mass distribution of polypropylene affects its mechanical properties and processability. Based on succinate of Basell Poliolefin Italy and a Ziegler-Natta (Z-N) catalyst taking cyanosuccinate developed by Beijing chemical research institute of China petrochemical industry, Inc. (China petrochemical industry for short) as an internal electron donor, the method can be used for preparing polypropylene with wide relative molecular mass distribution. In addition, when dicyclopentyldimethoxysilane (DCPDMS) is used as the external electron donor of the Z-N catalyst, polypropylene with wider relative molecular mass distribution can be obtained. However, these catalysts have poor hydrogen response, i.e., the melt flow rate (i.e., melt index MFR) of the polypropylene produced is low at the same amount of hydrogen. Although the method of asymmetric hydrogenation and asymmetric addition of external electron donor can obtain polypropylene with wide relative molecular mass distribution, it is difficult to realize the method in one reactor.
To meet the processing requirements for injection molded products, especially thin walled parts, a polymer with a high MFR is required. The method of increasing the MFR of polypropylene comprises: 1) after polymerization, a degradation agent is added to the polymer. Usually, one or more peroxides are used to increase the MFR by breaking the polymer chains in the polymer under certain reaction conditions. This is generally referred to as a controlled rheology technique. 2) During the polymerization, the amount of hydrogen used as a relative molecular mass modifier is increased, thereby achieving the purpose of improving MFR. 3) In the polymerization process, a catalyst system sensitive to a relative molecular mass regulator is employed. By selecting the combination of different catalyst components, cocatalyst and external electron donor, the catalyst system becomes more sensitive to the relative molecular mass regulator (hydrogen is the most commonly used relative molecular mass regulator), and the high MFR polypropylene can be obtained in the presence of a small amount of hydrogen. The use of controlled rheology to produce high MFR polypropylene not only increases the cost of manufacture of the product, but also causes the product to have an unpleasant odor, thereby limiting its range of application; in addition, in controlled rheology, it is common for high relative molecular mass polymer segments to break first, thereby narrowing the relative molecular mass distribution of the polymer. The process of producing high MFR polypropylene by increasing the amount of hydrogen used is also very limited. On the one hand, the hydrogen addition is limited due to the pressure design of the device; on the other hand, the excessive hydrogen consumption can bring about the problems of great reduction of catalyst activity, reduction of polymer isotactic index, reduction of device heat exchange capacity, reduction of productivity and the like.
The olefin polymer having a high MFR, a high isotactic index (i.e., isotacticity), and a broad relative molecular mass distribution is superior in strength and rigidity, but it is difficult to produce an olefin polymer having a high MFR, a high isotactic index, and a broad relative molecular mass distribution at the same time by the above-mentioned method.
Disclosure of Invention
The invention aims to overcome the problem of narrow molecular weight distribution of polypropylene in the prior art, and provides an external electron donor composition, an olefin polymerization catalyst and application thereof, polyolefin and a preparation method thereof.
In order to achieve the above objects, a first aspect of the present invention provides an external electron donor composition comprising a first external electron donor compound and a second external electron donor compound, wherein the first external electron donor compound is at least one selected from compounds having a structure represented by formula I:
in the formula I, R 1 And R 2 Each independently selected from C 1 -C 10 Alkyl of (1), C 6 -C 20 Any one of the aryl groups of (1)Seed;
R 3 、R 4 、R 5 and R 6 Each independently selected from hydrogen, halogen radicals, C 1 -C 10 Alkyl radical of (1), C 3 -C 12 Cycloalkyl and C 6 -C 20 Any one of the aryl groups of (a);
R 7 and R 8 Each independently selected from C 1 -C 5 Any one of the alkyl groups of (a);
R 1 and R 2 Identical or different, R 3 、R 4 、R 5 、R 6 Same or different, R 7 And R 8 The same or different;
the second external electron donor compound has a structure shown in formula II:
the molar ratio of the first external electron donor compound to the second external electron donor compound is 1-10: 1.
in a second aspect, the present invention provides an olefin polymerization catalyst comprising:
(1) the solid component is obtained by the contact reaction of a titanium-containing compound, a magnesium-containing compound and an internal electron donor compound;
(2) an organoaluminum compound; and
(3) an external electron donor composition;
the external electron donor composition is the external electron donor composition of the first aspect.
In a third aspect the present invention provides the use of an olefin polymerisation catalyst as described above in an olefin polymerisation reaction.
In a fourth aspect, the present invention provides a process for preparing a polyolefin, the process comprising: olefin monomers are polymerized under olefin polymerization conditions in the presence of an olefin polymerization catalyst as described above.
In a fifth aspect, the present invention provides a polyolefin prepared by the process of the fourth aspect.
By adopting the technical scheme, the first external electron donor compound and the second external electron donor compound are combined for use, the obtained olefin polymerization catalyst has high hydrogen regulation sensitivity, and can be used for preparing polyolefin with wider molecular weight distribution and higher melt index, particularly polypropylene with molecular weight distribution of 5-9 and melt index of 50-200g/10min, with higher catalytic activity when used for olefin polymerization reaction, so that the preparation of the polypropylene with high MFR, high isotactic index and wide relative molecular weight distribution in a single reactor is realized.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
The present invention provides, in a first aspect, an external electron donor composition comprising a first external electron donor compound and a second external electron donor compound, wherein the first external electron donor compound is at least one selected from compounds having a structure represented by formula I:
in the formula I, R 1 And R 2 Each independently selected from C 1 -C 10 Alkyl of (1), C 6 -C 20 Any one of the aryl groups of (1);
R 3 、R 4 、R 5 and R 6 Each independently selected from hydrogen, halogen radicals, C 1 -C 10 Alkyl of (1), C 3 -C 12 Cycloalkyl and C 6 -C 20 Any one of the aryl groups of (1);
R 7 and R 8 Each independently selected from C 1 -C 5 Any one of the alkyl groups of (a);
R 1 and R 2 Same or different, R 3 、R 4 、R 5 、R 6 Same or different, R 7 And R 8 The same or different;
the second external electron donor compound has a structure shown in formula II:
the molar ratio of the first external electron donor compound to the second external electron donor compound is 1-10: 1.
in some embodiments of the present invention, a part of the external electron donor compound is used for complexing with aluminum alkyl to reduce the reducing power of the aluminum alkyl, and the other part is used for complexing with a Ziegler-Natta catalyst active center to inhibit the active center with poor isotactic orientation, thereby further improving the isotactic orientation of the active center with high isotactic orientation. The different electron donors and Ziegler-Natta catalyst active centers have different strengths of action. The invention combines the first external electron donor compound and the second external electron donor compound for use, and utilizes the combination of the combined external electron donor and the diester-containing Ziegler-Natta catalyst to prepare the polyolefin with wider molecular weight distribution and higher melt index with higher catalytic activity.
In some embodiments of the invention, C 1 -C 10 The alkyl group of (a) means an alkyl group having a total number of carbon atoms of 1 to 10, including straight-chain and branched chain alkyl groups, for example, including, but not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl and the like, preferably any of methyl, ethyl and isopropyl.
In some embodiments of the invention, the alkanyl groups are defined similarly to above, only by the number of carbon atoms, and the invention is not described in detail hereinafter.
In some embodiments of the invention, C 6 -C 20 The aryl group of (b) refers to an aryl group having a total number of carbon atoms of 6 to 20, including an unsubstituted aryl group and a substituted aryl group, wherein the substituted aryl group includes an alkaryl group (alkyl-substituted aryl group) and an aralkyl group (aryl-substituted alkyl group), for example, including, but not limited to, phenyl, 2, 6-dimethylphenyl, 2, 6-diisopropylphenyl, o-tolyl, m-tolyl, p-tolyl, o-ethylphenyl, m-ethylphenyl, p-ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, sec-butylphenyl, isobutylphenyl, tert-butylphenyl, naphthyl, anthryl, phenanthryl, benzyl, etc., preferably any one of phenyl, 2, 6-dimethylphenyl, and 2, 6-diisopropylphenyl, more preferably phenyl.
In some embodiments of the present invention, the aryl group has a definition similar to that described above, only differing in the number of carbon atoms, and the present invention will not be described in detail hereinafter.
In some embodiments of the invention, C 3 -C 12 Cycloalkyl of (c) refers to a cycloalkyl group having a total number of carbon atoms of 3 to 12, for example, including but not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like, preferably cyclohexyl.
In some embodiments of the present invention, the cycloalkyl group has a definition similar to that described above, except that the number of carbon atoms is different, and the present invention will not be described in detail below.
In some embodiments of the invention, preferably, in formula I, R 1 And R 2 Each independently selected from any one of methyl, ethyl, isopropyl, phenyl, 2, 6-dimethylphenyl and 2, 6-diisopropylphenyl, more preferably R 1 And R 2 Each independently selected from any one of phenyl, 2, 6-dimethylphenyl and 2, 6-diisopropylphenyl.
In some embodiments of the invention, preferably, in formula I, R 3 、R 4 、R 5 And R 6 Each independently selected from any one of hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, isopropyl, tert-butyl, isobutyl, cyclopentyl, cyclohexyl, phenyl, 2, 6-dimethylphenyl and 2, 6-diisopropylphenyl, more preferably R 3 、R 4 And R 5 Each independently of the other is hydrogen, R 6 And is selected from any one of hydrogen, methyl, ethyl and isopropyl.
In some embodiments of the invention, preferably, in formula I, R 7 And R 8 Each independently selected from any one of methyl, ethyl, n-propyl and isopropyl, more preferably R 7 And R 8 Each independently is methyl.
According to a preferred embodiment of the present invention, the first external electron donor compound is at least one selected from the group consisting of a compound represented by formula I-1, a compound represented by formula I-2, and a compound represented by formula I-3:
in some embodiments of the present invention, the molar ratio of the first external electron donor compound to the second external electron donor compound is from 1 to 10: 1. preferably, the molar ratio of the first external electron donor compound to the second external electron donor compound is from 2.5 to 9: 1, more preferably 3 to 8: 1, more preferably 3 to 5: 1. in the invention, a new active center formed by coordination of the first external electron donor compound and the active center of the catalyst can induce polymerization to obtain a polymer with high activity and high isotacticity; the new active center formed by the coordination of the second external electron donor compound and the active center of the catalyst can induce polymerization to obtain a polymer with both high melt index and high molecular weight distribution index; by adjusting the proportion of the two external electron donor compounds, the optimum value of the polymer performance can be achieved by making up for the deficiencies of the two external electron donor compounds.
In some embodiments of the present invention, the inventors have found that by specifically selecting the aforementioned preferred first external electron donor compound for use in combination with the second external electron donor compound having the structure of formula II and using the combination of the external electron donor compound and the diester-containing Ziegler-Natta catalyst in the preparation of polyolefins, the resulting olefin polymer has a broader molecular weight distribution and a higher melt index.
In some embodiments of the present invention, the first external electron donor compound having the structure shown in formula I can be prepared by the following method:
(1) under the Grignard reaction condition, the compound shown in the formula III is firstly contacted with metal magnesium in a first solvent to obtain a Grignard reagent,
(2) under the condition of substitution reaction, the Grignard reagent is in second contact with silane shown in a formula IV in a second solvent to obtain a first external electron donor compound,
in the formula IV, R 1 And R 2 Are the same or different and are each independently selected from C 1 -C 10 Alkyl radical of (1), C 6 -C 20 Any one of the aryl groups of (1);
in the formula III, R 3 、R 4 、R 5 And R 6 Identical or different, each independently selected from hydrogen, halogen radicals, C 1 -C 10 Alkyl radical of (1), C 3 -C 12 Cycloalkyl and C 6 -C 20 Any one of the aryl groups of (1);
in the formula III, R 7 Is C 1 -C 5 Any one of the alkyl groups of (1); x 1 Is any one of halogen atoms;
in the formula IV, X 2 And X 3 The halogen atoms are the same or different and each independently any one of halogen atoms.
In some embodiments of the invention, in formulas III and IV, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 And R 7 Are as defined in formula I.
In some embodiments of the invention, in formula III, X 1 Is any one of halogen atoms, and specific examples of the halogen atom may include, but are not limited to: fluorine, chlorine, bromine and iodine. Preferably, X 1 Is bromine.
In some embodiments of the invention, in formula IV, X 2 And X 3 The same or different, each independently is any one of halogen atoms, and specific examples of the halogen atoms may include, but are not limited to: fluorine, chlorine, bromine and iodine. Preferably, X 2 And X 3 Are all chlorine.
In some embodiments of the present invention, preferably, the compound represented by formula III is selected from any one of o-bromoanisole, 1-bromo-2-methoxy-3-methylbenzene and 1-bromo-2-methoxy-3-isopropylbenzene.
In some embodiments of the present invention, preferably, the silane of formula IV is diphenyldichlorosilane.
In some embodiments of the present invention, preferably, the molar ratio of the compound represented by formula III to the magnesium metal may be 1: 1-2, the molar ratio of the compound of formula III to the silane of formula IV may be 1: 0.9-1.2.
In some embodiments of the present invention, preferably, in step (1), the temperature of the first contacting may be 25 to 90 ℃, and the first solvent may be at least one of tetrahydrofuran, diethyl ether, ethylene glycol dimethyl ether and dimethoxymethane, preferably tetrahydrofuran.
In some embodiments of the present invention, preferably, in the step (2), the temperature of the second contacting may be 0 to 90 ℃, and the second solvent may be at least one of tetrahydrofuran, diethyl ether, ethylene glycol dimethyl ether and dimethoxymethane, preferably tetrahydrofuran.
In some embodiments of the present invention, in the step (2), the second contacting preferably comprises a third contacting and a fourth contacting performed sequentiallyWherein the third contacting may be carried out at a temperature of 0-30 ℃ and the duration of the third contacting may be 0.5-2 hours; the fourth contacting may be performed at a temperature of 0 to 100 ℃, and the duration of the fourth contacting may be 0.5 to 12 hours. The fourth contacting is carried out in the presence of at least one basic substance, preferably an amine, more preferably a trialkylamine, and further preferably triethylamine, and at least one alcohol; the alcohol is preferably C 1 -C 6 More preferably methanol. The molar ratio of the basic substance to the silane of formula IV may be 1.0 to 1.2: 1, the molar ratio of the alcohol to the silane of formula IV may be from 1 to 5: 1.
in some embodiments of the present invention, in the step (2), the mixture obtained by the second contacting may be separated by a conventional method, so as to obtain the first external electron donor compound. As an example, the mixture obtained by the second contacting in step (2) may be subjected to distillation, column chromatography or a combination thereof to obtain the first external electron donor compound.
In some embodiments of the present invention, the preparation method of the second external electron donor compound having the structure shown in formula II is not particularly limited, and the second external electron donor compound can be prepared by a conventional method, for example, the method disclosed in CN102850389A can be referred to for preparing the second external electron donor compound shown in formula II.
In a second aspect, the present invention provides an olefin polymerization catalyst comprising:
(1) the solid component is obtained by the contact reaction of a titanium-containing compound, a magnesium-containing compound and an internal electron donor compound;
(2) an organoaluminum compound; and
(3) an external electron donor composition;
the external electron donor composition is the external electron donor composition described in the first aspect, and the external electron donor composition contains a first external electron donor compound and a second external electron donor compound, and the types and the amounts of the first external electron donor compound and the second external electron donor compound may be selected according to the foregoing description, which will not be described herein again.
In some embodiments of the present invention, the solid component is obtained by a contact reaction of a titanium-containing compound, a magnesium-containing compound, and an internal electron donor compound.
In some embodiments of the present invention, in the olefin polymerization catalyst, the content of titanium element largely determines the activity of the catalyst, and in a certain range, the increase of the content of titanium is beneficial to the improvement of the activity of the catalyst; the content of the internal electron donor determines the isotacticity of the polyolefin to a great extent, and in a certain range, the improvement of the content of the internal electron donor can improve the isotacticity of the polyolefin. And the magnesium element is used as an inert component for adjusting the contents of the titanium element and the internal electron donor. In order to obtain a polyolefin having both high isotacticity and high melt index, it is preferable that the molar ratio of the titanium-containing compound in terms of titanium element, the magnesium-containing compound in terms of magnesium element, and the internal electron donor compound is 1: 1-50: 0.1 to 1.5, more preferably 1: 5-40: 0.2 to 1.2, more preferably 1: 10-30: 0.5-1.
In some embodiments of the present invention, preferably, the magnesium-containing compound is provided in the form of a magnesium-containing carrier, and the titanium-containing compound and the internal electron donor compound are supported on the magnesium-containing carrier.
In some embodiments of the present invention, the preparation method of the solid component is not particularly limited, and the solid component may be prepared by a conventional method, for example, the solid component may be prepared by a method disclosed in CN1330086A, CN1463990A, CN1397568A, CN1528793A, CN1563112A, CN1034548A, CN1047302A, CN1091748A, CN1109067A, CN1110281A, and CN 1199056A.
In some embodiments of the present invention, preferably, the method for preparing the solid component comprises:
(1) dispersing a magnesium-containing compound in a dispersion medium to obtain a magnesium-containing dispersion medium;
(2) carrying out fifth contact on the magnesium-containing dispersion medium, a first titanium-containing compound and a first internal electron donor compound to obtain a first dispersion liquid;
(3) carrying out sixth contact on the first dispersion liquid, a second titanium-containing compound and a second internal electron donor compound to obtain a second dispersion liquid;
(4) and removing the dispersion medium in the second dispersion liquid to obtain the solid component.
In some embodiments of the present invention, the magnesium-containing compound is selected from at least one of magnesium chloride, magnesium bromide and magnesium iodide, more preferably magnesium chloride.
In some embodiments of the invention, the dispersing medium is selected from C 5 -C 12 Alkanols and C 6 -C 12 Preferably isooctanol and/or decane.
Preferably, the dispersion medium is C 5 -C 12 Alkanols and C 6 -C 12 More preferably isooctanol and decane; said C is 5 -C 12 And said C 6 -C 12 The weight ratio of the alkanes of (a) may be 1: 0.5-2, more preferably 1: 0.8-1.5.
In some embodiments of the present invention, preferably, the weight ratio of the magnesium-containing compound to the dispersion medium may be 1: 5-20.
In some embodiments of the invention, the first titanium-containing compound is selected from at least one of titanate esters, for example, at least one of tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, and tetrabutyl titanate. Preferably, the first titanium compound is tetrabutyl titanate.
In some embodiments of the present invention, the second titanium-containing compound is at least one selected from inorganic titanium compounds, for example, may be selected from titanium tetrahalides and/or titanium trihalides, preferably titanium tetrahalides, such as titanium tetrachloride, titanium tetrabromide, titanium tetrafluoride, and the like, and more preferably titanium tetrachloride.
In some embodiments of the invention, preferably, the molar ratio of the first titanium-containing compound to the second titanium-containing compound is 1: 80-320.
In some embodiments of the present invention, the first internal electron donor compound and the second internal electron donor compound are each independently selected from at least one of phthalate type internal electron donor compounds, for example, may be selected from at least one of phthalate type internal electron donor compounds, succinate type internal electron donor compounds, and salicylate type internal electron donor compounds; preferably, the first internal electron donor compound and the second internal electron donor compound are each independently selected from at least one of dialkyl phthalate type internal electron donor compounds, for example, may be selected from at least one of di-tert-butyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, di-n-propyl phthalate, diisopropyl phthalate and diethyl phthalate, more preferably at least one of diisobutyl phthalate, di-n-butyl phthalate and di-n-propyl phthalate; the first internal electron donor compound and the second internal electron donor compound may be the same or different, and preferably are the same.
In some embodiments of the present invention, in order to obtain a solid catalyst component with good performance, preferably, the molar ratio of the first internal electron donor compound to the second internal electron donor compound may be 1: 0.2-1. The composite internal electron donor (the first internal electron donor is different from the second internal electron donor) can realize the purpose of making up for the deficiencies of the performances among various internal electron donors; the internal electron donor is added in batches (the first internal electron donor is the same as the second internal electron donor) so that the internal electron donor is loaded more firmly.
In some embodiments of the present invention, the fifth contacting may be performed at a temperature of 100-.
In some embodiments of the present invention, the sixth contact may be performed at a temperature of 100-130 ℃, and the duration of the second contact may be 1-5 hours.
In some embodiments of the present invention, the molar ratio of the external electron donor composition to the titanium-containing compound in terms of titanium element is from 2 to 50: 1, preferably 5 to 30: 1.
in some embodiments of the present invention, the molar ratio of the organoaluminum compound, calculated as aluminum element, to the titanium-containing compound, calculated as titanium element, is in the range of from 10 to 1000: 1, preferably 40 to 800: 1.
in some embodiments of the present invention, in the olefin polymerization catalyst, the addition of aluminum (aluminum alkyl) may cause the internal electron donor originally supported to fall off, while the addition of the external electron donor may just make up for the deficiency. The titanium with catalytic activity has a new coordination environment, so that different catalytic performances are shown, and polyolefins with different performances are obtained. The first external electron donor compound and the second external electron donor compound are used in combination, the obtained olefin polymerization catalyst is high in hydrogen regulation sensitivity, and when the catalyst is used for olefin polymerization reaction, polyolefin with wider molecular weight distribution and higher melt index can be prepared with higher catalytic activity.
In some embodiments of the present invention, the organoaluminum compound is preferably at least one of aluminum alkyls, more preferably at least one of trialkylaluminums. The alkyl group is preferably C 1 -C 6 More preferably at least one of ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl. Further preferably, the organoaluminum compound is triethylaluminum and/or triisobutylaluminum.
In some embodiments of the present invention, the method for using the olefin polymerization catalyst is not particularly limited, and a method adopted in olefin polymerization existing in the art may be adopted, and in order to obtain a better catalytic effect, the solid component, the organoaluminum compound and the external electron donor compound are preferably added into a polymerization reaction system simultaneously, and a catalyst is formed by pre-complexing for catalyzing a polymerization reaction.
According to the invention, by adopting the external electron donor composition disclosed by the invention, the first external electron donor compound and the second external electron donor compound are combined for use, the obtained olefin polymerization catalyst has high hydrogen regulation sensitivity, and when the olefin polymerization catalyst is used for olefin polymerization reaction, polyolefin with wider molecular weight distribution and higher melt index, especially polypropylene with 5-9 molecular weight distribution and 50-200g/10min can be prepared with higher catalytic activity. The melt index is measured according to test standard ASTM D1238, wherein the measurement conditions include: the temperature was 230 ℃ and the load was 2.16 kg.
In a third aspect the present invention provides the use of an olefin polymerisation catalyst as described above in an olefin polymerisation reaction.
In a fourth aspect, the present invention provides a process for preparing a polyolefin, the process comprising: olefin monomers are polymerized under olefin polymerization conditions in the presence of the olefin polymerization catalyst as described above.
In some embodiments of the present invention, the polymerization reaction may be a bulk polymerization reaction or a gas phase polymerization reaction. The olefin polymerization reaction may be carried out under conventional conditions, and the present invention is not particularly limited thereto.
Preferably, the olefin polymerization conditions include: the polymerization temperature is 50-80 ℃, more preferably 65-75 ℃; the polymerization time is 1 to 3 hours, more preferably 1.5 to 2 hours.
Preferably, the olefin monomer is selected from the group consisting of ethylene, propylene, and C, such as 1-butene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, 1-pentene, 2-pentene, and 1-hexene 4 -C 8 More preferably propylene.
According to the method for preparing the polyolefin, the polyolefin with wider molecular weight distribution and higher melt index can be obtained by adopting the olefin polymerization catalyst.
In a fifth aspect, the present invention provides a polyolefin prepared by the process of the fourth aspect.
In some embodiments of the present invention, preferably, the polyolefin has a molecular weight distribution of 5 to 9, a melt index of 50 to 200g/10 min;
more preferably, the polyolefin has a molecular weight distribution of 6 to 9 and a melt index of 100-150g/10 min;
further preferably, the polyolefin has a molecular weight distribution of 8.5 to 9 and a melt index of 130-150g/10 min.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, all the raw materials were commercially available unless otherwise specified.
In the following examples and comparative examples, the test methods involved are as follows:
(1) the isotacticity of polypropylene is measured by using a heptane extraction method, and the specific operation method is as follows:
placing 2g of polypropylene in a Soxhlet extractor, extracting for 6 hours by using boiling heptane, drying the rest polypropylene to constant weight, and taking the mass ratio of the rest polypropylene to the polypropylene added for the first time as an isotacticity;
(2) the melt index of polypropylene is measured according to test standard ASTM D1238, wherein the measurement conditions include: the temperature is 230 ℃, and the load is 2.16 kg;
(3) the molecular weight and molecular weight distribution MWD (MWD. Mw/Mn) of polypropylene were measured by high temperature gel permeation chromatography (CPC) using PL-GPC220 using trichlorobenzene as a solvent at 150 deg.C (standard is polystyrene, flow rate: 1.0mL/min, column: 3xPlgel 10. mu. m M1 xED-B300x7.5nm);
(4) catalytic activity of the catalyst: evaluating the catalytic activity of the catalyst by comparing the weight of the polypropylene obtained after polymerization with the dosage weight of the catalyst;
(5) component content analysis of the catalyst: the content of the titanium element is measured by a colorimetric method; the determination of the content of the magnesium element adopts a titration method; the content of internal electron donor is determined by extraction method.
Preparation examples 1 to 3 are illustrative of the first external electron donor compound of the present invention and the preparation method thereof.
Preparation example 1
Preparation example 1 for preparing a first external electron donor compound A represented by formula I-1:
(1) preparation of Grignard reagents
Taking a 500 ml three-neck flask with a magneton, a spherical condenser tube and a constant-pressure dropping funnel, and adding magnesium powder (28.8 g, 1.2 mol) and a little iodine elementary substance under the protection of nitrogen; adding o-bromoanisole (1.0 mol) and tetrahydrofuran (200 ml) into a constant-pressure dropping funnel, then dropwise adding 5 ml of tetrahydrofuran solution of o-bromoanisole into the flask, and stirring for 3-5 minutes to initiate reaction; then dropwise adding a tetrahydrofuran solution of o-bromoanisole; after the completion of the dropwise addition, the mixture was refluxed under heating for 1 hour to complete the preparation of the Grignard reagent.
(2) Synthesis of silanes
Taking a 2.5L three-neck flask with a magneton and a spherical condenser, adding diphenyldichlorosilane (253 g, 1.0 mol) and 500 ml of tetrahydrofuran under the protection of nitrogen; placing the flask in an ice-water bath, and then slowly adding the Grignard reagent into the flask by using an injector; after the dropwise addition, slowly heating to room temperature, and reacting for 12 hours; the flask was then placed again in an ice-water bath and triethylamine (101 g, 1.0 mol) and methanol (100 ml) were added; finally refluxing for 6 hours completes the reaction. The product was separated by distillation under reduced pressure, and the obtained product was identified as the first external electron donor compound a represented by formula I-1 by nmr hydrogen spectroscopy (yield 83 wt%).
Preparation example 2
Preparation example 2 for preparing a first external electron donor compound B represented by formula I-2:
the procedure was as in preparation example 1, except that in step (1), an equal amount of 1-bromo-2-methoxy-3-methylbenzene was used
The product obtained by replacing o-bromoanisole was identified as the first external electron donor compound B represented by formula I-2 by NMR (yield 75 wt%).
Preparation example 3
Preparation example 3 for preparing a first external electron donor compound C represented by formula I-3:
the procedure of preparation example 1 was followed except that, in step (1), 1-bromo-2-methoxy-3-isopropylbenzene was used in an equal amount
The product obtained was determined to be the first external electron donor compound C represented by formula I-3 by NMR hydrogen spectroscopy instead of o-bromoanisole (yield 69 wt%).
Preparation example 4 is intended to illustrate the second external electron donor compound of the present invention and the preparation method thereof.
Preparation example 4
A second external electron donor compound represented by formula II was prepared by the method disclosed in example 5 with reference to CN 102850389A:
examples 1 to 7 are for illustrating the olefin polymerization catalyst and the polyolefin production method of the present invention.
The solid components used in examples 1 to 7 and comparative examples 1 to 4 were prepared as follows:
(1) sequentially adding 4.94g of anhydrous magnesium chloride, 18.9g of isooctanol and 30mL of decane into a reactor subjected to high-purity nitrogen full displacement, stirring, heating to 130 ℃, and then maintaining for 2 hours to obtain a magnesium-containing dispersion medium;
(2) adding 2.65g of tetrabutyl titanate and 10mmol of diisobutyl phthalate to a magnesium-containing dispersion medium, continuing the reaction at a temperature of 130 ℃ for 1 hour, and then cooling to room temperature (here, room temperature is 25 ℃) to obtain a first dispersion;
(3) adding 200mL of titanium tetrachloride into a reaction kettle, stirring, precooling to-20 ℃, maintaining for 2 hours, dropwise adding the first dispersion into the titanium tetrachloride, heating up after dropwise adding is finished, heating up to 110 ℃ within 2 hours, then adding 5mmol of diisobutyl phthalate, continuing to react for 2 hours at the temperature of 110 ℃, removing the reaction liquid, adding 200mL of titanium tetrachloride again, and reacting for 2 hours to obtain a second dispersion;
(4) the reaction liquid in the second dispersion was removed, and the resulting solid matter was washed 10 times with hexane at 60 ℃ to obtain a solid component Z after drying.
In the solid component Z, the molar ratio of titanium tetrachloride in terms of titanium element, magnesium chloride in terms of magnesium element and diisobutylphthalate is 1: 22: 0.85; the content of titanium element was 2.36 wt%.
Example 1
Heating and vacuumizing a 5L high-pressure reaction kettle, removing air and water, replacing with nitrogen, repeating for three times, adding 20mg of a solid component Z, 6mmol of triethylaluminum (the molar ratio of Al to Ti is 600), 0.175mmol of a first external electron donor compound A and 0.025mmol of a second external electron donor compound (the molar ratio of the first external electron donor compound A to the second external electron donor compound is 7; the molar ratio of the external electron donor compound is 20 based on silicon), adding 84mmol of hydrogen and 1000g of propylene, heating to 70 ℃, reacting at the temperature for 1 hour, cooling, releasing pressure, discharging and drying to obtain polypropylene powder particles, wherein the specific performance test results of the polypropylene powder particles are shown in Table 1.
Example 2
Propylene polymerization was performed according to the method of example 1, except that the amount of the first external electron donor compound a added was 0.167mmol, and the amount of the second external electron donor compound added was 0.033mmol (the molar ratio of the first external electron donor compound a to the second external electron donor compound was 5), to obtain polypropylene powder particles, and the results of the specific performance test of the polypropylene powder particles were as shown in table 1.
Example 3
Propylene polymerization was carried out in the same manner as in example 1, except that the amount of the first external electron donor compound A added was 0.15mmol and the amount of the second external electron donor compound added was 0.05mmol (the molar ratio of the first external electron donor compound A to the second external electron donor compound was 3), to obtain polypropylene powder particles, and the specific performance test results of the polypropylene powder particles are shown in Table 1.
Example 4
Propylene polymerization was carried out in the same manner as in example 1, except that the amount of the first external electron donor compound A added was 0.1mmol and the amount of the second external electron donor compound added was 0.1mmol (the molar ratio of the first external electron donor compound A to the second external electron donor compound was 1), to obtain polypropylene powder particles, and the specific performance test results of the polypropylene powder particles are shown in Table 1.
Example 5
Heating and vacuumizing a 5L high-pressure reaction kettle, removing air and water, replacing the high-pressure reaction kettle with nitrogen, repeating the steps for three times, adding 20mg of a solid component Z, 6mmol of triethylaluminum (the molar ratio of Al to Ti is 600), 0.15mmol of a first external electron donor compound B and 0.05mmol of a second external electron donor compound (the molar ratio of the first external electron donor compound B to the second external electron donor compound is 3; the molar ratio of Si to Ti is 20 based on silicon), adding 84mmol of hydrogen and 1000g of propylene, heating to 70 ℃, reacting at the temperature for 1 hour, cooling, depressurizing, discharging and drying to obtain polypropylene powder particles, wherein the specific performance test results of the polypropylene powder particles are shown in Table 1.
Example 6
Heating and vacuumizing a 5L high-pressure reaction kettle, removing air and water, replacing with nitrogen, repeating for three times, adding 20mg of a solid component Z, 6mmol of triethylaluminum (the molar ratio of Al to Ti is 600), 0.15mmol of a first external electron donor compound C and 0.05mmol of a second external electron donor compound (the molar ratio of the first external electron donor compound C to the second external electron donor compound is 3; the external electron donor composition is calculated by silicon, the molar ratio of Si to Ti is 20), adding 84mmol of hydrogen and 1000g of propylene, heating to 70 ℃, reacting at the temperature for 1 hour, cooling, depressurizing, discharging and drying to obtain polypropylene powder particles, wherein specific performance test results of the polypropylene powder particles are shown in Table 1.
Example 7
Propylene polymerization was conducted in the same manner as in example 3 except that the external electron donor composition was used in an amount of 40 mole ratio of Si/Ti based on Si element to obtain polypropylene powder particles, and the results of the performance test of the polypropylene powder particles are shown in Table 1.
Comparative example 1
Propylene was polymerized by the method of example 3, except that 0.2mmol of the first external electron donor compound A was added and the second external electron donor compound was not added (the first external electron donor compound A was calculated as Si element, and the Si/Ti molar ratio was 20), to obtain polypropylene powder particles, and the specific performance test results of the polypropylene powder particles are shown in Table 1.
Comparative example 2
Propylene was polymerized by the method of example 3, except that the first external electron donor compound a was not added, and 0.2mmol of the second external electron donor compound (the second external electron donor compound is based on Si element, and the Si/Ti molar ratio is 20) was added to obtain polypropylene powder particles, and the specific performance test results of the polypropylene powder particles are shown in table 1.
Comparative example 3
Propylene was polymerized by the method of example 3, except that the amount of the first external electron donor compound a added was 0.183mmol and the amount of the second external electron donor compound added was 0.017mmol (the molar ratio of the first external electron donor compound a to the second external electron donor compound was 11), to obtain polypropylene powder particles, and the results of the specific performance test of the polypropylene powder particles are shown in table 1.
Comparative example 4
Propylene polymerization was conducted in the same manner as in example 3 except that 9, 9-bis (methoxymethyl) fluorene (BMF) and Tetraethoxysilane (TEOS) were used as the external electron donor composition (the molar ratio of BMF to TEOS was 2.5: 97.5, and the molar ratio of the amount of the external electron donor composition added to Ti was 15), to obtain polypropylene powder particles, and the specific performance test results of the polypropylene powder particles were as shown in Table 1.
TABLE 1
As can be seen from the results of table 1:
in examples 1 to 4, as the ratio of the first external electron donor compound to the second external electron donor compound was gradually decreased, the melt index and the molecular weight distribution index of the polymer tended to increase first and then decrease; when the molar ratio of the first external electron donor compound to the second external electron donor compound is 3, the melt index and the molecular weight distribution index of the polymer reach peak values (melt index of 148.4g/10min, molecular weight distribution of 8.8).
In examples 3, 5 and 6, when the molar ratio of the first external electron donor compound to the second external electron donor compound is within the preferred range of the present invention and the amount of the external electron donor composition added is within the preferred range of the present invention, the activity of the catalyst can be further improved and polymers having a higher melt index and a broader molecular weight distribution can be obtained.
In example 7, when the amount of the external electron donor composition added is increased, the melt index and the molecular weight distribution index of the polymer are decreased.
In comparative examples 1 and 2, when the first external electron donor compound was used alone, the catalyst had excellent activity and the isotacticity of the polymer was good, but the melt index and the molecular weight distribution index were very low; when the second external electron donor compound is used alone, although a polymer having a high melt index and a high molecular weight distribution index can be obtained, the activity of the catalyst and the isotacticity of the polymer are poor.
In comparative example 3, when the molar ratio of the first external electron donor compound and the second external electron donor compound is outside the range defined in the present invention, a polymer having both a high melt index and a high molecular weight distribution index cannot be obtained.
In comparative example 4, using the external electron donor composition outside the range defined in the present invention, the external electron donor composition did not have an effect of adjusting the molecular weight distribution of the polymer although the melt index of the resulting polymer was high.
In conclusion, the olefin polymerization catalyst obtained by the external electron donor composition provided by the invention can be used for preparing polypropylene with high MFR, high isotactic index and wide relative molecular mass distribution in a single reactor.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (33)
1. An external electron donor composition comprising a first external electron donor compound and a second external electron donor compound, wherein the first external electron donor compound is at least one selected from compounds having a structure represented by formula I:
in the formula I, R 1 And R 2 Each independently selected from C 1 -C 10 Alkyl of (1), C 6 -C 20 Any one of the aryl groups of (a);
R 3 、R 4 、R 5 and R 6 Each independently selected from hydrogen, halogen radicals, C 1 -C 10 Alkyl radical of (1), C 3 -C 12 Cycloalkyl and C 6 -C 20 Any one of the aryl groups of (a);
R 7 and R 8 Each independently selected from C 1 -C 5 Any one of the alkyl groups of (a);
R 1 and R 2 Same or different, R 3 、R 4 、R 5 、R 6 Identical or different, R 7 And R 8 The same or different;
the second external electron donor compound has a structure shown in formula II:
the molar ratio of the first external electron donor compound to the second external electron donor compound is 1-10: 1.
2. an external electron donor composition according to claim 1, wherein, in formula I, R 1 And R 2 Each independently selected from any one of methyl, ethyl, isopropyl, phenyl, 2, 6-dimethylphenyl and 2, 6-diisopropylphenyl.
3. An external electron donor composition according to claim 2, wherein, in formula I, R 1 And R 2 Each independently selected from any one of phenyl, 2, 6-dimethylphenyl and 2, 6-diisopropylphenyl.
4. An external electron donor composition according to claim 1, wherein, in formula I, R 3 、R 4 、R 5 And R 6 Each independently selected from any one of hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, isopropyl, tert-butyl, isobutyl, cyclopentyl, cyclohexyl, phenyl, 2, 6-dimethylphenyl and 2, 6-diisopropylphenyl.
5. An external electron donor composition according to claim 4, wherein in formula I, R 3 、R 4 And R 5 Each independently of the other is hydrogen, R 6 And is selected from any one of hydrogen, methyl, ethyl and isopropyl.
6. An external electron donor composition according to claim 1, wherein in formula I, R 7 And R 8 Each independently selected from any one of methyl, ethyl, n-propyl and isopropyl.
7. An external electron donor composition according to claim 6, wherein in formula I, R 7 And R 8 Each independently is methyl.
8. An external electron donor composition according to any of claims 1-7, wherein the first external electron donor compound is selected from at least one of compounds of formula I-1, compounds of formula I-2 and compounds of formula I-3:
9. an external electron donor composition according to any of claims 1 to 7, wherein the molar ratio of the first external electron donor compound to the second external electron donor compound is from 2.5 to 9: 1.
10. the external electron donor composition of claim 9, wherein the molar ratio of the first external electron donor compound to the second external electron donor compound is 3-8: 1.
11. the external electron donor composition of claim 10, wherein the molar ratio of the first external electron donor compound and the second external electron donor compound is 3-5: 1.
12. an olefin polymerization catalyst, characterized in that the olefin polymerization catalyst comprises:
(1) the solid component is obtained by a titanium-containing compound, a magnesium-containing compound and an internal electron donor compound through contact reaction;
(2) an organoaluminum compound; and
(3) an external electron donor composition;
the external electron donor composition is the external electron donor composition of any of claims 1-11.
13. The olefin polymerization catalyst according to claim 12, wherein the molar ratio of the titanium-containing compound in terms of titanium element, the magnesium-containing compound in terms of magnesium element, and the internal electron donor compound is 1: 1-50: 0.1-1.5.
14. The olefin polymerization catalyst according to claim 13, wherein the molar ratio of the titanium-containing compound in terms of titanium element, the magnesium-containing compound in terms of magnesium element, and the internal electron donor compound is 1: 5-40: 0.2-1.2.
15. The olefin polymerization catalyst according to claim 14, wherein the molar ratio of the titanium-containing compound in terms of titanium element, the magnesium-containing compound in terms of magnesium element, and the internal electron donor compound is 1: 10-30: 0.5-1.
16. The olefin polymerization catalyst according to claim 12, wherein the titanium-containing compound is at least one selected from the group consisting of tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetrabutyl titanate, titanium tetrachloride, titanium tetrabromide, and titanium tetrafluoride.
17. The olefin polymerization catalyst according to claim 16, wherein the titanium-containing compound is tetrabutyl titanate and/or titanium tetrachloride.
18. The olefin polymerization catalyst according to claim 12, wherein the magnesium-containing compound is selected from at least one of magnesium chloride, magnesium bromide and magnesium iodide.
19. The olefin polymerization catalyst of claim 18, wherein the magnesium-containing compound is magnesium chloride.
20. The olefin polymerization catalyst according to claim 12, wherein the internal electron donor compound is at least one selected from the group consisting of di-tert-butyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, di-n-propyl phthalate, diisopropyl phthalate and diethyl phthalate.
21. The olefin polymerization catalyst according to claim 20, wherein the internal electron donor compound is at least one of diisobutyl phthalate, di-n-butyl phthalate, and di-n-propyl phthalate.
22. The olefin polymerization catalyst of any one of claims 12-21, wherein the molar ratio of the external electron donor composition to the titanium-containing compound as titanium element is from 2 to 50: 1.
23. the olefin polymerization catalyst according to claim 22, wherein the molar ratio of the external electron donor composition to the titanium-containing compound as titanium element is from 5 to 30: 1.
24. the olefin polymerization catalyst according to any one of claims 12 to 21, wherein the molar ratio of the organoaluminum compound, calculated as aluminum element, to the titanium-containing compound, calculated as titanium element, is from 10 to 1000: 1.
25. the olefin polymerization catalyst according to claim 24, wherein the molar ratio of the organoaluminum compound in terms of aluminum element to the titanium-containing compound in terms of titanium element is 40 to 800: 1.
26. the olefin polymerization catalyst according to any one of claims 12 to 21, wherein the organoaluminum compound is at least one selected from the group consisting of triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, triisobutylaluminum, tri-n-butylaluminum, and tri-tert-butylaluminum.
27. The olefin polymerization catalyst according to claim 26, wherein the organoaluminum compound is triethylaluminum and/or triisobutylaluminum.
28. Use of an olefin polymerisation catalyst as claimed in any one of claims 12 to 27 in an olefin polymerisation reaction.
29. A process for preparing a polyolefin, the process comprising: polymerizing an olefin monomer under olefin polymerization conditions in the presence of the olefin polymerization catalyst of any one of claims 12-27.
30. The process of claim 29, wherein the olefin polymerization conditions comprise: the polymerization temperature is 50-80 ℃; the polymerization time is 1 to 3 hours.
31. The process of claim 30, wherein the olefin polymerization conditions comprise: the polymerization temperature is 65-75 ℃; the polymerization time is 1.5 to 2 hours.
32. The process of claim 29, wherein the olefin monomer is selected from at least one of propylene, 1-butene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, 1-pentene, 2-pentene, and 1-hexene.
33. The process of claim 32, wherein the olefin monomer is propylene.
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