CN114702531B - Metallocene, catalyst containing the same, synthesis and application thereof - Google Patents
Metallocene, catalyst containing the same, synthesis and application thereof Download PDFInfo
- Publication number
- CN114702531B CN114702531B CN202110000205.XA CN202110000205A CN114702531B CN 114702531 B CN114702531 B CN 114702531B CN 202110000205 A CN202110000205 A CN 202110000205A CN 114702531 B CN114702531 B CN 114702531B
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- Prior art keywords
- catalyst
- solvent
- olefin polymerization
- reaction according
- polymerization reaction
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- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- 230000015572 biosynthetic process Effects 0.000 title description 5
- 238000003786 synthesis reaction Methods 0.000 title description 5
- 150000001336 alkenes Chemical class 0.000 claims abstract description 43
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000002904 solvent Substances 0.000 claims abstract description 40
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 34
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 24
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 239000002685 polymerization catalyst Substances 0.000 claims abstract description 7
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims abstract 7
- 150000001639 boron compounds Chemical class 0.000 claims abstract 5
- 239000003426 co-catalyst Substances 0.000 claims abstract 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 65
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 51
- 238000006243 chemical reaction Methods 0.000 claims description 47
- 239000000243 solution Substances 0.000 claims description 43
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- -1 lithium aluminum hydride Chemical compound 0.000 claims description 35
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 14
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 14
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- 238000006384 oligomerization reaction Methods 0.000 claims description 12
- 239000003377 acid catalyst Substances 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 11
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 10
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 10
- 238000000605 extraction Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 7
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 7
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 7
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 7
- RZWZRACFZGVKFM-UHFFFAOYSA-N propanoyl chloride Chemical compound CCC(Cl)=O RZWZRACFZGVKFM-UHFFFAOYSA-N 0.000 claims description 7
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 claims description 7
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 7
- 150000001263 acyl chlorides Chemical group 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 6
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 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 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229940050176 methyl chloride Drugs 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 claims description 3
- 239000012346 acetyl chloride Substances 0.000 claims description 3
- DVECBJCOGJRVPX-UHFFFAOYSA-N butyryl chloride Chemical compound CCCC(Cl)=O DVECBJCOGJRVPX-UHFFFAOYSA-N 0.000 claims description 3
- CCIVGXIOQKPBKL-UHFFFAOYSA-N ethanesulfonic acid Chemical compound CCS(O)(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-N 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- ABXKXVWOKXSBNR-UHFFFAOYSA-N CCC[Mg]CCC Chemical compound CCC[Mg]CCC ABXKXVWOKXSBNR-UHFFFAOYSA-N 0.000 claims description 2
- QQTGJVBUIOTPGZ-UHFFFAOYSA-N CCC[Zn]CCC Chemical compound CCC[Zn]CCC QQTGJVBUIOTPGZ-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- KYHHMFUFEIHUHB-UHFFFAOYSA-N di-tert-butylzinc Chemical compound CC(C)(C)[Zn]C(C)(C)C KYHHMFUFEIHUHB-UHFFFAOYSA-N 0.000 claims description 2
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 claims description 2
- FRLYMSHUDNORBC-UHFFFAOYSA-N diisopropylzinc Chemical compound [Zn+2].C[CH-]C.C[CH-]C FRLYMSHUDNORBC-UHFFFAOYSA-N 0.000 claims description 2
- KJJBSBKRXUVBMX-UHFFFAOYSA-N magnesium;butane Chemical compound [Mg+2].CCC[CH2-].CCC[CH2-] KJJBSBKRXUVBMX-UHFFFAOYSA-N 0.000 claims description 2
- DLPASUVGCQPFFO-UHFFFAOYSA-N magnesium;ethane Chemical compound [Mg+2].[CH2-]C.[CH2-]C DLPASUVGCQPFFO-UHFFFAOYSA-N 0.000 claims description 2
- DQZLQYHGCKLKGU-UHFFFAOYSA-N magnesium;propane Chemical compound [Mg+2].C[CH-]C.C[CH-]C DQZLQYHGCKLKGU-UHFFFAOYSA-N 0.000 claims description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 2
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 claims description 2
- HEPBQSXQJMTVFI-UHFFFAOYSA-N zinc;butane Chemical compound [Zn+2].CCC[CH2-].CCC[CH2-] HEPBQSXQJMTVFI-UHFFFAOYSA-N 0.000 claims description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical class CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims 1
- 239000002585 base Substances 0.000 claims 1
- 239000005416 organic matter Substances 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- 238000001308 synthesis method Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 238000005829 trimerization reaction Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 description 32
- 238000000034 method Methods 0.000 description 23
- 238000000921 elemental analysis Methods 0.000 description 13
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 12
- 238000005292 vacuum distillation Methods 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 229920000098 polyolefin Polymers 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 229910052726 zirconium Inorganic materials 0.000 description 7
- OUYLXVQKVBXUGW-UHFFFAOYSA-N 2,3-dimethyl-1h-pyrrole Chemical compound CC=1C=CNC=1C OUYLXVQKVBXUGW-UHFFFAOYSA-N 0.000 description 6
- ZMMRKRFMSDTOLV-UHFFFAOYSA-N cyclopenta-1,3-diene zirconium Chemical compound [Zr].C1C=CC=C1.C1C=CC=C1 ZMMRKRFMSDTOLV-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000012968 metallocene catalyst Substances 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 239000004711 α-olefin Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- BZYUMXXOAYSFOW-UHFFFAOYSA-N 2,3-dimethylthiophene Chemical group CC=1C=CSC=1C BZYUMXXOAYSFOW-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- FOKNRIPIBMCNAE-UHFFFAOYSA-J [Cl-].[Cl-].[Cl-].[Cl-].[Zr+4].CCCCC1=CC=CC1 Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Zr+4].CCCCC1=CC=CC1 FOKNRIPIBMCNAE-UHFFFAOYSA-J 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000012718 coordination polymerization Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000895 extractive distillation Methods 0.000 description 2
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 2
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- TVCXVUHHCUYLGX-UHFFFAOYSA-N 2-Methylpyrrole Chemical compound CC1=CC=CN1 TVCXVUHHCUYLGX-UHFFFAOYSA-N 0.000 description 1
- VMZCDNSFRSVYKQ-UHFFFAOYSA-N 2-phenylacetyl chloride Chemical compound ClC(=O)CC1=CC=CC=C1 VMZCDNSFRSVYKQ-UHFFFAOYSA-N 0.000 description 1
- MFEILWXBDBCWKF-UHFFFAOYSA-N 3-phenylpropanoyl chloride Chemical compound ClC(=O)CCC1=CC=CC=C1 MFEILWXBDBCWKF-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229920010524 Syndiotactic polystyrene Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Chemical group 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/26—Catalytic processes with hydrides or organic compounds
- C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
- C07C2/34—Metal-hydrocarbon complexes
-
- 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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/20—Olefin oligomerisation or telomerisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
本发明公开了一种烯烃聚合催化剂。该催化剂包括多取代的环戊二烯并五元杂环茂金属、有机硼化物、烷基金属以及溶剂；茂金属为主催化剂，有机硼化物、烷基金属为助催化剂；茂金属、有机硼化物、烷基金属的摩尔比为1：(0.8～1.4)：(10～500)；溶剂在催化剂中的重量占比为70～90%。本发明催化剂采用了新型的茂金属结构，有效调控了茂金属的电子和空间效应，提高了重烯烃聚合的三聚、四聚和五聚端烯烃产物的收率。The present invention discloses an olefin polymerization catalyst. The catalyst comprises a polysubstituted cyclopentadienyl five-membered heterocyclic metallocene, an organic boron compound, an alkyl metal and a solvent; the metallocene is the main catalyst, and the organic boron compound and the alkyl metal are the co-catalysts; the molar ratio of the metallocene, the organic boron compound and the alkyl metal is 1: (0.8-1.4): (10-500); the weight proportion of the solvent in the catalyst is 70-90%. The catalyst of the present invention adopts a new metallocene structure, effectively regulates the electronic and spatial effects of the metallocene, and improves the yield of trimerization, tetramerization and pentamerization terminal olefin products of heavy olefin polymerization.
Description
Technical Field
The invention relates to a metallocene and application thereof. In particular to a novel structure metallocene and synthesis and application thereof.
Background
Polyolefin has become a synthetic polymer material widely used in our daily life, and the market demand of traditional polyolefin materials such as polyethylene and polypropylene is still increasing. Polyolefin materials having specific functions such as optical properties continue to be of interest. The design of the high-efficiency transition metal complex can accurately control olefin coordination polymerization, so that a novel polyolefin material which is difficult to synthesize by the traditional catalyst is synthesized. Therefore, research for designing efficient transition metal complexes to accurately control coordination polymerization of olefins has received considerable attention.
The metallocene catalyst can be used for synthesizing a series of high-performance polyolefin products, such as isotactic polypropylene, syndiotactic polypropylene, atactic polypropylene, high-density polyethylene, low-density polyethylene, syndiotactic polystyrene, cycloolefin copolymer, polybutene, PAO and the like. The metallocene catalyst has remarkable advantages in the aspect of controlling the synthesis of polyolefin products, the catalyst structure is further optimized, a new metallocene catalyst is synthesized, and polyolefin products with excellent performance can be synthesized.
CN1020101897 describes a class of metallocene catalyst structures containing N, O atoms in the side chain, which have higher activity for olefin polymerization. Also described in CN102245620 is a broad class of metallocene complexes having a substituent at the 5-position of the indenyl ring and optionally a substituted furyl or thienyl group at the 2-position of the indenyl ring, which catalysts improve the absorption efficiency of ethylene or alpha-olefins and can give rubber components, in particular ethylene/propylene copolymer components, having high molecular weights. One class of metallocene catalysts containing S or O heterocycles is described in CN 105985372A, which catalyzes the copolymerization of long chain alpha-olefins. CN2016112389522 describes a bridged metallocene compound containing a heterocyclic structure for copolymerization of ethylene with alpha-olefins, which improves the insertion rate of alpha-olefins.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a metallocene with a novel structure, a catalyst containing the metallocene, and synthesis and application thereof.
According to a first aspect of the present invention there is provided a metallocene of novel structure.
A polysubstituted cyclopenta five-membered heterocyclic metallocene has a structural formula shown in the specification:
Wherein X is sulfur, nitrogen or oxygen, etc., preferably sulfur or nitrogen, R 1、R2、R3 is an alkyl group such as CH 3、C2H5、C3H7、C6H5, preferably CH 3、C2H5, M is Zr, ti or Hf, preferably Zr, Z is Cl, br, I, CH 3、C2H5、C3H7 or C 4H9, etc., preferably Cl, br, I or C 2H5, and M is the valence of M metal-2.
According to a second aspect of the present invention, there is provided a method of synthesizing the metallocene described above.
A method for synthesizing polysubstituted cyclopenta five-membered heterocyclic metallocene, which comprises the following steps:
(1) Adding the substituted acyl chloride and the substituted five-membered heterocycle into a solvent, uniformly stirring, cooling to-40-0 ℃, then adding a catalyst, stirring and reacting for 10-24 hours, and separating a reaction material to obtain a product Pa (number Pa);
(2) Adding the Pa product obtained in the step (1) and hexamethylenetetramine into acetic anhydride, stirring and reacting for 24-48 hours at the reaction temperature of 80-100 ℃, adding alkali liquor, stirring and reacting for 1-4 hours, separating organic matters by an extraction technology, adding the extract and a strong acid catalyst into a solvent, stirring and reacting at the reaction temperature of room temperature-50 ℃ for 1-4 hours, and separating to obtain a product Pb;
(3) Adding the product Pb obtained in the step (2) into diethyl ether to prepare a solution Ep, adding lithium aluminum hydride into diethyl ether to prepare lithium aluminum hydride diethyl ether solution Es, cooling the solution Es to-20 to-40 ℃, dropwise adding the solution Ep into the solution Es, heating to room temperature to 40 ℃ to react for 1-2 h, and separating by adopting an extraction-reduced pressure distillation technology to obtain a product Pc;
(4) Adding the product Pc obtained in the step (3) and a strong acid catalyst into a solvent, heating and refluxing for 0.5-2 h, and separating to obtain a product Pd;
(5) Dissolving the product Pd prepared in the step (4) in a solvent, cooling to-40-0 ℃, dropwise adding alkyl lithium, stirring and reacting for 0.5-3 h at the reaction temperature of room temperature-40 ℃, adding chloride, stirring and reacting for 24-48 h at the reaction temperature of room temperature-40 ℃ to obtain a solution S;
(6) And (3) pumping the solvent in the solution S obtained in the step (5), adding methyl chloride for dissolution, carrying out solid-liquid separation, and carrying out distillation concentration to obtain the product CpM.
Further, the substituted acyl chloride structure in the step (1) is R-CH 2 -CO-Cl, and R is various alkyl groups, aromatic hydrocarbon and the like. Specifically, the substituted acyl chloride structure may be acetyl chloride, propionyl chloride, butyryl chloride, phenylacetyl chloride or phenylpropionyl chloride, etc. The five-membered heterocyclic ring has the structure thatR (R1, R2) is various alkyl and aromatic hydrocarbon. The solvent is at least one of benzene, toluene, tetrahydrofuran, N-dimethylformamide, dimethyl sulfoxide and the like, and preferably benzene (0.8765 g/cm 3) or toluene.
Further, the catalyst in the step (1) is anhydrous aluminum chloride or anhydrous tin chloride, preferably anhydrous tin chloride. The extraction-reduced pressure distillation is a conventional technology in the art, and the extractant used in the extraction process is at least one of dichloromethane, chloroform, dichloroethane, benzene, toluene and the like, preferably benzene.
Further, in the step (1), the molar ratio of the substituted acyl chloride to the substituted five-membered heterocycle to the catalyst is 1 (0.8-1.2): (0.01-0.1), and the weight ratio of the substituted five-membered heterocycle to the solvent is 1 (4-10). In the step (1), stirring and reacting for 10-24 hours. The separation in step (1) is carried out by methods conventional in the art, such as by extractive-vacuum distillation techniques.
The alkali liquor in the step (2) is an aqueous solution of alkali, and the alkali is sodium hydroxide, sodium tert-butoxide, sodium bicarbonate and the like, preferably sodium hydroxide. The extractant is dichloromethane, chloroform, dichloroethane, benzene, toluene, etc., preferably dichloromethane. The strong acid catalyst is methylsulfonic acid, ethylsulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, hydrochloric acid, sulfuric acid, etc., preferably methylsulfonic acid.
In the step (2), the concentration of the alkali liquor is 1-4 mol/L. The molar ratio of Pa, hexamethylenetetramine and acetic anhydride is 1 (0.8-1.6): (1.2-2.0), and the molar ratio of alkali to acetic anhydride is 1 (5-10). The molar ratio of the Pa product to the strong acid catalyst is 1 (0.1-0.5). The weight ratio of Pa product to solvent is generally 1 (4-10). The separation of the reaction mass in step (2) is carried out by methods conventional in the art, such as by extractive-vacuum distillation techniques.
In the step (3), the concentration of the prepared solution Ep is 1-3 mol/L. The concentration of the lithium aluminum hydride diethyl ether solution is generally 0.1-0.3 mol/L. The molar ratio of Pb to lithium aluminum hydride is1 (0.2-0.4).
The strong acid catalyst in the step (4) is methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid (172 g/mol), hydrochloric acid, sulfuric acid, etc., preferably p-toluenesulfonic acid. The solvent is chloroform, carbon tetrachloride, benzene, toluene, etc., preferably benzene. Further, the molar ratio of Pc to the strongly acidic catalyst is 1 (0.02-0.05), and the weight ratio of Pc to the solvent is 1 (10-18). The separation in step (4) is performed by procedures well known in the art, such as extractive-vacuum distillation techniques.
The chloride salt in the step (5) is zirconium chloride, hafnium chloride, titanium chloride and the like. Zirconium chloride is preferred. The solvent in the step (5) is diethyl ether, tetrahydrofuran, and the like. Tetrahydrofuran is preferred. Further, the molar ratio of Pd to butyllithium to zirconium chloride is 1 (1.8-2.4): 0.4-0.6. The weight ratio of Pd to the solvent is 1 (8-20).
The alkyl lithium in the step (5) comprises ethyl lithium, propyl lithium, butyl lithium and the like. Butyl lithium is preferred. The concentration of the alkyl lithium solution is 2-4 mol/L.
In the step (6), the weight ratio of S to dichloromethane is 1 (10-20). The chloromethane is one of dichloromethane, chloroform and carbon tetrachloride.
According to a third aspect of the present invention there is also provided an olefin polymerization catalyst comprising the polysubstituted cyclopenta-five-membered heterocyclic metallocene as described hereinabove.
The olefin polymerization catalyst comprises polysubstituted cyclopenta five-membered heterocyclic metallocene, organic boride, alkyl metal and solvent, wherein the metallocene is used as a main catalyst, the organic boride and the alkyl metal are used as cocatalysts, and the molar ratio of the metallocene to the organic boride to the alkyl metal is1 (0.8-1.4) (10-500). Preferably 1 (0.9-1.3), wherein the weight ratio of the solvent in the catalyst is 70-90%.
Further, the organic boride is at least one selected from BF3、B(CF3)3、[MePhNH][B(CF3)3]、[(Me)2PhNH][B(CF3)4]、[R2NH][B(CF3)3]、[R3N][B(CF3)3]、[R3NH][B(CF3)4]、[Ph3C][B(CF3)2]、[NH3][B(CH3)3]、[Ph(Me)2N][B(C6F5)3]、[Ph(Me)2NH][B(C6F5)4], wherein r=c 2-C10 alkyl, ph is phenyl, and Me is methyl. The organoboride is preferably [ (Me) 2PhNH][B(CF3)4]、[R3NH][B(CF3)4 ] or [ Ph (Me) 2NH][B(C6F5)4 ], more preferably [ Ph (Me) 2NH][B(C6F5)4 ].
Further, the alkyl metal comprises at least one of alkyl magnesium, alkyl aluminum and alkyl zinc. The alkyl magnesium is at least one selected from the group consisting of diethyl magnesium, dipropyl magnesium, diisopropyl magnesium and dibutyl magnesium, the alkyl aluminum is at least one selected from the group consisting of trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisopropyl aluminum, tributyl aluminum and tri-tert-butyl aluminum, and the alkyl zinc is at least one selected from diethyl zinc, dipropyl zinc, diisopropyl zinc, dibutyl zinc and di-tert-butyl zinc. Preferably, the metal alkyls are tributylaluminum and tri-t-butylaluminum, more preferably tri-t-butylaluminum.
Further, the solvent may be at least one of benzene, toluene, n-octane, n-decane, alkylated oil, and the like.
According to a fourth aspect of the present invention, there is also provided an olefin oligomerization reaction wherein the above-described olefin polymerization catalyst is employed.
Specifically, the olefin oligomerization reaction comprises introducing an olefin and a catalyst into an autoclave, and carrying out polymerization under oligomerization reaction conditions.
Further, the oligomerization conditions are such that the reaction temperature is 40 to 100 ℃, preferably 60 to 80 ℃, and the reaction time is 1 to 8 hours, preferably 2 to 4 hours.
Compared with the prior art, the catalyst and the preparation method have the following beneficial effects:
The catalyst adopts a novel metallocene structure, effectively regulates and controls the electron and space effects of the metallocene, and can obviously improve the trimerization, tetramerization and pentameric end olefin product yield of heavy olefin polymerization. Specifically, the five-membered heterocyclic ring increases the aromaticity of cyclopentadiene. And meanwhile, the existence of the hetero atom shifts the electron cloud of the aromatic ring, so that the alkyl or hydrogen atom on the metallocene is stabilized, the exposure of the cation center is promoted, the coupling of macromolecular olefin and the cation center is promoted, and the chain initiation and the chain growth are realized. The existence of the substituent group further promotes the movement of electrons to zirconium metal, reduces the electropositivity of zirconium metal, is beneficial to beta-H elimination reaction, realizes chain termination, prevents the appearance of olefin polymers, effectively adjusts three factors, optimizes the catalytic performance of metallocene, and improves the selectivity of oligomers such as trimerization, tetramerization, pentamer and the like of heavy olefin polymerization. Meanwhile, the steric hindrance and the power supply effect prevent the bimolecular dehydrogenation reaction of the metallocene, effectively reduce the generation of hydrogenation saturated products of olefin reactants, and improve the reaction activity of the catalyst.
Detailed Description
The technical scheme of the invention is further described below with reference to specific embodiments.
The organic solvent used in the experiment was purified on a Milkalona SolvPurer A/G3 solvent purification system, the purification of which is a procedure well known to those skilled in the art. The required anhydrous and anaerobic operation was performed in a Milkalona Super (1220/750) glove box. Product analysis used agilent 7890A gas chromatography. The elemental detection of the catalyst was performed by using a ZSX100e type X-ray fluorescence spectrometer manufactured by Japanese national institute of technology.
The reagents and solvents used in the examples were derived from carbofuran and were chemically pure.
Example 1
(1) 92G of propionyl chloride (92.5 g/mol) and 95g of 2, 3-dimethylpyrrole (95 g/mol) are added to 736g of benzene (0.8765 g/cm 3), stirred well, cooled to-20℃and 13g of anhydrous tin chloride (260 g/mol) are then added dropwise. The reaction was stirred for 20h. The product Pa1 (151 g/mol) was isolated by extractive-vacuum distillation. The yield thereof was found to be 91%.
(2) 75.5G of the Pa1 product obtained in the step (1) and 91g of hexamethylenetetramine (140 g/mol) were added to 92g of acetic anhydride (102 g/mol), and the mixture was stirred and reacted for 20 hours at a reaction temperature of 90 ℃. 56mL of sodium hydroxide with the concentration of 2mol/L is added, and the reaction is stirred for 3 hours. Extraction techniques separate organics. The extract and 14.4g of methanesulfonic acid (96 g/mol) were then added to 608g of methylene chloride and the reaction was stirred at 30℃for 2h. The Pb1 product was isolated by extractive distillation under reduced pressure. The yield thereof was found to be 88%.
(3) 41G of the product Pb1 (163 g/mol) obtained in step (2) was added to 125mL of diethyl ether to prepare a solution Ep1.Ep1 was present at a concentration of 2mol/L. 2.9g of lithium aluminum hydride (38 g/mol) was added to 375mL of diethyl ether to prepare a solution of lithium aluminum hydride in diethyl ether at a concentration of 0.2mol/L. The solution was cooled to-30 ℃. Ep1 was added dropwise to the lithium aluminum hydride diethyl ether solution. The temperature was raised to 30℃and the reaction was carried out for 2h. The product P1c was isolated by extractive-vacuum distillation. The yield thereof was found to be 84%.
(4) 41G of the product Pc1 (165 g/mol) from step (3) and 1.2g of benzenesulfonic acid (158 g/mol) were added to 615g of benzene and heated under reflux for 1.5h. The product Pd1 was isolated using an extraction-vacuum distillation technique. The yield thereof was found to be 89%.
(5) 18G of the product Pd1 (147 g/mol) prepared in the step (4) was dissolved in 270g of tetrahydrofuran, cooled to-40℃and 131mL of a 2mol/L butyllithium hexane solution was added dropwise thereto, and the reaction was stirred for 2 hours at a reaction temperature of 30 ℃. 14.6g of zirconium chloride (233 g/mol) was then added thereto and the reaction was stirred for 30 hours at a reaction temperature of 30℃to give a solution S.
(6) And (3) pumping the solvent in the solution S1 obtained in the step (4), adding 560g of dichloromethane for dissolution, carrying out solid-liquid separation, and carrying out distillation concentration to obtain the product CpM1. The yield thereof was found to be 94%. The overall yield of CpM1 was 56%.
The metallocene product is characterized by an elemental analysis method and has the following structural general formula:
Wherein R1 and R2, R3 are CH 3, X is nitrogen element, M is Zr, Z is Cl, and M is 2.
The element composition of the polysubstituted cyclopenta five-membered heterocyclic metallocene is N2C20ZrCl2H24, and the theoretical weight percentage composition is 6.17wt% N:52.86wt% C:20.04wt% Zr:15.64wt% Cl:5.29wt% H. As can be seen from the elemental analysis of Table 1, the elemental composition of the synthesized polysubstituted cyclopenta five-membered heterocyclic metallocene is in accordance with the theoretical composition, indicating that the zirconocene was synthesized.
Example 2
(1) 92G of propionyl chloride (92.5 g/mol) and 114g of 2, 3-dimethylpyrrole (95 g/mol) are added to 920g of benzene (0.8765 g/cm 3), stirred well, cooled to-20℃and then 26g of anhydrous tin chloride (260 g/mol) are added dropwise. The reaction was stirred for 20h. The product Pa2 (151 g/mol) was isolated by extractive-vacuum distillation. The yield thereof was found to be 88%.
(2) 75.5G of the Pa product obtained in step (1) and 112g of hexamethylenetetramine (140 g/mol) were added to 102g of acetic anhydride (102 g/mol), and the mixture was stirred and reacted for 20 hours at a reaction temperature of 90 ℃. 50mL of sodium hydroxide with the concentration of 2mol/L is added, and the reaction is stirred for 3 hours. Extraction techniques separate organics. The extract and 24g of methanesulfonic acid (96 g/mol) were then added to 755g of dichloromethane and the reaction was stirred at 30℃for 2h. The Pb2 product was isolated by extractive distillation under reduced pressure. The yield thereof was found to be 81%.
(3) 41G of Pb2 (163 g/mol) obtained in step (2) was added to 83mL of diethyl ether to prepare a solution Ep2.Ep2 was present at a concentration of 3mol/L. 3.8g of lithium aluminum hydride (38 g/mol) was added to 1000mL of diethyl ether to prepare a solution of lithium aluminum hydride in diethyl ether at a concentration of 0.1mol/L. The solution was cooled to-30 ℃. Ep2 was added dropwise to the lithium aluminum hydride diethyl ether solution. The temperature was raised to 30℃and the reaction was carried out for 2h. The product Pc2 was isolated by extraction-vacuum distillation. The yield thereof was found to be 79%.
(4) 41G of the product Pc2 (165 g/mol) obtained in step (3) and 2g of benzenesulfonic acid (158 g/mol) were added to 738g of benzene and heated under reflux for 1.5h. The product Pd2 was isolated using an extraction-vacuum distillation technique. The yield thereof was found to be 91%.
(5) 18G of Pd2 (147 g/mol) as a product prepared in the step (4) was dissolved in 360g of tetrahydrofuran, cooled to-40℃and 150mL of a 2mol/L solution of butyllithium hexane was added dropwise thereto, and the reaction was stirred for 2 hours at a reaction temperature of 30 ℃. 17.5g of zirconium chloride (233 g/mol) was then added thereto and the reaction was stirred for 30 hours at a reaction temperature of 30℃to give a solution S.
(6) And (3) pumping the solvent in the solution S2 obtained in the step (4), adding 700g of dichloromethane for dissolution, carrying out solid-liquid separation, and carrying out distillation concentration to obtain the product CpM2. The yield thereof was found to be 93%. The overall yield of CpM2 was 47%.
The metallocene product is characterized by an elemental analysis method and has the following structural general formula:
Wherein R1 and R2, R3 are CH 3, X is nitrogen element, M is Zr, Z is Cl, and M is 2.
The element composition of the polysubstituted cyclopenta five-membered heterocyclic metallocene is N2C20ZrCl2H24, and the theoretical weight percentage composition is 6.17wt% N:52.86wt% C:20.04wt% Zr:15.64wt% Cl:5.29wt% H. As can be seen from the elemental analysis of Table 1, the elemental composition of the synthesized polysubstituted cyclopenta five-membered heterocyclic metallocene is in accordance with the theoretical composition, indicating that the zirconocene was synthesized.
Example 3
(1) 92G of propionyl chloride (92.5 g/mol) and 76g of 2, 3-dimethylpyrrole (95 g/mol) were added to 368g of benzene (0.8765 g/cm 3), stirred well, cooled to-20℃and then 2.6g of anhydrous tin chloride (260 g/mol) were added dropwise. The reaction was stirred for 20h. The product Pa3 (151 g/mol) was isolated by extractive-vacuum distillation. The yield thereof was found to be 79%.
(2) 75.5G of the Pa3 product obtained in the step (1) and 56g of hexamethylenetetramine (140 g/mol) were added to 61g of acetic anhydride (102 g/mol), and the mixture was stirred and reacted for 20 hours at a reaction temperature of 90 ℃. 60mL of sodium hydroxide with the concentration of 2mol/L is added, and the reaction is stirred for 3 hours. Extraction techniques separate organics. The extract and 4.8g of methanesulfonic acid (96 g/mol) were then added to 302g of methylene chloride and the reaction was stirred at 30℃for 2h. Separating Pb3 by extraction-reduced pressure distillation. The yield thereof was found to be 78%.
(3) 41G of Pb3 (163 g/mol) obtained in step 2 was added to 250mL of diethyl ether to prepare a solution Ep3.Ep3 was present at a concentration of 1mol/L. 1.9g of lithium aluminum hydride (38 g/mol) was added to 167mL of diethyl ether to prepare a solution of lithium aluminum hydride in diethyl ether at a concentration of 0.3mol/L. The solution was cooled to-30 ℃. Ep was added dropwise to the lithium aluminum hydride diethyl ether solution. The temperature was raised to 30℃and the reaction was carried out for 2h. The product Pc3 was isolated by extraction-vacuum distillation. The yield thereof was found to be 74%.
(4) 41G of the product Pc3 (165 g/mol) obtained in step (3) and 0.8g of benzenesulfonic acid (158 g/mol) were added to 410g of benzene, and the mixture was refluxed for 1.5 hours. The product Pd3 was isolated using an extraction-vacuum distillation technique. The yield thereof was found to be 81%.
(5) 18G of the product Pd3 (147 g/mol) prepared in the step (4) was dissolved in 144g of tetrahydrofuran, cooled to-40℃and 112mL of a 2mol/L butyllithium hexane solution was added dropwise thereto, and the reaction was stirred for 2 hours at a reaction temperature of 30 ℃. 11.6g of zirconium chloride (233 g/mol) was then added thereto and the reaction was stirred for 30 hours at a reaction temperature of 30℃to give a solution S.
(6) And (3) pumping the solvent in the solution S3 obtained in the step (4), adding 320g of dichloromethane for dissolution, carrying out solid-liquid separation, and carrying out distillation concentration to obtain the product CpM3. The yield thereof was found to be 84%. The overall yield of CpM3 was 31%.
The metallocene product is characterized by an elemental analysis method and has the following structural general formula:
Wherein R1 and R2, R3 are CH 3, X is nitrogen element, M is Zr, Z is Cl, and M is 2.
The element composition of the polysubstituted cyclopenta five-membered heterocyclic metallocene is N2C20ZrCl2H24, and the theoretical weight percentage composition is 6.17wt% N:52.86wt% C:20.04wt% Zr:15.64wt% Cl:5.29wt% H. As can be seen from the elemental analysis of Table 1, the elemental composition of the synthesized polysubstituted cyclopenta five-membered heterocyclic metallocene is in accordance with the theoretical composition, indicating that the zirconocene was synthesized.
Example 4
CpM4 of the invention was prepared in the same manner as in example 1 except that acetyl chloride was used in place of propionyl chloride and 2-methylpyrrole was used in place of 2, 3-dimethylpyrrole. The overall yield of CpM4 was 53%.
The metallocene product is characterized by an elemental analysis method and has the following structural general formula:
wherein R1 and R3 are H, R2 is CH 3, X is nitrogen element, M is Zr, Z is Cl, and M is 2.
The element composition of the polysubstituted cyclopenta five-membered heterocyclic metallocene is N2C16ZrCl2H16, and the theoretical weight percentage composition is 7.03wt% N, 48.24wt% C, 22.86wt% Zr, 17.84wt% Cl, 4.02wt% H. As can be seen from the elemental analysis of Table 1, the elemental composition of the synthesized polysubstituted cyclopenta five-membered heterocyclic metallocene is in accordance with the theoretical composition, indicating that the zirconocene was synthesized.
Example 5
CpM5 of the invention was prepared as in example 1 except that 2, 3-dimethylpyrrole was replaced with 2, 3-dimethylthiophene. The overall yield of CpM5 was 56%.
The metallocene product is characterized by an elemental analysis method and has the following structural general formula:
wherein R1 and R2, R3 are CH3, X is sulfur element, M is Zr, Z is Cl, and M is 2.
The element composition of the polysubstituted cyclopenta five-membered heterocyclic metallocene is S2C20ZrCl2H24, and the theoretical weight percentage composition is 13.06wt% S:48.98wt% C:18.57wt% Zr:14.49wt% Cl:4.90wt% H. As can be seen from the elemental analysis of Table 1, the elemental composition of the synthesized polysubstituted cyclopenta five-membered heterocyclic metallocene is in accordance with the theoretical composition, indicating that the zirconocene was synthesized.
Example 6
The CpM6 of the invention was prepared in the same manner as in example 1 except that butyryl chloride was used in place of propionyl chloride and 2, 3-dimethylthiophene was used in place of 2, 3-dimethylpyrrole. The overall yield of CpM6 was 48%.
The metallocene product is characterized by an elemental analysis method and has the following structural general formula:
Wherein R1 is CH 3HC2, R2 and R3 are CH 3, X is sulfur element, M is Zr, Z is Cl, and M is 2.
The element composition of the polysubstituted cyclopenta five-membered heterocyclic metallocene is S2C22ZrCl2H28, and the theoretical weight percentage composition is 12.36wt% S:50.97wt% C:17.56wt% Zr:13.71wt% Cl:5.40wt% H. As can be seen from the elemental analysis of Table 1, the elemental composition of the synthesized polysubstituted cyclopenta five-membered heterocyclic metallocene is in accordance with the theoretical composition, indicating that the zirconocene was synthesized.
TABLE 1 metallocene elemental analysis
Example 7
4.68G of the metallocene CpM1 prepared in example 1 (468 g/mol), 10.9g of [ Ph (Me) 2NH][B(C6F5)4 ] (1089 g/mol) and 39.6g of tributyl aluminum (198 g/mol) were added to 497g of the alkylate, and stirred well to obtain catalyst composition C1.
The molar ratio of the alkyl metal is 1:1:20, and the weight ratio of the solvent in the catalyst is 90%.
Example 8
4.68G of the metallocene CpM1 prepared in example 1 (468 g/mol), 14.1g of [ Ph (Me) 2NH][B(C6F5)4 ] (1089 g/mol) and 99g of tributyl aluminum (198 g/mol) were added to 274g of alkylate and stirred well to obtain catalyst composition C2.
The molar ratio of the alkyl metal is 1:1.3:50, and the weight ratio of the solvent in the catalyst is 70%.
Example 9
4.68G of the metallocene CpM1 prepared in example 1 (468 g/mol), 9.8g of [ Ph (Me) 2NH][B(C6F5)4 ] (1089 g/mol) and 198g of tributyl aluminum (198 g/mol) were added to 850g of the alkylate and stirred well to obtain catalyst composition C3.
The molar ratio of the alkyl metal is 1:0.9:100, and the weight ratio of the solvent in the catalyst is 80%.
Example 10
Catalyst C4 of the present invention was prepared as in example 7, except CpM4 prepared in example 4 was used.
Example 11
Catalyst C5 of the present invention was prepared as in example 7, except CpM5 prepared in example 5 was used.
Example 12
Catalyst C6 of the present invention was prepared as in example 7, except CpM6 prepared in example 6 was used.
TABLE2 molar composition of the catalyst components
Examples 13 to 16
The 1-decene oligomerization reaction was carried out in an autoclave equipped with electromagnetic stirring. Before the reaction, the autoclave was cleaned, heated in an oil bath at 140 ℃ and evacuated to negative pressure, and maintained for 0.5h. The autoclave was charged with high purity nitrogen and then evacuated, and the above was repeated three times. The reaction vessel was cooled to the reaction temperature. Heating in oil bath, and stirring. The liquid 1-decene steel cylinder and the catalyst feeding tank are respectively connected with a metering pump, and the 1-decene and the catalyst are introduced into the autoclave through the metering pump. The reaction temperature was 70℃and the reaction time was 2 hours.
Specific process conditions and reaction results are shown in Table 3.
TABLE 3 Process conditions and results
Comparative example 1
The existing metallocene catalyst adopts n-butyl cyclopentadiene zirconium chloride metallocene and methylaluminoxane to catalyze butene oligomerization, 4.06g of n-butyl cyclopentadiene zirconium chloride metallocene and 58g of methylaluminoxane and 14L 1-decene are respectively added into an autoclave, stirred and heated. The reaction conditions were 3MPa, 70℃and 2 hours. The conversion of 1-decene was 59mol% and the total selectivity to C 30+C40+C50 was 42wt%.
By comparing the catalyst of the invention with the existing catalyst, the activity and the total selectivity of C30+C40+C50 of the catalyst of the invention can be found to be obviously superior to the existing catalyst.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6451938B1 (en) * | 1997-02-25 | 2002-09-17 | Exxon Mobil Chemical Patents Inc. | Polymerization catalyst system comprising heterocyclic fused cyclopentadienide ligands |
| WO2006065844A2 (en) * | 2004-12-16 | 2006-06-22 | Exxonmobil Chemical Patents Inc. | Process for producing substituted metallocene compounds for olefin polymerization |
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| KR100645631B1 (en) * | 2000-02-10 | 2006-11-13 | 에스케이 주식회사 | Metallocene catalyst for producing polyethylene, preparation method thereof and polymerization method using the same |
| CN1132856C (en) * | 2000-11-02 | 2003-12-31 | 中国石油化工股份有限公司 | Catalyst for polymerizing semi-metallocene with olefin and its preparing process and application |
| US7989670B2 (en) * | 2005-07-19 | 2011-08-02 | Exxonmobil Chemical Patents Inc. | Process to produce high viscosity fluids |
| WO2007028536A2 (en) * | 2005-09-06 | 2007-03-15 | Basell Polyolefine Gmbh | Process for preparing olefin polymers in the presence of catalyst systems having photochromic groups |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6451938B1 (en) * | 1997-02-25 | 2002-09-17 | Exxon Mobil Chemical Patents Inc. | Polymerization catalyst system comprising heterocyclic fused cyclopentadienide ligands |
| WO2006065844A2 (en) * | 2004-12-16 | 2006-06-22 | Exxonmobil Chemical Patents Inc. | Process for producing substituted metallocene compounds for olefin polymerization |
Non-Patent Citations (3)
| Title |
|---|
| Ilya E. Nifant’ev et al..Structurally uniform 1-hexene,1-octene, and 1-decene oligomers: Zirconocene/MAO-catalyzed preparation, characterization, and prospects of their use as low-viscosity low-temperature oil base stocks.《Applied Catalysis A,General》.2017,第549卷第42 页 Scheme 2，第41-42页，第42-43页第2.3部分和第47 页Scheme 4，第44-46页第3部分. * |
| Ilya E. Nifant’ev et al..Structurally uniform 1-hexene,1-octene, and 1-decene oligomers: Zirconocene/MAO-catalyzed preparation, characterization, and prospects of their use as low-viscosity low-temperature oil base stocks.《Applied Catalysis A,General》.2017,第549卷第42 页 Scheme 2，第46页Table 3. * |
| STN检索报告;Columbus, Ohio, US Registry[Online];《STN Registry》;20171025;第1-15页 * |
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