CN111729688B - 一类含中性配位侧基单茂第四副族金属配合物的用途 - Google Patents
一类含中性配位侧基单茂第四副族金属配合物的用途 Download PDFInfo
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- CN111729688B CN111729688B CN202010659311.4A CN202010659311A CN111729688B CN 111729688 B CN111729688 B CN 111729688B CN 202010659311 A CN202010659311 A CN 202010659311A CN 111729688 B CN111729688 B CN 111729688B
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- Prior art keywords
- ring
- aluminum
- metal complex
- metallocene
- alkyl
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- 230000007935 neutral effect Effects 0.000 title claims abstract description 55
- 150000004696 coordination complex Chemical class 0.000 title claims abstract description 44
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 title claims abstract description 12
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 24
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000004711 α-olefin Substances 0.000 claims abstract description 17
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 14
- 125000005234 alkyl aluminium group Chemical group 0.000 claims abstract description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052796 boron Inorganic materials 0.000 claims abstract description 6
- -1 monomethylcyclopentadienyl Chemical group 0.000 claims description 64
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 55
- 239000005977 Ethylene Substances 0.000 claims description 55
- 238000006384 oligomerization reaction Methods 0.000 claims description 36
- 125000004432 carbon atom Chemical group C* 0.000 claims description 26
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 125000003118 aryl group Chemical group 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 125000001931 aliphatic group Chemical group 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical group C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 8
- BUDQDWGNQVEFAC-UHFFFAOYSA-N Dihydropyran Chemical group C1COC=CC1 BUDQDWGNQVEFAC-UHFFFAOYSA-N 0.000 claims description 6
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 6
- 238000004817 gas chromatography Methods 0.000 claims description 6
- 229910052735 hafnium Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 6
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical group C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 150000001639 boron compounds Chemical class 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 125000002188 cycloheptatrienyl group Chemical group C1(=CC=CC=CC1)* 0.000 claims description 4
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 4
- 125000004852 dihydrofuranyl group Chemical group O1C(CC=C1)* 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([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
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical group C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 claims description 2
- OXBLVCZKDOZZOJ-UHFFFAOYSA-N 2,3-Dihydrothiophene Chemical group C1CC=CS1 OXBLVCZKDOZZOJ-UHFFFAOYSA-N 0.000 claims description 2
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 claims description 2
- KYNSBQPICQTCGU-UHFFFAOYSA-N Benzopyrane Chemical group C1=CC=C2C=CCOC2=C1 KYNSBQPICQTCGU-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- DLRWQFGNMJLEOD-UHFFFAOYSA-N CCN(CC)Cl(N(C)C)(N(C(C)C)C(C)C)(N([Si](C)(C)C)[Si](C)(C)C)(OC)(OCC)OC(C)C Chemical compound CCN(CC)Cl(N(C)C)(N(C(C)C)C(C)C)(N([Si](C)(C)C)[Si](C)(C)C)(OC)(OCC)OC(C)C DLRWQFGNMJLEOD-UHFFFAOYSA-N 0.000 claims description 2
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 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 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- MYBJXSAXGLILJD-UHFFFAOYSA-N diethyl(methyl)alumane Chemical compound CC[Al](C)CC MYBJXSAXGLILJD-UHFFFAOYSA-N 0.000 claims description 2
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 claims description 2
- MWNKMBHGMZHEMM-UHFFFAOYSA-N dimethylalumanylium;ethanolate Chemical compound CCO[Al](C)C MWNKMBHGMZHEMM-UHFFFAOYSA-N 0.000 claims description 2
- SHGOGDWTZKFNSC-UHFFFAOYSA-N ethyl(dimethyl)alumane Chemical compound CC[Al](C)C SHGOGDWTZKFNSC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 claims description 2
- BQBCXNQILNPAPX-UHFFFAOYSA-N methoxy(dimethyl)alumane Chemical compound [O-]C.C[Al+]C BQBCXNQILNPAPX-UHFFFAOYSA-N 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 claims description 2
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 claims description 2
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 claims description 2
- PYLGJXLKFZZEBJ-UHFFFAOYSA-N tricyclopentylalumane Chemical compound C1CCCC1[Al](C1CCCC1)C1CCCC1 PYLGJXLKFZZEBJ-UHFFFAOYSA-N 0.000 claims description 2
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 claims description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-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
- 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 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 150000001336 alkenes Chemical class 0.000 abstract description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 2
- 239000002671 adjuvant Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 239000007789 gas Substances 0.000 description 11
- 239000012263 liquid product Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 6
- 239000003446 ligand Substances 0.000 description 5
- 239000004014 plasticizer Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000010687 lubricating oil Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 150000003623 transition metal compounds Chemical class 0.000 description 3
- 238000005829 trimerization reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000002199 base oil Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000012459 cleaning agent Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 239000008396 flotation agent Substances 0.000 description 2
- 231100000086 high toxicity Toxicity 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 231100000989 no adverse effect Toxicity 0.000 description 2
- 229920006124 polyolefin elastomer Polymers 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- VYQNWZOUAUKGHI-UHFFFAOYSA-N monobenzone Chemical compound C1=CC(O)=CC=C1OCC1=CC=CC=C1 VYQNWZOUAUKGHI-UHFFFAOYSA-N 0.000 description 1
- 229960000990 monobenzone Drugs 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Classifications
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/006—Hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/016—Macromolecular compounds
-
- 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
- C07C2/14—Catalytic processes with inorganic acids; with salts or anhydrides of acids
- C07C2/20—Acids of halogen; Salts thereof ; Complexes thereof with organic compounds
- C07C2/22—Metal halides; Complexes thereof with organic compounds
-
- 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
-
- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/003—Organic compounds containing only carbon and hydrogen
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/02—Well-defined hydrocarbons
- C10M105/04—Well-defined hydrocarbons aliphatic
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
- C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
- C10M107/04—Polyethene
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Abstract
本发明涉及催化烯烃聚合反应技术领域，具体公开了一类含中性配位侧基单茂第四副族金属配合物的用途，所述含中性配位侧基单茂第四副族金属配合物的结构如式1或式2所示：
本发明以所述的含中性配位侧基单茂第四副族金属配合物为主催化剂，以烷基铝氧烷或烷基铝与有机硼助剂的混合物为助催化剂，用于催化烯烃聚合反应，可以高选择性生成1‑己烯或C10及C10以上的α‑烯烃。
Description
技术领域
本发明属于催化烯烃聚合反应技术领域，特别涉及一类含中性配位侧基单茂第四副族金属配合物在催化乙烯齐聚反应中的应用。
背景技术
α-烯烃作为一种重要的有机原料和中间体产品，被广泛应用于生产聚α-烯烃的单体和聚烯烃产品的共聚单体、表面活性剂、润滑油、增塑剂、助剂和精细化学品。近年来，随着聚烯烃工业的发展，世界上对α-烯烃的需求量不断增加。工业上生产α-烯烃的方法主要有石蜡裂解、烷烃脱氢、醇脱水和乙烯齐聚等方法。通过催化乙烯齐聚选择性生产α-烯烃的方法是最经济有效的方法。
目前，用于乙烯选择性齐聚最普遍的催化体系是含有金属铬的催化体系如Philips三聚催化体系，然而重金属铬毒性较大，会对环境造成污染。随着科学技术的发展，近年来陆续有用其他过渡金属化合物催化乙烯齐聚的报道，主要是第四、第五副族的过渡金属化合物。到目前为止，大部分报道的用于催化乙烯三聚产生1-己烯的第四副族单茂金属配合物体系的催化活性都比较低，很难用于工业生产，而且只能催化乙烯三聚产生1-己烯，不能选择性生产其它α-烯烃。因此，开发能够催化乙烯齐聚选择性生产C10及以上α-烯烃的新型催化剂，是本技术领域需要解决的一个重要课题。
发明内容
为解决上述背景技术中提出的问题，本发明的目的在于提供一种用含中性配位侧基单茂第四副族金属配合物高活性催化乙烯选择性齐聚的方法，通过调节配体上取代基和反应条件，可以催化乙烯齐聚选择性生成1-己烯或C10及C10以上α-烯烃。迄今为止尚未有关于催化乙烯齐聚选择性生成C10及以上α-烯烃的报道。C10及以上α-烯烃作为共聚单体能够显著提高聚烯烃产品的机械和加工性能，作为增塑剂、洗涤剂以及油品添加剂等具有很好的应用前景。
为实现上述目的，本发明提供如下技术方案：
一类含中性配位侧基单茂第四副族金属配合物的用途，以所述的含中性配位侧基单茂第四副族金属配合物为主催化剂，以烷基铝氧烷和/或改性烷基铝氧烷和/或有机硼类化合物为助催化剂，用于催化乙烯齐聚选择性生成1-己烯或C10及C10以上α-烯烃。
进一步的，在所述的含中性配位侧基单茂第四副族金属配合物的用途中，其中助催化剂中铝与主催化剂中金属的摩尔比为5-10000:1，助催化剂中硼与主催化剂中金属的摩尔比为0-2:1，催化乙烯齐聚的反应温度为-20至200℃。
进一步的，在所述的含中性配位侧基单茂第四副族金属配合物的用途中，所述助催化剂中铝与主催化剂中金属的摩尔比为60-5000:1，助催化剂中硼与主催化剂中金属的摩尔比为1-1.5:1，催化乙烯齐聚的反应温度为-20至90℃。
再进一步的，本发明所述含中性配位侧基单茂第四副族金属配合物的用途，以所述的含中性配位侧基单茂第四副族金属配合物为主催化剂，以烷基铝氧烷、改性烷基铝氧烷、烷基铝/有机硼类化合物复合体系或其它可以起同样活化作用的试剂为助催化剂，用于催化乙烯齐聚反应。通过调节配体上取代基和反应条件，可以高活性催化乙烯齐聚选择性生成1-己烯或C10及C10以上α-烯烃。
再进一步的，在所述的含中性配位侧基单茂第四副族金属配合物的用途中，一类含中性配位侧基单茂第四副族金属配合物，其结构如式1或式2所示：
其中，中心金属M为Ti(钛元素)、Zr(锆元素)或Hf(铪元素)中的任意一种；
Cp#为环戊二烯基、取代环戊二烯基、茚基、取代茚基、芴基、取代芴基、环庚三烯基或取代环庚三烯基中的任意一种；
配位原子A为O(氧元素)、N(氮元素)或S(硫元素)；
R1、R2和R3各自独立地选自氢、1-30个碳数的烷基、1-30个碳数的环烷基、1-30个碳数的芳基取代烷基、1-30个碳数的硅烷基取代烷基、1-30个碳数的苯基或1-30个碳数的芳基，或者，R1、R2和R3相互连接，形成脂肪环或芳香环；
结构单元
为取代或未取代的脂肪环或芳香环；
X1、X2和X3各自独立地选自1-30个碳数的烷基、1-30个碳数的芳基取代烷基、1-30个碳数的硅烷基取代烷基、1-30个碳数的芳基、1-30个碳数的胺基、1-30个碳数的烷氧基或卤素；
根据中心金属M周围配位环境的拥挤程度不同，配位原子A可以与M配位，也可以不与M配位。
作为本发明进一步的方案：在结构如式1或式2所示的含中性配位侧基单茂第四副族金属配合物中，M为Ti、Zr或Hf；Cp#为环戊二烯基、一甲基环戊二烯基、二甲基环戊二烯基、三甲基环戊二烯基、四甲基环戊二烯基、二甲基二苯基环戊二烯基、二苯基环戊二烯基、茚基、一甲基茚基、二甲基茚基、苯并茚基、2-甲基苯并茚基、2-甲基-4-苯基茚基、芴基、二甲基芴基、二叔丁基芴基、环庚三烯基或二苯并环庚三烯基；A为O、N或S。
作为本发明再进一步的方案：在结构如式1或式2所示的含中性配位侧基单茂第四副族金属配合物中，R1、R2和R3相同或不同，分别为H、甲基、乙基、正丙基、异丙基、叔丁基、环戊基、环己基、金刚烷基、三甲基硅基、苯基、邻甲苯基、对甲苯基、3,5-二甲基苯基或3,5-二叔丁基苯基；或者是R1、R2和R3相互连接，形成五元或六元脂肪环或芳香环。
作为本发明再进一步的方案：在结构如式1或式2所示的含中性配位侧基单茂第四副族金属配合物中，结构单元
为取代或未取代的五元脂肪环或芳香环，或者取代或未取代的六元脂肪环或芳香环。
作为本发明再进一步的方案：在结构如式1或式2所示的含中性配位侧基单茂第四副族金属配合物中，X1、X2和X3相同或不同，分别为甲基、苄基、新戊基、三甲基硅甲基、二甲氨基、二乙氨基、二异丙氨基、双三甲基硅氨基、甲氧基、乙氧基、异丙氧基、氯或溴。
作为本发明再进一步的方案：在结构如式1或式2所示的含中性配位侧基单茂第四副族金属配合物中，进一步优选为:M为Ti、Zr或Hf；Cp#为环戊二烯基、四甲基环戊二烯基、二甲基二苯基环戊二烯基、3，4-二苯基环戊二烯基、茚基、2-甲基茚基、2-甲基-4-苯基茚基、2-甲基苯并茚基、芴基、4,7-二甲基芴基或4,7-二叔丁基芴基；A为O、N或S；R1、R2和R3相同或不同，分别为H、甲基、乙基、异丙基、叔丁基或苯基；结构单元
为呋喃环、烷基取代呋喃环、苯并呋喃环、二氢呋喃环、烷基取代二氢呋喃环、噻吩环、烷基取代噻吩环、二氢噻吩环、二氢吡喃环、烷基取代二氢吡喃环、苯并吡喃环、二氢吡喃环、硫代二氢吡喃环、吡啶环、烷基取代吡啶环、喹啉环或异喹啉环；X1、X2和X3相同或不同，分别为甲基、苄基、三甲基硅甲基、二甲氨基、甲氧基、异丙氧基、氯或溴。
本发明所述含中性配位侧基单茂第四副族金属配合物的用途中，所述的烷基铝氧烷为甲基铝氧烷(MAO)或改性甲基铝氧烷(MMAO)；所述的烷基铝为三甲基铝、三乙基铝、三丙基铝、三异丙基铝、三丁基铝、三异丁基铝、二甲基氯化铝、三环戊基铝、三异戊基铝、三己基铝、三辛基铝、二甲基乙基铝、甲基二乙基铝、二甲基甲氧基铝、二甲基乙氧基铝、二乙基氯化铝、乙基二氯化铝或倍半乙基氯化铝；所述的有机硼类化合物为Ph3CB(C6F5)4、B(C6F5)3、Me3CB(C6F5)4、PhMe2HNB(C6F5)4或PhQ2HNB(C6F5)4；其中，Ph表示苯基，Me表示甲基，在PhQ2HNB(C6F5)4中的Q为2-18个碳原子烷基。
作为本发明再进一步的方案：在本发明所述的含中性配位侧基单茂第四副族金属配合物的用途中，所述的烷基铝优选三甲基铝、三乙基铝、三异丁基铝、乙基二氯化铝或倍半乙基氯化铝；所述的烷基铝氧烷优选甲基铝氧烷；所述的有机硼助剂优选Ph3CB(C6F5)4。
作为本发明再进一步的方案：在本发明所述的含中性配位侧基单茂第四副族金属配合物的用途中，所述的催化烯烃聚合反应可以在任何对催化剂体系无不利影响的溶剂中进行，也可以在无溶剂条件下进行。乙烯的压力可根据需要确定。乙烯压力范围为0-150大气压。聚合反应温度可以在-20℃至200℃范围变化，优选的温度范围为-20℃至120℃。
作为本发明再进一步的方案：在本发明所述的含中性配位侧基单茂第四副族金属配合物的用途中，所述催化乙烯齐聚的具体反应步骤为：在乙烯存在条件下，向聚合釜加入主催化剂和助催化剂，在-20至150℃条件下搅拌反应0-600分钟，然后加入适量乙醇终止乙烯齐聚反应，将反应体系温度降至室温，将乙烯齐聚产物通过气相色谱检测。具体是将气体产品收集于气体计量罐中，液相产品收集于锥形瓶中，气液相产品计量后用气相色谱进行成分分析，通过保留值、峰面积对齐聚产物进行分析。
作为本发明再进一步的方案：在本发明所述的含中性配位侧基单茂第四副族金属配合物的用途中，所述的催化乙烯齐聚反应可以在任何对催化剂体系无不利影响的溶剂中进行，也可以在无溶剂条件下进行。乙烯的压力可根据需要确定。乙烯压力范围为0-150大气压。聚合反应温度可以在-20℃至200℃范围变化，优选的温度范围为-20℃至120℃。
与现有技术相比，本发明的有益效果是：
本发明提供一类含中性配位侧基单茂第四副族金属配合物的用途，这种含中性配位侧基单茂第四副族金属配合物可以催化乙烯齐聚选择性生成1-己烯或C10及C10以上的α-烯烃，相对于毒性较大的铬系催化剂，本发明所述的含中性配位侧基单茂第四副族金属配合物作为催化剂对环境友好，污染小；同时，本发明所述的含中性配位侧基单茂第四副族金属配合物结构稳定，在催化反应过程中稳定性好、寿命长、催化活性高；而且，本发明所述的含中性配位侧基单茂第四副族金属配合物用于催化乙烯齐聚反应，通过调节配体上取代基和反应条件，可以高选择性生成1-己烯或C10及C10以上的α-烯烃，所得α-烯烃可以作为增塑剂、清洁剂、乳化剂、浮选剂、粘合剂使用，也可以通过均聚合成润滑油基础油，还可以作为共单体与乙烯、丙烯等共聚合成线性低密度聚乙烯和聚烯烃弹性体，具有广范的应用领域。
具体实施方式
下面通过实施例进一步说明本发明，但本发明并不限于此。本发明的实施例可以使本专业的技术人员更全面的理解本发明。实施例中所用主催化剂为下图所示含中性配位侧基单茂第四副族金属配合物C1-C40,以下各实施例中所用D含中性配位侧基单茂第四副族金属配合物C1-C40可以参照文献(Austr.J.Chem.,1964,17,558；J.Am.Chem.Soc.,1968,90,4479；Inorg.Chem.,1970,9,289；Orgunometallics,1984,3,18；Acta Cryst.,1984,40,598；J Organornet.Chem.,1994,480,C10；Chem.Ber.,1996,129,459；Angew.Chem.2001,113,2584；Chem.Commun.,2003,22,2816；J.Mol.Catal.A,2004,214,227；J.Mol.Catal.A,2014,387,20)中的方法合成，属于现有技术，这里并不作赘述。
以下给出40个典型的本发明的含中性配位侧基单茂第四副族金属配合物C1-C40的结构示意图：
实施例1：(甲基铝氧烷活化催化体系的乙烯聚合)：将装有磁力搅拌子的聚合釜加热到120℃，抽真空1小时，充入0.1MPa的乙烯气体，加入60mL含烷基基铝氧烷的甲苯溶液，然后将20mL含1μmol主催化剂(即分别是以上含中性配位侧基单茂第四副族金属配合物C1-C40)的甲苯溶液加入反应釜，将乙烯压力升至0.5MPa，搅拌反应30分钟，加入1mL乙醇作为终止剂，终止乙烯齐聚反应。然后将反应液温度降至室温，将气体产品收集于气体计量罐中，液相产品收集于锥形瓶中。气液相产品计量后进行气相色谱分析，所得数据如表1所示。
表1乙烯齐聚结果[1]
[1]助催化剂为甲基铝氧烷；[2]助催化剂为改性甲基铝氧烷；[3]乙烯压力为20个大气压；[4]乙烯压力为80个大气压；[5]乙烯压力为100个大气压；[6]乙烯压力为150个大气压。
实施例2(三异丁基铝/Ph3CB(C6F5)4活化催化体系的乙烯聚合)：将装有磁力搅拌子的聚合釜加热到120℃，抽真空1小时，充入0.1MPa的乙烯气体，加入60mL含三异丁基铝的甲苯溶液，然后将20mL含1μmol主催化剂(即分别是以上含中性配位侧基单茂第四副族金属配合物C1-C40)和1.5当量Ph3CB(C6F5)4的甲苯溶液加入反应釜，将乙烯压力升至0.5MPa，在30℃下搅拌反应30分钟，加入1mL乙醇作为终止剂，终止乙烯齐聚反应。然后将反应液温度降至室温，将气体产品收集于气体计量罐中，液相产品收集于锥形瓶中，气液相产品计量后进行气相色谱分析，所得数据如表2所示。
表2乙烯齐聚结果
实施例3：将装有磁力搅拌子的聚合釜加热到120℃，抽真空1小时，充入0.1MPa的乙烯气体，加入60mL含烷基铝的甲苯溶液，然后将20mL含1μmol主催化剂(即是以上含中性配位侧基单茂第四副族金属配合物C1)和1.5当量助催化剂(分别依次为iBu3Al(三异丁基铝)、Me3Al、Et3Al、Et2AlCl、Et3Al2Cl3)的甲苯溶液加入反应釜，将乙烯压力升至0.5MPa，在30℃下搅拌反应30分钟，加入1mL乙醇作为终止剂，终止乙烯齐聚反应。然后将反应液温度降至室温，将气体产品收集于气体计量罐中，液相产品收集于锥形瓶中，气液相产品计量后进行气相色谱分析，所得数据如表3所示。
表3乙烯齐聚结果
其中，在表3中，催化剂C1[1]的组别即是含中性配位侧基单茂第四副族金属配合物C1为主催化剂，iBu3Al(三异丁基铝)为助催化剂所对应的乙烯齐聚反应组别。相应的，C1[2]的助催化剂为Me3Al；C1[3]的助催化剂为Et3Al；C1[4]的助催化剂为Et2AlCl；C1[5]的助催化剂为Et3Al2Cl3。
从以上结果可以看出，本发明以所述的含中性配位侧基单茂第四副族金属配合物为主催化剂，以烷基铝氧烷或烷基铝与有机硼助剂的混合物为助催化剂，用于催化烯烃聚合反应，此类催化剂适用于催化乙烯齐聚选择性制备α-烯烃方面的应用。本发明所述的含中性配位侧基单茂第四副族金属配合物用于催化乙烯齐聚反应，通过调节配体上取代基和反应条件，可以高选择性生成1-己烯或C10及C10以上的α-烯烃，所得α-烯烃可以作为增塑剂、清洁剂、乳化剂、浮选剂、粘合剂使用，也可以通过均聚合成润滑油基础油，还可以作为共单体与乙烯、丙烯等共聚合成线性低密度聚乙烯和聚烯烃弹性体，具有广范的应用领域。
上面对本发明的较佳实施方式作了详细说明，但是本发明并不限于上述实施方式，在本领域的普通技术人员所具备的知识范围内，还可以在不脱离本发明宗旨的前提下作出各种变化。这里无需也无法对所有的实施方式予以穷举。而由此所引申出的显而易见的变化或变动仍处于本发明的保护范围之中。
Claims (10)
1.一类含中性配位侧基单茂第四副族金属配合物的用途，其特征在于，以所述的含中性配位侧基单茂第四副族金属配合物为主催化剂，以烷基铝氧烷和/或改性烷基铝氧烷和/或有机硼类化合物为助催化剂，用于催化乙烯齐聚选择性生成1-己烯或C10及C10以上α-烯烃；所述的含中性配位侧基单茂第四副族金属配合物的结构如式1或式2所示：
其中，中心金属M为Ti、Zr或Hf中的任意一种；
Cp#为环戊二烯基、一甲基环戊二烯基、二甲基环戊二烯基、三甲基环戊二烯基、四甲基环戊二烯基、二甲基二苯基环戊二烯基、二苯基环戊二烯基、茚基、一甲基茚基、二甲基茚基、苯并茚基、2-甲基苯并茚基、2-甲基-4-苯基茚基、芴基、二甲基芴基、二叔丁基芴基、环庚三烯基或二苯并环庚三烯基；
配位原子A为O、N或S；
R1、R2和R3各自独立地选自氢、1-30个碳数的烷基、1-30个碳数的环烷基、1-30个碳数的芳基取代烷基、1-30个碳数的硅烷基取代烷基、1-30个碳数的苯基或1-30个碳数的芳基，或者，R1、R2和R3相互连接，形成脂肪环或芳香环；
结构单元
为取代或未取代的脂肪环或芳香环；
X1、X2和X3各自独立地选自1-30个碳数的烷基、1-30个碳数的芳基取代烷基、1-30个碳数的硅烷基取代烷基、1-30个碳数的芳基、1-30个碳数的胺基、1-30个碳数的烷氧基或卤素。
2.根据权利要求1所述的含中性配位侧基单茂第四副族金属配合物的用途，其特征在于，在所述的含中性配位侧基单茂第四副族金属配合物中，根据中心金属M周围配位环境的拥挤程度不同，配位原子A可以与中心金属M配位，也可以不与中心金属M配位。
3.根据权利要求1所述的含中性配位侧基单茂第四副族金属配合物的用途，其特征在于，在所述的含中性配位侧基单茂第四副族金属配合物中，M为Ti、Zr或Hf；A为O、N或S；R1、R2和R3相同或不同，分别为H、甲基、乙基、正丙基、异丙基、叔丁基、环戊基、环己基、金刚烷基、三甲基硅基、苯基、邻甲苯基、对甲苯基、3,5-二甲基苯基或3,5-二叔丁基苯基；或者是R1、R2和R3相互连接，形成五元或六元脂肪环或芳香环；X1、X2和X3相同或不同，分别为甲基、苄基、新戊基、三甲基硅甲基、二甲氨基、二乙氨基、二异丙氨基、双三甲基硅氨基、甲氧基、乙氧基、异丙氧基、氯或溴。
4.根据权利要求1所述的含中性配位侧基单茂第四副族金属配合物的用途，其特征在于，在所述的含中性配位侧基单茂第四副族金属配合物中，结构单元
为取代或未取代的五元脂肪环或芳香环，或者取代或未取代的六元脂肪环或芳香环。
5.根据权利要求1所述的含中性配位侧基单茂第四副族金属配合物的用途，其特征在于，在所述的含中性配位侧基单茂第四副族金属配合物中，M为Ti、Zr或Hf；Cp#为环戊二烯基、四甲基环戊二烯基、二甲基二苯基环戊二烯基、3，4-二苯基环戊二烯基、茚基、2-甲基茚基、2-甲基-4-苯基茚基、2-甲基苯并茚基、芴基、4,7-二甲基芴基或4,7-二叔丁基芴基；A为O、N或S；R1、R2和R3相同或不同，分别为H、甲基、乙基、异丙基、叔丁基或苯基；结构单元
为呋喃环、烷基取代呋喃环、苯并呋喃环、二氢呋喃环、烷基取代二氢呋喃环、噻吩环、烷基取代噻吩环、二氢噻吩环、二氢吡喃环、烷基取代二氢吡喃环、苯并吡喃环、二氢吡喃环、硫代二氢吡喃环、吡啶环、烷基取代吡啶环、喹啉环或异喹啉环；X1、X2和X3相同或不同，分别为甲基、苄基、三甲基硅甲基、二甲氨基、甲氧基、异丙氧基、氯或溴。
6.根据权利要求1所述的含中性配位侧基单茂第四副族金属配合物的用途，其特征在于，所述助催化剂中铝与主催化剂中金属的摩尔比为5-10000:1，助催化剂中硼与主催化剂中金属的摩尔比为0-2:1，催化乙烯齐聚的反应温度为-20至200℃。
7.根据权利要求6所述的含中性配位侧基单茂第四副族金属配合物的用途，其特征在于，所述助催化剂中铝与主催化剂中金属的摩尔比为60-5000:1，助催化剂中硼与主催化剂中金属的摩尔比为1-1.5:1，催化乙烯齐聚的反应温度为-20至90℃。
8.根据权利要求1所述的含中性配位侧基单茂第四副族金属配合物的用途，其特征在于，所述的烷基铝氧烷为甲基铝氧烷或改性甲基铝氧烷；所述的烷基铝为三甲基铝、三乙基铝、三丙基铝、三异丙基铝、三丁基铝、三异丁基铝、二甲基氯化铝、三环戊基铝、三异戊基铝、三己基铝、三辛基铝、二甲基乙基铝、甲基二乙基铝、二甲基甲氧基铝、二甲基乙氧基铝、二乙基氯化铝、乙基二氯化铝或倍半乙基氯化铝；所述的有机硼类化合物为Ph3CB(C6F5)4、B(C6F5)3、Me3CB(C6F5)4、PhMe2HNB(C6F5)4或PhQ2HNB(C6F5)4；其中，Ph表示苯基，Me表示甲基，在PhQ2HNB(C6F5)4中的Q为2-18个碳原子烷基。
9.根据权利要求8所述的含中性配位侧基单茂第四副族金属配合物的用途，其特征在于，所述的烷基铝是三甲基铝、三乙基铝、三异丁基铝、乙基二氯化铝或倍半乙基氯化铝；所述的烷基铝氧烷是甲基铝氧烷；所述的有机硼助剂是Ph3CB(C6F5)4。
10.根据权利要求1所述的含中性配位侧基单茂第四副族金属配合物的用途，其特征在于，所述催化乙烯齐聚的具体反应步骤为：在乙烯存在条件下，向聚合釜加入主催化剂和助催化剂，在-20至150℃条件下搅拌反应0-600分钟，然后加入适量乙醇终止乙烯齐聚反应，将反应体系温度降至室温，将乙烯齐聚产物通过气相色谱检测。
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