CN104797586B - 具有杂原子的过渡金属化合物、包含其的催化剂组合物及使用其制备聚合物的方法 - Google Patents
具有杂原子的过渡金属化合物、包含其的催化剂组合物及使用其制备聚合物的方法 Download PDFInfo
- Publication number
- CN104797586B CN104797586B CN201480003124.3A CN201480003124A CN104797586B CN 104797586 B CN104797586 B CN 104797586B CN 201480003124 A CN201480003124 A CN 201480003124A CN 104797586 B CN104797586 B CN 104797586B
- Authority
- CN
- China
- Prior art keywords
- chemical formula
- carbon atoms
- alkyl
- carbon
- carbon atom
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 94
- 229920000642 polymer Polymers 0.000 title claims abstract description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 150000002736 metal compounds Chemical class 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title abstract description 12
- 229920001577 copolymer Polymers 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims description 100
- 125000004432 carbon atom Chemical group C* 0.000 claims description 61
- 150000001721 carbon Chemical group 0.000 claims description 54
- 125000000217 alkyl group Chemical group 0.000 claims description 47
- 239000001257 hydrogen Substances 0.000 claims description 44
- 229910052739 hydrogen Inorganic materials 0.000 claims description 44
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 39
- 150000001875 compounds Chemical class 0.000 claims description 38
- 125000003118 aryl group Chemical group 0.000 claims description 34
- 238000002360 preparation method Methods 0.000 claims description 29
- 239000004411 aluminium Substances 0.000 claims description 26
- 229910052782 aluminium Inorganic materials 0.000 claims description 26
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 22
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 19
- 229910052796 boron Inorganic materials 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 18
- -1 cation lewis acid Chemical class 0.000 claims description 18
- 125000003342 alkenyl group Chemical group 0.000 claims description 15
- 125000001931 aliphatic group Chemical group 0.000 claims description 14
- 125000001424 substituent group Chemical group 0.000 claims description 14
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 12
- 229910052736 halogen Inorganic materials 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000003426 co-catalyst Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 8
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 229920000098 polyolefin Polymers 0.000 claims description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 5
- 238000006467 substitution reaction Methods 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002841 Lewis acid Substances 0.000 claims description 4
- 229920001519 homopolymer Polymers 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000004104 aryloxy group Chemical group 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- 150000007517 lewis acids Chemical class 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 150000002431 hydrogen Chemical group 0.000 claims 4
- 238000007334 copolymerization reaction Methods 0.000 abstract description 8
- 238000010276 construction Methods 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000004913 activation Effects 0.000 description 9
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 125000002524 organometallic group Chemical group 0.000 description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 229910000765 intermetallic Inorganic materials 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 6
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- IMFACGCPASFAPR-UHFFFAOYSA-O tributylazanium Chemical compound CCCC[NH+](CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-O 0.000 description 5
- 239000004711 α-olefin Substances 0.000 description 5
- LBUJPTNKIBCYBY-UHFFFAOYSA-N 1,2,3,4-tetrahydroquinoline Chemical compound C1=CC=C2CCCNC2=C1 LBUJPTNKIBCYBY-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical class CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 4
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 4
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000012190 activator Substances 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229930192474 thiophene Natural products 0.000 description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VKMQKNJWQNCEQV-UHFFFAOYSA-N (4-methylphenyl)boron Chemical compound [B]C1=CC=C(C)C=C1 VKMQKNJWQNCEQV-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 0 CC=*CC(*)(**)NO Chemical compound CC=*CC(*)(**)NO 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000002152 alkylating effect Effects 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-O diethylammonium Chemical compound CC[NH2+]CC HPNMFZURTQLUMO-UHFFFAOYSA-O 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 125000004836 hexamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- OLFPYUPGPBITMH-UHFFFAOYSA-N tritylium Chemical compound C1=CC=CC=C1[C+](C=1C=CC=CC=1)C1=CC=CC=C1 OLFPYUPGPBITMH-UHFFFAOYSA-N 0.000 description 2
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 description 1
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 description 1
- UDMMZSJNHAWYKX-UHFFFAOYSA-N 4-phenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C(C=C2)CCC21C1=CC=CC=C1 UDMMZSJNHAWYKX-UHFFFAOYSA-N 0.000 description 1
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 1
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229920010524 Syndiotactic polystyrene Polymers 0.000 description 1
- 229910010068 TiCl2 Inorganic materials 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-O butylazanium Chemical compound CCCC[NH3+] HQABUPZFAYXKJW-UHFFFAOYSA-O 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 1
- MYBJXSAXGLILJD-UHFFFAOYSA-N diethyl(methyl)alumane Chemical compound CC[Al](C)CC MYBJXSAXGLILJD-UHFFFAOYSA-N 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 description 1
- MWNKMBHGMZHEMM-UHFFFAOYSA-N dimethylalumanylium;ethanolate Chemical compound CCO[Al](C)C MWNKMBHGMZHEMM-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- BQBCXNQILNPAPX-UHFFFAOYSA-N methoxy(dimethyl)alumane Chemical compound [O-]C.C[Al+]C BQBCXNQILNPAPX-UHFFFAOYSA-N 0.000 description 1
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 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
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 125000000369 oxido group Chemical group [*]=O 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 229940095068 tetradecene Drugs 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- CMHHITPYCHHOGT-UHFFFAOYSA-N tributylborane Chemical compound CCCCB(CCCC)CCCC CMHHITPYCHHOGT-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical group CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- JQPMDTQDAXRDGS-UHFFFAOYSA-N triphenylalumane Chemical compound C1=CC=CC=C1[Al](C=1C=CC=CC=1)C1=CC=CC=C1 JQPMDTQDAXRDGS-UHFFFAOYSA-N 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- XDSSGQHOYWGIKC-UHFFFAOYSA-N tris(2-methylpropyl)borane Chemical compound CC(C)CB(CC(C)C)CC(C)C XDSSGQHOYWGIKC-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/28—Titanium compounds
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
- B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
- B01J31/146—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of boron
-
- 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
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
-
- 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
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/184—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine mixed aromatic/aliphatic ring systems, e.g. indoline
-
- 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
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
-
- 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
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/72—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44
- C08F4/74—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from refractory metals
- C08F4/76—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from refractory metals selected from titanium, zirconium, hafnium, vanadium, niobium or tantalum
-
- 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
- B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
- B01J2231/12—Olefin polymerisation or copolymerisation
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/46—Titanium
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/49—Hafnium
-
- 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
- B01J2540/00—Compositional aspects of coordination complexes or ligands in catalyst systems
- B01J2540/30—Non-coordinating groups comprising sulfur
-
- 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
- B01J2540/00—Compositional aspects of coordination complexes or ligands in catalyst systems
- B01J2540/60—Groups characterized by their function
- B01J2540/62—Activating groups
-
- 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
- C08F2420/00—Metallocene catalysts
- C08F2420/02—Cp or analog bridged to a non-Cp X anionic donor
-
- 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
- C08F2420/00—Metallocene catalysts
- C08F2420/06—Cp analog where at least one of the carbon atoms of the non-coordinating part of the condensed ring is replaced by a heteroatom
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65904—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with another component of C08F4/64
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Polyethers (AREA)
Abstract
本发明公开了具有新结构并包括杂原子的过渡金属化合物、包含其的催化剂组合物及使用其制备聚合物的方法。根据本发明的一个实施方案的过渡金属化合物具有良好的共聚性质并且使用其可制备低密度聚合物。因此可制备具有各种用途的共聚物。
Description
技术领域
本发明涉及具有新结构的过渡金属化合物、包含其的催化剂组合物及使用其制备聚合物的方法。更具体地,本发明涉及包含杂原子并具有新结构的过渡金属化合物、包含其的催化剂组合物及使用所述催化剂组合物的聚合物的制备方法。
背景技术
在20世纪90年代初,Dow Co.报道了[Me2Si(Me4C5)NtBu]TiCl2(限制几何构型催化剂(Constrained-Geometry Catalyst),下文中缩写为CGC)(美国专利No.5,064,802),并且当与通常已知的金属茂催化剂相比时,CGC在乙烯和α-烯烃的共聚反应中的优良方面可概括为以下两点:(1)在高聚合温度下,显示出高活性并且制备了具有高分子量的聚合物,以及(2)具有较大位阻的α-烯烃如1-己烯和1-辛烯的共聚度是优良的。此外,随着逐渐认识到CGC在进行聚合反应期间的各种性质,在学术界和工业界积极进行了努力以合成其衍生物并将其用作聚合催化剂。
作为一种途径,已进行了金属化合物的合成及其聚合,所述金属化合物中引入了氮取代基和多种桥代替硅桥。迄今为止已知的典型金属化合物举例为以下化合物(1)至(4)(Chem.Rev.2003,103,283)。
以上化合物(1)至(4)各自独立地引入了磷桥(1)、亚乙基或亚丙基桥(2)、次甲基桥(3)或亚甲基桥(4)来代替CGC结构的硅桥。然而,当与应用CGC获得的那些结果相比,通过应用乙烯聚合或与α-烯烃共聚不能获得关于活性、共聚性能等的改善结果。
作为另一种途径,大量合成了由氧配体(oxido ligand)而不是CGC的胺基配体构成的化合物,并且在一定程度上已对使用其的聚合反应进行了尝试。以下概括了其实例。
T.J.Marks等报道了化合物(5)并且其特征在于环戊二烯(Cp)衍生物与氧配体通过邻亚苯基桥连(Organometallics 1997,16,5958)。Mu等报道了具有相同桥连基团的化合物和使用其的聚合反应(Organometallics 2004,23,540)。此外,Rothwell等报道了茚基配体与氧配体通过相同邻亚苯基桥连(Chem.Commun.2003,1034)。Whitby等报道了化合物(6)并且其特征在于环戊二烯基配体与氧配体通过三个碳原子桥连(Organometallics 1999,18,348)。据报道,上述催化剂在间同立构聚苯乙烯聚合反应中显示出活性。Hessen等还报道了类似的化合物(Organometallics 1998,17,1652)。Rau等报道了化合物(7)并且其特征在于在高温和高压(210℃,150MPa)下在乙烯聚合反应和乙烯/1-己烯共聚反应中显示出活性(J.Organomet.Chem.2000,608,71)。此外,Sumitomo Co.提交了与化合物(7)具有类似结构的催化剂(8)的合成以及在高温和高压下使用其进行的聚合反应(美国专利No.6,548,686)。然而,上述尝试中的许多催化剂都没有实际应用于商业工厂。因此,需要显示出进一步改善的聚合性能的催化剂,并且需要催化剂的简单制备方法。
[现有技术文献]
[专利文献]
美国专利No.5,064,802
美国专利No.6,548,686
[非专利文献]
Chem.Rev.2003,103,283
Organometallics 1997,16,5958
Organometallics 2004,23,540
Chem.Commun.2003,1034
Organometallics 1999,18,348
Organometallics 1998,17,1652
J.Organomet.Chem.2000,608,71
发明内容
技术问题
在本发明中,描述了包含杂原子并具有新结构的过渡金属化合物、包含其的催化剂组合物及使用所述催化剂组合物制备聚合物的方法。
技术方案
根据本发明的一个方面,提供了以下化学式1的过渡金属化合物。
[化学式1]
在以上化学式1中,
M是第4族过渡金属,
Q1和Q2相同或不同,并且各自独立地为氢、卤素、具有1至20个碳原子的烷基、具有2至20个碳原子的烯基、具有6至20个碳原子的芳基、具有6至20个碳原子的烷基芳基、具有7至20个碳原子的芳基烷基、具有1至20个碳原子的烷基氨基、具有6至20个碳原子的芳基氨基或具有1至20个碳原子的次烷基。
R1至R4相同或不同,并且各自独立地为氢、甲硅烷基、具有1至20个碳原子的烷基、具有2至20个碳原子的烯基、具有6至20个碳原子的芳基、具有7至20个碳原子的烷基芳基、具有7至20个碳原子的芳基烷基、经具有1至20个碳原子的烃基取代的第14族金属的类金属基;R1和R2可彼此连接,或者R3和R4可彼此连接,以形成具有5至20个碳原子的脂族环或具有6至20个碳原子的芳香环;所述脂族环或所述芳香环可经卤素、具有1至20个碳原子的烷基、具有2至20个碳原子的烯基或具有6至20个碳原子的芳基取代。
R5至R9相同或不同,并且各自独立地为氢、具有1至20个碳原子的烷基、具有2至20个碳原子的烯基、具有6至20个碳原子的芳基、具有7至20个碳原子的烷基芳基、具有7至20个碳原子的芳基烷基;R5至R9中的至少两个可彼此连接以形成具有5至20个碳原子的脂族环或具有6至20个碳原子的芳香环;所述脂族环或所述芳香环可经卤素、具有1至20个碳原子的烷基、具有2至20个碳原子的烯基或具有6至20个碳原子的芳基取代。
根据本发明的另一个方面,提供了包含以上化学式1的过渡金属化合物的催化剂组合物。
根据本发明的又一个方面,提供了使用所述催化剂组合物的聚合物的制备方法。
有益效果
在根据本发明的过渡金属化合物中,胺基配体和邻亚苯基形成稠环,并且控制与邻亚苯基结合的五元环π配体中引入的噻吩的杂原子位置。因此,可将过渡金属化合物用作具有良好共聚性质的催化剂,并且通过使用其可制备具有低密度的聚合物。
具体实施方式
根据本发明的一个方面,提供了上述化学式1的过渡金属化合物。
在本发明所述的化学式1的过渡金属化合物中,金属位点与连接至引入胺基的亚苯基桥的环戊二烯基配体连接为环,并且其结构具有窄的Cp-M-N角和单体可接近的宽的Q1-M-Q2角。因此,环戊二烯、亚苯基桥、氮和金属位点按顺序连接,并且可形成稳定性且刚性更大的五边形环结构。此外,在由以上化学式1表示的化合物的结构中,噻吩是稠合的,使得杂环的硫(S)原子与环戊二烯的3位结合,从而增加用作催化剂时的活性并且明显地增加待制备的聚合物的分子量。因此,以上化学式1的过渡金属化合物可起具有良好共聚性质并且用于制备具有低密度的聚合物的催化剂的作用。
在一个实施方案中,当将所述化合物与助催化剂如甲基铝氧烷或B(C6F5)3反应并活化之后用于烯烃聚合反应时,甚至在高聚合温度下也可制备具有高活性、高分子量和高共聚度的聚烯烃。特别地,由于因催化剂的结构特征而可引入大量α-烯烃以及具有0.91g/cc至0.93g/cc的低密度的线性聚乙烯,所以可产生具有小于0.91g/cc的低密度的聚烯烃共聚物。特别地,通过使用包含过渡金属化合物的催化剂组合物可制备这样的聚合物:其相对于限制几何构型催化剂(CGC,下文中称为“CGC”)具有窄的分子量分布(MWD,下文中称为“MWD”)、良好的共聚性质以及在低密度区中的高分子量。此外,可将各种取代基引入与噻吩和喹啉稠合的环戊二烯基中,并且可容易地控制金属周围的电子环境和空间环境,因此,可控制由此产生的聚烯烃的结构和物理性质。以上化学式1的化合物可优选地用于制备用于使烯烃单体聚合的催化剂,但是本发明不限于此。所述过渡金属化合物可用于任何其他的应用领域。
在本发明中,烷基和烯基可为直链或支化链的烷基或烯基。
在本发明中,甲硅烷基可为经具有1至20个碳原子的烷基取代的甲硅烷基,例如三甲基硅烷基或三乙基硅烷基。
在本发明中,芳基包括单环芳基或多环芳基,例如苯基、萘基、蒽基、菲基、基、芘基等。
根据本发明的一个实施方案,以上化学式1中的R8和R9彼此结合以形成五元或六元脂族环。以上化学式1可由以下化学式2表示:
[化学式2]
在以上化学式2中,
Cy是五元脂族环或六元脂族环,
每个R10独立地为氢、具有1至20个碳原子的烷基、具有2至20个碳原子的烯基、具有6至20个碳原子的芳基、具有7至20个碳原子的烷基芳基或具有7至20个碳原子的芳基烷基,
当Cy是五元脂族环时,m是1至4的整数,并且当Cy是六元脂族环时,m是1至6的整数,并且
其余的取代基与化学式1中所限定的相同。
根据本发明的另一个方面,以上化学式2可由以下化学式3或4表示。
[化学式3]
在以上化学式3中,
R11至R16各自独立地为氢、具有1至20个碳原子的烷基、具有2至20个碳原子的烯基、具有6至20个碳原子的芳基、具有7至20个碳原子的烷基芳基或具有7至20个碳原子的芳基烷基,并且
其余的取代基与化学式1中所限定的相同。
[化学式4]
在以上化学式4中,
R17至R20各自独立地为氢、具有1至20个碳原子的烷基、具有2至20个碳原子的烯基、具有6至20个碳原子的芳基、具有7至20个碳原子的烷基芳基或具有7至20个碳原子的芳基烷基,并且
其余的取代基与化学式1中所限定的相同。
根据本发明的另一个方面,以上化学式2可由以下化学式5或6表示。
[化学式5]
在以上化学式5中,
R和R11至R16各自独立地为氢、具有1至20个碳原子的烷基、具有2至20个碳原子的烯基、具有6至20个碳原子的芳基、具有7至20个碳原子的烷基芳基或具有7至20个碳原子的芳基烷基,p是1至4的整数,并且
其余的取代基与化学式1中所限定的相同。
[化学式6]
在以上化学式6中,
R和R17至R20各自独立地为氢、具有1至20个碳原子的烷基、具有2至20个碳原子的烯基、具有6至20个碳原子的芳基、具有7至20个碳原子的烷基芳基或具有7至20个碳原子的芳基烷基,p是1至4的整数,并且
其余的取代基与化学式1中所限定的相同。
根据本发明的另一个方面,R1和R2是氢或具有1至20个碳原子的烷基。
根据本发明的另一个方面,R1和R2是氢或具有1至6个碳原子的烷基。
根据本发明的另一个方面,R1和R2是氢或甲基。
根据本发明的另一个方面,R1和R2中的至少一个是具有1至20个碳原子的烷基。
根据本发明的另一个方面,R1是具有1至20个碳原子的烷基,并且R2是氢。
根据本发明的另一个方面,R1是具有1至6个碳原子的烷基,并且R2是氢。
根据本发明的另一个方面,R1是甲基,并且R2是氢。
根据本发明的另一个方面,R1和R2是具有1至20个碳原子的烷基。
根据本发明的另一个方面,R1和R2是具有1至6个碳原子的烷基。
根据本发明的另一个方面,R1和R2是甲基。
根据本发明的另一个方面,R3至R7相同或不同,并且各自独立地为氢、具有1至20个碳原子的烷基或具有2至20个碳原子的烯基。
根据本发明的另一个方面,R3至R7相同或不同,并且各自独立地为氢或具有1至20个碳原子的烷基。
根据本发明的另一个方面,R3至R7是氢。
根据本发明的另一个方面,以上式3的R11至R16各自独立地为氢、具有1至20个碳原子的烷基或具有2至20个碳原子的烯基。
根据本发明的另一个方面,以上化学式3的R11至R16各自独立地为氢或具有1至20个碳原子的烷基。
根据本发明的另一个方面,以上化学式3的R11至R16中的至少一个是具有1至20个碳原子的烷基。
根据本发明的另一个方面,在以上化学式3中,R11至R15是氢,并且R16是具有1至20个碳原子的烷基。
根据本发明的另一个方面,在以上化学式3中,R11至R15是氢,并且R16是具有1至6个碳原子的烷基。
根据本发明的另一个方面,在以上化学式3中,R11至R15是氢,并且R16是甲基。
根据本发明的另一个方面,以上化学式3的R11至R16是氢。
根据本发明的另一个方面,以上化学式4的R17至R20独立地为氢、具有1至20个碳原子的烷基或具有2至20个碳原子的烯基。
根据本发明的另一个方面,以上化学式4的R17至R20独立地为氢或具有1至20个碳原子的烷基。
根据本发明的另一个方面,以上化学式4的R17至R20中的至少一个是具有1至20个碳原子的烷基。
根据本发明的另一个方面,在以上化学式4中,R17至R19是氢,并且R20是具有1至20个碳原子的烷基。
根据本发明的另一个方面,在以上化学式4中,R17至R19是氢,并且R20是具有1至6个碳原子的烷基。
根据本发明的另一个方面,在以上化学式4中,R17至R19是氢,并且R20是甲基。
根据本发明的另一个方面,以上化学式4的R17至R20是氢。
根据本发明的另一个方面,M是Ti、Hf或Zr。
根据本发明的另一个方面,M是Ti。
根据本发明的另一个方面,Q1和Q2各自独立地为卤素。
根据本发明的另一个方面,Q1和Q2是C1。
根据本发明的另一个方面,在以上化学式3或5中,R1、R2和R11至R16是氢或具有1至6个碳原子的烷基。
根据本发明的另一个方面,在以上化学式3或5中,R1和R2是具有1至6个碳原子的烷基,并且R11至R16是氢。
根据本发明的另一个方面,在以上化学式3或5中,R1和R16是具有1至6个碳原子的烷基,R2是氢或具有1至6个碳原子的烷基,并且R11至R15是氢。
根据本发明的另一个方面,在以上化学式4或6中,R1、R2和R17至R20是氢或具有1至6个碳原子的烷基。
根据本发明的另一个方面,在以上化学式4或6中,R1和R2是具有1至6个碳原子的烷基,并且R17至R20是氢。
根据本发明的另一个方面,在以上化学式4或6中,R1和R20是具有1至6个碳原子的烷基,R2是氢或具有1至6个碳原子的烷基,并且R17至R19是氢。
根据本发明的另一个方面,以上化学式1的化合物选自由以下化学式表示的化合物。
以上化学式1的化合物可通过以下反应来制备。
[反应1]
在以上反应1中,取代基与以上化学式3中所限定的相同。
目标化合物的取代基可通过改变以上反应中所使用的起始材料和反应物来改变。此外,虽然在以上反应1中使用四氢喹啉,但是化学式4的化合物可通过使用二氢吲哚代替四氢喹啉来制备。
在本发明中,提供了包含以上化学式1的化合物的催化剂组合物。
所述催化剂组合物还可包含助催化剂。可使用本领域中已知的材料作为助催化剂。
例如,催化剂组合物还可包含以下化学式7至12中的至少一种作为助催化剂。
[化学式7]
-[Al(R21)-O]a-
在以上化学式中,每个R21独立地为卤素基团、具有1至20个碳原子的烃基基团或经卤素取代的具有1至20个碳原子的烃基基团;并且a是至少为2的整数;
[化学式8]
D(R22)3
在以上化学式中,D是铝或硼;每个R22独立地为卤素基团、具有1至20个碳原子的烃基基团或经卤素取代的具有1至20个碳原子的烃基基团;
[化学式9]
[L-H]+[Z(A)4]-或[L]+[Z(A)4]-
在以上化学式中,L是中性路易斯酸或阳离子路易斯酸;H是氢原子;Z是第13族元素;每个A独立地为具有6至20个碳原子的芳基或具有1至20个碳原子的烷基,其中至少一个氢原子可被取代基取代;并且所述取代基是卤素、具有1至20个碳原子的烃基、具有1至20个碳原子的烷氧基或具有6至20个碳原子的芳氧基。
作为催化剂组合物的制备方法,提供了第一制备方法,其包括:通过使由以上化学式1表示的过渡金属化合物与由以上化学式7或8表示的化合物相接触获得混合物的步骤;以及将由以上化学式9表示的化合物添加至混合物中的步骤。
提供了通过使由以上化学式1表示的过渡金属化合物与由以上化学式9表示的化合物相接触的催化剂组合物的第二制备方法。
在催化剂组合物的制备方法的第一方法中,由以上化学式7或8表示的化合物相对于由以上化学式1表示的过渡金属化合物的摩尔比优选地为1∶2至1∶5,000,更优选地为1∶10至1∶1,000,并且最优选地为1∶20至1∶500。
同时,由以上化学式9表示的化合物相对于由以上化学式1表示的过渡金属化合物的摩尔比优选地为1∶1至1∶25,更优选地为1∶1至1∶10,并且最优选地为1∶1至1∶5。
在由以上化学式7或8表示的化合物相对于由以上化学式1表示的过渡金属化合物的摩尔比小于1∶2的情况下,烷基化试剂的量非常小,并且金属化合物的烷基化可能进行得不完全;而在摩尔比超过1∶5,000的情况下,虽然可进行金属化合物的烷基化,但是还可能进行剩余烷基化试剂与以上化学式9的活化剂之间的副反应,并且可能使烷基化金属化合物的活化进行得不完全。此外,在由以上化学式9表示的化合物相对于由以上化学式1表示的过渡金属化合物的摩尔比小于1∶1的情况下,活化剂的量相对较小,金属化合物的活化可能进行得不完全,并且可劣化催化剂组合物的活性;而在摩尔比超过1∶25的情况下,虽然金属化合物的活化可进行完全,但是剩余的过量活化剂可增加催化剂组合物的生产成本或者可劣化由此制备的聚合物的纯度。
在催化剂组合物的制备方法的第二方法中,由以上化学式9表示的化合物相对于由以上化学式1表示的过渡金属化合物的摩尔比优选地为1∶1至1∶500,更优选地为1∶1至1∶50,并且最优选地为1∶2至1∶25。在摩尔比小于1∶1的情况下,活化剂的量相对较小,并且可劣化催化剂组合物的活化;而在摩尔比超过1∶500的情况下,虽然金属化合物的活化可进行完全,但是剩余的过量活化剂可增加催化剂组合物的生产成本或者可劣化由此制备的聚合物的纯度。
可使用烃溶剂如戊烷、己烷、庚烷等或芳香族溶剂如苯、甲苯等作为组合物制备期间所使用的反应溶剂,但是本发明不限于此,并且可使用本领域所使用的所有溶剂。
此外,以上化学式1的过渡金属化合物和助催化剂可作为由载体负载的负载型使用。二氧化硅或氧化铝可用作载体。
只有在使用烷基铝氧烷时,由以上化学式7表示的化合物才没有具体限制。优选地,所述化合物包括甲基铝氧烷、乙基铝氧烷、异丁基铝氧烷、丁基铝氧烷等,并且甲基铝氧烷是特别优选的化合物。
由以上化学式8表示的化合物没有具体限制,并且优选地包括三甲基铝、三乙基铝、三异丁基铝、三丙基铝、三丁基铝、二甲基氯化铝、三异丙基铝、三仲丁基铝、三环戊基铝、三戊基铝、三异戊基铝、三己基铝、三辛基铝、乙基二甲基铝、甲基二乙基铝、三苯基铝、三对甲苯基铝、二甲基甲氧基铝、二甲基乙氧基铝、三甲基硼、三乙基硼、三异丁基硼、三丙基硼、三丁基硼等,并且特别优选的化合物选自三甲基铝、三乙基铝和三异丁基铝。
由以上化学式9表示的化合物的实例包括:三乙基铵四苯基硼、三丁基铵四苯基硼、三甲基铵四苯基硼、三丙基铵四苯基硼、三甲基铵四(对甲苯基)硼、三甲基铵四(邻,对-二甲基苯基)硼、三丁基铵四(对-三氟甲基苯基)硼、三甲基铵四(对-三氟甲基苯基)硼、三丁基铵四五氟苯基硼、N,N-二乙基苯铵四苯基硼、N,N-二乙基苯铵四五氟苯基硼、二乙基铵四五氟苯基硼、三苯基磷鎓四苯基硼、三甲基磷鎓四苯基硼、三乙基铵四苯基铝、三丁基铵四苯基铝、三甲基铵四苯基铝、三丙基铵四苯基铝、三甲基铵四(对-甲苯基)铝、三丙基铵四(对-甲苯基)铝、三乙基铵四(邻,对-二甲基苯基)铝、三丁基铵四(对-三氟甲基苯基)铝、三甲基铵四(对-三氟甲基苯基)铝、三丁基铵四五氟苯基铝、N,N-二乙基苯铵四苯基铝、N,N-二乙基苯铵四五氟苯基铝、二乙基铵四五四苯基铝、三苯基磷鎓四苯基铝、三甲基磷鎓四苯基铝、三丙基铵四(对-甲苯基)硼、三乙基铵四(邻,对-二甲基苯基)硼、三苯基碳鎓四(对三氟甲基苯基)硼、三苯基碳鎓四五氟苯基硼等。
可通过使包含以上化学式1的过渡金属化合物的催化剂组合物和选自由化学式7至9表示的化合物中的至少一种化合物与至少一种烯烃单体相接触来制备聚烯烃均聚物或共聚物。
使用催化剂组合物的最优选制备方法是溶液法。在组合物与无机载体如二氧化硅一起使用的情况下,也可使用淤浆法或气相法。
在制备方法中,可在将催化剂组合物溶解于或稀释于溶剂之后插入活化所述催化剂组合物,所述溶剂为具有5至12个碳原子的脂肪族烃溶剂如戊烷、己烷、庚烷、壬烷、癸烷及其异构体,芳香族烃溶剂如甲苯和苯,或者经氯原子取代的烃溶剂如二氯甲烷和氯苯。优选地,可在通过用少量烷基铝处理来除去作为催化剂毒物(catalyst poison)起作用的少量水或空气之后使用所述溶剂,并且可在另外使用助催化剂的情况下使用。
可使用金属化合物和助催化剂聚合的烯烃单体可包括:乙烯、α-烯烃、环烯烃等,并且也可使具有至少两个双键的二烯烯烃单体和三烯烯烃单体聚合。单体的特定实例可包括:乙烯、丙烯、1-丁烯、1-戊烯、4-甲基-1-戊烯、1-己烯、1-庚烯、1-辛烯、1-癸烯、1-十一碳烯、1-十二碳烯、1-十四碳烯、1-十六碳烯、1-二十碳烯(icocene)、降冰片烯、降冰片二烯、次乙基降冰片烯、苯基降冰片烯、乙烯基降冰片烯、二环戊二烯、1,4-丁二烯、1,5-戊二烯、1,6-己二烯、苯乙烯、α-甲基苯乙烯、二乙烯基苯、3-氯甲基苯乙烯等。这些单体中至少两种的混合物可发生共聚反应。
特别地,在使用催化剂组合物的本发明制备方法中,具有高分子量和低于或等于0.91g/cc的聚合物密度的共聚物可以以乙烯与具有较大位阻的单体如1-辛烯在大于或等于90℃的高反应温度下的共聚反应来制备。
根据一个方面,通过本发明的制备方法制备的聚合物的密度小于0.91g/cc。
根据另一个方面,通过本发明的制备方法制备的聚合物的密度小于0.89g/cc。
根据一个方面,通过本发明的制备方法制备的聚合物的密度小于或等于0.885g/cc。
根据一个方面,通过本发明的制备方法制备的聚合物的Tc小于或等于75℃。
根据一个方面,通过本发明的制备方法制备的聚合物的Tm小于或等于95℃。
根据一个方面,通过本发明的制备方法制备的聚合物的Tm小于或等于91℃。
根据一个方面,通过本发明的制备方法制备的聚合物的Tm小于87℃。
根据一个方面,通过本发明的制备方法制备的聚合物的Mw大于或等于100,000。
根据另一个方面,通过本发明的制备方法制备的聚合物的Mw为100,000至1,000,000。
根据一个方面,通过本发明的制备方法制备的聚合物的MWD小于或等于3。
根据另一个方面,通过本发明的制备方法制备的聚合物的MWD为1至3。
根据另一个方面,通过本发明的制备方法制备的聚合物的MWD为1.5至2.9。
根据另一个方面,通过本发明的制备方法制备的聚合物的MWD为2至2.85。
根据一个方面,根据本发明的聚合物的MWD为1至3,Mw为100,000至1,000,000,并且密度小于0.91g/cc。
实施发明的方式
下文中,将参照以下实施方案更具体地解释本发明。这些实施方案用于帮助理解本发明,而本发明的范围不限于此。
除非另有说明,否则有机试剂和溶剂均购自Aldrich Co.并且在通过标准方法纯化后使用。在合成的所有步骤中,阻断空气和湿气以增加实验的重现性。
过渡金属化合物的合成
酮化合物的合成
根据文献[Ryabov等.Organometallics,2002,21,14,2842-2853]中所述的方法进行合成。
1H NMR(CDCl3):δ1.35(d,3H,CH3),2.78(dd,1H),3.05(m,1H,(CH2)2),3.43(dd,1H),1.91(m,6H,Cp-CH3),7.14(d,1H),7.34(d,1H)ppm
配体的合成
在-40℃下向溶解在10mL乙醚中的1,2,3,4-四氢喹啉(560mg,4.2mmol)缓慢地逐滴添加正丁基锂(4.6mmol,1.1当量)。使温度缓慢升高至室温,随后在室温下搅拌4小时。使温度再次降低至-40℃,并向其中注入CO2(气体),随后将反应在低温下维持0.5小时。缓慢升高温度,并通过鼓泡器移除剩余的CO2(气体)。在-20℃下添入THF(4.6mmol,0.37ml)和tBuLi(4.6mmol),随后在-20℃的低温下老化2小时。将上述酮化合物(540mg,3.57mmol)溶解在二乙醚溶液中并缓慢地逐滴添加。在室温下搅拌12小时之后,添加10mL水并添加盐酸(2N,20mL),随后搅拌2分钟。萃取有机溶剂并用NaHCO3水溶液中和。萃取有机溶剂并用MgSO4移除水。通过硅胶柱色谱,获得黄色油状物(230mg,24%产率)
1H NMR(C6D6):δ1.83(s,3H,CH3),2.40~2.38(m,4H,Cp-H喹啉-CH2),2.62~2.60(m,2H,喹啉-CH2),2.61~2.59(m,2H,喹啉-NCH2),2.81~2.77(d,2H,喹啉-NCH2),2.97~2.94(d,2H,喹啉-NCH2),3.69(宽峰,1H,N-H),6.77~6.74(t,1H,芳香族),6.83~6.82(s,1H,芳香族),6.93~6.92(s,1H,芳香族),7.11~7.10(s,1H,芳香族),7.30(s,1H,芳香族),7.72~7.70(d,1H,芳香族)ppm
过渡金属化合物的合成
在20℃下将正丁基锂(1.15mmol,2.1当量)缓慢添加至上述配体(147mg,0.55mmol)中。观察到黄色浆体的形成,使温度缓慢升高至室温,随后在室温下搅拌12小时。
逐滴添加TiCl4DME(154mg,0.55mmol,1.0当量),随后在室温下搅拌12小时。移除溶剂之后,用甲苯萃取剩余的产物以获得红色固体(63mg,产率30%)。
1H NMR(C6D6):δ1.46~1.467(t,2H,喹啉-NCH2),1.81(s,3H,Cp-CH3),2.10~2.07(t,2H,喹啉-NCH2),4.45~4.41(m,2H,N-CH2),4.53~4.50(m,2H,N-CH2),6.00(Cp,1H),6.38~6.37(d,1H,芳香族)6.70~6.69(d,1H,芳香族)6.85~6.83(m,2H,芳香族)6.98~6.96(d,1H,芳香族)ppm
聚合物的制备实施例
实施例1和2以及比较例1和2
将己烷溶剂(1.0L)和1-辛烯(0.84M)添入2L的高压釜反应器中,随后将反应器预热至120℃。同时,提前用乙烯(35巴)填充反应器的压力。将下表1第一栏中的化合物(2.0μmol)分别添入反应器中,同时使用高压氩气进行加压,所述化合物用三异丁基铝化合物和二甲基苯铵四(五氟苯基)硼酸盐助催化剂(20μmol)进行处理(摩尔比Al∶Ti=10∶1)。然后,使共聚反应进行8分钟。之后,排出剩余的乙烯气体,并将聚合物溶液添加至过量乙醇中以导致沉淀。所沉淀的聚合物分别用乙醇和丙酮洗涤两次或三次,并在80℃的真空烘箱中干燥多于12小时。然后,评估物理性质。
物理性质(重量、活性、熔融指数、熔点、密度)的评估
根据ASTM D-1238测量聚合物的熔融指数(MI)(条件E,190℃,2.16kg负载)。聚合物的熔点(Tm)通过使用TA Co.制造的差示扫描热量计2920(DSC)获得。即,使温度升高至200℃,保持5分钟,降低至30℃并再次升高,测量DSC曲线的顶点作为熔点。在这种情况中,温度的升高速率和降低速率是10℃/分钟,并且在温度第二次升高期间获得熔点。此外,聚合物的密度通过以下过程来测量:通过在180℃下使用经抗氧化剂(1,000ppm)处理的样品的压模制造厚度为3mm且半径为2cm的片,以10℃/分钟的速率冷却,并使用Mettler天平进行测量。
下表1中说明了以上实施例和比较例中所制备的聚合物的物理性质。
表1
工业适用性
根据本发明一个实施方案的过渡金属化合物具有良好的共聚性质,并且使用其可制备具有低密度的聚合物。因此,可制备具有各种用途的共聚物。
Claims (12)
1.一种以下化学式2的过渡金属化合物:
[化学式2]
在以上化学式2中,
M是第4族过渡金属,
Q1和Q2相同或不同,并且各自独立地为卤素,
R1至R4相同或不同,并且各自独立地为氢、或具有1至20个碳原子的烷基,并且
R5至R7相同或不同,并且独立地为氢、具有1至20个碳原子的烷基、具有2至20个碳原子的烯基、具有6至20个碳原子的芳基、具有7至20个碳原子的烷基芳基、具有7至20个碳原子的芳基烷基;R5至R7中的至少两个可彼此连接以形成具有5至20个碳原子的脂族环或具有6至20个碳原子的芳香环;所述脂族环或所述芳香环可经卤素、具有1至20个碳原子的烷基、具有2至20个碳原子的烯基或具有6至20个碳原子的芳基取代,
Cy是五元或六元脂族环,
每个R10独立地为氢、具有1至20个碳原子的烷基、具有2至20个碳原子的烯基、具有6至20个碳原子的芳基、具有7至20个碳原子的烷基芳基或具有7至20个碳原子的芳基烷基,并且
当Cy是五元脂族环时,m是1至4的整数,并且当Cy是六元脂族环时,m是1至6的整数。
2.根据权利要求1所述的过渡金属化合物,其中以上化学式2由以下化学式3或化学式4表示:
[化学式3]
在以上化学式3中,
R11至R16各自独立地为氢、具有1至20个碳原子的烷基、具有2至20个碳原子的烯基、具有6至20个碳原子的芳基、具有7至20个碳原子的烷基芳基或具有7至20个碳原子的芳基烷基,并且
其余的取代基与在化学式2中所限定的相同,
[化学式4]
在以上化学式4中,
R17至R20各自独立地为氢、具有1至20个碳原子的烷基、具有2至20个碳原子的烯基、具有6至20个碳原子的芳基、具有7至20个碳原子的烷基芳基或具有7至20个碳原子的芳基烷基,并且
其余的取代基与在化学式2中所限定的相同。
3.根据权利要求2所述的过渡金属化合物,其中R16和R20独立地是氢或具有1至20个碳原子的烷基。
4.根据权利要求1所述的过渡金属化合物,其中M是Ti、Hf或Zr。
5.根据权利要求1所述的过渡金属化合物,其中以上化学式2的所述化合物是选自由以下化学式表示的化合物中的一种或者其至少两种的混合物:
6.一种催化剂组合物,包含根据权利要求1至5中任一项所述的过渡金属化合物。
7.根据权利要求6所述的催化剂组合物,其还包含至少一种助催化剂。
8.根据权利要求7所述的催化剂组合物,其中所述助催化剂包含选自以下化学式7至9中的至少一种:
[化学式7]
-[Al(R22)-O]a-
在以上化学式中,每个R22独立地为卤素基团、具有1至20个碳原子的烃基基团或经卤素取代的具有1至20个碳原子的烃基基团;并且a是至少为2的整数;
[化学式8]
D(R22)3
在以上化学式中,D是铝或硼;每个R22独立地与上述相同;
[化学式9]
[L-H]+[Z(A)4]-或[L]+[Z(A)4]-
在以上化学式中,L是中性路易斯酸或阳离子路易斯酸;H是氢原子;Z是第13族元素;每个A独立地为具有6至20个碳原子的芳基或具有1至20个碳原子的烷基,其中至少一个氢原子可独立地被取代基取代;并且所述取代基是卤素、具有1至20个碳原子的烃基、具有1至20个碳原子的烷氧基或具有6至20个碳原子的芳氧基。
9.根据权利要求6所述的催化剂组合物,其还包含反应溶剂。
10.一种负载催化剂,其中根据权利要求6所述的催化剂组合物通过载体来负载。
11.一种聚合物的制备方法,其使用根据权利要求6所述的催化剂组合物,其中所述聚合物是聚烯烃的均聚物或共聚物。
12.一种聚合物的制备方法,其使用根据权利要求10所述的负载催化剂,其中所述聚合物是聚烯烃的均聚物或共聚物。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR20130123476 | 2013-10-16 | ||
KR10-2013-0123476 | 2013-10-16 | ||
PCT/KR2014/009753 WO2015057001A1 (ko) | 2013-10-16 | 2014-10-16 | 헤테로 원자를 갖는 전이금속 화합물, 이를 포함하는 촉매 조성물 및 이를 이용한 중합체의 제조방법 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN104797586A CN104797586A (zh) | 2015-07-22 |
CN104797586B true CN104797586B (zh) | 2017-08-08 |
Family
ID=52828375
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201480003124.3A Active CN104797586B (zh) | 2013-10-16 | 2014-10-16 | 具有杂原子的过渡金属化合物、包含其的催化剂组合物及使用其制备聚合物的方法 |
Country Status (5)
Country | Link |
---|---|
US (1) | US9359388B2 (zh) |
EP (1) | EP2905285B1 (zh) |
KR (1) | KR101689063B1 (zh) |
CN (1) | CN104797586B (zh) |
WO (1) | WO2015057001A1 (zh) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101731177B1 (ko) * | 2014-12-24 | 2017-04-27 | 주식회사 엘지화학 | 헤테로 원자를 갖는 전이금속 화합물, 이를 포함하는 촉매 조성물 및 이를 이용한 중합체의 제조방법 |
KR102050573B1 (ko) * | 2015-10-21 | 2019-11-29 | 주식회사 엘지화학 | 전이금속 화합물, 이를 포함하는 촉매 조성물 및 이를 이용한 폴리올레핀의 제조 방법 |
KR101924198B1 (ko) * | 2015-12-23 | 2018-11-30 | 주식회사 엘지화학 | 필름 가공성 및 투명도가 우수한 저밀도 폴리에틸렌 공중합체 |
KR102320012B1 (ko) * | 2018-01-12 | 2021-11-02 | 주식회사 엘지화학 | 리간드 화합물, 전이금속 화합물 및 이를 포함하는 촉매 조성물 |
KR102306523B1 (ko) * | 2018-11-19 | 2021-09-29 | 롯데케미칼 주식회사 | 티오펜-축합고리 사이클로펜타디에닐 리간드 및 메탈로센 촉매 조성물의 제조방법 |
KR102524952B1 (ko) * | 2019-06-13 | 2023-04-24 | 주식회사 엘지화학 | 신규 전이금속 화합물 및 이를 이용한 폴리프로필렌의 제조방법 |
CN114890987B (zh) * | 2022-04-13 | 2023-12-19 | 万华化学集团股份有限公司 | 一种硫酚-噻吩配体及其制备方法、烯烃聚合催化剂及其制备方法、应用 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003201308A (ja) * | 2002-01-07 | 2003-07-18 | Idemitsu Petrochem Co Ltd | オレフィン重合用触媒及びポリオレフィンの製造方法 |
CN101213218A (zh) * | 2006-03-24 | 2008-07-02 | Lg化学株式会社 | 过渡金属配合物、包含该过渡金属配合物的催化剂组合物以及使用该催化剂组合物的烯烃聚合物 |
KR101066969B1 (ko) * | 2007-05-18 | 2011-09-22 | 주식회사 엘지화학 | 공중합성이 뛰어난 전이금속 촉매를 이용한 올레핀중합체의 제조 방법 |
CN102834402A (zh) * | 2010-04-12 | 2012-12-19 | 湖南石油化学株式会社 | 含有来源于四氢喹啉衍生物的噻吩稠合的环戊二烯基配体的第4族金属化合物及利用该化合物的烯烃聚合 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5064802A (en) | 1989-09-14 | 1991-11-12 | The Dow Chemical Company | Metal complex compounds |
SG99905A1 (en) | 2000-06-21 | 2003-11-27 | Sumitomo Chemical Co | Transition metal compound, catalyst for addition polymerization, and process for producing addition polymer |
KR100875421B1 (ko) | 2006-07-27 | 2008-12-23 | 엘지전자 주식회사 | 영상 캡처 방법 및 이를 구현할 수 있는 단말기 |
KR100976131B1 (ko) | 2007-01-10 | 2010-08-16 | 주식회사 엘지화학 | 전이금속 화합물의 제조 방법, 상기 방법으로 제조된전이금속 화합물 및 상기 전이금속 화합물을 포함하는 촉매조성물 |
KR20080101791A (ko) * | 2007-05-16 | 2008-11-21 | 주식회사 엘지화학 | 장쇄분지를 포함하는 에틸렌-알파올레핀 공중합체 |
ES2596719T3 (es) | 2010-04-12 | 2017-01-11 | Lotte Chemical Corporation | Procedimiento de preparación de un copolímero de olefin-dieno usando un compuesto de metal de transición que incluye un ligando de ciclopentadienilo de anillo condensado con tiofeno |
WO2011129592A2 (ko) | 2010-04-12 | 2011-10-20 | 호남석유화학 주식회사 | 올레핀 중합용 담지 촉매 및 이를 사용한 폴리올레핀의 제조방법 |
US8889804B2 (en) | 2010-04-12 | 2014-11-18 | Lotte Chemical Corporation | Method for preparing polypropylene using transition metal compound containing thiophene-fused cyclopentadienyl ligand |
KR101384401B1 (ko) | 2010-04-12 | 2014-04-25 | 롯데케미칼 주식회사 | 올레핀 중합용 담지 촉매 및 이를 사용한 폴리올레핀의 제조방법 |
-
2014
- 2014-10-16 WO PCT/KR2014/009753 patent/WO2015057001A1/ko active Application Filing
- 2014-10-16 CN CN201480003124.3A patent/CN104797586B/zh active Active
- 2014-10-16 US US14/439,159 patent/US9359388B2/en active Active
- 2014-10-16 KR KR1020140139992A patent/KR101689063B1/ko active IP Right Grant
- 2014-10-16 EP EP14853389.6A patent/EP2905285B1/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003201308A (ja) * | 2002-01-07 | 2003-07-18 | Idemitsu Petrochem Co Ltd | オレフィン重合用触媒及びポリオレフィンの製造方法 |
CN101213218A (zh) * | 2006-03-24 | 2008-07-02 | Lg化学株式会社 | 过渡金属配合物、包含该过渡金属配合物的催化剂组合物以及使用该催化剂组合物的烯烃聚合物 |
KR101066969B1 (ko) * | 2007-05-18 | 2011-09-22 | 주식회사 엘지화학 | 공중합성이 뛰어난 전이금속 촉매를 이용한 올레핀중합체의 제조 방법 |
CN102834402A (zh) * | 2010-04-12 | 2012-12-19 | 湖南石油化学株式会社 | 含有来源于四氢喹啉衍生物的噻吩稠合的环戊二烯基配体的第4族金属化合物及利用该化合物的烯烃聚合 |
Non-Patent Citations (2)
Title |
---|
Constrained geometry complexes of titanium (IV) and zirconium (IV) involving cyclopentadienyl fused to thiophene ring;Alexey N. Ryabov et al.;《Journal of Organometallic Chemistry》;20050805;第690卷;第4213–4221页 * |
Preparation of half-metallocenes of thiophene-fused and tetrahydroquinoline-linked cyclopentadienyl ligands for ethylene/a-olefin copolymerization;Ji Hae Park et al.;《Dalton Trans.》;20100921;第39卷;第9995页图,9994页摘要 * |
Also Published As
Publication number | Publication date |
---|---|
CN104797586A (zh) | 2015-07-22 |
EP2905285A4 (en) | 2015-11-18 |
US9359388B2 (en) | 2016-06-07 |
EP2905285A1 (en) | 2015-08-12 |
WO2015057001A1 (ko) | 2015-04-23 |
EP2905285B1 (en) | 2017-04-05 |
US20150239916A1 (en) | 2015-08-27 |
KR101689063B1 (ko) | 2016-12-22 |
KR20150044413A (ko) | 2015-04-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN104797586B (zh) | 具有杂原子的过渡金属化合物、包含其的催化剂组合物及使用其制备聚合物的方法 | |
EP2873671B1 (en) | Transition metal compound, catalyst composition containing same, and method for preparing polymer by using same | |
JP6469832B2 (ja) | リガンド化合物、遷移金属化合物及びこれを含む触媒組成物 | |
EP3219718B1 (en) | Ligand compound, transition metal compound, and catalyst composition containing compounds | |
KR101603016B1 (ko) | 촉매 조성물 및 이를 포함하는 중합체의 제조방법 | |
KR100843603B1 (ko) | 전이금속 화합물, 이를 포함하는 촉매 조성물 및 이를이용한 올레핀 중합 | |
US9376519B2 (en) | Transition metal compound, catalytic composition including the same, and method for preparing polymer using the same | |
EP3219719B1 (en) | Transition metal compound and catalyst composition containing same | |
KR102236921B1 (ko) | 전이금속 화합물 및 알킬알루미녹산을 포함하는 촉매 조성물, 이를 이용한 중합체의 제조방법, 및 이를 이용하여 제조된 중합체 | |
KR102054466B1 (ko) | 전이금속 화합물을 포함하는 촉매 조성물 및 이를 이용한 중합체의 제조방법 | |
KR102558310B1 (ko) | 전이금속 화합물, 이를 포함하는 촉매 조성물 및 이를 이용한 중합체의 제조방법 | |
CN106661143B (zh) | 具有杂原子的过渡金属化合物、包含该化合物的催化剂组合物和使用该催化剂组合物的聚合物的制备方法 | |
CN111094306B (zh) | 配体化合物,过渡金属化合物和包含所述过渡金属化合物的催化剂组合物 | |
KR101785705B1 (ko) | 촉매 조성물 및 이를 이용한 폴리올레핀의 제조방법 | |
KR102423660B1 (ko) | 전이금속 화합물 및 이를 포함하는 촉매 조성물 | |
CN111094307B (zh) | 配体化合物,过渡金属化合物和包含其的催化剂组合物 | |
KR102223719B1 (ko) | 리간드 화합물, 전이금속 화합물 및 이를 포함하는 촉매 조성물 | |
KR20170068330A (ko) | 신규한 전이금속 화합물 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
EXSB | Decision made by sipo to initiate substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |