WO2011129594A2 - 티오펜-축합고리 사이클로펜타디에닐 리간드를 포함하는 전이금속 화합물을 사용한 올레핀-디엔 공중합체의 제조방법 - Google Patents
티오펜-축합고리 사이클로펜타디에닐 리간드를 포함하는 전이금속 화합물을 사용한 올레핀-디엔 공중합체의 제조방법 Download PDFInfo
- Publication number
- WO2011129594A2 WO2011129594A2 PCT/KR2011/002585 KR2011002585W WO2011129594A2 WO 2011129594 A2 WO2011129594 A2 WO 2011129594A2 KR 2011002585 W KR2011002585 W KR 2011002585W WO 2011129594 A2 WO2011129594 A2 WO 2011129594A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- olefin
- formula
- transition metal
- diene
- ketal
- Prior art date
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- 150000003623 transition metal compounds Chemical class 0.000 title claims abstract description 60
- 229920001577 copolymer Polymers 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 46
- 239000003446 ligand Substances 0.000 title description 13
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 title description 10
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 title description 3
- 239000000178 monomer Substances 0.000 claims abstract description 51
- 150000001993 dienes Chemical class 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 23
- 150000001336 alkenes Chemical class 0.000 claims abstract description 21
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 76
- 239000000126 substance Substances 0.000 claims description 32
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 31
- 125000001033 ether group Chemical group 0.000 claims description 31
- -1 cationic Lewis acid Chemical class 0.000 claims description 26
- 125000000217 alkyl group Chemical group 0.000 claims description 22
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 21
- 238000006116 polymerization reaction Methods 0.000 claims description 21
- 229910052736 halogen Inorganic materials 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 150000002367 halogens Chemical class 0.000 claims description 13
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims description 12
- 239000004711 α-olefin Substances 0.000 claims description 11
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 8
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052796 boron Inorganic materials 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 6
- 150000001925 cycloalkenes Chemical class 0.000 claims description 6
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 6
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- 150000003624 transition metals Chemical class 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 125000004104 aryloxy group Chemical group 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 229920000858 Cyclodextrin Polymers 0.000 claims description 3
- 239000002841 Lewis acid Substances 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- 125000001118 alkylidene group Chemical group 0.000 claims description 3
- 229910001570 bauxite Inorganic materials 0.000 claims description 3
- 229910052795 boron group element Inorganic materials 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 claims description 3
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 3
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims 10
- 125000006649 (C2-C20) alkynyl group Chemical group 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- 230000000704 physical effect Effects 0.000 abstract description 8
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 62
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 44
- 150000001241 acetals Chemical class 0.000 description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 239000002904 solvent Substances 0.000 description 14
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 13
- RURFJXKOXIWFJX-UHFFFAOYSA-N (2,3,4,6-tetrafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C=C(F)C(F)=C1F RURFJXKOXIWFJX-UHFFFAOYSA-N 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 238000005481 NMR spectroscopy Methods 0.000 description 12
- 239000002243 precursor Substances 0.000 description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 11
- 239000005977 Ethylene Substances 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical compound C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 description 8
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 6
- 239000000395 magnesium oxide Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000002815 homogeneous catalyst Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- 229920001897 terpolymer Polymers 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 4
- 150000007523 nucleic acids Chemical class 0.000 description 4
- 102000039446 nucleic acids Human genes 0.000 description 4
- 108020004707 nucleic acids Proteins 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 4
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 4
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 125000005234 alkyl aluminium group Chemical group 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 3
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 3
- 229930192474 thiophene Natural products 0.000 description 3
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 3
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- LBUJPTNKIBCYBY-UHFFFAOYSA-N 1,2,3,4-tetrahydroquinoline Chemical compound C1=CC=C2CCCNC2=C1 LBUJPTNKIBCYBY-UHFFFAOYSA-N 0.000 description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 2
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- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 2
- JLGIRMVCNXRIMN-UHFFFAOYSA-N 2-(2,6-dimethylphenyl)sulfanyl-1,3-dimethylbenzene Chemical compound CC1=CC=CC(C)=C1SC1=C(C)C=CC=C1C JLGIRMVCNXRIMN-UHFFFAOYSA-N 0.000 description 2
- CJSBUWDGPXGFGA-UHFFFAOYSA-N 4-methylpenta-1,3-diene Chemical compound CC(C)=CC=C CJSBUWDGPXGFGA-UHFFFAOYSA-N 0.000 description 2
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
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- 150000004703 alkoxides Chemical class 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 229960001701 chloroform Drugs 0.000 description 2
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- 239000012954 diazonium Substances 0.000 description 2
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- XBPCUCUWBYBCDP-UHFFFAOYSA-O dicyclohexylazanium Chemical compound C1CCCCC1[NH2+]C1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-O 0.000 description 2
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- SRLHDBRENZFCIN-UHFFFAOYSA-N n,n-di(butan-2-yl)butan-2-amine Chemical compound CCC(C)N(C(C)CC)C(C)CC SRLHDBRENZFCIN-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
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- CYXMOAZSOPXQOD-UHFFFAOYSA-N 1-methyl-2-(2-methylphenoxy)benzene Chemical compound CC1=CC=CC=C1OC1=CC=CC=C1C CYXMOAZSOPXQOD-UHFFFAOYSA-N 0.000 description 1
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- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
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- IOHAVGDJBFVWGE-UHFFFAOYSA-N 2-ethylidene-3-propan-2-ylidenebicyclo[2.2.1]hept-5-ene Chemical compound C1C2C=CC1C(=CC)C2=C(C)C IOHAVGDJBFVWGE-UHFFFAOYSA-N 0.000 description 1
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- WTQBISBWKRKLIJ-UHFFFAOYSA-N 5-methylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C)CC1C=C2 WTQBISBWKRKLIJ-UHFFFAOYSA-N 0.000 description 1
- KUFDSEQTHICIIF-UHFFFAOYSA-N 6-methylhepta-1,5-diene Chemical compound CC(C)=CCCC=C KUFDSEQTHICIIF-UHFFFAOYSA-N 0.000 description 1
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- JLTDJTHDQAWBAV-UHFFFAOYSA-O dimethyl(phenyl)azanium Chemical compound C[NH+](C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-O 0.000 description 1
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- 238000001035 drying Methods 0.000 description 1
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- 229960003750 ethyl chloride Drugs 0.000 description 1
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- 125000005843 halogen group Chemical group 0.000 description 1
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- GEAWFZNTIFJMHR-UHFFFAOYSA-N hepta-1,6-diene Chemical compound C=CCCCC=C GEAWFZNTIFJMHR-UHFFFAOYSA-N 0.000 description 1
- JAGYXYUAYDLKNO-UHFFFAOYSA-N hepta-2,5-diene Chemical compound CC=CCC=CC JAGYXYUAYDLKNO-UHFFFAOYSA-N 0.000 description 1
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- AHAREKHAZNPPMI-UHFFFAOYSA-N hexa-1,3-diene Chemical compound CCC=CC=C AHAREKHAZNPPMI-UHFFFAOYSA-N 0.000 description 1
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 239000011147 inorganic material Substances 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- DKUIXLPCCDROFD-UHFFFAOYSA-N methanolate;methylaluminum(2+) Chemical compound [O-]C.[O-]C.[Al+2]C DKUIXLPCCDROFD-UHFFFAOYSA-N 0.000 description 1
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 description 1
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- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- UOHDQQRXTGKZDG-UHFFFAOYSA-N pent-1-ene Chemical compound CCCC=C.CCCC=C UOHDQQRXTGKZDG-UHFFFAOYSA-N 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
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- 150000003254 radicals Chemical group 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000005270 trialkylamine group Chemical group 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
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- YGRHYJIWZFEDBT-UHFFFAOYSA-N tridecylaluminum Chemical compound CCCCCCCCCCCCC[Al] YGRHYJIWZFEDBT-UHFFFAOYSA-N 0.000 description 1
- 150000005671 trienes Chemical class 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 compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- WXRGABKACDFXMG-UHFFFAOYSA-N trimethylborane Chemical compound CB(C)C WXRGABKACDFXMG-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-O triphenylphosphanium Chemical compound C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-O 0.000 description 1
- ZMPKTELQGVLZTD-UHFFFAOYSA-N tripropylborane Chemical compound CCCB(CCC)CCC ZMPKTELQGVLZTD-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
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000011345 viscous material Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—Ethene
-
- 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
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
-
- 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
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- 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
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- 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
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- 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
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- 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
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- 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+
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/943—Polymerization with metallocene catalysts
Definitions
- the present invention relates to a process for preparing an olefin-diene copolymer using a transition metal compound comprising a thiophene-condensed ring cyclopentadienyl ligand.
- the present invention is to provide a method for producing an olefin-diene copolymer using a catalyst having excellent copolymerization activity with respect to the olefin monomer and the diene monomer and easily controlling the physical properties of the copolymer.
- the present invention is a.
- It provides a method for producing an olefin-diene copolymer comprising the step of polymerizing at least one olefin monomer and at least one diene monomer in the presence of a catalyst comprising a transition metal compound represented by the following formula (1). :
- M is a Group 4 transition metal
- Q 1 and Q 2 are each independently halogen, (d-o) alkyl, (C 2 -C 20 ) alkenyl, (C 2-
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 are each independently hydrogen; (C! -O) alkyl with or without acetal, ketal or ether groups; (C 2 -C 20 ) alkenyl with or without acetal, ketal or ether groups; Acetal, ketal or (C 2 o) alkyl (C 6 -C 20 ) aryl with or without ether groups; (C 6 -C 20 ) aryl (-C20) alkyl with or without acetal, ketal or ether groups; Or (dC 2 o) silyl with or without acetal, ketal or ether groups; R 1 and R 2 may be connected to each other to form a ring, and R 3 and R 4 may be connected to each other to form a ring, and two or more of R 5 to R 10 may be connected to each other to form a ring Can do it;
- R ′′, R 12 and R 13 are each independently hydrogen; (CC 20 ) alkyl with or without acetal, ketal or ether groups; (C 2 -C 20 ) alk with or without acetal, ketal or ether groups Kenyl; (C ⁇ o) alkyl (c 6 -c 20 ) aryl with or without acetal, ketal or ether groups; (C 6 -C 20 ) aryl with or without acetal, ketal or ether groups (C ⁇ o) silyl with or without acetal, ketal or ether groups; (C ⁇ o) alkoxy; or (C 6 -C 20 ) aryloxy; R 11 and R 12 or R 12 R 13 may be connected to each other to form a ring, wherein, in the transition metal compound represented by Formula 1,
- M is titanium (Ti), zirconium (Zr) or hafnium (Hf);
- Q 1 and Q 2 are each independently cetyl or chlorine;
- R 1 , R 2 , R 3 , R 4 and R 5 are each independently hydrogen or methyl;
- R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 are each preferably hydrogen.
- the catalyst may further include one or more cocatalyst compounds selected from the group consisting of compounds represented by the following formula (6), (7) and (8):
- Each R 61 is independently a halogen radical, a (d-Czo) hydrocarbyl radical or a ( ⁇ -0 ) hydrocarbyl radical substituted with halogen;
- a is an integer of 2 or more
- D is aluminum or boron
- Each R 71 is independently a halogen radical, a (d-o) hydrocarbyl radical or a (d-o) hydrocarbyl radical substituted with halogen;
- L is a neutral or cationic Lewis acid
- Z is a Group 13 element
- A are each independently one or more hydrogen atoms are halogen, (dC 20) hydrocarbyl, (dC 2 o) alkoxy or (C 6 -C 20) substituted by an aryloxy radical (C 6 -C 20) aryl, or (d-o) alkyl radicals.
- R 61 of Chemical Formula 6 is methyl, ethyl, n-butyl or isobutyl; D in Formula 7 is aluminum and R 71 is methyl or isobutyl, or D is boron and R 71 is pentafluorophenyl; [LH] + in Formula 8 is a dimethylanilinium cation; [Z (A) 4 ]-is [B (C 6 F 5 ) 4 ]-; [L] + may be [(C 6 ) 3 C] + .
- the content of the cocatalyst compound may be 1: 1: 1: 100,000 based on the molar ratio of the metal contained in the cocatalyst compound to 1 mol of the transition metal contained in the transition metal compound represented by Chemical Formula 1.
- the catalyst is a transition metal compound represented by Formula 1 is Si0 2 , A1 2 0 3 , MgO, MgCl 2 , CaCl 2 , Zr0 2 , Ti0 2 , B 2 0 3 , CaO, ZnO, BaO, Th0 2 , Si0 2 -Al 2 0 3 , Si0 2 -MgO, Si0 2 -Ti0 2 , Si0 2 -V 2 0 5 , Si0 2 -Cr0 2 0 3 , Si0 2 -Ti0 2 -MgO, bauxite, zeolite, starch And cyclodextrine may be supported on at least one carrier selected from the group consisting of.
- the olefin monomer is (C 2 -C 20 ) alpha-olefin ( ⁇ -Olefm), (C 3 -C 20 ) cycloolefin (Cyclo-olefin) or (C 3 -C 20 ) cyclodiolefin (Cyclo -diolefin) may be one or more selected from the group consisting of.
- the diene monomer is (c 4- c 20 ) conjugated diene, (c 5- c 20 ) aliphatic non-conjugated diene, (c 5- c 20 ) cyclic non-conjugated diene and (C 6 -C 20 ) aromatic non-porous It may be at least one selected from the group consisting of liquid diene.
- the polymerization step may be carried out under a temperature of -50 to 500 ° C and a pressure of 1 to 3000 atm.
- the content ratio of the diene monomer to the olefin monomer polymerized in the olefin diene copolymer may be 1: 0.1 to 1:10.
- the olefin-diene copolymer has a weight average molecular weight of 10,000 to 1,000,000; Molecular weight distribution (Mw / Mn) is 1 to 10; The density may be between 0.850 and 0.920 g / ml.
- the method for preparing an olefin-diene copolymer according to the present invention uses a transition metal compound having a new structure as a catalyst, and thus has a high copolymerization activity of an olepin monomer and a diene monomer, thereby providing excellent process efficiency and a fine structure of the copolymer. It can be easily controlled, it is possible to easily prepare the oleic-diene copolymer having the desired physical properties.
- the present inventors have formed a condensed ring in which an amido ligand and an ortho-phenylene form a condensed ring, and a pentagonal ring py-ligand is attached to a thiophene heterocyclic ring. New ligands fused by In addition, it was confirmed that the transition metal compound including the ligand showed higher catalytic activity than the transition metal compound to which the thiophenhetero ring was not fused, and a polymer having a high molecular weight could be prepared.
- the transition metal compound containing the ligand of the new structure when used for the preparation of the lelepin-diene co-polymer, the fine structure of the copolymer can be easily controlled, and the olefin having a high content of diene comonomer and a high molecular weight- It was confirmed that the diene copolymer can be prepared, to complete the present invention.
- the invention is in accordance with one embodiment,
- It provides a method for producing an olefin-diene copolymer comprising the step of polymerizing at least one olefin monomer and at least one diene monomer in the presence of a catalyst comprising a transition metal compound represented by the formula (1). :
- M is a Group 4 transition metal
- Q 1 and Q 2 are each independently halogen, (C ⁇ o) alkyl, (C 2 -C 20 ) alkenyl, (C 2-
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 are each independently hydrogen; ( ⁇ -3 ⁇ 4 0 ) alkyl with or without acetal, ketal or ether groups; (C 2 -C 20 ) alkenyl with or without acetal, ketal or ether groups; (C ⁇ o) alkyl (C 6 -C 20 ) aryl with or without acetal, ketal or ether groups; (C 6 -C 20 ) aryl (-C20) alkyl with or without acetal, ketal or ether groups; Or (d-Qjo) silyl with or without acetal, ketal or ether groups;
- the R 1 and R 2 may be connected to each other to form a ring
- the R 3 and R 4 may be connected to each other to form a ring
- at least two of the R 5 to R 10 Can be linked to each other to
- R 11, R 12 and R are each independently hydrogen; ( ⁇ -3 ⁇ 4 0 ) alkyl with or without acetal, ketal or ether groups; (C 2 -c 20 ) alkenyl with or without acetal, ketal or ether groups; ( ⁇ -0 ) alkyl (C 6 -C 20 ) aryl with or without acetal, ketal or ether groups; (C 6 -C 20 ) aryl (-C 20 ) alkyl with or without acetal, ketal or ether groups; (DC 2 o) silyl with or without acetal, ketal or ether groups; (d-Czo) alkoxy; Or (C 6 -C 20 ) aryloxy; R 11 and R 12 or R 12 and R 13 may be connected to each other to form a ring.
- the catalyst includes a transition metal compound represented by Chemical Formula 1.
- the transition metal compound of Formula 1 is activated by a cocatalyst compound to be described later to impart activity to the olepan polymerization reaction.
- the transition metal compound represented by Formula 1 is a new compound in which an amido ligand and an ortho-phenylene form a condensed ring, and a 5-membered ring pi-ligand bonded to the ortho-phenylene is fused by a thiophene hetero ring.
- Ligands of the structure Accordingly, the transition metal compound has a high copolymerization activity of oleprene-diene, in particular, compared to a transition metal compound to which a thiophene hetero ring is not fused.
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 may be each independently substituted with a substituent including an acetal, ketal or ether group, it may be more advantageous to support on the surface of the carrier when substituted with such a substituent.
- M is preferably titanium (Ti), zirconium (Zr) or hafnium (Hi).
- Q 1 and Q 2 are preferably each independently halogen or (d-Czo) alkyl, more preferably chlorine or methyl.
- R 1 , R 2 , R 3 , R 4 and R 5 may be each independently hydrogen or (d-o) alkyl, preferably each independently Hydrogen or methyl. More preferably, the R 1 , R 2 , R 3 , R 4 and R 5 may be each independently hydrogen or methyl, provided that at least one of R 3 and R 4 is methyl, R 5 may be methyl have.
- R 6 , R 7 , R 8 , R 9 , R 10 , R ′′, R 12, and R 13 are each preferably hydrogen.
- the transition metal compound represented by Chemical Formula 1 is preferable to include such substituents for electronic and three-dimensional environmental control around the metal. Meanwhile, the transition metal compound represented by Formula 1 may be obtained from a precursor compound represented by Formula 2:
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 are each represented by Formula 1 As defined.
- the precursor compound represented by the formula (2) is (a) after reacting a tetrahydroquinoline derivative represented by the formula (3) with alkyllithium Adding carbon dioxide to prepare a compound represented by Formula 4; And (b) reacting the compound represented by Chemical Formula 4 with alkyllithium, and then adding the compound represented by Chemical Formula 5 and treating with acid.
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R ′′, R 12, and R 13 are Each is as defined in the formula (1).
- R 1 , R 2 , R 3 , R 4, and R 5 may be each independently hydrogen or (d-o) alkyl, and preferably each independently Hydrogen or methyl. More preferably, R 1 , R 2 , R 3 , R 4 and R 5 may be each independently hydrogen or methyl, provided that at least one of R 3 and R 4 is methyl and R 5 may be methyl have.
- R ⁇ 6> , R ⁇ 7> , R ⁇ 8> , R ⁇ 9> , R ⁇ 10> , R ⁇ 11> , R ⁇ 12> and R ⁇ 13> are hydrogen, respectively. This ensures the accessibility and reactivity of the starting material, it is advantageous to control the electronic and three-dimensional environment of the transition metal compound of formula (1) to be prepared.
- Step (a) is a reaction in which the tetrahydroquinoline derivative represented by Chemical Formula 3 is reacted with alkyllithium and then converted into a compound represented by Chemical Formula 4 by adding carbon dioxide, which is according to a method described in the known literature. (Tetrahedron Lett. 1985, 26, 5935; Tetrahedronl 986, 42,2571; J. Chem. SC. Perkin Trans. 1989, 16)
- step (b) a reaction of alkyllithium to the compound represented by Chemical Formula 4 causes deprotonation reaction to generate an ortho-lithium compound, and the compound represented by Chemical Formula 5 is reacted with acid to treat the acid. It is possible to obtain a transition metal compound precursor represented by the formula (2).
- reaction of generating an ortho-lithium compound by reacting alkyllithium with the compound represented by Chemical Formula 4 can be understood through known literature (Organometallics 2007, 27,6685; Korean Patent Publication No. 2008-0065868), In the present invention, it is possible to obtain a transition metal compound precursor represented by Chemical Formula 2 by reacting the compound represented by Chemical Formula 5 and treating an acid.
- the compound represented by Chemical Formula 5 may be prepared through various known methods. Banungsik 1 below shows an example of them, and not only can be manufactured in one step but also inexpensive starting materials. It can be used to make the transition metal compound precursor of the present invention easy and economical (J. Organanomet Chem., 2005, 690,4213).
- various known methods may be used to synthesize the transition metal compound represented by Chemical Formula 1 from the precursor compound represented by Chemical Formula 2 obtained through the above method.
- the catalyst used in the production method of the present invention may further comprise a cocatalyst compound.
- the promoter compound serves to activate the transition metal compound represented by Chemical Formula 1 described above. Therefore, any cocatalyst compound capable of activating the transition metal compound without lowering the activity of the catalyst according to the present invention can be used without limitation in its configuration.
- the promoter compound is preferably at least one selected from the group consisting of compounds represented by the following formula (6), (7) and (8):
- Each R 61 is independently a halogen radical, a (d-o) hydrocarbyl radical or a (d-Czo) hydrocarbyl radical substituted with halogen;
- a is an integer of 2 or more
- D is aluminum or boron
- R 7i are each independently a halogen radical, (! C - o) a hydrocarbyl (! C -C 20) radical or a halogen substituted with Bill hydrocarbyl radical;
- L is a neutral or cationic Lewis acid
- Z is a Group 13 element
- A are each independently one or more hydrogen atoms are halogen, (- C 20) hydrocarbyl, (d- o) alkoxy or (C 6 -C 20) aryloxy the (C 6 -C 20) substituted by an aryl radical or ( C ⁇ o) alkyl radical.
- the cocatalyst compound represented by Chemical Formula 6 is not particularly limited as long as it is alkylaluminoxane, preferably methylaluminoxane, ethylaluminoxane, butylaluminoxane, butylaluminoxane, or nucleosilaluminate.
- alkylaluminoxane preferably methylaluminoxane, ethylaluminoxane, butylaluminoxane, butylaluminoxane, or nucleosilaluminate.
- Hexyl acid Hexylaluminoxane
- octyl aluminoxane Octylaluminoxane
- decyl aluminoxane decyl aluminoxane
- the promoter compound represented by the formula (7) is trimethylaluminum, triethylaluminum, tributylaluminum, trihexylaluminum, trioctyl aluminum, tridecylluminum, tridecyl Trialkylaluminum such as aluminum (Tridecylaluminum); Dialkylaluminum alkoxides such as dimethylaluminum methoxide, dimethylaluminum methoxide, and dibutylaluminum methoxide; Dialkylaluminum alkoxides such as dimethylaluminum chloride, diethylaluminum chloride, and dimethyliilumina chloride such as DDiieetthhyyllaalluummiinnuumm chloride and dibutylaluminum chloride; methylaluminum alkoxide; Alkylaluminum dialkoxide, such as Methylaluminum dimethoxide, Eth
- cocatalyst compound represented by Equation 8 is trimethylammonium tetrakis (pentafluorophenyl) borate (Trimethylammonium
- cocatalyst compound represented by Formula 8 may be di- (i-propyl) ammonium tetrakis (pentafluorophenyl) borate (di- (i-propyl) ammonium
- dialkylammoniums such as tetrakis (pentafluorophenyl) borate); Triphenylphosphonium tetrakis (pentafluorofluorophenyl) borate
- Trial 3 ⁇ 4 phosphonium such as tetrakis (pentafluorophenyl) borate), tri (2,6-dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate (Tri (2,6-dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate) ; Diphenyloxonium tetrakis (pentafluorofonyl) borate
- dialkyloxoniums such as tetrakis (pentafluororphenyl) borate), di (2,6-dimethylphenyloxonium tetrakis (pentafluorophenyl) borate) diphenylsulfonium such as di (2,6-dimethylphenyl oxonium tetrakis (pentafluorophenyl) borate); Phosphorus tetrakis (pentafluorophenyl) borate (diphenylsulfonium
- dialkylsulfoniums such as tetrakis (pentafluorophenyl) borate), bis (2,6-dimethylphenyl) sulfonium tetrakis (pentafluorophenyl) borate (bis (2,6-dimethylphenyl) sulfonium tetrakis (pentafluorophenyl) borate) ; And trophylium tetrakis (pentafluorophenyl) borate tetrakis (pentafluorophenyl) borate), triphenylmethyl carbenium tetrakis (pentafluorophenyl) borate (triphenylmethylcarbenium
- Carbonium salts such as benzene (diazonium) tetrakis (pentafluorophenyl) borate (benzene (diazonium) tetrakis (pentafluorophenyl) borate) and the like.
- R 61 is preferably methyl, ethyl, n-butyl or isobutyl;
- D is aluminum and R 71 is methyl or isobutyl, or D is boron and R 71 is pentafluorophenyl;
- [LH] + in Formula 8 is a dimethylanilinium cation, [Z (A) 4]-is [B (C 6 F 5 ) 4 ]-, and [L] + is [(C 6 H 5 ) 3 C] + is preferred.
- the addition amount of the promoter compound may be determined in consideration of the addition amount of the transition metal compound represented by the formula (1) and the amount required to fully activate the transition metal compound.
- the content of the promoter compound is 1: 1 to 100 based on the molar ratio of the metal contained in the promoter compound to 1 mol of the transition metal contained in the transition metal compound represented by Formula 1 above. 000, preferably 1: 1-10,000, more preferably 1: 1-50,000.
- the promoter compound represented by Chemical Formula 6 is 1: 1 1: 100,000, preferably 1: 5-50,000, and more preferably 1:10 20,000 of the transition metal compound represented by Chemical Formula 1 May be included in the molar ratio.
- the ratio of the transition metal compounds is 1: 1 to 100, preferably 1: 1 to 10, and more preferably 1 : 1 to 3 It can be included as a molar ratio of.
- aluminum may vary depending on the amount of water in the polymerization system, but 1: 1 to 1,000, preferably 1: 1 for the transition metal compounds. It may be included in a molar ratio of ⁇ 500, more preferably 1: 1-100.
- the cocatalyst compound represented by Formula 8 may be included in a molar ratio of 1: 1 to 100, preferably 1: 1 to 10, more preferably 1: 1 to 4 with respect to the transition metal compounds.
- the catalyst used in the production method of the present invention may be a transition metal compound represented by the formula (1), or the transition metal compound and the promoter compound supported on the carrier.
- the carrier of the inorganic or organic material used in the preparation of the catalyst in the technical field to which the present invention belongs may be used without limitation.
- the carrier is Si0 2 , A1 2 0 3 , MgO,
- the carrier includes a hydroxyl group on the surface, and may be one or more carriers selected from the group consisting of silica, silica-alumina, and salica-magnesia.
- the method for supporting the transition metal compound and the cocatalyst compound on the carrier as described above. Directly supporting the transition metal compound on a dehydrated carrier; A method of supporting the transition metal compound after pretreating the carrier with the promoter compound; A method of post-treatment with a cocatalyst compound after supporting the transition metal compound on the carrier; After reacting the transition metal compound and the cocatalyst compound, a method of adding a carrier and reacting the same may be used.
- Pentane Hexane, Heptane, Octane, Nonane, Decane
- Aliphatic hydrocarbon solvents such as Undecane and Dodecane
- Aromatic hydrocarbon solvents such as benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, and toluene
- Dichloromethane Trichloromethane, Dichloroethane, Halogenated aliphatic hydrocarbon solvents such as trichloroethane; Or combinations thereof.
- the process of supporting the transition metal compound and the cocatalyst compound on a carrier is carried out at a temperature of -70 to 200 V, preferably -50 to 150 ° C., more preferably 0 to 100 ° C. It is advantageous in terms of efficiency of the process.
- the method for producing an ellepin-diene copolymer according to the present invention includes the step of polymerizing at least one olefin monomer and at least one diene monomer in the presence of a catalyst as described above.
- the type of the olefin monomer and the diene monomer is not particularly limited, and monomers conventional in the art to which the present invention pertains may be used.
- the olefinic monomers are (C 2 -C 20 ) alpha-olefin ( ⁇ -Olefin), (C 3 -C 20 ) cycloolefin (Cyclo-olefin) or (C 3 C 20 ) cyclodiolefin (Cyclo-diolefm), substituted or unsubstituted styrene may be one or more selected from the group consisting of.
- the olefinic monomer is C 2 comprising ethylene (ethylene), propylene (Propylene), 1-butene (1-Butene), 1-pentene (1-Pentene) and 1-nuxene (1-Hexene) -C 20 alpha-olefin ( ⁇ -Olefm); C 3 including Cyclopentene, Cyclohexene, Cyclopentadiene, Cyclohexadiene, Norbonene and Methyl-2-Norbonene -C 20 cycloolefins or cyclodiolefins; Substituted Styrene in which an alkyl group, an alkoxy group, a halogen group, an amine group, a silyl group, a haloalkyl group, or the like is bonded to styrene or a phenyl ring of styrene; Or a combination thereof.
- C 2 comprising ethylene (ethylene), propylene
- the diene monomer may be a (C 4 -C 20 ) conjugated diene, (C 5 -C 20 ) aliphatic nonconjugated diene, (C 5 -C 20 ) cyclic nonconjugated diene and (C 6 -C 20 ) aromatic nonporous It may be at least one selected from the group consisting of liquid diene.
- the diene monomer is butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,2-dimethyl-1,3-butadiene, 1,4-dimethyl-1,3-butadiene, 1 -Ethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 1,3-nuxadiene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 3-methyl-1, C 4 -C 20 conjugated diene monomers such as 3-pentadiene, 2,4-dimethyl--pentadiene and 3-ethyl-1,3-pentadiene; 1,4-pentadiene, 1,4-nucleus Diene, 1,5-nuxadiene, 2-methyl-1,5-nuxadiene, 1,6-heptadiene, 6-methyl-1,5-heptadiene, 1,6-octadiene, 1,7-o
- 2,3-diisopropenylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propyl-2,5-norbornadiene C 6 -C 20 triene monomers such as, 1,3,7-octatriene and 1,4,9-decatriene may be used.
- the polymerization step may be performed in a slurry phase, a liquid phase, a gas phase, or a bulk phase.
- a solvent or an olefin monomer itself may be used as a medium.
- solvents usable in the polymerization step include butane (Butane), isobutane (Isobutane), pentane (Pentane), nucleic acid (Hexane), heptane (Octane), Nonane (Nonane), decane (Decane) Aliphatic hydrocarbon solvents such as Undecane, Dodecane, Cyclopentane, Methylcyclopentane and Cyclohexane; Benzene, Monochlorobenzene, Dichlorobenzene, Trichlorobenzene : Toluene : Xylene : Aromatic hydrocarbons such as chlorobenzene
- Dichloromethane Trichloromethane : Chloroethane, Dichloroethane : Halogenated aliphatic hydrocarbons such as Trichloroethane, 1,2-Dichloroethane, etc. menstruum; Or a combination thereof.
- the addition amount of the catalyst may be determined within the range in which the polymerization reaction of the monomer can occur in accordance with the slurry phase, liquid phase, gas phase or bulk process, and is not particularly limited.
- the addition amount of the catalyst is the transition per unit volume (L) of the monomer, based on the concentration of jeungsim metal (M) of the metal compound 10- 8 mol / L to 1 mol / L, preferably from 10 may be a 7 mol / L to about 10 "1 mol / L, more preferably from preferably from 10 ⁇ 7 mol / L to about 10 ⁇ 2 mol / L.
- the polymerization step may be performed in a batch type, semi-continuous type or continuous type reaction.
- the temperature and the output conditions of the polymerization step can be determined in consideration of the efficiency of the polymerization reaction according to the type of reaction and the type of reaction to be applied, it is not particularly limited.
- the polymerization step may be carried out at a temperature of -50 to 500 V, preferably 0 to 400 ° C, more preferably 0 to 300 ° C.
- the polymerization step may be carried out under a pressure of 1 to 3000 atm, preferably 1 to 1000 atm, more preferably 1 to 500 atm.
- the method for producing an olefin-diene copolymer according to the present invention by using the above-described catalyst, it is possible to easily control the fine structure of the copolymer, olefin having a high content of the diene comonomer, a large molecular weight and the desired physical properties -Diene copolymers can be prepared.
- the content ratio of the diene monomer to the olefin monomer polymerized to the olefin-diene copolymer is 1: 0.1 to 1:10, preferably 1: 0.1 to 1: 5, more preferably 1: 0.1 to May be 1: 1.
- the olefin-diene copolymer may have a weight average molecular weight (Mw) of 10,000 to 1,000,000, preferably 50,000 to 800,000, more preferably 50,000 to 500,000.
- the olefin-diene copolymer may have a molecular weight distribution (Mw / Mn) of 1 to 10, preferably 1.5 to 8, more preferably 1.5 to 6.
- the olefin-diene copolymer may have a density of 0.850 to 0.920 g / ml.
- the method for preparing a copolymer according to the present invention may be carried out in addition to the above-described steps, further comprising a step that can be conventionally performed in the art before or after the step, by the steps described above
- the manufacturing method of the invention is not limited.
- preferred embodiments are provided to help understanding of the present invention. However, the following examples are only for illustrating the present invention, and the present invention is not limited thereto.
- each compound is different in the type of substituents, and the type of each substituent is summarized in a table at the bottom of the compound (for example, the compound D-2 has the position of R a being hydrogen, R b and Means a compound in which the position of R c is substituted with a methyl group.).
- the Schlemk flask containing 1,2,3,4-tetrahydroquinoline (1.00 g, 7.51 mmol) and diethyl ether (16 mL) solution was immersed in a -78 ° C low temperature bath to lower the temperature, and then stirred n- Butyllithium (3.0 mL, 7.5 mmol, 2.5 M nucleic acid solution) was slowly injected under a nitrogen atmosphere. After stirring for about one hour at -78 ° C, the temperature was slowly raised to room temperature. A pale yellow solid precipitated and the butane gas produced was removed via a bubbler. The temperature was lowered back to -78 ° C and then carbon dioxide was injected.
- Tetrahydrofuran (0.60 g, 8.3 mmol) and t-butyllithium (4.9 mL, 8.3 mmol, 1.7 M pentane solution) were injected in turn under nitrogen atmosphere at -20 ° C and stirred for about 2 hours.
- a tetrahydrofuran solution (19 mL) in which lithium chloride and the compound Cl (1.06 g, 6.38 mmol) was dissolved was injected under a nitrogen atmosphere. After stirring for one hour at -20 ° C, the temperature was slowly raised to room temperature. After stirring for 1 hour at room temperature, water (15 mL) was injected to terminate the reaction. The solution was transferred to a separatory funnel to extract the organic layer.
- the extracted organic layer was placed in a separatory funnel again, and then hydrochloric acid (2N, 40 mL) was added thereto. After shaking for about 2 minutes, neutralized by slowly adding an aqueous sodium bicarbonate solution (60 mL). The organic layer was taken, moisture was removed with anhydrous magnesium sulfate, and then the solvent was removed to obtain a viscous substance.
- the compound was purified by silica gel column chromatography using a mixture of nucleic acid and ethyl acetate (Wv, 50: 1) to obtain 7 mg of compound (yield 43%).
- a precursor compound D-2 was synthesized under the same conditions and methods as in Example i-1, except that compound C-2 was used instead of compound C-1 (yield 53%).
- the transition metal compound E-2 was synthesized under the same conditions and methods as in Example ii-1 (yield 53%).
- Flammable D Flammable E-6 Methyllithium (1.63 g, 3.55 mmol, 1.6 M diethyl ether solution) was dissolved in -30 ° C at the temperature of compound D-4 (0.58 g, 1.79 mmol). Add dropwise to ether solution (10 mL). After stirring the solution at room temperature overnight, the temperature was lowered to -30 ° C., and then Ti (NMe 2 ) 2 Cl 2 (0.37 g, 1.79 mmol) was added all at once. The solution was stirred for 3 hours and then all solvents were removed using a vacuum pump. The resulting solid was dissolved in toluene (8 mL) and then Me 2 SiCl 2 (U6 g, 8.96 mmol) was added. The solution was stirred at 801: for 3 days and then the solvent was removed using a vacuum pump. A red solid compound was obtained (0.59 g, 75% yield). ⁇ In the NMR spectrum, two stereo compounds were found to be 2: 1.
- the molecular weight and molecular weight distribution of the polymer produced after the polymerization were GPC (Gel Permeation)
- the monomer content in the polymer was analyzed by FT-IR (Fourier Transform Infrared Spectrometer, device name: MAGNA-IR550 Spectrometer, manufacturer: Nicolet) and 13 C NMR (device name: Avance 400 Spectrometer, manufacturer: Bruker).
- High-pressure half unggi at room temperature After replacing the inside of the (inner volume 2L, stainless steel) with nitrogen, and the framework toluene methylaluminoxane 10 in 950 ml of methyl aluminoxane about 10 ml (to toluene weight 0/0 solution, A1 criteria 15 mmol, manufacturer: Albemarle) was added followed by 50 ml of 1,7-octadiene co-equivalent. Subsequently, a solution (2 ⁇ 1,7.5 ⁇ 0 1) in which the transition metal compound E-6 according to Example ii-6 was dissolved in toluene was injected. Thereafter, the temperature was increased to 70 ° C., ethylene gas was introduced, and polymerization reaction was performed for 30 minutes while maintaining the total pressure of 7.2 bar.
- a propylene-1,7-octadiene co-polymer (19.4 g) was obtained in the same conditions and methods as in Example iii-1, except that 100 g of propylene was used instead of ethylene as the olefin monomer.
- Example iii-3 Ethylene-propylene-1,7-octadiene terpolymer (15.9 g) was obtained in the same conditions and methods as in Example iii-1, except that 50 g of ethylene and 50 g of propylene were used as the olefin monomer.
- Example iii-1 Ethylene-propylene-dicyclopenta under the same conditions and methods as in Example iii-1, except that 50 g of ethylene and 50 g of propylene were used as olefinic monomers, and dicyclopentadiene was used instead of 1,7-octadiene. Diene terpolymer (54.3 g) was obtained.
- Example iii-1 Ethylene-propylene under the same conditions and methods as in Example iii-1, except that 50 g of ethylene and 50 g of propylene were used as olefinic monomers, and 5-vinyl-2-norbornene was used instead of 1,7-octadiene. -5-Vinyl-2-norbornene terpolymer (10.0 g) was obtained.
- Example iii except that 20 g of ethylene and 20 g of propylene were used as the olefin monomer, 5-vinyl-2-norbornene was used instead of 1,7-octadiene, and the polymerization temperature was adjusted to 180 ° C. Ethylene-propylene-5-vinyl-2-norbornene terpolymer (6.0 g) was obtained by the same conditions and methods as for -1. (Comparative Example iii-1)
- Example iii-1 except for using bisdendenylzirconium dichloride (Ind 2 ZrCl 2 , manufactured by Strem) instead of the transition metal compound E-6, under the same conditions and methods as in Example iii-1, Ethylene-1,7-octadiene copolymer (23.0 g) was obtained.
- bisdendenylzirconium dichloride Ind 2 ZrCl 2 , manufactured by Strem
- Example iii-5 With the same conditions and methods as in Example iii-5, except that bisdendenylzirconium dichloride (Ind 2 ZrCl 2 , manufactured by Strem) was used instead of the transition metal compound E-6 in Example iii-5. Ethylene-propylene-5-vinyl-2-norbornene terpolymer was obtained (7.0 g). TABLE i
- N.D. means no melting due to the properties of the polymer.
- Examples iii-1 to Example iii-6 are the present invention.
- the catalyst according to the high content of the comonomer it was confirmed that the olefin-diene copolymer having a high molecular weight can be prepared.
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US13/640,941 US8916662B2 (en) | 2010-04-12 | 2011-04-12 | Method for preparing olefin-diene copolymer using transition metal compound containing thiophene-fused cyclopentadienyl ligand |
CN2011800186857A CN102892797A (zh) | 2010-04-12 | 2011-04-12 | 使用包含噻吩稠合的环戊二烯基配体的过渡金属化合物制备烯烃-二烯共聚物的方法 |
EP11769060.2A EP2559714B1 (en) | 2010-04-12 | 2011-04-12 | Method for preparing olefin-diene copolymer using transition metal compound including thiophene-condensed ring cyclopentadienyl ligand |
CN201510072186.6A CN104672364A (zh) | 2010-04-12 | 2011-04-12 | 使用包含噻吩稠合的环戊二烯基配体的过渡金属化合物制备烯烃-二烯共聚物的方法 |
JP2013504821A JP5468708B2 (ja) | 2010-04-12 | 2011-04-12 | チオフェン−縮合環シクロペンタジエニルリガンドを含む遷移金属化合物を使用したオレフィン−ジエン共重合体の製造方法 |
CN201180018492.1A CN102844338B (zh) | 2010-04-12 | 2011-04-12 | 用于烯烃聚合的催化剂组合物以及利用该催化剂组合物的聚烯烃的制备方法 |
PCT/KR2011/002585 WO2011129594A2 (ko) | 2010-04-12 | 2011-04-12 | 티오펜-축합고리 사이클로펜타디에닐 리간드를 포함하는 전이금속 화합물을 사용한 올레핀-디엔 공중합체의 제조방법 |
ES11769060.2T ES2596719T3 (es) | 2010-04-12 | 2011-04-12 | 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 |
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KR10-2010-0057102 | 2010-06-16 | ||
PCT/KR2011/002585 WO2011129594A2 (ko) | 2010-04-12 | 2011-04-12 | 티오펜-축합고리 사이클로펜타디에닐 리간드를 포함하는 전이금속 화합물을 사용한 올레핀-디엔 공중합체의 제조방법 |
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JP5567209B2 (ja) * | 2010-04-12 | 2014-08-06 | ロッテ ケミカル コーポレーション | オレフィン重合用担持触媒およびこれを用いたポリオレフィンの製造方法 |
EP2559710B1 (en) | 2010-04-12 | 2016-07-13 | Lotte Chemical Corporation | Catalyst composition for polymerizing olefin and method for preparing polyolefin using same |
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KR101384450B1 (ko) | 2010-04-12 | 2014-04-25 | 롯데케미칼 주식회사 | 티오펜-축합고리 사이클로펜타디에닐 리간드를 포함하는 전이금속 화합물을 사용한 올레핀-디엔 공중합체의 제조방법 |
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2011
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- 2011-04-12 WO PCT/KR2011/002585 patent/WO2011129594A2/ko active Application Filing
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KR20080065868A (ko) | 2007-01-10 | 2008-07-15 | 주식회사 엘지화학 | 전이금속 화합물의 제조 방법, 상기 방법으로 제조된전이금속 화합물 및 상기 전이금속 화합물을 포함하는 촉매조성물 |
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Also Published As
Publication number | Publication date |
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CN102844338B (zh) | 2015-03-25 |
EP2559714A2 (en) | 2013-02-20 |
CN102892797A (zh) | 2013-01-23 |
ES2596719T3 (es) | 2017-01-11 |
CN102844338A (zh) | 2012-12-26 |
US20130211024A1 (en) | 2013-08-15 |
US8916662B2 (en) | 2014-12-23 |
JP2013528674A (ja) | 2013-07-11 |
CN104672364A (zh) | 2015-06-03 |
EP2559714A4 (en) | 2014-01-08 |
JP5468708B2 (ja) | 2014-04-09 |
WO2011129594A3 (ko) | 2012-03-29 |
EP2559714B1 (en) | 2016-08-10 |
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