CN104513280B - Bridged dinuclear metallocene compound for sPP (sPP), and preparation method and application thereof - Google Patents
Bridged dinuclear metallocene compound for sPP (sPP), and preparation method and application thereof Download PDFInfo
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- CN104513280B CN104513280B CN201410820139.0A CN201410820139A CN104513280B CN 104513280 B CN104513280 B CN 104513280B CN 201410820139 A CN201410820139 A CN 201410820139A CN 104513280 B CN104513280 B CN 104513280B
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- -1 methylene, ethyl Chemical group 0.000 claims abstract description 47
- 239000003446 ligand Substances 0.000 claims abstract description 26
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims abstract description 20
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000460 chlorine Substances 0.000 claims abstract description 14
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 13
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 13
- 239000004342 Benzoyl peroxide Substances 0.000 claims abstract description 9
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims abstract description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000019400 benzoyl peroxide Nutrition 0.000 claims abstract description 9
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 9
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 9
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 9
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 109
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 51
- 239000007787 solid Substances 0.000 claims description 42
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 238000001914 filtration Methods 0.000 claims description 32
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- 229910007928 ZrCl2 Inorganic materials 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 26
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 25
- 239000007789 gas Substances 0.000 claims description 24
- 238000001556 precipitation Methods 0.000 claims description 23
- 239000012074 organic phase Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 238000004440 column chromatography Methods 0.000 claims description 9
- 239000012071 phase Substances 0.000 claims description 8
- 229920002554 vinyl polymer Polymers 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 229910007932 ZrCl4 Inorganic materials 0.000 claims description 5
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 5
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 229910007926 ZrCl Inorganic materials 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 230000033228 biological regulation Effects 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 125000006285 dibromobenzyl group Chemical group 0.000 claims 1
- 125000003250 fulvenyl group Chemical class C1(=CC=CC1=C)* 0.000 claims 1
- 239000000725 suspension Substances 0.000 claims 1
- 238000010792 warming Methods 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 29
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 27
- 238000006116 polymerization reaction Methods 0.000 abstract description 21
- 239000003054 catalyst Substances 0.000 abstract description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 12
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 abstract description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 abstract 2
- XTCAGVVVEIJFON-UHFFFAOYSA-N 9h-fluorene;lithium Chemical compound [Li].C1=CC=C2CC3=CC=CC=C3C2=C1 XTCAGVVVEIJFON-UHFFFAOYSA-N 0.000 abstract 1
- MDQUTQCPJZOGGT-UHFFFAOYSA-N lithium;9h-fluoren-9-ide Chemical compound [Li+].C1=CC=C2C3=CC=CC=C3[CH-]C2=C1 MDQUTQCPJZOGGT-UHFFFAOYSA-N 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 229920000642 polymer Polymers 0.000 description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 22
- 230000015572 biosynthetic process Effects 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 238000003786 synthesis reaction Methods 0.000 description 16
- 239000006228 supernatant Substances 0.000 description 15
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 13
- 239000003426 co-catalyst Substances 0.000 description 12
- 150000001336 alkenes Chemical class 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 150000002220 fluorenes Chemical group 0.000 description 9
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 8
- 239000005977 Ethylene Substances 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 230000037048 polymerization activity Effects 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 7
- 229960000583 acetic acid Drugs 0.000 description 7
- 230000002378 acidificating effect Effects 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 238000000605 extraction Methods 0.000 description 7
- 238000007172 homogeneous catalysis Methods 0.000 description 7
- JAZNSOPOXXXZQO-UHFFFAOYSA-N [N].CCO Chemical compound [N].CCO JAZNSOPOXXXZQO-UHFFFAOYSA-N 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000005457 ice water Substances 0.000 description 5
- 210000003097 mucus Anatomy 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000012968 metallocene catalyst Substances 0.000 description 4
- PGTKVMVZBBZCKQ-UHFFFAOYSA-N Fulvene Chemical compound C=C1C=CC=C1 PGTKVMVZBBZCKQ-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 2
- BULLHRADHZGONG-UHFFFAOYSA-N [cyclopenta-2,4-dien-1-ylidene(phenyl)methyl]benzene Chemical compound C1=CC=CC1=C(C=1C=CC=CC=1)C1=CC=CC=C1 BULLHRADHZGONG-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- LCKDOHRDONNZTG-UHFFFAOYSA-N 1,2-dibromo-9h-fluorene Chemical class C1=CC=C2CC3=C(Br)C(Br)=CC=C3C2=C1 LCKDOHRDONNZTG-UHFFFAOYSA-N 0.000 description 1
- BCBKMEUFTPYMKQ-UHFFFAOYSA-N 1,2-dichloro-9h-fluorene Chemical class C1=CC=C2CC3=C(Cl)C(Cl)=CC=C3C2=C1 BCBKMEUFTPYMKQ-UHFFFAOYSA-N 0.000 description 1
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 1
- KKHFRAFPESRGGD-UHFFFAOYSA-N 1,3-dimethyl-7-[3-(n-methylanilino)propyl]purine-2,6-dione Chemical compound C1=NC=2N(C)C(=O)N(C)C(=O)C=2N1CCCN(C)C1=CC=CC=C1 KKHFRAFPESRGGD-UHFFFAOYSA-N 0.000 description 1
- UNILWMWFPHPYOR-KXEYIPSPSA-M 1-[6-[2-[3-[3-[3-[2-[2-[3-[[2-[2-[[(2r)-1-[[2-[[(2r)-1-[3-[2-[2-[3-[[2-(2-amino-2-oxoethoxy)acetyl]amino]propoxy]ethoxy]ethoxy]propylamino]-3-hydroxy-1-oxopropan-2-yl]amino]-2-oxoethyl]amino]-3-[(2r)-2,3-di(hexadecanoyloxy)propyl]sulfanyl-1-oxopropan-2-yl Chemical compound O=C1C(SCCC(=O)NCCCOCCOCCOCCCNC(=O)COCC(=O)N[C@@H](CSC[C@@H](COC(=O)CCCCCCCCCCCCCCC)OC(=O)CCCCCCCCCCCCCCC)C(=O)NCC(=O)N[C@H](CO)C(=O)NCCCOCCOCCOCCCNC(=O)COCC(N)=O)CC(=O)N1CCNC(=O)CCCCCN\1C2=CC=C(S([O-])(=O)=O)C=C2CC/1=C/C=C/C=C/C1=[N+](CC)C2=CC=C(S([O-])(=O)=O)C=C2C1 UNILWMWFPHPYOR-KXEYIPSPSA-M 0.000 description 1
- NPRYCHLHHVWLQZ-TURQNECASA-N 2-amino-9-[(2R,3S,4S,5R)-4-fluoro-3-hydroxy-5-(hydroxymethyl)oxolan-2-yl]-7-prop-2-ynylpurin-8-one Chemical compound NC1=NC=C2N(C(N(C2=N1)[C@@H]1O[C@@H]([C@H]([C@H]1O)F)CO)=O)CC#C NPRYCHLHHVWLQZ-TURQNECASA-N 0.000 description 1
- NVKDFGCILHNHRS-UHFFFAOYSA-N C1(C=CC=C1)[Au] Chemical compound C1(C=CC=C1)[Au] NVKDFGCILHNHRS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- ZMMRKRFMSDTOLV-UHFFFAOYSA-N cyclopenta-1,3-diene zirconium Chemical class [Zr].C1C=CC=C1.C1C=CC=C1 ZMMRKRFMSDTOLV-UHFFFAOYSA-N 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- BJXYHBKEQFQVES-NWDGAFQWSA-N enpatoran Chemical compound N[C@H]1CN(C[C@H](C1)C(F)(F)F)C1=C2C=CC=NC2=C(C=C1)C#N BJXYHBKEQFQVES-NWDGAFQWSA-N 0.000 description 1
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- DYGBNAYFDZEYBA-UHFFFAOYSA-N n-(cyclopropylmethyl)-2-[4-(4-methoxybenzoyl)piperidin-1-yl]-n-[(4-oxo-1,5,7,8-tetrahydropyrano[4,3-d]pyrimidin-2-yl)methyl]acetamide Chemical compound C1=CC(OC)=CC=C1C(=O)C1CCN(CC(=O)N(CC2CC2)CC=2NC(=O)C=3COCCC=3N=2)CC1 DYGBNAYFDZEYBA-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
-
- 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
- C08F10/04—Monomers containing three or four carbon atoms
- C08F10/06—Propene
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
Abstract
The invention provides a bridged dinuclear metallocene compound for sPP (sPP), and a preparation method and application thereof. The structure of the metallocene compound is shown as a formula I:wherein: r1Selected from hydrogen, methyl, methylene, ethyl and phenyl, R2Selected from hydrogen, tert-butyl, bromine and chlorine. The preparation method of the compound comprises the following steps: reacting p-xylene, N-bromosuccinimide and benzoyl peroxide to obtain p-dibromide benzyl; reacting a fulvene compound with a fluorene lithium compound to obtain a bridged fluorene lithium salt;reacting p-dibromide benzyl with bridged fluorecenocene lithium salt to obtain a ligand; and reacting the ligand with n-butyllithium and then zirconium tetrachloride to obtain the bridged dinuclear metallocene compound for sPP. The invention also provides the application of the metallocene compound as a catalyst for catalyzing propylene polymerization reaction.
Description
Technical field
The present invention relates to a kind of sPP bridged binuclear metallocene compounds and preparation method and application, belong to metallocene
Catalyst technical field.
Background technology
Since Fina companies in 1993 since liquid phase annular-pipe reactor scale up test goes out sPP, Basell,
The offshore company such as Huntsman, Dow, ExxonMobil company and Mitsui Dong Ya companies, light extraction petro-chemical corporation successively endeavours
In the exploitation of sPP.Current Fina companies and Basell, ExxonMobil, Japanese light extraction petro-chemical corporation have been achieved with the industry of sPP
Metaplasia is produced.
This monokaryon metallocene catalyst turns into the emphasis of scientists from all over the world's research, is catalyzed by the monokaryon of patent protection
Agent almost covers the various aspects of the research field, it is difficult to there is big original creativity.With certain abutment bridging type monokaryon
Metallocene compound is coupled together, and it is a brand-new research field to obtain doube bridge metallocene.
Alt,Helmut G(Helmut G.Alt,Rainer Ernst.Dinuclear ansa zirconocene
complexes as dual-site catalysts for the polymerization of ethylene[J]
.Journal of Molecular Catalysis A:The .11-27 of Chemical 195. (2003)) having synthesized bridged binuclear should
Catalyst, its structure as shown in Formula IV, for propylene polymerization, activity (93000kg mol-1h-1atm-1) than corresponding monokaryon cyclopentadienyl
Metallic catalyst Me2Si(2-Me-I-Ind)(2-Me-4-Ph-I-Ind)ZrCl2(LZrCl2=446000kg mol-1h-1atm-1) low, but the polyacrylic molecular weight for preparing increased, and atactic degree also increases (6.1wt%versus<0.2wt%
for LZrCl2)。
Afterwards, Alt (Deppner, M.Alkylidenverbr ü ckte, symmetrische, zweikernige
Metallocenkomplexe als Katalysatoren für die Propylenpolymerisation[J]
.Journal of organometallic chemistry.2005,690(12):2861-2871.) have also been made and grind accordingly
Study carefully, synthesized the asymmetric binuclear metallocene catalyst of carbon bridging of different length, such as compound of the structure as shown in Formula VII.
When carbon bridge length is less than 5 carbon atoms, the molecular weight distribution (MWD wider of resulting polymers>10).Found in propylene polymerization,
It is full 9-11% with isotacticity that gained is polyacrylic.
Stephan Jungling(Jüngling,S.,R.Müllhaupt and H.Plenio.Cooperative
effects in binuclear zirconocenes:their synthesis and use as catalyst in
propene polym-erization[J].Journal of organometallic chemistry.1993,460(2):
A series of benzene bridged binuclear Zirconocenes, such as compound of the structure as shown in Formula VIII 191-195.) are synthesized.With monokaryon
Catalyst system and catalyzing is compared, and catalysis propylene polymerization activity reduces (2.6 × 105GPP/mol Zr h, monokaryon catalyst system and catalyzing be 3 ×
105GPP/mol Zr h), molecular weight reduction (GPC：Mn=2200g/mol, monokaryon catalyst system and catalyzing Mn=3400g/mol).And
And, with monokaryon catalyst system and catalyzing conversely, with the increase of AI/Zr ratios, molecular weight reduction.
Sierra(Cano Sierra,J.Formation of Dinuclear Titanium and Zirconium
Complexes by Olefin Metathesis-Catalytic Preparation of Organometallic
Catalyst Systems[J].Chemistry-A European Journal.2003,9(15):The synthesis such as 3618-3622.)
Dinuclear catalyst, its structure as shown in Formula IX, the catalyst vinyl polymerization, under the room temperature (25 DEG C), activity is at a fairly low,
When temperature is 60 DEG C, activity is very high, is catalyzed propylene polymerization, and at room temperature (25 DEG C) and 60 DEG C, activity is mean level, molecular weight
It is at a fairly low, at room temperature, 36% isotactic polypropylene can be obtained, at 60 DEG C, obtain 12% random polypropylene.
It can be seen that, the research of doube bridge metallocene has turned into the research core of this area, develops new bridged binuclear cyclopentadienyl gold
Category compound is still one of this area problem demanding prompt solution.
The content of the invention
In order to solve the above technical problems, present invention aim at provide a kind of sPP bridged binuclear metallocene compound and
Its preparation method and application.The bridged binuclear metallocene compound that the present invention is provided is high as the activity of catalyst, can be used in
Catalysis propylene polymerization.
To reach above-mentioned purpose, the present invention provides a kind of sPP bridged binuclear metallocene compounds, its structure such as Formulas I institute
Show：
Wherein：R1Selected from hydrogen (H), methyl (- CH3), methylene (- C2H5), ethylWith phenyl (-
C6H5), R2Selected from hydrogen, the tert-butyl group (tBu), bromine (Br) and chlorine (Cl).
Specific embodiment of the invention, it is preferable that above-mentioned sPP with bridged binuclear metallocene compound include but
It is not limited to：
[(CH3)2C(C5H3)(C13H8)ZrCl2]2(CH2C6H4CH2)、
[(C6H5)2C(C5H3)(C13H8)ZrCl2]2(CH2C6H4CH2)、
[(CH2)5C(C5H3)(C13H8)ZrCl2]2(CH2C6H4CH2)、
[(CH3)2C(C5H3)((tBu)2C13H6)ZrCl2]2(CH2C6H4CH2)、
[(C6H5)2C(C5H3)((tBu)2C13H6)ZrCl2]2(CH2C6H4CH2)、
[(CH2)5C(C5H3)(Cl2C13H6)ZrCl2]2(CH2C6H4CH2) and
[(CH3)2C(C5H3)(Br2C13H6)ZrCl2]2(CH2C6H4CH2)。
The present invention introduces methyl, methylene, ethyl, phenyl on the carbon abutment of the luxuriant ring of connection and fluorenes ring, draws on fluorenyl
Enter the tert-butyl group, bromine, chlorine, obtain a series of bridged binuclear metallocene compound, it is possible to increase complex compound yield, should using
During compound for catalysis propylene polymerization, activity is higher, and a normality is also higher.
Bridged binuclear metallocene compound of the invention steric configuration stabilization, connection Cp (cyclopentadienyl) and
The C atoms of Flu (fluorenyl) limit the rotation of luxuriant ring, if not having C bridgings between Cp and Flu, luxuriant ring can be rotated freely, made
Do not fixed into central metal surrounding space configuration, after bridging, the steric configuration of luxuriant ring is just relatively fixed；Connected with to dibenzyl
Two Cp bridges, just make its steric configuration more stablize, and form the constrained geometry configuration metallocene compound of carbon bridging, are conducive to
Propylene Selectivity is polymerized.
On the other hand, the present invention also provides a kind of preparation method of above-mentioned sPP bridged binuclear metallocene compounds, its
Comprise the following steps：
(1) react paraxylene, N- bromo-succinimides (NBS) and benzoyl peroxide (BPO), to prepare
To cyclite；
(2) rich vinyl compound is made to be reacted with fluorenes lithium class compound, to prepare bridging fluorenes cyclopentadienyl lithium salts；
The structure of the rich vinyl compound as shown in Formula II,
Wherein：R1Hydrogen, methyl, methylene, ethyl and phenyl.
The structure of the fluorenes lithium class compound as shown in formula III,
Wherein, R2Hydrogen, methyl, methylene, ethyl and phenyl.
(3) the bridging fluorenes cyclopentadienyl lithium salts obtained to cyclite and step (2) for obtaining step (1) reacts, to prepare
Ligand L；
The structure of the ligand L is as shown in formula IV：
Wherein：R1Selected from hydrogen, methyl, methylene, ethyl and phenyl, R2Selected from hydrogen, the tert-butyl group, bromine and chlorine.
(4) make ligand L and n-BuLi (nBuLi) reaction obtains four lithium salts, then is reacted with zirconium chloride, to prepare
Described sPP bridged binuclear metallocene compounds.
In above-mentioned preparation method, it is preferable that step (1) includes：At argon gas protection and 70 DEG C to 90 DEG C, with four
Chlorination carbon is solvent, makes paraxylene, N- bromo-succinimides and benzoyl peroxide back flow reaction 10-30 hours, wherein
The mass ratio of paraxylene, N- bromo-succinimides and benzoyl peroxide is 5.04：30：2, it is subsequently cooled to 0 DEG C to 40
DEG C, filtrate is taken after filtering, after being placed 10-24 hours at -40 DEG C to -20 DEG C, white crystal is separated out, as to cyclite.
In above-mentioned preparation method, it is preferable that step (2) includes：At -40 to 10 DEG C, by rich vinyl compound
Diethyl ether solution was added drop-wise in the diethyl ether solution of fluorenes lithium class compound in 10 minutes to 30 minutes, wherein rich vinyl compound and fluorenes
The mol ratio of lithium class compound is 1：1 to 1.3：1, after (about reacting 8 hours) to be precipitated occurs, then react 10 to 30 hours, point
Separate out lower floor's solid (preferably being separated using press filtration), wash (preferably being washed twice using ether, hexane washed once) and
After draining, pale pink solid, as bridging fluorenes cyclopentadienyl lithium salts are obtained.
In above-mentioned preparation method, it is preferable that step (3) includes：At -40 DEG C to 0 DEG C, step (1) is obtained
Tetrahydrofuran (THF) solution to cyclite was added drop-wise to the bridging fluorenes cyclopentadienyl lithium salts that step (2) is obtained in 10 minutes to 30 minutes
Tetrahydrofuran solution in, wherein, to cyclite and bridging fluorenes cyclopentadienyl lithium salts mol ratio be 1：1 to 1：2.2, then rise to naturally
30 DEG C, reaction adds dilute acid soln to be hydrolyzed for 30 to 50 hours afterwards, and regulation pH value divides liquid to neutral (preferably using acetic acid)
After take organic phase, water ether extraction (extraction times can be for twice) then merges with organic phase, then it is scrubbed (preferably
Using saturated common salt water washing), dry (preferably using anhydrous magnesium sulfate dry 6 hours), filtering, removal solvent and (preferably use
Vacuum rotation is except solvent or removed under reduced pressure solvent), after column chromatography for separation, obtain mucus, as ligand L.
In above-mentioned preparation method, it is preferable that step (4) includes：At -40 DEG C to 0 DEG C, in the tetrahydrochysene furan of ligand L
Mutter and the hexane solution of n-BuLi is added in solution, wherein ligand L and the mol ratio of n-BuLi is 1：4 to 1：5, Ran Housheng
Temperature is reacted 20-60 hours to 25 DEG C to 50 DEG C, and the solid obtained after separation is suspended with tetrahydrofuran, then at -80 DEG C to -70
At DEG C, ZrCl is added42THF, wherein ligand L and ZrCl4The mol ratio of 2THF is 1：1.8 to 1：2, it is warmed up to 20 DEG C to 30
DEG C, react 40-60 hour, then remove solvent (preferably use and drain), with dichloromethane extraction (extraction time can be two
It is secondary), concentration, add n-hexane, then crystallization obtains solid at -40 DEG C to -20 DEG C, as described sPP bridgings pair
Core metallocene compound.
In above-mentioned preparation method, it is preferable that the fluorenes lithium class compound is prepared by the following method and obtains：
At -10 DEG C to 20 DEG C, in the presence of an organic, n-BuLi is added drop-wise in compound of fluorene class, wherein n-BuLi with
The mol ratio of compound of fluorene class is 1：1 to 1.2：1,21 DEG C to 30 DEG C, after stirring reaction 10-20 hours are then risen to naturally, Gu
Liquid is separated (preferably using press filtration), solid scrubbed (preferably being washed twice using n-hexane), drain after, obtain described fluorenes lithium
Class compound, wherein, the structure of the compound of fluorene class is shown as a formula V：
Wherein, R2Selected from hydrogen, the tert-butyl group, bromine and chlorine.
On the other hand, the present invention also provides above-mentioned sPP bridged binuclear metallocene compounds in propylene polymerization
As the application of catalyst.
In the applications described above, it is preferable that sPP bridged binuclear metallocene compounds are used as major catalyst, methyl
Aikyiaiurnirsoxan beta (MAO) is 500 to 2000 with the amount ratio of co-catalyst as co-catalyst, major catalyst.
In the applications described above, the propylene polymerization can be carried out in accordance with the following methods：For example, being in propylene pressure
Under 0.1MPa, with toluene as solvent, the toluene solution with bridged binuclear metallocene compound, co-catalyst containing sPP are added
MAO, in the 0.5 hour reaction time at 0 DEG C of reaction temperature, is catalyzed propylene polymerization.
The present invention uses bridged binuclear metallocene catalyst/MAO systems, under the effect of minor proportion co-catalyst, to third
Alkene polymerization obtains normality between greater activity, polymer and reaches more than 80%.
In sum, the sPP that the present invention is provided is simple with the synthetic route of bridged binuclear metallocene compound, product yield
Height, isolates and purifies easily, needs co-catalyst few for being catalyzed during propylene polymerization, and catalysis activity is high, and normality is high between polymer.
Specific embodiment
In order to be more clearly understood to technical characteristic of the invention, purpose and beneficial effect, now to skill of the invention
Art scheme carry out it is described further below, but it is not intended that to it is of the invention can practical range restriction.
Embodiment 1
[(the CH of ligand L 13)2C(C5H4)(C13H9)]2(CH2C6H4CH2) synthesis
[(the CH of ligand L 13)2C(C5H4)(C13H9)]2(CH2C6H4CH2) synthetic route it is as follows:
Argon gas protection under, with carbon tetrachloride as solvent, by paraxylene (5.04g, 47.53mmol), NBS (30g) and
BPO (2g) reacts in being added to bottle, heating, and when being heated to 70 DEG C, solid and liquid in bottle start melting, after stabilization, after
Continuous heating, to 80 DEG C, back flow reaction 20 hours cools, and there is white solid on upper strata, and the pale yellow clear liquid of lower floor is cooled to 40 DEG C,
Filtering, takes filtrate, is put into refrigerator, after 24h, precipitation white crystal, and about 5g, as to cyclite, yield 40%.
Fluorenes (10g, 60.24mmol), n-hexane 100mL, ether 20mL are added in 200mL Schlenk bottles, at 0 DEG C, slowly
It is slow to be added dropwisenBuLi (36.7mL, 1.64mol/L), has precipitation to generate immediately.Naturally it is warmed to room temperature, stirring reaction is quiet to 20 hours
Put, press filtration removes supernatant, solid n-hexane is washed 2 times.Drain to obtain yellow solid powder 8g, as fluorenes lithium, yield
86.7%.
0 DEG C, ether (40mL) solution of 6,6- dimethyl fulvenes (5.11g, 48.18mmol) is added drop-wise to fluorenes lithium
(FluLi) in ether (80mL) solution of (8g, 48.18mmol), there is precipitation to occur after 8h, continue 20 hours amounts of having of reaction and sink
Form sediment and generate, press filtration, solid ether is washed twice, washed once with hexane, drains, and obtains solid 9.18g, i.e. yield 70%.
Above-mentioned bridging fluorenes cyclopentadienyl lithium salts (15.19mmol) of 4.3g is dissolved in 50mLTHF, and yellow is general red, under ice bath, slowly drips
Plus to THF (40mL) solution (pale yellow) of cyclite (2.01g, 7.59mmol), be warmed to room temperature naturally, afterwards, color somewhat adds
Deep, dark red partially yellow, to neutrality, point liquid takes organic phase to 40 hours vinegar acid for adjusting pH of stirring reaction, and water phase ether is extracted twice, and closes
And organic phase, saturated common salt water washing, anhydrous magnesium sulfate dries 6h, filters, and vacuum rotation removes solvent, and column chromatography for separation obtains 1.47g
Mucus, as ligand L 1, yield 30%.
[(the CH of complex compound 13)2C(C5H3)(C13H8)ZrCl2]2(CH2C6H4CH2) synthesis
0 DEG C of condition, BuLi (8mmol) is added drop-wise in the diethyl ether solution of ligand L 1 (1.29g, 2mmol), has solid to generate,
Heating response removes supernatant liquor after 40 hours, solid is drained with ether, obtains solid 1.12g, plus tetrahydrofuran, liquid nitrogen ethanol
Under the conditions of -78 DEG C of bath, ZrCl is added42THF (1.26g, 3.34mmol), is warmed to room temperature naturally, reacts 50 hours, in elimination
Layer clear liquid, removal of solvent under reduced pressure, solid is extracted twice (30mL × 2) with dichloromethane, is concentrated into 20mL, adds n-hexane to adjust pole
Property, put in -20 DEG C of refrigerators, yellow substance is separated out, press filtration removes supernatant, and precipitation is drained, and obtains yellow powder 547mg, as network
Compound 1, yield 34%.Fusing point：210 DEG C of decomposition.1H NMR (δ, ppm, DCCl3, 400MHz)：7.65-7.67(m,4H,ArH),
7.28-7.30(m,8H,ArH),7.12-7.14(m,8H,ArH),7.09-7.15(m,4H,CpH),7.01(s,2H,CpH),
3.05(s,4H,ArCH2,),1.18(s,12H,CH3), it was demonstrated that prepare complex compound 1 really.
Homogeneous catalysis propylene polymerization under normal pressure
To have magnetic stir bar, wireway 100mL there-necked flasks ethylene gas replace 3 times, under nitrogen protection, successively
Toluene 50mL, co-catalyst MAO 2.5mL (1.60M) [Al/M=1000], 2.0 μm of ol complex compounds 1 is added to be passed through third under normal pressure
Alkene gas, starts polymerisation at 0 DEG C, and stirring reaction 30min closes propylene gas cylinder, terminates anti-with 10% acidic alcohol
Should, polymer is transferred in beaker, is stood overnight, and is filtered and with the abundant washing copolymer of ethanol, and perseverance is dried under vacuum at 80 DEG C
Weight, weighs polymer quality 4.2g, polymerization activity 2.1 × 106Gpolymer/molMh, removes random thing laggard with dimethylbenzene
Row from13C NMR are characterized, and calculating learns, normality is up to 85% between the rrrr of resulting polymer.
Embodiment 2
[(the C of ligand L 26H5)2C(C5H4)(C13H9)]2(CH2C6H4CH2) synthesis
Under the conditions of 0 DEG C, ether (40mL) solution of 6,6- diphenyl fulvene (11.08g, 48.18mmol) is added drop-wise to
In ether (80mL) solution of FluLi (8g, 48.18mmol), there is precipitation to occur after 8 hours, reaction is largely precipitated after 20 hours
Generation, press filtration removes solvent, and solid ether is washed twice, washed once with hexane, drains, and obtains solid 12.41g, yield 65%.
The above-mentioned lithium salts (15.19mmol) of 6.18g is dissolved in 50mLTHF, and yellow is general red, under ice bath, is slowly added dropwise to two
THF (40mL) solution (pale yellow) of bromine Bian (2.01g, 7.59mmol), is warmed to room temperature naturally, and solution colour somewhat adds afterwards
It is deep, it is dark red partially yellow, react two days.Hydrolysis acetic acid adjusts ph to neutrality, and point liquid takes organic phase, and water phase ether is extracted twice, and closes
And organic phase, saturated common salt water washing, anhydrous magnesium sulfate dries 6h, filters, and vacuum rotation removes solvent, and column chromatography for separation obtains 2.31g
Mucus, yield 34%.
[(the C of complex compound 26H5)2C(C5H3)(C13H8)ZrCl2]2(CH2C6H4CH2) synthesis
Under the conditions of ice-water bath,nBuLi (8mmol) is added drop-wise in the diethyl ether solution of ligand L 2 (1.788g, 2mmol), there is solid
Body is generated, and is flowed back anti-40 hours, and supernatant liquor is removed in press filtration, is washed once with ether, is drained, and obtains solid 1.62g, plus tetrahydrochysene furan
Mutter, liquid nitrogen ethanol bath under the conditions of -78 DEG C, adds ZrCl42THF (1.33g, 3.53mmol), is warmed to room temperature naturally, reaction 40
Hour, reaction solution is yellow, and removal of solvent under reduced pressure, dichloromethane is extracted twice (30mL × 2), is concentrated into 20mL, plus n-hexane
Polarity is adjusted, is put in -20 DEG C of refrigerators, separate out yellow substance, press filtration removes supernatant, and precipitation is drained, and obtains yellow powder 640mg, receives
Rate 30%.240 DEG C of decomposition of fusing point.1H NMR (δ, ppm, DCCl3, 400MHz)：7.55-7.47(m,8H,ArH),7.31-7.21
(m,8H,ArH),7.16-7.10(m,4H,ArH),7.05(s,20H,ArH),7.00-6.92(m,4H,CpH),6.6(s,2H,
CpH), 3.03 (s, 4H, ArCH2), it was demonstrated that prepare complex compound 2 really.
Homogeneous catalysis propylene polymerization under normal pressure
To have magnetic stir bar, wireway 100mL there-necked flasks ethylene gas replace 3 times, under nitrogen protection, successively
Toluene 50mL, co-catalyst MAO 2.5mL (1.60M) [Al/M=1000], 2.0 μm of ol complex compounds 2 is added to be passed through third under normal pressure
Alkene gas, starts polymerisation at 0 DEG C, and stirring reaction 30min closes propylene gas cylinder, terminates anti-with 10% acidic alcohol
Should, polymer is transferred in beaker, is stood overnight, and is filtered and with the abundant washing copolymer of ethanol, and perseverance is dried under vacuum at 80 DEG C
Weight, weighs polymer quality 3.0g, polymerization activity 1.5 × 106Gpolymer/molMh, removes random thing laggard with dimethylbenzene
Row from13C NMR are characterized, and calculating learns, normality is up to 84% between the rrrr of resulting polymer.
Embodiment 3
[(the CH of ligand L 32)5C(C5H4)(C13H9)]2(CH2C6H4CH2) synthesis
Under ice bath, ether (40mL) solution of 6,6- pentamethylenes fulvene (8.89g, 48.18mmol) is added drop-wise to FluLi
In ether (80mL) solution of (8g, 48.18mmol), generation is not precipitated during dropwise addition, after about 8h, there is precipitation to occur, reaction
A large amount of precipitation generations after 20 hours, press filtration, solid ether is washed twice, washed once with hexane, drains, and obtains solid 11.49g, is produced
Rate 68%.
The above-mentioned lithium salts (15.19mmol) of 4.91g is dissolved in 50mLTHF, and yellow is general red, under ice bath, is slowly added dropwise to two
THF (40mL) solution (pale yellow) of bromine Bian (2.01g, 7.59mmol), after being warmed to room temperature naturally, color is somewhat deepened,
It is dark red partially yellow, react 40 hours.Hydrolysis, to neutrality, point liquid takes organic phase to vinegar acid for adjusting pH, and water phase ether is extracted twice, and merges
Organic phase, saturated common salt water washing, anhydrous magnesium sulfate dries 6h, filtering, and decompression removes solvent, and column chromatography for separation obtains 1.54g and glues
Liquid, yield 28%.
[(the CH of complex compound 32)5C(C5H3)(C13H8)ZrCl2]2(CH2C6H4CH2) synthesis
Under the conditions of ice-water bath,nBuLi (8mmol) is added drop-wise in the diethyl ether solution of part (1.45g, 2mmol), has solid to give birth to
Into supernatant liquor is removed in back flow reaction two days, press filtration, is washed once with ether, is drained, and obtains solid 1.32g, plus tetrahydrofuran, liquid
Nitrogen ethanol bath, under the conditions of -78 DEG C, adds ZrCl42THF (1.33g, 3.52mmol), is warmed to room temperature naturally, reaction 2 days, instead
Answer liquid for yellow, removal of solvent under reduced pressure, dichloromethane is extracted twice (30mL × 2), be concentrated into 20mL, plus some n-hexanes adjust pole
Property, put in -20 DEG C of refrigerators, yellow substance is separated out, press filtration removes supernatant, and precipitation is drained, and obtains yellow powder 476mg, yield
26%.Fusing point：270 DEG C of decomposition.1H NMR (δ, ppm, DCCl3, 400MHz)：7.66-7.68(m,4H,ArH),7.29-7.31
(m,8H,ArH),7.17-7.20(m,8H,ArH),7.10-7.15(m,4H,CpH),7.03(s,2H,CpH),3.04(s,4H,
ArCH2,),0.80-0.83(m,6H,CH2),1.12-1.19(m,8H,CH2),1.48-1.49(m,6H,CH2), it was demonstrated that make really
It is standby to have obtained complex compound 3.
Homogeneous catalysis propylene polymerization under normal pressure
To have magnetic stir bar, wireway 100mL there-necked flasks ethylene gas replace 3 times, under nitrogen protection, successively
Toluene 50mL, co-catalyst MAO 2.5mL (1.60M) [Al/M=1000], 2.0 μm of ol complex compounds 3 is added to be passed through third under normal pressure
Alkene gas, starts polymerisation at 0 DEG C, and stirring reaction 30min closes propylene gas cylinder, terminates anti-with 10% acidic alcohol
Should, polymer is transferred in beaker, is stood overnight, and is filtered and with the abundant washing copolymer of ethanol, and perseverance is dried under vacuum at 80 DEG C
Weight, weighs polymer quality 2.2g, polymerization activity 1.1 × 106Gpolymer/molMh, removes random thing laggard with dimethylbenzene
Row from13C NMR are characterized, and calculating learns, normality is up to 82% between the rrrr of resulting polymer.
Embodiment 4
[(the CH of ligand L 43)2C(C5H4)((tBu)2C13H7)]2(CH2C6H4CH2) synthesis
Under ice bath, ether (40mL) solution of 6,6- dimethyl fulvenes (5.11g, 48.18mmol) is added drop-wise to 2,7- bis-
In ether (80mL) solution of tert-butyl group fluorenes lithium (13.39g, 48.18mmol), generation is not precipitated during dropwise addition, after about 8h, had
Precipitation occurs, the next morning, and a large amount of precipitation generations, press filtration, solid ether is washed twice, washed once with hexane, drain, must consolidate
Body 14.57g, yield 70%.
The above-mentioned lithium salts (15.19mmol) of 6.5g is dissolved in 50mLTHF, and yellow is general red, under ice bath, is slowly added drop-wise to dibromo
THF (40mL) solution (pale yellow) of Bian (2.01g, 7.59mmol), does not have significant change, is warmed to room temperature naturally, and afterwards, color is slightly
It is micro- to deepen a little, it is dark red partially yellow, react two days.Hydrolysis, to neutrality, point liquid takes organic phase, the extraction of water phase ether to vinegar acid for adjusting pH
Twice, merge organic phase, saturated common salt water washing, anhydrous magnesium sulfate dries 6h, filter, vacuum is revolved and removes solvent, column chromatography for separation,
Obtain 2.06g, yield 28%.
[(the CH of complex compound 43)2C(C5H3)((tBu)2C13H6)ZrCl2]2(CH2C6H4CH2) synthesis
Under the conditions of 0 DEG C,nBuLi (8mmol) is added drop-wise in the diethyl ether solution of part (1.93g, 2mmol), has solid to generate,
Supernatant liquor is removed in back flow reaction two days, press filtration, is washed once with ether, is drained, and obtains solid 1.72g, plus tetrahydrofuran, liquid nitrogen second
Alcohol is bathed, and under the conditions of -78 DEG C, adds ZrCl22THF (1.310g, 3.47mmol), is warmed to room temperature naturally, reacts 2 days, reaction solution
It is yellow, removal of solvent under reduced pressure, dichloromethane is extracted twice (30mL × 2), is concentrated into 20mL, plus some n-hexanes adjust polarity,
Put in -20 DEG C of refrigerators, separate out yellow substance, press filtration removes supernatant, and precipitation is drained, and obtains yellow powder 624mg, yield 28%.1H NMR (δ, ppm, DCCl3, 400MHz)：7.71(s,4H,ArH),7.65-7.60(m,4H,ArH),7.43-7.39(m,4H,
ArH),7.14-7.11(m,4H,ArH),6.93-6.87(m,4H,CpH),6.81-6.85(s,2H,CpH),3.04(s,4H,
ArCH2,),1.29(s,1.10(s,12H,CpCH3).1.14(s,36H,-CMe3), it was demonstrated that prepare complex compound 4 really.
Homogeneous catalysis propylene polymerization under normal pressure
To have magnetic stir bar, wireway 100mL there-necked flasks ethylene gas replace 3 times, under nitrogen protection, successively
Toluene 50mL, co-catalyst MAO2.5mL (1.60M) [Al/M=1000], 2.0 μm of ol complex compounds 4 is added to be passed through third under normal pressure
Alkene gas, starts polymerisation at 0 DEG C, and stirring reaction 30min closes propylene gas cylinder, terminates anti-with 10% acidic alcohol
Should, polymer is transferred in beaker, is stood overnight, and is filtered and with the abundant washing copolymer of ethanol, and perseverance is dried under vacuum at 80 DEG C
Weight, weighs polymer quality 5.0g, polymerization activity 2.5 × 106Gpolymer/molMh, removes random thing laggard with dimethylbenzene
Row from13C NMR are characterized, and calculating learns, normality is up to 82% between the rrrr of resulting polymer.
Embodiment 5
[(the C of ligand L 56H5)2C(C5H4)((tBu)2C13H7)]2(CH2C6H4CH2) synthesis
Under condition of ice bath, ether (40mL) solution of 6,6- diphenyl fulvene (11.08g, 48.18mmol) is added drop-wise to 2,
In ether (80mL) solution of 7- di-tert-butyl-fluorenes lithium (13.39g, 48.18mmol), after 8h, there is precipitation to occur, continue to react
After 20 hours, a large amount of precipitation generations, press filtration, solid ether is washed twice, washed once with hexane, drains, and obtains solid 9.18g, is received
Rate 70%.
The above-mentioned lithium salts (15.19mmol) of 7.88g is dissolved in 50mLTHF, and yellow is general red, under ice bath, is slowly added dropwise to two
THF (40mL) solution (pale yellow) of bromine Bian (2.01g, 7.59mmol), after being warmed to room temperature naturally, color is somewhat deepened,
It is dark red partially yellow, react 40 hours.Hydrolysis, to neutrality, point liquid takes organic phase to vinegar acid for adjusting pH, and water phase ether is extracted twice, and merges
Organic phase, saturated common salt water washing, anhydrous magnesium sulfate dries 6h, filtering, and vacuum rotation removes solvent, and column chromatography for separation obtains 2.55g and glues
Liquid, yield 30%.
[(the C of complex compound 56H5)2C(C5H3)((tBu)2C13H6)ZrCl2]2(CH2C6H4CH2) synthesis
Under the conditions of ice-water bath,nBuLi (8mmol) is added drop-wise in the diethyl ether solution of part (2.24g, 2mmol), has solid to give birth to
Into supernatant liquor is removed in back flow reaction 45 hours, press filtration, and precipitation ether is washed once, drained, and obtains solid 2.04g, plus tetrahydrochysene furan
Mutter, liquid nitrogen ethanol bath under the conditions of -48 DEG C, adds ZrCl22THF (1.347g, 3.57mmol), is warmed to room temperature naturally, reaction 2
My god, reaction solution is yellow, and removal of solvent under reduced pressure, dichloromethane is extracted twice (30mL × 2), is concentrated into 20mL, plus n-hexane is adjusted
Polarity, puts in -20 DEG C of refrigerators, separates out yellow substance, and press filtration removes supernatant, and precipitation is drained, and obtains yellow powder 740mg, yield
29%.1H NMR (δ, ppm, DCCl3, 400MHz)：7.68(s,4H,ArH),7.605-7.55(m,4H,ArH),7.40-7.34
(m,4H,ArH),7.11-7.07(m,4H,ArH),7.03(s,20H,ArH),6.91-6.80(m,4H,CpH),6.56(s,2H,
CpH), 3.07 (s, 4H, ArCH2),1.15(s,36H,CMe3), it was demonstrated that prepare complex compound 5 really.
Homogeneous catalysis propylene polymerization under normal pressure
To have magnetic stir bar, wireway 100mL there-necked flasks ethylene gas replace 3 times, under nitrogen protection, successively
Toluene 50mL, co-catalyst MAO 2.5mL (1.60M) [Al/M=1000], 2.0 μm of ol complex compounds 5 is added to be passed through third under normal pressure
Alkene gas, starts polymerisation at 0 DEG C, and stirring reaction 30min closes propylene gas cylinder, terminates anti-with 10% acidic alcohol
Should, polymer is transferred in beaker, is stood overnight, and is filtered and with the abundant washing copolymer of ethanol, and perseverance is dried under vacuum at 80 DEG C
Weight, weighs polymer quality 5.6g, polymerization activity 2.8 × 106Gpolymer/molMh, removes random thing laggard with dimethylbenzene
Row from13C NMR are characterized, and calculating learns, normality is up to 81% between the rrrr of resulting polymer.
Embodiment 6
[(the CH of ligand L 62)5C(C5H4)(Cl2C13H7)]2(CH2C6H4CH2) synthesis
Under ice bath, ether (40mL) solution of 6,6- pentamethylenes fulvene (8.89g, 48.18mmol) is added drop-wise to 2,7-
In ether (80mL) solution of dichloro fluorenes (11.18g, 48.18mmol), precipitation occurs slowly, a large amount of precipitation lifes after 24 hours
Into press filtration, solid ether is washed twice, is washed once with hexane, is drained, and obtains solid 11.49g, yield 68%.
The above-mentioned lithium salts (15.19mmol) of 5.94g is dissolved in 50mLTHF, and yellow is general red, under ice bath, is slowly added dropwise to two
THF (40mL) solution (pale yellow) of bromine Bian (2.01g, 7.59mmol), is warmed to room temperature naturally, reacts 50 hours afterwards.Hydrolysis, vinegar
To neutrality, point liquid takes organic phase to acid for adjusting pH, and water phase ether is extracted twice, and merges organic phase, and saturated common salt water washing is anhydrous
Magnesium sulfate dries 6h, and filtering, decompression removes solvent, and column chromatography for separation obtains 1.83g mucus, yield 28%.
[(the CH of complex compound 62)5C(C5H3)(Cl2C13H6)ZrCl2]2(CH2C6H4CH2) synthesis
Under the conditions of ice-water bath,nBuLi (8mmol) is added drop-wise in the diethyl ether solution of part (1.72g, 2mmol), has solid to give birth to
Into, supernatant liquor is removed in back flow reaction 50 hours, press filtration, is washed once with ether, is drained, and obtains solid 1.62g, plus tetrahydrofuran,
Liquid nitrogen ethanol bath, under the conditions of -50 DEG C, adds ZrCl22THF (1.381g, 3.66mmol), is warmed to room temperature naturally, and reaction 55 is small
When, reaction solution is yellow, and removal of solvent under reduced pressure, dichloromethane is extracted twice (30mL × 2), is concentrated into 20mL, plus n-hexane is adjusted
Polarity, puts in -20 DEG C of refrigerators, separates out yellow substance, and press filtration removes supernatant, and precipitation is drained, and obtains yellow powder 645mg, yield
30%.1H NMR (δ, ppm, DCCl3, 400MHz)：7.72-7.76(m,4H,ArH),7.64(s,4H,ArH),7.42-7.38
(m,4H,ArH),7.12-7.11(m,4H,ArH),7.07-7.05(m,4H,CpH),6.97(s,2H,CpH),3.01(s,4H,
ArCH2,),0.78-0.80(m,6H,CH2),1.10-1.16(m,8H,CH2),1.40-1.37(m,6H,CH2), it was demonstrated that make really
It is standby to have obtained complex compound 6.
Homogeneous catalysis propylene polymerization under normal pressure
To have magnetic stir bar, wireway 100mL there-necked flasks ethylene gas replace 3 times, under nitrogen protection, successively
Toluene 50mL, co-catalyst MAO 2.5mL (1.60M) [Al/M=1000], 2.0 μm of ol complex compounds 6 is added to be passed through third under normal pressure
Alkene gas, starts polymerisation at 0 DEG C, and stirring reaction 30min closes propylene gas cylinder, terminates anti-with 10% acidic alcohol
Should, polymer is transferred in beaker, is stood overnight, and is filtered and with the abundant washing copolymer of ethanol, and perseverance is dried under vacuum at 80 DEG C
Weight, weighs polymer quality 1.7g, polymerization activity 8.5 × 105Gpolymer/molMh, removes random thing laggard with dimethylbenzene
Row from13C NMR are characterized, and calculating learns, normality is up to 80% between the rrrr of resulting polymer.
Embodiment 7
[(the CH of ligand L 73)2C(C5H4)(Br2C13H7)]2(CH2C6H4CH2) synthesis
Under ice bath, by 6- methyl, ether (40mL) solution of 6- ethyls fulvene (5.78g, 48.18mmol) is added drop-wise to 2,7-
In ether (80mL) solution of dibromo fluorenes (15.56g, 48.18mmol), generation is not precipitated during dropwise addition, after about 8h, there is precipitation
Occur, the next morning, a large amount of precipitation generations, press filtration, solid ether is washed twice, washed once with hexane, drains, and obtains solid
9.92g, yield 72%.
The lithium salts (15.19mmol) of 6.88g is dissolved in 50mLTHF, and yellow is general red, under ice bath, is slowly added drop-wise to dibromo
THF (40mL) solution (pale yellow) of Bian (2.01g, 7.59mmol), after being warmed to room temperature naturally, reacts 65 hours.Hydrolysis, acetic acid
Ph is to neutrality for regulation, and point liquid takes organic phase, and water phase ether is extracted twice, and merges organic phase, saturated common salt water washing, anhydrous sulphur
Sour magnesium dries 6h, filtering, and vacuum rotation removes solvent, and column chromatography for separation obtains 2.1g mucus, yield 28%.
[(the CH of complex compound 73)2C(C5H3)(Br2C13H6)ZrCl2]2(CH2C6H4CH2) synthesis
Under the conditions of ice-water bath,nBuLi (8mmol) is added drop-wise in the diethyl ether solution of part (1.97g, 2mmol), has solid to give birth to
Into supernatant liquor is removed in back flow reaction two days, press filtration, is washed once with ether, is drained, and obtains solid 1.83g, plus tetrahydrofuran, liquid
Nitrogen ethanol bath, under the conditions of -60 DEG C, adds ZrCl22THF (1.366g, 3.62mmol), is warmed to room temperature naturally, reaction 2 days, instead
Answer liquid for yellow, removal of solvent under reduced pressure, dichloromethane is extracted twice (30mL × 2), be concentrated into 20mL, plus some n-hexanes adjust pole
Property, put in -20 DEG C of refrigerators, yellow substance is separated out, press filtration removes supernatant, and precipitation is drained, and obtains yellow powder 730mg, yield
31%.1H NMR (δ, ppm, DCCl3, 400MHz)：7.70(s,4H,ArH),7.60-7.55(m,4H,ArH),7.44-7.50
(m,4H,ArH),7.16-7.19(m,4H,ArH),7.01-7.06(m,4H,CpH),6.97(s,2H,CpH),3.01(s,4H,
ArCH2,),1.12(s,12H,CH3), it was demonstrated that prepare complex compound 7 really.
Homogeneous catalysis propylene polymerization under normal pressure
To have magnetic stir bar, wireway 100mL there-necked flasks ethylene gas replace 3 times, under nitrogen protection, successively
Toluene 50mL, co-catalyst MAO 2.5mL (1.60M) [Al/M=1000], 2.0 μm of ol complex compounds 7 is added to be passed through third under normal pressure
Alkene gas, starts polymerisation at 0 DEG C, and stirring reaction 30min closes propylene gas cylinder, terminates anti-with 10% acidic alcohol
Should, polymer is transferred in beaker, is stood overnight, and is filtered and with the abundant washing copolymer of ethanol, and perseverance is dried under vacuum at 80 DEG C
Weight, weighs polymer quality 1.92g, polymerization activity 9.6 × 105Gpolymer/molMh, after removing random thing with dimethylbenzene
Carry out from13C NMR are characterized, and calculating learns, normality is up to 82% between the rrrr of resulting polymer.
Claims (7)
1. a kind of sPP preparation methods of bridged binuclear metallocene compound, it is comprised the following steps：
(1) react paraxylene, N- bromo-succinimides and benzoyl peroxide, to prepare to cyclite；
(2) rich vinyl compound is made to be reacted with fluorenes lithium class compound, to prepare bridging fluorenes cyclopentadienyl lithium salts；
The structure of the rich vinyl compound as shown in Formula II,
Wherein：R1Selected from hydrogen, methyl,Ethyl and phenyl, and work as R1ForWhen, two R1Only
One presence；
The structure of the fluorenes lithium class compound as shown in formula III,
Wherein, R2Hydrogen, the tert-butyl group, bromine and chlorine；
(3) the bridging fluorenes cyclopentadienyl lithium salts obtained to cyclite and step (2) for obtaining step (1) reacts, to prepare part
L；
The structure of the ligand L is as shown in formula IV：
Wherein：R1Selected from hydrogen, methyl,Ethyl and phenyl, and work as R1ForWhen, two R1Only
One presence；R2Selected from hydrogen, the tert-butyl group, bromine and chlorine；
(4) reaction of ligand L and n-BuLi is obtained four lithium salts, then with ZrCl42THF reacts, to prepare described sPP
Use bridged binuclear metallocene compound；
The sPP structures of bridged binuclear metallocene compound are shown in formula I：
Wherein：R1Selected from hydrogen, methyl,Ethyl and phenyl, and work as R1ForWhen, two R1Only
One presence；R2Selected from hydrogen, the tert-butyl group, bromine and chlorine.
2. preparation method according to claim 1, wherein, step (1) includes：Protected and 70 DEG C to 90 DEG C in argon gas
Under, with carbon tetrachloride as solvent, make paraxylene, N- bromo-succinimides and benzoyl peroxide back flow reaction 10-30 small
When, wherein the mass ratio of paraxylene, N- bromo-succinimides and benzoyl peroxide is 5.04：30：2, it is subsequently cooled to 0
DEG C to 40 DEG C, filtrate is taken after filtering, after being placed 10-24 hour at -40 DEG C to -20 DEG C, precipitation white crystal, as to dibromo
Benzyl.
3. preparation method according to claim 1, wherein, step (2) includes：At -40 to 10 DEG C, by fulvene class chemical combination
The diethyl ether solution of thing was added drop-wise in the diethyl ether solution of fluorenes lithium class compound in 10 minutes to 30 minutes, wherein rich vinyl compound
It is 1 with the mol ratio of fluorenes lithium class compound：1 to 1.3：1, after appearance to be precipitated, then react 10 to 30 hours, isolate lower floor and consolidate
Body, after washing and draining, obtains pale pink solid, as bridging fluorenes cyclopentadienyl lithium salts.
4. preparation method according to claim 1, wherein, step (3) includes：At -40 DEG C to 0 DEG C, step (1) is obtained
To the tetrahydrofuran solution to cyclite bridging fluorenes cyclopentadienyl lithium salts that step (2) obtains was added drop-wise in 10 minutes to 30 minutes
In tetrahydrofuran solution, wherein, the mol ratio to cyclite and bridging fluorenes cyclopentadienyl lithium salts is 1：1 to 1：2.2,30 are then risen to naturally
DEG C, reaction adds dilute acid soln to be hydrolyzed for 30 to 50 hours afterwards, and regulation pH value takes organic phase, water phase to neutrality after point liquid
Extracted with ether, then merged with organic phase, then after scrubbed, dry, filtering, removal solvent, column chromatography for separation, glued
Liquid, as ligand L.
5. preparation method according to claim 1, wherein, step (4) includes：At -40 DEG C to 0 DEG C, the four of ligand L
The hexane solution of n-BuLi is added in hydrogen tetrahydrofuran solution, wherein ligand L and the mol ratio of n-BuLi is 1：4 to 1：5, so
After be warming up to 25 DEG C to 50 DEG C, react 20-60 hour, the solid obtained after separation tetrahydrofuran suspension, then at -80 DEG C
At to -70 DEG C, ZrCl is added42THF, wherein ligand L and ZrCl4The mol ratio of 2THF is 1：1.8 to 1：2, it is warmed up to 20
DEG C to 30 DEG C, react 40-60 hour, then remove solvent, extracted with dichloromethane, concentrated, add n-hexane, then-
Crystallization obtains solid, as described sPP bridged binuclear metallocene compounds at 40 DEG C to -20 DEG C.
6. the preparation method according to claim 1 or 3, wherein, the fluorenes lithium class compound is to be prepared by the following method：
At -10 DEG C to 20 DEG C, in the presence of an organic, n-BuLi is added drop-wise in compound of fluorene class, wherein n-BuLi with
The mol ratio of compound of fluorene class is 1：1 to 1.2：1,21 DEG C to 30 DEG C, after stirring reaction 10-20 hours are then risen to naturally, Gu
Liquid is separated, solid is scrubbed, drain after, obtain described fluorenes lithium class compound, wherein, the structure such as formula of the compound of fluorene class
Shown in V：
Wherein, R2Selected from hydrogen, the tert-butyl group, bromine and chlorine.
7. preparation method according to claim 1, wherein, the sPP bridged binuclears metallocene compound is：
[(CH3)2C(C5H3)(C13H8)ZrCl2]2(CH2C6H4CH2)、
[(C6H5)2C(C5H3)(C13H8)ZrCl2]2(CH2C6H4CH2)、
[(CH2)5C(C5H3)(C13H8)ZrCl2]2(CH2C6H4CH2)、
[(CH3)2C(C5H3)((tBu)2C13H6)ZrCl2]2(CH2C6H4CH2)、
[(C6H5)2C(C5H3)((tBu)2C13H6)ZrCl2]2(CH2C6H4CH2)、
[(CH2)5C(C5H3)(Cl2C13H6)ZrCl2]2(CH2C6H4CH2) or
[(CH3)2C(C5H3)(Br2C13H6)ZrCl2]2(CH2C6H4CH2)。
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