CN1805980A - 生产单中心聚烯烃的方法 - Google Patents
生产单中心聚烯烃的方法 Download PDFInfo
- Publication number
- CN1805980A CN1805980A CN200480016854.3A CN200480016854A CN1805980A CN 1805980 A CN1805980 A CN 1805980A CN 200480016854 A CN200480016854 A CN 200480016854A CN 1805980 A CN1805980 A CN 1805980A
- Authority
- CN
- China
- Prior art keywords
- indeno
- indyl
- zrcl
- reactor
- alpha
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 68
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 25
- 230000008569 process Effects 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000000203 mixture Substances 0.000 claims abstract description 46
- 239000001257 hydrogen Substances 0.000 claims abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 25
- 239000012190 activator Substances 0.000 claims abstract description 22
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003446 ligand Substances 0.000 claims abstract description 16
- -1 indenoindolyl Chemical group 0.000 claims abstract description 13
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 8
- 150000003624 transition metals Chemical class 0.000 claims abstract description 8
- 150000001336 alkenes Chemical class 0.000 claims abstract description 5
- 239000000178 monomer Substances 0.000 claims abstract description 4
- 229910007926 ZrCl Inorganic materials 0.000 claims description 54
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 38
- 239000004711 α-olefin Substances 0.000 claims description 23
- 229920001903 high density polyethylene Polymers 0.000 claims description 21
- 239000004700 high-density polyethylene Substances 0.000 claims description 21
- RXXXUIOZOITBII-UHFFFAOYSA-N indeno[1,2-g]indole Chemical compound C1=C2C=CC=CC2=C2C1=C1N=CC=C1C=C2 RXXXUIOZOITBII-UHFFFAOYSA-N 0.000 claims description 16
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 15
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 15
- 239000005977 Ethylene Substances 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 11
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical group C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- 150000002431 hydrogen Chemical class 0.000 claims description 9
- 229910008045 Si-Si Inorganic materials 0.000 claims description 8
- 229910006411 Si—Si Inorganic materials 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 claims description 7
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 6
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 5
- 125000004104 aryloxy group Chemical group 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 5
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims description 5
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- GXGJIOMUZAGVEH-UHFFFAOYSA-N Chamazulene Chemical group CCC1=CC=C(C)C2=CC=C(C)C2=C1 GXGJIOMUZAGVEH-UHFFFAOYSA-N 0.000 claims description 3
- 125000003282 alkyl amino group Chemical group 0.000 claims description 3
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 3
- 229910000085 borane Inorganic materials 0.000 claims description 3
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 3
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 3
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001449 anionic compounds Chemical class 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- QLNAVQRIWDRPHA-UHFFFAOYSA-N iminophosphane Chemical compound P=N QLNAVQRIWDRPHA-UHFFFAOYSA-N 0.000 claims description 2
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 claims description 2
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical group [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 125000005493 quinolyl group Chemical group 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims 1
- 125000001424 substituent group Chemical group 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 2
- 230000009977 dual effect Effects 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 48
- 239000003054 catalyst Substances 0.000 description 22
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 239000007787 solid Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 229910052814 silicon oxide Inorganic materials 0.000 description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- DOZCTPAUYJQGBD-UHFFFAOYSA-N indeno[1,2-b]indole Chemical class C1=CC=C2C=C3C4=CC=CC=C4N=C3C2=C1 DOZCTPAUYJQGBD-UHFFFAOYSA-N 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- KJGFNDCSTWGUDT-UHFFFAOYSA-N (2-methylanilino)azanium;chloride Chemical compound Cl.CC1=CC=CC=C1NN KJGFNDCSTWGUDT-UHFFFAOYSA-N 0.000 description 2
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- JFWBIRAGFWPMTI-UHFFFAOYSA-N [Zr].[CH]1C=CC=C1 Chemical compound [Zr].[CH]1C=CC=C1 JFWBIRAGFWPMTI-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- DCBDOYDVQJVXOH-UHFFFAOYSA-N azane;1h-indole Chemical compound N.C1=CC=C2NC=CC2=C1 DCBDOYDVQJVXOH-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- QNXSIUBBGPHDDE-UHFFFAOYSA-N indan-1-one Chemical compound C1=CC=C2C(=O)CCC2=C1 QNXSIUBBGPHDDE-UHFFFAOYSA-N 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229920001179 medium density polyethylene Polymers 0.000 description 2
- 239000004701 medium-density polyethylene Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000007069 methylation reaction Methods 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BLDFSDCBQJUWFG-UHFFFAOYSA-N 2-(methylamino)-1,2-diphenylethanol Chemical compound C=1C=CC=CC=1C(NC)C(O)C1=CC=CC=C1 BLDFSDCBQJUWFG-UHFFFAOYSA-N 0.000 description 1
- BKILWHYRLBCASZ-UHFFFAOYSA-M 2-[bis(2-hydroxyethyl)amino]ethanol;2-hydroxypropanoate;phenylmercury(1+) Chemical compound CC(O)C([O-])=O.[Hg+]C1=CC=CC=C1.OCCN(CCO)CCO BKILWHYRLBCASZ-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- SMWDFEZZVXVKRB-UHFFFAOYSA-N anhydrous quinoline Natural products N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- NUUNDIOOYFEMQN-UHFFFAOYSA-N cyclopenta-1,3-diene;sodium Chemical compound [Na].C1C=CC=C1 NUUNDIOOYFEMQN-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- PSHMSSXLYVAENJ-UHFFFAOYSA-N dilithium;[oxido(oxoboranyloxy)boranyl]oxy-oxoboranyloxyborinate Chemical compound [Li+].[Li+].O=BOB([O-])OB([O-])OB=O PSHMSSXLYVAENJ-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- BSPJVRORVHKCQW-UHFFFAOYSA-N indeno[2,1-b]indole Chemical group C1=CC=C2C3=C4C=CC=CC4=CC3=NC2=C1 BSPJVRORVHKCQW-UHFFFAOYSA-N 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 150000002899 organoaluminium compounds Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000005554 pyridyloxy group Chemical group 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical group CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- MXSVLWZRHLXFKH-UHFFFAOYSA-N triphenylborane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 MXSVLWZRHLXFKH-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2308/00—Chemical blending or stepwise polymerisation process with the same catalyst
-
- 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
- Y10S526/905—Polymerization in presence of transition metal containing catalyst in presence of hydrogen
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
公开一种两段烯烃聚合方法。本方法使用一种含桥联茚并吲哚基配体的4族过渡金属配合物和一种活化剂,本方法是在多个反应阶段或多个反应器内实施的。在所有阶段或反应器内都使用相同的配合物和相同的活化剂。在不同阶段或反应器内通过改变单体组成、氢气浓度或二者皆变来制备不同的聚烯烃。因此,本发明方法能生产具有宽分子量分布、宽组成分布或二者兼有的聚烯烃。
Description
技术领域
本发明涉及一种生产单中心聚烯烃的的方法。更具体地说,本发明涉及一种在不同聚合反应阶段或反应器中使用同一单中心催化剂和同一活化剂的两段工艺方法。
背景技术
单中心聚烯烃具有窄分子量分布和均匀的组成分布(即共聚单体重复单元沿聚合物链均匀分布)。窄分子量分布与均匀组成分布相结合是单中心聚烯烃与由Ziegler或铬催化剂制成的传统聚烯烃的区别。较之Ziegler聚烯烃,单中心聚烯烃在抗冲击性能、拉伸强度和光学性能方面有所改进。
但是,分子量分布的均匀性会导致单中心聚烯烃热加工性能的降低。在Ziegler常用的条件下很难加工单中心聚烯烃。可加工性的降低限制了单中心聚烯烃的发展,因为改变加工条件需要很大投资。因此,非常期望能制备既具有单中心催化剂所提供的改进物理性能又能呈现类似于传统聚烯烃加工特性的聚烯烃。
达到此目的的一条途经是使用混合催化剂体系。例如。US5747594提及一种两段聚合法。在第一阶段,用单中心催化剂使乙烯与高级α-烯烃聚合,第二阶段使用Ziegler催化剂继续聚合。因此,产物是单中心聚烯烃与Ziegler聚烯烃的混合物。两种聚合物的分子量和组成不同而得到热加工性能得到改进的产物。另外,美国专利6127484提及一种多反应区的方法,是在第一反应区使用单中心催化剂而在后一反应区使用Ziegler催化剂。
另一方法是采用一种单中心催化剂在两个不同聚合反应器中以不同活化剂进行操作。例如,在一个反应器中使用铝氧烷而在另一反应器中使用离子型活化剂。使用不同活化剂导致在不同反应区制备的聚合物具有不同的分子量,如此组合的聚烯烃具有宽的分子量分布和改进的加工性能,参见美国专利6372864。
但是,使用混合催化剂或活化剂通常会存在操作问题。两种不同催化剂或活化剂可能会彼此干扰。例如,Ziegler催化剂常用的有机铝化合物会使单中心催化剂中毒。因此,当使用两种互不相容的催化剂体系时会发生催化剂失活的情况。催化剂失活会使成本上升且使情况变得复杂。例如参见美国专利5371053和5442019。
总之,需要两段法工艺来生产单中心聚烯烃。理想的情况是两段法在不同反应阶段或反应器内生产具有不同分子量和不同组成的聚烯烃。理想的情况是两段法将在所有阶段或反应器内使用同一单中心催化剂和同一活化剂,
发明内容
本发明是一种两段烯烃聚合方法。本方法使用含桥联茚并吲哚基配体的4族过渡金属配合物和活化剂,本方法是在多个反应阶段或多个反应器内实施的。在所有阶段或反应器内都使用相同的配合物和相同的活化剂。在不同阶段或反应器内通过改变单体组成、氢气浓度或二者皆变来制备不同的聚烯烃。因此,本发明方法能生产具有宽分子量分布、宽组成分布或二者兼有的聚烯烃。
我们发现含桥联茚并吲哚基配体的单中心催化剂具有很强的将高浓度高级α-烯烃引入聚乙烯的能力而不会损害其分子量。这一特点类似于传统的Ziegler催化剂且使含桥联茚并吲哚基配体的单中心催化剂能很好地用于两段工艺方法。本发明的方法省去了混用催化剂或混用活化剂的需求,而这是已知的两段烯烃聚合工艺所必须的。
具体实施方式
本发明方法使用一种含桥联茚并吲哚基配体的4族过渡金属配合物。配合物优选具有下式结构:
M是4族过渡金属,B是桥基,L1是茚并吲哚基配体,L2是选自环戊二烯基、茚基、芴基、硼杂芳基(boraarys)、吡咯基、azaborolinyls、喹啉基、茚并吲哚基和膦亚胺,L3和L4可相同或不同,独立选自氢、卤素、烷基、芳基、烷氧基、芳氧基、甲硅烷氧基、烷氨基和芳氨基。
优选的4族过渡金属是锆和钛。特别优选锆。茚并吲哚基配体是通过将茚并吲哚化合物用强碱脱去质子来生成的。“茚并吲哚化合物”的意思是同时有吲哚和茚环的有机化合物。各自的闭合五元环稠合起来,即它们共用两个碳原子。优选的环稠合方式为吲哚氮与茚基环上仅有的sp3-杂化碳彼此处于“反”位。这就是茚并[1,2-b]环体系:
适合的环体系还包括吲哚氮与茚的sp3-杂化碳彼此β位连接,即它们处在分子同侧的环体系。这就是茚并[2,1-b]吲哚环体系。
环体系可以被取代。适宜的L1包括下式所代表的化合物:
和
其中R1选自烷基、芳基、芳烷基和甲硅烷基,R2到R10可相同或不同,且选自氢、烷基、芳基、芳烷基、烷芳基、甲硅烷基、卤素、烷氧基、芳氧基、甲硅烷氧基、硝基、二烷基氨基和二芳基氨基。
制备茚并吲哚化合物的方法是已知的。适宜的方法和化合物例如公开于美国专利6232260和其中所列的参考文献,包括Buu-Hoi和Xuong,
J.Chem.Soc.(1952)2225的方法。适用的方法还出现在PCT国际申请WO 99/24446中。
茚并吲哚基配体桥联另一个配体且二者都与过渡金属配位。优选另一个配体是第二个茚并吲哚基配体或选自取代或非取代的环戊二烯基和、芴基和茚基配体,适用的其它配体还包括杂原子配体如硼杂芳基(boraaryl)、吡咯基、吲哚基、喹啉氧基、吡啶氧基和azaborolinyl,这些配体描述于美国专利5554775、5539124、5637660和5902866。
桥基B共价连接茚并吲哚基配体和另一个配体。适宜的桥基包括CR2、C2R4、SiR2、Si2R4、GeR2、Ge2R4、R2SiCR2、NR和PR。优选B选自二烷基甲硅烷基、二芳基甲硅烷基、四烷基二硅烷基、亚乙基、亚异丙基、亚甲基、二亚甲基、1,2-亚联苯基、1,4-亚联苯基等。特别优选为亚甲基、二亚甲基、亚异丙基和二甲基甲硅烷基。
L3和L4可相同或不同,优选自氢、卤素、烷基、芳基、烷氧基、芳氧基、甲硅烷氧基、烷氨基和芳氨基等。优选L3和L4的至少一个是卤素。更优选L3和L4都是卤素。最优选L3和L4都是氯。卤素配体很容易活化。
适宜配合物的实例包括
Me2Si(茚并[1,2-b]吲哚基)(Cp)ZrCl2、
Me2Si(茚并[1,2-b]吲哚基)2ZrCl2、
Me2Si(茚并[2,1-b]吲哚基)(Cp)ZrCl2、
Me2Si(茚并[2,1-b]吲哚基)2ZrCl2、
Me2C(茚并[1,2-b]吲哚基)(Cp)ZrCl2、
Me2C(茚并[1,2-b]吲哚基)2ZrCl2、
Me2C(茚并[2,1-b]吲哚基)(Cp)ZrCl2、
Me2C(茚并[2,1-b]吲哚基)2ZrCl2、
Ph2C(茚并[1,2-b]吲哚基)(Cp)ZrCl2、
Ph2C(茚并[1,2-b]吲哚基)2ZrCl2、
Ph2C(茚并[2,1-b]吲哚基)(Cp)ZrCl2、
Ph2C(茚并[2,1-b]吲哚基)2ZrCl2、
Me2Si(茚并[1,2-b]吲哚基)(Flu)ZrCl2、
Me2Si(茚并[2,1-b]吲哚基)(Flu)ZrCl2、
Me2C(茚并[1,2-b]吲哚基)(Flu)ZrCl2、
Me2C(茚并[2,1-b]吲哚基)(Flu)ZrCl2、
Ph2C(茚并[1,2-b]吲哚基)(Flu)ZrCl2、
Ph2C(茚并[2,1-b]吲哚基)(Flu)ZrCl2、
(CH2-CH2)(茚并[1,2-b]吲哚基)(Cp)ZrCl2、
(CH2-CH2)(茚并[1,2-b]吲哚基)2ZrCl2、
(CH2-CH2)(茚并[2,1-b]吲哚基)(Cp)ZrCl2、
(CH2-CH2)(茚并[2,1-b]吲哚基)2ZrCl2、
((CH3)2Si-Si(CH3)2))(茚并[1,2-b]吲哚基)(Cp)ZrCl2、
((CH3)2Si-Si(CH3)2))(茚并[1,2-b]吲哚基)2ZrCl2、
((CH3)2Si-Si(CH3)2))(茚并[2,1-b]吲哚基)(Cp)ZrCl2、
((CH3)2Si-Si(CH3)2))(茚并[2,1-b]吲哚基)2ZrCl2等,以及它们的混合物。制备配合物的方法是已知的。例如,共同待审专利序列号10/123774提及一种典型的合成方案。
任选将配合物固定于载体上。载体优选是一种多孔型材料如无机氧化物和氯化物以及有机聚合物树脂。优选的无机氧化物包括2,3,4,5,13或14族元素的氧化物。优选载体包括氧化硅、氧化硅-氧化铝、氧化镁、氧化钛、氧化锆、氯化镁和交联聚苯乙烯。最优选为氧化硅。
优选载体的表面积在约2-700m2/g范围,优选约5-10m2/g。孔体积在约0.1-4.0ml/g范围,平均粒径在约10-500μm范围,平均孔径在约10-1000。优选用热处理法、化学改性法或并用两方法将它们改性。对于热处理法,优选将载体在50-800℃下加热。更优选温度为50-300℃。
适宜的化学改性剂包括有机铝、有机硅、有机镁和有机硼化合物。优选有机硅和有机硼化合物如六甲基二硅氮烷和三乙基硼烷。担载单中心催化剂的适用技术是已知的,例如美国专利6211311讨论了担载含杂原子配体的单中心催化剂的方法。负载的配合物适用于气相和浆液聚合工艺。
配合物是与活化剂一起使用的。适用的活化剂包括铝氧烷、烷基铝氧烷、烷基铝卤化物、硼或铝的阴离子化合物、三烷基硼和三芳基硼化合物。实例包括甲基铝氧烷(MAO)、聚甲基铝氧烷(PMAO)、乙基铝氧烷、二异丁基铝氧烷、三乙基铝、二乙基氯化铝、三甲基铝、三异丁基铝、四(五氟苯基)硼酸锂、四(五氟苯基)铝酸锂、四(五氟苯基)硼酸二甲基苯铵、四(五氟苯基)硼酸三苯甲游基、三苯基硼烷、三正辛基硼烷等以及它们的混合物。优选MAO、PMAO和三(五氟苯基)硼烷。
活化剂可与配合物混合并将混合物固定于载体上。或者,将配合物和活化剂分别加入聚合反应器内。活化剂的常用量在0.01-100000、优选0.1-1000且最优选0.5-300mol/mol配合物的范围。
适用的α-烯烃包括C2-10烯烃。例如是乙烯、丙烯、1-丁烯、1-戊烯、1-己烯、1-辛烯、4-甲基-1-戊烯以及它们的混合物。当使用单一烯烃时,生成出均聚物。可通过本发明方法制备的特别令人感兴趣的均聚物包括聚乙烯和聚丙烯。当使用两种或多种烯烃时,则生成共聚物。可通过本发明方法制备的特别令人感兴趣的共聚物包括乙烯与1-丁烯、1-戊烯、1-己烯或1-辛烯的共聚物。
本方法或是以多阶段方式或是在多个反应器内实施。“多阶段”的意思是在单个反应器内包括两或多段。反应器可以是搅拌釜或管式反应器。“多个反应器”的意思是使用两或多个反应器。反应器可以是串联或并联。在不同段或反应器制备不同聚合物。因此,组合后的聚烯烃具有宽分子量分布、宽组成分布或二者兼有。这类聚烯烃能克服传统单中心聚烯烃在热加工过程如挤出和注射过程中的难题。
例如,本方法可按两个串联阶段方式实施。通过改变两个阶段中氢气浓度和乙烯/长链α-烯烃比例,可以在不同阶段生产不同密度和/或分子量的聚乙烯。例如,在第一段,通过仅用乙烯或是乙烯/高级α-烯烃重量比大于95/5的乙烯与高级α-烯烃混合物来制备高密度聚乙烯(HDPE),在第二段,通过使用乙烯/高级α-烯烃摩尔比小于95/5的单体混合物来生产线型低密度聚乙烯(LLDPE)。类似地,在第一段可使用高氢气浓度来降低HDPE的分子量和在第二段使用低浓度氢气使所生产的LLDPE具有较高的分子量。因此,本方法所生产的聚乙烯合组合有第一段的HDPE和第二段的LLDPE。
ASTM D-4976-98:
聚乙烯模塑和挤出材料的标准规格中对HDPE和LLDPE下了定义。HDPE具有0.941g/cc或更高的密度,LDPE具有0.910-0.925g/cc的密度。本方法的产物可以是HDPE、LLDPE,或是中密度聚乙烯(MDPE,密度为0.926-0.940g/cc),这取决于各段或各反应器所制备的聚合物相对量。优选30%-70%的产物是第一段制备的。第一段和第二段的聚合物可以任何传统方式混合。它们可在一个混合罐和挤出机中进行混合。
优选在第一段采用0.001/1-10/1范围的氢气/乙烯摩尔比。优选第二段的氢气/乙烯摩尔比小于1/1。
多反应器方法有别于多段法的地方是:多反应器方法中,聚合过程的每一阶段是在不同的反应器内进行的。例如,当使用两个串联的反应器时,在第一个反应器内可制备HDPE,然后将产物转移到第二个反应器来生产LLDPE。或者,两个反应器并联,各自生产不同的聚合物。然后再将两种聚合物混合。多反应器方法的条件与上文所讨论的多段法的类似。
下列实施例仅仅是例示本发明。本领域技术人员应能认识到在本发明精神和权利要求范围内的许多变动。
实施例1
制备二甲基甲硅烷基桥联的茚并[1,2-b]吲哚基环戊二烯基锆配合物
(a)制备茚并[1,2-b]吲哚
将1-茚酮(30.6g,232mmol)和对甲苯肼盐酸化物(37.0g,233mmol)于EtOH(350ml)和HCl水溶液(12N,18ml)中的混合物加热至回流90分钟。将混合物冷却并过滤,固体先用EtOH(600ml)后用20%EtOH水溶液(400ml)最后用己烷(200ml)洗涤。将乳白色固体真空干燥(36.5g,72%)。
(b)N-甲基化反应
将产物(a)(36.5g,166mmol)、NaOH水溶液(112ml,20M,2.2mol)、C16H33NMe3Br(0.65g,1.78mmol)和甲苯(112ml)的混合物在室温下强力搅拌。滴加Mel(17.0ml,273mmol)的甲苯(15ml)溶液,并将混合物室温下搅拌4h并回流3h。冷却时形成晶体,过滤并用冷(-78℃)EtOH(300ml)然后用己烷(100ml)洗涤。分层,将水层用甲苯(2×100ml)洗涤。合并有机层并用Na2SO4干燥并过滤。真空移出挥发物,干燥沉淀物并与结晶产物2合并(总收率25.7g,66%)。
(c)产生阴离子
将正丁基锂(n-BuLi)(120ml,2.5M,1.6mol)滴加入产物(b)(43.9g,188mmol)的甲苯(560ml)溶液中。1小时后形成沉淀。将混合物静置48小时,过滤。固体用甲苯(500ml)然后用己烷(500ml)洗涤,真空干燥(40.3g,90%)。
(d)与二氯二甲基硅烷反应
将产物(c)(23.3g,97.4mmol)于甲苯(240ml)和Et2O(160ml)中的溶液加入到SiCl2Me2(60.0ml,495mmol)的Et2O(170ml)溶液中。混合物变得浑浊,搅拌48小时并用Celite过滤。真空移去挥发物,得到一灰色固体(24.8g,78%)。
(e)产生双阴离子
将环戊二烯钠(16.0ml,2M,32.0mmol)加入4(9.62g,29.5mmol)的Et2O(240ml)溶液中。立刻形成固体,将混合物室温下过夜。粗混合物用H2O(100ml)洗涤。有机相用Na2SO4干燥并过滤。蒸发至干得到一油状物。将油状物溶解于Et2O(250ml)并冷却至-78℃。滴加正丁基锂(28.0ml,2.5M,70mmol)并将混合物慢慢回升到室温。连续搅拌24小时。形成黄色固体,将混合物过滤,真空干燥固体(12.3g,99%)。
(f)制备锆配合物
将步骤(e)的双阴离子(7.94g,21.6mmol)以固体形式加入到ZrCl4(5.03g,21.6mmol)的甲苯(250ml)和Et2O(50ml)溶液中。混合物变为桔黄色,室温下放置48小时,然后过滤。固体用甲苯(200ml)之后用己烷(50ml)洗涤。真空干燥得到配合物(4.0g,36%)。
实施例2
制备氧化硅负载的Me2Si桥联的茚并[1,2-b]吲哚基Cp配合物
将氧化硅(Davision 948)于250℃下煅烧4小时。将甲基铝氧烷(4.21M MAO甲苯溶液1.2ml,Albemarle的产品)加入到4.0g已煅烧的氧化硅样品中,将混合物搅拌10分钟。来自实施例1的锆配合物(40mg)和三(五氟苯基)硼烷(“F15”,99mg)溶解于另一MAO溶液中(2.5ml),将此混合物加入到预处理的氧化硅中。除去挥发物得到一绿色的自由流动粉末,其Al/Zr摩尔比为233。
实施例3
用氧化硅负载的Me2Si桥联的茚并[1,2-b]吲哚基Cp配合物进行两段聚乙烯聚合过程
阶段1:制备高密度聚乙烯
将一个2L不锈钢反应器中装入异丁烷(900ml)、三异丁基铝(0.8ml 1.0M己烷溶液)和氢气(由7ml容器测定为100psig压降)。将反应器用乙烯加压到350psig,并将反应器物料加热到70℃。将来自实施例2的氧化硅负载[1,2-b]配合物(0.17g)注入反应器开始聚合。按照保持反应器压力在350psig的要求供应乙烯。65分钟后,反应器排气。
阶段2:制备线型低密度聚乙烯
将1-丁烯(20ml)加入到阶段1的反应混合物中,并将反应器用新鲜的乙烯加压到350psig。反应器中不加新鲜氢气。在70℃下连续聚合30分钟。反应器排气并收集聚合物。DSC显示所生产的聚合物有两个不同的熔点(Tm):134℃(Tm1)和105℃(Tm2)。Tm1和Tm2分别代表HDPE和LLDPE。聚合物产物的分子量为2.0×105且Mw/Mn=3.7。
比较实施例4
制备非桥联的茚并[1,2-b]吲哚基环戊二烯基锆配合物
(a)制备茚并[1,2-b]吲哚
将1-茚酮(30.6g,232mmol)和对甲苯肼盐酸化物(37.0g,233mmol)于EtOH(350ml)和HCl水溶液(12N,18ml)中的混合物加热至回流90分钟。将混合物冷却并过滤,固体先用EtOH(600ml)后用20%EtOH水溶液(400ml)最后用己烷(200ml)洗涤。将乳白色固体真空干燥(36.5g,72%)。
(b)N-甲基化反应
将产物(a)(36.5g,166mmol)、NaOH水溶液(112ml,20M,2.2mol)、C16H33NMe3Br(0.65g,1.78mmol)和甲苯(112ml)的混合物在室温下强力搅拌。滴加Mel(17.0ml,273mmol)的甲苯(15ml)溶液,并将混合物室温下搅拌4h并回流3h。冷却时形成晶体,过滤并用冷(-78℃)EtOH(300ml)然后用己烷(100ml)洗涤。分层,将水层用甲苯(2×100ml)洗涤。合并有机层并用Na2SO4干燥并过滤。真空移出挥发物,干燥沉淀物并与结晶产物2合并(总收率25.7g,66%)。
(c)产生阴离子
将正丁基锂(n-BuLi)(120ml,2.5M,1.6mol)滴加入产物(b)(43.9g,188mmol)的甲苯(560ml)溶液中。1小时后形成沉淀。将混合物静置48小时,过滤。固体用甲苯(500ml)然后用甲烷(500ml)洗涤,真空干燥(40.3g,90%)。
(d)制备非桥联配合物
在250ml装有搅拌棒的烧瓶内加入产物(c)(10.0g,42.0mmol)和甲苯(95ml)制成淤浆液。慢慢加入二***(35ml),得到一暗桔黄色溶液。室温强力搅拌下,将此溶液历时15分钟加入(C5H5)ZrCl3(11.1g,42.0mmol)于甲苯(190ml)和Et2O(19Oml)中的淤浆液内。混合物变成深红色,室温下放置过夜。过滤淤浆液,收集红色固体并真空干燥(16.5g,78%)。
比较实施例5
制备氧化硅负载的非桥联茚并[1,2-b]吲哚基环Cp配合物
重复实施例2的步骤,只是使用的是比较实施例4的非桥联配合物。
比较实施例6
用氧化硅负载的非桥联的茚并[1,2-b]吲哚基Cp配合物进行两段聚乙烯聚合过程
重复实施例3的步骤,只是使用的是比较实施例5的氧化硅负载的非桥联茚并[1,2-b]吲哚基Cp配合物,所生产聚合物具有较低的Mw(1.5×105)和窄分子量分布(Mw/Mn=2.4)。这表明非桥联的配合物不能给出宽分子量分布。
Claims (23)
1.一种在多个反应阶段或多个反应器中,于含桥联茚并吲哚基配体的4族过渡金属配合物和活化剂存在条件下将一和多种α-烯烃进行聚合的两段工艺方法,其中在所有阶段或反应器内都使用相同的配合物和相同的活化剂,且在每个阶段或每个反应器内使用不同的单体组成、不同的氢气浓度或二者皆不同来制备不同组成、不同分子量分布或二者皆不同的聚烯烃。
3.权利要求2的方法,其中M选自Zr和Ti。
4.权利要求2的方法,其中M是Zr。
5.权利要求2的方法,其中B选自CR2、C2R4、SiR2、Si2R4、GeR2、Ge2R4、R2SiCR2、NR和PR,其中取代基R可相同或不同,独立选自氢、烷基、环烷基、芳基、烷芳基和芳烷基。
6.权利要求2的方法,其中B选自亚甲基、二亚甲基、亚异丙基和二甲基甲硅烷基。
8.权利要求2的方法,其中L3和L4可相同或不同,选自卤素。
9.权利要求2的方法,其中L3和L4都是氯。
10.权利要求1的方法,其中配合物选自
Me2Si(茚并[1,2-b]吲哚基)(Cp)ZrCl2、
Me2Si(茚并[1,2-b]吲哚基)2ZrCl2、
Me2Si(茚并[2,1-b]吲哚基)(Cp)ZrCl2、
Me2Si(茚并[2,1-b]吲哚基)2ZrCl2、
Me2C(茚并[1,2-b]吲哚基)(Cp)ZrCl2、
Me2C(茚并[1,2-b]吲哚基)2ZrCl2、
Me2C(茚并[2,1-b]吲哚基)(Cp)ZrCl2、
Me2C(茚并[2,1-b]吲哚基)2ZrCl2、
Ph2C(茚并[1,2-b]吲哚基)(Cp)ZrCl2、
Ph2C(茚并[1,2-b]吲哚基)2ZrCl2、
Ph2C(茚并[2,1-b]吲哚基)(Cp)ZrCl2、
Ph2C(茚并[2,1-b]吲哚基)2ZrCl2、
Me2Si(茚并[1,2-b]吲哚基)(Flu)ZrCl2、
Me2Si(茚并[2,1-b]吲哚基)(Flu)ZrCl2、
Me2C(茚并[1,2-b]吲哚基)(Flu)ZrCl2、
Me2C(茚并[2,1-b]吲哚基)(Flu)ZrCl2、
Ph2C(茚并[1,2-b]吲哚基)(Flu)ZrCl2、
Ph2C(茚并[2,1-b]吲哚基)(Flu)ZrCl2、
(CH2-CH2)(茚并[1,2-b]吲哚基)(Cp)ZrCl2、
(CH2-CH2)(茚并[1,2-b]吲哚基)2ZrCl2、
(CH2-CH2)(茚并[2,1-b]吲哚基)(Cp)ZrCl2、
(CH2-CH2)(茚并[2,1-b]吲哚基)2ZrCl2、
((CH3)2Si-Si(CH3)2))(茚并[1,2-b]吲哚基)(Cp)ZrCl2、
((CH3)2Si-Si(CH3)2))(茚并[1,2-b]吲哚基)2ZrCl2、
((CH3)2Si-Si(CH3)2))(茚并[2,1-b]吲哚基)(Cp)ZrCl2、
((CH3)2Si-Si(CH3)2))(茚并[2,1-b]吲哚基)2ZrCl2,以及它们的混合物。
11.权利要求1的方法,其中配合物是负载型的。
12.权利要求1的方法,其中活化剂选自铝氧烷、烷基铝氧烷、烷基铝卤化物、硼或铝的阴离子化合物、三烷基硼和三芳基硼化合物,以及它们的混合物。
13.权利要求1的方法,其中活化剂是甲基铝氧烷(MAO)或聚甲基铝氧烷(PMAO)。
14.权利要求1的方法,其中活化剂是三(五氟苯基)硼烷。
15.权利要求1的方法,其中α-烯烃选自乙烯、丙烯、1-丁烯、1-戊烯、1-己烯、1-辛烯、4-甲基-1-戊烯以及它们的混合物。
16.权利要求1的方法,其中α-烯烃是乙烯与C3-10α-烯烃的混合物。
17.权利要求1的方法,其中烯烃是乙烯与1-丁烯的混合物。
18.权利要求1的方法,其中包括两个次序的阶段:
(1)在氢气存在下,按乙烯/α-烯烃重量比大于95/5和氢气/乙烯摩尔比在0.001/1-10/1范围的条件,将乙烯或乙烯与C3-10α-烯烃的混合物在反应器内进行聚合来生产高密度聚乙烯(HDPE);和
(2)按乙烯/α-烯烃重量比小于95/5和氢气/乙烯摩尔比小于1/1的条件,将乙烯与C3-10α-烯烃的混合物加入反应器继续进行聚合来生产线型低密度聚乙烯(LLDPE)。
19.权利要求18的方法,其中30%-70%的产物是第一段制备的。
20.权利要求1的方法,其中包括两个串联反应器:
(1)第一反应器中,在氢气存在下,按乙烯/α-烯烃重量比大于95/5和氢气/乙烯摩尔比在0.001/1-10/1范围的条件,将乙烯或乙烯与C3-10α-烯烃的混合物在反应器内进行聚合来生产高密度聚乙烯(HDPE);和
(2)将(1)的产物转移到第二反应器,并按乙烯/α-烯烃重量比小于95/5和氢气/乙烯摩尔比小于1/1的条件,将乙烯与C3-10α-烯烃的混合物加入反应器继续进行聚合来生产线型低密度聚乙烯(LLDPE)。
21.权利要求20的方法,其中30%-70%的产物是第一反应器制备的。
22.权利要求1的方法,其中包括两个并联反应器:
(1)第一反应器中,在氢气存在下,按乙烯/α-烯烃重量比大于95/5和氢气/乙烯摩尔比在0.001/1-10/1范围的条件,将乙烯或乙烯与C3-10α-烯烃的混合物在反应器内进行聚合来生产高密度聚乙烯(HDPE);和
(2)第二反应器中,按乙烯/α-烯烃重量比小于95/5和氢气/乙烯摩尔比小于1/1的条件,将乙烯与C3-10α-烯烃的混合物进行聚合来生产线型低密度聚乙烯(LLDPE);
其中要将第一反应器和第二反应器的产物进行混合。
23.权利要求22的方法,其中30%-70%的产物是第一反应器制备的。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/462,493 | 2003-06-16 | ||
US10/462,493 US6995216B2 (en) | 2003-06-16 | 2003-06-16 | Process for manufacturing single-site polyolefins |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1805980A true CN1805980A (zh) | 2006-07-19 |
CN100467497C CN100467497C (zh) | 2009-03-11 |
Family
ID=33511481
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN200480016854.3A Expired - Fee Related CN100467497C (zh) | 2003-06-16 | 2004-05-18 | 生产单中心聚烯烃的方法 |
Country Status (5)
Country | Link |
---|---|
US (1) | US6995216B2 (zh) |
EP (1) | EP1636278A1 (zh) |
CN (1) | CN100467497C (zh) |
CA (1) | CA2529663A1 (zh) |
WO (1) | WO2005000920A1 (zh) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016124157A1 (zh) * | 2015-02-06 | 2016-08-11 | 中国石油天然气股份有限公司 | 含杂原子的π-配体的茂金属络合物及其制备方法、其催化剂体系和催化剂体系的应用 |
CN105985368A (zh) * | 2015-02-06 | 2016-10-05 | 中国石油天然气股份有限公司 | 含杂原子的π-配体的茂金属络合物及其制备方法、其催化剂体系和催化剂体系的应用 |
CN105985383B (zh) * | 2015-02-06 | 2019-09-03 | 中国石油天然气股份有限公司 | 含杂原子的π-配体的茂金属络合物及其制备方法、其催化剂体系和催化剂体系的应用 |
CN114127130A (zh) * | 2019-05-29 | 2022-03-01 | 博里利斯股份公司 | 催化剂体系的改进制备 |
Families Citing this family (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6520005B2 (en) | 1994-12-22 | 2003-02-18 | Kla-Tencor Corporation | System for sensing a sample |
US7189675B2 (en) * | 2005-03-07 | 2007-03-13 | Equistar Chemicals, Lp | Olefin polymerization catalyst on plasma-contacted support |
US7429635B2 (en) * | 2006-09-28 | 2008-09-30 | Equistar Chemicals, Lp | Preparation of ultra high molecular weight linear low density polyethylene |
US7781549B2 (en) | 2007-09-04 | 2010-08-24 | Equistar Chemicals, Lp | Olefin polymerization process |
US7723451B2 (en) * | 2007-09-04 | 2010-05-25 | Equistar Chemicals, Lp | Olefin polymerization process |
US7655740B2 (en) | 2007-09-04 | 2010-02-02 | Equistar Chemicals, Lp | Olefin polymerization process |
US7829641B2 (en) * | 2008-07-16 | 2010-11-09 | Equistar Chemicals, Lp | Process for the preparation of multimodal polyethylene resins |
KR101152413B1 (ko) * | 2008-09-12 | 2012-06-05 | 에스케이이노베이션 주식회사 | 에틸렌 공중합체 및 이의 제조방법 |
EP2513160B1 (en) | 2009-12-18 | 2014-03-12 | Total Research & Technology Feluy | Method for improving ethylene polymerization reaction |
CA2724943A1 (en) | 2010-12-10 | 2012-06-10 | Nova Chemicals Corporation | Catalyst activation in a dual reactor process |
KR101606825B1 (ko) * | 2013-11-28 | 2016-03-28 | 주식회사 엘지화학 | 혼성 담지 메탈로센 촉매의 제조방법 |
KR101703274B1 (ko) * | 2014-08-12 | 2017-02-22 | 주식회사 엘지화학 | 메탈로센 화합물, 이를 포함하는 촉매 조성물 및 이를 이용한 올레핀 중합체의 제조방법 |
WO2016024818A1 (ko) * | 2014-08-12 | 2016-02-18 | 주식회사 엘지화학 | 메탈로센 화합물, 이를 포함하는 촉매 조성물 및 이를 이용한 올레핀 중합체의 제조방법 |
KR101725352B1 (ko) * | 2014-09-30 | 2017-04-10 | 주식회사 엘지화학 | 폴리올레핀의 제조 방법 및 이로부터 제조된 폴리올레핀 |
KR101784463B1 (ko) * | 2014-10-06 | 2017-10-11 | 주식회사 엘지화학 | 리간드 화합물, 메탈로센 화합물 및 이를 이용하는 올레핀계 중합체의 제조방법 |
JP6440832B2 (ja) * | 2014-12-15 | 2018-12-19 | エルジー・ケム・リミテッド | メタロセン化合物、メタロセン担持触媒およびこれを用いるポリオレフィンの製造方法 |
KR101920401B1 (ko) * | 2016-12-06 | 2019-02-08 | 한화케미칼 주식회사 | 올레핀 중합 촉매용 전이금속 화합물, 이를 포함하는 올레핀 중합 촉매 및 이를 이용하여 중합된 폴리올레핀 |
WO2023187552A1 (en) | 2022-03-22 | 2023-10-05 | Nova Chemicals (International) S.A. | Organometallic complex, olefin polymerization catalyst system and polymerization process |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5371053A (en) * | 1993-05-18 | 1994-12-06 | Exxon Chemical Patents Inc. | Process for deactivating Ziegler-Natta and metallocene catalysts |
US5442019A (en) * | 1994-03-25 | 1995-08-15 | Exxon Chemical Company | Process for transitioning between incompatible polymerization catalysts |
US5792534A (en) * | 1994-10-21 | 1998-08-11 | The Dow Chemical Company | Polyolefin film exhibiting heat resistivity, low hexane extractives and controlled modulus |
US5539124A (en) * | 1994-12-19 | 1996-07-23 | Occidental Chemical Corporation | Polymerization catalysts based on transition metal complexes with ligands containing pyrrolyl ring |
US5554775A (en) * | 1995-01-17 | 1996-09-10 | Occidental Chemical Corporation | Borabenzene based olefin polymerization catalysts |
US5637660A (en) * | 1995-04-17 | 1997-06-10 | Lyondell Petrochemical Company | Polymerization of α-olefins with transition metal catalysts based on bidentate ligands containing pyridine or quinoline moiety |
JPH11504361A (ja) * | 1995-04-25 | 1999-04-20 | ライオンデル ペトロケミカル カンパニー | オレフィンの重合の触媒としてのアザボロリニル金属錯体 |
EP0881237A1 (en) * | 1997-05-26 | 1998-12-02 | Fina Research S.A. | Process to produce bimodal polyolefins with metallocene catalysts using two reaction zones |
AU1870999A (en) | 1997-11-12 | 1999-05-31 | Montell Technology Company B.V. | Metallocenes and catalysts for olefin-polymerisation |
CA2245375C (en) * | 1998-08-19 | 2006-08-15 | Nova Chemicals Ltd. | Dual reactor polyethylene process using a phosphinimine catalyst |
EP0989141A1 (en) * | 1998-09-25 | 2000-03-29 | Fina Research S.A. | Production of multimodal polyethelene |
US6127484A (en) * | 1999-04-29 | 2000-10-03 | Equistar Chemicals, Lp | Olefin polymerization process |
US6211311B1 (en) * | 1999-05-25 | 2001-04-03 | Equistar Chemicals, L.P. | Supported olefin polymerization catalysts |
US6232260B1 (en) * | 1999-10-14 | 2001-05-15 | Equistar Chemicals, L.P. | Single-site catalysts for olefin polymerization |
FI111954B (fi) * | 2000-02-21 | 2003-10-15 | Borealis Tech Oy | Menetelmä polyeteenipäällysteen valmistamiseksi substraatille |
US6486270B1 (en) * | 2000-08-25 | 2002-11-26 | Equistar Chemicals, Lp | High molecular weight, medium density polyethylene |
US7365137B2 (en) | 2001-07-17 | 2008-04-29 | Basell Polyolefine Gmbh | Multistep process for the (co) polymerization of olefins |
US6756455B2 (en) * | 2002-05-31 | 2004-06-29 | Equistar Chemicals, Lp | High-temperature solution process for polyolefin manufacture |
-
2003
- 2003-06-16 US US10/462,493 patent/US6995216B2/en not_active Expired - Lifetime
-
2004
- 2004-05-18 WO PCT/US2004/015479 patent/WO2005000920A1/en active Application Filing
- 2004-05-18 EP EP04752488A patent/EP1636278A1/en not_active Withdrawn
- 2004-05-18 CA CA002529663A patent/CA2529663A1/en not_active Abandoned
- 2004-05-18 CN CN200480016854.3A patent/CN100467497C/zh not_active Expired - Fee Related
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016124157A1 (zh) * | 2015-02-06 | 2016-08-11 | 中国石油天然气股份有限公司 | 含杂原子的π-配体的茂金属络合物及其制备方法、其催化剂体系和催化剂体系的应用 |
CN105985368A (zh) * | 2015-02-06 | 2016-10-05 | 中国石油天然气股份有限公司 | 含杂原子的π-配体的茂金属络合物及其制备方法、其催化剂体系和催化剂体系的应用 |
CN105985383B (zh) * | 2015-02-06 | 2019-09-03 | 中国石油天然气股份有限公司 | 含杂原子的π-配体的茂金属络合物及其制备方法、其催化剂体系和催化剂体系的应用 |
CN105985368B (zh) * | 2015-02-06 | 2020-03-10 | 中国石油天然气股份有限公司 | 含杂原子的π-配体的茂金属络合物及其制备方法、其催化剂体系和催化剂体系的应用 |
CN114127130A (zh) * | 2019-05-29 | 2022-03-01 | 博里利斯股份公司 | 催化剂体系的改进制备 |
Also Published As
Publication number | Publication date |
---|---|
CN100467497C (zh) | 2009-03-11 |
US6995216B2 (en) | 2006-02-07 |
US20040254310A1 (en) | 2004-12-16 |
EP1636278A1 (en) | 2006-03-22 |
WO2005000920A1 (en) | 2005-01-06 |
CA2529663A1 (en) | 2005-01-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN100467497C (zh) | 生产单中心聚烯烃的方法 | |
CN1809596A (zh) | 烯烃聚合的多催化剂体系 | |
CN101796085B (zh) | 具有多峰分子量分布的乙烯共聚物及其制备方法 | |
US9029486B2 (en) | Supported metallocene catalyst, method for preparing the same and method for preparing polyolefin using the same | |
US7473745B2 (en) | Preparation of multimodal polyethylene | |
CN102421808B (zh) | 烯烃类聚合物及包含该聚合物的纤维 | |
KR100567304B1 (ko) | 촉매 시스템 및 그의 중합 방법에서의 용도 | |
CN1222546C (zh) | 用单一的金属茂催化剂和单一的单体制备e-p共聚物 | |
CN1398272A (zh) | 丙烯抗冲共聚物 | |
CN1646583A (zh) | 用茚并吲哚基催化剂使烯烃聚合的方法 | |
CN1489602A (zh) | 双位烯烃聚合催化剂组合物 | |
WO2011073379A1 (en) | Process for the preparation of a particulate polyethylene product | |
CN1684984A (zh) | 单反应器中制双模态聚烯烃的含茂铪组分双位催化剂体系 | |
KR20050027268A (ko) | 폴리올레핀 블럭 공중합체 | |
EP2513163A1 (en) | Process for the preparation of a particulate bimodal polyethylene product | |
CN1308354C (zh) | 双金属茚并吲哚基催化剂 | |
CN1302022C (zh) | 用于生产聚烯烃的基体和方法 | |
KR101600583B1 (ko) | 이핵 메탈로센 화합물, 및 이의 제조방법 | |
CN1820035A (zh) | 烯烃聚合法 | |
CN1178949C (zh) | 作为聚合催化剂的环戊二烯基过渡金属配合物 | |
CN1172960C (zh) | 生产用于气相聚合反应的高度多产负载离子催化剂的方法 | |
CN105308059A (zh) | 催化剂组合物、其制备方法及使用其制备聚烯烃的方法 | |
CN1756776A (zh) | 丙烯聚合方法 | |
CN1867594A (zh) | 烯烃聚合方法 | |
CN1351087A (zh) | 氢锆化基体及聚烯烃生产方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C17 | Cessation of patent right | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090311 Termination date: 20100518 |