CN1249762A - 聚合方法 - Google Patents
聚合方法 Download PDFInfo
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- CN1249762A CN1249762A CN98803187A CN98803187A CN1249762A CN 1249762 A CN1249762 A CN 1249762A CN 98803187 A CN98803187 A CN 98803187A CN 98803187 A CN98803187 A CN 98803187A CN 1249762 A CN1249762 A CN 1249762A
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- reactor
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- aforementioned
- paraffinic hydrocarbons
- alkyl
- Prior art date
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- 238000006116 polymerization reaction Methods 0.000 title claims description 20
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical group CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 239000012190 activator Substances 0.000 claims abstract description 9
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 43
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 42
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 29
- 229930195733 hydrocarbon Natural products 0.000 claims description 22
- 150000002430 hydrocarbons Chemical class 0.000 claims description 22
- 239000000377 silicon dioxide Substances 0.000 claims description 20
- -1 5-cyclopentadienyl Chemical group 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000003446 ligand Substances 0.000 claims description 11
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- 229910052726 zirconium Inorganic materials 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 7
- 229910052796 boron Inorganic materials 0.000 claims description 7
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 6
- 125000001188 haloalkyl group Chemical group 0.000 claims description 6
- 125000002897 diene group Chemical group 0.000 claims description 5
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000004104 aryloxy group Chemical group 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 125000003800 germyl group Chemical group [H][Ge]([H])([H])[*] 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 4
- 150000007527 lewis bases Chemical class 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 125000005353 silylalkyl group Chemical group 0.000 claims description 3
- 239000002879 Lewis base Substances 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 2
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000005325 aryloxy aryl group Chemical group 0.000 claims description 2
- 239000001273 butane Substances 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 2
- 125000001475 halogen functional group Chemical group 0.000 claims description 2
- 150000004678 hydrides Chemical class 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 125000005647 linker group Chemical group 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical group CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 20
- 238000001816 cooling Methods 0.000 description 16
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 239000002585 base Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical class CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 6
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 6
- 150000001993 dienes Chemical class 0.000 description 5
- 238000010926 purge Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 3
- 241000216843 Ursus arctos horribilis Species 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- DPUXQWOMYBMHRN-UHFFFAOYSA-N hexa-2,3-diene Chemical compound CCC=C=CC DPUXQWOMYBMHRN-UHFFFAOYSA-N 0.000 description 3
- 229910052809 inorganic oxide Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical group [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- FDYAUVYPZOQMFE-UHFFFAOYSA-N C1(CC=C(C=C1)C)(C)C=CC=C Chemical compound C1(CC=C(C=C1)C)(C)C=CC=C FDYAUVYPZOQMFE-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 125000001118 alkylidene group Chemical group 0.000 description 2
- 150000001399 aluminium compounds Chemical class 0.000 description 2
- 150000001639 boron compounds Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- YSRFHVJGXPIDGR-UHFFFAOYSA-N dimethylsilane titanium Chemical compound [Ti].C[SiH2]C YSRFHVJGXPIDGR-UHFFFAOYSA-N 0.000 description 2
- 238000005243 fluidization Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N perisophthalic acid Natural products OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical group C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- LDJKKLGZOYXYHE-UHFFFAOYSA-N 1,1'-biphenyl buta-1,3-diene Chemical compound C=CC=C.C1=CC=CC=C1C1=CC=CC=C1 LDJKKLGZOYXYHE-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
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- QLKINISCYVCLTE-UHFFFAOYSA-N 6-phenylhexa-2,4-dienylbenzene Chemical compound C=1C=CC=CC=1CC=CC=CCC1=CC=CC=C1 QLKINISCYVCLTE-UHFFFAOYSA-N 0.000 description 1
- GMSBPKZRTZHCPB-UHFFFAOYSA-N C=CC=CC.[Ti+2].C[SiH2]C Chemical compound C=CC=CC.[Ti+2].C[SiH2]C GMSBPKZRTZHCPB-UHFFFAOYSA-N 0.000 description 1
- JDXIHCVTYCJQHO-UHFFFAOYSA-N O1CCOCC1.[Ge] Chemical compound O1CCOCC1.[Ge] JDXIHCVTYCJQHO-UHFFFAOYSA-N 0.000 description 1
- AYDQIZKZTQHYIY-UHFFFAOYSA-N OC(=O)C1(C)CC(C(O)=O)=CC=C1 Chemical compound OC(=O)C1(C)CC(C(O)=O)=CC=C1 AYDQIZKZTQHYIY-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 125000005103 alkyl silyl group Chemical group 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- JPYQFYIEOUVJDU-UHFFFAOYSA-N beclamide Chemical group ClCCC(=O)NCC1=CC=CC=C1 JPYQFYIEOUVJDU-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- KKNWHLHBSVUXKT-UHFFFAOYSA-N dimethyl-(2-methyl-1H-inden-1-yl)silane titanium(2+) Chemical compound [Ti+2].CC=1C(C2=CC=CC=C2C1)[SiH](C)C KKNWHLHBSVUXKT-UHFFFAOYSA-N 0.000 description 1
- WODAGJKOTBCQIL-UHFFFAOYSA-N dimethylsilane titanium(2+) Chemical compound [Ti+2].C[SiH2]C WODAGJKOTBCQIL-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 229910000078 germane Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000002955 immunomodulating agent Substances 0.000 description 1
- 229940121354 immunomodulator Drugs 0.000 description 1
- 230000002584 immunomodulator Effects 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- ZCBSOTLLNBJIEK-UHFFFAOYSA-N silane titanium Chemical compound [SiH4].[Ti] ZCBSOTLLNBJIEK-UHFFFAOYSA-N 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- MJOXZELXZLIYPI-UHFFFAOYSA-N titanium(2+) Chemical compound [Ti+2] MJOXZELXZLIYPI-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- HWVLYABDVUZMFQ-UHFFFAOYSA-N zirconium(2+) Chemical compound [Zr+2] HWVLYABDVUZMFQ-UHFFFAOYSA-N 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- C08F2/00—Processes of polymerisation
- C08F2/34—Polymerisation in gaseous state
-
- 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
-
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Abstract
在一个包括(a)一种金属茂和(b)一种活化剂的催化剂体系的存在下,在气相中进行的烯烃聚合通过将一种低级链烷烃加入到反应器中而得到了改善。优选的链烷烃是戊烷并且优选以液态形式加入到反应器中。所述催化剂体系的活性可以通过所述链烷烃的加入而改善。
Description
本发明涉及一种聚合方法,具体地说,本发明涉及一种使用包括活化金属茂配合物的催化体系进行烯烃聚合的气相方法。
基于金属茂配合物的催化剂已经广泛用于烯烃的聚合。这些配合物在一般包括作为所述配合物的一种双(环戊二烯基)过渡金属和一种助催化剂的催化体系中使用。这种双(Cp)过渡金属配合物被称为金属茂并且一般以钛或锆金属为基础,使用时用铝化合物诸如铝氧烷作为助催化剂。在气相方法中使用时,这种双(Cp)金属茂体系可载于硅石上。这种催化体系说明于EP 129368和EP 206794中。
新近另一类过渡金属配合物已经用于制备烯烃聚合物。这种配合物具有单个环戊二烯基环配位体和一个结合金属原子的杂原子并且也可与铝氧烷结合使用。这些配合物被称为具有‘受限的几何结构’并且描述于EP 420436和EP 416815中。
类似的催化体系公开于EP418044和WO92/00333中。在这些体系中,催化体系包括一种单(环戊二烯基)杂原子金属配合物和一种离子激活剂化合物并且这种体系已经被称为离子单(环戊二烯基)催化剂。可以例举的用于这种体系的典型离子激活剂是硼酸盐。
WO95/00526描述了钛或锆配合物,其中所述过渡金属均是+2形式氧化态。所述配合物也包括一个与所述金属形成一个π-配合物的中性、共轭或非共轭二烯配位体。这种配合物通过与一种活化助催化剂例如铝氧烷、硼烷或硼酸盐结合形成了催化剂。在气相聚合方法中使用时,这种催化剂也适合于载于硅石上。
另一种类型的催化体系描述于WO96/04290中。这里所述金属茂配合物以双(Cp)配合物代表,但是它也包括可与所述金属结合成π-配合物或σ-配合物的共轭二烯。
已经公开金属茂配合物适合用于气相烯烃聚合的方法。例如EP206794、EP 696293、EP 719289、EP 802202、EP 659773、EP593083和EP 739360公开了金属茂配合物在气相中的使用。
现在我们已惊异地发现在使用活化的金属茂催化体系的气相方法中通过往反应器中注入一种惰性液体可获得催化活性的提高。
尤其我们发现低级链烷烃特别适合于这个目的。
因此按照本发明,提供了一种用于气相烯烃聚合的方法,所述方法在一种包括(a)一种金属茂和(b)一种活化剂的催化体系的存在下进行,特征在于一种低级链烷烃被加入到气相反应器中。
所述链烷烃优选被直接加入到反应器中。
R’总是独立地选自氢、烃基、甲硅烷基、甲锗烷基、卤代、氰基和其组合,所述R’至多具有20个非氢原子并且任选两个R’基团(这里R’不是氢、卤代或氰基)一起形成一种其二价衍生物,其与所述环戊二烯基环的相邻位置相连形成一稠环结构;
X是一个具有至多30个非氢原子的中性η4-键合的二烯基团,它与M形成一种π-配合物;
Y是-O-、-S-、-NR*-、-PR*-;
M是+2形式氧化态的钛或锆;
Z*是SiR2、CR* 2、SiR* 2SiR* 2、CR* 2CR* 2、CR*=CR*、CR2SiR* 2或GeR* 2;其中
R*总是独立地为氢或者为选自烃基、甲硅烷基、卤代烷基、卤代芳基和其组合的一个成员,所述R*至多具有10个非氢原子,并且任选两个来自Z*(当R*不是氢时)的R*基团或一个来自Z*的R*基团和一个来自Y的R*基团形成一个环***。
最优选的配合物是酰胺基硅烷或酰胺基链烷二基配合物,其中所述金属为钛。
高度优选的二烯基团是1,4-二苯基-1,3-丁二烯、1,3-戊二烯、1,4-二苄基-1,3-丁二烯、3-甲基-1,3-戊二烯。
优选配合物的说明性而非限定性的实例有(叔丁基酰胺基)(四甲基-η5-环戊二烯基)二甲基硅烷钛(II)1,4-二苯基-1,3-丁二烯、
(叔丁基酰胺基)(四甲基-η5-环戊二烯基)二甲基硅烷钛(II)1,3-戊二烯、
(叔丁基酰胺基)(2-甲基茚基)二甲基硅烷钛(II)1,4-二苯基-1,3-丁二烯。
这些配合物通过与活化助催化剂结合而被赋予了催化活性。适合的助催化剂包括铝氧烷,特别是甲基铝氧烷(MAO)或强路易斯酸如三(烃基)硼化合物或卤化衍生物。
一种特别优选的活化剂是三(五氟苯基)硼。
其它适用于本发明方法中的配合物是那些所述金属为较高价态的配合物。这种配合物公开于EP 416815和EP 491842中,两者均通过引用并入本文。所述配合物具有以下通式:式中:
Cp*是一单个η5-环戊二烯基或η5-取代的环戊二烯基基团,任选通过-Z-Y-共价结合到M上并且符合于下式:式中R总是为氢或者为选自卤素、烷基、芳基、卤代烷基、烷氧基、芳氧基、甲硅烷基和其至多20个非氢原子的组合的部分,或者两个或多个R基团一起形成一个稠环***;
M是以η5键合形式结合到环戊二烯基或取代环戊二烯基基团上的锆、钛或铪并且是处于+3或+4的价态;
X总是为氢化物或为选自卤代、烷基、芳基、甲硅烷基、甲锗烷基、芳氧基、烷氧基、酰胺、甲硅烷氧基和至多具有20个非氢原子的其组合(例如卤代烷基、卤代芳基、卤代甲硅烷基、烷芳基、芳烷基、甲硅烷基烷基、芳氧基芳基和烷氧基烷基、酰胺基烷基、酰胺基芳基)的部分和至多具有20个非氢原子的中性路易斯碱配位体;
n根据M的价态为1或2;
Z是一个二价部分,包括氧、硼或元素周期表14族的一个成员;
Y是一个共价结合到所述金属上的连接基团,包括氮、磷、氧或硫,或任选Z和Y一起形成一个稠合环***。
最优选的配合物是其中Y为相应于式(-NR1)或(-PR1)的含氮或含磷基团的配合物,其中R1是C1-C10烷基或C6-C10芳基并且其中Z是SiR”2、CR”2、SiR”2SiR”2、CR”=CR”或GeR”2,其中R”是氢或烃基。
最优选的配合物是那些M为钛或锆的配合物。
适合的配合物的说明性而非限定性的实例有(叔丁基酰胺基)(四甲基-η5-环戊二烯基)二甲基硅烷钛二甲基、(叔丁基酰胺基)二苄基(四甲基-η5-环戊二烯基)硅烷锆二苄基、(苄基酰胺基)二甲基(四甲基-η5-环戊二烯基)硅烷钛二氯化物、(苯基phosphido)二甲基(四甲基-η5-环戊二烯基)硅烷锆二苄基等。
这些配合物与活化助催化剂结合被赋予了催化活性。适用的助催化剂包括铝氧烷,特别是甲基铝氧烷(MAO)或强路易斯酸如三(烃基)硼化合物或卤化衍生物。
特别适合作为活化剂的是三(五氟苯基)硼。
也适合用于按照本发明的方法的还有具有下面通式的金属茂配合物:
M是Zr、Ti或Hf
Y是一个单价配位体
Cp是一个未取代或取代的环戊二烯基配位体,和
Z是一个桥连基团。
典型的Y基团为卤素或烷基,所述环戊二烯基配位体可被烷基取代或两个取代基可结合形成一个稠环如茚基。
Z一般为亚烷基、二烷基甲硅烷基或二烷锗基桥连基团。
特别适用的配合物有例如亚乙基双(茚基)锆二氯化物或亚乙基双(茚基)锆二甲基。
这种金属茂配合物一般在铝氧烷助催化剂存在下使用。
适用于按照本发明的方法的这种金属茂配合物的例子公开于EP129368、EP 206794和EP 260130中。
当这种双(Cp)金属茂配合物也包括二烯配位体时,它们也适用于本发明的方法中。具有这种二烯配位体的双(Cp)金属茂配合物可通过下式表示:式中
M是钛、锆或铪,
D是一稳定的共轭二烯,任选由一个或多个烃基、甲硅烷基、烃基甲硅烷基、甲硅烷基烃基或其组合取代,或者可含有一个路易斯碱官能度,所述D具有4-40个非氢原子并与M形成一个π-配合物。
Z是一个桥连基团,包括具有1-20个碳原子的亚烷基或一个二烷基甲硅烷基或锗烷基或烷基膦或氨基,
R是氢或具有1-10个碳原子的烷基,x是1-6。
通过X-射线衍射或NMR证实在该类型化合物中最优选的金属茂配合物是那些D配位体以η3方式与M原子π-键合的配合物。这种金属茂配合物的特征在于M原子为+2氧化态。
优选的配合物是那些M为锆以及Z为亚乙基(CH2CH2)的配合物。
所述D配位体最优选选自:
s-反-η4,4-二苯基-1,3-丁二烯;s-反-η4-3-甲基-1,3-戊二烯;s-反-η4-1,4-二苄基-1,3-丁二烯;s-反-η4-2,4-己二烯;s-反-η4-1,4-二甲苯基-1,3-丁二烯;s-反-η4-1,4-双(三甲基甲硅烷基)-1,3-丁二烯;s-顺-η4-1,4-二苯基-1,3-丁二烯;s-顺-η4-3-甲基-1,3-戊二烯;s-顺-η4-2,4-己二烯;s-顺-η4-2,4-己二烯;s-顺-η4-1,3-戊二烯;s-顺-η4-1,4-二甲苯基-1,3-丁二烯和s-顺-η4-1,4-双(三甲基甲硅烷基)-1,3-丁二烯,所述s-顺二烯基团与所述金属形成如此中定义的π-配合物。
特别适合的是外取代的二烯,特别是1,4-二苯基取代的丁二烯。
这些配合物的制备广泛描述于WO96/04290中,该专利也列出了可供本发明使用的适合代表的例子。
当所述二烯基团D具有路易斯碱官能度时,那么它可能选自下列基团:
-NR2、-PR2、-AsR2、-OR、-SR
特别优选的这种类型的二烯是二烷基氨基苯基取代的二烯烃例如1-苯基-4-(N,N1-二乙基氨基苯基)-1,3-丁二烯。
特别优选的配合物是亚乙基双(茚基)锆(II)1,4-二苯基丁二烯。
在本发明的方法中使用的配合物与活化剂的摩尔比率范围为1∶10000到100∶1。优选的范围是1∶5000到10∶1,最优选的范围为1∶10到1∶1。
所述链烷烃可选自包括丁烷、戊烷、异戊烷或己烷的低级链烷烃。优选所述链烷烃为戊烷。
链烷烃可在单体加入前加入到气相反应器中。优选其作为液体在室温下加入并且被直接加入到反应器中。或者所述链烷烃可在聚合过程中连续加入到反应器中。
在气相中使用的按照本发明方法的配合物可载于载体上。或者所述金属茂配合物也可不载于载体上使用。
当载于载体上时,所述载体可以是任何有机或无机惰性固体物。特别是多孔载体诸如滑石、无机氧化物和树脂载体材料诸如聚烯烃。可用的适合无机氧化物材料包括第2、13、14或15族的金属氧化物诸如硅石、矾土、硅石-矾土和其混合物。其它可单独使用或与硅石、铝土或硅石-矾土混合使用的无机氧化物有氧化镁、二氧化钛或氧化锆。也可使用其它适用的载体材料诸如细碎的聚烯烃如聚乙烯。
可载按照本发明的催化剂的最优选载体材料是硅石。
优选所述硅石子使用前干燥,这一般通过在升高的温度诸如200-850℃下加热来进行。
在一个优选的方案中,载于载体上的催化剂可通过将所述活化剂在一适合的溶剂中的溶液加入到用三烷基铝化合物处理的活化硅石的淤浆中并接着加入金属茂配合物在相同溶剂中的溶液来制备。或者所述配合物也可在加入活化剂前加入到三烷基铝处理的硅石中。
一种适合于制备负载催化剂的溶剂是甲苯。
适用的三烷基铝化合物是三甲基铝(TMA)、三乙基铝(TEA)或三异丁基铝(TIBAL)。
按照本发明的方法适用于烯烃的聚合,特别是乙烯的均聚或乙烯与其它α-烯烃特别是具有3到10个碳原子的α-烯烃的共聚。最优选的α-烯烃是1-丁烯、1-己烯和4-甲基-1-戊烯。
本发明的方法可用任何适用的气相方法进行。
例如常规的搅拌床反应器诸如公开于US 3256263和US 4012573中的这种反应器可以适用。但是,按照本发明的方法特别适用于包括一流化床的气相方法中。在这种方法中,生长聚合物颗粒的流化床被支承在流化栅条上面。所述床通过使用包括向上通过栅条的循环气流的流化介质来维持。
一种特定类型的流化床操作利用循环气流冷却来帮助流化床的冷却。含夹带液的冷却的循环气流被返回到在流化栅条下面的流化床中。例如EP 89691、EP 699212和EP 784637公开了这种气相方法。
另一种类型的气相方法描述于WO94/28032中,其中一循环气流被冷却并被分成一气流和一液流。所冷却的液体可以是一种惰性液体,也可以是一种可冷凝的单体。为了提供流化床的冷却,所分离的液流被直接导入到流化床中。
在这种流化床方法中,所述链烷烃可通过任何方式加入到反应器中。例如,所述链烷烃可直接加入到反应器中,或者所述链烷烃也可例如通过加入到循环管线、催化剂注入***等中间接加入。
所述链烷烃可在聚合过程中连续加入到流化床反应器中。
就气相方法特别是流化床反应器来说,在按照本发明的方法中链烯烃的适用量可优选用稳定态条件下链烷烃与催化剂的重量比来表示。链烷烃与催化剂的重量比大于或等于10。所述重量比值优选为10-10000。
或者所述链烷烃的量也可用稳定态条件下链烷烃与反应器中聚合物量的重量比率来表示。链烷烃与聚合物的最小重量比值为0.010,其优选的范围为0.010-0.5,最优选的范围为0.018-0.5。
在低的共聚用单体浓度的聚合条件下链烷烃特别有效。
使用按照本发明的方法,可制备具有0.905-0.960g/cc的密度和0.1-20的熔体指数[按照ASTM D 1238条件E(2.16kg,在190℃)的聚合物。
本发明将进一步就下面实施例来加以说明。
实施例1
负载的催化剂1的制备
将7.0公斤Crosfield ES 70硅石(在500℃活化)在110升己烷中制成淤浆。加入9.32升0.976M TEA的己烷溶液,并将淤浆在30℃搅拌2小时。让硅石沉降,并移除己烷上清液。将硅石用己烷洗涤几次直到在洗出液中Al的浓度达到<1毫摩尔Al/升。然后将硅石在40℃真空干燥。
将50克这种TEA处理的ES 70硅石在250毫升干燥甲苯中制成淤浆。加入10.4毫升10.7%(重量)(叔丁基酰胺基)(四甲基-n5-环戊二烯基)二甲基硅烷钛戊-1,3-二烯的甲苯溶液并将混合物剧烈摇晃。然后加入29.4毫升7.85%(重量)三(五氟苯基)硼的甲苯溶液。将混合物摇晃均匀后在40℃真空除去溶剂而得到一种橄榄绿色粉末。
实施例2
负载的催化剂2的制备
将2.5公斤Crosfield ES 70硅石(在500℃活化)在110升己烷中制成淤浆。加入4.00升0.976M TEA的己烷溶液,并将淤浆在30℃搅拌2小时。让硅石沉降,并移除己烷上清液。将硅石用己烷洗涤几次直到在洗出液中Al的浓度达到<1毫摩尔Al/升。然后将硅石在40℃真空干燥。
将10克这种TEA处理的ES 70硅石在40毫升干燥甲苯中制成淤浆。加入2.1毫升10.7%(重量)(叔丁基酰胺基)(四甲基-n5-环戊二烯基)二甲基硅烷钛戊-1,3-二烯的甲苯溶液并将混合物剧烈摇晃。然后加入5.9毫升7.85%(重量)三(五氟苯基)硼的甲苯溶液。将混合物摇晃均匀后在40℃真空除去溶剂而得到一种橄榄绿色粉末。
实施例3
聚合
将347克NaCl加入到预先已在85℃、N2清洗流下烘干的2.5升体积的、搅拌、干燥相反应器中。将反应器冷却到25℃并将5毫升干燥戊烷加入到反应器中。将反应器密封并将温度升到85℃。将1.19克TIBAL处理的硅石加入到反应器中并搅拌15分钟。将反应器冷却到70℃并加入6.5巴C2H4。然后将H2和1-己烯导入到反应器中。将0.309克实施例1制备的催化剂和0.912克TIBAL处理的硅石的混合物用高压N2注入到反应器中。在所述试验的其余时间里,温度、C2H4压力和H2及1-己烷水平均保持恒定。总聚合时间为233分钟。在试验期间,平均的H2/C2H4比率为0.0038,平均的1-己烯/C2H4比率为0.0062。将反应器放空和冷却,在洗除盐后回收262克聚合物,给出了33.6克/克催化剂.小时.巴的活性。聚合物密度为0.9175克/毫升并且M1(2.16)为2.10。
实施例4
聚合
将289克NaCl加入到预先已在85℃、N2清洗流下烘干的2.5升体积的、搅拌、干燥相反应器中。将反应器冷却到25℃并将5毫升干燥戊烷加入到反应器中。将反应器密封并将温度升到85℃。将1.30克TIBAL处理的硅石加入到反应器中并搅拌15分钟。将反应器冷却到70℃并加入6.5巴的C2H4。然后将H2和1-己烯导入到反应器中。将0.289克实施例1制备的催化剂和0.853克TIBAL处理的硅石的混合物用高压N2注入到反应器中。在所述试验的其余时间里,温度、C2H4压力和H2及1-己烯水平均保持恒定。总聚合时间为105分钟。在试验期间,平均的H2/C2H4比率为0.0040,平均的1-己烯/C2H4比率为0.0060。将反应器放空和冷却,在洗除盐后回收144克聚合物,给出了43.8克/克催化剂.小时.巴的活性。聚合物密度为0.9175克/毫升并且M1(2.16)为3.10。
实施例5
(对比)
将344克NaCl加入到预先已在85℃、N2清洗流下烘干的2.5升体积的、搅拌、干燥相反应器中。将1.30克TIBAL处理的硅石加入到反应器中并搅拌15分钟。将反应器冷却到70℃并加入6.5巴C2H4。然后将H2和1-己烯导入到反应器中。将0.213克实施例1制备的催化剂和0.781克TIBAL处理的硅石的混合物用高压N2注入到反应器中。在所述试验的其余时间里,温度、C2H4压力和H2及1-己烯水平均保持恒定。总聚合时间为166分钟。在试验期间,平均的H2/C2H4比率为0.0039,平均的1-己烯/C2H4比率为0.0053。将反应器放空和冷却,在洗除盐后回收101克聚合物,给出了26.3克/克催化剂.小时.巴的活性。
实施例6
聚合
将273克NaCl加入到预先已在85℃、N2清洗流下烘干的2.5升体积的、搅拌、干燥相反应器中。将反应器冷却到25℃并将5毫升干燥戊烷加入到反应器中。将反应器密封并将温度升到85℃。将1.21克TIBAL处理的硅石加入到反应器中并搅拌15分钟。将反应器冷却到70℃并加入6.5巴C2H4。然后将H2和1-己烯导入到反应器中。将0.217克实施例2制备的催化剂和0.755克TIBAL处理的硅石的混合物用高压N2注入到反应器中。在所述试验的其余时间里,温度、C2H4压力和H2及1-己烯水平均保持恒定。总聚合时间为132分钟。在试验期间,平均的H2/C2H4比率为0.0042,平均的1-己烯/C2H4比率为0.0044。将反应器放空和冷却,在洗除盐后回收122克聚合物,给出了39.3克/克催化剂.小时.巴的活性。聚合物密度为0.918克/毫升并且M1(2.16)为4.4。
实施例7
(对比)
将322克NaCl加入到预先已在85℃、N2清洗流下烘干的2.5升体积的搅拌干燥相反应器中。将1.19克TIBAL处理的硅石加入到反应器中并搅拌15分钟。将反应器冷却到70℃并加入6.5巴C2H4。然后将H2和1-己烯导入到反应器中。将0.220克实施例2制备的催化剂和0.754克TIBAL处理的硅石的混合物用高压N2注入到反应器中。在所述试验的其余时间里,温度、C2H4压力和H2及1-己烯水平均保持恒定。总聚合时间为123分钟。在试验期间,平均的H2/C2H4比率为0.0035,平均的1-己烯/C2H4比率为0.0037。将反应器放空和冷却,在洗除盐后回收85克聚合物,给出了29.0克/克催化剂.小时.巴的活性。聚合物密度为0.919克/毫升并且M1(2.16)为0.8。
Claims (15)
1.一种在气相反应器中烯烃聚合的方法,所述方法在一个包括(a)一种金属茂和(b)一种活化剂的催化剂体系的存在下进行,特征在于一种低级链烷烃被加入到所述气相反应器中。
2.按照权利要求1的方法,其中所述低级链烷烃选自丁烷、戊烷、异戊烷或己烷。
3.按照权利要求2的方法,其中所述链烷烃是戊烷。
4.按照前述权利要求中任一项的方法,其中所述链烷烃被直接加入到反应器中。
5.按照前述权利要求中任一项的方法,其中所述链烷烃以液体形式加入到反应器中。
R’总是独立地选自氢、烃基、甲硅烷基、甲锗烷基、卤代、氰基和其组合,所述R’至多具有20个非氢原子并且任选两个R’基团(这里R’不是氢、卤代或氰基)一起形成一种其二价衍生物,其与所述环戊二烯基环的相邻位置相连形成一稠环结构;
X是一个具有至多30个非氢原子的中性η4-键合的二烯基团,它与M形成一种π-配合物;
Y是-O-、-S-、-NR*-、-PR*-;
M是+2形式氧化态的钛或锆;
Z*是SiR2、CR* 2、SiR* 2SiR* 2、CR* 2CR* 2、CR*=CR*、CR2SiR* 2或GeR* 2;其中
R*总是独立地为氢或者为选自烃基、甲硅烷基、卤代烷基、卤代芳基和其组合的一个成员,所述R*至多具有10个非氢原子,并且任选两个来自Z*(当R*不是氢时)的R*基团或一个来自Z*的R*基团和一个来自Y的R*基团形成一个环***。
Cp*是一单个η5-环戊二烯基或η5-取代的环戊二烯基基团,任选通过-Z-Y-共价结合到M上并且符合于下式:中R总是为氢或者为选自卤素、烷基、芳基、卤代烷基、烷氧基、芳氧基、甲硅烷基和其至多20个非氢原子的组合的部分,或者两个或多个R基团一起形成一个稠环***;
M是以η5键合形式结合到环戊二烯基或取代的环戊二烯基基团上的锆、钛或铪并且是处于+3或+4的价态;
X总是为氢化物或为选自卤代、烷基、芳基、甲硅烷基、甲锗烷基、芳氧基、烷氧基、酰胺、甲硅烷氧基和至多具有20个非氢原子的其组合(例如卤代烷基、卤代芳基、卤代甲硅烷基、烷芳基、芳烷基、甲硅烷基烷基、芳氧基芳基和烷氧基烷基、酰胺基烷基、酰胺基芳基)的部分和至多具有20个非氢原子的中性路易斯碱配位体;
n根据M的价态为1或2;
Z是一个二价部分,包括氧、硼或元素周期表14族的一个成员;
Y是一个共价结合到所述金属上的连接基团,包括氮、磷、氧或硫,或任选Z和Y一起形成一个稠合环***。
8.按照前述权利要求中任一项的方法,其中所述活化剂是三(五氟苯基)硼。
9.按照前述权利要求中任一项的方法,其中所述金属茂被载于载体上。
10.按照权利要求13的方法,其中所述金属茂被载于硅石上。
11.按照前述权利要求中任一项的方法,其中所述聚合方法在流化床反应器中进行。
12.按照权利要求11的方法,其中所述链烷烃被连续加入到所述流化床反应器中。
13.按照前述权利要求中任一项的方法,其中在稳定态条件下,链烷烃与催化剂的重量比率为10-10000。
14.按照前述权利要求中任一项的方法,其中在稳定态条件下,在反应器中链烷烃与聚合物的重量比率为0.010-0.5。
15.按照权利要求14的方法,其中在反应器中链烷烃与聚合物的重量比率范围为0.018-0.5。
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BR9806744A (pt) | 2000-03-14 |
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ZA98225B (en) | 1999-07-12 |
EP0952993B1 (en) | 2004-10-06 |
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PL334549A1 (en) | 2000-03-13 |
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EP0952993A1 (en) | 1999-11-03 |
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HUP0000776A3 (en) | 2000-11-28 |
EG22048A (en) | 2002-06-30 |
AU5565798A (en) | 1998-08-03 |
AU747055B2 (en) | 2002-05-09 |
NO993432D0 (no) | 1999-07-12 |
ATE278716T1 (de) | 2004-10-15 |
US6437062B1 (en) | 2002-08-20 |
AR014339A1 (es) | 2001-02-28 |
NZ336639A (en) | 2001-11-30 |
WO1998030605A1 (en) | 1998-07-16 |
SK93699A3 (en) | 2000-05-16 |
KR100580902B1 (ko) | 2006-05-17 |
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