CN1865208A - Magnesium compound, solid catalyst component for olefin polymerization, catalyst for olefin polymerization, and process for producing polyolefin - Google Patents
Magnesium compound, solid catalyst component for olefin polymerization, catalyst for olefin polymerization, and process for producing polyolefin Download PDFInfo
- Publication number
- CN1865208A CN1865208A CN 200610077334 CN200610077334A CN1865208A CN 1865208 A CN1865208 A CN 1865208A CN 200610077334 CN200610077334 CN 200610077334 CN 200610077334 A CN200610077334 A CN 200610077334A CN 1865208 A CN1865208 A CN 1865208A
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- China
- Prior art keywords
- magnesium
- compound
- preparation
- halogen
- magnesium compound
- Prior art date
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- 150000002681 magnesium compounds Chemical class 0.000 title claims abstract description 275
- 239000011949 solid catalyst Substances 0.000 title claims abstract description 147
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 114
- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 33
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims description 39
- 229920000098 polyolefin Polymers 0.000 title claims description 26
- 230000008569 process Effects 0.000 title description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 145
- 150000001875 compounds Chemical class 0.000 claims abstract description 98
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 92
- 150000002367 halogens Chemical class 0.000 claims abstract description 91
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 62
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 39
- 125000005843 halogen group Chemical group 0.000 claims abstract description 23
- 238000002360 preparation method Methods 0.000 claims description 191
- 239000002245 particle Substances 0.000 claims description 71
- 238000009826 distribution Methods 0.000 claims description 68
- 238000006243 chemical reaction Methods 0.000 claims description 56
- 150000002366 halogen compounds Chemical class 0.000 claims description 25
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 21
- 229910052740 iodine Inorganic materials 0.000 claims description 21
- 239000011630 iodine Substances 0.000 claims description 21
- 230000000379 polymerizing effect Effects 0.000 claims description 15
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 14
- 150000002899 organoaluminium compounds Chemical class 0.000 claims description 9
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims description 7
- 239000005049 silicon tetrachloride Substances 0.000 claims description 7
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 abstract description 47
- 229910052749 magnesium Inorganic materials 0.000 abstract description 28
- 125000004429 atom Chemical group 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 69
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 69
- -1 alkoxyl magnesium Chemical compound 0.000 description 59
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 35
- 239000002002 slurry Substances 0.000 description 35
- 230000000052 comparative effect Effects 0.000 description 34
- 230000037048 polymerization activity Effects 0.000 description 29
- 238000003756 stirring Methods 0.000 description 28
- 238000005520 cutting process Methods 0.000 description 24
- 229940091250 magnesium supplement Drugs 0.000 description 23
- 229910052757 nitrogen Inorganic materials 0.000 description 20
- 239000000126 substance Substances 0.000 description 15
- 238000005406 washing Methods 0.000 description 15
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 description 14
- 230000000694 effects Effects 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- 230000008676 import Effects 0.000 description 10
- 239000012442 inert solvent Substances 0.000 description 10
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 10
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 10
- 229910052719 titanium Inorganic materials 0.000 description 10
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 10
- 150000002148 esters Chemical class 0.000 description 9
- 229920001155 polypropylene Polymers 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000010936 titanium Substances 0.000 description 9
- 150000002431 hydrogen Chemical class 0.000 description 8
- 238000010298 pulverizing process Methods 0.000 description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 239000004411 aluminium Substances 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 description 6
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- 230000001476 alcoholic effect Effects 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 230000009849 deactivation Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- YZBOVSFWWNVKRJ-UHFFFAOYSA-N Monobutylphthalate Chemical class CCCCOC(=O)C1=CC=CC=C1C(O)=O YZBOVSFWWNVKRJ-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 229960002337 magnesium chloride Drugs 0.000 description 4
- 229940073589 magnesium chloride anhydrous Drugs 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical class COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000010191 image analysis Methods 0.000 description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- BBLDTXFLAHKYFJ-UHFFFAOYSA-N 2,2,5,5-tetramethyloxolane Chemical compound CC1(C)CCC(C)(C)O1 BBLDTXFLAHKYFJ-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
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- ZZHNUBIHHLQNHX-UHFFFAOYSA-N butoxysilane Chemical class CCCCO[SiH3] ZZHNUBIHHLQNHX-UHFFFAOYSA-N 0.000 description 2
- XGZGKDQVCBHSGI-UHFFFAOYSA-N butyl(triethoxy)silane Chemical compound CCCC[Si](OCC)(OCC)OCC XGZGKDQVCBHSGI-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- YYUODOUSPSBQCB-UHFFFAOYSA-N cyclohexyl-dimethoxy-(2-methylpropyl)silane Chemical compound CC(C)C[Si](OC)(OC)C1CCCCC1 YYUODOUSPSBQCB-UHFFFAOYSA-N 0.000 description 2
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical class Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- 150000003608 titanium Chemical class 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
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- JFNOHUKJHAEWPT-UHFFFAOYSA-N (2,3-diethylphenyl) dihydrogen phosphate Chemical compound CCC1=CC=CC(OP(O)(O)=O)=C1CC JFNOHUKJHAEWPT-UHFFFAOYSA-N 0.000 description 1
- AUEJBKCWXPYRGZ-UHFFFAOYSA-N 1,1'-biphenyl diethoxysilane Chemical compound C(C)O[SiH2]OCC.C1(=CC=CC=C1)C1=CC=CC=C1 AUEJBKCWXPYRGZ-UHFFFAOYSA-N 0.000 description 1
- XULIXFLCVXWHRF-UHFFFAOYSA-N 1,2,2,6,6-pentamethylpiperidine Chemical compound CN1C(C)(C)CCCC1(C)C XULIXFLCVXWHRF-UHFFFAOYSA-N 0.000 description 1
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 1
- SDRZFSPCVYEJTP-UHFFFAOYSA-N 1-ethenylcyclohexene Chemical compound C=CC1=CCCCC1 SDRZFSPCVYEJTP-UHFFFAOYSA-N 0.000 description 1
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- GPORRIDBUMYDBI-UHFFFAOYSA-N 1h-inden-1-yl(trimethoxy)silane Chemical compound C1=CC=C2C([Si](OC)(OC)OC)C=CC2=C1 GPORRIDBUMYDBI-UHFFFAOYSA-N 0.000 description 1
- KPWDGTGXUYRARH-UHFFFAOYSA-N 2,2,2-trichloroethanol Chemical compound OCC(Cl)(Cl)Cl KPWDGTGXUYRARH-UHFFFAOYSA-N 0.000 description 1
- CGQUNQXEUGWOAL-UHFFFAOYSA-N 2,2,5,5-tetraethyloxolane Chemical compound CCC1(CC)CCC(CC)(CC)O1 CGQUNQXEUGWOAL-UHFFFAOYSA-N 0.000 description 1
- POWUJINVZSHIGY-UHFFFAOYSA-N 2,6-di(propan-2-yl)piperidine Chemical class CC(C)C1CCCC(C(C)C)N1 POWUJINVZSHIGY-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 1
- HQFVIEXGUZDHOJ-UHFFFAOYSA-N 4-methyl-2,6-di(propan-2-yl)piperidine Chemical compound CC(C)C1CC(C)CC(C(C)C)N1 HQFVIEXGUZDHOJ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- GBTUHNBIKJUSFT-UHFFFAOYSA-N CC1C(CCC1)[SiH](OC)OC Chemical compound CC1C(CCC1)[SiH](OC)OC GBTUHNBIKJUSFT-UHFFFAOYSA-N 0.000 description 1
- RHKSUESHSAXWHA-UHFFFAOYSA-N CCCCCCO[Mg] Chemical compound CCCCCCO[Mg] RHKSUESHSAXWHA-UHFFFAOYSA-N 0.000 description 1
- PNOKYPRWZDSLSD-UHFFFAOYSA-N CCCCCCO[Ti] Chemical compound CCCCCCO[Ti] PNOKYPRWZDSLSD-UHFFFAOYSA-N 0.000 description 1
- MVHZHMKEBJJTCH-UHFFFAOYSA-N CN(C)C.CO[SiH3] Chemical compound CN(C)C.CO[SiH3] MVHZHMKEBJJTCH-UHFFFAOYSA-N 0.000 description 1
- NXKGJIRLCQBHFD-UHFFFAOYSA-N CO[SiH](OC)CC(C)C Chemical compound CO[SiH](OC)CC(C)C NXKGJIRLCQBHFD-UHFFFAOYSA-N 0.000 description 1
- ZALOHOLPKHYYAX-UHFFFAOYSA-L CO[Ti](Cl)(Cl)OC Chemical compound CO[Ti](Cl)(Cl)OC ZALOHOLPKHYYAX-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- WRYCSMQKUKOKBP-UHFFFAOYSA-N Imidazolidine Chemical compound C1CNCN1 WRYCSMQKUKOKBP-UHFFFAOYSA-N 0.000 description 1
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- HFTSQAKJLBPKBD-UHFFFAOYSA-N magnesium;butan-1-olate Chemical compound [Mg+2].CCCC[O-].CCCC[O-] HFTSQAKJLBPKBD-UHFFFAOYSA-N 0.000 description 1
- MBTRTTIWMFMDQR-UHFFFAOYSA-M magnesium;butan-1-olate;bromide Chemical compound [Br-].CCCCO[Mg+] MBTRTTIWMFMDQR-UHFFFAOYSA-M 0.000 description 1
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- 239000000178 monomer Substances 0.000 description 1
- VGIVLIHKENZQHQ-UHFFFAOYSA-N n,n,n',n'-tetramethylmethanediamine Chemical compound CN(C)CN(C)C VGIVLIHKENZQHQ-UHFFFAOYSA-N 0.000 description 1
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- LTEDQKPGOZDGRZ-UHFFFAOYSA-L propan-2-olate;titanium(4+);dichloride Chemical compound Cl[Ti+2]Cl.CC(C)[O-].CC(C)[O-] LTEDQKPGOZDGRZ-UHFFFAOYSA-L 0.000 description 1
- FLALGSYYVIWTFQ-UHFFFAOYSA-K propan-2-olate;titanium(4+);trichloride Chemical class [Cl-].[Cl-].[Cl-].CC(C)O[Ti+3] FLALGSYYVIWTFQ-UHFFFAOYSA-K 0.000 description 1
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- AIFMYMZGQVTROK-UHFFFAOYSA-N silicon tetrabromide Chemical compound Br[Si](Br)(Br)Br AIFMYMZGQVTROK-UHFFFAOYSA-N 0.000 description 1
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- HXLWJGIPGJFBEZ-UHFFFAOYSA-N tert-butyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(C)(C)C HXLWJGIPGJFBEZ-UHFFFAOYSA-N 0.000 description 1
- RTZXSWUXDHSDMQ-UHFFFAOYSA-N tert-butyl-cyclohexyl-dimethoxysilane Chemical compound CO[Si](OC)(C(C)(C)C)C1CCCCC1 RTZXSWUXDHSDMQ-UHFFFAOYSA-N 0.000 description 1
- VMDQOUFBCDKESZ-UHFFFAOYSA-N tert-butyl-cyclopentyl-dimethoxysilane Chemical compound CO[Si](OC)(C(C)(C)C)C1CCCC1 VMDQOUFBCDKESZ-UHFFFAOYSA-N 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 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
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- HUZZQXYTKNNCOU-UHFFFAOYSA-N triethyl(methoxy)silane Chemical compound CC[Si](CC)(CC)OC HUZZQXYTKNNCOU-UHFFFAOYSA-N 0.000 description 1
- XYJRNCYWTVGEEG-UHFFFAOYSA-N trimethoxy(2-methylpropyl)silane Chemical compound CO[Si](OC)(OC)CC(C)C XYJRNCYWTVGEEG-UHFFFAOYSA-N 0.000 description 1
- VYHWVLSMXFMGPI-UHFFFAOYSA-N trimethoxy(3-methylbutyl)silane Chemical compound CO[Si](OC)(OC)CCC(C)C VYHWVLSMXFMGPI-UHFFFAOYSA-N 0.000 description 1
- HILHCDFHSDUYNX-UHFFFAOYSA-N trimethoxy(pentyl)silane Chemical compound CCCCC[Si](OC)(OC)OC HILHCDFHSDUYNX-UHFFFAOYSA-N 0.000 description 1
- IOPAQHDEQBHWEB-UHFFFAOYSA-N trimethoxy-(2-methylcyclopentyl)silane Chemical compound CO[Si](OC)(OC)C1CCCC1C IOPAQHDEQBHWEB-UHFFFAOYSA-N 0.000 description 1
- OJAJJFGMKAZGRZ-UHFFFAOYSA-N trimethyl(phenoxy)silane Chemical compound C[Si](C)(C)OC1=CC=CC=C1 OJAJJFGMKAZGRZ-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- 238000012725 vapour phase polymerization Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a magnesium compound obtained by reacting metallic magnesium having a sphericity of less than 4.00, represented by the following formula (I), an alcohol, and a halogen and/or a halogen-containing compound containing 0.0001 gram atom or more of a halogen atom to 1 gram atom of the metallic magnesium: s ═ L1/L2)3(I) [ in the formula, L1The maximum diameter L of the magnesium metal in the projection view obtained by image processing of the magnesium metal taken with a scanning electron microscope2Diameter of a circle representing a projected area equal to the above-mentioned metal magnesium](ii) a A solid catalyst component obtained by using the magnesium compound and the titanium compound, and a catalyst for olefin polymerization obtained by using the solid catalyst component.
Description
The application is that May 19 2003 applying date, the application number of PCT international application is PCT/JP2003/006195, and denomination of invention is divided an application for " magnesium compound, solid catalyst component for olefin polymerization, catalyst for olefines polymerizing and preparation of polyolefins method ".
Technical field
The present invention relates to magnesium compound, solid catalyst component for olefin polymerization, catalyst for olefines polymerizing and preparation of polyolefins method.
Background technology
Originally in the catalyst field of for olefines polymerization of olefines homopolymerizations such as ethene or propylene or copolymerization, extensively adopt the technology of magnesium compounds such as the magnesium chloride do not pulverized or alkoxyl magnesium, seek the improvement etc. of the powder morphology of the raising of catalyst activity and olefin polymer whereby as support material.
For example, for forms such as the particle diameter of improveing olefin polymer and shapes, the spy opens the method that clear 63-280707 communique etc. discloses load magnesium compound on inorganic oxides such as silicon-dioxide; In addition, the spy open clear 58-000811 communique etc. disclose once be dissolved in the pure equal solvent magnesium compound after, the method that it is separated out.
Yet, these methods since must carry out magnesium compound load, dissolve and processing such as separate out, operation is very loaded down with trivial details.In addition, the shortcoming of these methods is that only high in polymerization initial stage activity of such catalysts, the stability of catalyzer is poor.
In addition, the spy opens flat 4-130107 communique and discloses to adopt and make the halogen of MAGNESIUM METAL, alcohol and specified quantitative react resulting magnesium compound, as the method for support of the catalyst.Yet, when adopting this method, depending on the proterties of MAGNESIUM METAL particle, the preparation condition of magnesium compound etc., the sphericity of resulting carrier and polymeric powder, size distribution etc. may not be thought very good.
The present invention considers from above-mentioned viewpoint, its purpose is to provide catalyst performances such as a kind of legislate and polymerization activity not reduce, narrow diameter distribution, and/or provide magnesium compound, solid catalyst component for olefin polymerization, catalyst for olefines polymerizing and the preparation of polyolefins method that is similar to the globular olefin polymer.
What the present inventor furtherd investigate in order to achieve the above object found that, having specific sphericity or size distribution exponential MAGNESIUM METAL or from the resulting magnesium compound of the MAGNESIUM METAL of thickness below particular value of oxide film thereon or have the MAGNESIUM METAL of specific median size, alcohol and the halogen and/or the halogen-containing compound of specified quantitative, under specific agitation condition, make prepared magnesium compound of reaction and titanium compound reaction and the preparation solid catalyst component for olefin polymerization, can solve above-mentioned problem whereby, finish the present invention.
Summary of the invention
According to the present invention, can provide following magnesium compound etc.
[1] a kind of magnesium compound, it makes with the sphericity (S) of following formula (I) expression and obtains less than 4.00 MAGNESIUM METAL, alcohol and with respect to halogen and/or the reaction of halogen-containing compound that above-mentioned MAGNESIUM METAL 1 grammeatom contains the above halogen atom of 0.0001 grammeatom,
S＝(L
1/L
2)
3 (I)
[in the formula, L
1Expression is photographed with scanning electron microscope, carries out the sciagraph longest diameter of the above-mentioned MAGNESIUM METAL that picture processing obtains, L
2Expression equals the circular diameter of the shadow area of above-mentioned MAGNESIUM METAL].
[2] a kind of magnesium compound, it makes with the size distribution index (P) of following formula (II) expression and obtains less than 4.0 MAGNESIUM METAL, alcohol and with respect to halogen and/or the reaction of halogen-containing compound that above-mentioned MAGNESIUM METAL 1 grammeatom contains the above halogen atom of 0.0001 grammeatom
P＝(D
90/D
10) (II)
[in the formula, D
90Expression is corresponding to the particle diameter of the above-mentioned MAGNESIUM METAL of accumulating weight mark 90%, D
10Expression is corresponding to the particle diameter of the above-mentioned MAGNESIUM METAL of accumulating weight mark 10%].
[3] a kind of magnesium compound, it is the median size (D of handle corresponding to the above-mentioned MAGNESIUM METAL of accumulating weight mark 50%
50) be the MAGNESIUM METAL of 50～2,000 μ m; With respect to the mol ratio (ROH/Mg) of 1 mole of above-mentioned MAGNESIUM METAL 4～40 alcohol; And the halogen and/or the halogen-containing compound that contain the halogen atom more than 0.0001 grammeatom with respect to above-mentioned MAGNESIUM METAL 1 grammeatom, in configuration has the steel basin of stir shaft of agitating vane of blade diameter d (m), stir with revolution n (inferior/minute), make n
3d
2Reach 4.3 * 10
3～4.0 * 10
6And the magnesium compound that reaction obtains.
[4] a kind of magnesium compound, it is to contain the halogen of the above halogen atom of 0.0001 grammeatom and/or the reaction of halogen-containing compound and the magnesium compound that obtains the MAGNESIUM METAL below the oxide film thereon thickness 1 μ m, alcohol and with respect to above-mentioned MAGNESIUM METAL 1 grammeatom.
[5] any one described magnesium compound in above-mentioned [1]～[4], wherein, halogen is an iodine.
[6] any one described magnesium compound in above-mentioned [1]～[5], wherein, above-mentioned halogen-containing compound is a magnesium chloride.
[7] any one described magnesium compound in above-mentioned [1]～[6], wherein, above-mentioned MAGNESIUM METAL, alcohol, and the temperature of reaction of halogen and/or halogen-containing compound be 30～90 ℃.
[8] magnesium compound described in above-mentioned [1] wherein, is lower than 1.30 with the sphericity of following formula (III) expression (S '),
S’＝(L
3/L
4)
3 (III)
[in the formula, L
3Expression is photographed with scanning electron microscope, carries out the sciagraph longest diameter of the above-mentioned magnesium compound that picture processing obtains, L
4Expression equals the circular diameter of the shadow area of above-mentioned magnesium compound].
[9] magnesium compound described in above-mentioned [2] or [4], wherein, with the size distribution index of following general formula (IV) expression (P ') less than 3.4,
P’＝(D
90/D
10) (IV)
[in the formula, D
90Expression is corresponding to the particle diameter of the above-mentioned magnesium compound of accumulating weight mark 90%, D
10Expression is corresponding to the particle diameter of the above-mentioned magnesium compound of accumulating weight mark 10%].
[10] magnesium compound described in above-mentioned [3], wherein, the size distribution index of usefulness following formula (IV) expression (P ') less than 3.4, the sphericity of usefulness following formula (III) expression (S ') less than 1.30.
[11] magnesium compound described in above-mentioned [4], wherein, above-mentioned MAGNESIUM METAL is that the median size of particlized reaches MAGNESIUM METAL below the 1cm in inert atmosphere.
[12] a kind of solid catalyst component for olefin polymerization, its by any one described magnesium compound of (a) [1]～[11] and (b) titanium compound reaction obtain.
[13] solid catalyst component for olefin polymerization described in above-mentioned [12], its also by (c) halogen compounds and/or (d) the sub-property compound of power supply reaction obtain.
[14] solid catalyst component for olefin polymerization described in above-mentioned [13], wherein, above-mentioned halogen compounds (c) is a silicon tetrachloride.
[15] a kind of catalyst for olefines polymerizing, it is by following compounds [A] and [B], or following compounds [A], [B] and [C] constitute,
Any one described solid catalyst component for olefin polymerization of [A] [12]～[14];
[B] organo-aluminium compound;
[C] the sub-property compound of powering.
[16] a kind of preparation of polyolefins method wherein adopts the catalyst for olefines polymerizing described in [15].
[17] a kind of magnesium compound preparation method, it makes with the sphericity (S) of following formula (I) expression and contains the halogen and/or the reaction of halogen-containing compound of the above halogen atom of 0.0001 grammeatom less than 4.00 MAGNESIUM METAL, alcohol and with respect to above-mentioned MAGNESIUM METAL 1 grammeatom,
S＝(L
1/L
2)
3(I)
[in the formula, L
1Expression is photographed with scanning electron microscope, carries out the longest diameter of the sciagraph of the above-mentioned MAGNESIUM METAL that picture processing obtains, L
2Expression equals the circular diameter of the shadow area of above-mentioned MAGNESIUM METAL].
[18] a kind of magnesium compound preparation method, it makes with the size distribution index (P) of following formula (II) expression less than 4.0 MAGNESIUM METAL, alcohol and contain the halogen and/or the reaction of halogen-containing compound of the above halogen atom of 0.0001 grammeatom with respect to above-mentioned MAGNESIUM METAL 1 grammeatom
P＝(D
90/D
10)(II)
[in the formula, D
90Expression is corresponding to the particle diameter of the above-mentioned MAGNESIUM METAL of accumulating weight mark 90%, D
10Expression is corresponding to the particle diameter of the above-mentioned MAGNESIUM METAL of accumulating weight mark 10%].
[19] a kind of magnesium compound preparation method, it is the median size (D corresponding to accumulating weight mark 50%
50) be 50～2, the MAGNESIUM METAL of 000 μ m, be 4～40 alcohol and the halogen and/or the halogen-containing compound that contain the above halogen atom of 0.0001 grammeatom with respect to above-mentioned MAGNESIUM METAL 1 grammeatom with respect to the mol ratio (ROH/Mg) of 1 mole of above-mentioned MAGNESIUM METAL, in configuration has the steel basin of stir shaft of agitating vane of blade diameter d (m), carry out stirring reaction with revolution n (inferior/minute) and make n
3d
2Reach 4.3 * 10
3～4.0 * 10
6And the magnesium compound preparation method of reaction.
[20] a kind of magnesium compound preparation method, it is to contain the halogen of the above halogen atom of 0.0001 grammeatom and/or the reaction of halogen-containing compound and obtain the preparation method of magnesium compound the MAGNESIUM METAL below the oxide film thereon thickness 1 μ m, alcohol and with respect to above-mentioned MAGNESIUM METAL 1 grammeatom.
Description of drawings
Fig. 1 is the preparation method's of expression catalyst for olefines polymerizing of the present invention and olefin polymer a mode chart.
Fig. 2 is the preparation method's of expression catalyst for olefines polymerizing of the present invention and olefin polymer a mode chart.
Fig. 3 is the preparation method's of expression catalyst for olefines polymerizing of the present invention and olefin polymer a mode chart.
Fig. 4 is the preparation method's of expression catalyst for olefines polymerizing of the present invention and olefin polymer a mode chart.
Embodiment
Below various catalyst components of using among the present invention etc. are illustrated.Given below is preferred example, but the present invention is not subjected to their qualification.
1. catalyst component
[A1] solid catalyst component for olefin polymerization
(a1) magnesium compound
In the present invention, as magnesium compound (a1), consider from polymer particle shape and polymerization activity, employing with the sphericity (S) of following formula (I) expression less than 4.00, preferably less than 2.50 MAGNESIUM METAL, alcohol, and contain the halogen of the above halogen atom of 0.0001 grammeatom and/or the reaction of halogen-containing compound and the compound that obtains with respect to MAGNESIUM METAL 1 grammeatom
S＝(L
1/L
2)
3(I)
[in the formula, L
1Expression is photographed with scanning electron microscope, carries out the longest diameter of the sciagraph of the MAGNESIUM METAL that picture processing obtains, L
2Expression equals the circular diameter of the shadow area of MAGNESIUM METAL].
When the sphericity (S) of MAGNESIUM METAL 4.00 when above, not only the particle shape of polymkeric substance is poor, and polymerization activity also descends, and is unfavorable.We think that this is because when adopting the low MAGNESIUM METAL of sphericity, the low macroparticle solid catalyst component of generation polymerization activity.
Also have, the spherical degree of sphericity (S) expression object, the object of S=1 is represented proper sphere shape.Therefore, S is more near 1, and each particle of expression MAGNESIUM METAL is more near proper sphere shape.
This sphericity (S) is lower than 4.00 MAGNESIUM METAL, can adopt cutting system such as lathe, file and adopt the combination of ball mill pulverizing etc., or be prepared with efflorescence method (fusion, spray method).
Alcohol, it is preferred adopting the lower alcohol of carbon number 1～6.Particularly when adopting ethanol, can obtain the solid product that catalyst performance such as polymerization activity significantly improves, be preferred.Purity and water content to alcohol are not particularly limited, and when adopting many pure of water content, generate the magnesium hydroxide tunicle at metallic magnesium surface, so, adopt water content below 1%, it is preferred particularly adopting the following alcohol of 2000ppm.In addition, in order to obtain the better particle shape olefin polymer of (each particle shape and size distribution claim form below sometimes), moisture is fewer better, generally wishes below 200ppm.
Halogen can use chlorine, Ju, iodine, and it is specially suitable using iodine.
In addition, the halogen atom of halogen-containing compound, chlorine, bromine, iodine are preferred.In halogen-containing compound, halogen-containing metallic compound is particularly preferred.As halogen-containing compound, concrete use MgCl
2, MgI
2, Mg (OEt) Cl, Mg (OEt) I, MgBr
2, CaCl
2, NaCl, KBr etc. are suitable.Wherein, MgCl
2Be particularly preferred.The state of these compounds, shape, granularity etc. are not particularly limited, and can be arbitrarily, and the solution that for example can be used as pure series solvent (for example ethanol) uses.
Preferred iodine or MgCl
2Reason, by inference, can think owing to can improve the effect of the solubleness of magnesium compound in ethanol.
The consumption of alcohol is with respect to 1 mole preferred 2～100 moles of MAGNESIUM METAL, preferred especially 5～50 moles.When the consumption of alcohol was too much, the yield of the magnesium compound (a1) that form is good often descended, and had served as after a little while, and the stirring in the reactive tank often can not be carried out smoothly.Yet, its mol ratio is not particularly limited.
The consumption of halogen or halogen-containing compound, with respect to MAGNESIUM METAL 1 grammeatom, the halogen atom in halogen or the halogen contained compound is more than 0.0001 grammeatom, more than preferred 0.0005 grammeatom, more preferably more than 0.001 grammeatom.When being lower than 0.0001 grammeatom, when resulting magnesium compound (a1) was used as the carrier of solid catalyst component, the form of polymerization activity or olefin polymer became bad.
In the present invention, halogen or halogen-containing compound both can have been distinguished use separately, also can be used in combination more than 2 kinds.In addition, when halogen and halogen-containing compound are used in combination, whole halogen atom amounts in halogen and the halogen-containing compound, with respect to MAGNESIUM METAL 1 grammeatom reach more than 0.0001 grammeatom, more than preferred 0.0005 grammeatom, more preferably more than 0.001 grammeatom.
Also have, the consumption upper limit of halogen and/or halogen-containing compound is not particularly limited, suitably selection gets final product the scope that can obtain magnesium compound of the present invention (a1) in.Generally speaking, to be lower than 0.06 grammeatom be preferred to its consumption.
In the present invention, the consumption of halogen and/or halogen-containing compound, by suitably selection in above-mentioned scope, when the preparation of magnesium compound (a1), its particle diameter can freely be controlled.
When the preparation of magnesium compound (a1), MAGNESIUM METAL, alcohol and halogen and/or halogen-containing compound reaction (common 1～30 hour) with above-mentioned sphericity (S) are not extremely found till the hydrogen generation.The concrete following method that adopts is prepared: when using iodine as halogen, behind the solid-state iodine of input, heating makes the method for its reaction in the alcoholic solution of MAGNESIUM METAL; Drip the alcoholic solution of iodine in the alcoholic solution of MAGNESIUM METAL after, heating makes the method for its reaction; And the alcoholic solution of the alcoholic solution limit dropping iodine of limit heating of metal magnesium makes the method for its reaction etc.
Also have, any method is all preferably in rare gas element (for example nitrogen, argon gas) atmosphere, and the visual field is closed and adopted inert organic solvents stable hydrocarbon such as (for example) normal hexanes to react.
About MAGNESIUM METAL, alcohol, and the temperature of reaction of halogen and/or halogen-containing compound, usually at 30～90 ℃, preferred 30～60 ℃, when at this range of reaction temperature, performance improves.By inference, can think that this is because the balance of speed of response and solubleness is good, can generate uniform magnesium compound.
About the interpolation of MAGNESIUM METAL, alcohol and halogen and/or halogen contained compound, needn't at first various full doses be added, portion-wise addition also can.For example, can enumerate and divide the method for adding MAGNESIUM METAL for several times again after initial full dose is in advance added alcohol.This situation can prevent from a period of time of hydrogen to take place in a large number, considers it is preferred from the security aspect.In addition, reactive tank also can miniaturization.In addition, can also prevent a large amount of spittle that caused alcohol or halogen etc. take place in a period of time of hydrogen.Divide for several times and add,, be not particularly limited as long as decide according to the scale of reactive tank, when consider to operate miscellaneous the time, it is suitable dividing 5～10 times usually.
In addition, reaction itself can be adopted any of intermittent type, continous way.Also have, as the method for improvement, can be in the alcohol that initial full dose is added a small amount of earlier MAGNESIUM METAL of adding, the resultant that generates by reaction is separated in another groove, after the removal, adds the operation of MAGNESIUM METAL more on a small quantity and carry out repeatedly.
When the magnesium compound that obtains like this (a1) is used to prepare solid catalyst component [A1], both can adopt the exsiccant product, also can adopt the product that after filtration, washs with inert solvents such as heptane.
In either case, the neat operations such as classification of size distribution needn't be pulverized or make to the magnesium compound that obtains among the present invention (a1), promptly can be used as the carrier of solid catalyst component.Magnesium compound of the present invention (a1) is approximate spherical, and size distribution is also sharp-pointed, and the deviation of each particle sphericity is little.
Magnesium compound (a1) is usually less than 1.30 with the sphericity of following formula (III) expression (S '), preferably is lower than 1.28.
S’＝(L
3/L
4)
3 (III)
[in the formula, L
3Expression is photographed with scanning electron microscope, carries out the longest diameter of the sciagraph of the magnesium compound that picture processing obtains, L
4Expression equals the circular diameter of magnesium compound shadow area].
Magnesium compound (a1) with this sphericity (S ') considers it is preferred from the form of catalytic activity and polymer particle.
Also have, same with the situation of the sphericity (S) of MAGNESIUM METAL about sphericity (S '), S ' is more approximate 1, the more approximate proper sphere shape of each particle of magnesium compound (a1).
In addition, magnesium compound (a1), with the size distribution index of following formula (IV) expression (P ') usually less than 4.0, preferably less than 3.8:
P’＝(D
90/D
10) (IV)
[in the formula, D
90Expression is corresponding to the particle diameter of the magnesium compound (a1) of accumulating weight mark 90%, D
10Expression is corresponding to the particle diameter of the magnesium compound (a1) of accumulating weight mark 10%].
When employing had the magnesium compound (a1) of this size distribution index (P '), polymerization activity was higher, can obtain the better polymkeric substance of particle shape.
Also have, the degree of the size distribution broadness of size distribution index (P ') expression magnesium compound (a1), this value is littler, and size distribution is narrower, and is more sharp-pointed, represents that the content of the magnesium compound (a1) that particle diameter is neat is many.
This sphericity (S ') is less than 1.30 and the magnesium compound (a1) of size distribution index (P ') less than 4.0, can be prepared by the MAGNESIUM METAL that employing has an above-mentioned sphericity (S).
Magnesium compound (a1) both can use separately, also can be used in combination more than 2 kinds.
This magnesium compound (a1) is a solid, is made of alkoxyl magnesium in fact.As the object lesson of alkoxyl magnesium, can enumerate dialkoxy magnesium and two aryloxy magnesium such as dimethoxy magnesium, diethoxy magnesium, dipropoxy magnesium, dibutoxy magnesium, two hexyloxy magnesium, two octyloxy magnesium, two phenoxy group magnesium, two cyclohexyloxy magnesium; Alkoxyl group magnesium halides such as butoxy magnesium chloride, cyclohexyloxy magnesium chloride, phenoxy group magnesium chloride, oxyethyl group magnesium chloride, oxyethyl group magnesium bromide, butoxy magnesium bromide, oxyethyl group magnesium iodide and aryloxy magnesium halide etc.Wherein, consider from polymerization activity and legislate aspect that dialkoxy magnesium is preferred, diethoxy magnesium is particularly preferred.
(b1) titanium compound
As titanium compound, consider that from aspects such as polymerization activities the compound that preferably adopts following logical formula V to represent is:
TiX
n(OR)
4-n (V)
[in the formula, X is a halogen atom, and R is the alkyl of 1～10 of carbonatoms, they both can be identical also can be different.N is 0～4 integer].
In logical formula V, as halogen atom X, chlorine atom and bromine atoms are preferred, and the chlorine atom is particularly preferred.As alkyl R, alkyl, alkenyl, cycloalkenyl, aryl and aralkyl etc. are preferred, and the straight or branched alkyl is particularly preferred.In addition, R both can be saturated base or unsaturated group, also can be straight chain or have side chain, or cyclic, in addition, can also sulfur-bearing, assorted elements such as nitrogen, oxygen, silicon, phosphorus.As the object lesson of R, can enumerate methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, n-pentyl, n-hexyl, n-heptyl, n-octyl, positive decyl, allyl group, butenyl, cyclopentyl, cyclohexyl, cyclohexenyl, phenyl, tolyl, benzyl, styroyl etc.N preferred 4.
As the object lesson of the titanium compound of representing with above-mentioned general formula (V) (b1), can enumerate four titan-alkoxides such as tetramethoxy titanium, purity titanium tetraethoxide, four positive propoxy titaniums, tetraisopropoxy titanium, four titanium n-butoxide, four isobutoxy titaniums, Fourth Ring hexyloxy titanium, four phenoxide titaniums; Titanium tetrahalides such as titanium tetrachloride, titanium tetrabromide, titanium tetra iodide; Three halogenated alkoxy titaniums such as methoxyl group titanous chloride, oxyethyl group titanous chloride, propoxy-titanous chloride, n-butoxy titanous chloride, oxyethyl group three Juization titaniums; Dihalide dialkoxy titaniums such as dimethoxy titanium dichloride, diethoxy titanium dichloride, diisopropoxy titanium dichloride, two positive propoxy titanium dichloride, diethoxy dibrominated titanium; Single halogenation tri-alkoxy titaniums such as trimethoxy titanium chloride, three hexyloxy titanium chlorides, three isopropoxy titanium chlorides, three positive propoxy titanium chlorides, three n-butoxy titanium chlorides etc.Wherein, consider that from the polymerization activity aspect high halogenated titanium-containing compound, particularly titanium tetrachloride are preferred.These titanium compounds (b1) both can have been distinguished use separately, also can be used in combination more than 2 kinds.
(c1) halogen compounds
In the solid catalyst component for olefin polymerization, can adopt halogen compounds (c1) as required.When adopting halogen compounds (c1), owing to can improve the particle shape of olefin polymer or size distribution is narrowed down, so be preferred.As such halogen compounds (c1), can enumerate halogens such as iodine, bromine, chlorine, fluorine; Hydrogen halide such as hydrogen iodide, hydrogen bromide, hydrogenchloride, hydrogen fluoride; Silicon tetrachloride, Silicon bromide; Halo silicon such as trichlorosilane, dichlorosilane, chlorosilane; Halohydrocarbon such as tetracol phenixin, hexachloroethane; Halohydrins such as trichloro-ethyl alcohol; Right-halogen substituted phenols such as chlorophenol; Halo boron such as boron trichloride; Aluminum halides such as aluminum chloride; Tin halides such as tin tetrachloride etc.Wherein, consider that from controlling polymers particle diameter aspect silicon tetrachloride is particularly preferred.These halogenated compounds (c) both can have been distinguished use separately, also can be used in combination more than 2 kinds.
(d1) the sub-property compound of power supply
In the solid catalyst component for olefin polymerization, can adopt power supply sub-property compound (d1) as required.When adopting the sub-property compound of power supply (d1), because the situation of the legislate that improves olefin polymer is arranged, so be preferred.As power supply sub-property compound (d1), can enumerate the oxygenatedchemicalss such as ethers such as ester class, monoether, diether or polyethers of alcohols, phenols, ketone, aldehydes, carboxylic acid, propanedioic acid, organic acid and mineral acid, perhaps nitrogenous compounds such as ammonia, amine, nitrile, isocyanic ester.Wherein, the multi-carboxylate is preferred, and aromatic series multi-carboxylate class is preferred, considers that from the polymerization activity aspect aromatic dicarboxylic acid monoesters and/or diester are particularly preferred.In addition, the organic radical of these ester portions, straight chain shape, a chain or ring-shaped fat alkyl are preferred.
Concrete can enumerate phthalic acid, naphthalene-1, the 2-dicarboxylic acid, naphthalene-2, the 3-dicarboxylic acid, 5,6,7,8-naphthane-1, the 2-dicarboxylic acid, 5,6,7,8-naphthane-2, the 3-dicarboxylic acid, indane-4, the 5-dicarboxylic acid, indane-5, the methyl esters of dicarboxylic acid such as 6-dicarboxylic acid, ethyl ester, n-propyl, isopropyl ester, positive butyl ester, isobutyl ester, the tert-butyl ester, n-pentyl ester, 1-methyl butyl ester, 2-methyl butyl ester, 3-methyl butyl ester, 1,1-dimethyl propyl ester, 1-methyl pentyl ester, 2-methyl pentyl ester, 3-methyl pentyl ester, 4-methyl pentyl ester, 1-ethyl butyl ester, 2-ethyl butyl ester, just own ester, cyclohexyl, positive heptyl ester, n-octyl, positive ninth of the ten Heavenly Stems ester, the own ester of 2-methyl, the own ester of 3-methyl, the own ester of 4-methyl, the 2-ethylhexyl, the 3-ethylhexyl, the 4-ethylhexyl, 2-ethyl pentyl ester, 3-methyl pentyl ester, 2-ethyl pentyl ester, dialkyls such as 3-ethyl pentyl ester.Wherein, the organic radical of ester portion be carbonatoms more than 4 the straight chain shape or the phthalate esters of chain aliphatic alkyl be preferred.As preferred object lesson, can enumerate n-butyl phthalate, diisobutyl phthalate, heptyl phthalate ester, diethyl phthalate etc.These sub-property compounds (d1) of powering both can have been distinguished use separately, also can be used in combination more than 2 kinds.
[A2] solid catalyst component for olefin polymerization
(a2) magnesium compound
In the present invention, as magnesium compound (a2), consider from the form of polymeric powder, form improvement and polymerization activity, adopt with the size distribution index (P) of following formula (II) expression less than 4.0, preferably less than 3.0 MAGNESIUM METAL, alcohol, and contain the halogen of the above halogen atom of 0.0001 grammeatom and/or the reaction of halogen-containing compound and the compound that obtains with respect to MAGNESIUM METAL 1 grammeatom:
P＝(D
90/D
10)(II)
[in the formula, D
90Expression is corresponding to the particle diameter of the MAGNESIUM METAL of accumulating weight mark 90%, D
10Expression is corresponding to the particle diameter of the MAGNESIUM METAL of accumulating weight mark 10%].
When adopting the MAGNESIUM METAL of size distribution index (P) 4.0 or more, owing to obtaining the high solid catalyst component of catalyst activity, so be unfavorable from the magnesium compound that its reaction is obtained.
This size distribution index (P) is lower than 4.0 MAGNESIUM METAL (a2), can be by the particle that adopts cutting, mechanical disintegration or molten atomizing to obtain, with screen cloth etc. in addition classification etc. make.
MAGNESIUM METAL as long as satisfy the condition of above-mentioned size distribution index (P), is not particularly limited its shape etc.Therefore, the MAGNESIUM METAL of any particle diameter can be used, for example MAGNESIUM METAL such as granular, banded, Powdered can be used.
Also have, corresponding to the median size D of MAGNESIUM METAL accumulating weight mark 50%
50Preferably reach 10～10,000 μ m, and median size D
50It is particularly preferred reaching 50～2,000 μ m.When median size hour, reaction is fierce, is difficult to control, and when particle diameter was excessive, the reaction times strengthened, or the worry of production efficiency decline is arranged.In addition, when departing from this scope, forms such as the size distribution of resulting magnesium compound and sphericity often worsen.
About alcohol, halogen, halogen-containing compound, since identical with the content of record in the magnesium compound (a1), the Therefore, omited explanation.
When the preparation of magnesium compound (a2), the MAGNESIUM METAL with above-mentioned size distribution index (P), alcohol, and halogen and/or halogen-containing compound, (a1) reacts equally with magnesium compound usually.
Magnesium compound of the present invention (a2), same with magnesium compound (a1), needn't pulverize or make the neat and operations such as classification carried out of size distribution, can be used as the carrier of solid catalyst component, it is approximate spherical, size distribution is also sharp-pointed, and the sphericity deviation of each particle is little.
Magnesium compound (a2), and the size distribution index of usefulness following formula (IV) expression (P ') usually less than 3.4, preferably less than 3.2.
When employing had the magnesium compound (a2) of this size distribution index (P '), polymerization activity further improved, and can obtain the better polymkeric substance of particle shape.
In addition, magnesium compound (a2), the sphericity of usefulness following formula (III) expression (S ') usually less than 2.00, preferably less than 1.50.
Magnesium compound (a2) with this sphericity (S ') considers it is preferred from catalyst activity and polymer particle form aspect.
This size distribution index (P ') can prepare by the MAGNESIUM METAL with above-mentioned size distribution index (P) less than 3.4 and the magnesium compound (a2) of sphericity (S ') less than 2.00.
Magnesium compound (a2) both can use separately, also can use the combination of magnesium compound more than the 2 kinds back with the preparation of condition diverse ways.
This magnesium compound (a2) is a solid, comes down to be made of alkoxyl magnesium.The object lesson of alkoxyl magnesium, same with magnesium compound (a1).
(b2) titanium compound
Titanium compound (b2), since same with the middle titanium compound (b1) that adopts of solid catalyst component [A1], so explanation is omitted.
(c2) halogen compounds
Halogen compounds (c2), since same with the middle halogen compounds (c1) that adopts of solid catalyst component [A1], so explanation is omitted.
(d2) the sub-property compound of power supply
The sub-property compound (d2) of powering and since with solid catalyst component [A1] in the sub-property of the power supply compound (d1) that adopts same, so the explanation omission.
[A3] solid catalyst component for olefin polymerization
(a3) magnesium compound
In the present invention, as magnesium compound (a3), it is the median size (D corresponding to accumulating weight mark 50%
50) reach 50～2, the MAGNESIUM METAL of 000 μ m, halogen and/or halogen-containing compound that the mol ratio (ROH/Mg) of 1 mole of MAGNESIUM METAL is reached 4～40 alcohol and contains the above halogen atom of 0.0001 grammeatom with respect to MAGNESIUM METAL 1 grammeatom, in the steel basin of stir shaft with the agitating vane that has disposed blade diameter d (m), with revolution n (inferior/minute) when carrying out stirring reaction, stir, make n
3d
2Reach 4.3 * 10
3～4.0 * 10
6And the compound that obtains.
Work as D
50, ROH/Mg and n
3d
2When departing from above-mentioned scope, the size distribution of resulting polymer powder broadens, and sphericity descends, and condenses.
By inference, about D
50, it is as follows that its reason can be thought.Magnesium compound is tabular aggregate, the collision of the speed of response cohesion of plate crystal (promote) and interparticle collision, particle and wall or cut off the equilibrium state of (suppressing crystalline condenses), the particle diameter of left and right sides magnesium compound and shape from fluidic.From this point,, can obtain more homogeneous polymer from whole the carrying out of reaction beginning.Generally speaking, from this point of specific surface area, small particle size person's speed of response is accelerated, but the change of small particle size magnesium tunicle is many.Can think that this point has influence on reaction uniformity.About ROH/Mg, by inference, when magnesium density was too high, the ununiformity that produce to stir was crossed when rare when concentration, and interparticle collision is insufficient, all is unfavorable.About n
3d
2, by inference, in the time of a little less than stirring, flowing becomes inhomogeneous, and the result makes reaction inhomogeneous.On the other hand, when stirring when strong, the magnesium compound of generation also is difficult to be condensed into plate crystal.
D
50Preferred 75～1,800 μ m, ROH/Mg is preferred 5～20, n
3d
1Preferred 1.3 * 10
4～8.4 * 10
5
This median size (D
50) reach the MAGNESIUM METAL of 50～2,000 μ m, can adopt mechanical disintegration, cutting, molten atomizing to prepare.
In addition, blade diameter d and stirred for several n are not particularly limited, can be at n
3d
2Satisfy the interior suitably adjusting of scope of above-mentioned condition.
At this moment, as agitating vane, can use slurry such as Maxwell's hybrid blade, Off Le ゾ one Application blade, oar formula (flat shape blade), tilting blade, turbine blade, anchor formula blade to mix use when stirring any and all can.In addition, both general shape can be used, also multistage shape can be used.In addition, also can polylith baffle plate (flow deflector) be set vertically in the wall side of steel basin.
Wherein, it is particularly preferred stirring with Maxwell's hybrid blade of being with flow deflector.
As long as MAGNESIUM METAL satisfies above-mentioned median size (D
50) condition get final product, and its shape etc. is not particularly limited.Therefore, particle shape arbitrarily, MAGNESIUM METAL such as for example granular, banded, Powdered all can adopt.
About alcohol, halogen, halogen-containing compound, except that above-mentioned, since the same with the content of record in the magnesium compound (a1), so explanation is omitted.
In the preparation of magnesium compound (a3), normally having above-mentioned median size (D
50) MAGNESIUM METAL, the alcohol of above-mentioned mol ratio (ROH/Mg) and the halogen and/or the halogen-containing compound of above-mentioned grammeatom ratio, under above-mentioned agitation condition, (a1) reacts equally with magnesium compound.
Magnesium compound of the present invention (a3), same with magnesium compound (a1), needn't pulverize or make the neat operations such as classification of size distribution, can be used as the carrier of solid catalyst component, approximate spherical, size distribution is also sharp-pointed, and the deviation of each particle sphericity is little.
Magnesium compound (a3), and the size distribution index of usefulness following formula (IV) expression (P ') usually less than 3.4, preferably less than 3.2.
When employing had the magnesium compound (a3) of this size distribution index (P '), catalyst activity was higher, can obtain the better polymkeric substance of particle shape.
In addition, magnesium compound (a3), the sphericity of usefulness following formula (III) expression (S ') usually less than 1.30, preferably less than 1.28.
Magnesium compound (a3) with this sphericity (S ') considers it is preferred from catalyst activity and polymer particle form.
This size distribution index (P ') is less than 3.4 and the magnesium compound (a3) of sphericity (S ') less than 1.30, can prepare by reacting under above-mentioned agitation condition by above-mentioned MAGNESIUM METAL, alcohol, and halogen and/or halogen-containing compound.
Magnesium compound (a3) both can use separately, also can use the combination of magnesium compound more than the 2 kinds back with the preparation of condition diverse ways.
This magnesium compound (a3) is a solid state, comes down to be made of alkoxyl magnesium.The object lesson of alkoxyl magnesium, same with magnesium compound (a1).
(b3) titanium compound
Titanium compound (b3) and since with solid catalyst component [A1] in the titanium compound that adopts
(b1) same, so explanation is omitted.
(c3) halogen compounds
Halogen compounds (c3), since same with the middle halogen compounds (c1) that adopts of solid catalyst component [A1], so explanation is omitted.
(d3) the sub-property compound of power supply
The sub-property compound (d3) of powering and since with solid catalyst component [A1] in the sub-property of the power supply compound (d1) that adopts same, so the explanation omission.
[A4] solid catalyst component for olefin polymerization
(a4) magnesium compound
In the present invention, as magnesium compound (a4), consider from polymer particle shape and polymerization activity, use oxide film thereon thickness 1 μ m is following, preferred 0.5 μ m is following, preferred especially 0.1 μ m is following MAGNESIUM METAL, alcohol and contain the halogen of the above halogen atom of 0.0001 grammeatom and/or the reaction of halogen-containing compound and the magnesium compound that obtains with respect to MAGNESIUM METAL 1 grammeatom.
When adopting oxide film thereon thickness to surpass the MAGNESIUM METAL of 1 μ m, the particle shape of the magnesium compound of making (a4) worsens, and polymerization activity and the polyolefinic particle shape that obtains worsen.
As the compound that forms oxide film thereon, can enumerate Mg (OH)
2, MgO, MgCO
3, MgSO
4Deng, their double salt, and their compound that contains crystal water.As the object lesson of the compound that contains crystal water, can enumerate MgSO
47H
2O etc. as double salt, can enumerate (MgCO
3)
4Mg (OH)
25H
2O.The content of these compounds is usually below 1 weight %.
The MAGNESIUM METAL of this oxide film thereon thickness below 1 μ m can be made by carry out granulation (cutting, pulverizing, classification or molten atomizing) in inert gas atmospheres such as nitrogen.
About magnesium compound (a4),, the shape of MAGNESIUM METAL etc. is not particularly limited if oxide film thereon thickness is below 1 μ m.Therefore, can adopt the MAGNESIUM METAL of any particle diameter, for example can adopt granular, banded, Powdered etc. MAGNESIUM METAL.But in order to ensure reaction uniformity, it is preferred adopting the following particle of median size 1cm.During particle below preparation median size 1cm, processing such as the cutting of MAGNESIUM METAL, pulverizing, classification or molten atomizing are preferred in inert atmospheres such as nitrogen.
About alcohol, halogen, halogen-containing compound, since the same with the content of record in the magnesium compound (a1), so explanation is omitted.
In the preparation of magnesium compound (a4), normally the MAGNESIUM METAL that satisfies above-mentioned condition, alcohol and halogen and/or halogen-containing compound, (a1) reacts equally with magnesium compound.
Magnesium compound of the present invention (a4), same with magnesium compound (a1), needn't pulverize or make the neat operations such as classification of size distribution, can be used as the carrier of solid catalyst component, it is approximate spherical, and size distribution is also sharp-pointed, and the deviation of each particle sphericity is little.
Magnesium compound (a4), and the size distribution index of usefulness following formula (IV) expression (P ') usually less than 3.4, preferably less than 3.2.
In addition, magnesium compound (a4), the sphericity of usefulness following formula (III) expression (S ') usually less than 2.00, preferably less than 1.50.
This size distribution index (P ') is considered from catalyst activity and polymer particle form less than 3.4 and the magnesium compound (a4) of sphericity (S ') less than 2.00, is preferred.This magnesium compound (a4) can prepare by adopting above-mentioned MAGNESIUM METAL.
Magnesium compound (a4) both can use separately, also can make up the back more than 2 kinds and use.
This magnesium compound (a4) is a solid state, comes down to be made of alkoxyl magnesium.Alkoxyl magnesium and magnesium compound (a1) are same.
(b4) titanium compound
Titanium compound (b4), since same with the middle titanium compound (b1) that adopts of solid catalyst component [A1], so explanation is omitted.
(c4) halogen compounds
Halogen compounds (c4), since same with the middle halogen compounds (c1) that adopts of solid catalyst component [A1], so explanation is omitted.
(d4) the sub-property compound of power supply
The sub-property compound (d4) of powering and since with solid catalyst component [A1] in the sub-property of the power supply compound (d1) that adopts same, so the explanation omission.
[B] organo-aluminium compound
As the organo-aluminium compound that uses among the present invention [B], be not particularly limited, but the preferred organo-aluminium compound with alkyl, halogen atom, hydrogen atom, alkoxyl group that adopts; Aikyiaiurnirsoxan beta (ア Le ミ ノ キ サ Application) and these mixture.Concrete can enumerate trialkylaluminiums such as trimethyl aluminium, triethyl aluminum, triisopropylaluminiuand, triisobutyl aluminium, trioctylaluminum; Dialkyl group monochlor(in)ate aluminium such as diethyl monochlor(in)ate aluminium, di-isopropyl monochlor(in)ate aluminium, diisobutyl monochlor(in)ate aluminium, dioctyl monochlor(in)ate aluminium; Alkyl sesquialter aluminum chloride such as ethyl sesquialter aluminum chloride; Chain aikyiaiurnirsoxan beta such as methylaluminoxane etc.Wherein, it is preferred having the trialkylaluminium of the low alkyl group of carbonatoms 1～5, particularly trimethyl aluminium, triethyl aluminum, tri-propyl aluminum and triisobutyl aluminium.These organo-aluminium compounds [B] both can have been distinguished separately and use, and also can be used in combination more than 2 kinds.
[C] the sub-property compound of powering
In catalyst for olefines polymerizing, can adopt power supply sub-property compound [C] as required.When adopting the sub-property compound of power supply [C], often can improve the legislate of olefin polymer, so be preferred.As power supply sub-property compound [C], can adopt silicoorganic compound, nitrogenous compound, P contained compound and oxygenatedchemicals with alkoxyl group.Wherein, it is particularly preferred adopting the silicoorganic compound with alkoxyl group.
Object lesson as silicoorganic compound with alkoxyl group, can enumerate the trimethylammonium methoxy silane, trimethylethoxysilane, the triethyl methoxy silane, triethyl-ethoxy-silicane alkane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, ethyl sec.-propyl dimethoxy silane, propyl group sec.-propyl dimethoxy silane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, isopropyl butyl dimethoxy silane, di-t-butyl dimethoxy silane, tertiary butyl methyl dimethoxysilane, tertiary butyl ethyl dimethoxy silane, tertiary butyl propyl group dimethoxy silane, tertiary butyl sec.-propyl dimethoxy silane, tertiary butyl butyl dimethoxy silane, tertiary butyl isobutyl-dimethoxy silane, the tertiary butyl (sec-butyl) dimethoxy silane, tertiary butyl amyl group dimethoxy silane, tertiary butyl hexyl dimethoxy silane, tertiary butyl heptyl dimethoxy silane, tertiary butyl octyl group dimethoxy silane, tertiary butyl nonyl dimethoxy silane, tertiary butyl decyl dimethoxy silane, the tertiary butyl (3,3,3 trifluoromethyl propyl group) dimethoxy silane, cyclohexyl methyl dimethoxy silane, cyclohexyl ethyl dimethoxy silane, cyclohexyl propyl group dimethoxy silane, cyclohexyl isobutyl-dimethoxy silane, dimethoxy silane, dicyclohexyl dimethoxy silane, cyclohexyl tertiary butyl dimethoxy silane, cyclopentyl-methyl dimethoxy silane, cyclopentyl ethyl dimethoxy silane, cyclopentyl propyl group dimethoxy silane, cyclopentyl tertiary butyl dimethoxy silane, dicyclopentyl dimethoxyl silane, cyclopentyl cyclohexyl dimethoxy silane, two (2-methylcyclopentyl) dimethoxy silane, two (2, the 3-dimethylcyclopentyl) dimethoxy silane, Alpha-Naphthyl-1,1,2-trimethylammonium propyl group dimethoxy silane, n-tetradecane base-1,1,2-trimethylammonium propyl group dimethoxy silane, 1,1,2-trimethylammonium propyl group methyl dimethoxysilane, 1,1,2-trimethylammonium propyl group ethyl dimethoxy silane, 1,1,2-trimethylammonium propyl group sec.-propyl dimethoxy silane, 1,1,2-trimethylammonium propyl group cyclopentyl dimethoxy silane, 1,1,2-trimethylammonium propyl group cyclohexyl dimethoxy silane, 1,1,2-trimethylammonium propyl group tetradecyl dimethoxy silane, dimethoxydiphenylsilane, the phenylbenzene diethoxy silane, phenyl triethoxysilane, methyltrimethoxy silane, Union carbide A-162, ethyl trimethoxy silane, ethyl triethoxysilane, propyl trimethoxy silicane, the sec.-propyl Trimethoxy silane, the butyl triethoxyl silane, the butyl triethoxyl silane, the isobutyl-Trimethoxy silane, tert-butyl trimethoxy silane, the sec-butyl Trimethoxy silane, amyltrimethoxysilane, the isopentyl Trimethoxy silane, the cyclopentyl Trimethoxy silane, cyclohexyl trimethoxy silane, the norcamphyl Trimethoxy silane, the indenyl Trimethoxy silane, 2-methylcyclopentyl Trimethoxy silane, ethyl three isopropoxy silane, methylcyclopentyl (tert.-butoxy) dimethoxy silane, sec.-propyl (tert.-butoxy) dimethoxy silane, the tertiary butyl (tertiary butyl) dimethoxy silane, (isobutoxy) dimethoxy silane, the tertiary butyl (tert.-butoxy) dimethoxy silane, vinyltriethoxysilane, vinyl three butoxy silanes, the chlorine triethoxyl silane, γ-r-chloropropyl trimethoxyl silane, γ-An Jibingjisanyiyangjiguiwan, 1,1,2-trimethylammonium propyl trimethoxy silicane, 1,1,2-trimethylammonium propyl group isopropoxy dimethoxy silane, 1,1,2-trimethylammonium propyl group (tert.-butoxy) dimethoxy silane, tetramethoxy-silicane, tetraethoxysilane, four butoxy silanes, tetraisobutoxy-silicane alkane, tetraethyl silicate, butyl silicate, trimethyl phenoxysilane, methyl three allyloxy silane, vinyl three ('beta '-methoxy oxyethyl group) silane, vinyltriacetoxy silane, dimethyl tetraethoxy sily oxide etc.Wherein, dicyclopentyl dimethoxyl silane, cyclohexyl isobutyl-dimethoxy silane, cyclohexyl methyl dimethoxy silane are preferred.
In addition,, can enumerate silicon compound that does not have the Si-O-C key and organic compound with O-C key are reacted in advance, or make it react resulting compound in that alpha-olefines polymerization is fashionable as this silicoorganic compound.Concrete can enumerate silicon tetrachloride and the resulting compound of alcohol reaction etc.
As the object lesson of nitrogenous compound, can enumerate 2,6-di-isopropyl piperidines, 2,6-di-isopropyl-4-methyl piperidine, N-methyl-2,2,6,6-tetramethyl piperidine etc. 2,6-substituted piperidine class; 2,5-di-isopropyl azo pyridine (ア ゾ リ ジ Application), N-methyl-2,2,5,5-tetramethyl-azo pyridine etc. 2,5-replaces azo pyridine class; N, N, N ', N '-tetramethyl-methylene diamine, N, N, N ', the methylene diamine class that N '-tetraethyl-methylene diamine etc. replace; 1,3-dibenzyl imidazole alkane, 1, the imidazolidine that 3-dibenzyl-2-phenylimidazolidines, etc. replace etc.
As the object lesson of P contained compound, can enumerate phosphorous acid esters such as triethyl phosphate, tricresyl phosphate n-propyl, tricresyl phosphate isopropyl ester, TRI N BUTYL PHOSPHATE, three iso-butyl ester of phosphoric acid, diethyl normal-butyl phosphoric acid ester, diethyl phenyl phosphoric acid ester etc.
As the object lesson of oxygenatedchemicals, can enumerate 2,2,5,5-tetramethyl-tetrahydrofuran (THF), 2,2,5,5-tetraethyl-tetrahydrofuran (THF) etc. 2,5-substituted tetrahydrofuran class; 1,1-dimethoxy-2,3,4,5-tetrachlorocycbpentadiene, 9, Methylal(dimethoxymethane) derivatives such as 9-dimethoxy fluorenes, phenylbenzene Methylal(dimethoxymethane) etc.
These sub-property compounds [C] of powering both can have been distinguished use separately, also can be used in combination more than 2 kinds.
2. the compound method of solid catalyst component
Compound method as solid catalyst component [A1]～[A4], for example, can enumerate above-mentioned magnesium compound (a1)～(a4), titanium compound (b1)～(b4), halogen compounds (c1)～(c4) as required and/or the sub-property compound (d1) of powering～after (d4) contacting, reacting, preferably carry out the method for 1 time (more than 1 time) and titanium compound (b1)～(b4) contact, react again.When carrying out contacting more than 2 times with titanium compound (b1)～(b4), on the magnesium compound that plays the support of the catalyst effect (a1)～(a4), abundant load titanium compound (b1)～(b4).Engagement sequence end about other is particularly limited.
These various compositions both can make its contact in the presence of inert solvents such as hydrocarbon, make its contact after also can diluting each composition with inert solvents such as hydrocarbon in advance.As inert solvent, for example, can enumerate aliphatic hydrocarbons such as Skellysolve A, iso-pentane, normal hexane, normal heptane, octane, octane-iso; Aromatic hydrocarbon or these mixtures such as benzene,toluene,xylene.Wherein, it is preferred using aliphatic hydrocarbon.
Titanium compound (b1)～(b4) uses 0.5～100 mole, preferred 1～50 mole for 1 mole usually with respect to the magnesium of magnesium compound (a1)～(a4).When being lower than 0.5 mole, the polymerization activity of unit titanium often descends.On the other hand, when being higher than 100 moles, the polymerization activity of unit solid catalyst component often descends.
When adopting halogen compounds (c1)～(c4), use 0.005～100 mole usually for 1 mole with respect to the magnesium of magnesium compound (a1)～(a4).When being lower than 0.005 mole, the polymerization activity of unit titanium and the legislate of polymkeric substance often descend.On the other hand, when being higher than 100 moles, the polymerization activity of unit solid catalyst component often descends.
When adopting the sub-compound of power supply (d1)～(d4),, use 0.01～10 mole, preferred 0.05～0.15 mole usually to 1 mole in the magnesium of magnesium compound (a1)～(a4).When being lower than 0.01 mole, the legislate of polymkeric substance often descends.On the other hand, when being higher than 10 moles, the polymerization activity of unit titanium often descends.
The contact temperature of these compounds is generally-20～200 ℃, preferred 20～150 ℃.In addition, be generally 1 minute～24 hours duration of contact, preferred 10 minutes～6 hours.When adopting this contact temperature and/or duration of contact, the polymerization activity height can obtain the good olefin polymer of polymer morphology.The pressure of this moment when using solvent, changes according to its kind, contact temperature, carries out in the scope of 0～5MPa, preferred 0～1MPa usually.In addition, in contact process, consider, preferably stir from contact homogeneity and contact efficiency aspect.Also have, these contact conditions, to the contact reacts of the 2nd later titanium compound (b1)～(b4) too.
About the operating of contacts of titanium compound (b1)～(b4), when using solvent,, use below 5,000 milliliters preferred 10～1,000 milliliter solvent usually with respect to 1 mole of titanium compound (b1)～(b4).When this ratio departs from above-mentioned scope, the homogeneity of contact and the situation that contact efficiency worsens are arranged.
Also have, after the 1st contact of all cpds, reaction, wash with 90～150 ℃, the inert solvent of preferred 120～140 ℃ of temperature usually.When wash temperature was outside above-mentioned scope, the raising effect of catalyst activity and legislate often can not be given full play to.As inert solvent, can adopt and above-mentioned same aliphatic hydrocarbon and aromatic hydrocarbon.
Also have, be not particularly limited about contact, the reacted wash temperature of the 2nd later titanium compound (b1)～(b4), but consider from the legislate aspect, it is preferred adopting 90～150 ℃, the inert solvent washing of preferred 120～140 ℃ of temperature usually.
As washing methods, be not particularly limited, but modes such as decant, filtration are preferred.Consumption, washing time, washing times about inert solvent are not particularly limited yet, usually use 100～100,000 milliliter, preferred 1,000～50 for 1 mole with respect to magnesium compound (a1)～(a4), 000 milliliter of solvent carried out 1 minute～24 hours, preferred 10 minutes～6 hours usually.When this ratio departed from above-mentioned scope, washing often became incomplete.
The pressure of this moment is changed according to solvent types, wash temperature etc., but usually at 0～5MPa, preferably carry out in the scope at 0～1MPa.In addition, in washing operation, consider that from washing homogeneity and detersive efficiency aspect it is preferred stirring.Also have, resulting solid catalyst component [A1]～[A4] also can preserve in drying regime or in inert solvents such as hydrocarbon.
3. the preparation method of olefin polymer
Consumption about the various compositions of catalyst for olefines polymerizing of the present invention is not particularly limited, but solid catalyst component [A1]～[A4] is converted into titanium atom, and the consumption of every liter of reaction volume reaches the scope of 0.00005～1 mmole usually.
The consumption of organo-aluminium compound [B] makes that aluminium/titanium (atomic ratio) reaches 1～1,000 usually, preferred 10～1,000 scope.When atomic ratio departed from this scope, it is insufficient that catalyst activity often becomes.
In addition, when adopting the sub-property compound of power supply [C], its consumption reach usually make [C]/[B] (mol ratio) 0.001～5.0, preferred 0.01～2.0, more preferably 0.05～1.0 scope.When mol ratio departs from this scope, often can not get sufficient catalyst activity and legislate.But, when carrying out pre-polymerization, can further reduce the consumption of the sub-property compound of power supply [C].
As the alkene that uses among the present invention, the alpha-olefin of representing with following general formula (VI) is preferred.
R
1-CH＝CH
2 (VI)
In above-mentioned general formula (VI), R
1Be hydrogen atom or alkyl, and alkyl both can be saturated base or unsaturated group, also can be straight chain shape alkyl or alkyl or the cyclic hydrocarbon group with side chain.Concrete can enumerate ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-decene, 3-Methyl-1-pentene, 4-methyl-1-pentene, vinyl cyclohexene, divinyl, isoprene, m-pentadiene etc.These alkene both can use separately, also can 2 kinds be used in combination.In these alkene, ethene, propylene are specially suitable.
In olefinic polymerization of the present invention, consider from the legislate of polymerization activity, polymkeric substance and powder morphology, also can carry out pre-polymerization earlier according to hope after, carry out this polymerization again.At this moment, solid catalyst component [A1]～[A4], organo-aluminium compound [B] and the sub-property of power supply as required compound [C], being mixed the catalyzer that is constituted with the ratio of regulation respectively exists down, alkene is being carried out pre-polymerization usually under the pressure about normal pressure～5MPa under the temperature of 0～100 ℃ of scope, then, in the presence of catalyzer and prepolymer, make alkene carry out this polymerization.By carrying out pre-polymerization, can seek the raising of polymerization activity and the improvement of polymer particle shape.
Be not particularly limited about this this polymeric polymerized form, solution polymerization, slurry polymerization, vapour phase polymerization, mass polymerization etc. are any all to be suitable for, in addition, batchwise polymerization, successive polymerization etc. are any all to be suitable for, and step polymerization of 2 under the different condition or multistep polymerization also are suitable for.
About reaction conditions, its polymerization pressure is not particularly limited, consider that from the polymerization activity aspect be generally normal atmosphere～8MPa, preferred 0.2～5MPa, polymerization temperature is generally 0～200 ℃, preferred 30～100 ℃ scope.Polymerization time is decided according to the kind and the polymerization temperature of raw material olefin, is generally 5 minutes～20 hours, preferred about 10 minutes～10 hours.
The molecular weight of olefin polymer can be by adding chain-transfer agent, and preferred hydrogenation is regulated.In addition, also can there be rare gas elementes such as nitrogen.About the catalyst component among the present invention, can be solid catalyst component [A1]～[A4], organo-aluminium compound [B] and the sub-property compound [C] of powering, with the regulation ratio mix, contact after, import alkene again and carry out polymerization, also can be after contact, slaking afterwards imports alkene and carries out polymerization about 0.2～3 hour.In addition, this catalyst component also can be suspended in inert solvent or the alkene and supply with.In the present invention, the aftertreatment after the polymerization can be undertaken by method commonly used.Promptly, in gaseous polymerization, after polymerization from the polymer powder that polymerizer is derived, in order to remove wherein contained alkene etc., nitrogen gas stream etc. is passed through, in addition, also can carry out granulation with forcing machine as required, at this moment, in order to make the catalyzer complete deactivation, can also add a spot of water, alcohol etc.In addition, in mass polymerization, after the polymerization, from the polymkeric substance of deriving, can carry out granulation behind the separating monomer fully by polymerizer.
Embodiment
Specifically describe the present invention below by embodiment, but the present invention is not limited by the following example.Also have the sphericity of MAGNESIUM METAL (S), size distribution index (P), median size (D
50) and oxide film thereon thickness; The sphericity of magnesium compound (S '), size distribution index (P '); The sphericity of polymeric powder (S "), size distribution index (P "); The legislate of polymkeric substance [mmmm] is obtained by laxative remedy:
(1) sphericity of MAGNESIUM METAL (S): MAGNESIUM METAL, (preparation of OLYMPUS society, BHS-751P) image in 40 times of photographies carries out picture processing with polarizing microscope.Adopt image analysis apparatus (preparation of nexsus society), cut the following particle of 20 pixels (1 pixel is 10.4 μ m * 10.4 μ m), about 300 of remaining particle is carried out picture processing, obtain the longest diameter L on the particle sciagraph
1And be equal to the circular diameter L of shadow area
2, (I) calculates according to following formula.
(2) the size distribution index (P) of MAGNESIUM METAL: the size distribution of measuring with sieve is mapped on lognormal probability graph paper, with 50% particle diameter as median size (D
50), obtain 90% particle diameter (D respectively
90) and 10% particle diameter (D
10), (II) calculates from following formula.
(3) MAGNESIUM METAL median size (D
50): the size distribution of measuring with sieve is mapped on lognormal probability graph paper, with 50% particle diameter as median size (D
50) obtain.
(4) the oxide film thereon thickness of MAGNESIUM METAL: analyze with ESCA (chemical analysis electronic spectrograph).Concrete is that MAGNESIUM METAL is carried out the Ar ion etching, to analyzing to reaching 3 μ m deeply from utmost point upper layer, with standard reagent (MgCO
3, Mg (OH)
2, MgSO
4, MgO, MgSO
47H
2O and (MgCO
3)
4Mg (OH)
25H
2O) oxide film thereon that exists is confirmed.
(5) sphericity of magnesium compound (S '): (NEC (strain) preparation JSM-25SIII), is photographed in acceleration voltage 5kV, 300 times (embodiment 15～18 is 150 times), obtains negative film with scanning electron microscope dried magnesium compound.Then, with this negative film of penetrant method picture processing.Adopt image analysis apparatus (preparation of nexsus society), cut the following particle of 20 pixels (1 pixel is 0.695 μ m * 0.695 μ m, and embodiment 15～18 is 1.389 μ m * 1.389 μ m), to remaining particle about 2,000 is carried out picture processing, obtains longest diameter L on the particle sciagraph
3And be equal to the circular diameter L of shadow area
4, (III) calculates according to following formula.
(6) the size distribution index of magnesium compound (P '): under magnesium compound is suspended in state in the hydrocarbon, measure particle diameter, this size distribution mapped on lognormal probability graph paper with light transmission method, with 50% particle diameter as median size (D
50), obtain 90% particle diameter (D respectively
90) and 10% particle diameter (D
10), (IV) calculates from following formula.
(7) sphericity of polymeric powder (S "): in embodiment 1～4, comparative example 1～3, use with the same method of the sphericity of magnesium compound (S ') and calculate.
In embodiment 5～14, relatively low 4～12, (preparation of OLYMPUS society, BHS-751P) image in 40 times of photographies carries out picture processing with polarizing microscope to polyolefin powder.Picture processing is removed 1 pixel as 10.4 μ m * 10.4 μ m, beyond about 300 are resolved, uses with the same method of the sphericity of magnesium compound (S ') and calculates.
In embodiment 15～18, the comparative example 13～15, polyolefin powder carries out picture processing with direct reflection method, in image analysis is handled, except that 1 pixel as 0.0813mm * 0.0813mm, use with the same method of the sphericity of magnesium compound (S ') and calculate.
(8) the size distribution index of polymeric powder (P "): use with the same method of the size distribution index (P) of magnesium compound and calculate.
(9) legislate of polymkeric substance [mmmm]: polymer dissolution 1,2, in the 4-trichlorobenzene, is used
13C-NMR (NEC (strain) preparation, trade(brand)name: EX-400), carry out quantitatively in 130 ℃ of methyl signals that adopt the complete decoupling method of proton to measure.
Also have, so-called isotaxy pentamer mark [mmmm], mean adopt that A.Zambelli etc. proposes in Macromolecules magazine, the 6th volume, 925 pages (1973) from
13Isotaxy mark in the pentamer unit in the polypropylene molecular chain that C-NMR spectrum is obtained.
In addition,
13The ownership of C-NMR spectrum peak decision method is carried out according to the ownership method that A.Zambelli etc. proposes in Macromolecules magazine, the 8th volume, 687 pages (1975).
Embodiment 1
(1) preparation of magnesium compound
Cross through nitrogen replacement, in the internal volume there-necked flask 0.5 liter, belt stirrer, put into through ethanol 122g (2.64 grammeatom), the iodine 0.8g (6.3 milligram-atom) of processed and the MAGNESIUM METAL 8g (0.33 grammeatom) (preparing) of sphericity 1.85 with spray method.Make their reactions in 78 ℃ of stirrings (350rpm), in system, reach and do not take place till the hydrogen, obtain magnesium compound (diethoxy magnesium).The results are shown in table 1.
(2) preparation of solid catalyst component
With nitrogen replacement, in the internal volume there-necked flask 0.5 liter, belt stirrer, put into magnesium compound (carrier) 16g of above-mentioned (1) preparation, through 80 milliliters of the octanes of processed.Be heated to 40 ℃, add 2.4 milliliters of silicon tetrachlorides (23 mmole), stir after 20 minutes, add 3.4 milliliters of n-butyl phthalates (13 mmole).This solution is warming up to 80 ℃, drips 77 milliliters of titanium tetrachlorides (0.70 mole) with dropping funnel then, stir for 125 ℃ in interior temperature and supported operation in 1 hour.Then, carry out thorough washing with the dehydration octane.Then, add 122 milliliters of titanium tetrachlorides (1.11 moles) again, carried out the 2nd time in 2 hours in 125 ℃ of stirrings of interior temperature and support operation.Then, carry out thorough washing, obtain solid catalyst component with the octane that dewaters.
(3) propylene slurry polymerization
The autoclave of the stainless steel of 1 liter of internal volume, belt stirrer thorough drying in addition, through behind the nitrogen replacement, put into through 500 milliliters of the octanes of processed.The solid catalyst component that adds preparation in triethyl aluminum 2.0 mmoles, dicyclopentyl dimethoxyl silane 0.25 mmole, above-mentioned (2) inward is converted into Ti atom 0.0025 mmole, import hydrogen 0.1MPa, then, the limit imports propylene limit increasing temperature and pressure to 80 ℃, stagnation pressure 0.8MPa, carries out polymerization in 1 hour.
Then, content is taken out in cooling, step-down, puts into 2 liters of methyl alcohol, carries out catalyst deactivation.Filter material, vacuum-drying obtains propene polymer (polypropylene).The results are shown in table 1.
Embodiment 2
(1) preparation of magnesium compound
The iodine amount that adopts in embodiment 1 (1) is 0.24g (1.9 milligram-atom), 50 ℃ of temperature of reaction, the stirred for several 525rpm, and other and embodiment 1 (1) operate equally, obtain magnesium compound.The results are shown in table 1.
(2) preparation of solid catalyst component
Magnesium compound of preparation, other and embodiment 1 (2) operate equally, prepare solid catalyst component in embodiment 1 (2) middle employing above-mentioned (1).
(3) propylene slurry polymerization
Solid catalyst component of preparation, other and embodiment 1 (3) operate equally, carry out propylene polymerization in embodiment 1 (3) middle employing above-mentioned (2).The results are shown in table 1.
Embodiment 3
(1) preparation of magnesium compound
Adopt Magnesium Chloride Anhydrous 0.30g (6.3 milligram-atom) to replace the iodine in embodiment 1 (1), other and embodiment 1 (1) operate equally, obtain magnesium compound.The results are shown in table 1.
(2) preparation of solid catalyst component
Magnesium compound of preparation, other and embodiment 1 (2) operate equally, prepare solid catalyst component in embodiment 1 (2) middle employing above-mentioned (1).
(3) propylene slurry polymerization
Solid catalyst component of preparation, other and embodiment 1 (3) operate equally, carry out propylene polymerization in embodiment 1 (3) middle employing above-mentioned (2).The results are shown in table 1.
Embodiment 4
(1) preparation of magnesium compound
Except the MAGNESIUM METAL (with cutting, the preparation of ball mill method) of embodiment 1 (1) middle employing sphericity 2.93, other and embodiment 1 (1) operate equally, obtain magnesium compound.The results are shown in table 1.
(2) preparation of solid catalyst component
Magnesium compound of preparation, other and embodiment 1 (2) operate equally, prepare solid catalyst component in embodiment 1 (2) middle employing above-mentioned (1).
(3) slurry polymerization of propylene
Solid catalyst component of preparation, other and embodiment 1 (3) operate equally, carry out propylene polymerization in embodiment 1 (3) middle employing above-mentioned (2).The results are shown in table 1.
Comparative example 1
(1) preparation of magnesium compound
Except adopting sphericity among the embodiment 1 (1) is 5.20 the MAGNESIUM METAL (preparing with cutting system), and other is operated equally with embodiment 1 (1), obtains magnesium compound.The results are shown in table 1.
(2) preparation of solid catalyst component
Magnesium compound of preparation, other and embodiment 1 (2) operate equally, prepare solid catalyst component in embodiment 1 (2) middle employing above-mentioned (1).
(3) propylene slurry polymerization
Solid catalyst component of preparation, other and embodiment 1 (3) operate equally, carry out propylene polymerization in embodiment 1 (3) middle employing above-mentioned (2).The results are shown in table 1.
Comparative example 2
(1) preparation of magnesium compound
Except adopting the MAGNESIUM METAL (preparing with cutting system) of sphericity 5.80 among the embodiment 1 (1), beyond 60 ℃ of the temperature of reaction, other is operated equally with embodiment 1 (1), obtains magnesium compound.The results are shown in table 1.
(2) preparation of solid catalyst component
Magnesium compound of preparation, other and embodiment 1 (2) operate equally, prepare solid catalyst component in embodiment 1 (2) middle employing above-mentioned (1).
(3) propylene slurry polymerization
Solid catalyst component of preparation, other and embodiment 1 (3) operate equally, carry out propylene polymerization in embodiment 1 (3) middle employing above-mentioned (2).The results are shown in table 1.
Comparative example 3
(1) preparation of magnesium compound
Adopt in embodiment 3 (1) the MAGNESIUM METAL (preparing with cutting system) of sphericity 6.95, other and embodiment 3 (1) operate equally, obtain magnesium compound.The results are shown in table 1.
(2) preparation of solid catalyst component
Magnesium compound of preparation, other and embodiment 1 (2) operate equally, prepare solid catalyst component in embodiment 1 (2) middle employing above-mentioned (1).
(3) propylene slurry polymerization
Solid catalyst component of preparation, other and embodiment 1 (3) operate equally, carry out propylene polymerization in embodiment 1 (3) middle employing above-mentioned (2).The results are shown in table 1.
Table 1
| Classification | Index | Unit | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Carrier | The sphericity of metal M g (S) | 1.85 | 1.85 | 1.85 | 2.93 | 5.20 | 5.80 | 6.95 | |
| Initiator type | I 2 | I 2 | MgCl 2 | I 2 | I 2 | I 2 | MgCl 2 | ||
| Halogen and/or halogen-containing compound/Mg -Compound/Mg | (grammeatom ratio) | 0.019 | 0.0057 | 0.019 | 0.019 | 0.019 | 0.019 | 0.019 | |
| Temperature of reaction | (℃) | 78 | 50 | 78 | 78 | 78 | 60 | 78 | |
| Revolution | (rpm) | 350 | 525 | 350 | 350 | 350 | 350 | 350 | |
| Median size (D 50) | (μm) | 68 | 34 | 69 | 67 | 76 | 62 | 80 | |
| Sphericity (S ') | 1.23 | 1.21 | 1.25 | 1.28 | 1.34 | 1.38 | 1.85 | ||
| The size distribution index (P ') | 3.4 | 3.3 | 3.7 | 3.8 | 4.9 | 3.8 | 6.9 | ||
| Polymkeric substance | Polymerization activity | (kg/g-Cat) | 16.8 | 24.9 | 16.3 | 15.8 | 13.1 | 15.0 | 12.7 |
| Legislate ([mmmm]) | (mol％) | 98.3 | 98.4 | 98.2 | 98.3 | 98.2 | 98.3 | 98.3 | |
| Median size (D 50) | (μm) | 1230 | 660 | 1210 | 1250 | 1320 | 1040 | 1380 | |
| Sphericity (S ") | 1.23 | 1.20 | 1.24 | 1.29 | 1.36 | 1.40 | 1.90 | ||
| The size distribution index (P ") | 3.5 | 3.4 | 3.8 | 3.8 | 5.2 | 3.9 | 7.2 |
Embodiment 5
(1) preparation of magnesium compound
Cross through nitrogen replacement, in the internal volume there-necked flask 0.5 liter, belt stirrer, put into through ethanol 122g (2.64 grammeatom), the iodine 0.8g (6.3 milligram-atom) of processed and the MAGNESIUM METAL 8g (0.33 grammeatom) of size distribution index 1.4 (cutting, pulverize the back classification).Make their reactions in 78 ℃ of stirrings (350rpm), in system, reach and do not take place till the hydrogen, obtain magnesium compound (diethoxy magnesium).The results are shown in table 2.
(2) preparation of solid catalyst component
With nitrogen replacement, in the internal volume there-necked flask 0.5 liter, belt stirrer, put into magnesium compound (carrier) 16g of above-mentioned (1) preparation, through 80 milliliters of the octanes of processed.Be heated to 40 ℃, add silicon tetrachloride 2.4 milliliters (23 mmoles) and stir after 20 minutes, add 3.4 milliliters of n-butyl phthalates (13 mmole).This solution is warming up to 80 ℃, then drips 77 milliliters of titanium tetrachlorides (0.70 mole), stir for 125 ℃ in interior temperature and carried out load operation in 1 hour with dropping funnel.Then, the octane with dehydration carries out thorough washing.And then add 122 milliliters of titanium tetrachlorides (1.11 moles), and stirred 2 hours for 125 ℃ in interior temperature, carry out the 2nd time and support operation.Then, carry out thorough washing, obtain solid catalyst component with the octane that dewaters.
(3) propylene slurry polymerization
The autoclave of the stainless steel of 1 liter of internal volume, belt stirrer thorough drying in addition, through behind the nitrogen replacement, put into through 500 milliliters of the octanes of processed.The solid catalyst component that adds preparation in triethyl aluminum 2.0 mmoles, dicyclopentyl dimethoxyl silane 0.25 mmole, above-mentioned (2) inward is converted into Ti atom 0.0025 mmole, import hydrogen 0.1MPa, then, the limit imports propylene limit increasing temperature and pressure to 80 ℃, stagnation pressure 0.8MPa, carries out polymerization in 1 hour.
Then, content is taken out in cooling, step-down, puts into 2 liters of methyl alcohol, carries out catalyst deactivation.Filter material, vacuum-drying obtains propene polymer (polypropylene).The results are shown in table 2.
Embodiment 6
(1) preparation of magnesium compound
Except the consumption of iodine among the embodiment 5 (1) is 0.24g (1.9 milligram-atom), 50 ℃ of temperature of reaction beyond the stirred for several 525rpm, with embodiment 5 (1) same operations, obtain magnesium compound.The results are shown in table 2.
(2) preparation of solid catalyst component
In embodiment 5 (2), adopt the magnesium compound of preparation in above-mentioned (1), with embodiment 5 (2) same operations, preparation solid catalyst component.
(3) propylene slurry polymerization
In embodiment 5 (3), adopt the solid catalyst component of preparation in above-mentioned (2),, carry out propylene polymerization with embodiment 5 (3) same operations.The results are shown in table 2.
Embodiment 7
(1) preparation of magnesium compound
In embodiment 5 (1),,, obtain magnesium compound with embodiment 5 (1) same operations with Magnesium Chloride Anhydrous 0.30g (6.3 milligram-atom) the replacement iodine.The results are shown in table 1.
(2) preparation of solid catalyst component
In embodiment 5 (2), adopt the magnesium compound of preparation in above-mentioned (1), with embodiment 5 (2) same operations, preparation solid catalyst component.
(3) propylene slurry polymerization
In embodiment 5 (3), adopt the solid catalyst component of preparation in above-mentioned (2),, carry out propylene polymerization with embodiment 5 (3) same operations.The results are shown in table 2.
Embodiment 8
(1) preparation of magnesium compound
In embodiment 5 (1), adopt the MAGNESIUM METAL (cutting, pulverizing back classification) of size distribution index 3.0,, obtain magnesium compound with embodiment 5 (1) same operations.The results are shown in table 2.
(2) preparation of solid catalyst component
In embodiment 5 (2), adopt the magnesium compound of preparation in above-mentioned (1), with embodiment 5 (2) same operations, preparation solid catalyst component.
(3) propylene slurry polymerization
In embodiment 5 (3), adopt the solid catalyst component of preparation in above-mentioned (2),, carry out propylene polymerization with embodiment 5 (3) same operations.The results are shown in table 2.
Embodiment 9
(1) preparation of magnesium compound
In embodiment 5 (1), adopt the MAGNESIUM METAL (cutting, pulverizing back classification) of size distribution index 1.8,, obtain magnesium compound with embodiment 5 (1) same operations.The results are shown in table 2.
(2) preparation of solid catalyst component
In embodiment 5 (2), adopt the magnesium compound of preparation in above-mentioned (1), with embodiment 5 (2) same operations, preparation solid catalyst component.
(3) propylene slurry polymerization
In embodiment 5 (3), adopt the solid catalyst component of preparation in above-mentioned (2),, carry out propylene polymerization with embodiment 5 (3) same operations.The results are shown in table 2.
Comparative example 4
(1) preparation of magnesium compound
Except the MAGNESIUM METAL that adopts size distribution indexes 4.9 among the embodiment 5 (1) (cutting, pulverize the back classification, during classification, take the particle of various particle diameters on a large scale) in addition, with embodiment 5 (1) same operations, obtains magnesium compound.The results are shown in table 2.
(2) preparation of solid catalyst component
In embodiment 5 (2), adopt the magnesium compound of preparation in above-mentioned (1), with embodiment 5 (2) same operations, preparation solid catalyst component.
(3) propylene slurry polymerization
In embodiment 5 (3), adopt the solid catalyst component of preparation in above-mentioned (2),, carry out propylene polymerization with embodiment 5 (3) same operations.The results are shown in table 2.
Comparative example 5
(1) preparation of magnesium compound
Except the MAGNESIUM METAL that adopt size distribution indexes 5.4 among the embodiment 5 (1) (cutting, pulverize the back classification, during classification, take the particle of various particle diameters on a large scale), beyond 60 ℃ of the temperature of reaction,, obtain magnesium compound with embodiment 5 (1) same operations.The results are shown in table 2.
(2) preparation of solid catalyst component
In embodiment 5 (2), adopt the magnesium compound of preparation in above-mentioned (1), with embodiment 5 (2) same operations, preparation solid catalyst component.
(3) propylene slurry polymerization
In embodiment 5 (3), adopt the solid catalyst component of preparation in above-mentioned (2),, carry out propylene polymerization with embodiment 5 (3) same operations.The results are shown in table 2.
Comparative example 6
(1) preparation of magnesium compound
In embodiment 7 (1), adopt the MAGNESIUM METAL (only cut, pulverize) of size distribution index 7.0,, obtain magnesium compound with embodiment 7 (1) same operations.The results are shown in table 2.
(2) preparation of solid catalyst component
In embodiment 5 (2), adopt the magnesium compound of preparation in above-mentioned (1), with embodiment 5 (2) same operations, preparation solid catalyst component.
(3) propylene slurry polymerization
In embodiment 5 (3), adopt the solid catalyst component of preparation in above-mentioned (2),, carry out propylene polymerization with embodiment 5 (3) same operations.The results are shown in table 2.
Table 2
| Classification | Index | Unit | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Comparative example 4 | Comparative example 5 | Comparative example 6 |
| Carrier | The size distribution index (P) of metal M g | 1.4 | 1.4 | 1.4 | 3.0 | 1.8 | 4.9 | 5.4 | 7.0 | |
| Initiator type | I 2 | I 2 | MgCl 2 | I 2 | I 2 | I 2 | I 2 | MgCl 2 | ||
| Halogen and/or halogen contained compound/Mg | (grammeatom ratio) | 0.019 | 0.0057 | 0.019 | 0.019 | 0.019 | 0.019 | 0.019 | 0.019 | |
| Temperature of reaction | (℃) | 78 | 50 | 78 | 78 | 78 | 78 | 60 | 78 | |
| Revolution | (rpm) | 350 | 525 | 350 | 350 | 350 | 350 | 350 | 350 | |
| Median size (D 50) | (μm) | 69 | 34 | 70 | 68 | 69 | 74 | 61 | 77 | |
| The size distribution index (P ') | 2.8 | 2.6 | 2.9 | 3.1 | 3.2 | 4.8 | 3.8 | 6.2 | ||
| Sphericity (S ')) | 1.30 | 1.28 | 1.31 | 1.32 | 1.30 | 1.36 | 1.35 | 1.63 | ||
| Polymkeric substance | Polymerization activity | (kg/g-Cat) | 16.4 | 23.9 | 15.5 | 15.7 | 16.4 | 13.8 | 15.4 | 13.2 |
| Legislate ([mmmm]) | (mol％) | 98.3 | 98.4 | 98.2 | 98.3 | 98.3 | 98.2 | 98.3 | 98.3 | |
| Median size (D 50) | (μm) | 1,240 | 650 | 1,190 | 1,220 | 1,240 | 1,300 | 1,030 | 1,340 | |
| The size distribution index (P ") | 2.9 | 2.7 | 3.0 | 3.2 | 3.4 | 5.0 | 3.9 | 6.4 | ||
| Sphericity (S ")) | 1.30 | 1.28 | 1.30 | 1.33 | 1.30 | 1.38 | 1.36 | 1.65 |
Embodiment 10
(1) preparation of magnesium compound
That cross through nitrogen replacement, 5 liters of internal volumes, with agitator (the Mercks Wei blade of 4 flow deflectors, blade diameter d=0.09m) in the there-necked flask, put into ethanol 2,274g (49 grammeatom), iodine 12g (95 milligram-atom) and median size (D through processed
50) the MAGNESIUM METAL 120g (4.9 grammeatom) (cutting, pulverize product) (ethanol/MAGNESIUM METAL (ROH/Mg) (mol ratio)=10) of 400 μ m.In 78 ℃ of stirrings (stirred for several n=250 (inferior/minute) (calling rpm in the following text), n
3d
2=1.27 * 10
5) make their reactions, in system, reach and do not take place till the hydrogen, obtain magnesium compound (diethoxy magnesium).The results are shown in table 3.
(2) preparation of solid catalyst component
With nitrogen replacement, in the internal volume there-necked flask 0.5 liter, belt stirrer, put into magnesium compound (carrier) 16g of above-mentioned (1) preparation, through 80 milliliters of the octanes of processed.Be heated to 40 ℃, add silicon tetrachloride 2.4 milliliters (23 mmoles) and stir after 20 minutes, add 3.4 milliliters of n-butyl phthalates (13 mmole).This solution is warming up to 80 ℃, drips 77 milliliters of titanium tetrachlorides (0.70 mole) with dropping funnel then, stir for 125 ℃ in interior temperature and supported operation in 1 hour.Then, the octane with dehydration carries out thorough washing.Then, add 122 milliliters of titanium tetrachlorides (1.11 moles) again, carried out the 2nd time in 2 hours in 125 ℃ of stirrings of interior temperature and support operation.Then, carry out thorough washing, obtain solid catalyst component with the octane that dewaters.
(3) propylene slurry polymerization
The autoclave of the stainless steel of 1 liter of internal volume, belt stirrer thorough drying in addition, through behind the nitrogen replacement, put into through 500 milliliters of the heptane of processed.The solid catalyst component that adds preparation in triethyl aluminum 2.0 mmoles, dicyclopentyl dimethoxyl silane 0.25 mmole, above-mentioned (2) inward is converted into Ti atom 0.0025 mmole, import hydrogen 0.1MPa, then, the limit imports propylene limit increasing temperature and pressure to 80 ℃, stagnation pressure 0.8MPa, carries out polymerization in 1 hour.
Then, inner thing is taken out in cooling, step-down, puts into 2 liters of methyl alcohol, carries out catalyst deactivation.Filter material, vacuum-drying obtains propene polymer (polypropylene).The results are shown in table 3.
Embodiment 11
(1) preparation of magnesium compound
In embodiment 10 (1), except the iodine consumption is that 3.6g (28 milligram-atom), 50 ℃ of temperature of reaction, stirred for several (n) are 375rpm (n
3d
2=4.27 * 10
5) in addition,, obtain magnesium compound with embodiment 10 (1) same operations.The results are shown in table 3.
(2) preparation of solid catalyst component
In embodiment 10 (2), adopt the magnesium compound of preparation in above-mentioned (1), with embodiment 10 (2) same operations, preparation solid catalyst component.
(3) propylene slurry polymerization
In embodiment 10 (3), adopt the solid catalyst component of preparation in above-mentioned (2),, carry out propylene polymerization with embodiment 10 (3) same operations.The results are shown in table 3.
Embodiment 12
(1) preparation of magnesium compound
In embodiment 10 (1), except replace iodine, MAGNESIUM METAL 40g (1.6 grammeatom), ROH/Mg=30 with Magnesium Chloride Anhydrous 1.5g (31 milligram-atom),, obtain magnesium compound with embodiment 10 (1) same operations.The results are shown in table 3.
(2) preparation of solid catalyst component
In embodiment 10 (2), adopt the magnesium compound of preparation in above-mentioned (1), with embodiment 10 (2) same operations, preparation solid catalyst component.
(3) propylene slurry polymerization
In embodiment 10 (3), adopt the solid catalyst component of preparation in above-mentioned (2),, carry out propylene polymerization with embodiment 10 (3) same operations.The results are shown in table 3.
Embodiment 13
(1) preparation of magnesium compound
In embodiment 10 (1), except using median size (D
50) MAGNESIUM METAL (cutting, pulverize product), the ethanol/MAGNESIUM METAL (mol ratio) 8 of 75 μ m, stirred for several n=150rpm (n
3d
2=2.73 * 10
4) in addition,, obtain magnesium compound with embodiment 1 (1) same operation.The results are shown in table 3.
(2) preparation of solid catalyst component
In embodiment 10 (2), adopt the magnesium compound of preparation in above-mentioned (1), with embodiment 10 (2) same operations, preparation solid catalyst component.
(3) propylene slurry polymerization
In embodiment 10 (3), adopt beyond the solid catalyst component of preparation in above-mentioned (2), with embodiment 10 (3) same operations, carry out propylene polymerization.The results are shown in table 3.
Embodiment 14
(1) preparation of magnesium compound
In embodiment 13 (1), except using median size (D
50) MAGNESIUM METAL (cutting, pulverize product), stirred for several (n) 400rpm (n of 1,800 μ m
3d
2=5.18 * 10
5) in addition,, obtain magnesium compound with embodiment 13 (1) same operations.The results are shown in table 3.
(2) preparation of solid catalyst component
In embodiment 10 (2), adopt the magnesium compound of preparation in above-mentioned (1), with embodiment 10 (2) same operations, preparation solid catalyst component.
(3) propylene slurry polymerization
In embodiment 10 (3), adopt beyond the solid catalyst component of preparation in above-mentioned (2), with embodiment 10 (3) same operations, carry out propylene polymerization.The results are shown in table 3.
Comparative example 7
(1) preparation of magnesium compound
In embodiment 13 (1), except using median size (D
50) MAGNESIUM METAL (cutting, pulverize product), stirred for several (n) 250rpm (n of 2400 μ m
3d
2=1.27 * 10
5) in addition,, obtain magnesium compound with embodiment 13 (1) same operations.The results are shown in table 3.
(2) preparation of solid catalyst component
In embodiment 10 (2), adopt the magnesium compound of preparation in above-mentioned (1), with embodiment 10 (2) same operations, preparation solid catalyst component.
(3) slurry polymerization of propylene
In embodiment 10 (3), adopt beyond the solid catalyst component of preparation in above-mentioned (2), with embodiment 10 (3) same operations, carry out propylene polymerization.The results are shown in table 3.
Comparative example 8
(1) preparation of magnesium compound
In embodiment 11 (1), except using median size (D
50) MAGNESIUM METAL (cutting, pulverize product), the iodine consumption of 40 μ m be 3.6g (28 milligram-atom), stirred for several (n) 200rpm (n
3d
2=6.48 * 10
4) in addition,, obtain magnesium compound with embodiment 10 (1) same operations.The results are shown in table 3.
(2) preparation of solid catalyst component
In embodiment 10 (2), adopt the magnesium compound of preparation in above-mentioned (1), with embodiment 10 (2) same operations, preparation solid catalyst component.
(3) propylene slurry polymerization
In embodiment 10 (3), adopt beyond the solid catalyst component of preparation in above-mentioned (2), with embodiment 10 (3) same operations, carry out propylene polymerization.The results are shown in table 3.
Comparative example 9
(1) preparation of magnesium compound
In embodiment 10 (1),,, obtain magnesium compound with embodiment 10 (1) same operations except ethanol/MAGNESIUM METAL (mol ratio) is 50.The results are shown in table 3.
(2) preparation of solid catalyst component
In embodiment 10 (2), adopt the magnesium compound of preparation in above-mentioned (1), with embodiment 10 (2) same operations, preparation solid catalyst component.
(3) propylene slurry polymerization
In embodiment 10 (3), adopt beyond the solid catalyst component of preparation in above-mentioned (2), with embodiment 10 (3) same operations, carry out propylene polymerization.The results are shown in table 3.
Comparative example 10
(1) preparation of magnesium compound
In embodiment 10 (1),,, obtain magnesium compound with embodiment 10 (1) same operations except ethanol/MAGNESIUM METAL (mol ratio) is 3.The results are shown in table 3.
(2) preparation of solid catalyst component
In embodiment 10 (2), adopt the magnesium compound of preparation in above-mentioned (1), with embodiment 10 (2) same operations, preparation solid catalyst component.
(3) propylene slurry polymerization
In embodiment 10 (3), adopt beyond the solid catalyst component of preparation in above-mentioned (2), with embodiment 10 (3) same operations, carry out propylene polymerization.The results are shown in table 3.
Comparative example 11
(1) preparation of magnesium compound
In embodiment 13 (1), except using median size (D
50) MAGNESIUM METAL (cutting, pulverize product), the stirred for several (n) of 600 μ m be 60rpm (n
3d
2=1.75 * 10
3) in addition,, obtain magnesium compound with embodiment 13 (1) same operations.The results are shown in table 3.
(2) preparation of solid catalyst component
In embodiment 10 (2), adopt the magnesium compound of preparation in above-mentioned (1), with embodiment 10 (2) same operations, preparation solid catalyst component.
(3) propylene slurry polymerization
In embodiment 10 (3), adopt beyond the solid catalyst component of preparation in above-mentioned (2), with embodiment 10 (3) same operations, carry out propylene polymerization.The results are shown in table 3.
Comparative example 12
(1) preparation of magnesium compound
In embodiment 13 (1), except using median size (D
50) MAGNESIUM METAL (cutting, pulverize product), the stirred for several (n) of 200 μ m be 800rpm (n
3d
2=4.15 * 10
6) in addition,, obtain magnesium compound with embodiment 13 (1) same operations.The results are shown in table 3.
(2) preparation of solid catalyst component
In embodiment 10 (2), adopt the magnesium compound of preparation in above-mentioned (1), with embodiment 10 (2) same operations, preparation solid catalyst component.
(3) propylene slurry polymerization
In embodiment 10 (3), adopt beyond the solid catalyst component of preparation in above-mentioned (2), with embodiment 10 (3) same operations, carry out propylene polymerization.The results are shown in table 3.
Table 3
| Classification | Index | Unit | Embodiment 10 | Embodiment 11 | Embodiment 12 | Embodiment 13 | Embodiment 14 | Comparative example 7 | Comparative example 8 | Comparative example 9 | Comparative example 10 | Comparative example 11 | Comparative example 12 |
| Metal M g | Median size (D 50) | (μm) | 400 | 400 | 400 | 75 | 1,800 | 2,400 | 40 | 400 | 400 | 600 | 200 |
| Carrier | Initiator type | I 2 | I 2 | MgCl 2 | I 2 | I 2 | I 2 | I 2 | I 2 | I 2 | I 2 | I 2 | |
| Halogen and/or halogen contained compound/Mg | The grammeatom ratio | 0.019 | 0.0057 | 0.019 | 0.019 | 0.019 | 0.019 | 0.0057 | 0.019 | 0.019 | 0.019 | 0.019 | |
| ROH/Mg | (mole) | 10 | 10 | 30 | 8 | 8 | 8 | 10 | 50 | 3 | 8 | 8 | |
| Temperature of reaction | (℃) | 78 | 50 | 78 | 78 | 78 | 78 | 78 | 78 | 78 | 78 | 78 | |
| Revolution (n) | (rpm) | 250 | 375 | 250 | 150 | 400 | 250 | 200 | 250 | 250 | 60 | 800 | |
| The diameter of agitating vane (d) | (m) | 0.09 | 0.09 | 0.09 | 0.09 | 0.09 | 0.09 | 0.09 | 0.09 | 0.09 | 0.09 | 0.09 | |
| Agitation condition (n 2d 2) | 1.27E+05 | 4.27E+05 | 1.27E+05 | 2.73E+04 | 5.18E+05 | 1.27E+05 | 6.48E+04 | 1.27E+05 | 1.27E+05 | 1.75E+03 | 4.15E+06 | ||
| Median size (D 50) | (μm) | 72 | 35 | 77 | 34 | 54 | 103 | 15 | 88 | 64 | 77 | 17 | |
| Size distribution index (P) | 3.0 | 2.9 | 3.2 | 3.1 | 3.2 | 4.3 | 4.4 | 4.7 | 4.8 | 4.7 | 4.8 | ||
| Sphericity (S) | 1.24 | 1.23 | 1.26 | 1.27 | 1.26 | 1.48 | 1.73 | 1.63 | 1.65 | 1.98 | 1.78 | ||
| Polymkeric substance | Polymerization activity | (kg/g-Cat) | 15.7 | 23.8 | 14.6 | 16.4 | 16.1 | 13.2 | 12.9 | 12.7 | 11.9 | 12.5 | 12.2 |
| Legislate | (mol％) | 98.4 | 98.4 | 98.3 | 98.3 | 98.4 | 98.1 | 98.2 | 98.3 | 98.2 | 98.2 | 98.3 | |
| Median size (D 50) | (μm) | 1,310 | 650 | 1,330 | 580 | 1,040 | 1,800 | 330 | 1,690 | 1,220 | 1,340 | 360 | |
| The size distribution index (P ') | 3.1 | 3.0 | 3.3 | 3.2 | 3.3 | 4.5 | 4.8 | 4.9 | 5.0 | 4.9 | 5.1 | ||
| Sphericity (S ') | 1.24 | 1.23 | 1.26 | 1.28 | 1.27 | 1.48 | 1.75 | 1.65 | 1.68 | 2.04 | 1.48 |
Embodiment 15
(1) preparation of magnesium compound
Cross through nitrogen replacement, in the internal volume there-necked flask 0.5 liter, belt stirrer, put into through ethanol 122g (2.64 grammeatom), the iodine 0.8g (6.3 milligram-atom) of processed and the MAGNESIUM METAL 8g (0.33 grammeatom) (obtaining median size 400 μ m at nitrogen atmosphere with cutting, pulverizing, classification) of oxide film thereon thickness 0.05 μ m.Make their reactions in 78 ℃ of stirrings (revolution 350rpm), in system, reach and do not take place till the hydrogen, obtain magnesium compound (diethoxy magnesium).The results are shown in table 4.
(2) preparation of solid catalyst component
With nitrogen replacement, in the internal volume there-necked flask 0.5 liter, belt stirrer, put into magnesium compound (carrier) 16g of above-mentioned (1) preparation, through 80 milliliters of the octanes of processed.Be heated to 40 ℃, add 2.4 milliliters of silicon tetrachlorides (23 mmole), stir after 20 minutes, add 3.4 milliliters of n-butyl phthalates (13 mmole).This solution is warming up to 80 ℃, then, drips 77 milliliters of titanium tetrachlorides (0.70 mole), stirred 1 hour for 125 ℃, support operation in interior temperature with dropping funnel.Then, carry out thorough washing with the dehydration octane.Add 122 milliliters of titanium tetrachlorides (1.11 moles) again, stirred 2 hours for 125 ℃, carry out the 2nd time and support operation in interior temperature.Then, carry out thorough washing, obtain solid catalyst component with the octane that dewaters.
(3) propylene slurry polymerization
The autoclave of the stainless steel of 1 liter of internal volume, belt stirrer thorough drying in addition, through behind the nitrogen replacement, add through 500 milliliters of the heptane of processed.The solid catalyst component of preparation is converted into Ti atom 0.0025 mmole in wherein adding triethyl aluminum 2.0 mmoles, dicyclopentyl dimethoxyl silane 0.25 mmole, above-mentioned (2), import hydrogen 0.1MPa, then, the limit imports propylene limit increasing temperature and pressure to 80 ℃, stagnation pressure 0.8MPa, carries out polymerization in 1 hour.
Then, inner thing is taken out in cooling, step-down, puts into 2 liters of methyl alcohol, carries out catalyst deactivation.Filter material, vacuum-drying obtains propene polymer (polypropylene).The results are shown in table 4.
Embodiment 16
(1) preparation of magnesium compound
Except the consumption of iodine among the embodiment 15 (1) is 0.24g (1.9 milligram-atom), 50 ℃ of temperature of reaction beyond the revolution 525rpm, with embodiment 15 (1) same operations, obtain magnesium compound.The results are shown in table 4.
(2) preparation of solid catalyst component
In embodiment 15 (2), adopt the magnesium compound of preparation in above-mentioned (1), with embodiment 15 (2) same operations, preparation solid catalyst component.
(3) propylene slurry polymerization
In embodiment 15 (3), adopt the solid catalyst component of preparation in above-mentioned (2),, carry out propylene polymerization with embodiment 15 (3) same operations.The results are shown in table 4.
Embodiment 17
(1) preparation of magnesium compound
In embodiment 15 (1),,, obtain magnesium compound with embodiment 15 (1) same operations with Magnesium Chloride Anhydrous 0.30g (6.3 milligram-atom) the replacement iodine.The results are shown in table 4.
(2) preparation of solid catalyst component
In embodiment 15 (2), adopt the magnesium compound of preparation in above-mentioned (1), with embodiment 15 (2) same operations, preparation solid catalyst component.
(3) propylene slurry polymerization
In embodiment 15 (3), adopt the solid catalyst component of preparation in above-mentioned (2),, carry out propylene polymerization with embodiment 15 (3) same operations.The results are shown in table 4.
Embodiment 18
(1) preparation of magnesium compound
Except the MAGNESIUM METAL (in nitrogen atmosphere, obtaining median size 400 μ m) that adopts oxide film thereon thickness 0.5 μ m among the embodiment 15 (1) with cutting, pulverizing, classification in addition, operate equally with embodiment 15 (1), obtain magnesium compound.The results are shown in table 4.
(2) preparation of solid catalyst component
In embodiment 15 (2), adopt the magnesium compound of preparation in above-mentioned (1), with embodiment 15 (2) same operations, preparation solid catalyst component.
(3) propylene slurry polymerization
In embodiment 15 (3), adopt the solid catalyst component of preparation in above-mentioned (2),, carry out propylene polymerization with embodiment 15 (3) same operations.The results are shown in table 4.
Comparative example 13
(1) preparation of magnesium compound
Except the MAGNESIUM METAL (in air, obtaining median size 300 μ m) that adopts oxide film thereon thickness 2 μ m among the embodiment 15 (1) with cutting, pulverizing, classification in addition, operate equally with embodiment 15 (1), obtain magnesium compound.The results are shown in table 4.
(2) preparation of solid catalyst component
In embodiment 15 (2), adopt the magnesium compound of preparation in above-mentioned (1), with embodiment 15 (2) same operations, preparation solid catalyst component.
(3) propylene slurry polymerization
In embodiment 15 (3), adopt the solid catalyst component of preparation in above-mentioned (2),, carry out propylene polymerization with embodiment 15 (3) same operations.The results are shown in table 4.
Comparative example 14
(1) preparation of magnesium compound
Except adopt among the embodiment 17 (1) with the same MAGNESIUM METAL of comparative example 1, with embodiment 17 (1) same operations, obtain magnesium compound.The results are shown in table 4.
(2) preparation of solid catalyst component
In embodiment 15 (2), adopt the magnesium compound of preparation in above-mentioned (1), with embodiment 15 (2) same operations, preparation solid catalyst component.
(3) propylene slurry polymerization
In embodiment 15 (3), adopt the solid catalyst component of preparation in above-mentioned (2),, carry out propylene polymerization with embodiment 15 (3) same operations.The results are shown in table 4.
Comparative example 15
(1) preparation of magnesium compound
Except adopt among the embodiment 15 (1) with 60 ℃ of same MAGNESIUM METAL, the temperature of reaction of comparative example 13, with embodiment 15 (1) same operations, obtain magnesium compound.The results are shown in table 4.
(2) preparation of solid catalyst component
In embodiment 15 (2), adopt the magnesium compound of preparation in above-mentioned (1), with embodiment 15 (2) same operations, preparation solid catalyst component.
(3) propylene slurry polymerization
In embodiment 15 (3), adopt the solid catalyst component of preparation in above-mentioned (2),, carry out propylene polymerization with embodiment 15 (3) same operations.The results are shown in table 4.
Table 4
| Classification | Index | Unit | Embodiment 15 | Embodiment 16 | Embodiment 17 | Embodiment 18 | Comparative example 13 | Comparative example 14 | Comparative example 15 |
| Carrier | The thickness of the oxide film of metal M g | (μm) | 0.05 | 0.05 | 0.05 | 0.5 | 2 | 2 | 2 |
| Initiator type | I 2 | I 2 | MgCl 2 | I 2 | I 2 | MgCl 2 | I 2 | ||
| Halogen and/or halogen-containing compound/Mg | (grammeatom ratio) | 0.019 | 0.0057 | 0.019 | 0.019 | 0.019 | 0.019 | 0.019 | |
| Temperature of reaction | (℃) | 78 | 50 | 78 | 78 | 78 | 78 | 60 | |
| Revolution | (rpm) | 350 | 525 | 350 | 350 | 350 | 350 | 350 | |
| Median size (D 50) | (μm) | 68 | 35 | 69 | 70 | 72 | 73 | 49 | |
| The size distribution index (P ') | 3.0 | 2.9 | 3.0 | 3.2 | 4.7 | 4.9 | 3.8 | ||
| Sphericity (S ') | 1.30 | 1.28 | 1.32 | 1.31 | 1.50 | 1.53 | 1.40 | ||
| Polymkeric substance | Polymerization activity | (kg/g-Cat) | 16.2 | 24.2 | 15.9 | 15.0 | 13.3 | 13.2 | 14.9 |
| Legislate ([mmmm]) | (mol％) | 98.4 | 98.4 | 98.3 | 98.3 | 98.2 | 98.2 | 98.3 | |
| Median size (D 50) | (μm) | 1,250 | 650 | 1,200 | 1,220 | 1,250 | 1,280 | 1,080 | |
| The size distribution index (P ") | 3.1 | 2.9 | 3.1 | 3.3 | 4.6 | 4.8 | 3.942 | ||
| Sphericity (S ")) | 1.29 | 1.28 | 1.32 | 1.31 | 1.52 | 1.55 | 1.64 |
The invention provides magnesium compound, solid catalyst component for olefin polymerization, catalyst for olefines polymerizing and preparation of polyolefins method that a kind of olefin polymer that does not make catalytic performance decline, narrow diameter distribution and/or almost sphericals such as legislate and polymerization activity is used.
Claims (11)
1. magnesium compound, it is by containing the halogen and/or the reaction of halogen-containing compound of the above halogen atom of 0.0001 grammeatom and obtain less than 4.0 MAGNESIUM METAL, alcohol and with respect to above-mentioned MAGNESIUM METAL 1 grammeatom with the size distribution index (P) of following formula (II) expression,
P＝(D
90/D
10) (II)
In the formula, D
90Expression is corresponding to the particle diameter of the above-mentioned MAGNESIUM METAL of accumulating weight mark 90%, D
10Expression is corresponding to the particle diameter of the above-mentioned MAGNESIUM METAL of accumulating weight mark 10%.
2. according to the described magnesium compound of claim 1, wherein, above-mentioned halogen is an iodine.
3. according to the described magnesium compound of claim 1, wherein, above-mentioned halogen-containing compound is a magnesium chloride.
4. according to the described magnesium compound of claim 1, wherein, above-mentioned MAGNESIUM METAL, alcohol, and the temperature of reaction of halogen and/or halogen-containing compound be 30～90 ℃.
5. according to the described magnesium compound of claim 1, wherein, with the size distribution index of following formula (IV) expression (P ') less than 3.4,
P’＝(D
90/D
10) (IV)
In the formula, D
90Expression is corresponding to the particle diameter of the above-mentioned magnesium compound of accumulating weight mark 90%, D
10Expression is corresponding to the particle diameter of the above-mentioned magnesium compound of accumulating weight mark 10%.
6. solid catalyst component for olefin polymerization, its be by the described magnesium compound of (a) claim 1 and (b) the titanium compound reaction obtain.
7. according to the solid catalyst component for olefin polymerization described in the claim 6, its also by (c) halogen compounds and/or (d) the sub-property compound reaction of power supply obtain.
8. according to the solid catalyst component for olefin polymerization described in the claim 7, wherein, above-mentioned halogen compounds (c) is a silicon tetrachloride.
9. catalyst for olefines polymerizing, it comprises following compounds [A] and [B], or comprises following compounds [A], [B] and [C]:
Solid catalyst component for olefin polymerization described in [A] claim 6;
[B] organo-aluminium compound;
[C] the sub-property compound of powering.
10. preparation of polyolefins method, it adopts the catalyst for olefines polymerizing described in the claim 9.
11. magnesium compound preparation method, it makes with the size distribution index (P) of following formula (II) expression less than 4.0 MAGNESIUM METAL, alcohol and contain the halogen and/or the reaction of halogen-containing compound of the above halogen atom of 0.0001 grammeatom with respect to above-mentioned MAGNESIUM METAL 1 grammeatom
P＝D
90/D
10 (II)
In the formula, D
90Expression is corresponding to the particle diameter of the above-mentioned MAGNESIUM METAL of accumulating weight mark 90%, D
10Expression is corresponding to the particle diameter of the above-mentioned MAGNESIUM METAL of accumulating weight mark 10%.
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| JP2002150280 | 2002-05-24 | ||
| JP2002151091 | 2002-05-24 | ||
| JP2002150279 | 2002-05-24 | ||
| JP2002151092 | 2002-05-24 | ||
| JP2002150279A JP4170667B2 (en) | 2002-05-24 | 2002-05-24 | Magnesium compound, solid catalyst component for olefin polymerization, catalyst for olefin polymerization, and method for producing polyolefin |
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| CNB2006100773344A Expired - Lifetime CN100519496C (en) | 2002-05-24 | 2003-05-19 | Magnesium compound, solid catalyst component for olefin polymerization, catalyst for olefin polymerization, and process for producing polyolefin |
| CN2006100773359A Expired - Lifetime CN1865138B (en) | 2002-05-24 | 2003-05-19 | Magnesium compound, solid catalyst component for olefin polymerization, catalyst for olefin polymerization, and process for producing polyolefin |
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| CN102918067A (en) * | 2010-05-27 | 2013-02-06 | 三星Total株式会社 | Production method for a spherical carrier for an olefin polymerization catalyst, and a solid catalyst using the same and propylene polymers |
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| KR101126918B1 (en) * | 2009-12-28 | 2012-03-20 | 호남석유화학 주식회사 | Preparing method of catalyst for polyolefin polymerization, Catalyst prepared thereby, and Preparing method of polyolefin using the catalyst |
| KR101126946B1 (en) * | 2009-12-28 | 2012-03-20 | 호남석유화학 주식회사 | Catalyst for Polyolepin Polymerization, and preparation method thereof |
| CN103772547B (en) * | 2012-10-23 | 2016-04-27 | 中国石油化工股份有限公司 | For catalyst component and the catalyzer thereof of ethylene polymerization |
| CN105732851B (en) * | 2014-12-08 | 2018-07-10 | 中国石油天然气股份有限公司 | The preparation method and application of magnesium ethylate ball type carrier ethylene rolymerization catalyst |
| TW201906806A (en) * | 2017-06-15 | 2019-02-16 | 日商東邦鈦股份有限公司 | Dialkoxymagnesium, a method for producing dialkoxymagnesium, solid catalyst component for olefin polymerization, and a method for producing olefin polymerization |
| CN112299984B (en) * | 2019-08-01 | 2022-03-01 | 中国科学院化学研究所 | Preparation method of spherical diethoxy magnesium |
| JP2022031142A (en) | 2020-08-07 | 2022-02-18 | 住友化学株式会社 | Solid catalyst component for olefin polymerization |
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| CA2315214A1 (en) * | 1997-12-23 | 1999-07-08 | Borealis Technology Oy | Catalyst component comprising magnesium, titanium, a halogen and an electron donor, its preparation and use |
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