CN1898278A - Magnesium dichloride-ethanol adducts and atalyst components obtained therefrom - Google Patents
Magnesium dichloride-ethanol adducts and atalyst components obtained therefrom Download PDFInfo
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- CN1898278A CN1898278A CNA2004800382994A CN200480038299A CN1898278A CN 1898278 A CN1898278 A CN 1898278A CN A2004800382994 A CNA2004800382994 A CN A2004800382994A CN 200480038299 A CN200480038299 A CN 200480038299A CN 1898278 A CN1898278 A CN 1898278A
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- Prior art keywords
- adducts
- compound
- catalyst component
- formula
- alkyl
- Prior art date
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- Granted
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- OLSMQDUPRYIMTC-UHFFFAOYSA-L magnesium;ethanol;dichloride Chemical class [Mg+2].[Cl-].[Cl-].CCO OLSMQDUPRYIMTC-UHFFFAOYSA-L 0.000 title description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 239000002879 Lewis base Substances 0.000 claims abstract description 19
- 150000007527 lewis bases Chemical class 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims description 26
- 238000006116 polymerization reaction Methods 0.000 claims description 19
- 239000010936 titanium Substances 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 230000004927 fusion Effects 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- -1 4-butyleneglycol Chemical compound 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 10
- 150000002736 metal compounds Chemical class 0.000 claims description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- WWUVJRULCWHUSA-UHFFFAOYSA-N 2-methyl-1-pentene Chemical compound CCCC(C)=C WWUVJRULCWHUSA-UHFFFAOYSA-N 0.000 claims description 4
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 claims description 4
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 125000001033 ether group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 150000003609 titanium compounds Chemical class 0.000 claims description 3
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 claims description 2
- WOFPPJOZXUTRAU-UHFFFAOYSA-N 2-Ethyl-1-hexanol Natural products CCCCC(O)CCC WOFPPJOZXUTRAU-UHFFFAOYSA-N 0.000 claims description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 2
- NNJLWNMDOUHCBG-UHFFFAOYSA-N C1(=CC=CC=C1)O.CC1=C(C=C(C(=O)O)C=C1)C(=O)O Chemical compound C1(=CC=CC=C1)O.CC1=C(C=C(C(=O)O)C=C1)C(=O)O NNJLWNMDOUHCBG-UHFFFAOYSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- 229930195725 Mannitol Natural products 0.000 claims description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 2
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 2
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 claims description 2
- 229940043279 diisopropylamine Drugs 0.000 claims description 2
- 150000002367 halogens Chemical group 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000000594 mannitol Substances 0.000 claims description 2
- 235000010355 mannitol Nutrition 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229960004418 trolamine Drugs 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims 2
- 229910052723 transition metal Inorganic materials 0.000 claims 1
- 150000003624 transition metals Chemical class 0.000 claims 1
- 229940086542 triethylamine Drugs 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 16
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 18
- 239000007787 solid Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000007429 general method Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 7
- 239000004615 ingredient Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000004711 α-olefin Substances 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000011949 solid catalyst Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 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 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 150000003377 silicon compounds Chemical class 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 239000012809 cooling fluid Substances 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 238000004945 emulsification Methods 0.000 description 3
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 150000001399 aluminium compounds Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 235000011147 magnesium chloride Nutrition 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229940099259 vaseline Drugs 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- UVGKQRAGAYVWQV-UHFFFAOYSA-N 2,3-dimethylbutan-2-yl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(C)(C)C(C)C UVGKQRAGAYVWQV-UHFFFAOYSA-N 0.000 description 1
- YPULLIUIYKMONV-UHFFFAOYSA-N C(C)(=O)N.COCOC.C(C)#N Chemical compound C(C)(=O)N.COCOC.C(C)#N YPULLIUIYKMONV-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000004708 Very-low-density polyethylene Substances 0.000 description 1
- 238000002083 X-ray spectrum Methods 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000007860 aryl ester derivatives Chemical class 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- VPCAAUUIFCAFRZ-UHFFFAOYSA-N butylalumane Chemical compound CCCC[AlH2] VPCAAUUIFCAFRZ-UHFFFAOYSA-N 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- MEWFSXFFGFDHGV-UHFFFAOYSA-N cyclohexyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C1CCCCC1 MEWFSXFFGFDHGV-UHFFFAOYSA-N 0.000 description 1
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical group CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- HXLWJGIPGJFBEZ-UHFFFAOYSA-N tert-butyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(C)(C)C HXLWJGIPGJFBEZ-UHFFFAOYSA-N 0.000 description 1
- NETBVGNWMHLXRP-UHFFFAOYSA-N tert-butyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C(C)(C)C NETBVGNWMHLXRP-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 229920001866 very low density polyethylene Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Adducts are provided comprising MgCl2, ethanol and a Lewis base (LB), said compounds being present in molar ratios defined by the following formula MgC12.(EtOH)n(LB)p in which n is from 2 to 6 and p has values satisfying the following equation p/(n+p)<=0.1. The said adducts can be used as precursor in the preparation of high activity ZN catalysts.
Description
The present invention relates to have the special chemistry and the magnesium dichloride/ethanol adducts of physical property profile.Adducts of the present invention is particularly suitable as the precursor of the catalyst component that is used for olefinic polymerization.
MgCl
2Alcohol adducts and they are used for the catalyst component of olefinic polymerization in preparation this area that is applied in is known.
USP 4,399, and 054 has described the catalyst component that is used for olefinic polymerization, and it is by with MgCl
2NEtOH adducts and halogenated transition metal compounds are reacted and are obtained.This adducts is to prepare with the adducts of collecting the spherical particle form by making the emulsification of fused adducts and cool off emulsion fast in immiscible dispersion medium in cooling fluid.The report that does not have the physics of the degree of crystallinity of relevant this adducts to characterize.
Disclosed MgCl in WO98/44009
2Alcohol adducts has the characteristic of improvement, with specific X-ray diffraction spectral characterization, wherein 2 θ diffraction angle are 5 ° to 15 °, be 8.8+0.2 °, 9.4 ± 0.2 ° and 9.8+0.2 ° in 2 θ diffraction angle and locate to exist three main diffracted rays, the strongest position alignment diffraction is 2 θ=8.8 ± 0.2 °, and the intensity of other two diffracted rays is at least 0.2 times of intensity of the strongest diffracted ray.Described adducts can have formula MgCl
2MEtOHnH
2O.
Wherein m is 2.2 to 3.8, and n is 0.01 to 0.6.Except above-mentioned X ray spectrum, also using dsc (DSC) to distribute characterizes above-mentioned adducts, wherein be lower than 90 ℃ and do not have the peak, even perhaps have the peak being lower than described temperature, total the fusion enthalpy relevant with described peak also is lower than 30% of fusion enthalpy in temperature.
These adductss are to obtain by specific preparation method, relate to MgCl
2Comprising the long reaction times and do not having inert diluent or use reaction under the condition of alcohol of gasification with alcohol.Among the embodiment without any mentioning the water-content part.The catalyst component that obtains from these adductss obtain than adducts from prior art those have the enhanced activity.But the angle of obtainable economic interests from the operation of full scale plant always needs available to have the active catalyst component that still improves.In the world, please among the WO03/082930 MgCl have been described
2The mEtOH adducts, wherein m is 2.5 to 3.2, and it is optional to comprise based on the height of the adducts gross weight water to maximum 1% weight, and in the DSC that characterizes distributed, high melting temperature (Tm) peak had surpassed 109 ℃, and relevant fusion enthalpy (Δ H) is 103J/g or lower.With respect to catalyzer by the preparation of the adducts of prior art, the catalyst component that obtains from adducts of the present invention can give be used for olefinic polymerization catalyzer with the active feature of enhanced.Though the result is good, for the adducts that obtains to expect, must in system, carry out strict control to water, this may cause this method, and some is too loaded down with trivial details.In addition, relevant fusion enthalpy is owing to the influence of crystallization tendency may increase along with time course, and this behavior may cause adducts may bring the deterioration of some performance to catalyst component when reacting with transistion metal compound.Therefore, can to generate the adducts with high polymerization activity and catalyst component of relative low fusion enthalpy be very important in acquisition.And if postpone the increase of this low relatively fusion enthalpy at least along with the process of time, it is useful making transformation in the catalyst component with useful performance be more prone to.
Therefore the present invention relates to comprise MgCl
2, ethanol and be different from the adducts of the Lewis base (LB) of water, described compound is with by following formula MgCl
2(EtOH)
n(LB)
pThe mol ratio of determining exists, and wherein n is 2 to 6, the formula p/ (n+p)≤0.1 below the value of p satisfies.
Formula p/ (n+p)≤0.05 below the value of preferred p satisfies, more preferably p/ (n+p)≤0.0125.
Lewis base can be selected from carboxylic acid, amide, aldehyde, ester, ether, ester, ketone, silane, amine, pure and mild nitrile.Preferred Lewis base is selected from ether, ester and formula RX
mCompound, wherein R is the alkyl with 1 to 20 carbon atom, X is-NH
2,-NHR or-the OH group, m is 1 or higher.
R is preferably alkyl or the alkylidene group (alkiliden) with 1 to 10 carbon atom, preferred 2 to 6 carbon atoms.X is preferably-OH, and m is 1 to 6, is preferably 1,2 or 3.
Preferred ether is the C2-C20 aliphatic ether, particularly preferably has the cyclic ethers of 3-5 carbon atom, for example tetrahydrofuran (THF), diox.The suitable linear or cyclic aliphatic ethers that has two or more ether groups in addition.Preferred ester is the C1-C4 alkyl ester of the alkyl ester of C1-C10 aliphatic carboxylic acid, particularly mono carboxylic acid of aliphatic series, for example ethyl acetate and methyl-formiate.
Formula RX
mThe representative example of compound be methyl alcohol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol, amylalcohol, 2-methyl-1-pentene alcohol, 2-ethyl-1-hexanol, phenol, 4-methyl isophthalic acid-phenol, 2,6-dimethyl-1-phenol, hexalin, cyclopentanol, ethylene glycol, propylene glycol, 1, the 4-butyleneglycol, glycerol, N.F,USP MANNITOL, polyvinyl alcohol, acetonitrile, quadrol (ethylenediammine), the 3-picoline, trolamine (triethanolammine), triethylamine (triethylammine), diisopropylamine (diisopropylammine).
The representative example of other Lewis base is acetic acid, acetonitrile methylal acetamide, methane amide.
Generally speaking, the fusion enthalpy relevant with described adducts is lower than 100J/g, most preferably 85-95J/g.As mentioning in front, these values are to be no earlier than the adducts of measuring preparation in preceding 2 days.But the applicant has been noted that the fusion enthalpy of adducts of the present invention is along with the tendency that the process of time increases is lower.For example all later these increase to zero or only are confined to 2-4J/g.
Water may reside in these adductss.Based on MgCl
2, ethanol and LB summation, its content can be lower than 0.8% weight, preferably is lower than 0.6% weight.
Especially ironically, in DSC distributed, adducts only showed a peak, but may have other peak in 95-98 ℃ of zone.Under a kind of situation in back, the fusion enthalpy relevant with them is lower than 30% of total fusion enthalpy, preferably is lower than 20, more preferably less than 10%.Dsc analysis is that the apparatus and method that will describe below adopting are carried out.
Can also characterize adducts of the present invention by X-ray diffraction spectrum, but this not necessarily, wherein 2 θ diffraction angle are that to have 2 θ diffraction angle in 5 ° to 15 ° the scope be three main diffracted rays of 8.8 ± 0.2 °, 9.4 ± 0.2 ° and 9.8 ± 0.2 °, the strongest diffracted ray is positioned at 2 θ=8.8 ± 0.2 ° to be located, and the intensity of other two diffracted rays is at least 0.2 times of intensity of the strongest diffracted ray.
Can prepare adducts of the present invention by several different methods.The general method that particularly is described in WO98/44009 is suitable.A kind of mode that reduces water-content is carefully to control the water-content of initial reactant.In fact MgCl
2With EtOH all be highly hygroscopic, be easy to combination water in their structure.The result is exactly, if the water-content of reactant is higher relatively, even do not add entry, final MgCl as independent component
2-EtOH adducts also may contain too high water-content.The method of the water-content in control or the reduction solid or liquid is well known in the art.For example, MgCl
2In water-content can be by in the pyritous baking oven, it being carried out drying or reducing by itself and compound to responding property of glassware for drinking water are reacted.As an example, can use HCl stream from MgCl
2The middle moisture of removing.Water in the fluid can remove by multiple technologies, for example distills, or fluid is contacted with the material that can absorb water, such as molecular sieve.When having taked these preventive measures, can carry out the reaction of magnesium chloride and alcoholic acid to prepare adducts of the present invention by several different methods.
According to one of these methods, be dispersed in the magnesium dichloride particle to the fused adducts and be in the immiscible and chemically inert inert liq, be equal to or higher than MgCl
2Under the melt temperature of ethanol adducts the heating this system, add then desired amount vapor phase alcohol and prepare adducts.According to their physical properties, LB can same MgCl
2Add together together or with the EtOH of gas phase.Temperature remains and makes the complete fused value of adducts.
Subsequently do not dissolve each other with it and chemically inert liquid medium in this molten adduct of emulsification, then by this adducts is contacted with the inertia cooling fluid with its quick cooling, thereby make adducts curing.
MgCl
2Disperseing wherein liquid can be any molten adduct not to be dissolved each other and chemically inert liquid.For example, can use aliphatic series, aromatics or clicyclic hydrocarbon and silicone oil.Special preferred aliphatic series hydrocarbon, for example vaseline oil.MgCl
2Particle is dispersed in after the inert liq, and mixture preferably is being higher than 125 ℃, more preferably is being higher than under 150 ℃ the temperature and heats.Easily, be equal to or less than the alcohol that adds gasification under the temperature of mixture temperature.
According to other method, by not existing under the inert liquid dispersant with MgCl
2, LB and ethanol contacts, this system of heating under the melt temperature of adducts or higher temperature keeps described condition to prepare adducts of the present invention to obtain complete fused adducts.Then it is not dissolved each other and chemically inert liquid medium in the described molten adduct of emulsification, at last adducts is contacted with the inertia cooling fluid and with its quick cooling, thereby makes adducts curing.Particularly, preferably under agitation condition, adducts is being equal to or higher than and keeps under the temperature of its melt temperature equaling or more than 10 hours, preferred 10 to 150 hours, more preferably time of 20 to 100 hours.Perhaps, solidify, can carry out the spray cooling method of molten adduct for making adducts.
All these methods obtain having the solid adduct of spherical-like morphology, and it is fit to the spherical catalyst component that preparation is used for olefinic polymerization, particularly gas phase polymerization process very much.Among Bao Gao the embodiment, describe the preparation of adducts of the present invention in detail below, particularly pure and mild glycol is as the situation of LB.Yet described preparation method has general validity, can successfully be applied to comprise the preparation of the adducts of other LB of the present invention.
The catalyst component that will use in olefinic polymerization comprises the IV that loads on the periodic table of elements on the adducts of the present invention transistion metal compound to VI family.
The suitable method for preparing described catalyst component comprises the reaction of adducts of the present invention and transistion metal compound.Particularly preferably be formula Ti (OR) in the transistion metal compound
nX
Y-nTitanium compound, wherein n is 0 to y; Y is the valency of titanium; X is a halogen, and R is alkyl or the COR group with 1-8 carbon atom.Particularly preferably be titanium compound in the middle of them, for example titanium tetrahalide or titanium halogen alcoholate with at least one Ti-halogen bond.Preferred concrete titanium compound is TiCl
3, TiCl
4, Ti (OBu)
4, Ti (OBu) Cl
3, Ti (OBu)
2Cl
2, Ti (OBu)
3Cl.Reaction is preferred to be passed through at cold TiCl
4Suspension adducts in (common 0 ℃); Then the mixture heating up that will so obtain to high to 80-130 ℃ and keep this temperature to carry out in 0.5-2 hour.Subsequently with excessive TiCl
4Remove, collect solid ingredient.Use TiCl
4Processing can carry out one or many.
The reaction of transistion metal compound and adducts can also be carried out in the presence of electronic donor compound capable (the inner body of giving), and particularly preparation is used for the stereospecific catalyst of olefinic polymerization.Described electronic donor compound capable can be selected from ester, ether, amine, silane and ketone.Particularly single or polycarboxylic alkyl and aryl ester, the ester of for example preferred phenylformic acid, phthalic acid, propanedioic acid and succsinic acid.The specific examples of such ester is n-butyl phthalate, diisobutyl phthalate, dinoctyl phthalate, diethyl 2,2-di-isopropyl succinate, diethyl 2,2-dicyclohexyl succinate, ethyl benzoate and right-ethoxyethyl group benzoic ether.In addition, can advantageously use 1,3 diether of following formula:
Wherein R, R
1, R
II, R
III, R
IVAnd R
VBe same to each other or different to each other to hydrogen or have the alkyl of 1 to 18 carbon atom, R
VIAnd R
VIIBe same to each other or different to each other and have and R-R
VIdentical implication, difference are that they can not be hydrogen; R-R
VIIIn one or more groups can connect into ring.Especially preferred R wherein
VIAnd R
VIIBe selected from C
1-C
41 of alkyl, the 3-diether.
Usually the amount of the electronic donor compound capable that exists and the mol ratio of magnesium are 1: 4 to 1: 20.
The particle of preferred ingredient of solid catalyst has globular form in fact, and mean diameter is 5 to 150 μ m.Term in fact the globular form represent those than major axis be equal to or less than 1.5 than the ratio of minor axis, preferably less than 1.3 particle.
Before reacting with transistion metal compound, can also allow adducts of the present invention through dealcoholation treatment, purpose is in order to reduce the porosity of pure content and increase adducts self.Can carry out dealcoholysis by known method, for example the method for describing among the EP-A-395083.According to the degree of dealcoholation treatment, can obtain the adducts of part dealcoholysis, pure content is generally 0.1 to 2.6 mol of alcohol/every mole of MgCl
2After the dealcoholation treatment,, make the reaction of adducts and transistion metal compound to obtain ingredient of solid catalyst according to above-described technology.Ingredient of solid catalyst indicator gauge area of the present invention (according to the B.E.T. method) is generally 10 to 500m
2/ g, preferred 20 to 350m
2/ g, total porosity (according to the B.E.T. method) is greater than 0.15cm
3/ g, preferred 0.2 to 0.6cm
3/ g.
By with the reaction of Al-alkylate, catalyst component of the present invention is formed for alpha-olefin CH
2=CHR polymeric catalyzer, wherein R is hydrogen or the alkyl with 1-12 carbon atom.Preferred alkyl-Al compound is selected from trialkyl aluminium compound, for example triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum, tri-n-octylaluminium.Also can also use aluminum alkyl halide, alkyl aluminum hydride or alkylaluminium sesquichloride, for example AlEt
2Cl and Al
2Et
3Cl
3, choose wantonly and mix with described trialkyl aluminium compound.
The Al/Ti ratio is generally 20 to 800 greater than 1.
For the situation of the stereoregulated polymerization of alpha-olefin (for example propylene and 1-butylene), can use and prepare top disclosed catalyzer as the identical or different electronic donor compound capable (external donor) of the inner compound that uses to body.Is the situation of polycarboxylate, particularly phthalic ester in inside to body, and preferred external donor is selected from and contains at least that the Si-OR key has formula R
a 1R
b 2Si (OR
3)
cSilane compound, wherein a and b are 0 to 2 integer, c is 1 to 3 integer, (a+b+c) and be 4, R
1, R
2And R
3Be alkyl, cycloalkyl or aryl with 1-18 carbon atom.In the particularly preferred silicon compound, a is 1, and b is 1, and c is 2, R
1And R
2At least one of them is selected from branched-chain alkyl, cycloalkyl or the aryl with 3-10 carbon atom, R
3Be C
1-C
10Alkyl group, particularly methyl.The example of so preferred silicon compound is methylcyclohexyl dimethoxy silane, dimethoxydiphenylsilane, methyl-t-butyldimethoxysilane, dicyclopentyl dimethoxyl silane.In addition, in the also preferred silicon compound, a is 0, and c is 3, R
2Be branched-chain alkyl or cycloalkyl, R
3Be methyl.The example of so preferred silicon compound is cyclohexyl trimethoxy silane, tert-butyl trimethoxy silane and 1,1,2-trimethylammonium propyl group-Trimethoxy silane (thexyltrimethoxysilane).
Can also use to have 1 of aforementioned formula, the 3-diether is as external donor.Yet when using 1, the 3-diether is given under the situation of body as inside, can avoid using external donor, because the stereospecificity of catalyzer is enough high.
As noted, component of the present invention and the catalyzer that obtains thus are at formula CH
2Obtained application in (being total to) polymerization process of the alkene of=CHR, wherein R is hydrogen or the alkyl with 1-12 carbon atom.
Catalyzer of the present invention can be used for any olefine polymerizing process known in the art.For example, they can be applicable to use unreactive hydrocarbons solvent as the slurry polymerization of thinner or use the mass polymerization of liquid monomer (for example propylene) as reaction medium.In addition, they also can be used for the polymerization process that carries out in one or more fluidized-beds or mechanical stirring reactor gas phase operation.
Polymerization is carried out under preferred 40 to the 80 ℃ temperature usually at 20 to 120 ℃.When carrying out in being aggregated in gas phase, working pressure is generally 0.1 to 10MPa, and preferred 1 to 5MPa.In mass polymerization, working pressure is generally 1 to 6MPa, and preferred 1.5 to 4MPa.
Catalyzer of the present invention is very useful in the polyolefin product of preparation wide range.The specific examples of the olefin polymer that can prepare is: high density ethylene polymer (HDPE, density is greater than 0.940g/cc), contain Alathon and ethene and have the multipolymer of the alpha-olefin of 3-12 carbon atom; Linear low density of polyethylene (LLDPE, density is lower than 0.940g/cc) and extra-low density and extremely-low density (VLDPE and ULDPE, density is lower than 0.920g/cc, to 0.880g/cc), be made up of ethene and one or more multipolymers with alpha-olefin of 3-12 carbon atom, the molar content of units derived from ethylene is higher than 80%; The crystalline copolymer of isotatic polypropylene and propylene and ethene and/or other alpha-olefin, the unitary content of derived from propylene is higher than 85% weight; The multipolymer of propylene and 1-butylene is 1 to 40% weight derived from the unitary content of 1-butylene; Contain crystalline polypropylene matrix and comprise propylene and ethene with or the heterophasic copolymer of the amorphous phase of the multipolymer of other alpha-olefin.
The following examples are to illustrate and unrestricted the present invention itself for example.
Characterize
Determine the various character report below according to following method:
Adopt PERKIN ELMER DSC 7 instruments scanning speed with 5 ℃/minute in 5-125 ℃ of scope to carry out dsc measurement.The aluminium glue capsule of capacity that sample the be housed 40 μ ls of use in drying box is to avoid the aquation of sample.Analyze the content of determining pure and mild other LB by GC.
Embodiment
The general method of preparation catalyst component
At 0 ℃ with 800cm
3TiCl
4Be incorporated into 11 steel reactors with agitator; In room temperature and under stirring with the 16g adducts with introducing wherein for a certain amount of diisobutyl phthalate of body as inside, making the mol ratio to body/Mg is 10.In 90 minutes, integral body is heated to 100 ℃ and kept these conditions 120 minutes.Stop to stir, under the temperature of 100 ℃ of maintenances, liquid phase is separated with precipitated solid after 30 minutes.By (500rpm) adding 750cm under agitation condition
3TiCl
4And, keep described condition to carry out the further processing of solids in 60 minutes 120 ℃ of heated mixt 10 minutes.Interrupt then stirring, under the temperature of 120 ℃ of maintenances, liquid phase is separated with precipitated solid after 30 minutes.Use 500cm at 60 ℃ then
3Anhydrous hexane carry out 3 times the washing, at room temperature use 500cm
3Anhydrous hexane carry out 3 times the washing.Subsequently the ingredient of solid catalyst 40-45 ℃ of temperature under nitrogen environment that obtains carried out vacuum-drying.
The general method of aggregation test
Use has 4 liters of steel autoclave pressures of agitator, pressure warning unit, thermometer, Catalyt feeding system, monomer supply line and temperature control chuck.In reactor, pack into the ingredient of solid catalyst 0 of 0.01gr., the TEAL of 76g, the dicyclopentyl dimethoxyl silane of 0.076g, 3.21 propylene and 1.51 hydrogen.Under agitation with system at 10 minutes internal heating to 70 ℃ and kept under these conditions 120 minutes.At the polymeric terminal point, by removing any unreacted monomer collected polymer and vacuum-drying.
Embodiment 1
Have IKA RE 166 agitators in room temperature with under stirring, containing the MgCl that introduces 93.16g in the container type reactor of anhydrous EtOH of 136.63g and 0.93g butanols
2In case MgCl
2Adding finishes, and temperature is elevated to 125 ℃ and kept 3 hours.Then, introduce 1600cm
3The OB55 vaseline oil, keep 125 ℃ temperature, reach the stirring of 1500rpm and kept this value two minutes.After this moment, mixture is discharged in the container that contains hexane, keeps stirring and cooling, so that final temp is no more than 12 ℃.After 12 hours, with the MgCl that collects
2The solids of EtOH adducts are with hexane wash and in 40 ℃ of vacuum-dryings.The compositional analysis demonstration contains the EtOH of 54.2% weight and the butanols of 0.3% weight.
DSC distributes and shows 105.6 ℃ peak, and relevant fusion enthalpy is 90.1J/g.
According to the catalyst component of above-described general polymerization method test by general method preparation, what provide the results are shown in table 1.
Embodiment 2
Carry out the method (MgCl identical with embodiment 1
292.64g, ethanol 138.55g), difference is that the amount of butanols increases to 2.77g.With the MgCl that collects
2The solids of EtOH adducts are with hexane wash and in 40 ℃ of vacuum-dryings.The compositional analysis demonstration contains the EtOH of 51.1% weight and 0.7% butanols.
DSC distributes and shows 107.5 ℃ peak, and relevant fusion enthalpy is 89.7J/g.
According to the catalyst component of above-described general polymerization method test by general method preparation, what provide the results are shown in table 1.
Embodiment 3
Carry out the method (MgCl identical with embodiment 1
286.0g, ethanol 128.34g), difference is to use the ethylene glycol of 0.86g to replace butanols.With the MgCl that collects
2The solids of EtOH adducts are with hexane wash and in 40 ℃ of vacuum-dryings.The compositional analysis demonstration contains the EtOH of 57.2% weight and 0.4% ethylene glycol.
DSC distributes and shows 107.4 ℃ peak, and relevant fusion enthalpy is 90.1J/g.
According to the catalyst component of above-described general polymerization method test by general method preparation, what provide the results are shown in table 1.
Comparing embodiment 1
Repeat the method for embodiment 1, difference is not use butanols.Compositional analysis shows that adducts contains the EtOH of 55.1% weight.DSC distributes and shows 109 ℃ peak, and relevant fusion enthalpy is 102J/g.According to the catalyst component of above-described general polymerization method test by general method preparation, what provide the results are shown in table 1.
Table 1
| Embodiment | Active | I.I： | Inject bulk density |
| 1 | 65.1 | 97.4 | 0.41 |
| 2 | 65 | 98.3 | 0.41 |
| 3 | 69.6 | 97.9 | 0.42 |
| Comparing embodiment 1 | 54 | 98.0 | 0.376 |
Claims (12)
1. one kind comprises MgCl
2, ethanol and be different from the adducts of the Lewis base (LB) of water, the mol ratio that described each compound exists is by following formula MgCl
2(EtOH)
n(LB)
pDetermine that wherein n is 2 to 6, the formula p/ (n+p)≤0.1 below the value of p satisfies.
2. the adducts of claim 1, the formula p/ (n+p)≤0.0125 below wherein the value of p satisfies.
3. the adducts of claim 1, wherein LB is selected from ether, ester and formula RX
mCompound, wherein R is the alkyl with 1 to 20 carbon atom, X is-NH
2,-NHR or-the OH group, m is 1 or higher.
4. the adducts of claim 3, wherein compound R X
mBe selected from methyl alcohol, propyl alcohol, Virahol, propyl carbinol, sec-butyl alcohol, the trimethyl carbinol, amylalcohol, 2-methyl-1-pentene alcohol, 2-ethyl-1-hexanol, phenol, 4-methyl isophthalic acid-phenol, 2,6-dimethyl-1-phenol, hexalin, cyclopentanol, ethylene glycol, propylene glycol, 4-butyleneglycol, glycerol, N.F,USP MANNITOL, polyvinyl alcohol, acetonitrile, quadrol, 3-picoline, trolamine, triethylamine, diisopropylamine.
5. the adducts of claim 1, described adducts has the fusion enthalpy that is lower than 100J/g.
6. catalyst component that is used for olefinic polymerization, described catalyst component comprises the reaction product of each adducts in transistion metal compound and the aforementioned claim.
7. the catalyst component of claim 6, wherein transition metal is selected from formula Ti (OR)
nX
Y-nTitanium compound, wherein n is 0 to y; Y is the valency of titanium; X is a halogen, and R is alkyl or the COR group with 1-8 carbon atom.
8. the catalyst component of claim 7, wherein titanium compound is selected from TiCl
3, TiCl
4, Ti (OBu)
4, Ti (OBu) Cl
3, Ti (OBu)
2Cl
2, Ti (OBu)
3Cl.
9. the catalyst component of claim 10, wherein the electronic donor compound capable that is reflected at of transistion metal compound and adducts carries out under existing.
10. the catalyst component of claim 13, wherein electron donor(ED) is selected from ester, ether, amine and ketone.
11. be used for the catalyzer of olefinic polymerization, described catalyst pack contains right and requires each catalyst component and the reaction product of al-alkyl compound in 7 to 10.
12. be used for formula CH
2The polymerization process of the alkene of=CHR, wherein R is hydrogen or the alkyl with 1-12 carbon atom, described method is carried out in the presence of the catalyzer of claim 11.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP03104960.4 | 2003-12-23 | ||
| EP03104960 | 2003-12-23 |
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|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011044761A1 (en) * | 2009-10-16 | 2011-04-21 | 中国石油化工股份有限公司 | Carrier for olefin polymerization catalyst, preparation method and application thereof |
| CN102574947A (en) * | 2009-09-15 | 2012-07-11 | 巴塞尔聚烯烃意大利有限责任公司 | Magnesium dichloride-alcohol adducts and catalyst components obtained |
| CN103119072A (en) * | 2010-09-30 | 2013-05-22 | 巴塞尔聚烯烃意大利有限责任公司 | Magnesium dichloride-alcohol adducts and catalyst components obtained therefrom |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1098272B (en) * | 1978-08-22 | 1985-09-07 | Montedison Spa | COMPONENTS, CATALYSTS AND CATALYSTS FOR THE POLYMERIZATION OF ALPHA-OLEFINS |
| IT1230134B (en) * | 1989-04-28 | 1991-10-14 | Himont Inc | COMPONENTS AND CATALYSTS FOR THE POLYMERIZATION OF OLEFINE. |
| ES2213898T3 (en) * | 1997-03-29 | 2004-09-01 | Basell Poliolefine Italia S.P.A. | MAGNESIUM / ALCOHOL DICHLORIDE ADUCTS, PROCEDURE FOR THE PREPARATION AND CATALYST COMPONENTS OBTAINED FROM THESE. |
| JPH10298224A (en) * | 1997-04-24 | 1998-11-10 | Nippon Polyolefin Kk | Titanium complex compound, solid catalyst component for olefin polymerization prepared by using the same, olefin polymerization catalyst, and production of olefin polymer |
| CN1128822C (en) * | 1999-02-26 | 2003-11-26 | 中国石油化工集团公司 | Process for preparing catalyst carrier for olefin polymerization |
| EP1114070B1 (en) * | 1999-06-04 | 2003-12-10 | LG Chemical Ltd. | Process for preparing polyolefin polymerization catalysts |
| WO2003082930A2 (en) * | 2002-03-29 | 2003-10-09 | Basell Poliolefine Italia S.P.A. | Magnesium dichloride-ethanol adducts and catalyst components obtained therefrom |
| AU2003258647A1 (en) * | 2002-09-17 | 2004-04-08 | Basell Poliolefine Italia S.P.A | Magnesium dichloride-ethanol adducts and catalyst components obtained therefrom |
-
2004
- 2004-11-24 CN CNB2004800382994A patent/CN100519597C/en not_active Expired - Fee Related
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102574947A (en) * | 2009-09-15 | 2012-07-11 | 巴塞尔聚烯烃意大利有限责任公司 | Magnesium dichloride-alcohol adducts and catalyst components obtained |
| CN102574947B (en) * | 2009-09-15 | 2014-04-02 | 巴塞尔聚烯烃意大利有限责任公司 | Magnesium dichloride-alcohol adducts and catalyst components obtained |
| WO2011044761A1 (en) * | 2009-10-16 | 2011-04-21 | 中国石油化工股份有限公司 | Carrier for olefin polymerization catalyst, preparation method and application thereof |
| CN102124036A (en) * | 2009-10-16 | 2011-07-13 | 中国石油化工股份有限公司 | Carrier for olefin polymerization catalyst, preparation method and application thereof |
| US9321857B2 (en) | 2009-10-16 | 2016-04-26 | China Petroleum & Chemical Corporation | Carrier for olefin polymerization catalyst, preparation method and application thereof |
| CN103119072A (en) * | 2010-09-30 | 2013-05-22 | 巴塞尔聚烯烃意大利有限责任公司 | Magnesium dichloride-alcohol adducts and catalyst components obtained therefrom |
| CN103119072B (en) * | 2010-09-30 | 2016-03-30 | 巴塞尔聚烯烃意大利有限责任公司 | Magnesium dichloride-alcohol adducts and the catalyst component obtained by it |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2007517784A (en) | 2007-07-05 |
| CN100519597C (en) | 2009-07-29 |
| JP4733053B2 (en) | 2011-07-27 |
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