CN101050248B - Process for the preparation of a catalyst component and components therefrom obtained - Google Patents
Process for the preparation of a catalyst component and components therefrom obtained Download PDFInfo
- Publication number
- CN101050248B CN101050248B CN2007101050949A CN200710105094A CN101050248B CN 101050248 B CN101050248 B CN 101050248B CN 2007101050949 A CN2007101050949 A CN 2007101050949A CN 200710105094 A CN200710105094 A CN 200710105094A CN 101050248 B CN101050248 B CN 101050248B
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- China
- Prior art keywords
- compound
- catalyzer
- catalyst component
- solid catalyst
- ingredient
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 49
- 230000008569 process Effects 0.000 title abstract description 15
- 238000002360 preparation method Methods 0.000 title description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 60
- 239000011949 solid catalyst Substances 0.000 claims abstract description 17
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 16
- -1 aliphatic ethers Chemical class 0.000 claims abstract description 11
- 150000001408 amides Chemical class 0.000 claims abstract description 6
- 150000001412 amines Chemical class 0.000 claims abstract description 6
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims abstract description 5
- 150000002576 ketones Chemical class 0.000 claims abstract description 5
- 239000010936 titanium Substances 0.000 claims description 33
- 239000011777 magnesium Substances 0.000 claims description 22
- 239000004615 ingredient Substances 0.000 claims description 14
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical class CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000002367 halogens Chemical group 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 235000011147 magnesium chloride Nutrition 0.000 claims description 5
- 150000002825 nitriles Chemical class 0.000 claims description 5
- 150000001399 aluminium compounds Chemical class 0.000 claims description 4
- 150000002195 fatty ethers Chemical class 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 125000003158 alcohol group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 abstract description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 18
- 150000002148 esters Chemical class 0.000 abstract description 7
- 150000002826 nitrites Chemical class 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 51
- 239000007787 solid Substances 0.000 description 25
- 239000000203 mixture Substances 0.000 description 24
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 23
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 238000007334 copolymerization reaction Methods 0.000 description 18
- 239000007788 liquid Substances 0.000 description 15
- 230000008570 general process Effects 0.000 description 14
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 14
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 14
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 150000003609 titanium compounds Chemical class 0.000 description 10
- 229910052749 magnesium Inorganic materials 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 150000003377 silicon compounds Chemical class 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 150000007514 bases Chemical class 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 238000004062 sedimentation Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 229910004356 Ti Raw Inorganic materials 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000004292 cyclic ethers Chemical class 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 230000001603 reducing effect Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- VPCAAUUIFCAFRZ-UHFFFAOYSA-N butylalumane Chemical compound CCCC[AlH2] VPCAAUUIFCAFRZ-UHFFFAOYSA-N 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005243 fluidization Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 150000005826 halohydrocarbons Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 150000002899 organoaluminium compounds Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 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 2
- 238000009987 spinning Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- HXLWJGIPGJFBEZ-UHFFFAOYSA-N tert-butyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(C)(C)C HXLWJGIPGJFBEZ-UHFFFAOYSA-N 0.000 description 2
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 2
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-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
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910003902 SiCl 4 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000004708 Very-low-density polyethylene Substances 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- MEWFSXFFGFDHGV-UHFFFAOYSA-N cyclohexyl(trimethoxy)silane Chemical group CO[Si](OC)(OC)C1CCCCC1 MEWFSXFFGFDHGV-UHFFFAOYSA-N 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- CZWLNMOIEMTDJY-UHFFFAOYSA-N hexyl(trimethoxy)silane Chemical compound CCCCCC[Si](OC)(OC)OC CZWLNMOIEMTDJY-UHFFFAOYSA-N 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical group CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 229920001866 very low density polyethylene Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention provides a solid catalyst component for the polymeriztion of olefins comprising a Ti compound and an electron donor (ED) selected from alcohol, ketones, amines, amides, nitrites, alkoxysilanes, aliphatic ethers, and esters of aliphatic carboxylic acids supported on Mg dichloride in which the ED/Ti molar ratio ranges from 1.5 to 3.5 and the Mg/Ti molar ratio is higher than 5.5. The invention also provides a catalyst for the polymerization of olefins using the solid catalyst component and a process for the (co)polymerization of olefins CH2=CHR.
Description
The application is dividing an application of the PCT/EP2004/005186 application for a patent for invention that is entitled as " preparation method of catalyst component and thus obtained component " submitted on May 7th, 2004, and it number is 200480014844.6 that original application gets into national applications that the China national stage obtains.
Technical field
The present invention relates to a kind of alkene CH
2The preparation method of=CHR catalyst for polymerization component, wherein R is hydrogen or the alkyl that has 1-12 carbon atom.Particularly, the present invention relates to a kind of preparation method who loads on the magnesium dichloride and comprise the catalyst component of Ti compound and electron donor, also relate to more thus obtained catalyst components.These catalyst components when it changes catalyzer into, are specially adapted to produce the multipolymer of ethene and terminal olefin, because of it can make terminal olefin along the polymer chain uniform distribution and be uniform distribution in various polymer chains.
Background technology
Comprising the catalyzer that is carried on the titanium compound on the magnesium halogenide is that prior art is known.This type catalyzer for example is described in the United States Patent(USP) No. 4298718.Said catalyzer comprises the titanium tetrahalide that loads on the magnesium halogenide.Although this catalyzer has very high activity in the polymerization of the terminal olefin of similar propylene, their stereospecificity is not fine.Obtain the direction-sense significant improvement of stereo for electron compound through in ingredient of solid catalyst, adding some.Nowadays the secret formula for preparing these catalyzer comprises at first makes MgCl
2Or its precursor and to electron compound and titanium compound (TiCl normally
4) contact, use hot TiCl then
4Liquid carries out one or more processing to thus obtained solid.The specific examples of these methods especially is disclosed among the EP491566.These methods have obtained in propylene polymerization, to have the high usually activity and the catalyst component of stereospecificity, but also have some defectives simultaneously.For example these class methods are difficult to the final quantity that body is given in accurately adjustment, because use hot TiCl
4Its overwhelming majority has been taken away in the continuous processing of carrying out.In addition, the electron donor of some type is only because they are using TiCl
4Unstable and can not be used for this method when heat-treating.These defectives are closely bound up with some polyethylene catalysts that need give body ability works better in a large number.
A kind of can for example being described among the USP4521573 with in a large number being fixed on method for preparing catalyst on the catalyst component to body, this preparation method comprise use excessive greatly give electron compound, these give electron compound for MgCl
2With titanium compound played the effect of solvent.Can catalyst component be separated from solution through deposition or crystallization then.There are several shortcomings in this method.The first, some can not use for body, and they can not play the effect of solvent because consider its chemical structure.The second, can not prepare catalyst component with high porosity, be deposited on the porous inert carrier successively only if from said catalyst component, remove a large amount of give body or catalyzer.Yet under latter instance, need other step and more material, the result makes complex technical process and cost improve.More shortcoming is that the polymerization activity that these catalyzer show is quite low usually.
In the European patent application EP 452156, at the AlEt of high molar weight
3Exist down the catalyzer that makes according to certain technological process further with other handling to electron compound, said technological process comprises adding gives body afterwards with excessive hot TiCl
4Carry out one or more processing.But this method is for improving the content of electron donor in catalyst component and infeasible, because it will make the hyperergy compound (AlEt of catalyst component itself and very high amount greatly
3) contact, this will greatly change the performance of preformed catalyst component.
Therefore importantly provide to be suitable for preparing the method that contains to the catalyst component of body, can adjust content at an easy rate in the method, and wherein catalyst component can demonstrate other performances or keep those performances derived from its basic comprising composition to body.
Summary of the invention
Therefore one aspect of the present invention is a kind of MgCl of loading on
2On the preparation method of catalyst component; This catalyst component uses Mg compound, Ti compound and gives electron compound (ED) as basic compound; Saidly be selected from alcohol, glycol, ester, ketone, amine, acid amides, nitrile, organoalkoxysilane and fatty ether to electron compound; Said method comprises two or more reactions step; Said reaction comprise near few a kind of said basic compound individually or the form of mixtures that constitutes major constituent with basic compound wherein as the fresh reactant thing, and said method is characterised in that the basic compound that in the final step of said one or more reactions step, is used as the fresh reactant thing is the ED compound.
Another aspect of the invention is can be by the catalyst component of aforesaid method acquisition.
Embodiment
In the present invention, term " fresh reactant thing " is intended to represent an amount of compound basically that contact with reaction mixture for the first time.
Term " wherein basic compound constitutes the mixture of major constituent " expression must be a major constituent according to molar weight meter basic compound for other possible compounds (not comprising the inert solvent or the thinner that are used for handling said mixture).
Can using perhaps for electron compound (ED) separately uses with the form of the thing that is mixed with each other.
Preferred ester is C
1-C
20The C of the alkyl ester of aliphatic carboxylic acid, particularly aliphatic monocarboxylic acid
1-C
8Alkyl ester, for example ETHYLE ACETATE, methyl-formiate, ethyl formate, methyl acetate, propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate.
Preferred organoalkoxysilane is formula R
a 5R
b 6Si (OR
7)
cShown those, wherein a and b are 0 to 2 integers, c is 1 to 4 integer, and (a+b+c) sum is 4; R
5, R
6And R
7Be to have 1-18 carbon atom and optional heteroatomic alkyl, naphthenic base or the aryl of comprising.Particularly preferably be such silicon compound, wherein a is 0 or 1, and c is 2 or 3, R
6Be optional comprise heteroatomic alkyl or cycloalkyl, R
7It is methyl.The instance of the preferred silicon compound of this type is methyltrimethoxy silane, dimethyldimethoxysil,ne, trimethylammonium methoxy silane and tert-butyl trimethoxy silane.
Preferred alcohol is formula R
3Shown in the OH those, wherein R
3Group is C
1-C
20Alkyl.Preferably, r
3Be C
1-C
10Alkyl.Specific examples is methyl alcohol, ethanol, Virahol and butanols.
Preferred amine is formula NR
4 3Shown those, wherein R
4Group is hydrogen or C independently
1-C
20Alkyl, condition are that they are not hydrogen simultaneously.Preferably, R
4Be C
1-C
10Alkyl.Specific examples is diethylamine (dietilamine), diisopropylamine and triethylamine.
Preferred acid amides is formula R
5CONR
6 2Shown those, wherein R
3And R
6Be hydrogen or C independently
1-C
20Alkyl.Specific examples is methane amide and ethanamide.
Preferred nitrile is formula R
3Shown in the CN those, wherein R
3Has aforesaid identical definition.Specific examples is an acetonitrile.
Preferred glycol is that the total number of carbon atoms is lower than those glycol of 50.Particularly preferably be in the middle of them the total number of carbon atoms be lower than 25 1,2 or 1, the 3-glycol.Specific examples is a terepthaloyl moietie, 1,2-Ucar 35 and 1, ammediol.
Preferably the ED compound is selected from acid amides, ester and organoalkoxysilane.
Suitable titanium compound is tetrahalide or formula TiX
n(OR
1)
4-nShown compound, 0≤n≤3 wherein, X is a halogen, is preferably chlorine, and R
1Be C
1-C
10Alkyl.Titanium tetrachloride is preferred compound.
In the catalyst component by the inventive method acquisition, MgCl
2Be carrier is carrier, even can use other carriers of minute quantity.MgCl
2Can use like this, perhaps can obtain from the Mg compound as precursor, this precursor can change MgCl into through the reaction with halogenated compound
2Particularly preferably be the MgCl that uses activity form
2, it is widely known by the people as the carrier of Ziegler-Natta catalyst according to patent documentation record.Patent USP4298718 and USP4495338 have described first and in the ziegler-natta catalyzed system, have used these compounds.Can know by these patents; The activity form magnesium dihalide that in catalyst component for olefin, is used as carrier or altogether-carrier is characterised in that the X-beta ray spectrum, and wherein nonactive halid ASTM is with reference to the strongest diffracted ray that occurs in spectrum card strength reduction but also broaden not only.At the strength reduction of strong line described in the X-beta ray spectrum of preferred activity form magnesium dihalide, and replaced by halogen, its maximum strength is shifted to the less angle for the strongest line.
The inventive method implements very simple according to its initial version.In fact; This method comprises at first makes titanium compound contact with Mg compound (preferred magnesium dihalide); Randomly contact in the presence of inert media comprises the intermediate product that is carried on the titanium compound on the magnesium dihalide thereby prepare, and can also it be separated if desired.Subsequently, the ED compound is contacted under certain condition with this intermediate product, this condition is that the ED compound perhaps joins in the reaction mixture with the form of mixtures with other compounds separately, is major constituent according to molar weight meter ED compound wherein.Can the product that ED handled be washed so that reclaim final product with appropriate solvent then.If necessary, the processing of carrying out with desirable ED compound can repeat one or many.If preformed MgCl
2As initial compounds, so preferably it is an activity form.Patent USP4298718 and USP4495338 have described the MgCl that how to produce activity form
2Titanium compound is preferably titanium tetrachloride.
Made improvement several times to this basic skills, improved each time purpose all is to hope to give catalyzer or this method itself to bring some characteristic.Therefore, as stated, can be with the magnesium dihalide precursor as initial basic Mg compound.This can be for example from formula MgR '
2Select in the shown Mg compound, wherein R ' group can be optional substituted C1-C20 alkyl, OR group, OCOR group, halogen independently, and wherein R is optional substituted C1-C20 alkyl, and condition is that R ' group is not halogen simultaneously.Same suitable as precursor be magnesium dihalide with the Lewis base that suits between Louis (Lewis) adducts.Special and preferred one type is by MgX
2(R " OH)
mAdducts constitutes, wherein R " group is C
1-C
20Alkyl, preferred C
1-C
10Alkyl, X are halogens and are preferably chlorine that m is 0.1 to 6, is preferably 0.5 to 3 and more preferably 0.5 to 2.Usually can through make pure and mild magnesium dichloride with the not miscible unreactive hydrocarbons of adducts in the presence of mix, under agitation condition and under the melt temperature (100-130 ℃) of adducts, operate and make this type adducts.Then, make the emulsion rapid quench, cause adducts to solidify the formation spheroidal particle thus.The exemplary process for preparing these spherical adduct for example is recorded among USP4469648, USP4399054 and the WO98/44009.Other method that can be used for spheroidization is the spray cooling described in the USP5100849 and 4829034 for example.
Interested especially is that wherein m is 0.15 to 1.7 MgCl
2(EtOH)
mAdducts, such adducts is according to being prepared as follows: make the higher adducts of pure content in nitrogen gas stream, be decreased to above-mentioned value through the dealcoholation treatment process of being heated up to pure content under in 50 to 150 ℃ of temperature.This type process description is in EP395083.
Can also carry out dealcoholation treatment through making adducts with can contacting according to chemical process with the compound that alcohol groups reacts.
Usually these characteristics through the adducts of dealcoholation treatment are that also porosity (measuring by mercury process) is 0.15-2.5cm
3/ g, preferred 0.25-1.5cm
3/ g, this is owing to the hole of radius up to 0.1 micron.
MgX
2(R " OH)
mAdducts generally changes corresponding halogenide into through the reaction with the dealcoholation compound.Dealcoholysis reagent can be any chemical reagent that has the functionality that can react with the OH base.One group of concrete dealcoholysis reagent is alkylaluminium cpd.Suitable alkylaluminium cpd is a trialkyl aluminium compound, for example triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum, tri-n-octylaluminium and three (2,4,4-trimethylammonium-amyl group) aluminium.Can also use trialkyl aluminium compound and aluminum alkyl halide, alkyl aluminum hydride or alkylaluminium sesquichloride (such as AlEt
2Cl or Al
2Et
3Cl
3) mixture that forms.
Be known that alkylaluminium cpd has reducing activity with regard to the Ti compound.Therefore, if should activity undesirable, can add for example O of passivator before in implementation step (b)
2, avoid the reduction of titanium compound thus.
Another group available dealcoholysis reagent is halogen-containing silicon compound.The specific examples of these silicon compounds comprises formula SiX
4-nY
nShown silicon halogenide, wherein X and Y represent halogen atom, for example Cl and Br, and n is 0 to 3 number.Especially preferably use SiCl
4
In a specific embodiments of the present invention, preferably when carrying out dealcoholization, also comprise the reactions step of using titanium compound.Therefore, these adductss can with above-mentioned TiX
n(OR
1)
4-nCompound (or its possible mixture) reacts, and it is preferably titanium tetrachloride.Make adducts be suspended in TiCl
4In (normally cold), kept 0.5-2 hour, carry out reaction thus with the Ti compound with mixture heating up to 80-130 ℃ temperature and under this temperature.Processing with titanium compound carries out can be implemented one or many.Preferably it is repeated twice.Can also in the presence of as stated to electron compound, carry out.In the final stage of this method, be recovered to solid by traditional method (spinning is filtered in for example sedimentation and remove liquid) separate out suspended liquid, and can be with this solid of solvent wash.Although wash with unreactive hydrocarbons liquid usually, also can use more polar solvent (for example having high dielectric constant), such as halohydrocarbon.
The solid-state midbody of gained can also carry out aftertreatment with the special compound that is suitable for giving its specified property.For instance, it can with reducing compound for example alkylaluminium cpd handle so that reduce the oxidation state of institute's titanium-containing compound in the solid.
Another example of the processing that can carry out midbody is a prepolymerization step.Can with any alkene CH
2=CHR carries out prepolymerization, and wherein R is H or C
1-C
10Alkyl.Particularly; Especially preferably make ethene or propylene or its mixture and one or more terminal olefin generation prepolymerizations; Said mixture comprises the terminal olefin up to 20% mole; The amount of formed polymkeric substance is that about 0.1 gram extremely restrains/restrain solid-state midbody up to about 1000, is preferably about 0.5 to about 500 and restrains/restrain solid-state midbody.Prepolymerization step can carry out in liquid phase or gas phase under 0 to 80 ℃ temperature, preferred 5 to 70 ℃ temperature.Especially preferably make midbody and ethene or propylene generation prepolymerization to prepare the polymkeric substance that its amount is 0.5 to 20 gram/gram midbody.Use suitable promotor (coatalyst) for example organo-aluminium compound carry out prepolymerization, it also can be used in combination with one or more external donors of following detailed description.
As stated, intermediate product can contacted being fixed to body under the condition on the solid of significant quantity with the ED compound.Because this method is widely applicable, thereby the used amount of body of giving can have nothing in common with each other.For instance, the mol ratio of Ti content can be 0.5 to 20 in it and the intermediate product, is preferably 1 to 10.Though do not have strict demand, for example contact in the liquid hydrocarbon at liquid medium usually.The temperature that comes in contact can change with the difference of reagent.In general temperature is-10 ℃ to 150 ℃, is preferably 0 ℃ to 120 ℃.Be understood that and avoid temperature to cause any concrete reagent to take place to decompose or degraded, even this temperature falls into suitable usually scope.Equally, the treatment time also can be along with such as the variation of other conditions such as reagent person's character, temperature, concentration and change.As this contacting step of generalized case sustainable 10 minutes to 10 hours more often is 0.5 to 5 hour.If desired, in order further to improve the final content of giving body, this step can repeat one or many.When this step finishes, be recovered to solid by traditional method (for example sedimentation with remove liquid, filtration, spinning) separate out suspended liquid, and can be with this solid of solvent wash.Although wash with unreactive hydrocarbons liquid usually, also can use more polar solvent (for example having high dielectric constant), such as halohydrocarbon or oxygenated hydrocarbon.
Equally in this case, the gained solid also can carry out aftertreatment with the special compound that is suitable for giving its specified property.For instance, it can with reducing compound for example alkylaluminium cpd handle so that reduce the oxidation state of institute's titanium-containing compound in the solid.
Explain that various different amounts may be used to the inventive method to body with regard to titanium content.The catalyzer of all acquisitions demonstrates good performance usually, especially at the equal polymerization of ethene and itself and C
3-C
10Show superperformance in the copolymerization of terminal olefin, to make the ethylene that contains up to 20% mole of terminal olefin.Interested especially is the catalyst component that comprises Ti compound and electron donor (ED) that is carried on the magnesium dichloride; Electron donor is selected from alcohol, ketone, amine, acid amides, nitrile, organoalkoxysilane, fatty ether and aliphatic carboxylic acid esters; Wherein the ED/Ti mol ratio is 1.5 to 3.5, and the Mg/Ti mol ratio is higher than 5.5.Preferably, the ED/Ti mol ratio is preferably 2 to 3.4, and more preferably 2.2 to 3.3.Preferably, the Mg/Ti mol ratio is 7 to 110, more preferably 8 to 80, particularly 8 to 50.
Be that aforesaid those are given body preferably to body.In addition, equally preferably fatty ether, particularly C2-C20 fatty ether.Especially preferred is the cyclic ethers that preferably has 3-5 carbon atom, for example THF (THF) Huo diox.Use the ester of similar ETHYLE ACETATE and so on can obtain fabulous result as the ED compound.Equally preferably has above-mentioned composition (sadcomposition) and through pre-polymerized catalyst.
According to currently known methods through making the reaction of itself and organo-aluminium compound and changing ingredient of solid catalyst of the present invention into catalyst for olefines polymerizing.
Particularly, target of the present invention is alkene CH
2=CHR catalyst for polymerization, wherein R is hydrogen or the alkyl that has 1-12 carbon atom, this catalyst for olefines polymerizing comprises the reaction product of following material:
(a) aforesaid ingredient of solid catalyst,
(b) alkylaluminium cpd with, randomly
(c) the outside electron compound of giving.
Alkylaluminium cpd can be preferably selected from trialkyl aluminium compound, for example trimethylaluminium (TMA), triethyl aluminum (TEAL), triisobutyl aluminium (TIBA), three n-butylaluminum, tri-n-hexyl aluminum, tri-n-octylaluminium.Can use aluminum alkyl halide equally, particularly aluminum alkyls muriate, for example diethylaluminum chloride (DEAC), di-isobutyl aluminum chloride, Al-sesquichloride and chlorodimethylalumiu (DMAC).Can also use and the preferred mixture that uses trialkylaluminium and aluminum alkyl halide under some situation.Wherein special preferred mixture TEAL/DEAC and TIBA/DEAC.
The outside electron compound of giving can be equal to or be different from ED used in the ingredient of solid catalyst.Preferably, it is selected from ether, ester, amine, ketone, nitrile, silane and above-mentioned mixture.Particularly it can advantageously be selected from C
2-C
20Fatty ether especially preferably has the cyclic ethers of 3-5 carbon atom, and cyclic ethers is THF 、 diox for example.
In addition, also can advantageously be selected from formula R for electron compound
a 5R
b 6Si (OR
7)
cShown silicon compound, wherein a and b are 0 to 2 integers, c is 1 to 3 integer, and (a+b+c) sum is 4; R
5, R
6And R
7Be optional alkyl, naphthenic base or the aryl that comprises the heteroatomic 1-18 of a having carbon atom.Particularly preferably be such silicon compound, wherein a is 0, and c is 3, R
6Be optional comprise heteroatomic branched-chain alkyl or naphthenic base, R
7It is methyl.The instance of the preferred silicon compound of this type is cyclohexyl trimethoxy silane, tert-butyl trimethoxy silane and uncle's hexyl Trimethoxy silane.
Said components (a)-(c) can be put into respectively in the reactor drum, and they can bring into play its activity under polymerizing condition.But, particularly advantageous embodiment is that said components contacts for some time in advance, randomly contact in the presence of small amounts of olefins, and this time is 0.1 to 120 minute, is preferably 1 to 60 minute.Contact in advance can be carried out in liquid diluent in 0 to 90 ℃, preferred 20 to 70 ℃ TR.
The catalyst system that so forms can directly be used in main polymerization technique process, perhaps changes it, and it also can carry out prepolymerization in advance, if especially do not make solid-state midbody carry out prepolymerized situation.Prepolymerization step is normally preferred when main polymerization technique process is carried out in gas phase.Can with any alkene CH
2=CHR carries out prepolymerization, and wherein R is H or C
1-C
10Alkyl.Particularly; Especially preferably make ethene or propylene or its mixture and one or more terminal olefin generation prepolymerizations; Said mixture comprises the terminal olefin up to 20% mole, and the amount of formed polymkeric substance is that about 0.1 gram/gram solid ingredient is extremely up to about 1000 gram/gram ingredients of solid catalyst.Prepolymerization step can carry out in liquid phase or gas phase under 0 to 80 ℃ temperature, preferred 5 to 70 ℃ temperature.Prepolymerization step can be used as the part series connection of continuous polymerization technique to carry out, and perhaps in periodical operation technology, carries out separately.Especially preferably make catalyzer of the present invention and ethene or propylene generation batch pre-polymerization, to prepare a certain amount of polymkeric substance, its amount is 0.5 to 20 gram/gram catalyst component.Pre-polymerized catalyst components can be for further processing with titanium compound before being used for main polymerization procedure equally.Especially preferably use TiCl this moment
4Pre-polymerized catalyst components is suspended in the liquid Ti compound (mixture that randomly forms with liquid diluent), mixture heating up to 60-120 ℃ and under this temperature, kept 0.5-2 hour, is carried out the reaction with the Ti compound thus.
The case description of gas phase process wherein can use catalyzer of the present invention in WO92/21706, USP5733987 and WO93/03078.These process methodes comprise preparatory contacting step, the prepolymerization step of catalyst component and the gas phase polymerisation step of in one or more reactor drums, in a series of fluidizations or churned mechanically bed, carrying out.In specific embodiments, gas phase process can suitably carry out according to the following step:
(i) make the catalyst component (a) and (b) under 0 to 90 ℃ temperature, contact for some time of 0.1 to 120 minute with optional (c); Randomly
(ii) with one or more formulas CH
2The alkene of=CHR carries out prepolymerization, and wherein R is H or C
1-C
10Alkyl, be about 0.1 to up to about 1000 gram/gram ingredients of solid catalyst (a) up to the amount of formed polymkeric substance; With
(iii) in one or more fluidizations or churned mechanically bed bioreactor, in the presence of from (i) or product (ii), make ethene or itself and terminal olefin CH with the gas phase mode
2The mixture generation polymerization of=CHR, wherein R is the alkyl that has 1-10 carbon atom.
As previously mentioned, catalyzer of the present invention is particularly useful for making linear low density polyethylene (LLDPE, its density is lower than 0.940g/cm
3) and extra-low density and ultra-low density polyethylene (VLDPE and ULDPE, its density is lower than 0.920g/cm
3, to 0.880g/cm
3), it is made up of ethene and one or more multipolymers that contains the terminal olefin of 3 to 12 carbon atoms, and the molar content of ethylene-derived units is higher than 80%.But, they can be used to prepare multiple polyolefin products equally, for example comprise that (HDPE, its density is higher than 0.940g/cm to high density ethylene polymer
3) interior, it comprises Alathon and ethene and contains the multipolymer of the terminal olefin formation of 3 to 12 carbon atoms; The elastocopolymer of ethene and propylene, and the elasticity terpolymer of ethene and propylene and a small amount of diene formation, the weight content of therein ethylene derived units is about 30-70%; Isotactic polyprophlene, and the propylene derived unit content of propylene and ethene and/or the formation of other terminal olefins is higher than the crystallinity multipolymer of 85wt%; Through the shock resistance propene polymer that the mixture order of occurrence polymerization that makes propylene and propylene and ethene obtains, it contains the ethene up to 30wt%; The multipolymer of propylene and 1-butylene, wherein the quantity of 1-butylene derived units between 10 to 40wt%.
Adopt non-limiting way to provide the following example to further describe the present invention.
Characteristic
Measure performance according to following method:
Melting index: under 190 ℃, measure according to ASTM D-1238 condition " E " (load is 2.16Kg) and " F " (load is 21.6Kg);
Xylene soluble fraction: the solvability under measuring 25 ℃ according to following method in YLENE: will about 2.5g polymkeric substance and 250ml o-Xylol input is furnished with water cooler and reflux exchanger and shroud as for nitrogen under round-bottomed flask in.With gained mixture heating up to 135 ℃ and keep stirring 60 minutes.Under the continuously stirring effect, make final solution be cooled to 25 ℃, then with its filtration.Thereby in 140 ℃ nitrogen gas stream, make the filtrating evaporation reach constant weight afterwards.The content of said xylene soluble cut is recently expressed with the percentage that accounts for original 2.5 grams.
Co-monomer content:
By the ft-ir measurement 1-butylene.
Measure than 1-butylene high-grade terminal olefin more through infrared analysis.
Effective density: ASTM-D 1505
Heat is analyzed: adopt differential scanning calorimeter DSC Perkin-Elmer to carry out calorimetric measurement.This instrument is calibrated with indium and tin standard substance.The sample (5-10mg) that will come from institute's weighing of melting index measurement is sealed in the aluminium pot; 5 ℃ of following constant temperature 3 minutes; Be heated to 200 ℃ with 20 ℃/minute speed, and under this temperature, keep the sufficiently long time (5 minutes) so that all crystallisates melt fully.Then, be cooled to-20 ℃ with 20 ℃/minute speed after, peak temperature is assumed to Tc (Tc).After 0 ℃ of held 5 minutes, sample is heated to 200 ℃ with 20 ℃/minute speed.In second time heating procedure, peak temperature is assumed to melt temperature (Tm), and should the zone as total melting enthalpy (Δ H).
The mensuration of Mg, Ti: (ICP) measures by the inductively coupled plasma emmission spectrum.
The mensuration of Cl: measure through potentiometric titration.
The mensuration of ED: by means of gas chromatographic analysis.
Embodiment
Prepare spherical MgCl
2
(EtOH) general process of adducts
Embodiment 2 described method preparations according to USP4399054 contain the magnesium chloride of 3 mol of alcohol of having an appointment and the adducts of alcohol, but under 2000RPM, operate rather than 10000RPM.
In nitrogen gas stream, in 50-150 ℃ TR, prepare and comprise the adducts of the alcohol of decrement (47wt%, 35wt%, 25wt% and 15wt%) gradually through thermal treatment.
The general process of the midbody of preparation ingredient of solid catalyst:
250mL TiCl packs in nitrogen dashes the 500mL four neck round-bottomed flasks of sweeping under 0 ℃
4Then, under same temperature, under stirring action, add the as above prepared spherical MgCl of 25wt% alcoholic acid 17.5g that comprises
2/ EtOH adducts.Within an hour temperature is being increased to 130 ℃ and kept 60 minutes., no longer stir, make solid product sedimentation and siphon remove supernatant liquid thereafter.
(5 * 100mL) washings six times are also washed once under 25 ℃ with anhydrous hexane down at 60 ℃ with this solid.At last, make solid dry and analyze (Ti=4.9wt% under vacuum; Mg=19.4wt%).
The general process (midbody contacts with ED) for preparing final ingredient of solid catalyst
Dash and to drop into 200mL anhydrous hexane and the as above prepared solid-state intermediate component of 10g in the 500mL four neck round-bottomed flasks of sweeping in that mechanical stirrer and nitrogen are housed under the room temperature.Under same temperature, under agitation drip a certain amount of desirable ED so that mol ratio ED/Ti is 4.Temperature is increased to 50 ℃, and mixture was stirred 3 hours.Then, no longer stir, make solid product sedimentation and siphon remove supernatant liquid.
Down (3 * 100mL) wash this solid 3 times, with its recovery, vacuum-drying and analyze with anhydrous hexane at 25 ℃.
Ethylene/alpha-olefin copolymerization: general process
4.5 liters of stainless steel autoclaves are purified 60 minutes with the mobile pure nitrogen gas down at 70 ℃, and this stainless steel autoclave is equipped with the feeding line and the catalyst injection of magnetic stirrer, temperature and pressure telltale and ethene, propane, 1-butylene, hydrogen and uses steel cylinder.Then this autoclave is washed with propane, be heated to 75 ℃, the propane of the 800g that packs at last, 1-butylene (amount shown in table 2 and 4), ethene (7.0 crust, dividing potential drop) and hydrogen (shown in table 2 and 4).
According to following order at a 100cm
3Three neck glass flask in add: 50cm
3Anhydrous hexane, 9.6cm
3(vol) 10wt%TEA/ hexane solution (or promotor shown in the table 2 of equivalent and 4), the solid catalyst (amount shown in the table 2 and 4) of electron compound (table 2 and 4) and embodiment is given in optional outside.They were mixed and at room temperature stir 5 minutes, adopt superpressure nitrogen that it is put in the reaction kettle through steel cylinder then.
Under continuously stirring, total pressure was kept constant 60 minutes down at 75 ℃ through ethylene feed.Make the reaction kettle decompression at last and make temperature drop to 30 ℃.The polymkeric substance that reclaims is dry and weigh in 70 ℃ nitrogen gas stream.
Embodiment 1-12
Adopt the different electron compounds (ED) of giving to prepare a series of catalyst components.The spherical MgCl that comprises 25wt%EtOH that use makes by above-mentioned steps
2(EtOH) adducts prepares catalyzer, at first uses TiCl according to above-mentioned steps
4Processing to be to make midbody, then according to general process make its with charge ratio shown in the table 1 in the specific ED compound that adopts contact.
The catalyzer that will so make under specified conditions shown in the table 2 according to above-mentioned general process then be used for carry out the copolymerization of ethene, table 2 also comprises the data of relevant polymer features.
Embodiment 13-14
According to adopting AcOEt to prepare catalyzer as electron donor with the said identical step of embodiment 1-12, difference is that molar feed ratio ED/Ti is respectively 8,4 and 1.The catalyzer that will so make under specified conditions shown in the table 4 according to above-mentioned general process then be used for carry out the copolymerization of ethene, table 4 also comprises the data of relevant polymer features.
Embodiment 15
The solid-state midbody that will make according to general process is expelled in the autoclave and under nitrogen atmosphere and 30 ℃, in anhydrous hexane (solid concentration is 40g/L), keeps stirring.Adopt a certain amount of by triethyl aluminum (TEA) thus the 10wt% solution that in hexane, forms comes treating suspension to make ratio TEA/ solid=0.5wt/wt.Slowly add the propylene that its amount equals 0.7 times of solid original bulk with the speed that is suitable for making temperature be held constant at 30 ℃ then.Stop polymerization after 30 minutes.With this solid of anhydrous hexane 3 times, it is suspended in the hexane once more, and handles according to general process as the ED compound with AcOEt under 25 ℃, difference is that the AcOEt/Ti raw materials components mole ratio is 8.The representative record of catalyst component is in table 3, and the outcome record of copolymerization is in table 4.
Embodiment 16
According to adopting AcOEt to prepare catalyzer as ED with the said identical step of embodiment 1-12, difference is that the temperature that comes in contact is 0 ℃.The representative record of catalyst component is in table 3, and the outcome record of copolymerization is in table 4.
Embodiment 17
According to adopting AcOEt to prepare catalyzer as ED with the said identical step of embodiment 1-12, difference is in heptane, to contact under 100 ℃ rather than in hexane, carry out.The representative record of catalyst component in table 3 and the outcome record of copolymerization in table 4.
Embodiment 18
According to adopting AcOEt to prepare catalyzer as ED with the said identical step of embodiment 1-12, difference is in toluene, to contact rather than in hexane, carry out.The representative record of catalyst component in table 3 and the outcome record of copolymerization in table 4.
Embodiment 19
According to adopting AcOEt to prepare catalyzer as ED with the said identical step of embodiment 1-12, difference is to have carried out contacting step twice.For the first time being under the AcOEt/Ti raw materials components mole ratio is 1 condition, to carry out 30 minutes, is for the second time to use after the hexane wash solid under the AcOEt/Ti raw materials components mole ratio is 4 condition to continue contact 2.5 hours.The representative record of catalyst component in table 3 and the outcome record of copolymerization in table 4.
Embodiment 20
According to adopting AcOEt to prepare catalyzer as ED with the said identical step of embodiment 1-12, difference is that the ED contacting step has been carried out 1 hour.The representative record of catalyst component in table 3 and the outcome record of copolymerization in table 4.
Embodiment 21
According to adopting AcOEt to prepare catalyzer as ED with the said identical step of embodiment 1-12, difference is that the ED contacting step has been carried out 2 hours.The representative record of catalyst component in table 3 and the outcome record of copolymerization in table 4.
Embodiment 22
According to adopting AcOEt to prepare catalyzer as ED with the said identical step of embodiment 1-12, difference is that the ED contacting step has been carried out 5 hours.The representative record of catalyst component in table 3 and the outcome record of copolymerization in table 4.
Embodiment 23
According to general process, 90 ℃ with nitrogen atmosphere under the solid-state midbody that will make in anhydrous heptane, stir (solids concn is 40g/L) with monochlor(in)ate diethyl aluminum (DEAC), the Al/Ti mol ratio of used DEAC is 10.No longer stir after 1 hour, make solid product sedimentation and siphon remove supernatant liquid.Under foregoing the same terms, carry out the DEAC processing second time then.With anhydrous heptane once, and with anhydrous hexane washed twice at room temperature 90 ℃ of following wash solids.With solid vacuum-drying and analyze (Ti
Always=4.6wt%; Ti
3+=2.9wt%; Mg=20wt%).Carry out the contacting step with ED like the said employing of general process AcOEt as ED then, difference is to be 2 hours in the reaction times.The representative record of catalyst component in table 3 and the outcome record of copolymerization in table 4.
Embodiment 24
Make like the embodiment 15 said prepolymerization midbodys that make to be suspended in the hexane, stir down and under 50 ℃, use TiCl
4Handle 1 hour (prepolymer/TiCl
4=24wt/wt).Wash this solid 3 times with anhydrous hexane down at 25 ℃, and then be suspended in the hexane.Handle with AcOEt as general process is said subsequently, difference is that the ED/Ti raw materials components mole ratio is 8.The representative record of catalyst component in table 3 and the outcome record of copolymerization in table 4.
Embodiment 25
According to adopting AcOEt to prepare catalyzer as ED with the said identical step of embodiment 1-12, TiCl when difference is the solid-state midbody of preparation
4Treating processes is being carried out under 100 ℃ rather than under 130 ℃, is being carried out, and interts the TiCl second time that under 100 ℃, carries out before the washing
4Handle (30 minutes).(Ti?1.9wt％；Mg?19.4wt％)。The representative record of catalyst component in table 3 and the outcome record of copolymerization in table 4.
Embodiment 26
According to preparing catalyzer with the said identical step of embodiment 1-12, difference is that ED is made up of AcOEt/THF mixture (1/1mol/mol) in the ED contacting step.The total mol ratio of ED/Ti equals 4.The representative record of catalyst component in table 3 and the outcome record of copolymerization in table 4.
Embodiment 27
According to the described step preparation of the embodiment 1 (a) of USP4220554 MgCl
2Precursor.Use TiCl then
4The solid of handling so acquisition is operated according to general process so that make solid-state midbody, and difference is TiCl
4Treating processes 120 ℃ down rather than under 130 ℃, carry out, and before washing, intert the TiCl that under 120 ℃, carries out for twice again
4Handle (30 minutes).(2 * 100mL) are washing this solid 2 times and under 25 ℃, are washing 2 times under 60 ℃ with anhydrous hexane.At last, with solid vacuum-drying and analyze (Ti=5.8wt%; Mg=18.8wt%).Carry out contacting step according to general process with AcOEt.The representative record of catalyst component in table 3 and the outcome record of copolymerization in table 4.
Embodiment 28-30
According to adopting AcOEt to prepare catalyst component as electron donor with the said identical step of embodiment 1-13, difference is initial spherical MgCl
2(EtOH) the pure content of adducts is respectively 47.3%, 35% and 14.3%.The representative record of catalyst component in table 3 and the outcome record of copolymerization in table 4.
Table 1
Table 2
Table 3
Table 4
THF is as external donor (except the embodiment 33); Al/THF=5
Claims (12)
1. solid catalyst component for olefine polymerization; It comprises Ti compound and the electron donor ED that is carried on the magnesium dichloride; Electron donor is selected from alcohol, ketone, amine, acid amides, nitrile, organoalkoxysilane, fatty ether and aliphatic carboxylic acid esters; Wherein the ED/Ti mol ratio is 1.5 to 3.5, and the Mg/Ti mol ratio is for being higher than 5.5 to 80.
2. the ingredient of solid catalyst of claim 1, wherein the ED/Ti mol ratio is 2 to 3.4, the Mg/Ti mol ratio is 7 to 50.
3. claim 1 or 2 ingredient of solid catalyst, wherein the ED compound is selected from annular aliphatic ether and aliphatic carboxylic acid esters.
4. the ingredient of solid catalyst of claim 3, wherein the ED compound is ETHYLE ACETATE or THF.
5. the ingredient of solid catalyst of claim 1, wherein titanium atom is derived from titanium tetrahalide or formula TiX
n(OR
1)
4-nShown compound, 0≤n≤3 wherein, X is a halogen, R
1Be C
1-C
10Alkyl.
6. catalyst for olefines polymerizing, it comprises through making following material come in contact the product that obtains:
(a) each ingredient of solid catalyst among the claim 1-5,
(b) one or more alkylaluminium cpds with, randomly
(c) the outside electron compound of giving.
7. the catalyzer of claim 6, wherein alkylaluminium cpd is a trialkylaluminium.
8. the catalyzer of claim 6, wherein alkylaluminium cpd is an aluminum alkyl halide.
9. the catalyzer of claim 6, wherein alkylaluminium cpd is through trialkyl aluminium compound is mixed the product that obtains with aluminum alkyl halide.
10. the catalyzer of claim 6, wherein outside is C to electron compound
2-C
20Fatty ether.
11. the catalyzer of claim 10, wherein ether is THF.
12. an alkene CH2=CHR (being total to) polymeric method, wherein R is hydrogen or the alkyl that has 1-12 carbon atom, this method according to claim 6-11 each catalyzer in the presence of implement.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP03076697.6 | 2003-05-29 | ||
| EP03076697 | 2003-05-29 | ||
| US48296603P | 2003-06-27 | 2003-06-27 | |
| US60/482,966 | 2003-06-27 |
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| CNB2004800148446A Division CN100523011C (en) | 2003-05-29 | 2004-05-07 | Process for the preparation of a catalyst component and components therefrom obtained |
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| CN101050248B true CN101050248B (en) | 2012-05-09 |
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| CNB2004800148446A Expired - Lifetime CN100523011C (en) | 2003-05-29 | 2004-05-07 | Process for the preparation of a catalyst component and components therefrom obtained |
| CN2007101050949A Expired - Lifetime CN101050248B (en) | 2003-05-29 | 2004-05-07 | Process for the preparation of a catalyst component and components therefrom obtained |
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|---|---|
| CN (2) | CN100523011C (en) |
| ES (1) | ES2625904T3 (en) |
| ZA (1) | ZA200509245B (en) |
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| US20110319571A1 (en) * | 2010-06-29 | 2011-12-29 | Botros Maged G | Polyolefin adhesive composition |
| US10138310B2 (en) | 2010-08-24 | 2018-11-27 | Equistar Chemicals, Lp | Preparation of LLDPE resins and films having low gels |
| CN103087224B (en) * | 2011-10-28 | 2015-03-11 | 中国石油化工股份有限公司 | Catalyst ingredient used for ethylene polymerization, and preparation method thereof |
| CN105985490A (en) * | 2015-02-16 | 2016-10-05 | 中国石油天然气股份有限公司 | Preparation method of heat-resistant polyethylene copolymer, heat-resistant polyethylene copolymer and pipe |
| CN110546174A (en) * | 2017-05-12 | 2019-12-06 | 巴塞尔聚烯烃意大利有限公司 | Method for activating ethylene polymerization catalyst |
| RU2740916C1 (en) | 2017-07-19 | 2021-01-21 | Чайна Петролеум Энд Кемикал Корпорейшн | Olefin polymerisation catalyst comprising cyclotriveratrilene and derivatives thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5278118A (en) * | 1986-10-02 | 1994-01-11 | Ausimont, S.P.A. | Catalysts for the preparation of elastomeric olefinic copolymers |
| CN1215410A (en) * | 1996-03-29 | 1999-04-28 | 博里利斯股份公司 | Novel composition, its preparation and use |
| CN1262693A (en) * | 1998-03-23 | 2000-08-09 | 蒙特尔技术有限公司 | Prepolymerized catalyst components for polymerization of olefins |
| CN1410457A (en) * | 2002-11-08 | 2003-04-16 | 营口市向阳催化剂有限责任公司 | Preparation method of solid titanium catalyst component used for olefine polymerization |
-
2004
- 2004-05-07 CN CNB2004800148446A patent/CN100523011C/en not_active Expired - Lifetime
- 2004-05-07 CN CN2007101050949A patent/CN101050248B/en not_active Expired - Lifetime
- 2004-05-07 ES ES04731636.9T patent/ES2625904T3/en not_active Expired - Lifetime
-
2005
- 2005-11-15 ZA ZA200509245A patent/ZA200509245B/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5278118A (en) * | 1986-10-02 | 1994-01-11 | Ausimont, S.P.A. | Catalysts for the preparation of elastomeric olefinic copolymers |
| CN1215410A (en) * | 1996-03-29 | 1999-04-28 | 博里利斯股份公司 | Novel composition, its preparation and use |
| CN1262693A (en) * | 1998-03-23 | 2000-08-09 | 蒙特尔技术有限公司 | Prepolymerized catalyst components for polymerization of olefins |
| CN1410457A (en) * | 2002-11-08 | 2003-04-16 | 营口市向阳催化剂有限责任公司 | Preparation method of solid titanium catalyst component used for olefine polymerization |
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| Publication number | Publication date |
|---|---|
| ZA200509245B (en) | 2007-04-25 |
| CN100523011C (en) | 2009-08-05 |
| CN1798774A (en) | 2006-07-05 |
| CN101050248A (en) | 2007-10-10 |
| ES2625904T3 (en) | 2017-07-20 |
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