CN100549038C - A kind of preparation method of polyethylene catalysts of loaded by semi-metallocene - Google Patents
A kind of preparation method of polyethylene catalysts of loaded by semi-metallocene Download PDFInfo
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- CN100549038C CN100549038C CNB2006100664436A CN200610066443A CN100549038C CN 100549038 C CN100549038 C CN 100549038C CN B2006100664436 A CNB2006100664436 A CN B2006100664436A CN 200610066443 A CN200610066443 A CN 200610066443A CN 100549038 C CN100549038 C CN 100549038C
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- Prior art keywords
- magnesium chloride
- alkyl
- semi
- metallocene
- titanium
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- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- -1 polyethylene Polymers 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 9
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 9
- 239000010936 titanium Substances 0.000 claims abstract description 58
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 44
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 38
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 31
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000007787 solid Substances 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 12
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 12
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims abstract description 11
- 239000003446 ligand Substances 0.000 claims abstract description 7
- 125000002877 alkyl aryl group Chemical group 0.000 claims abstract description 6
- 150000002191 fatty alcohols Chemical class 0.000 claims abstract description 6
- 239000003495 polar organic solvent Substances 0.000 claims abstract description 6
- 125000001424 substituent group Chemical group 0.000 claims abstract description 5
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims abstract description 4
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 125000005843 halogen group Chemical group 0.000 claims abstract 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 22
- 239000011777 magnesium Substances 0.000 claims description 16
- 229910052749 magnesium Inorganic materials 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical group C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 13
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 12
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 5
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 4
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical class C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- 125000003454 indenyl group Chemical class C1(C=CC2=CC=CC=C12)* 0.000 claims description 4
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 3
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 3
- 125000005234 alkyl aluminium group Chemical group 0.000 claims 3
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 claims 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims 2
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims 1
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims 1
- 125000003710 aryl alkyl group Chemical group 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 claims 1
- 239000004480 active ingredient Substances 0.000 abstract description 16
- 229940073589 magnesium chloride anhydrous Drugs 0.000 abstract description 15
- 229920000642 polymer Polymers 0.000 abstract description 5
- 239000002245 particle Substances 0.000 abstract description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 53
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 description 27
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000004411 aluminium Substances 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 10
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 8
- 229960002337 magnesium chloride Drugs 0.000 description 7
- 206010013786 Dry skin Diseases 0.000 description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 239000012968 metallocene catalyst Substances 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 5
- 125000005595 acetylacetonate group Chemical group 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- NUUNDIOOYFEMQN-UHFFFAOYSA-N cyclopenta-1,3-diene;sodium Chemical compound [Na].C1C=CC=C1 NUUNDIOOYFEMQN-UHFFFAOYSA-N 0.000 description 5
- 238000010926 purge Methods 0.000 description 5
- 230000004913 activation Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229940091250 magnesium supplement Drugs 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- SQRHAANADRNQIZ-UHFFFAOYSA-J [Cl-].[Ti+4].FC(C(=O)CC(C)=O)(F)F.[Cl-].[Cl-].[Cl-] Chemical compound [Cl-].[Ti+4].FC(C(=O)CC(C)=O)(F)F.[Cl-].[Cl-].[Cl-] SQRHAANADRNQIZ-UHFFFAOYSA-J 0.000 description 2
- ODXIOILULYNFCU-UHFFFAOYSA-N [Ti].CC(=O)CC(=O)C(F)(F)F Chemical compound [Ti].CC(=O)CC(=O)C(F)(F)F ODXIOILULYNFCU-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229920010524 Syndiotactic polystyrene Polymers 0.000 description 1
- CHUDKYNHLQLNTQ-UHFFFAOYSA-L [Cl-].[Cl-].[Ti+2].FC(C(=O)CC(C)=O)(F)F.C1=CC=CC1 Chemical compound [Cl-].[Cl-].[Ti+2].FC(C(=O)CC(C)=O)(F)F.C1=CC=CC1 CHUDKYNHLQLNTQ-UHFFFAOYSA-L 0.000 description 1
- QILWEOSASFLHFA-UHFFFAOYSA-L [Cl-].[Cl-].[Ti+2].FC(C(=O)CC(C)=O)(F)F.CC1=CC=CC1 Chemical compound [Cl-].[Cl-].[Ti+2].FC(C(=O)CC(C)=O)(F)F.CC1=CC=CC1 QILWEOSASFLHFA-UHFFFAOYSA-L 0.000 description 1
- TVFSCFCSLVQZCA-UHFFFAOYSA-J [Cl-].[Ti+4].C(C)C(=O)C(=O)C.[Cl-].[Cl-].[Cl-] Chemical compound [Cl-].[Ti+4].C(C)C(=O)C(=O)C.[Cl-].[Cl-].[Cl-] TVFSCFCSLVQZCA-UHFFFAOYSA-J 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 235000014121 butter Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000002097 pentamethylcyclopentadienyl group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000012725 vapour phase polymerization Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
A kind of preparation method of polyethylene catalysts of loaded by semi-metallocene comprises Magnesium Chloride Anhydrous is suspended in the unreactive hydrocarbons solvent, with Ti (OR
1)
4And C
2～C
8The abundant contact reacts of Fatty Alcohol(C12-C14 and C12-C18), obtain carrier after the drying, above-mentioned dry back carrier is handled after drying with aluminum alkyls in the presence of unreactive hydrocarbons solvent, again in the presence of polar organic solvent, with the abundant contact reacts of semi-metallocene active ingredient, collect the solids after drying, in the formula (I) with formula (I) expression formula, R and R ' can be identical or inequality, are C
1～C
12Alkyl, C
6～C
9Alkaryl or C
1～C
12Perfluoroalkyl, Cp ' has 1～5 substituent R for containing the ligand groups of cyclopentadienyl skeleton on the cyclopentadienyl skeleton
2, two adjacent substituting groups can be connected with each other and form the above condensed ring of binary, R on its skeleton
2Be selected from C
1～C
18Alkyl or perfluoroalkyl, C
6～C
24Aralkyl or alkaryl, X is a halogen, n is 1～3 integer.The catalyzer of this method preparation carries titanium amount height, and the resulting polymers particle form is good.
Description
Technical field
The present invention is a kind of preparation method of polyethylene catalysts of loaded by semi-metallocene.Specifically, be the preparation method of the polyethylene catalysts of a kind of load semi-metallocene active ingredient of containing the beta-diketo derivative part.
Background technology
After metallocene catalyst, the Nonmetallocene compound that contains coordination heteroatom ligands such as aerobic, nitrogen in the another kind of conjugated system more and more causes people's attention and concern in the application aspect polyolefine, the especially polyethylene catalysts.The Nonmetallocene compound that contains Sauerstoffatom in the part, as being that the titanium compound of part can only be used for styrene polymerization usually with beta-diketon and derivative, disclosing a kind of as CN1158859A is the catalyst system of the synthesis of syndiotactic polystyrene of Primary Catalysts with the beta-diketon titanium chloride.Its preferred Primary Catalysts is methyl ethyl diketone titanium chloride and diphenylpropane-1,3-dione(DPPO) titanium chloride.This catalyzer can prepare normality and the higher polystyrene of heat resisting temperature between height.
Usually wanting loadization, loadization during metallocene and non-metallocene catalyst are used is in order to satisfy more polymerization technique process, as the operational requirement of vapour phase polymerization, slurry polymerization.Simultaneously, loadization can improve the catalytic efficiency of active ingredient, can increase the stability in active centre, improve the form of polymkeric substance, improve the apparent density of polymkeric substance, the loadization of metallocene and non-metallocene catalyst can also reduce the consumption of promotor significantly, reduces catalyst production cost.Usually the load of metallocene or non-luxuriant polyolefin catalyst, all are first composite reactive components, be metallocene or non-half metallocene, and then title complex loaded on form supported catalyst on the carrier, disclosing a kind of as USP5869417 is active ingredient with the metallocene, molecular sieve is the preparation method of the loaded catalyst of carrier, and the used carrier of this patent is for having 7～15
The macroporous structure molecular sieve in aperture, as faujusite, SAPO-37 etc., the catalyzer that load metallocene makes on above-mentioned molecular sieve carrier can be used for ethene, propylene or cinnamic polymerization.
CN1461756A discloses a kind of non-metallocene catalyst and loaded catalyst thereof; the part of this catalyzer is the acyl-naphthaline phenolic compound; the an alkali metal salt of catalyzer employing acyl group naphthols and transition metal halide react at a lower temperature and make; its loaded catalyst is that described Nonmetallocene active ingredient solids is dispersed in the solvent, makes with the carrier reaction again.
CN1418227A discloses a kind of preceding body catalyst that comprises bidentate ligand that contains, and preceding body catalyst forms supported catalyst with the carrier reaction earlier with after the aluminum alkyls effect again.People such as K.Soga are at J.Polyrn.Sci., Polym.Chem.Ed.35, the polymerization that the cyclopentadiene titanous chloride is carried on the catalyzer that makes on the magnesium chloride support discussed in the article that 291-297 delivers, this catalyzer and triisobutyl aluminum cocatalyst are used and can prepare polypropylene, and have high polymerization activity.
CN00124667.4 discloses ethylene rolymerization catalyst and the preparation method that a kind of semi-metallocene catalyst active constituent loading that will contain the beta-diketo derivative part makes on butter, but owing to be the method that adopts co-precipitation, therefore the granules of catalyst form that makes with this method is bad, and there is saturation value during load active component, cause charge capacity limited, it is lower that the loaded catalyst that makes carries the titanium amount, therefore the polymerization efficiency of unit mass catalyzer is not high, the resulting polymers bulk density is low, and form is bad.
CN1128822C discloses a kind of preparation method of carrier for olefin polymerization catalyst, is Magnesium Chloride Anhydrous is suspended in the unreactive hydrocarbons solvent, and is pre-dispersed with alkoxy titanium compound earlier, uses C again
2～C
8Alcohol activate, the mol ratio of used alcohol and Magnesium Chloride Anhydrous is 0.05～2.5.The carrier that makes need not the solid ingredient that dealcoholysis gets final product direct load Ziegler-Natta type catalyzer.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of polyethylene catalysts of loaded by semi-metallocene, the loaded catalyst of this method preparation has advantages of high catalytic activity.
The preparation method of the polyethylene catalysts of loaded by semi-metallocene provided by the invention comprises the steps:
(1) Magnesium Chloride Anhydrous is suspended in the unreactive hydrocarbons solvent, in 30～200 ℃ and Ti (OR
1)
4And C
2～C
8The abundant contact reacts of Fatty Alcohol(C12-C14 and C12-C18), then solid drying is obtained carrier, described Ti (OR
1)
4With the mol ratio of Magnesium Chloride Anhydrous be 0.01～0.2, Fatty Alcohol(C12-C14 and C12-C18) and Magnesium Chloride Anhydrous mol ratio are 0.1～1.0, formula Ti (OR
1)
4In R
1Be selected from C
1～C
7Alkyl;
(2) (1) step dry back carrier is handled after drying with aluminum alkyls in the presence of unreactive hydrocarbons solvent, the mol ratio of aluminum alkyls and magnesium chloride is 0.1～2.0;
(3) in the presence of polar organic solvent, magnesium chloride support that will obtain after will handling with aluminum alkyls and the abundant contact reacts of semi-metallocene active ingredient with formula (I) expression formula are collected the solids after drying,
In the formula (I), R and R ' can be identical or inequality, are C
1～C
12Alkyl, C
6～C
9Alkaryl or C
1～C
12Perfluoroalkyl, Cp ' has 1～5 substituent R for containing the ligand groups of cyclopentadienyl skeleton on the cyclopentadienyl skeleton
2, two adjacent substituting groups can be connected with each other and form the above condensed ring of binary, R on its skeleton
2Be selected from C
1～C
18Alkyl or perfluoroalkyl, C
6～C
24Aralkyl or alkaryl, X is a halogen, n is 1～3 integer.
As carrier, load contains the semi-metallocene active ingredient of beta-diketo derivative part with Magnesium Chloride Anhydrous activation back in the present invention, and the catalyzer that makes carries titanium amount height, and has good mobility and intensity.This catalyzer is used for ethylene polymerization, has catalytic activity preferably, and the resulting polymers particle form is good, has higher bulk density.
Embodiment
The inventive method is suspended in Magnesium Chloride Anhydrous in the unreactive hydrocarbons solvent, with Ti (OR)
4Contact reacts activates with ROH again, makes the magnesium dichloride-alcohol carrier, and then with aluminum alkyls the magnesium dichloride-alcohol carrier is handled, and the described semi-metallocene active ingredient of load type (I) is made load type non-metallocene catalyst again.Therefore the pure consumption of activation Magnesium Chloride Anhydrous is few in the inventive method, so magnesium chloride is in solid-stately in treating processes all the time, can make activation back carrier have good form, and the supported catalyst that makes also has particle form preferably.In addition, because year titanium amount of the feed ratio of semi-metallocene active ingredient and carrier and loaded catalyst is directly proportional, thereby the supported catalyst that makes carries titanium amount height, makes the unit mass activity of such catalysts obviously improve.
Substituting group in the semi-metallocene active ingredient of the described formula of the inventive method (I) in R and the R ' difference beta-diketonate ligand, R and the preferred C of R ' difference
1～C
3Alkyl, C
1～C
3Perfluoroalkyl or C
6～C
9Alkaryl, more preferably methyl or phenyl.Cp ' has 1～5 substituent R for containing the ligand groups of cyclopentadienyl skeleton on the cyclopentadienyl skeleton
2Suitable Cp ' is for cyclopentadiene or contain substituent cyclopentadienyl, preferred cyclopentadienyl, C
1～C
4The alkyl list replaces or polysubstituted cyclopentadienyl, fluorenyl or indenyl, as methyl cyclopentadienyl, butyl cyclopentadienyl, 1-butyl-3-methyl cyclopentadienyl or pentamethyl-cyclopentadienyl, more preferably cyclopentadienyl, fluorenyl or indenyl.The preferred chlorine of X.
The compound of comparatively preferred formula (I) has: cyclopentadiene-(methyl ethyl diketone)-titanium dichloride, cyclopentadiene-two (methyl ethyl diketone)-titanium chloride, cyclopentadiene-tri acetylacetonato titanium, cyclopentadiene-(diphenylpropane-1,3-dione(DPPO))-titanium dichloride, cyclopentadiene-two (diphenylpropane-1,3-dione(DPPO))-titanium chloride, cyclopentadiene-three (diphenylpropane-1,3-dione(DPPO)) titanium, methyl cyclopentadiene-(methyl ethyl diketone)-titanium dichloride, methyl cyclopentadiene-two (methyl ethyl diketone)-titanium chloride, methyl cyclopentadiene-tri acetylacetonato titanium, methyl cyclopentadiene-(diphenylpropane-1,3-dione(DPPO))-titanium dichloride, methyl cyclopentadiene-two (diphenylpropane-1,3-dione(DPPO))-titanium chloride, methyl cyclopentadiene-three (diphenylpropane-1,3-dione(DPPO)) titanium, butyl cyclopentadiene-(methyl ethyl diketone)-titanium dichloride, butyl cyclopentadiene-two (methyl ethyl diketone)-titanium chloride, butyl cyclopentadiene-tri acetylacetonato titanium, butyl cyclopentadiene-(diphenylpropane-1,3-dione(DPPO))-titanium dichloride, butyl cyclopentadiene-two (diphenylpropane-1,3-dione(DPPO))-titanium chloride, butyl cyclopentadiene-three (diphenylpropane-1,3-dione(DPPO)) titanium, pentamethyl-cyclopentadiene-(methyl ethyl diketone)-titanium dichloride, pentamethyl-cyclopentadiene-two (methyl ethyl diketone)-titanium chloride, pentamethyl-cyclopentadiene-tri acetylacetonato titanium, pentamethyl-cyclopentadiene-(diphenylpropane-1,3-dione(DPPO))-titanium dichloride, pentamethyl-cyclopentadiene-two (diphenylpropane-1,3-dione(DPPO))-titanium chloride, pentamethyl-cyclopentadiene-three (diphenylpropane-1,3-dione(DPPO)) titanium, cyclopentadiene-(trifluoroacetylacetone) titanium dichloride, cyclopentadiene-two (trifluoroacetylacetone) titanium chloride, cyclopentadiene-three (trifluoroacetylacetone) titanium, methyl cyclopentadiene-(trifluoroacetylacetone) titanium dichloride, methyl cyclopentadiene-two (trifluoroacetylacetone) titanium chloride, methyl cyclopentadiene-three (trifluoroacetylacetone) titanium, indenyl-(methyl ethyl diketone)-titanium dichloride, indenyl-two (methyl ethyl diketone)-titanium chloride, indenyl-tri acetylacetonato titanium, indenyl-(diphenylpropane-1,3-dione(DPPO))-titanium dichloride, indenyl-two (diphenylpropane-1,3-dione(DPPO))-titanium chloride, indenyl-three (diphenylpropane-1,3-dione(DPPO)) titanium.
The inventive method (1) step is the activation treatment step of anhydrous chlorides of rase magnesium carrier, Magnesium Chloride Anhydrous is suspended in the unreactive hydrocarbons, with Ti (OR
1)
4With the alcohol reaction, be preferably elder generation's adding Ti (OR in Magnesium Chloride Anhydrous suspension
1)
4React, add alcohol again and react.Described Ti (OR
1)
4Preferred ethanolato-titanium, titanium propanolate or titanium butoxide, described Ti (OR
1)
4With the mol ratio of Magnesium Chloride Anhydrous preferred 0.01～0.1.
The preferred C of the described unreactive hydrocarbons solvent of the inventive method
5～C
10Alkane, more preferably hexane, decane, heptane or octane.The suitable mass ratio of unreactive hydrocarbons solvent and Magnesium Chloride Anhydrous is 5～100, preferred 5～20.Described Fatty Alcohol(C12-C14 and C12-C18) preferred alcohol, propyl alcohol, Virahol, butanols, isopropylcarbinol, amylalcohol, hexanol, enanthol, octanol or isooctyl alcohol.
The inventive method (2) step is with aluminum alkyls carrier to be handled, preferred triethyl aluminum of described aluminum alkyls or triisobutyl aluminium, the mol ratio of aluminum alkyls and magnesium chloride preferred 0.1～1.0.The temperature of carrier being handled with aluminum alkyls is-20～20 ℃, preferred-10～10 ℃.
Described (3) step is the loaded by semi-metallocene active ingredient, and described polar organic solvent is selected from C
1～C
5Chloroparaffin, as methylene dichloride, trichloromethane, ethylene dichloride or tetracol phenixin.The temperature of reaction of carrier and semi-metallocene active ingredient is 30～200 ℃, preferred 50～100 ℃.In the loading process, add the semi-metallocene active ingredient amount should to make the mol ratio of magnesium chloride and semi-metallocene active ingredient be 1～20, preferred 1～10.
Titanium content is 3.0～10 quality % in the catalyzer of the inventive method preparation, preferred 4.0～8.0 quality %, more preferably 5.1～8.0 quality %, Mg content is 2.5～20.0 quality %, preferred 5.0～15.0 quality %, aluminium content are 0.5～3.0 quality %, preferred 0.8～2.0 quality %.
The described Magnesium Chloride Anhydrous of the inventive method, its water content should be less than 1.0 quality %, and average particle size is 30～40 microns, and specific surface area is 10～20 meters
2/ gram.
The preparation method of described formula (I) semi-metallocene active ingredient is: in the presence of ether, make TiX
4With general formula be R '-C (O)-CH
2The beta-diketone compound of-C (O)-R reacts under reflux temperature by 1: 1～3 mol ratio, removes and desolvates, and obtains the beta diketone titanium compound.Then at organic solvent, as toluene exist make down an alkali metal salt Cp ' M of containing the cyclopentadienyl skeleton compound and beta diketone titanium compound by etc. molar ratio reaction, method is the beta diketone titanium compound to be dissolved in toluene earlier be mixed with solution preferably, and then add Cp ' M, and react at-15～25 ℃, remove and desolvate, the most handy ether washing of gained solid matter, or as required the solid matter recrystallization is purified, the recrystallization solvent for use is a polar organic solvent, as halogenated alkane.M among described Cp ' M is a basic metal, preferred sodium.The more detailed preparation method of described semi-metallocene active ingredient is referring to CN1295088A.
The loaded catalyst of the present invention preparation is applicable to the copolymerization of ethylene homo or ethene and alpha-olefin, also needs to add aikyiaiurnirsoxan beta during polymerization or aluminum alkyls is a promotor, and polymerization temperature is 10～100 ℃, preferred 30～80 ℃.Polymerization can adopt body, slurry or technology such as gas-phase fluidized-bed to carry out.The mol ratio of titanium in aluminium and the Primary Catalysts in promotor during polyreaction, promptly the Al/Ti mol ratio is 25～2000, preferred 100～1500.
Described aikyiaiurnirsoxan beta can be linear or cyclic, preferable methyl aikyiaiurnirsoxan beta, ethyl aikyiaiurnirsoxan beta or isobutyl aluminium alkoxide, the preferred triethyl aluminum of described aluminum alkyls, triisobutyl aluminium, three hexyl aluminium or their mixture.
Below by example in detail the present invention, but the present invention is not limited to this.
Example 1
Prepare loaded catalyst with the inventive method.
(1) preparation cyclopentadiene-(diphenylpropane-1,3-dione(DPPO)) titanium dichloride
With concentration is the TiCl of 4.74 quality %
4Diethyl ether solution, the diethyl ether solution of the diphenylpropane-1,3-dione(DPPO) of 56.06 quality % (production of Shanghai chemical reagent work) adds in the encloses container, and makes TiCl
4With the mol ratio of diphenylpropane-1,3-dione(DPPO) be 1: 1, be heated with stirring to reflux temperature, reacted 1 hour, filter, solid makes (diphenylpropane-1,3-dione(DPPO)) titanous chloride with ether washing 3 times.
Get 5.5 milliliters of cyclopentadiene and be dissolved in 25 milliliters of tetrahydrofuran (THF)s ,-10 ℃ add 1.4 gram sodium Metal 99.5 reactions 2 hours, and removal of solvent under reduced pressure obtains 4.67 gram cyclopentadiene sodium.
(diphenylpropane-1,3-dione(DPPO)) titanous chloride is dissolved in the solution that toluene is made into 94.35 quality %, adding concentration at-10 ℃ then is the toluene solution of the cyclopentadiene sodium of 22.02 quality %, and the mol ratio that makes (diphenylpropane-1,3-dione(DPPO)) titanous chloride and cyclopentadiene sodium is 1: 1,20 ℃ of stirring reactions 5 hours, filter, wash 3 times with ether, 50 ℃ of dryings 24 hours make cyclopentadiene-(diphenylpropane-1,3-dione(DPPO)) titanium dichloride.
(2) preparation loaded catalyst
(a) get 40 milliliters of exsiccant hexanes, the there-necked flask that places nitrogen purging to cross stirs 0.30 milliliter (8.8 * 10 of adding down
-4Mol) titanium n-butoxide adds Magnesium Chloride Anhydrous (production of Jinzhou aluminium manufacturer) 2.0 grams (2.1 * 10 then
-2Mol), it is suspended in the hexane, is heated to 70 ℃, under this temperature, stirred 30 minutes, drip propyl carbinol again 0.8 milliliter (8.7 * 10
-3Mol), stirred suspension 30 minutes filters, and solid is with 30 milliliters of hexane wash three times, and 30 ℃ of dryings 2 hours must mobile good white powder carrier a.
(b) there-necked flask that places nitrogen purging to cross carrier a, add 40 milliliters of exsiccant hexanes, stirring down, adding 6.4 ml concns are the hexane solution of the triethyl aluminum of 1 mol, 0 ℃ was reacted 2 hours, filter, solid is with 30 milliliters of hexane wash three times, and 30 ℃ of dryings 2 hours obtain the carrier b that aluminum alkyls is handled.
(c) there-necked flask that places nitrogen purging to cross carrier b adds 40 milliliters of exsiccant hexanes, will contain 2.8 grams (6.88 * 10
-3Mol) dichloromethane solution of cyclopentadiene-(diphenylpropane-1,3-dione(DPPO)) titanium dichloride splashes into wherein for 30 milliliters, be heated to 70 ℃ of stirring reactions 1 hour, and filtered, solid is with 30 milliliters of hexane wash three times, 30 ℃ of dryings 2 hours obtain mobile well deep yellow powder catalyst A.The titanium content that plasma emission spectrum (ICP) method records catalyst A is 5.34 quality %, and Mg content is 10.84 quality %, and aluminium content is 1.23 quality %.
Example 2
Method by example 1 prepares supported catalyst B, and different is to add 40 milliliters in (c) step to contain 3.7 grams (9.10 * 10
-3Mol) dichloromethane solution of cyclopentadiene-(diphenylpropane-1,3-dione(DPPO)) titanium dichloride, the titanium content of the catalyst B that obtains is 6.23 quality %, and Mg content is 9.12 quality %, and aluminium content is 1.01 quality %.
Example 3
Method by example 1 prepares supported catalyst C, and different is to add 45 milliliters in (c) step to contain 4.4 grams (1.08 * 10
-2Mol) dichloromethane solution of cyclopentadiene-(diphenylpropane-1,3-dione(DPPO)) titanium dichloride, the titanium content of the catalyzer C that obtains is 7.08 quality %, and Mg content is 8.62 quality %, and aluminium content is 0.92 quality %.
Example 4
Method by example 1 prepares supported catalyst D, and the amount of the propyl carbinol that adds in different is (a) step is 1.2 milliliter (1.3 * 10
-2Mol), (b) adding 8.7 ml concns in the step is the hexane solution of the triethyl aluminum of 1 mol, and the titanium content of the catalyzer D that obtains is 5.45 quality %, and Mg content is 10.24 quality %, and aluminium content is 1.35 quality %.
Example 5
Method by example 1 prepares supported catalyst E, and different is that the propyl carbinol that adds in (a) step is 0.4 milliliter (4.3 * 10
-3Mol), (b) adding 3.6 ml concns in the step is the hexane solution of the triethyl aluminum of 1 mol, and the titanium content of the catalyzer E that obtains is 3.5 quality %, and Mg content is 13.13 quality %, and aluminium content is 1.02 quality %.
Example 6
Method by example 1 prepares supported catalyst F, and different is that the propyl carbinol that adds in (a) step is 1.6 milliliter (1.7 * 10
-2Mol), (b) adding 10.5 ml concns in the step is the hexane solution of the triethyl aluminum of 1 mol, and the titanium content of the catalyzer F that makes is 4.5 quality %, and Mg content is 11.19 quality %, and aluminium content is 1.64 quality %.
Example 7
Method by example 1 prepares supported catalyst G, and different is to add 0.5 milliliter (8.7 * 10 in (a) step
-3Mol) ethanol, (b) adding 7.4 ml concns in the step is the hexane solution of the triethyl aluminum of 1 mol, and the titanium content of the catalyzer G that makes is 4.66 quality %, and Mg content is 11.32 quality %, and aluminium content is 1.14 quality %.
Example 8
Method by example 1 prepares supported catalyst H, and different is to add 1.5 milliliter (8.7 * 10 in (a) step
-3Mol) isooctyl alcohol, (b) adding 5.4 ml concns in the step is the hexane solution of the triethyl aluminum of 1 mol, and the titanium content of the catalyzer H that makes is 3.5 quality %, and Mg content is 12.93 quality %, and aluminium content is 1.03 quality %.
Example 9
Method by example 1 prepares supported catalyst I, different is that adding 5.4 ml concns are the hexane solution of the triisobutyl aluminium of 1 mol in (b) step, the titanium content of the catalyst I that makes is 5.28 quality %, and Mg content is 10.94 quality %, and aluminium content is 1.27 quality %.
Example 10
(1) preparation cyclopentadiene-(methyl ethyl diketone) titanium dichloride
With concentration is the TiCl of 4.47 quality %
4Diethyl ether solution, concentration are that the diethyl ether solution of 2.51 quality % methyl ethyl diketones adds in the closed reactor, and make TiCl
4With the mol ratio of methyl ethyl diketone be 1: 1, be heated with stirring to reflux temperature, reacted 1 hour, cross and to filter out ether, solid makes (methyl ethyl diketone) titanous chloride with ether washing 3 times.
Above-mentioned (methyl ethyl diketone) titanous chloride is dissolved in the solution that toluene is made 63.37 quality %, adding concentration at-10 ℃ is the toluene solution of the cyclopentadiene sodium of 22.0 quality %, and to make the mol ratio of cyclopentadiene sodium and (methyl ethyl diketone) titanous chloride be 1: 1,20 ℃ of stirring reactions 5 hours, remove by filter toluene, solid washs 3 times with ether, use 30 milliliters of methylene dichloride dissolved solidss again, remove by filter insolubles, filtrate is concentrated into dried, 50 ℃ of dryings obtained cyclopentadiene-(methyl ethyl diketone)-titanium dichloride in 4 hours.
(2) preparation loaded catalyst
Prepare supported catalyst J by example 1 (2) one step process, different is to add in (c) step to contain 1.8 grams (6.34 * 10
-3Mol) dichloromethane solution of cyclopentadiene-(methyl ethyl diketone) titanium dichloride is 30 milliliters, and the titanium content of the catalyzer J that makes is 5.62 quality %, and Mg content is 10.76 quality %, and aluminium content is 1.21 quality %.
Comparative Examples 1
Prepare catalyzer M according to the CN00124667 method.Get water content and put into reaction flask less than dry magnesium chloride 1.2 grams of 1.0 quality %, add 60 milliliters of exsiccant tetrahydrofuran (THF)s, 55 ℃ of reactions formed adduct solution in 1 hour.Slowly splash into 15 milliliters of dichloromethane solutions that are dissolved with 0.51 gram cyclopentadiene-(diphenylpropane-1,3-dione(DPPO)) titanium dichloride in the reaction flask, 20 ℃ of stirring reactions 1 hour, stop to stir, add 100 milliliters of hexane solutions, staticly settled 2 hours, filter, solid was obtained 1.01 gram pink colour catalyzer M in 6 hours 20 ℃ of dryings.The titanium content of catalyzer M is 1.11 quality %, and Mg content is 13.36 quality %.
Example 11～21
Following example carries out the reaction of normal pressure ethylene homo.
250 milliliters of round-bottomed flasks are vacuumized back nitrogen purging three times, feed ethene behind the emptying nitrogen, keep-up pressure and be 0.1MPa, add toluene solution, the 50 milliliters of exsiccant hexanes of the methylaluminoxane that 9.6 ml concns are 10 quality % (MAO) and contain the catalyzer of 0.03mmolTi, 40 ℃ of polyreactions 0.5 hour are used the HCl termination reaction.The Al/Ti mol ratio is 500 during polymerization.Each example catalyst system therefor, catalytic activity and polymer property see Table 1.
Example 22～32
Following example carries out the high-pressure ethylene homopolymerization.
2 liters of stainless steel autoclaves are vacuumized back nitrogen purging three times, feed ethene behind the emptying nitrogen, keep-up pressure and be 0.8MPa, the catalyzer that adds hexane solution that 20 ml concns are the triethyl aluminum of 10 quality %, 1 liter of exsiccant hexane and 0.1mmolTi, 70 ℃ of polyreactions 2 hours, use the HCl termination reaction, the Al/Ti mol ratio is 200 during polymerization.Each example catalyst system therefor, catalytic activity and polymer property see Table 2.
By table 1 and table 2 data as can be known, the catalyzer of the inventive method preparation has the higher titanium amount of carrying than comparative catalyst M, and therefore, the catalyst activity of unit mass is higher, has higher actual application value.
Table 1
Table 2
Claims (9)
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