CN101824104B - Catalyst component for vinyl polymerization and preparation method thereof - Google Patents
Catalyst component for vinyl polymerization and preparation method thereof Download PDFInfo
- Publication number
- CN101824104B CN101824104B CN2009100788822A CN200910078882A CN101824104B CN 101824104 B CN101824104 B CN 101824104B CN 2009100788822 A CN2009100788822 A CN 2009100788822A CN 200910078882 A CN200910078882 A CN 200910078882A CN 101824104 B CN101824104 B CN 101824104B
- Authority
- CN
- China
- Prior art keywords
- chromium
- carrier
- titanium
- component
- oxide
- 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.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims description 59
- 238000002360 preparation method Methods 0.000 title claims description 31
- 238000006116 polymerization reaction Methods 0.000 title description 23
- 229920002554 vinyl polymer Polymers 0.000 title description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 title description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 77
- 239000011651 chromium Substances 0.000 claims description 74
- 229910052804 chromium Inorganic materials 0.000 claims description 73
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 71
- 239000011777 magnesium Substances 0.000 claims description 36
- 239000010936 titanium Substances 0.000 claims description 36
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 27
- SXSVTGQIXJXKJR-UHFFFAOYSA-N [Mg].[Ti] Chemical compound [Mg].[Ti] SXSVTGQIXJXKJR-UHFFFAOYSA-N 0.000 claims description 26
- 239000000377 silicon dioxide Substances 0.000 claims description 22
- 229960001866 silicon dioxide Drugs 0.000 claims description 22
- 239000012041 precatalyst Substances 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 18
- 239000005977 Ethylene Substances 0.000 claims description 17
- 229910052719 titanium Inorganic materials 0.000 claims description 17
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 16
- 239000002685 polymerization catalyst Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 6
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 6
- 150000002902 organometallic compounds Chemical class 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052810 boron oxide Inorganic materials 0.000 claims description 3
- 229940117975 chromium trioxide Drugs 0.000 claims description 3
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 claims description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 230000007704 transition Effects 0.000 claims description 3
- CYHOFESITORDDD-UHFFFAOYSA-M C(CCC)O[Cr](=O)(=O)O Chemical group C(CCC)O[Cr](=O)(=O)O CYHOFESITORDDD-UHFFFAOYSA-M 0.000 claims description 2
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 27
- 239000000460 chlorine Chemical group 0.000 description 22
- 239000000741 silica gel Substances 0.000 description 18
- 229910002027 silica gel Inorganic materials 0.000 description 18
- 229910052749 magnesium Inorganic materials 0.000 description 17
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 239000011148 porous material Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 230000004913 activation Effects 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 7
- -1 alkoxy titanium compound Chemical class 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 206010013786 Dry skin Diseases 0.000 description 6
- 238000007664 blowing Methods 0.000 description 6
- XEHUIDSUOAGHBW-UHFFFAOYSA-N chromium;pentane-2,4-dione Chemical compound [Cr].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O XEHUIDSUOAGHBW-UHFFFAOYSA-N 0.000 description 6
- 238000005243 fluidization Methods 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 150000002681 magnesium compounds Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 230000037048 polymerization activity Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000000017 hydrogel Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 239000011630 iodine Chemical group 0.000 description 2
- 229910052740 iodine Chemical group 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- PCBPVYHMZBWMAZ-UHFFFAOYSA-N 5-methylbicyclo[2.2.1]hept-2-ene Chemical group C1C2C(C)CC1C=C2 PCBPVYHMZBWMAZ-UHFFFAOYSA-N 0.000 description 1
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 1
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical group CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 1
- LDLDYFCCDKENPD-UHFFFAOYSA-N ethenylcyclohexane Chemical compound C=CC1CCCCC1 LDLDYFCCDKENPD-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 125000005574 norbornylene group Chemical group 0.000 description 1
- ZJKABZNFELLAQQ-UHFFFAOYSA-N octane Chemical compound CCCCCCCC.CCCCCCCC ZJKABZNFELLAQQ-UHFFFAOYSA-N 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 229930015698 phenylpropene Natural products 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000002910 structure generation Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention provides a catalyst component for vinyl polymerization and a preparation method thereof. The component uses an oxide as a carrier, and a titanium-magnesium compound and a chromium compound are loaded on the carrier together, wherein the chromium content is between 0.1 and 10 weight percent; the titanium content is between 0.1 and 12 weight percent; the magnesium content is between 0.05 and 10 weight percent; and the titanium-magnesium compound is a compound the molecular formula of which is [Ti2(OR1)2(OR2)2(OR3)2(OR4)2X]2Mg2X2. When the catalyst component is used for the vinyl polymerization, the catalyst has high activity and the prepared vingi ethane polymer also has high melt index.
Description
Technical field
The present invention relates to a kind of supported chrome series catalysts component that is used for ethylene homo or ethene and alpha-olefin copolymer, more particularly, relate to a kind of with titanium, magnesium-modified supported chrome series catalysts component and the preparation method and the application of this catalyst component.
Technical background
Ethene polymers has been widely used as various membrane products and has used resin material, and requires ethene polymers to have different characteristic according to film system method and purpose.For example, the polymkeric substance that has lower molecular weight and a narrow molecular weight distributions is applicable to the goods through injection moulding film system.On the other hand, the polymkeric substance that has higher molecular weight and a wide molecular weight distribution is applicable to the goods through blowing or aerated film method for making film system.To ultra high molecular weight polyethylene, this quasi-polyethylene had enough intensity, has good processing properties simultaneously during (for example pipe applications) needed in many application.
Ethene polymers with wide molecular weight distribution can be through using the chromium-based catalysts preparation; Described chromium-based catalysts is calcined in non-reduced atmosphere and is made its activation through loading on chromium cpd on the inorganic oxide carrier, the chromium atom of partial load is converted into the sexavalent chrome atom obtains.In the art, above-mentioned catalyzer is commonly referred to the Phillips catalyzer, and detail operations is referring to Adances in catalyst 1985,33:47～98M.P.McDaniel.Be immersed on the silicon-dioxide carriers such as (silica gel) with chromic salt, the catalyzer that obtains is removed after the moisture, uses dry air fluidized drying and activation under 400～1000 ℃ of temperature again, and this catalyzer is deposited in dry air or in the rare gas element.This type catalyst component composition generally comprises carrier, active ingredient, is with or without promotor; Wherein carrier is an inorganic oxide; Active ingredient is the organic or inorganic compound of chromium; Promotor is an organometallics, but each the concrete component concentration and the preparation method of catalyzer have nothing in common with each other, thereby gained catalyst performance price differs greatly.
The characteristics of chrome catalysts are for chainpropagation and chain transfer to have different activity center ratio.This catalyzer tends to produce short polymer chain and comonomer is combined with short polymer chain with high frequency, might have the comonomer and the side chain of uneven distribution between each macromole of the polymkeric substance that obtains thus.Therefore, the polymkeric substance of processing can be wide molecular weight distribution, thereby has good processing properties.But this catalyzer also often has shortcomings such as induction time is long, the product melting index is low, copolymerization performance is poor, hydrogen regulation performance is insensitive.In order to overcome these shortcomings of chrome catalysts, the chromium-based catalysts of many modifications has appearred successively.Generally speaking, before preparation or in the preparation process, add some compounds, as contain the compound of elements such as titanium, fluorine, aluminium, magnesium, zirconium, realize chemical modification, improve the catalytic performance of chromium-based catalysts chrome catalysts or carrier.
For example: U.S. Pat 3887494 discloses a kind of Preparation of catalysts method that is used for olefinic polymerization.Titanium compound is mixed with a kind of mineral acid; Alkalimetal silicate added in this mixture form hydrogel, then aging this hydrogel when pH value is about 6.0,90 ℃; Water then; Ammonium salt solution or olefin(e) acid flush away basic metal add a certain amount of water-soluble organic compounds, thereby separation of organic substances and water form xerogel from this mixture.Contain the xerogel of chromium 482 ℃ of-982 ℃ of following activation, be formed for the catalyzer of olefinic polymerization.
Chinese patent CN1165553C discloses a kind of Preparation of catalysts method that is used for olefinic polymerization.The clear solution of water glass, titanium sulfate and chromium sulphate is mixed preparation silica-titania-chromium gel, and the pH value of regulator solution is neutral, and experience is aging for the first time, and is aging for the second time under the PH of alkalescence condition then, final drying.
Chinese patent CN 1471431A discloses the compound of the silicon oxide-containing that a kind of new magnesium handles, and is suitable as the carrier of chromium base olefin polymerization catalyst system.Make Mg (NO
3)
26H
2O and Cr (NO
3)
39H
2The O contact generates compsn, is that the compsn of gained contacts formation Marinco H, drying compsn with alkali.The introducing of magnesium in this catalyzer has increased the surface-area of carrier, has caused the minimizing of long chain branching in the polyvinyl resin, and HMW partly reduces, and polymkeric substance has good impact property in high molecular weight film is used.
Above-mentioned patent successively uses titanium, magnesium that chromium-based catalysts is carried out modification; The existence of titanium, magnesium has produced remarkable influence to chromium-based catalysts, and along with the adding of titanium, magnesium, the copolymerization performance of catalyzer is improved; The molecular weight of polymkeric substance reduces; The melting index of resin increases, and the blowing performance of resin has obtained very big improvement, and the tear resistance of the film of blowing is better.But; All adopt the co-precipitation or the cogelled method of silicon oxide, titanium, magnesium and chromium cpd in the patent; Begin to prepare chromium-containing catalyst from the silica gel of titaniferous, magnesium, chromium; The acquisition of carrier need be to co-precipitation or cogelled spraying drying or the azeotropic drying of carrying out, and the gained carrier also need carry out aging for a long time under basic neutral pH value, even needs to add aperture protective agent.Such preparation process is very complicated, and the consumption time is long, owing to the pore structure generation decisive influence of ageing process to catalyst, so the less stable of Preparation of Catalyst.
Summary of the invention
One of the object of the invention is to the problems referred to above, and a kind of preparation method is provided simple catalyst component, and this catalyst component is when being used for vinyl polymerization, and activity of such catalysts is very high, and the ethene polymers that obtains simultaneously has high fusion index.
Two of the object of the invention has provided the above-mentioned preparation method who is used for the ethylene polymerization catalysts component.
Three of the object of the invention has provided a kind of catalyzer that can produce the high fusion index olefin polymer.
A kind of ethylene polymerization catalysts component that is used for of the present invention; This component is as carrier with oxide compound; Titanium magnesium compound and chromium cpd load on the carrier jointly, and wherein chromium content is 0.1-10wt%, and titanium content is 0.1-12wt%; Mg content is 0.05-10wt%, and described oxide carrier is a kind of in aluminum oxide, silicon-dioxide, titanium oxide, boron oxide and the zirconium white or their mixture; The molecular formula of described titanium magnesium compound is [Ti
2(OR
1)
2(OR
2)
2(OR
3)
2(OR
4)
2X]
2Mg
2X
2, substituent R wherein
1, R
2, R
3And R
4Identical or different, be selected from hydrogen, halogen, C
1-C
20The alkyl of straight or branched, C
3-C
20Naphthenic base, C
6-C
20Aryl, C
7-C
20Alkaryl and C
7-C
20A kind of in the aralkyl, substituent X is fluorine, chlorine, bromine or iodine; Described chromium cpd is the water-soluble or oil-soluble chromium cpd that contains that can be transformed into chromic oxide through overactivation.
Oxide carrier described in the present invention is generally the porous inorganic particulate that contains hydroxyl, is good with spheric soild oxide carrier.Like a kind of or its mixture in aluminum oxide, silicon-dioxide (silica gel), titanium oxide, boron oxide, zirconium white, the phosphagel phosphaljel, preferred silica gel is as carrier, and can select specific surface area for use is 245-375m
2The silica-gel carrier of/g, also can select specific surface area for use is 410-620m
2The silica-gel carrier of/g.Along with the carrier specific surface area increases, the hydrogen accent ability of catalyzer reduces; Along with specific surface area reduces, the polymerization activity of catalyzer reduces; Selected carrier silica gel also should have suitable pore volume.Can select pore volume for use is 1.1-1.8cm
3The carrier silica gel of/g, also can select pore volume for use is 2.4-3.7cm
3The carrier silica gel of/g.Along with the pore volume reduction of carrier silica gel, the hydrogen of catalyzer is transferred ability drop, but high pore volume carrier silica gel must be through the solution extraction preparation, and cost is higher.Can directly adopt the carrier that is purchased, the content of carrier in catalyzer is 70-100wt%, preferred 90-99wt%.
Oxide carrier described in the present invention will carry out drying treatment to remove free-water before load.Drying treatment can be carried out in air, also can in rare gas element, carry out, and also can under vacuum state, accomplish.The temperature of drying treatment can be 80-280 ℃, and the time is 1-10 hour.
The molecular formula of titanium magnesium compound of the present invention is [Ti
2(OR
1)
2(OR
2)
2(OR
3)
2(OR
4)
2X]
2Mg
2X
2, substituent R wherein
1, R
2, R
3And R
4Can be the same or different, be selected from hydrogen, halogen, C
1-C
20The alkyl of straight or branched, C
3-C
20Naphthenic base, C
6-C
20Aryl, C
7-C
20Alkaryl, C
7-C
20A kind of in the aralkyl; Wherein substituent X is for being fluorine, chlorine, bromine or iodine.Concrete titanium magnesium compound is like [Ti
2(OC
2H
5)
2Cl]
2Mg
2Cl
2, [Ti
2(OC
3H
7)
2Cl]
2Mg
2Cl
2, [Ti
2(Oi-C
3H
7)
2Cl]
2Mg
2Cl
2, [Ti
2(OC
4H
9)
2Cl]
2Mg
2Cl
2, [Ti
2(Oi-C
4H
9)
2Cl]
2Mg
2Cl
2, [Ti
2(OC
2H
5)
2Br]
2Mg
2Br
2, [Ti
2(OC
2H
5)
2I]
2Mg
2I
2Deng.This compound can obtaining through following method: alkoxy titanium compound and magnesium compound are reacted in alkane form solution; Carry out recrystallization then; Can obtain the titanium magnesium compound; Wherein in the alkoxy titanium compound in Ti and the magnesium compound mol ratio of Mg be 1: 1～8: 1, detail operations is referring to Inorganica Chimica Acta.180 (1991) 245-249.
Chromium cpd of the present invention is the water-soluble or oil-soluble chromium cpd that contains that can be transformed into chromic oxide through overactivation.Water miscible chromium cpd such as chromium trioxide, chromium acetate, chromium nitrate or their crystalline hydrate or their mixture; Oil-soluble chromium cpd such as tertiary butyl chromate, two luxuriant chromium, Acetyl Acetone acid chromium.In these chromium cpds, preferably use chromium trioxide or chromium nitrate.
The present invention is used for the preparation method of ethylene polymerization catalysts component, and it may further comprise the steps:
(1) 100～250 ℃ of following drying treatment oxide carrier 1-10 hour;
(2) the titanium magnesium compound solution is contacted with the oxide carrier that step (1) obtains with chromium cpd solution, wherein the solvent phase in titanium magnesium compound solution and the chromium cpd solution is same, and solvent is C
4～C
20Alkane or C
1～C
20Alcohol, the weight ratio of carrier and Ti are 10: 1～1000: 1, and the weight ratio of carrier and chromium is 10: 1～1000: 1, remove subsequently and desolvate, and obtain carrying the pre-catalyst of chromium;
(3) carry the chromium pre-catalyst in air, with what step (2) obtained 400～1000 ℃ of following calcinings 1-10 hour.
Solvent described in the step (2) in titanium magnesium compound solution and the chromium cpd solution is selected from and can makes titanium magnesium compound dissolved hydrocarbon or alcohol, and hydro carbons is C
4-C
20Alkane, preferred C
4-C
8Alkane, like Trimethylmethane, iso-pentane, Skellysolve A, normal hexane, normal heptane or octane etc.Alcohols is C
1-C
20Alcohol, preferred C
1-C
8Alcohol, like methyl alcohol, ethanol, propyl alcohol, Virahol, 1-hexanol or isooctyl alcohol etc.
The carried catalyst of being made up of titanium magnesium compound, chromium cpd and silica-gel carrier must could form the final catalyst component and be used for polymerization through activation.The activatory process is in air, to carry out high-temperature calcination, and the incinerating temperature is 400-1000 ℃, preferred 600-800 ℃.Calcining and activating can be in dry air a step accomplish, also can for example carry out in the carbon monoxide at reducing gas earlier, in air, accomplish final activation then.Can also be under 300-600 ℃ through the final catalyzer of incinerating, with the carbon monoxide reduction, cool to room temperature seals preservation in atmosphere of inert gases then.
The present invention also provides a kind of ethylene polymerization catalysts that is used for, and comprises following component:
(1) the above-mentioned ethylene polymerization catalysts component that is used for;
(2) promotor is the mixture of one or more compounds in the organometallic compound of first, second and third or four main groups or second transition group in the periodic table of elements; The mol ratio of organometallic compound and chromium is 0.1: 1～100: 1, preferred 0.5: 1～50: 1.
Described promotor is the mixture of one or more compounds in the organometallic compound of first, second and third or four main groups or second transition group in the periodic table of elements.Concrete like n-Butyl Lithium, triethyl-boron, trimethylaluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, ethyl aluminum dichloride and zinc ethyl etc.The C of alkoxide
1-C
10Aluminum alkyls such as oxyethyl group diethyl aluminum, methoxyl group diethyl aluminum etc.In addition, also can use MAO, ethyl aikyiaiurnirsoxan beta or butyl aikyiaiurnirsoxan beta etc.
Catalyzer of the present invention can be used for ethylene homo, also can be used for ethene and other olefin-copolymerization.Described other alkene can be to contain C
3-C
20Terminal olefin, aromatic vinyl compound, alicyclic ring vinyl compound, one or more in the cycloolefin.Like propylene, butylene, hexene, 3-methyl-1-butene, 3-ethyl-1-amylene, vinylbenzene, allyl benzene, vinyl cyclohexane, vinyl pentamethylene, tetrahydrobenzene, norbornylene, 5-methyl-2-norbornylene etc.
Catalyzer of the present invention can be used for intermittently or continuous mode production, can be used for solution, gas phase and slurry phase polymerisation technology, is specially adapted to slurry phase polymerisation technology.When using slurry polymerization processes, generally select a kind of inert alkane as thinner, polymer beads can be dispersed in thinner with slurry form, reaction end back is through flash distillation or remove by filter thinner.Common thinner has propane, Trimethylmethane, pentane, hexane, heptane.Typical polymerizing condition be polymerization temperature at 20 ℃-250 ℃, be preferably in 50 ℃-160 ℃; Polymeric pressure is preferably in 5atm-80atm at 1atm-100atm.Can use the melting index and the molecular weight of hydrogen telomerized polymer in the polymerization technique.
Ethene polymers melting index with catalyst component production of the present invention can be controlled between the 0.01g/10min-4000g/10min, and controllable density is built in 0.915-0.975g/cm
3Between.
Catalyst component preparation method of the present invention is very simple; Again since titanium and magnesium simultaneously active site chromium is exerted an influence; Make this catalyst component when being used for vinyl polymerization, activity of such catalysts is very high, and can obtain having the ethene polymers than high fusion index.
Embodiment
Provide following examples so that the present invention is described better, be not used for limiting scope of the present invention.
Testing method:
1, melt index (M.I): measure according to ASTM D1238-99
2, density: ASTM D-1505 measures
3, molecular weight distribution index (Mw/Mn): gel gc (GPC) is measured
4, ethylene polymerization activity: the weight with every gram catalyzer gained resin is represented
Embodiment 1
The preparation of titanium magnesium compound
In the 150ml heptane, add the magnesium chloride of 5g (52.6mmol) and the purity titanium tetraethoxide of 34.3g (150mmol), three hours postcooling of reflux filter out mother liquor, and then add 100ml heptane recrystallization, obtain the white crystal [Ti of 23.6g
2(OC
2H
5)
2Cl]
2Mg
2Cl
2
The preparation of catalyst component
10g silica gel A (W.R.Grece & Co.-Com, 955, pore volume is about 1.1-1.8cm
3/ g, surface-area is about 245-375m
2/ g), successively adding and containing 2.6g titanium magnesium compound [Ti after 4 hours 200 ℃ of dryings under the nitrogen fluidisation
2(OC
2H
5)
2Cl]
2Mg
2Cl
2Aqueous isopropanol flood with the aqueous isopropanol that contains the 0.75g chromium acetylacetonate, after Virahol is evaporated, obtain containing the pre-catalyst of chromium.Pre-catalyst is placed 1.75 inches silica tube activation, and the sintered quartz dish is equipped with in the bottom of 1.75 inches silica tubes.Pre-catalyst is loaded on the dish, with dry air with about 1.6-1.8 standard cubic foot/hour linear velocity upwards blow over this dish.Open all electric furnaces around the silica tube, make temperature rise to 600 ℃ of calcinings 3 hours, obtain the activatory chromium-based catalysts with 400 ℃ speed per hour.Chromium content is about 1wt% in the final control catalyst component, and titanium content is about 5wt%, and Mg content is about 2.8wt%, and the content of chromium, titanium, magnesium is listed in table 1 in the catalyst component, and the polymerization evaluation result of catalyzer is listed in table 2.
Embodiment 2
The preparation of titanium magnesium compound
Preparing method with titanium magnesium compound among the embodiment 1 is identical.
The preparation of catalyst component
(pore volume is about 2.4-3.7cm to 10g silica gel B for PQ Corporation, MS3050
3/ g, surface-area is about 410-620m
2/ g), successively adding and containing 2.6g titanium magnesium compound [Ti after 4 hours 200 ℃ of dryings under the nitrogen fluidisation
2(OC
2H
5)
2Cl]
2Mg
2Cl
2Aqueous isopropanol flood with the aqueous isopropanol that contains the 0.75g chromium acetylacetonate, after Virahol is evaporated, obtain containing the pre-catalyst of chromium.Pre-catalyst is placed 1.75 inches silica tube activation, and the sintered quartz dish is equipped with in the bottom of 1.75 inches silica tubes.Pre-catalyst is loaded on the dish, with dry air with about 1.6-1.8 standard cubic foot/hour linear velocity upwards blow over this dish.Open all electric furnaces around the silica tube, make temperature rise to 600 ℃ of calcinings 3 hours, obtain the activatory chromium-based catalysts with 400 ℃ speed per hour.Chromium content is about 1wt% in the final control catalyst component, and the content of chromium, titanium, magnesium is listed in table 1 in the catalyst component, and the polymerization evaluation result of catalyzer is listed in table 2.
Embodiment 3
The preparation of titanium magnesium compound
Preparing method with titanium magnesium compound among the embodiment 1 is identical.
The preparation of catalyst component
10g silica gel A (W.R.Grece & Co.-Com, 955, pore volume is about 1.1-1.8cm
3/ g, surface-area is about 245-375m
2/ g), successively adding and containing 1.6g titanium magnesium compound [Ti after 4 hours 200 ℃ of dryings under the nitrogen fluidisation
2(OC
2H
5)
2Cl]
2Mg
2Cl
2Aqueous isopropanol flood with the aqueous isopropanol that contains the 0.38g chromium acetylacetonate, after Virahol is evaporated, obtain containing the pre-catalyst of chromium.Pre-catalyst is placed 1.75 inches silica tube activation, and the sintered quartz dish is equipped with in the bottom of 1.75 inches silica tubes.Pre-catalyst is loaded on the dish, with dry air with about 1.6-1.8 standard cubic foot/hour linear velocity upwards blow over this dish.Open all electric furnaces around the silica tube, make temperature rise to 600 ℃ of calcinings 3 hours, obtain the activatory chromium-based catalysts with 400 ℃ speed per hour.The content of chromium, titanium, magnesium is listed in table 1 in the catalyst component, and the polymerization evaluation result of catalyzer is listed in table 2.
Embodiment 4
The preparation of titanium magnesium compound
Preparing method with titanium magnesium compound among the embodiment 1 is identical.
The preparation of catalyst component
10g silica gel A (W.R.Grece & Co.-Com, 955, pore volume is about 1.1-1.8cm
3/ g, surface-area is about 245-375m
2/ g), successively adding and containing 1.9g titanium magnesium compound [Ti after 4 hours 200 ℃ of dryings under the nitrogen fluidisation
2(OC
2H
5)
2Cl]
2Mg
2Cl
2Aqueous isopropanol flood with the aqueous isopropanol that contains the 2.38g chromium acetylacetonate, after Virahol is evaporated, obtain containing the pre-catalyst of chromium.Pre-catalyst is placed 1.75 inches silica tube activation, and the sintered quartz dish is equipped with in the bottom of 1.75 inches silica tubes.Pre-catalyst is loaded on the dish, with dry air with about 1.6-1.8 standard cubic foot/hour linear velocity upwards blow over this dish.Open all electric furnaces around the silica tube, make temperature rise to 600 ℃ of calcinings 3 hours, obtain the activatory chromium-based catalysts with 400 ℃ speed per hour.The content of chromium, titanium, magnesium is listed in table 1 in the catalyst component, and the polymerization evaluation result of catalyzer is listed in table 2.
Comparative Examples 1
10g silica gel A (W.R.Grece & Co.-Com, 955, pore volume is about 1.1-1.8cm
3/ g, surface-area is about 245-375m
2/ g) under the nitrogen fluidisation 200 ℃ of dryings 4 hours, add the aqueous isopropanol that contains the 0.75g chromium acetylacetonate then and flood, after Virahol is evaporated, obtain containing the pre-catalyst of chromium.Pre-catalyst is placed 1.75 inches silica tube activation, and the sintered quartz dish is equipped with in the bottom of 1.75 inches silica tubes.Catalyzer is loaded on the dish, with dry air with about 1.6-1.8 standard cubic foot/hour linear velocity upwards blow over this dish.Open all electric furnaces around the silica tube, make temperature rise to 600 ℃ of calcinings 3 hours, obtain the activatory chromium-based catalysts with 400 ℃ speed per hour.Chromium content is about 1wt% in the final control catalyst component, and the content of chromium, titanium, magnesium is listed in table 1 in the catalyst component, and the polymerization evaluation result of catalyzer is listed in table 2.
Comparative Examples 2
(pore volume is about 2.4-3.7cm to 10g silica gel B for PQ Corporation, MS3050
3/ g, surface-area is about 410-620m
2/ g) under the nitrogen fluidisation 200 ℃ of dryings 4 hours, add the aqueous isopropanol that contains the 0.75g chromium acetylacetonate then and flood, after Virahol is evaporated, obtain containing the pre-catalyst of chromium.Pre-catalyst is placed 1.75 inches silica tube activation, and the sintered quartz dish is equipped with in the bottom of 1.75 inches silica tubes.Catalyzer is loaded on the dish, with dry air with about 1.6-1.8 standard cubic foot/hour linear velocity upwards blow over this dish.Open all electric furnaces around the silica tube, make temperature, obtain activatory chromium-based catalysts component with per hour 600 ℃ of calcinings of speed 3 hours of 400 ℃.Chromium content is about 1wt% in the final control catalyst component, and the content of chromium, titanium, magnesium is listed in table 1 in the catalyst component, and the polymerization evaluation result of catalyzer is listed in table 2.
Comparative Examples 3
The catalyst component preparation method carries out according to embodiment among the Chinese patent CN 1,655,533 1, adopts twice-aged and uses spraying drying, and the gained catalyst component uses the polyreaction evaluation method described in the present invention to estimate.
Comparative Examples 4
The catalyst component preparation method carries out according to embodiment among the Chinese patent CN 1,471,431 3, and by silicon oxide and the cogelled carrier that forms catalyst system of magnesium compound, the gained catalyzer uses the polyreaction evaluation method described in the present invention to estimate.
Vinyl polymerization:
The catalyst component of the foregoing description is carried out vinyl polymerization respectively.The polyreaction evaluation is carried out in one 2 liters autoclave, and the speed of stirring is 450rmp, and reaction kettle has the stainless steel chuck, and the liquid medium in the chuck is control reaction temperature accurately.After fully replacing with high purity nitrogen, add 1 liter purifying hexane under a little more than atmospheric condition, the triethyl aluminium solution and the ingredient of solid catalyst that add then; Add an amount of hydrogen, the temperature of system is raised to 80 ℃, feed ethene at last and make the pressure in the still reach 10.0atm; Keep the constant reaction of stagnation pressure one hour, after the finishing polymerization, stop to feed ethene; After the slow release of reaction kettle, Vilaterm is separated from hexane, carried out at last weighing after the drying.Polymerization activity is used the per hour polymkeric substance total amount (gPE/gCat.hr) of every gram Catalyst Production, and the polymerization result of catalyst component is listed in the table 1.
By above-mentioned polymerization procedure the ingredient of solid catalyst in embodiment and the Comparative Examples is carried out vinyl polymerization respectively, polymerization result is listed in table 2.
The content of Ti, Mg, Cr in table 1. catalyzer
| Catalyzer | Ti(wt％) | Mg(wt％) | Cr(wt％) |
| Embodiment 1 | 4.2 | 1.1 | 1.1 |
| Comparative Examples 1 | 0 | 0 | 1.2 |
| Embodiment 2 | 4.3 | 1.2 | 1.0 |
| Comparative Examples 2 | 0 | 0 | 0.9 |
| Embodiment 3 | 2.5 | 0.6 | 0.5 |
| Embodiment 4 | 2.2 | 0.5 | 3.2 |
| Comparative Examples 3 | 4.6 | 0 | 1.1 |
| Comparative Examples 4 | 0 | 4.5 | 0.9 |
The evaluation result of table 2. catalyzer
| Catalyzer | Active (gPE/gCat.hr) | Density (cm 3/g) | MI 2.16 (g/10min) | MI 21.6 (g/10min) | MI 21.6/MI 2.16 |
| Embodiment 1 | 523 | 0.946 | 0.25 | 25.3 | 101 |
| Comparative Examples 1 | 367 | 0.951 | 0.26 | 22.1 | 85 |
| Embodiment 2 | 560 | 0.948 | 0.24 | 28.3 | 118 |
| Comparative Examples 2 | 410 | 0.952 | 0.19 | 14.4 | 76 |
| Embodiment 3 | 320 | 0.947 | 0.23 | 18.4 | 80 |
| Embodiment 4 | 356 | 0.949 | 0.23 | 20.8 | 90 |
| Comparative Examples 3 | 420 | 0.949 | 0.26 | 23.7 | 91 |
| Comparative Examples 4 | 440 | 0.952 | 0.28 | 23.5 | 84 |
From table 2, can find out; The introducing of titanium magnesium compound has improved activity of such catalysts and melting index; The polyvinyl resin shear loading (HLMI/MI) of preparation is bigger; Just show polymkeric substance flowing better under stress, and required character in these many just extruding shaping technique (like film forming and blowing) shows also that simultaneously polymkeric substance has wider molecular weight distribution.The blowing performance of resin has obtained very big improvement, and the tear resistance of the film of blowing is better.
Claims (7)
1. one kind is used for the ethylene polymerization catalysts component; This component is as carrier with oxide compound; Titanium magnesium compound and chromium cpd load on the carrier jointly, and wherein chromium content is 0.1-10wt%, and titanium content is 0.1-12wt%; Mg content is 0.05-10wt%, and described oxide carrier is a kind of in aluminum oxide, silicon-dioxide, titanium oxide, boron oxide and the zirconium white or their mixture; The molecular formula of described titanium magnesium compound is [Ti
2(OC
2H
5)
2Cl]
2Mg
2Cl
2Described chromium cpd is the water-soluble or oil-soluble chromium cpd that contains that can be transformed into chromic oxide through overactivation.
2. the ethylene polymerization catalysts component that is used for according to claim 1, wherein said water miscible chromium cpd are chromium trioxide, chromium acetate, chromium nitrate or their crystalline hydrate or their mixture; Oil-soluble chromium cpd is tertiary butyl chromate, two luxuriant chromium or Acetyl Acetone acid chromium.
3. any one described preparation method who is used for the ethylene polymerization catalysts component of claim 1～2, it may further comprise the steps:
(1) 100～250 ℃ of following drying treatment oxide carrier 1～10 hour;
(2) the titanium magnesium compound solution is contacted with the oxide carrier that step (1) obtains with chromium cpd solution, wherein the solvent phase in titanium magnesium compound solution and the chromium cpd solution is same, and solvent is C
4～C
20Alkane or C
1～C
20Alcohol, the weight ratio of carrier and Ti are 10: 1～1000: 1, and the weight ratio of carrier and chromium is 10: 1～1000: 1, remove subsequently and desolvate, and obtain the pre-catalyst component of load chromium;
The pre-catalyst component of the chromium of load that (3) step (2) is obtained in air, 400～1000 ℃ down calcining obtain catalyst component after 1-10 hour.
4. the preparation method who is used for the ethylene polymerization catalysts component according to claim 3, wherein the solvent described in the step (2) is C
4～C
8Alkane or C
1～C
8Alcohol.
5. the preparation method who is used for the ethylene polymerization catalysts component according to claim 3, wherein the calcining temperature in the step (3) is 600～800 ℃.
6. one kind is used for ethylene polymerization catalysts, comprises following component:
(1) the described ethylene polymerization catalysts component that is used for of one of claim 1～2;
(2) promotor is the mixture of one or more compounds in the organometallic compound of first, second and third or four main groups or second transition group in the periodic table of elements; The mol ratio of organometallic compound and chromium is 0.1: 1～100: 1.
7. will be according to right with regard to the 6 described ethylene polymerization catalysts that are used for, wherein the mol ratio of promotor organometallic compound and chromium is 0.5: 1～50: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100788822A CN101824104B (en) | 2009-03-05 | 2009-03-05 | Catalyst component for vinyl polymerization and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100788822A CN101824104B (en) | 2009-03-05 | 2009-03-05 | Catalyst component for vinyl polymerization and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101824104A CN101824104A (en) | 2010-09-08 |
| CN101824104B true CN101824104B (en) | 2012-03-07 |
Family
ID=42688287
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100788822A Active CN101824104B (en) | 2009-03-05 | 2009-03-05 | Catalyst component for vinyl polymerization and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101824104B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103772538B (en) * | 2012-10-19 | 2016-08-17 | 中国石油化工股份有限公司 | A kind of catalytic component for vinyl polymerization and preparation method thereof |
| CN103772539A (en) * | 2012-10-19 | 2014-05-07 | 中国石油化工股份有限公司 | Catalyst for ethylene polymerization, preparation method and application thereof |
| CN106317267B (en) * | 2015-06-16 | 2018-12-28 | 中国石油化工股份有限公司 | A kind of catalytic component and preparation method thereof for vinyl polymerization |
| CN108690151B (en) * | 2017-04-07 | 2020-12-18 | 中国石油化工股份有限公司 | Catalyst system for olefin polymerization and olefin polymerization method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4363746A (en) * | 1979-05-29 | 1982-12-14 | Phillips Petroleum Company | Composition of matter and method of preparing same, catalyst, method of producing the catalyst and polymerization process employing the catalyst |
| US4801572A (en) * | 1987-05-28 | 1989-01-31 | Mobil Oil Corporation | Modified chromium-containing catalyst composition for polymerizing alpha-olefins and method of preparing same |
| CN1624007A (en) * | 2004-11-04 | 2005-06-08 | 沈阳化工学院 | Catalyst system for the polymerization or copolymerization of ethylene and its use |
| CN101173013A (en) * | 2006-10-31 | 2008-05-07 | 中国石油化工股份有限公司 | Load titanized chromium catalyst, producing method and application in polymerization of ethylene of the same |
-
2009
- 2009-03-05 CN CN2009100788822A patent/CN101824104B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4363746A (en) * | 1979-05-29 | 1982-12-14 | Phillips Petroleum Company | Composition of matter and method of preparing same, catalyst, method of producing the catalyst and polymerization process employing the catalyst |
| US4801572A (en) * | 1987-05-28 | 1989-01-31 | Mobil Oil Corporation | Modified chromium-containing catalyst composition for polymerizing alpha-olefins and method of preparing same |
| CN1624007A (en) * | 2004-11-04 | 2005-06-08 | 沈阳化工学院 | Catalyst system for the polymerization or copolymerization of ethylene and its use |
| CN101173013A (en) * | 2006-10-31 | 2008-05-07 | 中国石油化工股份有限公司 | Load titanized chromium catalyst, producing method and application in polymerization of ethylene of the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101824104A (en) | 2010-09-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100601257B1 (en) | Catalyst composition for monomer polymerization | |
| US6107230A (en) | Compositions that can produce polymers | |
| US7504463B2 (en) | Production of broad molecular weight polyethylene | |
| CN101173013B (en) | Load titanized chromium catalyst, producing method and application in polymerization of ethylene of the same | |
| CZ122296A3 (en) | Ethylene polymer and process for preparing thereof | |
| EP1569969B1 (en) | Supported chromium catalyst and its use for preparing homopolymers and copolymers of ethylene | |
| CN103626899A (en) | Inorganic carrier supported chrome-vanadium double-center composite catalyst as well as preparation method and application thereof | |
| CN101134790B (en) | Catalyst component for ethylene polymerization reaction and catalyst | |
| CN106317267B (en) | A kind of catalytic component and preparation method thereof for vinyl polymerization | |
| CN101824104B (en) | Catalyst component for vinyl polymerization and preparation method thereof | |
| CN105566521A (en) | Chromium-based polyethylene catalyst and preparation method thereof | |
| CN102432711A (en) | Catalyst component for ethylene polymerization and preparation method thereof | |
| CN102453154A (en) | Organic chromium catalyst for ethylene polymerization and preparation method thereof | |
| CN103772540A (en) | Loaded chromium base catalyst, preparation method and application thereof | |
| CN106467588B (en) | A kind of catalytic component, preparation method and application for vinyl polymerization | |
| CN106467583B (en) | A kind of catalytic component, preparation method and application for vinyl polymerization | |
| CN106467589B (en) | A kind of catalytic component, preparation method and application for vinyl polymerization | |
| CN102286123A (en) | catalyst component of ethylene polymerization and preparation method thereof | |
| CN103772538A (en) | Catalyst component for ethylene polymerization, and preparation method thereof | |
| CN108976322A (en) | Modified Chromium-polyethylencatalyst catalyst and preparation method thereof | |
| CN108976327A (en) | The preparation method of film high-density polyethylene resin | |
| CN108690150A (en) | A kind of catalyst system and olefine polymerizing process for olefinic polymerization | |
| CN107434831B (en) | Chromium-based catalyst component, preparation method thereof and chromium-based catalyst | |
| CN103772539A (en) | Catalyst for ethylene polymerization, preparation method and application thereof | |
| CN108690151B (en) | Catalyst system for olefin polymerization and olefin polymerization method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |