CN1326886C - 聚烯烃生产方法 - Google Patents
聚烯烃生产方法 Download PDFInfo
- Publication number
- CN1326886C CN1326886C CNB998168815A CN99816881A CN1326886C CN 1326886 C CN1326886 C CN 1326886C CN B998168815 A CNB998168815 A CN B998168815A CN 99816881 A CN99816881 A CN 99816881A CN 1326886 C CN1326886 C CN 1326886C
- Authority
- CN
- China
- Prior art keywords
- alkene
- catalyst
- olefin polymerization
- polymerisation medium
- aluminium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims abstract description 86
- 229920000098 polyolefin Polymers 0.000 title description 14
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 83
- 150000001336 alkenes Chemical class 0.000 claims abstract description 76
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims abstract description 74
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052782 aluminium Inorganic materials 0.000 claims description 80
- -1 nickel alkylated salicylamide aldehyde Chemical class 0.000 claims description 74
- 239000004411 aluminium Substances 0.000 claims description 70
- 239000003054 catalyst Substances 0.000 claims description 45
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 39
- 239000010936 titanium Substances 0.000 claims description 36
- 239000001272 nitrous oxide Substances 0.000 claims description 35
- 230000003068 static effect Effects 0.000 claims description 35
- 229910052719 titanium Inorganic materials 0.000 claims description 32
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 31
- 238000006555 catalytic reaction Methods 0.000 claims description 30
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 28
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- 239000011954 Ziegler–Natta catalyst Substances 0.000 claims description 20
- 239000000377 silicon dioxide Substances 0.000 claims description 19
- 150000005826 halohydrocarbons Chemical class 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 239000011651 chromium Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 235000012239 silicon dioxide Nutrition 0.000 claims description 15
- 229960001866 silicon dioxide Drugs 0.000 claims description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 14
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 14
- 229910052804 chromium Inorganic materials 0.000 claims description 14
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 11
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 230000000737 periodic effect Effects 0.000 claims description 10
- 229910052726 zirconium Inorganic materials 0.000 claims description 10
- 229910052720 vanadium Inorganic materials 0.000 claims description 9
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 8
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 claims description 8
- 229910000071 diazene Inorganic materials 0.000 claims description 8
- 229960001701 chloroform Drugs 0.000 claims description 7
- 238000009826 distribution Methods 0.000 claims description 7
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 6
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 claims description 6
- 235000019404 dichlorodifluoromethane Nutrition 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- 150000001768 cations Chemical class 0.000 claims description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 3
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 claims description 3
- XWCDCDSDNJVCLO-UHFFFAOYSA-N Chlorofluoromethane Chemical compound FCCl XWCDCDSDNJVCLO-UHFFFAOYSA-N 0.000 claims description 3
- 239000004338 Dichlorodifluoromethane Substances 0.000 claims description 3
- AFYPFACVUDMOHA-UHFFFAOYSA-N chlorotrifluoromethane Chemical compound FC(F)(F)Cl AFYPFACVUDMOHA-UHFFFAOYSA-N 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 3
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 4
- 125000004432 carbon atom Chemical group C* 0.000 claims 2
- 229920001519 homopolymer Polymers 0.000 abstract description 3
- 239000002685 polymerization catalyst Substances 0.000 abstract description 2
- 229960001730 nitrous oxide Drugs 0.000 abstract 2
- 235000013842 nitrous oxide Nutrition 0.000 abstract 2
- 150000001875 compounds Chemical class 0.000 description 33
- 238000005660 chlorination reaction Methods 0.000 description 20
- 239000007789 gas Substances 0.000 description 19
- 229910052723 transition metal Inorganic materials 0.000 description 19
- 150000003624 transition metals Chemical class 0.000 description 19
- 125000002524 organometallic group Chemical group 0.000 description 18
- 239000000126 substance Substances 0.000 description 16
- 239000004698 Polyethylene Substances 0.000 description 15
- 229920000573 polyethylene Polymers 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 14
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 13
- 239000002245 particle Substances 0.000 description 13
- 125000003118 aryl group Chemical group 0.000 description 11
- 238000005984 hydrogenation reaction Methods 0.000 description 10
- 125000003963 dichloro group Chemical group Cl* 0.000 description 9
- 238000005243 fluidization Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 7
- 150000001639 boron compounds Chemical class 0.000 description 7
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- 229910052749 magnesium Inorganic materials 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 239000000523 sample Substances 0.000 description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 239000011324 bead Substances 0.000 description 6
- 229910052796 boron Inorganic materials 0.000 description 6
- VPCAAUUIFCAFRZ-UHFFFAOYSA-N butylalumane Chemical compound CCCC[AlH2] VPCAAUUIFCAFRZ-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- 150000001721 carbon Chemical group 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 5
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 5
- KEVMYFLMMDUPJE-UHFFFAOYSA-N 2,7-dimethyloctane Chemical group CC(C)CCCCC(C)C KEVMYFLMMDUPJE-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 238000012685 gas phase polymerization Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 150000002899 organoaluminium compounds Chemical class 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 4
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 4
- 238000004846 x-ray emission Methods 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- MGDOJPNDRJNJBK-UHFFFAOYSA-N ethylaluminum Chemical compound [Al].C[CH2] MGDOJPNDRJNJBK-UHFFFAOYSA-N 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 150000002902 organometallic compounds Chemical class 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 2
- RBSJZRXTFLJSDW-UHFFFAOYSA-N 1$l^{2}-arsole Chemical compound [As]1C=CC=C1 RBSJZRXTFLJSDW-UHFFFAOYSA-N 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical group ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- DJMUYABFXCIYSC-UHFFFAOYSA-N 1H-phosphole Chemical compound C=1C=CPC=1 DJMUYABFXCIYSC-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- NCHZQHKXEUBHOH-UHFFFAOYSA-M C(C)[Al+]CC.I(=O)(=O)[O-] Chemical compound C(C)[Al+]CC.I(=O)(=O)[O-] NCHZQHKXEUBHOH-UHFFFAOYSA-M 0.000 description 2
- TZSUMGXYCFAANX-UHFFFAOYSA-N C1(C=CC=C1)[Cr] Chemical compound C1(C=CC=C1)[Cr] TZSUMGXYCFAANX-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000003851 azoles Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 229920006178 high molecular weight high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 238000005304 joining Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 125000005062 perfluorophenyl group Chemical group FC1=C(C(=C(C(=C1F)F)F)F)* 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 description 1
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 1
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 1
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 1
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical group C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 1
- KLAWFKRMCIXRFS-UHFFFAOYSA-N 5-ethenylidenebicyclo[2.2.1]hept-2-ene Chemical group C1C2C(=C=C)CC1C=C2 KLAWFKRMCIXRFS-UHFFFAOYSA-N 0.000 description 1
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- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- BYMXSHDQPNKPQG-UHFFFAOYSA-N CCCCC1=CC(C)([Zr])C=C1 Chemical compound CCCCC1=CC(C)([Zr])C=C1 BYMXSHDQPNKPQG-UHFFFAOYSA-N 0.000 description 1
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- 239000005977 Ethylene Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
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- 239000004902 Softening Agent Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical class [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
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- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
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- AZWXAPCAJCYGIA-UHFFFAOYSA-N bis(2-methylpropyl)alumane Chemical compound CC(C)C[AlH]CC(C)C AZWXAPCAJCYGIA-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
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- SHOVVTSKTTYFGP-UHFFFAOYSA-L butylaluminum(2+);dichloride Chemical compound CCCC[Al](Cl)Cl SHOVVTSKTTYFGP-UHFFFAOYSA-L 0.000 description 1
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- 125000002091 cationic group Chemical group 0.000 description 1
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- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
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- 150000002576 ketones Chemical class 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
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- 239000000314 lubricant Substances 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229960001708 magnesium carbonate Drugs 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
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- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
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- 238000012544 monitoring process Methods 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- RBLGTYCOUOIUNY-UHFFFAOYSA-L octylaluminum(2+);dichloride Chemical compound CCCCCCCC[Al](Cl)Cl RBLGTYCOUOIUNY-UHFFFAOYSA-L 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- XIPFMBOWZXULIA-UHFFFAOYSA-N pivalamide Chemical compound CC(C)(C)C(N)=O XIPFMBOWZXULIA-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910002028 silica xerogel Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000007970 thio esters Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical group CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 1
- RGGPNXQUMRMPRA-UHFFFAOYSA-N triethylgallium Chemical compound CC[Ga](CC)CC RGGPNXQUMRMPRA-UHFFFAOYSA-N 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000012725 vapour phase polymerization Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/901—Monomer polymerized in vapor state in presence of transition metal containing catalyst
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Polyethers (AREA)
Abstract
一种生产烯烃均聚物和共聚物的方法,涉及烯烃和/或烯烃与至少一种或多种其它烯烃在聚合条件下与烯烃聚合催化剂和数量足以减少聚合介质中静电荷的一氧化二氮进行接触。还提供一种通过加入一氧化二氮来减少烯烃聚合中静电荷的方法。
Description
技术领域
本发明涉及一种采用适合烯烃聚合的催化剂和用量足以减少聚合反应器内静电荷的一氧化二氮来生产聚烯烃的聚合方法。一氧化二氮作为催化剂的应用还提供适合模塑和薄膜应用的聚烯烃。
发明背景
诸如聚乙烯之类的聚烯烃是众所周知的,应用于许多领域。特别是线型聚乙烯聚合物,具有区别于其它聚乙烯聚合物例如通常被称之为LDPE(低密度聚乙烯)的支化乙烯均聚物的性质。这些性质中的某些描述在Anderson等人的美国专利4,076,698中。
生产聚乙烯和聚丙烯聚合物尤其有用的聚合介质是气相法。其例子可见诸于美国专利3,709,853、4,003,712、4,011,382、4,302,566、4,543,399、4,882,400、5,352,749和5,541,270,以及加拿大专利991,798和比利时专利839,380。
已知有各种各样用于烯烃聚合的催化剂。下面是此类催化剂的例子:
1.氧化铬催化剂,使乙烯聚合成为宽分子量分布的高分子量高密度聚乙烯(HDPE),典型的此种催化剂基于Cr(6+),并承载在载体上。
2.有机铬催化剂,例如双(三苯基甲硅烷基)铬酸酯,承载于二氧化硅上并以有机铝化合物予以活化,以及载于二氧化硅上的双(环戊二烯基)铬。
3.齐格勒-纳塔催化剂,其典型组成包括一种过渡金属组分和一种有机金属助催化剂,而典型的助催化剂是有机铝化合物。
4.一种使烯烃聚合成为分子量分布(MWD)介于1~2.5的烯烃均聚物和共聚物的烯烃聚合催化剂。
5.金属茂催化剂,典型组成为:具有至少一个取代或未取代的环戊二烯基或环戊二烯基部分的过渡金属,以及有机金属助催化剂,后者的典型是烷基铝氧烷如甲基铝氧烷或者芳基取代的硼化合物。
6.美国专利5,777,120中所述类型的族13催化剂,例如阳离子铝烷基酰胺化(amidinate)络合物并配以有机金属助催化剂,其中典型的助催化剂是烷基铝氧烷如甲基铝氧烷或者芳基取代的硼化合物。
7.美国专利5,866,663中描述的那种类型催化剂,例如阳离子镍烷基二亚胺络合物并配以有机金属助催化剂,其中典型的助催化剂是烷基铝氧烷如甲基铝氧烷或者芳基取代的硼化合物。
8.《有机金属(Organometallics)》,1998,卷17,pp.3149~3151,中描述的那种类型催化剂,例如中性镍烷基水杨醛二亚氨基(salicylaldiminato)络合物。
9.《美国化学学会会志(Journal of the American ChemicalSociety)》,1998,卷120,pp.7143~7144,中描述的那种类型催化剂,例如阳离子铁烷基吡啶二亚胺络合物并配以有机金属助催化剂,其中典型的助催化剂是烷基铝氧烷如甲基铝氧烷或者芳基取代的硼化合物。
10.《美国化学学会会志(Journal of the American ChemicalSociety)》,1996,卷118,pp.10008~10009,中描述的那种类型催化剂,例如阳离子钛烷基二酰胺络合物并配以有机金属助催化剂,其中典型的助催化剂是烷基铝氧烷如甲基铝氧烷或者芳基取代的硼化合物。
上述催化剂由,或者可以由惰性多孔颗粒载体承载着。
聚合过程,特别是气相聚合过程中普遍遇到的一个问题就是附聚物的生成。附聚物可在各种各样的部位生成,例如聚合反应器和气流循环用的管道中。由于附聚物的生成,可能不得不将反应器停下来。
当聚合反应器内生成附聚物时,会出现许多不利的效应。例如,附聚物会堵塞聚合物出料系统从而中断聚合物从聚合反应器的排出。再者,倘若附聚物下落并覆盖流化栅的一部分,就可能发生流化效率的损失。这会导致更大附聚物的生成,最终可导致整个流化床的损失。不论出现哪种情况,可能都不得不停止反应器。
现已发现附聚物的生成可能是由于聚合介质中存在非常细小的聚合物颗粒所致。这些细小聚合物颗粒的存在又可能是细小催化剂颗粒在聚合介质中的引入或者催化剂破碎的结果。
这些细颗粒据信将沉积并静电粘附在聚合反应器以及与气流循环相关的设备,如热交换器的内壁上。如果细颗粒保持其活性,则聚合反应将继续进行,于是颗粒尺寸将长大,从而导致附聚物的生成。这些附聚物当在聚合反应器内生成时,往往呈片状形式。
为解决附聚物在气相聚合过程中形成的问题已提出若干解决方案。这些解决方案包括细聚合物颗粒的失活、控制催化剂活性以及减少静电荷。下面是范例解决方案。
欧洲专利申请0359444A1描述了在聚合反应器中引入少量活性缓聚剂以使聚合速率或在所生产聚合物中过渡金属的含量基本上保持恒定。据说此方法会生产出不形成附聚物的聚合物。
美国专利4,739,015中描述了使用气体含氧化合物或液体或固体含活泼氢的化合物来防止聚合物自身粘结或粘结在聚合设备的内壁上。
在美国专利4,803,251中描述了利用一组化学添加剂来减少板结的一种方法,其中添加剂会在反应器中产生正负两种电荷,并且被进料到反应器中的用量为每百万分之几(ppm)部分/单体部分,以防止形成不希望的正或负电荷。
可以用来中和流化床反应器中静电荷的其它方法和其它添加剂见于美国专利4,792,592、4,803,251、4,855,370、4,876,320、5,162,463、5,194,526和5,200,477中。
用来减少或消除静电荷的其它方法包括(1)在流化床中安装接地装置,(2)通过放电作用将气体或颗粒电离,以产生可以中和颗粒上静电荷的离子,以及(3)使用放射源来产生辐射,该辐射能够生成用来中和颗粒上静电荷的离子。
因此希望提供一种生产聚烯烃,特别是聚乙烯的方法,其中与静电荷相关的问题得以减少。
发明概述
本发明的聚合方法包括:向包含一种烯烃,特别是乙烯,以及任选的至少一种或多种其它烯烃的聚合介质中引入烯烃聚合催化剂和一氧化二氮(N2O),后者的用量足以将聚合介质中的静电荷降低到低于同一聚合方法但不用一氧化二氮时将出现的水平。
本发明还涉及一种减少烯烃,特别是乙烯,以及任选的至少一种或多种其它烯烃在聚合介质,特别是气相中进行聚合时的静电荷的方法,该方法在烯烃聚合催化剂和一氧化二氮(N2O)存在下进行,后者的用量足以将聚合介质中的静电荷降低到低于同一聚合方法但不用一氧化二氮时将出现的水平。
所有在此提及的周期表中的各族元素参照在“《化学与工程报道(Chemical and Engineering News)》”,63(5),27,1985中发表的元素周期表。在此表中,族的编号是从1到18。
发明详述
本发明聚合方法包括:向包含一种烯烃,特别是乙烯,以及任选的至少一种或多种其它烯烃的聚合介质中引入烯烃聚合催化剂和一氧化二氮(N2O),后者的用量足以将聚合介质中的静电荷降低到低于同一聚合方法但不用一氧化二氮时将出现的水平。
本发明还涉及一种减少烯烃,特别是乙烯,以及任选的至少一种或多种其它烯烃在聚合介质,特别是气相中进行聚合时的静电荷的方法,该方法在烯烃聚合催化剂和一氧化二氮(N2O)存在下进行,后者的用量足以将聚合介质中的静电荷降低到低于同一聚合方法但不用一氧化二氮时将出现的水平。
任选地,可在聚合介质中加入卤代烃。任何卤代烃均可用于本发明方法中。希望的话,可以使用一种以上的卤代烃。此类卤代烃的典型是一卤和多卤代饱和或不饱和1~12个碳原子的脂族、脂环族或芳族烃。本发明方法优选使用二氯甲烷、氯仿、四氯化碳、氯氟甲烷、氯二氟甲烷、二氯二氟甲烷、氟二氯甲烷、氯三氟甲烷、氟三氯甲烷和1,2-二氯乙烷。最优选用于本发明方法的是氯仿。
在本发明中,任何能使烯烃聚合的催化剂均可使用。优选的是,该烯烃聚合催化剂包含至少一种选自本文规定的元素周期表,族3、4、5、6、7、8、9、10、11、12和/或13的金属。该烯烃聚合催化剂可以是中性或阳离子的。烯烃聚合催化剂的范例金属是钛、锆、钒、铁、铬、镍和铝。
此种聚合催化剂的例子是:
1.任何含族6元素的化合物。优选的是含铬化合物。例子是使乙烯聚合成为宽分子量分布的高分子量高密度聚乙烯(HDPE)的氧化铬催化剂。典型的这类催化剂基于Cr(6+)并且承载在载体上。例子还有有机铬催化剂,例如双(三苯基甲硅烷基)铬酸酯,载于二氧化硅上并以有机铝化合物予以活化,以及载于二氧化硅上的双(环戊二烯基)铬。
2.齐格勒-纳塔催化剂,其典型组成包括一种过渡金属组分和一种有机金属助催化剂,而典型的助催化剂是有机铝化合物。
3.一种使烯烃聚合成为分子量分布(MWD)介于1~2.5的烯烃共聚体的烯烃聚合催化剂。
4.金属茂催化剂,其组成为:一种过渡金属组分,具有至少一个选自取代或未取代环戊二烯基、取代或未取代戊二烯基、取代或未取代吡咯、取代或未取代phosphole、取代或未取代arsole、取代或未取代boratabenzene以及取代或未取代碳硼烷的部分,以及一种有机金属助催化剂,后者的典型是烷基铝氧烷如甲基铝氧烷或者芳基取代的硼化合物。
5.任何含族13元素的化合物。优选含铝化合物。例子是美国专利5,777,120中所述类型的催化剂,例如阳离子铝烷基酰胺化(amidinate)络合物并配以有机金属助催化剂,其中典型的助催化剂是烷基铝氧烷如甲基铝氧烷或者芳基取代的含硼化合物。
6.任何含族10元素的化合物。优选含镍化合物。例子是美国专利5,866,663中描述的那种类型催化剂,例如阳离子镍烷基二亚胺络合物并配以有机金属助催化剂,其中典型的助催化剂是烷基铝氧烷如甲基铝氧烷或者芳基取代的含硼化合物。另一例子是《有机金属(Organometallics)》,1998,卷17,pp.3149~3151,中描述的那种类型催化剂,例如中性镍烷基水杨醛二亚氨基(salicylaldiminato)络合物。
7.任何含族8元素的化合物。优选含铁化舍物。例子是《美国化学学会会志(Journal of the American Chemical Society)》,1998,卷120,pp.7143~7144,中描述的那种类型催化剂,例如阳离子铁烷基吡啶二亚胺络合物并配以有机金属助催化剂,其中典型的助催化剂是烷基铝氧烷如甲基铝氧烷或者芳基取代的含硼化合物。
8.任何含族4元素的化合物。优选含钛和含锆的化合物。例子是《美国化学学会会志(Journal of the American ChemicalSociety)》,1996,卷118,pp.10008~10009,中描述的那种类型催化剂,例如阳离子钛烷基二酰胺络合物并配以有机金属助催化剂,其中典型的助催化剂是烷基铝氧烷如甲基铝氧烷或者芳基取代的含硼化合物。
上述催化剂由,或者可以由惰性多孔颗粒载体承载着。
上述烯烃聚合催化剂可按任何方式引入到本发明方法中。例如,催化剂各组分可以溶液、淤浆或干燥自由流动粉末的形式直接引入到聚合介质中。该催化剂,若需要助催化剂的话,则可在加入到聚合介质中之前预混合形成一种活化催化剂,或者诸组分可分别加入到聚合介质中,或者诸组分可预混合然后与一种或多种烯烃进行接触以生成预聚物,然后以预聚物形式加入到聚合介质中。当催化剂组分在引入到反应器之前进行预混合时,可在催化剂中加入任何电子给体化合物以控制催化剂的活性水平。再有,在如上所述烯烃聚合催化剂存在下进行聚合反应期间,可向其中加入附加有机金属化合物。该附加有机金属化舍物可与作为助催化剂使用的相同或不同。
烯烃聚合催化剂组分中任何一个或全部可由载体承载着。载体可以是任何粒状有机或无机材料。优选的是,载体颗粒的粒度不大于约200μm(直径)。载体材料最优选的粒度可通过实验轻易地确定。优选的是,载体的平均粒度介于5~200μm(直径),更优选10~150μm,最优选20~100μm。
合适的无机载体的例子包括金属氧化物、金属氢氧化物、金属卤化物或其它金属盐,例如硫酸盐、碳酸盐、磷酸盐、硝酸盐和硅酸盐。适合在这里使用的无机载体例子是元素周期表中族1和2的金属的化合物,例如钠或钾盐,以及镁或钙的氧化物或盐,例如钠、钾、镁或钙的氯化物、硫酸盐、碳酸盐、磷酸盐或硅酸盐,以及例如镁或钙的氧化物或氢氧化物。适合使用的还有无机氧化物如二氧化硅、氧化钛、氧化铝、氧化锆、氧化铬、氧化硼、硅烷化二氧化硅、二氧化硅水凝胶、二氧化硅干凝胶、二氧化硅气凝胶,以及混合氧化物如滑石、二氧化硅/氧化铬、二氧化硅/氧化铬/氧化钛、二氧化硅/氧化铝、二氧化硅/氧化钛、二氧化硅/氧化镁、二氧化硅/氧化镁/氧化钛,磷酸铝凝胶、二氧化硅共凝胶以及诸如此类。无机氧化物可包含少量碳酸盐、硝酸盐、硫酸盐和氧化物,例如碳酸钠、碳酸钾、碳酸钙、碳酸镁、硫酸钠、硫酸铝、硫酸钡、硝酸钾、硝酸镁、硝酸铝、氧化钠、氧化钾和氧化锂。优选载体含有至少一种选自氯化镁、二氧化硅、氧化铝或其混合物的组分作为主要组分。
合适的有机载体的例子包括聚合物,如聚乙烯、聚丙烯、乙烯与α-烯烃的共聚物、聚苯乙烯、官能化聚苯乙烯、聚酰胺和聚酯。
齐格勒-纳塔催化剂在工业上是熟知的。最简单形式的齐格勒-纳塔催化剂由一种含至少一种过渡金属的组分和一种含至少一种有机金属化合物的助催化剂组成。过渡金属组分的金属是选自《化学与工程报道(Chemical and Engineering News)》,63(5),27,1985中发表的元素周期表中族4、5、6、7、8、9和/或10的金属。在该版本中,族的编号从1排到18。此种过渡金属的例子是钛、锆、钒、铬、锰、铁、钴、镍等,及其混合物。在优选的实施方案中,过渡金属选自钛、锆、钒和铬,而在更优选的实施方案中,过渡金属是钛。齐格勒-纳塔催化剂可任选地包含镁和/或氯。此种含镁和氯的催化剂可按照本领域已知的任何方式制备。
本发明方法使用的助催化剂可以是任何有机金属化合物或其混合物,只要它在烯烃聚合中能活化齐格勒-纳塔催化剂中的过渡金属组分。具体地说,与过渡金属组分起反应的有机金属助催化剂化合物包含选自上面所描述的元素周期表中族1、2、11、12、13和/或14的金属。此类金属的例子是锂、镁、铜、锌、硼、硅等,或其混合物。
优选的是,助催化剂是至少一种通式XnER3-n的化合物,
或其混合物,
其中
X是氢、卤素或卤素的混合物,选自氟、氯、溴和碘;
n介于0~2;
E是元素周期表中族13的元素,如硼、铝和镓;以及
R是烃基,含有1~100个碳原子和0~10个氧原子,通过碳或氧键连接到族13元素上。
适合这里使用的R基团的例子是C1-100烷基、C1-100烷氧基、C2-100链烯基、C4-100二烯基、C3-100环烷基、C3-100环烷氧基、C3-100环烯基、C4-100环二烯基、C6-100芳基、C7-100芳烷基、C7-100芳烷氧基以及C7-100烷芳基。R基团的例子还有含1~100个碳原子和1~10个氧原子的烃基。
本发明方法使用的助催化剂的例子,当n=0时,是三甲基铝、三乙基硼烷、三乙基镓烷、三乙基铝、三正丙基铝、三正丁基铝、三正戊基铝、三异戊二烯基铝、三正己基铝、三正庚基铝、三正辛基铝、三异丙基铝、三异丁基铝、三(环己基甲基)铝、二甲基铝的甲醇盐、二甲基铝的乙醇盐、二乙基铝的乙醇盐等。当n=1时,化合物的例子是氯化(二甲基铝)、氯化(二乙基铝)、氯化(二正丙基铝)、氯化(二正丁基铝)、氯化(二正戊基铝)、氯化(二异戊二烯基铝)、氯化(二正己基铝)、氯化(二正庚基铝)、氯化(二正辛基铝)、氯化(二异丙基铝)、氯化(二异丁基铝)、氯化双(环己基甲基)铝、氟化(二乙基铝)、溴化(二乙基铝)、碘化(二乙基铝)、氢化二甲基铝、氢化二乙基铝、氢化二正丙基铝、氢化二正丁基铝、氢化二正戊基铝、氢化二异戊二烯基铝、氢化二正己基铝、氢化二正庚基铝、氢化二正辛基铝、氢化二异丙基铝、氢化二异丁基铝、氢化双(环己基甲基)铝、氯甲基铝的甲醇盐、氯甲基铝的乙醇盐、氯乙基铝的乙醇盐等。当n=2时,化合物的例子是二氯(甲基铝)、二氯(乙基铝)、二氯(正丙基铝)、二氯(正丁基铝)、二氯(正戊基铝)、二氯(异戊二烯基铝)、二氯(正己基铝)、二氯(正庚基铝)、二氯(正辛基铝)、二氯(异丙基铝)、二氯(异丁基铝)、二氯(环己基甲基)铝以及诸如此类。例子还有烷基铝倍半醇盐,例如甲基铝倍半甲醇盐、乙基铝倍半乙醇盐、正丁基铝倍半正丁醇盐以及诸如此类。例子还有烷基铝倍半卤化物,例如甲基铝倍半氯化物、乙基铝倍半氯化物、异丁基铝倍半氯化物、乙基铝倍半氟化物、乙基铝倍半溴化物、乙基铝倍半碘化物以及诸如此类。
作为助催化剂,这里优选使用的是三烷基铝,如三甲基铝、三乙基铝、三正丙基铝、三正丁基铝、三异丁基铝、三正己基铝、三异己基铝、三-2-甲基戊基铝、三正辛基铝、三正癸基铝;以及二烷基铝卤化物,例如氯化(二甲基铝)、氯化(二乙基铝)、氯化(二丁基铝)、氯化(二异丁基铝)、溴化(二乙基铝)和碘化(二乙基铝);以及烷基铝倍半卤化物,例如甲基铝倍半氯化物、乙基铝倍半氯化物、正丁基铝倍半氯化物、异丁基铝倍半氯化物、乙基铝倍半氟化物、乙基铝倍半溴化物以及乙基铝倍半碘化物。
作为助催化剂,这里最优选使用的是三烷基铝,例如三甲基铝、三乙基铝、三正丙基铝、三正丁基铝、三异丁基铝、三正己基铝、三异己基铝、三-2-甲基戊基铝、三正辛基铝;以及二烷基铝卤化物,例如氯化(二甲基铝)、氯化(二乙基铝)、氯化(二丁基铝)、氯化(二异丁基铝);和烷基铝倍半卤化物,例如甲基铝倍半氯化物、乙基铝倍半氯化物、正丁基铝倍半氯化物和异丁基铝倍半氯化物。
上述助催化剂的混合物也可用作这里的助催化剂。
另外,还可在齐格勒-纳塔催化剂中加入任何电子给体。电子给体化合物优选地选自醚、硫醚、酯、硫代酸酯、胺、酰胺、酮、腈、膦、硅烷、酸酐、酰卤、酸酰胺、醛,以及有机酸衍生物。作为电子给体,更优选的是含1~50个碳原子和1~30个杂原子的化合物或其混合物,其中杂原子元素选自元素周期表中族14、15、16和17。
齐格勒-纳塔催化剂可按本领域已知的任何方法制备。该催化剂可采取溶液、淤浆或干燥自由流动粉末的形式。齐格勒-纳塔催化剂的用量为足以生产出要求数量的聚烯烃。
金属茂催化剂在工业上是熟知的,典型地由过渡金属组分和助催化剂构成。过渡金属组分具有至少一个选自取代或未取代环戊二烯基、取代或未取代戊二烯基、取代或未取代吡咯、取代或未取代phosphole、取代或未取代arsole、取代或未取代boratabenzene以及取代或未取代碳硼烷的部分。过渡金属选自元素周期表中族3、4、5、6、7、8、9和10。此类过渡金属的例子是钛、锆、铪、钒、铬、锰、铁、钴、镍等,及其混合物。在优选的实施方案中,过渡金属选自族4、5或6,例如钛、锆、铪、钒和铬,在更优选的实施方案中,过渡金属是钛或锆或其混合物。
金属茂催化剂的助催化剂组分可以是任何化合物或其混合物,只要它在烯烃聚合中能活化金属茂催化剂的过渡金属组分。典型的助催化剂是烷基铝氧烷如甲基铝氧烷(MAO),以及芳基取代的硼化合物,例如,三(全氟苯基)硼烷以及四(全氟苯基)硼酸盐。
有许多参考文献详细描述了金属茂催化剂。例如,金属茂催化剂描述于美国专利4,564,647、4,752,597、5,106,804、5,132,380、5,227,440、5,296,565、5,324,800、5,331,071、5,332,706、5,350,723、5,399,635、5,466,766、5,468,702、5,474,962、5,578,537和5,863,853。
在实施本发明聚合方法时,助催化剂,若使用的话,以足以生成要求聚烯烃的任何用量加入到聚合介质中。助催化剂的优选用量,按照助催化剂与烯烃聚合催化剂的金属组分之间的摩尔比计介于约0.5∶1~约10000∶1。在更优选的实施方案中,助催化剂与金属组分的摩尔比介于约0.5∶1~约1000∶1。
本发明的聚合方法可以采用任何合适的方法来实施,例如,溶液法、淤浆法和气相法。按照本发明用来生产聚烯烃聚合物的一种特别可取的方法是优选采用流化床反应器的气相聚合方法。此类型的反应器以及操作反应器的方法是熟知的并且完整地描述于美国专利3,709,853;4,003,712;4,000,382;4,012,573;4,302,566;4,543,399;4,882,400;5,352,749;5,541,270;加拿大专利991,798和比利时专利839,380。这些专利公开了气相聚合方法,其中的聚合介质或者被机械搅拌或者被气相单体和稀释剂的连续气流所流化。这些专利的全文并入本文作为参考文献。
一般来说,本发明的聚合方法可以以连续气相方法如流化床方法来实施。用于本发明方法的流化床反应器通常包含一个反应区和一个所谓的减速区。反应区包含一个由生长中的聚合物颗粒、形成的聚合物颗粒和少量催化剂颗粒组成的床,这些颗粒被气相单体和稀释剂的连续气流所流化,气流经过反应区以除去聚合中的热量。任选地,一些循环气体可以被冷却和压缩以形成在重新进入反应区时能提高循环气流散热能力的液体。合适的气流速度可以通过简单的实验容易地确定。使气相单体补充到循环气流中的速率等于在颗粒状聚合物产物和与其相关的单体从反应器中排出的速率,并调节流经反应器的气体组成以使反应区内的气体组成基本保持稳定状态。离开反应区的气体流经减速区,在此夹带的颗粒被除去。较细小的夹带颗粒和粉尘可以在旋风除尘器和/或精制过滤器中除去。气体流经热交换器,在其中除去聚合热,在压缩机中压缩,然后返回到反应区。
更详细地说,在这里流化床方法的反应器温度范围是从约30℃到约150℃。考虑到反应器中聚合物产物的烧结温度,通常将反应器的操作温度调节到可行的最高温度。
本发明的方法适合于生产烯烃,特别是乙烯的均聚物,和/或烯烃,特别是乙烯和至少一种或多种其它烯烃的共聚物,三元共聚物之类。优选的烯烃是α-烯烃。这些烯烃,举例来说,可以含有2-16个碳原子。在这里采用本发明的方法特别优选制备的是聚乙烯。这些聚乙烯优选是乙烯的均聚物以及乙烯和至少一种α-烯烃的共聚体,其中乙烯含量是所包括的总单体重量的至少大约50%。可以在此使用的烯烃的例子是乙烯、丙烯、1-丁烯、1-戊烯、1-己烯、1-庚烯、1-辛烯、4-甲基-1-戊烯、1-癸烯、1-十二碳烯、1-十六碳烯之类。在此还可以使用的是多烯如1,3-己二烯、1,4-己二烯、环戊二烯、二环戊二烯、4-乙烯基环己1-烯、1,5-环辛二烯、5-亚乙烯基-2-降冰片烯和5-乙烯基-2-降冰片烯,以及聚合介质中原位形成的烯烃。当烯烃在聚合介质中原位形成时,可能会形成含有长链支化的聚烯烃。
在实施本发明的聚合方法时,以任何方式加入一氧化二氮以用来减少聚合介质中的静电荷。例如,一氧化二氮可以加入到预先形成的催化剂中,在预聚合步骤期间加入到预聚物中,加入到预先形成的预聚物中和/或加入到聚合介质中。在使用时一氧化二氮可以任选地与助催化剂预先混合。一氧化二氮以足以将聚合介质中的静电荷降低到低于在相同聚合方法中不存在一氧化二氮时所产生静电荷水平的任意用量加入。优选一氧化二氮在聚合介质中的加入量范围是约1ppm到约10000ppm(体积)。
在实施本发明的聚合方法时,卤代烃可以按照足以实现所需聚烯烃生产的任何用量加入到聚合介质中。卤代烃的优选加入量,按卤代烃与烯烃聚合催化剂金属组分之间的摩尔比计介于约0.001∶1~约100∶1。在更优选的实施方案中,卤代烃与金属组分的摩尔比介于约0.001∶1~约10∶1。
一氧化二氮和任选的卤代烃可按任何方式加入到聚合介质中。一氧化二氮和卤代烃可在即将加入到聚合介质中之前加入到烯烃聚合催化剂中,或者与催化剂分别按本领域已知的任何方式加入到聚合介质中。例如,一氧化二氮可任选地在加入到聚合介质中之前与卤代烃进行预混合。
若采用气相流化床方法进行烯烃聚合,有利的是,在散热方法之前加入一氧化二氮,例如在热交换器之前,以便除了减少聚合反应器中静电荷之外还可减慢所述散热方法的结垢速率。
由本发明生产的聚烯烃的分子量能够以任何已知的方式加以控制,例如,通过使用氢气。举例来说,聚乙烯分子量的控制可以由当聚合介质中氢气与乙烯的摩尔比增加时聚合物熔体指数(I2)的提高得到证实。
分子量分布(MWD)或多分散性是一种熟知的聚合物特性。MWD通常被描述为重均分子量(Mw)与数均分子量(Mn)之比。比值Mw/Mn可采用凝胶渗透色谱技术直接进行测定。聚合物的MWD用Waters GelPermeation Chromatograph系列150C并配备Ultrastyrogel柱和折射率检测器来测定。在这一新方法中,仪器的操作温度设定在140℃,洗脱溶剂是邻二氯苯,标定标准包括10种分子量精确已知、分子量范围从1000到1300000的聚苯乙烯,以及一种聚乙烯标准NBS1475。
任何传统添加剂都可以添加到由本发明得到的聚烯烃中。添加剂的例子包括成核剂,热稳定剂,酚类、硫类和磷类抗氧化剂,润滑剂,抗静电剂,分散剂,铜损伤抑制剂,中和剂,发泡剂,增塑剂,消泡剂,阻燃剂,交联剂,流动促进剂如过氧化物,紫外线吸收剂,光稳定剂,防老化稳定剂,焊接强度改进剂,增滑剂,防粘剂,防雾剂,染料,颜料,天然油,合成油,蜡,填料和橡胶成分。
本发明的聚烯烃,特别是聚乙烯,可以用本领域内任何已知的技术制作成薄膜。例如,可以通过已知的流延成膜、吹塑成膜和挤出涂布技术来生产薄膜。
另外,聚烯烃,特别是聚乙烯还可利用任何熟知的技术制成其它制品,例如模塑制品。
通过参照以下实施例将更容易理解本发明。当然一旦本发明完全公开,就会有许多对于本领域技术人员而言变得显而易见的本发明的其它形式,并且相应地将会认识到这些实施例只是出于说明的目的而列举,并不理解为以任何方式限制本发明的范围。
实施例
在下面的实例中,将采用下面列出的测试程序来评估本发明聚烯烃的分析性质。
a)密度按照ASTM D-4883从按照ASTM D1928制造的试样板上测得;
b)熔体指数(MI),I2,按照ASTM D-1238,条件E,在190℃测定并以分克每分钟(dg/min)为单位表示;
c)高载荷熔体指数(HLMI),I21,按照ASTM D-1238,条件F,在上面熔体指数(MI)试验使用重量的10倍(载荷)条件下进行测定;
d)熔体流动速率(MFR)=I21/I2或高载荷熔体指数/熔体指数;
e)产物中残留钛的含量。产物中残留钛的含量通过X射线荧光光谱法(XRF)测量,使用菲力普连续X射线分光光度计,型号PW1480。要测评的聚合物样品被压缩模塑成直径大约43mm的圆板以适合分光光度计中的样品固定器,并且厚度为3到5mm,有一个光滑的平坦表面。然后将此模塑检测样品置于XRF的测量装置中并测量由检测样品中的钛产生的X射线荧光。然后基于通过测量含有已知钛量的聚乙烯校准样品而得到的校准曲线来测定残留钛的含量。残留钛的含量以相对于聚合物基质的每百万分之一(ppm)为单位给出。
实例1中使用的齐格勒-纳塔催化剂是按照欧洲专利申请EP0703246A1的实例1-a制备的。催化剂以预聚物形式使用,预聚物按照欧洲专利申请EP0703246A1的实例1-b制备。于是获得含约34g聚乙烯每毫摩尔钛的预聚物。
聚合方法
实例1采用的聚合方法在此是在用于气相聚合的流化床反应器中进行的,此反应器由一个直径为0.74米、高度为7米的垂直圆筒和顶部的一个减速室组成。在反应器的下部有流化栅和用于气体循环的外部管道,此管道将减速室的顶部连接到反应器下部位于流化栅下面的某一位置。循环管道装配有用来使气体循环的压缩机以及传热装置如热交换器。具体地说,这些管道用来将乙烯;1-己烯;氢气和氮气这些代表流经流化床的气体反应混合物中主要成分的气体进料到循环管道中。在流化栅上方,反应器包含由重均直径约0.5mm~约1.4mm的颗粒构成的聚乙烯粉末组成的流化床。含有乙烯、烯烃共聚单体、氢气、氮气和少量其它组分的气体反应混合物在范围大约2.12×105kg/m2~2.27×105kg/m2的压力下和向上的流化速率,在此称之为流化速度,范围大约0.49米/秒~大约0.64米/秒的条件下流经流化床。
在实例1中,齐格勒-纳塔催化剂,如上所述呈预聚物形式,间歇地引入到反应器中。所述催化剂含有镁、氯和钛。该预聚物形式包含约34克聚乙烯每毫摩尔钛,以及一定数量的三正辛基铝(TnOA),使得摩尔比Al/Ti为约1.1∶1。调节预聚物向反应器中的引入速率,以便达到要求的生产速率。聚合期间,当使用附加助催化剂时,在位于传热方法下游的某一点连续地引入到气态反应混合物循环管道中。附加助催化剂的进料速率,按三烷基铝与钛的摩尔比(Al/Ti)表示,被定义为助催化剂进料速率(三烷基铝摩尔数每小时)与预聚物进料速率(钛的摩尔数每小时)之比。氯仿(CHCl3)溶于正己烷的溶液,以约0.5wt%的浓度连续地引入到气态反应混合物循环管道中。任选卤代烃的进料速率,按CHCl3与钛的摩尔比(CHCl3/Ti)表示,被定义为CHCl3的进料速率(CHCl3的摩尔数每小时)与催化剂或预聚物的进料速率(钛的摩尔数每小时)之比。
一氧化二氮(N2O),若在下面的实例中使用的话,被用于减少聚合介质中的静电荷。气态一氧化二氮连续地引入到气态反应混合物的循环管道中。一氧化二氮在聚合介质中的浓度以体积ppm为单位表示。
流化床中的静电荷用Auburn国际(有限)公司(丹佛,马萨诸塞州)提供的Correflow 3400型静电监测仪(ESM)进行测量。静电探针安装在反应器的垂直圆筒部位,高度为在聚合物颗粒流化床之中。静电探针测量聚合介质和地面之间的电流。静电荷的减少定义为检测电流绝对量的减少和/或检测电流变化率的减少。
实例1
初始工艺条件载于表1中。聚合反应器安排成生产熔体指数为0.6dg/min、密度为0.920g/cm3的乙烯与1-己烯的共聚物。测定静电荷水平。然后,以60ppm(体积)的比例向反应器回路中加入一氧化二氮。加入三甲基铝以维持73kg/小时的生产速率。测定聚合反应器中的静电荷水平,结果发现,由于一氧化二氮的加入,静电荷水平下降。
表1:初始反应器条件,实例1
反应器压力(kg/m2)反应器温度(℃)流化速度(m/s)流化堆密度(kg/m3)反应器床层高度(m)乙烯(mol%)H2/C2(摩尔比)C6/C2(摩尔比)CHCl3/Ti预聚物流速(kg/h)生产速率(kg/h)残留钛(ppm)密度(g/cm3)熔体指数,I2(dg/min)熔体流动速率(I21/I2) | 2.24×105860.642603.3260.1450.1460.040.36738.50.9200.629 |
实例2
按照实例1的方法,但以下各项例外。实例2中使用的齐格勒-纳塔催化剂是由Toho钛公司按产品名THC-C提供的。催化剂是钛基催化剂,由氯化镁承载。该催化剂直接加入到聚合介质中。三甲基铝作为助催化剂加入到聚合介质中。催化剂加入速率和助催化剂加入速率按照生产约91kg聚合产物每小时的要求调节,其中残留钛含量约1ppm。
此外,C6/C2和H2/C2摩尔比调节到生产出的乙烯/1-己烯共聚物具有约0.6dg/min的目标熔体指数和约0.920g/cm3的目标密度。
测定聚合反应器中的静电荷水平。然后,向聚合介质中加入一氧化二氮并预期静电荷水平的降低。
实例3
按照实例1的方法,但以下各项例外。实例3中使用的齐格勒-纳塔催化剂是由(Grace Davison(巴尔的摩,马里兰)按产品名XPO-5021提供的。催化剂是钛基催化剂,由二氧化硅承载着。该催化剂直接加入到聚合介质中。三乙基铝作为助催化剂加入到聚合介质中。催化剂加入速率和助催化剂加入速率按照生产约91kg聚合产物每小时的要求调节,其中残留钛含量约1ppm。
此外,C6/C2和H2/C2摩尔比调节到生产出的乙烯/1-己烯共聚物具有约0.6dg/min的熔体指数和约0.920g/cm3的密度。
测定聚合反应器中的静电荷水平。然后,向聚合介质中加入一氧化二氮并预期静电荷水平的降低。
实例4~6
按照实例1的方法,但不同的是,不采用齐格勒-纳塔催化剂而采用如下二氧化硅承载的金属茂催化剂:
实例4二氯化双(1一丁基-3-甲基环戊二烯基)锆和甲基铝氧烷
实例5双(1-丁基-3-甲基环戊二烯基)二甲基二茂锆和三(全氟苯基)硼烷
实例6(叔丁酰氨基)二甲基(四甲基-η5-环戊二烯基)硅烷钛二甲基和三苯基甲基四(全氟苯基)硼酸盐
C6/C2和H2/C2摩尔比调节到生产出的乙烯/1-己烯共聚物具有约0.6dg/min的目标熔体指数和约0.920g/cm3的目标密度。
测定聚合介质中的静电荷水平。在上述实例4~6的每一个中,由于一氧化二氮的加入,预期聚合介质中的静电荷水平均应降低。
由本发明的聚烯烃可制备薄膜。
诸如模塑制品之类的制品也可由本发明的聚烯烃制备。
应该清楚地认识到在此描述的本发明形式只是说明性的,而无意用来限制本发明的范围。本发明包括落在下列权利要求范围内的所有变换形式。
Claims (38)
1.一种烯烃和/或烯烃与至少一种或多种其它烯烃的聚合方法,包括:在一种存在静电荷的聚合介质中,在聚合条件下将烯烃和/或烯烃与至少一种或多种其它烯烃,与一种烯烃聚合催化剂和一氧化二氮进行接触,其中一氧化二氮的存在量足以将聚合介质中的静电荷降低到低于不存在该一氧化二氮时将获得的水平。
2.权利要求1的方法,其中该烯烃聚合催化剂包含至少一种选自元素周期表中族3、4、5、6、7、8、9、10、11、12和/或13的金属。
3.权利要求2的方法,其中该金属选自钛、锆、钒、铁、铬、镍和铝。
4.权利要求3的方法,其中该金属选自钛、锆和钒。
5.权利要求1的方法,其中烯烃聚合催化剂承载在一种载体上。
6.权利要求5的方法,其中载体选自二氧化硅、氧化铝、氯化镁及其混合物。
7.权利要求2的方法,其中烯烃聚合催化剂选自氧化铬催化剂、有机铬催化剂、齐格勒-纳塔催化剂、金属茂催化剂、阳离子铝烷基酰胺化催化剂、阳离子镍烷基二亚胺催化剂、中性镍烷基水杨醛二亚氨基催化剂、阳离子铁烷基吡啶二亚胺催化剂以及阳离子钛烷基二酰胺催化剂。
8.权利要求7的方法,其中烯烃聚合催化剂选自氧化铬催化剂、有机铬催化剂、齐格勒-纳塔催化剂以及金属茂催化剂。
9.权利要求8的方法,其中烯烃聚合催化剂选自氧化铬催化剂、齐格勒-纳塔催化剂和金属茂催化剂。
10.权利要求1的方法,其中烯烃聚合催化剂是使烯烃聚合成为分子量分布(MWD)介于1~2.5的烯烃均聚物和共聚物的烯烃聚合催化剂。
11.权利要求1的方法,还包括在聚合介质中加入卤代烃。
12.权利要求11的方法,其中卤代烃选自二氯甲烷、氯仿、四氯化碳、氯氟甲烷、氯二氟甲烷、二氯二氟甲烷、氟二氯甲烷、氯三氟甲烷、氟三氯甲烷和1,2-二氯乙烷。
13.权利要求12的方法,其中卤代烃是氯仿。
14.权利要求1的方法,其中一氧化二氮的加入量介于1ppm~10,000ppm(体积)。
15.权利要求1的方法,其中聚合介质是气相。
16.权利要求1的方法,其中聚合介质是淤浆相。
17.权利要求1的方法,其中烯烃是乙烯,而至少一种或多种其它烯烃选自3~16个碳原子的烯烃。
18.权利要求17的方法,其中至少一种或多种其它烯烃选自1-辛烯、1-己烯、4-甲基-1-戊烯、1-戊烯、1-丁烯和丙烯。
19.权利要求17的方法,其中由乙烯与至少一种或多种烯烃聚合而成的共聚物包含占共聚物重量至少50wt%的乙烯。
20.一种减少烯烃和/或烯烃与至少一种或多种其它烯烃在聚合介质中、在烯烃聚合催化剂存在下进行聚合时的静电荷的方法,包括向聚合介质中引入一氧化二氮,其用量足以将聚合介质中的静电荷降低到低于不存在一氧化二氮时将获得的水平。
21.权利要求20的方法,其中烯烃聚合催化剂包含至少一种选自元素周期表中族3、4、5、6、7、8、9、10、11、12和/或13的金属。
22.权利要求21的方法,其中该金属选自钛、锆、钒、铁、铬、镍和铝。
23.权利要求22的方法,其中该金属选自钛、锆和钒。
24.权利要求20的方法,其中烯烃聚合催化剂承载在一种载体上。
25.权利要求24的方法,其中载体选自二氧化硅、氧化铝、氯化镁及其混合物。
26.权利要求21的方法,其中烯烃聚合催化剂选自氧化铬催化剂、有机铬催化剂、齐格勒-纳塔催化剂、金属茂催化剂、阳离子铝烷基酰胺化催化剂、阳离子镍烷基二亚胺催化剂、中性镍烷基水杨醛二亚氨基催化剂、阳离子铁烷基吡啶二亚胺催化剂以及阳离子钛烷基二酰胺催化剂。
27.权利要求26的方法,其中烯烃聚合催化剂选自氧化铬催化剂、有机铬催化剂、齐格勒-纳塔催化剂以及金属茂催化剂。
28.权利要求27的方法,其中烯烃聚合催化剂选自氧化铬催化剂、齐格勒-纳塔催化剂和金属茂催化剂。
29.权利要求20的方法,其中烯烃聚合催化剂是使烯烃聚合成为分子量分布(MWD)介于1~2.5的烯烃均聚物和共聚物的烯烃聚合催化剂。
30.权利要求20的方法,还包括在聚合介质中加入卤代烃。
31.权利要求30的方法,其中卤代烃选自二氯甲烷、氯仿、四氯化碳、氯氟甲烷、氯二氟甲烷、二氯二氟甲烷、氟二氯甲烷、氯三氟甲烷、氟三氯甲烷和1,2-二氯乙烷。
32.权利要求31的方法,其中卤代烃是氯仿。
33.权利要求20的方法,其中一氧化二氮在聚合介质中的加入量介于1ppm~10,000ppm(体积)。
34.权利要求20的方法,其中聚合介质是气相。
35.权利要求20的方法,其中聚合介质是淤浆相。
36.权利要求20的方法,其中烯烃是乙烯,而至少一种或多种其它烯烃选自3~16个碳原子的烯烃。
37.权利要求36的方法,其中至少一种或多种其它烯烃选自1-辛烯、1-己烯、4-甲基-1-戊烯、1-戊烯、1-丁烯和丙烯。
38.权利要求36的方法,其中由乙烯与至少一种或多种烯烃聚合而成的共聚物包含占共聚物重量至少50wt%的乙烯。
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- 1999-10-14 KR KR1020027002635A patent/KR100626900B1/ko active IP Right Grant
- 1999-10-14 WO PCT/US1999/023864 patent/WO2001016190A1/en active IP Right Grant
- 1999-10-14 EP EP99953160A patent/EP1208122B1/en not_active Expired - Lifetime
- 1999-10-14 MX MXPA02002149A patent/MXPA02002149A/es unknown
- 1999-10-14 JP JP2001520747A patent/JP2003508557A/ja active Pending
- 1999-10-14 BR BRPI9917467-7A patent/BR9917467B1/pt not_active IP Right Cessation
- 1999-10-14 CN CNB998168815A patent/CN1326886C/zh not_active Expired - Lifetime
- 1999-10-14 DE DE69922551T patent/DE69922551T2/de not_active Expired - Lifetime
- 1999-10-14 CA CA002384105A patent/CA2384105A1/en not_active Abandoned
- 1999-10-27 MY MYPI99004623A patent/MY133912A/en unknown
- 1999-10-27 TW TW088118577A patent/TW490471B/zh not_active IP Right Cessation
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Also Published As
Publication number | Publication date |
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MXPA02002149A (es) | 2002-09-18 |
JP2010261053A (ja) | 2010-11-18 |
CA2384105A1 (en) | 2001-03-08 |
DE69922551T2 (de) | 2005-04-14 |
MY133912A (en) | 2007-11-30 |
DE69922551D1 (de) | 2005-01-13 |
US6187879B1 (en) | 2001-02-13 |
JP2003508557A (ja) | 2003-03-04 |
EP1208122A1 (en) | 2002-05-29 |
EP1208122B1 (en) | 2004-12-08 |
BR9917467B1 (pt) | 2009-01-13 |
KR20020026000A (ko) | 2002-04-04 |
CN1367796A (zh) | 2002-09-04 |
JP5662083B2 (ja) | 2015-01-28 |
BR9917467A (pt) | 2002-04-30 |
WO2001016190A1 (en) | 2001-03-08 |
TW490471B (en) | 2002-06-11 |
KR100626900B1 (ko) | 2006-09-20 |
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