CN1296396C - Supported chromium catalysts and their use for the preparation of ethylene homo-and copolymers - Google Patents
Supported chromium catalysts and their use for the preparation of ethylene homo-and copolymers Download PDFInfo
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- CN1296396C CN1296396C CNB2003801050169A CN200380105016A CN1296396C CN 1296396 C CN1296396 C CN 1296396C CN B2003801050169 A CNB2003801050169 A CN B2003801050169A CN 200380105016 A CN200380105016 A CN 200380105016A CN 1296396 C CN1296396 C CN 1296396C
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- Prior art keywords
- chromium
- weight
- preferred
- catalyst
- carrier
- Prior art date
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000011651 chromium Substances 0.000 title claims abstract description 51
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 49
- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title abstract description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title description 20
- 239000005977 Ethylene Substances 0.000 title description 3
- 229920001577 copolymer Polymers 0.000 title 1
- 238000000034 method Methods 0.000 claims abstract description 53
- 239000000463 material Substances 0.000 claims abstract description 34
- 239000012041 precatalyst Substances 0.000 claims abstract description 30
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 28
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 150000001845 chromium compounds Chemical class 0.000 claims abstract 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- 239000007787 solid Substances 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 23
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- 229910002027 silica gel Inorganic materials 0.000 claims description 13
- 239000000741 silica gel Substances 0.000 claims description 13
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 12
- GVHCUJZTWMCYJM-UHFFFAOYSA-N chromium(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GVHCUJZTWMCYJM-UHFFFAOYSA-N 0.000 claims description 7
- 230000008569 process Effects 0.000 abstract description 11
- 230000003213 activating effect Effects 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 abstract 1
- -1 polyethylene Polymers 0.000 description 23
- 239000000017 hydrogel Substances 0.000 description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- 239000000126 substance Substances 0.000 description 17
- 239000007788 liquid Substances 0.000 description 15
- 239000002245 particle Substances 0.000 description 15
- 238000001035 drying Methods 0.000 description 13
- 229960001866 silicon dioxide Drugs 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000010936 titanium Substances 0.000 description 12
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- 229910052719 titanium Inorganic materials 0.000 description 11
- 239000004711 α-olefin Substances 0.000 description 11
- 230000004913 activation Effects 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 238000004090 dissolution Methods 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 239000012071 phase Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 239000000010 aprotic solvent Substances 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 239000004411 aluminium Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000002902 organometallic compounds Chemical class 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 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 description 4
- 229920001038 ethylene copolymer Polymers 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 238000012685 gas phase polymerization Methods 0.000 description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- JWZZKOKVBUJMES-UHFFFAOYSA-N (+-)-Isoprenaline Chemical compound CC(C)NCC(O)C1=CC=C(O)C(O)=C1 JWZZKOKVBUJMES-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000012190 activator Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 230000002650 habitual effect Effects 0.000 description 3
- 230000001976 improved effect Effects 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 235000019353 potassium silicate Nutrition 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 229910002028 silica xerogel Inorganic materials 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances 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
- 239000012159 carrier gas Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 239000007863 gel particle Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- LXPCOISGJFXEJE-UHFFFAOYSA-N oxifentorex Chemical compound C=1C=CC=CC=1C[N+](C)([O-])C(C)CC1=CC=CC=C1 LXPCOISGJFXEJE-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000005201 scrubbing Methods 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical group CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 description 1
- MNCMBBIFTVWHIP-UHFFFAOYSA-N 1-anthracen-9-yl-2,2,2-trifluoroethanone Chemical group C1=CC=C2C(C(=O)C(F)(F)F)=C(C=CC=C3)C3=CC2=C1 MNCMBBIFTVWHIP-UHFFFAOYSA-N 0.000 description 1
- SDRZFSPCVYEJTP-UHFFFAOYSA-N 1-ethenylcyclohexene Chemical compound C=CC1=CCCCC1 SDRZFSPCVYEJTP-UHFFFAOYSA-N 0.000 description 1
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- DJOWTWWHMWQATC-KYHIUUMWSA-N Karpoxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1(O)C(C)(C)CC(O)CC1(C)O)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C DJOWTWWHMWQATC-KYHIUUMWSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 125000002078 anthracen-1-yl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C([*])=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 125000000748 anthracen-2-yl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C([H])=C([*])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- GDFLGQIOWFLLOC-UHFFFAOYSA-N azane;2-hydroxypropanoic acid;titanium Chemical compound [NH4+].[Ti].CC(O)C([O-])=O GDFLGQIOWFLLOC-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical class CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229940117975 chromium trioxide Drugs 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- IGIOUAZJUMGWPQ-UHFFFAOYSA-N chromium(3+);hydrate Chemical compound O.[Cr+3] IGIOUAZJUMGWPQ-UHFFFAOYSA-N 0.000 description 1
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 1
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 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
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 1
- 239000004913 cyclooctene Substances 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 description 1
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical group CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 125000001905 inorganic group Chemical group 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000003808 methanol extraction Methods 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- YSTQWZZQKCCBAY-UHFFFAOYSA-L methylaluminum(2+);dichloride Chemical compound C[Al](Cl)Cl YSTQWZZQKCCBAY-UHFFFAOYSA-L 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- QYZLKGVUSQXAMU-UHFFFAOYSA-N penta-1,4-diene Chemical compound C=CCC=C QYZLKGVUSQXAMU-UHFFFAOYSA-N 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000002444 silanisation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-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
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
A process for the preparation of a supported, titanized chromium catalyst comprising the steps of: A) contacting the support material with a protic medium comprising a titanium compound and a chromium compound, B) optionally removing the solvent, C) optionally calcining the precatalyst obtained after step B) and D) selectively activating the precatalyst obtained after step B) or C) in an oxygen-containing atmosphere at from 400 to 1100 ℃.
Description
The present invention relates to the chrome catalysts of the titanizing on the carrier of the novel copolymerization that is used for ethylene homo reaction and ethene and alpha-olefin, the purposes that is used to prepare their method and is used for olefinic polyreaction.
For example, can use the titanium compound on the carrier, Ziegler-Natta catalyst as is well known, perhaps use the chromium cpd on the carrier, philip catalyst as is well known prepares the multipolymer of Alathon and ethene and higher alpha-olefin such as 1-butylene, 1-amylene, 1-hexene or 1-octene by polyreaction.For example, when the homopolymer that uses ethene and multipolymer were used for blown-film extrusion, polymkeric substance has good harmony between mechanical property and processing characteristics be very important.
Known, the chrome catalysts on the carrier is suitable for producing the ethylene copolymer with good mechanical property very much.The polymer properties that obtains in polyreaction depends on the preparation method of the chrome catalysts of use, especially the type that depends on solid support material, as the type of the chromium cpd of its chemical structure, composition, surface-area or pore volume, use, polyvoltine compound more, as application order or the roasting and the activation method of the existence of titanium compound, aluminum alkyls or carbon monoxide, various components.The parent material that it is to use combines with the step that is applied to carrier, and the chrome catalysts that it has generated expection subsequently is used to prepare the polymkeric substance that has for the desired performance characteristic of application-specific.
Chrome catalysts on the carrier is titanizing normally, and promptly they not only comprise chromium cpd but also comprise the titanium compound of variable ratio, for example can influence molar mass distribution and HLMI (high load melt index) by means of these titanium compounds.Titanium compound is normally finished in the preparation process at hydrogel in the application on the carrier, has generated SiO
2-TiO
2Cogelled.At this, titanium dioxide is uniform distribution in whole solid support material.A shortcoming is that only some can be used for polyreaction in the total titanium oxide of the hole surface of catalyzer.Reason has for this reason developed the embodiment of the chrome catalysts of a large amount of relevant titanizings, and wherein, titanium compound in the step that the doping with chromium cpd separates, is applied to hole surface in the target mode usually.
Therefore, for example, EP-A-882740 has described a kind of method that is used to prepare the chrome catalysts on the carrier, and wherein solid support material has 450 to 600m
2The specific surface area of/g and elder generation are applied to carrier with the chromium component, use titanium compound subsequently, and wherein titanizing effect (titanization) is to finish under at least 300 ℃ temperature.
The EP-A-882741 instruction: when the chrome catalysts on the use carrier, the polyethylene that can obtain having good final tensile strength, its solid support material of the chrome catalysts on this carrier has 400m at least
2The specific surface area of/g and taken off water before use and in its preparation process is applied to carrier with the chromium component earlier, and uses titanium compound subsequently.
Having described in JP 54141893 and JP 57049605 is having proton under the inert condition, chromium cpd in the aprotic solvent and the application of the mixture of titanium compound on carrier.
But, proton being had under the inert condition, the preparation of organometallic compound and processing are complicated and expensive, because solvent must carry out drying before use.In addition, only there is the chromium cpd of minute quantity to dissolve in the non-proton medium.Usually only can obtain the deliquescent increase of chromium cpd in aprotic solvent by complicated synthetic method.
An object of the present invention is to provide a kind of not too complicated method of novelty of the chrome catalysts that is used to prepare the titanizing on the carrier.
We have found that by a kind of method that is used to prepare the chrome catalysts of the titanizing on the carrier and can finish this purpose, it comprises the following steps:
A) solid support material is contacted with the aprotic medium that comprises titanium compound and chromium cpd,
B) optionally remove solvent,
C) optionally roasting at step B) after the pre-catalyst that obtains and
D) in oxygen containing atmosphere, 400 ℃ under 1100 ℃, optionally activate at step B) or C) after the pre-catalyst that obtains.
The present invention further provides the chrome catalysts of the titanizing on the novel carrier, it is suitable for ethene and if desired, other common monomeric polyreaction, and it can be obtained by method of the present invention.For for simplicity, the chrome catalysts that this is used for the titanizing on the carrier of novelty of copolymerization of the homopolymerization of ethene and ethene and alpha-olefin will be called as " chrome catalysts of the present invention " hereinafter.
It is at least a according to chrome catalysts of the present invention that the present invention has also proposed a kind of use, the polyreaction of the mixture by ethene or ethene and alpha-olefin, be prepared the method for Alathon and ethene and alpha-olefin copolymer, Alathon that obtains thus and multipolymer and the purposes that is used to produce film thereof.
Therefore, have been found that now when using chrome catalysts of the present invention, can obtain the Alathon of fabulous productive rate and especially its multipolymer.The film product that obtains thus also has very high thorn resistance.
Consider prior art, can not expect that this novel method may obtain very active catalyzer, it can generate ethene polymers, and when this ethene polymers inflation was produced film, it can present fabulous mechanical property.
A kind of composition of chrome catalysts of the present invention is a solid support material, especially a kind of inoganic solids, and it is porous normally.The solid support material of preferred oxidation, it can also contain hydroxyl.This inorganic, metal oxide can be spheric or granulous.Known these solid examples of person skilled in the art have aluminum oxide, silicon-dioxide (silica gel), titanium dioxide and blended oxide compound or cogelled thereof, and aluminum phosphate.Other suitable solid support material can obtain by the improvement of hole surface, for example, the compound (BE-A-61,275) by element boron, (US 4 for the compound of aluminium, 284,527), the compound (DE-A 36 35 715) of compound of silicon (EP-A-0 166 157) or phosphorus.The preferred silica gel that uses.Preferred spheric or granulous silica gel, it can carry out spraying drying in former instance.
Preferred solid support material is a silica xerogel in small, broken bits, and for example it can be prepared described in DE-A25 40 279.Silica xerogel in small, broken bits preferably is prepared by the following step:
A) using a kind of solids content is that 10 to 25% weight are (with SiO
2Calculate) and mainly be spheric, its particle dia is 1 to 8mm pelletized silica hydrogel, it can be obtained by the following step:
A1) water glass solution with sodium or potassium is incorporated in a kind of eddy current of aqueous mineral acid, radially and be tangential to mobile principal direction,
A2) silica hydrosol that generates is sprayed in the gaseous medium, with the formation drop,
A3) water-sol of injection is solidified in gaseous medium,
A4) by washing, without pre-ageing, what make generation is not saliferous of spheric hydrogel particle mostly,
B) go out at least 60% water that in hydrogel, exists by liquid organic extractant,
C) gel that generates was being carried out drying 30 minutes up to 180 ℃ with under the reduced pressure of 13mbar, till not having further weight loss generation (xerogel generation) and
D) particle dia with the xerogel that obtains is adjusted to 20 to 2000 μ m.
The first step of solid support material preparation a) in, use to have 10 to 25% weight (with SiO
2Calculate), preferred 12 to 20% weight, the high solid content of especially preferred 14 to 20% weight and be that the spheric silica hydrogel is very important mainly.This silica hydrogel is with as step a1) to a4) described in ad hoc fashion be prepared.Step a1) to a3) in DE-A 21 03 243, more detailed description is arranged.Step a4), i.e. the washing of hydrogel can be carried out in the mode of any hope, and for example the use contains little ammonia (pH reaches about 10) and the water up to 80 ℃ is undertaken by counter-current principle.
Extracting preferred use of water outlet (step b)) from hydrogel is selected from by C
1-C
4-alcohol and/or C
3-C
5One group the organic liquid that-ketone is formed, organic liquid especially preferred and that water soluble mixes carries out.Especially preferred alcohol is the trimethyl carbinol, Virahol, ethanol and methyl alcohol.In ketone, preferred acetone.Organic liquid also can be made up of the mixture of above-mentioned organic liquid; In any case organic liquid contains before extraction and is less than 5% weight, preferably is less than the water of 3% weight.Extraction can be carried out on habitual extraction plant such as column extractor.
Preferably at from 30 to 140 ℃, especially preferably from 80 to 110 ℃ and preferably from 1.3mbar to atmospheric pressure condition under carry out drying (step c)).Because vapour pressure, the rising of temperature must be followed the rising of pressure, and vice versa.
The adjusting (step d)) of the particle dia of the xerogel that generates can be in the mode of any hope as by grinding and screening is carried out.
For example, preferred solid support material generates by the spray-dried hydrogel that has ground, appropriately sieved, and for this purpose, this hydrogel mixes with water or fatty alcohol.Basic particle is the porous granulous hydrogel particle that has suitably ground with sieved, and its average particle diameter is 1 to 20 μ m, preferred 1 to 5 μ m.The preferred SiO that has ground with sieved that uses
2Hydrogel.
Usually, the average particle diameter of carrier particle is in the scope of 1 to 1000 μ m, preferably in the scope of 10 to 500 μ m and especially preferably in the scope of 30 to 150 μ m.
The average pore volume of the solid support material that uses is 0.1 to 10ml/g, especially from 0.8 to 4.0ml/g and especially preferred in 1 to 25ml/g scope.
Usually, carrier particle has from 10 to 1000m
2/ g, especially from 100 to 600m
2/ g, more specifically from 200 to 550m
2The specific surface area of/g.
Specific surface area and average pore volume according to the BET method by the nitrogen absorption measurement, for example, as by S.Brunauer, P.Emmett and E.Teller are at " JACS " (Journalof the American Chemical Society), 60, (1939) are described in the 209-319 page or leaf.
In addition, carrier particle used according to the invention has 80 to 250 , the average pore diameter of preferred 90 to 210 and especially preferred 95 to 200 .The average pore diameter of representing with is that numerical value by average pore volume is (with cm
3/ g represents) divided by the numerical value of specific surface area (with m
2/ g represents) again the result be multiply by 40000 and calculate.The suitable carriers material also can commercially availablely obtain.
In the method for the invention, solid support material also can partly or wholly be improved before use.For example, solid support material can at 200 to 1000 ℃, be with or without under the existence of fluorizating agent such as ammonium hexafluorosilicate and handle under oxidation or non-oxide condition.For example, can change the content of water and/or OH group with this method.In the method for the invention, preferably before use, under reduced pressure, under 100 to 200 ℃, carried out drying 1 to 10 hour with solid support material.
Steps A) in, solid support material is contacted with aprotic medium, aprotic medium comprises, preferably is made up of titanium compound and chromium cpd.Titanium compound and chromium cpd are dissolved or suspended in the protonic solvent, and preferably the two is all dissolved.Make titanium compound and chromium cpd with any order, side by side or as premixed mixture contact with solvent.Preferably titanium compound and chromium cpd are mixed with solvent separately with any order.With aprotic medium with before solid support material contacts, the reaction times is usually at 10 seconds to 24 hours, preferably at 1 minute to 10 hours with especially preferably in 10 minutes to 5 hours scopes.
As titanium compound, preferably using molecular formula is (RO)
nX
4-nThe tetravalence compound of Ti, wherein radicals R is identical or different and respectively is organosilicon or the carbon organic substituent that contains 1 to 20 carbon atom, as line style, branching or cyclic C
1-C
20-alkyl such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, sec.-amyl sec-pentyl secondary amyl, isopentyl, n-hexyl, cyclohexyl, n-heptyl or n-octyl, C
6-C
18-aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl and 1-phenanthryl or trialkylsilkl such as trimethyl silyl or triethylsilyl.Preferred R is C line style or branching
1-C
6-alkyl such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl or n-hexyl.X can be halogen such as fluorine, chlorine, bromine or iodine, preferred chlorine.N is 0 to 4 and preferably 4.Also can use the mixture of multiple titanium compound.Preferred titanium compound may be dissolved in the protonic solvent, and the therefore preferred tetrol salt (tetralkoxides) that uses titanium is because they have good solubility in many solvents.Except the compound of titanium and simple aliphatic alkoxide, also may there be part such as the two alkoxide or the oxyethyl group amide (ethoxyaminate) of two functionality.The compound that is particularly useful is can two (trolamine) two (sec.-propyl) titanates soluble in water or lactic acid ammonium salt-titanium complex.
Chromium cpd can comprise inorganic or organic group.Preferred inorganic chromium cpd.The example of chromium cpd comprises chromium trioxide and chromium hydroxide and trivalent chromium and organic and salt mineral acid, as chromium acetate, chromium+oxalic acid, chromium sulphate and chromium nitrate and chromic inner complex, as acetylacetonate chromium.In these materials, especially preferably use chromium nitrate (III) 9-hydrate and acetylacetonate chromium.In preferred chromium cpd, the oxidation state of chromium be lower than 6 and preferred chromium be in 2,3 or 4 oxidation state.
Aprotic medium is a kind of solvent or comprises 1 to 100% weight, the solvent mixture of the protonic solvent of preferred 50 to 100% weight and especially preferred 100% weight or protonic solvent and 99 to 0% weight, the mixture of preferred 50 to 0% weight and especially preferred 0% weight aprotic solvent or the mixture of aprotic solvent, per-cent is all based on aprotic medium in every kind of situation.
For example, protonic solvent is pure R
1-OH, amine NR
1 2-xH
X+1, C
1-C
5-carboxylic acid and inorganic aqueous acids such as rare spirit of salt or sulfuric acid, water, ammoniacal liquor or its mixture, preferred alcohols R
1-OH, wherein R
1Independent each other, respectively be C
1-C
20-alkyl, C
2-C
20-alkenyl, C
6-C
20-aryl, contain 1 to 10 carbon atom and contain the alkylaryl or the SiR of 6 to 20 carbon atoms at aryl moiety at moieties
2 3, R wherein
2Independent each other, respectively be C
1-C
20-alkyl, C
2-C
20-alkenyl, C
6-C
20-aryl, contain 1 to 10 carbon atom and be 1 or 2 at alkylaryl and x that aryl moiety contains 6 to 20 carbon atoms at moieties.Possible R
1Or R
2The example of group has: can be C line style or branching
1-C
20-alkyl, as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl or dodecyl, itself can contain C
6-C
10-aryl is as substituent 5 to 7 yuan of cycloalkyl, as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, ring nonyl or cyclo-dodecyl, can be line style, cyclic or branching and wherein two keys can be at C middle or the end position
2-C
20-alkenyl as vinyl, 1-allyl group, 2-allyl group, 3-allyl group, butenyl, pentenyl, hexenyl, cyclopentenyl, cyclohexenyl, cyclooctene base or cyclooctadiene base, can be with more alkyl as substituent C
6-C
20-aryl, as phenyl, naphthyl, xenyl, anthryl, neighbour-,-, right-tolyl, 2,3-, 2,4-, 2,5-or 2,6-xylyl, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6-or 3,4, the 5-trimethylphenyl maybe can be with more alkyl as substituent arylalkyl, as benzyl, neighbour-,-, right-methyl-benzyl, 1-or 2-ethylphenyl, wherein in each case, two R
1Or two R
2Also can connect together and form 5 or 6 yuan of rings, organic group R
1And R
2Also can replace by halogen such as fluorine, chlorine or bromine.Preferred carboxylic acid is C
1-C
3Carboxylic acid is as formic acid or acetate.Preferred pure R
1-OH is methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, 1-butanols, 2-butanols, 1-amylalcohol, 2-amylalcohol, 1-hexanol, 2-Ethylhexyl Alcohol, 2,2-dimethyl ethanol or 2,2-dimethyl propyl alcohol, especially methyl alcohol, ethanol, 1-propyl alcohol, 1-butanols, 1-amylalcohol, 1-hexanol or 2-Ethylhexyl Alcohol.The water-content of preferred aprotic medium is less than 20% weight.
The example of aprotic solvent has aliphatic series and aromatic hydrocarbons, as pentane, hexane, heptane, octane, octane-iso, nonane, dodecane, hexanaphthene, benzene and C
7-C
10Alkylbenzene such as toluene, dimethylbenzene or ethylbenzene.
Solid support material is contacted with the mode of the aprotic medium that comprises titanium compound and chromium cpd with any hope.Like this, the mixture of aprotic medium, titanium compound and chromium cpd can be joined in the solid support material and maybe solid support material can be incorporated in this mixture.Also can in advance solid support material be become slurry in suspension medium.The suspension medium that uses and the mixture of aprotic medium comprise 1 to 100% weight, the protonic solvent of preferred 50 to 100% weight and especially preferred 100% weight or the mixture of protonic solvent and 99 to 0% weight, the aprotic solvent of preferred 50 to 0% weight and especially preferred 0% weight or the mixture of aprotic solvent, in each case, per-cent all is based on the suspension medium of use and the mixture of aprotic medium.Same preferred this suspension medium is an aprotic medium used according to the invention.
Chromium cpd is usually with 0.05 to 20% weight, and the concentration of preferred 0.1 to 15% weight and especially preferred 0.5 to 10% weight exists, and this weight is based on aprotic medium.Titanium compound is normally with 0.05 to 30% weight, and the concentration of preferred 0.1 to 20% weight and especially preferred 0.5 to 15% weight exists, and this weight is based on aprotic medium.The mol ratio of chromium cpd and titanium compound is usually at 10: 1 to 1: 10, in preferred 5: 1 to 1: 7 and especially preferred 4: 1 to 1: 5 scope.
Usually with solid support material with the gel particles on the carrier: the weight ratio of the titanium in the titanium compound is 100: 0.1 to 100: 12, especially 100: 1 to 100: 6, with the carrier gel particle: the weight ratio of the chromium in the chromium cpd is 100: 0.1 to 100: 10, especially by 100: 3 feeds at 100: 0.3.
Reactions steps A) can under 0 to 150 ℃, carry out.Consider the reason of cost, preferred room temperature.
At step B subsequently) in, can optionally remove solvent, preferably carry out under the pressure of 1mbar with 10mbar at 20 to 150 ℃.The part or all of solvent of preferred removal.The pre-catalyst that obtains with this method can maybe can contain some residual moisture by complete drying.Still the volatile component of Cun Zaiing is preferably to be no more than 20% weight, the amount that especially is no more than 10% weight exists, and this weight ratio is based on the pre-catalyst that contains chromium that has not also activated.
By reactions steps B) pre-catalyst that obtains can carry out step D immediately) or can be in advance at step C) in anhydrous inert gas atmosphere, under condition more than 280 ℃, carry out roasting.Preferably under 280 to 800 ℃, carrying out roasting 10 to 1000 minutes on the fluidized-bed.
Then will be with this method by step B) or the intermediate that C) obtains at step D) under oxidizing condition, as in oxygen containing atmosphere, under 400 to 1000 ℃, activating.Preferably with step B) or C) in the intermediate that obtains on fluidized-bed, directly activate by replacing rare gas element with oxygen containing gas and temperature being increased to activation temperature.With intermediate advantageously therein oxygen with in the no water flow that exists greater than 10% volumetric concentration, at 400 to 1100 ℃, especially heated 10 to 1000 minutes under 500 to 800 ℃, especially 150 to 750 minutes, then with its cool to room temperature, generated the philip catalyst stand-by according to the present invention.The activatory top temperature is lower than from step B) or the sintering temperature of intermediate C), preferably be lower than its 20-100 ℃ at least.This oxygenizement also can be carried out having in the presence of suitable fluorizating agent such as the ammonium hexafluorosilicate.
The preferable methods that is used to prepare the chrome catalysts of this titanizing on carrier comprises the following steps:
A) make solid support material contact the aprotic medium that comprises titanium compound and chromium cpd,
B) remove solvent,
C) roasting is at step B) after the pre-catalyst that obtains and
D) in oxygen containing atmosphere in activation under 400 ℃ to 1100 ℃ the condition at step C) after the pre-catalyst that obtains.
Especially preferably by steps A) to D) method formed.
Chrome catalysts of the present invention advantageously has 0.1 to 5% weight, especially the chromium content of 0.3 to 2% weight and 0.5 to 10% weight, the especially titanium content of 1 to 5% weight.
Catalyst body of the present invention ties up in the polyreaction of 1-alkene has short inductive phase.
The stand-by chrome catalysts that generates according to the present invention also can reduce in suspensoid or in the gas phase before use, and for example by ethene and/or alpha-olefin, carbon monoxide or boron triethyl, perhaps it also can be improved by the silanization effect.The mol ratio of reductive agent and chromium (chromium of chrome catalysts to be restored according to the present invention) is usually at 0.05: 1 to 500: 1, and preferred 0.1: 1 to 50: 1, especially in 0.5: 1 to 5.0: 1 the scope.
In suspensoid, reduction temperature is usually 10 to 200 ℃ scope, and in preferred 10 to the 100 ℃ scope, pressure is in 0.1 to 500bar scope, and preferred 1 in the scope of 200bar.
Reduction temperature in fluidized-bed process is usually 10 to 1000 ℃ scope, preferred 10 to 800 ℃ scope, especially 10 to 600 ℃.Usually, vapour phase reduction is preferably carried out in 1 to 100bar and especially 5 to 20bar scope 0.1 to the pressure range of 500bar.
In vapour phase reduction reaction, chrome catalysts to be restored carries out fluidisation by inert carrier gas flow such as nitrogen or argon gas usually on fluidized-bed reactor.Usually load carrier gas stream with reductive agent, wherein the preferred liquid reductive agent has the vapour pressure of 1mbar at least under standard conditions.
Chrome catalysts of the present invention is for being that the conventional process of carrying out olefinic polyreaction under 5 to 400bar prepares the homopolymer of ethene and the multipolymer of ethene and alpha-olefin is very useful with the known temperature and pressure that is used in 20 to 300 ℃ of scopes, for example solution method, the suspension method in agitated autoclave or loop reactor, stir gas phase or gas fluidized bed method, its can be continuously or intermittent type ground carry out.Correspondingly, the favourable pressure and temperature scope that is used to carry out this process depends on polymerisation process very much.
Especially, in these polymerization processes, temperature is set to 50 to 150 ℃, and preferred 70 to 120 ℃ and pressure are generally 1 in the scope of 400bar.As solvent or suspension medium, can be with unreactive hydrocarbons such as Trimethylmethane or those monomers self, for example higher alkene such as propylene, butylene or the hexene of using liquefaction or liquid.The solids content of suspensoid is usually in 10 to 80% weight ranges.Polyreaction can intermittent type ground as is carried out in agitated autoclave, perhaps continuously as in tubular reactor, preferably carries out on loop reactor.Especially, it can use as the Philips's piston-flow process (PF method) described at US-3 242 150 and US-3 248 179 and carry out.
According to the present invention, in the polymerisation process of mentioning, preferred gas phase polymerization, the especially gas phase polymerization in gas-phase fluidized-bed reactor.Although have been found that a plurality of processing steps and spray-dired solid support material, in gas phase polymerization, there is not fine dust to generate.Usually, this is reflected under the temperature that is lower than the polymkeric substance softening temperature several years at least and carries out.Gas phase polymerization also can carry out under condensation, that supercool coagulates or postcritical pattern.
Different polymerisation process perhaps or even identical polymerisation process, if desired, can be together in series to form the stepwise polyreaction.But the specific catalyst composition makes and can obtain easily from single reaction vessel according to polymkeric substance of the present invention.
Can be monoolefine and the diolefine that in molecule, contains 3 to 15 carbon atoms with the example of the suitable alpha-olefin of ethylene copolymerization.The type more suitably alpha-olefin is propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene, 1-decene, 1-dodecylene and 1-15 carbenes and conjugated and unconjugated diolefine: divinyl, 1,3-pentadiene, 2,3-dimethylbutadiene, 1,4-pentadiene, 1,5-hexadiene and vinyl cyclohexene.Also can use these monomeric mixtures altogether.Preferred 1-butylene, 1-hexene or 1-octene, especially the 1-hexene of using.
In order to control molar mass, in polyreaction, can advantageously use hydrogen as conditioning agent.
Have been found that by catalyzer of the present invention, in the presence of the element organometallic compound that I, the II of the periodic table of elements, III or IV main group or second transition group are arranged, the polyreaction of carrying out this 1-alkene is favourable.The compound that is well suited for of the type is same dentate (homoleptic) C of lithium, boron, aluminium or zinc
1-C
10-alkylate, for example, n-Butyl Lithium, triethyl-boron, trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-butyl aluminum, three hexyl aluminium, trioctylaluminum and zinc ethyl.And, C
1-C
10-aluminum dialkyl alkoxide also is very suitable as the diethyl aluminum methylate.Also may use chlorodimethylalumiu, methylaluminium dichloride, sesquialter methyl chloride aluminium or diethylaluminum chloride.Especially preferred n-Butyl Lithium and three hexyl aluminium are as organometallic compound.The mixture of above-mentioned organometallic compound also is very suitable usually.
Organometallic compound: the mol ratio of chromium is usually in 0.1: 1 to 50: 1 scope, preferably in 1: 1 to 50: 1 scope.But owing to can use many activators such as aluminum alkyls simultaneously, to remove catalyzer poison (being known as scavenging agent), therefore the amount of using depends on the impurity that exists in other parent material.But the person skilled in the art can determine its optimum amount by simple test.
In above-mentioned polymerization process, chrome catalysts of the present invention also can use with the catalyzer that another kind is suitable for alpha-olefin polymerization.Preferred chrome catalysts of the present invention uses with the chrome catalysts on carrier that another kind is customarily used in alpha-olefin polymerization.The application of two kinds of different chrome catalysts on carrier for example, has been described in WO 92/17511.Polyreaction also can use two or more chrome catalysts of the present invention to carry out simultaneously.The catalyzer of the especially preferred non-titanizing of chrome catalysts according to the present invention on carrier uses and carries out this polyreaction.For example, in US-3 798 202, described the mixture of the chrome catalysts on titanizing and the carrier non-titanizing, but in this case, the titanizing effect only after being applied to carrier, the chromium component is carried out.
, it can be mixed with before monomer contacts at these two kinds of different philip catalysts, be introduced in together then in the reactor, perhaps they can for example be introduced in the reactor at many points apart from each other.
Alathon prepared in accordance with the present invention and multipolymer have usually according to DIN 53479 measure 0.9 to 0.97g/cm
3In the scope, preferably 0.92 to 0.96g/cm
3In the scope and especially preferably 0.925 to 0.945g/cm
3Density in the scope, measure down at different load (seeing in the bracket) with foundation DIN 53735, for the situation of MI is 0 to the 10g/10min scope, preferably 0.01 to the 1g/10min scope and especially preferably 0.05 arrive in the 0.6g/10min scope and under the HLMI situation, be 1 to the 50g/10min scope, preferably 3 to the 30g/10min scope and especially 5 arrive melt flow index in the 25g/10min scope (MI (190 ℃/2.16kg) or HLMI (190 ℃/21.6kg)).
Weight-average molar mass M
wUsually arrive the 7000000g/mol scope 10000, preferably arrive in the 500000g/mol scope 100000.At 135 ℃, use the polyethylene standard sample 1,2, the molar mass distribution M that measures in the 4-trichlorobenzene by GPC (gel permeation chromatography)
w/ M
nUsually in 3 to 50 scopes, preferably in 8 to 30 scopes with especially preferably in 15 to 30 scopes.
Usually, the ethene polymers of producing in reactor is fusion and homogenizing in forcing machine.Then, the melt flow index of extrudate can be different with the relevant parameters of original polymer with density, but also in specific scope according to the present invention.
Use therein in the olefinic polyreaction of catalyzer prepared in accordance with the present invention, can prepare Alathon or ethene and contain the common monomeric multipolymer of 3 to 12 carbon atoms, wherein in multipolymer altogether monomeric amount up to 10% mole.Preferred multipolymer contains 0.3 to 1.5% mole hexene, especially preferred 0.5 to 1% mole hexene, and this molar percentage is based on polymkeric substance.
Ethylene copolymer prepared in accordance with the present invention also can form mixture with other olefin polymer, especially Alathon and multipolymer.On the one hand, these mixtures can be prepared by the simultaneous polymerization reaction of above-mentioned a large amount of chrome catalysts.On the other hand, these mixtures also can be simply obtained by subsequently the polymkeric substance prepared in accordance with the present invention and the fusion of other Alathon or multipolymer.MFI, the HLMI of same preferred these mixtures, density, common monomer content, M
wAnd M
w/ M
nOnly using in the polymer phase scope together of the chrome catalysts preparation that contains titanium with those according to the present invention.
In addition, ethylene copolymer, polymeric blends and adulterant may further include known in fact auxiliary and/or additive, as processing stabilizers, light and thermally stable agent, and habitual additive such as lubricant, antioxidant, anti-hard caking agent and antistatic agent, if desired, and tinting material.The kind of these additives and consumption are known to the person skilled in the art.
Polymkeric substance prepared in accordance with the present invention also can be subsequently improved by grafting, crosslinked, hydrogenation or other functionalization, and it is known for the person skilled in the art.
For example, polymkeric substance prepared in accordance with the present invention is very useful for the blown film workshop with high yield production film.The film that comprises polymkeric substance prepared in accordance with the present invention has the favorable mechanical performance.The high thorn resistance of the film of Sheng Chaning also merits attention thus.
The film that obtains with this method especially is suitable for packaging field and is used for the load bag (duty sacks) of big weight and is used for food department.And this film has only very low adhesion tendency, therefore can not make with lubricator with anti-caking additive or only use seldom to measure these materials and make it pass through machine.
Philip catalyst prepared in accordance with the present invention has special beyond thought advantage.It is very useful for homopolymerization and the copolyreaction of carrying out ethene with habitual and known particulate forms method in gas fluidised bed polymerisation reaction.At this, it has obtained having (being total to) polymkeric substance of good form and excellent processing characteristics with high yield.Especially, catalyzer of the present invention has presented good common monomeric introducing performance, even and also can obtain high yield under low activation temperature.Therefore be particularly useful by (being total to) polymkeric substance of philip catalyst preparation of the present invention technology for blown film method and blow moulding.
The following example has illustrated the present invention.
The productive rate of catalyzer with: the scale of the amount/philip catalyst of the polymkeric substance of separating shows that the two all uses g unit.
Melt flow index be according to ISO 1133 under the loading condiction of 190 ℃ and 21.6kg (190 ℃/21.6kg, (190 ℃/2.16kg MI) are measured HLMI) and under the loading condiction of 2.16kg.
Density [g/cm
3] measure according to ISO 1183.
Tap density (BD) [g/l] is measured according to DIN 53468.
Anti-environmental stress cracking (ESCR) is to measure with the disk pressure head test (RI) of Basell.Test conditions: disk (is made by molded disk, diameter: 38mm, thickness: 1mm is ruling on simultaneously at it with having 20mm is long and 200 μ m are dark wiping head) under 50 or 80 ℃, be immersed in the aqueous solution of Lutensol FSA of 5% intensity, and load with the air pressure of 3bar.Measurement can form the time of origin (representing with h) of the stress rupture that pressure falls in measuring apparatus.
The measurement of dart impact strength is to carry out on the film of 20 μ m according to ASTM 1709A.
Staudinger (Staudinger) index (η) [dl/g] is gone up the use naphthane at 130 ℃ at automatic Ubbelohde viscometer (Lauda PVS 1) and is measured (ISO 1628:130 ℃, 0.001g/ml naphthane) as solvent.
Molar mass distribution and the average M of deutero-thus
n, M
wAnd M
w/ M
nBe by the high-temperature gel permeation chromatography method, use method, under following condition, measure: solvent based on DIN 55672: 1,2, the 4-trichlorobenzene; Flow velocity: 1ml/min; Temperature: 140 ℃; Use the calibration of PE standard.
Shortenings in tabulating down is:
T
PolyTemperature in the polymerization process
M
wWeight-average molar mass
M
nMumber average molar mass
Density polymers density
The DDI dart impact
The anti-environmental stress cracking of ESCR
The volume percent of each component in the % volume polymer reaction process
Prod. with the catalyzer of the gram number/use of the polymkeric substance that obtains
The productive rate of the catalyzer that the gram numerical table shows
The melt flow index of HLMI under the 21.6kg weighing load
The amount of the three hexyl aluminium that THA uses
η Staudinger index
The milligram number of the catalyzer that mg cat. uses in polyreaction
Vinyl group in the Vinyl polymkeric substance in per 1000 carbon atoms
Embodiment and comparative experiments
Embodiment 1
Described in DE 2 540 279, prepare solid support material.
The preparation of silica xerogel
Use as at as shown in the figure of DE-A 2 103 243 and mixing nozzle that have following column data: the diameter of the cylindrical mixing section that is formed by plastics tubing is 14mm, and the length of mixing zone (comprising mixing portion afterwards) is 350mm.Close in the mixing section end of approaching inlet, the tangential hand-hole that is used for mineral acid of a diameter 4mm is arranged near this end.The back has other four to have the 4mm diameter equally and be used for water glass solution, has the hole of identical inflow direction, and its pitch of holes of measuring on the longitudinal direction of mixing section is 30mm.Therefore, the length in elementary mixing district and diameter are 10: 1 than approximately.For secondary mixing region subsequently, this ratio is 15.As spray nozzle, can with one flat, the pipe of slight kidney shape places the exit end of plastics tubing.
This mixing device be supplied with the sulfuric acid of 33% weight strength of 325l/h of 20 ℃ and about 3bar working pressure and same 20 ℃ of temperature and equally the density of about 3bar pressure be that the water glass solution of the 1100l/h of 1.20kg/l is (by the SiO of 27% weight that contains dilute with water
2Na with 8% weight
2The industrial-grade sodium silicate preparation of O).In mixing section with the plastics tubing proper alignment, it is the unsettled water-sol of 7-8 that (progressive) neutralization has progressively caused generating pH, and it stopped about 0.1 second in the mixing region, back before spurting into atmosphere by nozzle adapter with fan-shaped liquid jet, homogenized fully up to it.By in the range of air, injection stream scatter and forms a grain drop at it, because surface tension, it was rendered as spherical substantially and solidify to form hydrogel sphere in an about second, still was in state of flight simultaneously.These spheroids have slick surface, and are transparent as hyaloid, comprise the SiO of about 17% weight
2, have following particle size distribution:
＞8mm 10% weight
6-8mm 45% weight
4-6mm 34% weight
＜4mm 11% weight
(can arbitrarily change particle size distribution by using other nozzle adapter.) at the range terminal point of hydrogel sphere, it is collected in the scrubbing tower, almost completely has been full of hydrogel sphere in the scrubbing tower, and can utilize the water that contains some ammonia and about 50 ℃ of temperature therein, with successive adverse current method, the salt in the flush away hydrogel sphere and not wearing out immediately.
Separate these diameters at 2 spheroids that arrive in the 6mm scope by screening, these spheroids of 112kg are placed an extraction container, its top has an inlet, the overflow of sieve bottom and swan neck shape, this overflow links to each other with tube bottom, and keep the liquid level in the tube enough high, make hydrogel sphere to be covered by liquid fully.Use this hydrogel of methanol extraction.
To carry out drying (under 120 ℃, 20mbar pressure condition, carrying out 12 hours) then with the spheroid that this method obtains, till under 180 ℃, 13mbar pressure condition, also not having further weight loss to take place through 30 minutes.
Grind subsequently these with this method drying spheroid, separate the xerogel particle of these diameters by screening at 40 to 300 μ m.Pore volume is 1.9ml/g.
Four different third titanium oxide of 39ml are joined 11.6g Chromium trinitrate nonahydrate (III) (Cr (NO
3)
3* 9H
2O) in the solution in 700ml methyl alcohol.This Chromium trinitrate nonahydrate (III) and the solution of four different third titanium oxide in methyl alcohol are transparent and do not present muddiness.To join with the solution that this method obtains in the above-mentioned silica-gel carrier of 150g.Stirred this suspensoid 1 hour, then with it under 80 ℃, on rotary evaporator, use vacuum-evaporation to do.The pre-catalyst that obtains with this method contains the chromium of 1% weight and the titanium of 4% weight, and this per-cent is based on the weight of pre-catalyst.
Comparative example C1
Do not add four different third titanium oxide, repeat embodiment 1.The pre-catalyst that obtains with this method contains the chromium of 1% weight, and this per-cent is based on the amount of pre-catalyst.
Embodiment 2
In dissolution reactor, (III) is dissolved in the 6.5l methyl alcohol while stirring with the 400g Chromium trinitrate nonahydrate.Stir after 1 hour, add 0.97l four different third titanium oxide, and with this mixture restir 5 minutes.Subsequently with on the 5kg silica-gel carrier Sylopol SG332 5N (commercially available getting) of this solution through being pumped in double cone dryer in 1 hour by Grace.Use this dissolution reactor of 1.5l methanol rinse then, then it is joined on the carrier equally.Stir this suspensoid then 1 hour and be heated 95 ℃ subsequently, and under 900mbar, distill out methyl alcohol.After about 3 hours, pressure is reduced to 300mbar, and under these conditions with dry again 2 hours of product.The pre-catalyst that obtains with this method contains the chromium of 1% weight and the titanium of 3% weight, and this per-cent is based on the weight of pre-catalyst.
Comparative example C2
Use the silica-gel carrier Sylopol SG3325N of 5kg and the 9 nitric hydrate chromium (III) of 120g, but do not add 4 third titanium oxide, repeat the step of embodiment 2.The pre-catalyst that obtains with this method contains the chromium of 0.3% weight, and this per-cent is based on the weight of pre-catalyst.
Embodiment 3
1000g Chromium trinitrate nonahydrate (III) and 21l methyl alcohol are mixed in dissolution reactor while stirring.Stir after 1 hour, 2.3l four different third titanium oxide are joined in this solution, stirred this mixed solution 5 minutes.Subsequently with on the 18kg silica-gel carrier XPO2107 (commercially available getting) in the double cone dryer of this solution through being pumped in Rotating with Uniform in 1 hour (its in this double cone dryer dry 7 hours in advance under 130 ℃ and the 10mbar) by Grace.After the adding,, equally this rinsing liquid is joined on the silica-gel carrier with 5 these dissolution reactor of l methanol rinse.This suspensoid of restir 1 hour uses down vacuum to carry out drying at 90 ℃ then, till pressure reaches 10mbar during 100 ℃ of temperature after 1 hour.The pre-catalyst that obtains with this method contains the chromium of 0.7% weight and the titanium of 2% weight, and this per-cent is based on the weight of pre-catalyst.
Comparative example C3
3.5l four different third titanium oxide are mixed in dissolution reactor while stirring with the 20l heptane.Stir after 10 minutes, on the 18kg silica-gel carrier XPO2107 in the double cone dryer of this solution through being pumped in Rotating with Uniform in 1 hour (its in this double cone dryer dry 7 hours in advance under 130 ℃ and the 10mbar).With this dissolution reactor of 5l heptane rinsing, this rinsing liquid is moved in the double cone dryer equally.Stirred this suspensoid then 1 hour.Use vacuum to carry out drying down at 90 ℃ it subsequently, till pressure reached 10mbar when temperature was 100 ℃ after 1 hour.Subsequently 1000g Chromium trinitrate nonahydrate (III) and 23l methyl alcohol are mixed in dissolution reactor while stirring.Stir after 1 hour, with this solution through being pumped in 1 hour on the titanium compound on the carrier in the double cone dryer of rotation.After the adding, with this dissolution reactor of 5l methanol rinse, this rinsing liquid is transferred in this double cone dryer equally.Again this suspensoid was stirred 1 hour, use vacuum to carry out drying down at 90 ℃ then, till pressure reached 10mbar when temperature was 100 ℃ after 1 hour.The pre-catalyst that obtains with this method contains the chromium of 0.7% weight and the titanium of 3% weight, and this per-cent is based on the weight of pre-catalyst.
Activation
Utilize the air in fluidized-bed activator to activate down at 600 or 650 ℃.For the pre-activated catalyzer, it was heated to 300 ℃ through 1 hour, kept this temperature 1 hour, be heated the activation temperature of expection subsequently, keep this temperature 2 hours (embodiment 1 and C1) or 5 hours (embodiment 2,3, C2 and C3), with postcooling.Under condition of nitrogen gas, its cooling is lower than 300 ℃.To be heated to 750 ℃ activation temperature from the pre-catalyst of embodiment 1, C1 and C2, be heated to 600 ℃ activation temperature, and be heated to 520 ℃ activation temperature from the pre-catalyst of embodiment 3 and C3 from the pre-catalyst of embodiment 2.
Polyreaction
Polymerization reaction experiment in the table 1 is that (the suspensoid medium: total pressure is that 40bar and discharge capacity are to carry out under the 25kg/h Trimethylmethane) at 180l PF loop reactor (=particle generates loop reactor) under the condition of defined in table 1.Catalyzer described in embodiment 1 and the C1 is as catalyzer.
Polymerization reaction experiment in the table 2 is on continuous gas-phase fluidized-bed reactor (as at the Lupotech G described in the WO99/29736A1), is that 20bar and discharge capacity are to carry out under the 50kg/h at stagnation pressure under the condition of defined in table.
To under the shielding gas condition, on ZSK40, carry out granulation at 200 ℃ with the product of vapor phase process preparation.The process of producing film is from W﹠amp; H has and carries out on the blown film equipment of 60/25D forcing machine.Embodiment 2, C2,3 and C3 described in catalyzer as catalyzer.
The results are summarized in the table of polyreaction and product test.
Table 1: the polyreaction in the loop reactor
| Catalyzer from embodiment | T poly [℃] | C 2H 4The % volume | C 6H 12The % volume | Prod. [g/g ] | Tap density [g/l] | HLMI[g /10min ] | Density [g/cm 3] | M w/M n | ESCR 50℃ [h] |
| 1 | 104.5 | 15 | 0.11 | 15625 | 466 | 12.7 | 0.9557 | 14 | 4 |
| V1 | 106.6 | 10.1 | 0.14 | 5100 | 470 | 9.9 | 0.9565 | 12 | 6 |
Table 2: the polyreaction in the gas phase
| Catalyzer from embodiment | T poly [℃] | THA [g/h] | C 2H 4The % volume | C 6H 12The % volume | Prod. [g/g] | HLMI[g/ 10min] | Density [g/cm 3] | M w/M n | ESC R80℃ [h] | DDI [g] |
| 2 | 113 | 0.45 | 54.8 | 0.39 | 3799 | 25.8 | 0.9393 | 20 | 17 | |
| V2 | 112.2 | 0.4 | 55.4 | 0.33 | 7136 | 23.6 | 0.9394 | 10.2 | 13 | |
| 3 | 103.5 | 0.5 | 53.4 | 1.05 | 3692 | 19.6 | 0.9323 | 25.5 | 163 | |
| v3 | 103.5 | 0.5 | 52.8 | 1.02 | 2921 | 16.5 | 0.9339 | 35.2 | 158 |
Embodiment 4
1430g Chromium trinitrate nonahydrate (III) and 26l methyl alcohol are mixed in dissolution reactor while stirring.Stir after 1 hour, join 2.3l four different third titanium oxide in this solution and stirred this mixture 5 minutes.Subsequently this solution was pumped on the 18kg silica-gel carrier XPO2107 (commercially available the getting by Grace) through 1 hour.After the adding, with this dissolution reactor of 4l methanol rinse, and this rinsing liquid joins on the silica-gel carrier equally.With this suspensoid restir 1 hour, use down at 95 ℃ then and carry out drying.The pre-catalyst that obtains with this method contains the chromium of 1% weight and the titanium of 2% weight, and this per-cent is based on the weight of pre-catalyst.
Comparative example C4
By with 4.86g CrO
3With 10g MgSO
4Suspensoid in the 300ml hexane joins preparation di-t-butyl chromic salt in the solution of the 9.45ml trimethyl carbinol in the 50ml hexane.Stir after 15 minutes, filter this solution, obtain the hexane solution of di-t-butyl chromic salt.
31.5ml four different third titanium oxide are joined on the silica-gel carrier XPO2107 (getting by Grace is commercially available) of 250g with the di-t-butyl chromatedsolution.Stirred this suspensoid then 1 hour.Distill out hexane, use vacuum to carry out drying down at 80 ℃ the solid that generates subsequently.The pre-catalyst that obtains with this method contains the chromium of 1% weight and the titanium of 2% weight, and this per-cent is based on the weight of pre-catalyst.
Activation
Under 520 ℃, utilize the air in the fluidized-bed activator to activate as mentioned above.
Polyreaction
Polymerization reaction experiment in the table 3 is in the 1l autoclave in (suspension medium: Trimethylmethane 400ml, 10ml hexane), and total pressure is to carry out finishing in 90 minutes under the 40bar, 100 ℃.Catalyzer described in embodiment 4 and the C4 is as catalyzer.The two all shows the productive rate of the about 6000g polymkeric substance of every g catalyzer.Raw catalyst compares to the catalyzer (comparative example C4) for preparing in non-proton medium, can obtain having higher molecular weight (M
wAnd M
n) and than wide molecular weight distribution (M
w/ M
n) and the ethylene copolymer of about equal densities.
Table 3: the polyreaction in autoclave
| Catalyzer from embodiment | mg Kat. | THA∶Cr(m ol) | n [dl/g] | M w [g/mol] | Density [g/cm 3] | M w/M n | Vinyl |
| 4 | 45 | 1∶12 | 6.68 | 515388 | 0.9434 | 61.54 | 1.61 |
| v4 | 44 | 1∶13 | 4.39 | 381997 | 0.9446 | 55.81 | 2.04 |
Claims (6)
1, a kind of method that is used to prepare the chrome catalysts of the titanizing on the carrier, it comprises the following steps:
A) make solid support material be less than 20% weight water-content and comprise titanium compound and the aprotic medium of chromium cpd contacts with having,
B) optionally remove solvent,
C) optionally roasting at step B) after the pre-catalyst that obtains and
D) in oxygen containing atmosphere, from 400 ℃ under 1100 ℃, optionally activate at step B) or C) after the pre-catalyst that obtains.
2, the method for claim 1, wherein solid support material is a silica gel.
3, method as claimed in claim 1 or 2, wherein chromium cpd is the inorganic chromium compound.
4, method as claimed in claim 3, wherein the inorganic chromium compound is Chromium trinitrate nonahydrate (III).
5, method as claimed in claim 1 or 2, wherein titanium compound is the mixture of four different third titanium oxide, four positive fourth titanium oxide or these two kinds of titanium compounds.
6, method as claimed in claim 1 or 2, wherein aprotic medium is a methyl alcohol.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2002157740 DE10257740A1 (en) | 2002-12-10 | 2002-12-10 | Preparation of supported, titanized chromium catalysts for the polymerization or copolymerization of olefins, e.g. ethylene, used in film production, involves the use of protic medium comprising titanium and chromium compounds |
| DE10257740.4 | 2002-12-10 | ||
| US60/446,936 | 2003-02-12 | ||
| US60/467,633 | 2003-05-02 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1720269A CN1720269A (en) | 2006-01-11 |
| CN1296396C true CN1296396C (en) | 2007-01-24 |
Family
ID=32336188
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003801050169A Expired - Lifetime CN1296396C (en) | 2002-12-10 | 2003-12-09 | Supported chromium catalysts and their use for the preparation of ethylene homo-and copolymers |
Country Status (2)
| Country | Link |
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| CN (1) | CN1296396C (en) |
| DE (1) | DE10257740A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2322567A1 (en) * | 2009-11-10 | 2011-05-18 | Ineos Europe Limited | Process for the polymerisation of olefins |
| US20120238714A1 (en) * | 2009-11-10 | 2012-09-20 | Ineos Commercial Services Uk Limited | Process for the polymerisation of olefins |
| EP2646147B1 (en) * | 2010-11-30 | 2018-11-14 | Basell Polyolefine GmbH | Method for activation of chromium containing catalyst precursor for polymerization and polymerization method involving said catalyst activation method |
| US9988467B2 (en) * | 2013-03-28 | 2018-06-05 | Saudi Basic Industries Corporation | Polymerization process for the production of high density polyethylene |
| US10213766B2 (en) * | 2015-09-18 | 2019-02-26 | Chevron Phillips Chemical Company Lp | Methods of preparing a catalyst |
| WO2021173148A1 (en) * | 2020-02-28 | 2021-09-02 | Ecovyst Catalyst Technologies Llc | Chromium-on-silica catalysts and methods of making the same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4435314A (en) * | 1981-08-06 | 1984-03-06 | Stamicarbon B.V. | Process of preparing a polymerization catalyst and preparation of ethylene polymers with this catalyst |
| US4442275A (en) * | 1982-03-09 | 1984-04-10 | Phillips Petroleum Company | Polymerization process using catalyst having aqueous titanation of support with solubilized Ti(OR)4 |
| WO2002002652A2 (en) * | 2000-07-05 | 2002-01-10 | Basell Polyolefine Gmbh | Suspended chrome catalyst containing titanium and the use thereof for producing ethylene homopolymers and copolymers |
-
2002
- 2002-12-10 DE DE2002157740 patent/DE10257740A1/en not_active Withdrawn
-
2003
- 2003-12-09 CN CNB2003801050169A patent/CN1296396C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4435314A (en) * | 1981-08-06 | 1984-03-06 | Stamicarbon B.V. | Process of preparing a polymerization catalyst and preparation of ethylene polymers with this catalyst |
| US4442275A (en) * | 1982-03-09 | 1984-04-10 | Phillips Petroleum Company | Polymerization process using catalyst having aqueous titanation of support with solubilized Ti(OR)4 |
| WO2002002652A2 (en) * | 2000-07-05 | 2002-01-10 | Basell Polyolefine Gmbh | Suspended chrome catalyst containing titanium and the use thereof for producing ethylene homopolymers and copolymers |
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|---|---|
| DE10257740A1 (en) | 2004-06-24 |
| CN1720269A (en) | 2006-01-11 |
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