EP1049727A1 - Catalyst system for gas phase polymerisation of conjugated dienes - Google Patents
Catalyst system for gas phase polymerisation of conjugated dienesInfo
- Publication number
- EP1049727A1 EP1049727A1 EP99903606A EP99903606A EP1049727A1 EP 1049727 A1 EP1049727 A1 EP 1049727A1 EP 99903606 A EP99903606 A EP 99903606A EP 99903606 A EP99903606 A EP 99903606A EP 1049727 A1 EP1049727 A1 EP 1049727A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalyst system
- iii
- catalyst
- cocatalyst
- polymerization
- 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.)
- Withdrawn
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- 150000001993 dienes Chemical class 0.000 title claims abstract description 16
- 239000003426 co-catalyst Substances 0.000 claims abstract description 28
- -1 rare earth compound Chemical class 0.000 claims abstract description 18
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 8
- 239000002841 Lewis acid Substances 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 27
- 238000006116 polymerization reaction Methods 0.000 claims description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000006229 carbon black Substances 0.000 claims description 11
- 239000012876 carrier material Substances 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000005062 Polybutadiene Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 6
- 239000004480 active ingredient Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 150000007942 carboxylates Chemical class 0.000 claims description 3
- 229920002857 polybutadiene Polymers 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000005594 diketone group Chemical group 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 229920001195 polyisoprene Polymers 0.000 claims 2
- 239000004927 clay Substances 0.000 claims 1
- 150000004678 hydrides Chemical class 0.000 claims 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical group II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 229920001971 elastomer Polymers 0.000 abstract description 5
- 239000005060 rubber Substances 0.000 abstract description 5
- 239000004411 aluminium Substances 0.000 abstract 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 21
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 19
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 16
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical group [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 10
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 9
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 9
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 8
- 238000005054 agglomeration Methods 0.000 description 8
- 230000002776 aggregation Effects 0.000 description 8
- 235000019241 carbon black Nutrition 0.000 description 8
- 230000037048 polymerization activity Effects 0.000 description 8
- LHBNLZDGIPPZLL-UHFFFAOYSA-K praseodymium(iii) chloride Chemical compound Cl[Pr](Cl)Cl LHBNLZDGIPPZLL-UHFFFAOYSA-K 0.000 description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 229910052779 Neodymium Chemical group 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- 229910014323 Lanthanum(III) bromide Inorganic materials 0.000 description 6
- XKUYOJZZLGFZTC-UHFFFAOYSA-K lanthanum(iii) bromide Chemical compound Br[La](Br)Br XKUYOJZZLGFZTC-UHFFFAOYSA-K 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- LBWLQVSRPJHLEY-UHFFFAOYSA-K neodymium(3+);tribromide Chemical compound Br[Nd](Br)Br LBWLQVSRPJHLEY-UHFFFAOYSA-K 0.000 description 6
- 239000011236 particulate material Substances 0.000 description 6
- PLKCYEBERAEWDR-UHFFFAOYSA-K praseodymium(3+);tribromide Chemical compound Br[Pr](Br)Br PLKCYEBERAEWDR-UHFFFAOYSA-K 0.000 description 6
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 5
- 239000012442 inert solvent Substances 0.000 description 5
- 229910052746 lanthanum Inorganic materials 0.000 description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical group [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000012685 gas phase polymerization Methods 0.000 description 4
- 229910003480 inorganic solid Inorganic materials 0.000 description 4
- WCWKKSOQLQEJTE-UHFFFAOYSA-N praseodymium(3+) Chemical compound [Pr+3] WCWKKSOQLQEJTE-UHFFFAOYSA-N 0.000 description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 4
- 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 3
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- CZMAIROVPAYCMU-UHFFFAOYSA-N lanthanum(3+) Chemical compound [La+3] CZMAIROVPAYCMU-UHFFFAOYSA-N 0.000 description 3
- 229940049964 oleate Drugs 0.000 description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 3
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 2
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 2
- NMXLXQGHBSPIDR-UHFFFAOYSA-N 2-(2-methylpropyl)oxaluminane Chemical compound CC(C)C[Al]1CCCCO1 NMXLXQGHBSPIDR-UHFFFAOYSA-N 0.000 description 2
- XZMKUVNUDMQGLO-UHFFFAOYSA-N 2-ethylhexan-1-olate;neodymium(3+) Chemical compound [Nd+3].CCCCC(CC)C[O-].CCCCC(CC)C[O-].CCCCC(CC)C[O-] XZMKUVNUDMQGLO-UHFFFAOYSA-N 0.000 description 2
- QBKTXRLYEHZACW-UHFFFAOYSA-K 2-ethylhexanoate;neodymium(3+) Chemical compound [Nd+3].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O QBKTXRLYEHZACW-UHFFFAOYSA-K 0.000 description 2
- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical compound C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- YBTXYRSEXVNDOQ-UHFFFAOYSA-N C(CCCCCCCCC)[O-].[Nd+3].C(CCCCCCCCC)[O-].C(CCCCCCCCC)[O-] Chemical compound C(CCCCCCCCC)[O-].[Nd+3].C(CCCCCCCCC)[O-].C(CCCCCCCCC)[O-] YBTXYRSEXVNDOQ-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- AZWXAPCAJCYGIA-UHFFFAOYSA-N bis(2-methylpropyl)alumane Chemical compound CC(C)C[AlH]CC(C)C AZWXAPCAJCYGIA-UHFFFAOYSA-N 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical group [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- JJSGABFIILQOEY-UHFFFAOYSA-M diethylalumanylium;bromide Chemical compound CC[Al](Br)CC JJSGABFIILQOEY-UHFFFAOYSA-M 0.000 description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 2
- MGDOJPNDRJNJBK-UHFFFAOYSA-N ethylaluminum Chemical compound [Al].C[CH2] MGDOJPNDRJNJBK-UHFFFAOYSA-N 0.000 description 2
- JFICPAADTOQAMU-UHFFFAOYSA-L ethylaluminum(2+);dibromide Chemical compound CC[Al](Br)Br JFICPAADTOQAMU-UHFFFAOYSA-L 0.000 description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 2
- 230000007717 exclusion Effects 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical group [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000004071 soot Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 2
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-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
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 1
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 1
- PPNFILUQDVDXDA-UHFFFAOYSA-K 2-ethylhexanoate;lanthanum(3+) Chemical compound [La+3].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O PPNFILUQDVDXDA-UHFFFAOYSA-K 0.000 description 1
- LJLKMNSTMFZSEO-UHFFFAOYSA-K 2-ethylhexanoate;praseodymium(3+) Chemical compound [Pr+3].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O LJLKMNSTMFZSEO-UHFFFAOYSA-K 0.000 description 1
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- XRBLOPCCLRDKJO-UHFFFAOYSA-N C(C)C(C[O-])CCCC.[La+3].C(C)C(C[O-])CCCC.C(C)C(C[O-])CCCC Chemical compound C(C)C(C[O-])CCCC.[La+3].C(C)C(C[O-])CCCC.C(C)C(C[O-])CCCC XRBLOPCCLRDKJO-UHFFFAOYSA-N 0.000 description 1
- HFCMDKFFOOECKP-UHFFFAOYSA-N C(C)C(C[O-])CCCC.[Pr+3].C(C)C(C[O-])CCCC.C(C)C(C[O-])CCCC Chemical compound C(C)C(C[O-])CCCC.[Pr+3].C(C)C(C[O-])CCCC.C(C)C(C[O-])CCCC HFCMDKFFOOECKP-UHFFFAOYSA-N 0.000 description 1
- AVOOJGZNRAQOEO-UHFFFAOYSA-N C(CCCCCCCCC)[O-].[La+3].C(CCCCCCCCC)[O-].C(CCCCCCCCC)[O-] Chemical compound C(CCCCCCCCC)[O-].[La+3].C(CCCCCCCCC)[O-].C(CCCCCCCCC)[O-] AVOOJGZNRAQOEO-UHFFFAOYSA-N 0.000 description 1
- ACUOWFBJMGDGQW-UHFFFAOYSA-N C(CCCCCCCCC)[O-].[Pr+3].C(CCCCCCCCC)[O-].C(CCCCCCCCC)[O-] Chemical compound C(CCCCCCCCC)[O-].[Pr+3].C(CCCCCCCCC)[O-].C(CCCCCCCCC)[O-] ACUOWFBJMGDGQW-UHFFFAOYSA-N 0.000 description 1
- MLGMKBHDVSSSCC-UHFFFAOYSA-K C1(CCCCC1)C(=O)[O-].[La+3].C1(CCCCC1)C(=O)[O-].C1(CCCCC1)C(=O)[O-] Chemical compound C1(CCCCC1)C(=O)[O-].[La+3].C1(CCCCC1)C(=O)[O-].C1(CCCCC1)C(=O)[O-] MLGMKBHDVSSSCC-UHFFFAOYSA-K 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 241000589614 Pseudomonas stutzeri Species 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- PTISNQVXRPCWIC-UHFFFAOYSA-K [Pr+3].CCC([O-])=O.CCC([O-])=O.CCC([O-])=O Chemical compound [Pr+3].CCC([O-])=O.CCC([O-])=O.CCC([O-])=O PTISNQVXRPCWIC-UHFFFAOYSA-K 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- PQLAYKMGZDUDLQ-UHFFFAOYSA-K aluminium bromide Chemical compound Br[Al](Br)Br PQLAYKMGZDUDLQ-UHFFFAOYSA-K 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- NZIXICKPQWIFAU-UHFFFAOYSA-K bromo(dimethyl)alumane;dibromo(methyl)alumane Chemical compound C[Al](C)Br.C[Al](Br)Br NZIXICKPQWIFAU-UHFFFAOYSA-K 0.000 description 1
- ACBSZXDTALWBAM-UHFFFAOYSA-N butan-1-olate praseodymium(3+) Chemical compound [Pr+3].CCCC[O-].CCCC[O-].CCCC[O-] ACBSZXDTALWBAM-UHFFFAOYSA-N 0.000 description 1
- NYPANIKZEAZXAE-UHFFFAOYSA-N butan-1-olate;lanthanum(3+) Chemical compound [La+3].CCCC[O-].CCCC[O-].CCCC[O-] NYPANIKZEAZXAE-UHFFFAOYSA-N 0.000 description 1
- YPEWLXGESTWIDH-UHFFFAOYSA-N butan-1-olate;neodymium(3+) Chemical compound [Nd+3].CCCC[O-].CCCC[O-].CCCC[O-] YPEWLXGESTWIDH-UHFFFAOYSA-N 0.000 description 1
- QQHRHLXGCZWTDK-UHFFFAOYSA-L butylaluminum(2+);dibromide Chemical compound [Br-].[Br-].CCCC[Al+2] QQHRHLXGCZWTDK-UHFFFAOYSA-L 0.000 description 1
- SHOVVTSKTTYFGP-UHFFFAOYSA-L butylaluminum(2+);dichloride Chemical compound CCCC[Al](Cl)Cl SHOVVTSKTTYFGP-UHFFFAOYSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- HYZXMVILOKSUKA-UHFFFAOYSA-K chloro(dimethyl)alumane;dichloro(methyl)alumane Chemical compound C[Al](C)Cl.C[Al](Cl)Cl HYZXMVILOKSUKA-UHFFFAOYSA-K 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- ACIIURKHTPQCPL-UHFFFAOYSA-K cyclohexanecarboxylate;neodymium(3+) Chemical compound [Nd+3].[O-]C(=O)C1CCCCC1.[O-]C(=O)C1CCCCC1.[O-]C(=O)C1CCCCC1 ACIIURKHTPQCPL-UHFFFAOYSA-K 0.000 description 1
- CHNDFUGIWKLFGN-UHFFFAOYSA-K cyclohexanecarboxylate;praseodymium(3+) Chemical compound [Pr+3].[O-]C(=O)C1CCCCC1.[O-]C(=O)C1CCCCC1.[O-]C(=O)C1CCCCC1 CHNDFUGIWKLFGN-UHFFFAOYSA-K 0.000 description 1
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical compound CC[AlH]CC HJXBDPDUCXORKZ-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- CJSBUWDGPXGFGA-UHFFFAOYSA-N dimethyl-butadiene Natural products CC(C)=CC=C CJSBUWDGPXGFGA-UHFFFAOYSA-N 0.000 description 1
- ZGMHEOLLTWPGQX-UHFFFAOYSA-M dimethylalumanylium;bromide Chemical compound C[Al](C)Br ZGMHEOLLTWPGQX-UHFFFAOYSA-M 0.000 description 1
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910052740 iodine Chemical group 0.000 description 1
- 239000011630 iodine Chemical group 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- ILPVRBLJWLAMPB-UHFFFAOYSA-N lanthanum(3+) propan-1-olate Chemical compound [La+3].CCC[O-].CCC[O-].CCC[O-] ILPVRBLJWLAMPB-UHFFFAOYSA-N 0.000 description 1
- HDIBUQNJDKISLA-MUCWUPSWSA-K lanthanum(3+);(e)-4-oxopent-2-en-2-olate Chemical compound [La+3].C\C([O-])=C/C(C)=O.C\C([O-])=C/C(C)=O.C\C([O-])=C/C(C)=O HDIBUQNJDKISLA-MUCWUPSWSA-K 0.000 description 1
- RWXOJQGSZWUIEJ-UHFFFAOYSA-K lanthanum(3+);octadecanoate Chemical compound [La+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O RWXOJQGSZWUIEJ-UHFFFAOYSA-K 0.000 description 1
- SORGMJIXNUWMMR-UHFFFAOYSA-N lanthanum(3+);propan-2-olate Chemical compound [La+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SORGMJIXNUWMMR-UHFFFAOYSA-N 0.000 description 1
- ILRDAEXCKRFJPK-UHFFFAOYSA-K lanthanum(3+);tribenzoate Chemical compound [La+3].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 ILRDAEXCKRFJPK-UHFFFAOYSA-K 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XBKBZMOLSULOEA-UHFFFAOYSA-L methylaluminum(2+);dibromide Chemical compound C[Al](Br)Br XBKBZMOLSULOEA-UHFFFAOYSA-L 0.000 description 1
- YSTQWZZQKCCBAY-UHFFFAOYSA-L methylaluminum(2+);dichloride Chemical compound C[Al](Cl)Cl YSTQWZZQKCCBAY-UHFFFAOYSA-L 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 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 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SIINVGJQWZKNSJ-UHFFFAOYSA-K neodymium(3+);octadecanoate Chemical compound [Nd+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O SIINVGJQWZKNSJ-UHFFFAOYSA-K 0.000 description 1
- ARWCRSVRKCNEDI-UHFFFAOYSA-K neodymium(3+);octanoate Chemical compound [Nd+3].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O ARWCRSVRKCNEDI-UHFFFAOYSA-K 0.000 description 1
- IRGLOWNFSUBRSR-UHFFFAOYSA-N neodymium(3+);propan-1-olate Chemical compound [Nd+3].CCC[O-].CCC[O-].CCC[O-] IRGLOWNFSUBRSR-UHFFFAOYSA-N 0.000 description 1
- HZHUIQPXRWTHNF-UHFFFAOYSA-N neodymium(3+);propan-2-olate Chemical compound [Nd+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] HZHUIQPXRWTHNF-UHFFFAOYSA-N 0.000 description 1
- RILQQYPQBCNTQF-UHFFFAOYSA-K neodymium(3+);propanoate Chemical compound [Nd+3].CCC([O-])=O.CCC([O-])=O.CCC([O-])=O RILQQYPQBCNTQF-UHFFFAOYSA-K 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- HKITTYDLDOKDRC-UHFFFAOYSA-K octadecanoate;praseodymium(3+) Chemical compound [Pr+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HKITTYDLDOKDRC-UHFFFAOYSA-K 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- RETHCFDWOPJAIU-UHFFFAOYSA-N praseodymium(3+);propan-1-olate Chemical compound [Pr+3].CCC[O-].CCC[O-].CCC[O-] RETHCFDWOPJAIU-UHFFFAOYSA-N 0.000 description 1
- UMIVUKFKISBKQB-UHFFFAOYSA-N praseodymium(3+);propan-2-olate Chemical compound [Pr+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] UMIVUKFKISBKQB-UHFFFAOYSA-N 0.000 description 1
- XDFGURDROXHOOM-UHFFFAOYSA-K praseodymium(3+);tribenzoate Chemical compound [Pr+3].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 XDFGURDROXHOOM-UHFFFAOYSA-K 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- ZIYNWDQDHKSRCE-UHFFFAOYSA-N tricyclohexylalumane Chemical compound C1CCCCC1[Al](C1CCCCC1)C1CCCCC1 ZIYNWDQDHKSRCE-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- JOJQVUCWSDRWJE-UHFFFAOYSA-N tripentylalumane Chemical compound CCCCC[Al](CCCCC)CCCCC JOJQVUCWSDRWJE-UHFFFAOYSA-N 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000003911 water pollution Methods 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
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—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
- C08F4/52—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 selected from boron, aluminium, gallium, indium, thallium or rare earths
Definitions
- the invention relates to a catalyst system for gas phase polymerization of conjugated dienes, consisting of a rare earth compound, an organoaluminum compound, a further Lewis acid, optionally a conjugated diene, an inert, inorganic or organic carrier material and additionally one applied to an inorganic or organic carrier material Co-catalyst while improving the flowability of the rubber produced in this way.
- Polybutadiene with a high proportion of cis-1,4 units has been produced on an industrial scale for a long time and used for the production of tires and other rubber products.
- EP-B-0605001 claims the use of silica of a certain particle size as carrier material and inert particulate materials to improve the flowability of sticky polymers.
- EP-A-0442452 describes the use of inert particulate materials
- Particle diameters of 0.01-10 ⁇ m to improve the flowability of sticky polymers in polymerizations described above the softening temperature of said sticky polymers.
- EP-A-0530709 describes the use of inert particulate materials
- Particle diameters of 0.01-150 ⁇ m to improve the flowability of sticky polymers in polymerizations described above the softening temperature of said sticky polymers.
- WO-96/04323 describes the use of inert particulate materials to improve the flowability of BR and IR in polymerizations, the reactor temperature being below the dew point of one of the constituents of the cycle gas.
- EP-A-704464 describes a resin particle with a sticky core and a non-sticky shell which consists of 10-90% ethylene.
- EP-A-570960 describes a resin particle with a sticky core and a non-sticky shell made of inert particulate particles.
- WO-97/08211 describes the addition of stabilizers in a carrier
- M is a trivalent element of the rare earths with the
- Atomic numbers 57 to 71 means
- R is an alkyl radical with C 1 -C 2 n
- R 1 identical or different, denote a d-Cio-alkyl radical
- X represents chlorine, bromine or iodine
- x represents 0 or 1, - 5 -
- y 1 to 6
- n 1 to 50
- D a particulate, inorganic or organic solid with a specific surface area greater than 10 m 2 / g (BET), a grain size of 10 to 1000 ⁇ m, preferably 100 to 500 ⁇ m, and a pore volume of 0.3 to 15 ml / g (if soot is used, additional DBP adsorption of more than 30 ml / 100 g),
- All co-catalytically active constituents are suitable as co-catalysts, in particular the materials listed under B).
- All particulate materials are suitable as support materials for these cocatalysts, in particular the materials listed under D).
- a cocatalyst eg aluminum alkyl
- the moving reaction mass runs, for example, in a stirred fixed bed or a fluidized bed, through spontaneous agglomeration and gluing into an unstable state of fluidization.
- the result is a drastically reduced reactor service life.
- the supported co-catalyst solids according to the invention are metered into the gas phase process and they have the desired effect through intimate contact with the above or u. can evolve occupied Nd catalyst described in EP-B-0647657.
- the distribution within the reactor or the fluidized mass is more homogeneous than is the case, for example, when a liquid co-catalyst material is injected into the reaction volume. Also completely unexpected was the effect that the effectiveness of the cocatalyst in separately supported form is significantly higher compared to the same amount of cocatalyst carried together with the catalyst.
- the reaction acceleration or activity increase achieved by the separate support of the cocatalyst is well over 30% compared to the common support.
- M is a trivalent element of the rare earths with atomic numbers 57 to 71 identified in the periodic table.
- Preferred compounds are those in which M is lanthanum, cerium, praseodymium or neodymium or a mixture of rare earth elements, which has at least one the
- Compounds in which M is lanthanum or neodymium or a mixture of rare earths which contain at least 30% by weight of lanthanum or neodymium are very particularly preferred.
- radicals R in the formulas (I) to (IV) are, in particular, straight-chain or branched alkyl radicals having 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl , Isopropyl, isobutyl, tert-butyl, 2-ethylhexyl, neo-pentyl, neo-octyl, neo-decyl, neo-dodecyl.
- neodymium (III) -n-propanolate As alcoholates of component A) z. B. called: neodymium (III) -n-propanolate, neodymium (III) -n-butanolate, neodymium (III) -n-decanolate, neodymium (III) -isopropanolate, neodymium (III) -2-ethyl-hexanolate , Praseodymium (III) -n-propanolate, praseodymium (III) -n-butanolate, praseodymium (III) -n-decanolate, praseodymium (III) -iso-propanolate, praseodymium (III) -2-ethyl-hexanolate, Lanthanum (III) -n-propanolate, lanthanum (III) -n-butanolate,
- Suitable carboxylates of component A) are: lanthanum (III) ⁇ ropionate, lanthanum
- component A) lanthanum (III) acetyl acetonate, praseodymium (III) acetylacetonate, neodymium (III) acetylacetonate, preferably neodymium (III) acetylacetonate.
- Examples of addition compounds of component A) with donors are: lanthanum (III) chloride with tributyl phosphate, lanthanum (III) chloride with tetrahydrofuran, lanthanum (III) chloride with isopropanol, lanthanum (III) chloride with pyridine, Lanthanum (III) chloride with 2-ethylhexanol, lanthanum (III) chloride with ethanol, praseodymium (III) chloride with tributyl phosphate, praseodymium (III) chloride with tetrahydrofuran, praseodymium (III) chloride with isopropanol , Praseodymium (III) chloride with pyridine, praseodymium (III) chloride with 2-ethylhexanol, praseodymium (III) chloride with ethanol, neodymium (III) chloride with tributyl phosphate, ne
- neodymium (III) bromide with pyridine neodymium (III) bromide with 2-ethylhexanol
- neodymium (III) bromide with ethanol preferably lanthanum (III) chloride with tributyl phosphate, lanthanum (III) chloride with pyridine, lanthanum (III) chloride with 2-ethylhexanol, praseodymium (III) chloride with tributyl phosphate, praseodymium (III) chloride with 2-ethylhexanol, neodymium (III) chloride with tributyl phosphate, neodymium (III) chloride with tetrahydrofuran, neodymium (III) chloride with 2-ethylhexanol, neodymium (III) chloride with pyridine, neodymium (III) chloride with ethanol, preferably
- the rare earth compounds can be used individually or as a mixture with one another.
- Neodymnaphthenate used as component A was Neodymnaphthenate used as component A.
- R 1 is a straight-chain or branched alkyl radical having 1 to 10 C atoms, preferably 1 to 4 C atoms.
- suitable aluminum alkyls of the formula (V) are:
- Triethyl aluminum, triisobutyl aluminum and di-iso-butyl aluminum hydride are preferred.
- Di-isobutyl aluminum hydride is particularly preferred.
- alumoxanes (VI) and (VII) are: methylalumoxane, ethylalumoxane and isobutylalumoxane, preferably methylalumoxane and isobutylalumoxane.
- Lewis acids are used as component C).
- examples include the organometallic halides in which the metal atom belongs to group 3 a) or 4a), and halides of the elements in groups 3a), 4a) and 5a) des
- Diethyl aluminum chloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride, diethyl aluminum bromide, ethyl aluminum sesquibromide and / or ethyl aluminum dibromide are preferably used.
- reaction products of aluminum compounds, as described as component B), with halogens or halogen compounds, for. B. triethyl aluminum with bromine or triethyl aluminum with butyl chloride can be used.
- the reaction can be carried out separately, or the amount of alkyl aluminum compound required for the reaction is added to the amount required as component B).
- Ethyl aluminum sesquichloride, butyl chloride and butyl bromide are preferred.
- BET m 2 / g
- a grain size of 10 to 1000 ⁇ m preferably 50 to 500 ⁇ m
- a pore volume 0.3 to 15 ml / g, preferably from 0.5 to 5 ml / g used.
- DBP adsorption is used as a suitability criterion in addition to the pore volume. This should be between 10 to 300 ml / 100 g, preferably between 60 to 150 ml / 100 g, particularly preferably between 90 and 130 ml / 100 g. - 10 -
- the specific surface area (BET) is determined in the usual way according to S. Brunauer, P.H. Emmet and Teller, J. Anorg. Chem.Soc. 60 (2), 309 (1938), the pore volume is determined by the centrifugation method according to M. McDaniel., J.CoUoid Interface Sei. 78, 31 (1980) and the DBP adsorption according to DIN 53 601.
- inorganic solids particularly suitable as inorganic solids are silica gels, precipitated silicas, clays, aluminosilicates, talc, zeolites, carbon black, inorganic oxides such as silicon dioxide, aluminum oxide, magnesium oxide, titanium dioxide, silicon carbide.
- Silica gels, precipitated silicas, zeolites and carbon black are preferred, particularly preferred precipitated silicas and carbon black.
- inert is understood to mean that the solids are composed in this way or by pretreatment, such as e.g. Calcine, pretreated so that the reactive surface does not hinder the formation of an active catalyst or reacts with the monomers.
- the inorganic solids can be used individually or in a mixture with one another.
- polymeric materials preferably in the form of free-flowing powders, which are so designed or pretreated by pretreatment, such as drying, for example, that the reactive surface does not hinder the formation of an active catalyst, or with the monomers reacted, a grain size in the range of 10 to 1000 microns and which have a pore volume in the range of 0.3 to 15 ml g.
- pretreatment such as drying, for example, that the reactive surface does not hinder the formation of an active catalyst, or with the monomers reacted
- a grain size in the range of 10 to 1000 microns and which have a pore volume in the range of 0.3 to 15 ml g.
- An example of such a material is powdered polypropylene. - 11 -
- the molar ratio in which the catalyst components A) to D) are used can be varied within wide limits.
- the molar ratio of component A) to component B) is 1: 1 to 1: 1000, preferably 1: 3 to 1: 200, particularly preferably 1: 3 to 1: 100.
- the molar ratio of component A) to component C) is 1: 0.4 to 1:15, preferably 1: 0.5 to 1: 8.
- component D For 100 g of component D) 0.1 mmol to 1 mol of component A), preferably 1 to 50 mmol of component A) are used.
- This component E) is a conjugated diene, which can be the same diene that is later to be polymerized with the catalyst. Butadiene and isoprene are preferably used.
- the amount of E) is preferably 1 to 1000 mol, based on 1 mol of component A), particularly preferably 1 to 100 mol, based on 1 mol of component A). 1 to 50 mol, based on 1 mol of component A), of E) are very particularly preferably used.
- the supported co-catalyst according to the invention is produced by applying a solution of the co-catalyst or cocatalysts preferably described under B) to the particulate solid D).
- the solid is agitated, e.g. in a stirred tank with a conventional stirring unit, such as. B. a cross bar stirrer or a spiral stirrer, or in a further preferred form in a ploughshare mixer.
- a conventional stirring unit such as. B. a cross bar stirrer or a spiral stirrer, or in a further preferred form in a ploughshare mixer.
- the support material can also be impregnated with a cocatalyst solution in a fluidized bed. This is done on the carrier material by an inert gas stream - 12 -
- the drug solution is applied, e.g. by spraying with a nozzle.
- the inert gas can be returned to the reactor via an internal circuit after it has been freed from the solvent which is also transported.
- the inert solvent can be reused for the preparation of the active ingredient solution.
- the co-catalyst system can react with air and / or moisture, it is advantageous to dry the solid powder D) before applying the co-catalyst solution, to remove the air and under an inert gas atmosphere before, during and after the application of the co- Keep catalyst solution.
- the application of the co-catalyst solution is preferably controlled so that the added, preferably atomized, solution is immediately taken up by the solid D). The formation of clumps and inhomogeneities is thus minimized.
- the catalyst system and / or supported co-catalyst can also be prepared continuously.
- the efficiency level of the catalyst system by adjusting the ratio of the metered amount of supported co-catalyst material to the Nd catalyst present.
- the solids ulver can thus continue to be easily stirred and moved as a free-flowing powder after the application of the active ingredient solution.
- inert solvent used within wide limits. As shown, however, the amount is kept as low as possible for ecological and economic reasons.
- the amount depends on the amount and the solubility of the co-catalyst component (s) and the pore volume / DBP adsorption of component D).
- the supported cocatalyst can be produced in a wide temperature range.
- the temperature is between the melting point and boiling point of the cocatalyst component B) or the inert solvent.
- the usual procedure is at temperatures from -20 to 100 ° C, preferably 20 to 40 ° C.
- the inert solvent is removed by distillation.
- the distillation can be carried out both in the same container in which the impregnation was carried out and in a separate apparatus, e.g. a fluidized bed dryer. When removing the solvent, the entry of air and moisture must be avoided.
- the distillation is carried out at temperatures from 0 to 150 ° C., preferably at 10 to 80 ° C., and pressures from 0.001 mbar to 20 bar absolute, preferably 0.001 mbar to normal pressure.
- the distillation can also be carried out continuously.
- the condensate collected under inert conditions can be reused without further processing as a solvent for the active ingredients used in the impregnation.
- the inert solvent is not removed.
- the invention also relates to the use of the supported co-catalyst prepared according to the invention in a process for the polymerization of conjugated dienes, e.g. of 1,3-butadiene, isoprene, pentadiene or dimethylbutadiene in the gas phase.
- conjugated dienes e.g. of 1,3-butadiene, isoprene, pentadiene or dimethylbutadiene in the gas phase.
- This polymerization is carried out by bringing the gaseous conjugated diene into contact with the above-described or, inter alia, EP-B-0647657 and the supported co-catalyst prepared according to the invention. Further gases can be mixed into the gaseous monomer, which serve either for dilution or heat dissipation or for regulating the molecular weight.
- merisatio ⁇ can be carried out at pressures from lmbar to 50 bar, preferably 1 to 20 bar.
- the polymerization is carried out at temperatures from -20 to 250 ° C., preferably at 0 to 200 ° C., particularly preferably at 20 to 160 ° C.
- the polymerization can be accomplished in any apparatus suitable for gas phase polymerization.
- So z. B a stirred reactor, a rotating reactor or a fluidized bed reactor or a combination of these types of reactors.
- the polymers obtained have a cis-1,4 double bond content of about 60 to 99%.
- the molecular weight can be changed by the composition of the catalyst and by varying the polymerization conditions. Molecular weights of 10 3 to 10 6 , as measured with GPC (gel permeation chromatography as described, for example, in M. Hoffmann, H. Krömer, R. Kuhn,
- the Mooney viscosity, ML (1 + 4 ', 100 ° C)) is usually in the range between 30 and 180 ME.
- the polymerization in the gas phase can also be used to produce very high molecular weight polymers, which are only accessible with extremely great effort because of the high viscosity and the possibility of transfer reactions through the solvent used.
- the polymers obtained can be compounded and vulcanized in the usual way.
- the polymerization of 1,3-butadiene is carried out as follows:
- an apparatus which is suitable for keeping the powdery catalyst and the supported particulate cocatalyst in motion. That can e.g. B. by stirring, turning and / or a gas stream.
- the inert gas initially located in the gas space e.g. B. nitrogen is replaced by the gaseous monomer.
- An immediate polymerization starts and the temperature rises.
- the monomer, optionally diluted, is fed to the reactor with an inert gas so rapidly that the desired reaction temperature is not exceeded.
- the reaction temperature can also be set in the usual way by heating or cooling.
- the polymerization is terminated by switching off the monomer feed.
- the polymer can be further treated in the known manner by deactivating the catalyst and treating the polymer with known anti-aging agents.
- the following examples are intended to illustrate the use of the catalyst system described here for the gas-phase polymerization of conjugated dienes, consisting of a rare earth compound, an organoaluminum compound, a further Lewis acid, optionally a conjugated diene, an inert, inorganic or organic support material and additionally one on one Describe inorganic or organic support material applied co-catalyst while improving the flowability of the rubber produced here, but without restricting it to the examples, and clarify the unexpected and significant increase in activity when using the co-catalyst system according to the invention in addition to the catalyst system described above.
- conjugated dienes consisting of a rare earth compound, an organoaluminum compound, a further Lewis acid, optionally a conjugated diene, an inert, inorganic or organic support material and additionally one on one Describe inorganic or organic support material applied co-catalyst while improving the flowability of the rubber produced here, but without restricting it to the examples, and clarify the unexpected and significant increase in activity when
- Zeosil 1165 MP was used as the support material for the cocatalyst.
- Zeosil 1165 MP is an agglomerated precipitated silica from Rhönen-Poulenc with a BET surface area of 139 m 2 / g.
- the pore volume is 1.97 ml / g.
- the Zeosil 1165 MP is dried at 900 ° C in a rotary kiln in a nitrogen countercurrent and then filled with the exclusion of air and moisture.
- Carbon black N115 a product from Degussa, was also used as the carrier material.
- the carbon black has a BET surface area of 145 m 2 / g and a DBP adsorption of 113 ml / 100 g.
- the average particle diameter is 485 ⁇ m. This material was dried under nitrogen at 450 ° C. for 32 hours and transferred and stored under nitrogen.
- the inside temperature should be 20 to 30 ° C. - 17 -
- the mixture is stirred at 20 ° C. for 30 minutes and then the hexane is distilled off at 0.1 mbar and 50 ° C. 1055 g of a free-flowing white powder are obtained.
- EASC and 7.4 mmol of isoprene per 100 g of material were conveyed into the reactor by means of a lock, and the reaction temperature was regulated via the jacket circuit in such a way that a temperature of 80 ° C. could be established in the stirred bed.
- the polymerization was started by metering preheated gaseous butadiene into the reactor, starting with a butadiene partial pressure of 2 bar. At the start of the reaction, the bed temperature rose to about 84 ° C. despite jacket countercooling, and the reaction was able to proceed after 10 minutes run isothermally at 80 ° C over the entire course.
- the experiment was carried out in the semi-batch mode, ie the amount of butadiene consumed in the reaction was always replenished, but no catalyst and no supported cocatalyst, and no product was removed until the end of the experiment.
- the rapid increase in the agitated bed from the beginning which is also referred to as a pseudo fluidized bed due to the vigorous mixing with the spiral stirrer, was well observed in the glass reactor, and a steady increase in the product grain size of a few 100 initially ⁇ m in diameter to more than 1 mm in the end. Slight particle agglomerations occurred in the course of the reaction, but did not significantly impede mixing.
- the product was discharged via a ball valve in the bottom plate of the reactor and then immediately by mixing in 3 g of stearic acid and 3 g of Vulkanox BKF
- the average polymerization activity of the catalyst system in this experiment was about 220 [kg BR / (mol Nd ⁇ bar butadiene • h)].
- Example 3a The polymerization was carried out as in Example 3a), but this time, together with the Nd catalyst described, 4.5 g of the supported cocatalyst from Example Ib) according to the invention were conveyed into the reactor using the lock.
- Example 3a The polymerization was carried out as in Example 3a), but this time, together with the Nd catalyst described, 4.5 g of a zeosil which had been pretreated according to Example la) but not covered with DIB AH according to Example Ib) were conveyed into the reactor via the lock .
- Example 3a The polymerization was carried out as in Example 3a), 3 g of a carbon black-supported catalyst as described initially or, inter alia, in EP-B-0647657, with an occupancy of 3.7 mmol Nd, 148 mmol DIBAH, 3, 7 mmol EASC and 7.4 isoprene per 100 g material were used.
- the bed temperature rose to about 86 ° C. despite jacket countercooling.
- the reaction could be carried out isothermally at 80 ° C. over the entire course. Slight particle agglomerations occurred in the course of the reaction, but did not significantly impede mixing.
- the product was discharged via a ball valve in the bottom plate of the reactor and then immediately stopped and stabilized on the roller by mixing in 3 g of stearic acid and 3 g of Vulkanox BKF from Bayer AG. - 20 -
- the average polymerization activity of the catalyst system in this experiment was about 450 [kg BR / (mol Nd • bar butadiene • h)].
- Example 4a The polymerization was carried out as in Example 4a), but this time, together with the Nd catalyst described, 12 g of the supported co-catalyst according to the invention from Example 2) were conveyed into the reactor using the lock.
- Example 4a The polymerization was carried out as in Example 4a), but this time, together with the Nd catalyst described, 20 g of a carbon black previously pretreated according to Example la) but not coated with DIBAH according to Example 2) were conveyed into the reactor via the lock.
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Abstract
A catalyst system for gas phase polymerisation of conjugated dienes, consisting of a rare earth compound, an aluminium organic compound, another Lewis acid, optionally a conjugated diene, an inert inorganic or organic support and a co-catalyst applied to an inorganic support, in order to improve the flowability of rubber thus produced.
Description
Katalysatorsvstem zur Gasphasenpolymerisation von konjugierten DienenCatalyst system for gas phase polymerization of conjugated dienes
Die Erfindung betrifft ein Katalysatorsystem zur Gasphasenpolymerisation von konjugierten Dienen, bestehend aus einer Verbindung der Seltenen Erden, einer aluminiumorganischen Verbindung, einer weiteren Lewissäure, ggf. einem konjugierten Dien, einem inerten, anorganischen oder organischen Trägermaterial und zusätzlich einem auf einem anorganischen oder organischen Trägermaterial aufgebrachtem Co-Katalysator unter Verbesserung der Fließfähigkeit des hierbei hergestellten Kautschuks.The invention relates to a catalyst system for gas phase polymerization of conjugated dienes, consisting of a rare earth compound, an organoaluminum compound, a further Lewis acid, optionally a conjugated diene, an inert, inorganic or organic carrier material and additionally one applied to an inorganic or organic carrier material Co-catalyst while improving the flowability of the rubber produced in this way.
Polybutadien mit einem hohen Anteil an cis-l,4-Einheiten wird seit längerer Zeit in großtechnischem Maßstab produziert und für die Herstellung von Reifen und anderen Gummiwaren verwendet.Polybutadiene with a high proportion of cis-1,4 units has been produced on an industrial scale for a long time and used for the production of tires and other rubber products.
Aus umweltrelevanten Gründen ist man bestrebt, die Polymerisation dieses und anderer konjugierter Diene in der Gasphase durchzuführen, da dabei keine Lösungsmittel eingesetzt werden müssen und Emission und Abwasserbelastung verringert werden können.For environmental reasons, efforts are being made to carry out the polymerization of this and other conjugated dienes in the gas phase, since no solvents have to be used and emission and waste water pollution can be reduced.
Zusätzlich kann man durch das Verfahren neuartige Kautschuke mit besonderenIn addition, the process can be used to create novel rubbers with special ones
Produkteigenschaften herstellen. Insbesondere erhält man im Polymeren besonders gut dispergierte Füllstoffe, wenn diese bei der Polymerisation als Träger der Aktivkomponente des Katalysators zugegen sind.Establish product properties. In particular, particularly well-dispersed fillers are obtained in the polymer if they are present during the polymerization as a carrier of the active component of the catalyst.
Aus der EP-B-0647657 ist bereits bekannt, daß man die Polymerisation von konjugierten Dienen, insbesondere von Butadien, ohne Zusatz von Lösungsmitteln in der Gasphase durchführen kann, indem man ein Katalysatorsystem auf der Basis von Verbindungen der Seltenen Erden, einer aluminiumorganischen Verbindung auf einem teilchenförmigen, inerten, anorganischen Feststoff mit einer spezifischen Oberfläche größer als 10 m2/g (BET) und einem Porenvolumen von 0,3 bis 15 ml/g verwendet.
- 2 -From EP-B-0647657 it is already known that the polymerization of conjugated dienes, in particular butadiene, can be carried out in the gas phase without the addition of solvents by using a catalyst system based on rare earth compounds, an organoaluminum compound a particulate, inert, inorganic solid with a specific surface area greater than 10 m 2 / g (BET) and a pore volume of 0.3 to 15 ml / g. - 2 -
In EP-B-0605001 wird die Verwendung von Silica einer bestimmten Teilchengröße als Trägermaterial und inerten teilchenförmigen Materialien zur Verbesserung der Fließfähigkeit von klebrigen Polymeren beansprucht.EP-B-0605001 claims the use of silica of a certain particle size as carrier material and inert particulate materials to improve the flowability of sticky polymers.
In EP-A-0442452 wird die Verwendung von inerten teilchenförmigen Materialien mitEP-A-0442452 describes the use of inert particulate materials
Partikeldurchmessern von 0,01-10 μm zur Verbesserung der Fließfähigkeit von klebrigen Polymeren bei Polymerisationen oberhalb der Erweichungstemperatur der besagten klebrigen Polymeren beschrieben.Particle diameters of 0.01-10 μm to improve the flowability of sticky polymers in polymerizations described above the softening temperature of said sticky polymers.
In EP-A-0530709 wird die Verwendung von inerten teilchenförmigen Materialien mitEP-A-0530709 describes the use of inert particulate materials
Partikeldurchmessern von 0,01-150 μm zur Verbesserung der Fließfähigkeit von klebrigen Polymeren bei Polymerisationen oberhalb der Erweichungstemperatur der besagten klebrigen Polymeren beschrieben.Particle diameters of 0.01-150 μm to improve the flowability of sticky polymers in polymerizations described above the softening temperature of said sticky polymers.
In WO-88/02379 wird die Verwendung von inerten pulverigen anorganischenWO-88/02379 describes the use of inert powdery inorganic
Materialien in Mengen zwischen 0,005-0,2 Gew.-Prozent bezogen auf das Wirbelbettes zur Verbesserung der Fließfähigkeit von Polymeren beansprucht.Materials in amounts between 0.005-0.2% by weight based on the fluidized bed to improve the flowability of polymers.
In WO-96/04323 wird die Verwendung von inerten teilchenförmigen Materialien zur Verbesserung der Fließfähigkeit von BR und IR bei Polymerisationen beschrieben, wobei die Reaktortemperatur unterhalb des Taupunktes einer der Bestandteile des Kreisgases liegt.WO-96/04323 describes the use of inert particulate materials to improve the flowability of BR and IR in polymerizations, the reactor temperature being below the dew point of one of the constituents of the cycle gas.
In EP-A-704464 wird ein Harzpartikel mit klebrigem Kern und einer nicht-klebrigen Hülle, die zu 10-90 % aus Ethylen besteht, beschrieben.EP-A-704464 describes a resin particle with a sticky core and a non-sticky shell which consists of 10-90% ethylene.
In EP-A-570960 wird ein Harzpartikel mit klebrigem Kern und einer nicht-klebrigen Hülle aus inerten partikelförmigen Teilchen beschrieben.EP-A-570960 describes a resin particle with a sticky core and a non-sticky shell made of inert particulate particles.
In sämtlichen oben beschriebenen Verfahren wird mit inerten Materialien gearbeitet, wobei auf den Begriff inert verstärkt Wert gelegt wird.
Die US-PS-5 162 463 hingegen lehrt, daß die Agglomeration der klebrigen Partikel in einem Wirbelbett vermieden werden kann, indem ein inertes Material, das mit einer Polysiloxanschicht überzogen ist, in das Wirbelbett dosiert wird.In all of the processes described above, inert materials are used, with increasing emphasis being placed on the term inert. US Pat. No. 5,162,463, on the other hand, teaches that agglomeration of the sticky particles in a fluidized bed can be avoided by metering an inert material which is coated with a polysiloxane layer into the fluidized bed.
Schließlich beschreibt die WO-97/08211 die Zugabe von Stabilisatoren in geträgerterFinally, WO-97/08211 describes the addition of stabilizers in a carrier
Form.Shape.
Für den Fachmann war es nun völlig unerwartet, daß durch den Einsatz von mit Co- Katalysatoren belegten teilchenförmigen Materialien die Aktivität des u. a. in EP-B- 0647657 geschützten Katalysatorsystems bestehend ausIt was now completely unexpected for the person skilled in the art that through the use of particulate materials coated with cocatalysts, the activity of u. a. in EP-B-0647657 protected catalyst system consisting of
A) einem Alkoholat der Seltenen Erden (I), einem Carboxylat der Seltenen Erden (II), einer Komplexverbindung der Seltenen Erden mit Diketonen (III)A) an alcoholate of rare earths (I), a carboxylate of rare earths (II), a complex compound of rare earths with diketones (III)
und/oderand or
einer Additionsverbindung der Halogenide der Seltenen Erden mit einer Sauerstoff- oder Stickstoff-Donator- Verbindung (IV) folgender Formeln:an addition compound of the rare earth halides with an oxygen or nitrogen donor compound (IV) of the following formulas:
(RO)3M (I)(RO) 3 M (I)
(R-CO2)3M (II)(R-CO 2 ) 3 M (II)
(R — C- CH- R)3M(R - C- CH- R) 3 sts
(III)(III)
O OO O
undand
MX3 • y Donator (IV)
- 4 -MX 3 • y Donor (IV) - 4 -
einem Aluminiumtrialkyl, einem Dialkylaluminiumhydrid und/oder einem Alumoxan der Formeln (V) - (VII):an aluminum trialkyl, a dialkyl aluminum hydride and / or an alumoxane of the formulas (V) - (VII):
Al(H)x(R1)3.x (V)Al (H) x (R 1 ) 3 . x (V)
R'R '
R1 (A-O)nAi /R 1 (AO) n Ai /
1 R (VI) 1 R (VI)
R1 R 1
undand
c (A O) n+1c (A O) n + 1
RR
wobei in den Formelnbeing in the formulas
M ein dreiwertiges Element der Seltenen Erden mit denM is a trivalent element of the rare earths with the
Ordnungszahlen 57 bis 71 bedeutet,Atomic numbers 57 to 71 means
die Restethe rest
R, gleich oder verschieden, einen Alkylrest mit Cι-C2n bedeuten,R, identical or different, is an alkyl radical with C 1 -C 2 n,
die Restethe rest
R1, gleich oder verschieden, einen d-Cio- Alkylrest bedeuten,R 1 , identical or different, denote a d-Cio-alkyl radical,
X für Chlor, Brom oder Iod stehtX represents chlorine, bromine or iodine
x für 0 oder 1 steht,
- 5 -x represents 0 or 1, - 5 -
y 1 bis 6 bedeutet undy is 1 to 6 and
n 1 bis 50 bedeutet,n means 1 to 50,
C) einer weiteren Lewissäure undC) a further Lewis acid and
D) einem teilchenförmigen, anorganischen oder organischen Feststoff mit einer spezifischen Oberfläche größer als 10 m2/g (BET), einer Korngröße von 10 bis 1000 μm, bevorzugt 100 bis 500 μm, und einem Porenvolumen von 0,3 bis 15 ml/g (bei der Verwendung von Ruß zusätzlich einer DBP-Adsorption von mehr als 30 ml/ 100 g),D) a particulate, inorganic or organic solid with a specific surface area greater than 10 m 2 / g (BET), a grain size of 10 to 1000 μm, preferably 100 to 500 μm, and a pore volume of 0.3 to 15 ml / g (if soot is used, additional DBP adsorption of more than 30 ml / 100 g),
sehr stark gesteigert werden kann.can be increased very strongly.
Als Co-Catalysatoren eignen sich sämtlich Co-katalytisch aktiven Bestandteile, insbesondere die unter B) aufgeführten Materialien. Als Trägermaterialien für diese Co-Katalysatoren eignen sich sämtliche partikelförmigen Materialien, insbesonder die unter D) aufgeführten Materialien.All co-catalytically active constituents are suitable as co-catalysts, in particular the materials listed under B). All particulate materials are suitable as support materials for these cocatalysts, in particular the materials listed under D).
Dosiert man dagegen einen unter B) beschriebenen Co-Katalysator (z.B. Aluminium- alkyl) in flüssiger Phase, sei es in konzentrierter Form oder in verdünnter Lösung, vor und/oder während der Polymerisation in den Reaktionsraum, so läuft die bewegte Reaktionsmasse, beispielsweise in einem gerührten Festbett oder einer Wirbelschicht, durch spontane Agglomeration und Verklebung in einen instabilen Zustand der Fluidi- sierung hinein. Eine drastisch verkürzte Reaktorstandzeit ist die Folge. Nicht so, wenn die erfindungsgemäßen geträgerten Co-Katalysator-Feststoffe in den Gasphasenprozeß eindosiert werden und sie die gewünschte Wirkung durch den innigen Kontakt mit dem oben bzw. u a. in EP-B-0647657 beschriebenen belegten Nd-Katalysator entfalten können. Des weiteren fällt die Verteilung innerhalb des Reaktors bzw. der fluidisierten Masse deutlicher homogener aus als es beispielsweise bei der Eindüsung eines flüssigen Co-Katalysatormaterials in das Reaktionsvolumen der Fall ist.
Völlig unerwartet war auch der Effekt, daß die Wirksamkeit des Co-Katalysators in separat geträgerter Form deutlich höher ist, verglichen mit der gleichen Menge Co- Katalysator gemeinsam mit dem Katalysator geträgert. Die durch die separate Trägerung des Co-Katalysators erzielte Reaktionsbeschleunigung, bzw. Aktivitäts- Steigerung beträgt weit über 30 % verglichen mit der gemeinsamen Trägerung.If, on the other hand, a cocatalyst (eg aluminum alkyl) described under B) is metered into the liquid phase, be it in concentrated form or in dilute solution, before and / or during the polymerization, the moving reaction mass runs, for example, in a stirred fixed bed or a fluidized bed, through spontaneous agglomeration and gluing into an unstable state of fluidization. The result is a drastically reduced reactor service life. Not so if the supported co-catalyst solids according to the invention are metered into the gas phase process and they have the desired effect through intimate contact with the above or u. can evolve occupied Nd catalyst described in EP-B-0647657. Furthermore, the distribution within the reactor or the fluidized mass is more homogeneous than is the case, for example, when a liquid co-catalyst material is injected into the reaction volume. Also completely unexpected was the effect that the effectiveness of the cocatalyst in separately supported form is significantly higher compared to the same amount of cocatalyst carried together with the catalyst. The reaction acceleration or activity increase achieved by the separate support of the cocatalyst is well over 30% compared to the common support.
In der Komponente A) bedeutet M ein dreiwertiges Element der Seltenen Erden mit den im Periodensystem gekennzeichneten Ordnungszahlen 57 bis 71. Bevorzugt werden solche Verbindungen, in denen M Lanthan, Cer, Praseodym oder Neodym oder ein Gemisch von Elementen der Seltenen Erden, welches mindestens eines derIn component A), M is a trivalent element of the rare earths with atomic numbers 57 to 71 identified in the periodic table. Preferred compounds are those in which M is lanthanum, cerium, praseodymium or neodymium or a mixture of rare earth elements, which has at least one the
Elemente Lanthan, Cer, Praseodym oder Neodym zu wenigstens 10 Gew.% enthält, bedeutet. Ganz besonders bevorzugt sind Verbindungen, in denen M Lanthan oder Neodym, bzw. ein Gemisch von Seltenen Erden, welches Lanthan oder Neodym zu mindestens 30 Gew.% enthält, bedeutet.Contains elements of lanthanum, cerium, praseodymium or neodymium in at least 10% by weight. Compounds in which M is lanthanum or neodymium or a mixture of rare earths which contain at least 30% by weight of lanthanum or neodymium are very particularly preferred.
Als Reste R in den Formeln (I) bis (IV) sind insbesondere geradkettige oder verzweigte Alkylreste mit 1 bis 20 Kohlenstoffatomen, bevorzugt 1 bis 15 Kohlenstoffatomen, zu nennen, wie Methyl, Ethyl, n-Propyl, n-Butyl, n-Pentyl, Isopropyl, Isobutyl, tert.-Butyl, 2-Ethylhexyl, neo-Pentyl, neo-Octyl, neo-Decyl, neo-Dodecyl.The radicals R in the formulas (I) to (IV) are, in particular, straight-chain or branched alkyl radicals having 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl , Isopropyl, isobutyl, tert-butyl, 2-ethylhexyl, neo-pentyl, neo-octyl, neo-decyl, neo-dodecyl.
Als Alkoholate der Komponente A) werden z. B. genannt: Neodym(III)-n-propanolat, Neodym(III)-n-butanolat, Neodym(III)-n-decanolat, Neodym(III)-iso-propanolat, Neodym(III)-2-ethyl-hexanolat, Praseodym(III)-n-propanolat, Praseodym(III)-n- butanolat, Praseodym(III)-n-decanolat, Praseodym(III)-iso-propanolat, Praseo- dym(III)-2-ethyl-hexanolat, Lanthan(III)-n-propanolat, Lanthan(III)-n-butanolat, Lan- than(III)-n-decanolat, Lanthan(III)-isopropanolat, Lanthan(III)-2-ethyl-hexanolat, bevorzugt Neodym(III)-n-butanolat, Neodym(III)-n-decanolat, Neodym(III)-2-ethyl- hexanolat.As alcoholates of component A) z. B. called: neodymium (III) -n-propanolate, neodymium (III) -n-butanolate, neodymium (III) -n-decanolate, neodymium (III) -isopropanolate, neodymium (III) -2-ethyl-hexanolate , Praseodymium (III) -n-propanolate, praseodymium (III) -n-butanolate, praseodymium (III) -n-decanolate, praseodymium (III) -iso-propanolate, praseodymium (III) -2-ethyl-hexanolate, Lanthanum (III) -n-propanolate, lanthanum (III) -n-butanolate, lanthanum (III) -n-decanolate, lanthanum (III) -isopropanolate, lanthanum (III) -2-ethyl-hexanolate, preferably neodymium ( III) -n-butanolate, neodymium (III) -n-decanolate, neodymium (III) -2-ethylhexanolate.
Als Carboxylate der Komponente A) sind geeignet: Lanthan(III)-ρropionat, Lanthan-Suitable carboxylates of component A) are: lanthanum (III) ρropionate, lanthanum
(IΙI)-diethylacetat, Lanthan(III)-2-ethyl-hexanoat, Lanthan(III)-stearat, Lanthan(III)- benzoat, Lanthan(III)-cyclohexancarboxylat, Lanthan(III)-oleat, Lanthan(III)-versa-
tat, Lanthan(III)-naphthenat, Praseodym(III)-propionat, Praseodym(III)-diethylacetat, Praseodym(III)-2-ethylhexanoat, Praseodym(III)-stearat, Praseodym(III)-benzoat, Praseodym(III)-cyclohexancarboxylat, Praseodym(III)-oleat, Praseodym(III)-versatat, Praseodym(III)-naphthenat, Neodym(III)-propionat, Neodym(III)-diethylacetat, Neo- dym(III)-2-ethylhexanoat, Neodym(III)-stearat, Neodym(III)-bezoat, Neodym(III)- cyclohexancarboxylat, Neodym(III)-oleat, Neodym(III)-versatat, Neodym(III)-naph- thenat, bevorzugt Neodym(III)-2-ethylhexanoat, Neodym(III)-versatat, Neodym(III)- naphthenat. Besonders bevorzugt wird Neodymversatat eingesetzt.(IΙI) diethyl acetate, lanthanum (III) -2-ethyl-hexanoate, lanthanum (III) stearate, lanthanum (III) benzoate, lanthanum (III) cyclohexane carboxylate, lanthanum (III) oleate, lanthanum (III) - versa- tat, lanthanum (III) naphthenate, praseodymium (III) propionate, praseodymium (III) diethyl acetate, praseodymium (III) -2-ethylhexanoate, praseodymium (III) stearate, praseodymium (III) benzoate, praseodymium (III) -cyclohexane carboxylate, praseodymium (III) oleate, praseodymium (III) versatate, praseodymium (III) naphthenate, neodymium (III) propionate, neodymium (III) diethyl acetate, neodymium (III) -2-ethylhexanoate, neodymium (III) stearate, neodymium (III) bezoate, neodymium (III) cyclohexane carboxylate, neodymium (III) oleate, neodymium (III) versatate, neodymium (III) naphthenate, preferably neodymium (III) -2 -ethylhexanoate, neodymium (III) versatate, neodymium (III) naphthenate. Neodymium versatate is particularly preferably used.
Als Komplexverbindungen der Komponente A) seien genannt: Lanthan(III)-acetyl- acetonat, Praseodym(III)-acetylacetonat, Neodym(III)-acetylacetonat, bevorzugt Neodym(III)-acetylacetonat.The following may be mentioned as complex compounds of component A): lanthanum (III) acetyl acetonate, praseodymium (III) acetylacetonate, neodymium (III) acetylacetonate, preferably neodymium (III) acetylacetonate.
Als Additionsverbindungen der Komponente A) mit Donatoren werden beispielsweise genannt: Lanthan(III)-chlorid mit Tributylphosphat, Lanthan(III)-chlorid mit Tetrahydrofüran, Lanthan(III)-chlorid mit iso-Propanol, Lanthan(III)-chlorid mit Pyridin, Lanthan(III)-chlorid mit 2-Ethylhexanol, Lanthan(III)-chlorid mit Ethanol, Praseo- dym(III)-chlorid mit Tributylphosphat, Praseodym(III)-chlorid mit Tetrahydrofüran, Praseodym(III)-chlord mit iso-Propanol, Praseodym(III)-chlorid mit Pyridin, Praseo- dym(III)-chlorid mit 2-Ethylhexanol, Praseodym(III)-chlorid mit Ethanol, Neo- dym(III)-chlorid mit Tributylphosphat, Neodym(HI)-chlorid mit Tetrahydrofüran, Neodym(III)-chlorid mit iso-Propanol, Neodym(III)-chlorid mit Pyridin, Neo- dym(III)-chlorid mit 2-Ethylhexanol, Neodym(III)-chlorid mit Ethanol, Lanthan(III)- bromid mit Tributylphosphat, Lanthan(III)-bromid mit Tetrahydrofüran, Lanthan(III)- bromid mit iso-Propanol, Lanthan(III)-bromid mit Pyridin, Lanthan(III)-bromid mit 2-Examples of addition compounds of component A) with donors are: lanthanum (III) chloride with tributyl phosphate, lanthanum (III) chloride with tetrahydrofuran, lanthanum (III) chloride with isopropanol, lanthanum (III) chloride with pyridine, Lanthanum (III) chloride with 2-ethylhexanol, lanthanum (III) chloride with ethanol, praseodymium (III) chloride with tributyl phosphate, praseodymium (III) chloride with tetrahydrofuran, praseodymium (III) chloride with isopropanol , Praseodymium (III) chloride with pyridine, praseodymium (III) chloride with 2-ethylhexanol, praseodymium (III) chloride with ethanol, neodymium (III) chloride with tributyl phosphate, neodymium (HI) chloride with Tetrahydrofuran, neodymium (III) chloride with isopropanol, neodymium (III) chloride with pyridine, neodymium (III) chloride with 2-ethylhexanol, neodymium (III) chloride with ethanol, lanthanum (III) bromide with tributyl phosphate, lanthanum (III) bromide with tetrahydrofuran, lanthanum (III) bromide with isopropanol, lanthanum (III) bromide with pyridine, lanthanum (III) bromide with 2-
Ethylhexanol, Lanthan(III)-bromid mit Ethanol, Praseodym(III)-bromid mit Tributylphosphat, Praseodym(III)-bromid mit Tetrahydrofüran, Praseodym(III)-bromid mit iso-Propanol, Praseodym(III)-bromid mit Pyridin, Praseodym(III)-bromid mit 2- Ethylhexanol, Praseodym(III)-bromid mit Ethanol, Neodym(III)-bromid mit Tributyl- phosphat, Neodym(III)-bromid mit Tetrahydrofüran, Neodym(III)-bromid mit iso-Ethylhexanol, lanthanum (III) bromide with ethanol, praseodymium (III) bromide with tributyl phosphate, praseodymium (III) bromide with tetrahydrofuran, praseodymium (III) bromide with isopropanol, praseodymium (III) bromide with pyridine, praseodymium (III) bromide with 2-ethylhexanol, praseodymium (III) bromide with ethanol, neodymium (III) bromide with tributyl phosphate, neodymium (III) bromide with tetrahydrofuran, neodymium (III) bromide with iso-
Propanol, Neodym(III)-bromid mit Pyridin, Neodym(III)-bromid mit 2-Ethylhexanol, Neodym(III)-bromid mit Ethanol, bevorzugt Lanthan(III)-chlorid mit Tributyl-
phosphat, Lanthan(III)-chlorid mit Pyridin, Lanthan(III)-chlorid mit 2-Ethylhexanol, Praseodym(III)-chlorid mit Tributylphosphat, Praseodym(III)-chlorid mit 2-Ethyl- hexanol, Neodym(III)-chlorid mit Tributylphosphat, Neodym(III)-chlorid mit Tetrahydrofüran, Neodym(III)-chlorid mit 2-Ethylhexanol, Neodym(III)-chlorid mit Pyri- din, Neodym(III)-chlorid mit 2-Ethylhexanol, Neodym(III)-chlorid mit Ethanol.Propanol, neodymium (III) bromide with pyridine, neodymium (III) bromide with 2-ethylhexanol, neodymium (III) bromide with ethanol, preferably lanthanum (III) chloride with tributyl phosphate, lanthanum (III) chloride with pyridine, lanthanum (III) chloride with 2-ethylhexanol, praseodymium (III) chloride with tributyl phosphate, praseodymium (III) chloride with 2-ethylhexanol, neodymium (III) chloride with tributyl phosphate, neodymium (III) chloride with tetrahydrofuran, neodymium (III) chloride with 2-ethylhexanol, neodymium (III) chloride with pyridine, neodymium (III) chloride with 2-ethylhexanol, neodymium (III) - chloride with ethanol.
Die Verbindungen der Seltenen Erden können einzeln oder im Gemisch untereinander eingesetzt werden.The rare earth compounds can be used individually or as a mixture with one another.
Ganz besonders bevorzugt werden Neodymversatat, Neodymoctanoat und/oderNeodymium versatate, neodymium octanoate and / or are very particularly preferred
Neodymnaphthenat als Komponente A) eingesetzt.Neodymnaphthenate used as component A).
In der Formel (V) bis (VII) der Komponente B) bedeutet R1 einen geradkettigen oder verzweigten Alkylrest mit 1 bis 10 C-Atomen, bevorzugt 1 bis 4 C-Atomen. Beispiele für geeignete Aluminiumalkyle der Formel (V) sind:In the formula (V) to (VII) of component B), R 1 is a straight-chain or branched alkyl radical having 1 to 10 C atoms, preferably 1 to 4 C atoms. Examples of suitable aluminum alkyls of the formula (V) are:
Trimethylaluminium, Triethylaluminium, Tri-n-propylaluminium, Triisopropylalumi- nium, Tri-n-butylaluminium, Triisobutylaluminium, Tripentylaluminium, Trihexylalu- minium, Tricyclohexylaluminium, Trioctylaluminium, Diethylaluminiumhydrid, Di-n- butylaluminiumhydrid und Di-isobutylaluminiumhydrid. Bevorzugt werden Triethylaluminium, Triisobutylaluminium und Di-iso-butylaluminiumhydrid. Besonders bevorzugt wird Di-isobutylaluminiumhydrid.Trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, triisopropyl aluminum, tri-n-butyl aluminum, triisobutyl aluminum, tripentyl aluminum, trihexyl aluminum, tricyclohexyl aluminum, trioctyl aluminum, diethyl aluminum hydride and aluminum hydride, di-aluminum hydride. Triethyl aluminum, triisobutyl aluminum and di-iso-butyl aluminum hydride are preferred. Di-isobutyl aluminum hydride is particularly preferred.
Als Beispiele für Alumoxane (VI) und (VII) werden genannt: Methylalumoxan, Ethylalumoxan und iso-Butylalumoxan, bevorzugt Methylalumoxan und iso-Butyl- alumoxan.Examples of alumoxanes (VI) and (VII) are: methylalumoxane, ethylalumoxane and isobutylalumoxane, preferably methylalumoxane and isobutylalumoxane.
Als Komponente C) werden sogenannte Lewis-Säuren eingesetzt. Beispielhaft seien die Organometallhalogenide erwähnt, in denen das Metallatom der Gruppe 3 a) oder 4a) angehört, sowie Halogenide der Elemente der Gruppe 3a), 4a) und 5a) desSo-called Lewis acids are used as component C). Examples include the organometallic halides in which the metal atom belongs to group 3 a) or 4a), and halides of the elements in groups 3a), 4a) and 5a) des
Periodensystems, wie es im „Handbook of Chemistry and Physics" 45th Edition 1964- 65 dargestellt ist. Genannt werden insbesondere:
Methylaluminiumdibromid, Methylaluminiumdichlorid, Ethylaluminiumdibromid, Ethylaluminiumdichlorid, Butylaluminiumdibromid, Butylaluminiumdichlorid, Dimethylaluminiumbromid, Dimethylaluminiumchlorid, Diethylaluminiumbromid, Diethylaluminiumchlorid, Dibutylaaluminiumbromid, Dibutylaluminiumchlorid,Periodic table, as shown in the "Handbook of Chemistry and Physics" 45th Edition 1964-65. The following are mentioned in particular: Methyl aluminum dibromide, methyl aluminum dichloride, ethyl aluminum dibromide, ethyl aluminum dichloride, butyl aluminum dibromide, butyl aluminum dichloride, dimethyl aluminum bromide, dimethyl aluminum chloride, diethyl aluminum bromide, diethyl aluminum chloride, dibutyalaluminum chloride,
Methylaluminiumsesquibromid, Methylaluminiumsesquichlorid, Ethylaluminiumses- quibromid, Ethylaluminiumsesquichlorid, Aluminiumtribromid, Antimontrichlorid, Antimonpentachlorid, Phosphortrichlorid, Phosphorpentachlorid, Zinntetrachlorid.Methyl aluminum sesquibromide, methyl aluminum sesquichloride, ethyl aluminum sesquibromide, ethyl aluminum sesquichloride, aluminum tribromide, antimony trichloride, antimony pentachloride, phosphorus trichloride, phosphorus pentachloride, tin tetrachloride.
Bevorzugt werden Diethylaluminiumchlorid, Ethylaluminiumsesquichlorid, Ethylaluminiumdichlorid, Diethylaluminiumbromid, Ethylaluminiumsesquibromid und/oder Ethylaluminiumdibromid eingesetzt.Diethyl aluminum chloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride, diethyl aluminum bromide, ethyl aluminum sesquibromide and / or ethyl aluminum dibromide are preferably used.
Als Komponente C) können auch die Reaktionsprodukte aus Aluminiumverbindungen, wie sie als Komponente B) beschrieben werden, mit Halogenen oder Halogenverbindungen, z. B. Triethylaluminium mit Brom oder Triethylaluminium mit Butylchlorid, eingesetzt werden. In diesem Fall kann die Umsetzung getrennt durchgeführt werden, oder die für die Umsetzung benötigte Menge der Alkylaluminiumver- bindung wird zu der als Komponente B) benötigten Menge addiert.As component C), the reaction products of aluminum compounds, as described as component B), with halogens or halogen compounds, for. B. triethyl aluminum with bromine or triethyl aluminum with butyl chloride can be used. In this case, the reaction can be carried out separately, or the amount of alkyl aluminum compound required for the reaction is added to the amount required as component B).
Bevorzugt werden Ethylaluminiumsesquichlorid, Butylchlorid und Butylbromid.Ethyl aluminum sesquichloride, butyl chloride and butyl bromide are preferred.
Als Komponente D) werden teilchenförmige, anorganische oder organische Feststoffe mit einer spezifischen Oberfläche größer als 10, bevorzugt 10 bis 1 000 m2/g (BET), einer Korngröße von 10 bis 1000 μm, bevorzugt 50 bis 500 μm, und einem Porenvolumen von 0,3 bis 15 ml/g, bevorzugt von 0,5 bis 5 ml/g eingesetzt. Bei der Verwendung von Rußen wird zusätzlich zum Porenvolumen die DBP-Adsorption als Eignungskriterium herangezogen. Diese soll zwischen 10 bis 300 ml/ 100 g liegen, bevorzugt zwischen 60 bis 150 ml/100 g, besonders bevorzugt zwischen 90 und 130 ml/100 g.
- 10 -As component D), particulate, inorganic or organic solids with a specific surface area greater than 10, preferably 10 to 1000 m 2 / g (BET), a grain size of 10 to 1000 μm, preferably 50 to 500 μm, and a pore volume of 0.3 to 15 ml / g, preferably from 0.5 to 5 ml / g used. When using carbon blacks, DBP adsorption is used as a suitability criterion in addition to the pore volume. This should be between 10 to 300 ml / 100 g, preferably between 60 to 150 ml / 100 g, particularly preferably between 90 and 130 ml / 100 g. - 10 -
Die spezifische Oberfläche (BET) wird in üblicher Weise bestimmt nach S. Brunauer, P.H. Emmet und Teller, J. Anorg. Chem.Soc. 60 (2), 309 (1938), das Porenvolumen wird bestimmt durch die Zentrifügationsmethode nach M. McDaniel., J.CoUoid Interface Sei. 78, 31 (1980) und die DBP-Adsorption nach DIN 53 601.The specific surface area (BET) is determined in the usual way according to S. Brunauer, P.H. Emmet and Teller, J. Anorg. Chem.Soc. 60 (2), 309 (1938), the pore volume is determined by the centrifugation method according to M. McDaniel., J.CoUoid Interface Sei. 78, 31 (1980) and the DBP adsorption according to DIN 53 601.
Als anorganische Feststoffe eignen sich insbesondere Silicagele, Fällungskieselsäuren, Tone, Alumosilikate, Talkum, Zeolithe, Ruß, anorganische Oxide, wie Siliciumdioxid, Aluminiumoxid, Magnesiumoxid, Titandioxid, Siliciumcarbid. Bevorzugt sind Silicagele, Fällungskieselsäuren, Zeolithe und Ruß, besonders bevorzugt Fällungskiesel- säuren und Ruß. Unter inert wird in diesem Fall verstanden, daß die Feststoffe so beschaffen sind, bzw. durch eine Vorbehandlung, wie z.B. Kalzinieren, so vorbehandelt werden, daß die reaktive Oberfläche die Bildung eines aktiven Katalysator nicht behindert, bzw. mit den Monomeren reagiert.Particularly suitable as inorganic solids are silica gels, precipitated silicas, clays, aluminosilicates, talc, zeolites, carbon black, inorganic oxides such as silicon dioxide, aluminum oxide, magnesium oxide, titanium dioxide, silicon carbide. Silica gels, precipitated silicas, zeolites and carbon black are preferred, particularly preferred precipitated silicas and carbon black. In this case, inert is understood to mean that the solids are composed in this way or by pretreatment, such as e.g. Calcine, pretreated so that the reactive surface does not hinder the formation of an active catalyst or reacts with the monomers.
Die genannten anorganischen Feststoffe, die der obengenannten Spezifikation genügen und deshalb für den Einsatz geeignet sind, werden beispielsweise näher beschrieben in Ullmanns, Enzyclopädie der technischen Chemie, Band 21, S. 439 ff. (Silicagele), Band 23, S. 311 ff. (Tone), Band 14, S. 633 ff. (Ruße), Band 24, S575 ff. und Band 17, S. 9 ff. (Zeolithe).The above-mentioned inorganic solids, which meet the above-mentioned specification and are therefore suitable for use, are described in more detail, for example, in Ullmanns, Encyclopedia of Industrial Chemistry, volume 21, p. 439 ff. (Silica gel), volume 23, p. 311 ff. (Tone), volume 14, p. 633 ff. (Soot), volume 24, S575 ff. And volume 17, p. 9 ff. (Zeolites).
Die anorganischen Feststoffe können einzeln oder im Gemisch untereinander eingesetzt werden.The inorganic solids can be used individually or in a mixture with one another.
Als organische Feststoffe eignen sich ebenfalls polymere Materialien, bevorzugt in Form frei fließender Pulver, die so beschaffen sind, bzw. durch eine Vorbehandlung, wie z.B. Trocknen, so vorbehandelt werden, daß die reaktive Oberfläche die Bildung eines aktiven Katalysator nicht behindert, bzw. mit den Monomeren reagiert, eine Korngröße im Bereich von 10 bis 1000 μm und die ein Porenvolumen im Bereich von 0,3 bis 15 ml g aufweisen. Ein Beispiel für ein derartiges Material ist pulverförmiges Polypropylen.
- 11 -Also suitable as organic solids are polymeric materials, preferably in the form of free-flowing powders, which are so designed or pretreated by pretreatment, such as drying, for example, that the reactive surface does not hinder the formation of an active catalyst, or with the monomers reacted, a grain size in the range of 10 to 1000 microns and which have a pore volume in the range of 0.3 to 15 ml g. An example of such a material is powdered polypropylene. - 11 -
Das Molverhältnis, in denen die Katalysatorkomponenten A) bis D) eingesetzt werden, kann in weiten Grenzen variiert werden.The molar ratio in which the catalyst components A) to D) are used can be varied within wide limits.
Das Molverhältnis der Komponente A) zu Komponente B) beträgt 1 : 1 bis 1 :1000, bevorzugt 1:3 bis 1 :200, besonders bevorzugt 1:3 bis 1 :100. Das Molverhältnis der Komponente A) zu Komponente C) beträgt 1:0,4 bis 1 :15, bevorzugt 1 :0,5 bis 1 :8.The molar ratio of component A) to component B) is 1: 1 to 1: 1000, preferably 1: 3 to 1: 200, particularly preferably 1: 3 to 1: 100. The molar ratio of component A) to component C) is 1: 0.4 to 1:15, preferably 1: 0.5 to 1: 8.
Auf 100g der Komponente D) werden 0,lmMol bis 1 Mol der Komponente A), bevorzugt 1 bis 50mMol der Komponente A) eingesetzt.For 100 g of component D) 0.1 mmol to 1 mol of component A), preferably 1 to 50 mmol of component A) are used.
Es ist auch möglich, den Katalysatorkomponenten A) bis D) noch eine weitere Komponente E) zuzusetzen. Diese Komponente E) ist ein konjugiertes Dien, das dasselbe Dien sein kann, das später mit dem Katalysator polymerisiert werden soll. Bevorzugt werden verwendet Butadien und Isopren.It is also possible to add a further component E) to the catalyst components A) to D). This component E) is a conjugated diene, which can be the same diene that is later to be polymerized with the catalyst. Butadiene and isoprene are preferably used.
Wird die Komponente E) dem Katalysator zugesetzt, so beträgt die Menge an E) bevorzugt 1 bis 1000 mol, bezogen auf 1 mol der Komponente A), besonders bevorzugt 1 bis 100 mol, bezogen auf 1 mol der Komponente A). Ganz besonders bevorzugt werden 1 bis 50 mol, bezogen auf 1 mol der Komponente A), an E) eingesetzt.If component E) is added to the catalyst, the amount of E) is preferably 1 to 1000 mol, based on 1 mol of component A), particularly preferably 1 to 100 mol, based on 1 mol of component A). 1 to 50 mol, based on 1 mol of component A), of E) are very particularly preferably used.
Die Herstellung des erfindungsgemäßen geträgerten Co-Katalysators wird durchgeführt, indem eine Lösung des oder der vorzugsweise unter B) beschriebenen Co- Katalysators bzw. Cokatalysatoren auf den teilchenförmigen Feststoff D) aufgetragen wird.The supported co-catalyst according to the invention is produced by applying a solution of the co-catalyst or cocatalysts preferably described under B) to the particulate solid D).
Vorzugsweise vor, während und ggf. nach dem Auftragen der Co-Katalysatorlösung wird der Feststoff bewegt, z.B. in einem Rührkessel mit einem konventionellen Rühraggregat, wie z. B. einem Kreuzbalkenrührer oder einem Wendelrührer, oder in einer weitereren bevorzugten Form in einem Pflugscharmischer.Preferably before, during and possibly after the application of the cocatalyst solution, the solid is agitated, e.g. in a stirred tank with a conventional stirring unit, such as. B. a cross bar stirrer or a spiral stirrer, or in a further preferred form in a ploughshare mixer.
Die Imprägnierung des Trägermaterials mit Co-Katalysatorlösung kann auch in einem Wirbelbett erfolgen. Dabei wird auf das Trägermaterial, das durch einen Inertgasstrom
- 12 -The support material can also be impregnated with a cocatalyst solution in a fluidized bed. This is done on the carrier material by an inert gas stream - 12 -
fluidisiert wird, die Wirkstofflösung aufgebracht, z.B. durch Versprühen mittels einer Düse. Über einen internen Kreislauf kann das Inertgas, nachdem es von mittransportiertem Lösungsmittel befreit wurde, in den Reaktor zurückgeführt werden. Das inerte Lösungsmittel kann zur Zubereitung der Wirkstofflösung wiederverwendet werden.is fluidized, the drug solution is applied, e.g. by spraying with a nozzle. The inert gas can be returned to the reactor via an internal circuit after it has been freed from the solvent which is also transported. The inert solvent can be reused for the preparation of the active ingredient solution.
Da das Co-Katalysatorsystem mit Luft und/oder Feuchtigkeit reagieren kann, ist es vorteilhaft, das Feststoffpulver D) vor dem Auftragen der Co-Katalysatorlösung zu trocknen, die Luft zu entfernen und unter einer Inertgasatmosphäre vor, während und nach dem Auftragen der Co-Katalysatorlösung zu halten. Das Auftragen der Co-Kata- lysatorlösung erfolgt vorzugsweise so gesteuert, daß die zugegebene, vorzugsweise verdüste, Lösung sofort vom Feststoff D) aufgenommen wird. Die Bildung von Ver- klumpungen und Inhomogenitäten wird somit minimiert.Since the co-catalyst system can react with air and / or moisture, it is advantageous to dry the solid powder D) before applying the co-catalyst solution, to remove the air and under an inert gas atmosphere before, during and after the application of the co- Keep catalyst solution. The application of the co-catalyst solution is preferably controlled so that the added, preferably atomized, solution is immediately taken up by the solid D). The formation of clumps and inhomogeneities is thus minimized.
Die Herstellung des erfindungsgemäßen Katalysatorsystems und/oder geträgerten Co- Katalysators kann auch kontinuierlich durchgeführt werden.The catalyst system and / or supported co-catalyst can also be prepared continuously.
Desweiteren ist es möglich, durch Einstellen des Verhältnisses der zudosierten Menge an geträgertem Co-Katalysator-Material zu vorhandenem Nd-Katalysator das Wirksamkeitsniveau des Katalysatorsystems zu steuern. Vorzugsweise sollte nur soviel Co- Katalysatorlösung auf den Feststoff aufgetragen werden wie dieser aufnehmen kann.Furthermore, it is possible to control the efficiency level of the catalyst system by adjusting the ratio of the metered amount of supported co-catalyst material to the Nd catalyst present. Preferably, only as much cocatalyst solution should be applied to the solid as it can absorb.
Das Feststofi ulver kann somit als frei fließendes Pulver nach dem Auftragen der Wirkstofflösung weiterhin leicht gerührt und bewegt werden.The solids ulver can thus continue to be easily stirred and moved as a free-flowing powder after the application of the active ingredient solution.
Im Prinzip ist es zwar möglich, die Menge des eingesetzten inerten Lösungsmittels in weiten Grenzen zu variieren. Wie dargestellt wird aber aus ökologischen und ökonomischen Gründen die Menge möglichst gering gehalten. Die Menge richtet sich nach der Menge und der Löslichkeit des bzw. der Co-Katalysator-Komponenten sowie dem Porenvolumen/DBP-Adsorption der Komponente D). Bevorzugt wird eine Menge von 10 bis 2 000 Teilen des Lösungsmittels, bezogen auf 100 Teile der Kom- ponente D), eingesetzt.
- 13 -In principle, it is possible to vary the amount of inert solvent used within wide limits. As shown, however, the amount is kept as low as possible for ecological and economic reasons. The amount depends on the amount and the solubility of the co-catalyst component (s) and the pore volume / DBP adsorption of component D). An amount of 10 to 2,000 parts of the solvent, based on 100 parts of component D), is preferably used. - 13 -
Die Herstellung des geträgerten Co-Katalysators kann in einem weiten Temperaturbereich erfolgen. Im allgemeinen liegt die Temperatur zwischen Schmelz- und Siedepunkt der Co-Katalysator-Komponente B) bzw. des inerten Lösungsmittels. Üblicherweise wird bei Temperaturen von -20 bis 100°C, vorzugsweise 20 bis 40°C, ge- arbeitet.The supported cocatalyst can be produced in a wide temperature range. In general, the temperature is between the melting point and boiling point of the cocatalyst component B) or the inert solvent. The usual procedure is at temperatures from -20 to 100 ° C, preferably 20 to 40 ° C.
Im Anschluß an die Imprägnierung des Trägermaterials mit Wirkstofflösung wird in einer bevorzugten Ausführungsform das inerte Lösungsmittel destillativ entfernt. Die Destillation kann sowohl in dem gleichen Behälter, in dem auch die Imprägnierung durchgeführt wurde, als auch in einer separaten Apparatur, z.B. einem Wirbelschichttrockner erfolgen. Bei der Entfernung des Lösungsmittels muß der Zutritt von Luft und Feuchtigkeit vermieden werden. Die Destillation wird je nach verwendetem Lösungsmittel bei Temperaturen von 0 bis 150 °C, vorzugsweise bei 10 bis 80°C, und Drücken von 0,001 mbar bis 20 bar absolut, vorzugsweise 0,001 mbar bis Normal- druck durchgeführt. Die Destillation kann auch kontinuierlich durchgeführt werden.In a preferred embodiment, following the impregnation of the carrier material with active ingredient solution, the inert solvent is removed by distillation. The distillation can be carried out both in the same container in which the impregnation was carried out and in a separate apparatus, e.g. a fluidized bed dryer. When removing the solvent, the entry of air and moisture must be avoided. Depending on the solvent used, the distillation is carried out at temperatures from 0 to 150 ° C., preferably at 10 to 80 ° C., and pressures from 0.001 mbar to 20 bar absolute, preferably 0.001 mbar to normal pressure. The distillation can also be carried out continuously.
Das unter Inertbedingungen aufgefangene Kondensat kann ohne weitere Aufarbeitung als Lösungsmittel für die in der Imprägnierung eingesetzten Wirkstoffe wiederverwendet werden.The condensate collected under inert conditions can be reused without further processing as a solvent for the active ingredients used in the impregnation.
In einer weiteren bevorzugten Ausführungsform wird das inerte Lösungsmittel nicht entfernt.In a further preferred embodiment, the inert solvent is not removed.
Die Erfindung betrifft auch den Einsatz des erfindungsgemäß hergestellten geträgerten Co-Katalysators in einem Verfahren zur Polymerisation von konjugierten Dienen, z.B. von 1,3-Butadien, Isopren, Pentadien oder Dimethylbutadien in der Gasphase.The invention also relates to the use of the supported co-catalyst prepared according to the invention in a process for the polymerization of conjugated dienes, e.g. of 1,3-butadiene, isoprene, pentadiene or dimethylbutadiene in the gas phase.
Diese Polymerisation erfolgt, indem man das gasförmige konjugierte Dien mit dem oben bzw. u.a. in EP-B-0647657 beschriebenen sowie dem erfindungsgemäß hergestellten geträgerten Co-Katalysator in Berührung bringt. Dem gasförmigen Mono- meren können weitere Gase zugemischt werden, die entweder der Verdünnung bzw. der Wärmeabführung oder der Regelung des Molekulargewichtes dienen. Die Poly-
- 14 -This polymerization is carried out by bringing the gaseous conjugated diene into contact with the above-described or, inter alia, EP-B-0647657 and the supported co-catalyst prepared according to the invention. Further gases can be mixed into the gaseous monomer, which serve either for dilution or heat dissipation or for regulating the molecular weight. The poly - 14 -
merisatioη kann bei Drücken von lmbar bis 50 bar, bevorzugt 1 bis 20 bar, durchgeführt werden.merisatioη can be carried out at pressures from lmbar to 50 bar, preferably 1 to 20 bar.
Im allgemeinen wird die Polymerisation bei Temperaturen von -20 bis 250°C, bevorzugt bei 0 bis 200°C, besonders bevorzugt bei 20 bis 160°C, durchgeführt.In general, the polymerization is carried out at temperatures from -20 to 250 ° C., preferably at 0 to 200 ° C., particularly preferably at 20 to 160 ° C.
Die Polymerisation kann in jeder für eine Gasphasenpolymerisation geeigneten Apparatur bewerkstelligt werden. So kann z. B. ein Rührreaktor, ein Drehreaktor oder ein Fließbettreaktor oder eine Kombination dieser Reaktortypen verwendet werden.The polymerization can be accomplished in any apparatus suitable for gas phase polymerization. So z. B. a stirred reactor, a rotating reactor or a fluidized bed reactor or a combination of these types of reactors.
Die erhaltenen Polymerisate weisen einen Gehalt an cis-l,4-Doppelbindungen von etwa 60 bis 99 % auf. Das Molgewicht kann durch die Zusammensetzung des Katalysators und durch die Variation der Polymerisationsbedingungen verändert werden. Üblich sind Molgewichte von 103 bis 106, gemessen mit GPC (Gel-Permeations- Chromatographie wie z.B. beschrieben in M. Hoffmann, H. Krömer, R. Kuhn,The polymers obtained have a cis-1,4 double bond content of about 60 to 99%. The molecular weight can be changed by the composition of the catalyst and by varying the polymerization conditions. Molecular weights of 10 3 to 10 6 , as measured with GPC (gel permeation chromatography as described, for example, in M. Hoffmann, H. Krömer, R. Kuhn,
„Polymeranalytik 1", Georg Thieme Verlag, Stuttgart, 1977, S. 349 ff. mit universeller Eichung)."Polymeranalytik 1", Georg Thieme Verlag, Stuttgart, 1977, pp. 349 ff. With universal calibration).
Die Mooneyviskosität, ML (1+4', 100°C)), liegt üblicherweise im Bereich zwischen 30 und 180 ME. Durch die Polymerisation in der Gasphase können auch sehr hochmolekulare Polymere hergestellt werden, die durch Lösungspolymerisation wegen der hohen Viskosität und der Möglichkeit von Übertragungsreaktionen durch das verwendete Lösungsmittel nur unter extrem hohem Aufwand zugänglich sind.The Mooney viscosity, ML (1 + 4 ', 100 ° C)) is usually in the range between 30 and 180 ME. The polymerization in the gas phase can also be used to produce very high molecular weight polymers, which are only accessible with extremely great effort because of the high viscosity and the possibility of transfer reactions through the solvent used.
Die erhaltenen Polymerisate können auf übliche Weise kompoundiert und vulkanisiert werden.The polymers obtained can be compounded and vulcanized in the usual way.
In einer gängigen Ausführungsform wird bei der Polymerisation von 1,3 -Butadien wie folgt verfahren:In a common embodiment, the polymerization of 1,3-butadiene is carried out as follows:
Das oben bzw. u. a. in EP-B-0647657 beschriebene Katalysatorsystem wird nach vorheriger Mischung mit dem erfindungsgemäß hergestellten Co-Katalysatorsystem
- 15 -The catalyst system described above or, inter alia, in EP-B-0647657 is, after prior mixing with the co-catalyst system prepared according to the invention - 15 -
oder aber separat davon wird in eine Apparatur überführt, die geeignet ist, den pulver- förmigen Katalysator sowie den geträgerten teilchenförmigen Co-Katalysator in Bewegung zu halten. Das kann z. B. durch Rühren, Drehen und/oder einen Gasstrom erfolgen. Das zunächst im Gasraum befindliche inerte Gas, z. B. Stickstoff, wird durch das gasförmige Monomere ersetzt. Dabei setzt eine sofortige Polymerisation ein und die Temperatur steigt an. Das Monomere wird, gegebenenfalls verdünnt, mit einem Inertgas so schnell dem Reaktor zugeführt, daß die gewünschte Reaktionstemperatur nicht überschritten wird. Die Reaktionstemperatur kann auch auf übliche Weise durch Heizen bzw. Kühlen eingestellt werden. Die Polymerisation wird durch Abstellen der Monomerzuführ beendet. Das Polymere kann in der bekannten Weise weiterbehandelt werden, indem man den Katalysator desaktiviert und das Polymere mit bekannten Alterungsschutzmitteln behandelt.or else separately it is transferred to an apparatus which is suitable for keeping the powdery catalyst and the supported particulate cocatalyst in motion. That can e.g. B. by stirring, turning and / or a gas stream. The inert gas initially located in the gas space, e.g. B. nitrogen is replaced by the gaseous monomer. An immediate polymerization starts and the temperature rises. The monomer, optionally diluted, is fed to the reactor with an inert gas so rapidly that the desired reaction temperature is not exceeded. The reaction temperature can also be set in the usual way by heating or cooling. The polymerization is terminated by switching off the monomer feed. The polymer can be further treated in the known manner by deactivating the catalyst and treating the polymer with known anti-aging agents.
Die nachfolgenden Beispiele sollen die Verwendung des vorliegend beschriebenen Katalysatorsystems zur Gasphasenpolymerisation von konjugierten Dienen, bestehend aus einer Verbindung der Seltenen Erden, einer aluminiumorganischen Verbindung, einer weiteren Lewissäure, ggf. einem konjugierten Dien, einem inerten, anorganischen oder organischen Trägermaterial und zusätzlich einem auf einem anorganischen oder organischen Trägermaterial aufgebrachtem Co-Katalysator unter Ver- besserung der Fließfähigkeit des hierbei hergestellten Kautschuks beschreiben, ohne diese jedoch auf die Beispiele einzuschränken, sowie die unerwartete und deutliche Aktivitätssteigerung bei Verwendung des erfindungsgemäßen Co-Katalysatorsystems zusätzlich zum oben beschriebenen Katalysatorsystem verdeutlichen.
The following examples are intended to illustrate the use of the catalyst system described here for the gas-phase polymerization of conjugated dienes, consisting of a rare earth compound, an organoaluminum compound, a further Lewis acid, optionally a conjugated diene, an inert, inorganic or organic support material and additionally one on one Describe inorganic or organic support material applied co-catalyst while improving the flowability of the rubber produced here, but without restricting it to the examples, and clarify the unexpected and significant increase in activity when using the co-catalyst system according to the invention in addition to the catalyst system described above.
- 16 -- 16 -
BeispieleExamples
Beispiel 1example 1
la) Vorbehandlung des Trägermaterials für den Co-Katalysator:la) pretreatment of the support material for the cocatalyst:
Als Trägermaterial fiir den Co-Katalysator wurde Zeosil 1165 MP verwendet. Zeosil 1165 MP ist eine agglomerierte Fällungskieselsäure der Fa. Rhöne-Poulenc mit einer Oberfläche nach BET von 139 m2/g. Das Porenvolumen beträgt 1,97 ml/g. Vor dem Einsatz wird das Zeosil 1165 MP bei 900°C im Drehrohrofen im Stickstoff-Gegenstrom getrocknet und anschließend unter Ausschluß von Luft und Feuchtigkeit abgefüllt.Zeosil 1165 MP was used as the support material for the cocatalyst. Zeosil 1165 MP is an agglomerated precipitated silica from Rhönen-Poulenc with a BET surface area of 139 m 2 / g. The pore volume is 1.97 ml / g. Before use, the Zeosil 1165 MP is dried at 900 ° C in a rotary kiln in a nitrogen countercurrent and then filled with the exclusion of air and moisture.
Des weiteren wurde Ruß N115, ein Produkt der Fa. Degussa, als Trägermaterial verwendet. Der Ruß hat eine Oberfläche nach BET von 145 m2/g und eine DBP-Adsorption von 113 ml/ 100 g. Der Mittelwert des Partikeldurchmessers beträgt 485 μm. Dieses Material wurde bei 450°C 32 h unter Stickstoff getrocknet und unter Stickstoff umgefüllt und gelagert.Carbon black N115, a product from Degussa, was also used as the carrier material. The carbon black has a BET surface area of 145 m 2 / g and a DBP adsorption of 113 ml / 100 g. The average particle diameter is 485 μm. This material was dried under nitrogen at 450 ° C. for 32 hours and transferred and stored under nitrogen.
lb) Herstellung eines geträgerten Co-Katalysatorslb) Preparation of a supported co-catalyst
Allgemeine Hinweise:General information:
Die meisten der verwendeten reinen oder in Lösung vorliegenden Co-Katalysator- Ausgangsstoffe sowie der fertig geträgerte Co-Katalysator sind luft- und feuchtigkeitsempfindlich. Einwiegen, Reaktion und Abfüllen müssen in Schlenck-Arbeits- technik unter Ausschluß von Sauerstoff und Feuchtigkeit vorgenommen werden.Most of the pure or solution-based cocatalyst starting materials used, as well as the fully supported cocatalyst, are sensitive to air and moisture. Weighing-in, reaction and filling must be carried out using Schlenck work technology to the exclusion of oxygen and moisture.
1000 g vorbehandeltes Zeosil 1165 werden im 10-Liter-Doppelmantelgefäß unter Schutzgas vorgelegt und mit dem Schrägblattrührer intensiv durchmischt (1001000 g of pretreated Zeosil 1165 are placed in a 10 liter double jacket vessel under protective gas and mixed thoroughly with the inclined blade stirrer (100
U/min). Eine Lösung von 71 g (0,5 mol) DIBAH in 876 g Hexan wird innerhalb vonRpm). A solution of 71 g (0.5 mol) of DIBAH in 876 g of hexane is added within
3 Stunden auf den Träger gepumpt. Die Innentemperatur soll 20 bis 30 °C betragen.
- 17 -Pumped on the carrier for 3 hours. The inside temperature should be 20 to 30 ° C. - 17 -
Nach der Belegung wird 30 Minuten bei 20 °C nachgerührt und anschließend das Hexan bei 0,1 mbar und 50 °C abdestilliert. Man erhält 1055 g eines freifließenden weißen Pulvers.After the coating, the mixture is stirred at 20 ° C. for 30 minutes and then the hexane is distilled off at 0.1 mbar and 50 ° C. 1055 g of a free-flowing white powder are obtained.
Beispiel 2Example 2
Es gelten die gleichen allgemeinen Hinweise wie bei Beispiel 1. Das Trägermaterial wird wie in Beispiel 1 beschrieben vorbehandelt.The same general instructions apply as for example 1. The carrier material is pretreated as described in example 1.
1000 g vorbehandelter Ruß N 115 (Fa. Degussa) werden im 10-Liter-Doppelmantel- gefäß unter Schutzgas vorgelegt und mit dem Schrägblattrührer intensiv durchmischt (100 U/min). Eine Lösung von 71 g (0,5 mol) DIBAH in 600 g Hexan wird innerhalb von 3 Stunden auf den Träger gepumpt. Die Innentemperatur soll 20 bis 30 °C betragen. Nach der Belegung wird 30 Minuten bei 20 °C nachgerührt und anschließend das Hexan bei 0,1 mbar und 50 °C abdestilliert. Man erhält 1060 g eines freifließenden schwarzen Pulvers.1000 g of pretreated carbon black N 115 (from Degussa) are placed in a 10-liter double-jacket vessel under protective gas and mixed thoroughly with the inclined-blade stirrer (100 rpm). A solution of 71 g (0.5 mol) of DIBAH in 600 g of hexane is pumped onto the support within 3 hours. The inside temperature should be 20 to 30 ° C. After the coating, the mixture is stirred at 20 ° C. for 30 minutes and then the hexane is distilled off at 0.1 mbar and 50 ° C. 1060 g of a free-flowing black powder are obtained.
Polymerisationen:Polymerizations:
Beispiel 3aExample 3a
Die Polymerisation wurde durchgeführt in einem mit einem Wendelrührer ausgestatteten 2-Liter-Büchi-Glasautoklaven, der vor Reaktionsbeginn mit einem bar Stickstoff beaufschlagt war. 3 g eines Zeosil-geträgerten Katalysators, wie in EP-B- 0647657 beschrieben, in diesem Fall mit 3,7 mmol Nd, 148 mmol DIBAH, 3,7 mmolThe polymerization was carried out in a 2 liter Büchi glass autoclave equipped with a spiral stirrer, which was charged with a bar of nitrogen before the start of the reaction. 3 g of a Zeosil-supported catalyst, as described in EP-B-0647657, in this case with 3.7 mmol Nd, 148 mmol DIBAH, 3.7 mmol
EASC und 7,4 mmol Isopren pro 100 g Material belegt, wurden mittels einer Schleuse in den Reaktor befördert, und die Reaktionstemperatur wurde über den Mantelkreislauf so eingeregelt, daß sich in der gerührten Schüttung eine Temperatur von 80°C einstellen konnte. Die Polymerisation wurde durch Eindosierung von vorge- heiztem gasförmigen Butadien in den Reaktor gestartet, wobei ein Butadien-Partial- druck von 2 bar angefahren wurde. Zu Reaktionsstart stieg die Schüttungstemperatur trotz Mantel-Gegenkühlung auf etwa 84°C an, nach 10 Minuten konnte die Reaktion
über den gesamten Verlauf isotherm bei 80°C gefahren werden. Der Versuch wurde in der Semi-Batch-Fahrweise durchgeführt, d.h. es wurde stets die in der Reaktion verbrauchte Butadienmenge nachdosiert, jedoch kein Katalysator und auch kein geträgerter Co-Katalysator, und es wurde auch bis zum Versuchsende kein Produkt ausgeschleust. Das von Beginn an rasche Anwachsen der gerührten Schüttung, die aufgrund der heftigen Durchmischung mit dem Wendelrührer auch als Pseudo-Wirbel- bett bezeichnet werden soll, konnte in dem Glasreaktor gut beobachtet werden, des weiteren ein stetiger Anstieg der Produkt-Korngröße von zunächst wenigen 100 μm im Durchmesser auf zuletzt mehr als 1 mm. Im Reaktionsverlauf kam es zu leichten Partikel- Agglomerationen, die die Durchmischung aber nicht wesentlich behinderten.EASC and 7.4 mmol of isoprene per 100 g of material were conveyed into the reactor by means of a lock, and the reaction temperature was regulated via the jacket circuit in such a way that a temperature of 80 ° C. could be established in the stirred bed. The polymerization was started by metering preheated gaseous butadiene into the reactor, starting with a butadiene partial pressure of 2 bar. At the start of the reaction, the bed temperature rose to about 84 ° C. despite jacket countercooling, and the reaction was able to proceed after 10 minutes run isothermally at 80 ° C over the entire course. The experiment was carried out in the semi-batch mode, ie the amount of butadiene consumed in the reaction was always replenished, but no catalyst and no supported cocatalyst, and no product was removed until the end of the experiment. The rapid increase in the agitated bed from the beginning, which is also referred to as a pseudo fluidized bed due to the vigorous mixing with the spiral stirrer, was well observed in the glass reactor, and a steady increase in the product grain size of a few 100 initially μm in diameter to more than 1 mm in the end. Slight particle agglomerations occurred in the course of the reaction, but did not significantly impede mixing.
Nach 2 2 Stunden wurde der Versuch beendet.The experiment was ended after 22 hours.
Das Produkt wurde nach Abreaktion des noch im Reaktor befindlichen Restbutadiens über einen Kugelhahn in der Bodenplatte des Reaktors abgelassen und anschließend unverzüglich durch Einmischen von 3 g Stearinsäure und 3 g Vulkanox BKF derAfter the residual butadiene still in the reactor had reacted, the product was discharged via a ball valve in the bottom plate of the reactor and then immediately by mixing in 3 g of stearic acid and 3 g of Vulkanox BKF
Bayer AG auf der Walze abgestoppt und stabilisiert.Bayer AG stopped and stabilized on the roller.
Die mittlere Polymerisationsaktivität des Katalysatorsystems betrug in diesem Experiment etwa 220 [kg BR / (mol Nd ■ bar Butadien • h)].The average polymerization activity of the catalyst system in this experiment was about 220 [kg BR / (mol Nd ■ bar butadiene • h)].
Beispiel 3bExample 3b
Die Polymerisation wurde durchgeführt wie in Beispiel 3a), jedoch wurden diesmal gemeinsam mit dem beschriebenen Nd-Katalysator 4,5 g des erfindungsgemäßen ge- trägerten Co-Katalysators aus Beispiel lb) mittels der Schleuse in den Reaktor befördert.The polymerization was carried out as in Example 3a), but this time, together with the Nd catalyst described, 4.5 g of the supported cocatalyst from Example Ib) according to the invention were conveyed into the reactor using the lock.
Im Laufe dieses Versuches wurde keine Partikelagglomeration beobachtet. Es wurde außerdem ein deutlicher Anstieg der Polymerisationsaktivität des Katalysatorsystems registriert, der im Mittel über 2'Λ Stunden rund 40% beträgt. Anfänglich liegt dieNo particle agglomeration was observed in the course of this experiment. There was also a significant increase in the polymerization activity of the catalyst system, which was about 40% on average over 2'Λ hours. Initially, that is
Aktivität rund 30 % über der in Beispiel 3a) gemessenen, zum Ende der Reaktion hin sogar 50% darüber. Das bedeutet gleichzeitig einen deutlich schwächer ausgeprägten
- 19 -Activity around 30% above that measured in Example 3a) and even 50% above at the end of the reaction. At the same time, this means a significantly weaker one - 19 -
relativen Abfall der Polymerisationsaktivität mit der Zeit bei Verwendung des geträgerten Co-Katalysatorsystems gegenüber dem System ohne geträgerten Co-Katalysator.relative decrease in polymerization activity with time when using the supported co-catalyst system compared to the system without supported co-catalyst.
Beispiel 3cExample 3c
Die Polymerisation wurde durchgeführt wie in Beispiel 3a), jedoch wurden diesmal gemeinsam mit dem beschriebenen Nd-Katalysator 4,5 g eines vorab gemäß Beispiel la) vorbehandelten, jedoch nicht gemäß Beispiel lb) mit DIB AH belegten Zeosils mittels der Schleuse in den Reaktor befördert.The polymerization was carried out as in Example 3a), but this time, together with the Nd catalyst described, 4.5 g of a zeosil which had been pretreated according to Example la) but not covered with DIB AH according to Example Ib) were conveyed into the reactor via the lock .
Im Laufe dieses Versuches wurde keine Partikelagglomeration beobachtet. Die Polymerisationsaktivität entsprach im gesamten Reaktionszeitraum im Rahmen der Reproduzierbarkeitsgenauigkeit der aus Beispiel 3a).No particle agglomeration was observed in the course of this experiment. Within the scope of the reproducibility accuracy, the polymerization activity corresponded to that from Example 3a) over the entire reaction period.
Beispiel 4aExample 4a
Die Polymerisation wurde wie in Beispiel 3a) durchgeführt, wobei 3 g eines ruß- geträgerten Katalysators, wie er anfangs bzw. u. a. in EP-B-0647657 beschrieben wurde, mit einer Belegung von 3,7 mmol Nd, 148 mmol DIBAH, 3,7 mmol EASC und 7,4 Isopren auf 100 g Material, verwendet wurden. Zu Reaktionsstart stieg die Schüttungstemperatur trotz Mantel-Gegenkühlung auf etwa 86°C an, nach 15 Minuten konnte die Reaktion über den gesamten Verlauf isotherm bei 80°C ge- fahren werden. Im Reaktionsverlauf kam es zu leichten Partikel- Agglomerationen, die die Durchmischung aber nicht wesentlich behinderten. Nach 2XA Stunden wurde der Versuch beendet.The polymerization was carried out as in Example 3a), 3 g of a carbon black-supported catalyst as described initially or, inter alia, in EP-B-0647657, with an occupancy of 3.7 mmol Nd, 148 mmol DIBAH, 3, 7 mmol EASC and 7.4 isoprene per 100 g material were used. At the start of the reaction, the bed temperature rose to about 86 ° C. despite jacket countercooling. After 15 minutes, the reaction could be carried out isothermally at 80 ° C. over the entire course. Slight particle agglomerations occurred in the course of the reaction, but did not significantly impede mixing. The experiment was ended after 2 × A hours.
Das Produkt wurde nach Abreaktion des noch im Reaktor befindlichen Restbutadiens über einen Kugelhahn in der Bodenplatte des Reaktors abgelassen und anschließend unverzüglich durch Einmischen von 3 g Stearinsäure und 3 g Vulkanox BKF der Bayer AG auf der Walze abgestoppt und stabilisiert.
- 20 -After the residual butadiene still in the reactor had reacted, the product was discharged via a ball valve in the bottom plate of the reactor and then immediately stopped and stabilized on the roller by mixing in 3 g of stearic acid and 3 g of Vulkanox BKF from Bayer AG. - 20 -
Die mittlere Polymerisationsaktivität des Katalysatorsystems betrug in diesem Experiment etwa 450 [kg BR / (mol Nd • bar Butadien • h)].The average polymerization activity of the catalyst system in this experiment was about 450 [kg BR / (mol Nd • bar butadiene • h)].
Beispiel 4bExample 4b
Die Polymerisation wurde durchgeführt wie in Beispiel 4a), jedoch wurden diesmal gemeinsam mit dem beschriebenen Nd-Katalysator 12 g des erfindungsgemäßen geträgerten Co-Katalysators aus Beispiel 2) mittels der Schleuse in den Reaktor befördert.The polymerization was carried out as in Example 4a), but this time, together with the Nd catalyst described, 12 g of the supported co-catalyst according to the invention from Example 2) were conveyed into the reactor using the lock.
Im Laufe dieses Versuches wurde keine Partikelagglomeration beobachtet. Es wurde außerdem ein deutlicher Anstieg der Polymerisationsaktivität des Katalysatorsystems registriert, der im Mittel über 2Vι Stunden rund 63% beträgt. Anfänglich liegt die Aktivität rund 50 % über der in Beispiel 4a) gemessenen, zum Ende der Reaktion hin sogar 80%) darüber. Auch hier ist der relative Abfall der Polymerisationsaktivität mit der Zeit bei Verwendung des geträgerten Co-Katalysatorsystems gegenüber dem System ohne geträgerten Co-Katalysator deutlich weniger ausgeprägt.No particle agglomeration was observed in the course of this experiment. There was also a significant increase in the polymerization activity of the catalyst system, which is about 63% on average over 2 hours. Initially, the activity is around 50% above that measured in Example 4a), and even 80% towards the end of the reaction). Here, too, the relative drop in the polymerization activity over time when using the supported co-catalyst system is significantly less pronounced compared to the system without a supported co-catalyst.
Beispiel 4cExample 4c
Die Polymerisation wurde durchgeführt wie in Beispiel 4a), jedoch wurden diesmal gemeinsam mit dem beschriebenen Nd-Katalysator 20 g eines vorab gemäß Beispiel la) vorbehandelten, jedoch nicht gemäß Beispiel 2) mit DIBAH belegten Rußes mittels der Schleuse in den Reaktor befördert.The polymerization was carried out as in Example 4a), but this time, together with the Nd catalyst described, 20 g of a carbon black previously pretreated according to Example la) but not coated with DIBAH according to Example 2) were conveyed into the reactor via the lock.
Im Laufe dieses Versuches wurde keine Partikelagglomeration beobachtet. Die Polymerisationsaktivität entsprach im gesamten Reaktionszeitraum im Rahmen der Repro- duzierbarkeitsgenauigkeit der aus Beispiel 4a).
No particle agglomeration was observed in the course of this experiment. Within the scope of the reproducibility accuracy, the polymerization activity corresponded to that from Example 4a) over the entire reaction period.
Claims
1. Katalysatorsystem im wesentlichen bestehend aus:1. Catalyst system essentially consisting of:
A) einem Alkoholat der Seltenen Erden (I), einem Carboxylat der Seltenen Erden (II), einer Komplexverbindung der Seltenen Erden mit Diketonen (III)A) an alcoholate of rare earths (I), a carboxylate of rare earths (II), a complex compound of rare earths with diketones (III)
und/oderand or
einer Additionsverbindung der Halogenide der Seltenen Erden mit einer Sauerstoff- oder Stickstoff-Donator- Verbindung (IV) folgender Formeln:an addition compound of the rare earth halides with an oxygen or nitrogen donor compound (IV) of the following formulas:
(RO)3M (I)(RO) 3 M (I)
(R-CO2)3M (II)(R-CO 2 ) 3 M (II)
(R- CH- C— R)3 (R-CH-C-R) 3
(III)(III)
O OO O
undand
MX3 y Donator (IV)MX 3 y Donor (IV)
B) einem Aluminiumtrialkyl und/oder einem Dialkylaluminiumhydrid derB) an aluminum trialkyl and / or a dialkylaluminium hydride
Formel (V) und/oder einem Alumoxan der Formeln (VI) - (VII):Formula (V) and / or an alumoxane of the formulas (VI) - (VII):
Al(H)x(R1)3.x (V)
22 -Al (H) x (R 1 ) 3 . x (V) 22 -
R1 (A-O)nAI^R 1 (AO) n AI ^
R (VI) R1 R (VI) R 1
undand
r (AP)=Γr (AP) = Γ
(NU)(NU)
R'R '
wobei in den Formelnbeing in the formulas
die Reste R, gleich oder verschieden, für einen Alkylrest mit CyCiQ stehen,the radicals R, identical or different, stand for an alkyl radical with CyCi Q ,
M ein dreiwertiges Element der Seltenen Erden mit den Ordnungszahlen 57 bis 71 bedeutet,M denotes a trivalent element of the rare earths with the atomic numbers 57 to 71,
X für Chlor, Brom oder Iod steht,X represents chlorine, bromine or iodine,
x für 0 oder 1 steht,x represents 0 or 1,
y 1 bis 6 bedeutet undy is 1 to 6 and
n 1 bis 50 bedeutet,n means 1 to 50,
die Reste R1, gleich oder verschieden, für einen Alkylrest mit Cj-Cio stehen,the radicals R 1 , identical or different, stand for an alkyl radical with C j -Cio,
einer weiteren Lewissäure und
- 23 -another Lewis acid and - 23 -
D) einem inerten, teilchenförmigen, anorganischen oder organischen Feststoff mit einer spezifischen Oberfläche größer als 10 m2/g (BET) und einem Porenvolumen von 0,3 bis 15 ml/g und bei der Verwendung von Ruß zusätzlich einer DBP-Adsorption von 10-300 ml/100 g,D) an inert, particulate, inorganic or organic solid with a specific surface area greater than 10 m 2 / g (BET) and a pore volume of 0.3 to 15 ml / g and, if carbon black is used, a DBP adsorption of 10 -300 ml / 100 g,
und zusätzlich einem auf einem anorganischen oder organischen Trägermaterial aufgebrachtem Co-Katalysator.and additionally a cocatalyst applied to an inorganic or organic support material.
2. Katalysatorsystem nach Anspruch 1, dadurch gekennzeichnet, daß als Träger- material für den Co-Katalysator Silica, Ruß, Fällungskieselsäure, Zeolithe,2. Catalyst system according to claim 1, characterized in that silica, carbon black, precipitated silica, zeolites, as support material for the co-catalyst,
Ton, Talkum, organische Feststoffe und/oder Mischungen aus zwei oder drei oder mehreren dieser Substanzen eingesetzt wird.Clay, talc, organic solids and / or mixtures of two or three or more of these substances is used.
3. Katalysatorsystem nach Anspruch 1 bis 2, dadurch gekennzeichnet, daß der geträgerte Co-Katalysator in Mengen zwischen 0,1 und 50 Massenprozent bezogen auf die Fest- bzw. Wirbelbettmenge eingesetzt wird.3. A catalyst system according to claim 1 to 2, characterized in that the supported cocatalyst is used in amounts between 0.1 and 50 percent by mass based on the amount of fixed or fluidized bed.
4. Katalysatorsystem nach Anspruch 1 bis 3, dadurch gekennzeichnet, daß das Trägermaterial zumindest während des Auftragens des Co-Katalysators be- wegt wird.4. Catalyst system according to claim 1 to 3, characterized in that the carrier material is moved at least during the application of the cocatalyst.
5. Katalysatorsystem nach einem oder mehreren der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß das Trägermaterial vor dem Auftragen getrocknet, von Sauerstoff befreit und unter einer Inertgasatmosphäre vor, während und nach dem Auftragen des Co-Katalysators gehalten wird.5. A catalyst system according to one or more of claims 1 to 4, characterized in that the support material is dried before application, freed from oxygen and is kept under an inert gas atmosphere before, during and after application of the co-catalyst.
6. Katalysatorsystem nach einem oder mehreren der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß die Aufbringungsgeschwindigkeit der Co-Katalysator- Lösung so gesteuert wird, daß die zugegebene Lösung sofort vom Träger- material aufgenommen wird.
- 24 -6. Catalyst system according to one or more of claims 1 to 5, characterized in that the rate of application of the co-catalyst solution is controlled so that the added solution is immediately absorbed by the support material. - 24 -
7. Katalysatorsystem nach einem oder mehreren der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß durch das Verhältnis geträgerter Co-Katalysator zu restlichem Katalysatorsystem das Wirksamkeitsniveau des Katalysatorsystems eingestellt wird.7. A catalyst system according to one or more of claims 1 to 6, characterized in that the effectiveness level of the catalyst system is set by the ratio of supported cocatalyst to the remaining catalyst system.
8. Katalysatorsystem nach einem oder mehreren der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß das Trägermaterial gleichmäßig mit Wirkstoffen belegt ist.8. A catalyst system according to one or more of claims 1 to 7, characterized in that the carrier material is evenly coated with active ingredients.
9. Katalysatorsystem nach einem oder mehreren der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß ein Trägermaterial mit einer Korngröße von 10 bis 1000 μm verwendet wird.9. A catalyst system according to one or more of claims 1 to 8, characterized in that a support material with a grain size of 10 to 1000 microns is used.
10. Katalysatorsystem nach einem oder mehreren der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß es vollständig oder in einzelnen Komponenten in einem10. A catalyst system according to one or more of claims 1 to 9, characterized in that it is completely or in individual components in one
Wirbelbettreaktor hergestellt wird.Fluidized bed reactor is produced.
11. Verfahren zur Polymerisation von konjugierten Dienen in der Gasphase, dadurch gekennzeichnet, daß ein Katalysatorsystem nach einem oder mehreren der Ansprüche 1 bis 10 eingesetzt wird.11. A process for the polymerization of conjugated dienes in the gas phase, characterized in that a catalyst system according to one or more of claims 1 to 10 is used.
12. Verwendung von mit Co-Katalysatoren belegten Trägermaterialien in einem Verfahren zur Polymerisation von konjugierten Dienen in der Gasphase.12. Use of support materials coated with co-catalysts in a process for the polymerization of conjugated dienes in the gas phase.
13. Verwendung von mit Teilen des Katalysatorsystems belegten Trägermaterialen in einem Verfahren zur Polymerisation in der Gasphase.13. Use of support materials covered with parts of the catalyst system in a process for polymerization in the gas phase.
14. Verwendung nach Anspruch 12 oder 13, dadurch gekennzeichnet, daß als das Trägermaterial für die aktive Komponente Silica, Ruß, Fällungskieselsäure oder organische Feststoffe eingesetzt werden.
- 25 -14. Use according to claim 12 or 13, characterized in that silica, carbon black, precipitated silica or organic solids are used as the carrier material for the active component. - 25 -
15. Partikel mit einem Kern aus Polybutadien oder Polyisopren und einer Hülle aus mit Co-Katalysator belegtem Trägermaterial hergestellt nach einem oder mehreren der Ansprüche 1 bis 14.15. Particles with a core made of polybutadiene or polyisoprene and a shell made of support material coated with cocatalyst prepared according to one or more of claims 1 to 14.
16. Partikel mit einem Kern aus Polybutadien oder Polyisopren und einer Hülle aus mit Co-Katalysator belegtem Trägermaterial.
16. Particles with a core made of polybutadiene or polyisoprene and a shell made of support material coated with cocatalyst.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19801857 | 1998-01-20 | ||
DE19801857A DE19801857A1 (en) | 1998-01-20 | 1998-01-20 | Catalyst system used in gas phase polymerization of conjugated dienes |
PCT/EP1999/000032 WO1999037694A1 (en) | 1998-01-20 | 1999-01-07 | Catalyst system for gas phase polymerisation of conjugated dienes |
Publications (1)
Publication Number | Publication Date |
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EP1049727A1 true EP1049727A1 (en) | 2000-11-08 |
Family
ID=7855060
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EP99903606A Withdrawn EP1049727A1 (en) | 1998-01-20 | 1999-01-07 | Catalyst system for gas phase polymerisation of conjugated dienes |
Country Status (7)
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US (1) | US6576727B1 (en) |
EP (1) | EP1049727A1 (en) |
JP (1) | JP2002501092A (en) |
AU (1) | AU2420099A (en) |
CA (1) | CA2318054A1 (en) |
DE (1) | DE19801857A1 (en) |
WO (1) | WO1999037694A1 (en) |
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EP1274754A1 (en) * | 2000-03-24 | 2003-01-15 | Bayer Aktiengesellschaft | Method for polymerizing conjugated diolefins (dienes) with catalysts of rare earths in the presence of vinyl aromatic solvents |
JP6034623B2 (en) * | 2012-08-29 | 2016-11-30 | 株式会社ブリヂストン | Method for producing polymerization catalyst composition and polymerization catalyst composition |
JP6751207B2 (en) | 2016-10-31 | 2020-09-02 | 株式会社ブリヂストン | Method for preparing catalyst for in-line bulk polymerization |
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US4898847A (en) * | 1986-07-03 | 1990-02-06 | Vyzkumny Ustav Makromolekularni Chemie | Catalyst and method for production of polymers and copolymers of 1-alkenes |
US5225458A (en) | 1986-10-02 | 1993-07-06 | Bp Chemicals Limited | Powder of (co)polymer of one or more 1-olefins blended with pulverulent inorganic material |
US5126463A (en) | 1990-10-31 | 1992-06-30 | The Boc Group, Inc. | Process for the production of anhydrides |
EP0530709A1 (en) | 1991-08-30 | 1993-03-10 | Union Carbide Chemicals & Plastics Technology Corporation | Process for producing sticky polymers |
US5264506A (en) | 1992-12-30 | 1993-11-23 | Union Carbide Chemicals & Plastics Technology Corporation | Process for producing sticky polymers |
DE4334045A1 (en) * | 1993-10-06 | 1995-04-13 | Bayer Ag | Catalyst, its production and use for gas phase polymerization of conjugated dienes |
US5453471B1 (en) * | 1994-08-02 | 1999-02-09 | Carbide Chemicals & Plastics T | Gas phase polymerization process |
MY112177A (en) | 1994-09-30 | 2001-04-30 | Mitsui Chemicals Inc | Olefin polymerization catalyst and process for olefin polymerization |
US5652304A (en) | 1995-08-31 | 1997-07-29 | The Goodyear Tire & Rubber Company | Vapor phase synthesis of rubbery polymers |
-
1998
- 1998-01-20 DE DE19801857A patent/DE19801857A1/en not_active Ceased
-
1999
- 1999-01-07 CA CA002318054A patent/CA2318054A1/en not_active Abandoned
- 1999-01-07 WO PCT/EP1999/000032 patent/WO1999037694A1/en not_active Application Discontinuation
- 1999-01-07 AU AU24200/99A patent/AU2420099A/en not_active Abandoned
- 1999-01-07 EP EP99903606A patent/EP1049727A1/en not_active Withdrawn
- 1999-01-07 JP JP2000528610A patent/JP2002501092A/en active Pending
- 1999-01-07 US US09/600,283 patent/US6576727B1/en not_active Expired - Fee Related
Non-Patent Citations (1)
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See references of WO9937694A1 * |
Also Published As
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DE19801857A1 (en) | 1999-07-22 |
WO1999037694A1 (en) | 1999-07-29 |
AU2420099A (en) | 1999-08-09 |
US6576727B1 (en) | 2003-06-10 |
CA2318054A1 (en) | 1999-07-29 |
JP2002501092A (en) | 2002-01-15 |
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