NO169130B - PROCEDURE FOR POLYMERIZING A LIQUID ALFA OLEFI - Google Patents
PROCEDURE FOR POLYMERIZING A LIQUID ALFA OLEFI Download PDFInfo
- Publication number
- NO169130B NO169130B NO882303A NO882303A NO169130B NO 169130 B NO169130 B NO 169130B NO 882303 A NO882303 A NO 882303A NO 882303 A NO882303 A NO 882303A NO 169130 B NO169130 B NO 169130B
- Authority
- NO
- Norway
- Prior art keywords
- liquid
- range
- olefin
- reactor
- ratio
- Prior art date
Links
- 239000007788 liquid Substances 0.000 title claims description 30
- 238000000034 method Methods 0.000 title claims description 15
- 230000000379 polymerizing effect Effects 0.000 title description 2
- -1 hydrocarbyl aluminum Chemical compound 0.000 claims description 25
- 239000004711 α-olefin Substances 0.000 claims description 23
- 239000003054 catalyst Substances 0.000 claims description 22
- 239000012018 catalyst precursor Substances 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 16
- 239000010936 titanium Substances 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 14
- 239000011777 magnesium Substances 0.000 claims description 13
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 239000012071 phase Substances 0.000 claims description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical group CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 9
- 239000000178 monomer Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 239000004743 Polypropylene Substances 0.000 description 6
- 150000004820 halides Chemical class 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 150000002681 magnesium compounds Chemical class 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 150000004703 alkoxides Chemical group 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- CPDVHGLWIFENDJ-UHFFFAOYSA-N dihexylalumane Chemical compound C(CCCCC)[AlH]CCCCCC CPDVHGLWIFENDJ-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 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
- FNAIRYWIXALZFN-UHFFFAOYSA-N 1,1,1-trichloro-8-fluorooctane Chemical compound FCCCCCCCC(Cl)(Cl)Cl FNAIRYWIXALZFN-UHFFFAOYSA-N 0.000 description 1
- AVGQTJUPLKNPQP-UHFFFAOYSA-N 1,1,1-trichloropropane Chemical compound CCC(Cl)(Cl)Cl AVGQTJUPLKNPQP-UHFFFAOYSA-N 0.000 description 1
- DAIRXERGRJFMSC-UHFFFAOYSA-N 1,1,2-trichlorocyclohexane Chemical compound ClC1CCCCC1(Cl)Cl DAIRXERGRJFMSC-UHFFFAOYSA-N 0.000 description 1
- FRCHKSNAZZFGCA-UHFFFAOYSA-N 1,1-dichloro-1-fluoroethane Chemical compound CC(F)(Cl)Cl FRCHKSNAZZFGCA-UHFFFAOYSA-N 0.000 description 1
- SEQRDAAUNCRFIT-UHFFFAOYSA-N 1,1-dichlorobutane Chemical compound CCCC(Cl)Cl SEQRDAAUNCRFIT-UHFFFAOYSA-N 0.000 description 1
- UAIVFDJJMVMUGY-UHFFFAOYSA-N 1,2,4-trimethylpiperazine Chemical compound CC1CN(C)CCN1C UAIVFDJJMVMUGY-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- HEXGQYBAXAYZSP-UHFFFAOYSA-N 1,2-dibromo-1,1-difluorodecane Chemical compound CCCCCCCCC(Br)C(F)(F)Br HEXGQYBAXAYZSP-UHFFFAOYSA-N 0.000 description 1
- CSOWEPYJECMZOB-UHFFFAOYSA-N 1,2-dibromo-3,4-dichlorobenzene Chemical compound ClC1=CC=C(Br)C(Br)=C1Cl CSOWEPYJECMZOB-UHFFFAOYSA-N 0.000 description 1
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- SQCZQTSHSZLZIQ-UHFFFAOYSA-N 1-chloropentane Chemical compound CCCCCCl SQCZQTSHSZLZIQ-UHFFFAOYSA-N 0.000 description 1
- SQAINHDHICKHLX-UHFFFAOYSA-N 1-naphthaldehyde Chemical compound C1=CC=C2C(C=O)=CC=CC2=C1 SQAINHDHICKHLX-UHFFFAOYSA-N 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- LQIIEHBULBHJKX-UHFFFAOYSA-N 2-methylpropylalumane Chemical compound CC(C)C[AlH2] LQIIEHBULBHJKX-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- HRAQMGWTPNOILP-UHFFFAOYSA-N 4-Ethoxy ethylbenzoate Chemical compound CCOC(=O)C1=CC=C(OCC)C=C1 HRAQMGWTPNOILP-UHFFFAOYSA-N 0.000 description 1
- CAHQGWAXKLQREW-UHFFFAOYSA-N Benzal chloride Chemical compound ClC(Cl)C1=CC=CC=C1 CAHQGWAXKLQREW-UHFFFAOYSA-N 0.000 description 1
- BFUSYPZFNHPSSK-UHFFFAOYSA-L CCC([O-])=O.[Mg+]Oc1ccccc1 Chemical compound CCC([O-])=O.[Mg+]Oc1ccccc1 BFUSYPZFNHPSSK-UHFFFAOYSA-L 0.000 description 1
- OJHDIPVPPJCQLB-UHFFFAOYSA-M CCO[Mg+].CCCCCCCC([O-])=O Chemical compound CCO[Mg+].CCCCCCCC([O-])=O OJHDIPVPPJCQLB-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- CJWANOYUFBSCHS-UHFFFAOYSA-L [Br-].[Br-].CCO[Ti+2]OCC Chemical compound [Br-].[Br-].CCO[Ti+2]OCC CJWANOYUFBSCHS-UHFFFAOYSA-L 0.000 description 1
- MJAANYBZHGEMLW-UHFFFAOYSA-K [I-].[I-].[I-].CC(C)O[Ti+3] Chemical compound [I-].[I-].[I-].CC(C)O[Ti+3] MJAANYBZHGEMLW-UHFFFAOYSA-K 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical class [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- QLLIVWGEMPGTMR-UHFFFAOYSA-N dihexyl(2-methylpropyl)alumane Chemical compound CCCCCC[Al](CC(C)C)CCCCCC QLLIVWGEMPGTMR-UHFFFAOYSA-N 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- JJOYCHKVKWDMEA-UHFFFAOYSA-N ethyl cyclohexanecarboxylate Chemical compound CCOC(=O)C1CCCCC1 JJOYCHKVKWDMEA-UHFFFAOYSA-N 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229940052308 general anesthetics halogenated hydrocarbons Drugs 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- QEILTXGPELUNQS-UHFFFAOYSA-N hexyl-bis(2-methylpropyl)alumane Chemical compound CCCCCC[Al](CC(C)C)CC(C)C QEILTXGPELUNQS-UHFFFAOYSA-N 0.000 description 1
- OIPWQYPOWLBLMR-UHFFFAOYSA-N hexylalumane Chemical compound CCCCCC[AlH2] OIPWQYPOWLBLMR-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000004678 hydrides Chemical group 0.000 description 1
- 150000002466 imines Chemical class 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
- 150000002576 ketones Chemical class 0.000 description 1
- CQQJGTPWCKCEOQ-UHFFFAOYSA-L magnesium dipropionate Chemical compound [Mg+2].CCC([O-])=O.CCC([O-])=O CQQJGTPWCKCEOQ-UHFFFAOYSA-L 0.000 description 1
- ZWPMNIKELFUJFK-UHFFFAOYSA-N magnesium ethanolate 2-methylpropan-1-olate Chemical compound CCO[Mg+].CC(C)C[O-] ZWPMNIKELFUJFK-UHFFFAOYSA-N 0.000 description 1
- IXUQHZKXQCGDFB-UHFFFAOYSA-M magnesium;2-methylpropan-1-olate;chloride Chemical compound [Mg+2].[Cl-].CC(C)C[O-] IXUQHZKXQCGDFB-UHFFFAOYSA-M 0.000 description 1
- BLNJKHPHTNRBEV-UHFFFAOYSA-N magnesium;3-methyl-1-(3-methylbutoxy)butane Chemical compound [Mg].CC(C)CCOCCC(C)C BLNJKHPHTNRBEV-UHFFFAOYSA-N 0.000 description 1
- HFTSQAKJLBPKBD-UHFFFAOYSA-N magnesium;butan-1-olate Chemical compound [Mg+2].CCCC[O-].CCCC[O-] HFTSQAKJLBPKBD-UHFFFAOYSA-N 0.000 description 1
- KRPXAHXWPZLBKL-UHFFFAOYSA-L magnesium;diphenoxide Chemical compound [Mg+2].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 KRPXAHXWPZLBKL-UHFFFAOYSA-L 0.000 description 1
- POTHEAWBPOJYFZ-UHFFFAOYSA-L magnesium;dodecanoate;chloride Chemical compound [Mg+2].[Cl-].CCCCCCCCCCCC([O-])=O POTHEAWBPOJYFZ-UHFFFAOYSA-L 0.000 description 1
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-UHFFFAOYSA-N 0.000 description 1
- SWMSUKCRKOWDGN-UHFFFAOYSA-M magnesium;ethanolate;bromide Chemical compound [Br-].CCO[Mg+] SWMSUKCRKOWDGN-UHFFFAOYSA-M 0.000 description 1
- KNYMLHYLKKLARR-UHFFFAOYSA-M magnesium;ethanolate;phenoxide Chemical compound [Mg+2].CC[O-].[O-]C1=CC=CC=C1 KNYMLHYLKKLARR-UHFFFAOYSA-M 0.000 description 1
- LPGLZESAVBXHSU-UHFFFAOYSA-L magnesium;iodide;phenoxide Chemical compound [Mg+2].[I-].[O-]C1=CC=CC=C1 LPGLZESAVBXHSU-UHFFFAOYSA-L 0.000 description 1
- HPBJPFJVNDHMEG-UHFFFAOYSA-L magnesium;octanoate Chemical compound [Mg+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O HPBJPFJVNDHMEG-UHFFFAOYSA-L 0.000 description 1
- ORPJQHHQRCLVIC-UHFFFAOYSA-N magnesium;propan-2-olate Chemical compound CC(C)O[Mg]OC(C)C ORPJQHHQRCLVIC-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 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
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002899 organoaluminium compounds Chemical class 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000008039 phosphoramides Chemical class 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- QMKUYPGVVVLYSR-UHFFFAOYSA-N propyl 2,2-dimethylpropanoate Chemical compound CCCOC(=O)C(C)(C)C QMKUYPGVVVLYSR-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 150000001629 stilbenes Chemical class 0.000 description 1
- 235000021286 stilbenes Nutrition 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
- 150000003609 titanium compounds Chemical class 0.000 description 1
- ZLMGMVJGEULFPP-UHFFFAOYSA-J titanium(4+) trichloride phenoxide Chemical compound Cl[Ti](Cl)(Cl)OC1=CC=CC=C1 ZLMGMVJGEULFPP-UHFFFAOYSA-J 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- MCWWHQMTJNSXPX-UHFFFAOYSA-N tribenzylalumane Chemical compound C=1C=CC=CC=1C[Al](CC=1C=CC=CC=1)CC1=CC=CC=C1 MCWWHQMTJNSXPX-UHFFFAOYSA-N 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- YGRHYJIWZFEDBT-UHFFFAOYSA-N tridecylaluminum Chemical compound CCCCCCCCCCCCC[Al] YGRHYJIWZFEDBT-UHFFFAOYSA-N 0.000 description 1
- XBEXIHMRFRFRAM-UHFFFAOYSA-N tridodecylalumane Chemical compound CCCCCCCCCCCC[Al](CCCCCCCCCCCC)CCCCCCCCCCCC XBEXIHMRFRFRAM-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
- JQPMDTQDAXRDGS-UHFFFAOYSA-N triphenylalumane Chemical compound C1=CC=CC=C1[Al](C=1C=CC=CC=1)C1=CC=CC=C1 JQPMDTQDAXRDGS-UHFFFAOYSA-N 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
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Description
Foreliggende oppfinnelse angår en fremgangsmåte for polymerisering av et flytende a-olefin hvorved katalysatorens ytelse er forbedret. The present invention relates to a method for polymerizing a liquid α-olefin, whereby the performance of the catalyst is improved.
Polymeriseringskatalysatorer har generelt forskjellige iboende begrensninger som ikke ganske enkelt kan overvinnes ved mindre sammensetningsjusteringer. For å overvinne disse begrensninger er det foreslått et bredt spektrum av forbehandlinger, skreddersydd for å spesifisere katalysatorer. Disse forbehandlinger er funnet å være effektive ved forbedring av katalysatoraktiviteten; stereospesifisiteten; og den kinetiske nedbrytningsoppførsel; og evnen i katalysatoren til å overleve under de høye polymeriseringstempera-turer (øket termisk stabilitet). Polymerization catalysts generally have various inherent limitations that cannot simply be overcome by minor compositional adjustments. To overcome these limitations, a wide range of pretreatments, tailored to specific catalysts, have been proposed. These pretreatments have been found to be effective in improving catalyst activity; the stereospecificity; and the kinetic degradation behavior; and the ability of the catalyst to survive under the high polymerization temperatures (increased thermal stability).
Den kjente teknikk søker konstant efter å identifisere det spesielle sett trinn og betingelser som vil forbedre ytelsen for en spesiell katalysator i en polymeriseringsomgivelse. The prior art is constantly seeking to identify the particular set of steps and conditions that will improve the performance of a particular catalyst in a polymerization environment.
En gjenstand for foreliggende oppfinnelse er derfor å tilveiebringe en fremgangsmåte for polymerisering av en eller flere monomerer i en flytende masse i nærvær av en katalysator omfattende en katalysatorforløper, vanligvis en fast komplekskomponent, som inkluderer magnesium, titan, klor og en elektrondonor; en organoaluminumforbindelse; og et selektivt kontrollmiddel hvorved aktiviteten for katalysatoren forbedres på samme måte som de andre nevnte karakte-ristika. An object of the present invention is therefore to provide a method for the polymerization of one or more monomers in a liquid mass in the presence of a catalyst comprising a catalyst precursor, usually a solid complex component, which includes magnesium, titanium, chlorine and an electron donor; an organoaluminum compound; and a selective control agent whereby the activity of the catalyst is improved in the same way as the other mentioned characteristics.
Andre gjenstander og fordeler vil være åpenbare ut fra det nedenfor følgende. Other items and benefits will be obvious from what follows.
I henhold til foreliggende oppfinnelse er det oppdaget en fremgangsmåte for polymerisering av et flytende a-olefin per se eller i kombinasjon med ett eller flere andre a-olefiner som i seg selv er flytende eller er oppløst i væsker, idet hvert a-olefin har 2 til 12 karbonatomer. Omfattende et første trinn a) i vaeskefase og et andre trinn b) i gassfase, og denne fremgangsmåte karakteriseres ved at det i trinn a) benyttes en katalysator omfattende: (i) en katalysatorforløper bestående i det vesentlige av magnesium, titan, klor, og som elektrondonor, en mono- eller polykarboksylsyreester, der forholdet i Mg:Ti er 3:1 til 30:1; forholdet Cl:Mg er 2:1 til 3:1; og forholdet Mg:elektrondonor er 1:1 til 60: 1; (ii) en hydrokarbylaluminiumkokatalysator; (iii) et selektivitetsregulerende middel, idet dette middel er forskjellig fra elektrondonoren; og According to the present invention, a method has been discovered for the polymerization of a liquid α-olefin per se or in combination with one or more other α-olefins which are themselves liquid or are dissolved in liquids, each α-olefin having 2 to 12 carbon atoms. Comprising a first step a) in liquid phase and a second step b) in gas phase, and this method is characterized by the fact that in step a) a catalyst is used comprising: (i) a catalyst precursor consisting essentially of magnesium, titanium, chlorine, and as electron donor, a mono- or polycarboxylic acid ester, where the ratio in Mg:Ti is 3:1 to 30:1; the Cl:Mg ratio is 2:1 to 3:1; and the Mg:electron donor ratio is 1:1 to 60:1; (ii) a hydrocarbyl aluminum cocatalyst; (iii) a selectivity regulating agent, this agent being different from the electron donor; and
(iv) hydrogen, (iv) hydrogen,
idet vektforholdet mellom a-olefin(er) og katalys-atorforløper er minst 6000:1, og idet polymeriseringen foregår i en væskefasereaktor i et tidsrom innen området 10 til 400 sekunder ved en temperatur innen området 20 til 100°C, hvorved benyttede a-olefiner partielt polymeriseres; og at in that the weight ratio between α-olefin(s) and catalyst precursor is at least 6000:1, and in that the polymerization takes place in a liquid phase reactor for a time within the range of 10 to 400 seconds at a temperature in the range of 20 to 100°C, whereby used a- olefins are partially polymerized; and that
i trinn (b) innføres blandingen fra trinn (a) til minst en gassfasereaktor ved en temperatur innen området 40° C til 150°C på en slik måte at ikke-polymeriserte oc-olefiner i det vesentlige polymeriseres. in step (b) the mixture from step (a) is introduced into at least one gas phase reactor at a temperature within the range of 40°C to 150°C in such a way that non-polymerized o-olefins are substantially polymerized.
Katalysatoren består av en katalysatorforløper som inkluderer magnesium, titan, klor og en elektrondonor; en organoalumi-niumforbindelse som kan henvises til som en kokatalysator; og et selektivitetsregulerende middel. Det selektivitetsregulerende middel er definert som et additiv som modifiserer katalysatorf or løperen på en slik måte at man øker den totale prosentandel fremstilt isotaktisk krystallinske polymer. The catalyst consists of a catalyst precursor that includes magnesium, titanium, chlorine and an electron donor; an organoaluminum compound which may be referred to as a cocatalyst; and a selectivity-regulating agent. The selectivity regulating agent is defined as an additive which modifies the catalyst carrier in such a way as to increase the total percentage of isotactic crystalline polymer produced.
En beskrivelse av en utførelsesform av katalysatoren kan finnes i US-PS 4 414 132. I dette tilfellet blir katalysator-forløperen oppnådd ved halogenering av en magnesiumforbin-delse med formelen MgR2_nXn, der R er et alkoksyd eller en aryloksydgruppe, hver R er lik eller forskjellig, X er et halogen, og n er lik 0 eller 1, med et tetravalent titanhalogenid i nærvær av et halogenhydrokarbon og en elektrondonor, og bringe det halogenerte produkt i kontakt med et tetravalent titanhalogenid, eventuelt å behandle det oppnådde faststoff med et aromatisk syreklorid, vasking av det halogenerte produkt for å fjerne ikke-omsatte titanforbin-delser, og å gjenvinne det faste produkt. A description of an embodiment of the catalyst can be found in US-PS 4,414,132. In this case, the catalyst precursor is obtained by halogenation of a magnesium compound of the formula MgR2_nXn, where R is an alkoxide or an aryloxide group, each R is equal to or differently, X is a halogen, and n is equal to 0 or 1, with a tetravalent titanium halide in the presence of a halogen hydrocarbon and an electron donor, and contacting the halogenated product with a tetravalent titanium halide, optionally treating the resulting solid with an aromatic acid chloride , washing the halogenated product to remove unreacted titanium compounds, and to recover the solid product.
Atom- eller molforholdene for katalysatorkomponentene er som følger: The atomic or molar ratios of the catalyst components are as follows:
Egnede halogenholdige magnesiumforbindelser som kan benyttes for å fremstille katalysatorforløperen er alkoksy- og aryloksymagnesiumhalogenider som isobutoksymagnesiumklorid, etoksymagnesiumbromid, fenoksymagnesiumjodid, kumyloksy-magnesiumbromid og naftenoksymagnesiumklorid. Suitable halogen-containing magnesium compounds that can be used to prepare the catalyst precursor are alkoxy and aryloxymagnesium halides such as isobutoxymagnesium chloride, ethoxymagnesium bromide, phenoxymagnesium iodide, cumyloxymagnesium bromide and naphthenoxymagnesium chloride.
Magnesiumforbindelser som kan benyttes er magnesiumdialk-oksyder, -diaryloksyder og -karboksylater med 2 til 24 karbonatomer som magnesium-di-iso-propoksyd, magnesium-dietoksyd, magnesiumdibutoksyd, magnesiumdifenoksyd, magnesiumdinaftenoksyd og etoksymagnesiumisobutoksyd, magnesiumdioktanoat og magnesiumdipropionat. Magnesium compounds that can be used are magnesium dialk-oxides, -diaryloxides and -carboxylates with 2 to 24 carbon atoms such as magnesium di-isopropoxide, magnesium diethoxide, magnesium dibutoxide, magnesium diphenoxide, magnesium dinaphthenoxide and ethoxymagnesium isobutoxide, magnesium dioctanoate and magnesium dipropionate.
Magnesiumforbindelser med en alkoksyd- og aryloksydgruppe kan også benyttes. Eksempler på slike forbindelser er etoksy-magnesiumfenoksyd og naftenoksydmagnesiumisoamyloksyd. Også egnet er forbindelser med en karboksylatgruppe og en alkoksyd-, aryloksyd- eller halogenidgruppe som etoksy-magnesiumoktanoat, fenoksymagnesiumpropionat og klor-magnesiumdodecanoat. Magnesium compounds with an alkoxide and aryloxide group can also be used. Examples of such compounds are ethoxymagnesium phenoxide and naphthenoxide magnesium isoamyloxide. Also suitable are compounds with a carboxylate group and an alkoxide, aryloxide or halide group such as ethoxymagnesium octanoate, phenoxymagnesium propionate and chloromagnesium dodecanoate.
Egnede halogenider av tetravalent titan er aryloksy- eller alkoksydl- og -trihalogenider som diheksoksytitandlklorid, dietoksytitandibromid, isopropoksytitantrijodid og fenoksy-titantriklorld; idet titantetraklorid er foretrukket. Suitable halides of tetravalent titanium are aryloxy- or alkoxy- and -trihalides such as dihexoxytitanium chloride, diethoxytitanium dibromide, isopropoxytitanium triiodide and phenoxytitanium trichlorid; with titanium tetrachloride being preferred.
Halogenhydrokarbonene som benyttes kan være aromatiske eller al ifatiske. Hvert alifatiske halogenhydrokarbon inneholder fortrinnsvis fra 1 til 12 karbonatomer og minst 2 halogen-atomer. De alifatiske halogenhydrokarboner omfatter dibrom-metan, triklormetan, 1,2-dikloretan, diklorbutan, 1,1,3-trikloretan, triklorcykloheksan, diklorfluoretan, triklor-propan, triklorfouoroktan, dibromdifluordecan, heksaklorietan og tetrakloridisooktan. Karbontetraklorid og 1,1,3-triklor-etan er foretrukket. Alifatiske halogenhydrokarboner som inneholder kun et halogenatom pr. molekyl som butylklorid og amylklorid kan også benyttes. Egnede aromatiske halogenhydrokarboner er klorbenzen, brombenzen, diklorbenzen, diklordibrombenzen, naftylklorid, klortoluen og diklortoluen. KLorbenzen er det mest foretrukne av halogenhydrokarbonene. The halohydrocarbons used can be aromatic or aliphatic. Each aliphatic halohydrocarbon preferably contains from 1 to 12 carbon atoms and at least 2 halogen atoms. The aliphatic halogen hydrocarbons include dibromomethane, trichloromethane, 1,2-dichloroethane, dichlorobutane, 1,1,3-trichloroethane, trichlorocyclohexane, dichlorofluoroethane, trichloropropane, trichlorofluorooctane, dibromodifluorodecane, hexachloroethane and tetrachloride isooctane. Carbon tetrachloride and 1,1,3-trichloroethane are preferred. Aliphatic halogen hydrocarbons containing only one halogen atom per molecules such as butyl chloride and amyl chloride can also be used. Suitable aromatic halohydrocarbons are chlorobenzene, bromobenzene, dichlorobenzene, dichlorodibromobenzene, naphthyl chloride, chlorotoluene and dichlorotoluene. Chlorobenzene is the most preferred of the halogenated hydrocarbons.
Egnede elektrondonorer som kan benyttes i Mg/Ti-komplekset (som indre donor) eller som et selektivt kontrollmiddel (som ytre donor), separat eller i kompleks med organoaluminium-forbindelsen, er etere, mono- eller polykarboksylsyreestere, ketoner, fenoler, aminer, amider, iminer, nitriler, silaner, fosfiner, fosfitter, stilbener, arsiner, fosforamider og alkoholater. Det skal imidlertid være klart at selektivitets-kontrollmidlet (den ytre donor) må være forskjellig fra elektrondonoren, dvs. den indre donor. Suitable electron donors that can be used in the Mg/Ti complex (as internal donor) or as a selective control agent (as external donor), separately or in complex with the organoaluminium compound, are ethers, mono- or polycarboxylic acid esters, ketones, phenols, amines, amides, imines, nitriles, silanes, phosphines, phosphites, stilbenes, arsines, phosphoramides and alcoholates. However, it should be clear that the selectivity control agent (the external donor) must be different from the electron donor, i.e. the internal donor.
Eksempler er estere av karboksylsyrer som etyl- og metyl-benzoat, p-metoksyetylbenzoat, p-etoksymetylbenzoat, p-etoksyetylbenzoat, etylakrylat, metylmetakrylat, etylacetat, p-kloretylbenzoat, p-aminoheksylbenzoat, isopropylnaftenat, n-amyltoluat, etylcykloheksanoat og propylpivalat. Ytterligere eksempler er N,N,N',N'-tetrametyletylendiamin, 1,2,4-trimetylpiperazin og 2,2,6,6-tetrametylpiperidin. Examples are esters of carboxylic acids such as ethyl and methyl benzoate, p-methoxyethyl benzoate, p-ethoxymethyl benzoate, p-ethoxyethyl benzoate, ethyl acrylate, methyl methacrylate, ethyl acetate, p-chloroethyl benzoate, p-aminohexyl benzoate, isopropyl naphthenate, n-amyl toluate, ethyl cyclohexanoate and propyl pivalate. Further examples are N,N,N',N'-tetramethylethylenediamine, 1,2,4-trimethylpiperazine and 2,2,6,6-tetramethylpiperidine.
Når elektrondonoren for bruk ved fremstilling av katalysator-forløperen (den indre donor) er det foretrukne etylbenzoat, er den foretrukne elektrondonor for bruk som det selektiv!-tetskontrollerende (den ytre donor) para-etoksyetylbenzoat. When the electron donor for use in the preparation of the catalyst precursor (the internal donor) is the preferred ethyl benzoate, the preferred electron donor for use as the selectivity controlling (the external donor) is para-ethoxyethyl benzoate.
Hydrokarbylaluminiumkokatalysatoren kan representeres ved formelen R3AI der R er en alkyl-, cykloalkyl-, aryl- eller hydridrest; minst en R er en hydrokarbylrest; to eller tre R-rester kan være forenet i en cyklisk rest som danner en heterocyklisk struktur; hver R kan være lik eller forskjellig; og hver R som er en hydrokarbylrest, har 1 til 20 karbonatomer og fortrinnsvis 1 til 10 karbonatomer. Videre kan hver alkylrest være rett eller forgrenet og en slik hydrokarbylrest kan være en blandet rest, for eksempel kan resten inneholde alkyl-, aryl- og/eller cykloalkylgrupper. Eksempler på egnede rester er metyl, etyl, propyl, iso-propyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, heksyl, 2-metylpentyl, heptyl, oktyl, isooktyl, 2-etylheksyl, 5,5-dimetylheksyl, nonyl, decyl, isodecyl, undecyl, dodecyl, fenyl, fenetyl, metoksyfenyl, benzyl, tolyl, xylyl, naftyl, naftal, metylnfatyl, cykloheksyl, cykloheptyl og cyklooktyl. The hydrocarbylaluminum cocatalyst can be represented by the formula R 3 AI where R is an alkyl, cycloalkyl, aryl or hydride residue; at least one R is a hydrocarbyl residue; two or three R residues may be united in a cyclic residue forming a heterocyclic structure; each R may be the same or different; and each R which is a hydrocarbyl residue has 1 to 20 carbon atoms and preferably 1 to 10 carbon atoms. Furthermore, each alkyl residue may be straight or branched and such a hydrocarbyl residue may be a mixed residue, for example the residue may contain alkyl, aryl and/or cycloalkyl groups. Examples of suitable residues are methyl, ethyl, propyl, iso-propyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, 2-methylpentyl, heptyl, octyl, isooctyl, 2-ethylhexyl, 5,5-dimethylhexyl, nonyl , decyl, isodecyl, undecyl, dodecyl, phenyl, phenethyl, methoxyphenyl, benzyl, tolyl, xylyl, naphthyl, naphthal, methylnfatyl, cyclohexyl, cycloheptyl and cyclooctyl.
Eksempler på egnede hydrokarbylaluminiumforbindelser er triisobutylaluminum, triheksylaluminum, di-isobutylaluminium-hydrid, diheksylaluminiumhydrid, isobutylalumiumdihydrid, heksylaluminiumdihydrid, di-isobutylheksylaluminium, isobutyldiheksylaluminium, trimetylaluminum, trietylaluminium, tripropylaluminium, triisopropylaluminium, tri-n-butylaluminium, trioktylaluminium, tridecylaluminium, tridodecylaluminium, tribenzylaluminium, trifenylaluminium, trinaftylaluminium og tritolylaluminium. De foretrukne hydrokarbylaluminiumforbindelser er trietylaluminium, triisobutylaluminium, triheksylaluminium, di-isobutylalumi-niumhydrid og diheksylaluminiumhydrid. Examples of suitable hydrocarbylaluminum compounds are triisobutylaluminum, trihexylaluminum, diisobutylaluminum hydride, dihexylaluminum hydride, isobutylaluminum dihydride, hexylaluminum dihydride, di-isobutylhexylaluminum, isobutyldihexylaluminum, trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, trioctylaluminum, tridecylaluminum, tridodecylaluminum, tribenzylaluminum, triphenylaluminum , trinaphthyl aluminum and tritolylaluminum. The preferred hydrocarbylaluminum compounds are triethylaluminum, triisobutylaluminum, trihexylaluminum, diisobutylaluminum hydride and dihexylaluminum hydride.
Syrehalogenidet som nevnes ovenfor er den forbindelse som tilsvarer esterforbindelsen som benyttes som den indre elektrondonor. Fortrinnsvis er halogenidet et klorid eller bromid. Syrehalogenidet kan inneholde 7 til 22 karbonatomer og en eller flere aromatiske ringer. The acid halide mentioned above is the compound corresponding to the ester compound used as the internal electron donor. Preferably the halide is a chloride or bromide. The acid halide may contain 7 to 22 carbon atoms and one or more aromatic rings.
Det første trinn er en væskepolymeriseringsreaksjon, det vil si at ikke mer enn ca. 10 vekt-# av polymeren fremstilles ved denne prosess. Dette første trinn, trinn (a) kan gjennomføres i en konvensjonell reaktor konstruert av et materiale som er inert overfor reaksjonsbetingelsene. Reaksjonen gjennomføres fortrinnsvis i en sløyfereaktor. Reaktoren fylles med en væske inneholdende et flytende a-olefin per se eller i kombinasjon med ett eller flere andre a-olefiner som i seg selv er flytende eller gassformige, oppløst i væsken, idet hvert a-olefin har 2 til 12 karbonatomer. Mens den foretrukne flytende monomer er flytende propylen, er andre væsker eller oppløselige a-olefiner som kan benyttes 1-buten, 1-heksen eller 1-dodecen. Eksempler på a-olefiner som kan oppløses i den flytende masse er etylen og propylen. The first step is a liquid polymerization reaction, i.e. no more than approx. 10% by weight of the polymer is produced by this process. This first step, step (a), can be carried out in a conventional reactor constructed of a material which is inert to the reaction conditions. The reaction is preferably carried out in a loop reactor. The reactor is filled with a liquid containing a liquid α-olefin per se or in combination with one or more other α-olefins which are themselves liquid or gaseous, dissolved in the liquid, each α-olefin having 2 to 12 carbon atoms. While the preferred liquid monomer is liquid propylene, other liquids or soluble α-olefins that may be used are 1-butene, 1-hexene, or 1-dodecene. Examples of α-olefins that can be dissolved in the liquid mass are ethylene and propylene.
Katalysatorforløperne i oppslemmingsform blir sammen med kokatalysator, selektivitetskontrollerende middel, a-olefin og hydrogen kontinuerlig matet til reaktoren i de ønskede forhold. The catalyst precursors in slurry form, together with cocatalyst, selectivity controlling agent, α-olefin and hydrogen are continuously fed to the reactor in the desired conditions.
Vektforholdet mellom a-olefin eller -olefiner og katalysator-forløper i den første reaktor, det vil si det første trinn, er minst ca. 6000:1 og ligger fortrinnsvis innen området ca. 9000:1 til ca. 50 000:1, hvorved oppholdstiden for den første reaktor ligger innen området ca. 10 til 400 sekunder og fortrinnsvis mellom ca. 40 og 200 sekunder; temperaturen som holdes i den første reaktor er ca. 20° C til ca. 100" C og fortrinnsvis ca. 40°C til ca. 80°C, mens trykket er tilstrekkelig til å holde monomeren(e) flytende er ca. 1034 til ca. 5516 x 10<3>Pa og fortrinnsvis ca. 1379 til ca. 4137 x 10<3>Pa; molforholdet hydrogen:a-olefin(er) ligger innen området ca. 0,0005:1 til ca. 0,01:1 og helst er ca. 0,001:1 til ca. 0,005:1; og der til slutt kondensator, hydrogen og en eller flere monomerer mates til den første reaktor i en mengde tilstrekkelig til å gi ca. 50 til ca. 2000, og fortrinnsvis ca. 100 til ca. 1500 kg polymer pr. kg kata-lysatorforløper . The weight ratio between α-olefin or -olefins and catalyst precursor in the first reactor, i.e. the first stage, is at least approx. 6000:1 and is preferably within the area approx. 9000:1 to approx. 50,000:1, whereby the residence time for the first reactor is within the range approx. 10 to 400 seconds and preferably between approx. 40 and 200 seconds; the temperature maintained in the first reactor is approx. 20° C to approx. 100" C and preferably about 40°C to about 80°C, while the pressure sufficient to keep the monomer(s) liquid is about 1034 to about 5516 x 10<3>Pa and preferably about 1379 to about .4137 x 10<3>Pa; the hydrogen:α-olefin(s) molar ratio is in the range of about 0.0005:1 to about 0.01:1 and preferably is about 0.001:1 to about 0.005:1 ; and where finally condenser, hydrogen and one or more monomers are fed to the first reactor in an amount sufficient to provide about 50 to about 2000, and preferably about 100 to about 1500 kg of polymer per kg of catalyst precursor .
Blandingen av katalysator og en eller flere flytende monomerer sirkuleres kontinuerlig under oppholdstiden og slippes kontinuerlig til en gassfasereaktor, fortrinnsvis en hvirvelsjiktsreaktor. Konvensjonelle sirkuleringsanordninger som impellerpumpen som nevnes i eksemplene, benyttes. Det skal her påpekes at i den foretrukne utførelsesform, er det i det vesentlige ingen forsinkelse mellom det første og andre trinn, imidlertid kan en viss forskyvningsteknikk benyttes mellom trinnene hvis dette er ønskelig, hvorved blandingen av katalysator og flytende monomer(er) passerer gjennom en temperaturgradient der temperaturen i blandingen gradvis heves fra den første reaktortemperatur til den andre reaktortemperatur på trinnsvis måte. Denne trinnvise hevning bør imidlertid gjennomføres i løpet av maksimalt ikke mer enn ca. 400 sekunder. I tillegg til blandingen fra trinn (a) som inkluderer katalysator, a-olefin og polymerisert a-olefin kan a-olefinmonomer(er) og hydrogen også innføres i gassfasereaktoren. The mixture of catalyst and one or more liquid monomers is continuously circulated during the residence time and is continuously discharged into a gas phase reactor, preferably a fluidized bed reactor. Conventional circulation devices such as the impeller pump mentioned in the examples are used. It should be pointed out here that in the preferred embodiment, there is essentially no delay between the first and second stages, however, a certain displacement technique can be used between the stages if this is desired, whereby the mixture of catalyst and liquid monomer(s) passes through a temperature gradient where the temperature in the mixture is gradually raised from the first reactor temperature to the second reactor temperature in a stepwise manner. However, this gradual lifting should be carried out during a maximum of no more than approx. 400 seconds. In addition to the mixture from step (a) which includes catalyst, α-olefin and polymerized α-olefin, α-olefin monomer(s) and hydrogen can also be introduced into the gas phase reactor.
Gassfasereaktoren kan være den hvirvelsjiktreaktor som er beskrevet i US-PS 4 482 687 eller en annen konvensjonell reaktor for gassfasefremstilling av for eksempel polypropylen- eller propylenkopolymerer. Sjiktet består vanligvis av den samme granulære harpiks som skal fremstilles i reaktoren. Således omfatter under polymeriseringen sjiktet de nydannede polymerpartikler, voksende polymerpartikler og katalysatorpartikler som er fluidiserte ved polymeriserbare hastighet tilstrekkelig til å forårsake at partiklene skilles og virker som fluid. Fluidiseringsgassen består av opp-rinnelig tilmatning, suppleringstilmatning og resirkulerings-gass, det vil si monomer og hvis ønskelig modifiserende midler og/eller en inert bærergass. The gas phase reactor can be the fluidized bed reactor described in US-PS 4,482,687 or another conventional reactor for gas phase production of, for example, polypropylene or propylene copolymers. The layer usually consists of the same granular resin that is to be produced in the reactor. Thus, during polymerization, the bed comprises newly formed polymer particles, growing polymer particles, and catalyst particles that are fluidized at a polymerizable rate sufficient to cause the particles to separate and act as a fluid. The fluidizing gas consists of initial feed, supplementary feed and recycling gas, that is monomer and, if desired, modifying agents and/or an inert carrier gas.
i Den vesentlige delen av reaktoren er beholderen, sjiktet og gassfordelingsplaten, innløps- og utløpsrør, en kompressor, en sirkuleringsgasskjøler og et produktutslippssystem. I beholderen over sjiktet er det en hastighetsreduksjonssone og i sjiktet en reaksjonssone. Begge ligger over gassfordelingsplaten. i The essential part of the reactor is the vessel, bed and gas distribution plate, inlet and outlet pipes, a compressor, a circulating gas cooler and a product discharge system. In the container above the bed there is a velocity reduction zone and in the bed a reaction zone. Both are located above the gas distribution plate.
Variasjoner i reaktoren kan innføres hvis ønskelig. En medfører relokalisering av cyklusgasskompressoren fra oppstrøms til nedstrøms for kjøleren og en annen medfører tilføring av en luftelinje fra toppen av produktutslipps-beholderen (omrørt produkttank) tilbake til toppen av den første reaktor for å forbedre oppfyllingsnivået for produkt-utløpsbeholderen. Variations in the reactor can be introduced if desired. One involves relocating the cycle gas compressor from upstream to downstream of the cooler and another involves feeding a vent line from the top of the product discharge vessel (stirred product tank) back to the top of the first reactor to improve the fill level of the product discharge vessel.
Virvelsjiktreaktoren som benyttes i det andre trinn arbeider ved en temperatur innen området ca. 40°C til 150°C, og fortrinnsvis ca. 60'C til ca. 120°C og et trykk mellom ca. 689,5 og 4826, fortrinnsvis 1724 til 3792 x 10<3>Pa. Hastig-heten for fluidiseringsgassen ligger innen området ca. 3 til 91 cm og fortrinnsvis mellom ca. 15 og 60 cm pr. sekund. Molforholdet hydrogen:oc-olef in(er) i virvelsj iktreaktoren ligger innen området ca. 0,005:1 til ca. 0,2:1 og ligger aller helst innen området ca. 0,01:1 til ca. 0,1:1. The fluidized bed reactor used in the second stage operates at a temperature within the range of approx. 40°C to 150°C, and preferably approx. 60'C to approx. 120°C and a pressure between approx. 689.5 and 4826, preferably 1724 to 3792 x 10<3>Pa. The velocity of the fluidizing gas is within the range of approx. 3 to 91 cm and preferably between approx. 15 and 60 cm per second. The molar ratio of hydrogen:oc-olefin(s) in the fluidized bed reactor is within the range of approx. 0.005:1 to approx. 0.2:1 and preferably lies within the range of approx. 0.01:1 to approx. 0.1:1.
Der det er ønskelig å fremstille en homopolymer slik som polypropylen eller en tilfeldig kopolymer slik som en propylen-etylen tilfeldig kopolymer, kan man benytte en hvirvelsjiktreaktor. Når det gjelder større krav til kopoly-meren, kan den andre hvirvelsjiktreaktor benyttes. I alle tilfeller blir reaktorene, det vil si sløyfereaktoren der det tilfeller blir reaktorene, det vil si sløyfereaktoren der det første trinn gjennomføres, den andre reaktor, det vi si hvirvelsjiktreaktoren, og hvis nødvendig, en tredje reaktor, også her et virvelsjikt, kjørt kontinuerlig in-line. Where it is desirable to produce a homopolymer such as polypropylene or a random copolymer such as a propylene-ethylene random copolymer, a fluidized bed reactor can be used. When it comes to greater requirements for the copolymer, the second fluidized bed reactor can be used. In all cases, the reactors, i.e. the loop reactor where there are cases, the reactors, i.e. the loop reactor where the first stage is carried out, the second reactor, the so-called fluidized bed reactor, and if necessary, a third reactor, also here a fluidized bed, are run continuously in-line.
Oppfinnelsen illustreres ved de følgende eksempler: The invention is illustrated by the following examples:
EKSEMPLENE 1- 6 EXAMPLES 1-6
En sløyfereaktor med en kappeutstyrt del for varmefjerning fylles med flytende propylen. Til denne reaktor settes en fremstilt katalysatorforløper med følgende omtrentlige sammensetning: TiCl4•12MgCl2<*>2C6H5C00C2H5. Katalysator-forløperen befinner seg i oppslemmingsform og transporteres til sløyfereaktoren ved bruk av flytende propylen. Vektforholdet mellom flytende propylen og katalysatorforløper er 12 500:1,2 (10 417:1). En kokatalysator, trietylaluminium, og et selektivitetsregulerende middel, para-etoksyetylbenzoat, i et molforhold på ca. 3:1, mates til reaktoren samtidig med katalysatorforløperen. Atomforholdet aluminium: titan er 35. Hydrogen mates også til sløyfereaktoren i et molforhold hydrogen:flytende propylen på 0,002:1. Trykket i sløyfe-reaktoren er 3792 x 10<3>Pa, temperaturen er ca. 55° C, det foreligger 590 kg polypropylen tUdannet pr. kg katalysator-forløper; strømningshastigheten gjennom sløyfereaktoren er ca. 5670 kg blanding av katalysator og flytende propylen pr. time, og oppholdstiden i sløyfereaktoren er 95 sekunder. A loop reactor with a jacketed section for heat removal is filled with liquid propylene. A manufactured catalyst precursor with the following approximate composition is added to this reactor: TiCl4•12MgCl2<*>2C6H5C00C2H5. The catalyst precursor is in slurry form and is transported to the loop reactor using liquid propylene. The weight ratio between liquid propylene and catalyst precursor is 12,500:1.2 (10,417:1). A cocatalyst, triethylaluminum, and a selectivity regulating agent, para-ethoxyethylbenzoate, in a molar ratio of approx. 3:1, is fed to the reactor at the same time as the catalyst precursor. The aluminum:titanium atomic ratio is 35. Hydrogen is also fed to the loop reactor at a hydrogen:liquid propylene molar ratio of 0.002:1. The pressure in the loop reactor is 3792 x 10<3>Pa, the temperature is approx. 55° C, there are 590 kg of polypropylene formed per kg catalyst precursor; the flow rate through the loop reactor is approx. 5670 kg mixture of catalyst and liquid propylene per hour, and the residence time in the loop reactor is 95 seconds.
Blandingen sirkuleres kontinuerlig gjennom sløyfereaktoren ved hjelp av en enkelt halvåpen impellersentrifugepumpe og slippes kontinuerlig ut fra sløyfereaktoren til en hvirvelsj iktreaktor der hovedpolymeriseringen skjer. Betingelsene under hvilke hvirvelsjiktreaktoren arbeider er omtrent som følger: The mixture is continuously circulated through the loop reactor by means of a single semi-open impeller centrifugal pump and continuously discharged from the loop reactor into a fluidized bed reactor where the main polymerization takes place. The conditions under which the fluidized bed reactor works are approximately as follows:
temperatur: 67 ° C temperature: 67 °C
trykk: 3379 x 10<3>Pa pressure: 3379 x 10<3>Pa
strømningshastighet: ca. 5670 kg pr. time blanding av katalysator og flytende propylen fra flow rate: approx. 5670 kg per hour mixture of catalyst and liquid propylene from
sløyfereaktoren pluss 3628 kg pr. time propylen matet direkte til virvelsjiktreaktoren the loop reactor plus 3628 kg per hour propylene fed directly to the fluidized bed reactor
Hvirvelsj iktgasshastighet: 0,24m/sek. Vortex gas velocity: 0.24m/sec.
Hydrogen mates også til hvirvelsjiktreaktoren i et molforhold hydrogen:propylen på 0,02:1. Hydrogen is also fed to the fluidized bed reactor in a hydrogen:propylene molar ratio of 0.02:1.
Ingen ytterligere katalysatorforløper, kokatalysator eller selektivt kontrollmiddel tilsettes til hvirvelsjiktreaktoren. No additional catalyst precursor, cocatalyst, or selective control agent is added to the fluidized bed reactor.
Eksemplet gjentas ved å utelate det første trinn. I dette tilfellet blir katalysator og propylen chargert direkte til hvirvelsj iktreaktoren. The example is repeated by omitting the first step. In this case, catalyst and propylene are charged directly to the fluidized bed reactor.
De to trinn og ett-trinnseksemplet ble gjentatt to ganger. The two-step and one-step example were repeated twice.
Tabellen viser følgende variabler og resultater: The table shows the following variables and results:
1. Al:Ti-atomforhold 1. Al:Ti atomic ratio
2. Xylenoppløselige stoffer: Fordi ikke-krystallinske polypropylen er oppløselig i xylen og krystallinsk polypropylen, som er foretrukket, ikke er oppløselig, er mengden xylenoppløselige stoffer en indikasjon på hvor mye krystallinsk polypropylen som er fremstilt. Verdien gis i vekt-5é-andeler beregnet på den totale vekt av polymeren. En verdi på mindre enn b% er kommersielt ønskelig. 3. Total produktivitet med første trinn gis i 1000 kg polymer pr. kg titan. Dette viser mengden polymer som fremstilles via to-trinnsprosessen, det vil si ifølge oppfinnelsen. 4. Produktivitet uten første trinn gis også i 1000 kg polymer pr. kg titan. Dette antyder produktiviteten ved bruk kun av hvirvelsjiktreaktoren. 5. Prosentual produktivitetsforbedring gir prosentandelen produktivitetsøkning for den fjerde kolonne i forhold til den femte kolonne, dvs. eksempel 1 sammenlignet med eksempel 2; eksempel 3 med eksempel 4; og eksempel 5 med eksempel 6. 2. Xylene solubles: Because non-crystalline polypropylene is soluble in xylene and crystalline polypropylene, which is preferred, is not soluble, the amount of xylene solubles is an indication of how much crystalline polypropylene has been produced. The value is given in weight-5é shares calculated on the total weight of the polymer. A value of less than b% is commercially desirable. 3. Total productivity with the first stage is given in 1000 kg of polymer per kg of titanium. This shows the amount of polymer produced via the two-step process, that is according to the invention. 4. Productivity without the first stage is also given in 1000 kg of polymer per kg of titanium. This suggests the productivity using only the fluidized bed reactor. 5. Percent Productivity Improvement gives the percentage productivity increase for the fourth column relative to the fifth column, i.e. Example 1 compared to Example 2; example 3 with example 4; and Example 5 with Example 6.
Det skal her påpekes at de i tabellen gitte data viser at bruken av det første trinn (a) resulterer i en vesentlig forbedring av katalysatorpolymeriseringsproduktiviteten. Denne økede produktivitet gjenspeiler den forbedrede katalysatoraktivitet, stereospesifisitet, den kinetiske nedbrytningsoppførsel og den termiske stabilitet. It should be pointed out here that the data given in the table show that the use of the first step (a) results in a significant improvement of the catalyst polymerization productivity. This increased productivity reflects the improved catalyst activity, stereospecificity, kinetic degradation behavior and thermal stability.
Claims (7)
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US91176386A | 1986-09-26 | 1986-09-26 | |
PCT/US1987/002421 WO1988002376A1 (en) | 1986-09-26 | 1987-09-28 | Process for the polymerization of a liquid monomer |
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