ITMI20011259A1 - PROCEDURE FOR THE (CO) POLYMERIZATION OF CONJUGATE DIENES - Google Patents
PROCEDURE FOR THE (CO) POLYMERIZATION OF CONJUGATE DIENES Download PDFInfo
- Publication number
- ITMI20011259A1 ITMI20011259A1 IT2001MI001259A ITMI20011259A ITMI20011259A1 IT MI20011259 A1 ITMI20011259 A1 IT MI20011259A1 IT 2001MI001259 A IT2001MI001259 A IT 2001MI001259A IT MI20011259 A ITMI20011259 A IT MI20011259A IT MI20011259 A1 ITMI20011259 A1 IT MI20011259A1
- Authority
- IT
- Italy
- Prior art keywords
- general formula
- aluminum
- complex
- alkyl
- process according
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 28
- 150000001993 dienes Chemical class 0.000 title claims description 10
- 238000006116 polymerization reaction Methods 0.000 title description 45
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 43
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 30
- 239000003446 ligand Substances 0.000 claims description 25
- 229910052782 aluminium Inorganic materials 0.000 claims description 24
- 230000003197 catalytic effect Effects 0.000 claims description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 17
- -1 aluminum alkyl halogens Chemical class 0.000 claims description 15
- 239000000460 chlorine Substances 0.000 claims description 15
- 229910052801 chlorine Inorganic materials 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 11
- KCALAFIVPCAXJI-UHFFFAOYSA-N 1,10-phenanthroline-5,6-dione Chemical compound C1=CC=C2C(=O)C(=O)C3=CC=CN=C3C2=N1 KCALAFIVPCAXJI-UHFFFAOYSA-N 0.000 claims description 10
- JDVMJFIBTWIYJX-UHFFFAOYSA-N 1,10-phenanthroline-5,6-diol Chemical compound Oc1c(O)c2cccnc2c2ncccc12 JDVMJFIBTWIYJX-UHFFFAOYSA-N 0.000 claims description 8
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 8
- CXTXIPLIPPLGBM-UHFFFAOYSA-N pyrido[2,3-b]indol-5-one Chemical compound N1=CC=CC2=C3C(=O)C=CC=C3N=C21 CXTXIPLIPPLGBM-UHFFFAOYSA-N 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 7
- 238000011065 in-situ storage Methods 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052794 bromium Chemical group 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 4
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- IYRGXJIJGHOCFS-UHFFFAOYSA-N neocuproine Chemical compound C1=C(C)N=C2C3=NC(C)=CC=C3C=CC2=C1 IYRGXJIJGHOCFS-UHFFFAOYSA-N 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 230000001588 bifunctional effect Effects 0.000 claims description 2
- 230000007717 exclusion Effects 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims 1
- 210000000056 organ Anatomy 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 29
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 235000019441 ethanol Nutrition 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 12
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 10
- 229920001195 polyisoprene Polymers 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 239000000178 monomer Substances 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 7
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 6
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000005062 Polybutadiene Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 229920002857 polybutadiene Polymers 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 4
- DHDHJYNTEFLIHY-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 description 3
- UJAQYOZROIFQHO-UHFFFAOYSA-N 5-methyl-1,10-phenanthroline Chemical compound C1=CC=C2C(C)=CC3=CC=CN=C3C2=N1 UJAQYOZROIFQHO-UHFFFAOYSA-N 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920001897 terpolymer Polymers 0.000 description 3
- BOGRNZQRTNVZCZ-AATRIKPKSA-N (3e)-3-methylpenta-1,3-diene Chemical compound C\C=C(/C)C=C BOGRNZQRTNVZCZ-AATRIKPKSA-N 0.000 description 2
- ZYECOAILUNWEAL-NUDFZHEQSA-N (4z)-4-[[2-methoxy-5-(phenylcarbamoyl)phenyl]hydrazinylidene]-n-(3-nitrophenyl)-3-oxonaphthalene-2-carboxamide Chemical compound COC1=CC=C(C(=O)NC=2C=CC=CC=2)C=C1N\N=C(C1=CC=CC=C1C=1)/C(=O)C=1C(=O)NC1=CC=CC([N+]([O-])=O)=C1 ZYECOAILUNWEAL-NUDFZHEQSA-N 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 2
- SLIBCJURSADKPV-UHFFFAOYSA-N 1,10-dihydro-1,10-phenanthroline-4,7-dione Chemical compound N1C=CC(=O)C2=CC=C3C(=O)C=CNC3=C21 SLIBCJURSADKPV-UHFFFAOYSA-N 0.000 description 2
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- BOGRNZQRTNVZCZ-UHFFFAOYSA-N 1,2-dimethyl-butadiene Natural products CC=C(C)C=C BOGRNZQRTNVZCZ-UHFFFAOYSA-N 0.000 description 2
- HNRMPXKDFBEGFZ-UHFFFAOYSA-N 2,2-dimethylbutane Chemical compound CCC(C)(C)C HNRMPXKDFBEGFZ-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- JIVLDFFWTQYGSR-UHFFFAOYSA-N 4,7-dimethyl-[1,10]phenanthroline Chemical compound C1=CC2=C(C)C=CN=C2C2=C1C(C)=CC=N2 JIVLDFFWTQYGSR-UHFFFAOYSA-N 0.000 description 2
- BRPQDJPJBCQFSR-UHFFFAOYSA-N 5,6-dimethyl-1,10-phenanthroline Chemical compound C1=CC=C2C(C)=C(C)C3=CC=CN=C3C2=N1 BRPQDJPJBCQFSR-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 101100219382 Caenorhabditis elegans cah-2 gene Proteins 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical compound CC[AlH]CC HJXBDPDUCXORKZ-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- OAEGRYMCJYIXQT-UHFFFAOYSA-N dithiooxamide Chemical compound NC(=S)C(N)=S OAEGRYMCJYIXQT-UHFFFAOYSA-N 0.000 description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 150000004698 iron complex Chemical class 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- ZIYNWDQDHKSRCE-UHFFFAOYSA-N tricyclohexylalumane Chemical compound C1CCCCC1[Al](C1CCCCC1)C1CCCCC1 ZIYNWDQDHKSRCE-UHFFFAOYSA-N 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- VYXHVRARDIDEHS-QGTKBVGQSA-N (1z,5z)-cycloocta-1,5-diene Chemical compound C\1C\C=C/CC\C=C/1 VYXHVRARDIDEHS-QGTKBVGQSA-N 0.000 description 1
- YUHZIUAREWNXJT-UHFFFAOYSA-N (2-fluoropyridin-3-yl)boronic acid Chemical class OB(O)C1=CC=CN=C1F YUHZIUAREWNXJT-UHFFFAOYSA-N 0.000 description 1
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 description 1
- SVJIEGOVQBGOSU-UHFFFAOYSA-N (4-methylphenyl)-propan-2-ylalumane Chemical compound C1(=CC=C(C=C1)[AlH]C(C)C)C SVJIEGOVQBGOSU-UHFFFAOYSA-N 0.000 description 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- PPQJCISYYXZCAE-UHFFFAOYSA-N 1,10-phenanthroline;hydrate Chemical compound O.C1=CN=C2C3=NC=CC=C3C=CC2=C1 PPQJCISYYXZCAE-UHFFFAOYSA-N 0.000 description 1
- HANWWAAUFXCNBS-UHFFFAOYSA-N 2,6,6-tris(2-methylpropyl)oxaluminane Chemical compound CC(C)C[Al]1CCCC(CC(C)C)(CC(C)C)O1 HANWWAAUFXCNBS-UHFFFAOYSA-N 0.000 description 1
- NPAXPTHCUCUHPT-UHFFFAOYSA-N 3,4,7,8-tetramethyl-1,10-phenanthroline Chemical compound CC1=CN=C2C3=NC=C(C)C(C)=C3C=CC2=C1C NPAXPTHCUCUHPT-UHFFFAOYSA-N 0.000 description 1
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 description 1
- BBDKZWKEPDTENS-UHFFFAOYSA-N 4-Vinylcyclohexene Chemical compound C=CC1CCC=CC1 BBDKZWKEPDTENS-UHFFFAOYSA-N 0.000 description 1
- NAZZKEZTSOOCSZ-UHFFFAOYSA-N 4-methyl-1,10-phenanthroline Chemical compound C1=CC2=CC=CN=C2C2=C1C(C)=CC=N2 NAZZKEZTSOOCSZ-UHFFFAOYSA-N 0.000 description 1
- PLKZZSKEJCNYEQ-UHFFFAOYSA-N 4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=C(O)C=C1 PLKZZSKEJCNYEQ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- DBEZPPFPFUCFCP-UHFFFAOYSA-N C(C)(CC)OCCSCCOC(C)CC Chemical compound C(C)(CC)OCCSCCOC(C)CC DBEZPPFPFUCFCP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical class CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical group 0.000 description 1
- 125000005103 alkyl silyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- CHMUSFDLUIXYMN-UHFFFAOYSA-N benzo[c][1,8]naphthyridine-9,10-dione Chemical compound N1=CC=CC2=C(C(C(=O)C=C3)=O)C3=CN=C21 CHMUSFDLUIXYMN-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-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
- LBKYCOGBBDATCR-UHFFFAOYSA-N benzyl(diethyl)alumane Chemical compound CC[Al](CC)CC1=CC=CC=C1 LBKYCOGBBDATCR-UHFFFAOYSA-N 0.000 description 1
- YLJFTSZNOGBPOG-UHFFFAOYSA-N benzyl(ethyl)alumane Chemical compound C(C1=CC=CC=C1)[AlH]CC YLJFTSZNOGBPOG-UHFFFAOYSA-N 0.000 description 1
- AIWXNWDZGADCFW-UHFFFAOYSA-N benzyl(propan-2-yl)alumane Chemical compound C(C1=CC=CC=C1)[AlH]C(C)C AIWXNWDZGADCFW-UHFFFAOYSA-N 0.000 description 1
- YGHMTLQLIZMTLJ-UHFFFAOYSA-N benzyl(propyl)alumane Chemical compound C(C1=CC=CC=C1)[AlH]CCC YGHMTLQLIZMTLJ-UHFFFAOYSA-N 0.000 description 1
- JQOREDBDOLZSJY-UHFFFAOYSA-H bis(2,2-dioxo-1,3,2,4-dioxathialumetan-4-yl) sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O JQOREDBDOLZSJY-UHFFFAOYSA-H 0.000 description 1
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 description 1
- LLHTVHHWJJDSSP-UHFFFAOYSA-N bis(4-methylphenyl)alumane Chemical compound C1(=CC=C(C=C1)[AlH]C1=CC=C(C=C1)C)C LLHTVHHWJJDSSP-UHFFFAOYSA-N 0.000 description 1
- XGIUDIMNNMKGDE-UHFFFAOYSA-N bis(trimethylsilyl)azanide Chemical compound C[Si](C)(C)[N-][Si](C)(C)C XGIUDIMNNMKGDE-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- 239000012043 crude product Substances 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
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([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
- OTACYDLCOLOKPA-UHFFFAOYSA-N dibenzyl(ethyl)alumane Chemical compound C=1C=CC=CC=1C[Al](CC)CC1=CC=CC=C1 OTACYDLCOLOKPA-UHFFFAOYSA-N 0.000 description 1
- DODCHQVKECHKRP-UHFFFAOYSA-N dibenzylalumane Chemical compound C(C1=CC=CC=C1)[AlH]CC1=CC=CC=C1 DODCHQVKECHKRP-UHFFFAOYSA-N 0.000 description 1
- WCYBYZBPWZTMDW-UHFFFAOYSA-N dibutylazanide Chemical compound CCCC[N-]CCCC WCYBYZBPWZTMDW-UHFFFAOYSA-N 0.000 description 1
- MVGUIMCFFQICHB-UHFFFAOYSA-N diethyl(phenyl)alumane Chemical compound CC[Al](CC)C1=CC=CC=C1 MVGUIMCFFQICHB-UHFFFAOYSA-N 0.000 description 1
- PASXEHKLXCTXJM-UHFFFAOYSA-N diethyl-(4-methylphenyl)alumane Chemical compound CC[Al](CC)C1=CC=C(C)C=C1 PASXEHKLXCTXJM-UHFFFAOYSA-N 0.000 description 1
- HRXSKIOIHQEGAI-UHFFFAOYSA-M diethylalumanylium;fluoride Chemical compound CC[Al](F)CC HRXSKIOIHQEGAI-UHFFFAOYSA-M 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- UZBQIPPOMKBLAS-UHFFFAOYSA-N diethylazanide Chemical compound CC[N-]CC UZBQIPPOMKBLAS-UHFFFAOYSA-N 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 description 1
- HIVRDDZUKVNKAO-UHFFFAOYSA-N diphenylalumane Chemical compound C1(=CC=CC=C1)[AlH]C1=CC=CC=C1 HIVRDDZUKVNKAO-UHFFFAOYSA-N 0.000 description 1
- XOCWTYIVWYOSGQ-UHFFFAOYSA-N dipropylalumane Chemical compound C(CC)[AlH]CCC XOCWTYIVWYOSGQ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- GCPCLEKQVMKXJM-UHFFFAOYSA-N ethoxy(diethyl)alumane Chemical compound CCO[Al](CC)CC GCPCLEKQVMKXJM-UHFFFAOYSA-N 0.000 description 1
- MNFTYNIMQNJVJI-UHFFFAOYSA-N ethoxy(dipropyl)alumane Chemical compound CC[O-].CCC[Al+]CCC MNFTYNIMQNJVJI-UHFFFAOYSA-N 0.000 description 1
- XGAIERUWZADBAO-UHFFFAOYSA-N ethoxy-bis(2-methylpropyl)alumane Chemical compound CCO[Al](CC(C)C)CC(C)C XGAIERUWZADBAO-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- SMCMEVQBOQDRPJ-UHFFFAOYSA-N ethyl(diphenyl)alumane Chemical compound C=1C=CC=CC=1[Al](CC)C1=CC=CC=C1 SMCMEVQBOQDRPJ-UHFFFAOYSA-N 0.000 description 1
- XLFSJFNMOZJHDV-UHFFFAOYSA-N ethyl-(4-methylphenyl)alumane Chemical compound C1(=CC=C(C=C1)[AlH]CC)C XLFSJFNMOZJHDV-UHFFFAOYSA-N 0.000 description 1
- NEPIVOURWZEXGS-UHFFFAOYSA-N ethyl-bis(4-methylphenyl)alumane Chemical compound C=1C=C(C)C=CC=1[Al](CC)C1=CC=C(C)C=C1 NEPIVOURWZEXGS-UHFFFAOYSA-N 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- PFCMCBTZGOMQIN-UHFFFAOYSA-N indeno[1,2-d]pyridazin-1-one Chemical compound C1=CC=C2C3=CN=NC(=O)C3=CC2=C1 PFCMCBTZGOMQIN-UHFFFAOYSA-N 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- HQPMOXUTKURVDV-UHFFFAOYSA-L iron(2+);sulfate;pentahydrate Chemical compound O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O HQPMOXUTKURVDV-UHFFFAOYSA-L 0.000 description 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- KXUHSQYYJYAXGZ-UHFFFAOYSA-N isobutylbenzene Chemical compound CC(C)CC1=CC=CC=C1 KXUHSQYYJYAXGZ-UHFFFAOYSA-N 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- KXPPDWYTBLMTPL-UHFFFAOYSA-N n-trimethylsilylethanamine Chemical compound CCN[Si](C)(C)C KXPPDWYTBLMTPL-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 125000002370 organoaluminium group Chemical group 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N para-hydroxytoluene Natural products CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- ZKGDHJAHOGRQEP-UHFFFAOYSA-N phenyl(propyl)alumane Chemical compound C1(=CC=CC=C1)[AlH]CCC ZKGDHJAHOGRQEP-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229950010765 pivalate Drugs 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 125000005309 thioalkoxy group Chemical group 0.000 description 1
- 125000005425 toluyl 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
- 125000002306 tributylsilyl group Chemical group C(CCC)[Si](CCCC)(CCCC)* 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- JOJQVUCWSDRWJE-UHFFFAOYSA-N tripentylalumane Chemical compound CCCCC[Al](CCCCC)CCCCC JOJQVUCWSDRWJE-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
- WSITXTIRYQMZHM-UHFFFAOYSA-N tris(4-methylphenyl)alumane Chemical compound C1=CC(C)=CC=C1[Al](C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WSITXTIRYQMZHM-UHFFFAOYSA-N 0.000 description 1
- 150000003738 xylenes Chemical class 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/02—Iron compounds
- C07F15/025—Iron compounds without a metal-carbon linkage
Description
"PROCEDIMENTO PER LA (CO)POLIMERIZZAZIONE DI DIENI "PROCEDURE FOR THE (CO) POLYMERIZATION OF DIENES
CONIUGATI " CONJUGATES "
DESCRIZIONE DESCRIPTION
La presente invenzione riguarda un procedimento per la preparazione di omopolimeri, copolimeri e relativi terpolimeri, a partire da dieni coniugati. The present invention relates to a process for the preparation of homopolymers, copolymers and related terpolymers, starting from conjugated dienes.
Più in particolare la presente invenzione riguarda un procedimento per la preparazione di omopolimeri, copolimeri e terpolimeri del 1,3-butadiene e dell'isoprene, caratterizzato dal fatto di essere effettuato in presenza di complessi del Ferro (II). More particularly, the present invention relates to a process for the preparation of homopolymers, copolymers and terpolymers of 1,3-butadiene and of isoprene, characterized in that it is carried out in the presence of Iron (II) complexes.
Per quanto concerne la polimerizzazione dell' 1,3-butadiene, Y. Zhang, H.Zhang, H.M.MA e Y. WU descrivono (Journal of Molecular Catalysis, 17 (1982), pagg. 65-76) la suddetta polimerizzazione in presenza di un catalizzatore a base di Fe(III) (acac)3 / fenantrolina e alluminio triisobutile (TIBA), utilizzando benzene come solvente. Il polibutadiene ottenuto presenta una pressoché uguale proporzione di unità 1,2 e 1,4-cis (50/50). Anche variando la quantità di legante utilizzato (fenantrolina), la microstruttura rimane equibinaria. Questo processo presenta anche l'inconveniente di produrre quantità discreta di geli. A. Yamamoto et al. (J.A.C.S., 4652, 1965) descrivono la preparazione del complesso Fe (bipy)2Et2 per reazione di Fe(acac)3, bipiridile e alluminiotrietile (TEA). Tale complesso, in benzene come solvente, ciclooligomerizza il butadiene dando il ciclootta-1,5-diene e 4-vinilcicloesene. Yamamoto afferma altresì che anche il sistema catalitico preparato in situ, ossia Fe(acac)3 bipy TEA, porta alla oligomerizzazione del butadiene. Regarding the polymerization of 1,3-butadiene, Y. Zhang, H. Zhang, H.M.MA and Y. WU describe (Journal of Molecular Catalysis, 17 (1982), pp. 65-76) the aforementioned polymerization in the presence of a catalyst based on Fe (III) (acac) 3 / phenanthroline and aluminum triisobutyl (TIBA), using benzene as a solvent. The obtained polybutadiene has an almost equal proportion of 1,2 and 1,4-cis units (50/50). Even by varying the amount of binder used (phenanthroline), the microstructure remains equibinary. This process also has the drawback of producing a fair amount of gels. A. Yamamoto et al. (J.A.C.S., 4652, 1965) describe the preparation of the Fe (bipy) 2Et2 complex by reaction of Fe (acac) 3, bipyridyl and aluminiotriethyl (TEA). This complex, in benzene as a solvent, cyclooligomerizes butadiene giving cycloocta-1,5-diene and 4-vinylcyclohexene. Yamamoto also states that the catalytic system prepared in situ, ie Fe (acac) 3 bipy TEA, also leads to the oligomerization of butadiene.
Risulta quindi evidente che entrambi i sistemi catalitici a base di Fe(III) sono insoddisfacenti per quanto riguarda la polimerizzazione del butadiene. It is therefore evident that both Fe (III) -based catalytic systems are unsatisfactory as regards the polymerization of butadiene.
Per quanto concerne la preparazione del poliisoprene, Sun e Wang (2, Acta Polymerica Sinica, 145, 1988) riportano la preparazione di un poliisoprene avente un tenore in unità 3,4 intorno al 70% utilizzando Fe(acac)3, A1R3, ed un'ammina in benzene. As regards the preparation of polyisoprene, Sun and Wang (2, Acta Polymerica Sinica, 145, 1988) report the preparation of a polyisoprene having a content of 3,4 units around 70% using Fe (acac) 3, A1R3, and an amine in benzene.
Nei brevetti US-A-5,239,023; US-A-5 ,356,997; Us-A-5,151,398; US-A-5,082,906; US-A- 5,061,765; la Goodyear descrive processi per la preparazione di poliisoprene e copolimeri isoprene / butadiene utilizzando un sistema catalitico costituito da un composto organico di Fe(III), un organoalluminio parzialmente idrolizzato con un composto protico (ad esempio acqua, alcol, acido carbossilico) ed una ammina aromatica chelante. Le rese in polimero sono tra 90 e 95%. La conversione del 95% è ottenuta dopo 1 o 2 ore a 10°C in esano. Per ottenere alte rese devono inoltre aggiungere quantità controllate di acqua all'alluminioalchile. In US-A-5,239,023 patents; US-A-5, 356.997; Us-A-5,151,398; US-A-5,082,906; US-A-5,061,765; Goodyear describes processes for the preparation of polyisoprene and isoprene / butadiene copolymers using a catalytic system consisting of an organic compound of Fe (III), an organoaluminium partially hydrolyzed with a protic compound (e.g. water, alcohol, carboxylic acid) and an amine chelating aromatic. The polymer yields are between 90 and 95%. The 95% conversion is obtained after 1 or 2 hours at 10 ° C in hexane. To obtain high yields they must also add controlled quantities of water to the aluminum alkyl.
E· stato ora trovato che complessi del Fe(II) superano gli inconvenienti soprariportati, dovuti all'utilizzo di complessi di Fe(III). Infatti i principali vantaggi dovuti all'uso dei complessi di Fe(II) della presente invenzione sono: attività più alte e più alto tenore di unità 3,4- per il poliisoprene e 1,2- per il polibutadiene, rispetto all'arte nota. L'utilizzo di complessi di Fe(II) definiti permette inoltre la formazione di una sola specie attiva come indicato dalla stretta distribuzione dei pesi molecolari (MWD = 1 - 1.2) It has now been found that Fe (II) complexes overcome the aforementioned drawbacks, due to the use of Fe (III) complexes. In fact, the main advantages due to the use of the Fe (II) complexes of the present invention are: higher activities and higher content of 3,4- units for the polyisoprene and 1,2- for the polybutadiene, with respect to the known art . The use of defined Fe (II) complexes also allows the formation of a single active species as indicated by the narrow molecular weight distribution (MWD = 1 - 1.2)
In accordo con ciò, la presente invenzione riguarda un procedimento per la omo e copolimerizzazione di dieni coniugati, particolarmente 1,3-butadiene ed isoprene, e la copolimerizzazione degli stessi, il suddetto processo essendo caratterizzato dal fatto di essere effettuato in presenza di un sistema catalitico comprendente un complesso, preformato o formato in situ, di formula generale (II) In accordance with this, the present invention relates to a process for the homo and copolymerization of conjugated dienes, particularly 1,3-butadiene and isoprene, and the copolymerization of the same, the aforesaid process being characterized in that it is carried out in the presence of a system catalytic comprising a complex, preformed or formed in situ, of general formula (II)
(II) (II)
ove n è un intero scelto tra 1 e 3; where n is an integer chosen between 1 and 3;
X è indipendentemente un gruppo di natura anionica legato al Fe(II) come anione in coppia ionica o con legame covalente di tipo "σ "; e X is independently an anionic group bonded to Fe (II) as anion in an ion pair or with a covalent bond of the "σ" type; And
"s" esprime il numero di gruppi X sufficienti a neutralizzare la formale carica di ossidazione di Fe(II), ed è uguale a 2 se tutti gruppi X sono monovalenti; "s" expresses the number of groups X sufficient to neutralize the formal oxidation charge of Fe (II), and is equal to 2 if all groups X are monovalent;
L è un legante di formula generale (I) L is a ligand of general formula (I)
(I) (THE)
in cui R1, R2, R3, R4, R5, R6, R7, R8, uguali o diversi tra loro, sono sostituenti di anello piridinico scelti tra idrogeno, alogeno, preferibilmente fluoro o cloro, -OH, -SH, radicale idrocarbilico monofunzionale avente da 1 a 20, preferibilmente da 1 a 10, atomi di carbonio; wherein R1, R2, R3, R4, R5, R6, R7, R8, equal or different from each other, are pyridine ring substituents selected from hydrogen, halogen, preferably fluorine or chlorine, -OH, -SH, monofunctional hydrocarbyl radical having from 1 to 20, preferably from 1 to 10, carbon atoms;
oppure coppie di sostituenti Ri-Ri+i, con "i" da 1 a 7, preferibilmente i = 4, presi assieme sono derivati bifunzionali scelti tra: or pairs of substituents Ri-Ri + i, with "i" from 1 to 7, preferably i = 4, taken together are bifunctional derivatives selected from:
(a) ove R9 e R10, uguali o diversi tra loro, hanno il significato sopraesposto per i radicali da R1 a R8; (b) -(CO)m- ove m è un intero da 1 a 2; (a) where R9 and R10, the same or different from each other, have the above meaning for the radicals from R1 to R8; (b) - (CO) m- where m is an integer from 1 to 2;
(c) - ove m è un intero da 1 a 2, R1 e R12, uguali o diversi tra loro, hanno il significato sopraesposto per i radicali da R1 a R8;(c) - where m is an integer from 1 to 2, R1 and R12, equal or different from each other, have the above meaning for the radicals from R1 to R8;
con l'esclusione dei composti di formula generale (I) in cui: with the exclusion of compounds of general formula (I) in which:
(al) ossia 4,7-diidrossi-1,10-fenantrolina; (al) i.e. 4,7-dihydroxy-1,10-phenanthroline;
(a2) ossia 2,9-dimetil-1,10-fenantrolina. (a2) i.e. 2,9-dimethyl-1,10-phenanthroline.
Forme di attuazione preferita del legante di formula generale (I) sono: Preferred embodiments of the ligand of general formula (I) are:
** Composto di formula generale (I) in cui in tal modo ottenendo il bipiridile; ** Compound of general formula (I) wherein thereby obtaining the bipyridyl;
** Composto di formula generale (I) in cui presi assieme, sono uguali a -CH=CH- in tal modo ottenendo la fenantrolina; ** Compound of general formula (I) in which taken together, they are equal to -CH = CH- thus obtaining phenanthroline;
** Composto di formula generale (I) in cui presi assieme, sono uguali a ** Compound of general formula (I) in which taken together, they are equal to
-CO-CO- in tal modo ottenendo il 1,10-fenantrolin-5,6-dione. ** Composto di formula generale (I) in cui presi assieme, sono uguali a -C(OH)=C(OH)- in tal modo ottenendo il 1,10-fenantrolin-5,6-diolo. -CO-CO- thereby obtaining 1,10-phenanthrolin-5,6-dione. ** Compound of general formula (I) in which taken together, they are equal to -C (OH) = C (OH) - thus obtaining 1,10-phenanthrolin-5,6-diol.
** Composto di formula generale (I) in cui presi assieme, sono uguali a -CO-in tal modo ottenendo il 1,9-diazafluoren-5-one. Oltre al bipiridile, alla fenantrolina, al fenantrolindione, al fenantrolindiolo ed al diazafluorenone, altri tipici ma non limitativi esempi di leganti L di formula generale (I) sono quindi : ** Compound of general formula (I) in which taken together, they are equal to -CO-thus obtaining 1,9-diazafluoren-5-one. In addition to bipyridyl, phenanthroline, phenanthrolindione, phenanthrolindiol and diazafluorenone, other typical but not limiting examples of L ligands of general formula (I) are therefore:
1) 5-metil-1,10-fenantrolina, ossia il composto di formula generale (I) in cui 1) 5-methyl-1,10-phenanthroline, that is the compound of general formula (I) in which
2) 6-metil-1,10-fenantrolina, ossia il composto di formula generale (I) in cui 2) 6-methyl-1,10-phenanthroline, that is the compound of general formula (I) in which
3) 5,6-dimetil-1,10-fenantrolina, ossia il composto di formula generale (I) in cui 3) 5,6-dimethyl-1,10-phenanthroline, that is the compound of general formula (I) in which
4) 4,7-dimetil-1,10-fenantrolina, ossia il composto di formula generale (I) in cui 4) 4,7-dimethyl-1,10-phenanthroline, that is the compound of general formula (I) in which
-CH=CH-; -CH = CH-;
5) 4,7-difenil-1,10-fenantrolina, ossia il composto di formula generale (I) in cui 5) 4,7-diphenyl-1,10-phenanthroline, that is the compound of general formula (I) in which
-CH=CH-; -CH = CH-;
6) 3,4,7,8-tetrametril-1,10-fenantrolina, ossia il composto di formula generale (I) in cui 6) 3,4,7,8-tetrametril-1,10-phenanthroline, i.e. the compound of general formula (I) in which
-CH=CH-. -CH = CH-.
Come sopra detto, X è indipendentemente un gruppo di natura anionica legato al Fe(II) come anione in coppia ionica o con legame covalente di tipo "σ ". As mentioned above, X is independently an anionic group bonded to Fe (II) as an anion in an ion pair or with a covalent bond of the "σ" type.
Il termine (X)n indica generalmente l'insieme dei gruppi a carattere anionico, indipendentemente dal numero effettivo e dal tipo di X presenti nel composto di formula (II). Gruppi anionici diversi tra loro sono inclusi nella suddetta definizione. Anche gruppi (X)n polivalenti o polidentati sono compresi nella portata della presente invenzione, ad esempio i gruppi ossalato, solfato, ftalato, acetilacetonato . The term (X) n generally indicates the set of anionic groups, regardless of the actual number and type of X present in the compound of formula (II). Different anion groups are included in the above definition. Also polyvalent or polyidentate (X) n groups are included in the scope of the present invention, for example the oxalate, sulfate, phthalate, acetylacetonate groups.
Esempi di gruppi (X)n sono gli alogenuri, specialmente cloruro e bromuro, i solfati, i solfati acidi, i gruppi alchil- e aril-solfonici, i fosfati e polifosfati, i gruppi alchil- e aril-fosfonici, idruro, i gruppi alchile lineare, ciclico o ramificato aventi da 1 a 15 atomi di carbonio, quale metile, etile, butile, isopropile, isoamile, ottile, decile, benzile, ciclopentile, cicloesile, 4-metilcicloesile, i gruppi alchilsilile aventi da 1 a 20 atomi di carbonio, quale, ad esempio, trimetilsilile, trietilsilile o tributilsilile, i gruppi arile aventi da 6 a 15 atomi di carbonio, quale fenile o toluile, i gruppi alcossile o tioalcossile aventi da 1 a 10 atomi di carbonio quale metossile, etossile, iso- o sec-butossile, etilsolfuro, i gruppi carbossilato o dicarbossilato, quale acetato, trifluoroacetato, propionato, butirrato, pivalato, stearato, benzoato, ossalato, maionato, ftalato, o ancora, un gruppo dialchilammide avente da 2 a 15 atomi di carbonio, quale dietilammide, dibutilammide, o alchilsilil-ammide, quale bis(trimetilsilil)ammide o etiltrimetilsililammide, i gruppi organici divalenti quali il gruppo trimetilene o tetrametilene, o il gruppo etilendiossi. Examples of (X) n groups are halides, especially chloride and bromide, sulphates, acid sulphates, alkyl- and aryl-sulfonic groups, phosphates and polyphosphates, alkyl- and aryl-phosphonic groups, hydride, linear, cyclic or branched alkyl having from 1 to 15 carbon atoms, such as methyl, ethyl, butyl, isopropyl, isoamyl, octyl, decyl, benzyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, the alkylsilyl groups having from 1 to 20 atoms of carbon, such as, for example, trimethylsilyl, triethylsilyl or tributylsilyl, the aryl groups having from 6 to 15 carbon atoms, such as phenyl or toluyl, the alkoxy or thioalkoxyl groups having from 1 to 10 carbon atoms such as methoxyl, ethoxyl, iso- or sec-butoxy, ethylsulfide, the carboxylate or dicarboxylate groups, such as acetate, trifluoroacetate, propionate, butyrate, pivalate, stearate, benzoate, oxalate, mayionate, phthalate, or a dialkylamide group having from 2 to 15 carbon atoms, such as diethylamide, dibutylamide, or alkylsilyl-amide, such as bis (trimethylsilyl) amide or ethyltrimethylsilylamide, the divalent organic groups such as the trimethylene or tetramethylene group, or the ethylenedioxy group.
Possono essere presenti anche gruppi o leganti diversi tra loro, se desiderato, come, ad esempio, un cloruro e un gruppo carbossilato o alcossido. Different groups or ligands can also be present, if desired, such as, for example, a chloride and a carboxylate or alkoxide group.
Per quanto concerne la preparazione dei complessi di formula generale (II), essa è descritta in letteratura, vedi ad esempio E. Konig, Coord. Chem. Rev., 3471 (1968). As regards the preparation of the complexes of general formula (II), it is described in the literature, see for example E. Konig, Coord. Chem. Rev., 3471 (1968).
Il sistema catalitico della presente invenzione comprende, oltre al complesso di Fe(II), anche uno o più organo-derivati dell'alluminio scelti tra (al) composti di formula generale (a2) alluminossani e relativi derivati, (a3) organoderivati dell'alluminio parzialmente idrolizzati, e relative miscele, (a4) (III) (con n = 1 o 2) o (IV) (n = 1-5) dove R è un gruppo alchilico X è cloro o bromo, preferibilmente cloro. Per quanto concerne gli organoderivati di alluminio (al), nei composti di formula generale è scelto tra alchile (cicloalchile compreso), arile, alchilarile, alcossile, idrogeno, fluoro; uguali o diversi tra loro, sono scelti tra alchile (cicloalchile compreso), arile, alchilarile, arilalchile. Tipici organo-derivati dell'alluminio (al) sono dietilalluminio idruro, di-n-propil alluminio idruro, di-nbutilalluminio idruro, diisobutil alluminio idruro, difenil alluminio idruro, di-p-tolil alluminio idruro, dibenzil alluminio idruro, dietil alluminio idruro, fenil-n-propil alluminio idruro, p-tolil etil alluminio idruro, p-tolil npropil alluminio idruro, p-tolil isopropil alluminio idruro, benzil etil alluminio idruro, benzil n-propil alluminio idruro, benzil isopropil alluminio idruro, dietilalluminio etossido, diisobutil alluminio etossido, dipropil alluminio etossido, trimetil alluminio, trietil alluminio, tri-npropil alluminio, triisobutil alluminio, tri-n-butil alluminio, tripentil alluminio, triesil alluminio, tricicloesil alluminio, triottil alluminio, trifenil alluminio, tri-p-tolil alluminio, tribenzil alluminio, etil difenil alluminio, etil di-p-tolil alluminio, etil dibenzil alluminio, dietil fenil alluminio, dietil p-tolil alluminio, dietil benzil alluminio. I trialchilalluminio composti sono generalmente preferiti. I trialchilalluminio composti preferiti includono il trietil alluminio (TEA), il tri-npropil alluminio, il triisobutil alluminio (TIBA), il triesil alluminio, il diisobutil alluminio idruro (DIBA-H) ed il dietil alluminio fluoruro. The catalytic system of the present invention includes, in addition to the Fe (II) complex, also one or more organo-derivatives of aluminum selected from (al) compounds of general formula (a2) aluminoxanes and relative derivatives, (a3) organoderivatives of partially hydrolyzed aluminum, and related mixtures, (a4) (III) (with n = 1 or 2) or (IV) (n = 1-5) where R is an alkyl group X is chlorine or bromine, preferably chlorine. As regards the aluminum (al) organoderivatives, in the compounds of general formula it is selected from alkyl (including cycloalkyl), aryl, alkylaryl, alkoxy, hydrogen, fluorine; equal or different from each other, they are selected from alkyl (including cycloalkyl), aryl, alkylaryl, arylalkyl. Typical organo-derivatives of aluminum (al) are diethyl aluminum hydride, di-n-propyl aluminum hydride, di-nbutyl aluminum hydride, diisobutyl aluminum hydride, diphenyl aluminum hydride, di-p-tolyl aluminum hydride, dibenzyl aluminum hydride, diethyl aluminum hydride , phenyl-n-propyl aluminum hydride, p-tolyl ethyl aluminum hydride, p-tolyl npropyl aluminum hydride, p-tolyl isopropyl aluminum hydride, benzyl ethyl aluminum hydride, benzyl n-propyl aluminum hydride, benzyl isopropyl aluminum hydride, diethyl aluminum ethoxide, diisobutyl aluminum ethoxide, dipropyl aluminum ethoxide, trimethyl aluminum, triethyl aluminum, tri-npropyl aluminum, triisobutyl aluminum, tri-n-butyl aluminum, tripentyl aluminum, triheyl aluminum, tricyclohexyl aluminum, tricyclohexyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum , tribenzyl aluminum, ethyl diphenyl aluminum, ethyl di-p-tolyl aluminum, ethyl dibenzyl aluminum, diethyl phenyl aluminum, diethyl p-tolyl aluminum, diethyl benzyl aluminum. The trialkylaluminium compounds are generally preferred. Preferred trialkylaluminium compounds include triethyl aluminum (TEA), tri-npropyl aluminum, triisobutyl aluminum (TIBA), triheyl aluminum, diisobutyl aluminum hydride (DIBA-H) and diethyl aluminum fluoride.
Per quanto concerne gli alluminossani (a2), trattasi, come ben noto, di composti contenenti legami Al-O-Al, con rapporto variabile O/Al, ottenibili nella tecnica per reazione, in condizioni controllate, di un alluminio alchile, o alogenuro di alluminio alchile, con acqua o altri composti contenenti quantità predeterminate di acqua disponibile, come, ad esempio, nel caso della reazione di alluminio trimetile con solfato di alluminio esaidrato, solfato di rame pentaidrato o solfato di ferro pentaidrato. Gli alluminossani preferibilmente utilizzabili per la formazione del catalizzatore di polimerizzazione della presente invenzione sono composti oligo- o poli-merici, ciclici e/o lineari, caratterizzati dalla presenza di unità ripetitive aventi la seguente formula: As regards aluminoxanes (a2), as is well known, these are compounds containing Al-O-Al bonds, with variable O / Al ratio, obtainable in the technique by reaction, under controlled conditions, of an aluminum alkyl, or halide of aluminum alkyl, with water or other compounds containing predetermined amounts of available water, such as, for example, in the case of the reaction of aluminum trimethyl with aluminum sulfate hexahydrate, copper sulfate pentahydrate or iron sulfate pentahydrate. The aluminoxanes which can preferably be used for the formation of the polymerization catalyst of the present invention are oligo- or polymeric compounds, cyclic and / or linear, characterized by the presence of repeating units having the following formula:
in cui R15 è un gruppo C1-C6 alchile, preferibilmente metile. Preferibilmente ciascuna molecola di alluminossano contiene da 4 a 70 unità ripetitive che possono anche non essere tutte uguali tra loro, ma contenere gruppi R15 differenti . wherein R15 is a C1-C6 alkyl group, preferably methyl. Preferably each aluminoxane molecule contains from 4 to 70 repetitive units which may not be all the same, but contain different R15 groups.
Per quanto concerne gli organo -derivati dell'alluminio parzialmente idrolizzati (a3), trattasi dei composti (al) addizionati di una quantità di sostanza protonante in rapporto molare da 0.001:1 a 0.2:1 sostanza protonante : alluminio derivato. La sostanza protonante è usualmente scelta tra acqua, alcol, acido, preferibilmente è l'acqua. Tuttavia possono essere usati anche metanolo, etanolo, alcol isopropilico, alcol n-propilico, t-butanolo, alcol isobutilico, alcol n-butilico, ed alcoli a più alto peso molecolare. Una vasta gamma di acidi carbossilici può essere altresì usata come sostanza protonante. Un esempio di questi acidi è l'acido stearico. As regards the partially hydrolyzed aluminum organo-derivatives (a3), these are compounds (al) with the addition of a quantity of protonant substance in a molar ratio from 0.001: 1 to 0.2: 1 protonant substance: aluminum derivative. The protonant substance is usually chosen from water, alcohol, acid, preferably water. However, methanol, ethanol, isopropyl alcohol, n-propyl alcohol, t-butanol, isobutyl alcohol, n-butyl alcohol, and higher molecular weight alcohols can also be used. A wide range of carboxylic acids can also be used as a protonant. An example of these acids is stearic acid.
Per quanto concerne gli organo-derivati di alluminio (a4), As regards the organo-derivatives of aluminum (a4),
(III) (con n = 1 o 2) o (IV) (n = 1-5), R è (III) (with n = 1 or 2) or (IV) (n = 1-5), R is
un gruppo alchilico Ci-C2o, X è cloro o bromo, preferibilmente cloro. Tipici esempi di composti di formula generale (III) sono (dietilcloroalluminio), AlMe2Cl (dimetilalluminiocloruro), AlEtCl2 (etilalluminiodicloruro), (diisobutilalluminiocloruro); tipici esempi di composti di formula generale (IV) sono Al2Et3Cl3 (etilalluminiosesquicloruro), Al2Me3Cl3 metilalluminiosesquicloruro). Nel procedimento della presente invenzione, il rapporto molare tra il complesso di formula generale (II) e l'alluminio è da 1:5 a 1:10000, preferibilmente da 1:10 a 1:500, ancor più preferibilmente da 1:20 a 1:100. a C1-C2o, X alkyl group is chlorine or bromine, preferably chlorine. Typical examples of compounds of general formula (III) are (diethylchloroaluminium), AlMe2Cl (dimethylaluminiumchloride), AlEtCl2 (ethylaluminiumdichloride), (diisobutylaluminiumchloride); typical examples of compounds of general formula (IV) are Al2Et3Cl3 (ethylaluminosquichloride), Al2Me3Cl3 methylaluminosquichloride). In the process of the present invention, the molar ratio between the complex of general formula (II) and aluminum is from 1: 5 to 1: 10000, preferably from 1:10 to 1: 500, even more preferably from 1:20 to 1: 100.
Nel caso in cui il complesso di formula generale (II) non sia preformato, bensì formato in situ, è preferibile usare un rapporto molare tra legante L e Fe(II) all'incirca uguale allo stechiometrico. Tuttavia si potranno ugualmente usare rapporti tra legante e Fe(II) superiori allo stechiometrico . In the case in which the complex of general formula (II) is not preformed, but formed in situ, it is preferable to use a molar ratio between ligand L and Fe (II) approximately equal to the stoichiometric. However, it is also possible to use ratios between ligand and Fe (II) higher than the stoichiometric.
Per quanto concerne la polimerizzazione del butadiene, la suddetta polimerizzazione viene preferibilmente effettuata in un mezzo di polimerizzazione comprendente un idrocarburo inerte che è solvente del butadiene e del sistema catalitico. Idrocarburi inerti utilizzabili nel processo di polimerizzazione comprendono idrocarburi alifatici, cicloalifatici, aromatici, monoolefinici e relative miscele. Più specificatamente opportuni idrocarburi sono quelli selezionati nel gruppo di idrocarburi alifatici da C4 a C8, nel gruppo di idrocarburi cicloalifatici da C5 a C10, nel gruppo di idrocarburi aromatici da C6 a C9, nel gruppo di idrocarburi monoolefinici da C4 a C6, e relative miscele. Tipici esempi non limitativi dei suddetti idrocarburi sono butano, pentano, esano, ciclopentano, cicloesano, benzene, toluene, xilene. As regards the polymerization of butadiene, the aforesaid polymerization is preferably carried out in a polymerization medium comprising an inert hydrocarbon which is a solvent of the butadiene and of the catalytic system. Inert hydrocarbons usable in the polymerization process include aliphatic, cycloaliphatic, aromatic, monoolefinic hydrocarbons and related mixtures. More specifically, suitable hydrocarbons are those selected in the group of aliphatic hydrocarbons from C4 to C8, in the group of cycloaliphatic hydrocarbons from C5 to C10, in the group of aromatic hydrocarbons from C6 to C9, in the group of monoolefinic hydrocarbons from C4 to C6, and related mixtures . Typical non-limiting examples of the above hydrocarbons are butane, pentane, hexane, cyclopentane, cyclohexane, benzene, toluene, xylene.
La concentrazione di 1,3-butadiene nel mezzo di polimerizzazione può variare in funzione del particolare mezzo solvente o diluente utilizzato. Nel caso in cui si usino solventi in cui sia il 1,3-butadiene che il prodotto polimerico sono entrambi solubili, la concentrazione di 1,3-butadiene è preferibilmente da 15 a 35 % peso rispetto al peso totale della miscela. The concentration of 1,3-butadiene in the polymerization medium can vary depending on the particular solvent or diluent medium used. In the case in which solvents are used in which both the 1,3-butadiene and the polymeric product are both soluble, the concentration of 1,3-butadiene is preferably from 15 to 35% by weight with respect to the total weight of the mixture.
La temperatura della polimerizzazione del butadiene è preferibilmente da -30°C a 60°C, il limite inferiore della temperatura essendo determinato più dal punto di congelamento della miscela di reazione piuttosto che dall'attività catalitica. Preferibilmente, il processo di polimerizzazione è effettuato ad una temperatura da -10°C a 40°C . The polymerization temperature of the butadiene is preferably from -30 ° C to 60 ° C, the lower limit of the temperature being determined more by the freezing point of the reaction mixture rather than by the catalytic activity. Preferably, the polymerization process is carried out at a temperature from -10 ° C to 40 ° C.
Per quanto concerne la polimerizzazione dell'isoprene, essa è preferibilmente una polimerizzazione in soluzione effettuata in solvente organico. Il solvente organico può essere un idrocarburo aromatico o un idrocarburo alifatico. Tipici esempi di opportuni solventi aromatici sono benzene, toluene, xileni, etilbenzene, dietilbenzene, isobutilbenzene, e relative miscele. Tuttavia, per motivi di igiene ambientale, i solventi alifatici sono altamente preferibili. Tipici esempi di opportuni solventi alifatici sono n-esano, cicloesano, metilcicloesano, isoesani, neptano, n-ottano, isoottani, n-decano, 2,2-dimetilbutano, etere di petrolio, cherosene, nafta, e relative miscele. E' importante che il solvente sia liquido alle condizioni (di temperatura e di pressione) di polimerizzazione. As regards the polymerization of isoprene, it is preferably a solution polymerization carried out in an organic solvent. The organic solvent can be an aromatic hydrocarbon or an aliphatic hydrocarbon. Typical examples of suitable aromatic solvents are benzene, toluene, xylenes, ethylbenzene, diethylbenzene, isobutylbenzene, and related mixtures. However, for reasons of environmental hygiene, aliphatic solvents are highly preferable. Typical examples of suitable aliphatic solvents are n-hexane, cyclohexane, methylcyclohexane, isohexanes, neptane, n-octane, isooctanes, n-decane, 2,2-dimethylbutane, petroleum ether, kerosene, naphtha, and related mixtures. It is important that the solvent is liquid under the conditions (temperature and pressure) of polymerization.
La polimerizzazione dell'isoprene è tipicamente effettuata nell'intervallo di temperatura da -10°C a 100°C. E' preferibile che la polimerizzazione sia effettuata in un intervallo di temperatura da 0°C a 50°C, ancor più preferibilmente da 10°C a 30°C. The polymerization of isoprene is typically carried out in the temperature range of -10 ° C to 100 ° C. It is preferable that the polymerization is carried out in a temperature range from 0 ° C to 50 ° C, even more preferably from 10 ° C to 30 ° C.
La suddetta polimerizzazione in soluzione è effettuata in un mezzo di polimerizzazione che comprende il solvente organico e i monomeri. Tali mezzi di polimerizzazione conterranno tipicamente da 5% peso a 35% peso di monomeri, rispetto al peso totale del mezzo di polimerizzazione. E' preferibile che il mezzo di polimerizzazione contenga da 10% peso a 30% peso di monomeri, ancor più preferibilmente da 15% peso a 25% peso. Come la polimerizzazione procede, il monomero si converte a polimero. Ne consegue che il mezzo di polimerizzazione conterrà tipicamente da 5% peso a 35% peso di monomeri e polimero, rispetto al peso totale del mezzo di reazione . The above solution polymerization is carried out in a polymerization medium which comprises the organic solvent and the monomers. Such polymerization media will typically contain from 5% by weight to 35% by weight of monomers, with respect to the total weight of the polymerization medium. It is preferable that the polymerization medium contains from 10% by weight to 30% by weight of monomers, even more preferably from 15% by weight to 25% by weight. As the polymerization proceeds, the monomer converts to polymer. It follows that the polymerization medium will typically contain from 5% by weight to 35% by weight of monomers and polymer, with respect to the total weight of the reaction medium.
La polimerizzazione dei monomeri (isoprene e/o butadiene) può essere effettuata in un processo batch, semicontinuo o continuo. In ogni caso la polimerizzazione ha inizio aggiungendo il sistema catalitico al mezzo di polimerizzazione contenente l'isoprene. I componenti del sistema catalitico possono essere premiscelati prima della loro aggiunta al mezzo di polimerizzazione oppure essere aggiunti uno alla volta al mezzo di polimerizzazione. E' tuttavia preferibile dapprima aggiungere l'isoprene monomero al mezzo di polimerizzazione, quindi aggiungere il composto di Alluminio, ed infine il complesso di Fe(II). The polymerization of the monomers (isoprene and / or butadiene) can be carried out in a batch, semi-continuous or continuous process. In any case, the polymerization begins by adding the catalytic system to the polymerization medium containing the isoprene. The components of the catalyst system can be premixed before their addition to the polymerization medium or be added one at a time to the polymerization medium. However, it is preferable to first add the monomer isoprene to the polymerization medium, then add the Aluminum compound, and finally the Fe (II) complex.
Utilizzando il sistema catalitico della presente invenzione, si possono ottenere conversioni molto elevate anche dopo ridotti tempi di reazione. Inoltre il sistema della presente invenzione consente di ottenere un poliisoprene essenzialmente esente da gel. Il 3,4-poliisoprene ottenibile con il processo della presente invenzione ha una viscosità in soluzione diluita inferiore a 5.0 dl/g, preferibilmente inferiore a 3.0 dl/g. Infatti è importante, al fine della processabilità, che il poliisoprene abbia una viscosità inferiore a 5.0 dl/g. By using the catalytic system of the present invention, very high conversions can be obtained even after short reaction times. Furthermore, the system of the present invention allows to obtain an essentially gel-free polyisoprene. The 3,4-polyisoprene obtainable with the process of the present invention has a viscosity in dilute solution lower than 5.0 dl / g, preferably lower than 3.0 dl / g. In fact it is important, for the purpose of processability, that the polyisoprene has a viscosity lower than 5.0 dl / g.
La reazione di polimerizzazione può essere fermata mediante l'aggiunta di un terminatore di polimerizzazione noto, al sistema di polimerizzazione, per inattivare il sistema catalitico, seguita dalle convenzionali fasi di desolventizzazione e essiccamento come sono tipicamente impiegate nella produzione di polidieni. Tipicamente, il terminatore impiegato per disattivare il sistema catalitico è un composto protico, il quale include, ma non è limitante, un alcol, un acido carbossilico, un acido inorganico, e acqua o una combinazione di essi. Un antiossidante quale 2,6-di-ter-butil-1,4 -metilfenolo può essere aggiunto, prima, dopo o con l'aggiunta del terminatore. La quantità di antiossidante è usualmente nel range tra 0,2% e 1% in peso rispetto al polimero. Al termine della polimerizzazione, il polidiene (ad esempio polibutadiene o poliisoprene) può essere recuperato secondo tecniche standard, preferibilmente mediante la tecnica della coagulazione. Eventuali residui del solvente possono essere rimossi dal polimero mediante evaporazione, che può essere facilitata da temperature elevate e dall'applicazione del vuoto. The polymerization reaction can be stopped by adding a known polymerization terminator to the polymerization system to inactivate the catalytic system, followed by the conventional desolventization and drying steps as are typically used in the production of polydidenes. Typically, the terminator employed to deactivate the catalytic system is a protic compound, which includes, but is not limiting, an alcohol, a carboxylic acid, an inorganic acid, and water or a combination thereof. An antioxidant such as 2,6-di-tert-butyl-1,4-methylphenol can be added before, after or with the addition of the terminator. The amount of antioxidant is usually in the range between 0.2% and 1% by weight with respect to the polymer. At the end of the polymerization, the polidiene (for example polybutadiene or polyisoprene) can be recovered according to standard techniques, preferably by the coagulation technique. Any solvent residues can be removed from the polymer by evaporation, which can be facilitated by high temperatures and the application of vacuum.
Il procedimento della presente invenzione può essere applicato non solo agli omopolimeri di dieni coniugati, particolarmente al polibutadiene ed al poliisoprene, ma anche a copolimeri e terpolimeri di dieni coniugati. Tipici esempi di questi dieni coniugati sono il 2,3-dimetil-l,3-butadiene, il 1,3-pentadiene, il 1,3-esadiene, il 3-metil-1,3-pentadiene . The process of the present invention can be applied not only to homopolymers of conjugated dienes, particularly to polybutadiene and polyisoprene, but also to copolymers and terpolymers of conjugated dienes. Typical examples of these conjugated dienes are 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 3-methyl-1,3-pentadiene.
Fanno altresì parte della presente invenzione i seguenti complessi di Fe(II): The following Fe (II) complexes also form part of the present invention:
** Complesso di Fe(II) di formula Fe(L)n(X)s in cui n=2, X=C1, s=2, L = 1,10-fenantrolin-5,6-dione; ** Fe (II) complex of formula Fe (L) n (X) s in which n = 2, X = C1, s = 2, L = 1,10-phenanthrolin-5,6-dione;
** Complesso di Fe(II) di formula Fe(L)n(X)s in cui n=l, X=C1, s=2, L = 1,10-fenantrolin-5,6-dione; ** Fe (II) complex of formula Fe (L) n (X) s in which n = 1, X = C1, s = 2, L = 1,10-phenanthrolin-5,6-dione;
** Complesso di Fe(II) di formula Fe(L)n(X)s in cui n=2, X=C1, s=2, L = 1,10-fenantrolin-5,6-diolo; ** Fe (II) complex of formula Fe (L) n (X) s in which n = 2, X = C1, s = 2, L = 1,10-phenanthrolin-5,6-diol;
** Complesso di Fe(II) di formula Fe(L)n(X)s in cui n=l, X=C1, s=2, L = 1,10-fenantrolin-5,6-diolo; ** Fe (II) complex of formula Fe (L) n (X) s in which n = 1, X = C1, s = 2, L = 1,10-phenanthrolin-5,6-diol;
** Complesso di Fe(II) di formula Fe(L)n(X)s in cui n=2, X=C1, s=2, L = 1,9-diaza-fluoren-5-one; ** Fe (II) complex of formula Fe (L) n (X) s in which n = 2, X = C1, s = 2, L = 1,9-diaza-fluoren-5-one;
** Complesso di Fe(II) di formula Fe(L)n(X)s in cui n=l X=C1, s=2, L = 1,9-diaza-fluoren-5-one. ** Fe (II) complex of formula Fe (L) n (X) s where n = 1 X = C1, s = 2, L = 1,9-diaza-fluoren-5-one.
I seguenti esempi sono riportati per una migliore illustrazione della presente invenzione. The following examples are given for a better illustration of the present invention.
ESEMPI EXAMPLES
I complessi di Fe(II) utilizzabili nel processo della presente invenzione sono stati preparati secondo il metodo riportato in letteratura (E. Konig, Coord. Chem. Rev., 3471 (1968). The Fe (II) complexes usable in the process of the present invention were prepared according to the method reported in the literature (E. Konig, Coord. Chem. Rev., 3471 (1968).
Qui di seguito il legante bipiridile sarà chiamato bipy; il legante 1,10-fenantrolina : phen; il legante 5-metil-1,10-fenantrolina : 5-Me-phen; il legante 5,6-dimetil-1,10-fenantrolina : 5,6-diMe-phen; il legante 4-metil-1,10-fenantrolina : 4-mephen; il legante 4,7-dimetil-1,10-fenantrolina : 4,7-diMe-phen; il legante 4,7-difenil-1,10-fenantrolina : 4,7-difenil-phen; il legante 3,4,7,8-tetrametil-1,10-fenantrolina : tetraMe-phen; il legante 1,10-fenantrolin-5,6-dione : fen-dione; il legante 1,10-fenantrolin-5,6-diolo : fen-diolo; il legante 1,9-diazafluoren-5-one : fluorenone; il legante 4,7-difenil-1,10-fenantrolina: batophen. Hereinafter the bipyridyl ligand will be called bipy; the ligand 1,10-phenanthroline: phen; the 5-methyl-1,10-phenanthroline: 5-Me-phen ligand; the ligand 5,6-dimethyl-1,10-phenanthroline: 5,6-diMe-phen; the ligand 4-methyl-1,10-phenanthroline: 4-mephen; the ligand 4,7-dimethyl-1,10-phenanthroline: 4,7-diMe-phen; the ligand 4,7-diphenyl-1,10-phenanthroline: 4,7-diphenyl-phen; the ligand 3,4,7,8-tetramethyl-1,10-phenanthroline: tetraMe-phen; the ligand 1,10-phenanthrolin-5,6-dione: phen-dione; the ligand 1,10-phenanthrolin-5,6-diol: phen-diol; the ligand 1,9-diazafluoren-5-one: fluorenone; the 4,7-diphenyl-1,10-phenanthroline binder: batophen.
A titolo comparativo sono riportati anche complessi di Fe(II) con due leganti non facenti parte della presente invenzione, per l'esattezza il legante 4,7-diidrossifenantrolina (4,7-DiOH-phen) ed il legante 2,9-dimetilfenantrolina (2,9-DiMephen). By way of comparison, complexes of Fe (II) with two ligands not forming part of the present invention are also reported, to be exact the ligand 4,7-dihydroxyphenanthroline (4,7-DiOH-phen) and the ligand 2,9-dimethylphenanthroline (2,9-DiMephen).
Per quanto concerne i derivati dell'alluminio, MAO è il metilalluminossano, TIBAO è il triisobutilalluminossano. As far as aluminum derivatives are concerned, MAO is methylaluminoxane, TIBAO is triisobutylaluminoxane.
SINTESI LEGANTI AZOTATI SYNTHESIS OF NITROGEN BINDERS
Es. 1 Sintesi di 1,10-fenantrolina-5,6-dione Ex. 1 Synthesis of 1,10-phenanthroline-5,6-dione
(secondo la ricetta di letteratura: W. Paw and R. Eisenberg, Inorg.Chem, 36, 2287 (1997)) (according to the literature recipe: W. Paw and R. Eisenberg, Inorg.Chem, 36, 2287 (1997))
26,4 g (0,133 moli) di Fenantrolina monoidrata (PM 198,2) 24,0 g (0,201moli) di KBr (PM 119) 26.4 g (0.133 moles) of Phenanthroline monohydrate (PM 198.2) 24.0 g (0.201 moles) of KBr (PM 119)
Miscela solfonitrica costituita da: Sulphonitic mixture consisting of:
240 mi di H2SO4 al 96% e 240 ml of 96% H2SO4 e
120 mi di HNO3 al 65 % 120 ml of 65% HNO3
In un pallone a tre colli munito di refrigerante, imbuto gocciolatore e mantenuto sotto battente di argon viene posta la miscela solida di fenantrolina e potassio bromuro raffreddando a -10°C tramite bagno termostatico. Si gocciola quindi la miscela solfonitrica raffreddata tra - 5 e -10°C. Si lascia salire a temperatura ambiente e si scalda fino a riflusso del bromo formatosi. La temperatura non supera in questa fase gli 80°C. Quando tutto il bromo è stato allontanato (1 ora circa) la temperatura raggiunge i 116-120°C. Si scalda per un totale di quattro ore, considerando anche il tempo di inizio riscaldamento. Si raffredda a temperatura ambiente e si versa la miscela in 3 Kg di ghiaccio. Si porta il pH ad un valore di circa 6 per neutralizzazione con NaOH al 30%. Si estrae la miscela neutralizzata con circa tre litri di cloruro di metilene da cui dopo essiccamento ed evaporazione si recuperano 27,0 g (96,7 % di resa) di prodotto puro all'analisi e che fonde a 254-255°C. Il prodotto cristallizzato da metanolo presenta un punto di fusione di 259-261°C. The solid mixture of phenanthroline and potassium bromide is placed in a three-necked flask equipped with a coolant, a dropping funnel and kept under an argon head, cooling to -10 ° C by means of a thermostatic bath. The cooled sulphonite mixture is then dropped to between - 5 and -10 ° C. It is allowed to rise to room temperature and heated until the bromine formed is refluxed. The temperature does not exceed 80 ° C in this phase. When all the bromine has been removed (about 1 hour) the temperature reaches 116-120 ° C. It heats up for a total of four hours, also considering the start-up time. It is cooled to room temperature and the mixture is poured into 3 kg of ice. The pH is brought to a value of about 6 by neutralization with 30% NaOH. The neutralized mixture is extracted with about three liters of methylene chloride from which, after drying and evaporation, 27.0 g (96.7% yield) of product pure upon analysis are recovered and which melts at 254-255 ° C. The product crystallized from methanol has a melting point of 259-261 ° C.
Sintesi di 1,9-diaza-fluoren-5-one Synthesis of 1,9-diaza-fluoren-5-one
(secondo la ricetta di letteratura: M.J. Plater et altri, J.Chem.Soc., Perkin Trans.1,971 (2000)) (according to the literature recipe: M.J. Plater et others, J.Chem.Soc., Perkin Trans. 1,971 (2000))
14.65 g (0,074 moli) di fenantrolina mono idrata (PM 198,2) 15,8 g (0,24 moli) di KOH solida all'85% sciolti in 1000 cc di H2O 14.65 g (0.074 mol) of monohydrated phenanthroline (PM 198.2) 15.8 g (0.24 mol) of 85% solid KOH dissolved in 1000 cc of H2O
33.65 g (0,213 moli) di KMn04 (PM 158) sciolti in 540 cc di H2O 33.65 g (0.213 moles) of KMn04 (PM 158) dissolved in 540 cc of H2O
Alla soluzione di fenantrolina in potassa scaldata a riflusso si gocciola in tre ore la soluzione di permanganato mantenuta a 70°C. Terminata l'aggiunta si lascia a riflusso ancora 10 minuti e quindi si filtra a caldo. La soluzione fredda viene estratta con cloroformio. Per evaporazione del solvente si ottengono 9,5 g di prodotto grezzo che viene cristallizzato da metanolo a dare 5,4 g di prodotto puro (40% di resa). The permanganate solution kept at 70 ° C is dropped into the solution of phenanthroline in potash heated to reflux in three hours. At the end of the addition it is left to reflux for another 10 minutes and then it is filtered while hot. The cold solution is extracted with chloroform. By evaporation of the solvent 9.5 g of crude product are obtained which is crystallized from methanol to give 5.4 g of pure product (40% yield).
1,10-fenantrolina-5, 6-diolo 1,10-phenanthroline-5, 6-diol
(secondo la ricetta di letteratura: W. Paw and R. Eisenberg, Inorg.Chem, 36, 2287 (1997)) (according to the literature recipe: W. Paw and R. Eisenberg, Inorg.Chem, 36, 2287 (1997))
2,1 g (10 mmoli) di 1,10-diaza-fenantren-5,6-dione (PM 210) 1 , 44 g (12 mmoli ) di ditiooxamide) (PM 120, 2) 2.1 g (10 mmol) of 1,10-diaza-phenanthren-5,6-dione (PM 210) 1, 44 g (12 mmol) of dithiooxamide) (PM 120, 2)
75 mi di EtOH degasato 75 ml of degassed EtOH
In un pallone mantenuto sotto atmosfera di argon si introduce il dione, la ditiooxamide e 1'etanolo. Si scalda la miscela a riflusso per 16 ore. Dopo raffreddamento si filtra mantenendo il tutto sotto argon quindi si lava il solido con etanolo e con cloroformio. Per essiccamento si ottengono 1,6 g (75 % di resa) di prodotto puro all'analisi NMR (PM 212). Dione, dithiooxamide and ethanol are introduced into a flask maintained under an argon atmosphere. The mixture is heated under reflux for 16 hours. After cooling it is filtered keeping everything under argon then the solid is washed with ethanol and chloroform. By drying 1.6 g (75% yield) of pure product are obtained by NMR analysis (PM 212).
Sintesi del Fe(fen-dione)2Cl2Synthesis of Fe (phen-dione) 2Cl2
Operando in atmosfera inerte d'azoto, in un pallone da 250 mi si introducono 0,55 g di FeCl2 (4,33 mmol), 20 ml etanolo anidro e degasato, e 1,82 g (8,66 mmol) di 1,10-fenantrolin-5,6-dione. La soluzione diventa immediatamente marronerosso, si lascia sotto agitazione vigorosa per una notte. Si recupera il solido per filtrazione e poi lo si essicca sotto vuoto . Operating in an inert nitrogen atmosphere, 0.55 g of FeCl2 (4.33 mmol), 20 ml anhydrous and degassed ethanol, and 1.82 g (8.66 mmol) of 1 are introduced into a 250 ml flask. 10-phenanthrolin-5,6-dione. The solution immediately turns red brown, is left under vigorous stirring overnight. The solid is recovered by filtration and then dried under vacuum.
Si ottengano 2,38 g di polvere rosso-viola (Resa = 100%). 2.38 g of red-violet powder are obtained (Yield = 100%).
Analisi elementare: Fe = 9,9 % (teorico = 10,2), cloro = 12,5% (teorico = 12,9) Elemental analysis: Fe = 9.9% (theoretical = 10.2), chlorine = 12.5% (theoretical = 12.9)
Sintesi del Fe (fen- dione) Cl2Synthesis of Fe (fen- dione) Cl2
In un provettone da 100 mi si pesano sotto argon 2.072 g (15,99 mmoli) di FeCl2 anidro e si sciolgono in 50 mi di alcool etilico degasato per riscaldamento a 50°C. Alla soluzione gialla riportata a T ambiente si aggiungono 0,336 g (1,599 limoli) di 1,10-fenantrolin-5,6-dione con istantanea formazione di un solido rosso. La sospensione è lasciata a T ambiente per tutta notte; successivamente, si filtra il residuo rosso e si essicca sotto vuoto. Si ottengono 0,5 g di polvere rosso-viola (Resa = 93%). In a 100 ml test tube 2,072 g (15.99 mmoles) of anhydrous FeCl2 are weighed under argon and dissolved in 50 ml of degassed ethyl alcohol by heating to 50 ° C. 0.336 g (1,599 limols) of 1,10-phenanthrolin-5,6-dione are added to the yellow solution brought to room T with instant formation of a red solid. The suspension is left at room T for the whole night; subsequently, the red residue is filtered and dried under vacuum. 0.5 g of red-violet powder are obtained (yield = 93%).
Analisi elementare: Fe 16,8% (16,57% teor.); CI 20,8% (21,04% teor.) Elemental analysis: Fe 16.8% (16.57% theor.); CI 20.8% (21.04% theor.)
Sintesi del Fe(fen-diolo)Cl2Synthesis of Fe (phen-diol) Cl2
Operando in atmosfera inerte d'azoto, in un pallone da 250 mi si introducono 2.072 g (15,99 mmoli) di FeCl2 anidro che si sciolgono in 50 mi di alcool etilico per riscladamento a 50°C. Alla soluzione si aggiungono 0,34 g (1,599 mmol) di 1,10-fenantrolin-5,6-diolo. Si lascia sotto agitazione per 8 ore. Si recupera il solido per filtrazione e poi lo si essicca sotto vuoto. Operating in an inert nitrogen atmosphere, 2,072 g (15.99 mmoles) of anhydrous FeCl2 are introduced into a 250 ml flask, which are dissolved in 50 ml of ethyl alcohol by heating to 50 ° C. 0.34 g (1.599 mmol) of 1,10-phenanthrolin-5,6-diol are added to the solution. It is left under stirring for 8 hours. The solid is recovered by filtration and then dried under vacuum.
Si ottengano 0,52 g di polvere rossa (Resa = 96%). 0.52 g of red powder are obtained (yield = 96%).
Analisi elementare: Fe = 16,5 % (teorico = 16,48 ), cloro = 20,3% (teorico = 20,92) Elemental analysis: Fe = 16.5% (theoretical = 16.48), chlorine = 20.3% (theoretical = 20.92)
Sintesi del Fe(fen-diolo)2C12Synthesis of Fe (phen-diol) 2C12
Operando in atmosfera inerte d'azoto, in un pallone da 250 mi si introducono 0,3 g di FeCl2 (2,36 mmol), 20 mi etanolo anidro e degasato, e lg (4,73 mmol) di 1,10-fenantrolin-5,6-diolo. Si lascia sotto agitazione vigorosa per 2 ore. Si recupera il solido per filtrazione e poi lo si essicca sotto vuoto . Operating in an inert nitrogen atmosphere, 0.3 g of FeCl2 (2.36 mmol), 20 ml anhydrous and degassed ethanol, and 1 g (4.73 mmol) of 1,10-phenanthrolin are introduced into a 250 ml flask. -5,6-diol. It is left under vigorous stirring for 2 hours. The solid is recovered by filtration and then dried under vacuum.
Si ottengono 1,2 g di polvere rossa (Resa = 93%). 1.2 g of red powder are obtained (yield = 93%).
Analisi elementare: Fe = 9,3 % (teorico = 10,13), cloro = 11,9% (teorico = 12,86) Elemental analysis: Fe = 9.3% (theoretical = 10.13), chlorine = 11.9% (theoretical = 12.86)
Sintesi del Fe(fluorenone)2C12Synthesis of Fe (fluorenone) 2C12
Operando in atmosfera inerte d'azoto, in un pallone da 250 mi si introducon 0,5 g di FeCl2 (3,94 mmol), 20 ml etanolo anidro e degasato, e 1,43 g (7,89 mmol) di 1,9-diazafluoren-5-one . Si lascia sotto agitazione vigorosa per 3 ore. Precipita un solido che si recupera per filtrazione e poi lo si essicca sotto vuoto. Si ottengano 1,93 g di polvere rosa (Resa = 93%). Operating in an inert nitrogen atmosphere, 0.5 g of FeCl2 (3.94 mmol), 20 ml anhydrous and degassed ethanol, and 1.43 g (7.89 mmol) of 1 are introduced into a 250 ml flask. 9-diazafluoren-5-one. It is left under vigorous stirring for 3 hours. A solid precipitates which is recovered by filtration and then dried under vacuum. 1.93 g of pink powder are obtained (yield = 93%).
Analisi elementare: Fe = 11,3 % (teorico = 11,3 ), cloro = 14,1% (teorico = 14,44). Elemental analysis: Fe = 11.3% (theoretical = 11.3), chlorine = 14.1% (theoretical = 14.44).
Sintesi del Fe(fluorenone)Cl2Synthesis of Fe (fluorenone) Cl2
Operando in atmosfera inerte d'azoto, in un pallone da 250 mi si introducono 2.072 g (15,99 mmoli) di FeCl2 anidro che si sciolgono in 50 mi di alcool etilico per riscladamento a 50°C. Alla soluzione si aggiungono 0,2 g (1,599 mmol) di 1,9-diaza-fluoren-5-one . Si lascia sotto agitazione per 8 ore. Si recupera il solido per filtrazione e poi lo si essicca sotto vuoto. Operating in an inert nitrogen atmosphere, 2,072 g (15.99 mmoles) of anhydrous FeCl2 are introduced into a 250 ml flask, which are dissolved in 50 ml of ethyl alcohol by heating to 50 ° C. To the solution are added 0.2 g (1.599 mmol) of 1,9-diaza-fluoren-5-one. It is left under stirring for 8 hours. The solid is recovered by filtration and then dried under vacuum.
Si ottengono 0,47 g di polvere rosa (Resa = 96%). 0.47 g of pink powder are obtained (yield = 96%).
Analisi elementare: Fe = 18 % (teorico = 18,08), cloro = 22,3% (teorico = 22,95) Elemental analysis: Fe = 18% (theoretical = 18.08), chlorine = 22.3% (theoretical = 22.95)
ESEMPI 1-27 EXAMPLES 1-27
La tabella 1 riporta i risultati delle prove 1-27 riguardanti la polimerizzazione del butadiene. Table 1 reports the results of tests 1-27 concerning the polymerization of butadiene.
ESEMPI 28-38 EXAMPLES 28-38
La tabella 2 riporta i risultati delle prove 28-38 riguardanti la polimerizzazione dell'isoprene. Table 2 reports the results of tests 28-38 concerning the polymerization of isoprene.
ESEMPI 39-40 EXAMPLES 39-40
La tabella 3 riporta i risultati delle prove 39-40 riguardanti la polimerizzazione di altri dieni coniugati. Procedura di polimerizzazione del butadiene. Table 3 reports the results of tests 39-40 concerning the polymerization of other conjugated dienes. Butadiene polymerization procedure.
In un provettino da 25 mL, mantenuto alla temperatura di -20°C, vengono condensati 2 mL di butadiene (ca. 1.4 g), seccato per passaggio attraverso una colonna di acciaio contenente setacci molecolari. Si introduce quindi il toluene (10.15 mL) e la soluzione così ottenuta viene portata alla temperatura di polimerizzazione desiderata. A questo punto si aggiungono il MAO (5x10<-3 >moli, 3.15 mL di soluzione toluenica al 10% in peso) ed il complesso di ferro (5x10<-6 >moli). La polimerizzazione viene terminata mediante aggiunta di metanolo contenente piccole quantità di acido cloridrico; il polimero viene coagulato e lavato ripetutamente in largo eccesso di metanolo, quindi seccato sotto vuoto a temperatura ambiente. In a 25 mL test tube, kept at a temperature of -20 ° C, 2 mL of butadiene (approx. 1.4 g) are condensed and dried by passing through a steel column containing molecular sieves. Toluene (10.15 mL) is then introduced and the solution thus obtained is brought to the desired polymerization temperature. At this point the MAO (5x10 <-3> moles, 3.15 mL of toluene solution at 10% by weight) and the iron complex (5x10 <-6> moles) are added. The polymerization is terminated by adding methanol containing small quantities of hydrochloric acid; the polymer is coagulated and washed repeatedly in large excess of methanol, then dried under vacuum at room temperature.
Nel caso del catalizzatore preparato in situ (esempio 2), l'ordine di introduzione dei reagenti è il seguente: toluene, monomero, legante, composto di ferro. Si fa invecchiare per circa 5-10 minuti e quindi si aggiunge il MAO o l'Alluminio alchile. In the case of the catalyst prepared in situ (example 2), the order of introduction of the reactants is as follows: toluene, monomer, ligand, iron compound. It is aged for about 5-10 minutes and then the MAO or the aluminum alkyl is added.
Procedura di polimerizzazione dell'isoprene. Isoprene polymerization procedure.
In un provettino codato da 25 mL, in cui sono stati fatti preventivamente 3 cicli vuoto-argon, vengono introdotti 10 mL di isoprene, seccato per distillazione su CaH2. Si introduce quindi il toluene nella quantità desiderata e la soluzione così ottenuta viene portata alla temperatura di polimerizzazione desiderata. A questo punto si aggiunge il cocatalizzatore a base di alluminio ed il complesso di Ferro (sospensione in toluene). La polimerizzazione viene terminata mediante aggiunta di metanolo contenente piccole quantità di acido cloridrico; il polimero viene coagulato e lavato ripetutamente in largo eccesso di metanolo, quindi seccato sotto vuoto a temperatura ambiente. 10 mL of isoprene, dried by distillation on CaH2, are introduced into a 25 mL coded test tube, in which 3 vacuum-argon cycles have been previously carried out. The toluene is then introduced in the desired quantity and the solution thus obtained is brought to the desired polymerization temperature. At this point, the aluminum-based cocatalyst and the iron complex (suspension in toluene) are added. The polymerization is terminated by adding methanol containing small quantities of hydrochloric acid; the polymer is coagulated and washed repeatedly in large excess of methanol, then dried under vacuum at room temperature.
Reagenti . Reagents.
Metilalluminossano (MAO) (prodotto Witco, soluzione toluenica al 10% in peso) è stato utilizzato senza ulteriore purificazione. Toluene (prodotto Fluka, grado di purezza > 99.5%) è stato fatto riflussare su Na per ca. 8h, quindi distillato e conservato su setacci molecolari in atmosfera di azoto. 1,3-Butadiene (Air Liquide, > 99.5% pure) viene evaporato direttamente dalla bombola prima di ogni prova di polimerizzazione, seccato per passaggio attraverso una colonna contenente setacci molecolari e condensato nel reattore di polimerizzazione raffreddato alla temperatura di ca. -20°C. (E)-1,3-pentadiene (Aldrich, 98% pure) sono stati fatti riflussare su calcio idruro per ca. 2h, quindi distillati trap-to trap e conservati in atmosfera di azoto. L'isoprene viene anidrificato per distillazione su CaH2. Methylaluminoxane (MAO) (Witco product, 10 wt% toluene solution) was used without further purification. Toluene (Fluka product, degree of purity> 99.5%) was refluxed on Na for approx. 8h, then distilled and stored on molecular sieves in a nitrogen atmosphere. 1,3-Butadiene (Air Liquide,> 99.5% pure) is evaporated directly from the cylinder before each polymerization test, dried by passing through a column containing molecular sieves and condensed in the polymerization reactor cooled to a temperature of approx. -20 ° C. (E) -1,3-pentadiene (Aldrich, 98% pure) were refluxed on calcium hydride for approx. 2h, then trap-to-trap distillates and stored in a nitrogen atmosphere. The isoprene is dried by distillation on CaH2.
2.3-dimetilbutadiene (Aldrich, 98% puro) 2.3-Dimethylbutadiene (Aldrich, 98% pure)
1.3-esadiene (Aldrich, 97% puro) 1.3-hexadiene (Aldrich, 97% pure)
3-metil-1,3-pentadiene (Aldrich, 99% puro) 3-methyl-1,3-pentadiene (Aldrich, 99% pure)
Le temperature di transizione vetrosa e di fusione sono state determinate mediante DSC (Differential Scanning Calorimetry) . La microstruttura del polimero è stata determinata mediante e Nuclear Magnetic Resonance (NMR). Il peso molecolare (Mn, Mw) e la distribuzione dei pesi molecolari (MWD) sono stati determinati mediante Gel Permetion Chromatography (GPC). The glass transition and melting temperatures were determined by Differential Scanning Calorimetry (DSC). The polymer microstructure was determined by and Nuclear Magnetic Resonance (NMR). The molecular weight (Mn, Mw) and the molecular weight distribution (MWD) were determined by Gel Permetion Chromatography (GPC).
Tabella 1. Polimerizzazione di butadiene con complessi di Ferro (II) Table 1. Polymerization of butadiene with Iron (II) complexes
COMMENTI ALLE TABELLE COMMENTS TO THE TABLES
a) Tabella 1 a) Table 1
I dati di tabella 1 mostrano che la presenza di Fe(II) non-complessato non catalizza la polimerizzazione del butadiene (esempio comparativo 1 in confronto con l'esempio 4). The data of table 1 show that the presence of non-complexed Fe (II) does not catalyze the polymerization of butadiene (comparative example 1 in comparison with example 4).
Inoltre sono efficaci sia i complessi preformati che formati in situ. Tuttavia il complesso formato in situ risulta leggermente meno efficace (esempio 2 in confronto con esempio 4). Furthermore, both pre-formed and in-situ formed assemblies are effective. However, the complex formed in situ is slightly less effective (example 2 in comparison with example 4).
I complessi della presente invenzione sono efficaci sia in presenza di Alluminio alchile che di MAO. Per quanto concerne gli alluminio alchili, i risultati sono pressoché equivalenti a prescindere dal tipo di radicale alchilico. The complexes of the present invention are effective both in the presence of aluminum alkyl and MAO. As far as aluminum alkyls are concerned, the results are almost equivalent regardless of the type of alkyl radical.
Inoltre fra i due alluminossani testati (MAO e TIBAO) i risultati sono pressoché equivalenti. Furthermore, between the two tested aluminoxanes (MAO and TIBAO) the results are almost equivalent.
Variando il tipo di legante, i risultati sono confrontabili (esempi 5, 10, 20). By varying the type of binder, the results are comparable (examples 5, 10, 20).
Leggermente meno veloci sono i complessi aventi una o più sostituzioni nel legante (esempi 12, 13, 15, 17, 19). Slightly less fast are the complexes having one or more substitutions in the ligand (examples 12, 13, 15, 17, 19).
Risultano inefficaci invece i complessi in cui il legante è alchil sostituito nelle posizioni 2 e 9, oppure diidrossisostituito nelle posizioni 4 e 7 (esempi comparativi 16C e 18C). On the other hand, complexes in which the ligand is alkyl substituted in positions 2 and 9, or dihydroxy substituted in positions 4 and 7 are ineffective (comparative examples 16C and 18C).
Per quanto concerne la microstruttura, il polibutadiene ottenuto ha un tenore in 1,2 tra il 60 e il 70%. As far as the microstructure is concerned, the polybutadiene obtained has a 1.2 content between 60 and 70%.
E' tuttavia importante notare la grandissima attività catalitica dei complessi della presente invenzione, molti dei quali danno conversione pressoché totale quasi istantaneamente (circa 1 minuto). However, it is important to note the very great catalytic activity of the complexes of the present invention, many of which give almost total conversion almost instantaneously (about 1 minute).
b) Tabella 2 b) Table 2
La tabella 2 mostra come i complessi della presente invenzione siano altrettanto efficaci per la omopolimerizzazione dell'isoprene. Table 2 shows how the complexes of the present invention are equally effective for the homopolymerization of isoprene.
Anche in questo caso, risultano inefficaci i complessi in cui il legante è alchil sostituito nelle posizioni 2 e 9, oppure diidrossisostituito nelle posizioni 4 e 7 (esempi comparativi 34C e 36C). Also in this case, complexes in which the ligand is alkyl substituted in positions 2 and 9, or dihydroxy substituted in positions 4 and 7 are ineffective (comparative examples 34C and 36C).
I complessi della presente invenzione sono efficaci sia in presenza di Alluminio alchile che di MAO. Per quanto concerne gli alluminio alchili, i risultati sono pressoché equivalenti a prescindere dal tipo di radicale alchilico. The complexes of the present invention are effective both in the presence of aluminum alkyl and MAO. As far as aluminum alkyls are concerned, the results are almost equivalent regardless of the type of alkyl radical.
Per quanto concerne la microstruttura del poliisoprene, è essenzialmente 3,4- (tra il 60 e il 70%). As for the microstructure of polyisoprene, it is essentially 3.4- (between 60 and 70%).
c) Tabella 3 c) Table 3
La tabella 3 mostra come i complessi del Ferro siano efficaci anche nella omopolimerizzazione di altri dieni coniugati . Table 3 shows how the Iron complexes are also effective in the homopolymerization of other conjugated dienes.
Claims (22)
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
IT2001MI001259A ITMI20011259A1 (en) | 2001-06-15 | 2001-06-15 | PROCEDURE FOR THE (CO) POLYMERIZATION OF CONJUGATE DIENES |
PCT/EP2002/006497 WO2002102861A2 (en) | 2001-06-15 | 2002-06-12 | Process for the (co)polymerization of conjugated dienes |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
IT2001MI001259A ITMI20011259A1 (en) | 2001-06-15 | 2001-06-15 | PROCEDURE FOR THE (CO) POLYMERIZATION OF CONJUGATE DIENES |
Publications (2)
Publication Number | Publication Date |
---|---|
ITMI20011259A0 ITMI20011259A0 (en) | 2001-06-15 |
ITMI20011259A1 true ITMI20011259A1 (en) | 2002-12-15 |
Family
ID=11447873
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
IT2001MI001259A ITMI20011259A1 (en) | 2001-06-15 | 2001-06-15 | PROCEDURE FOR THE (CO) POLYMERIZATION OF CONJUGATE DIENES |
Country Status (2)
Country | Link |
---|---|
IT (1) | ITMI20011259A1 (en) |
WO (1) | WO2002102861A2 (en) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IT201600105530A1 (en) | 2016-10-20 | 2018-04-20 | Versalis Spa | PROCEDURE FOR THE PREPARATION OF POLIBUTADIENE 1.2 SINDIOTATTICO IN THE PRESENCE OF A CATALYTIC SYSTEM INCLUDING A PYRIDYLUM IRON COMPLEX |
IT201600105714A1 (en) | 2016-10-20 | 2018-04-20 | Versalis Spa | PROCEDURE FOR THE PREPARATION OF (CO) POLYMERS OF DIENES CONJUGATED IN THE PRESENCE OF A CATALYTIC SYSTEM INCLUDING A PYRIDYLUM IRON COMPLEX (III) |
IT201700059763A1 (en) | 2017-05-31 | 2018-12-01 | Versalis Spa | BUTADIENE-ISOPRENE COPOLYMERS DI-BLOCK AND PROCEDURE FOR THEIR PREPARATION |
US20210395407A1 (en) | 2018-12-05 | 2021-12-23 | Bridgestone Corporation | Polybutadiene, method of producing polybutadiene, polybutadiene composition, tire, and resin member |
CN110305168B (en) * | 2019-06-27 | 2021-12-21 | 中国科学院青岛生物能源与过程研究所 | Substituted bipyridyl ferrous complex and preparation method and application thereof |
CN110305169B (en) * | 2019-06-27 | 2021-12-21 | 中国科学院青岛生物能源与过程研究所 | Substituted bipyridyl ferric iron complex and preparation method and application thereof |
CN110452272B (en) * | 2019-09-03 | 2022-03-01 | 中国科学院青岛生物能源与过程研究所 | Bipyridine iron complex, preparation method thereof and application thereof in conjugated diene polymerization |
EP3808753B1 (en) * | 2019-09-03 | 2022-08-03 | Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences | Bipyridine iron complex, preparation method thereof and application in polymerization of conjugated diene |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4169092A (en) * | 1968-02-28 | 1979-09-25 | Bayer John W | Transition metal-naphthyridine chemical complexes |
DD101903A1 (en) * | 1971-11-09 | 1973-11-20 | ||
US5061765A (en) * | 1990-10-22 | 1991-10-29 | The Goodyear Tire & Rubber Company | Process for the synthesis of a high vinyl isoprene-butadiene copolymer |
US5151398A (en) * | 1990-10-24 | 1992-09-29 | The Goodyear Tire & Rubber Company | Catalyst for the synthesis of crystalline 3,4-polyisoprene |
US5239023A (en) * | 1990-10-24 | 1993-08-24 | The Goodyear Tire & Rubber Company | Process for the synthesis of crystallizable 3,4-polyisoprene and isoprene-butadiene copolymers having high vinyl contents |
US5082906A (en) * | 1990-10-24 | 1992-01-21 | The Goodyear Tire & Rubber Company | Catalyst for the synthesis of crystalline 3,4-polyisoprene |
JP3334650B2 (en) * | 1998-05-08 | 2002-10-15 | 株式会社豊田中央研究所 | Cyclic conjugated diene polymer and polymerization method thereof |
US6479601B1 (en) * | 1999-08-06 | 2002-11-12 | The Goodyear Tire & Rubber Company | Transition metal catalysts for diene polymerizations |
EP1237964A1 (en) * | 1999-11-19 | 2002-09-11 | E.I. Du Pont De Nemours And Company | Copolymerization of ethylene and dienes |
-
2001
- 2001-06-15 IT IT2001MI001259A patent/ITMI20011259A1/en unknown
-
2002
- 2002-06-12 WO PCT/EP2002/006497 patent/WO2002102861A2/en not_active Application Discontinuation
Also Published As
Publication number | Publication date |
---|---|
WO2002102861A2 (en) | 2002-12-27 |
WO2002102861A3 (en) | 2003-11-20 |
ITMI20011259A0 (en) | 2001-06-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4668773A (en) | Organolanthanide catalysts | |
US4801666A (en) | Olefin and cycloalkene polymerization with organolanthanide catalysts | |
KR20000070111A (en) | Polymerization of Ethylene | |
EP3218385B1 (en) | Metallocenes and their use as polymerization catalysts | |
JP2002537302A (en) | Method for producing trifluoroarylaluminum etherate | |
BR112019008024B1 (en) | PROCESS FOR THE PREPARATION OF SYNDIOTATIC 1,2-POLYBUTADIENE IN THE PRESENCE OF A CATALYTIC SYSTEM COMPRISING A PYRIDYLIRON COMPLEX | |
US20030191015A1 (en) | Catalyst component for olefin polymerization | |
ITMI20011259A1 (en) | PROCEDURE FOR THE (CO) POLYMERIZATION OF CONJUGATE DIENES | |
Jia et al. | Scandium and gadolinium complexes with aryldiimine NCN pincer ligands: synthesis, characterization, and catalysis on isoprene and 1, 5-hexadiene polymerization | |
KR20150037307A (en) | Novel neodymium compound and catalysts for polymerizing diene comprising the same | |
CN111747976A (en) | Metal complex and preparation method and application thereof | |
CN102947319B (en) | Method and tertiary phosphine for phosphine oxides is reduced into corresponding tertiary phosphine in the presence of a catalyst is used for reducing in the presence of a catalyst the purposes of phosphine oxides | |
CN109956979B (en) | Heat-resistant asymmetric alpha-diimine nickel olefin catalyst and preparation method and application thereof | |
Li et al. | Zirconium complexes based on an ethylene linked amidinate–amido ligand: synthesis, characterization and ethylene polymerization | |
CN106795181A (en) | The pyridine complex of zirconium, the catalyst system and catalyzing of the pyridine complex comprising the zirconium and the technique for making conjugated diene (co) polymerization | |
Diether et al. | Rare-earth metal-promoted (double) C–H-bond activation of a lutidinyl-functionalized alkoxy ligand: formation of [ONC] pincer-type ligands and implications for isoprene polymerization | |
EP0900228A1 (en) | A method for producing octahydrofluorenyl metal complexes | |
JP2008297302A (en) | Addition compound of carboxylic acid with halide or halogenocarboxylate of rare earth element or gallium, anhydrous addition compound of halide of rare earth element or galium with ntirogen or oxygen donor, and production method and catalytic use thereof | |
ITMI20011813A1 (en) | COBALT COMPLEX USEFUL IN THE 1,3-BUTADIENE POLYMERIZATION | |
JP6596027B2 (en) | Method for the synthesis of indene | |
RU2342393C2 (en) | METHOD OF OBTAINING 1-ETHYL-1,2,3,3a,4,5,6,7,8,9-DECAHYDROCYCLONONE[b]ALUMINACYCLOPENTANE | |
JP2773362B2 (en) | Quinoxaline-palladium complex and method for producing the same | |
Hazin | From main group to transition metal-containing Brønsted acid initiators for the cationic polymerization of olefin monomers | |
RU2375369C2 (en) | Method of combined production of 3-ethyl-3-aluminapentacyclo-[12.5.1.02,13.04,12.015,19]-eicosa-4,16-diene and 3-ethyl-3-aluminapentacyclo-[12.5.1.02,13.04,12.015,19]-eicosa-4,17-diene | |
CN114933542A (en) | Novel nickel complex and preparation method of olefin polymer |