ITMI20011813A1 - COBALT COMPLEX USEFUL IN THE 1,3-BUTADIENE POLYMERIZATION - Google Patents
COBALT COMPLEX USEFUL IN THE 1,3-BUTADIENE POLYMERIZATION Download PDFInfo
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- ITMI20011813A1 ITMI20011813A1 IT2001MI001813A ITMI20011813A ITMI20011813A1 IT MI20011813 A1 ITMI20011813 A1 IT MI20011813A1 IT 2001MI001813 A IT2001MI001813 A IT 2001MI001813A IT MI20011813 A ITMI20011813 A IT MI20011813A IT MI20011813 A1 ITMI20011813 A1 IT MI20011813A1
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- Prior art keywords
- general formula
- process according
- aluminum
- cobalt
- derivatives
- Prior art date
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims description 41
- 238000006116 polymerization reaction Methods 0.000 title claims description 22
- 150000004700 cobalt complex Chemical class 0.000 title claims description 11
- 238000000034 method Methods 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 26
- 229920002857 polybutadiene Polymers 0.000 claims description 26
- 230000008569 process Effects 0.000 claims description 26
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 23
- 239000005062 Polybutadiene Substances 0.000 claims description 20
- -1 cobalt dichloride (tri-tert-butylphosphine) Chemical compound 0.000 claims description 17
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 230000003197 catalytic effect Effects 0.000 claims description 13
- 239000010941 cobalt Substances 0.000 claims description 13
- 229910017052 cobalt Inorganic materials 0.000 claims description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 12
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 239000003446 ligand Substances 0.000 claims description 8
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- IGNTWNVBGLNYDV-UHFFFAOYSA-N triisopropylphosphine Chemical compound CC(C)P(C(C)C)C(C)C IGNTWNVBGLNYDV-UHFFFAOYSA-N 0.000 claims description 7
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 150000001868 cobalt Chemical class 0.000 claims description 5
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Chemical group 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 238000010952 in-situ formation Methods 0.000 claims description 2
- 150000003017 phosphorus Chemical class 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 29
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 22
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 11
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 229920002223 polystyrene Polymers 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 150000003003 phosphines Chemical class 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000003849 aromatic solvent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-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
- 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
- 230000008901 benefit Effects 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
- 238000004364 calculation method Methods 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000002244 precipitate Substances 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
- 238000012360 testing method Methods 0.000 description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 3
- KCTAHLRCZMOTKM-UHFFFAOYSA-N tripropylphosphane Chemical compound CCCP(CCC)CCC KCTAHLRCZMOTKM-UHFFFAOYSA-N 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical compound CC[AlH]CC HJXBDPDUCXORKZ-UHFFFAOYSA-N 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 238000000569 multi-angle light scattering Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 2
- 239000010981 turquoise Substances 0.000 description 2
- 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
- PRPLGWFQYUPYBN-UHFFFAOYSA-N (4-methylphenyl)-propylalumane Chemical compound C1(=CC=C(C=C1)[AlH]CCC)C PRPLGWFQYUPYBN-UHFFFAOYSA-N 0.000 description 1
- GWUXLTRGPPIDJA-UHFFFAOYSA-N (4-methylphenyl)alumane Chemical compound CC1=CC=C([AlH2])C=C1 GWUXLTRGPPIDJA-UHFFFAOYSA-N 0.000 description 1
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- ZVEWFTICTSQBDM-UHFFFAOYSA-N 4-methylphenol Chemical compound [CH2]C1=CC=C(O)C=C1 ZVEWFTICTSQBDM-UHFFFAOYSA-N 0.000 description 1
- HLWDMZICIJJBOD-UHFFFAOYSA-K C(C)[Al](CC)Cl.C(CCCCCCCCCCCCCCCCC)(=O)[O-].[Co+2].C(CCCCCCCCCCCCCCCCC)(=O)[O-] Chemical compound C(C)[Al](CC)Cl.C(CCCCCCCCCCCCCCCCC)(=O)[O-].[Co+2].C(CCCCCCCCCCCCCCCCC)(=O)[O-] HLWDMZICIJJBOD-UHFFFAOYSA-K 0.000 description 1
- 101150041968 CDC13 gene Proteins 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 102100038916 Caspase-5 Human genes 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical class [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 101100112336 Homo sapiens CASP5 gene Proteins 0.000 description 1
- 101100273286 Mus musculus Casp4 gene Proteins 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 239000001273 butane Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 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
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 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
- VTZJFPSWNQFPCQ-UHFFFAOYSA-N dibutylaluminum Chemical compound CCCC[Al]CCCC VTZJFPSWNQFPCQ-UHFFFAOYSA-N 0.000 description 1
- KEZGKWMENDWULC-UHFFFAOYSA-J dichlorocobalt methylaluminum(2+) dichloride Chemical compound [Cl-].C[Al+2].[Co](Cl)Cl.[Cl-] KEZGKWMENDWULC-UHFFFAOYSA-J 0.000 description 1
- 150000001993 dienes Chemical class 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
- 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
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 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
- 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
- 238000011156 evaluation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 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
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N para-hydroxytoluene Natural products CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 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
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- BZWKPZBXAMTXNQ-UHFFFAOYSA-N sulfurocyanidic acid Chemical compound OS(=O)(=O)C#N BZWKPZBXAMTXNQ-UHFFFAOYSA-N 0.000 description 1
- 239000010414 supernatant solution Substances 0.000 description 1
- ZGNPLWZYVAFUNZ-UHFFFAOYSA-N tert-butylphosphane Chemical compound CC(C)(C)P ZGNPLWZYVAFUNZ-UHFFFAOYSA-N 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
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 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
- OXFUXNFMHFCELM-UHFFFAOYSA-N tripropan-2-yl phosphate Chemical class CC(C)OP(=O)(OC(C)C)OC(C)C OXFUXNFMHFCELM-UHFFFAOYSA-N 0.000 description 1
- CQXYINNETWHZTR-UHFFFAOYSA-N tritert-butyl phosphate Chemical compound CC(C)(C)OP(=O)(OC(C)(C)C)OC(C)(C)C CQXYINNETWHZTR-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F136/06—Butadiene
-
- 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
- C07F15/06—Cobalt compounds
- C07F15/065—Cobalt compounds without a metal-carbon linkage
Description
DESCRIZIONE dell'invenzione industriale DESCRIPTION of the industrial invention
La presente invenzione riguarda complessi di cobalto con particolari fosfine ed il loro uso nella polimerizzazione di 1,3-butadiene a dare polibutadieni ramificati ad alto contenuto di unità 1,4-cis . The present invention relates to cobalt complexes with particular phosphines and their use in the polymerization of 1,3-butadiene to give branched polybutadienes with a high content of 1,4-cis units.
Sono stati sviluppati vari tipi di catalizzatori e processi a base di cobalto per la polimerizzazione di 1,3-butadiene . Alcuni di questi catalizzatori forniscono un polibutadiene che contiene una alta percentuale di unità 1,4-cis e presenta ottime proprietà termiche e meccaniche. Inoltre il polibutadiene fatto con catalisi al cobalto, quando la reazione è condotta in benzene in presenza di regolatori di peso molecolare (ad esempio butene-1), è esente da geli e contiene ramificazioni che lo rendono ideale per la modifica di polistirene. Various types of cobalt-based catalysts and processes have been developed for the polymerization of 1,3-butadiene. Some of these catalysts provide a polybutadiene which contains a high percentage of 1,4-cis units and exhibits excellent thermal and mechanical properties. Furthermore, polybutadiene made with cobalt catalysis, when the reaction is carried out in benzene in the presence of molecular weight regulators (for example butene-1), is free from gels and contains ramifications which make it ideal for polystyrene modification.
Esempi di sistemi catalitici a base di cobalto eserciti in benzene sono descritti in vari documenti: US-A-3,135,725 descrive catalizzatori basati su sali di cobalto e alluminio alchili; US-A-3,046,265 descrive catalizzatori basati su alluminio alchili, cobalto alogenuri e acetil alogenuri; US-A-3,094,514 descrive cobalto cloruro-metilalluminio cloruro; GB-A-916,383 descrive cobalto ottanoato-etilalluminio cloruro; GB-A-916,384 descrive cobalto etilesanoatoetilalluminio cloruro; DE-A-1, 495,935 descrive cobalto ottanoato-dietilalluminio cloruro-acqua; GB-A-941,739 descrive cobalto stearato-dietilalluminio cloruro . Examples of cobalt-based catalytic systems exercised in benzene are described in various documents: US-A-3,135,725 describes catalysts based on cobalt and aluminum alkyl salts; US-A-3,046,265 describes catalysts based on aluminum alkyls, cobalt halides and acetyl halides; US-A-3,094,514 discloses cobalt chloride-methylaluminium chloride; GB-A-916.383 describes cobalt octanoate-ethylaluminium chloride; GB-A-916.384 discloses cobalt ethylhexanoate ethylaluminium chloride; DE-A-1, 495.935 describes cobalt octanoate-diethylaluminium chloride-water; GB-A-941,739 discloses cobalt stearate-diethylaluminium chloride.
Comunque, data la cancerogenicità, il benzene è un solvente non desiderato come dalle restrizioni imposte dalla OSHA (Occupational Safety and Health Agency) sulla concentrazione di benzene ammessa nelle zone di lavoro. E' sentita quindi l'esigenza di trovare sistemi catalitici a base di cobalto capaci di operare con altrettanta efficacia in solventi diversi dal benzene. However, given its carcinogenicity, benzene is an unwanted solvent as per the Occupational Safety and Health Agency (OSHA) restrictions on permissible benzene concentrations in work areas. The need is therefore felt to find catalytic systems based on cobalt capable of operating equally effectively in solvents other than benzene.
Catalizzatori a base di sali di cobalto e leganti fosfinici sono riportati fornire polibutadieni ad alto contenuto di unità 1,2 (ad esempio US-A-5,986,026; US-A-5,548,045; US-A-4,463,146; US-A-4,182,813; US-A-4,176,219; US-A-3,983,183; US-A-3,966,697). Catalysts based on cobalt salts and phosphine binders are reported to provide polybutadienes with a high content of 1,2 units (e.g. US-A-5,986,026; US-A-5,548,045; US-A-4,463,146; US-A-4,182,813; US -A-4,176,219; US-A-3,983,183; US-A-3,966,697).
E' stato ora trovato che particolari leganti trialchil fosfinici, aventi ben definiti valori di parametri sterici Θ, in combinazione con sali di cobalto e organo derivati dell'alluminio, sono in grado di fornire polibutadieni ramificati ad alto contenuto di unità 1,4-cis, non solo in solventi aromatici, ma anche in solventi idrocarburi alifatici. Il parametro Θ è una misura dell'ingombro sferico della fosfina ed è descritto da C.A. Tolman in Chemical Reviews 77, 313 (1977). It has now been found that particular trialkyl phosphine ligands, having well-defined values of steric parameters Θ, in combination with cobalt and organo-derived salts of aluminum, are able to provide branched polybutadienes with a high content of 1,4-cis units. , not only in aromatic solvents, but also in aliphatic hydrocarbon solvents. The parameter Θ is a measure of the spherical size of the phosphine and is described by C.A. Tolman in Chemical Reviews 77, 313 (1977).
In accordo con ciò, la presente invenzione riguarda un procedimento per la preparazione di polibutadiene ramificato ad alto contenuto di unità 1,4-cis mediante polimerizzazione di 1,3-butadiene, effettuato in presenza di uno o più solventi e di un sistema catalitico che comprende un complesso di Cobalto, preformato o formato in situ, di formula generale (I) In accordance with this, the present invention relates to a process for the preparation of branched polybutadiene with a high content of 1,4-cis units by polymerization of 1,3-butadiene, carried out in the presence of one or more solvents and a catalytic system which comprises a Cobalt complex, preformed or formed in situ, of general formula (I)
ove x è uno, due, o tre, preferibilmente 2; n è da 1 a 3; L è scelto tra uno o più leganti del Co; la carica positiva del complesso di cobalto di formula generale (I) essendo neutralizzata da uno o più anioni mono- o polivalenti; where x is one, two, or three, preferably 2; n is from 1 to 3; L is chosen from one or more Co ligands; the positive charge of the cobalt complex of general formula (I) being neutralized by one or more mono- or polyvalent anions;
caratterizzato dal fatto che il legante L è scelto tra i derivati del fosforo di formula generale da) characterized by the fact that the ligand L is chosen from the phosphorus derivatives of general formula da)
ove m è zero oppure uno, preferibilmente m=0; Ri, R2, uguali o diversi tra loro, sono scelti tra radicali alifatici e cicloalchilici monofunzionali, R3 è scelto tra -H e radicali alifatici e cicloalchilici monofunzionali, il composto di formula generale (la) avendo un valore di ingombro sferico teta (Θ) maggiore di 145°, preferibilmente maggiore di 150°. where m is zero or one, preferably m = 0; Ri, R2, the same or different from each other, are selected from aliphatic and monofunctional cycloalkyl radicals, R3 is selected from -H and aliphatic and monofunctional cycloalkyl radicals, the compound of general formula (la) having a spherical overall dimension theta (Θ) greater than 145 °, preferably greater than 150 °.
Nel caso di Co<+>, il rapporto molare tra L e Co è di 3/1; nel caso di Co<2+>, il rapporto molare tra L e Co è di 2/1. In the case of Co <+>, the molar ratio between L and Co is 3/1; in the case of Co <2+>, the molar ratio between L and Co is 2/1.
Con il termine "polibutadiene ad alto contenuto in unità 1,4-cis" si intende polibutadiene in cui almeno 80% delle unità butadieniche è concatenato in posizione 1,4-cis. With the term "polybutadiene with a high content in 1,4-cis units" we mean polybutadiene in which at least 80% of the butadiene units are concatenated in the 1,4-cis position.
Con il termine "polibutadiene ramificato" si intende un polibutadiene avente un valore di g (definito più avanti nella parte sperimentale) < 0.90, preferibilmente < 0.85. The term "branched polybutadiene" means a polybutadiene having a value of g (defined later in the experimental part) <0.90, preferably <0.85.
Nella forma di attuazione preferita nel composto di formula generale (I) il cobalto è bivalente, x=2 e n=2 . In the preferred embodiment in the compound of general formula (I) the cobalt is bivalent, x = 2 and n = 2.
Per quanto concerne gli anioni atti a neutralizzare la carica positiva del composto di formula generale (I), tipici ma non limitativi esempi sono alogenuri, solfocianuro, isocianato, solfato, solfato acido, fosfato, fosfato acido, carbossilati, dicarbossilati . Nella forma di attuazione preferita i suddetti anioni sono i cloruri. Ne consegue che la forma di attuazione preferita di (I) è COC12.2L. As regards the anions suitable for neutralizing the positive charge of the compound of general formula (I), typical but not limiting examples are halides, sulphocyanide, isocyanate, sulphate, acid sulphate, phosphate, acid phosphate, carboxylates, dicarboxylates. In the preferred embodiment, the aforesaid anions are chlorides. It follows that the preferred embodiment of (I) is COC12.2L.
Per quanto concerne il composto di fosforo di formula generale (la), esso deve avere un valore di Θ superiore a 145°, preferibilmente superiore a 150°. As regards the phosphorus compound of general formula (la), it must have a value of Θ higher than 145 °, preferably higher than 150 °.
Nella forma di attuazione preferita, nel composto di formula generale (la) m=0 e quindi il composto di formula generale (la) è una fosfina. In the preferred embodiment, in the compound of general formula (la) m = 0 and therefore the compound of general formula (la) is a phosphine.
Tipici ma non limitativi esempi di composti di formula generale (la) utili nel processo della presente invenzione sono tri-isopropilfosf ina Typical but not limiting examples of compounds of general formula (la) useful in the process of the present invention are tri-isopropylphosphates
Il sistema catalitico della presente invenzione comprende, oltre al complesso di cobalto di formula generale (I), anche uno o più cocatalizzatori selezionati tra organo-derivati dell'alluminio scelti tra: The catalytic system of the present invention comprises, in addition to the cobalt complex of general formula (I), also one or more cocatalysts selected from organo-derivatives of aluminum selected from:
(al) composti di formula generale (II) Al (Ra)(Rb)(Rc), (a2) alluminossani e relativi derivati, (al) compounds of general formula (II) Al (Ra) (Rb) (Rc), (a2) aluminoxanes and related derivatives,
(a3) organoderivati dell'alluminio parzialmente idrolizzati, e relative miscele, (a3) partially hydrolyzed aluminum organo-derivatives, and related mixtures,
(a4) alogeno alluminio alchili scelti tra (III) (a4) halogen aluminum alkyls selected from (III)
dove R è un gruppo alchilico C1-C20, X è cloro o bromo, preferibilmente cloro. where R is a C1-C20 alkyl group, X is chlorine or bromine, preferably chlorine.
Nella forma di attuazione preferita, 1'organoderivato dell'alluminio è scelto tra gli alluminossani e relativi derivati (a2). In the preferred embodiment, the aluminum organ derivative is selected from aluminoxanes and relative derivatives (a2).
Per quanto concerne gli organo-derivati di alluminio (al), nei composti di formula generale (II) Al (Ra)(Rb)(Rc), Ra è scelto tra alchile (cicloalchile compreso) , arile, alchilarile, alcossile, idrogeno, fluoro; Rb e Rc, uguali o diversi tra loro, sono scelti tra alchile (cicloalchile compreso) , arile, alchilarile, arilalchile. Tipici organo-derivati dell'alluminio (al) sono dietilalluminio idruro, din-propil alluminio idruro, di-n-butilalluminio 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 n-propil 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-n-propil 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-n-propil alluminio, il triisobutil alluminio (TIBA), il triesil alluminio, il diisobutil alluminio idruro (DIBA-H) ed il dietil alluminio fluoruro. As regards the organo-derivatives of aluminum (al), in the compounds of general formula (II) Al (Ra) (Rb) (Rc), Ra is selected from alkyl (including cycloalkyl), aryl, alkylaryl, alkoxy, hydrogen, fluorine; Rb and Rc, the same or different from each other, are selected from alkyl (including cycloalkyl), aryl, alkylaryl, arylalkyl. Typical organo-derivatives of aluminum (al) are diethyl aluminum hydride, din-propyl aluminum hydride, di-n-butyl 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 n-propyl 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-n-propyl aluminum, triisobutyl aluminum, tri-n-butyl aluminum, tripentin 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-n-propyl 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 A1-0-A1, con rapporto variabile O/Al, ottenibili 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 polimerici, ciclici e/o lineari, caratterizzati dalla presenza di unità ripetitive aventi la seguente formula : As far as aluminoxanes (a2) are concerned, as is well known, these are compounds containing A1-0-A1 bonds, with variable O / Al ratio, obtainable by reaction, under controlled conditions, of an alkyl aluminum, or alkyl aluminum halide , 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 Ris è un gruppo Ci-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 Ris is a C 1 -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, tbutanolo, 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 organo-derivatives of aluminum (a3), these are compounds (al) with the addition of a quantity of protonant substance in 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, tbutanol, 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), (III) As regards the organo-derivatives of aluminum (a4), (III)
R è un gruppo alchilico Ci-C2o/ X è cloro o bromo, preferibilmente cloro. Tipici esempi di composti di formula generale (III) sono AlEt2Cl (dietilcloroalluminio) , AlMe2Cl (dimetilalluminiocloruro) , AlEtCl2 (etilalluminiodicloruro) , Al(i-Bu)2Cl (diisobutilalluminiocloruro) ; tipici esempi di composti di formula generale (IV) sono Al2Et3Cl3 (etilalluminiosesquicloruro) , Al2Me3Cl3 metilalluminiosesquicloruro ) . R is a C1-C2o / X alkyl group is chlorine or bromine, preferably chlorine. Typical examples of compounds of general formula (III) are AlEt2Cl (diethylchloraluminium), AlMe2Cl (dimethylaluminiumchloride), AlEtCl2 (ethylaluminiumdichloride), Al (i-Bu) 2Cl (diisobutylaluminium chloride); typical examples of compounds of general formula (IV) are Al2Et3Cl3 (ethylaluminosquichloride), Al2Me3Cl3 methylaluminosquichloride).
Nel procedimento della presente invenzione, il rapporto molare tra il complesso di formula generale (I) e l'alluminio è da 1:5 a 1:10000, preferibilmente da 1:100 a 1:1000. In the process of the present invention, the molar ratio between the complex of general formula (I) and aluminum is from 1: 5 to 1: 10000, preferably from 1: 100 to 1: 1000.
Il complesso di cobalto di formula generale (I) è utilizzabile in rapporto molare rispetto al 1,3-butadiene che va da 1/10<5 >a 1/10<2>, preferibilmente da l/2xl0<4 >a 1/10<3>. The cobalt complex of general formula (I) can be used in molar ratio with respect to 1,3-butadiene ranging from 1/10 <5> to 1/10 <2>, preferably from 1 / 2xl0 <4> to 1 / 10 <3>.
Nel caso non si usi il complesso preformato di formula generale (I), bensì si utilizzi la tecnica della formazione in situ del complesso di formula generale (I), è preferibile usare un rapporto molare tra legante (L) e sale di cobalto superiore allo stechiometrico, preferibilmente, nel caso in cui il cobalto sia bivalente, da 2.1/1 a 4/1, ancor più preferibilmente da 2.2 a 2.5. If the preformed complex of general formula (I) is not used, but the technique of in situ formation of the complex of general formula (I) is used, it is preferable to use a molar ratio between ligand (L) and cobalt salt higher than stoichiometric, preferably, in the case in which the cobalt is bivalent, from 2.1 / 1 to 4/1, even more preferably from 2.2 to 2.5.
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, olefine comprese, cicloalifatici, aromatici e relative miscele. Più specificatamente opportuni idrocarburi sono quelli selezionati nel gruppo di idrocarburi alifatici, olefine comprese, da C4 a C8, nel gruppo di idrocarburi cicloalifatici da C5 a CIO, e relative miscele. Tipici esempi non limitativi dei suddetti idrocarburi sono butano, pentano, esano, eptano, ciclopentano, cicloesano, buteni. L'uso dei suddetti solventi alifatici e cicloalifatici è particolarmente raccomandabile in quanto riduce i problemi di impatto ambientale. Operando con questi solventi è possibile ottenere un polibutadiene ramificato, ossia dotato di ramificazioni, ad alto tenore in 1,4-cis. La presenza delle suddette ramificazioni è un requisito essenziale per l'utilizzo del suddetto polibutadiene come modificante del polistirene antiurto. 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 hydrocarbons, including olefins, cycloaliphatic, aromatic hydrocarbons and related mixtures. More specifically, suitable hydrocarbons are those selected from the group of aliphatic hydrocarbons, including olefins, from C4 to C8, from the group of cycloaliphatic hydrocarbons from C5 to CIO, and related mixtures. Typical non-limiting examples of the above hydrocarbons are butane, pentane, hexane, heptane, cyclopentane, cyclohexane, butenes. The use of the aforesaid aliphatic and cycloaliphatic solvents is particularly recommended as it reduces the problems of environmental impact. By operating with these solvents it is possible to obtain a branched polybutadiene, that is, with branches, with a high content of 1,4-cis. The presence of the aforesaid ramifications is an essential requirement for the use of the aforesaid polybutadiene as a modifier of the impact-resistant polystyrene.
Il processo della presente invenzione può essere altresì effettuato in presenza di solventi aromatici, particolarmente toluene, come tali o miscelati con solventi alifatici. Anche in questi solventi aromatici si ottiene polibutadiene ramificato ad alto tenore in 1,4-cis. The process of the present invention can also be carried out in the presence of aromatic solvents, particularly toluene, as such or mixed with aliphatic solvents. Also in these aromatic solvents branched polybutadiene with a high content of 1,4-cis is obtained.
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 di 1,3-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. Più preferibilmente, il processo di polimerizzazione è effettuato ad una temperatura da -10°C a 40°C. The polymerization temperature of 1,3-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. More preferably, the polymerization process is carried out at a temperature from -10 ° C to 40 ° C.
Il procedimento della presente invenzione può essere effettuato (vedi parte sperimentale) anche in assenza degli usuali regolatori di peso molecolare ben noti ai tecnici del ramo, ad esempio butene-1. Ciò costituisce un ulteriore vantaggio non indifferente del processo della presente invenzione. Infatti nel processo della presente invenzione il controllo del peso molecolare può essere effettuato variando il tipo di fosfina e/o il rapporto tra il composto di alluminio, particolarmente il MAO, ed il cobalto . The process of the present invention can be carried out (see experimental part) even in the absence of the usual molecular weight regulators well known to those skilled in the art, for example butene-1. This constitutes a further not insignificant advantage of the process of the present invention. In fact, in the process of the present invention, the control of the molecular weight can be carried out by varying the type of phosphine and / or the ratio between the aluminum compound, particularly the MAO, and the cobalt.
La reazione di polimerizzazione può essere fermata mediante l'aggiunta di uno o più terminatori di polimerizzazione i quali disattivano il sistema catalitico, seguita dalle convenzionali fasi di desolventizzazione, lavaggio ed essiccamento, operazioni usuali 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-diter-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. The polymerization reaction can be stopped by adding one or more polymerization terminators which deactivate the catalytic system, followed by the conventional desolventization, washing and drying steps, which are usual operations in the production of polydienes. 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-diter-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.
Al termine della polimerizzazione, il polibutadiene 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. At the end of the polymerization, the polybutadiene 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.
Oltre ai vantaggi sopradescritti, il processo della presente invenzione consente di ottenere polibutadiene a ridotto tenore in geli, particolarmente macro geli, tale da renderlo applicabile nel polistirene antiurto. In addition to the advantages described above, the process of the present invention allows to obtain polybutadiene with a reduced content in gels, particularly macro gels, such as to make it applicable in impact-resistant polystyrene.
La presente invenzione riguarda altresì, a titolo di composto nuovo, il complesso di cobalto di formula : The present invention also relates, by way of a new compound, to the cobalt complex having the formula:
ossia cobalto dicloruro (tri-ter-butilfosf ina) 2 . Tutti i complessi di formula generale (I) sono stati preparati seguendo le procedura sperimentale riportata in letteratura che prevede la reazione tra sale di cobalto e legante L in presenza di opportuno solvente (vedi ad esempio F.A. Cotton, O.D. Faut, D.M.L. Goodgame e R.H.Holm, J.Am. Chem. Soc., 83, 1780, 1961) . i.e. cobalt dichloride (tri-tert-butylphosphate) 2. All the complexes of general formula (I) were prepared following the experimental procedure reported in the literature which involves the reaction between cobalt salt and L ligand in the presence of a suitable solvent (see for example F.A. Cotton, O.D. Faut, D.M.L. Goodgame and R.H. Holm , J.Am. Chem. Soc., 83, 1780, 1961).
I seguenti esempi sono riportati per una migliore comprensione della presente invenzione. The following examples are given for a better understanding of the present invention.
Negli esempi saranno riportate anche le preparazioni di composti che non fanno parte della presente invenzione, ma saranno utilizzati come esempi comparativi nella valutazione come catalizzatori di polimerizzazione. In the examples, preparations of compounds which are not part of the present invention will also be reported, but will be used as comparative examples in the evaluation as polymerization catalysts.
ESEMPI EXAMPLES
** Sintesi di CoCl2 anidro ** Synthesis of anhydrous CoCl2
La quantità desiderata di CoCl2 <' >6 H20 (~28 g pari a 0.12 moli) viene dapprima riscaldata sotto vuoto mediante un bagno ad acqua, in modo da rimuovere parte delle molecole di acqua di cristallizzazione. The desired quantity of CoCl2 <'> 6 H20 (~ 28 g equal to 0.12 moles) is first heated under vacuum by means of a water bath, so as to remove part of the water molecules of crystallization.
Successivamente si tratta con cloruro di tionile (~ 80 mi), distillato di fresco. Avviene la seguente reazione : It is then treated with freshly distilled thionyl chloride (~ 80 ml). The following reaction occurs:
Si raffredda a 0°C, poiché si ha abbondante sviluppo di gas, ma una volta diminuito tale sviluppo, si pone a ricadere (~78°C) per circa 2 h, fino al completamento della reazione. It is cooled to 0 ° C, since there is abundant gas development, but once this development has decreased, it is left to reflux (~ 78 ° C) for about 2 h, until the reaction is complete.
A questo punto il cloruro di tionile è stato consumato quasi completamente; si lascia decantare e la soluzione supernatante viene rimossa mediante sifonamento . At this point the thionyl chloride was almost completely consumed; it is left to decant and the supernatant solution is removed by siphoning.
Il CoCl2 anidro, di colore blu, viene quindi seccato sotto vuoto per un'intera notte. The blue, anhydrous CoCl2 is then dried under vacuum for a whole night.
** Sintesi del complesso CoCl2(tri-npropilfosfina) 2 (catalizzatore comparativo) ** Synthesis of the CoCl2 complex (tri-npropylphosphine) 2 (comparative catalyst)
Ad una soluzione di CoCl2 (1.20 g, 9.22 -IO-3 moli) in etanolo (50 mi) si aggiunge sotto agitazione la tri-n-propilfosf ina (3.70 g, 2.31 IO-2 moli, 4.6 mi). Tri-n-propylphosphine (3.70 g, 2.31 10-2 moles, 4.6 ml) is added under stirring to a solution of CoCl2 (1.20 g, 9.22 -10-3 moles) in ethanol (50 ml).
La reazione è istantanea, la soluzione assume colorazione blu. Dopo circa 20 ore si porta a secchezza sotto vuoto a temperatura ambiente. The reaction is instantaneous, the solution takes on a blue color. After about 20 hours it is brought to dryness under vacuum at room temperature.
Si ottiene un prodotto cristallino di colore blu che viene lavato a freddo con pentano (2x20ml). A blue crystalline product is obtained which is cold washed with pentane (2x20ml).
Il residuo cristallino viene seccato sotto vuoto . The crystalline residue is dried under vacuum.
Complessivamente si ottengono 2.79 g di prodotto cristallino, di colore azzurro/blu, con una resa pari al 67.1%. Overall, 2.79 g of crystalline product are obtained, having a light blue / blue color, with a yield of 67.1%.
I risultati dell'analisi elementare sono in accordo con l The results of the elementary analysis are in agreement with l
** Sintesi del complesso CoCl2(trifenilfosfina)2 (catalizzatore comparativo) ** Synthesis of the CoCl2 complex (triphenylphosphine) 2 (comparative catalyst)
Una soluzione di CoCl2 (0.25 g, 1.90 IO-3 moli) in etanolo (25 mi) è stata aggiunta ad una sospensione di trifenilfosfina (1.01 g, 3.85 IO-3 moli) in etanolo (25 mi), mantenuta sotto agitazione. La reazione è istantanea, si osserva la formazione di un precipitato di colore azzurro la cui quantità aumenta con il passare delle ore. La sospensione viene lasciata sotto agitazione magnetica per circa 20 h. A solution of CoCl2 (0.25 g, 1.90 10-3 moles) in ethanol (25 ml) was added to a suspension of triphenylphosphine (1.01 g, 3.85 10-3 moles) in ethanol (25 ml), kept under stirring. The reaction is instantaneous, the formation of a blue precipitate is observed, the quantity of which increases with the passing of the hours. The suspension is left under magnetic stirring for about 20 h.
Si filtra quindi la sospensione; il solido rimasto sul filtro viene lavato con piccole quantità di etanolo e quindi asciugato sotto vuoto. Si recuperano ca. 0.71 g di prodotto azzurro pari ad una resa del 56.9 %. The suspension is then filtered; the solid remaining on the filter is washed with small quantities of ethanol and then dried under vacuum. Approx. 0.71 g of blue product equal to a yield of 56.9%.
I risultati dell'analisi elementare sono in accordo con la seguente struttura: The results of the elementary analysis are in agreement with the following structure:
** Sintesi del complesso CoCl2 (tri-isopropilfosfina)2 ** Synthesis of the CoCl2 complex (tri-isopropylphosphine) 2
Ad una soluzione di CoCl2 (0.31 g, 2.39 -IO-3 moli) in etanolo (~30 mi) si aggiunge mediante gocciolamento sotto agitazione una soluzione di triisopropilfosf ina (0.96 g, 5.98- IO-3 moli) in etanolo (~20 mi). To a solution of CoCl2 (0.31 g, 2.39 -IO-3 moles) in ethanol (~ 30 ml) a solution of triisopropylphosphine (0.96 g, 5.98- 10-3 moles) in ethanol (~ 20 me).
Si forma una leggera sospensione che viene mantenuta sotto agitazione per circa 20 h. Successivamente si porta a secchezza sotto vuoto ottenendo un residuo pecioso di colorazione blu intensa . A light suspension is formed which is kept under stirring for about 20 h. It is then brought to dryness under vacuum to obtain a pitchy residue of an intense blue color.
Si effettuano diversi lavaggi con pentano (3x20 mi) e con etanolo a freddo, in modo da rimuovere tracce di fosfina in eccesso e CoCl2 non reagito. Il residuo viene seccato sotto vuoto a temperatura ambiente per una intera notte. Several washes are carried out with pentane (3x20 ml) and with cold ethanol, in order to remove traces of excess phosphine and unreacted CoCl2. The residue is dried under vacuum at room temperature for a whole night.
Si recuperano 0.55 g di una polvere microcristallina di colore azzurro/blu, con una resa pari al 50.6%. 0.55 g of a blue / blue microcrystalline powder are recovered, with a yield equal to 50.6%.
I risultati dell'analisi elementare sono in accordo con la seguente struttura: The results of the elementary analysis are in agreement with the following structure:
** Sintesi del complesso CoCl2(tri-ter-butilfosfina)2 Ad una soluzione di CoCl2 (0.30 g, 2.26 -IO-3 moli ) in etanolo (Π30 mi) si aggiunge, mediante gocciolamento, sotto agitazione una soluzione di triter-butilfosfina, (1.14 g, 5.64- IO-3 moli) in etanolo (□20 mi). ** Synthesis of the CoCl2 complex (tri-tert-butylphosphine) 2 To a solution of CoCl2 (0.30 g, 2.26 -IO-3 moles) in ethanol (Π30 ml) a solution of triter-butylphosphine is added by dripping and stirring , (1.14 g, 5.64-10-3 moles) in ethanol (□ 20 ml).
Si ha la formazione di un precipitato azzurro/blu. A blue / blue precipitate is formed.
Si lascia la sospensione sotto agitazione magnetica per circa 20 h, successivamente si filtra su filtro da vuoto. The suspension is left under magnetic stirring for about 20 h, then it is filtered on a vacuum filter.
Il residuo viene seccato sotto vuoto, lavato con pentano (2x15 mi) e con etanolo (2x10 mi) a freddo (circa -50°C) , in modo da rimuovere tracce di fosfina in eccesso e CoCl2 non reagito. The residue is dried under vacuum, washed with pentane (2x15 ml) and cold ethanol (2x10 ml) (about -50 ° C), in order to remove traces of excess phosphine and unreacted CoCl2.
Il residuo viene seccato sotto vuoto a temperatura ambiente per una intera notte: si sono recuperati 0.75 g di prodotto azzurro/blu, con una resa del 62.1%. The residue is dried under vacuum at room temperature for a whole night: 0.75 g of blue / blue product were recovered, with a yield of 62.1%.
I risultati dell'analisi elementare sono in accordo con la seguente struttura: The results of the elementary analysis are in agreement with the following structure:
I.R.: v (CH3 t-butiie) — 2972, 2906, 2875, cm ; δ aa.(cH3j =1476, 1483, cm-1; δ B.ICH3) =1380 cm-1 I.R .: v (CH3 t-butiie) - 2972, 2906, 2875, cm; δ aa. (cH3j = 1476, 1483, cm-1; δ B.ICH3) = 1380 cm-1
** Sintesi del complesso CoCl2(tricicloesilfosfina)2 Ad una soluzione di CoCl2 (1.16 g, 8.90 -IO-3 moli) in etanolo (D55 mi), è stata aggiunta sotto agitazione la tricicloesilfosfina (6.24 g, 2.22- IO-2 moli). ** Synthesis of the CoCl2 complex (tricyclohexylphosphine) 2 To a solution of CoCl2 (1.16 g, 8.90 -IO-3 moles) in ethanol (D55 ml), tricyclohexylphosphine (6.24 g, 2.22- IO-2 moles) was added under stirring ).
Non si nota alcun cambiamento immediato, ma dopo alcuni minuti la soluzione assume una colorazione turchese con formazione di un precipitato dello stesso colore. There is no immediate change, but after a few minutes the solution takes on a turquoise color with the formation of a precipitate of the same color.
Si lascia la soluzione sotto agitazione per circa 20 h dopo di che si recupera un residuo che viene lavato più volte con pentano e successivamente con etanolo a freddo per rimuovere eventuali tracce di CoCl2 non reagito. The solution is left under stirring for about 20 h after which a residue is recovered which is washed several times with pentane and subsequently with cold ethanol to remove any traces of unreacted CoCl2.
Si recuperano 5.51 g di una polvere microcristallina di colore azzurro/turchese, con una resa pari al 89.6 %. 5.51 g of a blue / turquoise microcrystalline powder are recovered, with a yield equal to 89.6%.
I risultati dell'analisi elementare sono in accordo con la seguente struttura: The results of the elementary analysis are in agreement with the following structure:
** Sintesi "in situ" del complesso CoCl2(triisopropilfosfina)2 ** "In situ" synthesis of the CoCl2 complex (triisopropylphosphine) 2
In un provettone da 50 mi si introducono 26 mg (0.2 mmoli) di CoCl2 e 10 mi di toluene. Alla sospensione risultante vengono aggiunti 72 mg (0.45 mmoli) di triisopropilfosfina. Si mantiene in agitazione per circa 12 ore. Si prelevano quindi 0.5 mi di soluzione che vengono introdotti nel reattore di polimerizzazione contenente 10 mi di butadiene in eptano e MAO. La successiva procedura risulta identica al caso dell'uso di catalizzatore preformato. In a 50 ml test tube 26 mg (0.2 mmoles) of CoCl2 and 10 ml of toluene are introduced. 72 mg (0.45 mmol) of triisopropylphosphine are added to the resulting suspension. It is kept under stirring for about 12 hours. 0.5 ml of solution are then taken and introduced into the polymerization reactor containing 10 ml of butadiene in heptane and MAO. The subsequent procedure is identical to the case of the use of a preformed catalyst.
MODALITÀ' OPERATIVE E REAGENTI OPERATING MODES AND REAGENTS
Tutte le operazioni e le preparazioni riportate sono state condotte usando un sistema vuoto-azoto. All reported operations and preparations were carried out using a vacuum-nitrogen system.
L'azoto, allo scopo di eliminare eventuali tracce di umidità e di ossigeno, è stato purificato per passaggio attraverso tre colonne successive: la prima riempita con cloruro di calcio e idrossido di potassio, la seconda con catalizzatore BTS (a base di ossidi di rame) , la terza riempita con setacci molecolari . The nitrogen, in order to eliminate any traces of humidity and oxygen, was purified by passing through three successive columns: the first filled with calcium chloride and potassium hydroxide, the second with BTS catalyst (based on copper oxides ), the third filled with molecular sieves.
REAGENTI REAGENTS
Cobaitodicloruro esaidrato: prodotto Strem Chemicals (purezza 98%). Cobaitodichloride hexahydrate: Strem Chemicals product (purity 98%).
Tri-n-propilfosfina : prodotto Strem Chemicals (purezza minima 95%). Tri-n-propylphosphine: Strem Chemicals product (minimum purity 95%).
Tri-i-propilfosfina : prodotto Strem Chemicals (purezza minima 98%). Tri-i-propylphosphine: Strem Chemicals product (minimum purity 98%).
Tri-t-butilfosfina : prodotto Strem Chemicals (purezza minima 99%). Tri-t-butylphosphine: Strem Chemicals product (minimum purity 99%).
Tricicloesilfosfina : prodotto Strem Chemicals (purezza 97%). Tricyclohexylphosphine: Strem Chemicals product (97% purity).
Trifenilfosfina : prodotto Strem Chemicals (purezza 99%). Triphenylphosphine: Strem Chemicals product (purity 99%).
Metilalluminossano (MAAO): prodotto Witco, soluzione toluenica al 10% in peso, utilizzato tal quale . Methylaluminoxane (MAAO): Witco product, toluene solution at 10% by weight, used as it is.
Monomeri diolefinici Diolefin monomers
1,3-butadiene: prodotto Air Liquide (purezza superiore al 99.5%), purificato mediante passaggio attraverso una colonna di acciaio contenente idrossido di sodio e setacci molecolari. 1,3-butadiene: Air Liquide product (purity higher than 99.5%), purified by passing through a steel column containing sodium hydroxide and molecular sieves.
Polimerizzazione del butadiene Polymerization of butadiene
L'1,3-Butadiene, seccato facendolo passare attraverso una colonna di acciaio contenente setacci molecolari, è stato condensato direttamente nel reattore mantenuto sotto vuoto e raffreddato alla temperatura di -30°C. The 1,3-Butadiene, dried by passing it through a steel column containing molecular sieves, was condensed directly in the reactor kept under vacuum and cooled to a temperature of -30 ° C.
Le prove di polimerizzazione sono state condotte secondo la seguente procedura sperimentale: dopo aver introdotto il butadiene nel reattore è stato aggiunto il solvente, si è portato il tutto alla temperatura di polimerizzazione desiderata ed infine si sono aggiunti in successione il composto di alluminio ed il composto di cobalto. The polymerization tests were carried out according to the following experimental procedure: after having introduced the butadiene into the reactor, the solvent was added, everything was brought to the desired polymerization temperature and finally the aluminum compound and the compound were added in succession. cobalt.
La reazione di polimerizzazione è stata terminata versando il contenuto del provettino in un beaker contenente metanolo acidulato con piccole quantità di acido cloridrico; il polimero coagulato è stato lavato più volte con metanolo, seccato sotto vuoto a temperatura ambiente e recuperato. The polymerization reaction was terminated by pouring the contents of the test piece into a beaker containing methanol acidulated with small quantities of hydrochloric acid; the coagulated polymer was washed several times with methanol, dried under vacuum at room temperature and recovered.
Procedure analitiche Analytical procedures
ANALISI NMR NMR ANALYSIS
Gli spettri 1H e 13C NMR sono stati registrati con uno spettrofotometro Bruker AM 270 MHz. Gli spettri sono stati ottenuti in CDC13 a temperatura ambiente utilizzando tetrametilsilano come standard interno oppure in C2D2C14 ad alta temperatura (103°C; HMDS come standard interno). La concentrazione delle soluzioni polimeriche è del 10 % circa in peso. The 1H and 13C NMR spectra were recorded with a Bruker AM 270 MHz spectrophotometer. The spectra were obtained in CDC13 at room temperature using tetramethylsilane as internal standard or in C2D2C14 at high temperature (103 ° C; HMDS as internal standard). The concentration of the polymeric solutions is about 10% by weight.
La microstruttura dei polibutadieni ottenuti è stata determinata sulla base di quanto già noto in letteratura (vedi ad esempio V.D. Mochel, J.Polym. Sci, A-l 10, 1009, 1972; K.F. Elgert, G. Quack, B. Stutzel, Makromol. Chem. 175, 1955, 1974; D.Morero, A.Santambrogio, L.Porri, F. Ciampelli, Chim. Ind. (Milan) 41, 758, 1958). The microstructure of the obtained polybutadienes was determined on the basis of what is already known in the literature (see for example V.D. Mochel, J.Polym. Sci, A-l 10, 1009, 1972; K.F. Elgert, G. Quack, B. Stutzel, Makromol. Chem . 175, 1955, 1974; D. Morero, A. Santambrogio, L. Porri, F. Ciampelli, Chim. Ind. (Milan) 41, 758, 1958).
ANALISI G.P.C. G.P.C. ANALYSIS
Condizioni operative: Operating conditions:
° Pompa Agilent 1100 ° Agilent 1100 pump
° Detector I.R. Agilent 1100 ° Detector I.R. Agilent 1100
° Colonne PL Mixed-A ° Mixed-A PL columns
° Solvente / Eluente THF ° Solvent / Eluent THF
° Flusso 1 ml/min ° Flow 1 ml / min
° Temperatura 25°C ° Temperature 25 ° C
° Calcolo masse molecolari : metodo Universal Calibration ° Calculation of molecular masses: Universal Calibration method
Analisi G.P.C. / MALLS/ I.R G.P.C. Analysis / MALLS / I.R
Condizioni operative: Operating conditions:
° Pompa Agilent 1050 ° Agilent 1050 pump
Detector I.R. Agilent 1050 Detector I.R. Agilent 1050
Detector MALLS Dawn-DSP Wyatt - Technology, □ = 632,8 nm Detector MALLS Dawn-DSP Wyatt - Technology, □ = 632.8 nm
° Colonne PL 105-105-104-103 ° Columns PL 105-105-104-103
° Solvente / Eluente THF ° Solvent / Eluent THF
° Flusso 1 ml/min ° Flow 1 ml / min
° Temperatura 25°C ° Temperature 25 ° C
° Calcolo indice di branching g medio: rapporto tra raggio di girazione della macromolecola ramificata e quello della macromolecola lineare, a parità di peso molecolare; il rapporto viene eseguito per ogni punto del cromatogramma integrato, dopodiché viene eseguita la media su tutti i punti. Un polibutadiene si intende ramificato quando g < 0.90. MISURE DELLA VISCOSITÀ' IN STIRENE ° Calculation of the mean branching index g: ratio between the radius of gyration of the branched macromolecule and that of the linear macromolecule, with the same molecular weight; the report is performed for each point in the integrated chromatogram, after which all points are averaged. A polybutadiene is understood to be branched when g <0.90. VISCOSITY MEASUREMENTS IN STYRENE
° Solvente : Stirene ° Solvent: Styrene
° Concentrazione : 5% w/w ° Concentration: 5% w / w
° Capillare : Cannon - Fenske serie 200 ° Capillary: Cannon - Fenske 200 series
° Calcolo della viscosità □ = kt ° Calculation of viscosity □ = kt
ove k = costante del capillare; d = densità stirene; t = tempo di caduta entro il capillare. Valori di viscosità minori di 100 cP sono accettabili per la modifica del polistirene. where k = constant of the capillary; d = styrene density; t = time of fall into the capillary. Viscosity values less than 100 cP are acceptable for polystyrene modification.
DETERMINAZIONE DEL CONTENUTO DEI GELI DETERMINATION OF THE CONTENT OF THE GELI
Solvente: THF Solvent: THF
° Concentrazione: 0.3% w/w; ° Concentration: 0.3% w / w;
° Insolubile macro: reticella da 325 mesh; ° Insoluble macro: 325 mesh mesh;
° Insolubile micro: filtro in teflon da 0.2 Dm; ° Insoluble micro: 0.2 Dm Teflon filter;
Il % insolubile viene determinato per via gravimetrica, pesando il residuo su ciascun filtro ed esprimendolo in percentuale rispetto al peso iniziale. The insoluble% is determined gravimetrically, by weighing the residue on each filter and expressing it as a percentage of the initial weight.
Condizioni di polimerizzazione : butadiene, 10 mi; solvente: 90 mi; Co = lxlO<'5 >moli; temperatura: 15°C COMMENTO ALLA TABELLA 1 Polymerization conditions: butadiene, 10ml; solvent: 90 ml; Co = lx10 <'5> moles; temperature: 15 ° C COMMENT TO TABLE 1
Il sistema CoCl2 MAO sia in toluene che in eptano fornisce un polimero cis (circa 95-98%) lineare (g circa 1), come evidenziato dagli esempi b228 e b 335); la polimerizzazione effettuata in esano essendo più lenta. The CoCl2 MAO system both in toluene and in heptane provides a linear cis polymer (about 95-98%) (about 1 g), as evidenced by examples b228 and b 335); the polymerization carried out in hexane being slower.
L'utilizzo di un sistema catalitico a base di complessi di cobalto con fosfine (sia complessi della prior art che della presente invenzione) influenza l'attività catalitica e la microstruttura del polimero. Infatti usando fosfine ariliche della prior art si ottiene un polibutadiene a struttura mista 1,4-cis e 1,2- (vedi esempi comparativi b323 e b324). Usando invece fosfine alchiliche si è sorprendentemente trovato che si ottengono polibutadieni la cui microstruttura varia in funzione dell'ingombro sferico delle fosfine stesse. The use of a catalytic system based on complexes of cobalt with phosphines (both complexes of the prior art and of the present invention) influences the catalytic activity and the microstructure of the polymer. In fact, using aryl phosphines of the prior art, a polybutadiene with a mixed 1,4-cis and 1,2- structure is obtained (see comparative examples b323 and b324). By using instead alkyl phosphines it has surprisingly been found that polybutadienes are obtained whose microstructure varies according to the spherical size of the phosphines themselves.
Quando la fosfina è poco ingombrata (ad esempio nel caso di tri n-propilfosfina con 0=132° come negli esempi b327 e b328), si ottengono ancora polibutadieni a struttura mista con prevalenza di unità 1,2. When the phosphine is not cluttered (for example in the case of tri n-propylphosphine with 0 = 132 ° as in the examples b327 and b328), polybutadienes with a mixed structure with a prevalence of 1,2 units are still obtained.
Quando invece la fosfina è più ingombrata (Θ > 145°, come nel caso della tri isopropilfosfina (0=160°), della tri tert-butilfosfina (0=182°), e della tri cicloesilfosf ina (θ=170°), la struttura del PB che si ottiene è essenzialmente 1,4-cis (> 80%), vedi tabella 1. When instead the phosphine is more encumbered (Θ> 145 °, as in the case of the tri isopropylphosphine (0 = 160 °), of the tri tert-butylphosphine (0 = 182 °), and of the tri cyclohexylphosphine (θ = 170 °), the PB structure obtained is essentially 1,4-cis (> 80%), see table 1.
Inoltre l'uso delle fosfine ingombrate della presente invenzione presenta i seguenti vantaggi: Furthermore, the use of the bulky phosphines of the present invention has the following advantages:
** elevate attività catalitiche anche in solventi idrocarburici alifatici, sinora non utilizzati a motivo della loro scarsa attività (vedi esempi b330, b292, b332 in confronto con b335); ** high catalytic activities also in aliphatic hydrocarbon solvents, not used up to now due to their low activity (see examples b330, b292, b332 in comparison with b335);
** ottenimento di polibutadiene ramificato (0.70<g<0.90) sia in solvente alifatico che aromatico (vedi b283 e b330; b292 e b290; b332 e b284). E' da rilevare che la ramificazione del polibutadiene è un requisito fondamentale per l'utilizzo del polibutadiene stesso come modificante del polistirene antiurto; ** obtaining branched polybutadiene (0.70 <g <0.90) in both aliphatic and aromatic solvent (see b283 and b330; b292 and b290; b332 and b284). It should be noted that the branching of the polybutadiene is a fundamental requirement for the use of the polybutadiene itself as a modifier of the shockproof polystyrene;
** controllo del peso molecolare del PB anche senza l'utilizzo di butene-1. Il peso molecolare può infatti essere regolato variando il tipo di legante fosfinico, il rapporto Al/Co, ed il tipo di solvente; ** control of the molecular weight of the PB even without the use of butene-1. The molecular weight can in fact be adjusted by varying the type of phosphine binder, the Al / Co ratio, and the type of solvent;
** ottenimento di polibutadiene a basso tenore in geli ( ** obtaining of polybutadiene with a low content in gels (
** possibilità di regolare a piacere, all'interno dell'intervallo 80-96%, il tenore in 1,4-cis variando il tipo di fosfina utilizzata; infatti il contenuto in unità 1,4-cis è maggiore per le fosfine più ingombrate (vedi ter-butil fosfina rispetto alle altre due meno ingombrate); ** possibility of adjusting the 1,4-cis content at will, within the 80-96% range, by varying the type of phosphine used; in fact the content in 1,4-cis units is higher for the more bulky phosphines (see tert-butyl phosphine compared to the other two less bulky ones);
** il polibutadiene che si ottiene presenta un valore di viscosità in stirene <100 cP, il che lo rende utilizzabile per produrre polistirene antiurto (HIPS) . ** the polybutadiene obtained has a viscosity value in styrene <100 cP, which makes it usable to produce shockproof polystyrene (HIPS).
Claims (18)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT2001MI001813A ITMI20011813A1 (en) | 2001-08-24 | 2001-08-24 | COBALT COMPLEX USEFUL IN THE 1,3-BUTADIENE POLYMERIZATION |
| PCT/EP2002/008450 WO2003018649A1 (en) | 2001-08-24 | 2002-07-25 | Cobalt complexes useful in the polymerization of 1,3-butadiene |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT2001MI001813A ITMI20011813A1 (en) | 2001-08-24 | 2001-08-24 | COBALT COMPLEX USEFUL IN THE 1,3-BUTADIENE POLYMERIZATION |
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| ITMI20011813A0 ITMI20011813A0 (en) | 2001-08-24 |
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| ITMI20040076A1 (en) | 2004-01-22 | 2004-04-22 | Polimeri Europa Spa | PROCEDURE FOR THE PREPARATION OF LOW DEGREE POLYBUTADIENE |
| CN1293108C (en) * | 2004-04-12 | 2007-01-03 | 上海应用技术学院 | Method for one-step synthesizing supper branched polymer of containing structure of benzene methylene |
| CN103450374B (en) * | 2013-07-30 | 2015-12-23 | 浙江大学 | Two-component cobalt catalyst and the application in 1,3-butadiene solution polymerization or suspension polymerization thereof |
| ITMI20131830A1 (en) | 2013-11-05 | 2015-05-06 | Versalis Spa | STEREOREGULAR DI-BLOCK POLYBUTADIENS WITH STRUCTURE 1,4-CIS / 1,2 SINDIOTATTICA BY STEREOSPECIFIC POLYMERIZATION |
| ITMI20131828A1 (en) | 2013-11-05 | 2015-05-06 | Versalis Spa | STEREOREGULAR DI-BLOCK POLYBUTADIENS WITH STRUCTURE 1,4-CIS / 1,2 SINDIOTATTICA BY STEREOSPECIFIC POLYMERIZATION |
| IT201700085384A1 (en) * | 2017-07-26 | 2019-01-26 | Versalis Spa | PROCEDURE FOR THE PREPARATION OF POLIBUTADIENE 1.2 SINDIOTATTICO IN THE PRESENCE OF A CATALYTIC SYSTEM INCLUDING A COBALT COMPLEX WITH A PHOSPHINIC BINDER |
| IT202000028823A1 (en) | 2020-11-27 | 2022-05-27 | Consiglio Nazionale Ricerche | STEREOBLOCK DIENE COPOLYMERS AND RELATED PREPARATION PROCESS. |
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| US5879805A (en) * | 1997-09-09 | 1999-03-09 | Union Carbide Chemicals & Plastics Technology Corporation | Gas phase polymerization of vinylpolybutadiene |
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| WO2003018649A1 (en) | 2003-03-06 |
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