US3104249A - Organo-titanium compounds and a process of preparing them - Google Patents
Organo-titanium compounds and a process of preparing them Download PDFInfo
- Publication number
- US3104249A US3104249A US652381A US65238157A US3104249A US 3104249 A US3104249 A US 3104249A US 652381 A US652381 A US 652381A US 65238157 A US65238157 A US 65238157A US 3104249 A US3104249 A US 3104249A
- Authority
- US
- United States
- Prior art keywords
- titanium
- cyclopentadienyl
- compounds
- bis
- radical
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title description 8
- 230000008569 process Effects 0.000 title description 5
- 239000010936 titanium Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 14
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- QWHJQOJNNKDPBE-UHFFFAOYSA-N C1=CC=CC1[Ti](C)(C)C1C=CC=C1 Chemical compound C1=CC=CC1[Ti](C)(C)C1C=CC=C1 QWHJQOJNNKDPBE-UHFFFAOYSA-N 0.000 claims description 4
- -1 organo titanium compounds Chemical class 0.000 description 39
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 35
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 27
- 238000000354 decomposition reaction Methods 0.000 description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 239000000725 suspension Substances 0.000 description 10
- HPYIUKIBUJFXII-UHFFFAOYSA-N Cyclopentadienyl radical Chemical group [CH]1C=CC=C1 HPYIUKIBUJFXII-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- YMNCCEXICREQQV-UHFFFAOYSA-L cyclopenta-1,3-diene;titanium(4+);dichloride Chemical compound [Cl-].[Cl-].[Ti+4].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 YMNCCEXICREQQV-UHFFFAOYSA-L 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 150000003609 titanium compounds Chemical class 0.000 description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- JSEIGCXRVAGROG-UHFFFAOYSA-M C[Ti](Cl)(C1C=CC=C1)C1C=CC=C1 Chemical compound C[Ti](Cl)(C1C=CC=C1)C1C=CC=C1 JSEIGCXRVAGROG-UHFFFAOYSA-M 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 230000007717 exclusion Effects 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KWHYMFNLYQLACB-UHFFFAOYSA-M CC[Ti](Cl)(C1C=CC=C1)C1C=CC=C1 Chemical compound CC[Ti](Cl)(C1C=CC=C1)C1C=CC=C1 KWHYMFNLYQLACB-UHFFFAOYSA-M 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 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
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- NPOMAIJXMCXWGP-UHFFFAOYSA-N (cyanatodisulfanyl) cyanate Chemical compound N#COSSOC#N NPOMAIJXMCXWGP-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- KTOQRRDVVIDEAA-UHFFFAOYSA-N 2-methylpropane Chemical compound [CH2]C(C)C KTOQRRDVVIDEAA-UHFFFAOYSA-N 0.000 description 1
- QMYGFTJCQFEDST-UHFFFAOYSA-N 3-methoxybutyl acetate Chemical group COC(C)CCOC(C)=O QMYGFTJCQFEDST-UHFFFAOYSA-N 0.000 description 1
- 241001156002 Anthonomus pomorum Species 0.000 description 1
- RBQBNAVSUBXCGR-UHFFFAOYSA-M C1(C=CC=C1)[Ti](Cl)(CCC)C1C=CC=C1 Chemical compound C1(C=CC=C1)[Ti](Cl)(CCC)C1C=CC=C1 RBQBNAVSUBXCGR-UHFFFAOYSA-M 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 238000003747 Grignard reaction Methods 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- MFRXMZYAKSRDMT-UHFFFAOYSA-L [Br-].[Br-].C1(C=CC=C1)[Ti+2]C1C=CC=C1 Chemical compound [Br-].[Br-].C1(C=CC=C1)[Ti+2]C1C=CC=C1 MFRXMZYAKSRDMT-UHFFFAOYSA-L 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 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
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- SRKKQWSERFMTOX-UHFFFAOYSA-N cyclopentane;titanium Chemical class [Ti].[CH]1C=CC=C1 SRKKQWSERFMTOX-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- AXAZMDOAUQTMOW-UHFFFAOYSA-N dimethylzinc Chemical compound C[Zn]C AXAZMDOAUQTMOW-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- GDNCXORZAMVMIW-UHFFFAOYSA-N dodecane Chemical compound [CH2]CCCCCCCCCCC GDNCXORZAMVMIW-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical group II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- QBZXOWQOWPHHRA-UHFFFAOYSA-N lithium;ethane Chemical compound [Li+].[CH2-]C QBZXOWQOWPHHRA-UHFFFAOYSA-N 0.000 description 1
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 description 1
- VXWPONVCMVLXBW-UHFFFAOYSA-M magnesium;carbanide;iodide Chemical compound [CH3-].[Mg+2].[I-] VXWPONVCMVLXBW-UHFFFAOYSA-M 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002577 pseudohalo group Chemical group 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- OHUVHDUNQKJDKW-UHFFFAOYSA-N sodium;cyclopenta-1,3-diene Chemical compound [Na+].C=1C=C[CH-]C=1 OHUVHDUNQKJDKW-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M thiocyanate group Chemical group [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 125000005425 toluyl group Chemical group 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229940086542 triethylamine Drugs 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
- C07F17/00—Metallocenes
-
- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/28—Titanium compounds
Definitions
- the present invention relates to organo titanium compounds and a process of preparing them.
- organo-titanium compounds in which one or more alkyl groups are linked to the metal atom. It has, for example, been tried to prepare alkyl metal compounds of titanium ⁇ by causing the ethereal solutions of magnesium alkyl halides or lithium alkyls to act upon titaniumetetrachloride. Such reactions did, however, not lead to the expected organo-titanium compounds. Instead, the transition of the tetravalent titanium to a lower valence was observed.
- a titanium alkyl halide for example RTlClg
- R represents the cyclopentadienyl radical or a cyclopentadienyl radical substituted by one or more hydrocarbon radicals
- X represents alkoxyl groups, halogen groups or another acid radical, to react, suitably in the presence of an inert diluent, with alkyl metal compounds of the elements 1 of group I or II or subgroup H of the periodic table or of aluminum.
- titanium compounds which can be converted with special advantage to organo-metal alkyl compounds according to the invention, there are mentioned the bis-cyclopentadienyl-titanium dihalides.
- halogen is here meant to include also the pseudohalogens.
- X represents chlorine, bromine or iodine, the cyano group or thio-cyanate group, since the corresponding products are easier to obtain.
- dichloride since it is easily accessible and can be prepared in a simple manner from cyclopentadienyl sodium and titanium tetrachloride.
- the bis-cyclopentadienyl-titanium-dialkoxy compounds are advantageously used.
- alkoxy radicals are chiefly concerned those containing 1 to 4 carbon atoms such as methoxyl, ethoxyl, propoxyl, butoxyl or iso-butoxyl. 'If desired, the alkoxy groups may contain higher alkyl radicals, for example the ethylhexyl radical or the dodecyl radical.
- the cyclopentadienyl radical may be substituted by one or more identical or different hydrocarbon radicals, preferably by aliphatic hydrocarbon radicals containing 1 to 4 carbon atoms.
- hydrocarbon radicals preferably by aliphatic hydrocarbon radicals containing 1 to 4 carbon atoms.
- alkyl metal compounds of group I or II or sub-group II of the periodic table or of .aluminum for reacting the above mentioned titanium compounds there are used according to the invention alkyl metal compounds of group I or II or sub-group II of the periodic table or of .aluminum.
- magnesium alkyl halides known as Grignards compounds and lithium alkyl compounds
- the alkyl radical advantageously is a radical containing 1 to 4 carbon atoms, for example a methyl, ethyl, propyl, isopropyl, butyl or isobutyl radical.
- di-luents can be used all substances which are inert with respect to .ongano-metal compounds and liquid under reaction conditions such as ether, [for example dimethyl ether, diethyl ether, :dipropyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, dioxan, saturated aliphatic or cycloaliphatic hydrocarbons such as butane, pentane, hexane, heptane, octane, cyclohexane, cyclopentane, the alkyl derivatives thereof such as methylcyclohexane, methylcyclopentane or beuzine fractions containing the aforesaid or higher aliphatic hydrocarbons and which have been obtained :for example from petroleum or by the tFlSChfif-TI'OPSGh synthesis.
- ether for example dimethyl ether, diethyl ether, :
- aromatic hydrocarbons such as benzene, toluene or xylene
- tertiary amines such as trie-thylamine, trimethylamine or tripropylamine.
- amines containing different hydrocarbon radicals may be used.
- chlorinated hydrocarbons such as methalkyl compounds to be obtained.
- the reaction can be effected at a temperature within the range of C. and +100 C. Preferably a temperature between 20 C. and +30 C. is used, this ofiering the technically simplest way. In some cases the preferred temperature is below 0 C.
- the same working methods are used as in the case of other organo-metal compounds, i.e. the operation is carried out, inter alia, with the exclusion of air, for example under an atmosphere of nitrogen or another inert gas, and with the exclusion of moisture.
- the organo-titanium compounds according to the invention are new. They correspond to the (following [formula 7 R1 R: a
- R represents a cyclopentadienyl radical which assaults may be substituted by hydrocarbon radicals if desired
- R represents an aliphatic hydrocarbon radical
- Y is either identical with R or X whose meaning has been explained above.
- the new compounds are soluble in the above mentioned diluents. They have a yellow to orange or red coloration and are crystallized compounds which are substantially stable when exposed to air. On exposure to a strong action of light or on being heated they decompose, in which case intermediate formation of alkyl radicals probably takes place.
- dialkyl-bis-cyclopentadienyl titanium compounds as well as the mono-cyclopentadienyl titanium compounds melt with decomposition, the latter substances being, however, somewhat more stable.
- the compounds of the invention are stable in water. They can be used as catalysts, for example for the polymerization of olefins.
- EXAMPLE 1 In a vessel of a capacity of 250 ml. which was provided with a stirrer, a dropping vessel and a device for intense cooling, 2.5 g. millimols) of bis-cyclopentadienyl-titanium dichloride were stirred, at C. under a pure nitrogen atmosphere, with 80 ml. of dry methylene chloride, and in the course of /2 hour a solution of 1.0 g. (14 millirnols) of trimethylaluminum in 50 ml. of pentane was added dropwise. The dark red solution was allowed to react for 1 hour. Subsequently ml. of absolute other were added for deactivating any onganoaluminum compounds in excess.
- the product obtained was a mixture of bis-cyclopentadienyl methyl-titanium chloride and bis-cyclopentadienyl-titanium dichloride.
- the mixture could be severed by boiling with methylcyclohexane in which the methyl compound is moderately soluble but the dichloride is substantially insoluble.
- the ethereal solution was agitated two to three times with water, dried with a small amount of sodium sulfate and the solvent was removed under reduced pressure, and the crude biscyclopeutadienyl-dimethyl-titanium was obtained in the form of fine orange colored crystals of characteristic odor.
- the crude product was obtained in almost quantitative yield. It was dissolved at room temperature in about 200 ml. of pentane and caused to precipitate in the form of long orange-yellow needles by slowly cooling to 80 C. The product is suitably stored in the dark at a low temperature (solid carbon dioxide). The decomposition point was j+97 C., varied however a little depending on the velocity of heating. The yield of pure substance amounted to about 8.5 g.
- the etheral solution was freed from lithium salts by washing with water, dried with sodium sulfate and freed from solvent under reduced pressure.
- the bis-cyclopentadienyl-dimethyltitanium was obtained as a well crystallized orange colored mass.
- the yield of crude product amounted to 80% of the theoretical.
- EXAMPLE 7 A suspension of 2.5 g. (10 millimols) of bis-cyclopentadienyl-titanium dichloride in 80 ml. of absolute ether was reacted at room temperature as described in Example 4 with 11.0 ml. of an ethereal 2-molar methylmagnesiumiodide solution. After the usual working up, 1.2 g. of bis-cyclopentadienyl-dimethyl-titanium decomposing at 97 C. were obtained. The yield amounted to 58% EXAMPLE 8 In a vessel of a capacity of 500 ml. provided with a stirrer, 110 ml.
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Description
United States Patent 015 3,104,249 Patented Sept. 17, 1963 ice 3,104,249 ORGANO-TITANIUM COMPOUNDS AND A PROCESS OF PREPARING THEM Karl Clauss, Kelkheim-Hornau, Taunus, and Herbert Bestian, Frankfurt am Main, Germany, assignors, by mesne assignments, to Hercules Powder Company Incorporated, Wilmington, Del., a corporation of Delaware No Drawing. Filed Apr. 12, 1957, Ser. No. 652,381 Claims priority, application Germany Apr. 13, 1956 8 Claims. (Cl. 260-429.5)
The present invention relates to organo titanium compounds and a process of preparing them.
In spite of numerous attempts, it has hitherto been impossible to prepare organo-titanium compounds in which one or more alkyl groups are linked to the metal atom. It has, for example, been tried to prepare alkyl metal compounds of titanium {by causing the ethereal solutions of magnesium alkyl halides or lithium alkyls to act upon titaniumetetrachloride. Such reactions did, however, not lead to the expected organo-titanium compounds. Instead, the transition of the tetravalent titanium to a lower valence was observed. From the course of the reaction it was suggested that a titanium alkyl halide, for example RTlClg, was intermediately formed which, however, was not capable of existence and decomposed very rapidly according to the equation of the general formula (R1)2TlX2 wherein R represents the cyclopentadienyl radical or a cyclopentadienyl radical substituted by one or more hydrocarbon radicals, and X represents alkoxyl groups, halogen groups or another acid radical, to react, suitably in the presence of an inert diluent, with alkyl metal compounds of the elements 1 of group I or II or subgroup H of the periodic table or of aluminum. As titanium compounds which can be converted with special advantage to organo-metal alkyl compounds according to the invention, there are mentioned the bis-cyclopentadienyl-titanium dihalides. It is to be understood that the term halogen is here meant to include also the pseudohalogens. X represents chlorine, bromine or iodine, the cyano group or thio-cyanate group, since the corresponding products are easier to obtain. Of these compounds there comes primarily into consideration the dichloride since it is easily accessible and can be prepared in a simple manner from cyclopentadienyl sodium and titanium tetrachloride. In many cases the bis-cyclopentadienyl-titanium-dialkoxy compounds are advantageously used. As alkoxy radicals are chiefly concerned those containing 1 to 4 carbon atoms such as methoxyl, ethoxyl, propoxyl, butoxyl or iso-butoxyl. 'If desired, the alkoxy groups may contain higher alkyl radicals, for example the ethylhexyl radical or the dodecyl radical.
Instead of the aforesaid compounds there may also be used the coresponding diacetates or the coresponding compounds with other acid groups for example sulfate. If desired, compounds may be used in which the two radicals X are diiferent.
The cyclopentadienyl radical may be substituted by one or more identical or different hydrocarbon radicals, preferably by aliphatic hydrocarbon radicals containing 1 to 4 carbon atoms. There come into consideration for example, methyl, dimethyl, ethyl, propyl, isopropyl or butyl compounds.- If desired, there may also be used compounds such as dodecyl, phenyl, toluyl, benzyl or xylyl compounds.
For reacting the above mentioned titanium compounds there are used according to the invention alkyl metal compounds of group I or II or sub-group II of the periodic table or of .aluminum. In view of their high reactivity and easy preparation, magnesium alkyl halides, known as Grignards compounds and lithium alkyl compounds,
for example methyl compounds, are especially suitable. There may also be used with advantage magnesium dialkyls, zinc dialkyls, beryllium dialkyls, sodium alkyls or potassium alkyls. Of the aluminum alkyls there come chiefly into consideration aluminum .trialkyl and dialkylaluminum chloride or the mixture of alkylaluminum chlorides known as sesquichloride. In the alkyl compounds, the alkyl radical advantageously is a radical containing 1 to 4 carbon atoms, for example a methyl, ethyl, propyl, isopropyl, butyl or isobutyl radical. The reaction of the titanium compounds and the metal alkyls is suitably carried out in the presence of a diluent. In the case of a metal alkyl of low reactivity it is, however, also possible to use undiluted components.
As di-luents can be used all substances which are inert with respect to .ongano-metal compounds and liquid under reaction conditions such as ether, [for example dimethyl ether, diethyl ether, :dipropyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, dioxan, saturated aliphatic or cycloaliphatic hydrocarbons such as butane, pentane, hexane, heptane, octane, cyclohexane, cyclopentane, the alkyl derivatives thereof such as methylcyclohexane, methylcyclopentane or beuzine fractions containing the aforesaid or higher aliphatic hydrocarbons and which have been obtained :for example from petroleum or by the tFlSChfif-TI'OPSGh synthesis. There come tfiurther into consideration aromatic hydrocarbons such as benzene, toluene or xylene, tertiary amines such as trie-thylamine, trimethylamine or tripropylamine. If desired, amines containing different hydrocarbon radicals may be used.
In some cases chlorinated hydrocarbons such as methalkyl compounds to be obtained. The reaction can be effected at a temperature within the range of C. and +100 C. Preferably a temperature between 20 C. and +30 C. is used, this ofiering the technically simplest way. In some cases the preferred temperature is below 0 C. During the reaction the same working methods are used as in the case of other organo-metal compounds, i.e. the operation is carried out, inter alia, with the exclusion of air, for example under an atmosphere of nitrogen or another inert gas, and with the exclusion of moisture. The organo-titanium compounds according to the invention are new. They correspond to the (following [formula 7 R1 R: a
wherein R represents a cyclopentadienyl radical which amazes may be substituted by hydrocarbon radicals if desired, R represents an aliphatic hydrocarbon radical and Y is either identical with R or X whose meaning has been explained above. The new compounds are soluble in the above mentioned diluents. They have a yellow to orange or red coloration and are crystallized compounds which are substantially stable when exposed to air. On exposure to a strong action of light or on being heated they decompose, in which case intermediate formation of alkyl radicals probably takes place. When heated to temperatures above 100 C., the dialkyl-bis-cyclopentadienyl titanium compounds as well as the mono-cyclopentadienyl titanium compounds melt with decomposition, the latter substances being, however, somewhat more stable. The compounds of the invention are stable in water. They can be used as catalysts, for example for the polymerization of olefins.
In some cases it is of advantage, when reacting titanium compounds in which the two radicals X stand for halogen groups and/ or alkoxy radicals, to use methyl compounds of metals or group I or II of the periodic table, while proceeding at a temperature below C.
The following examples serve to illustrate the invention but they are not intended to limit it thereto:
EXAMPLE 1 In a vessel of a capacity of 250 ml. which was provided with a stirrer, a dropping vessel and a device for intense cooling, 2.5 g. millimols) of bis-cyclopentadienyl-titanium dichloride were stirred, at C. under a pure nitrogen atmosphere, with 80 ml. of dry methylene chloride, and in the course of /2 hour a solution of 1.0 g. (14 millirnols) of trimethylaluminum in 50 ml. of pentane was added dropwise. The dark red solution was allowed to react for 1 hour. Subsequently ml. of absolute other were added for deactivating any onganoaluminum compounds in excess. The solvents were removed under reduced pressure as far as possible, and the residue was mixed with 30 ml. of pentane and cooled to --80 C. The orange-red precipitate was suction-filtered on a cooled suction filter with the exclusion of air, washed with cooled pentane and dried under reduced pressure. In this manner 2.05 g. of small orangered crystals of bis-cyclopentadienyl-methyl-titanium chloride were obtained which melted at 168 C. to 170 C. with decomposition. The yield amounted to 90% of the theoretical. As could be seen from decomposition by means of an acid, the substance was already pure. It could be well recrystallized [from cyclohexane and methylcyclohexane. The methyl compound was soluble in water, in the cold, without decomposition; on the addition of acid the orange-yellow solution turned red with formation of methane.
Analysis by Decomposition by Means of an Acid 5 5)2 i( 3) EXAMPLE 2 In a Schlenk tube 10.0 in]. (about 100 millimols) of dimethylaluminurn chloride were added under a pure nitrogen atmosphere to a suspension of 10.0 g. millimols) of powdered bis-cyclopentadienyl-titanium dichloride in 20 ml. of absolute toluene. The Whole was thoroughly shaken and allowed to stand overnight at room temperature. After this time, solution was practically complete, ml. of absolute ether were slowly added, while cooling and shaking, during which procedure a crystallized red precipitate was obtained. The whole was allowed to stand for 2 hours at 80 C. The red mother liquor was then cautiously removed, and the crystals were washed several times with absolute ether and pentane and dried under reduced pressure. The yield amounted to about 7.5 g. of orange-colored crystal powder.
According to a total analysis the product obtained was a mixture of bis-cyclopentadienyl methyl-titanium chloride and bis-cyclopentadienyl-titanium dichloride.
(C H Ti(CH )Cl: Found-Ti, 21.0; C1, 18.17; C, 54.81; H, 5.50; Al, 0.02. Calcu1ated-Ti, 228.57; Cl, 20.96; C, 15.51; H, 57.80; Al, 5.73.
The mixture could be severed by boiling with methylcyclohexane in which the methyl compound is moderately soluble but the dichloride is substantially insoluble.
From the solution small orange-colored crystals were obtained on cooling. By adding pentane to the mother liquor and cooling to C., a further quantity of methyl compound could be obtained; it proved suitable to protect the solutions against light.
The yield amounted to about 4.5 g. of pure bis-cyclopentadienyl-methyl-titanium chloride or 50% of the theoretical. In addition thereto, a portion of the starting product was recovered.
Analysis-Found: Ti, 21.38; Cl, 15.48; C, 57.58; H, 5.89. Calculated: Ti, 20.96; Cl. 15.51; C, 57.80; H, 5.73.
Analysis by Decomposition by Means of an Acid 198 mg. of substance yielded 19.2 ml. of methane (at 0 C. under a pressure of 760 millimeters of mercury).
Theory: 19.4 ml. of methane (calculated for (C H Ti(CH Cl) EXAMPLE 3 In a vessel of a capacity of 500 ml. provided with a stirrer, a reflux condenser, a dropping, vessel and a thermometer, there were introduced 11.5 g. (46 millimols) of powdered bis-cyclopentadienyl-titanium dichloride and 200 ml. of absolute ether and the mixture was kept under a pure nitrogen atmosphere. In the course of about 2 hours, ml. of an ethereal l-molar methyllithium solution were added dropwise, while stirring and cooling to 10 to 15 C. and while avoiding strong action of light. The whole was stirred for a further hour and the yellow to orange colored solution was then decomposed by addition of ice Water.
The ethereal solution was agitated two to three times with water, dried with a small amount of sodium sulfate and the solvent was removed under reduced pressure, and the crude biscyclopeutadienyl-dimethyl-titanium was obtained in the form of fine orange colored crystals of characteristic odor. The crude product was obtained in almost quantitative yield. It was dissolved at room temperature in about 200 ml. of pentane and caused to precipitate in the form of long orange-yellow needles by slowly cooling to 80 C. The product is suitably stored in the dark at a low temperature (solid carbon dioxide). The decomposition point was j+97 C., varied however a little depending on the velocity of heating. The yield of pure substance amounted to about 8.5 g. (89% of the theoretical) Analysis.--(C H Ti(CH Found: Ti, 23.5; C, 68.58; H, 7.86; Cl. Calculated: M.W., 208.15; Ti, 23.01; C, 69.24; H, 7.75; CI,
Analysis by Decomposition by Means of an Acid 133.5 mg. of substance yielded 28.7 ml. of methane (at 0 C. under a pressure of 7 60 millimeters of mercury).
Theory: 28.8 ml. of methane (calculated for 5 s)2 3)2) EXAMPLE 4 In a vessel of a capacity of 250 ml. provided with a stirrer, a suspension of 6.76 g. (20 millimols) of finely powdered bis-cyclopentadienyl-titanium dibromide in 100 ml. of absolute. ether was introduced and kept under a pure nitrogen atmosphere, and in the course of 1 hour 40 m1. of an etheral 1.0-molar methyl-lithium solution were added dropwise at about C. During this procedure the starting product dissolved with an orange coloration. The whole was stirred for a further hour and 50 ml. of ice water were then added. The etheral solution was freed from lithium salts by washing with water, dried with sodium sulfate and freed from solvent under reduced pressure. The bis-cyclopentadienyl-dimethyltitanium was obtained as a well crystallized orange colored mass. The yield of crude product amounted to 80% of the theoretical.
For complete purification the crude product was dissolved at room temperature in just the suflicient amount of pentane and crystallized out by cooling to -80 C. 3.0 g. of orange colored needles were obtained (decomposition point 97 0.). Yield of the pure product: 72%.
EXAMPLE 5 A suspension of 4.32 g. millimols) of biscyclopentadienyl-diiodide in 100 ml. of absolute ether was reacted, as described in Example 4, with an ethereal solution of 20 millimols of methyl-lithium. During this process the color turned yellow-orange. After decomposition with water and the usual working up, a yield of crude bis-cyclopentad-ienyl-dimethyl-titanium of 85% of the theoretical was obtained. After recrystallization from pentane, the yield amounted to 1.58 g. or 76%.
EXAMPLE 6 A suspension of 2.35 g. (8 millimols) of finely powdered bis-cyclopentadienyl-titanium dithiocyan ate in 80 ml. of absolute ether was reacted, as described in Example 4, at room temperature with an ethereal solution of 60 millimols of methyl-lithium. The dark substance originally present at the bottom of the liquid disappeared and the liquid turned orange-yellow. After the usual aqueous working up, 1.5 g. of crude bis-cyclopentadienyl-dimethyltitanium (90%) were obtained. After recrystallization from pentane, the yield of the pure product amounted to 1.38 g. or 83%.
EXAMPLE 7 A suspension of 2.5 g. (10 millimols) of bis-cyclopentadienyl-titanium dichloride in 80 ml. of absolute ether was reacted at room temperature as described in Example 4 with 11.0 ml. of an ethereal 2-molar methylmagnesiumiodide solution. After the usual working up, 1.2 g. of bis-cyclopentadienyl-dimethyl-titanium decomposing at 97 C. were obtained. The yield amounted to 58% EXAMPLE 8 In a vessel of a capacity of 500 ml. provided with a stirrer, 110 ml. of a 0.4-molar n-propyl-lithium solution in pentane were slowly introduced dropwise into a suspension of 10.0 g. (40 millimols) of bis-cyclopentadienyltitanium dichloride in 100 ml. of absolute ether. The red substance at the bottom of the liquid dissolved. Towards the end of the reaction, the reaction mixture was redorange. Stirring was continued for a further hour at 50 C. and decomposition was then effected by addition of water. After the usual working up, 3.4 g. of biscyclopentadienyl-n-propyl-titanium chloride were obtained in the form of an orange powder of a decomposition point of about 160 C. The substance was only sparingly soluble in cold pentane but easily soluble in benzene, toluene etc.
Analysis by Decomposition by Means of an Acid 234 mg. of substance yielded 19.6 ml. of propane (at 0 C. under a pressure of 760 millimeters of mercury).
Theory: 20.4 ml. of propane (calculated for s s) 2 s rl 'EXAMPLE 9 In the usual vessel provided with a stirrer (capacity 250 ml.), a solution of 2 g. (about 20 millimols) of dimethylzinc in 30 of pentane was added, under a pure nitrogen atmosphere, slowly and uniformly and while stirring vigorously, to a suspension of 2.5 g. (10 millimols) of biscyclopentadienyl-titanium dichloride in 100 ml. of absolute pentane. After the addition the mixture was kept for 2 hours at the boil and worked up as usual. After recrystallization from pentane, 0.5 g. of orange-yellow needles decomposing at 97 C. were obtained, -i.e. 24% of the theoretical of bis-cyclopentadienyl-dimethyl-titaniurn.
EXAMPLE 10 A suspension of 5.6 g. (20 millimols) of bis-[l-methylcyclopentadienyl]-titanium-dichloride in ml. of absolute ether was reacted, :as describedin Example 4, at 10 C. to 15 C. while stirring with 40 ml. of ethereal 1.1-m0lar methyl-lithium solution. Stirring was continued for 1 hour and after the usual aqueous working up 3.1 g. of
Analysis by Decomposition by Means of an Acid 151 mg. of substance yielded 13.8 ml. of methane (at 0 C. under a pressure of 7 60 millimeters of mercury).
Theory: 14.3 ml. of methane (calculated for G I) 2 s)2) EXAMPLE 11 In an apparatus provided with a stirrer was placed a suspension of 5 g. (20 millimols) of bis-cyclopentadienyltitanium dichloride in 80 ml. of absolute ether. The suspension was cooled to 50 C. and kept under a pure nitrogen atmosphere. In the course of two hours, a solution of 20 mi-llimols of ethyllithium in pentane was introduced dropwise, while stirring vigorously, and the whole was allowed to react for a further hour, while cooling. The ether-pentane-solution was then freed from lithium chloride by means of water,'dried with sodium sulfate and evaporated to dryness under reduced pressure. The orange-yellow powder so obtained was dissolved in toluene, filtered and crystallized by addition of pentane. The yield of bis-cyclopentadienyl-ethyl-titanium chloride amounted to 1.8 g. (7.4 millimols) or 37% of the theoretical.
We claim:
1. Bis-cyclopentadienyl-methyl-titanium chloride.
2. Bis-cyclopentadienyLdimethyI-titanium.
3. Bis-cyclopentadienyl-propyl-titanium chloride.
4. Bis-( 1-methyl-cyclopeutadienyl) -dimethyl-titanium.
5. Bis-cyclopentadienyl-ethyl-titanium chloride.
6. A process for preparing a cyclopentadienyl alkyltitanium compound having the formula in which each R is selected from the group consisting of the cyclopentadienyl radical and the cyolopentadienyl radical substituted by 1 to 2 alkyl radicals each containing 1 to 4 carbon atoms, R is a saturated aliphatic hydrocarlbon radical of 1 to 4 carbon atoms and Y is selected from the group consisting of a saturated aliphatic hydrocarbon wherein R is as defined above and X is selected from the group consisting of a chlorine, bromine, iodine, cyano and thiocyano radical with (2) an aluminum alkyl compound containing at least one alkyl group, said alkyl group having 1 to 4 carbon atoms, (B) adding an ether to deactivate excessive aluminum alkyl compound, and (C) distilling off the solvents in vacuo to isolate the solid reaction product.
7. A process for preparing a cyclopentadienyl 'alkyl titanium compound having the formula in which each R is selected from the group consisting of the cyclopentadienyl radical and the cyclopentadienyl radical substituted by 1 to 2 alkyl radicals each containing 1 to 4 carbon atoms, R is a saturated aliphatic hydrocarbon radical of 1 to 4 carbon atoms and Y is selected from the group consisting of a saturated aliphatic hydrocarbon radical of l to 4 carbon atoms, a chlorine, bromine, iodine, cyano and thiocyano radical which process comprises the steps of (A) contacting in a liquid diluent selected from the group consisting of a saturated hydrocarbon, an aromatic hydrocarbon and chlorination productsthereof (1) a titanium compound of the formula wherein R is as defined above and X is selected from the group consisting of a chlorine, bromine, iodine, cyano and wherein each R is selected from the group consisting of the cyclopentadienyl radical and the cyclopentadienyl radical substituted by 1 to 2 alkyl radicals each containing 1 to 4 carbon atoms, and R is a saturated aliphatic hydrocarbon radical of 1 to. 4 carbon atoms.
References Cited in the file of this patent UNITED STATES PATENTS 2,356,476 Shappirio Aug. 22, 1944 2,827,446 Breslow Mar. 18, 1958 FOREIGN PATENTS 1,092,700 France Nov. 10, 1954 1,108,869 France, Sept. 14, 1955 OTHER REFERENCES Fischer et al.: Zeit. Naturforschung 8b, (1953).
Summers et al., J.A.C.S. 77, 3604-3606 (1955).
UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,104 249 September 17 1963 Karl Clause et a1,
It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.
Column 4, lines 7 and 8 strike out "'Caleulated-Ti 228 57; C1 20.96; C 15051 H 57 i 80; Al 5. "J3. and insert instead Calculated Miw, w 228.51"; Ti 20.96;
Cl 1551; C, 5180; H, 5. 73
Signed and sealed this 28th day of April 1964 (SEAL) Attest:
ERNEST Wu SWIDER EDWARD J. BRENNER Attesting Officer Commissioner of Patents
Claims (3)
- 2. BIS-CYCLOPENTADIENYL-DIMETHYL-TITANIUM.
- 4. BIS-(1-METHYL-CYLOPHENTADINYL)-DIMETHYL-TITANIUM.
- 8. A COMPOUND OF THE FORMULA
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DEF20038A DE1037446B (en) | 1956-04-13 | 1956-04-13 | Process for the production of organometallic titanium compounds |
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Cited By (17)
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EP0041361A1 (en) * | 1980-06-02 | 1981-12-09 | Hercules Incorporated | Preparation of block copolymers using dimethyl-bis(methylcyclopentadienyl)titanium |
US4882039A (en) * | 1986-12-04 | 1989-11-21 | Mobil Oil Corporation | Catalytic cracking of hydrocarbons with oxygen promoted alkali metal zeolite cracking catalyst |
US4937299A (en) * | 1983-06-06 | 1990-06-26 | Exxon Research & Engineering Company | Process and catalyst for producing reactor blend polyolefins |
US5003019A (en) * | 1987-03-02 | 1991-03-26 | Mitsui Petrochemical Industries, Ltd. | Cyclo-olefinic random copolymer, olefinic random copolymer, and process for producing cyclo-olefinic random copolymers |
US5324800A (en) * | 1983-06-06 | 1994-06-28 | Exxon Chemical Patents Inc. | Process and catalyst for polyolefin density and molecular weight control |
US5641843A (en) * | 1985-12-24 | 1997-06-24 | Mitsui Petrochemical Industries, Ltd. | Process for polymerization of alpha-olefins |
US5654248A (en) * | 1986-08-26 | 1997-08-05 | Mitsui Petrochemical Industries, Ltd. | Catalyst for polymerizing alpha-olefins and process for polymerization |
US5700749A (en) * | 1986-09-24 | 1997-12-23 | Mitsui Petrochemical Industries, Ltd. | Process for polymerizing olefins |
US5700750A (en) * | 1985-12-26 | 1997-12-23 | Mitsui Petrochemical Industries, Ltd. | Process for polymerization of alpha-olefins |
US5849975A (en) * | 1997-01-07 | 1998-12-15 | Chevron U.S.A. Inc. | Process for isomerization of normal olefin |
US5892082A (en) * | 1995-09-07 | 1999-04-06 | Merck & Co., Inc. | Process for the preparation of dimethyl titanocene |
US6013743A (en) * | 1985-12-24 | 2000-01-11 | Mitsui Chemicals Inc. | Process for polymerization of alpha-olefins |
US6063726A (en) * | 1986-08-26 | 2000-05-16 | Mitsui Chemicals, Inc. | Catalyst for polymerizing alpha-olefins and process for polymerization |
US6121394A (en) * | 1990-07-24 | 2000-09-19 | Mitsui Chemicals, Inc. | Metallocene-catalyzed olefin polymerization in the absence of aluminoxane |
US6153551A (en) * | 1997-07-14 | 2000-11-28 | Mobil Oil Corporation | Preparation of supported catalyst using trialkylaluminum-metallocene contact products |
US6255550B1 (en) | 1998-10-28 | 2001-07-03 | Merck & Co., Inc. | Stabilization of the reagent dimethyl titanocene |
US9045569B2 (en) | 2011-01-14 | 2015-06-02 | W. R. Grace & Co.-Conn. | Process of making modified metallocene catalyst, catalyst produced and use thereof |
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EP0041361A1 (en) * | 1980-06-02 | 1981-12-09 | Hercules Incorporated | Preparation of block copolymers using dimethyl-bis(methylcyclopentadienyl)titanium |
US5324800A (en) * | 1983-06-06 | 1994-06-28 | Exxon Chemical Patents Inc. | Process and catalyst for polyolefin density and molecular weight control |
US4937299A (en) * | 1983-06-06 | 1990-06-26 | Exxon Research & Engineering Company | Process and catalyst for producing reactor blend polyolefins |
US6013743A (en) * | 1985-12-24 | 2000-01-11 | Mitsui Chemicals Inc. | Process for polymerization of alpha-olefins |
US5641843A (en) * | 1985-12-24 | 1997-06-24 | Mitsui Petrochemical Industries, Ltd. | Process for polymerization of alpha-olefins |
US5807801A (en) * | 1985-12-26 | 1998-09-15 | Mitsui Petrochemical Industries, Ltd. | Catalyst for the polymerization of alpha-olefins |
US5700750A (en) * | 1985-12-26 | 1997-12-23 | Mitsui Petrochemical Industries, Ltd. | Process for polymerization of alpha-olefins |
US5654248A (en) * | 1986-08-26 | 1997-08-05 | Mitsui Petrochemical Industries, Ltd. | Catalyst for polymerizing alpha-olefins and process for polymerization |
US6063726A (en) * | 1986-08-26 | 2000-05-16 | Mitsui Chemicals, Inc. | Catalyst for polymerizing alpha-olefins and process for polymerization |
US5700749A (en) * | 1986-09-24 | 1997-12-23 | Mitsui Petrochemical Industries, Ltd. | Process for polymerizing olefins |
US4882039A (en) * | 1986-12-04 | 1989-11-21 | Mobil Oil Corporation | Catalytic cracking of hydrocarbons with oxygen promoted alkali metal zeolite cracking catalyst |
US5003019A (en) * | 1987-03-02 | 1991-03-26 | Mitsui Petrochemical Industries, Ltd. | Cyclo-olefinic random copolymer, olefinic random copolymer, and process for producing cyclo-olefinic random copolymers |
US6121394A (en) * | 1990-07-24 | 2000-09-19 | Mitsui Chemicals, Inc. | Metallocene-catalyzed olefin polymerization in the absence of aluminoxane |
US5892082A (en) * | 1995-09-07 | 1999-04-06 | Merck & Co., Inc. | Process for the preparation of dimethyl titanocene |
US5849975A (en) * | 1997-01-07 | 1998-12-15 | Chevron U.S.A. Inc. | Process for isomerization of normal olefin |
US6153551A (en) * | 1997-07-14 | 2000-11-28 | Mobil Oil Corporation | Preparation of supported catalyst using trialkylaluminum-metallocene contact products |
US6255550B1 (en) | 1998-10-28 | 2001-07-03 | Merck & Co., Inc. | Stabilization of the reagent dimethyl titanocene |
US9045569B2 (en) | 2011-01-14 | 2015-06-02 | W. R. Grace & Co.-Conn. | Process of making modified metallocene catalyst, catalyst produced and use thereof |
Also Published As
Publication number | Publication date |
---|---|
DE1037446B (en) | 1958-08-28 |
GB858540A (en) | 1961-01-11 |
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