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US3104249A - Organo-titanium compounds and a process of preparing them - Google Patents

Organo-titanium compounds and a process of preparing them Download PDF

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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
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Prior art keywords
titanium
cyclopentadienyl
compounds
bis
radical
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US652381A
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Clauss Karl
Bestian Herbert
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Hercules Powder Co
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Hercules Powder Co
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    • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
US652381A 1956-04-13 1957-04-12 Organo-titanium compounds and a process of preparing them Expired - Lifetime US3104249A (en)

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DEF20038A DE1037446B (de) 1956-04-13 1956-04-13 Verfahren zur Herstellung von metallorganischen Titanverbindungen

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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0041361A1 (de) * 1980-06-02 1981-12-09 Hercules Incorporated Herstellung von Blockcopolymeren mit Dimethyl-bis(methyl-cyclopentadienyl)titan
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
US5700750A (en) * 1985-12-26 1997-12-23 Mitsui Petrochemical Industries, Ltd. Process for polymerization of alpha-olefins
US5700749A (en) * 1986-09-24 1997-12-23 Mitsui Petrochemical Industries, Ltd. Process for polymerizing 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

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1265564A (de) * 1969-07-17 1972-03-01
DE4416894A1 (de) * 1994-05-13 1995-11-16 Witco Gmbh Verfahren zur Synthese von Mono- und Dimethylmetallocenen und deren Lösungen speziell für den Einsatz zur Polymerisation von Olefinen

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2356476A (en) * 1941-06-28 1944-08-22 Shappirio Sol Motor fuels
FR1092700A (fr) * 1952-12-10 1955-04-26 Ethyl Corp Perfectionnements relatifs aux antidétonants pour carburants
FR1108869A (fr) * 1953-09-23 1956-01-18 Union Carbide & Carbon Corp Procédé de fabrication de composés organo-métalliques
US2827446A (en) * 1955-09-27 1958-03-18 Hercules Powder Co Ltd Polymerization of ethylene

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2356476A (en) * 1941-06-28 1944-08-22 Shappirio Sol Motor fuels
FR1092700A (fr) * 1952-12-10 1955-04-26 Ethyl Corp Perfectionnements relatifs aux antidétonants pour carburants
FR1108869A (fr) * 1953-09-23 1956-01-18 Union Carbide & Carbon Corp Procédé de fabrication de composés organo-métalliques
US2827446A (en) * 1955-09-27 1958-03-18 Hercules Powder Co Ltd Polymerization of ethylene

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0041361A1 (de) * 1980-06-02 1981-12-09 Hercules Incorporated Herstellung von Blockcopolymeren mit Dimethyl-bis(methyl-cyclopentadienyl)titan
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
US5700750A (en) * 1985-12-26 1997-12-23 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
US6063726A (en) * 1986-08-26 2000-05-16 Mitsui Chemicals, Inc. Catalyst for polymerizing alpha-olefins and process for polymerization
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
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

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DE1037446B (de) 1958-08-28
GB858540A (en) 1961-01-11

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