US3021349A - Dimethyl titanium dichloride - Google Patents
Dimethyl titanium dichloride Download PDFInfo
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- US3021349A US3021349A US862474A US86247459A US3021349A US 3021349 A US3021349 A US 3021349A US 862474 A US862474 A US 862474A US 86247459 A US86247459 A US 86247459A US 3021349 A US3021349 A US 3021349A
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- Prior art keywords
- titanium
- dimethyl
- dimethyl titanium
- bis
- titanium dichloride
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- XWMCJIOSNAXGAT-UHFFFAOYSA-L [Cl-].[Cl-].C[Ti+2]C Chemical compound [Cl-].[Cl-].C[Ti+2]C XWMCJIOSNAXGAT-UHFFFAOYSA-L 0.000 title claims description 21
- TVCHACRVJZXHLX-UHFFFAOYSA-K carbanide;titanium(4+);trichloride Chemical compound [CH3-].Cl[Ti+](Cl)Cl TVCHACRVJZXHLX-UHFFFAOYSA-K 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- COOXAWDWHWRVRD-UHFFFAOYSA-N C[Ti]C Chemical compound C[Ti]C COOXAWDWHWRVRD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- YNBJMIXWGPOBGE-UHFFFAOYSA-N carbanide;cyclopenta-1,3-diene;titanium(4+) Chemical compound [CH3-].[CH3-].[Ti+4].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 YNBJMIXWGPOBGE-UHFFFAOYSA-N 0.000 description 14
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 11
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical class CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- JGALSKCCWGCHHM-UHFFFAOYSA-N [Ti]C Chemical compound [Ti]C JGALSKCCWGCHHM-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- -1 octanes Chemical compound 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000002152 alkylating effect Effects 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 235000013844 butane Nutrition 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 229930007927 cymene Natural products 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical class CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 150000003738 xylenes Chemical class 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- YACLCMMBHTUQON-UHFFFAOYSA-N 1-chloro-1-fluoroethane Chemical class CC(F)Cl YACLCMMBHTUQON-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 241000009298 Trigla lyra Species 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002483 hydrogen compounds Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/28—Titanium compounds
Definitions
- dimethyl titanium dichloride is produced in a useful form by contacting titanium tetrachloride or methyl titanium trichloride with bis(cyclopentadienyl) dimethyl titanium.
- Methyl titanium trichloride is produced by the reaction of titanium tetrachloride with one-half of an equimolecular amount of bis(cyclopentadienyl) dimethyl titanium at a temperature in the range of about 80 C. to about C. and dimethyl titanium dichloride is produced by reaction of methyl titanium tn'chloride with one-half of an equimolecular amount of bis(cyclopentadienyl) dimethyl titanium at a temperature in the same low range.
- the methyl titanium trichloride may be prepared separately by reaction of titanium tetrachloride with a metal alkyl such as lithium alkyl, or aluminum alkyl provided that the reaction is carried out at a temperature sufliciently low that reduction of the titanium tetrachloride to titanium trichloride, which normally occurs at room temperature or above, does not take place.
- a temperature of below about 0 C. is required to form the methyl titanium trichloride in this reaction and preferably a temperature of 30 C. to -60 C. or less is used.
- organotitanium compounds are sensitive to oxygen, active hydrogen compounds, and water, the reactions involved are carried out under anhydrous conditions and in an inert atmosphere.
- the process of this invention is preferably carried out in an organic diluent which is inert under the reaction conditions.
- organic diluents include the hydrocarbons saturated with respect to olefinic and acetylenic unsaturation, e.g., methane, ethane, propane, butanes, hexanes, heptanes, octanes, cyclohexane, methyl cyclopentane, benzene, toluene, xylenes, cumene, cymene, and the hydrogenated analogs of these aromatic hydrocarbons.
- the diluents which may also be used are the halogenated hydrocarbons, e.g., chloromethane, dichloromethane, chloroform, carbon tetrachloride, dichlorodifluoromethane, ethylene chloride, acetylene tetrachloride, chlorofluoroethanes, chlorobenzene, chlorinated toluene and similar halogenated hydrocarbons.
- halogenated hydrocarbons e.g., chloromethane, dichloromethane, chloroform, carbon tetrachloride, dichlorodifluoromethane, ethylene chloride, acetylene tetrachloride, chlorofluoroethanes, chlorobenzene, chlorinated toluene and similar halogenated hydrocarbons.
- the amount of diluent in the process is not critical and is sufiicient to produce a fluid reaction mixture.
- the process is carried out in the presence of the olefin to be polymerized and its prior isolation is not necessary.
- the process is carried out in the absence of unsaturated hydrocarbons.
- the dimethyl titanium dichloride may be freed of excess titanium halide by recrystallization of the dimethyl titanium dichloride from inert solvent such as aliphatic, alicyclic, or aromatic solvents boiling in the range from about -20 C. to about 250 C. such as butane, pentane, octane, cyclohexane, methyl cyclopentane, benzene, toluene, xylenes, cymene, cumene, or halogenated derivatives of these solvents such as methylene chloride, chloroform, and chlorobenzene, for example.
- solvent such as aliphatic, alicyclic, or aromatic solvents boiling in the range from about -20 C. to about 250 C.
- solvents such as butane, pentane, octane, cyclohexane, methyl cyclopentane, benzene, toluene, xylenes, cy
- the dimethyltitanium dichloride can be further purified by distillation or sublimation in high vacuum at temperatures from to 25 C.
- EXAMPLE 1 Preparation of methyltitanium trichlaride
- Five parts of bis(cyclopentadienyl) dimethyl titanium were dissolved in parts of a purified anhydrous toluene. After cooling the solution to 80 C., 9.5 parts of titanium tetrachloride were added as a 1.0 molar solution in pentane with agitation. The mixture was then warmed to 0 C. and agitated at that temperature for 4 hours. The volatile components were then removed by distillation under high vacuum at 10 C. The excess titanium tetrachloride and solvent were then removed from this distillate by fractionally distilling at 36 C. under high vacuum.
- the methyltitanium trichloride in the residue was dissolved by means of pentane. Analysis of an aliquot of this solution showed it to contain 0.52 millimole of titanium per gram and 1.60 millimoles of chlorine per gram or a 3:1 ratio of chlorine to titanium; theoretical value is 3.
- EXAMPLE 2 Preparation of dimethyl titanium dichloride A solution of 5.6 parts of methyl titanium trichloride in pentane was added to a solution of 5.7 parts of his- (cyclopentadienyl) dimethyl titanium in pentane at 40 C. The reaction mixture was allowed to warm to 0 C. and was agitated at that temperature for about 16 hours. It was then fractionally distilled at 0.2 mm. Hg. A first fraction taken at -36 C. to 0 C. was essentially solvent. The second fraction collected at 0 C. to 25 C. consisted of blackish purple crystals. These were dissolved and recrystallized twice from n-heptane. On analysis they were found to have a chlorine to titanium ratio of 2.0 (theory is 2.0)
- the compound prepared according to this invention is a violet to black substance, when in the solid state, and is sensitive to air, water, light, heat and halogens and dissolves in aliphatic and aromatic hydrocarbons and chlorinated hydrocarbon solvents to form a yellow solution.
- This catalyst is particu larly usefulin producing polymers of high viscosity and may be used as a pure catalyst orin combination with methyl titanium trichloride.
- Such a combination can be produced as a mixture in the process of this invention by regulating the amount of bis(cyclopentadienyl) dimethyl titanium used as the alkylating reagent.
- a particularly adyantageous characteristicof the present invention is" the limitation of the'replacement of the halogens on the titanium halide reagent to two by the bis(cyclopentadienyl) dimethyl titahium.
- dimethyl titanium dichloride which comprises reacting a material of the group consisting of titanium tetrachloride and methyl titanium trichloride with bis(cyclopentadienyl) dimethyl titanium at a temperature in the range of C. to 0 C.
- the method of producing dimethyl titanium dichloride which comprises reacting titanium tetrachloride with less thanan equimolecular amount of bis(cyclopentadienyl) dimethyl titanium at. atemperature in the range of. 80 C.v to 0 C;, separatingtmethyl titanium trichloride so produced and reacting the methyl titanium trichloride witha further amount of bis(cyclopentadienyl) dimethyl titanium at a temperature in the range of 80 C. to 0 C. and separating dimethyl titanium dichloride.
- the method of producing dimethyl titanium dichloride in admixture with methyl titanium trichloride which comprises reacting titanium tetrachloride with bis(cyclo pentadienyl) dimethyl titanium in a molecular ratio of between about 2:1 and about 1:1 at a temperature in therange of 80 C; to-O C. 7'
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Description
United States Patent Ofiice 3,021,349 Patented Feb. 13, 1962 3,021,349 DIMETHYL TITANIUM DICHLORIDE Edward H. de Butts, Wilmington, DeL, assignor to Hercules Powder Company, Wilmington, Del., :2 corporation of Delaware No Drawing. Filed Dec. 29, 1959, Ser. No. 862,474 3 Claims. (Cl. 260-4295) This invention relates to the preparation of organotitanium compounds and, more particularly, to the preparation of dimethyl titanium dichloride.
In accordance with the present invention, it has been found that dimethyl titanium dichloride is produced in a useful form by contacting titanium tetrachloride or methyl titanium trichloride with bis(cyclopentadienyl) dimethyl titanium.
Methyl titanium trichloride is produced by the reaction of titanium tetrachloride with one-half of an equimolecular amount of bis(cyclopentadienyl) dimethyl titanium at a temperature in the range of about 80 C. to about C. and dimethyl titanium dichloride is produced by reaction of methyl titanium tn'chloride with one-half of an equimolecular amount of bis(cyclopentadienyl) dimethyl titanium at a temperature in the same low range.
Bis(cyclopentadienyl) dimethyl titanium, which has been made available by the process of Piper and Wilkinson, J. Inorg. and Nuclear Chemistry, 3, 108 (1956), has been found to be a particularly useful alkylating reagent for these reactions.
When bis(cyclopentadienyl) dimethyl titanium is reacted in greater than one-half equimolecular amounts with titanium tetrachloride, it is possible to produce dimethyl titanium dichloride in a one-step reaction. When the ratio of titanium tetrachloride to bis(cyclopentadienyl) dimethyl titanium is between 2:1 and 1:1, a mixture of dimethyl titanium dichloride and methyl titanium trichloride is produced. When the ratio of titanium tetrachloride to bis(cyclopentadienyl) dimethyl titanium is less than 1:1, the product is substantially all dimethyl titanium dichloride.
If desired, the methyl titanium trichloride may be prepared separately by reaction of titanium tetrachloride with a metal alkyl such as lithium alkyl, or aluminum alkyl provided that the reaction is carried out at a temperature sufliciently low that reduction of the titanium tetrachloride to titanium trichloride, which normally occurs at room temperature or above, does not take place. Generally, a temperature of below about 0 C. is required to form the methyl titanium trichloride in this reaction and preferably a temperature of 30 C. to -60 C. or less is used.
Since the organotitanium compounds are sensitive to oxygen, active hydrogen compounds, and water, the reactions involved are carried out under anhydrous conditions and in an inert atmosphere.
The process of this invention is preferably carried out in an organic diluent which is inert under the reaction conditions. Such diluents include the hydrocarbons saturated with respect to olefinic and acetylenic unsaturation, e.g., methane, ethane, propane, butanes, hexanes, heptanes, octanes, cyclohexane, methyl cyclopentane, benzene, toluene, xylenes, cumene, cymene, and the hydrogenated analogs of these aromatic hydrocarbons. The diluents which may also be used are the halogenated hydrocarbons, e.g., chloromethane, dichloromethane, chloroform, carbon tetrachloride, dichlorodifluoromethane, ethylene chloride, acetylene tetrachloride, chlorofluoroethanes, chlorobenzene, chlorinated toluene and similar halogenated hydrocarbons.
The amount of diluent in the process is not critical and is sufiicient to produce a fluid reaction mixture.
When desired to produce the dimethyl titanium dichloride in situ for use in polymerization, the process is carried out in the presence of the olefin to be polymerized and its prior isolation is not necessary. When desired to produce the dimethyl titanium dichloride in a purified form, the process is carried out in the absence of unsaturated hydrocarbons.
The dimethyl titanium dichloride may be freed of excess titanium halide by recrystallization of the dimethyl titanium dichloride from inert solvent such as aliphatic, alicyclic, or aromatic solvents boiling in the range from about -20 C. to about 250 C. such as butane, pentane, octane, cyclohexane, methyl cyclopentane, benzene, toluene, xylenes, cymene, cumene, or halogenated derivatives of these solvents such as methylene chloride, chloroform, and chlorobenzene, for example.
The dimethyltitanium dichloride can be further purified by distillation or sublimation in high vacuum at temperatures from to 25 C.
The following examples illustrate the methods of this invention for carrying out the reactions involved. All parts and percentages are by weight.
EXAMPLE 1 Preparation of methyltitanium trichlaride Five parts of bis(cyclopentadienyl) dimethyl titanium were dissolved in parts of a purified anhydrous toluene. After cooling the solution to 80 C., 9.5 parts of titanium tetrachloride were added as a 1.0 molar solution in pentane with agitation. The mixture was then warmed to 0 C. and agitated at that temperature for 4 hours. The volatile components were then removed by distillation under high vacuum at 10 C. The excess titanium tetrachloride and solvent were then removed from this distillate by fractionally distilling at 36 C. under high vacuum. The methyltitanium trichloride in the residue was dissolved by means of pentane. Analysis of an aliquot of this solution showed it to contain 0.52 millimole of titanium per gram and 1.60 millimoles of chlorine per gram or a 3:1 ratio of chlorine to titanium; theoretical value is 3.
EXAMPLE 2 Preparation of dimethyl titanium dichloride A solution of 5.6 parts of methyl titanium trichloride in pentane was added to a solution of 5.7 parts of his- (cyclopentadienyl) dimethyl titanium in pentane at 40 C. The reaction mixture was allowed to warm to 0 C. and was agitated at that temperature for about 16 hours. It was then fractionally distilled at 0.2 mm. Hg. A first fraction taken at -36 C. to 0 C. was essentially solvent. The second fraction collected at 0 C. to 25 C. consisted of blackish purple crystals. These were dissolved and recrystallized twice from n-heptane. On analysis they were found to have a chlorine to titanium ratio of 2.0 (theory is 2.0)
EXAMPLE 3 To 10 moles of titanium tetrachloride in hexane solution was slowely added a solution of 20 moles bis(cyclopentadienyl) dimethyl titanium in hexane at -80 C. The solution was allowed to warm up to 0 C. and was then cooled again to 80 C. Black crystals of dimethyl titanium dichloride precipitated. These were separated by filtration and further purified by crystallization from hexane by dissolution at 0 C. followed by crystallization at 80 C. The crystals were distillable at 25 C. at 0.2 mm. pressure.
The compound prepared according to this invention is a violet to black substance, when in the solid state, and is sensitive to air, water, light, heat and halogens and dissolves in aliphatic and aromatic hydrocarbons and chlorinated hydrocarbon solvents to form a yellow solution.
to 30 'C, temperature range; This catalystis particu larly usefulin producing polymers of high viscosity and may be used as a pure catalyst orin combination with methyl titanium trichloride. Such a combination can be produced as a mixture in the process of this invention by regulating the amount of bis(cyclopentadienyl) dimethyl titanium used as the alkylating reagent. A particularly adyantageous characteristicof the present invention is" the limitation of the'replacement of the halogens on the titanium halide reagent to two by the bis(cyclopentadienyl) dimethyl titahium. i
application is a continuation-in-part of application Ser. No. 625,243, filed November 30, 1956, which discloses the preparation of the dimethyl titanium dichloride and methyl titanium trichloride in catalytically active form by reaction of"bistcyclopentadienyl) dimethyl titanium with titanium tetrachloride and the use thereof as catalysts in the polymerization of olefins.
What I claim and desire to protect by Letters Patent is:
1. The method of producing dimethyl titanium dichloride which comprises reacting a material of the group consisting of titanium tetrachloride and methyl titanium trichloride with bis(cyclopentadienyl) dimethyl titanium at a temperature in the range of C. to 0 C.
2. The method of producing dimethyl titanium dichloride which comprises reacting titanium tetrachloride with less thanan equimolecular amount of bis(cyclopentadienyl) dimethyl titanium at. atemperature in the range of. 80 C.v to 0 C;, separatingtmethyl titanium trichloride so produced and reacting the methyl titanium trichloride witha further amount of bis(cyclopentadienyl) dimethyl titanium at a temperature in the range of 80 C. to 0 C. and separating dimethyl titanium dichloride.
3. The method of producing dimethyl titanium dichloride in admixture with methyl titanium trichloridewhich comprises reacting titanium tetrachloride with bis(cyclo pentadienyl) dimethyl titanium in a molecular ratio of between about 2:1 and about 1:1 at a temperature in therange of 80 C; to-O C. 7'
UNITED I STATES PATENTS Brown et al Dec. 31, 1957 Kozikowski Dec. 8, 1959
Claims (1)
1. THE METHOD OF PRODUCING DIMETHYL TITANIUM DICHLORIDE WHICH COMPRISES REACTING A MATERIAL OF THE GROUP CONSISTING OF TITANIUM TETCHLORIDE AND METHYL TITANIUM TRICHLORIDE WITH BIS(CLOPENTADIENYL) DIMETHYL TITANIUM AT A TEMPERATURE IN THE RANGE OF -80* C. TO 0* C.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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US862474A US3021349A (en) | 1959-12-29 | 1959-12-29 | Dimethyl titanium dichloride |
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US862474A US3021349A (en) | 1959-12-29 | 1959-12-29 | Dimethyl titanium dichloride |
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US3021349A true US3021349A (en) | 1962-02-13 |
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US862474A Expired - Lifetime US3021349A (en) | 1959-12-29 | 1959-12-29 | Dimethyl titanium dichloride |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3453241A (en) * | 1965-03-11 | 1969-07-01 | Agfa Gevaert Nv | Preparation of highly polymeric polyesters in the presence of organo-titanium catalysts |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2818416A (en) * | 1952-12-10 | 1957-12-31 | Ethyl Corp | Cyclomatic compounds |
US2916503A (en) * | 1956-10-31 | 1959-12-08 | Ethyl Corp | Friedel-crafts reaction with metal cyclopentadienyl compounds |
-
1959
- 1959-12-29 US US862474A patent/US3021349A/en not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2818416A (en) * | 1952-12-10 | 1957-12-31 | Ethyl Corp | Cyclomatic compounds |
US2916503A (en) * | 1956-10-31 | 1959-12-08 | Ethyl Corp | Friedel-crafts reaction with metal cyclopentadienyl compounds |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3453241A (en) * | 1965-03-11 | 1969-07-01 | Agfa Gevaert Nv | Preparation of highly polymeric polyesters in the presence of organo-titanium catalysts |
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