WO2002079209A1 - Titanocene synthesis - Google Patents
Titanocene synthesis Download PDFInfo
- Publication number
- WO2002079209A1 WO2002079209A1 PCT/US2002/004164 US0204164W WO02079209A1 WO 2002079209 A1 WO2002079209 A1 WO 2002079209A1 US 0204164 W US0204164 W US 0204164W WO 02079209 A1 WO02079209 A1 WO 02079209A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- titanium
- complex
- titanocene
- titanium trichloride
- reagent
- 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.)
- Ceased
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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
Definitions
- This invention relates to titanium-trihalide complexes free from contamination with salts of metals other than titanium. More particularly, the invention relates to the synthesis of such adducts and to the conversion thereof to titanocenes.
- BACKGROUND OF THE INVENTION Application Serial No. 09/784,736 describes a method for converting a Ti(IV) compound to a complex of a Ti(III) compound free of foreign metal contaminations .
- a preferred embodiment of the invention entails the reduction of TiCl 4 with particulate titanium in the presence of a reagent which forms a titanium trichloride complex insoluble in the reduction reaction mixture. According to that application, the consequent titanium trichloride complex may be converted to a titanocene in known manner. See, e.g., United States patent 6,218,557. SUMMARY OF THE INVENTION
- This invention provides methods for the conversion to titanocenes of the titanium trichloride complex as described in application Serial No. 09/784,736. DETAILED DESCRIPTION OF THE INVENTION
- the invention may comprise a first step in which a titanium trichloride complex free of contamination with salts of other metals is produced.
- a second step of this invention may comprise treatment of a ligand with the titanium trichloride complex product of the first step to produce a titanocene.
- One example illustrative of the first step is to charge a flask with particulate titanium ( ⁇ 100 mesh, 0.25 mole, 11.9 g) and dimethoxyethane (DME) (2 kg).
- Product is aluminum and magnesium free.
- the reduction reaction may optionally be conducted in a medium comprising the complex-forming reagent per se or in such combination with any non- interfering medium.
- Suitable media include aliphatic and aromatic hydrocarbons; aromatic hydrocarbons are preferred.
- Another aspect of the invention may include conversion of the Ti(III) complexes to metallocenes, which are also free of contamination with the salts of metals other than titanium, useful as olefin polymerization catalyst ligands, as olefin polymerization catalysts per se, or as components of olefin polymerization catalyst systems .
- EXAMPLE 2 This example is a general illustration of the second step of the invention. The TiCl 3 *DME complex as produced in Example 1 is used instead of the TiCl 3 per se in each or any of the relevant examples of United States patent 6,218,557 to produce a titanocene.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
A method for producing a titanocene wherein a TiCl3 complex free from salts of metals other than titanium is reacted with a titanocene ligand.
Description
TITANOCENE SYNTHESIS This application is a continuation of United States application Serial No. 09/880,289 filed 13 June 2001, which in turn is a continuation-in-part of United States application Serial No. 09/784,736 filed 15
February 2001 (now United States patent 6,307,063 Bl issued 23 October 2001) .
FIELD OF THE INVENTION This invention relates to titanium-trihalide complexes free from contamination with salts of metals other than titanium. More particularly, the invention relates to the synthesis of such adducts and to the conversion thereof to titanocenes.
BACKGROUND OF THE INVENTION Application Serial No. 09/784,736 describes a method for converting a Ti(IV) compound to a complex of a Ti(III) compound free of foreign metal contaminations . A preferred embodiment of the invention entails the reduction of TiCl4 with particulate titanium in the presence of a reagent which forms a titanium trichloride complex insoluble in the reduction reaction mixture. According to that application, the consequent titanium trichloride complex may be converted to a titanocene in known manner. See, e.g., United States patent 6,218,557.
SUMMARY OF THE INVENTION
This invention provides methods for the conversion to titanocenes of the titanium trichloride complex as described in application Serial No. 09/784,736. DETAILED DESCRIPTION OF THE INVENTION
The invention may comprise a first step in which a titanium trichloride complex free of contamination with salts of other metals is produced. A second step of this invention may comprise treatment of a ligand with the titanium trichloride complex product of the first step to produce a titanocene.
EXAMPLE 1
One example illustrative of the first step is to charge a flask with particulate titanium (~100 mesh, 0.25 mole, 11.9 g) and dimethoxyethane (DME) (2 kg).
With cooling slowly, add titanium tetrachloride (0.77 mole, 146.3 g) , maintaining temperature at 0°C. After addition is complete, slowly warm to reflux, and hold at reflux for 8 hours. Cool to room temperature and filter. The cake comprises a TiCl3*DME complex which is free of contamination with any salt of a metal other than titanium. Dry the cake in vacua. Yield = 246 g;
85%, based on total charge of titanium (both TiCl4 and particulate titanium) . Analysis:
Ti = 16.6% CI = 36.6%
Theoretical :
Ti = 16.5% CI = 36.7%
Product is aluminum and magnesium free.
As explained in United States application Serial No. 09/784,736, the reduction reaction may optionally be conducted in a medium comprising the complex-forming reagent per se or in such combination with any non- interfering medium. Suitable media include aliphatic and aromatic hydrocarbons; aromatic hydrocarbons are preferred.
Compounds which form a complex with Ti(III) compounds are known. See German patent application DE 197 39 946 Al published March 18, 1999. Each such complex-forming compound which yields a Ti(III) complex insoluble in the TiCl4 reduction reaction mixture is useful in this invention. Preferred complex-forming compounds are ethers, typically tetrahydrofuran (THF) and DME .
Another aspect of the invention may include conversion of the Ti(III) complexes to metallocenes, which are also free of contamination with the salts of metals other than titanium, useful as olefin polymerization catalyst ligands, as olefin polymerization catalysts per se, or as components of olefin polymerization catalyst systems .
EXAMPLE 2 This example is a general illustration of the second step of the invention. The TiCl3*DME complex as produced in Example 1 is used instead of the TiCl3 per se in each or any of the relevant examples of United States patent 6,218,557 to produce a titanocene.
Claims
1. In a process for producing a titanocene wherein a titanium trichloride reagent is reacted with a ligand to produce a titanocene, the improvement which comprises utilizing as said titanium trichloride reagent, a titanium trichloride complex produced by treatment of titanium tetrachloride with particulate titanium in the presence of a reagent which forms a titanium trichloride complex wherein a titanium trichloride complex free of contamination with a salt of a metal other than titanium is produced.
2. The process of claim 1 wherein said treating is conducted in a non-interfering medium in which said titanium trichloride complex is insoluble.
3. The process of claim 1 wherein said treatment is accomplished in a medium which forms a titanium chloride complex.
4. The process of claim 1 wherein said treatment is accomplished in a medium comprising dimethoxyethane or tetrahydrofuran .
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002577833A JP2004519517A (en) | 2001-02-15 | 2002-02-13 | Titanocene synthesis |
| EP02724934A EP1360188A4 (en) | 2001-02-15 | 2002-02-13 | Titanocene synthesis |
| CA002405989A CA2405989A1 (en) | 2001-02-15 | 2002-02-13 | Titanocene synthesis |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/784,736 US6307063B1 (en) | 2001-02-15 | 2001-02-15 | Conversion of compounds of titanium in a plus 4 oxidation state to titanium compounds in a plus 3 oxidation state |
| US09/784,736 | 2001-02-15 | ||
| US09/880,289 US6444835B1 (en) | 2001-02-15 | 2001-06-13 | Titanocene synthesis |
| US09/880,289 | 2001-06-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2002079209A1 true WO2002079209A1 (en) | 2002-10-10 |
Family
ID=27120329
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US2002/004164 Ceased WO2002079209A1 (en) | 2001-02-15 | 2002-02-13 | Titanocene synthesis |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP1360188A4 (en) |
| JP (1) | JP2004519517A (en) |
| CA (1) | CA2405989A1 (en) |
| WO (1) | WO2002079209A1 (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5264950A (en) * | 1992-01-06 | 1993-11-23 | Kent State University | Light modulating device with polarizer and liquid crystal interspersed as spherical or randomly distorted droplets in isotropic polymer |
| US5367085A (en) * | 1993-09-20 | 1994-11-22 | Albemarle Corporation | Preparation of TiCl3 coordination complexes |
| DE19739946A1 (en) * | 1997-09-11 | 1999-03-18 | Targor Gmbh | Process for the production of metallocenes |
| US6093833A (en) * | 1999-01-14 | 2000-07-25 | Akzo Nobel N.V. | Process for producing trivalent titanium coordination complex |
| US6218557B1 (en) * | 1996-11-22 | 2001-04-17 | Boulder Scientific Company | Synthesis of titanocenes |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU941294A1 (en) * | 1980-04-18 | 1982-07-07 | Донецкий Ордена Трудового Красного Знамени Политехнический Институт | Process for producing titanium trichloride |
-
2002
- 2002-02-13 WO PCT/US2002/004164 patent/WO2002079209A1/en not_active Ceased
- 2002-02-13 EP EP02724934A patent/EP1360188A4/en not_active Withdrawn
- 2002-02-13 CA CA002405989A patent/CA2405989A1/en not_active Abandoned
- 2002-02-13 JP JP2002577833A patent/JP2004519517A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5264950A (en) * | 1992-01-06 | 1993-11-23 | Kent State University | Light modulating device with polarizer and liquid crystal interspersed as spherical or randomly distorted droplets in isotropic polymer |
| US5367085A (en) * | 1993-09-20 | 1994-11-22 | Albemarle Corporation | Preparation of TiCl3 coordination complexes |
| US5367085B1 (en) * | 1993-09-20 | 1997-02-25 | Albermarle Corp | Preparation of TiCl3 coordination complexes |
| US6218557B1 (en) * | 1996-11-22 | 2001-04-17 | Boulder Scientific Company | Synthesis of titanocenes |
| DE19739946A1 (en) * | 1997-09-11 | 1999-03-18 | Targor Gmbh | Process for the production of metallocenes |
| US6093833A (en) * | 1999-01-14 | 2000-07-25 | Akzo Nobel N.V. | Process for producing trivalent titanium coordination complex |
Non-Patent Citations (1)
| Title |
|---|
| See also references of EP1360188A4 * |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1360188A1 (en) | 2003-11-12 |
| EP1360188A4 (en) | 2007-03-07 |
| JP2004519517A (en) | 2004-07-02 |
| CA2405989A1 (en) | 2002-10-10 |
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