Organometallic compound in solid form, process for preparing the same and use thereof

Patent metadata

Field	Value
Publication number	US-9587041-B2
Application number	US-201314416609-A
Country	US
Kind code	B2
Filing date	Sep 24, 2013
Priority date	Sep 24, 2012
Publication date	Mar 7, 2017
Grant date	Mar 7, 2017

Abstract

The present invention provides a solid organomagnesium precursor having formula {Mg(OR′)X}.a{MgX 2 }.b{Mg(OR′) 2 }.c{R′OH}, wherein R′ is selected from a hydrocarbon group, X is selected from a halide group, and a:b:c is in range of 0.01-0.5:0.01-0.5:0.01-5 and process for preparing the same, said process comprising contacting a magnesium source with a solvating agent, an organohalide and an alcohol to obtain the solid organomagnesium precursor. The present invention also provides a process for preparing a catalyst system using the organomagnesium precursor and its use thereof for polymerization of olefins. The organomagnesium precursor is prepared as follows: At 0° C., magnesium in diethyl ether is reacted with the organohalide. After all magnesium has reacted, the calculated amount of alcohol was added and after the completion of addition, the ether was evaporated and a solid compound obtained.

First claim

We claim:

1. A process for preparation of a solid organomagnesium precursor having formula {Mg(OR′) X}.a{MgX 2 }.b{Mg(OR′) 2 }.c{R′OH}, wherein R′ is same and is selected from a hydrocarbon group, X is selected from a halide group, and a:b:c is in range of 0.01-0.5:0.01-0.5:0.01-5, said process comprising contacting a magnesium source with a solvating agent, an organohalide and an alcohol to obtain the solid organomagnesium precursor,
wherein the solvating agent is selected from a group consisting of dimethyl ether, diethyl ether, dipropyl ether, diisopropyl ether, ethylmethyl ether, n-butylmethyl ether, n-butylethyl ether, di-n-butyl ether, di-isobutyl ether, isobutylmethyl ether, and isobutylethyl ether, dioxane, tetrahydrofuran, 2-methyl tetrahydrofuran, tetrahydropyran and combination thereof.

2. The process as claimed in claim 1 , wherein the process is carried out in a single step or multiple steps.

3. The process as claimed in claim 1 , wherein the alcohol is added after the reaction of magnesium source with solvating agent and organohalide.

4. The process as claimed in claim 1 , wherein the organohalide is added after the reaction of magnesium with solvating agent followed by addition of alcohol.

5. The process as claimed in claim 1 , wherein a mixture or the organohalide and alcohol is added after the reaction of magnesium with solvating agent.

6. The process as claimed in claim 1 , wherein the solid organomagnesium precursor is stable.

7. The process as claimed in claim 6 , wherein the solid organomagnesium precursor is stable and isolated from the solvating agent either using reduced pressure with or without heating, through precipitation or recrystallization.

8. The process as claimed in claim 7 , wherein, the precipitated solid organomagnesium precursor is either used directly or in solution form for catalyst synthesis.

9. The process as claimed in claim 7 , wherein the precipitated solid is dissolved in a solvent to obtain a solution form of precipitated solid.

10. The process as claimed in claim 7 , wherein the solvent used for dissolving precipitated solid is selected from a group comprising of polar aliphatic hydrocarbons, non polar aliphatic hydrocarbons, polar aromatic hydrocarbons, non polar aromatic hydrocarbons and combination thereof.

11. The process as claimed in claim 7 , wherein a precipitation methodology is adopted during any stage of precursor synthesis.

12. The process as claimed in claim 7 , wherein the precipitated solid organomagnesium precursor is obtained by either reacting magnesium with organic halide in a solvating agent followed by precipitation in the mixture of alcohol and precipitating solvent, or by reacting magnesium with organic halide in solvating agent followed by addition of alcohol and then precipitating in precipitating solvent.

13. The process as claimed in claim 1 , wherein the magnesium source is selected from a group consisting of magnesium metal, dialkyl magnesium, alkyl/aryl magnesium halides and mixtures thereof; wherein:
(a) the magnesium metal is in form of powder, granules, ribbon, turnings, wire, block, lumps, chips;
(b) the dialkylmagnesium compounds is selected from a group comprising of dimethylmagnesium, diethylmagnesium, diisopropylmagnesium, dibutylmagnesium, dihexylmagnesium, dioctylmagnesium, ethylbutylmagnesium, and butyloctylmagnesium; and
(c) alkyl/aryl magnesium halides is selected from a group comprising of methylmagnesium chloride, ethylmagnesium chloride, isopropylmagnesium chloride, isobutylmagnesium chloride, tert-butylmagnesium chloride, benzylmagnesium chloride, methylmagnesium bromide, ethylmagnesium bromide, isopropylmagnesium bromide, isobutylmagnesium bromide, tert-butylmagnesium bromide, hexylmagnesium bromide, benzylmagnesium bromide, methylmagnesium iodide, ethylmagnesium iodide, isopropylmagnesium iodide, isobutylmagnesium iodide, tert-butylmagnesium iodide, and benzylmagnesium iodide.

14. The process as claimed in claim 1 , wherein the magnesium source is magnesium metal.

15. The process as claimed in claim 1 , wherein the organohalide is selected from a group consisting of alkyl halides, halogenated alkyl benzene/benzylic halides having an alkyl radical contains from about 10 to 15 carbon atoms and mixtures thereof; wherein:
(a) the alkyl halides is selected from a group comprising of methyl chloride, ethyl chloride, propyl chloride, isopropyl chloride, 1,1-dichloropropane, 1,2-dichloropropane, 1,3-dichloropropane, 2,3-dichloropropane, butyl chloride, 1,4-dichlorobutane, tert-butylchloride, amylchloride, tert-amylchloride, 2-chloropentane, 3-chloropentane, 1,5-dichloropentane, 1-chloro-8-iodoctane, 1-chloro-6-cyanohexane, cyclopentylchloride, cyclohexylchloride, chlorinated dodecane, chlorinated tetradecane, chlorinated eicosane, chlorinated pentacosane, chlorinated triacontane, iso-octylchloride, 5-chloro-5-methyl decane, 9-chloro-9-ethyl-6-methyl eiscosane; and
(b) the halogenated alkyl benzene/benzylic halides is selected from a group comprising of benzyl chloride and α,α′ dichloro xylene.

16. The process as claimed in claim 1 , wherein the organohalide is benzyl chloride or butyl chloride or their mixture.

17. The process as claimed in claim 1 , wherein the solvating agent is diethyl ether or tetrahydrofuran or their mixture.

18. The process as claimed in claim 1 , wherein the alcohol is selected from a group consisting of aliphatic alcohols, alicyclic alcohols, aromatic alcohols, aliphatic alcohols containing an alkoxy group, diols and mixture thereof; wherein:
(a) the aliphatic alcohols is selected from a group comprising of methanol, ethanol, propanol, butanol, iso-butanol, t-butanol, n-pentanol, iso-pentanol, hexanol, 2-methylpentanol, 2-ethylbutanol, n-heptanol, n-octanol, 2-ethylhexanol, decanol and dodecanol,
(b) the alicyclic alcohols is selected from a group comprising of cyclohexanol and methylcyclohexanol,
(c) the aromatic alcohols is selected from a group comprising of benzyl alcohol and methylbenzyl alcohol,
(d) the aliphatic alcohols containing an alkoxy group is selected from a group comprising of ethyl glycol and butyl glycol;
(e) the diols is selected from a group comprising of catechol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,8-octanediol, 1,2-propanediol, 1,2-butanediol, 2,3-butanediol, 1,3-butanediol, 1,2-pentanediol, p-menthane-3,8-diol, and 2-methyl-2,4-pentanediol.

19. The process as claimed in claim 1 , wherein the magnesium source is reacted with the organohalide in a molar ratio of between 1:20 to 1:0.2.

20. The process as claimed in claim 1 , wherein the magnesium source and solvating agent in a molar ratio of between 1:20 to 1:0.2.

21. The process as claimed in claim 1 , wherein the magnesium source, organohalide, and solvating agent are contacted at temperature between about −20° C. and about 200° C. and contact time is for about 0.5 to 12 h for the formation of a homogeneous solution of magnesium component in solvating agent.

22. The process as claimed in claim 1 , optionally required a reaction promoters, which is selected from a group consisting of iodine, the organohalides, inorganic halides, nitrogen halides, and mixture thereof; wherein:
(a) the inorganic halides is selected from a group comprising of CuCl, MnCl 2 , and AgCl; and
(b) the nitrogen halides is selected from a group comprising of N-halide succinimides, trihaloisocynauric acid, N-halophthalimide and hydrantoin compounds.

23. A solid or

Assignees

• Indian Oil Corp Ltd

Inventors

• Kaur Sukhdeep
• Singh Gurmeet
• Bantu Bhasker
• Kumar Naresh
• Kapur Gurpreet Singh
• Kant Shashi
• Basu Biswajit
• Malhotra Ravinder Kumar

Classifications

• C08F110/06 Primary

  Propene · CPC title

• C08F110/00

  Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond · CPC title

• C08F4/6541 Primary

  and metals of C08F4/64 or compounds thereof · CPC title

• C07F3/02 Primary

  Magnesium compounds · CPC title

• C08F2/34

  Polymerisation in gaseous state · CPC title