Precursor for catalyst, process for preparing the same and its use thereof

Patent metadata

Field	Value
Publication number	US-9890229-B2
Application number	US-201314416611-A
Country	US
Kind code	B2
Filing date	Sep 24, 2013
Priority date	Sep 24, 2012
Publication date	Feb 13, 2018
Grant date	Feb 13, 2018

Abstract

The present invention provides a liquid 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 0.1-99.8:0.1-99.8:0.1-99.8, and a process for preparing the same. The said process comprises contacting a magnesium source with an organohalide and alcohol in a solvent to form the liquid organomagnesium precursor. The present invention also provides a catalyst system using the organomagnesium precursor and its use thereof for polymerization of olefins. An illustrative example of the claimed process to make the organomagnesium precursor is: At 25° C., magnesium (powder or turnings) is added to organohalide, followed by alcohol in toluene. After heating to 90° C. and keeping there for 6 h the solution became viscous.

First claim

What is claimed Is:

1. A process for preparation of a liquid 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 0.1-99.8:0.1-99.8:0.1-99.8, said process comprising:
contacting a magnesium source with an organohalide and an alcohol in a solvent to form the organomagnesium precursor,
wherein the liquid organomagnesium precursor is synthesized through a single step.

2. The process as claimed in claim 1 , wherein the magnesium source is selected from the group consisting of magnesium metal, dialkyl magnesium, alkyl/aryl magnesium halides and mixtures thereof; wherein:
(a) the magnesium metal is in form of powder, ribbon, turnings, wire, granules, block, lumps, chips;
(b) the dialkylmagnesium compounds is selected from the group consisting of dimethylmagnesium, diethylmagnesium, diisopropylmagnesium, dibutylmagnesium, dihexylmagnesium, dioctylmagnesium, ethylbutylmagnesium, and butyloctylmagnesium; and
(c) alkyl/aryl magnesium halides is selected from the group consisting 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.

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

4. The process as claimed in claim 1 , wherein the organohalide is selected from the group consisting of alkyl halides either branched or linear, 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 the group consisting of methyl chloride, ethyl chloride, propyl chloride, isopropyl chloride, dichloromethane, chloroform, carbon tetrachloride, 1,1-dichloropropane, 1,2-dichloropropane, 1,3-dichloropropane, 2,3 -dichloropropane, n-butyl chloride, iso-butyl chloride, 1,4-dichlorobutane, tert-butylchloride, amylchloride, tert-amyl chloride, 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 the group consisting of benzyl chloride and α,α′ dichloro xylene.

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

6. The process as claimed in claim 1 , wherein the alcohol is selected from the 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 the group consisting of methanol, ethanol, propanol, n-butanol, iso-butanol, t-butanol, n-pentanol, iso-pentanol, n-hexanol , 2-methylpentanol, 2-ethylbutanol, n-heptanol, n-octanol, 2-ethylhexanol, decanol and dodecanol,
(b) the alicyclic alcohols is selected from the group consisting of cyclohexanol and methylcyclohexanol,
(c) the aromatic alcohols is selected from the group consisting of benzyl alcohol and methylbenzyl alcohol,
(d) the aliphatic alcohols containing an alkoxy group is selected from the group consisting of ethyl glycol and butyl glycol;
(e) the diols is selected from the group consisting 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.

7. The process as claimed in claim 1 , wherein the solvent is selected from the group consisting of a polar aromatic solvent, non-polar aromatic solvent, polar aliphatic solvent and a non-polar aliphatic solvent.

8. The process as claimed in claim 1 , wherein the solvent is selected from the group consisting of benzene, decane, kerosene, ethyl benzene, chlorobenzene, dichlorobenzene, toluene, o-chlorotoluene, xylene, dichloromethane, chloroform, cyclohexane and the like and their mixtures thereof.

9. The process as claimed in claim 1 , wherein the solvent is toluene or chlorobenzene or their mixture.

10. 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.

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

12. The process as claimed in claim 1 , wherein the magnesium source, organohalide, and alcohol compound in the solvent are contacted at temperature between about 0° C. and about 150° C., and the contact time is for about 0.5 to 12 h for the formation of a homogeneous solution of magnesium component in alcohol.

13. The process as claimed in claim 1 , further comprises a reaction promoter, which is selected from the group consisting of iodine, the organohalides, inorganic halides, nitrogen halides, ethers and mixture thereof; wherein:
(a) the inorganic halide is selected from the group consisting of CuCl, MnCl 2, and AgCl;
(b) the nitrogen halide is selected from the group consisting of N-halide succinimide, trihaloisocynauric acid, N-halophthalimide and hydrantoin compound; and
(c) the ether is selected from the group consisting of diethyl ether, dibutyl ether, t-butyl methyl ether, tetrahydrofuran, and dioxane.

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

15. The process as claimed in claim 1 , wherein the organomagnesium precursor is used for making olefin polymerization catalyst system without any further purification or isolation.

16. An 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 0.1-99.8:0.1-99.8:0.1-99.8.

17. A process for preparation of a catalyst composition, said process in a reaction system comprising:
(a) contacting titanium compound represented by M(OR′″) p X 4-p , where M is a transition metal and is Ti; X is a halogen atom; R′″ is a hydrocarbon group and p is an integer having value equal or less than 4 with a solution of 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 0.1-99.8:0.1-99.8:0.1-99.8, to obtain a resulting solution and the contact temperature of the organomagnesium precursor and the titanium compound is between about −50° C. and about 150° C.
(b) adding an internal donor before the step (a) either to the organomagnesium precursor or to the titanium compound and the contact time of the organomagnesium precursor or the titanium compound with the internal electron donor is either immediate or at least 1 minutes to 60 minutes at contact temperature of between about −50° C. and about 100° C.;
(c) treating the resulting solution obtained in the step (a) with a solution comprising nea

Assignees

• Indian Oil Corp Ltd

Inventors

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

Classifications

• B01J21/10

  Magnesium; Oxides or hydroxides thereof · CPC title

• C08F110/00

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

• C08F110/06 Primary

  Propene · CPC title

• C07F7/003

  without C-Metal linkages · CPC title

• B01J21/063

  Titanium; Oxides or hydroxides thereof · CPC title