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

Patent metadata

Field	Value
Publication number	US-10100136-B2
Application number	US-201615371193-A
Country	US
Kind code	B2
Filing date	Dec 6, 2016
Priority date	Sep 24, 2012
Publication date	Oct 16, 2018
Grant date	Oct 16, 2018

Abstract

The present invention provides a solid organomagnesium precursor having formula {Mg(OR′)X}.a{MgX2}.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.

First claim

We claim:

1. A process for preparation of a catalyst composition, said process comprising:
(a) contacting a solution of transition metal compound represented by M(OR′″) p X 4-p , where M is a transition metal and is selected from the group consisting of Ti, V, Zr, and Hf; X is a halogen atom; R′″ is a hydrocarbon group and p is an integer having value equal or less than 4, with 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 to obtain a resulting solution, and contact temperature of solid organomagnesium precursor and the transition metal compound is between about −50° C. and about 150° C.;
(b) prior to step (a), adding an internal donor either to the solid organomagnesium precursor component or to the titanium component, and the contact time of the said component with the internal donor is immediate or is 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 a titanium component in a solvent and recovering a solid titanium catalyst component and maintaining the recovered solid titanium catalyst component at a temperature value in the range of 100 to 120° C. for about 10 to 60 minutes; and
(d) optionally repeating step (c) for a predetermined number of times and then washed sufficiently with inert solvent at temperature 20° C. to 80° C. to obtain a solid catalyst composition,
wherein the solid organomagnesium precursor is prepared by a 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 the 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 in step (a) the transition metal compound is added to the organomagnesium compound or organomagnesium compound is added to transition metal compound.

3. The process as claimed in claim 1 , wherein step (b) comprises adding organomagnesium precursor with internal donor.

4. The process as claimed in claim 1 , wherein transition metal is titanium metal.

5. The process as claimed in claim 1 , wherein the transition metal compound represented by M(OR′″) p X 4-p is selected from the group consisting of transition metal tetrahalide, alkoxy transition metal trihalide or aryloxy transition metal trihalide, dialkoxy transition metal dihalide, trialkoxy transition metal monohalide, tetraalkoxy transition metal, and mixtures thereof; wherein:
(a) the transition metal tetrahalide is selected from the group consisting of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, vanadium tetrachloride, vanadium tetrabromide, vanadium tetraiodide, zirconium tetrachloride, zirconium tetrabromide, zirconium tetraiodide, hafnium tetrachloride, hafnium tetrabromide, and hafnium tetraiodide;
(b) alkoxy transition metal trihalide or aryloxy transition metal trihalide is selected from the group consisting of methoxytitanium trichloride, ethoxytitanium trichloride, butoxytitanium trichloride, phenoxytitanium trichloride, methoxyvanadium trichloride, ethoxyvanadium trichloride, butoxyvanadium trichloride, phenoxyvanadium trichloride, methoxyzirconium trichloride, ethoxyzirconium trichloride, butoxyzirconium trichloride, phenoxyzirconium trichloride, methoxyhafnium trichloride, ethoxyhafnium trichloride, butoxyhafnium trichloride, and phenoxyhafnium trichloride;
(c) dialkoxy transition metal dihalide is selected from the group consisting of diethoxy titanium dichloride, diethoxy vanadium dichloride, diethoxy zirconium dichloride, and diethoxy hafnium dichloride;
(d) trialkoxy transition metal monohalide is selected from the group consisting of triethoxy titanium chloride, triethoxy vanadium chloride, triethoxy zirconium chloride, and triethoxy hafnium chloride; and
(e) tetraalkoxy transition metal is selected from the group consisting of tetrabutoxy titanium, tetraethoxy titanium, tetrabutoxy vanadium, tetraethoxy vanadium, tetrabutoxy zirconium, tetraethoxy zirconium, tetrabutoxy hafnium, and tetraethoxy hafnium.

6. The process as claimed in claim 1 , wherein the internal electron donor used is selected from the group consisting of phthalates, benzoates, succinates, malonates, carbonates, diethers, and combinations thereof; wherein:
(a) the phthalate is selected from the group consisting of di-n-butyl phthalate, di-i-butyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, di-i-octyl phthalate, di-n-nonyl phthalate;
(b) the benzoate is selected from the group consisting of methyl benzoate, ethyl benzoate, propyl benzoate, phenyl benzoate, cyclohexyl benzoate, methyl toluate, ethyl toluate, p-ethoxy ethyl benzoate, p-isopropoxy ethyl benzoate;
(c) the succinate is selected from the group consisting of diethyl succinate, di-propyl succinate, diisopropyl succinate, dibutyl succinate, diisobutyl succinate;
(d) the malonate is selected from the group consisting of diethyl malonate, diethyl ethylmalonate, diethyl propyl malonate, diethyl isopropylmalonate, diethyl butylmalonate;
(e) the carbonate compound is selected from the group consisting of diethyl 1,2-cyclohexanedicarboxylate, di-2-ethylhexyl 1,2-cyclohexanedicarboxylate, di-2-isononyl 1,2-cyclohexanedicarboxylate, methyl anisate, ethyl anisate; and
(f) the diether compound is selected from the group consisting of 9,9-bis(methoxymethyl)fluorene, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-diisopentyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclohexyl-1,3-dimethoxypropane.

7. The process as claimed in claim 1 , wherein in step (a) the contact of organomagnesium compound with titanium compound is either neat or in solvent.

8. The process as claimed in claim 1 , wherein in step (a) the solid organomagnesium compound is used as solid or in solvent.

9. The process as claimed in claim 7 , wherein the solvent is selected from the group consisting of chlorinated aromatic hydrocarbon, non chlorinated aromatic hydrocarbon chlorinated aliphatic hydrocarbon, non chlorinated aliphatic hydrocarbon and combination thereof.

10. The process as claimed in claim 7 , wherein the solvent is comprising from 5 to 95 volume percent and is selected from the group consisting of benzene, decane, kerosene, ethyl benzene, chlorobenzene, dichlorobenzene, toluene, o-chlorotoluene, xylene, dichloromethane, chloroform, cyclohexane and combination thereof.

11. The process as claimed in claim 1 , wherein in step (b) the internal electron donor is used in an amount of from 0.01 to 0.5 moles, with respect to one mole of magnesium.

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

• C08F4/16

  of silicon, germanium, tin, lead, titanium, zirconium or hafnium · CPC title

• C08F2/34

  Polymerisation in gaseous state · CPC title

• C07F3/02 Primary

  Magnesium compounds · CPC title

• C08F110/06 Primary

  Propene · CPC title

• C08F110/00

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