Catalyst process modification and polymerization thereof

Patent metadata

Field	Value
Publication number	US-9873752-B2
Application number	US-201615007095-A
Country	US
Kind code	B2
Filing date	Jan 26, 2016
Priority date	Jan 27, 2015
Publication date	Jan 23, 2018
Grant date	Jan 23, 2018

Abstract

The present invention describes a process for preparation of catalyst component comprising contacting magnesium based precursor along with an internal donor based on phenylene dioates with an acyl halides in a solvent to obtain a solid precatalyst component; and contacting the solid precatalyst component with transition metal compound to obtain the catalyst component. The present invention also relates to a process for preparation of a catalyst system from said catalyst component and preparation of a polyolefins having free flowing characteristics with bulk densities (BD) of at least about 0.3 g/cc from the catalyst system.

First claim

We claim:

1. A process for the preparation of a catalyst component comprising:
(i) contacting magnesium based precursor along with an internal donor based on phenylene dioates with an acyl halide in a solvent to obtain, without the addition of a transition metal halide, a solid precatalyst component; and
(ii) contacting the solid precatalyst component with a transition metal compound to obtain the catalyst component.

2. The process of claim 1 , wherein the magnesium based precursor is liquid in nature and is prepared by contacting magnesium source with an organohalide and an alcohol in presence of a solvent in a single step.

3. The process of claim 1 , wherein the magnesium based precursor is solid in nature and is prepared by first contacting the magnesium source with an organohalide in presence of a solvating agent as the first step and then followed by the addition of an alcohol.

4. The process of claim 1 , wherein the internal donor based on phenylene dioates has the following structure (A)

wherein R 1 -R 6 groups are equal or different from each other and each of R 1 -R 6 are selected from the group consisting of hydrogen, halogen, C 1 -C 20 linear or branched alkyl group optionally linked with cyclic rings, C 6 -C 14 aryl groups, C 3 -C 15 cycloalkyl groups, C 1 -C 20 alkoxy group, a heteroatom, and combinations thereof.

5. The process of claim 4 , wherein in the structure (A), at least one of R 3 -R 6 is selected from the group consisting of hydrogen, halogen, C 1 -C 20 linear or branched alkyl group optionally linked with cyclic ring, C 6 -C 14 aryl groups, C 3 -C 15 cycloalkyl groups, C 1 -C 20 alkoxy group, a heteroatom, and combinations thereof and at least one of R 1 -R 2 selected from a group comprising of hydrogen, halogen, C 1 -C 20 linear or branched alkyl group optionally linked with cyclic ring, C 3 -C 15 cycloalkyl groups, a heteroatom, and combinations thereof.

6. The process of claim 1 , further comprising the addition of another internal donor selected from the group consisting of phthalates, benzoates, diethers, succinates, malonates, carbonates, silyl esters, amide esters and combinations thereof.

7. The process of claim 1 , wherein the acyl halide is represented by RCOX where R is H, C 1 -C 20 is linear or branched alkyl group which optionally linked with cyclic rings, C 6 -C 14 aryl groups, C 3 -C 15 cycloalkyl groups, C 1 -C 20 alkoxy group, optionally containing heteroatom and X is selected from halides.

8. The process of claim 1 , wherein the molar ratio of magnesium to acyl halide is in the range of 1:5 to 1:0.0001.

9. The process of claim 1 , wherein the solvent is aromatic or aliphatic and polar or non polar in nature and selected from the group consisting of benzene, decane, kerosene, ethyl benzene, chlorobenzene, dichlorobenzene, toluene, o-chlorotoluene, xylene, dichloromethane, chloroform, cyclohexane and combination thereof.

10. The process of claim 1 , wherein the contact time of the step (i) is immediate to 5 h, and heated to a temperature within the range of 10° C. to 200° C.

11. The process of claim 1 , wherein the magnesium based precursor is contacted first with the internal donor followed by the contact of the acyl halide or magnesium based precursor is first contacted with the acyl halide followed by the contact with internal donor or the internal donor is mixed with the acyl halide and then contacted with the magnesium precursor in presence of the solvent.

12. The process of claim 1 , wherein the solid precatalyst component is isolated.

13. The process of claim 1 , wherein the transition metal compound is selected from compounds 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 to or less than 4, the transition metal halide is selected from the group consisting of transition metal tetrahalide, alkoxy transition metal trihalide/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 and titanium tetraiodide and the likes for V, Zr and Hf;
(b) alkoxy transition metal trihalide/aryloxy transition metal trihalide is selected from the group consisting of methoxytitanium trichloride, ethoxytitanium trichloride, butoxytitanium trichloride and phenoxytitanium trichloride and the likes for V, Zr and Hf;
(c) dialkoxy transition metal dihalide is diethoxy transition metal dichloride and the likes for V, Zr and Hf;
(d) trialkoxy transition metal monohalide is triethoxy transition metal chloride and the likes for V, Zr and Hf; and
(e) tetraalkoxy transition metal is selected from the group consisting of tetrabutoxy titanium and tetraethoxy titanium and the likes for V, Zr and Hf.

14. The process of claim 1 , wherein the solid precatalyst component is contacted with the transition metal compound at a temperature in the range of −50° C. to 150° C., and is then heated at a rate of 0.1 to 10.0° C./minute.

15. The process of claim 1 , wherein the transition metal compound is added in amounts ranging from 1 to 20 moles with respect to one mole of magnesium.

16. The process of claim 1 , wherein the contact with transition metal compound is either neat or in solvent, and 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.

17. The process of claim 16 , wherein the solvent is comprising from 40 to 60 volume percent and selected from the group consisting of benzene, decane, kerosene, ethyl benzene, chlorobenzene, dichlorobenzene, toluene, o-chlorotoluene, xylene, dichloromethane, chloroform, cyclohexane and combination thereof.

18. The process of claim 1 , further comprising, repeating the contacting step (ii), one or more times for at least 10 minutes up to 60 minutes, at a temperature from about 25° C. to about 150° C.

19. The process of claim 18 , wherein acyl halides is added prior to each contacting step (ii) and said addition of acyl halides is carried out for immediate to 30 min.

20. A process for preparation of a catalyst system, said process comprising contacting the catalyst composition as obtained by claim 1 with at least one cocatalyst, and at least one external electron donor to obtain the catalyst system.

21. A process of polymerizing and/or copolymerizing olefins to obtain a polyolefins having bulk densities (BD) of at least about 0.3 g/cc, said process comprising the step of contacting an olefin having C 2 to C 20 carbon atoms under a polymerizing condition with the catalyst system as obtained by claim 20 .

Assignees

• Indian Oil Corp Ltd

Inventors

• Singh Gurmeet
• Bantu Bhasker
• Kaur Sukhdeep
• Kumar Naresh
• Negi Mahender Singh
• MOMIN Mohasin
• Rani Rashmi
• Kapur Gurpreet Singh
• Shashikant

Classifications

• C08F110/06 Primary

  Propene · CPC title

• C08F2500/12

  Melt flow index or melt flow ratio · CPC title

• C08F4/6546

  organo-magnesium compounds · CPC title

• C08F4/6465

  containing silicium · CPC title

• C08F10/06 Primary

  Propene · CPC title