Ziegler-Natta catalyst system with self-extinguishing properties suitable for olefin polymerization

Patent metadata

Field	Value
Publication number	US-11613592-B2
Application number	US-201916967286-A
Country	US
Kind code	B2
Filing date	Feb 7, 2019
Priority date	Feb 7, 2018
Publication date	Mar 28, 2023
Grant date	Mar 28, 2023

Abstract

The present disclosure relates to a Ziegler-Natta catalyst system with self-extinguishing properties suitable for olefin polymerization. The catalyst system of the present disclosure comprises a pro-catalyst, a co-catalyst, and an external donor having a mixture of a selectivity control agent and an activity control agent. The catalyst system of the present disclosure is adapted to prevent the temperature of the polymerization reaction to go beyond the softening temperature of the polymer, thereby exhibiting the self-extinguishing properties.

First claim

The invention claimed is:

1. A Ziegler-Natta catalyst system with self-extinguishing properties suitable for olefin polymerization, said catalyst system being characterized by having a fluorinated ester of a long chain fatty acid with C 4 -C 20 carbon atoms as an activity limiting agent.

2. The Ziegler-Natty catalyst system as claimed in claim 1 , wherein said activity limiting agent is a fluorinated ester of a long chain fatty acid with C 4 -C 20 carbon atoms having the following formula:

3. The Ziegler-Natta catalyst system as claimed in claim 2 , wherein said activity limiting agent is a fluorinated ester of a long chain fatty acid selected from the group consisting of trifluoro ethyl myristate and trifluoro ethyl palmitate.

4. The Ziegler-Natta catalyst system as claimed in claim 1 , wherein a selectivity control agent is mixed with said activity limiting agent in a weight ratio in the range of 1:5 to 1:10.

5. The Ziegler-Natta catalyst system with self-extinguishing properties suitable for olefin polymerization as claimed in claim 1 , wherein said catalyst system comprises:
a. a pro-catalyst comprising a magnesium compound, a titanium compound, and an internal donor;
b. an organo-aluminum co-catalyst; and
c. an external donor being a mixture of a selectivity control agent and said activity limiting agent as claimed in claim 1 .

6. The Ziegler-Natta catalyst system as claimed in claim 5 , wherein said internal donor is at least one compound selected from the group consisting of monoester, diester, diether, carbonate, urea, thiourea, ether-ester, succinates, malonates, and diisobutyl phthalate.

7. The Ziegler-Natta catalyst system as claimed in claim 5 , wherein said selectivity control agent is at least one silane compound selected from the group consisting of dicyclopentyldimethoxysilane, methylcyclohexyldimethoxysilane, diisopropyldimethoxysilane methylcyclohexyldiethoxysilane, di-n-butyl-dimethoxysilane, and dimethyidimethoxysilane.

8. The Ziegler-Natta catalyst system as claimed in claim 5 , wherein said titanium compound is at least one selected from the group consisting of titanium tetrachloride, titanium trichloride, titanium dichloride, and elemental titanium.

9. The Ziegler-Natty catalyst system as claimed in claim 5 , wherein said magnesium compound is at least one selected from the group consisting of magnesium halide, magnesium oxide, magnesium hydroxyl halides, and magnesium salts of inorganic oxygen containing acids.

10. The Ziegler-Natty catalyst system as claimed in claim 5 , wherein the organo-aluminum co-catalyst is at least one selected from the group consisting of triethylaluminum, tridecylaluminum, tri-n-butylaluminum, tri-isopropylaluminum, tri-isoprenylaluminum, triisobutylaluminum, ethyl aluminum sesquichloride, diethylaluminum chloride, di-isobutyl aluminum chloride, triphenylaluminum, tri-n-octylaluminum and tri-ndecylaluminum.

11. The Ziegler-Natta catalyst system as claimed in claim 5 , wherein the mole ratio of said co-catalyst to said titanium is in the range of 50:1 to 500:1.

12. The Ziegler-Natta catalyst system as claimed in claim 5 , wherein the mole ratio of said co-catalyst to said selectivity control agent is in the range of 2:1 to 50:1.

13. The Ziegler-Natta catalyst system as claimed in claim 5 , wherein the mole ratio of said co-catalyst to said activity control agent is in the range of 2:1 to 10:1.

14. The Ziegler-Natta catalyst system as claimed in claim 5 , wherein the self-extinguishing property of said catalyst system is triggered at a temperature in the range from 86° C. to 78° C.

15. The Ziegler-Natta catalyst system as claimed in claim 5 , includes nonpolar fluid medium, wherein said non-polar fluid medium is selected from hexane and heptane.

16. A process for in situ preparation of a Ziegler Natta Catalyst system as claimed in claim 1 suitable for olefin polymerization, said process comprising the following steps:
i. charging a reactor with a hydrocarbon fluid medium and a predetermined amount of a pro-catalyst comprising a magnesium compound, a titanium compound, and an internal donor, under inert atmosphere, to obtain a pro-catalyst slurry;
ii. adding a predetermined amount of an external donor being a mixture of a selectivity control agent and a fluorinated ester of a long chain fatty acid with C4-C20 carbon atoms as an activity limiting agent in said pro-catalyst slurry to obtain a First slurry; and
iii. adding an organo-aluminum co-catalyst in said first slurry to obtain said Ziegler Natta Catalyst system.

17. The process for olefin polymerization using said Ziegler Natta Catalyst system as claimed in claim 16 , said process comprises introducing an olefin into the reactor containing said Ziegler Natta Catalyst system to attain an olefin pressure in the range of 1 kg/cm2 to 10 kg/cm2 to obtain a reaction mixture; and subjecting said olefin to polymerization by beating said reaction mixture at a temperature in the range of 40° C. to 75° C. under stirring for a time period in the range of 1 hour to 5 hours to obtain a product mixture comprising polymer.

18. The process as claimed in claim 17 , wherein said olefin is selected from the group consisting of propylene and ethylene.

Assignees

• Reliance Industries Ltd

Inventors

• Gupta Virendrakumar
• Grubbs Robert
• Dhamaniya Sunil

Classifications

• C08F110/02

  Ethene · CPC title

• C08F10/06

  Propene · CPC title

• C08F2/38

  Polymerisation using regulators, e.g. chain terminating agents {, e.g. telomerisation} · CPC title

• C08F110/06 Primary

  Propene · CPC title

• C08F4/6494

  containing oxygen · CPC title