Heterogeneous Ziegler-Natta catalyst composition, a process for its preparation and a process for polymerizing olefin using the same

Patent metadata

Field	Value
Publication number	US-10544243-B2
Application number	US-201515114490-A
Country	US
Kind code	B2
Filing date	Feb 16, 2015
Priority date	Feb 17, 2014
Publication date	Jan 28, 2020
Grant date	Jan 28, 2020

Abstract

The present disclosure provides a Ziegler-Natta catalyst composition for preparing polymers of ethylene monomers having ultrahigh molecular weight, said composition comprises (i) a pro-catalyst component containing a reaction product of a magnesium containing compound and a titanium containing compound, characterized in that said pro-catalyst component comprises magnesium, titanium and chlorine in an amount ranging between 15 and 18 mole %; 20 and 23 mole %; and 60 and 64 mole %, respectively, all proportions being with respect to the total weight of the Ziegler-Natta catalyst composition; (ii) a co-catalyst component; and (iii) at least one external electron donor compound selected from the group of organosilane compounds having the general formula (I), wherein R 1 , R 2 , R 3 and R 4 are all the same or all are different, or some are the same, and are individually selected from the group consisting of linear or branched alkyl groups, cycloalkyl groups, aryl groups, alkoxy and aryloxy groups.

First claim

The invention claimed is:

1. A Ziegler-Natta catalyst composition for preparing polymers of ethylene monomers having ultrahigh molecular weight, said composition comprising:
i. a pro-catalyst component containing a reaction product of a magnesium containing compound and a titanium containing compound, wherein said pro-catalyst component comprises magnesium, titanium and chlorine in an amount ranging between 15 and 18 mole %; 20 and 23 mole %; and 60 and 64 mole %, respectively, all proportions being with respect to the pro-catalyst component;
ii. a co-catalyst component comprising at least one organoaluminum compound; and
iii. at least one external electron donor compound selected from the group of organosilane compounds having the general formula (I),

wherein R 1 , R 2 , R 3 and R 4 are all the same, or all are different, or some are the same, and are individually selected from the group consisting of linear or branched alkyl groups, cycloalkyl groups, aryl groups, alkoxy and aryloxy groups,
wherein the aluminum to titanium molar ratio ranges from 50:1 to 100:1.

2. The Ziegler-Natta catalyst composition as claimed in claim 1 , wherein the molar ratio of magnesium, titanium and chlorine is 1:1.3:3.7.

3. The Ziegler-Natta catalyst composition as claimed in claim 1 , wherein the co-catalyst component is at least one compound selected from the group consisting of methylaluminoxane, triisobutylaluminoxane, ethylaluminoxane, and polymethylaluminoxane.

4. The Ziegler-Natta catalyst composition as claimed in claim 1 , wherein said magnesium containing compound is at least one compound selected from the group consisting of magnesium halides, magnesium alkoxides, magnesium aryloxides, magnesium oxides, magnesium oxyhalides and magnesium salts of inorganic acids.

5. The Ziegler-Natta catalyst composition as claimed in claim 1 , wherein said magnesium containing compound is a compound selected from magnesium ethoxide and magnesium chloride.

6. The Ziegler-Natta catalyst composition as claimed in claim 1 , wherein said titanium containing compound is at least one compound selected from the group consisting of titanium halides, titanium alkoxides, titanium aryloxide, titanium oxides and titanium halo oxides.

7. The Ziegler-Natta catalyst composition as claimed in claim 1 , wherein said titanium containing compound is titanium tetrachloride.

8. The Ziegler-Natta catalyst composition as claimed in claim 1 , wherein the organosilane compound is at least one compound selected from the group consisting of tetraethoxysilane, cyclohexylmethyl dimethoxysilane, dicyclopentyl dimethoxysilane, isobutylisopropyl dimethoxy silane, n-propyltriethoxy silane, isobutyltriethoxy silane, phenyltriethoxy silane, diisopropyldimethoxy silane, diethyldimethoxy silane, diisobutyldimethoxy silane, aminopropyltriethoxy silane, diphenyldimethoxy silane and methyltrimethoxy silane.

9. The Ziegler-Natta catalyst composition as claimed in claim 1 , wherein silicon to titanium molar ratio ranges from 1:1 to 4:1.

10. A process for preparing a Ziegler-Natta catalyst composition of claim 1 , said process comprising the following steps:
i. reacting a pre-determined weight proportion of at least one magnesium containing compound and at least one titanium containing compound at elevated temperature and pressure for a pre-determined period of time to obtain a pro-catalyst component, wherein at least one of the titanium containing compound and the magnesium containing compound is a chloride compound;
ii. isolating said pro-catalyst component;
iii. adding a pre-determined weight proportion of an organoaluminum compound to an inert hydrocarbon liquid medium to obtain a mixture;
iv. adding to said mixture, said pro-catalyst component and agitating the obtained mass for a pre-determined period of time to obtain a mass containing an activated pro-catalyst component; and
v. adding a pre-determined weight proportion of at least one external electron donor compound to the mass and agitating further for a pre-determined period of time to obtain a Ziegler-Natta catalyst composition.

11. The process as claimed in claim 10 , wherein the organoaluminum compound is selected from the group consisting of methylaluminoxane, triisobutylaluminoxane, ethylaluminoxane, and polymethylaluminoxane.

12. The process as claimed in claim 10 , wherein said inert hydrocarbon liquid medium is at least one medium selected from the group consisting of pentane, hexane, cyclohexane, methyl cyclohexane, heptane, octane, decane, isopentane, and varsol.

13. A process for polymerization of ethylene monomers in the presence of the Ziegler-Natta catalyst composition of claim 1 , said process comprising the following steps:
contacting ethylene monomers with a Ziegler-Natta catalyst composition of claim 1 under polymerization reaction conditions of temperature ranging from 50 to 80° C., ethylene pressure ranging from 1 to 15 bars for a time period ranging from 1 to 5 hours and with agitation speed ranging from 300 to 1000 revolutions per minute (rpm) to obtain a polymer of ethylene having ultrahigh molecular weight.

14. A polymer of ethylene monomers having ultrahigh molecular weight prepared in accordance with the process as claimed in claim 13 , wherein the polymer of ethylene has a molecular weight ranging from 2 to 13 million g/mole; an intrinsic viscosity ranging from 18 to 54 dl/g; a bulk density ranging from 0.1 to 0.3 g/cc; crystallinity ranging from 50 to 70%; and porous and flaky morphology.

Assignees

• Reliance Industries Ltd

Inventors

• Patil Yogesh Popatrao
• Sarma Krishna Renganath
• Bagui Mahuya
• Patel Viralkumar
• Jasra Raksh Vir
• Mathur Ajit Behari
• Vakil Suketu

Classifications

• C08F110/02 Primary

  Ethene · CPC title

• C08F4/648

  inorganic · CPC title

• C08F2500/17

  Viscosity · CPC title

• C08F2500/18

  Bulk density · CPC title

• C08F2500/01

  High molecular weight, e.g. >800,000 Da. · CPC title