Homogeneous single site catalyst and its use in preparing linear polyethylene

Patent metadata

Field	Value
Publication number	US-12377404-B2
Application number	US-202117928335-A
Country	US
Kind code	B2
Filing date	May 28, 2021
Priority date	May 29, 2020
Publication date	Aug 5, 2025
Grant date	Aug 5, 2025

Abstract

The present invention discloses a homogeneous, single site catalyst of formula (I) and a process for preparation thereof using a ligand. The present invention further discloses a process for preparation of linear polyethylene of high molecular weight and degree of crystallinity by using the homogeneous, single site catalyst of formula I.

First claim

We claim:

1. A homogeneous, single site catalyst of formula (I)

wherein
R 1 -R 3 are selected from the group consisting of H, Alkyl and Aryl;
R 4 -R 6 are selected from the group consisting of H, Alkyl, Aryl, OMe and OEt;
R 7 -R 10 are selected from the group consisting of H, Alkyl and Aryl;
M is selected from the group consisting of Cr, Ti, Zr and Hf;
X is selected from the group consisting of Cl, Br and I;
n is selected from the group consisting of 2, 3 and 4;
Y is selected from the group consisting of S, O, —NH and —CH 2 ; and
E is CH2.

2. The catalyst as claimed in claim 1 , wherein representative structures of said catalyst of formula I are:

3. A process for a preparation of the catalyst of formula (I) as claimed in claim 1 , wherein said process comprising a step of reacting a ligand with a metal halide or an alkyl lithium at a temperature in the range of −80° C. to 30° C. for a time period in the range of 1 to 20 hours in a solvent to obtain the catalyst of formula (I),
wherein said ligand is selected from L1 to L10 having ligand L1 is (Z)-2-(cyclopenta-1,3-dien-1-yl)-N-(4-methoxyphenyl)-1-phenylethan-1-imine; the ligand L2 is (Z)-2-(cyclopenta-1,3-dien-1-yl)-N-(4-methoxyphenyl)-1-(o-tolyl)ethan-imine; the ligand L3 is (Z)-2-(cyclopenta-1,3-dien-1-yl)-1-(2,6-dimethylphenyl)-N-(4-methoxyphenyl)ethan-1-imine; the ligand L4 is (Z)-2-(cyclopenta-1,3-dien-1-yl)-1-(2,6-di-tert-butylphenyl)-N-(4-methoxyphenyl)ethan-1-imine the ligand L5 is (Z)—N-(4-methoxyphenyl)-1-phenyl-2-(2,3,4-trimethylcyclopenta-1,3-dien-1-yl)ethan-1-imine: the ligand L6 is (Z)—N-(4-methoxyphenyl)-1-(o-tolyl)-2-(2,3,4-trimethylcyclopenta-1,3-dien-1-yl)ethan-1-imine: the ligand L7 is (Z)-1-(2,6-dimethylphenyl)-N-(4-methoxyphenyl)-2-(2,3,4-trimethylcyclopenta-1,3-dien-1-yl)ethan-1-imine: the ligand L8 is (Z)-1-(2,6-di-tert-butylphenyl)-N-(4-methoxyphenyl)-2-(2,3,4-trimethylcyclopenta-1,3-dien-1-yl)ethan-1-imine: the ligand L9 is (E)-N-(4-methoxyphenyl)-2-phenyl-1-(thiophen-2-yl) ethan-1-imine and the ligand L10 is (E)-N-(2,6-dimethylphenyl)-1-(2-(2,3,4-trimethylcyclopenta-1,3-dien-1-yl)phenyl)methanimine.

4. The process as claimed in claim 3 , wherein said metal halide is selected from TiCl 4 , CrCl 3 ·3THF, ZrCl 4 ·2THF and HfCl 4 , said alkyl lithium is selected from butyl lithium (BuLi), and said solvent is selected from toluene, tetrahydrofuran and hexane.

5. The process as claimed in claim 3 , wherein said ligand L1 to L8 is prepared by a process comprising the steps of:
a) adding a solution of bromoacetyl bromide in dichloromethane to a solution mixture of N, O-dimethyl hydroxylamine hydrochloride and triethyl amine solution at 0° C. and allowing the resultant solution to warm to 28° C. and continuing stirring for one hour to obtain 2-bromo-N-methoxy-N-methylacetamide;
b) adding (un)substituted sodium cyclopentadienylide solution in THF dropwise to the stirring solution of step (a) at a temperature −78° C., stirring for 3 hours and adding dichloromethane to precipitate NaBr, and separating to obtain 2-(cyclopenta-1,3-dien-1-yl)-N-methoxy-N-methylacetamide;
c) adding solution of (un)substituted phenyl magnesium bromide in THF drop wise to a stirring solution of step (b) at 0° C. and continuing stirring to obtain 2-(cyclopenta-1,3-dien-1-yl)-1-phenylethan-1-one; and
d) mixing acetophenone derivatives of step (c) and p-anisidine and stirring in methanol at 70° C. for 15 to 17 hours in the presence of molecular sieves, filtering and removing the solvent to obtain the corresponding ligand.

6. A process for preparation of polyethylene using the catalyst of formula (I) as claimed in claim 1 comprising the steps of:
a) charging a toluene into an ethylene filled reactor in an inert atmosphere followed by adding methylaluminoxane (7 wt % aluminum in toluene), and
b) dissolving the catalyst of formula (I) as claimed in claim 1 in a solvent and adding to the reactor of step (a) and keeping the reactants stirred for 0.5 to 3 hours at a temperature range of 30-70° C. with ethylene being pumped continuously to obtain the polyethylene.

7. The process as claimed in claim 6 , wherein said solvent of step (b) is selected from dichloromethane or toluene.

8. The process as claimed in claim 7 , wherein said polyethylene is linear and has a molecular weight in the range of 50000 Da to 3 million Dalton.

9. The process as claimed in claim 7 , wherein said polyethylene has melting temperature in the range of 139-144° C., the degree of crystallinity in the range of 60-90%, the polydespersity index in the range of 1.5 to 10, and the turn over frequency in the range of >100-50000.

Assignees

• Council Scient Ind Res
• Gail India Ltd

Inventors

• Chikkali Samir Hujur
• Jawoor Shailaja
• Birajdar Rajkumar S
• Pawal Sandip B
• Thenmani Nandakumar
• Chugh Parivesh

Classifications

• C08F10/02

  Ethene · CPC title

• C08F4/6592

  containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring · CPC title

• C08F2/06

  Organic solvent · CPC title

• B01J2531/62

  Chromium · CPC title

• B01J2531/48

  Zirconium · CPC title