IP Library Granted Patent US 10,584,196
Granted Patent B2
US 10,584,196 · App. 15/739,649 · Granted Mar 10, 2020

Process for producing LLDPE resins

Inventors: Alexandra Romina Albunia (Linz, AT); Ravindra Tupe (Helsinki, FI); Victor Sumerin (Helsinki, FI); John Jamieson (Porvoo, FI); Jani Aho (Helsinki, FI); Markku Vahteri (Porvoo, FI); Jarmo Kela (Porvoo, FI); Renate Eckmayr (Linz, AT)
Assignee: BOREALIS AG
C08F210/16C08F2/001C08F2/14C08F2/34C08F4/022C08F110/02C08L23/06C08L23/0815C08F2410/01C08F2410/05C08F2500/08C08F2500/12C08F2800/20
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Quick Facts
Patent No.
US 10,584,196
App. No.
15/739,649
Granted
Mar 10, 2020
Kind
B2
Abstract

A process for producing copolymers of ethylene and at least one alpha-olefin having from 4 to 10 carbon atoms in the presence of a solid Ziegler-Natta catalyst comprising of magnesium, titanium, halogen and an internal organic compound, the copolymer having a density of from 906 to 937 kg/m 3 and a melt flow rate MFR 21 measured at 190° C. under 21.6 kg load of from 3 to 150 g/10 min. The process includes the steps of (A) homopolymerising ethylene or copolymerising ethylene and a first alpha-olefin having from 4 to 10 carbon atoms in a first polymerisation stage in the presence of the polymerisation catalyst, hydrogen and optionally the first alpha-olefin; (B) copolymerising ethylene and a second alpha-olefin having from 4 to 10 carbon atoms in a second polymerisation stage in the presence of the first homo- or copolymer of ethylene and the Ziegler-Natta catalyst; and (C) recovering the polymer mixture.

Claims (25)

1. A process for producing copolymers of ethylene and at least one alpha-olefin having from 4 to 10 carbon atoms in the presence of a solid Ziegler-Natta catalyst comprising of magnesium, titanium, halogen and an internal organic compound, the copolymer having a density of from 906 to 937 kg/m 3 and a melt flow rate MFR 21 measured at 190° C. under 21.6 kg load of from 3 to 150 g/10 min comprising the steps of:

(A) homopolymerising ethylene or copolymerising ethylene and a first alpha-olefin having from 4 to 10 carbon atoms in a first polymerisation stage in the presence of the polymerisation catalyst, hydrogen and optionally the first alpha-olefin wherein the molar ratio of hydrogen to ethylene in the fluid reaction mixture of the first polymerisation stage is from 200 to 50000 mol/kmol and the molar ratio of the first alpha-olefin to ethylene in the fluid reaction mixture of the first polymerisation stage is from 0 to 1500 mol/kmol, to produce a first homo- or copolymer of ethylene;

(B) copolymerising ethylene and a second alpha-olefin having from 4 to 10 carbon atoms in a second polymerisation stage in the presence of the first homo- or copolymer of ethylene and the solid Ziegler-Natta catalyst to produce a polymer mixture comprising the first homo- or copolymer of ethylene and a second copolymer of ethylene, the polymer mixture having a density of from 906 to 937 kg/m 3 and a melt flow rate MFR 21 of from 3 to 150 g/10 min;

(C) recovering the polymer mixture, characterised in that the polymerisation catalyst comprises an internal organic compound having the formula (I):

wherein in the formula (I) R 1 to R 5 are the same or different and can be are hydrogen, a linear or branched C1 to C8-alkyl group, or a C3-C8-alkylene group, or two or more of R 1 to R 5 optionally forms a ring, and the two oxygen-containing rings are individually saturated or partially unsaturated or unsaturated.

2. The process according to claim 1 , further comprising preparing the solid Ziegler-Natta catalyst component by the additional steps of:

(a) providing solid carrier particles of MgCl 2 .mROH adduct;

(b) pre-treating the solid carrier particles of step (a) with a compound of Group 13 metal;

(c) treating the pre-treated solid carrier particles of step (b) with a transition metal compound of Group 4 to 6;

(d) recovering the solid catalyst component;

(e) contacting the solid carrier particles with the internal organic compound compound having the formula (I) prior to the step (c); and

(f) passing the solid Ziegler-Natta catalyst component into the first polymerisation stage (A), wherein R in the adduct MgCl 2 .mROH is a linear or branched alkyl group with 1 to 12 carbon atoms and m is a number from 0 to 6.

3. The process according to claim 1 wherein the hydrogen to ethylene ratio in the fluid reaction phase of the first polymerisation stage is from 200 to 1000 mol/kmol.

4. The process according to claim 1 wherein the first homo- or copolymer of ethylene is a homopolymer of ethylene and no comonomer is present in the first polymerisation stage.

5. The process according to claim 1 wherein the first homo- or copolymer of ethylene is a copolymer of ethylene.

6. The process according to claim 5 wherein the first alpha-olefin is selected from the group consisting of 1-butene, 1-hexene and 4-methyl-1-pentene.

7. The process according to claim 6 wherein the molar ratio of the first alpha-olefin to ethylene in the fluid reaction mixture of the first polymerisation stage is from 200 to 1000 mol/kmol.

8. The process according to claim 1 wherein the polymer mixture has a melt flow rate MFR 21 of from 20 to 150 g/10 min; or a density of from 910 to 932 kg/m 3 ; or a melt flow rate MFR 21 of from 20 to 150 g/10 min and a density of from 910 to 932 kg/m 3 .

9. The process according claim 1 wherein the hydrogen to ethylene ratio in the fluid reaction mixture of the second polymerisation stage is from 10 to 150 mol/kmol.

10. The process according to claim 9 wherein the molar ratio of hydrogen to ethylene in the fluid reaction mixture of the second polymerisation stage is from 20 to 100 mol/kmol.

11. The process according to claim 1 wherein the second alpha-olefin having from 4 to 10 carbon atoms is selected from the group consisting of 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and mixtures thereof.

12. The process according to claim 11 wherein the molar ratio of the second alpha-olefin to ethylene in the fluid reaction mixture of the second polymerisation stage is from 50 to 400 mol/kmol.

13. The process according to claim 8 wherein the polymer mixture comprises from 35 to 57% by weight of the first polymer and from 43 to 65% by weight of the second copolymer.

14. The process according to claim 1 wherein the first polymerisation stage is conducted as a slurry polymerisation in a loop reactor; or the second polymerisation stage is conducted as a gas phase polymerisation in a fluidised bed; or the first polymerisation stage is conducted as a slurry polymerisation in a loop reactor and the second polymerisation stage is conducted as a gas phase polymerisation in a fluidised bed.

15. The process according to claim 14 wherein the dew point temperature of the gas mixture in the second polymerisation stage is not more than 65° C.

Assignments (2)
CHANGE OF ADDRESS Recorded Feb 23, 2022
From: BOREALIS AG
To: BOREALIS AG
Reel/Frame 059219/0949 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Dec 26, 2017
From: ALBUNIA, ALEXANDRA ROMINA; TUPE, RAVINDRA; SUMERIN, VICTOR; JAMIESON, JOHN; AHO, JANI; VAHTERI, MARKKU; KELA, JARMO; ECKMAYR, RENATE
To: BOREALIS AG
Reel/Frame 044486/0593 →