IP Library Granted Patent US 8,008,413
Granted Patent B2
US 8,008,413 · App. 12/312,875 · Granted Aug 30, 2011

Method for preparing copolymers

View Patent ↗
Loading inventors, assignments & file history…
Monitor This Case
Get email alerts when status or documents change.
Order Certified Copies
Most orders are placed with the USPTO same day — all within 24 business hours.
Order via The Patent Place →
Pre-filled with this patent's details
Quick Facts
Patent No.
US 8,008,413
App. No.
12/312,875
Granted
Aug 30, 2011
Kind
B2
Abstract

A method for the preparation of copolymers of ethylene and α-olefins having a fraction (%) of the molecular weight component of >1,000,000 of less than 6% comprises polymerising ethylene and an α-olefin in the presence of a supported polymerisation catalyst system comprising (a) a transition metal compound (b) a porous support material, and (c) an activator characterized in that the support material has been (i) dried at a temperature in the range 0° C. to 195° C. in an inert atmosphere, and (ii) treated with an organometallic compound. The resultant supported catalyst systems show improved productivity and allow for control of the resultant polymer properties. Particularly preferred supported catalyst systems are those comprising metallocene complexes.

Claims (38)

1. A method for the preparation of copolymers of ethylene and α-olefins having a fraction (%) of the molecular weight component of >1,000,000 of less than 6% said method comprising polymerising ethylene and an α-olefin in the presence of a supported polymerisation catalyst system comprising

(a) a transition metal compound,

(b) a porous support material, and

(c) an activator,

characterized in that the support material has been

(i) dried at a temperature in the range 0° C. to 195° C. in an inert atmosphere, and

(ii) treated with an organometallic compound.

2. A method according to claim 1 wherein the fraction (%) of the molecular weight component of >1,000,000 is less than 4%.

3. A method according to claim 1 wherein the fraction (%) of the molecular weight component of >1,000,000 is less than 2.5%.

4. A method according to claim 1 wherein the support material has been heated at a temperature in the range 25° C. to 195° C.

5. A method according to claim 1 wherein the support material has been heated at a temperature in the range 30° C. to 180° C.

6. A method according to claim 1 wherein the support material has been heated at a temperature in the range 30° C. to 95° C.

7. A method according to claim 1 wherein the support material is silica.

8. A method according to claim 1 wherein the organometallic compound is an organoaluminium compound.

9. A method according to claim 8 wherein the organoaluminium compound is a trialkylaluminium compound.

10. A method according to claim 9 wherein the trialkylaluminium compound is trisisobutylaluminium.

11. A method according to claim 1 wherein the support material is treated with the organometallic compound at a temperature in the range 20° C. to 100° C.

12. A method according to claim 11 wherein the support material is treated with the organometallic compound at room temperature.

13. A method according to claim 1 wherein the transition metal compound is a metallocene.

14. A method according to claim 13 wherein the metallocene has the general formula

wherein:—

R′ each occurrence is independently selected from hydrogen, hydrocarbyl, silyl, germyl, halo, cyano, and combinations thereof, said R′ having up to 20 nonhydrogen atoms, and optionally, two R′ groups (where R′ is not hydrogen, halo or cyano) together form a divalent derivative thereof connected to adjacent positions of the cyclopentadienyl ring to form a fused ring structure;

X is a neutral η 4 bonded diene group having up to 30 non-hydrogen atoms, which forms a π-complex with M;

Y is —O—, —S—, —NR*—, —PR*—,

M is titanium or zirconium in the +2 formal oxidation state;

Z* is SiR* 2 , CR* 2 , SiR* 2 SIR* 2 , CR* 2 CR* 2 , CR*═CR*, CR* 2 SiR* 2 , or

GeR* 2 , wherein:

R* each occurrence is independently hydrogen, or a member selected from hydrocarbyl, silyl, halogenated alkyl, halogenated aryl, and combinations thereof, said

R* having up to 10 non-hydrogen atoms, and optionally, two R* groups from Z* (when R* is not hydrogen), or an R* group from Z* and an R* group from Y form a ring system.

15. A method for the preparation of a supported polymerization catalyst system suitable for use in the method according to claim 13 said method comprising the following steps:

(i) drying a porous support material at a temperature in the range 0° C. to 195° C. in an inert atmosphere,

(ii) addition of an organometallic compound in a suitable solvent,

(iii) removal of the solvent,

(iv) addition of an activator in a suitable solvent to the support material,

(v) addition of a metallocene in a suitable solvent, and

(vi) removal of the solvent.

16. A method according to claim 1 wherein the α-olefin is 1-butene, 1-hexene, 4-methyl-1-pentene or 1-octene.

17. A method according to claim 1 wherein the ethylene and α-olefin are polymerized in the slurry or the gas phase.

Assignments (4)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Mar 5, 2014
From: INEOS COMMERCIAL SERVICES UK LIMITED
To: INEOS SALES (UK) LIMITED
Reel/Frame 032388/0553 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Oct 4, 2011
From: INEOS EUROPE LIMITED
To: INEOS COMMERCIAL SERVICES UK LIMITED
Reel/Frame 027060/0001 →
CORRECTIVE ASSIGNMENT TO CHANGE ASSIGNEE CITY OF RESIDENCE TO "HAMPSHIRE", PREVIOUSLY RECORDED AT REEL 022777, FRAME 0977. Recorded Jun 18, 2009
From: MASTROIANNI, SERGIO; SPITZMESSER, STEFAN KLAUS
To: INEOS EUROPE LIMITED
Reel/Frame 022851/0461 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded May 29, 2009
From: MASTROIANNI, SERGIO; SPITZMESSER, STEFAN KLAUS
To: INEOS EUROPE LIMITED
Reel/Frame 022777/0977 →