IP Library Granted Patent US 10,207,238
Granted Patent B2
US 10,207,238 · App. 13/025,532 · Granted Feb 19, 2019

Catalyst composition with mixed selectivity control agent and method

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 10,207,238
App. No.
13/025,532
Granted
Feb 19, 2019
Kind
B2
Abstract

The present disclosure provides a Ziegler-Natta catalyst composition comprising a procatalyst, a cocatalyst and a mixed external electron donor comprising a first selectivity control agent, a second selectivity control agent, and an activity limiting agent. A polymerization process incorporating the present catalyst composition produces a high-stiffness propylene-based polymer with a melt flow rate greater than about 50 g/10 min. The polymerization process occurs in a single reactor, utilizing standard hydrogen concentration with no visbreaking.

Claims (35)

1. A propylene-based polymer comprising:

dicyclopentyldimethoxysilane, an ethoxysilane, and at least about 5 ppm to about 150 ppm of an activity limiting agent (ALA) comprising a C 4 -C 30 aliphatic acid monoester, polymer wherein a mole ratio of dicyclopentyldimethoxysilane to ethoxysilane is 0.1-1:1, the propylene-based polymer:

(A) having a melt flow rate greater than about 100 g/10 min as measured in accordance with ASTM D 1238-01 at 230° C., 2.16 kg;

(B) having a xylene solubles content of from 0.1 weight percent to less than 2 weight percent;

(C) exhibiting a T MF greater than about 165° C.;

(D) wherein the ratio of combined moles of dicyclopentyldimethoxysilane and ethoxysilane to moles of activity limiting agent is about 0.43-2.33:1; and

(E) wherein the mole ratio of dicyclopentyldimethoxysilane to combined moles of dicyclopentyldimethoxysilane and ethoxysilane is about 0.2-0.5:1.

2. The propylene-based polymer of claim 1 wherein the ALA comprises isopropyl myristate.

3. The propylene-based polymer of claim 1 wherein the propylene-based polymer is uncracked.

4. The propylene-based polymer of claim 1 wherein the propylene-based polymer is a propylene homopolymer.

5. The propylene-based polymer of claim 1 comprising a silicon content less than about 200 ppm.

6. The propylene-based polymer of claim 1 comprising from about 1 ppm to about 100 ppm dicyclopentyldimethoxysilane.

7. The propylene-based polymer of claim 1 comprising a post-reactor oligomer content less than about 3000 ppm.

8. The propylene-based polymer of claim 1 wherein the ethoxysilane is selected from the group consisting of a diethoxysilane, a triethoxysilane, a tetraethoxysilane, and combinations thereof.

9. The propylene-based polymer of claim 1 wherein the ethoxysilane is selected from the group consisting of methylcyclohexyldiethoxysilane, diisobutyldiethoxysilane, tetraethoxysilane, n-propyltriethoxysilane, benzyltriethoxysilane, butenyltriethoxysilane, and (triethoxysilyl)cyclohexane.

10. The propylene-based polymer of claim 1 comprising tetraethoxysilane, and the ALA comprises isopropyl myristate.

11. The propylene-based polymer of claim 1 comprising n-propyltriethoxysilane, and the ALA comprises isopropyl myristate.

12. The propylene-based polymer of claim 1 comprising a phenylene dibenzoate.

13. The propylene-based polymer of claim 1 comprising 3-methyl-5-tert-butyl-1,2-phenylene dibenzoate.

14. The propylene-based polymer of claim 1 comprising a T MF greater than 170° C.

15. The propylene-based polymer of claim 1 comprising a T MF greater than 170° C. and a post-reactor oligomer content of less than about 3000 ppm.

16. A propylene-based polymer comprising:

dicyclopentyldimethoxysilane, an ethoxysilane, and at least about 5 ppm to about 150 ppm of an activity limiting agent (ALA) comprising a C 4 -C 30 aliphatic acid monoester, wherein a mole ratio of dicyclopentyldimethoxysilane to ethoxysilane is 0.1-1:1, wherein the ethoxysilane is selected from the group consisting of a diethoxysilane, a tetraethoxysilane, and combinations thereof, the propylene-based polymer:

(A) having a melt flow rate greater than about 100 g/10 min as measured in accordance with ASTM D 1238-01 at 230° C., 2.16 kg;

(B) having a xylene solubles content of from 0.1 weight percent to less than 2 weight percent;

(C) exhibiting a T MF greater than about 165° C.;

(D) wherein the ratio of combined moles of dicyclopentyldimethoxysilane and ethoxysilane to moles of activity limiting agent is about 0.43-2.33:1; and

(E) wherein the mole ratio of dicyclopentyldimethoxysilane to combined moles of dicyclopentyldimethoxysilane and ethoxysilane is about 0.2-0.5:1.

17. A propylene-based polymer comprising:

dicyclopentyldimethoxysilane, an ethoxysilane, wherein a mole ratio of dicyclopentyldimethoxysilane to ethoxysilane is 0.1-1:1, and at least about 5 ppm to about 150 ppm of an activity limiting agent (ALA) comprising a C 4 -C 30 aliphatic acid monoester, the propylene-based polymer:

(A) having a melt flow rate greater than 100 g/10 min as measured in accordance with ASTM D 1238-01 at 230° C., 2.16 kg;

(B) having a xylene solubles content of from 0.1 weight percent to less than 2 weight percent;

(C) exhibiting a T MF greater than about 165° C.;

(D) wherein the ratio of combined moles of dicyclopentyldimethoxysilane and ethoxysilane to moles of activity limiting agent is about 0.43-2.33:1; and

(E) wherein the mole ratio of dicyclopentyldimethoxysilane to combined moles of dicyclopentyldimethoxysilane and ethoxysilane is about 0.2-0.5:1.

Assignments (13)
NOTES SECURITY INTEREST Recorded Jan 29, 2026
From: W. R. GRACE & CO.-CONN.; ADVANCED REFINING TECHNOLOGIES LLC
To: WILMINGTON TRUST, NATIONAL ASSOCIATION, AS NOTES COLLATERAL AGENT
Reel/Frame 074532/0229 →
SECURITY INTEREST Recorded Aug 19, 2025
From: W. R. GRACE & CO.-CONN.
To: WILMINGTON TRUST, NATIONAL ASSOCIATION
Reel/Frame 072519/0265 →
SECURITY INTEREST Recorded Aug 19, 2025
From: W. R. GRACE & CO.-CONN.
To: WILMINGTON TRUST, NATIONAL ASSOCIATION
Reel/Frame 072519/0240 →
SECURITY AGREEMENT (NOTES) Recorded Aug 19, 2025
From: W. R. GRACE & CO.-CONN.
To: WILMINGTON TRUST, NATIONAL ASSOCIATION, AS NOTES COLLATERAL AGENT
Reel/Frame 072520/0653 →
SECURITY INTEREST Recorded Apr 2, 2023
From: W. R. GRACE & CO.-CONN.
To: WILMINGTON TRUST, NATIONAL ASSOCIATION
Reel/Frame 063199/0472 →
NOTES SECURITY AGREEMENT Recorded Sep 23, 2021
From: W. R. GRACE & CO.-CONN.
To: WILMINGTON TRUST, NATIONAL ASSOCIATION
Reel/Frame 057594/0156 →
TERM LOAN SECURITY AGREEMENT Recorded Sep 23, 2021
From: W. R. GRACE & CO.-CONN.
To: JPMORGAN CHASE BANK, N.A.
Reel/Frame 057594/0104 →
RELEASE OF SECURITY INTEREST Recorded Sep 23, 2021
From: GOLDMAN SACHS BANK USA
To: W. R. GRACE & CO.-CONN.
Reel/Frame 057594/0026 →
SECURITY INTEREST Recorded Apr 3, 2018
From: W. R. GRACE & CO.-CONN.
To: GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT
Reel/Frame 045828/0683 →
RELEASE OF SECURITY AGREEMENT RECORDED AT REEL/FRAME NO.: 032159/0384 Recorded Apr 3, 2018
From: GOLDMAN SACHS BANK USA, AS THE COLLATERAL AGENT
To: W.R. GRACE & CO.-CONN.
Reel/Frame 045832/0887 →
CORRECTIVE ASSIGNMENT TO CORRECT THE ASSIGNEE NAME TO "W. R. GRACE & CO. - CONN." PREVIOUSLY RECORDED ON REEL 032554 FRAME 0730. ASSIGNOR(S) HEREBY CONFIRMS THE ASSIGNEE NAME WAS PREVIOUSLY INCORRECTLY LISTED IN THE RECORDATION COVER SHEET DATED 3/28/2014 AS "W. R. GRACE & CO. CONN.". Recorded Apr 2, 2014
From: DOW GLOBAL TECHNOLOGIES LLC; UNION CARBIDE CHEMICALS & PLASTICS TECHNOLOGY LLC
To: W. R. GRACE & CO. - CONN.
Reel/Frame 032589/0554 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Mar 28, 2014
From: DOW GLOBAL TECHNOLOGIES LLC; UNION CARBIDE CHEMICALS & PLASTICS TECHNOLOGY LLC
To: W. R. GRACE & CO. CONN.
Reel/Frame 032554/0730 →
SECURITY AGREEMENT Recorded Feb 4, 2014
From: W.R. GRACE & CO.-CONN.
To: GOLDMAN SACHS BANK USA, AS THE COLLATERAL AGENT
Reel/Frame 032159/0384 →