IP Library Granted Patent US 10,059,784
Granted Patent B2
US 10,059,784 · App. 15/036,365 · Granted Aug 28, 2018

Procatalyst particles and polymerization process for impact copolymers

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Quick Facts
Patent No.
US 10,059,784
App. No.
15/036,365
Granted
Aug 28, 2018
Kind
B2
Abstract

Particles of a procatalyst composition having a particle size D50 from 19 microns to 30 microns. A polymerization process comprising halogenating, in the presence of a substituted phenylene aromatic diester, particles of a MagTi procatalyst precursor to form particles of a procatalyst composition having a particle size D50 from 19 microns to 30 microns; first contacting a propylene and optionally one or more first comonomers with a catalyst composition comprising the particles of the procatalyst composition in a first polymerization reactor to form an active propylene-based polymer; and second contacting the active propylene-based polymer with at least one second comonomer in a second polymerization reactor to form a propylene impact copolymer.

Claims (27)

1. A polymerization process comprising:

halogenating, in the presence of a substituted 1,2-, 1,3- or 1,4-phenylene aromatic diester, particles of a MagTi procatalyst precursor having a particle size D50 from 19 microns to 30 microns to form particles of a procatalyst composition having a particle size D50 from 19 microns to 30 microns;

wherein halogenating is carried out with a halogenating agent selected from a titanium halide having the formula Ti(OR e ) f X h :

wherein R e is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbon atoms or COR′, wherein R′ is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbon atoms; each OR e group is the same or different; X is independently chlorine, bromine or iodine, f is an integer from 0 to 3; h is an integer from 1 to 4; and f+h is 4;

first contacting, under first polymerization conditions, propylene monomer and optionally one or more first comonomers with a catalyst composition comprising the particles of the procatalyst composition in a first polymerization reactor to form an active propylene-based polymer having a melt flow rate greater than 100 g/10 min as measured in accordance with ASTM D 1238, 2.16 kg, 230° C.; and

second contacting, under second polymerization conditions, the active propylene-based polymer with at least one second comonomer in a second polymerization reactor to form a propylene impact copolymer.

2. The process of claim 1 wherein the at least one second comonomer is an olefin monomer.

3. The process of claim 1 comprising halogenating the particles of the MagTi procatalyst precursor in the presence of 3-methyl-5-t-butyl-1,2-phenylene dibenzoate.

4. The process of claim 1 wherein the halogenating agent is titanium tetrabromide, or titanium tetrachloride or titanium trichloride.

5. The process of claim 1 comprising forming propylene impact copolymer having an Fc from 10 wt % to 55 wt %.

6. The process of claim 1 comprising forming propylene impact copolymer having an Fc from 25 wt % to 55 wt %.

7. The process of claim 1 comprising forming propylene impact copolymer having an Fc from 30 wt % to 55 wt %.

8. The process of claim 1 comprising forming particles of propylene impact copolymer having a settled bulk density greater than 17 lbs/ft 3 .

9. The process of claim 1 wherein the substituted 1,2-phenylene aromatic diester has the structure (I),

wherein R 1 -R 14 are the same or different, each of R 1 -R 14 may be independently selected from a hydrogen, substituted hydrocarbyl group having 1 to 20 carbon atoms, an unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a heteroatom, and combinations thereof, provided that at least one of R 1 -R 14 is not hydrogen.

10. A polymerization process comprising:

halogenating, in the presence of a substituted 1,2-, 1,3- or 1,4-phenylene aromatic diester, particles of a MagTi procatalyst precursor having a particle size D50 from 19 microns to 30 microns to form particles of a procatalyst composition having a particle size D50 from 19 microns to 30 microns;

first contacting, under first polymerization conditions, propylene monomer and optionally one or more first comonomers with a catalyst composition comprising the particles of the procatalyst composition in a first polymerization reactor, comprising forming an active propylene-based polymer having a melt flow rate greater than 100 g/10 min as measured in accordance with ASTM D 1238, 2.16 kg, 230° C.; and

second contacting, under second polymerization conditions, the active propylene-based polymer with at least one second comonomer in a second polymerization reactor to form a propylene impact copolymer.

11. The process of claim 10 wherein the at least one second comonomer is an olefin monomer.

12. The process of claim 10 comprising halogenating the particles of the MagTi procatalyst precursor in the presence of 3-methyl-5-t-butyl-1,2-phenylene dibenzoate.

13. The process of claim 10 comprising forming propylene impact copolymer having an Fc from 10 wt % to 55 wt %.

14. The process of claim 10 comprising forming propylene impact copolymer having an Fc from 25 wt % to 55 wt %.

15. The process of claim 10 comprising forming propylene impact copolymer having an Fc from 30 wt % to 55 wt %.

16. The process of claim 10 comprising forming particles of propylene impact copolymer having a settled bulk density greater than 17 lbs/ft 3 .

17. The process of claim 10 wherein the substituted 1,2-phenylene aromatic diester has the structure (I),

wherein R 1 -R 14 are the same or different, each of R 1 -R 14 may be independently selected from a hydrogen, substituted hydrocarbyl group having 1 to 20 carbon atoms, an unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a heteroatom, and combinations thereof, provided that at least one of R 1 -R 14 is not hydrogen.

Assignments (9)
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 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 Feb 17, 2023
From: W.R. GRACE & CO.-CONN.
To: WILMINGTON TRUST, NATIONAL ASSOCIATION
Reel/Frame 062792/0510 →
RELEASE OF SECURITY INTEREST Recorded Sep 23, 2021
From: GOLDMAN SACHS BANK USA
To: W. R. GRACE & CO.-CONN.
Reel/Frame 057594/0026 →
TERM LOAN SECURITY AGREEMENT Recorded Sep 23, 2021
From: W. R. GRACE & CO.-CONN.
To: JPMORGAN CHASE BANK, N.A.
Reel/Frame 057594/0104 →
NOTES SECURITY AGREEMENT Recorded Sep 23, 2021
From: W. R. GRACE & CO.-CONN.
To: WILMINGTON TRUST, NATIONAL ASSOCIATION
Reel/Frame 057594/0156 →
SECURITY INTEREST Recorded Apr 3, 2018
From: W. R. GRACE & CO.-CONN.
To: GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT
Reel/Frame 045828/0683 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded May 17, 2016
From: DOW GLOBAL TECHNOLOGIES LLC
To: W. R. GRACE & CO.-CONN.
Reel/Frame 038619/0213 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded May 13, 2016
From: VAN EGMOND, JAN W.
To: DOW GLOBAL TECHNOLOGIES LLC
Reel/Frame 038704/0866 →