High activity catalyst supportation

Patent metadata

Field	Value
Publication number	US-9725537-B2
Application number	US-201615142084-A
Country	US
Kind code	B2
Filing date	Apr 29, 2016
Priority date	Jun 5, 2015
Publication date	Aug 8, 2017
Grant date	Aug 8, 2017

Abstract

This invention relates to single site catalyst supportation methods involving high temperature treatment (≧40° C., e.g., 100-130° C.) to improve catalyst activity for olefin polymerization, e.g., propylene polymerization, and to the supported catalyst systems obtained by the methods, e.g., single site catalyst systems supported on a support having high average particle size (PS≧30 μm), high surface area (SA≧200 m 2 /g), low pore volume (PV≦2 mL/g), and a mean pore diameter range of 1≦PD≦20 nm.

First claim

What is claimed is:

1. A process, comprising:
supporting an activator for a single site catalyst precursor compound on a support, the support having an average particle size of from 5 μm to 500 μm, a specific surface area of 10 m 2 /g or more, a pore volume of from 0.1 to 4 mL/g, a mean pore diameter of from 1 to 100 nm (10 to 200 Å), and comprising agglomerates of a plurality of primary particles; fragmenting the agglomerates; and
contacting the supported activator and a single site catalyst precursor compound to form a supported catalyst system having a bimodal particle size distribution comprised of at least about 5 vol % of the agglomerates and at least about 5 vol % of fragments of the agglomerates, based on the total volume of the supported catalyst system;
wherein the supporting, the contacting, or both, are at a temperature above 40° C.

2. The process of claim 1 , wherein the support has an average particle size of more than 30 μm up to 200 μm, a specific surface area of 200 m 2 /g or more, a pore volume of from 0.5 to 2 mL/g, and a mean pore diameter of from 1 to 35 nm (10 to 350 Å).

3. The process of claim 1 , wherein the support has an average particle size of more than 30 μm up to 200 μm, a specific surface area of 650 m 2 /g or more, a pore volume of from 0.5 to 2 mL/g, and a mean pore diameter of from 1 to 7 nm (10 to 70 Å).

4. The process of claim 1 , wherein the support has a specific surface area less than 650 m 2 /g, or the mean pore diameter is greater than 7 nm (70 Å), or both.

5. The process of claim 1 , wherein the primary particles have an average size of 1 nm to 50 μm.

6. The process of claim 1 , wherein the catalyst system formed in the contacting has a bimodal particle size distribution comprised of 10 to 90 vol % of fragments of the agglomerates, based on the total volume of the supported catalyst system.

7. The process of claim 1 , wherein the supporting and contacting are essentially free of fines formation.

8. The process of claim 1 , wherein the support comprises a metal oxide.

9. The process of claim 1 , wherein the support comprises spray dried silica having an average particle size of more than 50 μm, a specific surface area less than 1000 m 2 /g, or a combination thereof.

10. The process of claim 1 , wherein the activator comprises alumoxane.

11. The process of claim 1 , wherein the activator comprises methylalumoxane or modified methylalumoxane.

12. The process of claim 1 , further comprising contacting the supported activator with a co-activator selected from the group consisting of: trialkylaluminum, dialkylmagnesium, alkylmagnesium halide, and dialkylzinc.

13. The process of claim 1 , wherein the supporting, the contacting, or both, are at a temperature above 80° C.

14. The process of claim 1 , wherein the supporting, the contacting, or both, are at a temperature above 100° C. up to 130° C.

15. The process of claim 1 , wherein the single site catalyst precursor compound comprises a hafnocene.

16. The process of claim 1 , wherein the single site catalyst precursor compound comprises a zirconocene.

17. The process of claim 1 , wherein the single site catalyst precursor compound is selected from precursor compounds I and II;
wherein precursor compound I is represented by the following formula:
(Cp) m R A n M 4 Q k

wherein:
each Cp is a cyclopentadienyl moiety or a substituted cyclopentadienyl moiety substituted by one or more hydrocarbyl radicals having from 1 to 20 carbon atoms;
R A is a structural bridge between two Cp moieties;
M 4 is a transition metal selected from groups 4 or 5;
Q is a hydride or a hydrocarbyl group having from 1 to 20 carbon atoms or an alkenyl group having from 2 to 20 carbon atoms, or a halogen;
m is 1, 2, or 3, with the proviso that if m is 2 or 3, each Cp may be the same or different;
n is 0 or 1, with the proviso that n=0 if m=1; and
k is such that k+m is equal to the oxidation state of M 4 , with the proviso that if k is greater than 1, each Q may be the same or different; and
wherein precursor compound II is represented by the following formula:
R A (CpR″ p )(CpR* q )M 5 Q r

wherein:
each Cp is a cyclopentadienyl moiety or substituted cyclopentadienyl moiety;
each R* and R″ is a hydrocarbyl group having from 1 to 20 carbon atoms and may the same or different;
p is 0, 1, 2, 3, or 4;
q is 1, 2, 3, or 4;
R A is a structural bridge between the Cp moieties imparting stereorigidity to the metallocene compound;
M 5 is a group 4, 5, or 6 metal;
Q is a hydrocarbyl radical having 1 to 20 carbon atoms or is a halogen;
r is s minus 2, where s is the valence of M 5 ;
wherein (CpR* q ) has bilateral or pseudobilateral symmetry; R* q is selected such that (CpR* q ) forms a fluorenyl, alkyl substituted indenyl, or tetra-, tri-, or dialkyl substituted cyclopentadienyl radical; and (CpR″ p ) contains a bulky group in one and only one of the distal positions;
wherein the bulky group is of the formula AR w v ; and
where A is chosen from group 4 metals, oxygen, or nitrogen, and R w is a methyl radical or phenyl radical, and v is the valence of A minus 1.

18. The process of claim 1 , wherein the single site catalyst precursor compound is represented by the formula:

wherein:
M is a group 4, 5, or 6 metal;
T is a bridging group;
each X is, independently, an anionic leaving group;
each R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , and R 13 is, independently, halogen atom, hydrogen, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl, substituted germylcarbyl substituent or a —NR′ 2 , —SR′, —OR, —OSiR′ 3 or —PR′ 2 radical, wherein R′ is one of a halogen atom, a C 1 -C 10 alkyl group, or a C 6 -C 10 aryl group.

19. The process of claim 18 , wherein at least one of R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , and R 13 is a cyclopropyl substituent represented by the formula:

wherein each R′ in the cyclopropyl substituent is, independently, hydrogen,
a substituted hydrocarbyl group, an unsubstituted hydrocarbyl group, or a halogen.

20. The process of claim 18 , wherein:
M is selected from titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten;
each X is independently selected from hydrogen, halogen, hydroxy, substituted or unsubstituted C 1 to C 10 alkyl groups, substituted or unsubstituted C 1 to C 10 alkoxy groups, substituted or unsubstituted C 6 to C 14 aryl groups, substituted or unsubstituted C 6 to C 14 aryloxy groups, substituted or unsubstituted C 2 to C 10 alkenyl groups, substituted or unsubstituted C 7 to C 40 arylalkyl groups, substituted or unsubstituted C 7 to C 40 alkylaryl groups, and substituted or unsubstituted C 7 to C 40 arylalkenyl groups; or optionally are joined together to form a C 4 to C 40 alkanediyl group or a conjugated C 4 to C 40 diene ligand which is coordinated to M in a metallacyclopentene fashion; or optionally represent a conjugated diene, optionally, substituted with one or more groups independently selected from hydrocarbyl, trihydrocarbylsilyl, and trihydrocarbylsilylhydrocarbyl groups, said diene having a total of up to 40 atoms not co

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Luo Lubin
• Day Gregory S

Classifications

• C08F210/06

  Propene · CPC title

• C08F4/65916

  supported on a carrier, e.g. silica, MgCl2, polymer · CPC title

• C08F4/65912

  in combination with an organoaluminium compound · CPC title

• C08F110/06 Primary

  Propene · CPC title

• C08F4/02 Primary

  Carriers therefor · CPC title