High Activity Catalyst Supportation

Patent metadata

Field	Value
Publication number	US-2016355654-A1
Application number	US-201615142084-A
Country	US
Kind code	A1
Filing date	Apr 29, 2016
Priority date	Jun 5, 2015
Publication date	Dec 8, 2016
Grant date	—

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

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, and a mean pore diameter of from 1 to 100 nm (10 to 200 Å); and contacting the supported activator and a single site catalyst precursor compound to form a 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 support comprises agglomerates of a plurality of primary particles, and further comprising fragmenting the agglomerates.

6 . The process of claim 5 , wherein the catalyst system formed in the contacting has 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.

7 . The process of claim 5 , 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 cyclopropyls 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 counting hydrogen and forming a π complex with M; each R 2 , R 4 , R 8 , and R 10 is independently selected from hydrogen, halogen, substituted or unsubstituted C 1 to C

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Luo Lubin
• Day Gregory S

Classifications

• C08F4/02 Primary

  Carriers therefor · CPC title

• C08F4/65916

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

• C08F4/65927

  two cyclopentadienyl rings being mutually bridged · CPC title

• C08F4/65912

  in combination with an organoaluminium compound · CPC title

• C08F210/06

  Propene · CPC title