Single Site Catalyst Supportation

Patent metadata

Field	Value
Publication number	US-2016355656-A1
Application number	US-201615142321-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 catalyst supports having high surface area (SA≧400 m 2 /g), low pore volume (PV≦2 mL/g), a specific mean pore diameter range (PD=1-20 nm), and high average particle size (PS≧30 μm), supported catalysts, and supportation processes; and further relates to: high porosity (≧15%) and/or low pore diameter (PD<165 μm) propylene polymers; bimodal polymers and/or heterophasic copolymers based on the high porosity and/or low pore diameter propylene polymers; propylene polymerization processes using the supported catalysts and/or to prepare the high porosity and/or low pore diameter propylene polymers, bimodal polymers and/or heterophasic copolymers.

First claim

What is claimed is:

1 . A single site catalyst system comprising:
(a) a single site catalyst precursor compound; (b) an activator; and (c) a support having an average particle size of more than 30 μm up to 200 μm, a specific surface area of 400 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 20 nm (10 to 200 Å), the support comprising agglomerates of a plurality of primary particles.

2 . The catalyst system of claim 1 , wherein the average particle size is more than 50 μm, and the specific surface area is less than 1000 m 2 /g.

3 . The catalyst system of claim 1 , wherein the specific surface area is more than 650 m 2 /g, the mean pore diameter is less than 7 nm (70 Å), and the activator comprises methylalumoxane.

4 . The catalyst system of claim 1 , wherein the specific surface area is less than 650 m 2 /g, the mean pore diameter is more than 7 nm (70 Å), or a combination thereof.

5 . The catalyst system of claim 1 , wherein the primary particles have an average particle size from 1 nm to 50 μm.

6 . The catalyst system of claim 1 , wherein the agglomerates are at least partially encapsulated.

7 . The catalyst system of claim 1 , wherein the support comprises spray dried silica.

8 . The catalyst system of claim 1 , wherein the activator comprises methylalumoxane.

9 . The catalyst system of claim 1 , further comprising a co-activator selected from the group consisting of: trialkylaluminum, dialkylmagnesium, alkylmagnesium halide, and dialkylzinc.

10 . The catalyst system 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.

11 . A single site catalyst system comprising:
(a) a single site catalyst precursor compound; (b) an activator; (c) a support having an average particle size of more than 30 μm up to 200 μm, a specific surface area of 400 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 20 nm (10 to 200 Å); (d) a polypropylene matrix having a porosity of at least 15%, and a volume average median pore diameter of less than 165 μm, as determined by mercury intrusion porosimetry; and (e) active catalyst sites distributed in the matrix.

12 . A process, comprising:
supporting an activator for a single site precursor compound on a support, the support having an average particle size of more than 30 μm up to 200 μm, a specific surface area of 400 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 20 nm (10 to 200 Å); and contacting the activator and a single site catalyst precursor compound to form a supported catalyst system having an average particle size of more than 30 μm up to 200 μm.

13 . The process of claim 12 , wherein the support comprises agglomerates of a plurality of primary particles having an average size from 1 nm to 50 μm.

14 . The process of claim 12 , wherein the supported activator is essentially free of fines.

15 . The process of claim 12 , 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.

16 . The process of claim 12 , wherein the specific surface area is more than 650 m 2 /g, the mean pore diameter is less than 7 nm (70 Å), the activator comprises alumoxane, and the supporting comprises contacting the activator and the support at a temperature of 40° C. or below.

17 . The process of claim 12 , wherein the specific surface area is less than 650 m 2 /g or the mean pore diameter is greater than 7 nm (70 Å), or both, the activator comprises alumoxane, and the supporting comprises contacting the activator and the support at a temperature from −60 to 130° C.

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

19 . The process of claim 12 , 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 selec

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Luo Lubin
• Day Gregory S
• Yang Jian
• Holtcamp Matthew W

Classifications

• C08F110/06 Primary

  Propene · CPC title

• C08J2423/06

  Polyethene · CPC title

• C08J9/00 Primary

  Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof (mechanical aspects of shaping of plastics or substances in a plastic state for the production of porous or cellular articles B29C) · CPC title

• C08J2323/12

  Polypropene · CPC title

• C08F2420/09

  Cyclic bridge, i.e. Cp or analog where the bridging unit linking the two Cps or analogs is part of a cyclic group · CPC title