Catalyst system comprising supported alumoxane and unsupported alumoxane particles

Patent metadata

Field	Value
Publication number	US-10329360-B2
Application number	US-201615570849-A
Country	US
Kind code	B2
Filing date	Jun 3, 2016
Priority date	Jun 5, 2015
Publication date	Jun 25, 2019
Grant date	Jun 25, 2019

Abstract

The invention is directed to a supported olefin polymerization catalyst system comprising catalyst compound, silica support and alumoxane activator, where part of the alumoxane is present on the support and part of the alumoxane is not associated with the support, wherein the silica comprises silica particles having an average surface area of greater than about 400 m2/g, an average pore diameter of less than about 70 Angstroms, and wherein alumoxane is present on the support in an amount of less than 7 mmol Al/g silica and at least 1 wt % of alumoxane particles not associated with the support are present in the catalyst system, based upon the weight of the catalyst system.

First claim

What is claimed is:

1. A catalyst system comprising catalyst compound, silica support and alumoxane activator, where part of the alumoxane is present on the support, supported alumoxane, and part of the alumoxane is not associated with the support, unsupported alumoxane,
wherein:
i) the support comprises silica particles having, prior to combination with the alumoxane, an average surface area of greater than about 400 m 2 /g and an average pore diameter of less than about 70 Angstroms;
ii) alumoxane is present on the support in an amount of less than 7 mmol Al/g silica; and
iii) the catalyst system comprises at least 1 wt % of unsupported alumoxane particles, based upon the weight of the catalyst system.

2. The catalyst system of claim 1 , wherein the silica support, prior to combination with the alumoxane, has an average particle size of 50 μm or more.

3. The catalyst system of claim 1 , wherein the silica support, prior to combination with the alumoxane, has an average surface area of from 450 to 800 m 2 /g.

4. The catalyst system of claim 1 , wherein the silica support, prior to combination with the alumoxane, has an average pore diameter of from 50 to 70 Angstrom.

5. The catalyst system of claim 1 , wherein the silica support, prior to combination with the alumoxane, has an average pore volume of from about 0.5 to 2.5 ml/g of silica.

6. The catalyst system of claim 1 , wherein the weight ratio of the supported alumoxane to the unsupported alumoxane is from about 1:1 to 1:15.

7. The catalyst system of claim 1 , wherein the unsupported alumoxane particles have an average particle size of 2 to 20 μm.

8. The catalyst system of claim 1 , wherein the unsupported alumoxane particles have a surface area differing by 10% or more from the surface area of the supported alumoxane particles.

9. The catalyst system of claim 1 , wherein the alumoxane comprises methylalumoxane.

10. The catalyst system of claim 1 , wherein the support is spray dried.

11. The catalyst system of claim 1 , further comprising a co-activator selected from the group consisting of: trialkylaluminum, dialkylaluminum halide, dialkylaluminum alkoxide, dialkylmagnesium, alkylmagnesium halide, dialkylzinc, or any combination thereof.

12. The catalyst system of claim 1 , wherein the catalyst compound is selected from precursor compounds I or II;
wherein precursor compound I is represented by the following formula:
(Cp) m R A * n M 4 Q k   (I)

wherein:
each Cp is a cyclopentadienyl, indenyl, or fluorenyl moiety substituted by one or more hydrocarbyl radicals having from 1 to 20 carbon atoms;
R A * is a 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 is optionally 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 is optionally 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   (II)

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 is 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.

13. The catalyst system of claim 1 , wherein the catalyst compound is represented by the formula:

where:
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 R13 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.

14. The catalyst system of claim 1 , where the catalyst compound is represented by the formula:

M is a group 4 transition metal;
X 1 and X 2 are, independently, a univalent C 1 to C 20 hydrocarbyl radical, a C 1 to C 20 substituted hydrocarbyl radical, a heteroatom or a heteroatom-containing group, or X 1 and X 2 join together to form a C 4 to C 62 cyclic or polycyclic ring structure;
each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 is, independently, a hydrogen, a C 1 to C 40 hydrocarbyl radical, a substituted C 1 to C 40 hydrocarbyl radical, a heteroatom, a heteroatom-containing group, or two or more of R 1 to R 10 optionally independently join together to form a C 4 to C 62 cyclic or polycyclic ring structure, or a combination thereof;
Y is a divalent C 1 to C 20 hydrocarbyl or a substituted divalent hydrocarbyl group;
J is a C 7 to C 60 fused polycyclic group, which, optionally, comprises up to 20 atoms from groups 15 and 16, where at least one ring is aromatic and where at least one ring, which is optionally aromatic, has at least 5 members that is fused to at least one other cyclic group;
G is, independently, as defined for J, a hydrogen, a C 1 to C 60 hydrocarbyl radical, a substituted hydrocarbyl radical, a heteroatom, or a heteroatom-containing group, or optionally independently forms a C 4 to C 60 cyclic or polycyclic ring structure with R 6 , R 7 , or R 8 or a combination thereof; and
Y is a divalent C 1 to C 20 hydrocarbyl or a substituted divalent hydrocarbyl group
Q* is a group 15 or 16 atom;
z is 0 or 1;
J* is CR″ or N;
G* is CR″ or N; and
each R″, R*, R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , and R 27 is, independently, as defined for R 1 .

15. The catalyst system of claim 1 , where the catalyst compound is represented by the formula:

wherein M is a group 4 transition metal;
X 1 and X 2 are, independently, a univalent C 1 to C 20 hydrocarbyl radical, a C 1 to C 20 substituted hydrocarbyl radical, a heteroatom or a heteroatom-containing group, or X 1 and X 2 join together to form a C 4 to C 62 cyclic or polycyclic ring structure;
each R 1 , R 2 , R 3 , R 4 , R 5 ,

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Luo Lubin

Classifications

• C08F210/06

  Propene · CPC title

• C08F2/001

  Multistage polymerisation processes characterised by a change in reactor conditions without deactivating the intermediate polymer (C08F295/00, C08F297/00 take precedence) · CPC title

• C08F4/65916

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

• C08F4/02

  Carriers therefor · CPC title

• C08F10/06

  Propene · CPC title