Supported catalyst systems and processes for use thereof

Patent metadata

Field	Value
Publication number	US-10533063-B2
Application number	US-201615565603-A
Country	US
Kind code	B2
Filing date	Mar 10, 2016
Priority date	Apr 20, 2015
Publication date	Jan 14, 2020
Grant date	Jan 14, 2020

Abstract

This invention relates to a supported catalyst system and process for use thereof. In particular, the catalyst system includes a pyridyldiamido transition metal complex, a metallocene compound, a support material and, optionally, an activator. The catalyst system may be used for preparing multi-modal polyolefins.

First claim

The invention claimed is:

1. A supported catalyst system comprising:
(i) at least one first catalyst component comprising a pyridyldiamido transition metal complex;
(ii) at least one second catalyst component comprising a metallocene compound; and
(iii) a fluorided support material,
wherein the pyridyldiamido transition metal complex has the general formula (I):

wherein,
M is Ti, Zr, or Hf;
Z is —(R 14 ) p C-C(R 15 ) q —, where R 14 and R 15 are independently selected from the group consisting of hydrogen, hydrocarbyls, and substituted hydrocarbyls, and wherein adjacent R 14 and R 15 groups may be joined to form an aromatic or saturated, substituted or unsubstituted hydrocarbyl ring, where the ring has 5, 6, 7, or 8 ring carbon atoms and where substitutions on the ring can join to form additional rings,
p is 0, 1 or 2, and
q is 0, 1 or 2;
R 1 and R 11 are independently selected from the group consisting of hydrocarbyls, substituted hydrocarbyls, and silyl groups;
R 2 and R 10 are each, independently, -E(R 12 )(R 13 ) — with E being carbon, silicon, or germanium, and each R 12 and R 13 being independently selected from the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls, halogen, and phosphino, R 12 and R 13 may be joined to each other or to R 14 or R 15 to form a saturated, substituted or unsubstituted hydrocarbyl ring, where the ring has 4, 5, 6, or 7 ring carbon atoms and where substitutions on the ring can join to form additional rings, or R 12 and R 13 may be joined to form a saturated heterocyclic ring, or a saturated substituted heterocyclic ring where substitutions on the ring can join to form additional rings;
R 3 , R 4 , and R 5 are independently selected from the group consisting of hydrogen, hydrocarbyls (such as alkyls and aryls), substituted hydrocarbyls, alkoxy, aryloxy, halogen, amino, and silyl, and wherein adjacent R groups (R 3 & R 4 , and/or R 4 & R 5 ) may be joined to form a substituted or unsubstituted hydrocarbyl or heterocyclic ring, where the ring has 5, 6, 7, or 8 ring atoms and where substitutions on the ring can join to form additional rings;
L is an anionic leaving group, where the L groups may be the same or different and any two L groups may be linked to form a dianionic leaving group;
n is 0, 1, 2, 3, or 4;
L′ is neutral Lewis base; and
w is 0, 1, 2, 3, or 4.

2. The supported catalyst system of claim 1 , wherein the pyridyldiamido transition metal complex is represented by the formula (II):

wherein:
R 6 , R 7 , R 8 , and R 9 are independently selected from the group consisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, halogen, amino, and silyl, and the pairs of positions, and wherein adjacent R groups (R 6 &R 7 , and/or R 7 &R 8 , and/or R 8 &R 9 , and/or R 9 &R 10 ) may be joined to form a saturated, substituted or unsubstituted hydrocarbyl or heterocyclic ring, where the ring has 5, 6, 7, or 8 ring carbon atoms and where substitutions on the ring can join to form additional rings; and
M, L, L′, w, n, R 1 , R 2 , R 3 , R 4 , R 5 , R 10 and R 11 are as defined in claim 1 .

3. The supported catalyst system of claim 1 , wherein the pyridyldiamido transition metal complex is represented by the formula (III):

wherein,
R 6 , R 7 , R 8 , R 9 , R 16 , and R 17 are independently selected from the group consisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, halogen, amino, and silyl, and wherein adjacent R groups (R 6 & R 7 , and/or R 7 & R 16 , and/or R 16 & R 17 , and/or R 8 & R 9 ) may be joined to form a saturated, substituted or unsubstituted hydrocarbyl or heterocyclic ring, where the ring has 5, 6, 7, or 8 ring carbon atoms and where substitutions on the ring can join to form additional rings; and
M, L, L′, w, n, R 1 , R 2 , R 3 , R 4 , R 5 , R 10 and R 11 are as defined in claim 1 .

4. The supported catalyst system of claim 1 , wherein the metallocene compound is represented by the formula Cp A Cp B M′X′ n , wherein Cp A and Cp B may each be independently selected from the group consisting of cyclopentadienyl ligands and ligands isolobal to cyclopentadienyl, either or both Cp A and Cp B may contain heteroatoms, and either or both Cp A and Cp B may be substituted; wherein M′ is Ti, Zr, or Hf; wherein X′ may be any leaving group; wherein n is 0, 1, 2, 3, or 4.

5. The supported catalyst system of claim 1 , wherein the metallocene compound is selected from the group consisting of:
bis(cyclopentadienyl)zirconium dichloride,
bis(n-butylcyclopentadienyl)zirconium dichloride,
bis(n-butylcyclopentadienyl)zirconium dimethyl,
bis(pentamethylcyclopentadienyl)zirconium dichloride,
bis(pentamethylcyclopentadienyl)zirconium dimethyl,
bis(pentamethylcyclopentadienyl)hafnium dichloride,
bis(pentamethylcyclopentadienyl)zirconium dimethyl,
bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dichloride,
bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dimethyl,
bis(1-methyl-3-n-butylcyclopentadienyl)hafnium dichloride,
bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dimethyl,
bis(indenyl)zirconium dichloride, bis(indenyl)zirconium dimethyl,
bis(tetrahydro-1-indenyl)zirconium dichloride,
bis(tetrahydro-1-indenyl)zirconium dimethyl,
(n-propyl cyclopentadienyl, pentamethyl cyclopentadienyl)zirconium dichloride, and
(n-propylcyclopentadienyl, pentamethyl cyclopentadienyl)zirconium dimethyl.

6. The supported catalyst system of claim 1 , wherein the fluorided support material has a surface area in the range of from 10 to 700 m 2 /g and an average particle diameter in the range of from 10 to 500 μm.

7. The supported catalyst system of claim 1 , wherein the fluorided support material is selected from the group consisting of silica, alumina, silica-alumina, and combinations thereof.

8. The supported catalyst system of claim 1 , wherein the supported catalyst system further comprises an activator.

9. The supported catalyst system of claim 1 , wherein the fluorided support material has a fluorine concentration in the range of 0.6 to 3.5 wt %, based upon the weight of the fluorided support material.

10. The supported catalyst system of claim 1 , wherein the activator comprises alumoxane.

11. A process for polymerization of olefin monomers comprising contacting one or more monomers with a supported catalyst system, wherein the supported catalyst system comprises:
(i) at least one first catalyst component comprising a pyridyldiamido transition metal complex;
(ii) at least one second catalyst component comprising a metallocene compound; and
(iii) a fluorided support material,

wherein the pyridyldiamido transition metal complex has the general formula (I):

wherein,
M is Ti, Zr, or Hf;
Z is —(R 14 ) p C-C(R 15 ) q —, where R 14 and R 15 are independently selected from the group consisting of hydrogen, hydrocarbyls, and substituted hydrocarbyls, and wherein adjacent R 14 and R 15 groups may be joined to form an aromatic or saturated, substituted or unsubstituted hydrocarbyl ring, where the ring has 5, 6, 7, or 8 ring carbon atoms and where substitutions on the ring can join to form additional rings,
p is 0, 1 or 2, and
q is 0, 1 or 2;
R 1 and R 11 are independently select

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Ye Xuan
• Hagadorn John R
• Holtcamp Matthew W
• Day Gregory S
• Sanders David F
• Lopez-Barron Carlos R

Classifications

• C08F4/659

  Component covered by group C08F4/64 containing a transition metal-carbon bond {(C08F4/64003 - C08F4/64196 take precedence)} · CPC title

• C08F4/65925

  two cyclopentadienyl rings being mutually non-bridged · 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

• C08F2500/12

  Melt flow index or melt flow ratio · CPC title