Supported catalyst systems and processes for use thereof

Patent metadata

Field	Value
Publication number	US-10647786-B2
Application number	US-201615564572-A
Country	US
Kind code	B2
Filing date	Mar 10, 2016
Priority date	Apr 20, 2015
Publication date	May 12, 2020
Grant date	May 12, 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, an activator and a support material. The catalyst system may be used for preparing ultrahigh molecular weight polyolefins.

First claim

What is claimed is:

1. A supported catalyst system comprising:
(i) a pyridyldiamido transition metal complex having the general formula (II) or (III);

(ii) an activator; and
(iii) a fluorided support material;

wherein;
M is Ti, Zr, or Hf;
R 1 , R 1 , R 11 , and R 11 are independently selected from the group consisting of phenyl groups that are variously substituted with between zero to five substituents selected from F, Cl, Br, I, CF 3 , NO 2 , alkoxy groups having one to ten carbons, dialkylamino groups having one to ten carbons, hydrocarbyl groups having one to ten carbons, and substituted hydrocarbyl groups having one to ten carbons;
R 2 , R 2 , R 10 , and R 10 are independently —E(R 12 )(R 13 )— with E being carbon, 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 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 3 , R 4 , R 4 , R 5 , and R 5 are independently selected from the group consisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, aryloxy, halogen, amino, and silyl, and wherein adjacent R groups (R 3 & R 4 , R 3 & R 4 , R 4 & R 5 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;
R 6 , R 6 , R 7 , R 7 , R 8 , R 8 , R 9 , 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 the pairs of positions, and wherein adjacent R groups (R 6 & R 7 , R 7 & R 8 , R 8 & R 9 , R 9 &R 10 , R 6 & R 7 , R 7 & R 16 , 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;
L is an anionic leaving group selected from halide, alkyl, aryl, alkoxy, amido, hydrido, phenoxy, hydroxy, silyl, allyl, alkenyl, and alkynyl, 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 a neutral Lewis base selected from ethers, thio-ethers, amines, nitriles, imines, pyridines, and phosphines;
w is 0, 1, 2, 3 or 4, and
wherein the supported catalyst system increases an incorporation of a comonomer into a copolymer during polymerization of a monomer and the comonomer in the presence of the supported catalyst system as compared to a comparative catalyst system that is the same as the supported catalyst system except the support material in the comparative catalyst system is a non-fluorided support material.

2. The supported catalyst system of claim 1 , wherein the groups represented by R 3 to R 9 , or R 12 to R 15 each contain 2 to 20 carbon atoms, and wherein the groups represented by R 1 or R 11 each contain 6 to 20 carbon atoms.

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

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

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

6. The supported catalyst system of claim 1 , wherein the fluorided support material comprises fluorided silica.

7. A process for polymerization of olefin monomers comprising: contacting a monomer and a comonomer with a supported catalyst system to produce a copolymer, wherein the polymerization is carried out in the slurry or gas phase, and wherein the supported catalyst system comprises:
(i) a pyridyldiamido transition metal complex having the general formula (II) or (III);

(ii) an activator; and
(iii) a fluorided support material;

wherein:
M is Ti, Zr, or Hf;
R 1 , R 1 , R 11 , and R 11 are independently selected from the group consisting of phenyl groups that are variously substituted with between zero to five substituents selected from F, Cl, Br, I, CF 3 , NO 2 , alkoxy groups having one to ten carbons, dialkylamino groups having one to ten carbons, hydrocarbyl groups having one to ten carbons, and substituted hydrocarbyl groups having one to ten carbons;
R 2 , R 2 , R 10 , and R 10 are independently, —E(R 12 )(R 13 )— with E being carbon, 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 3 , R 3 , R 4 , R 4 , R 5 , and R 5 are independently selected from the group consisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, aryloxy, halogen, amino, and silyl, and wherein adjacent R groups (R 3 & R 4 , R 3 & R 4 , R 4 & R 5 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;
R 6 , R 6 , R 7 , R 7 , R 8 , R 8 , R 9 , 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 the pairs of positions, and wherein adjacent R groups (R 6 & R 7 , R 7 & R 8 , R 8 & R 9 , R 9 & R 10 , R 6 & R 7 , R 7 & R 16 , 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;
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;
w is 0, 1, 2, 3 or 4, and
wherein the supported catalyst system increases an incorporation of the comonomer into the copolymer as compared to a comparative catalyst system that is the same as the supported catalyst system except the support material in the comparative catalyst system is a non-fluorided support material.

8. The process of claim 7 , wherein the fluorided support material has a surface area in the range of from 10 m 2 /g to 700 m 2 /g and an average particle diameter in the range of from 10 μm to 500 μm.

9. The process of claim 7 , wherein the fluorided support material is selected from the group consisting of fluorided silica, fluorided alumina, fluorided silica-alumina, and combinations thereof.

10. The process of claim 7 , wherein the fluorided support material comprises a support material having a fluorine concentration

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Ye Xuan
• Hagadorn John R
• Holtcamp Matthew W
• Day Gregory S
• Sanders David F

Classifications

• C08F4/65916

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

• C08F4/60148

  NN(R)N · CPC title

• C08F4/65912

  in combination with an organoaluminium compound · CPC title

• C08F4/642

  Component covered by group C08F4/64 with an organo-aluminium compound {(C08F4/64003 - C08F4/64196 take precedence)} · CPC title

• C08F10/02

  Ethene · CPC title