Co-supported catalysts for the tandem trimerization and polymerization of ethylene to produce linear low density polyethylene

Patent metadata

Field	Value
Publication number	US-9969828-B2
Application number	US-201715411583-A
Country	US
Kind code	B2
Filing date	Jan 20, 2017
Priority date	Jan 21, 2016
Publication date	May 15, 2018
Grant date	May 15, 2018

Abstract

Linear low density polyethylene (LLDPE) is produced from an ethylene-only feed over a tandem catalyst system consisting of a phenoxy-imine titanium trimerization catalyst and a silylene-linked cyclopentadienyl/amido titanium polymerization catalyst co-supported on the same methylaluminoxane/silica particles. The level of 1-hexene incorporation in the LLDPE can be controlled by varying the ethylene pressure. Tandem, co-silica-supported ethylene trimerization and ethylene/1-hexene copolymerization catalysts produce linear low density polyethylene (LLDPE) from an ethylene-only feedstock. The percentage 1-hexene incorporation in the LLDPE may be varied by adjusting the amounts of the two catalysts on the silica support.

First claim

The invention claimed is:

1. A supported catalyst system, comprising:
a. a trimerization catalyst, wherein the trimerization catalyst is a cationic metal coordination complex of Formula Ia:

wherein,
M 1 is Ti, Zr, or Hf;
Z 1b and Z 1c are independently hydrogen or an optionally substituted substituent;
R 1a is selected from hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, heteroalkyl, substituted heteroalkyl, heteroaryl, substituted heteroaryl, cyclyl, substituted cyclyl, heterocyclyl, and substituted heterocyclyl;
R 1b , R 1c , R 1d , and R 1e are independently hydrogen or an optionally substituted substituent;
R 1f , R 1g , R 1h , and R 1i are independently hydrogen or an optionally substituted substituent; and
R 1j , R 1k , R 1l , and R 1m are independently hydrogen or an optionally substituted substituent;
b. a polymerization catalyst, wherein the polymerization catalyst is a cationic metal coordination complex of Formula IIa:

wherein,
M 2 is Ti, Zr, or Hf;
Z 2b is hydrogen or an optionally substituted substituent;
X 2a is O or N;
Q 2a is C or Si;
R 2a is absent when X 2a is O, or R 2a is selected from hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, heteroalkyl, substituted heteroalkyl, heteroaryl, substituted heteroaryl, cyclyl, substituted cyclyl, heterocyclyl, and substituted heterocyclyl when X 2a is N;
R 2b and R 2c are independently hydrogen or an optionally substituted substituent; and
R 2d , R 2e , R 2f , and R 2g are independently hydrogen or an optionally substituted substituent; and

c. an activated solid support, wherein the trimerization catalyst and the polymerization catalyst are attached to the activated solid support.

2. The supported catalyst system of claim 1 , wherein
M 1 is Ti;
M 2 is Ti;
Z 1b and Z 1c are independently selected from alkyl and substituted alkyl;
Z 2b is selected from alkyl and substituted alkyl; and
R 2b and R 2c are independently selected from hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, heteroalkyl, substituted heteroalkyl, heteroaryl, substituted heteroaryl, cyclyl, substituted cyclyl, heterocyclyl, and substituted heterocyclyl.

3. The supported catalyst system of claim 1 , wherein the cationic metal coordination complex of Formula Ia is:

and
the cationic metal coordination complex of Formula IIa is:

4. The supported catalyst system of claim 1 , wherein the activated solid support comprises an activator and a solid support, wherein the activator is attached to the solid support.

5. The supported catalyst system of claim 4 , wherein the activator is an aluminum compound.

6. The supported catalyst system of claim 4 , wherein the solid support comprises an inorganic material, an organic material, or a combination thereof.

7. The supported catalyst system of claim 1 , wherein the trimerization catalyst and the polymerization catalyst are attached to the same activated solid support.

8. A method to prepare a supported catalyst system of claim 1 , comprising:
a. obtaining a solid support;
b. contacting the solid support with an activator to obtain an activated solid support; and
c. contacting the activated solid support with a precatalyst mixture, wherein the precatalyst mixture comprises a trimerization precatalyst, a polymerization precatalyst, and an optional solvent, wherein the trimerization precatalyst is a metal coordination complex of Formula I:

wherein,
M 1 is Ti, Zr, or Hf;
Z 1a , Z 1b , and Z 1c are independently hydrogen or an optionally substituted substituent;
R 1a is selected from hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, heteroalkyl, substituted heteroalkyl, heteroaryl, substituted heteroaryl, cyclyl, substituted cyclyl, heterocyclyl, and substituted heterocyclyl;
R 1b , R 1c , R 1d , and R 1e are independently hydrogen or an optionally substituted substituent;
R 1f , R 1g , R 1h , and R 1i are independently hydrogen or an optionally substituted substituent; and
R 1j , R 1k , R 1l , and R 1m are independently hydrogen or an optionally substituted substituent; and

the polymerization precatalyst is a metal coordination complex of Formula II:

wherein,
M 2 is Ti, Zr, or Hf;
Z 2a and Z 2b are independently hydrogen or an optionally substituted substituent;
X 2a is O or N;
Q 2a is C or Si;
R 2a is absent when X 2a is O, or R 2a is selected from hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, heteroalkyl, substituted heteroalkyl, heteroaryl, substituted heteroaryl, cyclyl, substituted cyclyl, heterocyclyl, and substituted heterocyclyl when X 2a is N;
R 2b and R 2c are independently hydrogen or an optionally substituted substituent; and
R 2d , R 2e , R 2f , and R 2g are independently hydrogen or an optionally substituted substituent.

9. The method of claim 8 , wherein M 1 is Ti; and M 2 is Ti.

10. The method of claim 8 , wherein the metal coordination complex of Formula I is:

and
the metal coordination complex of Formula II is:

11. The method of claim 8 , wherein the activator comprises an aluminum compound.

12. The method of claim 8 , wherein the solid support comprises an inorganic material, an organic material, or a combination thereof.

13. A method for the preparation of a linear low density polyethylene (LLDPE) polymer, comprising:
a. providing a supported catalyst system of claim 1 ;
b. contacting the supported catalyst system of claim 1 with ethylene under conditions effective to promote the tandem trimerization and polymerization of ethylene to form the linear low density polyethylene polymer.

14. The method of claim 13 , wherein
M 1 is Ti;
M 2 is Ti;
Z 1b and Z 1c are independently selected from alkyl and substituted alkyl;
Z 2b is selected from alkyl and substituted alkyl; and
R 2b and R 2c are independently selected from hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, heteroalkyl, substituted heteroalkyl, heteroaryl, substituted heteroaryl, cyclyl, substituted cyclyl, heterocyclyl, and substituted heterocyclyl.

15. The method of claim 13 , wherein the cationic metal coordination complex of Formula Ia is:

and
the cationic metal coordination complex of Formula IIa is:

16. The method of claim 13 , wherein the activated solid support comprises an activator and a solid support, wherein the activator is attached to the solid support.

17. The method of claim 16 , wherein the activator is an aluminum co

Assignees

• California Inst Of Techn
• Univ King Fahd Pet & Minerals

Inventors

• Aluthge Dinesh C
• Sattler Aaron
• Al-Harthi Mamdouh
• Labinger Jay A
• Bercaw John E

Classifications

• C08F4/64124

  ONO · CPC title

• C08F210/16 Primary

  Copolymers of ethene with alpha-alkenes, e.g. EP rubbers · CPC title

• C08F4/60124

  ONO · CPC title

• C08F2500/08

  Low density, i.e. < 0.91 g/cm3 · CPC title

• C08F110/02

  Ethene · CPC title