Olefin polymerization catalyst system comprising mesoporous organosilica support

Patent metadata

Field	Value
Publication number	US-10155826-B2
Application number	US-201515526524-A
Country	US
Kind code	B2
Filing date	Dec 11, 2015
Priority date	Dec 12, 2014
Publication date	Dec 18, 2018
Grant date	Dec 18, 2018

Abstract

A catalyst system comprising a combination of: 1) one or more catalyst compounds comprising at least one oxygen linkage, such as a phenoxide transition metal compound; 2) a support comprising an organosilica material, which may be a mesoporous organosilica material; and 3) an optional activator. Useful catalysts include biphenyl phenol catalysts (BPP). The organosilica material may be a polymer of at least one monomer of Formula [Z 1 OZ 2 SiCH 2 ] 3 (I), where Z 1 represents a hydrogen atom, a C 1 -C 4 alkyl group, or a bond to a silicon atom of another monomer and Z 2 represents a hydroxyl group, a C 1 -C 4 alkoxy group, a C 1 -C 6 alkyl group, or an oxygen atom bonded to a silicon atom of another monomer. This invention further relates to processes to polymerize olefins comprising contacting one or more olefins with the above catalyst system.

First claim

What is claimed is:

1. A catalyst system comprising:
(1) one or more olefin polymerization catalyst compounds comprising a phenoxide transition metal compound;
(2) a catalyst support comprising an organosilica material that is a polymer of at least one monomer of Formula [Z 1 OZ 2 SiCH 2 ] 3 (I), wherein Z 1 represents a hydrogen atom, a C 1 -C 4 alkyl group, or a bond to a silicon atom of another monomer and Z 2 represents a hydroxyl group, a C 1 -C 4 alkoxy group, a C 1 -C 6 alkyl group, or an oxygen atom bonded to a silicon atom of another monomer; and
(3) an optional activator.

2. The catalyst system of claim 1 , wherein Z 2 represents a hydroxyl group, a C 1 -C 4 alkoxy group, or an oxygen atom bonded to a silicon atom of another monomer.

3. The catalyst system of claim 1 , wherein Z 1 represents a hydrogen atom, methyl, ethyl or a bond to a silicon atom of another monomer and Z 2 represents a hydroxyl group, methyl, ethyl, ethoxy, methoxy, or an oxygen bonded to a silicon atom of another monomer.

4. The catalyst system of claim 1 , wherein the polymer further comprises a second distinct monomer of Formula [Z 1 OZ 2 SiCH 2 ] 3 (I).

5. The catalyst system of claim 1 , wherein the organosilica material further comprises at least one monomer selected from the group consisting of:
(i) a monomer of Formula Z 3 OZ 4 Z 5 Z 6 Si (II), wherein Z 3 represents a hydrogen atom or a C 1 -C 4 alkyl group, or a bond to a silicon atom of another monomer; and Z 4 , Z 5 and Z 6 are each independently selected from the group consisting of a hydroxyl group, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, a nitrogen-containing C 1 -C 10 alkyl group, a nitrogen-containing heteroaralkyl group, and a nitrogen-containing optionally substituted heterocycloalkyl group, and an oxygen atom bonded to a silicon atom of another monomer;
(ii) a monomer of Formula Z 7 Z 8 Z 9 Si—R 1 —SiZ 7 Z 8 Z 9 (III), wherein Z 7 represents a hydroxyl group, a C 1 -C 4 alkoxy group, or an oxygen atom bonded to a silicon atom of another comonomer; Z 8 and Z 9 each independently represent a hydroxyl group, a C 1 -C 4 alkoxy group, a C 1 -C 4 alkyl group, or an oxygen bonded to a silicon atom of another monomer; and R 1 is selected from the group consisting of a C 1 -C 8 alkylene group, a C 2 -C 8 alkenylene group, a C 2 -C 8 alkynylene group, a nitrogen-containing C 2 -C 10 alkylene group, an optionally substituted C 6 -C 20 aralkyl and an optionally substituted C 4 -C 20 heterocycloalkyl group;
(iii) a trivalent metal oxide monomer of Formula M 1 (OZ 10 ) 3 (IV), wherein M 1 represents a Group 13 metal and Z 10 represents a hydrogen atom, a C 1 -C 6 alkyl or a bond to a silicon atom of another monomer;
(iv) a trivalent metal oxide monomer of Formula (Z 11 O) 2 M 2 —O—Si(OZ 12 ) 3 (V), wherein M 2 represents a Group 13 metal and Z 11 and Z 12 each independently represent a hydrogen atom, a C 1 -C 6 alkyl group, or a bond to a silicon atom of another monomer;
(v) a cyclic polyurea monomer of Formula

wherein each R 2 is a Z 13 OZ 14 Z 15 SiZ 16 group, wherein Z 13 represents a hydrogen atom, a C 1 -C 4 alkyl group, or a bond to a silicon atom of another monomer unit; Z 14 and Z 15 each independently represent a hydroxyl group, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or an oxygen atom bonded to a silicon atom of another monomer unit; and Z 16 represents a C 1 -C 8 alkylene group bonded to a nitrogen atom of the cyclic polyurea; and
(vi) any combinations thereof.

6. The catalyst system of claim 1 , wherein the catalyst support comprising the organosilica material has: i) an average pore diameter between about 2 nm and about 50 nm; ii) a pore volume about 0.1 cm 3 /g to about 10 cm 3 /g; and/or iii) a surface area of about 100 m 2 /g to about 2,500 m 2 /g.

7. The catalyst system of claim 1 , wherein the catalyst support comprising the organosilica material has an X-Ray Diffraction Spectrum exhibiting substantially no peaks above 4 degrees 2θ, and/or is made using substantially no added structure directing agent or porogen.

8. The catalyst system of claim 1 , wherein the phenoxide transition metal compound is selected from the group consisting of:
(A) a compound represented by Formula (VII):

wherein:
M is selected from the group consisting of Ti, Zr, and Hf;
each R 1 through R 9 may be independently selected from the group consisting of hydride, hydrocarbyl, lower hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, alkyl, lower alkyl, substituted alkyl, heteroalkyl, alkenyl, lower alkenyl, substituted alkenyl, heteroalkenyl, alkynyl, lower alkynyl, substituted alkynyl, heteroalkynyl, alkoxy, lower alkoxy, aryloxy, hydroxyl, alkylthio, lower alkyl thio, arylthio, thioxy, aryl, substituted aryl, heteroaryl, aralkyl, aralkylene, alkaryl, alkarylene, halide, haloalkyl, haloalkenyl, haloalkynyl, heteroalkyl, heterocycle, heteroaryl, heteroatom-containing group, silyl, boryl, phosphino, phosphine, amino, and amine; and
X is at least one leaving group.

9. The catalyst system of claim 8 , wherein M is selected from the group consisting of Ti, Zr, and Hf; each R 2 is selected from the group consisting of alkyls, aryls, and heteroaryls; each R 4 is selected from the group consisting of H, alkyls, and aryls; and X is selected from the group consisting of F, Cl, Br, I, Me, Bnz, CH 2 SiMe 3 , and C 1 to C 5 alkyls or alkenyls.

10. The catalyst system of claim 8 , wherein each R 1 is independently selected from the group consisting of CH 2 CH 2 , (CH 2 ) 3 , (CH 2 ) 4 , CH 2 CHMeCH 2 , CH 2 CMe 2 CH 2 , Me 2 Si, CH 2 SiMe 2 CH 2 , and CH 2 SiR 2 CH 2 ; each R 2 may be any aryl group with substituents in the 2 and 6 positions; each R 3 and R 5 through R 9 are H; each R 4 is selected from the group consisting of H, Methyl, Ethyl, Propyl, Butyl, and Pentyl; and X is selected from the group consisting of F, Cl, Br, I, Me, Bnz, CH 2 SiMe 3 , and C 1 to C 5 alkyls or alkenyls.

11. The catalyst system of claim 8 , wherein M is either Zr or Hf; each R 1 is either (CH 2 ) 3 or (CH 2 ) 4 ; each R 2 is selected from the group consisting of 2,6-Me 2 Ph, 2,6-Et 2 Ph, 2,6-Pr 2 -Ph, 2,6-Bu 2 Ph, 2-MeNapthyl, 2,4,6-Me 3 Ph, 2,4,6-Et 3 Ph, 2,4,6-Pr 3 Ph, and carbazole; each R 4 is selected from the group consisting of H, Methyl and Butyl; and X is selected from the group consisting of F, Cl, and Me.

12. The catalyst system of claim 8 , wherein R 1 is (CH 2 ) 3 ; each R 2 is either 2,4,6-Me3Ph or 2-MeNapthyl; each R 4 is CH 3 ; X is Cl; and M is Zr.

13. The catalyst system of claim 1 , further comprising at least one activator.

14. A process to produce polymer comprising:
i) contacting one or more olefin monomers, with a catalyst system of claim 13 , and
ii) obtaining a polymer.

15. The process of claim 14 , wherein the polymer is an ethylene polymer or a propylene polymer.

16. The process of claim 14 , wherein the process occurs at a temperature of from about 0° C. to about 300° C., at a pressure in the range of from about 0.35 MPa to about 10 MPa, and at a time up to 300 minutes.

17. The process of claim 14 , wherein the one or more olefin monomers comprise ethylene and one or more comonomer selected from propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, and mixtures thereof.

1

Assignees

• Exxonmobil Res & Eng Co

Inventors

• Holtcamp Matthew W
• Harlan Charles J
• Li Quanchang
• Mertens Machteld M W

Classifications

• C08F210/08

  Butenes · CPC title

• C08F210/14

  Monomers containing five or more carbon atoms · CPC title

• C08F210/06

  Propene · CPC title

• C08F210/02 Primary

  Ethene · CPC title

• B01D71/702

  Polysilsesquioxanes or combination of silica with bridging organosilane groups · CPC title