Olefin polymerization catalyst system comprising mesoporous organosilica support

Patent metadata

Field	Value
Publication number	US-10239967-B2
Application number	US-201515526512-A
Country	US
Kind code	B2
Filing date	Dec 11, 2015
Priority date	Dec 12, 2014
Publication date	Mar 26, 2019
Grant date	Mar 26, 2019

Abstract

A catalyst system comprising a combination of: 1) one or more catalyst compounds comprising at least one nitrogen linkage; 2) a support comprising an organosilica material, which is a mesoporous organosilica material; and 3) an optional activator. Useful catalysts include pyridyldiamido transition metal complexes, HN5 compounds, and bis(imino)pyridyl complexes. The organosilica material is a polymer of at least one monomer of Formula [Z 1 OZ 2 SiCH 2 ] 3 (1), 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 C1-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 nitrogen linkage to a Group 3-12 transition metal or a Group 13 or 14 main group metal;
(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:
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, 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 monomer; 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 aralkylene and an optionally substituted C 4 -C 20 heterocycloalkylene 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; 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; and Z 16 represents a C 1 -C 8 alkylene group bonded to a nitrogen atom of the cyclic polyurea; and
(vi) 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 one or more olefin polymerization catalyst compounds comprise at least one catalyst compound selected from the group consisting of:
(A) a compound represented by Formula (VII):

wherein:
M* is a Group 4 metal;
each E′ group is independently selected from carbon, silicon, or germanium;
each X′ is an anionic leaving group;
L* is a neutral Lewis base;
R′ 1 and R′ 13 are independently selected from the group consisting of hydrocarbyls, substituted hydrocarbyls, and silyl groups;
R′ 2 , R′ 3 , R′ 4 , R′ 5 , R′ 6 , R′ 7 , R′ 8 , R′ 9 , R′ 10 , R′ 11 , and R′ 12 are independently selected from the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls, halogen, and phosphino;
n′ is 1 or 2;
m′ is 0, 1, or 2; and
two X′ groups may be joined together to form a dianionic group;
two L* groups may be joined together to form a bidentate Lewis base;
an X′ group may be joined to an L* group to form a monoanionic bidentate group;
R′ 7 and R′ 8 may be joined to form a ring; and
R′ 10 and R′ 11 may be joined to form a ring;
(B) a compound represented by Formula (VIII):

wherein:
M is a Group 3-12 transition metal or a Group 13 or 14 main group metal;
each X is independently an anionic leaving group;
n is the formal oxidation state of M;
m is the formal charge of the ligand comprising Y, Z, and L;
Y is a Group 15 element;
Z is a Group 15 element;
L is a Group 15 or 16 element;
R 1 and R 2 are independently a C 1 to C 20 hydrocarbon group, a heteroatom-containing group having up to twenty carbon atoms, silicon, germanium, tin, lead, phosphorus, or a halogen, where R 1 and R 2 may also be interconnected to each other;
R 3 is absent or a hydrocarbon group, hydrogen, a halogen, or a heteroatom-containing group;
R 4 and R 5 are independently an aryl group, a substituted aryl group, a cyclic alkyl group, a substituted cyclic alkyl group, a cyclic aralkyl group, a substituted cyclic aralkyl group or multiple ring system; and
R 6 and R 7 are independently absent, or hydrogen, halogen, heteroatom or a hydrocarbyl group; and
(C) a compound represented by Formula (IX),

wherein:
M comprises a transition metal from Group 7, 8 or 9 of the Periodic Table of Elements;
X is an atom or group covalently or ionically bonded to the transition metal M;
n is 1, 2, 3, 4, or 5; and
R 1 to R 7 are independently selected from the group consisting of hydrogen, halogens, hydrocarbyls, and substituted hydrocarbyls, provided that when any two or more of R 1 to R 7 are hydrocarbyl or substituted hydrocarbyl, two or more may be linked to form one or more cyclic substituents.

9. The catalyst system of claim 8 , wherein the one or more olefin polymerization catalyst compounds comprise a catalyst compound of Formula (VII), wherein M* is hafnium, each E′ group is carbon, each X′ is an alkyl, aryl, hydride, alkylsilane, fluoride, chloride, bromide, iodide, triflate, carboxylate, or alkylsulfonate, each L* is a an ether, amine, or thioether, each R′ 1 and R′ 13 is an aryl group, each R′ 7 and R′ 8 is joined

Assignees

• Exxonmobil Res & Eng Co

Inventors

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

Classifications

• C10N2070/00

  Specific manufacturing methods for lubricant compositions · CPC title

• B01D53/228

  characterised by specific membranes · CPC title

• B01J2231/646

  of aromatic or heteroaromatic rings · CPC title

• B01J20/3212

  consisting of a polymer obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds · CPC title

• C10G45/64

  containing crystalline alumino-silicates, e.g. molecular sieves · CPC title