Olefin polymerization catalyst system comprising mesoporous organosilica support

Patent metadata

Field	Value
Publication number	US-2017327604-A1
Application number	US-201515526513-A
Country	US
Kind code	A1
Filing date	Dec 12, 2015
Priority date	Dec 12, 2014
Publication date	Nov 16, 2017
Grant date	—

Abstract

A catalyst system comprising a combination of: 1) an activator; 2) one or more metallocene catalyst compounds; 3) a support comprising an organosilica material, which is a mesoporous organosilica material. The organosilica material is 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 C1-C4 alkyl group, or a bond to a silic-on atom of another monomer and Z 2 represents a hydroxyl group, a C 1 -C 4 alkoxy group, a C 1 -C 6 salkyl 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

1 . A catalyst system comprising:
one or more olefin polymerization catalyst compounds; 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 an activator.

2 . The catalyst system of claim 1 , wherein olefin polymerization catalyst compound is a coordination polymerization catalyst compound.

3 . 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, and, optionally, Z 1 represents a hydrogen atom, methyl, ethyl or a bond 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, and a nitrogen-containing optionally substituted heterocycloalkyl group, and an oxygen atom bonded to a silicon atom of another monomer; 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; 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; 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; 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
any combinations thereof.

6 . The catalyst system of claim 1 , wherein the catalyst support comprising the organosilica material has:
an average pore diameter between about 2 nm and about 50 nm; a pore volume about 0.1 cm 3 /g to about 10 cm 3 /g; and/or 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 olefin polymerization catalyst compound comprises one or more metallocene compounds represented by the formula:
T y Cp m M 6 G n X 5 q wherein each Cp is, independently, a cyclopentadienyl group which may be substituted or unsubstituted, M 6 is a Group 4 transition metal, G is a heteroatom group represented by the Formula JR* z where J is N, P, O or S, and R* is a linear branched or cyclic hydrocarbyl group having from one to twenty carbon atoms and z is 1 or 2, T is a bridging group, and y is 0 or 1, X 5 is a leaving group, and m=1 or 2, n=0, 1, 2 or 3, q=0, 1, 2 or 3, and the sum of m+n+q is equal to the oxidation state of the transition metal.

9 . The catalyst system of claim 8 , wherein each Cp is a cyclopentadiene, indene or fluorene, which may be substituted or unsubstituted, each M 6 is titanium, zirconium, or hafnium, and each X 5 is, independently, a halide, a hydride, an alkyl group, an alkenyl group or an arylalkyl group.

10 . The catalyst system of claim 8 , wherein y is 1, m is one, n is 1, J is N, and R* is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, cyclooctyl, cyclododecyl, decyl, undecyl, dodecyl, adamantyl or an isomer thereof.

11 . The catalyst system of claim 1 , wherein the activator comprises an alkylalumoxane and/or a non-coordinating anion, preferably the activator comprises methylalumoxane, ethylalumoxane, N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate or a mixture thereof.

12 . The catalyst system of claim 1 , wherein the olefin polymerization catalyst compound comprises Ziegler-Natta catalyst compound.

13 . The catalyst system of claim 1 , wherein the one or more olefin polymerization catalyst compounds comprises one or more metallocene compounds of:
dimethylsilyl (tetramethylcyclopentadienyl)(cyclododecylamido)titanium dimethyl; dimethylsilyl (tetramethylcyclopentadienyl)(cyclododecylamido)titanium dichloride; dimethylsilyl (tetramethylcyclopentadienyl)(t-butylamido)titanium dimethyl; dimethylsilyl (tetramethylcyclopentadienyl)(t-butylamido)titanium dichloride; μ-(CH 3 ) 2 Si(cyclopentadienyl)(1-adamantylamido) M 7 (R 15 ) 2 ; μ-(CH 3 ) 2 Si(3-tertbutylcyclopentadienyl) (1-adamantylamido)M 7 (R 15 ) 2 ; μ-(CH 3 ) 2 (tetramethylcyclopentadienyl)(1-adamantylamido)M 7 (R 15 ) 2 ; μt-(CH 3 ) 2 Si(tetramethylcyclopentadienyl)(1-adamantylamido)M 7 (R 15 ) 2 μ-(CH 3 ) 2 C(tetramethylcyclopentadienyl)(1-adamantylamido)M 7 (R 15 ) 2 ; μ-(CH 3 ) 2 Si(tetramethylcyclopentadienyl)(1-tertbutylamido)M 7 (R 15 ) 2 ; μ-(CH 3 ) 2 Si(fluorenyl)(1-tertbutylamido)M 7 (R 15 ) 2 ; μ-(CH 3 ) 2 Si(tetramethylcyclopentadienyl)(1-cyclododecylamido)M 7 (R 15 ) 2 ; and μ-(C 6 H 5 ) 2 C(tetramethylcyclopentadienyl)(1-cyclododecylamido)M 7 (R 15 ) 2 ; where M 7 is selected from a group consisting of Ti, Zr, and Hf and R 15 is selected from halogen or C 1 -C 5 alkyl.

14 . The catalyst system of claim 1 , wherein the at least one metallocene compound comprises one or more of: Bis(tetrahydroindenyl)Hf Me 2 ; Bis(1-butyl,3-methylcyclopentadienyl)ZrCl 2 ; Bis-(n-butylcyclopentadienyl)ZrCl 2 ; (Dimethylsilyl) 2 O bis(indenyl)ZrCl 2 ; Dimethylsilyl(3-(3-methylbutyl)cyclopentadienyl)(2,3,4,5-tetramethylcyclopentadienyl) ZrCl 2 ; Dimethylsilylbis(tetrahydroindenyl)ZrCl 2 ; Dimethylsilyl-(3-phenyl-indenyl)(tetramethylcyclopentadienyl)ZrCl 2 ; Dimethylsilyl(3-neopent

Assignees

• Exxonmobil Res & Eng Co

Inventors

• Holtcamp Matthew W
• Day Gregory S
• Sanders David F
• Calabro David C
• Li Quanchang
• Mertens Machteld M W

Classifications

• C07D251/30

  Only oxygen atoms · CPC title

• C08F4/6592 Primary

  containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring · CPC title

• C08F4/02

  Carriers therefor · CPC title

• C08G77/60

  in which all the silicon atoms are connected by linkages other than oxygen atoms · CPC title

• C08F210/02

  Ethene · CPC title