# US 2016/0355654 A1 · High Activity Catalyst Supportation

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- Number: US 2016/0355654 A1
- Document ID: US20160355654A1
- Status: Published application
- Kind: A1
- Application number: 15/142,084
- Filed: 2016-04-29
- Published: 2016-12-08
- Earliest claimed: 2015-06-05
- Assignees: ExxonMobil Chemical Patents Inc.
- Applicants: ExxonMobil Chemical Patents Inc.
- Inventors: Lubin Luo; Gregory S. Day
- Web page: https://patentgrep.com/patent/US20160355654A1

## CPC

- C08F 110/06: Propene
- C08F 4/02: Carriers therefor
- C08F 4/65912: {in combination with an organoaluminium compound}
- C08F 4/65916: {supported on a carrier, e.g. silica, MgCl2, polymer}
- C08F 4/65927: {two cyclopentadienyl rings being mutually bridged}
- C08F 210/06: Propene
- C08F 2410/06: Catalyst characterized by its size
- C08F 2420/09: Cyclic bridge, i.e. Cp or analog where the bridging unit linking the two Cps or analogs is part of a cyclic group
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

## Abstract

This invention relates to single site catalyst supportation methods involving high temperature treatment (≧40° C., e.g., 100-130° C.) to improve catalyst activity for olefin polymerization, e.g., propylene polymerization, and to the supported catalyst systems obtained by the methods, e.g., single site catalyst systems supported on a support having high average particle size (PS≧30 μm), high surface area (SA≧200 m2/g), low pore volume (PV≦2 mL/g), and a mean pore diameter range of 1≦PD≦20 nm.

## Claims

### Claim 1

A process, comprising:
supporting an activator for a single site catalyst precursor compound on a support, the support having an average particle size of from 5 μm to 500 μm, a specific surface area of 10 m2/g or more, a pore volume of from 0.1 to 4 mL/g, and a mean pore diameter of from 1 to 100 nm (10 to 200 Å); and
contacting the supported activator and a single site catalyst precursor compound to form a supported catalyst system;
wherein the supporting, the contacting, or both, are at a temperature above 40° C.

### Claim 2 (depends on 1)

The process of claim 1, wherein the support has an average particle size of more than
30 μm up to 200 μm, a specific surface area of 200 m2/g or more, a pore volume of from 0.5 to 2 mL/g, and a mean pore diameter of from 1 to 35 nm (10 to 350 Å).

### Claim 3 (depends on 1)

The process of claim 1, wherein the support has an average particle size of more than
30 μm up to 200 μm, a specific surface area of 650 m2/g or more, a pore volume of from 0.5 to 2 mL/g, and a mean pore diameter of from 1 to 7 nm (10 to 70 Å).

### Claim 4 (depends on 1)

The process of claim 1, wherein the support has a specific surface area less than 650 m2/g, or the mean pore diameter is greater than 7 nm (70 Å), or both.

### Claim 5 (depends on 1)

The process of claim 1, wherein the support comprises agglomerates of a plurality of primary particles, and further comprising fragmenting the agglomerates.

### Claim 6 (depends on 5)

The process of claim 5, wherein the catalyst system formed in the contacting has a bimodal particle size distribution comprised of at least about 5 vol % of the agglomerates and at least about 5 vol % of fragments of the agglomerates, based on the total volume of the supported catalyst system.

### Claim 7 (depends on 5)

The process of claim 5, wherein the supporting and contacting are essentially free of fines formation.

### Claim 8 (depends on 1)

The process of claim 1, wherein the support comprises a metal oxide.

### Claim 9 (depends on 1)

The process of claim 1, wherein the support comprises spray dried silica having an average particle size of more than 50 μm, a specific surface area less than 1000 m2/g, or a combination thereof.

### Claim 10 (depends on 1)

The process of claim 1, wherein the activator comprises alumoxane.

### Claim 11 (depends on 1)

The process of claim 1, wherein the activator comprises methylalumoxane or modified methylalumoxane.

### Claim 12 (depends on 1)

The process of claim 1, further comprising contacting the supported activator with a co-activator selected from the group consisting of: trialkylaluminum, dialkylmagnesium, alkylmagnesium halide, and dialkylzinc.

### Claim 13 (depends on 1)

The process of claim 1, wherein the supporting, the contacting, or both, are at a temperature above 80° C.

### Claim 14 (depends on 1)

The process of claim 1, wherein the supporting, the contacting, or both, are at a temperature above 100° C. up to 130° C.

### Claim 15 (depends on 1)

The process of claim 1, wherein the single site catalyst precursor compound comprises a hafnocene.

### Claim 16 (depends on 1)

The process of claim 1, wherein the single site catalyst precursor compound comprises a zirconocene.

### Claim 17 (depends on 1)

The process of claim 1, wherein the single site catalyst precursor compound is selected from precursor compounds I and II;
wherein precursor compound I is represented by the following formula:
(Cp)mRAnM4Qk
wherein:
each Cp is a cyclopentadienyl moiety or a substituted cyclopentadienyl moiety substituted by one or more hydrocarbyl radicals having from 1 to 20 carbon atoms;
RA is a structural bridge between two Cp moieties;
M4 is a transition metal selected from groups 4 or 5;
Q is a hydride or a hydrocarbyl group having from 1 to 20 carbon atoms or an alkenyl group having from 2 to 20 carbon atoms, or a halogen;
m is 1, 2, or 3, with the proviso that if m is 2 or 3, each Cp may be the same or different;
n is 0 or 1, with the proviso that n=0 if m=1; and
k is such that k+m is equal to the oxidation state of M4, with the proviso that if k is greater than 1, each Q may be the same or different; and
wherein precursor compound II is represented by the following formula:
RA(CpR″p)(CpR*q)M5Qr
wherein:
each Cp is a cyclopentadienyl moiety or substituted cyclopentadienyl moiety;
each R* and R″ is a hydrocarbyl group having from 1 to 20 carbon atoms and may the same or different;
p is 0, 1, 2, 3, or 4;
q is 1, 2, 3, or 4;
RA is a structural bridge between the Cp moieties imparting stereorigidity to the metallocene compound;
M5 is a group 4, 5, or 6 metal;
Q is a hydrocarbyl radical having 1 to 20 carbon atoms or is a halogen;
r is s minus 2, where s is the valence of M5;
wherein (CpR*q) has bilateral or pseudobilateral symmetry; R*q is selected such that (CpR*q) forms a fluorenyl, alkyl substituted indenyl, or tetra-, tri-, or dialkyl substituted cyclopentadienyl radical; and (CpR″p) contains a bulky group in one and only one of the distal positions;
wherein the bulky group is of the formula ARwv; and
where A is chosen from group 4 metals, oxygen, or nitrogen, and Rw is a methyl radical or phenyl radical, and v is the valence of A minus 1.

### Claim 18 (depends on 1)

The process of claim 1, wherein the single site catalyst precursor compound is represented by the formula:
wherein:
M is a group 4, 5, or 6 metal;
T is a bridging group;
each X is, independently, an anionic leaving group;
each R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, and R13 is independently, halogen atom, hydrogen, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl, substituted germylcarbyl substituent or a —NR′2, —SR′, —OR, —OSiR′3 or —PR′2 radical, wherein R′ is one of a halogen atom, a C1-C10 alkyl group, or a C6-C10 aryl group.

### Claim 19 (depends on 18)

The process of claim 18, wherein at least one of R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, and R13 is a cyclopropyl substituent represented by the formula:
wherein each R′ in the cyclopropyls substituent is, independently, hydrogen, a substituted hydrocarbyl group, an unsubstituted hydrocarbyl group, or a halogen.

### Claim 20 (depends on 18)

The process of claim 18, wherein:
M is selected from titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten;
each X is independently selected from hydrogen, halogen, hydroxy, substituted or unsubstituted C1 to C10 alkyl groups, substituted or unsubstituted C1 to C10 alkoxy groups, substituted or unsubstituted C6 to C14 aryl groups, substituted or unsubstituted C6 to C14 aryloxy groups, substituted or unsubstituted C2 to C10 alkenyl groups, substituted or unsubstituted C7 to C40 arylalkyl groups, substituted or unsubstituted C7 to C40 alkylaryl groups, and substituted or unsubstituted C7 to C40 arylalkenyl groups; or optionally are joined together to form a C4 to C40 alkanediyl group or a conjugated C4 to C40 diene ligand which is coordinated to M in a metallacyclopentene fashion; or optionally represent a conjugated diene, optionally, substituted with one or more groups independently selected from hydrocarbyl, trihydrocarbylsilyl, and trihydrocarbylsilylhydrocarbyl groups, said diene having a total of up to 40 atoms not counting hydrogen and forming a π complex with M;
each R2, R4, R8, and R10 is independently selected from hydrogen, halogen, substituted or unsubstituted C1 to C10 alkyl groups, substituted or unsubstituted C6 to C14 aryl groups, substituted or unsubstituted C2 to C10 alkenyl groups, substituted or unsubstituted C7 to C40 arylalkyl groups, substituted or unsubstituted C7 to C40 alkylaryl groups, substituted or unsubstituted C8 to C40 arylalkenyl groups, and
NR′2, —SR′, —OR′, —SiR′3, —OSiR′3, and —PR′2 radicals wherein each R′ is independently selected from halogen, substituted or unsubstituted C1 to C10 alkyl groups and substituted or unsubstituted C6 to C14 aryl groups;
R3, R5, R6, R7, R9, R11, R12, and R13 are each selected from the group consisting of hydrogen, halogen, hydroxy, substituted or unsubstituted C1 to C10 alkyl groups, substituted or unsubstituted C1 to C10 alkoxy groups, substituted or unsubstituted C6 to C14 aryl groups, substituted or unsubstituted C6 to C14 aryloxy groups, substituted or unsubstituted C2 to C10 alkenyl groups, substituted or unsubstituted C7 to C40 arylalkyl groups, substituted or unsubstituted C7 to C40 alkylaryl groups, and C7 to C40 substituted or unsubstituted arylalkenyl groups; and
T is selected from:
—B(R14)—, —Al(R14)—, —Ge—, —Sn—, —O—, —S—, —SO—, —SO2—, —N(R14)—, —CO—, —P(R14)—, and —P(O)(R14)—;
wherein R14, R15, and R16 are each independently selected from hydrogen, halogen, C1 to C20 alkyl groups, C6 to C30 aryl groups, C1 to C20 alkoxy groups, C2 to C20 alkenyl groups, C7 to C40 arylalkyl groups, C8 to C40 arylalkenyl groups and C7 to C40 alkylaryl groups, optionally R14 and R15, together with the atom(s) connecting them, form a ring; and M3 is selected from carbon, silicon, germanium, and tin; or
T is represented by the formula:
wherein R17, R18, R19, R20, R21, R22, R23, and R24 are each independently selected from hydrogen, halogen, hydroxy, substituted or unsubstituted C1 to C10 alkyl groups, substituted or unsubstituted C1 to C10 alkoxy groups, substituted or unsubstituted C6 to C14 aryl groups, substituted or unsubstituted C6 to C14 aryloxy groups, substituted or unsubstituted C2 to C10 alkenyl groups, substituted or unsubstituted C7 to C40 alkylaryl groups, substituted or unsubstituted C7 to C40 alkylaryl groups and substituted or unsubstituted C8 to C40 arylalkenyl groups; optionally two or more adjacent radicals R17, R18, R19, R20, R21, R22, R23, and R24, including R20 and R21, together with the atoms connecting them, form one or more rings; and
M2 represents one or more carbon atoms, or a silicon, germanium, or tin atom.

### Claim 21 (depends on 1)

The process of claim 1, further comprising contacting the supported catalyst system and propylene monomer under polymerization conditions to form a matrix of porous propylene polymer comprising at least 50 mol % propylene and a mean pore diameter less than 165 μm as determined by mercury intrusion porosimetry; and dispersing active catalyst system sites within the matrix.

### Claim 22 (depends on 21)

The process of claim 21, further comprising contacting the dispersed active catalyst system sites with one or more alpha-olefin monomers under polymerization conditions.

### Claim 23 (depends on 1)

The supported catalyst system, comprising the single site catalyst precursor compound, the activator, the support, and prepared by the process of claim 1.

### Claim 24 (depends on 23)

The supported catalyst system of claim 23, wherein the support has an average particle size of more than 30 μm up to 200 μm, a specific surface area of 650 m2/g or more, a pore volume of from 0.5 to 2 mL/g, and a mean pore diameter of from 1 to 7 nm (10 to 70 Å).

### Claim 25 (depends on 23)

The supported catalyst system of claim 23, wherein the support comprises agglomerates of a plurality of primary particles, and wherein the supported catalyst system has a bimodal particle size distribution comprised of at least about 5 vol % of the catalyst system supported on the agglomerates and at least about 5 vol % of the catalyst system supported on the fragments of the agglomerates, based on the total volume of the supported catalyst system.