# US 2016/0355656 A1 · Single Site Catalyst Supportation

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- Number: US 2016/0355656 A1
- Document ID: US20160355656A1
- Status: Published application
- Kind: A1
- Application number: 15/142,321
- 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; Jian Yang; Matthew W. Holtcamp
- Web page: https://patentgrep.com/patent/US20160355656A1

## CPC

- C08J 9/00: Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof (mechanical aspects of shaping of plastics or substances in a plastic state for the production of porous or cellular articles B29C)
- C08F 4/02: Carriers therefor
- C08F 10/06: Propene
- C08F 110/06: Propene
- C08F 4/65912: {in combination with an organoaluminium compound}
- C08F 4/65916: {supported on a carrier, e.g. silica, MgCl2, polymer}
- C08F 4/6592: containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F 4/65927: {two cyclopentadienyl rings being mutually bridged}
- 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
- C08J 2323/12: Polypropene
- C08J 2423/06: Polyethene
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

## Abstract

This invention relates to catalyst supports having high surface area (SA≧400 m2/g), low pore volume (PV≦2 mL/g), a specific mean pore diameter range (PD=1-20 nm), and high average particle size (PS≧30 μm), supported catalysts, and supportation processes; and further relates to: high porosity (≧15%) and/or low pore diameter (PD<165 μm) propylene polymers; bimodal polymers and/or heterophasic copolymers based on the high porosity and/or low pore diameter propylene polymers; propylene polymerization processes using the supported catalysts and/or to prepare the high porosity and/or low pore diameter propylene polymers, bimodal polymers and/or heterophasic copolymers.

## Claims

### Claim 1

A single site catalyst system comprising:
(a) a single site catalyst precursor compound;
(b) an activator; and
(c) a support having an average particle size of more than 30 μm up to 200 μm, a specific surface area of 400 m2/g or more, a pore volume of from 0.5 to 2 mL/g, and a mean pore diameter of from 1 to 20 nm (10 to 200 Å), the support comprising agglomerates of a plurality of primary particles.

### Claim 2 (depends on 1)

The catalyst system of claim 1, wherein the average particle size is more than 50 μm, and the specific surface area is less than 1000 m2/g.

### Claim 3 (depends on 1)

The catalyst system of claim 1, wherein the specific surface area is more than 650 m2/g, the mean pore diameter is less than 7 nm (70 Å), and the activator comprises methylalumoxane.

### Claim 4 (depends on 1)

The catalyst system of claim 1, wherein the specific surface area is less than 650 m2/g, the mean pore diameter is more than 7 nm (70 Å), or a combination thereof.

### Claim 5 (depends on 1)

The catalyst system of claim 1, wherein the primary particles have an average particle size from 1 nm to 50 μm.

### Claim 6 (depends on 1)

The catalyst system of claim 1, wherein the agglomerates are at least partially encapsulated.

### Claim 7 (depends on 1)

The catalyst system of claim 1, wherein the support comprises spray dried silica.

### Claim 8 (depends on 1)

The catalyst system of claim 1, wherein the activator comprises methylalumoxane.

### Claim 9 (depends on 1)

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

### Claim 10 (depends on 1)

The catalyst system 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 11

A single site catalyst system comprising:
(a) a single site catalyst precursor compound;
(b) an activator;
(c) a support having an average particle size of more than 30 μm up to 200 μm, a specific surface area of 400 m2/g or more, a pore volume of from 0.5 to 2 mL/g, and a mean pore diameter of from 1 to 20 nm (10 to 200 Å);
(d) a polypropylene matrix having a porosity of at least 15%, and a volume average median pore diameter of less than 165 μm, as determined by mercury intrusion porosimetry; and
(e) active catalyst sites distributed in the matrix.

### Claim 12

A process, comprising:
supporting an activator for a single site precursor compound on a support, the support having an average particle size of more than 30 μm up to 200 μm, a specific surface area of 400 m2/g or more, a pore volume of from 0.5 to 2 mL/g, and a mean pore diameter of from 1 to 20 nm (10 to 200 Å); and
contacting the activator and a single site catalyst precursor compound to form a supported catalyst system having an average particle size of more than 30 μm up to 200 μm.

### Claim 13 (depends on 12)

The process of claim 12, wherein the support comprises agglomerates of a plurality of primary particles having an average size from 1 nm to 50 μm.

### Claim 14 (depends on 12)

The process of claim 12, wherein the supported activator is essentially free of fines.

### Claim 15 (depends on 12)

The process of claim 12, 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 16 (depends on 12)

The process of claim 12, wherein the specific surface area is more than 650 m2/g, the mean pore diameter is less than 7 nm (70 Å), the activator comprises alumoxane, and the supporting comprises contacting the activator and the support at a temperature of 40° C. or below.

### Claim 17 (depends on 12)

The process of claim 12, wherein the specific surface area is less than 650 m2/g or the mean pore diameter is greater than 7 nm (70 Å), or both, the activator comprises alumoxane, and the supporting comprises contacting the activator and the support at a temperature from −60 to 130° C.

### Claim 18 (depends on 12)

The process of claim 12, further comprising contacting the support with a co-activator selected from the group consisting of: trialkylaluminum, dialkylmagnesium, alkylmagnesium halide, and dialkylzinc.

### Claim 19 (depends on 12)

The process of claim 12, 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 20 (depends on 12)

The process of claim 12, 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 21 (depends on 20)

The process of claim 20, 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 22 (depends on 20)

The process of claim 20, 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 23

A process, comprising:
(a) contacting a single site catalyst precursor compound, an activator and a support, the support having an average particle size of more than 30 μm up to 200 μm, a specific surface area of 400 m2/g or more, a pore volume of from 0.5 to 2 mL/g, and a mean pore diameter of from 1 to 20 nm (10 to 200 Å), to form a supported catalyst system;
(b) 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
(c) dispersing active catalyst system sites within the matrix.

### Claim 24 (depends on 23)

The process of claim 23, further comprising (d) contacting the dispersed active catalyst system sites from (c) with one or more alpha-olefin monomers under polymerization.