# US 10,865,258 B2 · Mixed catalyst systems containing bridged metallocenes with a pendant group 13 element, processes for making a polymer product using same, and products made from same

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- Number: US 10,865,258 B2
- Document ID: US10865258B2
- Status: Granted
- Kind: B2
- Application number: 16/250,624
- Filed: 2019-01-17
- Published: 2019-09-19
- Granted: 2020-12-15
- Earliest claimed: 2018-01-31
- Assignees: ExxonMobil Chemical Patents Inc.
- Applicants: ExxonMobil Chemical Patents Inc.
- Inventors: Matthew W. Holtcamp; Subramaniam Kuppuswamy; Matthew S. Bedoya; Kevin A. Stevens; Ching-Tai Lue; Hasnain Rangwalla
- Web page: https://patentgrep.com/patent/US10865258B2

## CPC

- C08F 4/65927: {two cyclopentadienyl rings being mutually bridged}
- C08F 4/6428: {with an aluminoxane, i.e. a compound containing an Al-O-Al- group}
- C08F 4/6465: {containing silicium}
- C08F 4/65904: {in combination with another component of C08F4/64}
- C08F 4/65908: {in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+}
- C08F 4/65912: {in combination with an organoaluminium compound}
- C08F 4/65925: {two cyclopentadienyl rings being mutually non-bridged}
- C08F 210/16: Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
- C08F 4/65916: {supported on a carrier, e.g. silica, MgCl2, polymer}
- C08F 2420/10: Heteroatom-substituted bridge, i.e. Cp or analog where the bridge linking the two Cps or analogs is substituted by at least one group that contains a heteroatom
- C08F 2500/12: Melt flow index or melt flow ratio
- C08F 2800/10: as molar percentages
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

## Abstract

A mixed metallocene catalyst system can comprise at least one metallocene catalyst compound comprising a structure represented by formula (A) below and optionally at least one other metallocene catalyst compound having a structure represented by formula (B) below: A mixed metallocene catalyst system can additionally include a non-coordinating anion type activator comprising a supported alumoxane or aluminum alkyl, and optionally a scavenger. A process for making a polymeric product can comprise: contacting a C2-C22 alpha-olefin feed with the catalyst system to obtain a polymerization reaction mixture; and obtaining a polymer product from the polymerization reaction mixture. A polymer product can be made by the process.

## Claims

### Claim 1

A mixed metallocene catalyst system comprising at least one first metallocene catalyst compound represented by formula (A) below, at least one second metallocene catalyst compound different from the at least one first metallocene catalyst compound represented by formula (A), activator, optional support, and optional scavenger, wherein formula (A) is:
wherein:
each of R4 and R5 is a hydrogen, a substituted or unsubstituted linear, branched linear, or cyclic C1-C30 hydrocarbyl group, or a substituted or unsubstituted linear, branched linear, or cyclic C1-C30 hydrosilylcarbyl group;
R1 and R2 are each independently a hydrogen or a substituted or unsubstituted linear, branched linear, or cyclic C1-C30hydrocarbyl group, or R1 and R2, taken together with the carbon atoms in the first cyclopentadienyl ring to which they are directly connected, collectively form one or more substituted or unsubstituted rings annelated to the first cyclopentadienyl ring;
each of R10 and R11 is a hydrogen or a substituted or unsubstituted linear, branched linear, or cyclic C1-C30 hydrocarbyl group;
R12 and R13 are each independently a hydrogen or a substituted or unsubstituted linear, branched linear, or cyclic C1-C30 hydrocarbyl group, or R12 and R13, taken together with the carbon atoms in the second cyclopentadienyl ring to which they are directly connected, collectively form one or more substituted or unsubstituted rings annelated to the second cyclopentadienyl ring;
M is Hf, Ti, or Zr, and v is 4;
each X is independently a halogen, a hydride, an alkoxide, a substituted alkoxide, or a C1-C20 linear, branched, or cyclic hydrocarbyl group substituted with a heteroatom or heteroatom containing group, or a C1-C20 linear, branched, or cyclic hydrocarbyl group, or two or more X moieties optionally form a fused ring or ring system;
m is an integer equal to v-2; and
the bridging group (BG) comprises -[BA(R20)2]n—, wherein: n is an integer from 1 to 3; each BA, the same or different at each occurrence, is independently carbon, silicon, or germanium; and each R20, the same or different at each occurrence, is each independently a C1-C8 substituted or unsubstituted linear, branched, or cyclic hydrocarbyl group or a pendant group having a formula —R21-G13(X*)2, where each G13 is a group 13 element, each R21is independently a C1-C8 substituted or unsubstituted linear, branched, or cyclic hydrocarbyl group, and each X* is independently a halogen, a hydride, an alkoxide, a substituted alkoxide, or a C1-C20 substituted or unsubstituted linear or branched hydrocarbyl group, a C1-C20 cyclic hydrocarbyl group, or optionally two or more X* moieties optionally form a fused ring or ring system, provided that at least one R20 is a pendant group of the formula —R21-G13(X*)2.

### Claim 2 (depends on 1)

The mixed metallocene catalyst system of claim 1, wherein M in the first metallocene catalyst compound comprises Zr or Hf and m in the first metallocene catalyst compound is 2.

### Claim 3 (depends on 1)

The mixed metallocene catalyst system of claim 1, wherein each X in the first metallocene catalyst compound is independently a methyl, an ethyl, an n-propyl, an isopropyl, an n-butyl, a sec-butyl, an isobutyl, a tert-butyl, a phenyl, a benzyl, a chloride, a bromide, or an iodide.

### Claim 4 (depends on 1)

The mixed metallocene catalyst system of claim 1, wherein the first metallocene compound has a structure represented by formula (F-MC 1):
wherein:
R6, R7, R8, R9, R15, R16, R17, and R18 are each independently a hydrogen or a substituted or unsubstituted linear, branched linear, or cyclic C1-C6 hydrocarbyl group, and M, m, X, BG, and v are as defined in claim 1.

### Claim 5 (depends on 4)

The mixed metallocene catalyst system of claim 4, wherein at least eight of R4, R5, R6, R7, R8, R9, R10, R11, R15, R16, R17, and R18 in the first metallocene catalyst compound are a hydrogen.

### Claim 6 (depends on 5)

The mixed metallocene catalyst system of claim 5, wherein:
each of R4 and R5 in the first metallocene catalyst compound is a hydrogen or a substituted or unsubstituted linear, branched linear, or cyclic C1-C8 hydrocarbyl group;
each of R10 and R11 in the first metallocene catalyst compound is a hydrogen or a substituted or unsubstituted linear, branched linear, or cyclic C1-C8 hydrocarbyl group;
at least ten of R4, R5, R6, R7, R8, R9, R10, R11, R15, R16, R17, and R18 in the first metallocene catalyst compound are a hydrogen;
M in the first metallocene catalyst compound is Hf or Zr, and m in the first metallocene catalyst compound is 2;
each X in the first metallocene catalyst compound is independently a methyl, an ethyl, an n-propyl, an isopropyl, an n-butyl, a sec-butyl, an isobutyl, a tert-butyl, a phenyl, a benzyl, a chloride, a bromide, or an iodide; and
the bridging group (BG) in the first metallocene catalyst compound is -[BA(R20)2]—, wherein: the bridging atom, BA, is carbon or silicon; one R20 is a C1-C8 substituted or unsubstituted linear, branched, or cyclic hydrocarbyl group; and the other R20 is a pendant group having a formula —R21-G13(X*)2, where G13 is boron or aluminum, R21 is a C1-C8 substituted or unsubstituted linear, branched, or cyclic hydrocarbyl group, and each X* is independently a halogen, a hydride, an alkoxide, a substituted alkoxide, or a C1-C20 substituted or unsubstituted linear or branched hydrocarbyl group, a C1-C20 cyclic hydrocarbyl group, or two or more X* moieties optionally form a fused ring or ring system.

### Claim 7 (depends on 1)

The mixed metallocene catalyst system of claim 1, wherein the first metallocene catalyst compound has one or more of the following structures:
wherein:
each M is Hf or Zr;
each X is independently a methyl, an ethyl, an n-propyl, an isopropyl, an n-butyl, a sec-butyl, an isobutyl, a tert-butyl, a phenyl, a benzyl, a a chloride, a bromide, or an iodide;
R20 and R21 are each independently a C1-C8 substituted or unsubstituted linear, branched, or cyclic hydrocarbyl group; and
each G13 is boron or aluminum.

### Claim 8 (depends on 1)

The mixed metallocene catalyst system of claim 1, wherein the second metallocene catalyst compound has a structure represented by formula (B) below:
wherein:
each of R1, R2, R3, R4, and R5 is a hydrogen or a substituted or unsubstituted linear, branched linear, or cyclic C1-C30 hydrocarbyl group, or optionally any two neighboring groups of R1, R2, R3, R4, and R5, taken together with the carbon atoms in a first cyclopentadienyl ring to which they are directly connected, collectively form one or more substituted or unsubstituted rings annelated to the first cyclopentadienyl ring;
each of R6, R7, R8, R9, and R10 is a hydrogen or a substituted or unsubstituted linear, branched linear, or cyclic C1-C30 hydrocarbyl group, or optionally any two neighboring groups of R6, R7, R8, R9, and R10, taken together with the carbon atoms in a second cyclopentadienyl ring to which they are directly connected, collectively form one or more substituted or unsubstituted rings annelated to the second cyclopentadienyl ring;
M is Ti, Hf or Zr, v is 4;
m is an integer equal to v-2; and
each X is independently a halogen, a hydride, an amide, an alkoxide, a substituted alkoxide, a sulfide, a phosphide, a diene, an amine, a phosphine, an ether, or a C1-C20 substituted or unsubstituted linear, branched, or cyclic hydrocarbyl group, or two or more X moieties optionally form a fused ring or ring system.

### Claim 9 (depends on 8)

The mixed metallocene catalyst system of claim 8, wherein M in the second metallocene catalyst compound comprises Zr or Hf, and m in the second metallocene catalyst compound is 2.

### Claim 10 (depends on 8)

The mixed metallocene catalyst system of claim 8, wherein each X in the second metallocene catalyst compound is independently a methyl, an ethyl, an n-propyl, an isopropyl, an n-butyl, a sec-butyl, an isobutyl, a tert-butyl, a phenyl, a benzyl, a perfluorophenyl, a perfluorobenzyl, a chloride, a bromide, or an iodide.

### Claim 11 (depends on 8)

The mixed metallocene catalyst system of claim 8, wherein the second metallocene catalyst compound is a bridged metallocene compound, wherein R3 and R10 in formula (B) collectively form a bridging group (BG) comprising -[BA(R11)2]n—, wherein:
n in the second metallocene catalyst compound is an integer from 1 to 3;
each BA in the second metallocene catalyst compound, the same or different at each occurrence, is independently carbon, silicon, or germanium; and
each R11 in the second metallocene catalyst compound, the same or different at each occurrence, is each independently a C1-C8 substituted or unsubstituted linear, branched, or cyclic hydrocarbyl group.

### Claim 12 (depends on 8)

The mixed metallocene catalyst system of claim 8, wherein the second metallocene catalyst compound has a structure represented by formula (B-1) below:

### Claim 13 (depends on 1)

The mixed metallocene catalyst system of claim 1, where in the activator is an alumoxane.

### Claim 14 (depends on 1)

The mixed metallocene catalyst system of claim 1, further comprising support, wherein the activator is an alumoxane, where the activator is combined with the support prior to contact with the catalyst compound.

### Claim 15 (depends on 1)

The mixed metallocene catalyst system of claim 1 wherein the activator is selected from the group consisting of alumoxane, N,N-dimethylanilinium tetrakis(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis (3,5-bis(trifluoromethyl)perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluorophenyl)aluminate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)aluminate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis (3,5-bis(trifluoromethyl)perfluorophenyl)borate, triphenylcarbenium tetra(perfluorophenyl)borate, triphenylcarbenium tetrakis (perfluorophenyl) aluminate, triphenylcarbenium tetrakis(perfluoronaphthyl)aluminate, [Ph3C+][B(C6F5)4−], [Me3NH+][B(C6F5)4−], 1-(4(tris (pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium, 4-(tris (pentafluoro-phenyl)borate)-2,3,5,6-tetrafluoropyridine, and combinations thereof.

### Claim 16 (depends on 1)

The mixed metallocene catalyst system of claim 1, wherein each X* in the first metallocene catalyst compound is independently a methyl, an ethyl, an n-propyl, an isopropyl, an n-butyl, a sec-butyl, an isobutyl, a tert-butyl, a phenyl, a benzyl, a chloride, a bromide, or an iodide.

### Claim 17 (depends on 1)

The mixed metallocene catalyst system of claim 1, wherein the first and second metallocenes are represented by the formulas: