# US 11,993,667 B2 · Catalyst composition and method for preparing polyethylene

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- Number: US 11,993,667 B2
- Document ID: US11993667B2
- Status: Granted
- Kind: B2
- Application number: 17/466,696
- Filed: 2021-09-03
- Published: 2021-12-23
- Granted: 2024-05-28
- Earliest claimed: 2019-10-04
- Assignees: Chevron Phillips Chemical Company LP
- Applicants: Chevron Phillips Chemical Company LP
- Inventors: Graham R. Lief; Qing Yang; Eric J. Haschke
- Web page: https://patentgrep.com/patent/US11993667B2

## CPC

- C08F 110/02: Ethene
- C08F 210/16: Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
- C07F 17/00: Metallocenes
- C08F 4/65904: {in combination with another component of C08F4/64}
- C08F 4/65925: {two cyclopentadienyl rings being mutually non-bridged}
- C08F 4/65927: {two cyclopentadienyl rings being mutually bridged}
- C08F 4/65912: {in combination with an organoaluminium compound}
- C08F 4/65916: {supported on a carrier, e.g. silica, MgCl2, polymer}
- C08F 2420/07: Heteroatom-substituted Cp, i.e. Cp or analog where at least one of the substituent of the Cp or analog ring is or contains a heteroatom
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)

## Abstract

Disclosed are metallocene compounds, catalyst compositions comprising at least one metallocene compound, processes for polymerizing olefins, methods for making catalyst compositions, olefin polymers and articles made from olefin polymers. In an aspect, a metallocene compound and catalyst composition are disclosed in which the metallocene contains at least one indenyl ligand, the indenyl ligand containing at least one halogenated substituent, such as a fluorinated substituent. These metallocene compounds and catalyst compositions can produce polyethylene having unexpectedly low levels of short chain branching.

## Claims

### Claim 1

A catalyst composition for polymerizing olefins, the catalyst composition comprising:
a) a first metallocene compound having the formula:
(X1)(X2)(X3)(X4)M1, wherein
M1 is zirconium;
X1 is an indenyl ligand which is substituted at the 1-position with a group selected independently from
X2 is [1] an unsubstituted cyclopentadienyl ligand or an unsubstituted indenyl ligand, [2] a cyclopentadienyl ligand which is substituted with at least one hydrocarbyl substituent selected independently from a C1-C12 alkyl or a C2-C12 alkenyl, or [3] an indenyl ligand which is substituted at the 1-position with a group having the formula
wherein X1 and X2 are unbridged; and
X3 and X4 are each a chloride;
b) optionally, a co-catalyst comprising an organoaluminum compound, an organoboron compound, an organozinc compound, an organomagnesium compound, an organolithium compound, or any combination thereof; and
c) an activator comprising a solid oxide treated with an electron-withdrawing anion (activator-support), an organoboron compound, an organoborate compound, an ionizing ionic compound, an aluminoxane compound, or any combination thereof.

### Claim 2 (depends on 1)

The catalyst composition according to claim 1, wherein the first metallocene compound is selected from:
wherein R1 is C6F5 (IE-1) or R1 is H (IE-3);
wherein R2 is H and R3 is H (IE-4), R2 is CH2CH2CH═CH2 and R3 is H (IE-5); R2 is CH2CH2CH═CH2 and R3 is CH3 (IE-6); R2 is CH2CH═CH2 and R3 is H (IE-7), or R2 is CH2CH═CH2 and R3 is CH3 (IE-8);
or
any combination thereof.

### Claim 3 (depends on 1)

The catalyst composition according to claim 1, wherein the catalyst composition further comprises:
d) a second metallocene compound having the formula:
(X5)(X6)(X7)(X8)M2, wherein
M2 is titanium, zirconium, or hafnium;
X5 is an optionally substituted cyclopentadienyl, indenyl, or fluorenyl ligand, wherein the substituent is selected independently from a C1-C12 hydrocarbyl group;
X6 is an optionally substituted indenyl or fluorenyl ligand, wherein the substituent is selected independently from a C1-C12 hydrocarbyl group or a C1-C12 heterohydrocarbyl group;
wherein X5 and X6 are bridged by a bridging group selected from (>ERB2)x or >BRB, wherein x is an integer from 1 to 3, E in each occurrence is selected independently from a carbon atom or a silicon atom, RB in each occurrence is selected independently from H or a C1-C12 hydrocarbyl group, and wherein optionally, two RB moieties form a C3-C6 cyclic group; and
X7 and X8 are independently selected from a halide, hydride, a C1-C20 hydrocarbyl group, a C1-C20 heterohydrocarbyl group, tetrahydroborate, or OBRA2 or OSO2RA wherein RA is independently a C1-C12 hydrocarbyl group.

### Claim 4 (depends on 3)

The catalyst composition according to claim 3, wherein
X5 is unsubstituted or substituted with a C1-C6 alkyl or C2-C8 alkenyl group, and X6 is substituted with two substituents selected independently from a C1-C12 hydrocarbyl group; and
RB, in each occurrence, is selected independently from a C1-C6 alkyl or C2-C8 alkenyl group.

### Claim 5 (depends on 3)

The catalyst composition according to claim 3, wherein (>ERB2)x is selected from (—CRB2CRB2—), (—SiRB2SiRB2—), (—CRB2SiRB2—), (—CRB2CRB2CRB2—), (—SiRB2CRB2CRB2—), (—CRB2SiRB2CRB2—), (—SiRB2CRB2SiRB2—), (—SiRB2SiRB2CRB2—), or (—SiRB2SiRB2SiRB2—).

### Claim 6 (depends on 3)

A catalyst composition according to claim 3, wherein (>ERB2)x or >BRB is selected from >CMe2, >CPh2, >CHMe, >CHPh, >CH(tolyl), >CMeEt, >CMe(CH2CH2CH3), >CMe(CH2CH2CH2CH3), >CH(CH2CH2CH═CH2), >CMe(CH2CH2CH═CH2), >CEt(CH2CH2CH═CH2), >CPh(CH2CH2CH═CH2), >SiMe2, >SiPh2, >SiEt2, >Si(tolyD2, (—CH2CH2—), (—CMe2CMe2-), (—CH2CH2CH2—), (—CH2SiMe2CH2—), (—CH2SiPh2CH2—), (—SiMe2SiMe2-), >BMe, >BEt, >BPh, or >B(tolyl).

### Claim 7 (depends on 3)

A catalyst composition according to claim 3, wherein the second metallocene is selected from a compound having the formula:
wherein:
M4 is zirconium or hafnium;
X5 in each occurrence is independently F, Cl, Br, I, H, methyl, benzyl, phenyl, or methoxy;
RD in each occurrence is selected independently from H, C1-C12 alkyl, C2-C12 alkenyl, C6-C10 aryl, C7-C12 aralkyl, or C1-C12 hydrocarbyloxide;
E1 is C or Si;
RE in each occurrence is selected independently from H, C1-C12 alkyl, C2-C12 alkenyl, C6-C10 aryl, or C7-C12 aralkyl; and
RF is selected from H, C1-C12 alkyl, C2-C12 alkenyl, C6-C10 aryl, or C7-C12 aralkyl.

### Claim 8 (depends on 3)

A catalyst composition according to claim 3, wherein the second metallocene is selected from a compound having the formula:
wherein:
M4 is zirconium or hafnium;
X5 in each occurrence is independently Cl, Br, methyl, or benzyl;
RD in each occurrence is selected independently from H or t-butyl;
E1 is C;
RE in a first occurrence is methyl or phenyl, and RE in a second occurrence is methyl, phenyl, or CH2CH2CH═CH2; and
RF is H or CH2CH2CH2CH═CH2.

### Claim 9 (depends on 3)

A catalyst composition according to claim 3, wherein the second metallocene is selected from a compound having the formula:

### Claim 10 (depends on 1)

The catalyst composition according to claim 1, wherein the activator comprises a solid oxide treated with an electron-withdrawing anion, and wherein:
the solid oxide comprises silica, alumina, titania, zirconia, magnesia, boria, calcia, zinc oxide, silica-alumina, silica-coated alumina, silica-titania, silica-zirconia, silica-magnesia, alumina-titania, alumina-zirconia, zinc-aluminate, alumina-boria, silica-boria, aluminum phosphate, aluminophosphate, aluminophosphate-silica, magnesium aluminate, titania-zirconia, mullite, boehmite, heteropolytungstates, or any combination thereof; and
the electron-withdrawing anion comprises fluoride, chloride, bromide, iodide, sulfate, bisulfate, fluorosulfate, phosphate, fluorophosphate, triflate, mesylate, tosylate, thiosulfate, C1-C10, C6-C14 aryl sulfonate, trifluoroacetate, fluoroborate, fluorozirconate, fluorotitanate, or any combination thereof.

### Claim 11 (depends on 1)

A catalyst composition according to claim 1, wherein the activator comprises a solid oxide treated with an electron-withdrawing anion selected from fluorided alumina, chlorided alumina, bromided alumina, sulfated alumina, phosphated alumina, fluorided silica-alumina, chlorided silica-alumina, bromided silica-alumina, sulfated silica-alumina, phosphated silica-alumina, fluorided silica-zirconia, chlorided silica-zirconia, bromided silica-zirconia, sulfated silica-zirconia, phosphated silica-zirconia, fluorided mullite, chlorided mullite, bromided mullite, sulfated mullite, phosphated mullite, fluorided silica-coated alumina, chlorided silica-coated alumina, bromided silica-coated alumina, sulfated silica-coated alumina, phosphated silica-coated alumina, or any combination thereof.

### Claim 12 (depends on 1)

A catalyst composition according to claim 1, wherein:
a) the optional co-catalyst has a general formula:
i) M3(X10)n(X11)3-n, wherein M3 is boron or aluminum and n is from 1 to 3 inclusive;
ii) M4(X10)n(X11)2-n, wherein M4 is magnesium or zinc and n is from 1 to 2 inclusive; or
iii) M5X10, wherein M5 is Li;
b) X10 is independently hydride or a C1 to C20 hydrocarbyl; and
c) X11 is independently a halide, a hydride, a C1 to C20 hydrocarbyl, or a C1 to C20 hydrocarbyloxide.

### Claim 13 (depends on 1)

A catalyst composition according to claim 1, wherein the optional co-catalyst comprises trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminum chloride, or any combination thereof.

### Claim 14 (depends on 1)

The catalyst composition according to claim 1, wherein the first metallocene compound has the formula:

### Claim 15 (depends on 1)

The catalyst composition according to claim 1, wherein the first metallocene compound has the formula:

### Claim 16 (depends on 1)

The catalyst composition according to claim 1, wherein the first metallocene compound has the formula:

### Claim 17 (depends on 1)

The catalyst composition according to claim 1, wherein the first metallocene compound has the formula:

### Claim 18 (depends on 1)

The catalyst composition according to claim 1, wherein the first metallocene compound has the formula:

### Claim 19 (depends on 1)

The catalyst composition according to claim 1, wherein the first metallocene compound has the formula:

### Claim 20 (depends on 1)

The catalyst composition according to claim 1, wherein the first metallocene compound has the formula:

### Claim 21 (depends on 1)

The catalyst composition according to claim 1, wherein the first metallocene compound has the formula:

### Claim 22 (depends on 1)

The catalyst composition according to claim 1, wherein the first metallocene compound has the formula:

### Claim 23 (depends on 1)

A process for polymerizing olefins, the process comprising contacting at least one olefin monomer and the catalyst composition according to claim 1 under polymerization conditions to form an olefin polymer, wherein the at least one olefin monomer comprises ethylene or ethylene in combination with an olefin co-monomer selected from propylene, butene, pentene, hexene, heptene, octene, styrene, or a combination thereof.