# US 11,078,311 B2 · Single-site catalyst polyolefin polymerization process

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- Number: US 11,078,311 B2
- Document ID: US11078311B2
- Status: Granted
- Kind: B2
- Application number: 16/332,864
- Filed: 2017-09-27
- Published: 2020-01-23
- Granted: 2021-08-03
- Earliest claimed: 2016-10-26
- Assignees: ExxonMobil Chemical Patents Inc.
- Applicants: ExxonMobil Chemical Patents Inc.
- Inventors: Blu E. Englehorn
- Web page: https://patentgrep.com/patent/US11078311B2

## CPC

- C08F 110/06: Propene
- C08F 2/01: characterised by special features of the polymerisation apparatus used
- C08F 2/02: Polymerisation in bulk
- 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 210/16: Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
- 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

## Abstract

Disclosed is a method for polymerizing olefins comprising passing a heterogeneous single-site catalyst to a solution or slurry polymerization reactor in the absence of pre-polymerization, wherein the polymerization reactor operates at a temperature of at least 50° C. The heterogeneous single-site catalyst may be suspended and/or dissolved in a solvent selected from the group consisting of oils, aliphatic hydrocarbons and mixtures thereof. Also, the heterogeneous single-site catalyst may be passed to the polymerization reactor at a velocity of greater than 1 m/s or 3 m/s.

## Claims

### Claim 1

In a polymerization reactor system comprising a polymerization reactor, a pre-polymerization reactor and a catalyst injection line fluidly connected to both and directed to by-pass the pre-polymerization reactor, a method comprising passing a heterogeneous single-site catalyst to the catalyst injection line and contacting the heterogeneous single-site catalyst with propylene monomers in the polymerization reactor at a temperature of at least 50° C.

### Claim 2 (depends on 1)

The method of claim 1, comprising contacting the heterogeneous single-site catalyst and monomers at a temperature within a range from 50° C. to 120° C.

### Claim 3 (depends on 1)

The method of claim 1, wherein the polymerization is continuous.

### Claim 4 (depends on 1)

The method of claim 1, comprising passing the heterogeneous single-site catalyst to the polymerization reactor by contacting with a stream selected from the group consisting of C2 to C12 α-olefins, C4 to C12 alkanes, oil, and a mixtures thereof.

### Claim 5 (depends on 1)

The method of claim 1, comprising passing the heterogeneous single-site catalyst to the polymerization reactor at a velocity of at least 1 m/s.

### Claim 6 (depends on 1)

The method of claim 1, wherein the heterogeneous single-site catalyst comprises a heterogeneous single-site catalyst compound selected from metallocenes, metal salens, diamido metal compounds and alkoxide metal compounds, metal pyridyl-amides, and combinations thereof.

### Claim 7 (depends on 1)

The method of claim 1, wherein the heterogeneous single-site catalyst comprises a metallocene comprising any two ligands selected from cyclopentadienyl and ligands isolobal to cyclopentadienyl.

### Claim 8 (depends on 7)

The method of claim 7, wherein the cyclopentadienyl group is selected from the group consisting of indenyl, fluorenyl, cyclopenta[b]naphthalenyl, cyclopenta[a]naphthalenyl, cyclopenta[l]phenanthrenyl, cyclopenta[b]anthracenyl, cyclopenta[a]anthracenyl, indeno[1,2-b]anthracenyl, dibenzo[b,h]fluorenyl, benzo[b]fluorenyl, hydrogenated versions thereof, substituted versions thereof, and heterocyclic versions thereof.

### Claim 9 (depends on 1)

The method of claim 1, wherein the heterogeneous single-site catalyst comprises an asymmetric metallocene.

### Claim 10 (depends on 1)

The method of claim 1, wherein the single-site catalyst comprises metallocenes having structures represented by the following formulae:
wherein R2 and R8 are, independently, a C1 to C6 or C10 or C20 linear alkyl group, provided that at least one of R2 and R8 has at least 4 carbon atoms;
R4 and R10 are substituted or unsubstituted aryl groups;
M is a transition metal selected from Group 3 to 5 of the Periodic Table;
T is a bridging group;
each X is an anionic leaving group;
each R1, R3, R5, R6, R7, R9, R11, R12, R13, and R14 is, independently, hydrogen, or a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl, or substituted germylcarbyl substituents;
wherein either or both of R5 and R6 and R11 and R12 optionally join together to form a ring structure.

### Claim 11 (depends on 10)

The method of claim 10, wherein at least one of the aryl groups of R4 and R10 is:
substituted at an ortho position with at least one group selected from C1 to C40 hydrocarbyls, heteroatoms, and heteroatom containing groups, and/or
substituted at the 3′, 4′ or 5′ position with at least one group selected from C1 to C40 hydrocarbyls, heteroatoms, and heteroatom containing groups.

### Claim 12 (depends on 1)

The method of claim 1, wherein the heterogeneous single-site catalyst comprises an activator.

### Claim 13 (depends on 1)

The method of claim 1, wherein the support upon which the heterogeneous single-site catalyst is associated is selected from the group consisting of Groups 2, 4, 13, and 14 metal oxides and mixtures thereof.

### Claim 14 (depends on 1)

The method of claim 1, wherein the support upon which the heterogeneous single-site catalyst is associated has an average surface area of from 200 m2/g to 1400 m2/g.

### Claim 15 (depends on 1)

The method of claim 1, wherein the support upon which the heterogeneous single-site catalyst is associated comprises at least 60 wt % silica.

### Claim 16 (depends on 1)

The method of claim 1, comprising suspending the heterogeneous single-site catalyst in a solvent.

### Claim 17 (depends on 16)

The method of claim 16, wherein the concentration of the heterogeneous single-site catalyst in the solvent prior to entering the polymerization reactor is within a range from 1 wt % to 20 wt % by weight of the heterogeneous single-site catalyst and solvent.

### Claim 18 (depends on 16)

The method of claim 16, wherein the solvent is selected from the group consisting of oils, aliphatic hydrocarbons, and mixtures thereof.