# US 11,299,567 B2 · Lubricating oil compositions comprising dual metallocene-catalyzed bimodal copolymer compositions useful as viscosity modifiers

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- Number: US 11,299,567 B2
- Document ID: US11299567B2
- Status: Granted
- Kind: B2
- Application number: 16/315,294
- Filed: 2017-06-14
- Published: 2019-10-10
- Granted: 2022-04-12
- Earliest claimed: 2016-07-14
- Assignees: ExxonMobil Chemical Patents Inc.
- Applicants: ExxonMobil Chemical Patents Inc.
- Inventors: Jingwen Zhang; Rainer Kolb; Andy H. Tsou; Periagaram S. Ravishankar; Jo Ann M. Canich; Francis C. Rix
- Web page: https://patentgrep.com/patent/US11299567B2

## CPC

- C08F 210/16: Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
- C08F 4/65927: {two cyclopentadienyl rings being mutually bridged}
- C10M 143/02: Polyethylene
- C10M 143/04: containing propene
- C10M 143/06: containing butene
- C10M 143/08: containing aliphatic monomer having more than 4 carbon atoms
- C10M 171/02: Specified values of viscosity or viscosity index
- C10M 171/04: Specified molecular weight or molecular weight distribution
- C08F 4/65908: {in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+}
- 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 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 2500/02: Low molecular weight, e.g. <100,000 Da.
- C08F 2500/04: Broad molecular weight distribution, i.e. Mw/Mn > 6
- C08F 2500/05: Bimodal or multimodal molecular weight distribution
- C08F 2500/09: Long chain branches
- C08F 2500/17: Viscosity
- C08F 2800/20: as weight or mass percentages
- C10M 2205/022: Ethene
- C10M 2205/024: Propene
- C10M 2205/026: Butene
- C10M 2205/028: containing aliphatic monomers having more than four carbon atoms
- C10M 2205/0285: used as base material
- C10M 2207/289: containing free hydroxy groups
- C10M 2223/049: Phosphite
- C10N 2020/01: {Physico-chemical properties}
- C10N 2020/019: {Shear stability}
- C10N 2020/02: Viscosity; Viscosity index
- C10N 2020/04: Molecular weight; Molecular weight distribution
- C10N 2020/069: {Linear chain compounds}
- C10N 2020/071: {Branched chain compounds}
- C10N 2030/02: Pour-point; Viscosity index
- C10N 2030/08: Resistance to extreme temperature
- C10N 2030/54: {Fuel economy}
- C10N 2030/68: {Shear stability}
- C10N 2040/25: Internal-combustion engines
- C10N 2070/00: Specific manufacturing methods for lubricant compositions
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C10M: LUBRICATING COMPOSITIONS (well drilling compositions C09K8/02); USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION (mould release, i.e. separating, agents for metals B22C3/00, for plastics or substances in a plastic state, in general B29C33/56, for glass C03B40/02; textile lubricating compositions D06M11/00, D06M13/00, D06M15/00; immersion oils for microscopy G02B21/33)
- C10N: INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS

## Abstract

This application relates to copolymer compositions and copolymerization processes, as well as to lubricating oil compositions comprising such copolymer compositions as viscosity index improvers, and base oil. The copolymer compositions may be made using two different metallocene catalysts: one capable of producing high molecular weight copolymers; and one suitable for producing lower molecular weight copolymers having at least a portion of vinyl terminations, and the copolymer compositions produced thereby. Copolymer compositions may comprise (1) a first ethylene copolymer fraction having high molecular weight, exhibiting branching topology, and having relatively lower ethylene content (based on the weight of the first ethylene copolymer fraction); and (2) a second ethylene copolymer fraction having low molecular weight, exhibiting linear rheology, and having relatively higher ethylene content (based on the weight of the second ethylene copolymer fraction). Lubricating oil compositions comprising such copolymer compositions may exhibit superior viscosity properties.

## Claims

### Claim 1

A lubricating oil composition comprising a base oil and from 0.1 to 10 wt % of a bimodal ethylene copolymer composition;
wherein the bimodal ethylene copolymer composition comprises:
(a) a first ethylene copolymer fraction comprising units derived from ethylene and one or more C3-C12 α-olefins, and having (i) ethylene-derived content (C2first) within the range from 40 wt % to 60 wt %, based on the content of monomer-derived units in the first ethylene copolymer fraction; (ii) weight average molecular weight (Mw) within the range from 100,000 to 750,000 g/mol; and (iii) branching index g′ of less than or equal to 0.95; and
(b) a second ethylene copolymer fraction having units derived from ethylene and one or more C3-C12 α-olefins, and having (i) ethylene-derived content greater than or equal to C2first+3 wt %, based on the content of monomer-derived units in the second ethylene copolymer fraction; (ii) Mw at least 50,000 g/mol less than the Mw of the first ethylene copolymer fraction; and (iii) branching index g′ within the range from 0.96 to 1;
wherein said bimodal ethylene copolymer composition comprises 70 to 93 wt % of said first ethylene copolymer fraction, with the second ethylene copolymer fraction constituting the balance; and
further wherein the lubricating oil composition exhibits one or more of the following properties as measured at a concentration of 1.15 wt % of the bimodal ethylene copolymer composition in the lubricating oil composition, based on the total weight of the lubricating oil composition:
(i) High Temperature High Shear (HTHS) values, determined per ASTM D4683, within the range from 3.0 to 6.0 cP;
(ii) Kinematic viscosity at 100° C. (kv@100° C., determined per ASTM D445) within the range from 12 to 20 cSt;
(iii) Kinematic viscosity at 40° C. (kv@40° C., determined per ASTM D445) within the range from 95 to 120 cSt;
(iv) kv@100° C. after-shear (determined per ASTM D6278) within the range from 7 to 11 cSt;
(v) Viscosity Index (determined per ASTM D2270) of at least 140;
(vi) Thickening Efficiency (TE) within the range from 2.5 to 5.5; and
(vii) Shear Stability Index (SSI) less than 55.

### Claim 2 (depends on 1)

The lubricating oil composition of claim 1, wherein the lubricating oil composition exhibits each of properties (i)-(v) as measured at a concentration of 1.15 wt % of the bimodal ethylene copolymer composition in the lubricating oil composition.

### Claim 3 (depends on 1)

The lubricating oil composition of claim 1, wherein the lubricating oil composition exhibits HTHS within the range from 2.5 to 3.7 as measured at a concentration of 1.15 wt % of the bimodal ethylene copolymer composition in the lubricating oil composition.

### Claim 4 (depends on 3)

The lubricating oil composition of claim 3, wherein the lubricating oil composition exhibits HTHS within the range from 3.0 to 3.7 when the lubricating oil comprises 1.15 wt % of the bimodal ethylene copolymer composition.

### Claim 5 (depends on 1)

The lubricating oil composition of claim 1, wherein the second ethylene copolymer fraction has ethylene-derived content within the range from greater than 60 wt % to 80 wt %, and Mw within the range from 20,000 g/mol to 100,000 g/mol.

### Claim 6 (depends on 1)

The lubricating oil composition of claim 1, wherein the bimodal ethylene copolymer composition is made by copolymerization of ethylene and propylene in the presence of a first metallocene catalyst and a second metallocene catalyst,
wherein the first metallocene catalyst has structure in accordance with Formula (I):
where (1) J is a divalent bridging group comprising C, Si, or both; (2) M is a group 4 transition metal; (3) each X is independently a univalent anionic ligand, or two Xs are joined and bound to the metal atom to form a metallocycle ring, or two Xs are joined to form a chelating ligand, a diene ligand, or an alkylidene ligand; and (4) each R″1-R″10 is independently hydrogen, C1-C50 hydrocarbyl, substituted hydrocarbyl, halocarbyl, or substituted halocarbyl provided that any one or more of the pairs R″1 and R″2, R″3 and R″4, R″5 and R″6, R″6 and R″7, R″8 and R″9, and R″9 and R″10, may optionally be bonded together to form a saturated or partially saturated cyclic or fused ring structure;
further wherein the second metallocene catalyst has structure in accordance with Formula (II):
where: (1) J is a divalent bridging group comprising C, Si, or both; (2) M is Hf; (3) each X is independently a univalent anionic ligand, or two Xs are joined and bound to the metal atom to form a metallocycle ring, or two Xs are joined to form a chelating ligand, a diene ligand, or an alkylidene ligand; and (4) each R2-R7 is independently hydrogen, C1-C50 substituted or unsubstituted hydrocarbyl, or C1-C50 substituted or unsubstituted halocarbyl, provided that any one or more of the pairs R4 and R5, R5 and R6, and R6 and R7 may be bonded together to form a saturated or partially saturated cyclic or fused ring structure.

### Claim 7 (depends on 1)

The lubricating oil composition of claim 1, wherein the bimodal ethylene copolymer composition exhibits one or more of the following properties:
(A) ethylene-derived content within the range from 40 to 70 wt %;
(B) Mw within the range from 100,000 to 400,000 g/mol;
(C) number-average molecular weight (Mn) within the range from 20,000 to 100,000 g/mol;
(D) molecular weight distribution (MWD, taken as Mw/Mn) within the range from 2.5 to 9; and
(E) branching index g′ within the range from 0.6 to 0.95.

### Claim 8

A lubricating oil composition comprising (1) a base oil and (2) 1 to 1.5 wt % of a bimodal ethylene copolymer composition, based on the total weight of the lubricating oil composition;
wherein the bimodal ethylene copolymer composition comprises:
(a) a first ethylene copolymer fraction comprising units derived from ethylene and one or more C3-C12 α-olefins, and having (i) ethylene-derived content (C2first) within the range from 40 wt % to 60 wt %, based on the content of monomer-derived units in the first ethylene copolymer fraction; (ii) weight average molecular weight (Mw) within the range from 100,000 to 750,000 g/mol; and (iii) branching index g′ of less than or equal to 0.95; and
(b) a second ethylene copolymer fraction having units derived from ethylene and one or more C3-C12 α-olefins, and having (i) ethylene-derived content greater than or equal to C2first+3 wt %, based on the content of monomer-derived units in the second ethylene copolymer fraction; (ii) Mw at least 50,000 g/mol less than the Mw of the first ethylene copolymer fraction; and (iii) branching index g′ within the range from 0.96 to 1;
wherein said bimodal ethylene copolymer composition comprises 70 to 93 wt % of said first ethylene copolymer fraction, with the second ethylene copolymer fraction constituting the balance; and
further wherein the lubricating oil composition exhibits one or more of the following properties:
(i) High Temperature High Shear (HTHS) values, determined per ASTM D4683, within the range from 3.0 to 6.0 cP;
(ii) Kinematic viscosity at 100° C. (kv@100° C., determined per ASTM D445) within the range from 12 to 20 cSt;
(iii) Kinematic viscosity at 40° C. (kv@40° C., determined per ASTM D445) within the range from 95 to 120 cSt;
(iv) kv@100° C. after-shear (determined per ASTM D6278) within the range from 7 to 11 cSt;
(v) Viscosity Index (determined per ASTM D2270) of at least 140;
(vi) Thickening Efficiency (TE) within the range from 2.5 to 5.5; and
(vii) Shear Stability Index (SSI) less than 55.

### Claim 9 (depends on 8)

The lubricating oil composition of claim 8, wherein the base oil comprises an API Group I base stock oil.

### Claim 10 (depends on 8)

The lubricating oil composition of claim 8, wherein the base oil has Viscosity Index (determined per ASTM D2270, in the absence of the bimodal ethylene copolymer composition) within the range from 75 to 110.

### Claim 11 (depends on 8)

The lubricating oil composition of claim 8, exhibiting each of properties (i)-(v).

### Claim 12 (depends on 8)

The lubricating oil composition of claim 8, exhibiting HTHS within the range from 3.0 to 3.7.

### Claim 13 (depends on 8)

The lubricating oil composition of claim 8, wherein the second ethylene copolymer fraction has ethylene-derived content within the range from greater than 60 wt % to 80 wt %, and Mw within the range from 20,000 g/mol to 100,000 g/mol.

### Claim 14 (depends on 8)

The lubricating oil composition of claim 8, wherein the bimodal ethylene copolymer composition is made by copolymerization of ethylene and propylene in the presence of a first metallocene catalyst and a second metallocene catalyst,
wherein the first metallocene catalyst has structure in accordance with Formula (I):
where (1) J is a divalent bridging group comprising C, Si, or both; (2) M is a group 4 transition metal; (3) each X is independently a univalent anionic ligand, or two Xs are joined and bound to the metal atom to form a metallocycle ring, or two Xs are joined to form a chelating ligand, a diene ligand, or an alkylidene ligand; and (4) each R″1—R″10 is independently hydrogen, C1-C50 hydrocarbyl, substituted hydrocarbyl, halocarbyl, or substituted halocarbyl provided that any one or more of the pairs R″1 and R″2, R″3 and R″4, R″5 and R″6, R″6 and R″7, R″8 and R″9, and R″9 and R″10, may optionally be bonded together to form a saturated or partially saturated cyclic or fused ring structure;
further wherein the second metallocene catalyst has structure in accordance with Formula (II):
where: (1) J is a divalent bridging group comprising C, Si, or both; (2) M is Hf; (3) each X is independently a univalent anionic ligand, or two Xs are joined and bound to the metal atom to form a metallocycle ring, or two Xs are joined to form a chelating ligand, a diene ligand, or an alkylidene ligand; and (4) each R2-R7 is independently hydrogen, C1-C50 substituted or unsubstituted hydrocarbyl, or C1-C50 substituted or unsubstituted halocarbyl, provided that any one or more of the pairs R4 and R5, R5 and R6, and R6 and R7 may be bonded together to form a saturated or partially saturated cyclic or fused ring structure.

### Claim 15 (depends on 8)

The lubricating oil composition of claim 8, wherein the bimodal ethylene copolymer composition exhibits one or more of the following properties:
(A) ethylene-derived content within the range from 40 to 70 wt %;
(B) Mw within the range from 100,000 to 400,000 g/mol;
(C) number-average molecular weight (Mn) within the range from 20,000 to 100,000 g/mol;
(D) molecular weight distribution (MWD, taken as Mw/Mn) within the range from 2.5 to 9; and
(E) branching index g′ within the range from 0.6 to 0.95.