# US 12,006,383 B2 · Terpolymers of ethylene, 1,3-butadiene and an aromatic a-monoolefin

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- Number: US 12,006,383 B2
- Document ID: US12006383B2
- Status: Granted
- Kind: B2
- Application number: 17/415,540
- Filed: 2019-12-02
- Published: 2022-02-24
- Granted: 2024-06-11
- Earliest claimed: 2018-12-20
- Assignees: Compagnie Generale Des Etablissements Michelin
- Applicants: Compagnie Generale Des Etablissements Michelin
- Inventors: Emma Moreso; Vincent Lafaquiere; Julien Thuilliez
- Web page: https://patentgrep.com/patent/US12006383B2

## CPC

- C08F 210/02: Ethene
- B60C 1/00: Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- 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 2800/10: as molar percentages
- C08F 2810/20: leading to a crosslinking, either explicitly or inherently
- C08K 3/013: Fillers, pigments or reinforcing additives
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- B60C: VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)

## Abstract

A terpolymer of ethylene, of 1,3-butadiene and of an aromatic α-monoolefin is provided. The terpolymer contains more than 60 mol %, preferably at least 70 mol %, and preferably at most 90 mol % of ethylene units, at most 10 mol % of aromatic α-monoolefin units and 1,2-cyclohexanediyl units. Such a diene terpolymer rich in ethylene units has the advantage of exhibiting a reduced, or even zero, crystallinity.

## Claims

### Claim 1

A terpolymer of ethylene, of 1,3-butadiene and of an aromatic α-monoolefin, wherein the terpolymer contains:
more than 60 mol % of ethylene units,
at most 10 mol % of aromatic α-monoolefin units and
1,2-cyclohexanediyl units.

### Claim 2 (depends on 1)

The terpolymer according to claim 1, in which the content of ethylene units is at least 80 mol % and at most 90 mol % of the monomer units of the terpolymer.

### Claim 3 (depends on 1)

The terpolymer according to claim 1, in which the content of the 1,3-butadiene units is greater than 3 mol % of the monomer units of the terpolymer.

### Claim 4 (depends on 1)

The terpolymer according to claim 1, in which the aromatic α-monoolefin is styrene, a styrene substituted by one or more alkyl groups in the para, meta or ortho positions, or mixtures thereof.

### Claim 5 (depends on 1)

The terpolymer according to claim 1, in which the content of ethylene units ranges from 70 to 90 mol %, of the monomer units of the terpolymer, and the content of the 1,3-butadiene units ranges from 5 mol % to 20 mol % of the monomer units of the terpolymer.

### Claim 6 (depends on 1)

The terpolymer according to claim 1, in which the 1,2 units represent at least 50 mol % of the 1,3-butadiene units.

### Claim 7 (depends on 1)

The terpolymer according to claim 1, which terpolymer is an elastomer.

### Claim 8 (depends on 1)

A process for the synthesis of a terpolymer defined in claim 1, which comprises the polymerization of ethylene, of 1,3-butadiene and of an aromatic α-monoolefin in the presence of a catalytic system based on a rare-earth metallocene of formula (I) and on an organometallic compound as cocatalyst,
{P(Cp1)(Cp2)Met-G}b (I)
in which
Met represents a rare-earth metal atom,
the symbol G denoting a halogen atom X selected from the group consisting of chlorine, fluorine, bromine and iodine or a group comprising the BH4 borohydride moiety,
Cp1 and Cp2 are identical and are selected from the group consisting of indenyl groups substituted in position 2, substituted fluorenyl groups and the fluorenyl group,
P is a group bridging the 2 groups Cp1 and Cp2, and comprises a silicon or carbon atom,
b is equal to 1 or 2.

### Claim 9 (depends on 8)

The process according to claim 8, in which the rare-earth metallocene corresponds to the formula of formula (II)
{P(Flu)2NdG}b (II)
Nd denoting a neodymium atom,
G denoting a group comprising the borohydride BH4 moiety or denoting a halogen atom X selected from the group consisting of chlorine, fluorine, bromine and iodine,
Flu denoting a fluorenyl group of formula C13H8,
P being a group bridging the two Flu groups and comprising a silicon or carbon atom,
b is equal to 1 or 2.

### Claim 10 (depends on 9)

The process according to claim 9, in which the cocatalyst is a dialkylmagnesium compound or an alkylmagnesium halide.

### Claim 11 (depends on 8)

The process according to claim 8, in which G denotes a chlorine atom or the group of formula (III)
(BH4)(i+y)-Ly-Nx (III)
in which
L represents an alkali metal selected from the group consisting of lithium, sodium and potassium,
N represents a molecule of an ether,
x, which is or is not an integer, is equal to or greater than 0,
y, which is an integer, is equal to or greater than 0.

### Claim 12 (depends on 8)

The process according to claim 8, in which the bridge P corresponds to the formula ZR1R2, Z representing a silicon or carbon atom and R1 and R2, which are identical or different, each representing an alkyl group comprising from 1 to 20 carbon atoms.

### Claim 13 (depends on 8)

The process according to claim 8, in which the metallocene is (dimethylsilyl)(bisfluorenyl)neodymium borohydride of formulae (IIa) to (IIe):
[{Me2SiFlu2Nd(μ-BH4)2Li(THF)}2] (IIa)
[Me2SiFlu2Nd(μ-BH4)2Li(THF)] (IIb)
[Me2SiFlu2Nd(μ-BH4)(THF)] (IIc)
[{Me2SiFlu2Nd(μ-BH4)(THF)}2] (IId)
[Me2SiFlu2Nd(μ-BH4)] (IIe)
Flu representing the C13H8 group.

### Claim 14 (depends on 1)

A rubber composition based on a reinforcing filler, a crosslinking system and a terpolymer defined according to claim 1.

### Claim 15 (depends on 14)

A tire which comprises a composition defined in claim 14.

### Claim 16 (depends on 1)

The terpolymer according to claim 1, wherein the terpolymer contains at least 70 mol % of ethylene units.

### Claim 17 (depends on 1)

The terpolymer according to claim 1, in which the content of the 1,3-butadiene units is less than 20 mol % of the monomer units of the terpolymer.

### Claim 18 (depends on 1)

The terpolymer according to claim 1, in which the aromatic α-monoolefin is styrene.

### Claim 19 (depends on 1)

The terpolymer according to claim 1, in which the content of ethylene units ranges from 80 to 90 mol % of the monomer units of the terpolymer, and the content of the 1,3-butadiene units ranges from 5 mol % to 15 mol % of the monomer units of the terpolymer.

### Claim 20 (depends on 8)

The process according to claim 8, in which the cocatalyst is butyloctylmagnesium, dibutylmagnesium, butylethylmagnesium or butylmagnesium chloride.