# US 11,993,620 B2 · Aminosilyl-functionalized conjugated dienes, their preparation and their use in the production of rubbers

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- Number: US 11,993,620 B2
- Document ID: US11993620B2
- Status: Granted
- Kind: B2
- Application number: 17/272,831
- Filed: 2019-09-02
- Published: 2021-08-26
- Granted: 2024-05-28
- Earliest claimed: 2018-09-03
- Assignees: Synthos S.A.; Synthos Dwory 7 Spolka Z Ograniczona Odpowiedzialnoscia Spolka Jawna
- Applicants: Synthos S.A.; Synthos Dwory 7 Spolka Z Ograniczona Odpowiedzialnoscia Spolka Jawna
- Inventors: Maria Siolek-Komorek; Radoslaw Kozak; Pawel Weda; Robert Bogacz; Tomasz Skrok; Malgorzata Pierog
- Web page: https://patentgrep.com/patent/US11993620B2

## CPC

- C07F 7/10: containing nitrogen {having a Si-N linkage}
- C08L 9/06: Copolymers with styrene
- B60C 1/0016: {Compositions of the tread}
- C08F 236/10: with vinyl-aromatic monomers
- C08K 3/04: Carbon
- C08K 3/36: Silica
- C08L 19/006: {Rubber characterised by functional groups, e.g. telechelic diene polymers}
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- B60C: VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)

## Abstract

The invention relates to aminosilyl-functionalized conjugated dienes, their preparation and their use in the production of rubbers. Further, the invention relates to rubbers and rubber compositions, and tires produced therefrom. The functionalized conjugated dienes are selected from the group of compounds of formula (Ilia), (Nib), (lllc).

## Claims

### Claim 1

A method for the preparation of a functionalized conjugated diene selected from the group of compounds of formula (IIIa), (IIIb), (IIIc)
wherein
R is an organylene group optionally containing one or more heteroatoms selected from an oxygen atom, a sulfur atom, a nitrogen atom, and a silicon atom, and R has at least 6 carbon atoms in formula (IIIa) and at least 5 carbon atoms in formula (IIIb) and formula (IIIc),
R1 is selected from
i) a single bond,
ii) one or more of an oxygen atom, a sulfur atom, a group NR6, and a group SiR7R8; and
iii) an organylene group optionally containing one or more selected from an oxygen atom, a sulfur atom, a group NR6, and a group SiR7R8;
R2, R3, R6, R7, R8 can be the same or different and represent an organyl group optionally containing one or more heteroatoms selected from an oxygen atom, a sulfur atom, a nitrogen atom, and a silicon atom; and
i) R4 and R5 can be the same or different and each R4 and R5 independently represents an organyl group optionally containing one or more heteroatoms selected from a silicon atom, an oxygen atom, a sulfur atom, and a nitrogen atom;
or
ii) R4 and R5 are bonded to each other to form a heterocyclic ring containing the nitrogen atom and at least one carbon atom and, optionally, one or more heteroatoms selected from a silicon atom, an oxygen atom, a sulfur atom, and a nitrogen atom,
the method comprising reacting, under Grignard conditions, a conjugated diene halide selected from the group of compounds of formula (IIa), (IIb), (IIc)
wherein Y1 is selected from fluorine, chlorine, bromine, and iodine atoms,
with a compound of formula (IV)
wherein Y2 is selected from fluorine, chlorine, bromine, and iodine atoms.

### Claim 2

A method for the preparation of a functionalized conjugated diene selected from the group of compounds of formula (IIa), (IIIb), (IIIc)
wherein
R is an organylene group optionally containing one or more heteroatoms selected from an oxygen atom, a sulfur atom, a nitrogen atom, and a silicon atom, and R has at least 6 carbon atoms in formula (IIIa) and at least 5 carbon atoms in formula (Mb) and formula (IIIc),
R1 is selected from
i) a single bond,
ii) one or more of an oxygen atom, a sulfur atom, a group NR6, and a group SiR7R8; and
iii) an organylene group optionally containing one or more selected from an oxygen atom, a sulfur atom, a group NR6, and a group SiR7R8;
R2, R3, R6, R7, R8 can be the same or different and represent an organyl group optionally containing one or more heteroatoms selected from an oxygen atom, a sulfur atom, a nitrogen atom, and a silicon atom; and
i) R4 and R5 can be the same or different and each R4 and R5 independently represents an organyl group optionally containing one or more heteroatoms selected from a silicon atom, an oxygen atom, a sulfur atom, and a nitrogen atom;
or
ii) R4 and R5 are bonded to each other to form a heterocyclic ring containing the nitrogen atom and at least one carbon atom and, optionally, one or more heteroatoms selected from a silicon atom, an oxygen atom, a sulfur atom, and a nitrogen atom,
the method comprising
A) reacting, under Grignard conditions, a conjugated diene halide selected from the group of compounds of formula (IIa), (IIb), (IIc)
wherein Y1 is selected from fluorine, chlorine, bromine, and iodine atoms,
with a compound of formula (V)
wherein Y2 and Y3 are independently selected from fluorine, chlorine, bromine, and iodine atoms,
to result in a compound of formula (VIa), (VIb), (VIc)
and
B) reacting the compound of formula (VIa), (VIb), (VIc) with an amide of formula (VII)
wherein M is an alkali metal selected from lithium, sodium, and potassium.

### Claim 3

A functionalized conjugated diene selected from the group of compounds of formula (IIIa), (IIIb), (IIIc)
wherein
R is an organylene group optionally containing one or more heteroatoms selected from an oxygen atom, a sulfur atom, a nitrogen atom, and a silicon atom, and R has at least 6 carbon atoms in formula (IIIa) and at least 5 carbon atoms in formula (IIIb) and formula (IIIc),
R1 is selected from
i) a single bond,
ii) one or more of an oxygen atom, a sulfur atom, a group NR6, and a group SiR7R8; and
iii) an organylene group optionally containing one or more selected from an oxygen atom, a sulfur atom, a group NR6, and a group SiR7R8;
R2, R3, R6, R7, R8 can be the same or different and represent an organyl group optionally containing one or more heteroatoms selected from an oxygen atom, a sulfur atom, a nitrogen atom, and a silicon atom; and
i) R4 and R5 can be the same or different and each R4 and R5 independently represents an organyl group optionally containing one or more heteroatoms selected from a silicon atom, an oxygen atom, a sulfur atom, and a nitrogen atom;
or
ii) R4 and R5 are bonded to each other to form a heterocyclic ring containing the nitrogen atom and at least one carbon atom and, optionally, one or more heteroatoms selected from a silicon atom, an oxygen atom, a sulfur atom, and a nitrogen atom.

### Claim 4 (depends on 3)

The functionalized conjugated diene of claim 3, wherein R1 is i) a single bond.

### Claim 5 (depends on 3)

The functionalized conjugated diene of claim 3, wherein R2, R3, R6, R7, and R8 are the same or different and represent a linear or branched, saturated or unsaturated hydrocarbyl group.

### Claim 6 (depends on 3)

The functionalized conjugated diene of claim 3, wherein R4 and R5 are the same and represent a linear, branched or cyclic, saturated or unsaturated alkyl group.

### Claim 7 (depends on 3)

The functionalized conjugated diene of claim 3, wherein R is a linear or branched, saturated or unsaturated hydrocarbylene, hydrocarbylidene, or hydrocarbylidyne group.

### Claim 8 (depends on 3)

A method of producing an elastomeric copolymer, comprising copolymerizing the one or more functionalized conjugated dienes of claim 3 and one or more comonomers.

### Claim 9 (depends on 8)

The method of claim 8, wherein the elastomeric copolymer comprises, in addition to one or more units derived from the one or more functionalized conjugated dienes selected from the group of compounds of formula (IIIa), (IIIb), (Mc), units derived from one or more conjugated diene monomers,
wherein the conjugated diene monomer is selected from 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 2,3-dimethyl-1,3-pentadiene, 2-phenyl-1,3-butadiene, and 4,5-diethyl-1,3-octadiene.

### Claim 10 (depends on 8)

The method of claim 8, wherein the production of the elastomeric copolymer is by anionic polymerization or by coordination polymerization.

### Claim 11 (depends on 8)

The method of claim 8, wherein the elastomeric copolymer comprises units derived from one or more vinyl aromatic monomers,
wherein the vinyl aromatic monomer is selected from styrene, 1-vinylnaphthalene, 3-methyl styrene, 3,5-diethylstyrene, 4-propylstyrene, 2,4,6-trimethylstyrene, 4-dodecylstyrene, 3-methyl-5-n-hexylstyrene, 4-phenylstyrene, 2-ethyl-4-benzylstyrene, 3,5-diphenylstyrene, 2,3,4,5-tetraethylstyrene, 3-ethyl-1-vinylnaphthalene, 6-isopropyl-1-vinylnaphthalene, 6-cyclohexyl-1-vinylnaphthalene, 7-dodecyl-2-vinylnaphthalene, and α-methyl styrene.

### Claim 12 (depends on 8)

The method of claim 8, wherein the amount of units derived from the one or more functionalized conjugated dienes selected from of the group of compounds of formula (IIIa), (IIIb), (IIIc) is in a range of from 0.05 to 5 wt. %, based on the weight of the elastomeric copolymer.

### Claim 13

A method of anionic polymerization, comprising copolymerizing one or more conjugated diene monomers, optionally one or more vinyl aromatic monomers, and optionally one or more functionalized conjugated dienes selected from the group of compounds of formula (IIIa), (IIIb), (IIIc), with an initiator of an alkali metal salt derivative of a functionalized conjugated diene selected from the group of compounds of formula (IIIa), (IIIb), (IIIc)
wherein
R is an organylene group optionally containing one or more heteroatoms selected from an oxygen atom, a sulfur atom, a nitrogen atom, and a silicon atom, and R has at least 6 carbon atoms in formula (IIIa) and at least 5 carbon atoms in formula (IIIb) and formula (IIIc),
R1 is selected from
i) a single bond,
ii) one or more of an oxygen atom, a sulfur atom, a group NR6, and a group SiR7R8; and
iii) an organylene group optionally containing one or more selected from an oxygen atom, a sulfur atom, a group NR6, and a group SiR7R8;
R2, R3, R6, R7, R8 can be the same or different and represent an organyl group optionally containing one or more heteroatoms selected from an oxygen atom, a sulfur atom, a nitrogen atom, and a silicon atom; and
i) R4 and R5 can be the same or different and each R4 and R5 independently represents an organyl group optionally containing one or more heteroatoms selected from a silicon atom, an oxygen atom, a sulfur atom, and a nitrogen atom;
or
ii) R4 and R5 are bonded to each other to form a heterocyclic ring containing the nitrogen atom and at least one carbon atom and, optionally, one or more heteroatoms selected from a silicon atom, an oxygen atom, a sulfur atom, and a nitrogen atom,
as initiator for the anionic copolymerization of one or more conjugated diene monomers, optionally one or more vinyl aromatic monomers, and optionally one or more functionalized conjugated dienes selected from the group of compounds of formula (IIIa), (IIIb), (Mc).

### Claim 14

A process for the production of a copolymer component comprising coupled copolymer and terminally modified copolymer, the process comprising the following steps:
(1) providing an initiator component, wherein the initiator component comprises one or more alkali metal salt derivatives of a one or more functionalized conjugated dienes selected from the group of compounds of formula (IIIa), (IIIb), (IIIc)
wherein
R is an organylene group optionally containing one or more heteroatoms selected from an oxygen atom, a sulfur atom, a nitrogen atom, and a silicon atom, and R has at least 6 carbon atoms in formula (IIIa) and at least 5 carbon atoms in formula (IIIb) and formula (IIIc),
R1 is selected from
i) a single bond,
ii) one or more of an oxygen atom, a sulfur atom, a group NR6, and a group SiR7R8; and
iii) an organylene group optionally containing one or more selected from an oxygen atom, a sulfur atom, a group NR6, and a group SiR7R8;
R2, R3, R6, R7, R8 can be the same or different and represent an organyl group optionally containing one or more heteroatoms selected from an oxygen atom, a sulfur atom, a nitrogen atom, and a silicon atom; and
i) R4 and R5 can be the same or different and each R4 and R5 independently represents an organyl group optionally containing one or more heteroatoms selected from a silicon atom, an oxygen atom, a sulfur atom, and a nitrogen atom;
or
ii) R4 and R5 are bonded to each other to form a heterocyclic ring containing the nitrogen atom and at least one carbon atom and, optionally, one or more heteroatoms selected from a silicon atom, an oxygen atom, a sulfur atom, and a nitrogen atom,
wherein the alkali metal is selected from lithium, sodium, and potassium;
(2) contacting a monomer component comprising
i) one or more functionalized conjugated dienes selected from the group of compounds of formula (IIIa), (IIIb), (IIIc),
ii) one or more conjugated diene monomers and
iii) optionally one or more vinyl aromatic monomers,
with the initiator component, to initiate anionic copolymerization;
(3) continuing copolymerization, to result in a copolymer;
(4) optionally continuing copolymerization of the copolymer, in the presence of one or more functionalized monomers, to result in a functionalized copolymer;
(5) coupling a part of the copolymer of step (3) or the functionalized copolymer of step (4) with one or more coupling agents, to result in coupled copolymer; and
(6) terminally modifying a part of the copolymer of step (3) or the functionalized copolymer of step (4) with one or more terminal modifying agents, to result in terminally modified copolymer.

### Claim 15

A process for producing an elastomeric copolymer comprising subjecting
i) one or more functionalized conjugated dienes selected from the group of compounds of formula (IIIa), (IIIb), (IIIc)
wherein
R is an organylene group optionally containing one or more heteroatoms selected from an oxygen atom, a sulfur atom, a nitrogen atom, and a silicon atom, and R has at least 6 carbon atoms in formula (IIIa) and at least 5 carbon atoms in formula (IIIb) and formula (IIIc),
R1 is selected from
i) a single bond,
ii) one or more of an oxygen atom, a sulfur atom, a group NR6, and a group SiR7R8; and
iii) an organylene group optionally containing one or more selected from an oxygen atom, a sulfur atom, a group NR6, and a group SiR7R8;
R2, R3, R6, R7, R8 can be the same or different and represent an organyl group optionally containing one or more heteroatoms selected from an oxygen atom, a sulfur atom, a nitrogen atom, and a silicon atom; and
i) R4 and R5 can be the same or different and each R4 and R5 independently represents an organyl group optionally containing one or more heteroatoms selected from a silicon atom, an oxygen atom, a sulfur atom, and a nitrogen atom;
or
ii) R4 and R5 are bonded to each other to form a heterocyclic ring containing the nitrogen atom and at least one carbon atom and, optionally, one or more heteroatoms selected from a silicon atom, an oxygen atom, a sulfur atom, and a nitrogen atom,
ii) one or more conjugated diene monomers, and
iii) optionally one or more vinyl aromatic monomers
to anionic polymerization conditions.

### Claim 16

A process for producing an elastomeric copolymer comprising subjecting
i) one or more functionalized conjugated dienes selected from the group of compounds of formula (IIIa), (IIIb), (IIIc)
wherein
R is an organylene group optionally containing one or more heteroatoms selected from an oxygen atom, a sulfur atom, a nitrogen atom, and a silicon atom, and R has at least 6 carbon atoms in formula (IIIa) and at least 5 carbon atoms in formula (IIIb) and formula (IIIc),
R1 is selected from
i) a single bond,
ii) one or more of an oxygen atom, a sulfur atom, a group NR6, and a group SiR7R8; and
iii) an organylene group optionally containing one or more selected from an oxygen atom, a sulfur atom, a group NR6, and a group SiR7R8;
R2, R3, R6, R7, R8 can be the same or different and represent an organyl group optionally containing one or more heteroatoms selected from an oxygen atom, a sulfur atom, a nitrogen atom, and a silicon atom; and
i) R4 and R5 can be the same or different and each R4 and R5 independently represents an organyl group optionally containing one or more heteroatoms selected from a silicon atom, an oxygen atom, a sulfur atom, and a nitrogen atom;
or
ii) R4 and R5 are bonded to each other to form a heterocyclic ring containing the nitrogen atom and at least one carbon atom and, optionally, one or more heteroatoms selected from a silicon atom, an oxygen atom, a sulfur atom, and a nitrogen atom,
and
ii) one or more conjugated diene monomers
to Ziegler-Natta polymerization conditions.

### Claim 17 (depends on 16)

The process of claim 16, wherein the Ziegler-Natta polymerization conditions include a catalyst system comprising 1) metal chloride and 2) co-catalyst.

### Claim 18 (depends on 16)

The process of claim 16, wherein the Ziegler-Natta polymerization conditions include a catalyst system comprising 1) non-halide metal compound, 2) co-catalyst, and 3) halide donor compound.

### Claim 19

An elastomeric copolymer comprising repeat units that are derived from
A) 0.05 wt. % to 5 wt. %, by weight of the copolymer, of one or more functionalized conjugated dienes selected from the group of compounds of formula (IIIa), (IIIb), (IIIc)
wherein
R is an organylene group optionally containing one or more heteroatoms selected from an oxygen atom, a sulfur atom, a nitrogen atom, and a silicon atom, and R has at least 6 carbon atoms in formula (IIIa) and at least 5 carbon atoms in formula (IIIb) and formula (IIIc),
R1 is selected from
i) a single bond,
ii) one or more of an oxygen atom, a sulfur atom, a group NR6, and a group SiR7R8; and
iii) an organylene group optionally containing one or more selected from an oxygen atom, a sulfur atom, a group NR6, and a group SiR7R8;
R2, R3, R6, R7, R8 can be the same or different and represent an organyl group optionally containing one or more heteroatoms selected from an oxygen atom, a sulfur atom, a nitrogen atom, and a silicon atom; and
i) R4 and R5 can be the same or different and each R4 and R5 independently represents an organyl group optionally containing one or more heteroatoms selected from a silicon atom, an oxygen atom, a sulfur atom, and a nitrogen atom;
or
ii) R4 and R5 are bonded to each other to form a heterocyclic ring containing the nitrogen atom and at least one carbon atom and, optionally, one or more heteroatoms selected from a silicon atom, an oxygen atom, a sulfur atom, and a nitrogen atom;
B) 45 wt. % to 99.95 wt. %, by weight of the copolymer, of one or more conjugated diene monomers;
C) 0 wt. % to 50 wt. %, by weight of the copolymer, of one or more vinyl aromatic monomers.

### Claim 20 (depends on 19)

The elastomeric copolymer of claim 19, wherein the vinyl aromatic monomer is selected from styrene, 1-vinylnaphthalene, 3-methylstyrene, 3,5-diethylstyrene, 4-propylstyrene, 2,4,6-trimethylstyrene, 4-dodecylstyrene, 3-methyl-5-n-hexylstyrene, 4-phenylstyrene, 2-ethyl-4-benzylstyrene, 3,5-diphenylstyrene, 2,3,4,5-tetraethylstyrene, 3-ethyl-1-vinylnaphthalene, 6-isopropyl-1-vinylnaphthalene, 6-cyclohexyl-1-vinylnaphthalene, 7-dodecyl-2-vinylnaphthalene, and α-methylstyrene.

### Claim 21 (depends on 19)

The elastomeric copolymer of claim 19, wherein the amount of C) vinyl aromatic monomer is 8 to 45 wt. %, by weight of the copolymer.

### Claim 22 (depends on 19)

The elastomeric copolymer of claim 19, comprising less than 1 wt. % C) vinyl aromatic monomer (and preferably no C) vinyl aromatic monomer), wherein the amount of B) conjugated diene monomer is 95 to 99.95 wt. %, by weight of the copolymer.

### Claim 23 (depends on 19)

The elastomeric copolymer of claim 19, wherein the conjugated diene monomer is selected from 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 2,3-dimethyl-1,3-pentadiene, 2-phenyl-1,3-butadiene, and 4,5-diethyl-1,3-octadiene.

### Claim 24 (depends on 19)

The elastomeric copolymer of claim 19, wherein the copolymer comprises units having a linear structure.

### Claim 25 (depends on 19)

The elastomeric copolymer of claim 19, wherein the copolymer comprises units having a branched structure.

### Claim 26 (depends on 19)

The elastomeric copolymer of claim 19, wherein the copolymer comprises units having a star structure and being produced by the reaction of metal-terminated living linear copolymer with one or more coupling agents in anionic polymerization conditions.

### Claim 27 (depends on 19)

A method for producing a rubber comprising vulcanizing the elastomeric copolymer according to claim 19 in the presence of one or more vulcanizing agents.

### Claim 28 (depends on 5)

The functionalized conjugated diene of claim 5, wherein R2, R3, R6, R7, and R8 all represent CH3.

### Claim 29 (depends on 6)

The functionalized conjugated diene of claim 6, wherein R4 and R5 are the same and represent —CH(CH3)2 or CH3.

### Claim 30 (depends on 7)

The functionalized conjugated diene of claim 7, wherein the residue in formula (IIIa), (IIIb)), (IIIc)
is selected from a residue of terpenes and 4,8-dimethyl-1,3,7-nonatriene.

### Claim 31 (depends on 30)

The functionalized conjugated diene of claim 30, wherein the terpene is selected from myrcene and ocimene.

### Claim 32 (depends on 31)

The functionalized diene of claim 31, wherein the terpene is myrcene selected from α-myrcene and β-myrcene.

### Claim 33 (depends on 7)

The functionalized conjugated diene of claim 7, which is a myrcene derivative of formula (VIIIa), (IXa), or (Xa)

### Claim 34 (depends on 12)

The method of claim 12, wherein the amount of units derived from the one or more functionalized conjugated dienes selected from of the group of compounds of formula (IIIa), (IIIb), (IIIc) is in a range of from 0.6 to 1.0 wt. %, based on the weight of the elastomeric copolymer.

### Claim 35 (depends on 14)

The process of claim 14, wherein the initiator component comprises one or more alkali metal salt derivatives of a one or more functionalized conjugated dienes selected from the group of compounds of formula (IIIa), (IIIb), (IIIc), wherein the alkali metal is selected from lithium, sodium, and potassium.

### Claim 36 (depends on 18)

The process of claim 18, wherein the non-halide metal compound 1) is one or more Nd compounds, and the Nd compound is selected from neodymium carboxylates, neodymium alcoholates, neodymium phosphates, neodymium phosphonates, neodymium allyl compounds, neodymium cyclopentadienyl complexes, neodymium amides, and neodymium acetylacetonates.

### Claim 37 (depends on 19)

The elastomeric copolymer of claim 19, comprising no C) vinyl aromatic monomer.

### Claim 38 (depends on 19)

The elastomeric copolymer of claim 19, comprising 99.0 to 99.4 wt. %, by weight of the copolymer.

### Claim 39 (depends on 27)

A rubber composition comprising x) a rubber component comprising the rubber obtained by the method of claim 27.

### Claim 40 (depends on 39)

The rubber composition of claim 39, wherein the rubber composition further comprises y) one or more fillers.

### Claim 41 (depends on 40)

The rubber composition of claim 40, wherein the filler is selected from the group consisting of silica, carbon black and a mixture thereof.

### Claim 42 (depends on 40)

The rubber composition according to claim 40, wherein the amount of filler component y) is 10 to 150 parts by mass relative to 100 parts by mass of the rubber component x) (phr).

### Claim 43 (depends on 42)

The rubber composition of claim 42, wherein the amount of filler component y) is 30 to 130 phr.

### Claim 44 (depends on 39)

The rubber composition according to claim 39 wherein the rubber component x) also comprises one or more further rubbery polymers.

### Claim 45 (depends on 44)

A tire component comprising the rubber composition of claim 44.

### Claim 46 (depends on 45)

A tire comprising the tire component of claim 45.