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US 11,993,620 B2Granted
Aminosilyl-functionalized conjugated dienes, their preparation and their use in the production of rubbers
AssigneesSynthos S.A., Synthos Dwory 7 Spolka Z Ograniczona Odpowiedzialnoscia Spolka Jawna
InventorsMaria Siolek-Komorek, Radoslaw Kozak, Pawel Weda, Robert Bogacz, Tomasz Skrok, Malgorzata Pierog
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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).
Claims46
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.
13 more elements
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.
18 more elements
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.
9 more elements
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).
10 more elements
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.
21 more elements
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.
13 more elements
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.
13 more elements
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.
12 more elements
Dependencies are inferred from the claim text.