Aminosilyl-functionalized conjugated dienes, their preparation, and their use in the manufacture of rubber

Abstract

To provide aminosilyl-functionalized conjugated dienes, their preparation and their use in the production of rubbers.SOLUTION: The present invention provides the use of a functionalized conjugated diene represented by the following formula in the production of elastomeric copolymers, where R4 and R5 are the same, representing -CH(CH3)2 or -CH3.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to aminosilyl-functionalized conjugated dienes, their preparation, and their use in the manufacture of rubber. Additionally, the present invention relates to rubbers and rubber compositions, and tires made therefrom. [Background technology]

[0002] A variety of conjugated diene monomers are known that can be used to make synthetic rubbers. However, there is a need in the art for additional conjugated diene monomers that can be used in advantageous polymerization processes or that impart advantageous properties to rubbers made from such conjugated diene monomers.

[0003] Current state of the art The authors of Non-Patent Document 1 report the preparation of 2-silicon-substituted 1,3-dienes by Grignard chemistry. They further report the use of 2-silicon-substituted 1,3-dienes in a one-pot metathesis / Diels-Alder reaction in a regioselective and diastereoselective manner.

[0004] US Patent No. 5,999,623 teaches aminosilane-functionalized diene compounds useful for modifying conjugated diene monomers, optionally in polymerization with aromatic vinyl monomers, and thus for producing polymers, particularly elastomeric polymers, that can be used in rubber articles such as tires.

[0005] US Pat. Nos. 5,869,992 and 5,869,992 disclose aminosilyl-functionalized styrenes and methods for their preparation, as well as the use of styrene derivatives in the preparation of copolymers thereof. US Pat. No. 5,629,493 teaches the use of vinyl silanes in the manufacture of rubber. ... 1 -S 1 and monomer unit V 2 -A 2 and V 1 and V 2each represents a hydrocarbyl group containing a polymerizable carbon-carbon double bond, S 1 represents a substituted silyl group, and A 2 is an amino group or a nitrogen-containing heterocyclic group. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] European Patent Application Publication No. 3159346 [Patent Document 2] International Publication No. 2016 / 162473 [Patent Document 3] International Publication No. 2016 / 162528 [Patent Document 4] European Patent Application Publication No. 3064546 [Patent Document 5] European Patent Application Publication No. 2857446 [Non-patent literature]

[0007] [Non-Patent Document 1] P.P.C. Choudhury and M.E. Welker (Molecules 2015, 20, 16892-16907) Summary of the Invention [Problem to be solved by the invention]

[0008] It is therefore an object of the present invention to provide conjugated diene monomers for the production of synthetic rubber. These conjugated diene monomers should be based on readily available starting materials, should be accessible via simple synthetic routes, should be universally applicable, i.e., in a variety of different polymerization processes, and should impart advantageous properties to rubbers, rubber compositions, and tires made therefrom. [Means for solving the problem]

[0009] Surprisingly, it has been found that this problem can be solved by using certain aminosilyl-functionalized conjugated dienes. The functionalized conjugated dienes of the present invention are represented by the formula (IIIa), (IIIb), and (IIIc):

[0010] [ka]

[0011] [ka]

[0012] [ka] and selected from the group of compounds of the formula: R optionally comprises one or more heteroatoms selected from oxygen, sulfur, nitrogen, and silicon atoms, and a group of compounds of formula (Ia), (Ib), and (Ic) from which functionalized conjugated dienes of formula (IIIa), (IIIb), and (IIIc) are derived.

[0013] [ka] and an organylene group containing a starting conjugated diene selected from the group consisting of: R 1 teeth i) a single bond, ii) oxygen atom, sulfur atom, NR 6 group, and SiR 7 R 8 one or more of the groups, and iii) optionally an oxygen atom, a sulfur atom, NR 6 group, and SiR 7 R 8 an organylene group containing one or more selected from the group is selected from R 2 , R 3, R 6 , R 7 , R 8 may be the same or different and represent an organyl group optionally containing one or more heteroatoms selected from oxygen, sulfur, nitrogen, and silicon atoms; i)R 4 and R 5 may be the same or different, and R 4 and R 5 each independently represents an organyl group optionally containing one or more heteroatoms selected from silicon, oxygen, sulfur, and nitrogen atoms; or ii)R 4 and R 5 are bonded to each other to form a heterocycle containing a nitrogen atom and at least one carbon atom, and optionally one or more heteroatoms selected from silicon atoms, oxygen atoms, sulfur atoms, and nitrogen atoms.

[0014] The functionalized conjugated dienes of the present invention, when used, for example, in the production of solution styrene butadiene rubber (S-SBR) and Ziegler-Natta catalyzed (e.g., neodymium) butadiene rubber (Nd-BR), increase the polymer's interaction with the filler, thus increasing filler dispersion in the polymer matrix and aiding in improving the dynamic and mechanical properties of tire tread compounds.

[0015] In a first aspect, the present invention relates to a method for preparing functionalized conjugated dienes. In a second aspect, the present invention relates to functionalized conjugated dienes. In a third aspect, the present invention relates to a method for using functionalized conjugated dienes in the preparation of elastomeric copolymers.

[0016] In a fourth aspect, the present invention relates to a process for producing copolymer components, including coupled copolymers and end-modified copolymers. In a fifth aspect, the present invention relates to a process for producing an elastomeric copolymer comprising anionic polymerization conditions.

[0017] In a sixth aspect, the present invention relates to a process for producing an elastomeric copolymer comprising Ziegler-Natta polymerization conditions. In a seventh aspect, the present invention relates to an elastomeric copolymer.

[0018] In an eighth aspect, the present invention relates to a method of making rubber. In a ninth aspect, the present invention relates to a rubber. In a tenth aspect, the present invention relates to a rubber composition.

[0019] In an eleventh aspect, the present invention relates to a tire component. Finally, in a twelfth aspect, the invention relates to a tire. DETAILED DESCRIPTION OF THE INVENTION

[0020] In a first embodiment of the first aspect, the present invention provides compounds of formula (IIIa), (IIIb), (IIIc)

[0021] [ka]

[0022] [ka]

[0023] [ka] 1. A method for preparing a functionalized conjugated diene selected from the group of compounds of the formula: R optionally comprises one or more heteroatoms selected from oxygen, sulfur, nitrogen, and silicon atoms, and a group of compounds of formula (Ia), (Ib), (Ic) from which the functionalized conjugated dienes of formula (IIIa), (IIIb), (IIIc) are derived.

[0024] [ka] and an organylene group containing a starting conjugated diene selected from the group consisting of: R 1 teeth i) a single bond, ii) oxygen atom, sulfur atom, NR 6 group, and SiR 7 R 8 one or more of the groups, and iii) optionally an oxygen atom, a sulfur atom, NR 6 group, and SiR 7 R 8 an organylene group containing one or more selected from the group is selected from R 2 , R 3 , R 6 , R 7 , R 8 may be the same or different and represent an organyl group optionally containing one or more heteroatoms selected from oxygen, sulfur, nitrogen, and silicon atoms; i)R 4 and R 5 may be the same or different, and R 4 and R 5 each independently represents an organyl group optionally containing one or more heteroatoms selected from silicon, oxygen, sulfur, and nitrogen atoms; or ii)R 4 and R 5 are bonded to each other to form a heterocycle containing a nitrogen atom and at least one carbon atom, and optionally one or more heteroatoms selected from silicon atoms, oxygen atoms, sulfur atoms, and nitrogen atoms; The method comprises the step of:

[0025] [ka] a halogenated conjugated diene selected from the group consisting of: 1 is a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom (Y 1 is preferably a chlorine atom), and Compound of formula (IV)

[0026] [ka] wherein Y 2 involves reaction with a compound selected from fluorine, chlorine, bromine, and iodine atoms under Grignard conditions.

[0027] In a second embodiment of the first aspect, the present invention relates to a method for preparing a functionalized conjugated diene selected from the group of compounds of formula (IIIa), (IIIb), (IIIc), the method comprising: A) under Grignard conditions, a halogenated conjugated diene selected from the group consisting of compounds of formula (IIa), (IIb) and (IIc) and a compound of formula (V)

[0028] [ka] wherein Y 2 and Y 3 are independently selected from a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and preferably Y 2 and Y 3 are reacted with a compound having a chlorine atom to give compounds of formula (VIa), (VIb), and (VIc)

[0029] [ka] and obtaining a compound of formula (I) B) Compounds of formula (VIa), (VIb), (VIc) and formula (VII)

[0030] [ka] wherein M is an alkali metal selected from lithium, sodium, and potassium, and M is preferably sodium. Includes:

[0031] Y 1 The preparation of halogenated conjugated diene intermediates of formula (IIa), (IIb), and (IIc), in which is a chlorine atom, can be carried out using a chlorinating agent including trichloroisocyanuric acid, dichloroisocyanuric acid, an alkali metal salt of dichloroisocyanuric acid, or a mixture thereof. Further details regarding the synthesis of chlorinated conjugated diene intermediates are given in PCT / EP2018 / 070768.

[0032] The functionalized conjugated diene of the second aspect of the present invention is selected from the group of compounds of formula (IIIa), (IIIb), (IIIc):

[0033] [ka]

[0034] [ka]

[0035] [ka] During the ceremony, R optionally comprises one or more heteroatoms selected from oxygen, sulfur, nitrogen, and silicon atoms, and a group of compounds of formula (Ia), (Ib), (Ic) from which the functionalized conjugated dienes of formula (IIIa), (IIIb), (IIIc) are derived.

[0036] [ka] and an organylene group having at least 10 carbon atoms and containing a starting conjugated diene selected from R 1 teeth i) a single bond, ii) oxygen atom, sulfur atom, NR 6 group, and SiR 7 R 8 one or more of the groups, and iii) optionally an oxygen atom, a sulfur atom, NR 6 group, and SiR 7 R 8 an organylene group containing one or more selected from the group is selected from R 2 , R 3 , R 6 , R 7 , R 8 may be the same or different and represent an organyl group optionally containing one or more heteroatoms selected from oxygen, sulfur, nitrogen, and silicon atoms; i)R 4 and R 5 may be the same or different, and R 4 and R 5 each independently represents an organyl group optionally containing one or more heteroatoms selected from silicon, oxygen, sulfur, and nitrogen atoms; or ii)R 4 and R 5 are bonded to each other to form a heterocycle containing a nitrogen atom and at least one carbon atom, and optionally one or more heteroatoms selected from silicon atoms, oxygen atoms, sulfur atoms, and nitrogen atoms.

[0037] In the present description, an organyl group is any organic substituent, regardless of its functional type, having one free valence at a carbon atom. Preferably, the organyl group contains 1 to 10 carbon atoms and optionally one or more heteroatoms selected from silicon, oxygen, sulfur, and nitrogen atoms, or an aryl, heteroaryl, or aralkyl group containing 6 to 10 carbon atoms and optionally one or more heteroatoms selected from silicon, oxygen, sulfur, and nitrogen atoms.

[0038] Additionally, an organylene group is any organic substituent, regardless of functionality, that has two free valences on one carbon atom or one free valence on each of two carbon atoms. Preferably, R of the functionalized conjugated diene of the present invention 1 is i) a single bond.

[0039] Preferably, R 2 , R 3 , R 6 , R 7 , R 8 may be the same or different and represent an organyl group containing 1 to 10 carbon atoms and optionally one or more heteroatoms selected from silicon, oxygen, sulfur, and nitrogen atoms, or an aryl, heteroaryl, or aralkyl group containing 6 to 10 carbon atoms and optionally one or more heteroatoms selected from silicon, oxygen, sulfur, and nitrogen atoms.

[0040] R 2 , R 3 , R 6 , R 7 , and R 8 More preferably, R are the same or different and represent a linear or branched, saturated or unsaturated hydrocarbyl group (preferably containing 1 to 10 carbon atoms). 2 , R 3 , R 6 , R 7 , and R 8are the same or different and represent a linear or branched alkyl, aryl, or alkaryl group. More preferably, R 2 , R 3 , R 6 , R 7 , and R 8 are the same or different and represent CH3 or C6H5, and in particular R 2 , R 3 , R 6 , R 7 , and R 8 All represent CH3.

[0041] According to the present invention, R 4 and R 5 are each a group having at least a carbon atom bonded to a nitrogen atom, i.e., R 4 Groups and R 5 The group is R 4 or R 5 is not bonded to the nitrogen atom through any heteroatom that may optionally be present in

[0042] In embodiment i), R 4 and R 5 may be the same or different, and R 4 and R 5 each independently represents a linear, branched, or cyclic hydrocarbyl group containing 1 to 10 carbon atoms, optionally containing at least one heteroatom selected from silicon, oxygen, and nitrogen atoms, and the hydrocarbyl group is saturated or unsaturated.

[0043] Preferably, i) R 4 and R 5 are the same or different, and R 4 and R 5 each independently represent a linear, branched, or cyclic, saturated or unsaturated alkyl group containing 1 to 10 carbon atoms, the alkyl group optionally containing one or more heteroatoms selected from silicon atoms, oxygen atoms, sulfur atoms, and nitrogen atoms, or ii) R 4 and R 5are the same or different, and R 4 and R 5 each independently represents an aryl or aralkyl group containing 6 to 10 carbon atoms, and the alkyl group optionally contains one or more heteroatoms selected from silicon, oxygen, sulfur, and nitrogen atoms.

[0044] R 4 and R 5 are preferably the same and represent a linear, branched, or cyclic, saturated or unsaturated alkyl group. More preferably, R 4 and R 5 are the same and represent -CH(CH3)2 or CH3. Most preferably, R 4 and R 5 are the same and represent -CH(CH3)2.

[0045] The group of compounds of formula (Ia), (Ib) and (Ic) from which functionalized conjugated dienes of formula (IIIa), (IIIb) and (IIIc) are derived.

[0046] [ka] The conjugated diene selected from has at least 10 carbon atoms. Preferably, R is a linear or branched, saturated or unsaturated hydrocarbylene group, hydrocarbylidene group, or hydrocarbylidine group. More preferably, R is a branched, unsaturated hydrocarbylene group. Most preferably, the conjugated diene of formula (IIa), (IIb), or (IIc) is selected from terpene and 4,8-dimethyl-1,3,7-nonatriene. Even more preferably, the terpene is selected from myrcene and ocimene, and most preferably, the terpene is a myrcene selected from α-myrcene and β-myrcene.

[0047] The functionalized conjugated dienes according to the present invention in all embodiments are most preferably of formula (VIII), (IX), or (X):

[0048] [ka]

[0049] [ka]

[0050] [ka] It is a myrcene derivative. In particular, myrcene derivatives of formula (VIIIa), (IXa), or (Xa).

[0051] [ka]

[0052] [ka]

[0053] [ka] In a third aspect, the present invention relates to the use of one or more functionalized conjugated dienes of the second aspect in the preparation of an elastomeric copolymer, the elastomeric copolymer comprising units derived from one or more conjugated diene monomers in addition to one or more units derived from one or more functionalized conjugated dienes, preferably selected from the group of compounds of formula (IIIa), (IIIb), (IIIc).

[0054] The conjugated diene monomer used in the preparation of the elastomeric copolymer according to the third aspect of the present invention is preferably 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. More preferably, the conjugated diene monomer is selected from 1,3-butadiene and isoprene, and in particular, the conjugated diene monomer is 1,3-butadiene.

[0055] Preferably, the method of use according to the third aspect is in the preparation of elastomeric copolymers by 1) anionic polymerization or 2) coordination polymerization. It is preferred that the elastomeric copolymer further comprises units derived from one or more vinyl aromatic monomers. The vinyl aromatic monomer is preferably 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. More preferably, the vinyl aromatic monomer is selected from styrene, 3-methylstyrene, and α-methylstyrene. In particular, the vinyl aromatic monomer is styrene.

[0056] According to the present invention, the amount of units derived from one or more functionalized conjugated dienes selected from the group of compounds of formula (IIIa), (IIIb), (IIIc) is preferably in the range of 0.05 to 5 wt.%, more preferably in the range of 0.2 to 1.5 wt.%, most preferably in the range of 0.4 to 1.2 wt.%, for example in the range of 0.6 to 1.0 wt.%, such as about 0.8 wt.%, based on the weight of the elastomeric copolymer.

[0057] The method of use according to the third aspect may be the use of an alkali metal salt derivative of a functionalized conjugated diene selected from the group of compounds of formula (IIIa), (IIIb), (IIIc) as an 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), (IIIc).

[0058] In a fourth aspect, the present invention relates to a process for the preparation of a copolymer component comprising a coupled copolymer and a terminally modified copolymer, the process comprising the steps of: (1) providing an initiator component, the initiator component comprising one or more alkali metal salt derivatives of one or more functionalized conjugated dienes, preferably selected from the group of compounds of formula (IIIa), (IIIb), and (IIIc); (2)i) one or more functionalized conjugated dienes selected from the group consisting of compounds of formula (IIIa), (IIIb), and (IIIc); ii) one or more conjugated diene monomers; and iii) optionally one or more vinyl aromatic monomers; contacting a monomer component consisting of: (3) continuing the copolymerization to obtain a copolymer; (4) optionally continuing copolymerization of the copolymer in the presence of one or more functionalizing monomers to obtain a functionalized copolymer; (5) optionally coupling a portion of the copolymer of step (3) or a portion of the functionalized copolymer of step (4) with one or more coupling agents to obtain a coupled copolymer; (6) optionally end-modifying a portion of the copolymer of step (3) or a portion of the functionalized copolymer of step (4) with one or more end-modifying agents to obtain an end-modified copolymer.

[0059] In a fifth aspect, the present invention relates to a process for producing an elastomeric copolymer, comprising: i) one or more functionalized conjugated dienes selected from the group consisting of compounds of formula (IIIa), (IIIb), and (IIIc); ii) one or more conjugated diene monomers; iii) optionally one or more vinyl aromatic monomers; under anionic polymerization conditions. Preferably, the anionic polymerization conditions include initiating polymerization with an alkali metal salt derivative of one or more functionalized conjugated dienes of formula (IIIa), (IIIb), (IIIc), wherein the alkali metal is selected from lithium, sodium, and potassium.

[0060] Anionic polymerization can be used to obtain copolymers with linear or star structures. Branching can also be performed, for example, with divinylbenzene. Because it is difficult to fractionate specific polymer fractions, it is difficult to predict the level of branching. Therefore, copolymers obtained by anionic polymerization are characterized by their dispersion index, M w / M n and typically the dispersion index is: Linear copolymer: 1.01 to 2.0, Coupled copolymer: 1.1-3, Branched copolymer: 1.1~8.0.

[0061] According to a sixth aspect, the present invention relates to a process for the manufacture of an elastomeric copolymer, 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; subjecting the resulting mixture to Ziegler-Natta polymerization conditions.

[0062] Ziegler-Natta catalysts are used in the coordination polymerization of conjugated dienes (such as 1,3-butadiene). Typical catalyst compositions are two-, three-, or four-component systems. Two-component systems include a catalytic metal chloride (e.g., chlorides of Ni, Co, Ti, Nd, V, Ti, Zr, or Fe) and a cocatalyst (e.g., an alkylaluminum or alkylmagnesium compound). In three-component catalyst systems, a halide-free metal precursor (e.g., neodymium phosphate) is combined with a cocatalyst (e.g., an alkylaluminum or alkylmagnesium) and a halide donor. Adding a halide donor to a halide-free catalyst system significantly increases catalyst activity and cis-1,4 or trans-1,4 content. In four-component catalyst systems, a solubilizing agent for the metal salt or halide donor is used in addition to the components used in the three-component system.

[0063] The Ziegler-Natta polymerization conditions therefore preferably include a catalyst system comprising 1) a metal chloride and 2) a cocatalyst. More preferably, the metal chloride is selected from 1) chlorides of one or more of Ni, Co, Ti, Nd, V, Ti, Zr, and Fe, and the cocatalyst is selected from 2) one or more alkylaluminum compounds and alkylmagnesium compounds. The Ziegler-Natta polymerization conditions may also include the presence of an additional monomer.

[0064] Alternatively, the Ziegler-Natta polymerization conditions preferably include a catalyst system comprising 1) a non-halide metal compound, 2) a cocatalyst, and 3) a halide donor compound. The non-halide metal compound 1) is preferably one or more Nd compounds, more preferably selected from neodymium carboxylates, neodymium alcoholates, neodymium phosphates, neodymium phosphonates, neodymium allyl compounds, neodymium cyclopentadienyl complexes, neodymium amides, and neodymium acetylacetonates.

[0065] The most effective catalysts for the production of high-cis polybutadiene are neodymium-based three-component systems: 1) neodymium carboxylates (e.g., neodymium(III) versatate (NdV), neodymium(III) octoate (NdO), neodymium(III) isooctanoate (NdiO), neodymium(III) naphthenate (NdN), 2) neodymium alcoholates (e.g., Nd(OBu)3, Nd(OiPr)3), and 3) neodymium phosphates and phosphonates (e.g., neodymium(III) phosphates). 3) neodymium bis(2-ethylhexyl)phosphate (NdP, bis(2-ethylhexanol)phosphonate), 4) neodymium allyl compounds, 5) neodymium cyclopentadienyl complexes (e.g., monocyclopentadienyl neodymium dichloride (CpNdCl2), monocyclopentadienyl dialkyl neodymium (CpNdR2), monocyclopentadienyl diallyl neodymium (CpNd(η3-C3H5)2), monocyclopentadienyl trisallyl neodymium (e.g., Li Catalyst precursors such as salts of [CpNd(η3-C3H5)3]), dicyclopentadienyl neodymium monochloride (Cp2NdCl), dicyclopentadienyl monoalkyl neodymium (Cp2NdR), silylene-bridged dicyclopentadienyl neodymium derivatives (e.g., [R2Si(Cp)2]Nd(Cl / R)), 6) neodymium amides (e.g., Nd(N(SiMe3)2)3), or 7) neodymium acetylacetonate are used. ), AliBu3 (TIBA), AlOct3, methylalumoxane (MAO), tetraisobutyldialumoxane (TIBAO), B(C6F5)3, modified methylalumoxane (MMAO), hexaisobutylalumoxane (HIBAO), diisobutylaluminum hydride (DIBAH), MgR2, AlPr3, AlBu3, AlHex3, AlOct3, AlDodec3, AlEt3, or AlMe3.

[0066] Examples of halide donors are SiCl4, ethylaluminum sesquichloride (EASC), diethylaluminum chloride (DEAC), dimethylaluminum chloride, butyl chloride (BuCl), dibutylaluminum chloride, AlBr3, EtAlCl2, and Me3SiCl.

[0067] The copolymers produced by the sixth embodiment, i.e., by coordination polymerization, preferably have a linear or branched structure. The polymer structure is determined by the catalyst composition and is usually determined by the following formula (M w / M n ) as follows. Linear copolymer: 1.5 to 5.0, Branched copolymer: 1.5~20.0.

[0068] According to a seventh aspect, the present invention provides 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), 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; The present invention relates to an elastomeric copolymer comprising repeat units derived from

[0069] The amount of B) conjugated diene monomer in the elastomeric copolymer of the seventh embodiment is preferably from 50 to 92 wt.% by weight of the copolymer, more preferably from 60 to 90 wt.% by weight of the copolymer, especially from 65 to 80 wt.% by weight of the copolymer.

[0070] When present, the vinyl aromatic monomer is preferably 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.More preferably, the vinyl aromatic monomer is selected from styrene, 3-methylstyrene, and α-methylstyrene.In particular, the vinyl aromatic monomer is styrene.

[0071] The amount of C) vinyl aromatic monomer in the elastomeric copolymer according to the seventh aspect of the present invention is preferably 8 to 45 wt.% by weight of the copolymer, more preferably 10 to 40 wt.% by weight of the copolymer, especially 20 to 35 wt.% by weight of the copolymer.

[0072] Alternatively, the elastomeric copolymer comprises less than 1 wt.% of C) vinyl aromatic monomer (preferably no C) vinyl aromatic monomer), and the amount of B) conjugated diene monomer is 95 to 99.95 wt.% by weight of the copolymer, preferably 98 to 99.6 wt.% by weight of the copolymer, especially 99.0 to 99.4 wt.% by weight of the copolymer.

[0073] The conjugated diene monomer in the elastomeric copolymer according to the seventh embodiment is preferably 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. More preferably, the conjugated diene monomer is selected from 1,3-butadiene and isoprene. The conjugated diene monomer is particularly 1,3-butadiene.

[0074] The elastomeric copolymer according to the seventh aspect may comprise units with a linear structure. The copolymer may also contain units with branched structures. The elastomeric copolymer may also have a star structure and contain units prepared by the reaction of a metal-terminated living linear copolymer with one or more coupling agents under anionic polymerization conditions. I) a tin halide coupling agent (preferably the tin halide coupling agent is tin tetrachloride); or II) silicon halide coupling agents (preferably silicon halide coupling agents such as silicon tetrachloride, silicon tetrabromide, silicon tetrafluoride, silicon tetraiodide, hexachlorodisilane, hexabromodisilane, hexafluorodisilane, hexaiododisilane, octachlorotrisilane, octabromotrisilane, octafluorotrisilane, octaiodotrisilane, hexachlorodisiloxane, 2,2,4,4,6,6-hexachloro-2,4,6-trisilaheptane-1,2,3,4,5,6-hexakis[2-(methyldichlorosilyl)ethyl]benzene, and alkyl silicon halides of the general formula (XI)

[0075] [ka] wherein R 6 is a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, n is an integer from 0 to 2, and X can be a chlorine atom, bromine atom, fluorine atom, or iodine atom, and is selected from alkyl silicon halides. It could be.

[0076] In the elastomeric copolymer according to the seventh aspect, the fraction of units with star structure is preferably between 0 and 75% by weight of the copolymer. In an eighth aspect, the present invention relates to a method for producing rubber comprising vulcanizing an elastomeric copolymer according to the seventh aspect in the presence of one or more vulcanizing agents.

[0077] In a ninth aspect, the present invention relates to a rubber obtainable by the method of the eighth aspect. In a tenth aspect, the present invention relates to a rubber composition x) comprising a rubber component comprising a rubber according to the ninth aspect. Preferably, the rubber composition further comprises one or more fillers y). The fillers are preferably selected from the group consisting of silica and carbon black. Most preferably, the rubber composition comprises both silica and carbon black y).

[0078] In a preferred embodiment of the tenth aspect, the amount of filler component y) in the rubber composition is 10 to 150 parts by mass per 100 parts by mass of rubber component x) (phr). Preferably, the amount of filler component y) is 20 to 140 phr. More preferably, the amount of filler component y) is 30 to 130 phr.

[0079] Preferably, the rubber component x) in the rubber composition according to the tenth aspect additionally comprises one or more further rubbery polymers, preferably selected from the group consisting of natural rubber, synthetic isoprene rubber, butadiene rubber, styrene-butadiene rubber, ethylene-α-olefin copolymer rubber, ethylene-α-olefin-diene copolymer rubber, acrylonitrile-butadiene copolymer rubber, chloroprene rubber and halogenated butyl rubber.

[0080] A tire component according to an eleventh aspect of the present invention comprises the rubber composition according to the tenth aspect. Preferably, the tire component is a tire tread. A tire according to a twelfth aspect of the present invention comprises a tire component according to the eleventh aspect.

[0081] The advantages of the present invention will become more apparent from the following examples. Unless otherwise indicated, all percentages are given by weight. Example I. Monomer Synthesis: Example 1a A 1 L reactor equipped with a magnetic stirrer, a dropping funnel, and a reflux condenser equipped with a gas inlet attachment and an oil valve (Zaitsev washer) was charged with magnesium metal (13.2 g, 0.55 mol) under an argon atmosphere, followed by the addition of dry, deoxygenated tetrahydrofuran (THF, 200 mL) and diisobutylaluminum hydride (DIBAH) [(i-Bu)AlH, 1 mL, 5.61 mmol]. This was carried out at room temperature while stirring the reactor contents. Activation of the magnesium was continued until hydrogen bubbling ceased. Then, (N,N-diisopropylamino)dimethylchlorosilane (96.89 g, 0.50 mol) and the remaining portion of the solvent (300 mL) were added to the activated magnesium metal. The dropping funnel was charged with chloromyrcene (90.46 g, 0.53 mol). To initiate the reaction, 8.00 mL of chloromyrcene was added dropwise to the mixture (without stirring the reactor contents). Once clear signs of reaction progress were observed, the addition of the remaining chloromyrcene was initiated at a rate such that the reactor contents gradually boiled over a period of approximately 2 hours. After the addition of chloromyrcene was completed, the reactor temperature was maintained at 40°C for 1 hour, followed by cooling to room temperature. 0.6 mL of water was added to neutralize the slight excess of Grignard reagent. The solvent was then evaporated from the reaction mixture under reduced pressure, and 1.0 L of n-hexane was added to the reaction residue. The resulting suspension was filtered, and the precipitate was washed three times with 200 mL of n-hexane each. The solvent was then evaporated from the resulting filtrate at 40°C under reduced pressure until a constant pressure was reached. 146.30 g of product was obtained in a 91% yield.

[0082] GC-MS: 43 (2.85), 59 (13.97), 73 (12.42), 86 (2.46), 100 (4.14), 116 (37.16), 151 (1.84), 158 (100.00), 159 (14.65), 278 (0.64), 293 (0.35) II. Synthesis Examples of Functionalized Rubbers II.1 Application of functionalized myrcene in anionic polymerization To provide more details about the synthesis and properties of elastomers produced according to the present invention, functionalized styrene-butadiene copolymers with precisely controlled microstructure and macrostructure and functional groups are described below in Examples 2b, 3b, and 4b and compared to the non-functionalized copolymer described in Comparative Example 1b.

[0083] polymerization Inactivation step: A nitrogen-purged 2-liter reactor was charged with cyclohexane (1.2 kg) and treated with 1 gram of a 1.6 M solution of n-butyllithium in cyclohexane. The solution was heated to 70°C and vigorously stirred for 10 minutes to rinse and inert the reactor. The solvent was then removed through the drain valve and re-purged with nitrogen.

[0084] Example 1b (comparative) Cyclohexane (820 g) was added to an inerted 2-liter reactor, followed by styrene (31 g) and 1,3-butadiene (117 g). The inhibitors were removed from the styrene and 1,3-butadiene. Tetramethylethylenediamine (TMEDA, 2.21 mmol) was then added to provide random incorporation of styrene monomers from the butadiene-derived units and to increase the vinyl content. The solution in the reactor was heated to 60°C and continuously stirred during the entire process. Upon reaching the desired temperature, n-butyllithium (0.045 mmol) was added to quench any remaining impurities. Then, n-butyllithium (0.845 mmol) was added to initiate the polymerization process. The reaction was carried out isothermally for 60 minutes. After this, silicon tetrachloride (5.25 × 10 ) was added as a coupling agent. -2(mmol) was added to the polymer solution. Coupling was allowed to proceed for 5 min. The reaction solution was quenched using nitrogen-purged isopropyl alcohol (1 mmol) and rapidly stabilized by the addition of 2-methyl-4,6-bis(octylsulfanylmethyl)phenol (1.0 phr polymer). The polymer solution was treated with isopropanol, which resulted in precipitation of the polymer. The final product was dried overnight in a vacuum oven.

[0085] Example 2b (Myrcene derivative from the examples as comonomer) Cyclohexane (820 g) was added to an inerted 2-liter reactor, followed by styrene (31 g), the functionalized myrcene (0.59 g) of Example 1a, and 1,3-butadiene (117 g). The inhibitors were removed from the styrene and 1,3-butadiene. Next, 2,2-bis(2-tetrahydrofuryl)propane (DTHFP, 2.52 mmol) was added to provide random incorporation of styrene monomer from the butadiene-derived units and to increase the vinyl content. The solution in the reactor was heated to 60°C and continuously stirred during the entire process. When the desired temperature was reached, n-butyllithium (0.045 mmol) was added to quench any remaining impurities. Then, n-butyllithium (0.845 mmol) was added to initiate the polymerization process. The reaction was carried out as an isothermal process for 60 minutes. After this, silicon tetrachloride (6.30 × 10 ) was added as a coupling agent. -2 (mmol) was added to the polymer solution. Coupling was allowed to proceed for 5 min. The reaction solution was quenched using nitrogen-purged isopropyl alcohol (1 mmol) and rapidly stabilized by the addition of 2-methyl-4,6-bis(octylsulfanylmethyl)phenol (1.0 phr polymer). The polymer solution was treated with isopropanol, which resulted in precipitation of the polymer. The final product was dried overnight in a vacuum oven.

[0086] Example 3b (Myrcene Derivative from Example 1a Both as Initiator Component and as Comonomer) Cyclohexane (820 g) was added to a deactivated 2-liter reactor, followed by styrene (31 g), the functionalized myrcene (0.59 g) from Example 1a, and 1,3-butadiene (117 g). The inhibitors were removed from the styrene and 1,3-butadiene. Next, 2,2-bis(2-tetrahydrofuryl)propane (DTHFP, 3.69 mmol) was added to act as a styrene randomizer and increase the vinyl content from butadiene-derived units. The solution in the reactor was heated to 60°C and continuously stirred throughout the entire process. Upon reaching this temperature, n-butyllithium (0.045 mmol) was added to the reactor to quench any remaining impurities.

[0087] n-Butyllithium (1.23 mmol) and the functionalized myrcene (0.38 g) of Example 1a were mixed together in a burette, with a contact time of approximately 15 minutes, after which the mixture was added to initiate the polymerization process. The reaction was carried out as an isothermal process for 60 minutes. After this, silicon tetrachloride (6.30 × 10) was added as a coupling agent. -2 (mmol) was added to the polymer solution. Coupling was allowed to proceed for 5 min. The reaction solution was quenched using nitrogen-purged isopropyl alcohol (1 mmol) and rapidly stabilized by the addition of 2-methyl-4,6-bis(octylsulfanylmethyl)phenol (1.0 phr polymer). The polymer solution was treated with isopropanol, which resulted in precipitation of the polymer. The final product was dried overnight in a vacuum oven.

[0088] Example 4b (sequential polymerization) Butadiene-styrene copolymers were prepared in a cascade of three consecutive reactors, each with a volume of 10 L (Reactor 1), 20 L (Reactor 2), and 10 L (Reactor 3). Each reactor was equipped with a paddle stirrer. The stirring speed was 150-200 rpm, and the fill factor was 50%-60%. Hexane, styrene, 1,3-butadiene, 1,2-butadiene (anti-gelling additive), DTHFP, and the functionalized myrcene of Example 1a (the last three reactants as a solution in hexane) were introduced into the first reactor at flow rates of 10752.00 g / h, 398.00 g / h, 1499.00 g / h, 19.00 g / h, 102.00 g / h, and 46.03 g / h, respectively. The flow rate of n-butyllithium (as a solution in hexane) was 107.00 g / h, and the flow rate of the functionalized myrcene of Example 1a (as a solution in hexane) was 153.92 g / h. The n-butyllithium stream and the functionalized myrcene of Example 1a (50 / 50 by weight) were mixed together in a pipe static mixer before entering the reactor, with a contact time of approximately 15 minutes. The temperature in the reactor was 70-85°C. To obtain branched rubber, silicon tetrachloride was added to the inlet of Reactor 3 at the inlet of the static mixer in a ratio of 0.05 SiCl4 / activated n-butyllithium. The coupling reaction was carried out at 70-85°C. At the outlet of Reactor 3, 2-methyl-4,6-bis(octylsulfanylmethyl)phenol (as a solution in hexane) was added as an antioxidant (142 g / h).

[0089] The polymer solution was then transferred to a stripper. Distilled water in an amount twice the total mass of the polymer solution, a pH adjuster, and soap were added to the polymer solution, and the contents of the stripper were then treated with steam. Steam stripping was continued until all of the solvent was removed, yielding a finely powdered rubber. The finely powdered rubber was then removed from the stripper, cooled to room temperature, crushed, and dried in a hot air stream.

[0090] Characterization Vinyl content (%) 600MHz based on BS ISO 21561:20051 Determined by H-NMR.

[0091] Bound styrene content (%) 600MHz based on BS ISO21561:2005 1 Determined by H-NMR.

[0092] Molecular weight determination Gel permeation chromatography was performed using THF as the eluent and a multi-column (with guard column) from PSS Polymer Standards Service for sample preparation. A Wyatt Technologies Dawn Heleos II light scattering detector, DAD (PDA) Agilent 1260, was used. Multi-angle light scattering measurements were performed using an Infinity UV-VIS detector and an Agilent 1260 Infinity refractive index detector.

[0093] Glass transition temperature (℃) Determined based on PN-EN ISO 11357-1:2009. Mooney viscosity (ML(1+4) / 100℃) Determined according to ASTM D1646-07 using a large rotor under the following conditions: preheat = 1 minute, rotor run time = 4 minutes, and temperature = 100°C.

[0094] Vulcanization characteristics Determined according to ASTM D6204 using an Alpha Technologies RPA2000 Rubber Process Analyzer with a run time of 30 minutes and a temperature of 170°C.

[0095] Evaluation and measurement of rubber composition properties The polymers obtained from each of the examples were used to prepare vulcanized rubber compounds and the following test parameters were measured:

[0096] i) Tire prediction value (tan δ at 60°C, tan δ at 0°C, tan δ at -10°C) Vulcanized rubber compounds were used as test samples and this parameter was measured using a dynamic mechanical analyzer (DMA450+ MetraviB) in single shear mode under the conditions of dynamic strain = 2%, frequency = 10 Hz, heating rate 2.5 K / min in the temperature range of -70 to 70 °C.

[0097] ii) Rebound elasticity Determined based on ISO 4662. Table 1 shows the characterization results of the four samples synthesized for this study.

[0098] [Table 1] combination The rubbers obtained in Examples 2b, 3b, 4b, and Comparative Example 1b were compounded according to the "Rubber Composition Formulation" shown in Table 2. The solution styrene-butadiene rubber, filler, and rubber additives were compounded in a Banbury-type internal mixer (350E, Brabender GmbH & Co. KG) and a laboratory-sized two-roll mill. The rubber compounds were mixed in two different stages, with the final pass completed on the two-roll mill. The first stage was used to mix the polymer with oil, silica, silane coupling agent, 6PPD, and activator in several stages. The second stage further improved the silica distribution with the addition of carbon black, after which the compound was left to rest for 24 hours. The rubber compounds were conditioned for 4 hours to prepare for the final pass. Final mixing was performed on the two-roll mill. The final step was used to add the curing package. Each compound was then heated at 170°C for 10 minutes. 95+1.5 The rubber was then vulcanized for 10 minutes (based on the RPA results) to obtain vulcanizates. Each vulcanized rubber compound was evaluated and measured for the above-mentioned curing characteristics, tire prediction values, and rebound resilience. The results are shown in Table 3.

[0099] [Table 2]

[0100] [Table 3] From these results, it is clear that, based on the properties in the vulcanized state, in the silica mixture, SSBR3b according to the present invention provides superior reinforcement properties to the corresponding rubber composition 3c than those obtained from the control SSBR1b and from another SSBR2b according to the present invention. The data in Table 3 also show that SSBR4b obtained by sequential polymerization has better reinforcement properties than the control SSBR1b and SSBR2b.

[0101] Furthermore, the tire predictive values ​​of rubber composition 3c according to the invention are improved (in terms of rolling resistance) compared to those of control rubber composition 1c according to the invention and to those of rubber compositions 2c and 4c. Also, the tire predictive values ​​of rubber composition 2c according to the invention are improved compared to control rubber composition 1c. Furthermore, the tire predictive values ​​of rubber composition 4c according to the invention are improved compared to control rubber composition 1c, and in addition, the ice traction and dry traction are improved compared to those of rubber compositions 1c, 2c, and 3c.

[0102] II.2 Application of functionalized myrcene in coordination polymerization To provide more details regarding the synthesis and properties of elastomers made according to the present invention, Examples 6b and 8b below describe functionalized butadiene homopolymers having functional groups and compare them to the non-functionalized homopolymers described in Comparative Examples 5b and 7b. The amounts of starting materials used in these examples are listed in Table 4. The methods for measuring and evaluating properties are described below.

[0103] Polymerization (for additional information, see also the information above on anionically obtained polymers) For catalyst compositions and procedures, see the following publications: 1. Lars Friebe, Oskar Nuyken, and Werner Obrecht, "A Comparison of Neodymium Versatate, Neodymium Neopentanolate, and Neodymium Bis(2-ethylhexyl)phosphate in Ternary Ziegler Type Catalyst Systems With Regard to Their Impact on the Polymerization of 1,3-Butadiene," J. Macromol. Sci. A. (2005), 42, 7, 839-851. 2. Friebe, L., Nuyken, O., Windisch, H., and Obrecht, W., "Polymerization of 1,3-butadiene initiated by neodymium versatate / diisobutylaluminum hydride / ethylaluminum sesquichloride: Kinetics and conclusions about the reaction mechanism," Macromol. Chem. Phys., (2002), 203, 8, 1055-1064.

[0104] General Polymerization Description: A 20-liter reactor was charged with dry 1,3-butadiene, dry solvent (cyclohexane), and the functionalized myrcene from Example 1a and heated to 60°C. The catalysts were then added in the following order: bis(2-ethylhexyl) neodymium phosphate (NdP), diisobutylaluminum hydride (DIBAH) (both 0.1 mol / L solutions in cyclohexane). Polymerization was initiated by adding ethylaluminum sesquichloride (EASC) (1.0 mol / L solution in cyclohexane). The solution in the reactor was heated and continuously stirred throughout the entire process. The temperature of the reaction mixture was maintained between 60 and 90°C. The reaction solution was quenched using nitrogen-purged isopropyl alcohol and rapidly stabilized by adding 2-methyl-4,6-bis(octylsulfanylmethyl)phenol (1.0 phr polymer).

[0105] The polymer was recovered by conventional recovery operations using steam stripping of the solvent and drying in a stream of hot air. Details of the reaction conditions used and the characteristics of the resulting polymers are contained in Table 4 below.

[0106] [Table 4] Characterization (for additional information, see also the information above on anionically obtained polymers) Vinyl content, cis-1,4 content, trans-1,4 content (%) The microstructure of the butadiene rubber was determined by infrared spectroscopy (Thermo Scientific Nicolet Is10). The following peaks were used for quantitative determination of the poly(butadiene) microstructure: 735cm -1 (δ(cis-R-CH=CR-H), →cis-1,4, ε=0.192), 912cm -1 (δ(R-CH=CH-H), → vinyl (1,2), ε=1.0), 965cm -1(δ(trans-R-CH=CR-H), → trans-1,4, ε=0.769). This methodology is 1. M. Kraft, Struktur und Absorptionsspektroskopie der Kunststoffe, VCH, Weinheim1973, p.93, and 2.EOSchmalz, W.Kimmer, Z.Anal.Chem.1961, 181, 229 is described in.

[0107] Evaluation and determination of the properties of vulcanized rubber compositions (for additional information, see also the information above on anionically obtained polymers) Vulcanized rubber compounds were prepared using the polymers obtained from each of the examples and the following test parameters were measured:

[0108] i) Tire prediction value (tanδ at 60°C, tanδ at 0°C, tanδ at -10°C, J at 30°C) Using vulcanized rubber compositions as test samples, this parameter was measured using a dynamic mechanical analyzer (DMA450+ MetraviB) in shear mode under the conditions of tensile strain = 2%, frequency = 10 Hz, heating rate 2.5 K / min in the temperature range of -80 to 80 °C.

[0109] ii) Rebound elasticity Determined based on ISO4662. iii) Reinforcement factor It is expressed as the ratio between 300% modulus and 100% modulus and was determined according to PN-ISO7:2007 using a Zwick / Roel Z005.

[0110] iv) Silica dispersion Determined according to ISO 1134C, D, E; ASTM D7723 using disperGRADER Alpha Technologies.

[0111] Formulation (for additional information, see also the information above on anionically derived polymers) The rubbers obtained from Examples 6b and 8b and Comparative Examples 5b and 7b were compounded according to the compounding recipes shown in Table 5. The solution styrene-butadiene rubber, filler, and rubber additives were compounded in a Farrel-type internal mixer. The rubber compounds were mixed in three different stages, the first two stages being mixed in an internal mixer, and the third stage (final pass) being completed on a two-roll mill.

[0112] The first stage was used to mix the rubber with oil, silica, silane coupling agent, 6PPD, and activator in several stages. The second stage was carried out to further improve the silica distribution with the addition of carbon black, after which the compound was conditioned for 24 hours. The final mix was done on a two-roll mill. The last step was used to add the cure package. Then, the rubber was heated at 170°C. 95+1.5 Each compound was vulcanized for 10 minutes (based on the RPA results) to obtain a vulcanizate. Each vulcanized rubber compound was evaluated and measured for the above-mentioned cure characteristics, Payne effect, and tire prediction values. The results are shown in Table 6.

[0113] [Table 5]

[0114] [Table 6] The rubbers obtained in Examples 6c and 8c, and Comparative Examples 5c and 7c, respectively, were examined and compared with each other (functionalized vs. non-functionalized), see the results presented in Table 6.

[0115] Example 5c was compared with Example 6c, and Example 7c with Example 8c, because they correspond to similar Mooney ranges, i.e., the higher (58, 64) and lower ranges (44, 51).

[0116] In each case, tire predictions derived from DMA, such as rolling resistance, dry traction, and winter traction, were improved when functionalized (Examples 6c and 8c—Table 6) rubber was compared to unfunctionalized (Examples 5c and 7c—Table 6) rubber, as was the case for high-temperature rebound. In addition to much higher silica dispersion (dispeGRADER), the reinforcement index, the ratio of 300% modulus to 100% modulus, was also found to increase. This confirmed much higher interaction between the functionalized cis-polybutadiene rubber and the filler (silica) compared to using unfunctionalized rubber.

[0117] While certain representative embodiments and details have been shown for the purpose of illustrating the invention, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the scope of the invention, as defined by the following claims.

Claims

1. In the preparation of elastomeric copolymers, 【Chemistry 1】 The use of a functionalized conjugated diene of the formula: R ４ and R ５ are the same, -CH(CH ３ ) ２ or -CH ３ The use of functionalized conjugated dienes.

2. 2. The use of claim 1, wherein the elastomeric copolymer comprises units derived from one or more conjugated diene monomers in addition to one or more units derived from the functionalized conjugated diene of said formula.

3. 3. The use according to claim 2, 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.

4. The use according to any one of claims 1 to 3, wherein the preparation of the elastomeric copolymer is by anionic polymerization or by coordination polymerization.

5. The use according to any one of claims 1 to 4, wherein the elastomeric copolymer further comprises units derived from one or more vinyl aromatic monomers.

6. 6. The use according to claim 5, 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.

7. The use according to any one of claims 1 to 6, wherein the amount of units derived from said functionalized conjugated diene in said formula is in the range of 0.2 to 1.5 wt.%.

8. 1. Use of an alkali metal salt derivative of a functionalized conjugated diene as an initiator for the anionic copolymerization of one or more conjugated diene monomers, wherein the functionalized conjugated diene is The following formula 【Chemistry 2】 wherein R ４ and R ５ are the same, -CH(CH ３ ) ２ or -CH ３ That is, use.

9. 1. A process for producing a copolymer component comprising a coupled copolymer and a terminally modified copolymer, said process comprising the steps of: (1) providing an initiator component; (2) i) The following formula 【Transformation 3】 A functionalized conjugated diene of the formula: R 4 and R 5 are the same and are —CH(CH 3 ) 2 or —CH 3 ; a functionalized conjugated diene; ii) one or more conjugated diene monomers; A monomer component comprising contacting said initiator component to initiate anionic copolymerization; (3) continuing the copolymerization to obtain a copolymer; (4a) continuing copolymerization of the copolymer of step (3) in the presence of one or more functionalizing monomers to obtain a functionalized copolymer; (4b) coupling a portion of the functionalized copolymer with one or more coupling agents to obtain a coupled copolymer; or (5) coupling a portion of the copolymer of step (3) with one or more coupling agents to obtain a coupled copolymer; (6) end-modifying a portion of the copolymer of step (3) or a portion of the functionalized copolymer of step (4b) with one or more end-modifying agents to obtain an end-modified copolymer.

10. i) the following formula: 【Chemistry 4】 A functionalized conjugated diene of the formula: R ４ and R ５ are the same, -CH(CH ３ ) ２ or -CH ３ That is, a functionalized conjugated diene; ii) one or more conjugated diene monomers; under anionic polymerization conditions.

11. 11. The process of claim 10, wherein the anionic polymerization conditions include initiating the polymerization with an alkali metal salt derivative of the functionalized conjugated diene of the formula, wherein the alkali metal is selected from lithium, sodium, and potassium.

12. i) the following formula: 【Transformation 5】 A functionalized conjugated diene of the formula: R ４ and R ５ are the same, -CH(CH ３ ) ２ or -CH ３ That is, a functionalized conjugated diene; ii) one or more conjugated diene monomers; under Ziegler-Natta polymerization conditions.

13. 13. The process of claim 12, wherein the Ziegler-Natta polymerization conditions comprise a catalyst system comprising 1) a metal chloride and 2) a cocatalyst.

14. 14. The process of claim 13, wherein the metal chloride 1) is selected from chlorides of one or more of Ni, Co, Ti, Nd, V, Ti, Zr, and Fe, and the co-catalyst 2) is selected from one or more of alkylaluminum compounds and alkylmagnesium compounds.

15. 15. The process of claim 14, wherein the Ziegler-Natta polymerization conditions include a catalyst system comprising 1) a non-halide metal compound, 2) a cocatalyst, and 3) a halide donor compound.

16. 16. The process of claim 15, wherein the non-halide metal compound 1) is one or more Nd compounds selected from neodymium carboxylates, neodymium alcoholates, neodymium phosphates, neodymium phosphonates, neodymium allyl compounds, neodymium cyclopentadienyl complexes, neodymium amides, and neodymium acetylacetonates.

17. A) The following formula 【Transformation 6】 A functionalized conjugated diene of the formula: R ４ and R ５ are the same, -CH(CH ３ ) ２ or -CH ３ and 0.05 wt. % to 5 wt. % of a functionalized conjugated diene by weight of the copolymer; 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; An elastomeric copolymer comprising repeat units derived from

18. 18. The elastomeric copolymer of claim 17, wherein the amount of B) conjugated diene monomer is 50 to 92 wt. % by weight of the copolymer.

19. 19. The elastomeric copolymer of claim 17 or 18, 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.

20. 20. The elastomeric copolymer of any one of claims 17 to 19, wherein the amount of C) vinyl aromatic monomer is 8 to 45 wt.% by weight of the copolymer.

21. 18. The elastomeric copolymer of claim 17, comprising less than 1 wt. % of C) vinyl aromatic monomer, and the amount of B) conjugated diene monomer is 95 to 99.95 wt. % by weight of the copolymer.

22. 22. The elastomeric copolymer of any one of claims 17 to 21, 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.

23. The elastomeric copolymer according to any one of claims 17 to 22, wherein the copolymer comprises units having a linear structure.

24. The elastomeric copolymer according to any one of claims 17 to 23, wherein the copolymer comprises units having a branched structure.

25. 25. The elastomeric copolymer of any one of claims 17 to 24, wherein the copolymer has a star structure and comprises units prepared by the reaction of one or more coupling agents with a metal-terminated living linear copolymer under anionic polymerization conditions.

26. The following conditions a and b are satisfied: The a is I) the coupling agent is tin tetrachloride; or II) The coupling agent is selected from the group consisting of silicon tetrachloride, silicon tetrabromide, silicon tetrafluoride, silicon tetraiodide, hexachlorodisilane, hexabromodisilane, hexafluorodisilane, hexaiododisilane, octachlorotrisilane, octabromotrisilane, octafluorotrisilane, octaiodotrisilane, hexachlorodisiloxane, 2,2,4,4,6,6-hexachloro-2,4,6-trisilaheptane-1,2,3,4,5,6-hexakis[2-(methyldichlorosilyl)ethyl]benzene, and alkylsilyl halides of the general formula (XI) 【Transformation 7】 wherein R ６ is a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, n is an integer from 0 to 2, and X is selected from alkyl silicon halides which may be chlorine, bromine, fluorine, or iodine atoms; 26. The elastomeric copolymer of claim 25, wherein b is the fraction of units having a star structure from 0 to 75% by weight of the copolymer.

27. A method for producing rubber comprising vulcanizing the elastomeric copolymer of any one of claims 17 to 26 in the presence of one or more vulcanizing agents.

28. A rubber comprising a vulcanized elastomeric copolymer according to any one of claims 17 to 26.

29. 30. A rubber composition comprising: x) a rubber component comprising the rubber of claim 28; and y) one or more fillers.

30. 30. The rubber composition of claim 29, wherein the filler is selected from the group consisting of silica and carbon black.

31. The rubber composition according to claim 29 or 30, wherein the amount of the filler component y) is 10 to 150 parts by weight (phr) per 100 parts by weight of the rubber component x).

32. A tire component comprising the rubber composition according to any one of claims 29 to 31.

33. 33. The tire component of claim 32, wherein the tire component is a tire tread.

34. A tire comprising the tire component of claim 32 or 33.

35. The process of claim 9, wherein the monomer component of step (2) additionally comprises one or more vinyl aromatic monomers.

Images