1-amino-3-(oxyalkylalkoxysilyl)-2-propanol terminated diene rubber

Abstract

The present invention relates to 1-amino-3-(oxyalkylalkoxysilyl)-2-propanol terminated diene rubbers, their preparation, and uses.

Description

[Technical Field]

[0001] The present invention relates to 1-amino-3-(oxyalkylalkoxysilyl)-2-propanol terminated diene rubbers, their preparation, and uses. [Background technology]

[0002] The important properties of a tire tread are good adhesion to dry and wet surfaces, low rolling resistance, and high wear resistance. It is very difficult to improve the slip resistance of a tire without simultaneously reducing the rolling resistance and wear resistance. Low rolling resistance is important for low fuel consumption, and high wear resistance is an obvious factor for long mileage.

[0003] The wet slip resistance and rolling resistance of a tire tread depend largely on the dynamic mechanical properties of the rubber used to make the compound. Rubbers with high resilience at higher temperatures (60°C to 100°C) are used in treads to reduce rolling resistance. On the other hand, rubbers with high damping at low temperatures (0°C to 23°C) or low resilience within the 0°C to 23°C range are advantageous for improving wet grip. To meet this complex requirement profile, various rubber compounds are used in treads. Typically, a mixture of one or more rubbers with a relatively high glass transition temperature, such as styrene-butadiene rubber, is used with one or more rubbers with a relatively low glass transition temperature, such as polybutadiene with a high 1,4-cis content, or styrene-butadiene rubber with a low styrene and vinyl content, or polybutadiene produced in solution with an average 1,4-cis content and a low vinyl content.

[0004] Anionically polymerized solution rubbers containing double bonds, such as solution polybutadiene and solution styrene-butadiene rubber, offer advantages over their emulsion counterparts in the production of low rolling resistance tire treads. These advantages include vinyl content and the associated control of glass transition temperature and molecular branching. In practical applications, this provides a particular advantage in the relationship between wet slip resistance and rolling resistance of tires. A significant contribution to energy dissipation in tire treads, and therefore rolling resistance, comes from free polymer chain ends and the reversible accumulation and destruction of filler networks formed by fillers (mostly silica and / or carbon black) used in tire tread compounds.

[0005] The introduction of functional groups at the polymer chain ends and / or at the polymer chain initiation allows for physical or chemical bonding of these polymer chain ends or initiation to the filler surface, thereby limiting their mobility and thus reducing energy dissipation under dynamic stress on the tread. At the same time, these functional groups can improve the dispersion of the filler in the tire tread, thereby weakening the filler network and thus further reducing rolling resistance.

[0006] For this purpose, numerous methods have been developed for the end-group modification of diene rubbers. For example, Patent Document 1 describes the use of 4,4'-bis(dimethylamino)benzophenone or N-methylcaprolactam as functionalizing reagents. Patent Document 2 also describes the use of ethylene oxide and N-vinylpyrrolidone. Patent Document 3 describes end-group functionalization using functionalizing reagents containing -C(O)N<- or -C(S)N<- groups, such as 1,3-dimethyl-2-imidazolidinone. The disadvantage of these reagents is the poor stability of the Mooney viscosity of the functionalized rubber during storage, which requires the addition of auxiliaries for stabilization.

[0007] Methods for introducing functional groups into polymer chains initiated by functional anionic polymerization initiators are described, for example, in US Pat. No. 5,629,492 and US Pat. No. 5,629,492 (initiators with protected hydroxyl groups), US Pat. No. 5,629,492 (initiators containing thioethers), and US Pat. No. 5,629,492, US Pat. No. 5,629,492, and US Pat. No. 5,629,492 (alkali amides of secondary amines as polymerization initiators).

[0008] In particular, silanes and cyclosiloxanes having a total of at least two halogen and / or alkoxy and / or aryloxy substituents on the silicon atom are suitable for end-group functionalization of diene rubbers, since one of the listed substituents on the silicon atom can be easily replaced by an anionic diene polymer chain end in a rapid substitution reaction, and the aforementioned additional substituent is available, optionally after hydrolysis, as a functional group capable of interacting with fillers in tire tread compounds. Examples of such silanes can be found in U.S. Pat. No. 5,629,499, U.S. Pat. No. 5,629,499, U.S. Pat. No. 5,629,499, and U.S. Pat. No. 5,629,499.

[0009] The functional groups can be directly bonded to the silicon atom, or they can be bonded to silicon via an alkyl group. The functional groups directly bonded to silicon are usually alkoxy groups or halogens. The drawbacks of these silanes are the coupling via the reaction of several anionic polymer chains per silane molecule, the elimination of interfering components, and the coupling via the formation of Si-O-Si bonds during processing and storage. Patent Document 14, for example, describes 3-glycidoxypropyltrialkoxysilane as a suitable reagent for the production of diene rubbers with a high degree of coupling. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] European Patent Application Publication No. 0 180 141 A1 [Patent Document 2] European Patent Application Publication No. 0 864 606 A1 [Patent Document 3] JP-A-63-006-034 [Patent Document 4] European Patent Application Publication No. 0 513 217 A1 [Patent Document 5] European Patent Application Publication No. 0 675 140 A1 [Patent Document 6] US Patent Application Publication No. 2008 / 030 8204 A1 [Patent Document 7] U.S. Patent No. 5,792,820 [Patent Document 8] European Patent Application Publication No. 0 590 490 A1 [Patent Document 9] European Patent Application Publication No. 0 594 107 A1 [Patent Document 10] U.S. Patent No. 3,244,664 [Patent Document 11] U.S. Patent No. 4,185,042 [Patent Document 12] European Patent Application Publication No. 0 778 311 A1 [Patent Document 13] US Patent Application Publication No. 2005 / 0203251 A1 [Patent Document 14] European Patent Application Publication No. 3 431 511 A1 Summary of the Invention [Problem to be solved by the invention]

[0011] One of the objects of the present invention was to provide an end-group functionalized diene rubber and a method for its preparation which does not have the drawbacks of the state of the art and which makes it possible to maintain a low degree of coupling, especially when using alkoxysilanes as functionalizing reagents. [Means for solving the problem]

[0012] To solve this problem, a 1-amino-3-(oxyalkyl-alkoxysilyl)-2-propanol group, which is bonded to the polymer chain via an alkylamide group, is prepared as follows: [ka] An end group functionalized diene rubber has been proposed, wherein: R1, R2 are the same or different and preferably represent saturated or unsaturated organic groups which may contain one or more heteroatoms independently selected from O, N, S, and Si; R3, R4 are the same or different and represent saturated or unsaturated divalent organic groups which, in addition to C and H, can preferably contain one or more heteroatoms selected independently from O, N, S, and Si; R5 and R6 are the same or different and represent a saturated or unsaturated organic group; x+y=3, 1≦x≦3 and 0≦y≦2. DETAILED DESCRIPTION OF THE INVENTION

[0013] In a preferred embodiment, R1 and R2 are independently (i) saturated or unsaturated, unsubstituted, monosubstituted, or polysubstituted -C1-C 24 - alkyl; (ii) saturated or unsaturated, unsubstituted, monosubstituted, or polysubstituted -C1-C 24 -heteroalkyl; (iii) unsubstituted, monosubstituted, or polysubstituted 6- to 24-membered aryl, optionally bonded via a saturated or unsaturated, unsubstituted, monosubstituted, or polysubstituted -C1-C6-alkylene- or -C1-C6-heteroalkylene-; (iv) unsubstituted, monosubstituted, or polysubstituted 5- to 24-membered heteroaryl; in each case saturated or unsaturated, unsubstituted, monosubstituted, or polysubstituted 5- to 24-membered heteroaryl optionally bonded via -C1-C6-alkylene- or -C1-C6-heteroalkylene-; (v) saturated or unsaturated, unsubstituted, monosubstituted, or polysubstituted 3- to 24-membered cycloalkyl; in each case optionally bonded via saturated or unsaturated, unsubstituted, monosubstituted, or polysubstituted -C1-C6-alkylene- or -C1-C6-heteroalkylene-; and (vi) saturated or unsaturated, unsubstituted, monosubstituted, or polysubstituted 3- to 24-membered heterocycloalkyl; in each case saturated or unsaturated, unsubstituted, monosubstituted, or polysubstituted 3- to 24-membered heterocycloalkyl optionally bonded via -C1-C6-alkylene- or -C1-C6-heteroalkylene-; and / or R3 and R4 are independently (i) saturated or unsaturated, unsubstituted, monosubstituted or polysubstituted -C1-C6-alkylene-; (ii) saturated or unsaturated, unsubstituted, monosubstituted, or polysubstituted -C1-C6-heteroalkylene-; and (iii) unsubstituted, monosubstituted, or polysubstituted 6- to 14-membered arylene; and / or R5 and R6 are independently (i) saturated or unsaturated, unsubstituted, monosubstituted or polysubstituted -C1-C6-alkyl; (ii) saturated or unsaturated, unsubstituted, monosubstituted, or polysubstituted -C1-C6-heteroalkyl; and (iii) unsubstituted, monosubstituted, or polysubstituted 6- to 14-membered aryl; is selected from the group consisting of wherein "mono- or polysubstituted" in each occurrence independently means -F, -Cl, -Br, -I, -CN, =O, -CF3, -CF2H, -CFH2, -CF2Cl, -CFCl2, saturated or unsaturated and unsubstituted -C1-C 18 -alkyl, and saturated or unsaturated and unsubstituted -C1-C 18 -heteroalkyl means substituted with one or more substituents independently selected from each other:

[0014] Preferably, in the context of the above preferred embodiments, "mono- or polysubstituted" means, independently of one another, -F, -Cl, -Br, -I, -CN, -CF3, -CF2H, -CFH2, -CF2Cl, -CFCl2, Saturated or unsaturated and unsubstituted -C1-C 18 -alkyl, and Saturated or unsaturated and unsubstituted -C1-C 18 -heteroalkyl, It means that the group is substituted with one or more substituents selected from the following:

[0015] In yet another preferred embodiment, "mono- or poly-substituted" refers, independently of each other, to: saturated and unsubstituted -C1-C 18 -alkyl, and -C1-C6-alkyl-Si(O-C1-C6-alkyl)3 (in each case -C1-C6-alkyl is saturated and unsubstituted) It means that the group is substituted with one or more substituents selected from the following:

[0016] In one particularly preferred embodiment, R1 is (i) saturated or unsaturated and unsubstituted -C1-C6-alkyl; preferably (ii) saturated or unsaturated and unsubstituted -C1-C2-alkyl; and / or R2 is (i) saturated or unsaturated and unsubstituted -C1-C6-alkyl; preferably (ii) saturated or unsaturated and unsubstituted -C1-C2-alkyl; and / or R3 is (i) saturated or unsaturated and unsubstituted -C1-C6-alkylene-; preferably (ii) saturated or unsaturated and unsubstituted -C1-C3-alkylene-; and / or R4 is saturated or unsaturated and unsubstituted -C1-C6-alkylene-; and / or (i) R5 is saturated or unsaturated and unsubstituted -C1-C6-alkyl and R6 is saturated or unsaturated and unsubstituted -C1-C6-alkyl; preferably (ii) R5 is saturated or unsaturated and unsubstituted -C1-C6-alkyl, x is 3 and y is 0.

[0017] In one particularly preferred embodiment of the 1-amino-3-(oxyalkyl-alkoxysilyl)-2-propanol terminated polymer according to the present invention, R1 is saturated or unsaturated and unsubstituted -C1-C2-alkyl; and / or R2 is saturated or unsaturated and unsubstituted -C1-C2-alkyl; and / or R3 is saturated or unsaturated and unsubstituted -C1-C2-alkylene-; and / or R4 is saturated or unsaturated and unsubstituted -C1-C6-alkylene-; and / or (i) R5 is saturated or unsaturated and unsubstituted -C1-C6-alkyl and R6 is saturated or unsaturated and unsubstituted -C1-C6-alkyl; preferably (ii) R5 is saturated or unsaturated and unsubstituted -C1-C6-alkyl, x is 3 and y is 0.

[0018] The following definitions apply:

[0019] As used herein, the term "polymer" corresponds to the residue of the same name contained in a compound according to formula (I).

[0020] As used herein, the term "saturated or unsaturated alkyl" includes saturated alkyl and unsaturated alkyl such as alkenyl, alkynyl, etc. As used herein, the term "alkyl" means a normal, secondary, or tertiary, straight-chain or branched hydrocarbon with no sites of unsaturation. Examples are methyl, ethyl, 1-propyl (n-propyl), 2-propyl (iPr), 1-butyl, 2-methyl-1-propyl (i-Bu), 2-butyl (s-Bu), 2-dimethyl-2-propyl (t-Bu), 1-pentyl (n-pentyl), 2-pentyl, 3-pentyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 3-methyl-1-butyl, 2-methyl-1-butyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 3-methyl-3-pentyl, 2-methyl-3-pentyl, 2,3-dimethyl-2-butyl, and 3,3-dimethyl-2-butyl. As used herein, the term "alkenyl" refers to a normal, secondary, or tertiary, straight-chain or branched hydrocarbon having at least one site of unsaturation, i.e., at least one (usually 1 to 3, preferably 1) of a carbon-carbon sp double bond. Examples include, but are not limited to, ethylene or vinyl (-CH=CH), allyl (-CHCH=CH), and 5-hexenyl (-CHCHCHCHCH=CH). The double bond may be in the cis or trans configuration. As used herein, the term "alkynyl" refers to a normal, secondary, or tertiary, straight-chain or branched hydrocarbon having at least one site of unsaturation, i.e., at least one (usually 1 to 3, preferably 1) of a carbon-carbon sp triple bond. Examples include, but are not limited to, ethynyl (-C≡CH) and 1-propynyl (propargyl, -CHC≡CH).

[0021] As used herein, the term "saturated or unsaturated alkylene" includes saturated alkylene and unsaturated alkylene, such as alkenylene, alkynylene, and alkenynylene. As used herein, the term "alkylene" refers to a saturated, straight- or branched-chain hydrocarbon group having two monovalent radical centers derived by the removal of two hydrogen atoms from the same or two different carbon atoms of a parent alkane. Typical alkylene groups include, but are not limited to, methylene (-CH-), 1,2-ethyl (-CHCH-), 1,3-propyl (-CHCHCH-), 1,4-butyl (-CHCHCHCH-), and the like. As used herein, the term "alkenylene" refers to a straight- or branched-chain hydrocarbon group having at least one site of unsaturation, i.e., at least one site (usually 1 to 3, preferably 1), of a carbon-carbon sp2 double bond and having two monovalent radical centers derived by the removal of two hydrogen atoms from the same or two different carbon atoms of a parent alkene. As used herein, the term "alkynylene" means a straight or branched chain hydrocarbon group having at least one site of unsaturation (usually 1 to 3, preferably 1) of a carbon-carbon sp triple bond and having two monovalent radical centers derived by the removal of two hydrogen atoms from the same or two different carbon atoms of a parent alkyne.

[0022] As used herein, the term "saturated or unsaturated heteroalkyl" includes saturated heteroalkyl and unsaturated heteroalkyl, such as heteroalkenyl, heteroalkynyl, and heteroalkenynyl. As used herein, the term "heteroalkyl" refers to a straight-chain or branched-chain alkyl in which one or more carbon atoms (usually 1, 2, or 3) are replaced with a heteroatom, i.e., an oxygen atom, a nitrogen atom, a sulfur atom, or a silicon atom, provided that the chain does not contain two adjacent O atoms or two adjacent S atoms. This means that one or more -CH of the alkyl may be replaced with -NH, and / or one or more -CH of the alkyl may be replaced with -NH-, -O-, -S-, or -Si-. The S atom in the chain can be optionally oxidized with one or two oxygen atoms to give sulfoxide and sulfone, respectively. Furthermore, the heteroalkyl group in the benzofuran derivatives of the present invention can contain an oxo or thio group at any carbon or heteroatom that results in a stable compound. Representative heteroalkyl groups include, but are not limited to, alcohols, alkyl ethers (e.g., -methoxy, -ethoxy, -butoxy, etc.), primary, secondary, and tertiary alkylamines, amides, ketones, esters, alkyl sulfides, and alkyl sulfones. The term "heteroalkenyl" refers to a straight- or branched-chain alkenyl in which one or more carbon atoms (usually 1, 2, or 3) are replaced with an oxygen, nitrogen, or sulfur atom, provided that the chain does not contain two adjacent O atoms or two adjacent S atoms. Thus, the term heteroalkenyl includes imines, -O-alkenyl, -NH-alkenyl, -N(alkenyl), -N(alkyl)(alkenyl), and -S-alkenyl.As used herein, the term "heteroalkynyl" means a straight- or branched-chain alkynyl in which one or more carbon atoms (usually 1, 2, or 3) are replaced by an oxygen, nitrogen, or sulfur atom, provided that the chain does not include two adjacent O atoms or two adjacent S atoms. Thus, the term heteroalkynyl includes -cyano, -O-alkynyl, -NH-alkynyl, -N(alkynyl), -N(alkyl)(alkynyl), -N(alkenyl)(alkynyl), and -S-alkynyl.

[0023] As used herein, the term "saturated or unsaturated heteroalkylene" includes saturated heteroalkylene and unsaturated heteroalkylene such as heteroalkenylene, heteroalkynylene, and heteroalkenynylene. As used herein, the term "heteroalkylene" refers to a straight-chain or branched-chain alkylene in which one or more carbon atoms (usually 1, 2, or 3) are replaced with a heteroatom, i.e., an oxygen atom, a nitrogen atom, or a sulfur atom, provided that the chain does not contain two adjacent O atoms or two adjacent S atoms. As used herein, the term "heteroalkenylene" refers to a straight-chain or branched-chain alkenylene in which one or more carbon atoms (usually 1, 2, or 3) are replaced with an oxygen atom, a nitrogen atom, or a sulfur atom, provided that the chain does not contain two adjacent O atoms or two adjacent S atoms. As used herein, the term "heteroalkynylene" means a straight- or branched-chain alkynylene in which one or more carbon atoms (usually 1, 2, or 3) are replaced by an oxygen, nitrogen, or sulfur atom, provided that the chain does not contain two adjacent O atoms or two adjacent S atoms.

[0024] As used herein, the term "saturated or unsaturated cycloalkyl" includes saturated cycloalkyl and unsaturated cycloalkyl, such as cycloalkenyl and cycloalkynyl. As used herein, unless otherwise specified, the term "cycloalkyl" refers to saturated cyclic hydrocarbon groups, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, fenchyl, decalinyl, and adamantyl. As used herein, the term "cycloalkenyl" refers to a non-aromatic cyclic hydrocarbon group having unsaturation, i.e., at least one site (usually 1 to 3, preferably 1) of a carbon-carbon sp2 double bond. Examples include, but are not limited to, cyclopentenyl and cyclohexenyl. The double bond may be in a cis or trans configuration. As used herein, the term "cycloalkynyl" refers to a non-aromatic cyclic hydrocarbon group having unsaturation, i.e., at least one site (usually 1 to 3, preferably 1) of a carbon-carbon sp2 triple bond. An example is cyclohept-1-yne. A fused system of a cycloalkyl ring and a heterocycloalkyl ring is considered heterocycloalkyl regardless of the ring attached to the core structure. A fused system of a cycloalkyl ring and an aryl ring is considered aryl regardless of the ring attached to the core structure. A fused system of a cycloalkyl ring and a heteroaryl ring is considered heteroaryl regardless of the ring attached to the core structure.

[0025] As used herein, the term "saturated or unsaturated heterocycloalkyl" includes saturated heterocycloalkyls containing at least one heteroatom, i.e., N, O, or S, as a ring member, and unsaturated non-aromatic heterocycloalkyls. As used herein, unless otherwise specified, the term "heterocycloalkyl" refers to a "cycloalkyl" in which one or more carbon atoms (usually 1, 2, or 3) are replaced with oxygen, nitrogen, or sulfur atoms, provided that the chain does not include two adjacent O or two adjacent S atoms. As used herein, unless otherwise specified, the term "heterocycloalkenyl" refers to a "cycloalkenyl" in which one or more carbon atoms (usually 1, 2, or 3) are replaced with oxygen, nitrogen, or sulfur atoms, provided that the chain does not include two adjacent O or two adjacent S atoms. As used herein, unless otherwise specified, the term "heterocycloalkynyl" means a "cycloalkynyl" in which one or more carbon atoms (usually 1, 2, or 3) have been replaced with an oxygen, nitrogen, or sulfur atom, provided that the chain does not include two adjacent O atoms or two adjacent S atoms.Examples of saturated and unsaturated heterocycloalkyls include azepane, 1,4-oxazepane, azetane, azetidine, aziridine, azocane, diazepane, dioxane, dioxolane, dithiane, dithiolane, imidazolidine, isothiazolidine, isoxalidine, morpholine, oxazolidine, oxepane, oxetane, oxirane, piperazine, piperidine, pyrazolidine, pyrrolidine, quinuclidine, tetrahydrofuran, tetrahydropyran, tetrahydrothiopyran, thiazolidine, thietane, thiirane, thiolane, thiamine ... Examples of suitable cyclohexanes include, but are not limited to, morpholine, indoline, dihydrobenzofuran, dihydrobenzothiophene, 1,1-dioxothiacylcyclohexane, 2-azaspiro[3.3]-heptane, 2-oxaspiro[3.3]heptane, 7-azaspiro[3.5]nonane, 8-azabicyclo-[3.2.1]octane, 9-azabicyclo-[3.3.1]nonane, hexahydro-1H-pyrrolidine, hexahydrocyclopenta[c]pyrrole, octahydrocyclopenta[c]pyrrole, and octahydropyrrolo[1,2-a]pyrazine. Further heterocycloalkyls within the meaning of the present invention are described in Paquette, Leo A. "Principles of Modern Heterocyclic Chemistry" (WA Benjamin, New York, 1968), especially Chapters 1, 3, 4, 6, 7, and 9; "The Chemistry of Heterocyclic Compounds, A Series of Monographs" (John Wiley & Sons, New York, 1950 to the present), especially Volumes 13, 14, 16, 19, and 28; Katritzky, Alan R., Rees, C.W. and Scriven, E. "Comprehensive Heterocyclic Chemistry" (Pergamon Press, 1996); and J. Am. Chem. Soc. (1960) 82:5566. If the heterocycloalkyl does not contain nitrogen as a ring element, it is typically bonded via carbon.When a heterocycloalkyl contains nitrogen as a ring element, it can be attached via the nitrogen or carbon. A fused system of a heterocycloalkyl ring with a cycloalkyl ring is considered heterocycloalkyl regardless of the ring attached to the core structure. A fused system of a heterocycloalkyl ring with an aryl ring is considered heterocycloalkyl regardless of the ring attached to the core structure. A fused system of a heterocycloalkyl ring with a heteroaryl ring is considered heteroaryl regardless of the ring attached to the core structure.

[0026] As used herein, the term "aryl" refers to an aromatic hydrocarbon. Typical aryl groups include, but are not limited to, one ring or two or three rings fused together derived from benzene, naphthalene, anthracene, biphenyl, etc. A fused system of an aryl ring and a cycloalkyl ring is considered an aryl regardless of the ring attached to the core structure. A fused system of an aryl ring and a heterocycloalkyl ring is considered a heterocycloalkyl regardless of the ring attached to the core structure. Thus, indoline, dihydrobenzofuran, dihydrobenzothiophene, etc. are considered heterocycloalkyl according to the present invention. A fused system of an aryl ring and a heteroaryl ring is considered a heteroaryl regardless of the ring attached to the core structure.

[0027] As used herein, the term "arylene" refers to a divalent group derived from an arene by removing one hydrogen atom from two ring carbon atoms. One synonym is an arenediyl group. Examples of arylene include, but are not limited to, phenylene and benzene-1,2-diyl.

[0028] As used herein, the term "heteroaryl" refers to an aromatic ring system that contains at least one heteroatom, ie, N, O, or S, as a ring member of the aromatic ring system. Examples of heteroaryl include, but are not limited to, benzimidazole, benzisoxazole, benzazole, benzodioxole, benzofuran, benzothiadiazole, benzothiazole, benzothiophene, carbazole, cinnoline, dibenzofuran, furan, furazane, imidazole, imidazopyridine, indazole, indole, indolizine, isobenzofuran, isoindole, isoquinoline, isothiazole, isoxazole, naphthyridine, oxadiazole, oxazole, oxindole, phthalazine, purine, pyrazine, pyrazole, pyridazine, pyridine, pyrimidine, pyrrole, quinazoline, quinoline, quinoxaline, tetrazole, thiadiazole, thiazole, thiophene, triazine, triazole, and [1,2,4]triazolo[4,3-a]pyrimidine.

[0029] As used herein, the term "heteroarylene" means a divalent group derived from a heteroarene by removing one hydrogen atom from two ring carbon atoms.

[0030] The end-group functionalized diene rubbers according to the present invention are prepared or can be obtained by homopolymerization or copolymerization of conjugated dienes and copolymerization of conjugated dienes and vinyl aromatic monomers, followed by reaction with a suitable functionalizing reagent.

[0031] Preferred conjugated dienes are 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 1-phenyl-1,3-butadiene, 1,3-hexadiene, myrcene, ocimene, and / or farnesene. 1,3-butadiene and / or isoprene are particularly preferred.

[0032] For example, styrene, o-, m-, and / or p-methylstyrene, p-tert-butylstyrene, -methylstyrene, vinylnaphthalene, divinylbenzene, trivinylbenzene, and / or divinylnaphthalene can be used as vinyl aromatic comonomers. Styrene is particularly preferred.

[0033] In one particularly preferred embodiment, the 1-amino-3-(oxyalkyl-alkoxysilyl)-2-propanol terminated polymer according to the invention comprises a "polymer" obtainable by copolymerization of 1,3-butadiene and styrene.

[0034] These polymers are preferably prepared or obtainable by anionic solution polymerization or by polymerization using coordination catalysts. The coordination catalysts in this context are Ziegler-Natta catalysts or single-metal catalyst systems. Preferred coordination catalysts are those based on Ni, Co, Ti, Zr, Nd, V, Cr, Mo, W, or Fe.

[0035] Initiators for anionic solution polymerization are based on alkali metals or alkaline earth metals, such as methyllithium, ethyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, pentyllithium, n-hexyllithium, cyclohexyllithium, octyllithium, decyllithium, 2-(6-lithio-n-hexoxy)-tetrahydropyran, 3-(tert-butyldimethylsiloxy)-1-propyllithium, phenyllithium, 4-butyl-phenyllithium, 1-naphthyllithium, p-toluyllithium, as well as those derived from tertiary N-allylamines. Allyllithium compounds include [1-(dimethylamino)-2-propenyl]lithium, [1-[bis(phenylmethyl)amino]-2-propenyl]lithium, [1-(diphenylamino)-2-propenyl]lithium, and [1-(1-pyrrolidinyl)-2-propenyl]lithium; lithium amides of secondary amines, such as lithium pyrrolidide, lithium piperidide, lithium hexamethyleneimide, lithium 1-methylimidazolidide, lithium 1-methylpiperazide, lithium morpholide, lithium dicyclohexylamide, lithium dibenzylamide, and lithium diphenylamide. These allyllithium compounds and their lithium amides can also be prepared in situ by reacting an organolithium compound with the respective tertiary N-allylamine or the respective secondary amine. Bifunctional and polyfunctional organolithium compounds, such as 1,4-dilithiobutane and dilithium piperazide, can also be used. Preferably, n-butyllithium and sec-butyllithium are used.

[0036] Furthermore, for the microstructure of the polymer, well-known randomizers and control agents, such as diethyl ether, di-n-propyl ether, diisopropyl ether, di-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol di-n-butyl ether, ethylene glycol di-tert-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-butyl ether, diethylene glycol di-tert-butyl ether, 2-(2-ethoxyethoxy)-2-methyl Examples of suitable solvents that can be used include: dipropane, triethylene glycol dimethyl ether, tetrahydrofuran, ethyl tetrahydrofurfuryl ether, hexyl tetrahydrofurfuryl ether, 2,2-bis(2-tetrahydrofuryl)propane, dioxane, trimethylamine, triethylamine, N,N,N',N'-tetramethyl-ethylenediamine, N-methyl-morpholine, N-ethylmorpholine, 1,2-dipiperi-dinoethane, 1,2-dipyrrolidinoethane, 1,2-dimorpholinoethane, and potassium and sodium salts of alcohols, phenols, carboxylic acids, and sulfonic acids.

[0037] Such solution polymerizations are well known and are described, for example, in I. Franta, Elastomers and Rubber Compounding Materials; Elsevier 1989, pp. 113-131; Houben-Weyl, Methoden der Organischen Chemie, Thieme Verlag, Stuttgart, 1961, volume XIV / 1 pp. 645-673 or volume E 20 (1987), pp. 114-134 and 134-153; and Comprehensive Polymer Science, Vol. 4, Part II (Pergamon Press Ltd., Oxford 1989), pp. 53-108.

[0038] The production of the preferred diene homopolymers and diene copolymers is preferably carried out in a solvent. Preferred solvents for the polymerization are inert aprotic solvents, such as aliphatic hydrocarbons, such as isomeric butane, pentane, hexane, heptane, octane, decane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, or 1,4-dimethylcyclohexane, or alkenes, such as 1-butene, or aromatic hydrocarbons, such as benzene, toluene, ethylbenzene, xylene, diethylbenzene, or propylbenzene. These solvents can be used individually or in combination. Preferred solvents are cyclohexane, methylcyclopentane, and n-hexane. Mixing with polar solvents is also possible.

[0039] The amount of solvent in the method of the present invention is usually within the range of 100 to 1,000 g, preferably 200 to 700 g, based on 100 g of the total amount of monomers used. However, it is also possible to polymerize the monomers used in the absence of a solvent.

[0040] Polymerization can be carried out by first introducing the monomer and solvent, and then initiating the polymerization by adding an initiator or catalyst. Polymerization can also be carried out in a feed process, where the polymerization reactor is filled by adding the monomer and solvent, and the initiator or catalyst is introduced or added along with the monomer and solvent. Variations are possible, such as introducing the solvent into the reactor, adding the initiator or catalyst, and then adding the monomer. Furthermore, polymerization can be carried out in a continuous mode. In all cases, it is possible to add additional monomer and solvent during or at the end of the polymerization.

[0041] The polymerization time can vary from a few minutes to a few hours. The polymerization is usually carried out within a period of 10 minutes to 8 hours, preferably 20 minutes to 4 hours. It can be carried out both at normal pressure and at elevated pressure (1 to 10 bar).

[0042] Surprisingly, it has been found that 1-amino-3-(oxyalkylalkoxysilyl)-2-propanol terminated polymers can be prepared without the drawbacks of the state of the art by the sequential addition of 1) one or more cyclic urea derivatives and 2) one or more glycidoxyalkylsilanes as functionalizing reagents.

[0043] The cyclic urea derivative is represented by the formula (II): [ka] where R1, R2 are the same or different and preferably represent saturated or unsaturated organic groups which may contain one or more heteroatoms independently selected from O, N, S, and Si; R3 is a saturated or unsaturated divalent organic group which, in addition to C and H, can preferably contain one or more heteroatoms selected independently from O, N, S, and Si; Preferably, R1, R2 are the same or different and may preferably contain one or more heteroatoms independently selected from O, N, S, and Si. 24 )-alkyl group, -(C3-C 24 )-cycloalkyl group, -(C6-C 24 )-aryl group, -(C6-C 24 )-alkaryl group, or -(C6-C 24 )-aralkyl group; R3 is a -C2H4- group, a -C3H6- group, or a -C4H8-alkylene- group.

[0044] Preferably, R1 and R2 are both -CH3, and / or R3 is -CH2-CH2-.

[0045] Preferred examples of compounds of formula (II) include: 1,3-Dimethyl-2-imidazolidinone (1), 1,3-Diethyl-2-imidazolidinone (2), 1-Methyl-3-phenyl-2-imidazolidinone (3), 1,3-Diphenyl-2-imidazolidinone (4), 1,3-Dimethyl-2-imidazolidinone (1), 1,3-Dimethyl-2-imidazolidinone (2), 1,3-Dimethyl-2-imidazolidinone Imidazolidinone (3), 1,3-dimethyl-2-imidazolidinone (3), 1,3-dimethyl-2-imidazolidinone (3), 1,3-dimethyl-2-imidazolidinone (3), 1,3-dimethyl-2-imidazolidinone (4), 1,3-dimethyl-2-imidazolidinone (3), 3-diethenyl-2-imidazolidinone (5), 1,3,4-trimethyl-2-imidazolidinone Thiyl-2-imidazolidinone (6), 1,3-bis(trimethylsilyl)-2-imidazolidinone (7), 1,3-dihydro-1,3-dimethyl-2H-imidazol-2-one (8), tetrahydro-1,3-dimethyl-2(1H)-pyrimidinone (9), tetrahydro-1-methyl-3-phenyl-2(1H)-pyrimidinone (10), tetrahydro-1,3,5-trimethyl-2(1H)-pyrimidinone (11), tetrahydro-3,5-dimethyl-4H-1,3,5-oxadiazin-4-one (12), tetrahydro-1,3,5-trimethyl-1,3,5-triazin-2(1H)-one (13), hexahydro-1,3-dimethyl-2H-1,3-diazepin-2-one (14): [ka] These include, but are not limited to:

[0046] A particularly preferred example of the compound of formula (II) is 1,3-dimethyl-2-imidazolidinone (1): [ka] is.

[0047] The glycidoxyalkylsilane is represented by the formula (III) [ka] where R4 is a saturated or unsaturated divalent organic group which, in addition to C and H, can preferably contain one or more heteroatoms selected independently from O, N, S, and Si; R5 and R6 are the same or different and represent a saturated or unsaturated organic group; x+y=3, 1≦x≦3 and 0≦y≦2; Preferably, R4 is a -CH2-, -C2H4-, -C3H6-, or -C4H8-alkylene- group; R5 and R6 are methyl, ethyl, propyl, or phenyl groups.

[0048] Preferably, R4 is -(CH2) 2-4 -, y is 0, x is 3 and R5 is -C1-C4-alkyl.

[0049] Preferably, R4 is -CH2CH2CH2-, y is 0, x is 3, and R5 is -CH3 or -CH2CH3.

[0050] Preferred examples of compounds of formula (III) include: (3-glycidoxypropyl)trimethoxysilane (15), (3-glycidyloxypropyl)triethoxysilane (16), (3-glycidyloxypropyl)tripropoxysilane (17), (3-glycidyloxypropyl)triphenoxysilane (18), (3-glycidoxypropyl)methyldimethoxysilane (19), (3-glycidoxypropyl)dimethylmethoxysilane (20), (2-glycidoxyethyl)trimethoxysilane (21), glycidoxymethyltrimethoxysilane (22), (4-glycidoxybutyl)trimethoxysilane (23), (6-glycidyloxyhexyl)trimethoxysilane (24), [2-(glycidoxy)propyl]trimethoxysilane (25), 2-[[4-[(trimethoxysilyl)methyl]phenoxy]methyl]oxirane (26): [ka] These include, but are not limited to:

[0051] Particularly preferred examples of compounds of formula (III) include (3-glycidoxypropyl)trimethoxysilane (15) and (3-glycidyloxypropyl)triethoxysilane (16): [ka] These include, but are not limited to:

[0052] It has been found that end-group functionalized diene rubbers according to the present invention can be prepared by the sequential reaction of reactive polymer chain ends from anionic diene polymerization, first with a cyclic urea derivative and then with a glycidoxyalkylsilane.

[0053] In one particularly preferred embodiment of the 1-amino-3-(oxyalkyl-alkoxysilyl)-2-propanol terminated polymer according to the present invention, The "polymer" may be obtained by copolymerization of 1,3-butadiene with styrene; R1 is saturated or unsaturated and unsubstituted -C1-C2-alkyl; R2 is saturated or unsaturated and unsubstituted -C1-C2-alkyl; R3 is saturated or unsaturated and unsubstituted -C1-C3-alkylene-; R4 is saturated or unsaturated and unsubstituted -C3-alkylene-; R5 and R6 are, independently of each other, saturated or unsaturated and unsubstituted -C1-C2-alkyl; x+y=3, with 1≦x≦3 and 0≦y≦2; preferably x=3 and y=0.

[0054] In one particularly preferred embodiment of the 1-amino-3-(oxyalkyl-alkoxysilyl)-2-propanol terminated polymer according to the present invention, The "polymer" may be obtained by copolymerization of 1,3-butadiene with styrene; R1 is -CH3; R2 is -CH3; R3 is -CH2CH2-; R4 is -CH2CH2CH2-; x=3 and y=0; R5 is -CH3 or -CH2CH3.

[0055] Another aspect of the present invention relates to the sequential use of first a cyclic urea derivative and then a glycidoxyalkylsilane as functionalizing reagents for the preparation of the inventive end-group functionalized diene rubbers having end groups of formula (I) as described herein.

[0056] The end-group functionalized polymers according to the present invention preferably have an average molecular weight (number average, Mn) of 10,000 to 2,000,000 g / mol, preferably 100,000 to 1,000,000 g / mol, and a glass transition temperature of -110°C to +20°C, preferably -110°C to 0°C, and a Mooney viscosity [ML1+4(100°C)] of 10 to 200, preferably 30 to 150 Mooney units.

[0057] Another aspect of the present invention relates to a method for preparing end-group functionalized polymers of the present invention, in which one or more compounds of formula (II) are first added as a pure substance, in solution, or as a suspension to a polymer having reactive polymer chain ends. The addition is preferably carried out after the polymerization is complete, but can also be carried out before complete monomer conversion. The reaction of the compound of formula (II) with the polymer having reactive polymer chain ends is carried out at temperatures typically used for polymerization. The reaction time for the reaction of the compound of formula (II) with the reactive polymer chain ends can range from several minutes to several hours.

[0058] The amount of these compounds can be selected so that all reactive polymer chain ends are reacted with the compound of formula (II), or an insufficient amount of these compounds can be used. The amount of the compound of formula (II) used can vary over a wide range. A preferred amount is in the range of 0.3 to 2 molar equivalents, particularly preferably 0.6 to 1.5 molar equivalents, based on the amount of initiator or catalyst used in the polymerization.

[0059] In a subsequent step, the compound of formula (III) is then added as a pure substance, a solution, or a suspension to the polymer obtained from the previous step by adding the compound of formula (II). The reaction of the compound of formula (III) is carried out at temperatures commonly used for polymerization. The reaction time of the reaction of the compound of formula (III) can range from a few minutes to a few hours.

[0060] The amount of the compound of formula (III) used can vary over a wide range, with a preferred amount being in the range of 0.3 to 2 molar equivalents, particularly preferably 0.6 to 1.5 molar equivalents, based on the amount of the compound of formula (II) used.

[0061] In addition to the compounds of formula (II) and formula (III), coupling reagents typical of anionic diene polymerization can also be used to react with reactive polymer chain ends. Examples of such coupling reagents include silicon tetrachloride, methyltrichlorosilane, dimethyldichlorosilane, tin tetrachloride, dibutyltin dichloride, tetraalkoxysilane, ethylene glycol diglycidyl ether, and 1,2,4-tris(chloromethyl)benzene. Such coupling reagents can be added before, together with, or after the compound of formula (II).

[0062] After addition of the compounds of formula (II) and formula (III) and optionally a coupling reagent, conventional antioxidants, such as sterically hindered phenols, aromatic amines, phosphites, thioethers, are preferably added before or during the work-up of the 1-amino-3-(oxyalkylalkoxysilyl)-2-propanol terminated polymers according to the invention.

[0063] Furthermore, the usual extender oils used in diene rubbers, such as TDAE (Treated Distillate Aromatic Extract), MES (Mild Extraction Solvates), RAE (Residual Aromatic Extract), TRAE (Treated Residual Aromatic Extract), naphthenic oil, and heavy naphthenic oil, can be added. Fillers such as carbon black and silica, rubber, and rubber additives can also be added.

[0064] The solvent can be removed from the polymerization process by conventional methods such as distillation, stripping with steam, or application of a vacuum, if necessary at higher temperatures.

[0065] A further aspect of the invention is the use of an end-group functionalized polymer according to the invention to prepare a vulcanizable rubber composition.

[0066] Preferably, these vulcanizable rubber compositions further comprise additional rubbers, fillers, rubber chemicals, processing aids, and extender oils.

[0067] The additional rubbers are, for example, natural rubber and synthetic rubber. When present, their amount is usually in the range of 0.5 to 95% by weight, preferably 10 to 80% by weight, based on the total amount of polymers in the mixture. Again, the amount of additional rubber added is determined by the intended use of the present invention. Examples of such synthetic rubbers are BR (polybutadiene), acrylic acid alkyl ester copolymer, IR (polyisoprene), E-SBR (styrene-butadiene copolymer produced by emulsion polymerization), S-SBR (styrene-butadiene copolymer produced by solution polymerization), IIR (isobutylene-isoprene copolymer), NBR (butadiene-acrylonitrile copolymer), HNBR (partially or fully hydrogenated NBR rubber), EPDM (ethylene-propylene-diene terpolymer), and mixtures of these rubbers. Natural rubber, E-SBR and S-SBR with a glass temperature above -60°C, polybutadiene rubber with a high cis content (>90%) produced using catalysts based on Ni, Co, Ti or Nd, polybutadiene rubber with a vinyl content of up to 80%, and mixtures thereof are of particular interest for the production of automobile tires.

[0068] Any known filler used in the rubber industry may be considered as a filler for the rubber composition according to the present invention, including both active and inactive fillers.

[0069] Examples include, but are not limited to: 5 to 1000, preferably 20 to 400 m 2 Highly dispersed silicas, produced for example by precipitation of solutions of silicates or by flame hydrolysis of silicon halides, with a specific surface area (BET surface) of 10 ... 20~400m 2 / g BET surface and a primary particle size of 10 to 400 nm; synthetic silicates such as alkaline earth silicates such as aluminum silicate, magnesium silicate or calcium silicate; Natural silicates such as kaolin, montmorillonite, and other natural silicas; Glass fibres and glass fibre products (mats, strands) or microspheres; Metal oxides such as zinc oxide, calcium oxide, magnesium oxide, and aluminum oxide; Metal carbonates such as magnesium carbonate, calcium carbonate, and zinc carbonate; Metal hydroxides such as aluminum hydroxide and magnesium hydroxide; Metal sulfates such as calcium sulfate and barium sulfate; Carbon black: The carbon black used is flame soot, channel, furnace, gas soot, thermal, acetylene soot or carbon black produced by the arc process, having a BET surface of 9 to 200 m2 / g, such as SAF-, ISAF-LS-, ISAF-HM-, ISAF-LM-, ISAF-HS-, CF-, SCF-, HAF-LS-, HAF-, HAF-HS-, FF-HS-, SPF-, XCF-, FEF-LS-, FEF-, FEF-HS-, GPF-HS-, GPF-, APF-, SRF-LS-, SRF-LM-, SRF-HS-, SRF-HM- and MT- soot or ASTM Carbon blacks conforming to N110-, N219-, N220-, N231-, N234-, N242-, N294-, N326-, N327-, N330-, N332-, N339-, N347-, N351-, N356, N358, N375, N472, N539, N550, N568, N650, N660, N754, N762, N765, N774, N787, and N990; Rubber gels with particle sizes between 5 and 1000 nm, especially those based on BR, E-SBR, and / or polychloroprene.

[0070] Highly dispersed silica and / or carbon black are preferred as fillers.

[0071] These fillers can be used alone or in a mixture. In one particularly preferred embodiment, the rubber composition contains a mixture of a lightweight filler such as highly dispersed silica and carbon black as a filler, and the mixing ratio of the lightweight filler to the carbon black is 0.01:1 to 50:1, preferably 0.05:1 to 20:1 parts by weight.

[0072] The filler is used in an amount ranging from 10 to 500 parts by weight based on 100 parts by weight of rubber, preferably in an amount ranging from 20 to 200 parts by weight.

[0073] In a further embodiment of the present invention, the rubber composition also comprises rubber auxiliaries which function, for example, to improve the processing characteristics of the rubber composition, to crosslink the rubber composition, to improve the physical properties of vulcanizates made from the rubber composition according to the present invention for a special purpose, to improve the interaction between the rubber and the filler, or to bond the rubber to the filler.

[0074] Examples of rubber auxiliaries include crosslinking agents such as sulfur or sulfur donating compounds, as well as accelerators, antioxidants, heat stabilizers, light stabilizers, ozone stabilizers, processing aids, plasticizers, tackifiers, blowing agents, dyes, pigments, waxes, extenders, organic acids, silanes, inhibitors, metal oxides, extender oils such as DAE (Distillate Aromatic Extract), TDAE (Treated Distillate Aromatic Extract), MES (Mild Extraction Solvate), RAE (Residual Aromatic Extract), TRAE (Treated Residual Aromatic Extract), naphthenic oil, and heavy naphthenic oil, and activators.

[0075] The total amount of rubber additives ranges from 1 to 300 parts by weight based on 100 parts by weight of total rubber. Preferably, rubber auxiliaries are used in an amount within the range of 5 to 150 parts by weight.

[0076] The vulcanizable rubber composition can be made in a one-stage or multi-stage process, with two to three mixing stages being preferred. For example, sulfur and accelerators can be added in separate mixing stages on a roller, with temperatures in the range of 30°C to 90°C being preferred. The sulfur and accelerators are preferably added in the final mixing stage.

[0077] Suitable aggregates for producing the vulcanizable rubber composition include rollers, kneaders, internal mixers, or mixing extruders.

[0078] Another aspect of the present invention relates to the use of 1-amino-3-(oxyalkylalkoxysilyl)-2-propanol terminated polymers having end groups of formula (I) as described herein for preparing vulcanizable rubber compositions.

[0079] Another aspect of the present invention relates to a vulcanizable rubber composition comprising: a) a 1-amino-3-(oxyalkylalkoxysilyl)-2-propanol terminated polymer having terminal groups of formula (I) as described herein; and optionally, b) stabilizers, extender oils, fillers, rubbers, and / or additional rubber auxiliaries.

[0080] A further aspect of the present invention relates to the use of the vulcanizable rubber composition according to the invention for the production of rubber vulcanizates, in particular for the production of tires, in particular tire treads, having in particular low rolling resistance and high wet slip strength and abrasion resistance.

[0081] The vulcanizable rubber compositions according to the invention are also suitable for the production of shaped articles, for example cable sheaths, hoses, drive belts, conveyor belts, roll linings, shoe soles, sealing rings or damping elements.

[0082] Another aspect of the present invention relates to a molded article, in particular a tire, obtainable by the above-mentioned use, i.e. produced with vulcanization from the vulcanizable rubber composition according to the invention.

[0083] The following examples serve to illustrate the invention without limiting its scope. [Example]

[0084] The number average molecular weight Mn, polydispersity Mw / Mn, and degree of coupling of styrene-butadiene rubber were determined using GPC (calibrated with PS).

[0085] The Mooney viscosity ML(1+4) 100°C was determined in accordance with DIN 52523 / 52524.

[0086] The vinyl and styrene contents were determined by FTIR spectroscopy on the rubber films.

[0087] The glass transition temperature Tg was determined from the second heating curve at a heating rate of 20 K / s using DSC.

[0088] The temperature-dependent dynamic mechanical properties were determined by measuring the loss factor (tan δ) at 0°C and tan δ at 60°C. An Eplexor instrument (Eplexor 500 N) from Gabo was used for this purpose. Measurements were performed on Ares strips at 10 Hz in accordance with DIN 53513, in the temperature range from -100°C to 100°C. An Eplexor 500 N was used for this purpose. To determine the strain-dependent dynamic mechanical properties, ΔG' was determined as the difference between the shear modulus at 0.5% strain and the shear modulus at 15% strain. The maximum loss factor (tan δmax) was also determined. These measurements were performed on cylindrical specimens (20 x 6 mm) in accordance with DIN 53513-1990, at a frequency of 10 Hz, at 2 mm compression, at a temperature of 60°C, and in the strain range from 0.1% to 40% on an MTS elastomer testing system.

[0089] The impact resilience was measured according to DIN 53512 at 23°C and 60°C.

[0090] Styrene-butadiene copolymer Example 1: Synthesis of non-functionalized styrene-butadiene copolymer (comparative) An inert 20-L reactor was charged with 8.5 kg of hexane, 6.6 mmol of 2,2-bis(2-tetrahydrofuryl)-propane, and 12.1 mmol of n-butyllithium (as a 23 wt. % solution in hexane), and the contents were heated to 40°C. The heating circuit was then closed, and 1185 g of 1,3-butadiene and 315 g of styrene were added simultaneously. This was allowed to polymerize with stirring for 35 minutes, after which the reactor contents reached a peak temperature of 61°C. 12.1 mmol of n-octanol was then added to terminate the anionic polymer chain ends. The rubber solution was drained and stabilized with 3 g of Irganox® 1520 (2,4-bis(octylthiomethyl)-6-methylphenol), and the solvent was removed by steam stripping. The rubber powder was dried in a vacuum drying oven at 65°C for 16 hours.

[0091] The number average molecular weight Mn, molecular weight distribution Mw / Mn, degree of coupling (all from GPC measurements with PS calibration), Mooney viscosity ML1+4 at 100°C, vinyl and styrene contents (from FTIR measurements, data in wt% based on the total polymer), and glass transition temperature Tg (from DSC measurements) were measured for the dry rubber powder and are listed in Table 1.

[0092] Example 2: Functionalization of styrene-butadiene copolymer by reaction with 1,3-dimethyl-2-imidazolidinone (comparative example) The procedure was the same as in Example 1. However, instead of n-octanol, an equimolar amount of the functionalizing reagent 1,3-dimethyl-2-imidazolidinone (1) was added to the n-butyllithium, and the reactor contents were then stirred for an additional 5 minutes. The rubber was then discharged and stabilized with 3 g of Irganox® 1520 (2,4-bis(octylthiomethyl)-6-methylphenol), and the solvent was removed by steam stripping. The rubber powder was dried in a vacuum drying oven at 65°C for 16 hours.

[0093] Example 3: Functionalization of styrene-butadiene copolymer by reaction with (3-glycidoxypropyl)trimethoxysilane (comparative) The procedure was the same as in Example 2. As functionalization reagent, (3-glycidoxypropyl)trimethoxysilane (15) was added in an equimolar amount to n-butyl-lithium.

[0094] Example 4: Functionalization of styrene-butadiene copolymer by reaction with (3-glycidoxypropyl)triethoxysilane (comparative example) The procedure was the same as in Example 2. As functionalizing reagent, (3-glycidoxypropyl)triethoxysilane (16) was added in an equimolar amount to n-butyl-lithium.

[0095] Example 5: Functionalization of styrene-butadiene copolymer by sequential reaction with 1,3-dimethyl-2-imidazolidinone and (3-glycidoxypropyl)trimethoxysilane (inventive example) The procedure was the same as in Example 2. For functionalization, 1,3-dimethyl-2-imidazolidinone (1) was added first in an amount equimolar to n-butyl-lithium, stirred for 5 minutes, and then (3-glycidoxypropyl)trimethoxysilane (15) was added in an amount equimolar to n-butyl-lithium.

[0096] Example 6: Functionalization of styrene-butadiene copolymer by sequential reaction with 1,3-dimethyl-2-imidazolidinone and (3-glycidoxypropyl)triethoxysilane (inventive example) The procedure was the same as in Example 2. For functionalization, 1,3-dimethyl-2-imidazolidinone (1) was first added in an amount equimolar to n-butyl-lithium, stirred for 5 minutes, and then 3-glycidoxypropyltriethoxysilane (16) was added in an amount equimolar to n-butyl-lithium.

[0097] The polymer properties of the styrene-butadiene copolymers from Examples 1-6 are summarized in Table 1. Table 1 shows that the 1-amino-3-(oxyalkylalkoxysilyl)-2-propanol terminated polymers of Examples 5 and 6, which were prepared by the sequential addition of two functionalizing reagents according to Formulae (II) and (III), exhibited a significantly reduced degree of coupling compared to the polymers of Examples 3 and 4, which were prepared by adding the functionalizing reagent according to Formula (III) without first adding the functionalizing reagent according to Formula (II).

[0098] rubber compound Tire tread rubber compounds containing the styrene-butadiene copolymers of Examples 1-6 were prepared. The ingredients are listed in Table 2. The ingredients (excluding sulfur and accelerators) were mixed in a 1.5 L kneader. The sulfur and accelerator components were mixed on a roller at 40°C. The individual steps in the preparation of the mixtures are listed in Table 3.

[0099] [Table 1]

[0100] [Table 2]

[0101] [Table 3]

[0102] These rubber compounds were crosslinked at 160°C for 20 minutes. The physical properties of the corresponding vulcanizates 7-12 are listed in Table 4. The vulcanizate properties of the vulcanized rubber compound from Comparative Example 7, which has a non-functionalized styrene-butadiene copolymer as a compound component, are given an index of 100. All values ​​above 100 in Table 4 indicate a corresponding percentage improvement in each tested property.

[0103] [Table 4]

[0104] The rebound resilience at 60°C from temperature-dependent dynamic mechanical measurements, the loss factor tanδ at 60°C, and the maximum tanδ and modulus difference G' between low strain and high strain from strain-dependent dynamic mechanical measurements are indicators of tire rolling resistance. The loss factor tanδ at 0°C and the rebound resilience at 23°C are indicators of wet slip resistance.

[0105] As can be seen from Table 4, all vulcanizates containing functionalized diene rubber are characterized by improved values ​​of the tan δ at 0 °C wet grip index and the rolling resistance index. The vulcanizates from inventive examples 11 and 12 show the best overall picture for all property indexes.

Claims

1. 1-amino-3-(oxyalkylalkoxysilyl)-2-propanol terminated polymers according to general formula (I) [Chemical Formula 1] (where, the polymer is a diene rubber containing at least one carbon-carbon double bond and selected from homopolymers or copolymers of one or more conjugated dienes or copolymers of one or more conjugated dienes with one or more vinyl aromatic monomers; R １ teeth, (i) unsubstituted, monosubstituted, or polysubstituted —C １ -C ２４ -alkyl or -C ２ -C ２４ -alkenyl; (ii) unsubstituted, monosubstituted, or polysubstituted -C １ -C ２４ -heteroalkyl or -C ２ -C ２４ -heteroalkenyl; (iii) unsubstituted, monosubstituted, or polysubstituted 6- to 24-membered aryl, in each case unsubstituted, monosubstituted, or polysubstituted —C １ -C ６ -Alkylene or -C ２ -C ６ -alkenylene- or -C １ -C ６ -heteroalkylene or -C ２ -C ６ 6- to 24-membered aryl optionally bonded via -heteroalkenylene-; (iv) unsubstituted, monosubstituted, or polysubstituted 5- to 24-membered heteroaryl; in each case, unsubstituted, monosubstituted, or polysubstituted —C １ -C ６ -Alkylene or -C ２ -C ６ -alkenylene- or -C １ -C ６ -heteroalkylene or -C ２ -C ６ 5-24 membered heteroaryl optionally bonded via -heteroalkenylene-; (v) unsubstituted, monosubstituted, or polysubstituted 3- to 24-membered cycloalkyl or cycloalkenyl; in each case, unsubstituted, monosubstituted, or polysubstituted —C １ -C ６ -Alkylene or -C ２ -C ６ -alkenylene- or -C １ -C ６ -heteroalkylene or -C ２ -C ６ 3- to 24-membered cycloalkyl or cycloalkenyl optionally bonded via -heteroalkenylene-; and (vi) unsubstituted, monosubstituted, or polysubstituted 3- to 24-membered heterocycloalkyl or heterocycloalkenyl; in each case, unsubstituted, monosubstituted, or polysubstituted —C １ -C ６ -Alkylene or -C ２ -C ６ -alkenylene- or -C １ -C ６ -heteroalkylene or -C ２ -C ６ 3- to 24-membered heterocycloalkyl or heterocycloalkenyl optionally bonded via -heteroalkenylene-; is selected from the group consisting of R ２ teeth, (i) unsubstituted, monosubstituted, or polysubstituted —C １ -C ２４ -alkyl or -C ２ -C ２４ -alkenyl; (ii) unsubstituted, monosubstituted, or polysubstituted -C １ -C ２４ -heteroalkyl or -C ２ -C ２４ -heteroalkenyl; (iii) unsubstituted, monosubstituted, or polysubstituted 6- to 24-membered aryl, in each case unsubstituted, monosubstituted, or polysubstituted —C １ -C ６ -Alkylene or -C ２ -C ６ -alkenylene- or -C １ -C ６ -heteroalkylene or -C ２ -C ６ 6- to 24-membered aryl optionally bonded via -heteroalkenylene-; (iv) unsubstituted, monosubstituted, or polysubstituted 5- to 24-membered heteroaryl; in each case, unsubstituted, monosubstituted, or polysubstituted —C １ -C ６ -Alkylene or -C ２ -C ６ -alkenylene- or -C １ -C ６ -heteroalkylene or -C ２ -C ６ 5-24 membered heteroaryl optionally bonded via -heteroalkenylene-; (v) unsubstituted, monosubstituted, or polysubstituted 3- to 24-membered cycloalkyl or cycloalkenyl; in each case, unsubstituted, monosubstituted, or polysubstituted —C １ -C ６ -Alkylene or -C ２ -C ６ -alkenylene- or -C １ -C ６ 3- to 24-membered cycloalkyl or cycloalkenyl optionally bonded via -heteroalkylene or heteroalkenylene-; and (vi) unsubstituted, monosubstituted, or polysubstituted 3- to 24-membered heterocycloalkyl or heterocycloalkenyl; in each case, unsubstituted, monosubstituted, or polysubstituted —C １ -C ６ -Alkylene or -C ２ -C ６ -alkenylene- or -C １ -C ６ -heteroalkylene or -C ２ -C ６ 3- to 24-membered heterocycloalkyl or heterocycloalkenyl optionally bonded via -heteroalkenylene-; is selected from the group consisting of R ３ teeth, (i) unsubstituted, monosubstituted, or polysubstituted —C １ -C ６ -Alkylene or -C ２ -C ６ -alkenylene-; (ii) unsubstituted, monosubstituted, or polysubstituted -C １ -C ６ -heteroalkylene or -C ２ -C ６ -heteroalkenylene-; and (iii) unsubstituted, monosubstituted, or polysubstituted 6- to 14-membered arylene; is selected from the group consisting of R ４ teeth, (i) unsubstituted, monosubstituted, or polysubstituted —C １ -C ６ -Alkylene or -C ２ -C ６ -alkenylene-; (ii) unsubstituted, monosubstituted, or polysubstituted -C １ -C ６ -heteroalkylene or -C ２ -C ６ -heteroalkenylene-; and (iii) unsubstituted, monosubstituted, or polysubstituted 6- to 14-membered arylene; is selected from the group consisting of R ５ teeth, (i) unsubstituted, monosubstituted, or polysubstituted —C １ -C ６ -alkyl or -C ２ -C ６ -alkenyl; (ii) unsubstituted, monosubstituted, or polysubstituted -C １ -C ６ -heteroalkyl or -C ２ -C ６ -heteroalkenyl; and (iii) unsubstituted, monosubstituted, or polysubstituted 6- to 14-membered aryl; is selected from the group consisting of R ６ teeth, (i) unsubstituted, monosubstituted, or polysubstituted —C １ -C ６ -alkyl or -C ２ -C ６ -alkenyl; (ii) unsubstituted, monosubstituted, or polysubstituted -C １ -C ６ -heteroalkyl or -C ２ -C ６ -heteroalkenyl; and (iii) unsubstituted, monosubstituted, or polysubstituted 6- to 14-membered aryl; is selected from the group consisting of Here, "substitution" means -F, -Cl, -Br, -I, -CN, ═O, or -CF ３ , -CF ２ H, -CFH ２ , -CF ２ Cl, -CFCl ２ , -C １ -C １８ -alkyl or -C 2 -C １８ -alkenyl, or -C １ -C １８ -heteroalkyl or -C ２ -C １８ -heteroalkenyl, "monosubstituted" means substituted with one substituent, and "polysubstituted" means substituted with two or more substituents, wherein said two or more substituents are selected from -F, -Cl, -Br, -I, -CN, ═O, and -CF ３ , -CF ２ H, -CFH ２ , -CF ２ Cl, -CFCl ２ , -C １ -C １８ -alkyl or -C ２ -C １８ -alkenyl, or -C １ -C １８ -heteroalkyl or -C ２ -C １８ -heteroalkenyl; x+y=3, 1≦x≦3 and 0≦y≦2 (provided that if y is 0, then R ６ does not exist).

2. 2. The 1-amino-3-(oxyalkylalkoxysilyl)-2-propanol terminated polymer of claim 1, wherein the polymer is obtainable by a homopolymer or copolymer of 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 1-phenyl-1,3-butadiene, myrcene, farnesene, ocimene, 1,3-hexadiene, or a combination thereof; or by copolymerization of (i) 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 1-phenyl-1,3-butadiene, 1,3-hexadiene, myrcene, farnesene, ocimene, or a combination thereof with (ii) styrene, o-, m-, and / or p-methylstyrene, p-tert-butylstyrene, methylstyrene, vinylnaphthalene, divinylbenzene, trivinylbenzene, divinylnaphthalene, or a combination thereof.

3. The 1-amino-3-(oxyalkylalkoxysilyl)-2-propanol terminated polymer according to claim 1, wherein the polymer is obtainable by copolymerization of 1,3-butadiene and styrene or copolymerization of isoprene and styrene.

4. R １ is (i) an unsubstituted —C １ -C ６ -alkyl or -C ２ -C ６ -alkenyl, R ２ is (i) an unsubstituted —C １ -C ６ -alkyl or -C ２ -C ６ -alkenyl, R ３ is (i) an unsubstituted —C １ -C ６ -Alkylene or -C ２ -C ６ -alkenylene-, R ４ is an unsubstituted -C １ -C ６ -Alkylene or -C ２ -C ６ -alkenylene-, R ５ is an unsubstituted -C １ -C ６ -alkyl or -C ２ -C ６ 2. The 1-amino-3-(oxyalkylalkoxysilyl)-2-propanol terminated polymer of claim 1, wherein x is 3 and y is 0.

5. The polymer may be obtained by copolymerization of 1,3-butadiene and styrene; R １ is an unsubstituted -C １ -C ２ -alkyl or -C ２ -alkenyl; R ２ is an unsubstituted -C １ -C ２ -alkyl or -C ２ -alkenyl; R ３ is an unsubstituted -C １ -C ２ -Alkylene- or -C ２ -alkenylene-; R ４ is an unsubstituted -C ３ -alkylene or alkenylene-; R ５ and R ６ are each independently an unsubstituted —C １ -C ２ -alkyl or -C ２ -alkenyl; x+y=3, 1≦x≦3 and 0≦y≦2 (provided that if y is 0, then R ６ does not exist), The 1-amino-3-(oxyalkylalkoxysilyl)-2-propanol terminated polymer according to claim 1.

6. General formula (I) 【Chemistry 2】 1. A method for preparing a 1-amino-3-(oxyalkylalkoxysilyl)-2-propanol terminated polymer by: (a) providing a polymer comprising at least one carbon-carbon double bond; (b) General formula (II) 【Chemistry 3】 providing a cyclic urea derivative of the formula: (c) General formula (III) 【Chemistry 4】 providing a glycidoxyalkylsilane of formula (I); (d) adding said cyclic urea derivative of said general formula (II) to said polymer as a first functionalizing reagent to form a functionalized polymer intermediate; (e) subsequently adding said glycidoxyalkylsilane of said general formula (III) as a second functionalizing reagent to said functionalized polymer intermediate to form said 1-amino-3-(oxyalkylalkoxysilyl)-2-propanol terminated polymer according to general formula (I); the polymer is a diene rubber containing at least one carbon-carbon bond and selected from homopolymers of conjugated dienes, copolymers of one or more conjugated dienes, or copolymers of one or more conjugated dienes and one or more vinyl aromatic monomers; R １ teeth, (i) unsubstituted, monosubstituted, or polysubstituted —C １ -C ２４ -alkyl or -C ２ -C ２４ -alkenyl; (ii) unsubstituted, monosubstituted, or polysubstituted -C １ -C ２４ -heteroalkyl or -C ２ -C ２４ -heteroalkenyl; (iii) unsubstituted, monosubstituted, or polysubstituted 6- to 24-membered aryl, in each case unsubstituted, monosubstituted, or polysubstituted —C １ -C ６ -Alkylene or alkenylene- or -C １ -C ６ -heteroalkylene or -C ２ -C ６ 6- to 24-membered aryl optionally bonded via -heteroalkenylene-; (iv) unsubstituted, monosubstituted, or polysubstituted 5- to 24-membered heteroaryl; in each case, unsubstituted, monosubstituted, or polysubstituted —C １ -C ６ -Alkylene or -C ２ -C ６ -alkenylene- or -C １ -C ６ -heteroalkylene or -C ２ -C ６ 5-24 membered heteroaryl optionally bonded via -heteroalkenylene-; (v) unsubstituted, monosubstituted, or polysubstituted 3- to 24-membered cycloalkyl or cycloalkenyl; in each case, unsubstituted, monosubstituted, or polysubstituted —C １ -C ６ -Alkylene or -C ２ -C ６ -alkenylene- or -C １ -C ６ -heteroalkylene or -C ２ -C ６ 3- to 24-membered cycloalkyl or cycloalkenyl optionally bonded via -heteroalkenylene-; and (vi) unsubstituted, monosubstituted, or polysubstituted 3- to 24-membered heterocycloalkyl or heterocycloalkenyl; in each case, unsubstituted, monosubstituted, or polysubstituted —C １ -C ６ -Alkylene or -C ３ -C ６ -alkenylene- or -C １ -C ６ -heteroalkylene or -C ２ -C ６ 3- to 24-membered heterocycloalkyl or heterocycloalkenyl optionally bonded via -heteroalkenylene-; is selected from the group consisting of R ２ teeth, (i) unsubstituted, monosubstituted, or polysubstituted —C １ -C ２４ -alkyl or -C ２ -C ２４ -alkenyl; (ii) unsubstituted, monosubstituted, or polysubstituted -C １ -C ２４ -heteroalkyl or -C ２ -C ２４ -heteroalkenyl; (iii) unsubstituted, monosubstituted, or polysubstituted 6- to 24-membered aryl, in each case unsubstituted, monosubstituted, or polysubstituted —C １ -C ６ -Alkylene or -C ２ -C ６ -alkenylene- or -C １ -C ６ -heteroalkylene or -C ２ -C ６ 6- to 24-membered aryl optionally bonded via -heteroalkenylene-; (iv) unsubstituted, monosubstituted, or polysubstituted 5- to 24-membered heteroaryl; in each case, unsubstituted, monosubstituted, or polysubstituted —C １ -C ６ -Alkylene or -C ２ -C ６ -alkenylene- or -C １ -C ６ -heteroalkylene or -C ２ -C ６ 5-24 membered heteroaryl optionally bonded via -heteroalkenylene-; (v) unsubstituted, monosubstituted, or polysubstituted 3- to 24-membered cycloalkyl or cycloalkenyl, in each case unsubstituted, monosubstituted, or polysubstituted —C １ -C ６ -Alkylene or -C ２ -C ６ -alkenylene- or -C １ -C ６ -heteroalkylene or -C ２ -C ６ 3- to 24-membered cycloalkyl optionally bonded via -heteroalkenylene-; and (vi) unsubstituted, monosubstituted, or polysubstituted 3- to 24-membered heterocycloalkyl or heterocycloalkenyl; in each case, unsubstituted, monosubstituted, or polysubstituted —C １ -C ６ -Alkylene or -C ２ -C ６ -alkenylene- or -C １ -C ６ -heteroalkylene or -C ２ -C ６ 3- to 24-membered heterocycloalkyl or heterocycloalkenyl optionally bonded via -heteroalkenylene-; is selected from the group consisting of R ３ teeth, (i) unsubstituted, monosubstituted, or polysubstituted —C １ -C ６ -Alkylene or -C ２ -C ６ -alkenylene-; (ii) unsubstituted, monosubstituted, or polysubstituted -C １ -C ６ -heteroalkylene or -C ２ -C ６ -heteroalkenylene-; and (iii) unsubstituted, monosubstituted, or polysubstituted 6- to 14-membered arylene; is selected from the group consisting of R ４ teeth, (i) unsubstituted, monosubstituted, or polysubstituted —C １ -C ６ -Alkylene or -C ２ -C ６ -alkenylene-; (ii) unsubstituted, monosubstituted, or polysubstituted -C １ -C ６ -heteroalkylene or heteroalkenylene-; and (iii) unsubstituted, monosubstituted, or polysubstituted 6- to 14-membered arylene; is selected from the group consisting of R ５ teeth, (i) unsubstituted, monosubstituted, or polysubstituted —C １ -C ６ -alkyl or -C ２ -C ６ -alkenyl; (ii) unsubstituted, monosubstituted, or polysubstituted -C １ -C ６ -heteroalkyl or -C ２ -C ６ -heteroalkenyl; and (iii) unsubstituted, monosubstituted, or polysubstituted 6- to 14-membered aryl; is selected from the group consisting of R ６ teeth, (i) unsubstituted, monosubstituted, or polysubstituted —C １ -C ６ -alkyl or -C ２ -C ６ -alkenyl; (ii) unsubstituted, monosubstituted, or polysubstituted -C １ -C ６ -heteroalkyl or -C ２ -C ６ -heteroalkenyl; and (iii) unsubstituted, monosubstituted, or polysubstituted 6- to 14-membered aryl; is selected from the group consisting of "Substitution" includes -F, -Cl, -Br, -I, -CN, =O, and -CF ３ , -CF ２ H, -CFH ２ , -CF ２ Cl, -CFCl ２ , -C １ -C １８ -alkyl or -C ２ -C １８ -alkenyl, or -C １ -C １８ -heteroalkyl or -C ２ -C １８ -heteroalkenyl, "monosubstituted" means substituted with one substituent, and "polysubstituted" means substituted with two or more substituents, wherein said two or more substituents are selected from -F, -Cl, -Br, -I, -CN, ═O, and -CF ３ , -CF ２ H, -CFH ２ , -CF ２ Cl, -CFCl ２ , -C １ -C １８ -alkyl or -C ２ -C １８ -alkenyl, or -C １ -C １８ -heteroalkyl or -C ２ -C １８ -heteroalkenyl; x+y=3, 1≦x≦3 and 0≦y≦2 (provided that if y is 0, then R ６ does not exist), method.

7. 7. The method of claim 6, wherein the polymer is a homopolymer or copolymer of 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 1-phenyl-1,3-butadiene, myrcene, farnesene, ocimene, 1,3-hexadiene, or a combination thereof; or a copolymer of (i) 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 1-phenyl-1,3-butadiene, 1,3-hexadiene, myrcene, farnesene, ocimene, or a combination thereof, and (ii) styrene, o-, m-, and / or p-methylstyrene, p-tert-butylstyrene, methylstyrene, vinylnaphthalene, divinylbenzene, trivinylbenzene, divinylnaphthalene, or a combination thereof.

8. 7. The method of claim 6, wherein the polymer is obtainable by copolymerization of 1,3-butadiene and styrene or by copolymerization of isoprene and styrene.

9. R １ is (i) an unsubstituted —C １ -C ６ -alkyl or -C ２ -C ６ -alkenyl, R ２ is (i) an unsubstituted —C １ -C ６ -alkyl or -C ２ -C ６ -alkenyl, R ３ is (i) an unsubstituted —C １ -C ６ -Alkylene or -C ２ -C ６ -alkenylene-, R ４ is an unsubstituted -C １ -C ６ -Alkylene or -C ２ -C ６ -alkenylene-, R ５ is an unsubstituted -C １ -C ６ -alkyl or -C ２ -C ６ -alkenyl; x is 3 and y is 0.

10. The polymer may be obtained by copolymerization of 1,3-butadiene and styrene; R １ is an unsubstituted -C １ -C ２ -alkyl or -C ２ -alkenyl; R ２ is an unsubstituted -C １ -C ２ -alkyl or -C ２ -alkenyl; R ３ is an unsubstituted -C １ -C ２ -Alkylene or -C ２ -alkenylene-; R ４ is an unsubstituted -C ３ -alkylene or alkenylene-; R ５ and R ６ are each independently an unsubstituted —C １ -C ２ -alkyl or -C ２ -alkenyl; x+y=3, 1≦x≦3 and 0≦y≦2 (provided that if y is 0, then R ６ The method of claim 6 , wherein

11. 7. The method of claim 6, wherein step (a) is carried out by anionic solution polymerization or polymerization using a coordination catalyst.

12. 7. The method of claim 6, wherein step (a) is carried out by polymerization using a coordination catalyst, the coordination catalyst being selected from a Ziegler-Natta catalyst or a monometallic catalyst system.

13. 7. The method of claim 6, wherein step (a) is carried out in the presence of a solvent and an initiator.

14. 14. The method of claim 13, wherein step (a) is carried out in the presence of a solvent, and the solvent is selected from the group consisting of cyclohexane, methylcyclopentane, n-hexane, and mixtures thereof, or the initiator is selected from n-butyllithium or sec-butyllithium, or both.

15. The method of claim 6, wherein step (a) is carried out in the presence of a solvent, the solvent being selected from the group consisting of cyclohexane, methylcyclopentane, n-hexane, and mixtures thereof.

16. The method of claim 6, wherein step (a) is carried out in the presence of an initiator, the initiator being selected from n-butyllithium or sec-butyllithium.

17. 7. The method of claim 6, wherein step (a) is carried out within a period of 10 minutes to 8 hours.

18. below: (f) a coupling reagent before, together with or after the addition of said cyclic urea derivative of general formula (III), (g) adding the cyclic urea derivative of the general formula (III) and the cyclic carboxylic anhydride of the general formula (IV) followed by an antioxidant; (h) extender oil, (i) a filler, and (j) Rubber or rubber additives The method of claim 6, comprising the further step of adding:

19. 10. A molded article made from a vulcanizable composition comprising the polymer of claim 1, said making comprising vulcanizing said vulcanizable composition.

20. 20. The shaped article of claim 19, wherein the polymer is a homopolymer or copolymer of 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 1-phenyl-1,3-butadiene, myrcene, farnesene, ocimene, 1,3-hexadiene, or combinations thereof; or a copolymer of (i) 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 1-phenyl-1,3-butadiene, 1,3-hexadiene, myrcene, farnesene, ocimene, or combinations thereof, and (ii) styrene, o-, m-, and / or p-methylstyrene, p-tert-butylstyrene, methylstyrene, vinylnaphthalene, divinylbenzene, trivinylbenzene, divinylnaphthalene, or combinations thereof.

21. 20. The shaped article of claim 19, wherein the polymer is a copolymer of 1,3-butadiene and styrene or a copolymer of isoprene and styrene.

22. R １ is (i) an unsubstituted —C １ -C ６ -alkyl or -C ２ -C ６ -alkenyl, R ２ is (i) an unsubstituted —C １ -C ６ -alkyl or -C ２ -C ６ -alkenyl, R ３ is (i) an unsubstituted —C １ -C ６ -Alkylene or -C ２ -C ６ -alkenylene-, R ４ is an unsubstituted -C １ -C ６ -Alkylene or -C ２ -C ６ -alkenylene-, R ５ is an unsubstituted -C １ -C ６ - alkyl or alkenyl; x is 3 and y is 0.

23. the polymer is a copolymer of 1,3-butadiene and styrene; R １ is an unsubstituted -C １ -C ２ -alkyl or -C ２ -alkenyl; R ２ is an unsubstituted -C １ -C ２ -alkyl or -C ２ -alkenyl; R ３ is an unsubstituted -C １ -C ２ -Alkylene or -C ２ -alkenylene; R ４ is an unsubstituted -C ３ -alkylene or alkenylene-; R ５ and R ６ are each independently an unsubstituted —C １ -C ２ -alkyl or -C ２ -alkenyl; x+y=3, 1≦x≦3 and 0≦y≦2 (provided that if y is 0, then R ６ 20. The shaped article of claim 19, wherein

24. 20. The molded article of claim 19, selected from a cable sheath, a hose, a drive belt, a conveyor belt, a lining for a roll, a shoe sole, a sealing ring, a damping element.

25. 20. The molded article of claim 19, wherein the molded article is a tire.

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