Hydrogenated modified conjugated diene-based polymer, preparation method therefor and rubber composition comprising same

Abstract

The present invention relates to a highly branched and high molecular weight hydrogenated modified conjugated diene-based polymer, a preparation method therefor and a rubber composition comprising same. Provided are the modified conjugated diene-based polymer, the preparation method therefor and the rubber composition comprising same, the modified conjugated diene-based polymer comprising: a conjugated diene-based monomer-derived unit; and a modified part derived from a compound represented by chemical formula 1, wherein the hydrogenation rate of the conjugated diene-based monomer-derived unit is 40-90 mol%.

Description

Hydrogenation-modified conjugated diene polymer, method for manufacturing the same, and rubber composition containing the same

[0001] [Cross-reference with related applications]

[0002] This application claims the benefit of priority based on Korean patent application 10-2024-0194476 filed December 23, 2024, and all contents disclosed in the literature of said Korean patent applications are incorporated herein as part of this specification.

[0003] [Technology Field]

[0004] The present invention relates to a highly branched and high molecular weight hydrogenated modified conjugated diene polymer, a method for manufacturing the same, and a rubber composition containing the same.

[0005]

[0006] Recently, in response to the demand for lower fuel consumption in automobiles, conjugated diene polymers are required as rubber materials for tires that possess low driving resistance, excellent wear resistance and tensile properties, and handling stability characterized by wet road resistance.

[0007] In order to reduce the driving resistance of a tire, there is a method to minimize the hysteresis loss of vulcanized rubber, and indicators for evaluating such vulcanized rubber include rebound elasticity at 50°C to 80°C, tan δ, and Goodrich heat generation. That is, a rubber material with high rebound elasticity at the above temperature or low tan δ and Goodrich heat generation is preferred.

[0008] Natural rubber, polyisoprene rubber, or polybutadiene rubber are known as rubber materials with low hysteresis loss, but they have the problem of low wet road resistance. Accordingly, recently, conjugated diene polymers or copolymers such as styrene-butadiene rubber (hereinafter referred to as SBR) or butadiene rubber (hereinafter referred to as BR) are manufactured by emulsion polymerization or solution polymerization and are used as rubber for tires. Among these, the greatest advantage of solution polymerization compared to emulsion polymerization is that the vinyl structure content and styrene content, which define rubber properties, can be arbitrarily controlled, and molecular weight and properties can be controlled through coupling or modification. Therefore, since structural changes in the final manufactured SBR or BR are easy, and chain end movement can be reduced through chain end bonding or modification, and bonding strength with fillers such as silica or carbon black can be increased, SBR produced by solution polymerization is widely used as rubber material for tires.

[0009] When such solution-polymerized SBR is used as a rubber material for tires, increasing the vinyl content within the SBR raises the glass transition temperature of the rubber, thereby allowing for the control of required tire properties such as driving resistance and braking force, as well as reducing fuel consumption by appropriately controlling the glass transition temperature. The solution-polymerized SBR is manufactured using an anionic polymerization initiator, and the chain ends of the formed polymer are bonded or modified using various modifying agents. For example, U.S. Patent No. 4,397,994 discloses a technique in which active anions at the chain ends of a polymer obtained by polymerizing styrene-butadiene under a non-polar solvent using a monofunctional initiator, alkyl lithium, are bonded using a binder such as a tin compound.

[0010] Meanwhile, carbon black and silica are used as reinforcing fillers for tire treads. When silica is used as a reinforcing filler, it has the advantage of improving low hysteresis loss and wet road resistance. However, silica with a hydrophilic surface has the drawback of poor dispersibility due to its low affinity with rubber compared to carbon black with a hydrophobic surface. Therefore, it is necessary to use a separate silane coupling agent to improve dispersibility or to impart a bond between silica and rubber. Accordingly, methods are being attempted to introduce functional groups with affinity or reactivity with silica to the terminal ends of rubber molecules, but the effect is not sufficient.

[0011] [Prior Art Literature]

[0012] [Patent Literature]

[0013] (Patent Document 1) U.S. Patent No. 4,397,994

[0014]

[0015] The present invention was devised to solve the problems of the prior art described above, and aims to provide a hydrogenated conjugated diene polymer that is modified by a compound represented by Chemical Formula 1 having a plurality of coupling sites, has a highly branched structure and high molecular weight, and can improve compounding processability, tensile properties, and wear resistance when applied to a rubber composition.

[0016] In addition, the present invention aims to provide a method for manufacturing the above-mentioned hydrogenated conjugated diene-based polymer.

[0017] In addition, the present invention aims to provide a rubber composition with improved compounding processability, tensile properties, and wear resistance by including the above-mentioned hydrogenated conjugated diene polymer.

[0018]

[0019] According to one embodiment of the present invention for solving the above problems, the present invention provides a modified conjugated diene polymer, a method for manufacturing the same, and a rubber composition comprising the same.

[0020] (1) The present invention provides a hydrogenation-modified conjugated diene polymer comprising a conjugated diene monomer-derived unit; and a modified portion derived from a compound represented by the following chemical formula 1, wherein the hydrogenation rate of the conjugated diene monomer-derived unit is 40 mol% to 90 mol%:

[0021] [Chemical Formula 1]

[0022]

[0023] In the above chemical formula 1, R1, R2 and R4 to R7 are independently alkylene groups having 1 to 20 carbon atoms, and R3 is a single bond or an alkylene group having 1 to 20 carbon atoms, and A1 to A4 are independently -SiR8R9R 10 or a substituent represented by the following chemical formula 1a, and R8 to R 10 The groups are independently an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, wherein R8 to R 10 At least one of them is an alkoxy group having 1 to 20 carbon atoms, and n is an integer from 1 to 10, and

[0024] [Chemical Formula 1a]

[0025]

[0026] In the above chemical formula 1a, R 11 and R 12 are independently alkylene groups having 1 to 20 carbon atoms, and R 13 to R 18 is independently an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, wherein R 13 to R 15 At least one of and R 16 to R 18 At least one of them is an alkoxy group having 1 to 20 carbon atoms.

[0027] (2) In the above (1), the present invention is such that in the above formula 1, R1, R2 and R4 to R7 are independently alkylene groups having 1 to 10 carbon atoms, and R3 is a single bond or an alkylene group having 1 to 10 carbon atoms, and A1 to A4 are independently -SiR8R9R 10 and, the above R8 to R 10 The groups are independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, wherein R8 to R 10 At least one of the groups is an alkoxy group having 1 to 10 carbon atoms, and n is an integer from 2 to 8, providing a hydrogenated conjugated diene-based polymer.

[0028] (3) The present invention, in accordance with (1) or (2), wherein in Formula 1, R1, R2 and R4 to R7 are independently alkylene groups having 1 to 10 carbon atoms, R3 is a single bond or an alkylene group having 1 to 10 carbon atoms, A1 to A4 are independently substituents represented by Formula 1a, and in Formula 1a, R 11 and R 12 are independently alkylene groups having 1 to 10 carbon atoms, and R 13 to R 18 ☐ are independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, wherein R 13 to R 15 At least one of and R 16 to R 18 At least one of the groups is an alkoxy group having 1 to 10 carbon atoms, and n is an integer from 2 to 8, providing a hydrogenated conjugated diene-based polymer.

[0029] (4) The present invention provides a hydrogenation-modified conjugated diene polymer in any one of (1) to (3), wherein the compound represented by Formula 1 is selected from any one of the compounds represented by Formulas 1-1 to 1-4 below:

[0030] [Chemical Formula 1-1]

[0031]

[0032] [Chemical Formula 1-2]

[0033]

[0034] [Chemical Formula 1-3]

[0035]

[0036] [Chemical Formula 1-4]

[0037]

[0038] In the above chemical formulas 1-1 to 1-4, Me is a methyl group.

[0039] (5) The present invention provides a hydrogenated conjugated diene polymer in which the hydrogenation rate of the conjugated diene monomer-derived unit is 60 mol% to 90 mol% in any one of (1) to (4).

[0040] (6) The present invention provides a modified conjugated diene polymer having a weight-average molecular weight of 500,000 g / mol or more and 2,000,000 g / mol or less in any one of (1) to (5).

[0041] (7) The present invention provides a hydrogenated conjugated diene polymer having a Mooney viscosity of 60 or more and 180 or less as measured at 140°C in any one of (1) to (6).

[0042] (8) The present invention provides a hydrogenated conjugated diene polymer that further comprises an aromatic vinyl monomer-derived unit in any one of (1) to (7).

[0043] (9) The present invention provides a method for preparing a hydrogenation-modified conjugated diene polymer according to any one of (1) to (8), comprising: (S1) a step of polymerizing a conjugated diene monomer, or an aromatic vinyl monomer and a conjugated diene monomer in a hydrocarbon solvent containing an organometallic compound to produce an active polymer bound to an organometallic compound; (S2) a step of reacting the active polymer with a compound represented by the following chemical formula 1 to produce a modified active polymer; and (S3) a hydrogenation reaction step.

[0044] [Chemical Formula 1]

[0045]

[0046] In the above chemical formula 1, R1, R2 and R4 to R7 are independently alkylene groups having 1 to 20 carbon atoms, and R3 is a single bond or an alkylene group having 1 to 20 carbon atoms, and A1 to A4 are independently -SiR8R9R 10 or a substituent represented by the following chemical formula 1a, and R8 to R 10 The groups are independently an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, wherein R8 to R 10 At least one of them is an alkoxy group having 1 to 20 carbon atoms, and n is an integer from 1 to 10, and

[0047] [Chemical Formula 1a]

[0048]

[0049] In the above chemical formula 1a, R 11 and R 12 are independently alkylene groups having 1 to 20 carbon atoms, and R 13 to R 18 is independently an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, wherein R 13 to R 15 At least one of and R 16 to R 18At least one of them is an alkoxy group having 1 to 20 carbon atoms.

[0050] (10) The present invention provides a method for producing a hydrogenated conjugated diene polymer according to (9), wherein the organometallic compound is used in an amount of 0.01 to 10 mmol per 100 g of total monomer.

[0051] (11) The present invention provides a method for preparing a hydrogenation-modified conjugated diene-based polymer in which, in (9) or (10), the compound represented by Formula 1 and the organometallic compound are used in a molar ratio of 1:0.1 to 1:5.0.

[0052] (12) The present invention provides a method for preparing a hydrogenation-modified conjugated diene polymer, wherein in any one of (9) to (11), the compound represented by Formula 1 is selected from any one of the compounds represented by Formulas 1-1 to 1-4 below:

[0053] [Chemical Formula 1-1]

[0054]

[0055] [Chemical Formula 1-2]

[0056]

[0057] [Chemical Formula 1-3]

[0058]

[0059] [Chemical Formula 1-4]

[0060]

[0061] In the above chemical formulas 1-1 to 1-4, Me is a methyl group.

[0062] (13) The present invention provides a method for producing a hydrogenated conjugated diene polymer, wherein in any one of (9) to (12), the (S3) hydrogenation reaction is performed by contacting the modified active polymer with hydrogen gas in the presence of a hydrogenation catalyst.

[0063] (14) The present invention provides a method for producing a modified hydrogenated conjugated diene polymer, wherein in any one of (9) to (13), the hydrogenation reaction (S3) is performed in a temperature range of 0°C to 200°C and a pressure range of 0.1 MPa to 15 MPa.

[0064] (15) The present invention provides a rubber composition comprising a hydrogenated conjugated diene polymer and a filler according to any one of (1) to (8) above.

[0065]

[0066] The hydrogenation-modified conjugated diene polymer according to the present invention is modified into a compound represented by Formula 1, which has many polymer modification functional group sites capable of reacting with the active polymer end, and can have a high molecular weight through the introduction of a highly branched structure, so that while it is a hydrogenation polymer, when applied to a rubber composition, it can improve the compounding processability of the rubber composition while simultaneously improving tensile properties and wear resistance.

[0067] The rubber composition according to the present invention has excellent compounding processability, tensile properties, and wear resistance by including the hydrogenated modified conjugated diene polymer.

[0068]

[0069] Hereinafter, the present invention will be described in more detail to aid in understanding the invention.

[0070] Terms and words used in the description and claims of the present invention should not be interpreted as being limited to their ordinary or dictionary meanings, but should be interpreted in a meaning and concept consistent with the technical spirit of the present invention, based on the principle that the inventor can appropriately define the concept of the terms to best describe his invention.

[0071]

[0072] Definition of Terms

[0073] In this specification, the term "polymer" refers to a polymer compound produced by polymerizing monomers, whether of the same or different types. Thus, the general term polymer encompasses the term homopolymer, which is commonly used to refer to a polymer produced from a single type of monomer, and the term copolymer, as defined below.

[0074] In this specification, the term 'copolymer' refers to a polymer produced by the polymerization of at least two different monomers. Thus, the general term copolymer includes binary copolymers, which are commonly used to refer to polymers produced from two different monomers, and polymers produced from two or more different monomers.

[0075] In this specification, the term '1,2-vinyl bond content' refers to a mass (or weight) percentage of butadiene contained at the 1,2-position within the polymer chain of the polymer based on the portion derived from the conjugated diene monomer (butadiene, etc.) in the polymer (total amount of polymerized butadiene).

[0076] In this specification, the term 'styrene bond content' refers to the mass (or weight) percentage of styrene contained in the polymer chains of the polymer derived from an aromatic vinyl monomer (styrene, etc.) among the polymers.

[0077] In this specification, the term 'room temperature' means a temperature in its natural state without heating or cooling, and is a temperature of 20±5℃.

[0078] In this specification, the term 'substitution' may mean that a hydrogen of a functional group, atomic group, or compound is substituted with a specific substituent, and when a hydrogen of a functional group, atomic group, or compound is substituted with a specific substituent, one or more substituents may exist depending on the number of hydrogens present in the functional group, atomic group, or compound, and when multiple substituents exist, each substituent may be the same or different from one another.

[0079] In this specification, the term 'alkyl group' may mean a monovalent aliphatic saturated hydrocarbon and may include linear alkyl groups such as methyl, ethyl, propyl, and butyl; branched alkyl groups such as isopropyl, sec-butyl, tert-butyl, and neo-pentyl; and cyclic saturated hydrocarbons, or cyclic unsaturated hydrocarbons containing one or more unsaturated bonds.

[0080] In this specification, the term 'alkylene group' may refer to divalent aliphatic saturated hydrocarbons such as methylene, ethylene, propylene, and butylene.

[0081] In this specification, the terms 'derived unit', 'derived repeating unit', and 'derived functional group' may refer to a component, structure, or the substance itself derived from a substance.

[0082] In this specification, the term 'single bond' may refer to a single covalent bond itself that does not include a separate atomic or molecular group.

[0083] In this specification, the term 'hydrogenation rate' refers to the molar ratio of units in which unsaturated bonds among the conjugated diene monomer-derived units have been hydrogenated to become saturated bonds, relative to the total number of conjugated diene monomer-derived units within the polymer. Specifically, the following structural units (a), (b), (c), and (d) derived from conjugated diene monomers exist within the polymer, and the hydrogenation rate refers to the molar ratio of the sum of structural units (b) and (d) relative to the total number of structural units, which are structural units (a) through (d). Here, the hydrogenation rate is of the copolymer 1 It can be obtained by H NMR measurement.

[0084]

[0085] In this specification, the terms “comprising,” “having,” and their derivatives are not intended to exclude the presence of any additional components, steps, or procedures, whether or not they are specifically disclosed. To avoid any uncertainty, any composition claimed by the use of the term “comprising” may include any additional additives, adjuvants, or compounds, whether polymers or otherwise, unless otherwise stated. In contrast, the term “essentially composed of” excludes any other components, steps, or procedures from the scope of any subsequent description, except those not essential to operability. The term “composed of” excludes any components, steps, or procedures that are not specifically described or enumerated.

[0086]

[0087] Measurement methods and conditions

[0088] In this specification, 'weight-average molecular weight (Mw)' and 'molecular weight distribution (MWD)' were obtained by measuring the weight-average molecular weight (Mw) and number-average molecular weight (Mn) under the following conditions using a Gel permeation chromatograph (GPC) (PL GPC220, Agilent Technologies), obtaining a molecular weight distribution curve, and calculating the molecular weight distribution (PDI, MWD, Mw / Mn) from each of the measured molecular weights.

[0089] - Columns: Use a combination of two PLgel Olexis columns (Polymer Laboratories) and one PLgel mixed-C column (Polymer Laboratories).

[0090] - Solvent: Use a mixture of 2 wt% amine compound with tetrahydrofuran

[0091] - Flow rate: 1 ml / min

[0092] - Sample concentration: 1–2 mg / ml (diluted in THF)

[0093] - Infusion volume: 100 µl

[0094] - Column temperature: 40℃

[0095] - Detector: Refractive index

[0096] - Standard: Polystyrene (corrected by a cubic function)

[0097] In this specification, 'Moony viscosity' was measured using a Mooney viscometer, such as the MV2000E (ALPHA Technologies) Large Rotor, under conditions of 140°C and Rotor Speed ​​2±0.02 rpm. Specifically, after leaving the polymer at room temperature (23±5°C) for at least 30 minutes, 27±3g was taken and filled into the die cavity, and the measurement was taken while applying torque by operating the platen.

[0098]

[0099] Hydrogenated modified conjugated diene polymers

[0100] The present invention provides a hydrogenated conjugated diene polymer having a highly branched structure and high molecular weight, which can be applied to a rubber composition to improve its compounding processability, tensile properties, and wear resistance.

[0101] The hydrogenation-modified conjugated diene-based polymer according to one embodiment of the present invention comprises a conjugated diene-based monomer-derived unit; and a modified portion derived from a compound represented by the following chemical formula 1, wherein the hydrogenation rate of the conjugated diene-based monomer-derived unit is 40 mol% to 90 mol%.

[0102] [Chemical Formula 1]

[0103]

[0104] In the above chemical formula 1, R1, R2 and R4 to R7 are independently alkylene groups having 1 to 20 carbon atoms, and R3 is a single bond or an alkylene group having 1 to 20 carbon atoms, and A1 to A4 are independently -SiR8R9R 10 or a substituent represented by the following chemical formula 1a, and R8 to R 10 The groups are independently an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, wherein R8 to R 10 At least one of them is an alkoxy group having 1 to 20 carbon atoms, and n is an integer from 1 to 10, and

[0105] [Chemical Formula 1a]

[0106]

[0107] In the above chemical formula 1a,

[0108] R 11 and R 12 are independently alkylene groups having 1 to 20 carbon atoms, and R 13 to R 18is independently an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, wherein R 13 to R 15 At least one of and R 16 to R 18 At least one of them is an alkoxy group having 1 to 20 carbon atoms.

[0109] Specifically, in the above chemical formula 1, R1, R2 and R4 to R7 are independently alkylene groups having 1 to 10 carbon atoms, and R3 is a single bond or an alkylene group having 1 to 10 carbon atoms, and A1 to A4 are independently -SiR8R9R 10 and, the above R8 to R 10 The groups are independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, wherein R8 to R 10 At least one of them is an alkoxy group having 1 to 10 carbon atoms, and n may be an integer from 2 to 8. More specifically, in the above formula 1, R1, R2 and R4 to R7 are independently alkylene groups having 1 to 6 carbon atoms, and R3 is a single bond or an alkylene group having 1 to 6 carbon atoms, and A1 to A4 are independently -SiR8R9R 10 and, the above R8 to R 10 The groups are independently an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, wherein R8 to R 10 At least one of them is an alkoxy group having 1 to 6 carbon atoms, and n can be an integer from 2 to 6.

[0110] In addition, in the above Chemical Formula 1, R1, R2, and R4 to R7 are independently alkylene groups having 1 to 10 carbon atoms, R3 is a single bond or an alkylene group having 1 to 10 carbon atoms, A1 to A4 are independently substituents represented by Chemical Formula 1a, and in the above Chemical Formula 1a, R 11 and R 12are independently alkylene groups having 1 to 10 carbon atoms, and R 13 to R 18 ☐ are independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, wherein R 13 to R 15 At least one of and R 16 to R 18 At least one of them is an alkoxy group having 1 to 10 carbon atoms, and n may be an integer from 2 to 8. Specifically, in the above formula 1, R1, R2, and R4 to R7 are independently alkylene groups having 1 to 6 carbon atoms, R3 is a single bond or an alkylene group having 1 to 6 carbon atoms, A1 to A4 are independently substituents represented by formula 1a, and in the above formula 1a, R 11 and R 12 are independently alkylene groups having 1 to 6 carbon atoms, and R 13 to R 18 is independently an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, wherein R 13 to R 15 At least one of and R 16 to R 18 At least one of them is an alkoxy group having 1 to 6 carbon atoms, and n can be an integer from 2 to 6.

[0111] More specifically, the compound represented by the above chemical formula 1 may be any one selected from the compounds represented by the following chemical formulas 1-1 to 1-4.

[0112] [Chemical Formula 1-1]

[0113]

[0114] [Chemical Formula 1-2]

[0115]

[0116] [Chemical Formula 1-3]

[0117]

[0118] [Chemical Formula 1-4]

[0119]

[0120] In the above chemical formulas 1-1 to 1-4, Me is a methyl group.

[0121]

[0122] In addition, the hydrogenated conjugated diene-based polymer according to one embodiment of the present invention may be a hydrogenated polymer in which the hydrogenation rate of the conjugated diene-derived unit is 40 mol% to 90 mol%, and specifically, the hydrogenation rate may be 60 mol% to 90 mol%, 65 mol% to 90 mol%, or 70 mol% to 85 mol%. When the aforementioned hydrogenation rate is satisfied, it may be more advantageous for improving the wear resistance and rolling resistance of a rubber composition containing the hydrogenated conjugated diene-based polymer.

[0123] Meanwhile, the hydrogenation rate of the polymer may be influenced by the hydrogenation catalyst used in the hydrogenation reaction, the amount used, the reaction temperature, pressure conditions, and the reaction time. A hydrogenation-modified conjugated diene-based polymer according to one embodiment of the present invention can satisfy the aforementioned hydrogenation rate by being manufactured by a manufacturing method including the hydrogenation reaction described below.

[0124] Generally, hydrogenated (modified) conjugated diene polymers have a problem in that processability becomes poor due to an increase in Mooney viscosity when applied to rubber compositions through the aforementioned hydrogenation.

[0125] However, the hydrogenated conjugated diene polymer according to the present invention is modified with a compound represented by Formula 1, which provides a plurality of coupling sites, and can have a highly branched structure and high molecular weight characteristics due to an increase in coupling bonds between polymer chains. In addition, a modified portion, which is a filler-affinity functional group derived from the compound represented by Formula 1, is introduced into the polymer chain, and the affinity with the filler can be greatly increased. Therefore, when applied to hydrogenated polymers or rubber compositions, excellent compounding processability is achieved, and tensile properties and wear resistance are significantly improved.

[0126]

[0127] Meanwhile, the compound represented by the above chemical formula 1 may be produced from a manufacturing method comprising the step of reacting a compound represented by the following chemical formula 2 with a compound represented by the chemical formula 3 or a compound represented by the chemical formula 4.

[0128] [Chemical Formula 2]

[0129]

[0130] In the above chemical formula 2, R 19 and R 20 ☐ are independently alkylene groups having 1 to 20 carbon atoms, and R 21 is a single bond or an alkylene group having 1 to 20 carbon atoms, and m is an integer from 1 to 10, and

[0131] [Chemical Formula 3]

[0132]

[0133] In the above chemical formula 3,

[0134] R 22 is an alkylene group having 1 to 20 carbon atoms, and R 23 to R 25 is independently an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, wherein R 23 to R 25At least one of them is an alkoxy group having 1 to 20 carbon atoms, and X1 is a halogen element, and

[0135] [Chemical Formula 4]

[0136]

[0137] In the above chemical formula 4, R 26 to R 28 ☐ are independently alkylene groups having 1 to 20 carbon atoms, and R 29 to R 34 is independently an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, wherein R 29 to R 31 At least one of and R 32 to R 34 At least one of them is an alkoxy group having 1 to 20 carbon atoms, and X2 is a halogen element.

[0138] The above reaction can be carried out under basic conditions in a reaction solvent at a temperature of 120°C or higher, specifically at a temperature of 120°C to 200°C or 140°C to 180°C, in which case the reaction conversion rate may be superior, which may be advantageous for improving the yield.

[0139] The above basic conditions can be composed using a basic compound, and the basic compound can be any tertiary amine compound commonly used in the art without special limitation, but for example, triethylamine, diisopropylamine, or a mixture thereof can be used.

[0140] In addition, the above reaction may further utilize potassium iodide (KI), potassium bromide (KBr), or a mixture thereof acting as a catalyst as needed; in this case, it may be advantageous to achieve a smoother target reaction by increasing reaction activity and improving the reaction rate.

[0141] In addition, the compound represented by Chemical Formula 2 and the compound represented by Chemical Formula 3 or the compound represented by Chemical Formula 4 may be reacted in an appropriate ratio according to the stoichiometric ratio, but specifically, they may be reacted in a molar ratio of 1:4 to 8. In this case, the reaction rate can be improved without excessive residual material.

[0142] In addition, in the above chemical formula 2, R 19 and R 20 ☐ are independently alkylene groups having 1 to 10 carbon atoms, and R 21 is a single bond or an alkylene group having 1 to 10 carbon atoms, and m can be an integer from 2 to 8. Specifically, R 19 and R 20 ☐ are independently alkylene groups having 1 to 6 carbon atoms, and R 21 is a single bond or an alkylene group having 1 to 6 carbon atoms, and m can be an integer from 2 to 6.

[0143] In addition, in the above chemical formula 3, R 22 is an alkylene group having 1 to 10 carbon atoms, and R 23 to R 25 is independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, wherein R 23 to R 25 At least one of them is an alkoxy group having 1 to 10 carbon atoms, and X1 may be a halogen element. Here, the halogen element may be Br, Cl, I, or F.

[0144] Specifically, in the above chemical formula 3, R 22 is an alkylene group having 1 to 6 carbon atoms, and R 23 to R 25 is independently an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, wherein R 23 to R 25 At least one of them is an alkoxy group having 1 to 6 carbon atoms, and X1 may be Cl.

[0145] In addition, in the above chemical formula 4, R 26 to R 28 ☐ are independently alkylene groups having 1 to 10 carbon atoms, and R 29 to R 34 is independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, wherein R 29 to R 31 At least one of and R 32 to R 34 At least one of them is an alkoxy group having 1 to 10 carbon atoms, and X2 may be a halogen element. Here, the halogen element may be Br, Cl, I, or F.

[0146] Specifically, in the above chemical formula 4, R 26 to R 28 ☐ are independently alkylene groups having 1 to 6 carbon atoms, and R 29 to R 34 is independently an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, wherein R 29 to R 31 At least one of and R 32 to R 34 At least one of them is an alkoxy group having 1 to 6 carbon atoms, and X2 may be Cl.

[0147]

[0148] In addition, the hydrogenation-modified conjugated diene polymer has units derived from conjugated diene monomers as its main units, and the conjugated diene monomer may include a hydrocarbon compound having a conjugated molecular structure in which single bonds and double bonds (or multiple bonds) are alternately connected and having two double bonds within the molecule. In addition, the conjugated diene monomer may be one or more selected from the group consisting of, for example, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene, 2-phenyl-1,3-butadiene, 2-halo-1,3-butadiene (halo means halogen atom), 1,3-pentadiene, 1-methyl-1,3-pentadiene, 1,3-hexadiene, and 4,5-diethyl-1,3-octadiene.

[0149] In addition, the hydrogenation-modified conjugated diene-based polymer may further include aromatic vinyl monomers in addition to conjugated diene monomers, and may further include units derived therefrom. Examples of the aromatic vinyl monomers include styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, ethylstyrene, t-butylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene, 1-vinyl-5-hexylnaphthalene, 3-(2-pyrrolidino ethyl)styrene, 4-(2-pyrrolidino ethyl)styrene, and 3-(2-pyrrolidino-1-methyl It may be one or more selected from the group consisting of ethyl)-α-methylstyrene (3-(2-pyrrolidino-1-methyl ethyl)-α-methylstyrene).

[0150] As another example, the hydrogenated modified conjugated diene-based polymer may be a copolymer further comprising repeating units derived from a diene monomer having 1 to 10 carbon atoms together with repeating units derived from the conjugated diene monomer. The repeating units derived from the diene monomer may be repeating units derived from a diene monomer different from the conjugated diene monomer, and the diene monomer different from the conjugated diene monomer may be, for example, 1,2-butadiene. When the conjugated diene-based polymer is a copolymer further comprising a diene monomer, the conjugated diene-based polymer may contain repeating units derived from the diene monomer in an amount greater than 0 weight% to 1 weight%, greater than 0 weight% to 0.1 weight%, greater than 0 weight% to 0.01 weight%, or greater than 0 weight% to 0.001 weight%, and within this range, it has the effect of preventing gel formation.

[0151] According to one embodiment of the present invention, when two or more monomers are included in the chain of the conjugated diene-based polymer, the chain structure may have an intermediate form between a random copolymer and a block copolymer, and in this case, the control of the microstructure may be easy, and thus there is an effect of excellent balance between each physical property. The random copolymer may mean that the repeating units forming the copolymer are arranged in a disordered manner.

[0152]

[0153] According to one embodiment of the present invention, the hydrogenation-modified conjugated diene polymer may have a weight-average molecular weight (Mw) measured by gel permeation chromatography (GPC) of 500,000 g / mol to 2,000,000 g / mol, 700,000 g / mol to 2,000,000 g / mol, or 950,000 g / mol to 2,000,000 g / mol, and within this range, it is applied to a rubber composition to have excellent compounding processability and the effect of improving wear resistance.

[0154] In addition, the hydrogenation-modified conjugated diene-based polymer may have a molecular weight distribution of 1.0 to 5.0, and specifically, 1.5 to 4.0, 1.7 to 3.0, or 1.8 to 2.5.

[0155] In addition, the hydrogenated modified conjugated diene polymer according to one embodiment of the present invention may have a Mooney viscosity at 140°C measured under ASTM D1646 conditions of 60 or higher and 180 or lower, specifically 80 to 175, 90 to 150, 100 to 150, or 110 to 150. Although there may be various measures to evaluate processability, processability may be significantly excellent when the Mooney viscosity satisfies the above range.

[0156] In addition, the hydrogenated modified conjugated diene polymer may have a vinyl content of 5 wt% or more, 10 wt% or more, or 10 wt% to 60 wt%, and within this range, the glass transition temperature can be controlled to an appropriate range, thereby having excellent rolling resistance, wet road resistance, and low fuel consumption. Here, the vinyl content may refer to the content of a 1,2-added conjugated diene monomer rather than a 1,4-added conjugated diene monomer with respect to 100 wt% of a conjugated diene copolymer composed of a monomer having a vinyl group and an aromatic vinyl monomer.

[0157]

[0158] Method for preparing hydrogenation-modified conjugated diene polymer

[0159] In addition, the present invention provides a method for manufacturing the above hydrogenation-modified conjugated diene-based polymer.

[0160] A method for preparing a hydrogenated conjugated diene-based polymer according to one embodiment of the present invention comprises: (S1) a step of preparing an active polymer to which an organometal is bonded by polymerizing a conjugated diene-based monomer, or an aromatic vinyl-based monomer and a conjugated diene-based monomer, in a hydrocarbon solvent containing an organometallic compound (Step 1); (S2) a step of preparing a modified active polymer by reacting the active polymer with a compound represented by the following chemical formula 1 (Step 3); and (S3) a hydrogenation reaction step (Step 3).

[0161] [Chemical Formula 1]

[0162]

[0163] The definitions for each substituent of Chemical Formula 1 above are as previously defined.

[0164]

[0165] Step 1 above is a step for preparing an active polymer combined with an organometallic compound, which can be performed by polymerizing a conjugated diene monomer, or an aromatic vinyl monomer and a conjugated diene monomer, in a hydrocarbon solvent containing an organometallic compound.

[0166] The above hydrocarbon solvent is not particularly limited, but may be one or more selected from the group consisting of, for example, n-pentane, n-hexane, n-heptane, isooctane, cyclohexane, toluene, benzene, and xylene.

[0167] The above conjugated diene monomers and aromatic vinyl monomers are as previously defined.

[0168]

[0169] According to one embodiment of the present invention, the organometallic compound may be used in an amount of 0.01 to 10 mmol, 0.05 to 5 mmol, 0.1 to 2 mmol, 0.1 to 1 mmol, or 0.15 to 0.8 mmol based on 100 g of total monomer.

[0170] The above organometallic compound may be, for example, one or more selected from the group consisting of methyl lithium, ethyl lithium, propyl lithium, n-butyl lithium, s-butyl lithium, t-butyl lithium, hexyl lithium, n-decyl lithium, t-octyl lithium, phenyl lithium, 1-naphthyl lithium, n-eicosillithium, 4-butylphenyl lithium, 4-tolylithium, cyclohexyl lithium, 3,5-di-n-heptylcyclohexyl lithium, 4-cyclopentyl lithium, naphthyl sodium, naphthyl potassium, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide, and lithium isopropylamide.

[0171] Meanwhile, the polymerization of step 1 above may be carried out including a polar additive, and the polar additive may be added in an amount of 0.001 to 50g, 0.001 to 10g, 0.005 to 0.2g, or 0.01 to 0.2g based on 100g of total monomer.

[0172] In addition, the polar additive may be one or more selected from the group consisting of tetrahydrofuran, 2,2-di(tetrahydrofuryl)propane, diethyl ether, cyclopentyl ether, dipropyl ether, ethylenedimethyl ether, diethyl glycol, dimethyl ether, tertiary butoxyethoxyethane, bis(3-dimethylaminoethyl) ether, (dimethylaminoethyl)ethyl ether, trimethylamine, triethylamine, tripropylamine, and tetramethylethylenediamine, and specifically, it may be triethylamine or tetramethylethylenediamine. When the polar additive is included, it has the effect of inducing the easy formation of a random copolymer by compensating for the difference in reaction rates between conjugated diene monomers, or conjugated diene monomers and aromatic vinyl monomers when copolymerizing them.

[0173] The polymerization of Step 1 above may be, for example, anionic polymerization, and as a specific example, may be living anionic polymerization having an anionic active site at the polymerization end by a growth polymerization reaction by anion. In addition, the polymerization of Step 1 above may be thermal polymerization, isothermal polymerization, or constant-temperature polymerization (adiabatic polymerization). The constant-temperature polymerization may refer to a polymerization method that includes a step of polymerizing using the heat of reaction itself without arbitrarily applying heat after adding the organometallic compound; the thermal polymerization may refer to a polymerization method that increases the temperature by arbitrarily applying heat after adding the organometallic compound; and the isothermal polymerization may refer to a polymerization method that maintains a constant temperature of the polymer by increasing the heat or removing heat after adding the organometallic compound.

[0174] In addition, the polymerization of step 1 above may be carried out in a temperature range of, for example, -20°C to 80°C, 0°C to 80°C, 10°C to 80°C, or 10°C to 70°C.

[0175] The active polymer prepared by Step 1 above may refer to a polymer in which a polymer anion and an organometallic cation are combined.

[0176]

[0177] Step 2 above is a step of reacting the active polymer with a compound represented by Formula 1 to prepare a modified active polymer.

[0178] According to one embodiment of the present invention, the compound represented by Chemical Formula 1 can be used in an amount of 0.05 to 10 g, 0.05 to 5 g, specifically 0.05 to 1 g, based on 100 g of total monomer.

[0179] In addition, according to one embodiment of the present invention, the compound represented by Formula 1 and the organometallic compound can be used in a molar ratio of 1:0.1 to 1:5.0 or a molar ratio of 1:0.1 to 1:4.0, and a modification reaction with optimal performance can be performed within this range, thereby obtaining a high molecular weight conjugated diene polymer.

[0180] The reaction of step 2 above is a modification reaction to introduce a functional group derived from the modification agent into the active polymer, and may be carried out at 0°C to 90°C for 1 minute to 5 hours.

[0181] In addition, according to one embodiment of the present invention, the method for producing the hydrogenation-modified conjugated diene-based polymer may be carried out by a batch method or a continuous polymerization method comprising one or more reactors.

[0182]

[0183] Step 3 above is a step of carrying out a hydrogenation reaction to produce a hydrogenated modified conjugated diene-based polymer.

[0184] The above hydrogenation reaction can be carried out by contacting the modified active polymer with hydrogen gas in the presence of a hydrogenation catalyst.

[0185] In addition, the hydrogenation reaction may be carried out in an inert atmosphere, and the inert atmosphere may be formed using an inert gas. The inert gas may be one or more selected from, for example, helium, nitrogen, and argon, which does not react with any reactants during the hydrogenation reaction. In this case, air is undesirable because it can cause a decrease in activity by oxidizing or decomposing the hydrogenation catalyst.

[0186] The above hydrogenation catalyst may be used without special limitation as long as it is commonly used in the art, but, for example, it may be a supported heterogeneous catalyst in which a metal such as Ni, Pt, Pd, or Ru is supported on carbon, silica, alumina, diatomaceous earth, etc.; a Ziegler-type catalyst in which a transition metal salt of an organic acid salt or acetylacetone salt of Ni, Co, Fe, or Cr is used together with a reducing agent such as an organoaluminum; or a homogeneous catalyst of an organometallic complex such as Ti, Ru, Rh, or Zr.

[0187] As a specific example, the hydrogenation catalyst may be a titanocene compound or a mixture thereof with a reducing organometallic compound, and the titanocene compound may be a compound having a (substituted) cyclopentadienyl backbone, an indenyl backbone, or a fluorenyl backbone, such as biscyclopentadienyl titanium chloride or monopentamethylcyclopentadienyl titanium trichloride, and the reducing organometallic compound may be an organoalkali metal compound such as organolithium, an organomagnesium compound, an organoaluminum compound, an organoboron compound, or an organozinc compound.

[0188] In addition, the above hydrogenation catalyst may be used in an amount of 0.01 mmol to 20 mmol or 0.05 mmol to 5 mmol based on 100 g of modified active polymer, and in this case, the hydrogenation reaction can occur easily.

[0189] As another example, the above hydrogenation catalyst may be used in an amount such that the metallic component in the catalyst is 100 ppm or more, 150 ppm or more, or 150 ppm to 300 ppm based on 100 parts by weight of the modified active polymer, and in this case, the polymer produced may be advantageous in satisfying the aforementioned hydrogenation rate.

[0190] In addition, the hydrogenation reaction may be performed in a temperature range of 0°C to 200°C and a pressure range of 0.1 MPa to 15 MPa, specifically in a temperature range of 30°C to 150°C, 50°C to 120°C, or 70°C to 100°C, and under pressure conditions of 0.2 MPa to 10 MPa, 0.3 MPa to 5 MPa, or 0.5 MPa to 3 MPa. In this case, it may be advantageous for the polymer to be manufactured to satisfy the aforementioned hydrogenation rate. If the hydrogenation reaction is performed under the above temperature range conditions, the desired hydrogenation reaction can proceed smoothly without causing gelation or decomposition of the polymer, without a decrease in catalyst activity, a decrease in the hydrogenation reaction rate, or the use of an excessive hydrogenation catalyst.

[0191]

[0192] The above method for preparing a hydrogenated conjugated diene-based polymer may, for example, follow step 3 of the present invention and, if necessary, further include one or more steps among the solvent and unreacted monomer recovery and drying steps.

[0193]

[0194] Rubber composition

[0195] Furthermore, the present invention provides a rubber composition comprising the above-mentioned hydrogenated conjugated diene polymer.

[0196] The rubber composition according to one embodiment of the present invention may contain the hydrogenated conjugated diene polymer in an amount of 10% or more by weight, 10% to 100% by weight, or 20% to 90% by weight, and within this range, mechanical properties such as tensile strength and wear resistance are excellent, and there is an effect of excellent balance between each property.

[0197] In addition, the rubber composition may further include other rubber components as needed in addition to the hydrogenated conjugated diene polymer, wherein the rubber components may be included in an amount of 90% by weight or less relative to the total weight of the rubber composition. As a specific example, the other rubber components may be included in an amount of 1 to 900 parts by weight per 100 parts by weight of the modified conjugated diene polymer.

[0198] The above rubber component may be, for example, natural rubber or synthetic rubber, and specifically examples include natural rubber (NR) containing cis-1,4-polyisoprene; modified natural rubber such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber, which are obtained by modifying or purifying the above general natural rubber; It may be synthetic rubber such as styrene-butadiene copolymer (SBR), polybutadiene (BR), polyisoprene (IR), butyl rubber (IIR), ethylene-propylene copolymer, polyisobutylene-co-isoprene, neoprene, poly(ethylene-co-propylene), poly(styrene-co-butadiene), poly(styrene-co-isoprene), poly(styrene-co-isoprene-co-butadiene), poly(isoprene-co-butadiene), poly(ethylene-co-propylene-co-diene), polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, butyl halogenated rubber, etc., and any one or more of these may be used.

[0199] The above rubber composition may, for example, comprise 0.1 to 200 parts by weight, or 10 to 120 parts by weight, of a filler per 100 parts by weight of the hydrogenated modified conjugated diene-based polymer of the present invention. The filler may, for example, be a silica-based filler, and specific examples may include wet silica (hydrated silica), dry silica (anhydrous silica), calcium silicate, aluminum silicate, or colloidal silica, and preferably, it may be wet silica, which has the best effect of improving fracture characteristics and the best effect of achieving wet grip. In addition, the above rubber composition may further comprise a carbon black-based filler as needed.

[0200] As another example, when silica is used as the above-mentioned filler, a silane coupling agent may be used together to improve reinforcement and low heat generation, and as specific examples, the above-mentioned silane coupling agent is bis(3-triethoxysilylpropyl)tetrasulfide, bis(3-triethoxysilylpropyl)trisulfide, bis(3-triethoxysilylpropyl)disulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, bis(2-trimethoxysilylethyl)tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide. It may be 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-trimethoxysilylpropylbenzothiazolyltetrasulfide, 3-triethoxysilylpropylbenzolyltetrasulfide, 3-triethoxysilylpropylmethacrylate monosulfide, 3-trimethoxysilylpropylmethacrylate monosulfide, bis(3-diethoxymethylsilylpropyl)tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, or dimethoxymethylsilylpropylbenzothiazolyltetrasulfide, and any one or a mixture of two or more of these may be used. Preferably, considering the effect of improving reinforcement, it may be bis(3-triethoxysilylpropyl)polysulfide or 3-trimethoxysilylpropylbenzothiazyltetrasulfide.

[0201] In addition, since the rubber composition according to one embodiment of the present invention uses a hydrogenated conjugated diene polymer in which a functional group with high affinity for silica is introduced to the active site as a rubber component, the amount of silane coupling agent can be reduced compared to the usual case, and accordingly, the silane coupling agent can be used in an amount of 1 to 20 parts by weight or 5 to 15 parts by weight per 100 parts by weight of silica, and within this range, the effect as a coupling agent is sufficiently exhibited while preventing gelation of the rubber component.

[0202] The rubber composition according to one embodiment of the present invention may be sulfur-crosslinkable and may further include a vulcanizing agent. Specifically, the vulcanizing agent may be sulfur powder and may be included in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the rubber component, and within this range, the necessary elastic modulus and strength of the vulcanized rubber composition are secured while having excellent low fuel consumption.

[0203] In addition to the above-mentioned components, the rubber composition according to one embodiment of the present invention may further include various additives commonly used in the rubber industry, specifically vulcanization accelerators, process oils, plasticizers, anti-aging agents, anti-scotch agents, zinc white, stearic acid, thermosetting resins, or thermoplastic resins.

[0204] The above vulcanization accelerator may be a thiazole-based compound such as M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), or CZ (N-cyclohexyl-2-benzothiazylsulfenamide), or a guanidine-based compound such as DPG (diphenylguanidine), and may be included in an amount of 0.1 to 5 parts by weight per 100 parts by weight of rubber component.

[0205] The above process oil acts as a softening agent within the rubber composition and may be, for example, a paraffinic, naphthenic, or aromatic compound; aromatic process oil may be used when considering tensile strength and wear resistance, while naphthenic or paraffinic process oil may be used when considering hysteresis loss and low-temperature characteristics. The above process oil may be included, for example, in an amount of 100 parts by weight or less per 100 parts by weight of the rubber component, and within this range, it has the effect of preventing a decrease in the tensile strength and low heat generation (low fuel consumption) of the vulcanized rubber.

[0206] The above anti-aging agent may be, for example, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, or a high-temperature condensation product of diphenylamine and acetone, and may be used in an amount of 0.1 to 6 parts by weight per 100 parts by weight of rubber component.

[0207] The rubber composition according to one embodiment of the present invention can be obtained by mixing using a mixer such as a Banbury mixer, a roll mixer, or an internal mixer according to the above formulation, and a rubber composition with low heat generation and excellent wear resistance can be obtained by a vulcanization process after molding.

[0208] Accordingly, the above rubber composition can be useful for manufacturing various components of a tire, such as tire treads, undertreads, sidewalls, carcass coating rubber, belt coating rubber, bead fillers, choppers, or bead coating rubber, or various industrial rubber products such as anti-vibration rubber, belt conveyors, and hoses.

[0209]

[0210] In addition, the present invention provides a tire manufactured using the above rubber composition.

[0211] The above tire may include a tire or a tire tread.

[0212]

[0213] Examples

[0214] Hereinafter, the present invention will be described in detail with reference to examples in order to specifically explain the invention. However, the embodiments according to the present invention may be modified in various different forms, and the scope of the present invention should not be interpreted as being limited to the embodiments described below. The embodiments of the present invention are provided to more completely explain the invention to those with average knowledge in the art.

[0215] Preparation Example 1

[0216] 1.48 g (10 mmol) of 2,2'-(ethane-1,2-diylbis(oxy))bis(ethane-1-amine), 9.09 g (90 mmol) of triethylamine, 166 mg (1 mmol) of potassium iodide, and 15.8 g (80 mmol) of (3-chloropropyl)trimethoxysilane were reacted at 150°C for 24 hours while stirring. After the reaction was complete, the temperature was lowered to room temperature, 40 ml of a mixture of dimethylformamide and hexane (1:5 volume ratio) was added and stirred for 15 minutes, the dimethylformamide layer was extracted with hexane, and the solution and impurities were removed by vacuum distillation to prepare a light brown oil compound represented by Chemical Formula 1-1. The prepared compound is 1 It was confirmed to have been synthesized through H NMR analysis.

[0217] [Chemical Formula 1-1]

[0218]

[0219] In the above chemical formula 1-1, Me is a methyl group.

[0220] 1 H NMR (500 MHz, CDCl3) δ 3.57-3.51 (m, 44H), 2.65 (t, 4H), 2.44 (t, 8H), 1.54-1.51 (m, 8H), 0.61-0.57 (m, 8H).

[0221]

[0222] Preparation Example 2

[0223] 1.48 g (10 mmol) of 2,2'-(ethane-1,2-diylbis(oxy))bis(ethane-1-amine), 6.06 g (60 mmol) of triethylamine, 166 mg (1 mmol) of potassium iodide, and 17.5 g (42 mmol) of 3-chloro-N,N-bis(3-(trimethoxysilyl)propyl)propane-1-amine were reacted at 150°C for 24 hours while stirring. After the reaction was complete, the temperature was lowered to room temperature, 40 ml of a mixture of dimethylformamide and hexane (1:5 volume ratio) was added and stirred for 15 minutes, the dimethylformamide layer was extracted with hexane, and the solution and impurities were removed by vacuum distillation to prepare a light brown oil compound represented by Chemical Formula 1-2. The prepared compound 1 It was confirmed to have been synthesized through H NMR analysis.

[0224] [Chemical Formula 1-2]

[0225]

[0226] In the above chemical formula 1-2, Me is a methyl group.

[0227] 1 H NMR (500 MHz, CDCl3) δ 3.58 (s, 76H), 2.67-2.42 (m, 40H), 0.63-0.60 (m, 16 H).

[0228]

[0229] Preparation Example 3

[0230] 2.20 g (10 mmol) of 3,3'-((oxybis(ethane-2,1-diyl))bis(oxy))bis(propane-1-amine), 9.09 g (90 mmol) of triethylamine, 166 mg (1 mmol) of potassium iodide, and 15.8 g (80 mmol) of (3-chloropropyl)trimethoxysilane were reacted at 150°C for 24 hours while stirring. After the reaction was complete, the temperature was lowered to room temperature, 40 ml of a mixture of dimethylformamide and hexane (1:5 volume ratio) was added and stirred for 15 minutes, the dimethylformamide layer was extracted with hexane, and the solution and impurities were removed by vacuum distillation to prepare a light brown oil compound represented by Chemical Formula 1-3. The prepared compound 1 It was confirmed to have been synthesized through H NMR analysis.

[0231] [Chemical Formula 1-3]

[0232]

[0233] In the above chemical formula 1-3, Me is a methyl group.

[0234] 1 H NMR (500 MHz, CDCl3) δ 3.67-3.58 (m, 44H), 3.50-3.48 (m, 4H), 2.49-2.47 (m, 4H), 2.42-2.39 (m, 8H), 1.74-1.71 (m, 4H), 1.56-1.52 (m, 8H), 0.63-0.60 (m, 8H).

[0235]

[0236] Preparation Example 4

[0237] 2.20 g (10 mmol) of 3,3'-((oxybis(ethane-2,1-diyl))bis(oxy))bis(propane-1-amine), 6.06 g (60 mmol) of triethylamine, 166 mg (1 mmol) of potassium iodide, and 17.5 g (42 mmol) of 3-chloro-N,N-bis(3-(trimethoxysilyl)propyl)propane-1-amine were reacted at 150°C for 24 hours while stirring. After the reaction was complete, the temperature was lowered to room temperature, 40 ml of a mixture of dimethylformamide and hexane (1:5 volume ratio) was added and stirred for 15 minutes, the dimethylformamide layer was extracted with hexane, and the solution and impurities were removed by vacuum distillation to prepare a light brown oil compound represented by Chemical Formula 1-4. The prepared compound 1 It was confirmed to have been synthesized through H NMR analysis.

[0238] [Chemical Formula 1-4]

[0239]

[0240] In the above chemical formula 1-4, Me is a methyl group.

[0241] 1 H NMR (500 MHz, CDCl3) δ 3.65-3.68 (m, 80H), 3.49-3.47 (m, 4H), 2.49-2.41 (m, 36H), 1.74-1.72 (m, 4H), 1.55-1.54 (m, 24H), 0.63-0.60 (m, 16H).

[0242]

[0243] Preparation Example 5

[0244] 1 L of purified cyclohexane was introduced into a nitrogen-substituted dry reactor, 100 mmol of bis(η5-cyclopentadienyl)titanium dichloride was added, and while stirring, an n-hexane solution containing 200 mmol of trimethylaluminum was added and reacted at room temperature for 3 days to prepare a hydrogenation catalyst.

[0245]

[0246] Example 1

[0247] 4,733.0 g of n-hexane, 375.0 g of styrene, 593.8 g of 1,3-butadiene, and 1.4 g of N,N,N',N'-tetramethylethylenediamine (TMEDA) as a polar additive were added to a 20 L autoclave reactor, followed by the addition of 5.0 g of n-butyllithium (10 wt% in n-hexane), the internal temperature of the reactor was adjusted to 40°C, and an adiabatic heating reaction was carried out. After 30 minutes, 31.3 g of 1,3-butadiene was added to cap the polymer ends with butadiene. Subsequently, 1.9 g of the compound represented by Formula 1-1 prepared in Preparation Example 1 was added as a modifying agent and reacted for 0 minutes to prepare a modified active polymer ([TMEDA]:[act. Li]=0.46:1 molar ratio, [modifying agent]:[act. Li]=0.51:1 molar ratio). After the reaction was finished, the hydrogenation catalyst prepared in Preparation Example 5 and hydrogen were added, and the hydrogenation reaction was carried out for 30 minutes at 80°C and a hydrogen pressure of 0.7 MPa. At this time, the hydrogenation catalyst was added such that the titanium content was 150 ppm based on 100 parts by weight of the modified active polymer. Subsequently, 17 g of a solution in which the antioxidant Wingstay K was dissolved in hexane at 30 wt% was added. The polymer obtained as a result was placed in hot water heated with steam and stirred to remove the solvent, and then roll-dried to remove the remaining solvent and water to produce a hydrogenated modified styrene-butadiene copolymer.

[0248]

[0249] Example 2

[0250] A hydrogenated styrene-butadiene copolymer was prepared in the same manner as in Example 1, except that the compound represented by Formula 1-2 prepared in Preparation Example 2 was used instead of the compound represented by Formula 1-1 in Example 1 ([TMEDA]:[act. Li]=0.46:1 molar ratio, [modifier]:[act. Li]=0.26:1 molar ratio).

[0251]

[0252] Example 3

[0253] A hydrogenated styrene-butadiene copolymer was prepared in the same manner as in Example 1, except that the compound represented by Formula 1-3 prepared in Preparation Example 3 was used instead of the compound represented by Formula 1-1 in Example 1 ([TMEDA]:[act. Li]=0.46:1 molar ratio, [modifier]:[act. Li]=0.51:1 molar ratio).

[0254]

[0255] Example 4

[0256] A hydrogenated styrene-butadiene copolymer was prepared in the same manner as in Example 1, except that the compound represented by Formula 1-4 prepared in Preparation Example 4 was used instead of the compound represented by Formula 1-1 in Example 1 ([TMEDA]:[act. Li]=0.46:1 molar ratio, [modifier]:[act. Li]=0.26:1 molar ratio).

[0257]

[0258] Comparative Example 1

[0259] A modified styrene-butadiene copolymer was prepared in the same manner as in Example 1, except that SiCl4 was used instead of the compound represented by Formula 1-1 in Example 1 and no hydrogenation reaction was performed ([TMEDA]:[act. Li]=3.1:1 molar ratio, [modifier]:[act. Li]=0.48:1 molar ratio).

[0260]

[0261] Comparative Example 2

[0262] A hydrogenated styrene-butadiene copolymer was prepared by carrying out the same procedure as in Example 1, except that SiCl4 was used instead of the compound represented by Formula 1-1 in Example 1 ([TMEDA]:[act. Li]=3.1:1 molar ratio, [modifier]:[act. Li]=0.48:1 molar ratio).

[0263]

[0264] Comparative Example 3

[0265] A modified styrene-butadiene copolymer was prepared in the same manner as in Example 1, except that N-methyl-3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)propane-1-amine was used instead of the compound represented by Formula 1-1 in Example 1, and no hydrogenation reaction was performed ([TMEDA]:[act. Li]=3.1:1 molar ratio, [modifier]:[act. Li]=0.35:1 molar ratio).

[0266]

[0267] Comparative Example 4

[0268] A hydrogenated styrene-butadiene copolymer was prepared by carrying out the same procedure as in Example 1, except that N-methyl-3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)propane-1-amine was used instead of the compound represented by Formula 1-1 in Example 1 ([TMEDA]:[act. Li]=3.1:1 molar ratio, [modifier]:[act. Li]=0.35:1 molar ratio).

[0269]

[0270] Experimental Example 1

[0271] For each (hydrogenated) modified styrene-butadiene copolymer prepared in the above examples and comparative examples, the styrene unit content and vinyl content within the polymer, and the weight-average molecular weight (Mw, ×10⁻¹⁰) were respectively 4 g / mol), number average molecular weight (Mn, ×10⁻⁶) 4 g / mol), molecular weight distribution (MWD), Mooney viscosity (MV), and hydrogenation rate (mol%) were measured, respectively.

[0272] 1) Styrene bond content and 1,2-vinyl bond content

[0273] The styrene bond content (SM) and 1,2-vinyl bond content (Vi) in each polymer were measured and analyzed using Varian VNMRS 500 MHz NMR. For NMR measurements, 1,1,2,2-tetrachloroethane was used as the solvent, and the solvent peak was calculated as 6.00 ppm. The styrene unit bond content and 1,2-vinyl bond content were calculated by using peaks of 7.2–6.9 ppm as random styrene, 6.9–6.2 ppm as blocked styrene, 5.8–5.1 ppm as 1,4-vinyl and 1,2-vinyl, and 5.1–4.5 ppm as 1,2-vinyl.

[0274]

[0275] 2) Weight-average molecular weight (Mw, ×10⁻¹⁰) 4 g / mol), number average molecular weight (Mn, ×10⁻⁶) 4 g / mol) and molecular weight distribution (MWD)

[0276] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) were measured under the following conditions using gel permeation chromatography (GPC) (PL GPC220, Agilent Technologies), respectively, and the molecular weight distribution (MWD, Mw / Mn) was obtained by calculating from each of the measured molecular weights.

[0277] - Columns: Use a combination of two PLgel Olexis columns (Polymer Laboratories) and one PLgel mixed-C column (Polymer Laboratories).

[0278] - Solvent: Use a mixture of 2 wt% amine compound with tetrahydrofuran

[0279] - Flow rate: 1 mL / min

[0280] - Sample concentration: 1–2 mg / mL (diluted in THF)

[0281] - Infusion volume: 100 uL

[0282] - Column temperature: 40℃

[0283] - Detector: Refractive index

[0284] - Standard: Polystyrene (corrected by a cubic function)

[0285]

[0286] 3) Mooney dots

[0287] The above Mooney viscosity (MV, (ML1+4, @140℃)) was measured using the MV-2000 (ALPHA Technologies) at 140℃ with a Rotor Speed ​​of 2±0.02 rpm and a Large Rotor. The sample used was left at room temperature (23±5℃) for at least 30 minutes, then 27±3 g was collected, filled into the die cavity, and the Platen was operated to measure for 4 minutes.

[0288]

[0289] 4) Hydrogen addition rate (mol%)

[0290] For each copolymer, NMR spectra of structural units (a) to (d) were obtained using Varian VNMRS 500 MHz NMR, and the relative molar ratio of the sum of structural units (b) and (d) to the total structural units was calculated using the integral values ​​of each peak area. 1,1,2,2-tetrachloroethane was used as the solvent for the NMR measurement, and the solvent peak was calculated as 6.00 ppm. The relative molar ratio of the sum of structural units (b) and (d) to the total structural units was calculated by assigning 4.0–6.0 ppm to structural units (a) and (c) and 0.5–2.5 ppm to structural units (b) and (d).

[0291]

[0292]

[0293] As shown in Table 1 above, it was confirmed that Examples 1 to 4 showed a significantly increased weight-average molecular weight and a significantly increased Mooney viscosity compared to Comparative Examples 1 to 4, and that the hydrogen addition rate satisfied the suggested range of 75 mol% to 77 mol%.

[0294] Through this, it was confirmed that the modified conjugated diene polymer according to the present invention is modified by a compound represented by Formula 1, which provides a plurality of coupling sites, thereby increasing the inter-chain coupling bonds constituting the polymer, and at the same time, a modified portion derived from the compound is introduced into the polymer chain, resulting in a highly modified structure and high molecular weight.

[0295]

[0296] Experimental Example 2

[0297] In order to compare and analyze the physical properties of the rubber composition containing the modified styrene-butadiene copolymer prepared in the above examples and comparative examples and the molded article prepared therefrom, tensile properties, wear resistance, processability, and viscoelastic properties were measured. The results are shown in Table 3 below.

[0298] 1) Preparation of rubber specimens

[0299] The modified conjugated diene polymers of the examples and comparative examples were used as raw rubber and blended under the blending conditions shown in Table 2 below. The raw materials in Table 2 are each part by weight based on 100 parts by weight of rubber.

[0300]

[0301] Specifically, the rubber specimen is mixed through a first stage of mixing and a second stage of mixing. In the first stage of mixing, raw rubber, silica (filler), organosilane coupling agent (X50S, Evonik), process oil (TDAE oil), zinc oxide (ZnO), stearic acid, antioxidant (TMQ(RD) (2,2,4-trimethyl-1,2-dihydroquinoline polymer), anti-aging agent (6PPD ((dimethylbutyl)-N-phenyl-phenylenediamine)), and wax (microcrystaline wax) were mixed using a Banbury mixer equipped with a temperature control device. At this time, the temperature of the mixer was controlled, and a primary mixture was obtained at an discharge temperature of 150°C. In the second stage of mixing, after cooling the primary mixture to room temperature, the primary mixture, sulfur powder, rubber accelerator (DPG (diphenylguanidine)), and vulcanization accelerator (CZ (N-cyclohexyl-2-benzothiazylsulfenamide)) were added to the mixer, and A secondary mixture was obtained by mixing at a temperature of 100℃ or lower. Subsequently, a rubber specimen was prepared by undergoing a curing process at 160℃ for 20 minutes.

[0302]

[0303] 2) Tensile properties

[0304] Tensile properties were determined by manufacturing each test specimen in accordance with the tensile testing method of ASTM 412 and measuring the fracture strength (tensile strength) of the test specimen.

[0305] Specifically, tensile properties were measured at room temperature at a speed of 50 cm / min using a Universal Test Machine 4204 (Instron) tensile testing machine. The results in Table 3 are expressed as an Index (%) based on the results of Comparative Example 1, where a higher value indicates superior performance.

[0306]

[0307] 3) Viscoelastic properties

[0308] Viscoelastic properties were measured by varying the deformation in torsional mode at a frequency of 10 Hz and at each measurement temperature (-60℃ to 70℃) using a dynamic mechanical analyzer (TA Company) to measure tan δ. A lower tan δ at high temperature of 70℃ indicates less hysteresis loss and superior rotational resistance (fuel efficiency). However, the results in Table 3 are expressed as an index based on the measurement value of Comparative Example 1 as the reference value, so a higher value indicates superior performance.

[0309]

[0310] 4) Processability characteristics

[0311] The Mooney viscosity (MV, (ML1+4, at 125℃)) of the secondary compound obtained when manufacturing the rubber specimen in step 1) above was measured to compare and analyze the processability characteristics of each polymer. At this time, a lower Mooney viscosity measurement value indicates superior processability characteristics. However, the results in Table 3 are expressed as an index based on the measurement value of Comparative Example 1 as the reference value, so a higher value indicates superiority.

[0312] Specifically, using the MV-2000 (ALPHA Technologies) at 125℃ with a Rotor Speed ​​of 2±0.02 rpm and a Large Rotor, each secondary mixture was left at room temperature (23±5℃) for at least 30 minutes, then 27±3 g was collected, filled into the die cavity, and the Platen was operated to measure for 4 minutes.

[0313]

[0314] 5) Wear resistance (DIN wear test)

[0315] For each rubber specimen, a DIN abrasion test was conducted in accordance with ASTM D5963, and the results were expressed as the DIN loss index (loss volume index): ARIA (Abration Resistance Index, Method A). A higher value indicates superior performance.

[0316]

[0317] As shown in Table 3 above, it was confirmed that the hydrogenated modified styrene-butadiene copolymer of the examples has the effect of improving tensile properties, viscoelastic properties, wear resistance, and processability properties in a balanced manner. Specifically, compared to Comparative Example 1, Examples 1 to 4 showed tensile strength improved by about 10% or more and processability properties improved by 5% to 12%, while viscoelastic properties and wear resistance were significantly improved by more than 20%. Compared to Comparative Example 2, which is a hydrogenated modified conjugated diene polymer, it was confirmed that viscoelastic properties and wear resistance were greatly improved, while processability properties increased by about 60% or more.

[0318] In addition, compared to Comparative Example 3, which is an unhydrogenated modified conjugated diene polymer prepared using a conventionally known aminoalkoxysilane-based modifier, Examples 1 to 4 exhibited improved tensile strength and processability characteristics, while significantly improved viscoelasticity and wear resistance. Furthermore, compared to Comparative Example 4, which is a hydrogenated modified conjugated diene polymer prepared using an aminoalkoxysilane-based modifier, it was confirmed that the Examples 1 to 4 exhibited tensile strength and wear resistance at an equivalent level, while showing increased viscoelasticity and significantly improved processability characteristics.

[0319] Through the above results, it can be seen that the hydrogenation-modified conjugated diene polymer of the present invention is modified into a compound represented by Formula 1, which has many polymer modification functional group sites capable of reacting with the active polymer end, and includes a modified portion derived from the compound represented by Formula 1, thereby having excellent filler affinity and being able to have a high molecular weight through the introduction of a highly branched structure, so that it can be applied to a rubber composition without poor processability characteristics due to hydrogenation, thereby improving the compounding processability of the rubber composition while simultaneously improving tensile properties, viscoelastic properties, and wear resistance.

Claims

1. Units derived from conjugated diene monomers; and It comprises a modified portion derived from a compound represented by the following chemical formula 1, and Hydrogenated conjugated diene polymer having a hydrogenation rate of 40 mol% to 90 mol% of conjugated diene monomer-derived units: [Chemical Formula 1] In the above chemical formula 1, R1, R2 and R4 to R7 are independently alkylene groups having 1 to 20 carbon atoms, and R3 is a single bond or an alkylene group having 1 to 20 carbon atoms, and A1 to A4 are independently -SiR8R9R 10 or a substituent represented by the following chemical formula 1a, and R8 to R 10 The groups are independently an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, wherein R8 to R 10 At least one of them is an alkoxy group having 1 to 20 carbon atoms, and n is an integer from 1 to 10, and [Chemical Formula 1a] In the above chemical formula 1a, R 11 and R 12 are independently alkylene groups having 1 to 20 carbon atoms, and R 13 to R 18 is independently an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, wherein R 13 to R 15 At least one of and R 16 to R 18 At least one of them is an alkoxy group having 1 to 20 carbon atoms.

2. In Paragraph 1, In the above chemical formula 1, R1, R2 and R4 to R7 are independently alkylene groups having 1 to 10 carbon atoms, and R3 is a single bond or an alkylene group having 1 to 10 carbon atoms, and A1 to A4 are independently -SiR8R9R 10 and, the above R8 to R 10 The groups are independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, wherein R8 to R 10 A hydrogenated conjugated diene polymer in which at least one of the groups is an alkoxy group having 1 to 10 carbon atoms, and n is an integer from 2 to 8.

3. In Paragraph 1, In the above Chemical Formula 1, R1, R2 and R4 to R7 are independently alkylene groups having 1 to 10 carbon atoms, R3 is a single bond or an alkylene group having 1 to 10 carbon atoms, and A1 to A4 are independently substituents represented by Chemical Formula 1a. R in the above chemical formula 1a 11 and R 12 are independently alkylene groups having 1 to 10 carbon atoms, and R 13 to R 18 ☐ are independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, wherein R 13 to R 15 At least one of and R 16 to R 18 A hydrogenated conjugated diene polymer in which at least one of the groups is an alkoxy group having 1 to 10 carbon atoms, and n is an integer from 2 to 8.

4. In Paragraph 1, A hydrogenation-modified conjugated diene polymer in which the compound represented by Chemical Formula 1 above is any one selected from the compounds represented by Chemical Formulas 1-1 to 1-4 below: [Chemical Formula 1-1] [Chemical Formula 1-2] [Chemical Formula 1-3] [Chemical Formula 1-4] In the above chemical formulas 1-1 to 1-4, Me is a methyl group.

5. In Paragraph 1, Hydrogenated conjugated diene polymer having a hydrogenation rate of 60 mol% to 90 mol% of units derived from conjugated diene monomers.

6. In Paragraph 1, Hydrogenated conjugated diene polymer having a weight-average molecular weight of 500,000 g / mol or more and 2,000,000 g / mol or less.

7. In Paragraph 1, Hydrogenated conjugated diene polymer having a Mooney viscosity of 60 or more and 180 or less as measured at 140℃.

8. In Paragraph 1, A hydrogenation-modified conjugated diene polymer that further comprises units derived from aromatic vinyl monomers.

9. (S1) A step of preparing an active polymer bound to an organometallic compound by polymerizing a conjugated diene monomer, or an aromatic vinyl monomer and a conjugated diene monomer, in a hydrocarbon solvent containing an organometallic compound; (S2) A step of preparing a modified active polymer by reacting the above active polymer with a compound represented by the following chemical formula 1; and (S3) Method for preparing a hydrogenated conjugated diene polymer comprising a hydrogenation reaction step: [Chemical Formula 1] In the above chemical formula 1, R1, R2 and R4 to R7 are independently alkylene groups having 1 to 20 carbon atoms, and R3 is a single bond or an alkylene group having 1 to 20 carbon atoms, and A1 to A4 are independently -SiR8R9R 10 or a substituent represented by the following chemical formula 1a, and R8 to R 10 The groups are independently an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, wherein R8 to R 10 At least one of them is an alkoxy group having 1 to 20 carbon atoms, and n is an integer from 1 to 10, and [Chemical Formula 1a] In the above chemical formula 1a, R 11 and R 12 are independently alkylene groups having 1 to 20 carbon atoms, and R 13 to R 18 is independently an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, wherein R 13 to R 15 At least one of and R 16 to R 18 At least one of them is an alkoxy group having 1 to 20 carbon atoms.

10. In Paragraph 9, A method for preparing a hydrogenation-modified conjugated diene-based polymer using the above organometallic compound in an amount of 0.01 to 10 mmol per 100 g of total monomer.

11. In Paragraph 9, A method for preparing a hydrogenation-modified conjugated diene-based polymer using the compound represented by Chemical Formula 1 above in an amount of 0.1 to 5.0 moles based on 1 mole of organometallic compound.

12. In Paragraph 9, A method for preparing a hydrogenation-modified conjugated diene-based polymer, wherein the compound represented by Chemical Formula 1 above is any one selected from the compounds represented by Chemical Formulas 1-1 to 1-4 below: [Chemical Formula 1-1] [Chemical Formula 1-2] [Chemical Formula 1-3] [Chemical Formula 1-4] In the above chemical formulas 1-1 to 1-4, Me is a methyl group.

13. In Paragraph 9, A method for producing a hydrogenated conjugated diene polymer, wherein the above (S3) hydrogenation reaction is performed by contacting the modified active polymer with hydrogen gas in the presence of a hydrogenation catalyst.

14. In Paragraph 9, A method for preparing a hydrogenated conjugated diene polymer, wherein the above (S3) hydrogenation reaction is performed in a temperature range of 0°C to 200°C and a pressure range of 0.1 MPa to 15 MPa.

15. A rubber composition comprising a hydrogenated modified conjugated diene polymer and a filler according to claim 1.

Images