Modified conjugated diene-based polymer, method for preparing same, and rubber composition comprising same

Abstract

The present invention relates to a highly branched and high-molecular-weight modified conjugated diene-based polymer, a method for preparing same, and a rubber composition comprising same, and provides: a 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; a method for preparing same; and a rubber composition comprising same.

Description

Modified conjugated diene polymer, method for producing the same, and rubber composition comprising the same

[0001] [Cross-reference with related applications]

[0002] This application claims the benefit of priority to Korean Patent Application No. 10-2024-0115973, filed August 28, 2024, and Korean Patent Application No. 10-2024-0169911, filed November 25, 2024, the entire contents of which are incorporated herein by reference.

[0003] [Technical Field]

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

[0005]

[0006] In response to recent demands for fuel efficiency in automobiles, conjugated diene polymers with low driving resistance, excellent wear resistance and tensile properties, and steering stability represented by wet road resistance are in demand as rubber materials for tires.

[0007] In order to reduce the driving resistance of tires, there is a method to reduce the hysteresis loss of vulcanized rubber, and as evaluation indices of such vulcanized rubber, rebound elasticity, tan δ, and Goodrich heat generation at 50°C to 80°C are used. In other words, a rubber material having a large rebound elasticity or a small tan δ and Goodrich heat generation at the above temperature is desirable.

[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. Recently, conjugated diene polymers or copolymers such as styrene-butadiene rubber (hereinafter referred to as SBR) or butadiene rubber (hereinafter referred to as BR) have been manufactured through emulsion polymerization or solution polymerization and used as rubber for tires. Among these, the greatest advantage of solution polymerization over emulsion polymerization is that the vinyl structural content and styrene content, which determine the rubber properties, can be arbitrarily controlled, and the molecular weight and physical properties can be controlled through coupling or modification. Therefore, the structure of the final manufactured SBR or BR is easily changed, and the movement of the chain ends can be reduced through chain end bonding or modification, and the bonding strength with fillers such as silica or carbon black can be increased, so SBR manufactured through solution polymerization is widely used as a rubber material for tires.

[0009] When such solution-polymerized SBR is used as a rubber material for tires, not only can the required tire properties such as driving resistance and braking power be controlled by increasing the glass transition temperature of the rubber by increasing the vinyl content within the SBR, but fuel consumption can also be reduced 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 modifiers and used. For example, U.S. Patent No. 4,397,994 proposes a technology in which the active anions at the chain ends of the polymer obtained by polymerizing styrene-butadiene in a nonpolar solvent using a monofunctional initiator, alkyl lithium, are bonded using a bonding agent such as a tin compound.

[0010] Meanwhile, carbon black and silica are used as reinforcing fillers in tire treads. Using silica as a reinforcing filler offers the advantages of low hysteresis loss and improved wet road resistance. However, compared to carbon black with a hydrophobic surface, silica with a hydrophilic surface has a low affinity for rubber, resulting in poor dispersibility. Therefore, a separate silane coupling agent is needed to improve dispersibility or provide a silica-rubber bond. Therefore, methods of introducing functional groups with affinity or reactivity for silica to the ends of rubber molecules are being pursued, but the effects are not sufficient.

[0011] [Prior Art Literature]

[0012] [Patent Document]

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

[0014]

[0015] The present invention has been devised to solve the problems of the above-mentioned prior art, and aims to provide a modified conjugated diene polymer having a highly branched structure and high molecular weight by being modified with a compound represented by chemical formula 1 having a plurality of coupling sites, and which can be applied to a rubber composition to improve compounding processability, tensile properties, and wear resistance.

[0016] In addition, the present invention aims to provide a method for producing the above-described modified conjugated diene polymer.

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

[0018]

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

[0020] (1) The present invention provides a modified conjugated diene polymer comprising a unit derived from a conjugated diene monomer; and a modified portion derived from a compound represented by the following chemical formula 1:

[0021] [Chemical Formula 1]

[0022]

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

[0024] [Chemical Formula 1a]

[0025]

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

[0027] (2) In the present invention, in the above (1), in the above chemical formula 1, R1, R2 and R4 to R7 are each independently an alkylene group 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 -SiR8R9R 10 and the above R8 to R 10 are independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, R8 to R 10 A modified conjugated diene polymer is provided, wherein 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.

[0028] (3) In the present invention, in the above (1) or (2), in the above chemical formula 1, R1, R2 and R4 to R7 are each independently an alkylene group 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 each independently a substituent represented by chemical formula 1a, and in the above chemical formula 1a, R 11 and R 12 are independently an alkylene group having 1 to 10 carbon atoms, and R 13 Inland R 18 are independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, R 13 Inland R 15 At least one of and R 16 Inland R 18 A modified conjugated diene polymer is provided, wherein 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.

[0029] (4) The present invention provides a modified conjugated diene polymer, wherein the compound represented by the chemical formula 1 in any one of the above (1) to (3) is at least one selected from compounds represented by the following chemical formulas 1-1 to 1-4:

[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 modified conjugated diene polymer having a weight average molecular weight of 700,000 g / mol or more and 2,000,000 g / mol or less in any one of the above (1) to (4).

[0040] (6) The present invention provides a modified conjugated diene polymer having a molecular weight distribution of 1.0 or more and 5.0 or less in any one of the above (1) to (5).

[0041] (7) The present invention provides a modified conjugated diene polymer having a Mooney viscosity of 70 or more and 150 or less as measured at 140°C, in any one of the above (1) to (6).

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

[0043] (9) The present invention provides a method for producing a modified conjugated diene polymer according to any one of (1) to (8), comprising the steps of (S1) producing an active polymer to which an organometallic compound is bonded by polymerizing a conjugated diene monomer, or an aromatic vinyl monomer and a conjugated diene monomer in a hydrocarbon solvent containing an organometallic compound; and (S2) reacting the active polymer with a compound represented by the following chemical formula 1:

[0044] [Chemical Formula 1]

[0045]

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

[0047] [Chemical Formula 1a]

[0048]

[0049] In the above chemical formula 1a, R 11 and R 12 are independently an alkylene group having 1 to 20 carbon atoms, and R 13 Inland R 18 are independently an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, R 13 Inland R 15 At least one of and R 16 Inland R 18 At 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 modified conjugated diene polymer, wherein the organometallic compound is used in an amount of 0.01 to 10 mmol based on 100 g of total monomers in (9).

[0051] (11) The present invention provides a method for producing a modified conjugated diene polymer, wherein the compound represented by the chemical formula 1 and the organometallic compound are used in a molar ratio of 1:0.1 to 1:5.0 in (9) or (10).

[0052] (12) The present invention provides a method for producing a modified conjugated diene polymer, wherein the compound represented by the chemical formula 1 in any one of the above (9) to (11) is at least one selected from compounds represented by the following chemical formulas 1-1 to 1-4:

[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 rubber composition comprising a modified conjugated diene polymer according to any one of (1) to (8) and a filler.

[0063]

[0064] The modified conjugated diene polymer according to the present invention is modified with a compound represented by the chemical formula 1 having many polymer modification functional group sites capable of reacting with active polymer terminals, thereby introducing a highly branched structure and thus having a high molecular weight, and can be applied to a rubber composition to improve the compounding processability of the rubber composition while simultaneously improving tensile properties and wear resistance.

[0065] The rubber composition according to the present invention has excellent mixing processability, tensile properties, and wear resistance by including the modified conjugated diene polymer.

[0066]

[0067] Hereinafter, the present invention will be described in more detail to help understand the present invention.

[0068] The terms or words used in the description and claims of the present invention should not be interpreted as limited to their usual or dictionary meanings, but should be interpreted as meanings and concepts that conform to the technical idea of ​​the present invention, based on the principle that the inventor can appropriately define the concept of the term to explain his or her own invention in the best way.

[0069]

[0070] Definition of Terms

[0071] As used herein, the term "polymer" refers to a polymer compound prepared 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 prepared from a single monomer, and the term "copolymer," as defined below.

[0072] As used herein, the term "copolymer" refers to a polymer prepared by polymerizing at least two different monomers. Thus, the general term "copolymer" includes binary copolymers, which are commonly used to refer to polymers prepared from two different monomers, and polymers prepared from two or more different monomers.

[0073] The term '1,2-vinyl bond content' in this specification refers to the mass (or weight) percentage of butadiene contained in the 1,2-position within the polymer chain of the polymer based on the portion derived from a conjugated diene monomer (such as butadiene) in the polymer (total amount of polymerized butadiene).

[0074] The term 'styrene bond content' in this specification refers to the mass (or weight) percentage of styrene contained in the polymer chain of the polymer derived from an aromatic vinyl monomer (such as styrene) among the polymers.

[0075] In this specification, the term 'room temperature' means the temperature in its natural state without heating or cooling, which is a temperature of 20±5℃.

[0076] 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 two or more substituents may be present depending on the number of hydrogens present in the functional group, atomic group, or compound, and when multiple substituents are present, each substituent may be the same or different from each other.

[0077] In this specification, the term 'alkyl group' may mean a monovalent aliphatic saturated hydrocarbon, and may mean all of linear alkyl groups such as methyl, ethyl, propyl, and butyl; branched alkyl groups such as isopropyl, sec-butyl, tert-butyl, and neopentyl; and cyclic saturated hydrocarbons, or cyclic unsaturated hydrocarbons containing one or more unsaturated bonds.

[0078] In this specification, the term 'alkylene group' may mean a divalent aliphatic saturated hydrocarbon such as methylene, ethylene, propylene, and butylene.

[0079] In this specification, the terms 'derived unit', 'derived repeating unit' and 'derived functional group' may mean a component, structure or the substance itself derived from a substance.

[0080] In this specification, the term 'single bond' may mean a single covalent bond itself that does not involve separate atoms or molecular groups.

[0081] The terms "comprising," "having," and their derivatives, as used herein, are not intended to exclude the presence of any additional component, step, or procedure, whether or not specifically disclosed. In order to avoid any doubt, all compositions claimed through use of the term "comprising" may include any additional additive, adjuvant, or compound, whether polymeric or otherwise, unless stated to the contrary. In contrast, the term "consisting essentially of" excludes from the scope of any succeeding description any other component, step, or procedure, excepting those not essential to operability. The term "consisting of" excludes any component, step, or procedure not specifically described or listed.

[0082]

[0083] Measurement method and conditions

[0084] In this specification, 'weight average molecular weight (Mw)' and 'molecular weight distribution (MWD)' were measured by GPC (Gel permeation chromatograph) (PL GPC220, Agilent Technologies) under the following conditions, and a molecular weight distribution curve was obtained. The molecular weight distribution (PDI, MWD, Mw / Mn) was obtained by calculating from each of the measured molecular weights.

[0085] - Column: Two PLgel Olexis (Polymer Laboratories) columns and one PLgel mixed-C (Polymer Laboratories) column were used in combination.

[0086] - Solvent: Use a mixture of 2 wt% amine compound in tetrahydrofuran.

[0087] - Flow rate: 1 ml / min

[0088] - Sample concentration: 1~2 mg / ml (diluted in THF)

[0089] - Injection volume: 100 ㎕

[0090] - Column temperature: 40℃

[0091] - Detector: Refractive index

[0092] - Standard: Polystyrene (corrected with a cubic function)

[0093] In this specification, 'Mooney viscosity' was measured using a Mooney viscometer, e.g., a Large Rotor from MV2000E (ALPHA Technologies), at 140°C and a Rotor Speed ​​of 2±0.02 rpm. Specifically, the polymer was left at room temperature (23±5°C) for more than 30 minutes, 27±3 g was collected, filled into the die cavity, and the measurement was performed while operating the platen and applying torque.

[0094]

[0095] Modified conjugated diene polymer

[0096] The present invention provides a modified 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.

[0097] The modified conjugated diene polymer according to one embodiment of the present invention is characterized by including a unit derived from a conjugated diene monomer; and a modified portion derived from a compound represented by the following chemical formula 1.

[0098] [Chemical Formula 1]

[0099]

[0100] In the above chemical formula 1, R1, R2 and R4 to R7 are each independently an alkylene group having 1 to 20 carbon atoms, R3 is a single bond or an alkylene group having 1 to 20 carbon atoms, A1 to A4 are independently -SiR8R9R 10 Or a substituent represented by the following chemical formula 1a, and the above R8 to R 10 are independently an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, R8 to R 10 At least one of them is an alkoxy group having 1 to 20 carbon atoms, n is an integer from 1 to 10,

[0101] [Chemical Formula 1a]

[0102]

[0103] In the above chemical formula 1a,

[0104] R 11 and R 12 are independently an alkylene group having 1 to 20 carbon atoms, and R 13 Inland R 18 are independently an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, R 13 Inland R 15 At least one of and R 16 Inland R 18 At least one of them is an alkoxy group having 1 to 20 carbon atoms.

[0105] Specifically, in the above chemical formula 1, R1, R2 and R4 to R7 are each independently an alkylene group 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 -SiR8R9R 10 and the above R8 to R 10 are independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, 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 of 2 to 8. More specifically, in the above chemical formula 1, R1, R2 and R4 to R7 are each independently an alkylene group 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 -SiR8R9R 10 and the above R8 to R 10 are independently an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, 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.

[0106] In addition, in the above chemical formula 1, R1, R2 and R4 to R7 are each independently an alkylene group 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 each independently a substituent represented by chemical formula 1a, and in the above chemical formula 1a, R 11 and R 12 are independently an alkylene group having 1 to 10 carbon atoms, and R 13 Inland R 18 are independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, R 13 Inland R 15 At least one of and R 16 Inland 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 chemical formula 1, R1, R2 and R4 to R7 are each independently an alkylene group 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 each independently a substituent represented by the chemical formula 1a, and in the above chemical formula 1a, R 11 and R 12 are independently an alkylene group having 1 to 6 carbon atoms, and R 13 Inland R 18 are independently an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, R 13 Inland R 15 At least one of and R 16 Inland 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.

[0107] More specifically, the compound represented by the above chemical formula 1 may be at least one selected from compounds represented by the following chemical formulas 1-1 to 1-4.

[0108] [Chemical Formula 1-1]

[0109]

[0110] [Chemical Formula 1-2]

[0111]

[0112] [Chemical Formula 1-3]

[0113]

[0114] [Chemical Formula 1-4]

[0115]

[0116] In the above chemical formulas 1-1 to 1-4, Me is a methyl group.

[0117]

[0118] The modified conjugated diene polymer according to the present invention is modified with a compound represented by Chemical Formula 1 that provides a plurality of coupling sites, so that the polymer can have a significantly increased affinity for a filler by introducing a modified portion, which is a filler-affinity functional group derived from the compound represented by Chemical Formula 1, into the polymer chain along with an increase in coupling bonds between polymer chains, and can be applied to a rubber composition to improve compounding processability, tensile properties, and wear resistance.

[0119]

[0120] Meanwhile, the compound represented by the above chemical formula 1 may be produced from a production method including a step of reacting a compound represented by the following chemical formula 2 with a compound represented by the following chemical formula 3 or a compound represented by the following chemical formula 4.

[0121] [Chemical Formula 2]

[0122]

[0123] In the above chemical formula 2, R 19 and R 20 are independently an alkylene group having 1 to 20 carbon atoms, and R 21 is a single bond or an alkylene group having 1 to 20 carbon atoms, m is an integer from 1 to 10,

[0124] [Chemical Formula 3]

[0125]

[0126] In the above chemical formula 3, R 22 is an alkylene group having 1 to 20 carbon atoms, and R 23 Inland R 25 are independently an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, R 23 Inland R 25 At least one of them is an alkoxy group having 1 to 20 carbon atoms, X1 is a halogen element,

[0127] [Chemical Formula 4]

[0128]

[0129] In the above chemical formula 4, R 26 Inland R 28 are independently an alkylene group having 1 to 20 carbon atoms, and R 29 Inland R 34 are independently an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, R 29 Inland R 31 At least one of and R 32 Inland R 34 At least one of them is an alkoxy group having 1 to 20 carbon atoms, and X2 is a halogen element.

[0130] The above reaction can be carried out at a temperature of 120°C or higher, specifically 120°C to 200°C or 140°C to 180°C, in a reaction solvent under basic conditions. In this case, the reaction conversion rate can be better, which can be advantageous for improving the yield.

[0131] The above basic conditions can be formed using a basic compound, and the basic compound can be used without particular limitation as long as it is a tertiary amine compound commonly used in the art, but for example, triethylamine, diisopropylamine, or a mixture thereof can be used.

[0132] In addition, the above reaction may further use potassium iodide (KI), potassium bromide (KBr), or a mixture thereof, which acts as a catalyst, if necessary, and in this case, it may be advantageous to achieve a smoother target reaction by increasing the reaction activity and improving the reaction rate.

[0133] In addition, the compound represented by the above chemical formula 2 and the compound represented by the chemical formula 3 or the compound represented by the chemical formula 4 may be reacted at an appropriate ratio according to the stoichiometric ratio, but specifically, the reaction may be performed at a molar ratio of 1:4 to 8. In this case, the reaction rate may be improved without excessive residual substances.

[0134] Also, in the above chemical formula 2, R 19 and R 20 are independently an alkylene group 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 may be an integer from 2 to 8. Specifically, R 19 and R 20 are independently an alkylene group 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.

[0135] Also, in the above chemical formula 3, R 22 is an alkylene group having 1 to 10 carbon atoms, and R 23 Inland R 25 are independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, R 23 Inland 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.

[0136] Specifically, in the above chemical formula 3, R 22 is an alkylene group having 1 to 6 carbon atoms, and R23 Inland R 25 are independently an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, R 23 Inland R 25 At least one of them is an alkoxy group having 1 to 6 carbon atoms, and X1 may be Cl.

[0137] Also, in the above chemical formula 4, R 26 Inland R 28 are independently an alkylene group having 1 to 10 carbon atoms, and R 29 Inland R 34 are independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, R 29 Inland R 31 At least one of and R 32 Inland 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.

[0138] Specifically, in the above chemical formula 4, R 26 Inland R 28 are independently an alkylene group having 1 to 6 carbon atoms, and R 29 Inland R 34 are independently an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, R 29 Inland R 31 At least one of and R 32 Inland R 34 At least one of them is an alkoxy group having 1 to 6 carbon atoms, and X2 may be Cl.

[0139]

[0140] In addition, the above-described modified conjugated diene polymer has a conjugated diene monomer-derived unit as its main unit, and the conjugated diene monomer may have a conjugated molecular structure in which single bonds and double bonds (or multiple bonds) are alternately connected, and may include a hydrocarbon compound having two double bonds in the molecule. In addition, the conjugated diene monomer may be at least one 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 a halogen atom), 1,3-pentadiene, 1-methyl-1,3-pentadiene, 1,3-hexadiene, and 4,5-diethyl-1,3-octadiene.

[0141] In addition, the above-mentioned modified conjugated diene polymer may further include an aromatic vinyl monomer in addition to the conjugated diene monomer and may further include a derived unit thereof. The aromatic vinyl monomer may be, for example, 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 at least one selected from the group consisting of 3-(2-pyrrolidino-1-methyl ethyl)-α-methylstyrene.

[0142] As another example, the modified conjugated diene polymer may be a copolymer further comprising a repeating unit derived from a diene monomer having 1 to 10 carbon atoms, together with a repeating unit derived from the conjugated diene monomer. The repeating unit derived from the diene monomer may be a repeating unit 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 polymer is a copolymer further comprising a diene monomer, the conjugated diene polymer may comprise the diene monomer-derived repeating unit in an amount of more than 0 wt% to 1 wt%, more than 0 wt% to 0.1 wt%, more than 0 wt% to 0.01 wt%, or more than 0 wt% to 0.001 wt%, and within this range, there is an effect of preventing gel formation.

[0143] According to one embodiment of the present invention, when two or more monomers are included in the chain of the conjugated diene polymer, it can have a chain structure that is intermediate between a random copolymer and a block copolymer, in which case the microstructure can be easily controlled, and thus there is an excellent effect of balance between each physical property. The random copolymer can mean that the repeating units forming the copolymer are arranged in a random manner.

[0144]

[0145] According to one embodiment of the present invention, the modified conjugated diene polymer may have a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of 300,000 g / mol to 3,000,000 g / mol, 400,000 g / mol to 2,500,000 g / mol, 500,000 g / mol to 2,000,000 g / mol, 700,000 g / mol to 2,000,000 g / mol, 800,000 g / mol to 2,000,000 g / mol, or 900,000 g / mol to 2,000,000 g / mol, and within this range, when applied to a rubber composition, it has the effect of improving wear resistance while providing excellent compounding processability.

[0146] In addition, the modified conjugated diene polymer according to one embodiment of the present invention may be a high molecular weight polymer having a weight average molecular weight of 800,000 g / mol or more, preferably 1,000,000 g / mol or more, and thus a polymer having excellent tensile properties may be realized, and this can be achieved by implementing the effect of elongating the polymer chain along with controlling the microstructure when manufactured according to the above-described manufacturing method.

[0147] According to one embodiment of the present invention, the modified conjugated diene polymer may have a number average molecular weight (Mn) of 1,000 g / mol to 2,000,000 g / mol, 10,000 g / mol to 1,500,000 g / mol, or 100,000 g / mol to 1,200,000 g / mol, and the number average molecular weight may be preferably 400,000 g / mol or more, more preferably 500,000 g / mol or more. In addition, the peak top molecular weight (Mp) may be 1,000 g / mol to 3,000,000 g / mol, 10,000 g / mol to 2,000,000 g / mol, or 100,000 g / mol to 2,000,000 g / mol. Within this range, excellent driving resistance and wet road resistance are achieved.

[0148] Additionally, the modified conjugated diene polymer may have a molecular weight distribution of 1.0 to 5.0, specifically 1.5 to 4.0, 1.7 to 3.0, or 2.0 to 2.5.

[0149] As another example, the modified conjugated diene polymer may have a molecular weight distribution of 1.0 to 3.0, specifically 1.0 to 2.5, or 1.0 to 2.0.

[0150] In addition, the 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 70 to 150, specifically 75 to 150, 80 to 150, 85 to 150, 90 to 150, or 100 to 150. There may be various criteria for evaluating processability, but when the Mooney viscosity satisfies the above range, the processability may be considerably excellent.

[0151] As another example, the modified conjugated diene polymer according to one embodiment of the present invention must have a Mooney viscosity of 40 to 120 as measured under ASTM D1646 conditions, and preferably 45 to 100. There may be various measures for evaluating processability, but when the Mooney viscosity satisfies the above range, the processability may be considerably excellent.

[0152] In addition, the 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 may be adjusted to an appropriate range, thereby exhibiting excellent rolling resistance, wet road resistance, and fuel efficiency. Here, the vinyl content may refer to the content of a 1,2-added, not a 1,4-added, conjugated diene monomer relative to 100 wt% of a conjugated diene copolymer composed of a monomer having a vinyl group and an aromatic vinyl monomer.

[0153]

[0154] Method for producing a modified conjugated diene polymer

[0155] In addition, the present invention provides a method for producing the modified conjugated diene polymer.

[0156] The method for producing the modified conjugated diene polymer according to one embodiment of the present invention comprises the steps of (S1) producing an active polymer to which an organometallic compound is bonded by polymerizing a conjugated diene monomer, or an aromatic vinyl monomer and a conjugated diene monomer, in a hydrocarbon solvent containing an organometallic compound (step 1); and (S2) reacting the active polymer with a compound represented by the following chemical formula 1 (step 2).

[0157] [Chemical Formula 1]

[0158]

[0159] The definition of each substituent in the above chemical formula 1 is as defined above.

[0160]

[0161] The above step 1 is a step for producing an active polymer to which an organometallic compound is bound, and 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.

[0162] The hydrocarbon solvent is not particularly limited, but may be at least one selected from the group consisting of n-pentane, n-hexane, n-heptane, isooctane, cyclohexane, toluene, benzene, and xylene.

[0163] The above conjugated diene monomer and aromatic vinyl monomer are as defined above.

[0164]

[0165] According to one embodiment of the present invention, the organometallic compound can 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.

[0166] The above organometallic compound may be, for example, at least one selected from the group consisting of methyllithium, ethyllithium, propyllithium, n-butyllithium, s-butyllithium, t-butyllithium, hexyllithium, n-decyllithium, t-octyllithium, phenyllithium, 1-naphthyllithium, n-eicosyllithium, 4-butylphenyllithium, 4-tolyllithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium, naphthylsodium, naphthylpotassium, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide, and lithium isopropylamide.

[0167] Meanwhile, the polymerization of step 1 may be carried out including a polar additive, and the polar additive may be added in an amount of 0.001 to 50 g, 0.001 to 10 g, 0.005 to 0.2 g, or 0.01 to 0.2 g based on 100 g of total monomer.

[0168] In addition, the polar additive may be at least one selected from the group consisting of tetrahydrofuran, 2,2-di(tetrahydrofuryl)propane, diethyl ether, cyclopentyl ether, dipropyl ether, ethylenedimethyl ether, diethyl glycol, dimethyl ether, tert-butoxyethoxyethane, bis(3-dimethylaminoethyl)ether, (dimethylaminoethyl)ethyl ether, trimethylamine, triethylamine, tripropylamine, and tetramethylethylenediamine, and specifically, may be triethylamine or tetramethylethylenediamine, and when the polar additive is included, when copolymerizing a conjugated diene monomer, or a conjugated diene monomer and an aromatic vinyl monomer, there is an effect of inducing easy formation of a random copolymer by compensating for the difference in reaction speeds thereof.

[0169] 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 terminal by a growth polymerization reaction by anion. In addition, the polymerization of step 1 above may be temperature-raising polymerization, isothermal polymerization, or isothermal polymerization (adiabatic polymerization), and the isothermal polymerization may refer to a polymerization method including a step of polymerizing by the heat of reaction itself without arbitrarily applying heat after introducing an organometallic compound, the temperature-raising polymerization may refer to a polymerization method of increasing the temperature by arbitrarily applying heat after introducing the organometallic compound, and the isothermal polymerization may refer to a polymerization method of maintaining the temperature of the polymer product constant by increasing the heat by applying heat or removing heat after introducing the organometallic compound.

[0170] In addition, the polymerization of step 1 can 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.

[0171] The active polymer manufactured by the above step 1 may mean a polymer in which a polymer anion and an organic metal cation are combined.

[0172]

[0173] The above step 2 is a step of reacting the active polymer with the compound represented by the above chemical formula 1 to produce a modified conjugated diene polymer.

[0174] According to one embodiment of the present invention, the compound represented by the 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.

[0175] As another example, the compound represented by the above chemical formula 1 can be used in an amount of 0.01 mmol to 10 mmol based on 100 g of the total monomer.

[0176] In addition, according to one embodiment of the present invention, the compound represented by the chemical formula 1 and the organometallic compound can be used in a molar ratio of 1:0.1 to 10, a molar ratio of 1:0.1 to 1:5.0, a molar ratio of 1:0.1 to 1:4.0, or a molar ratio of 1:0.1 to 1:3, and a modification reaction with optimal performance can be performed within this range, thereby obtaining a high molecular weight conjugated diene polymer.

[0177] The reaction of step 2 above is a modification reaction for introducing a functional group derived from the denaturant into the active polymer, and may be performed at 0°C to 90°C for 1 minute to 5 hours.

[0178] In addition, according to one embodiment of the present invention, the method for producing the modified conjugated diene polymer may be performed by a batch method or a continuous polymerization method including one or more reactors.

[0179] The above-described method for producing a modified conjugated diene polymer may further include, as an example, one or more steps of solvent and unreacted monomer recovery and drying steps following step 2 of the present invention, if necessary.

[0180]

[0181] rubber composition

[0182] Furthermore, the present invention provides a rubber composition comprising the modified conjugated diene polymer.

[0183] The rubber composition according to one embodiment of the present invention may contain the modified conjugated diene polymer in an amount of 10 wt% or more, 10 wt% to 100 wt%, or 20 wt% to 90 wt%, and within this range, the rubber composition has excellent mechanical properties such as tensile strength and wear resistance, and has an excellent balance between each property.

[0184] In addition, the rubber composition may further include other rubber components as needed in addition to the modified conjugated diene polymer, and in this case, the rubber component may be included in an amount of 90% by weight or less based on the total weight of the rubber composition. As a specific example, the other rubber component may be included in an amount of 1 to 900 parts by weight based on 100 parts by weight of the modified conjugated diene polymer.

[0185] The above rubber component may be, for example, natural rubber or synthetic rubber, and specific examples thereof include natural rubber (NR) including cis-1,4-polyisoprene; modified natural rubber such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber, which are modified or refined from the above general natural rubber; It may be a 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, halogenated butyl rubber, and any one or a mixture of two or more of these may be used.

[0186] The above rubber composition may contain, for example, 0.1 to 200 parts by weight, or 10 to 120 parts by weight, of a filler based on 100 parts by weight of the modified conjugated diene polymer of the present invention. The filler may be, for example, a silica-based filler, and specific examples thereof include wet silica (hydrated silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate, or colloidal silica, and preferably wet silica, which has the best effect of improving fracture properties and achieving wet grip. In addition, the rubber composition may further contain a carbon black-based filler, if necessary.

[0187] As another example, when silica is used as the filler, a silane coupling agent may be used together to improve reinforcing properties and low heat generation properties, and specific examples of the silane coupling agent include 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, 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 the like, and any one or a mixture of two or more of these may be used. Preferably, considering the effect of improving reinforcing properties, it may be bis(3-triethoxysilylpropyl)polysulfide or 3-trimethoxysilylpropylbenzothiazyltetrasulfide.

[0188] In addition, since the rubber composition according to one embodiment of the present invention uses a modified conjugated diene polymer having a functional group having high affinity for silica introduced into an active site as a rubber component, the amount of the 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, based on 100 parts by weight of silica, and within this range, the effect as a coupling agent is sufficiently exerted while also having the effect of preventing gelation of the rubber component.

[0189] The rubber composition according to one embodiment of the present invention may be sulfur crosslinkable and may further include a vulcanizing agent. The vulcanizing agent may be specifically sulfur powder and may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the rubber component. Within this range, the vulcanized rubber composition secures the required elastic modulus and strength while exhibiting excellent fuel efficiency.

[0190] The rubber composition according to one embodiment of the present invention may further include, in addition to the above-described components, various additives commonly used in the rubber industry, specifically, a vulcanization accelerator, a process oil, a plasticizer, an anti-aging agent, a scorch inhibitor, zinc white, stearic acid, a thermosetting resin, or a thermoplastic resin.

[0191] The above-mentioned vulcanization accelerator may be, for example, a thiazole-based compound such as M(2-mercaptobenzothiazole), DM(dibenzothiazyl disulfide), 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 based on 100 parts by weight of the rubber component.

[0192] The above process oil acts as a softener in the rubber composition, and may be, for example, a paraffinic, naphthenic, or aromatic compound. When considering tensile strength and wear resistance, an aromatic process oil may be used, and when considering hysteresis loss and low-temperature characteristics, a naphthenic or paraffinic process oil may be used. The above process oil may be included in an amount of, for example, 100 parts by weight or less based on 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.

[0193] The above-mentioned 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 condensate of diphenylamine and acetone, and may be used in an amount of 0.1 to 6 parts by weight based on 100 parts by weight of the rubber component.

[0194] 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 compounding prescription, and a rubber composition having low heat generation and excellent wear resistance can be obtained by a vulcanization process after molding processing.

[0195] Accordingly, the rubber composition can be useful in the manufacture of various industrial rubber products such as tire tread, undertread, side wall, carcass coating rubber, belt coating rubber, bead filler, squeegee, or bead coating rubber, as well as various parts of a tire, such as vibration-proof rubber, belt conveyor, and hose.

[0196]

[0197] In addition, the present invention provides a tire manufactured using the rubber composition.

[0198] The above tire may include a tire or tire tread.

[0199]

[0200] Example

[0201] Hereinafter, the present invention will be described in detail with examples to specifically illustrate it. However, the examples according to the present invention may be modified in various ways, and the scope of the present invention should not be construed as being limited to the examples described below. These examples are provided to more fully explain the present invention to those of average skill in the art.

[0202] Manufacturing Example 1

[0203] 1.48 g (10 mmol) of 2,2'-(ethane-1,2-diylbis(oxy))bis(ethan-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 with stirring at 150°C for 24 hours. After completion of the reaction, the temperature was lowered to room temperature, and 40 ml (1:5 volume ratio) of a mixture of dimethylformamide and hexane was added, stirred for 15 minutes, and the dimethylformamide layer was extracted with hexane, and the solution and impurities were removed by distillation under reduced pressure to prepare a compound represented by the chemical formula 1-1 as a light brown oil. The prepared compound is 1 It was confirmed that it was synthesized through H NMR analysis.

[0204] [Chemical Formula 1-1]

[0205]

[0206] In the above chemical formula 1-1, Me is a methyl group.

[0207] 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).

[0208]

[0209] Manufacturing Example 2

[0210] 1.48 g (10 mmol) of 2,2'-(ethane-1,2-diylbis(oxy))bis(ethan-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)propan-1-amine were reacted with stirring at 150°C for 24 hours. After completion of the reaction, the temperature was lowered to room temperature, and 40 ml (1:5 volume ratio) of a mixture of dimethylformamide and hexane was added, stirred for 15 minutes, and the dimethylformamide layer was extracted with hexane, and the solution and impurities were removed by distillation under reduced pressure to prepare a compound represented by the chemical formula 1-2 as a light brown oil. The prepared compound is 1 It was confirmed that it was synthesized through H NMR analysis.

[0211] [Chemical Formula 1-2]

[0212]

[0213] In the above chemical formula 1-2, Me is a methyl group.

[0214] 1 H NMR (500 MHz, CDCl3) δ 3.58 (s, 76H), 2.67-2.42 (m, 40H), 0.63-0.60 (m, 16 H).

[0215]

[0216] Manufacturing Example 3

[0217] 2.20 g (10 mmol) of 3,3'-((oxybis(ethane-2,1-diyl))bis(oxy))bis(propan-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 with stirring at 150°C for 24 hours. After completion of the reaction, the temperature was lowered to room temperature, and 40 ml (1:5 volume ratio) of a mixture of dimethylformamide and hexane was added, stirred for 15 minutes, and the dimethylformamide layer was extracted with hexane, and the solution and impurities were removed by distillation under reduced pressure to prepare a compound represented by the chemical formula 1-3 as a light brown oil. The prepared compound is 1 It was confirmed that it was synthesized through H NMR analysis.

[0218] [Chemical Formula 1-3]

[0219]

[0220] In the above chemical formula 1-3, Me is a methyl group.

[0221] 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).

[0222]

[0223] Manufacturing Example 4

[0224] 2.20 g (10 mmol) of 3,3'-((oxybis(ethane-2,1-diyl))bis(oxy))bis(propan-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)propan-1-amine were reacted with stirring at 150°C for 24 hours. After completion of the reaction, the temperature was lowered to room temperature, and 40 ml (1:5 volume ratio) of a mixture of dimethylformamide and hexane was added, stirred for 15 minutes, and the dimethylformamide layer was extracted with hexane, and the solution and impurities were removed by distillation under reduced pressure to prepare a compound represented by the chemical formula 1-4 as a light brown oil. The prepared compound is 1 It was confirmed that it was synthesized through H NMR analysis.

[0225] [Chemical Formula 1-4]

[0226]

[0227] In the above chemical formula 1-4, Me is a methyl group.

[0228] 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).

[0229]

[0230] Example 1

[0231] In a 20 L autoclave reactor, 4,712.00 g of n-hexane, 210.00 g of styrene, 750.5 g of 1,3-butadiene, and 0.25 g of N,N,N',N'-tetramethylethylenediamine (TMEDA) as a polar additive were charged, then 5.00 g of n-butyllithium (10 wt% in n-hexane) was added, and the internal temperature of the reactor was adjusted to 40°C to conduct an adiabatic temperature-raising reaction. After 30 minutes, 39.50 g of 1,3-butadiene was added to cap the polymer terminals with butadiene. Afterwards, 1.90 g of the compound represented by Chemical Formula 1-1 manufactured in the above Manufacturing Example 1 was added as a denaturant and reacted for 40 minutes ([TMEDA]:[act. Li]=0.46:1 molar ratio, [denaturant]:[act. Li]=0.51:1 molar ratio). Afterwards, the reaction was stopped using ethanol, and 17 g of a solution in which Wingstay K, an antioxidant, was dissolved in hexane at 30 wt% was added. The resulting polymer 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, thereby manufacturing a modified styrene-butadiene copolymer.

[0232]

[0233] Example 2

[0234] A modified styrene-butadiene copolymer was manufactured in the same manner as in Example 1, except that the compound represented by Chemical Formula 1-2 manufactured in Preparation Example 2 was used instead of the compound represented by Chemical Formula 1-1 in Example 1 ([TMEDA]:[act. Li]=0.46:1 molar ratio, [modifier]:[act. Li]=0.26:1 molar ratio).

[0235]

[0236] Example 3

[0237] A modified styrene-butadiene copolymer was manufactured in the same manner as in Example 1, except that the compound represented by Chemical Formula 1-3 manufactured in Preparation Example 3 was used instead of the compound represented by Chemical Formula 1-1 in Example 1 ([TMEDA]:[act. Li]=0.46:1 molar ratio, [modifier]:[act. Li]=0.51:1 molar ratio).

[0238]

[0239] Example 4

[0240] A modified styrene-butadiene copolymer was manufactured in the same manner as in Example 1, except that the compound represented by Chemical Formula 1-4 manufactured in Preparation Example 4 was used instead of the compound represented by Chemical Formula 1-1 in Example 1 ([TMEDA]:[act. Li]=0.46:1 molar ratio, [modifier]:[act. Li]=0.26:1 molar ratio).

[0241]

[0242] Comparative Example 1

[0243] 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 Chemical Formula 1-1 in Example 1 ([TMEDA]:[act. Li]=0.46:1 molar ratio, [modifier]:[act. Li]=1:1 molar ratio).

[0244]

[0245] Comparative Example 2

[0246] 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)propan-1-amine was used instead of the compound represented by Chemical Formula 1-1 in Example 1 ([TMEDA]:[act. Li]=0.46:1 molar ratio, [modifier]:[act. Li]=0.6:1 molar ratio).

[0247]

[0248] Experimental Example 1. Evaluation of Polymer Properties

[0249] For each modified styrene-butadiene copolymer manufactured in the above examples and comparative examples, the styrene unit content and vinyl content in the polymer, and the weight average molecular weight (Mw, ×10 3 g / mol), number-average molecular weight (Mn, ×10 3 g / mol), molecular weight distribution (MWD) and Mooney viscosity (MV) were measured, respectively.

[0250]

[0251] 1) Styrene bond content and 1,2-vinyl bond content

[0252] The styrene bond content (SM) and 1,2-vinyl bond content (Vi) in each polymer were measured and analyzed using a Varian VNMRS 500 MHz NMR. 1,1,2,2-tetrachloroethane was used as the solvent for NMR measurements, and the solvent peak was calculated as 6.00 ppm. 7.2–6.9 ppm was random styrene, 6.9–6.2 ppm was block styrene, 5.8–5.1 ppm was 1,4-vinyl and 1,2-vinyl, and 5.1–4.5 ppm was 1,2-vinyl. Based on this, the styrene unit bond content and 1,2-vinyl bond content were calculated.

[0253]

[0254] 2) Weight average molecular weight (Mw, ×10 3 g / mol), number-average molecular weight (Mn, ×10 3 g / mol) and molecular weight distribution (MWD)

[0255] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) were measured using gel permeation chromatography (GPC) (PL GPC220, Agilent Technologies) under the following conditions, and the molecular weight distribution (MWD, Mw / Mn) was calculated from the measured molecular weights.

[0256] - Column: Two PLgel Olexis (Polymer Laboratories) columns and one PLgel mixed-C (Polymer Laboratories) column were used in combination.

[0257] - Solvent: Use a mixture of 2 wt% amine compound in tetrahydrofuran.

[0258] - Flow rate: 1 mL / min

[0259] - Sample concentration: 1~2 mg / mL (diluted in THF)

[0260] - Injection volume: 100 uL

[0261] - Column temperature: 40℃

[0262] - Detector: Refractive index

[0263] - Standard: Polystyrene (corrected with a cubic function)

[0264]

[0265] 3) Mooney point

[0266] The Mooney viscosity (MV, (ML1+4, @140℃)) above was measured using 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 more than 30 minutes, and then 27±3 g was collected and filled into the die cavity, and the platen was operated for measurement for 4 minutes.

[0267]

[0268] As shown in Table 1 above, it was confirmed that Examples 1 to 4 had a significantly increased weight average molecular weight and a significantly increased Mooney viscosity compared to Comparative Examples 1 to 2.

[0269] Through this, it was confirmed that the modified conjugated diene polymer according to the present invention was modified with a compound represented by chemical formula 1 that provides a number of coupling sites, thereby increasing the coupling bonds between chains constituting the polymer, and at the same time, a modified portion derived from the compound was introduced into the polymer chain, thereby being highly modified with a highly branched structure and high molecular weight.

[0270]

[0271] Experimental Example 2

[0272] In order to compare and analyze the properties of the rubber compositions containing the modified styrene-butadiene copolymers prepared in the above examples and comparative examples and the molded articles prepared therefrom, the tensile properties, wear resistance, processability, and viscoelastic properties were measured. The results are shown in Table 3 below.

[0273] 1) Manufacturing of rubber specimens

[0274] The modified conjugated diene polymers of the examples and comparative examples were mixed as raw rubber under the mixing 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.

[0275]

[0276] Specifically, the above rubber specimen is kneaded through first-stage kneading and second-stage kneading. In the first stage mixing, raw rubber, silica (filler), organosilane coupling agent (X50S, Evonik), process oil (TDAE oil), zincating agent (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 the first mixture was obtained at a discharge temperature of 150℃. In the second stage mixing, the first mixture was cooled to room temperature, and then the first mixture, sulfur powder, rubber accelerator (DPG (diphenylguanidine)) and vulcanization accelerator (CZ (N-cyclohexyl-2-benzothiazylsulfenamide)) were added to the mixer. and mixed at a temperature below 100℃ to obtain a secondary compound. Afterwards, a curing process was performed at 160℃ for 20 minutes to manufacture a rubber specimen.

[0277]

[0278] 2) Tensile properties

[0279] Tensile properties were measured by manufacturing each test specimen according to the tensile test method of ASTM 412, and measuring the tensile stress at 300% elongation (300% modulus), breaking strength (tensile strength), tensile rate, and toughness of the test specimen.

[0280] Specifically, tensile properties were measured at room temperature at a speed of 50 cm / min using a Universal Test Machin 4204 (Instron) tensile tester. The results in Table 3 are expressed as Index (%) based on the results of Comparative Example 1, with a higher value indicating better results.

[0281]

[0282] 3) Viscoelastic properties

[0283] Viscoelastic properties were measured by changing the strain at each measurement temperature (-60℃~70℃) at a frequency of 10 Hz in torsional mode using a dynamic mechanical analyzer (TA Corporation) and measuring tan δ. The higher the low-temperature 0℃ tan δ, the better the wet road resistance, and the lower the high-temperature 70℃ tan δ, the less hysteresis loss and the better the rolling resistance (fuel efficiency). However, the results in Table 3 are expressed by indexing the measured values ​​of Comparative Example 1 as the reference values, so a higher number indicates better.

[0284]

[0285] 4) Processability characteristics

[0286] The Mooney viscosity (MV, (ML1+4, at 125℃)) of the secondary compound obtained during the manufacture of the above 1) rubber specimen was measured to compare and analyze the processability characteristics of each polymer. At this time, the lower the Mooney viscosity measurement value, the better the processability characteristics are. However, the result values ​​in Table 3 are expressed by indexing the measurement value of Comparative Example 1 as the reference value, so a higher value indicates better results.

[0287] Specifically, using MV-2000 (ALPHA Technologies Co.), a large rotor at 125°C with a rotor speed of 2±0.02 rpm, each secondary compound was left at room temperature (23±5°C) for more than 30 minutes, and then 27±3 g was collected and filled into the die cavity, and the platen was operated for measurement for 4 minutes.

[0288]

[0289] 5) Wear resistance (DIN wear test)

[0290] For each rubber specimen, a DIN abrasion test was performed in accordance with ASTM D5963, and the DIN loss index (loss volume index: ARIA (Abration resistance index, Method A)) was expressed. A higher value indicates better performance.

[0291]

[0292] As shown in Table 3 above, it was confirmed that the modified styrene-butadiene copolymers of the examples had the effect of improving tensile properties, viscoelastic properties, wear resistance, and processability properties in a balanced manner. Specifically, Examples 1 to 4 showed tensile properties and processability properties that were significantly improved by about 10% or more compared to Comparative Example 1, and viscoelastic properties and wear resistance that were significantly improved by about 20% or more.

[0293] In addition, Comparative Example 2, which was manufactured using a conventionally known aminoalkoxysilane-based modifier, showed significantly lower tensile strength and processability characteristics compared to Comparative Example 1, and thus did not exhibit excellent balanced tensile properties, processability characteristics, wear resistance, and viscoelastic properties.

[0294] Through the above results, it can be seen that the modified conjugated diene polymer of the present invention has excellent filler affinity by including a modified portion derived from the compound represented by the chemical formula 1, which is modified with a compound represented by the chemical formula 1 having many polymer modification functional group sites capable of reacting with active polymer terminals, and can have a high molecular weight by introducing a highly branched structure, and thus has the effect of improving the compounding processability of the rubber composition when applied to the rubber composition while improving tensile properties, viscoelastic properties, and wear resistance at the same time.

Claims

1. Unit derived from conjugated diene monomer; and A modified conjugated diene polymer comprising a modified portion derived from a compound represented by the following chemical formula 1: [Chemical Formula 1] In the above chemical formula 1, R1, R2 and R4 to R7 are each independently an alkylene group having 1 to 20 carbon atoms, R3 is a single bond or an alkylene group having 1 to 20 carbon atoms, A1 to A4 are independently -SiR8R9R 10 Or a substituent represented by the following chemical formula 1a, and the above R8 to R 10 are independently an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, R8 to R 10 At least one of them is an alkoxy group having 1 to 20 carbon atoms, n is an integer from 1 to 10, [Chemical Formula 1a] In the above chemical formula 1a, R 11 and R 12 are independently an alkylene group having 1 to 20 carbon atoms, R 13 Inland R 18 are independently an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, R 13 Inland R 15 At least one of and R 16 Inland 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 each independently an alkylene group 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 -SiR8R9R 10 and the above R8 to R 10 are independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, R8 to R 10 A modified conjugated diene polymer, wherein 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 each independently an alkylene group 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 each independently a substituent represented by chemical formula 1a, In the above chemical formula 1a, R 11 and R 12 are independently an alkylene group having 1 to 10 carbon atoms, and R 13 Inland R 18 are independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, R 13 Inland R 15 At least one of and R 16 Inland R 18 A modified conjugated diene polymer, wherein 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 modified conjugated diene polymer wherein the compound represented by the above chemical formula 1 is any one selected from compounds represented by the following chemical formulas 1-1 to 1-4: [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, A modified conjugated diene polymer having a weight average molecular weight of 700,000 g / mol or more and 2,000,000 g / mol or less.

6. In paragraph 1, A modified conjugated diene polymer having a molecular weight distribution of 1.0 or more and 5.0 or less.

7. In paragraph 1, A modified conjugated diene polymer having a Mooney viscosity of 70 or more and 150 or less when measured at 140°C.

8. In paragraph 1, A modified conjugated diene polymer further comprising a unit derived from an aromatic vinyl monomer.

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

10. In paragraph 9, A method for producing a modified conjugated diene polymer using 0.01 to 10 mmol of the above organometallic compound based on 100 g of total monomers.

11. In paragraph 9, A method for producing a modified conjugated diene polymer, wherein the compound represented by the above chemical formula 1 and the organometallic compound are used in a molar ratio of 1:0.1 to 1:5.

0.

12. In paragraph 9, A method for producing a modified conjugated diene polymer, wherein the compound represented by the above chemical formula 1 is any one selected from compounds represented by the following chemical formulas 1-1 to 1-4: [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. A rubber composition comprising a modified conjugated diene polymer according to paragraph 1 and a filler.

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