Novel compound and method for preparing same

Abstract

The present invention provides a novel compound and a method for preparing same, the compound being a denaturizing agent useful in modifying rubber, particularly a polymer having a repeating unit derived from a conjugated diene-based monomer.

Description

Novel compound and method for preparing the same

[0001] [Cross-reference with related applications]

[0002] This application claims the benefit of priority to Korean Patent Application No. 10-2024-0040832, filed March 26, 2024, the entire disclosure of which is incorporated herein by reference.

[0003]

[0004] [Technical Field]

[0005] The present invention relates to a novel compound capable of highly modifying rubber and a method for producing the same.

[0006]

[0007] 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.

[0008] 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.

[0009] 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.

[0010] The above solution-polymerized SBR is manufactured using an anionic polymerization initiator, and a technology is used to introduce functional groups to the ends of the chains of the formed polymer by bonding or modifying them using various denaturing agents.

[0011] [Prior Art Literature]

[0012] [Patent Document]

[0013] (Patent Document 1) KR 1994-0021564 A (October 19, 1994)

[0014]

[0015] The present invention has been devised to solve the problems of the above-mentioned prior art, and aims to provide a novel compound useful as a rubber modifier capable of increasing the affinity between rubber and filler.

[0016] In addition, the present invention aims to provide a method for producing the compound.

[0017]

[0018] According to one embodiment of the present invention for solving the above problem, the present invention provides a novel compound and a method for producing the same.

[0019] (1) The present invention provides a compound represented by the following chemical formula 1:

[0020] [Chemical Formula 1]

[0021]

[0022] In the above chemical formula 1, R1, R3, R5 and R7 to R 12 are independently an alkylene group having 1 to 20 carbon atoms, R2, R4 and R6 are independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R 13 Inland R 24 are independently an alkyl group having 1 to 20 carbon atoms, and a, b, c, d, e and f are independently integers selected from 1 to 3.

[0023] (2) In the present invention, in the above (1), in the above chemical formula 1, R1, R3, R5 and R7 to R 12 are independently an alkylene group having 1 to 10 carbon atoms, R2, R4 and R6 are independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R 13 Inland R 24 are independently an alkyl group having 1 to 10 carbon atoms, and a, b, c, d, e and f are independently integers selected from 1 to 3.

[0024] (3) The present invention, in the above (1) or (2), in the above chemical formula 1, R1, R3, R5 and R7 to R 12 are independently an alkylene group having 1 to 6 carbon atoms, R2, R4 and R6 are independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 13 Inland R 24are independently an alkyl group having 1 to 6 carbon atoms, and a, b, c, d, e and f are independently integers selected from 1 to 3.

[0025] (4) The present invention provides a compound in which the compound represented by the chemical formula 1 in any one of the above (1) to (3) is any one selected from the compounds represented by the following chemical formulas 1-1 to 1-3:

[0026] [Chemical Formula 1-1]

[0027]

[0028] [Chemical Formula 1-2]

[0029]

[0030] [Chemical Formula 1-3]

[0031]

[0032] In the above chemical formulas 1-1 to 1-3, Me is a methyl group.

[0033] (5) The present invention provides a compound that is a modifier for modifying rubber in any one of the above (1) to (4).

[0034] (6) The present invention provides a compound that is a modifier for modifying a polymer containing a repeating unit derived from a conjugated diene monomer in any one of the above (1) to (5).

[0035] (7) The present invention provides a method for producing a compound represented by Chemical Formula 1, comprising a step of reacting a compound represented by Chemical Formula 2 and a compound represented by Chemical Formula 3 in any one of (1) to (6) above:

[0036] [Chemical Formula 2]

[0037]

[0038] In the above chemical formula 2, R 25 Inland R27 are independently hydrogen atoms or alkyl groups having 1 to 20 carbon atoms, X1 to X3 are independently halogen elements,

[0039] [Chemical Formula 3]

[0040]

[0041] In the above chemical formula 3, R 28 and R 29 is an alkylene group having 1 to 20 carbon atoms, and R 30 Inland R 33 are independently an alkyl group having 1 to 20 carbon atoms, g and h are independently an integer of 1 to 3,

[0042] [Chemical Formula 1]

[0043]

[0044] In the above chemical formula 1, R1, R3, R5 and R7 to R 12 are independently an alkylene group having 1 to 20 carbon atoms, R2, R4 and R6 are independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R 13 Inland R 24 are independently an alkyl group having 1 to 20 carbon atoms, and a, b, c, d, e and f are independently integers selected from 1 to 3.

[0045] (8) The present invention, in the above (7), in the above chemical formula 1, R1, R3, R5 and R7 to R 12 are independently an alkylene group having 1 to 10 carbon atoms, R2, R4 and R6 are independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R 13 Inland R 24 Provided is a method for preparing a compound in which each independently represents an alkyl group having 1 to 10 carbon atoms, and a, b, c, d, e and f are each independently an integer selected from 1 to 3.

[0046] (9) The present invention, in the above (7) or (8), in the above chemical formula 2, R 25 Inland R 27 Provided is a method for producing a compound in which X1 to X3 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and X1 to X3 are each independently a halogen element.

[0047] (10) The present invention relates to any one of the above (7) to (9), wherein in the above chemical formula 3, R 28 and R 29 is an alkylene group having 1 to 10 carbon atoms, and R 30 Inland R 33 Provided is a method for producing a compound in which each independently represents an alkyl group having 1 to 10 carbon atoms, and g and h are each independently an integer of 1 to 3.

[0048] (11) The present invention provides a method for producing a compound according to any one of the above (7) to (10), wherein the reaction is performed at a temperature of 25°C to 200°C in a reaction solvent under basic conditions.

[0049] (12) The present invention provides a method for producing a compound, wherein the compound represented by the chemical formula 2 and the compound represented by the chemical formula 3 are reacted in a molar ratio of 1:3 to 1:10 in any one of the above (7) to (11).

[0050]

[0051] The compound according to the present invention is applied to a modification reaction of rubber, particularly a polymer containing a repeating unit derived from a conjugated diene monomer, and has the effect of modifying the polymer at a high modification rate to maximize affinity with a filler.

[0052]

[0053] Hereinafter, the present invention will be described in more detail to help understand the present invention.

[0054] 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.

[0055]

[0056] Definition of Terms

[0057] 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.

[0058] 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.

[0059] 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).

[0060] 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.

[0061] 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℃.

[0062] 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.

[0063] 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.

[0064] In this specification, the term 'alkylene group' may mean a divalent aliphatic saturated hydrocarbon such as methylene, ethylene, propylene, and butylene.

[0065] 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.

[0066] 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.

[0067]

[0068] Measurement method and conditions

[0069] 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.

[0070] - Column: Two PLgel Olexis (Polymer Laboratories) columns and one PLgel mixed-C (Polymer Laboratories) column were used in combination.

[0071] - Solvent: Use a mixture of 2 wt% amine compound in tetrahydrofuran.

[0072] - Flow rate: 1 ml / min

[0073] - Sample concentration: 1~2 mg / ml (diluted in THF)

[0074] - Injection volume: 100 ㎕

[0075] - Column temperature: 40℃

[0076] - Detector: Refractive index

[0077] - Standard: Polystyrene (corrected with a cubic function)

[0078]

[0079] new compounds

[0080] The present invention provides a novel modifier compound capable of modifying a rubber, particularly a polymer containing a repeating unit derived from a conjugated diene monomer, to provide a modified polymer with a high degree of modification having high affinity for a filler.

[0081] The novel modifier compound according to one embodiment of the present invention is characterized by being a compound represented by the following chemical formula 1.

[0082] [Chemical Formula 1]

[0083]

[0084] In the above chemical formula 1,

[0085] R1, R3, R5 and R7 to R 12 are independently an alkylene group having 1 to 20 carbon atoms, R2, R4 and R6 are independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R 13 Inland R 24 are independently an alkyl group having 1 to 20 carbon atoms, and a, b, c, d, e and f are independently integers selected from 1 to 3.

[0086] Specifically, in the above chemical formula 1, R1, R3, R5 and R7 to R 12 are independently an alkylene group having 1 to 10 carbon atoms, R2, R4 and R6 are independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R 13 Inland R24 are independently an alkyl group having 1 to 10 carbon atoms, and a, b, c, d, e and f may be independently integers selected from 1 to 3.

[0087] More specifically, in the above chemical formula 1, R1, R3, R5 and R7 to R 12 are independently an alkylene group having 1 to 6 carbon atoms, R2, R4 and R6 are independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 13 Inland R 24 are independently an alkyl group having 1 to 6 carbon atoms, and a, b, c, d, e and f may be independently integers selected from 1 to 3.

[0088] 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 1-3.

[0089] [Chemical Formula 1-1]

[0090]

[0091] [Chemical Formula 1-2]

[0092]

[0093] [Chemical Formula 1-3]

[0094]

[0095] In the above chemical formulas 1-1 to 1-3, Me is a methyl group.

[0096]

[0097] In addition, the compound represented by the above chemical formula 1 may be a modifier for modifying rubber, and specifically, may be a modifier for modifying a polymer including a repeating unit derived from a conjugated diene monomer, wherein the polymer may be a homopolymer including a repeating unit derived from a conjugated diene monomer and a copolymer including a repeating unit derived from a monomer other than the conjugated diene monomer-derived semi-bond unit.

[0098]

[0099] Meanwhile, the compound represented by the chemical formula 1 according to the present invention can be applied as a modifying agent for a rubber modification reaction, i.e., for modifying rubber, by providing a number of coupling sites to increase the coupling rate between chains constituting the rubber, while simultaneously being introduced into the chain to modify the chain structure, thereby highly modifying the rubber, and thus can greatly increase the affinity with a filler compared to conventional modifying agent materials.

[0100] In addition, the nitrogen in the compound represented by the above chemical formula 1 can play a role in increasing the affinity between the rubber modified from the compound represented by the above chemical formula 1 and the filler, and since the compound represented by the above chemical formula 1 includes a plurality of coupling sites, the residual coupling sites (-Si-OR, alkoxy group) that do not react with the chains constituting the rubber after rubber modification can form a plurality of covalent bonds with the filler, thereby forming a strong bond.

[0101]

[0102] Method for preparing a compound

[0103] The present invention provides a method for producing a novel compound represented by the above chemical formula 1.

[0104] The method for producing the compound according to one embodiment of the present invention is characterized by including a step of reacting a compound represented by the following chemical formula 2 with a compound represented by the following chemical formula 3.

[0105] [Chemical Formula 2]

[0106]

[0107] In the above chemical formula 2,

[0108] R 25 Inland R 27 are independently hydrogen atoms or alkyl groups having 1 to 20 carbon atoms, X1 to X3 are independently halogen elements,

[0109] [Chemical Formula 3]

[0110]

[0111] In the above chemical formula 3,

[0112] R 28 and R 29 is an alkylene group having 1 to 20 carbon atoms, and R 30 Inland R 33 are independently an alkyl group having 1 to 20 carbon atoms, g and h are independently an integer of 1 to 3,

[0113] [Chemical Formula 1]

[0114]

[0115] In the above chemical formula 1,

[0116] R1, R3, R5 and R7 to R 12 are independently an alkylene group having 1 to 20 carbon atoms, R2, R4 and R6 are independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R 13 Inland R 24 are independently an alkyl group having 1 to 20 carbon atoms,

[0117] a, b, c, d, e and f are integers independently selected from 1 to 3.

[0118] In the above chemical formula 2, the halogen element may be Cl, Br, I or F.

[0119] The above reaction can be carried out at a temperature of 25°C to 200°C in a reaction solvent under basic conditions, in which case the reaction conversion rate can be better, which can be advantageous for improving the yield.

[0120] In addition, the above basic conditions may be formed by adding a basic compound, and the basic compound is not particularly limited and can be used if it is commonly used for the same purpose in the art, but for example, one or more selected from triethylamine, potassium carbonate, potassium hydroxide, and sodium hydroxide can be used.

[0121] In addition, the compound represented by the above chemical formula 2 and the compound represented by the chemical formula 3 may be reacted at an appropriate ratio according to the stoichiometric ratio, but specifically, they may be reacted at a molar ratio of 1:3 to 1:10. In this case, the unreacted compound may be small or may be easily removed.

[0122] Also, in the above chemical formula 2, R 25 Inland R 27 are independently hydrogen atoms or alkyl groups having 1 to 10 carbon atoms, and X1 to X3 can be independently halogen elements.

[0123] Specifically, in the above chemical formula 2, R 25 Inland R 27 are independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and X1 to X3 may be Br.

[0124] Also, in the above chemical formula 3, R 28 and R 29 is an alkylene group having 1 to 10 carbon atoms, and R 30 Inland R 33 are independently an alkyl group having 1 to 10 carbon atoms, and g and h can be independently integers of 1 to 3.

[0125] Specifically, in the above chemical formula 3, R 28 and R29 is an alkylene group having 1 to 6 carbon atoms, and R 30 Inland R 33 are independently an alkyl group having 1 to 6 carbon atoms, and g and h can be independently integers of 1 to 3.

[0126]

[0127] The compound represented by the chemical formula 1 prepared from the above is specifically R1, R3, R5 and R7 to R in the chemical formula 1 12 are independently an alkylene group having 1 to 10 carbon atoms, R2, R4 and R6 are independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R 13 Inland R 24 are independently an alkyl group having 1 to 10 carbon atoms, and a, b, c, d, e and f can be independently integers selected from 1 to 3.

[0128] In addition, in the above chemical formula 1, R1, R3, R5 and R7 to R 12 are independently an alkylene group having 1 to 6 carbon atoms, R2, R4 and R6 are independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 13 Inland R 24 are independently an alkyl group having 1 to 6 carbon atoms, and a, b, c, d, e and f can be independently integers selected from 1 to 3.

[0129]

[0130] Modified conjugated diene polymer

[0131] The present invention provides a modified conjugated diene polymer modified with a compound represented by the above chemical formula 1.

[0132] The modified conjugated diene polymer according to one embodiment of the present invention is characterized in that it includes a conjugated diene monomer-derived unit and a modifier residue, and the modifier includes a compound represented by the chemical formula 1.

[0133] Here, the compound represented by the above chemical formula 1 is as described above, so its detailed description is omitted.

[0134] The above-mentioned modified conjugated diene polymer has as its main unit a repeating unit derived from a conjugated diene monomer, and 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, and 2-halo-1,3-butadiene (halo means a halogen atom).

[0135] 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 repeating unit derived therefrom. The aromatic vinyl monomer may be, for example, styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 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 ethyl)-α-methylstyrene. It may be at least one selected from the group consisting of ethyl)-α-methylstyrene).

[0136] 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.

[0137] 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.

[0138] In addition, the above-described modified conjugated diene polymer includes a functional group derived from a modifier, and the modifier is for modifying the terminal of the polymer and means a unit derived from a compound represented by the above-described chemical formula 1.

[0139] 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, or 500,000 g / mol to 2,000,000 g / mol, and within this range, the driving resistance and wet road resistance are more balanced and excellent in effect.

[0140] 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.

[0141] 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.

[0142] In addition, the modified conjugated diene polymer may have a molecular weight distribution of 1.0 to 3.0, preferably 1.0 to 2.5, and more preferably 1.0 to 2.0.

[0143] In addition, 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 may preferably be 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.

[0144]

[0145] In addition, the above-described modified conjugated diene polymer can be manufactured by a conventional method, except that it is modified with a compound represented by Chemical Formula 1. For example, it can be manufactured by polymerizing a conjugated diene monomer or a conjugated diene monomer and an aromatic vinyl monomer in the presence of a hydrocarbon solvent and a polymerization initiator to manufacture an active polymer, and reacting the active polymer with the compound represented by Chemical Formula 1.

[0146] 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.

[0147] The polymerization initiator may be used in an amount of 0.1 to 3.0 equivalents based on 1.0 equivalent of the monomer, preferably 0.1 to 2.0 equivalents, more preferably 0.5 to 1.5 equivalents. In another example, the polymerization initiator may be used in an amount of 0.01 mmol to 10 mmol, 0.05 mmol to 5 mmol, 0.1 mmol to 2 mmol, 0.1 mmol to 1 mmol, or 0.15 to 0.8 mmol based on 100 g of the total monomer. Here, the total 100 g of the monomer may be a conjugated diene monomer, or may represent the total amount of the conjugated diene monomer and the aromatic vinyl monomer.

[0148] Meanwhile, the polymerization initiator may be an organometallic compound, and may be, for example, at least one selected from an organolithium compound, an organosodium compound, an organopotassium compound, an organorubidium compound, and an organocesium compound.

[0149] Specifically, the organometallic compound may be 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.

[0150] In addition, the polymerization can be performed by further using a polar additive, and in the case of homopolymerizing a conjugated diene monomer, the ratio of 1,2-bonds and 1,4-bonds can be controlled by controlling the reaction rate, and in the case of copolymerizing 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 rate between these monomers.

[0151] The total amount of the polar additive may be used in a ratio of 0.001 g to 50 g, or 0.002 g to 1.0 g, based on 100 g of the total monomer. As another example, the total amount of the polar additive may be used in a ratio of more than 0 g to 1 g, 0.01 g to 1 g, or 0.1 g to 0.9 g, based on 100 g of the total polymerization initiator.

[0152] The polar additive may be, for example, at least one selected from the group consisting of tetrahydrofuran, 2,2-di(2-tetrahydrofuryl)propane, diethyl ether, cyclopentyl ether, dipropyl ether, ethylene methyl ether, ethylene glycol dimethyl ether, diethylene glycol, dimethyl ether, tert-butoxyethoxyethane, bis(3-dimethylaminoethyl)ether, (dimethylaminoethyl)ethyl ether, trimethylamine, triethylamine, tripropylamine, N,N,N',N'-tetramethylethylenediamine, sodium mentholate, and 2-ethyl tetrahydrofurfuryl ether, and preferably 2,2-di(2-tetrahydrofuryl)propane, triethylamine, tetramethylethylenediamine, sodium mentholate, or It may be 2-ethyl tetrahydrofurfuryl ether.

[0153] Additionally, the above active polymer may mean a polymer in which a polymer anion and an organic metal cation of a polymerization initiator are combined.

[0154] The reaction of the above active polymer and the compound represented by Chemical Formula 1 may be a reaction between the anionic active site of the active polymer and the alkoxy group bonded to the silane of the compound represented by Chemical Formula 1. The compound represented by Chemical Formula 1 may be used in an amount of 0.01 mmol to 10 mmol based on 100 g of the total monomer. As another example, the compound represented by Chemical Formula 1 may be used in a molar ratio of 1:0.1 to 10, 1:0.1 to 5, or 1:0.1 to 1:3 based on 1 mol of the polymerization initiator of the step (S3).

[0155] At this time, the above reaction may be a modification reaction in which a compound represented by chemical formula 1 is simply bonded to an active polymer, or a coupling reaction in which an active polymer is connected based on a compound represented by chemical formula 1.

[0156]

[0157] Example

[0158] 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.

[0159] Example 1

[0160] 3.5 g (9.81 mmol) of 1,3,5-tris(bromomethyl)benzene, 10.05 g of bis(3-(trimethoxysilyl)propyl)amine and 5.08 g of triethylamine were reacted with stirring at 50°C for one night (12 hours). After completion of the reaction, the temperature was lowered to room temperature, 50 ml of hexane was added and stirred for 15 minutes. The solid by-products were removed with a celite filter and the solution and impurities were removed by distillation under reduced pressure to prepare a compound represented by 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.

[0161] [Chemical Formula 1-1]

[0162]

[0163] In the above chemical formula 1-1, Me is a methyl group.

[0164] 1 H NMR (500 MHz, CDCl3) δ 7.10 (s, 3H), 3.60-3.50 (m, 60H), 2.46-2.34 (m, 12H), 1.64-1.48 (m, 12H), 0.36-0.52 (m, 12H).

[0165]

[0166] Example 2

[0167] 3.5 g (8.77 mmol) of 1,3,5-tris(bromomethyl)-2,4,6-trimethylbenzene, 8.99 g of bis(3-(trimethoxysilyl)propyl)amine and 4.55 g of triethylamine were reacted with stirring at 50°C for one night (12 hours). After completion of the reaction, the temperature was lowered to room temperature, 50 ml of hexane was added, stirred for 15 minutes, and the solid byproducts were removed with a celite filter, and the solution and impurities were removed by distillation under reduced pressure to prepare a compound represented by 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.

[0168] [Chemical Formula 1-2]

[0169]

[0170] In the above chemical formula 1-2, Me is a methyl group.

[0171] 1 H NMR (500 MHz, CDCl3) δ 3.53 (s, 60H), 2.37 (dd, J=17.7, 10.7 Hz, 21H), 1.58-1.46 (m, 12H), 0.58-0.47 (m, 12H).

[0172]

[0173] Example 3

[0174] 3.5 g (7.94 mmol) of 1,3,5-tris(bromomethyl)-2,4,6-triethylbenzene, 8.13 g of bis(3-(trimethoxysilyl)propyl)amine, and 4.11 g of triethylamine were reacted at 50°C with stirring for one night (12 hours). After completion of the reaction, the temperature was lowered to room temperature, 50 ml of hexane was added, stirred for 15 minutes, and the solid byproducts were removed with a celite filter, 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.

[0175] [Chemical Formula 1-3]

[0176]

[0177] In the above chemical formula 1-3, Me is a methyl group.

[0178] 1 H NMR (500 MHz, CDCl3) δ 3.52 (d, J=3.0 Hz, 60H), 3.02 (dd, J=14.3, 6.9 Hz, 6H), 2.34 (dd, J=15.5, 8.6 Hz, 12H), 1.56-1.46 (m, 12H), 1.13-1.03 (m, 9H), 0.51-0.46 (m, 12H).

[0179]

[0180] Example 4

[0181] In a 10 L autoclave reactor, 64.5 g of styrene, 235.5 g of 1,3-butadiene, 2,000 g of n-hexane, and 0.42 g of DTP (2,2-di(2-(tetrahydrofuryl)propane)) as a polar additive were placed, and the internal temperature of the reactor was adjusted to 60°C. When 60°C was reached, 0.26 g of n-butyllithium was placed into the reactor and reacted. After 40 minutes, 0.44 g of the compound represented by Chemical Formula 1-1 prepared in Example 1 was added, and the reaction was continued for 40 minutes. The reaction was stopped using ethanol, and an antioxidant was added to obtain a polymer, which was dried to prepare a modified styrene-butadiene copolymer.

[0182]

[0183] Example 5

[0184] A modified styrene-butadiene copolymer was prepared in the same manner as in Example 4, except that the compound represented by Chemical Formula 1-2 prepared in Example 2 was used instead of the compound represented by Chemical Formula 1-1 in Example 4.

[0185]

[0186] Example 6

[0187] A modified styrene-butadiene copolymer was prepared in the same manner as in Example 4, except that the compound represented by Chemical Formula 1-3 prepared in Example 3 was used instead of the compound represented by Chemical Formula 1-1 in Example 4.

[0188]

[0189] Comparative example

[0190] A modified styrene-butadiene copolymer was prepared in the same manner as in Example 4, except that 3-(trimethoxysilyl)propylamine (Sigma-Aldrich) was used instead of the compound represented by Chemical Formula 1-1 in Example 4.

[0191]

[0192] Experimental Example 1. Evaluation of Polymer Properties

[0193] For each modified styrene-butadiene copolymer manufactured in the above examples and comparative examples, the weight average molecular weight (Mw, ×10 3 g / mol), maximum peak molecular weight (Mp, ×10 3 g / mol) and coupling number were measured, respectively. The results are shown in Table 1 below.

[0194] 1) Weight average molecular weight (Mw, ×10 3 g / mol), maximum peak molecular weight (Mp, ×10 3 g / mol)

[0195] The weight-average molecular weight (Mw) and maximum peak molecular weight (Mp) were measured using gel permeation chromatography (GPC) (PL GPC220, Agilent Technologies) under the following conditions. Meanwhile, a portion of the active polymer was collected, and the maximum peak molecular weight before denaturation was also measured.

[0196] - Column: Two PLgel Olexis (Polymer Laboratories) columns and one PLgel mixed-C (Polymer Laboratories) column were used in combination.

[0197] - Solvent: Use a mixture of 2 wt% amine compound in tetrahydrofuran.

[0198] - Flow rate: 1 mL / min

[0199] - Sample concentration: 1~2 mg / mL (diluted in THF)

[0200] - Injection volume: 100 uL

[0201] - Column temperature: 40℃

[0202] - Detector: Refractive index

[0203] - Standard: Polystyrene (corrected with a cubic function)

[0204]

[0205] 2) Number of couplings (CN)

[0206] The coupling number was calculated using the following mathematical formula 1 from the maximum peak molecular weight before modification measured in 1) above and the maximum peak molecular weight of the final modified polymer.

[0207] [Mathematical Formula 1]

[0208] Number of couplings = Mp2 / Mp1

[0209] In the above mathematical expression 1, Mp1 is the maximum peak molecular weight of the active polymer before modification, and Mp2 is the maximum peak molecular weight of the final modified polymer.

[0210]

[0211] As shown in Table 1 above, Examples 4 to 6 showed a significant increase in the weight average molecular weight and a significant increase in the number of couplings compared to the comparative examples. Through this, it was confirmed that the compound represented by Chemical Formula 1 according to the present invention is applied as a modifier for modifying a polymer, thereby providing a large number of coupling sites to increase the coupling rate between chains constituting the polymer, while at the same time being introduced into the chain to modify the chain structure, thereby highly modifying the polymer.

Claims

1. A compound represented by the following chemical formula 1: [Chemical Formula 1] In the above chemical formula 1, R1, R3, R5 and R7 to R 12 are independently an alkylene group having 1 to 20 carbon atoms, R2, R4 and R6 are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, R 13 Inland R 24 are independently an alkyl group having 1 to 20 carbon atoms, a, b, c, d, e and f are integers independently selected from 1 to 3.

2. In paragraph 1, In the above chemical formula 1, R1, R3, R5 and R7 to R 12 are independently an alkylene group having 1 to 10 carbon atoms, R2, R4 and R6 are independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R 13 Inland R 24 A compound in which are independently an alkyl group having 1 to 10 carbon atoms, and a, b, c, d, e and f are independently integers selected from 1 to 3.

3. In paragraph 1, In the above chemical formula 1, R1, R3, R5 and R7 to R 12 are independently an alkylene group having 1 to 6 carbon atoms, R2, R4 and R6 are independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 13 Inland R 24 A compound in which are each independently an alkyl group having 1 to 6 carbon atoms, and a, b, c, d, e and f are each independently an integer selected from 1 to 3.

4. In paragraph 1, The compound represented by the above chemical formula 1 is a compound selected from among compounds represented by the following chemical formulas 1-1 to 1-3: [Chemical Formula 1-1] [Chemical Formula 1-2] [Chemical Formula 1-3] In the above chemical formulas 1-1 to 1-3, Me is a methyl group.

5. In paragraph 1, A compound that is a modifier that modifies rubber.

6. In paragraph 1, A compound that is a modifier that modifies a polymer containing a repeating unit derived from a conjugated diene monomer.

7. A method for producing a compound represented by Chemical Formula 1, comprising the step of reacting a compound represented by Chemical Formula 2 with a compound represented by Chemical Formula 3: [Chemical Formula 2] In the above chemical formula 2, R 25 Inland R 27 are independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, X1 to X3 are independently halogen elements, [Chemical Formula 3] In the above chemical formula 3, R 28 and R 29 is an alkylene group having 1 to 20 carbon atoms, R 30 Inland R 33 are independently an alkyl group having 1 to 20 carbon atoms, g and h are independently integers from 1 to 3, [Chemical Formula 1] In the above chemical formula 1, R1, R3, R5 and R7 to R 12 are independently an alkylene group having 1 to 20 carbon atoms, R2, R4 and R6 are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, R 13 Inland R 24 are independently an alkyl group having 1 to 20 carbon atoms, a, b, c, d, e and f are integers independently selected from 1 to 3.

8. In paragraph 7, In the above chemical formula 1, R1, R3, R5 and R7 to R 12 are independently an alkylene group having 1 to 10 carbon atoms, R2, R4 and R6 are independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R 13 Inland R 24 A method for producing a compound in which each independently represents an alkyl group having 1 to 10 carbon atoms, and a, b, c, d, e and f are integers independently selected from 1 to 3.

9. In paragraph 7, In the above chemical formula 2, R 25 Inland R 27 A method for producing a compound in which X1 to X3 are independently hydrogen atoms or alkyl groups having 1 to 10 carbon atoms, and X1 to X3 are independently halogen elements.

10. In paragraph 7, In the above chemical formula 3, R 28 and R 29 is an alkylene group having 1 to 10 carbon atoms, and R 30 Inland R 33 A method for producing a compound wherein each independently represents an alkyl group having 1 to 10 carbon atoms, and g and h are each independently an integer of 1 to 3.

11. In paragraph 7, A method for producing a compound, wherein the above reaction is carried out under basic conditions and at a temperature of 25°C to 200°C in a reaction solvent.

12. In paragraph 7, A method for producing a compound, wherein the compound represented by the above chemical formula 2 and the compound represented by the chemical formula 3 are reacted in a molar ratio of 1:3 to 1:10.

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