RU2782599C2 - Modified polymer based on conjugated diene and rubber composition containing it - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: present invention relates to modified polymer based on conjugated diene, as well as to a composition for an element of a tire or rubber products, containing modified polymer based on conjugated diene. Modified polymer based on conjugated diene has a unimodal shape of a molecular-weight distribution curve according to gel-penetrating chromatography and molecular-weight distribution from 1.0 to less than 1.7. The specified polymer contains a functional group obtained from a modification initiator at one end and a functional group obtained from a modifier. The modification initiator is a product of a reaction of a compound

and a metal-organic compound. The modifier is a compound of formulas

Or

.

EFFECT: modified polymer based on conjugated diene, obtained by continuous polymerization has excellent recyclability and excellent physical properties, such as mechanical properties during stretching and viscoelastic properties.

12 cl, 5 dwg, 5 tbl, 7 ex

Description

Technical field

Cross-reference to related applications

[0001] This application claims the benefit of priority based on Korean Patent Applications No. 10-2017-0165578, filed on December 5, 2017, and No. 10-2018-0150918, filed on November 29, 2018, the entire contents of which are incorporated herein by links.

Technical field

[0002] The present invention relates to a modified conjugated diene based polymer having excellent processability, excellent tensile properties and viscoelastic properties, and a rubber composition comprising the same.

State of the art

[0003] According to recent requests for low fuel consumption vehicles, a conjugated diene-based polymer is required as a rubber material for tires, having a modular stability represented by wet skid resistance as well as low rolling resistance, and excellent abrasion resistance. and tensile properties.

[0004] In order to reduce the rolling resistance of tires, there is a method for reducing the hysteresis loss of the vulcanized rubber, and rebound resilience at 50 to 80°C, tan δ, Goodrich heat generation, or the like. used as an indicator of evaluation of vulcanized rubber. That is, it is desirable to use a rubber material having high rebound resilience at the above temperature, or a low tan δ value, or Goodrich heat generation.

[0005] Natural rubbers, polyisoprene rubbers, or polybutadiene rubbers are known as rubber materials having low hysteresis loss, but these rubbers have the limitation of low wet skid resistance. Thus, recently, conjugated diene-based polymers or copolymers such as styrene-butadiene rubbers (hereinafter referred to as "SBR") and butadiene rubbers (hereinafter referred to as "BR" ("BR")) are obtained by emulsion polymerization or solution polymerization to be used as tire rubbers. Of these polymerization methods, the biggest advantage of solution polymerization compared to emulsion polymerization is that the vinyl structure content and styrene content, which determine the physical properties of rubber, can be arbitrarily adjusted, and the molecular weight and physical properties can be controlled by bonding or modification. . Thus, SBR obtained by solution polymerization is widely used as a rubber material for tires, since it is easy to change the structure of the finally obtained SBR or BR, and the movement of chain ends can be reduced and the adhesion force to filler such as silicon dioxide and carbon black. , can be increased by linking or modifying chain endings.

[0006] If solution-polymerized SBR is used as a rubber material for tires, since the glass transition temperature of rubber increases with increasing vinyl content of SBR, physical properties such as running resistance and braking force required for tires can be controlled, and fuel consumption can also be reduced by appropriately controlling the glass transition temperature. The polymerized SBR solution is obtained using an anionic polymerization initiator and is used by linking or modifying the chain ends of the polymer thus obtained using various modifiers. For example, U.S. Pat. No. 4,397,994 discloses a method of coupling active chain terminating anions of a polymer obtained by polymerization of styrene and butadiene using an alkyl lithium, which is a monofunctional initiator, in a non-polar solvent using a binder such as a tin compound.

[0007] However, the polymerization of SBR or BR can be carried out by batch or continuous polymerization. In the case of batch polymerization, the molecular weight distribution of the thus obtained polymer is narrow, and batch polymerization is preferable from the point of view of improving physical properties, but the productivity is low and the processability of the polymer is poor. In the case of continuous polymerization, the polymerization can be carried out continuously, the productivity is excellent and the processability improvement is optimal, but the molecular weight distribution is wide and the physical properties are poor. Accordingly, in order to obtain SBR or BR, studies are undoubtedly required to simultaneously improve productivity, processability and physical properties.

Description of the invention

Technical task

[0008] The present invention has been made to solve the above-described problems of conventional technologies, and an object of the present invention is to provide a modified conjugated diene-based polymer obtained by continuous polymerization and having excellent processability and excellent physical properties such as tensile mechanical properties and viscoelastic properties, and a rubber composition comprising it.

Technical solution

[0009] In order to solve the above problems, in accordance with an embodiment of the present invention, there is provided a modified conjugated diene polymer having a unimodal shape of a molecular weight distribution curve by gel permeation chromatography (GPC)) and a molecular weight distribution (PPD (PDI) ; MWD (MWD)) from 1.0 to less than 1.7 and comprising a functional group derived from a modification initiator at one end and a functional group derived from a modifier represented by the following formula 2 or formula 3 at the other end, where the modification initiator is the reaction product of the compound represented by the following formula 1 and an organometallic compound:

[0010] Formula 1

,

,

[0011] in Formula 1:

[0012] R ₁ -R ₃ are each independently a hydrogen atom, an alkyl group of 1-30 carbon atoms, an alkenyl group of 2-30 carbon atoms, an alkynyl group of 2-30 carbon atoms, a heteroalkyl group of 1-30 carbon atoms , a heteroalkenyl group of 2-30 carbon atoms, a heteroalkynyl group of 2-30 carbon atoms, a cycloalkyl group of 5-30 carbon atoms, an aryl group of 6-30 carbon atoms, or a heterocyclic group of 3-30 carbon atoms;

[0013] R ₄ is a single bond, a substituted or unsubstituted alkylene group of 1-20 carbon atoms with a substituent, a substituted or unsubstituted cycloalkylene group of 5-20 carbon atoms with a substituent, or a substituted or unsubstituted arylene group of 6-20 carbon atoms with a substituent, where the substituent is an alkyl group of 1-10 carbon atoms, a cycloalkyl group of 5-10 carbon atoms, or an aryl group of 6-20 carbon atoms;

[0014] R ₅ is an alkyl group of 1-30 carbon atoms, an alkenyl group of 2-30 carbon atoms, an alkynyl group of 2-30 carbon atoms, a heteroalkyl group of 1-30 carbon atoms, a heteroalkenyl group of 2-30 carbon atoms carbon, a heteroalkynyl group of 2-30 carbon atoms, a cycloalkyl group of 5-30 carbon atoms, an aryl group of 6-30 carbon atoms, a heterocyclic group of 3-30 carbon atoms, or a functional group represented by the following formula 1a or formula 1b; and

[0015] "n" means an integer from 1 to 5, and at least one of the R ₅ groups means a functional group represented by the following formula 1a or formula 1b, in the case where "n" means an integer from 2 to 5, the plurality of R ₅ groups may be the same or different;

[0016] Formula 1a

,

,

[0017] in formula 1a:

[0018] R ₆ is a substituted or unsubstituted alkylene group of 1-20 carbon atoms with a substituent, a substituted or unsubstituted cycloalkylene group of 5-20 carbon atoms with a substituent, or a substituted or unsubstituted arylene group of 6-20 carbon atoms with a substituent, where the substituent is an alkyl group of 1-10 carbon atoms, a cycloalkyl group of 5-10 carbon atoms, or an aryl group of 6-20 carbon atoms;

[0019] R ₇ and R ₈ are each independently a substituted or unsubstituted alkylene group of 1-20 carbon atoms with an alkyl group of 1-10 carbon atoms, a cycloalkyl group of 5-10 carbon atoms, or an aryl group of 6-20 carbon atoms ;

[0020] R ₉ is a hydrogen atom, an alkyl group of 1-30 carbon atoms, an alkenyl group of 2-30 carbon atoms, an alkynyl group of 2-30 carbon atoms, a heteroalkyl group of 1-30 carbon atoms, a heteroalkenyl group of 2 -30 carbon atoms, a heteroalkynyl group of 2-30 carbon atoms, a cycloalkyl group of 5-30 carbon atoms, an aryl group of 6-30 carbon atoms, or a heterocyclic group of 3-30 carbon atoms; and

[0021] X represents N, O or S atoms, in the case where X represents O or S, R ₉ is not present;

[0022] Formula 1b

,

,

[0023] in formula 1b:

[0024] R ₁₀ is a substituted or unsubstituted alkylene group of 1-20 carbon atoms with a substituent, a substituted or unsubstituted cycloalkylene group of 5-20 carbon atoms with a substituent, or a substituted or unsubstituted arylene group of 6-20 carbon atoms with a substituent, where the substituent is an alkyl group of 1-10 carbon atoms, a cycloalkyl group of 5-10 carbon atoms, or an aryl group of 6-20 carbon atoms; and

[0025] R ₁₁ and R ₁₂ are each independently an alkyl group of 1-30 carbon atoms, an alkenyl group of 2-30 carbon atoms, an alkynyl group of 2-30 carbon atoms, a heteroalkyl group of 1-30 carbon atoms, a heteroalkenyl group 2-30 carbon atoms, a heteroalkynyl group of 2-30 carbon atoms, a cycloalkyl group of 5-30 carbon atoms, an aryl group of 6-30 carbon atoms, or a heterocyclic group of 3-30 carbon atoms;

[0026] Formula 2

,

,

[0027] in formula 2:

[0028] R ₂₀ is a single bond or an alkylene group of 1-10 carbon atoms;

[0029] R ₂₁ and R ₂₂ are each independently an alkyl group of 1-10 carbon atoms;

[0030] R ₂₃ is a single bond or an alkylene group of 1-10 carbon atoms;

[0031] R ₂₄ represents a hydrogen atom, an alkyl group of 1-10 carbon atoms, or a substituted, divalent, trivalent or tetravalent alkylsilyl group with an alkyl group of 1-10 carbon atoms;

[0032] "a" means an integer 2 or 3,

[0032] "c" means an integer from 1 to 3, and "b" means an integer from 0 to 2, where b+c=3;

[0034] Formula 3

,

,

[0035] in Formula 3:

[0036] A ₁ and A ₂ are each independently an alkylene group of 1-20 carbon atoms;

[0037] R ₂₅ -R ₂₈ each independently represent an alkyl group of 1-20 carbon atoms; and

[0038] L ₁ -L ₄ each independently represent a substituted, divalent, trivalent or tetravalent alkylsilyl group with an alkyl group of 1-10 carbon atoms or an alkyl group of 1-20 carbon atoms.

[0039] In addition, the present invention provides a rubber composition comprising a modified conjugated diene-based polymer and a filler.

Positive Effects

[0040] The modified conjugated diene polymer of the present invention is obtained by continuous polymerization to be described later, and has a unimodal gel permeation chromatography molecular weight distribution curve and a narrow molecular weight distribution of less than 1.7, and therefore has excellent processability, tensile properties and viscoelastic properties.

[0041] In addition, the modified conjugated diene polymer according to the present invention includes a functional group derived from a modification initiator at one end and a functional group derived from a modifier at the other end, thereby exhibiting further improved viscoelastic properties.

Brief description of the drawings

[0042] The following drawings, appended to the description, illustrate preferred examples of the present invention by way of example and serve to ensure that the technical concepts of the present invention are further understood along with the detailed description of the invention below, and thus the present invention should not be interpreted only with the help of objects in such drawings.

[0043] FIG. 1 shows a Gel Permeation Chromatography (GPC) molecular weight distribution curve of the modified conjugated diene based polymer of Example 1 according to an embodiment of the present invention.

[0044] FIG. 2 shows a Gel Permeation Chromatography (GPC) molecular weight distribution curve of the modified conjugated diene based polymer of Example 5 according to an embodiment of the present invention.

[0045] FIG. 3 shows a Gel Permeation Chromatography (GPC) molecular weight distribution curve of a modified conjugated diene-based polymer of Comparative Example 1 according to an embodiment of the present invention.

[0046] FIG. 4 shows a gel permeation chromatography (GPC) molecular weight distribution curve of a modified conjugated diene-based polymer of Reference Example 1 according to an embodiment of the present invention.

[0047] FIG. 5 shows a Gel Permeation Chromatography (GPC) molecular weight distribution curve of the modified conjugated diene-based polymer of Reference Example 2 according to an embodiment of the present invention.

The best way to carry out the invention

[0048] Hereinafter, the present invention is described in more detail to assist in understanding the present invention.

[0049] It should be understood that words or terms used in the description and claims of the present invention should not be interpreted as meaning defined in commonly used dictionaries. It will further be understood that words or terms should be interpreted as having a meaning that corresponds to their meaning for the technical idea of the invention, based on the principle that the inventor can correctly determine the meaning of words or terms in order to best explain the invention.

[0050] The term "alkyl group" as used in the present invention may mean a monovalent aliphatic saturated hydrocarbon and may include both a linear alkyl group such as methyl, ethyl, propyl and butyl and a branched alkyl group such as isopropyl, sec- butyl, tert-butyl and neopentyl.

[0051] The term "alkylene group" as used in the present invention may mean a divalent aliphatic saturated hydrocarbon such as methylene, ethylene, propylene and butylene.

[0052] The term "alkenyl group" as used in the present invention may mean a monovalent aliphatic unsaturated hydrocarbon containing one or two or more double bonds.

[0053] The term "alkynyl group" as used in the present invention may mean a monovalent aliphatic unsaturated hydrocarbon containing one or two or more triple bonds.

[0054] The term "cycloalkyl group" used in the present invention may mean a cyclic saturated hydrocarbon.

[0055] The term "aryl group" as used herein can mean a cyclic aromatic hydrocarbon and can include both a monocyclic aromatic hydrocarbon having a single ring and a polycyclic aromatic hydrocarbon having two or more linked rings.

[0056] The term "heteroalkyl group" as used in the present invention may mean an alkyl group in which a carbon atom (excluding the terminal carbon atom) in the alkyl group is replaced by one or more heteroatoms, where the heteroatom can be selected from N, O and S atoms .

[0057] The term "heteroalkenyl group" as used in the present invention may mean an alkenyl group in which a carbon atom (excluding the terminal carbon atom) in the alkenyl group is replaced by one or more heteroatoms, where the heteroatom can be selected from N, O and S atoms .

[0058] The term "heteroalkynyl group" used in the present invention may mean an alkynyl group in which a carbon atom (excluding the terminal carbon atom) in the alkynyl group is replaced by one or more heteroatoms, where the heteroatom can be selected from N, O and S atoms .

[0059] The term "heterocyclic group" as used in the present invention may mean a cycloalkyl group in which a carbon atom in a cyclic saturated hydrocarbon or a cyclic unsaturated hydrocarbon containing one or more unsaturated bonds is replaced by one or more heteroatoms, where the heteroatom can be selected from N, O and S atoms.

[0060] The terms "derived unit" and "derived functional group" used in the present invention may mean that the component or structure comes from some material, or the material itself.

[0061] The term "single bond" as used in the present invention may mean the very simple covalent bond, not including a single atomic or molecular group.

[0062] The present invention provides a modified conjugated diene polymer obtained by continuous polymerization and having excellent processability, a narrow molecular weight distribution, and excellent physical properties.

[0063] The modified conjugated diene polymer according to an embodiment of the present invention has a unimodal gel permeation chromatography (GPC) molecular weight distribution curve and a molecular weight distribution (MWD; MWD) of 1.0 to less than 1, 7 and includes a functional group derived from a modification initiator at one end and a functional group derived from a modifier represented by the following formula 2 or formula 3 at the other terminus, where the modification initiator is a reaction product of a compound represented by the following formula 1 and an organometallic connections:

[0064] Formula 1

,

,

[0065] in the formula 1, R ₁ -R ₃ are each independently a hydrogen atom, an alkyl group of 1-30 carbon atoms, an alkenyl group of 2-30 carbon atoms, an alkynyl group of 2-30 carbon atoms, a heteroalkyl group of 1- 30 carbon atoms, a heteroalkenyl group of 2-30 carbon atoms, a heteroalkynyl group of 2-30 carbon atoms, a cycloalkyl group of 5-30 carbon atoms, an aryl group of 6-30 carbon atoms, or a heterocyclic group of 3-30 carbon atoms; R ₄ is a single bond, a substituted or unsubstituted alkylene group of 1-20 carbon atoms with a substituent, a substituted or unsubstituted cycloalkylene group of 5-20 carbon atoms with a substituent, or a substituted or unsubstituted arylene group of 6-20 carbon atoms with a substituent, where the substituent is an alkyl group of 1-10 carbon atoms, a cycloalkyl group of 5-10 carbon atoms, or an aryl group of 6-20 carbon atoms; R ₅ represents an alkyl group of 1-30 carbon atoms, an alkenyl group of 2-30 carbon atoms, an alkynyl group of 2-30 carbon atoms, a heteroalkyl group of 1-30 carbon atoms, a heteroalkenyl group of 2-30 carbon atoms, a heteroalkynyl group a group of 2-30 carbon atoms, a cycloalkyl group of 5-30 carbon atoms, an aryl group of 6-30 carbon atoms, a heterocyclic group of 3-30 carbon atoms, or a functional group represented by the following formula 1a or formula 1b, "n" means an integer from 1 to 5, and at least one of the R ₅ groups is a functional group represented by the following formula 1a or formula 1b, where in the case where "n" is an integer from 2 to 5, the set of R ₅ groups can be the same or different;

[0066] Formula 1a

,

,

[0067] in formula 1a, R ₆ is a substituted or unsubstituted alkylene group of 1-20 carbon atoms with a substituent, a substituted or unsubstituted cycloalkylene group of 5-20 carbon atoms with a substituent, or a substituted or unsubstituted arylene group of 6-20 carbon atoms with a substituent, where the substituent is an alkyl group of 1-10 carbon atoms, a cycloalkyl group of 5-10 carbon atoms, or an aryl group of 6-20 carbon atoms; R ₇ and R ₈ are each independently a substituted or unsubstituted alkylene group of 1-20 carbon atoms with an alkyl group of 1-10 carbon atoms, a cycloalkyl group of 5-10 carbon atoms, or an aryl group of 6-20 carbon atoms; R ₉ is a hydrogen atom, an alkyl group of 1-30 carbon atoms, an alkenyl group of 2-30 carbon atoms, an alkynyl group of 2-30 carbon atoms, a heteroalkyl group of 1-30 carbon atoms, a heteroalkenyl group of 2-30 carbon atoms carbon, a heteroalkynyl group of 2-30 carbon atoms, a cycloalkyl group of 5-30 carbon atoms, an aryl group of 6-30 carbon atoms, or a heterocyclic group of 3-30 carbon atoms; and X is an N, O or S atom, in the case where X is an O or S atom, R ₉ is not present;

[0068] Formula 1b

,

,

[0069] in formula 1b, R ₁₀ is a substituted or unsubstituted alkylene group of 1-20 carbon atoms with a substituent, a substituted or unsubstituted cycloalkylene group of 5-20 carbon atoms with a substituent, or a substituted or unsubstituted arylene group of 6-20 carbon atoms with a substituent, where the substituent is an alkyl group of 1-10 carbon atoms, a cycloalkyl group of 5-10 carbon atoms, or an aryl group of 6-20 carbon atoms; and R ₁₁ and R ₁₂ are each independently an alkyl group of 1-30 carbon atoms, an alkenyl group of 2-30 carbon atoms, an alkynyl group of 2-30 carbon atoms, a heteroalkyl group of 1-30 carbon atoms, a heteroalkenyl group of 2 -30 carbon atoms, a heteroalkynyl group of 2-30 carbon atoms, a cycloalkyl group of 5-30 carbon atoms, an aryl group of 6-30 carbon atoms, or a heterocyclic group of 3-30 carbon atoms;

[0070] Formula 2

,

,

[0071] in formula 2, R ₂₀ is a single bond or an alkylene group of 1-10 carbon atoms; R ₂₁ and R ₂₂ each independently represent an alkyl group of 1-10 carbon atoms; R ₂₃ is a single bond or an alkylene group of 1-10 carbon atoms; R ₂₄ represents a hydrogen atom, an alkyl group of 1-10 carbon atoms, or a substituted, divalent, trivalent or tetravalent alkylsilyl group with an alkyl group of 1-10 carbon atoms, "a" means an integer of 2 or 3, "c" means an integer a number from 1 to 3, and "b" means an integer from 0 to 2, where b+c=3;

[0072] Formula 3

[0073] in Formula 3, A ₁ and A ₂ are each independently an alkylene group of 1-20 carbon atoms; R ₂₅ -R ₂₈ each independently represent an alkyl group of 1-20 carbon atoms; and L ₁ -L ₄ are each independently a substituted, divalent, trivalent or tetravalent alkylsilyl group with an alkyl group of 1-10 carbon atoms or an alkyl group of 1-20 carbon atoms.

[0074] According to an embodiment of the present invention, the modified conjugated diene polymer may include a repeating unit derived from the conjugated diene monomer, a functional group derived from a modification initiator, and a functional group derived from a modifier. The repeat unit derived from the conjugated diene monomer may refer to the repeat unit derived from the conjugated diene monomer during polymerization, and the functional group derived from the modification initiator and the functional group derived from the modifier may refer to functional groups derived from the modification initiator and the modifier, which are present at the ends of the polymer chain, respectively.

[0075] In addition, according to another embodiment of the present invention, the modified conjugated diene polymer may be a copolymer comprising a repeat unit derived from a conjugated diene monomer, a repeat unit derived from an aromatic vinyl monomer, a functional group derived from from the initiator of the modification, and a functional group derived from the modifier. In this case, the repeating unit derived from the aromatic vinyl monomer may mean the repeating unit formed by the aromatic vinyl monomer during polymerization.

[0076] According to an embodiment of the present invention, the conjugated diene monomer may be one or more monomers selected from the group consisting of 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 (halogen means a halogen atom).

[0077] The aromatic vinyl monomer may include, for example, one or more monomers selected from the group consisting of 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-pyrrolidinoethyl)styrene and 3-(2-pyrrolidino-1-methylethyl)-α-methylstyrene.

[0078] In another embodiment, the modified conjugated diene polymer may be a copolymer also comprising a repeat unit derived from a diene based monomer of 1-10 carbons together with a repeat unit derived from a conjugated diene monomer. The repeat unit derived from the diene based monomer may be a repeat unit derived from the diene based monomer other than the conjugated diene based monomer, and the diene based monomer other than the conjugated diene based monomer may be, for example , 1,2-butadiene. If the modified conjugated diene-based polymer is a copolymer further comprising a diene-based monomer, the modified conjugated diene-based polymer may include a repeating unit derived from the diene-based monomer in an amount of from more than 0 to 1% by mass, from more than 0 to 0.1% wt., from more than 0 to 0.01% wt. or from more than 0 to 0.001 mass%, and within this range, the effect of preventing gelation can be achieved.

[0079] According to an embodiment of the present invention, the copolymer may be a random copolymer, in which case the effect of an excellent balance between each of the physical properties can be achieved. A random copolymer may mean that the repeating units that make up the copolymer are arranged randomly.

[0080] The modified conjugated diene polymer according to an embodiment of the present invention may have a number average molecular weight (Mn) of 1,000 to 2,000,000 g/mol, 10,000 to 1,000,000 g/mol, or 100,000 to 800,000 g/mol, a weight average molecular mass (Mw) from 1000 to 3000000 g/mol, from 10000 to 2000000 g/mol or from 100000 to 2000000 g/mol, and a maximum molecular weight (Mp) from 1000 to 3000000 g/mol, from 10000 to 2000000 g/mol or from 100,000 to 2,000,000 g/mol. Within these ranges, rolling resistance and wet skid resistance are excellent. In another embodiment, the modified conjugated diene polymer may have a molecular weight distribution (MWD; MWD; Mw/Mn) of less than 1.7, from 1.0 to less than 1.7, or from 1.1 to less than 1.7, and within this range, tensile properties and viscoelastic properties are excellent and the ratio between physical properties is excellent.

[0081] On the other hand, the modified conjugated diene polymer may have a unimodal shape of the molecular weight distribution curve by gel permeation chromatography (GPC). Such a molecular weight distribution shows a polymer polymerized by continuous polymerization, and this means that the modified conjugated diene-based polymer has uniform properties. That is, the modified conjugated diene polymer according to the embodiment of the present invention is obtained by continuous polymerization, and it can have a unimodal molecular weight distribution curve and a molecular weight distribution of less than 1.7.

[0082] Generally, the molecular weight distribution curve of a conjugated diene based polymer produced by preparing a conjugated diene based polymer by a batch polymerization method and then carrying out a modification reaction is a molecular weight distribution curve of a multimodal, i.e., bimodal or more, distribution . In particular, in batch polymerization, the polymerization reaction is initiated after injection of all raw materials, and from the initiation point when polymerization is carried out with a plurality of initiators, chain development can proceed simultaneously. Accordingly, the development of each chain may be generally uniform, the molecular weight of the polymer chains thus obtained may be constant, and the molecular weight distribution may be substantially narrow, showing a unimodal shape. However, in the case where the modifier is injected and the modification reaction is carried out, there can be two cases, "unmodified version" and "modified and coupled version", two groups having a large difference in molecular weight can be formed among the polymer chains, and finally , a multimodal molecular weight distribution curve can be obtained having two or more peaks in the molecular weight distribution curve. However, in the continuous polymerization method according to the embodiment of the present invention other than batch polymerization, the initiator and raw materials are injected continuously, the initiation points when polymerization is initiated are different, and the polymerization is initiated at different points, including reaction initiation, an intermediate step reactions and the end of the reaction. Accordingly, after completion of the polymerization reaction, polymer chains with different molecular weights are obtained. Accordingly, in the curve showing the molecular weight distribution, no dominant peak is visible, and the broad molecular weight distribution curve is presented as a single peak. In addition, although the chain is linked, the polymerization of which is initiated at the end of the reaction, the molecular weight can be similar to the mass of the chain, the polymerization of which is initiated at the start of the reaction, and the difference in molecular weight distribution can be kept the same and in general the unimodal distribution curve is also may be withheld.

[0083] However, the modification conditions can be controlled to exhibit a unimodal shape, although the polymer is polymerized by a batch polymerization method and then modified. However, in this case, the entire polymer is required to be unbound, or the entire polymer is required to be bound. Otherwise, a unimodal molecular weight distribution curve may not appear.

[0084] In addition, as described above, in the case where the molecular weight distribution curve of the modified conjugated diene-based polymer shows a unimodal distribution, although the polymer is obtained by a batch polymerization method and the entire polymer is bonded, there are polymers having an equivalent molecular weight level, and therefore, the processability may be poor, and the number of functional groups that can interact with the filler such as silica and carbon black is reduced due to binding, and the compounding properties may be poor. In contrast, in the case where the entire polymer is not bonded, the functional groups at the end of the polymer, which are necessary for interaction with the filler, such as silica and carbon black, during processing, predominantly interact with the terminal functional groups of the polymer, and not with the filler, and interaction with the filler may be prohibited. Accordingly, the processability may deteriorate significantly, and finally, in the case where the polymer is controlled to exhibit a unimodal molecular weight distribution curve but obtained by a batch polymerization process, the processability and compounding properties of the modified conjugated diene-based polymer thus obtained may worsen, and processability can be especially noticeably worsened.

[0085] However, the binding state of the modified conjugated diene polymer can be checked by the binding number (C.N.), where the binding number means a value depending on the number of functional groups that are able to bind to the polymer present in the modifier after polymer modification. That is, the bonding number means the ratio of a polymer obtained by end modification without bonding between polymer chains and a polymer in which a plurality of polymer chains are linked with one modifier, and may be in the range of 1≤H.C.≤F, where F means the number functional groups in the modifier that are able to interact with the end of the active polymer. In other words, a modified conjugated diene based polymer having a binding number of 1 means that all polymer chains are unlinked, and a modified conjugated diene based polymer having a binding number of F means that all polymer chains are linked.

[0086] Accordingly, the modified conjugated diene polymer according to an embodiment of the present invention may have a unimodal molecular weight distribution curve and a binding number greater than 1 and less than the number of functional groups of the modifier used (1<N.S.<F) .

[0087] In another embodiment, the modified conjugated diene polymer may have a Si content of 50 ppm or more, 100 ppm or more, 100 to 10,000 ppm, or 100 to 5,000 ppm based on total weight, and within this range, mechanical properties such as tensile properties and viscoelastic properties of the rubber composition comprising the modified conjugated diene based polymer are excellent. The Si content may mean the number of Si atoms present in the modified conjugated diene based polymer. However, the Si atom can be derived from a functional group derived from the modifier.

[0088] In another embodiment, the modified conjugated diene polymer may have an N content of 50 ppm or more, 100 ppm or more, 100 to 10,000 ppm, or 100 to 5,000 ppm based on total weight, and within this range, mechanical properties such as tensile properties and viscoelastic properties of the rubber composition comprising the modified conjugated diene based polymer are excellent. The N content may mean the number of N atoms present in the modified conjugated diene polymer, in which case the N atom may be derived from a functional group derived from the modifier.

[0089] The Si content can be measured, for example, using the ICP analysis method, and the ICP analysis method can be performed using inductively coupled plasma optical emission spectroscopy (ICP-OES; Optima 7300DV). If inductively coupled plasma optical emission spectroscopy is used, the measurement can be made by adding approximately 0.7 g of the sample to a platinum (Pt) crucible, adding to it approximately 1 ml of concentrated sulfuric acid (98% wt., grade: for electronic instruments) , heating at 300°C for 3 hours, burning the sample in an electric oven (Thermo Scientific, Lindberg Blue M) according to the following program of three stages 1-3:

[0090] 1) stage 1: initial temperature 0°C, speed (t-pa/hour) 180°C/hour, temperature (hold time) 180°C (1 hour),

[0091] 2) stage 2: start temperature 180°C, speed (t-pa/hour) 85°C/hour, temperature (hold time) 370°C (2 hours), and

[0092] 3) stage 3: initial temperature 370°C, speed (t-pa/hour) 47°C/hour, temperature (hold time) 510°C (3 hours);

[0093] adding 1 ml of concentrated nitric acid (48 wt. %) and 20 μl of concentrated hydrofluoric acid (50 wt. %) to the residue, sealing the platinum crucible and shaking for 30 minutes or longer, adding 1 ml of boric acid to the sample, storing at 0°C for 2 hours or longer, diluted in 30 ml of ultrapure water and calcined.

[0094] In addition, the N content can be measured, for example, by the NSX analysis method, and the measurement by the NSX analysis method can be carried out using a trace nitrogen quantitative analyzer (NSX-2100H). For example, in the case where a trace nitrogen quantitative analyzer is used, the trace nitrogen quantitative analyzer (autosampler, horizontal furnace, PMT, and nitrogen detector) is turned on, the quantities of the flowing carrier gas are set so that Ar is 250 ml/min, O ₂ is 350 ml/min, and the ozonator is 300 ml/min, set the heater to 800°C, and the analyzer is kept for about 3 hours to stabilize. After stabilization of the analyzer, a calibration curve is obtained in the calibration intervals of 5 ppm, 10 ppm, 50 ppm, 100 ppm and 500 ppm using a nitrogen standard (AccuStandard S-22750-01-5 ml), get the area corresponding to each concentration and a straight line is obtained using the ratio of concentration to area. Then, a ceramic boat containing 20 mg of the test sample is placed on the autosampler of the analyzer and measurements are taken to obtain an area. The N content is calculated using the sample area thus obtained and the calibration curve.

[0095] In this case, the test sample used in the NSX analysis method is a modified conjugated diene-based polymer sample obtained by placing it in steam-heated hot water, agitating to remove solvents from it, and removing the remaining monomer and modifier. In addition, if oil is added to the test sample, the sample may be the sample after the oil has been extracted (removed) from it.

[0096] In another embodiment, the modified conjugated diene polymer may have a Mooney stress relaxation coefficient, measured at 100°C, of 0.7 or greater, 0.7 to 3.0, 0.7 to 2.5 or from 0.7 to 2.0.

[0097] Here, the Mooney stress relaxation coefficient means the change in stress exhibited in response to the same amount of strain, and it can be measured using a Mooney viscometer. Specifically, the Mooney stress relaxation coefficient is obtained as an absolute value by measuring the Mooney viscosity using the MV-2000E Large Rotor (Monsanto Co.) at a rotor speed of 2±0.02 rpm at 100°C, while the polymer is kept at room temperature (23±3°C) for 30 minutes or longer, take 27±3 g of polymer and place it in the die cavity, and then operate the press platen while applying torque, and then measure the value of the viscosity change gradient according to Mooney, shown when removing the torque.

[0098] However, the Mooney stress relaxation coefficient can be used as an indicator of the branching of the corresponding polymer structure. For example, if a polymer having an equivalent Mooney viscosity is compared, the Mooney stress relaxation coefficient may decrease with increasing degree of branching, and therefore can be used as an indicator of the degree of branching.

[0099] In addition, the modified conjugated diene polymer can have a Mooney viscosity at 100°C of 30 or more, 40 to 150, or 40 to 140, and within this range, processability and productivity can be excellent.

[00100] In another embodiment, the modified conjugated diene-based polymer may have a compression factor (g'), which is obtained by measurement by a gel permeation light scattering chromatography equipped with a viscometer, of 1.0 or more, preferably from 1.0 to 3.0 , more preferably from 1.0 to 1.3.

[00101] In this case, the compression factor (g') obtained by measurement by the gel permeation chromatography with light scattering, is the ratio of the true viscosity of the polymer having branching to the true viscosity of the linear polymer having the same absolute molecular weight, and can be used in as a branching index of the structure of the polymer having branching, that is, an index of the proportion occupied by branching. For example, as the compression factor decreases, the degree of branching of the respective polymer generally increases. Accordingly, if polymers having an equivalent absolute molecular weight are compared, the compression factor decreases with increasing branching, and the compression factor can be used as an indicator of the degree of branching.

[00102] In addition, the compression factor is obtained by evaluating a chromatogram obtained using a gel permeation light scattering chromatography measuring instrument equipped with a viscometer and calculating based on the viscosity of the solution and the light scattering method. Specifically, using a light scattering GPC instrument equipped with a light scattering detector in which two columns filled with polystyrene gel as a filler are connected and a viscometer, the absolute molecular weight and the true viscosity corresponding to each absolute molecular weight are obtained, and the the true viscosity of the linear polymer corresponding to the absolute molecular weight, and get the compression factor as a ratio of the true viscosity corresponding to each absolute molecular weight. For example, the compression factor is obtained as follows. The sample is injected into a light scattering GPC instrument (Viscotek TDAmax, Malvern Co.) equipped with a light scattering detector in which two columns packed with polystyrene gel as a filler and a viscometer are connected, and the absolute molecular weight is obtained from the light scattering detector. , the true viscosity [ƞ] relative to the absolute molecular weight is obtained from the light scattering detector and the viscometer, the true viscosity [ƞ] ₀ of the linear polymer relative to the absolute molecular weight is calculated by mathematical formula 2 below, and the average value of the true viscosity ratio ([ƞ]/ [ƞ] ₀ ) corresponding to each absolute molecular weight is represented as a compression factor. In this case, measurements are made using a mixed solution of tetrahydrofuran and N,N,N',N'-tetramethylethylenediamine (adjusted by mixing 20 ml of N,N,N',N'-tetramethylethylenediamine with 1 liter of tetrahydrofuran) as eluent and PL Olexix ( Agilent Co.) as a column under conditions of an oven temperature of 40°C and a THF flow rate of 1.0 ml/min. The test sample is prepared by dissolving 15 mg of polymer in 10 ml of THF.

[00103] Mathematical formula 2

[ƞ] ₀₌ 10 ^-3.883 Μ ^0.771

[00104] In the mathematical formula 2, M represents the absolute molecular weight.

[00105] In addition, the modified conjugated diene polymer may have a vinyl content of 5 wt%. or more, 10% of the mass. or more, or from 10 to 60% of the mass. Here, the vinyl content may mean the amount of not 1,4-attached, but 1,2-attached conjugated diene-based monomer relative to 100 wt%. a conjugated diene-based copolymer consisting of a monomer having a vinyl group and an aromatic vinyl monomer.

[00106] However, the modification initiator according to an embodiment of the present invention is obtained by reacting the compound represented by formula 1 with an organometallic compound, and can introduce a functional group at one end of the polymer chain thus polymerized at the same time as polymerization is initiated.

[00107] In particular, the compound represented by formula 1 may have formula 1, in which R ₁ -R ₃ each independently represents a hydrogen atom, an alkyl group of 1-10 carbon atoms, an alkenyl group of 2-10 carbon atoms, or alkynyl a group of 2-10 carbon atoms; R ₄ is a single bond or an unsubstituted alkylene group of 1-10 carbon atoms; R ₅ represents an alkyl group of 1-10 carbon atoms, an alkenyl group of 2-10 carbon atoms, an alkynyl group of 2-10 carbon atoms, or a functional group represented by the following formula 1a or formula 1b; in formula 1a, R ₆ is an unsubstituted alkylene group of 1-10 carbon atoms; R ₇ and R ₈ are each independently an unsubstituted alkylene group of 1-10 carbon atoms; and R ₉ is an alkyl group of 1-10 carbon atoms, a cycloalkyl group of 5-20 carbon atoms, an aryl group of 6-20 carbon atoms, or a heterocyclic group of 3-20 carbon atoms; and in formula 1b, R ₁₀ is an unsubstituted alkylene group of 1-10 carbon atoms; R ₁₁ and R ₁₂ each independently represent an alkyl group of 1-10 carbon atoms, a cycloalkyl group of 5-20 carbon atoms, an aryl group of 6-20 carbon atoms, or a heterocyclic group of 3-20 carbon atoms.

[00108] More specifically, the compound represented by formula 1 may be the compound represented by the following formulas 1-1 to 1-3:

[00109] Formula 1-1

[00110] Formula 1-2

[00111] Formula 1-3

[00112] In addition, the organometallic compound may be an organic alkali metal compound, for example, one or more compounds selected from an organolithium compound, an organosodium compound, an organopotassium compound, an organorubidium compound, and an organocesium compound.

[00113] In particular, the organometallic compound may be one or more of methyl lithium, ethyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, t-butyl lithium, n-decyl lithium, t-octyl lithium, phenyl lithium, 1-naphthyllithium, n-eicosyllithium, 4-butylphenyllithium, 4-tolyllithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium and 4-cyclopentyllithium.

[00114] In addition, the modifier according to the present invention may be a modifier for modifying the remaining one end of the conjugated diene-based polymer, and in a particular embodiment, may be a modifier having an affinity for silica. A modifier having an affinity for silica may mean a modifier including a functional group having an affinity for silica in the compound used as a modifier, and a functional group having an affinity for silica may mean a functional group that has excellent affinity for a filler, especially a silica-based filler, and is capable of interacting between the silica-based filler and the functional group derived from the modifier.

[00115] In particular, according to an embodiment of the present invention, the modifier may be a compound represented by formula 2, and in formula 2, R ₂₀ may be a single bond or an alkylene group of 1-5 carbon atoms; R ₂₁ and R ₂₂ each independently may represent an alkyl group of 1-5 carbon atoms; R ₂₃ may be a single bond or an alkylene group of 1-5 carbon atoms; R ₂₄ may be a hydrogen atom, an alkyl group of 1-5 carbon atoms, or a substituted tetravalent alkylsilyl group with an alkyl group of 1-5 carbon atoms, "a" may be the integer 2 or 3, "c" may be the integer a number from 1 to 3, and "b" may be an integer from 0 to 2, where the equation b+c=3 can be satisfied.

[00116] In a more specific embodiment, the compound represented by formula 2 may be selected from the group consisting of N,N-bis(3-(dimethoxy(methyl)silyl)propyl)-methyl-1-amine, N,N-bis (3-(diethoxy(methyl)silyl)propyl)methyl-1-amine, N,N-bis(3-(trimethoxysilyl)propyl)methyl-1-amine, N,N-bis(3-(triethoxysilyl)propyl) methyl-1-amine, N, N-diethyl-3-(trimethoxysilyl)propan-1-amine, N, N-diethyl-3-(triethoxysilyl)propan-1-amine, tri(trimethoxysilyl)amine, tri( 3-(trimethoxysilyl)propyl)amine, N,N-bis(3-(diethoxy(methyl)silyl)propyl)-1,1,1-trimethylsilamine and 3-(dimethoxy(methyl)silyl)-N,N-diethylpropane -1-amine.

[00117] In addition, in particular, according to another embodiment of the present invention, the modifier may be a compound represented by formula 3, and in formula 3, A ₁ and A ₂ each independently may represent an alkylene group of 1 to 10 carbon atoms; R ₂₅ -R ₂₈ each independently may be an alkyl group of 1-10 carbon atoms, and L ₁ -L ₄ each independently may be a substituted tetravalent alkylsilyl group of 1-5 carbon atoms or an alkyl group of 1-10 carbon atoms.

[00118] In a more specific embodiment, the compound represented by Formula 3 may be a compound selected from the group consisting of 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N, N-dimethylpropan-1-amine), 3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N, N-dimethyl-propan-1-amine), 3,3' -(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)-bis(N, N-dimethylpropan-1-amine), 3,3'-(1,1,3,3-tetramethoxy-disiloxane- 1,3-diyl)bis(N, N-diethylpropan-1-amine), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N, N-dipropylpropan-1 -amine), 3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N, N-diethyl-propan-1-amine), 3,3'-(1,1 ,3,3-tetrapropoxydisiloxane-1,3-diyl)-bis(N, N-diethylpropan-1-amine), 3,3'-(1,1,3,3-tetraethoxy-disiloxane-1,3-diyl )bis(N, N-dipropylpropan-1-amine), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N, N-dipropyl-propan-1-amine) , 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)-bis(N, N-diethylmethane-1-amine), 3,3'-(1,1,3,3 -tetraethoxy-disiloxane-1,3-diyl)bis(N, N- diethylmethane-1-amine), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N, N-diethylmethane-1-amine), 3,3'-(1, 1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N, N-dimethyl-methane-1-amine), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl )-bis(N, N-dipropylmethane-1-amine), 3,3'-(1,1,3,3-tetrapropoxy-disiloxane-1,3-diyl)bis(N, N-dimethylmethane-1-amine ), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N, N-dipropylmethane-1-amine), 3,3'-(1,1,3,3 -tetraethoxydisiloxane-1,3-diyl)bis(N, N-dimethyl-methane-1-amine), 3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)-bis(N , N-dipropylmethane-1-amine), N, N'-((1,1,3,3-tetramethoxy-disiloxane-1,3-diyl)bis(propane-3,1-diyl))bis(1, 1,1-trimethyl-N-(trimethylsilyl)silanamine), N, N'-((1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(propane-3,1-diyl))bis( 1,1,1-trimethyl-N-(trimethyl-silyl)silanamine), N, N'-((1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(propan-3,1-diyl ))bis(1,1,1-trimethyl-N-(trimethylsilyl)-silanamine), N, N'-((1,1,3,3-tetramethoxydisiloxane-1,3-diyl)-bis(propane-3 ,1-diyl))bis(1,1, 1-trimethyl-N-phenylsilanamine), N, N'-((1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(propan-3,1-diyl))-bis(1,1, 1-trimethyl-N-phenylsilanamine) and N, N'-((1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(propane-3,1-diyl))bis(1,1,1 -trimethyl-N-phenylsilanamine).

[00119] As described above, the modified conjugated diene polymer according to an embodiment of the present invention has a specific structure and may have a specific degree and shape of molecular weight distribution. Such a polymeric structure can be expressed in physical properties such as compression factor, Mooney stress relaxation coefficient, and binding number. The degree and shape of its molecular weight distribution can be expressed by the molecular weight distribution value, the shape of the molecular weight distribution curve and the binding number, and the modification of both ends by the modifier and the initiator of the modification can affect its structure and the degree and shape of its molecular weight distribution . The parameters expressing the structure of such a polymer and the characteristics relating to the molecular weight distribution can be satisfied by the method of preparation, which will be described later.

[00120] Further, preferably, the above-mentioned characteristics can be satisfied by the production method, but as long as all of the above-mentioned characteristics are fulfilled, implementation effects can be achieved in the present invention.

[00121] In addition, the present invention provides a process for producing a modified conjugated diene-based polymer.

[00122] A method for producing a modified conjugated diene based polymer according to an embodiment of the present invention may include polymerizing a conjugated diene based monomer, or a conjugated diene based monomer and an aromatic vinyl monomer in the presence of a modification initiator in a hydrocarbon solvent to obtain an active polymer comprising a functional group derived from a modification initiator (S1); and reacting or coupling the active polymer obtained in step (S1) with the modifier represented by formula 2 below or formula 3 (S2), where step (S1) is carried out continuously in two or more polymerization reactors, the polymerization conversion rate in the first reactor of polymerization reactors is 50% or less, and the modification initiator is a reaction product obtained by reacting the compound represented by Formula 1 below and an organometallic compound.

[00123] Formula 1

[00124] Formula 2

[00125] Formula 3

.

.

[00126] In formulas 1-3, R ₁ -R ₅ , R ₂₀ -R ₂₈ , A ₁ , A ₂ , L ₁ -L ₄ , "n", "a", "b" and "c" have the same values as described above.

[00127] The hydrocarbon solvent is not particularly limited and may be, for example, one or more solvents selected from the group consisting of n-pentane, n-hexane, n-heptane, isooctane, cyclohexane, toluene, benzene, and xylene.

[00128] In addition, the conjugated diene monomer and the aromatic vinyl monomer are the same as defined above.

[00129] According to an embodiment of the present invention, the modification initiator may be used in an amount of 0.01 to 10 mmol, 0.05 to 5 mmol, 0.1 to 2 mmol, 0.1 to 1 mmol, or 0.15 to 0.8 mmol based on total 100 g of monomers.

[00130] The polymerization step (S1) may be, for example, an anionic polymerization, and especially a living anionic polymerization, in which an anionic active moiety is formed at the polymerization terminal via an anion-assisted reaction. Further, the polymerization step (S1) can be carried out by heating polymerization, isothermal polymerization, or constant temperature polymerization (adiabatic polymerization). Constant temperature polymerization means a polymerization method including a polymerization step using a self-generated heat of reaction without the need to apply heat after adding a polymerization initiator, and heating polymerization means a polymerization method including injection of a polymerization initiator and raising the temperature optionally by applying heat. Isothermal polymerization means a polymerization process in which the temperature of the polymerization reactants is kept constant by applying heat or removing heat after adding a polymerization initiator.

[00131] In addition, according to an embodiment of the present invention, the polymerization in step (S1) can be carried out by further including a diene-based compound of 1 to 10 carbon atoms in addition to the conjugated diene-based monomer, in which case the effect of preventing gelation on the side wall of the reactor after running for a long time. The diene-based compound may be, for example, 1,2-butadiene.

[00132] The polymerization in step (S1) can be carried out in a temperature range of 80°C or less, -20 to 80°C, 0 to 80°C, 0 to 70°C, or 10 to 70°C, and within this range, a narrow molecular weight distribution of the polymer is controlled, and an effect of excellent improvement in physical properties can be achieved.

[00133] The active polymer obtained in step (S1) may mean a polymer in which a polymer anion and an organometallic cation are bound.

[00134] According to an embodiment of the present invention, a method for producing a modified conjugated diene polymer can be carried out in a plurality of reactors including two or more polymerization reactors and a modification reactor by a continuous polymerization method. In a specific embodiment, step (S1) may be carried out in two or more polymerization reactors, including the first reactor, and the number of polymerization reactors may be freely determined depending on the reaction conditions and environment. A continuous polymerization process may mean reaction processes of continuously supplying reactants to a reactor and continuously discharging the reaction products thus produced. With the continuous polymerization process, excellent productivity and processability as well as excellent uniformity of the polymer thus obtained can be achieved.

[00135] In addition, according to an embodiment of the present invention, in the case where the active polymer is continuously produced in the polymerization reactor, the polymerization conversion rate in the first reactor may be 50% or less, 10 to 50%, or 20 to 50 %, and within this range, side reactions occurring in the formation of the polymer after the initiation of the polymerization reaction can be limited, and a polymer with a linear structure can be induced during polymerization. Therefore, the narrow molecular weight distribution of the polymer can be controlled, and the effect of improving physical properties can be achieved.

[00136] In this case, the polymerization conversion rate can be controlled depending on the reaction temperature, residence time in the reactor, etc.

[00137] The polymerization conversion rate can be determined, for example, by measuring the solids concentration in the polymer solution phase comprising the polymer during polymerization of the polymer. In a particular embodiment, in order to fix the polymer solution, a cylindrical container is placed at the outlet of each polymerization reactor to fill the cylindrical container with some of the polymer solution. Then the cylindrical container is separated from the reactor, the mass (A) of the cylinder filled with the polymer solution is determined, the polymer solution in the cylindrical container is transferred to an aluminum container, for example, on an aluminum tray, the mass (B) of the cylindrical container from which the polymer solution is removed is determined , the aluminum container containing the polymer solution is dried in an oven at 140°C for 30 minutes, the mass (C) of the dried polymer is determined, and the calculation is carried out in accordance with the following mathematical equation 1:

[00138] Math Equation 1

[00139] However, the polymerization reagent polymerized in the first reactor may be fed into the polymerization reactor before the modification reactor in order, and the polymerization may be carried out until the final polymerization conversion rate becomes 95% or more. After the polymerization in the first reactor, the polymerization conversion rate of the second reactor, or each reactor from the second reactor to the polymerization reactor before the modification reactor, can be appropriately controlled to control the molecular weight distribution.

[00140] However, in step (S1) when producing the active polymer, the residence time of the polymerization reagent in the first reactor may be from 1 to 40 minutes, from 1 to 30 minutes, or from 5 to 30 minutes, and within this interval, the adjustment of the coefficient polymerization conversion is optimal, and therefore a narrow molecular weight distribution of the polymer can be controlled, and the effect of improving physical properties can be excellent.

[00141] The term “polymerization reagent” used in the present invention may mean a polymer type intermediate that is in the polymerization process in each reactor during step (S1), after the end of step (S1) or step (S2), before obtaining an active polymer or a modified conjugated diene based polymer, or may mean a polymer with a polymerization conversion rate of less than 95% that is in the process of polymerization in a reactor.

[00142] In accordance with an embodiment of the present invention, the molecular weight distribution (PPD, polydispersity index; MWD, molecular weight distribution; Mw/Mn) of the active polymer obtained in step (S1) may be less than 1.5, from 1.0 and up to less than 1.5, or from 1.1 to less than 1.5, and within this range, the molecular weight distribution of the modified conjugated diene-based polymer, which is obtained by a modification reaction or coupling with a modifier, is narrow, and the effect of improving the physical properties can be excellent.

[00143] However, the polymerization in step (S1) can be carried out by including a polar additive, and the polar additive can be added in a ratio of 0.001 to 50 g, 0.001 to 10 g, or 0.005 to 0.1 g of calculation for the total 100 g of monomers. In another embodiment, the polar additive may be added in a ratio of 0.001 to 10 g, 0.005 to 5 g, or 0.005 to 4 g per 1 mmol of modification initiator.

[00144] The polar additive may be, for example, one or more additives selected from the group consisting of tetrahydrofuran, 2,2-di(2-tetrahydrofuryl)propane, diethyl ether, cycloamyl ether, dipropyl ether, ethylene methyl ether, ethylene dimethyl ether, diethyl glycol, dimethyl ether, t-butoxyethoxyethane, bis(3-dimethylaminoethyl)ether, (dimethylaminoethyl)ethyl ether, trimethylamine, triethylamine, tripropylamine, N,N,N',N'-tetramethylethylenediamine, sodium mentholate and 2-ethyltetrahydrofurfuryl ether , and may preferably be triethylamine, tetramethylethylenediamine, sodium menthol or 2-ethyltetrahydrofurfuryl ether. If a polar additive is included, and if a conjugated diene-based monomer or a conjugated diene-based monomer and an aromatic vinyl-based monomer are copolymerized, the difference between their reaction rates can be compensated, and the effect of easily inducing the formation of a random copolymer can be achieved.

[00145] In accordance with an embodiment of the present invention, the reaction or coupling in step (S2) may be carried out in a modification reactor, in which case the modifier may be used in an amount of 0.01 to 10 mmol based on total 100 g of monomers. In another embodiment, the modifier can be used in a mole ratio of 1:0.1-10, 1:0.1-5, or 1:0.1 to 1:3, based on 1 mole of the modification initiator in step (S1).

[00146] In addition, according to an embodiment of the present invention, the modifier may be injected into the modification reactor, and step (S2) may be carried out in the modification reactor. In another embodiment, the modifier may be injected into the transfer portion to transfer the active polymer obtained in step (S1) to the modification reactor for step (S2), and the transfer portion may be reacted or bonded by mixing the active polymer and the modifier.

[00147] In addition, the present invention provides a rubber composition comprising a modified conjugated diene-based polymer.

[00148] The rubber composition may include a modified conjugated diene-based polymer in an amount of 10% by weight. or more, from 10 to 100 mass%, or 20 to 90 mass%, and within this range, mechanical properties such as tensile strength and abrasion resistance are excellent, and the effect of an excellent ratio between each of the physical properties.

[00149] In addition, the rubber composition may include, for example, from 0.1 to 200 mass., or from 10 to 120 mass. filler relative to 100 mass.h. modified polymer based on conjugated diene.

[00150] In addition, the rubber composition may include, for example, process oil, in which case the process oil can be from 20 to 60 wt. relative to 100 mass.h. modified polymer based on a conjugated diene.

[00151] In addition, in another embodiment, the present invention provides a rubber composition comprising 100 wt.h. modified polymer based on conjugated diene and from 20 to 60 wt.h. process oil, where the modified conjugated diene-based polymer has a polymer component with a molecular weight of 100,000 g/mol or more when converted by molecular weight according to a polystyrene standard in gel permeation chromatography (GPC) with a unimodal shape, a number average molecular weight of from 100,000 to 700,000 g/mol, molecular weight distribution of 2.5 or less, the amount of polymer component having a functional group, 50% of the mass. or more, the vinyl content of the butadiene unit is 20 to 80 mol %, the Si content and the N content are each 100 ppm or more based on mass, the Mooney stress relaxation coefficient measured at 100°C is 0.7 or more, and a compression factor obtained by measuring with a light scattering gel permeation chromatography method equipped with a viscometer, 1.0 or more.

[00152] However, in another embodiment of the present invention, the amount of the polymer component having a functional group indicates the degree of modification of the modified conjugated diene polymer, for example, the degree of modification can be obtained by evaluating each chromatogram using GPC in which the three columns with a polystyrene gel (Shodex), and a GPC in which a column with a silica gel (Zorbax) is attached, and determining the absorbance of the silica column by the difference between them.

[00153] In addition, the rubber composition may further include another rubber component, if necessary, in addition to the modified conjugated diene-based polymer, in which case the rubber component may be included in the amount of 90% of the mass. or less based on the total amount of the rubber composition. In a specific embodiment, the rubber component may be included in an amount of from 1 to 900 wt.h. based on 100 mass.h. modified copolymer based on conjugated diene.

[00154] The rubber component, for example, may be natural rubber or synthetic rubber, and especially may be natural rubber (NR), including cis-1,4-polyisoprene; modified natural rubber, which is obtained by modifying or refining conventional natural rubber such as epoxidized natural rubber (ENR), deprotonated natural rubber (DPNR), and hydrogenated natural rubber; and 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 and halogenated butyl rubber, and one or a mixture of two or more can be used.

[00155] The filler may be, for example, a silica-based filler, especially wet silica (hydrated silicate), dry silica (anhydrous silicate), calcium silicate, aluminum silicate, or colloidal silica. Preferably, the filler may be wet silica, which has the strongest destructive performance enhancing effect and a compatible adhesive effect on a wet surface. In addition, the rubber composition may also include a carbon-based filler, if necessary.

[00156] In another embodiment, if silica is used as a filler, a silane coupling agent can be used with it to improve reinforcement and low exothermic properties. Specific examples of the silane coupling agent may 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-dimethylthiocarbamoyltetra триэтоксисилилэтил-N, N-диметилтиокарбамоилтетрасульфид, 3-триметоксисилилпропилбензо-тиазолилтетрасульфид, 3-триэтоксисилилпропилбензоилтетрасульфид, 3-триэтоксисилилпропилметакрилатмоносульфид, 3-триметоксисилил-пропилметакрилатмоносульфид, бис(3-диэтоксиметилсилилпропил)-тетрасульфид, 3-меркаптопропилдиметоксиметилсилан, диметокси-метилсилилпропил-N, N-диметилтиокарбамоилтетрасульфид or dimethoxymethylsilylpropylbenzothiazolyltetrasulfi and any one or a mixture of two or more of them can be used. Preferably, bis(3-triethoxysilylpropyl)polysulfide or 3-trimethoxysilylpropylbenzothiazolyltetrasulfide can be used in view of the effect of improving reinforcing properties.

[00157] In addition, in the rubber composition according to the embodiment of the present invention, since a modified conjugated diene polymer in which a functional group having a high affinity for silica is in the active portion is used as the rubber component, the mixing amount of silane the binding agent may be less than in the usual case. Thus, the silane coupling agent may be used in an amount of 1 to 20 parts by mass, or 5 to 15 parts by mass. based on 100 mass.h. silicon dioxide. Due to the amount used in this range, the effect as a binding agent can be exhibited to a large extent, and the effect of preventing the gelation of the rubber component can be achieved.

[00158] The process oil in the rubber composition acts as an emollient and may include, for example, a paraffinic, naphthenic, or aromatic compound. An aromatic process oil may be used when considering tensile strength and abrasion resistance, and a naphthenic or paraffinic process oil may be used when considering hysteresis loss and low temperature properties. Technological oil can be included in the amount of 100 wt.h. or less based on 100 mass.h. rubber component. Within the above range, deterioration in tensile strength and low exothermic properties (low fuel consumption) of the vulcanized rubber can be prevented.

[00159] The rubber composition according to an embodiment of the present invention may be cross-linked with sulfur, and therefore may further include a vulcanizing agent. The vulcanizing agent, in particular, may be a powder of sulfur and may be included in an amount of from 0.1 to 10 wt.h. based on 100 mass.h. rubber component. Due to the amount used in this range, the elasticity and strength required for the vulcanized rubber composition can be secured and at the same time low fuel consumption can be achieved.

[00160] The rubber composition according to an embodiment of the present invention may also include various additives used in the general rubber industry, in addition to the components described above, in particular, a vulcanization accelerator, an antioxidant, a plasticizer, an antioxidant, an anti-scorch agent, zinc white, stearic acid, thermosetting resin or thermoplastic resin.

[00161] The vulcanization accelerator may include, for example, thiazole-based compounds such as 2-mercaptobenzothiazole (M), dibenzothiazyl disulfide (DM), and N-cyclohexyl-2-benzothiazylsulfenamide (CZ), or guanidine-based compounds such as diphenylguanidine (DPG), in an amount of from 0.1 to 5 wt.h. based on 100 mass.h. rubber component.

[00162] The antioxidant may include, for example, 2,6-di-tert-butyl-para-cresol, dibutylhydroxytoluene, 2,6-bis((dodecylthio)-methyl)-4-nonylphenol, or 2-methyl-4,6- bis((octylthio)methyl)phenol, and can be used in an amount of from 0.1 to 6 wt.h. based on 100 mass.h. rubber component.

[00163] The antioxidant may include, for example, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, 6-ethoxy-2,2,4 -trimethyl-1,2-dihydro-quinoline or a condensate of diphenylamine and acetone, obtained at high temperature, in an amount of from 0.1 to 6 mass.h. based on 100 mass.h. rubber component.

[00164] The rubber composition according to an embodiment of the present invention can be prepared by mixing using mixing and kneading equipment such as a Banbury mixer, rollers, and an internal mixer according to mixing recommendations. A rubber composition having low exothermic properties and good abrasive properties can be obtained by vulcanization after the molding process.

[00165] Thus, the rubber composition may be useful in the manufacture of any element of a tire, such as a tire tread, undertread, sidewall, carcass cover rubber, belt cover rubber, bead filler, bead tape, and bead cover rubber, or for production of rubber products in various industries such as vibration resistant rubber, conveyor belt and hose.

[00166] The present invention also provides a tire made using a rubber composition.

[00167] The tire may be a tire or a tire including a tire tread.

[00168] Hereinafter, the present invention is discussed in more detail with reference to embodiments. The embodiments according to the present invention can be converted to various other types, and the scope of the present invention should not be limited to the embodiments described below. Embodiments of the present invention are presented for the purpose of fully explaining the present invention to a person with an average level of knowledge in this field of technology.

[00169] Obtaining Example 1

[00170] Two 4 L vacuum-dried high pressure stainless steel reactors are prepared. 985 g of cyclohexane, 120 g of the compound represented by the formula 1-3 below, and 86 g of tetramethylethylenediamine are injected into the first high pressure reactor to obtain a first reaction solution. Simultaneously, 318 g of a liquid phase of 20% by weight are injected into the second high pressure reactor. n-butyllithium and 874 g of cyclohexane, a second reaction solution is obtained. In this case, the molar ratio of the compound represented by the formula 1-3, n-butyllithium and tetramethylethylenediamine is 1:1:1. While maintaining the pressure in each high pressure reactor at 7 bar, the first reaction solution is injected at an injection rate of 1.0 g/min through the first continuous type channel, and the second reaction solution is injected at an injection rate of 1.0 g/min through the second continuous type channel, respectively, into a continuous reactor using a mass flow meter. In this case, the temperature of the continuous reactor is maintained at -10°C, the internal pressure is maintained at 3 bar using a back pressure regulator, and the residence time in the reactor is adjusted to be within 10 minutes. The reaction is completed, the modification initiator is obtained.

[00171] Formula 1-3

.

.

[00172] Obtaining Example 2

[00173] Two 4 L vacuum-dried high pressure stainless steel reactors are prepared. 944 g of cyclohexane, 161 g of the compound represented by the following formula 1-1, and 86 g of tetramethylethylenediamine are injected into the first high pressure reactor to obtain a first reaction solution. Simultaneously, 318 g of a liquid phase of 20% by weight are injected into the second high pressure reactor. n-butyllithium and 874 g of cyclohexane, a second reaction solution is obtained. In this case, the molar ratio of the compound represented by formula 1-1 to n-butyllithium and tetramethylethylenediamine is 1:1:1. While maintaining the pressure in each high pressure reactor at 7 bar, the first reaction solution is injected at an injection rate of 1.0 g/min through the first continuous type channel, and the second reaction solution is injected at an injection rate of 1.0 g/min through the second continuous type channel, respectively, into a continuous reactor using a mass flow meter. In this case, the temperature of the continuous reactor is maintained at -10°C, the internal pressure is maintained at 3 bar using a back pressure regulator, and the residence time in the reactor is adjusted to be within 10 minutes. The reaction is completed, the modification initiator is obtained.

[00174] Formula 1-1

[00175] Obtaining Example 3

[00176] Two 4 L vacuum-dried high pressure stainless steel reactors are prepared. 898 g of cyclohexane, 207 g of the compound represented by the formula 1-2 below, and 86 g of tetramethylethylenediamine are injected into the first high pressure reactor to obtain a first reaction solution. Simultaneously, 318 g of a liquid phase of 20% by weight are injected into the second high pressure reactor. n-butyllithium and 874 g of cyclohexane, a second reaction solution is obtained. In this case, the molar ratio of the compound represented by the formula 1-2, n-butyllithium and tetramethylethylenediamine is 1:1:1. While maintaining the pressure in each high pressure reactor at 7 bar, the first reaction solution is injected at an injection rate of 1.0 g/min through the first continuous type channel, and the second reaction solution is injected at an injection rate of 1.0 g/min through the second continuous type channel, respectively, into a continuous reactor using a mass flow meter. In this case, the temperature of the continuous reactor is maintained at -10°C, the internal pressure is maintained at 3 bar using a back pressure regulator, and the residence time in the reactor is adjusted to be within 10 minutes. The reaction is completed, the modification initiator is obtained.

[00177] Formula 1-2

.

.

[00178] Example 1

[00179] In the first reactor of the continuous reactors, where three reactors are connected in series, injected with a solution of styrene, in which 60% of the mass. styrene dissolved in n-hexane, at a rate of 3.08 kg/hour, a solution of 1,3-butadiene, in which 60% of the mass. 1,3-butadiene is dissolved in n-hexane, at a rate of 12.90 kg/hour, n-hexane at a rate of 47.66 kg/hour, a solution of 1,2-butadiene, in which 2.0% of the mass. 1,2-butadiene is dissolved in n-hexane, at a rate of 10 g/hour, a solution in which 10% of the mass. 2,2-di(2-tetrahydrofuryl)propane was dissolved in hexane as a polar additive at a rate of 10.0 g/hour, and the modification initiator obtained in Preparation Example 1 at a rate of 292.50 g/hour. In this case, the temperature in the first reactor is maintained at about 50°C, and when the polymerization conversion rate reaches 43%, the polymerization reagent is transferred from the first reactor to the second reactor through a transfer pipe.

[00180] Then a solution of 1,3-butadiene is injected into the second reactor, in which 60% of the mass. 1,3-butadiene dissolved in n-hexane, at a rate of 0.68 kg/hour. In this case, the temperature in the second reactor is maintained at about 65°C, and when the polymerization conversion rate reaches 95%, the polymerization reagent is transferred from the second reactor to the third reactor through a transfer pipe.

[00181] The polymerization reagent is transferred from the second reactor to the third reactor, and a solution in which N,N-bis(3-(diethoxy(methyl)silyl)propyl)methyl-1-amine is dissolved as a modifier is injected into the third reactor [modifier: active Li=1:1 mol.]. The temperature of the third reactor is maintained at about 65°C.

[00182] After that, into the polymerization solution discharged from the third reactor, an IR1520 solution (BASF Co.) is injected, in which 30% of the mass is dissolved. IR1520, as an antioxidant at a speed of 170 g/hour and mix. The polymerization reagent thus obtained is placed in steam-heated hot water and agitated to remove solvents, and a modified conjugated diene-based polymer is obtained.

[00183] Example 2

[00184] A modified conjugated diene-based polymer is obtained by carrying out the same procedure as in example 1, except for continuously feeding into the third reactor a solution in which 3,3'-(1,1,3,3-tetramethoxy- disiloxane-1,3-diyl)bis-(N,N-diethylpropan-1-amine) instead of N,N-bis(3-(diethoxy(methyl)-silyl)propyl)methyl-1-amine as modifier [modifier :active Li=1:1 mol.].

[00185] Example 3

[00186] A modified conjugated diene-based polymer was obtained by carrying out the same procedure as in Example 1, except that the modification initiator obtained in Production Example 2 was continuously supplied to the first reactor in Example 1 instead of the modification initiator obtained in Production Example 1 , as a modification initiator at a rate of 292.5 g/h.

[00187] Example 4

[00188] A modified conjugated diene-based polymer was obtained by carrying out the same procedure as in Example 1, except that the modification initiator obtained in Production Example 3 was continuously supplied to the first reactor in Example 1 instead of the modification initiator obtained in Production Example 1 , as a modification initiator at a rate of 292.5 g/h.

[00189] Example 5

[00190] A modified conjugated diene-based polymer is obtained by carrying out the same procedure as in example 1, except for continuously feeding into the third reactor a solution in which 3-(dimethoxy(methyl)silyl)-N,N-diethylpropan- 1-amine instead of N,N-bis(3-(diethoxy(methyl)silyl)-propyl)methyl-1-amine, as a modifier [modifier: active Li=1:1 mol.].

[00191] Example 6

[00192] In the first reactor of the continuous reactors, where three reactors are connected in series, injected with a solution of styrene, in which 60% of the mass. styrene dissolved in n-hexane, at a rate of 6.58 kg/hour, a solution of 1,3-butadiene, in which 60% of the mass. 1,3-butadiene is dissolved in n-hexane, at a rate of 9.58 kg/hour, n-hexane at a rate of 47.66 kg/hour, a solution of 1,2-butadiene, in which 2.0% of the mass. 1,2-butadiene is dissolved in n-hexane, at a rate of 10 g/hour, a solution in which 10% of the mass. 2,2-di(2-tetrahydrofuryl)propane was dissolved in n-hexane, as a polar additive, at a rate of 10.0 g/hour, and the modification initiator obtained in Production Example 1 at a rate of 292.5 g/hour. In this case, the temperature of the first reactor is maintained at 50°C, and when the polymerization conversion rate reaches 43%, the polymerization reagent is transferred from the first reactor to the second reactor through a transfer pipe.

[00193] Then a solution of 1,3-butadiene is injected into the second reactor, in which 60% of the mass. 1,3-butadiene dissolved in n-hexane, at a rate of 0.50 kg/hour. In this case, the temperature in the second reactor is maintained at 65°C, and when the polymerization conversion rate reaches 95% or more, the polymerization reagent is transferred from the second reactor to the third reactor through a transfer pipe.

[00194] The polymerization reagent is transferred from the second reactor to the third reactor, and a solution in which N,N-bis(3-(diethoxy(methyl)silyl)propyl)methyl-1-amine is dissolved is injected into the third reactor as a modifier [modifier :active Li=1:1 mol.]. The temperature of the third reactor is maintained at 65°C.

[00195] After that, the IR1520 solution (BASF Co.) is injected into the polymerization solution discharged from the third reactor, in which 30% of the mass is dissolved. IR1520, as an antioxidant at a speed of 167 g/hour and mix. The polymerization reagent thus obtained is placed in steam-heated hot water and agitated to remove solvents, and a modified conjugated diene-based polymer is obtained.

[00196] Example 7

[00197] A modified conjugated diene polymer is obtained by carrying out the same procedure as in Example 6, except for transferring the polymerization reagent from the first reactor to the second reactor through a transfer pipe when the polymerization conversion rate reaches 41%, and continuously feeding into third solution reactor in which 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine) is dissolved as a modifier, [modifier: active Li =1:1 mol.].

[00198] Comparative Example 1

[00199] 100 g of styrene, 346 g of 1,3-butadiene, 2500 g of n-hexane and 0.78 g of 2,2-di(2-tetrahydrofuryl)propane are injected into a 20 L autoclave reactor as a polar additive, and internal the reactor temperature is raised to 50°C. After reaching an internal temperature of 50° C., 226.7 g of the modification initiator obtained in Production Example 1 was injected, and an adiabatic reaction was carried out with heating. Approximately 20 minutes later, 18.2 g of 1,3-butadiene are injected to close the ends of the polymer chain with butadiene. After 5 minutes, a solution is injected into the reactor in which 3-(dimethoxy(methyl)-silyl)-N, N-diethylpropan-1-amine is dissolved as a modifier and the reaction is carried out for 15 minutes [modifier: active Li=1:1 mol .]. Then, the polymerization reaction was stopped using ethanol, and 2.35 g of the antioxidant IR1520 (BASF Co.) was added. The polymerization agent thus obtained is injected into hot steam-heated water and stirred to remove solvents to obtain a modified styrene-butadiene copolymer.

[00200] Comparative Example 2

[00201] In the first reactor of continuous reactors, where three reactors are connected in series, injected with a solution of styrene, in which 60% of the mass. styrene dissolved in n-hexane, at a rate of 3.08 kg/hour, a solution of 1,3-butadiene, in which 60% of the mass. 1,3-butadiene is dissolved in n-hexane, at a rate of 12.90 kg/hour, n-hexane at a rate of 47.66 kg/hour, a solution of 1,2-butadiene, in which 2.0% of the mass. 1,2-butadiene is dissolved in n-hexane, at a rate of 10 g/hour, a solution in which 10% of the mass. 2,2-di(2-tetrahydrofuryl)propane is dissolved in n-hexane, as a polar additive at a rate of 10.0 g/h, and a solution of n-butyl lithium, in which 15% wt. n-butyllithium dissolved in n-hexane as a polymerization initiator at a rate of 39.0 g/h. In this case, the temperature of the first reactor is maintained at 55°C, and when the polymerization conversion rate reaches 48%, the polymerization reagent is transferred from the first reactor to the second reactor through a transfer pipe.

[00202] Then a solution of 1,3-butadiene is injected into the second reactor, in which 60% of the mass. 1,3-butadiene dissolved in n-hexane, at a rate of 0.68 kg/hour. In this case, the temperature in the second reactor is maintained at 65°C, and when the polymerization conversion rate reaches 95% or more, the polymerization reagent is transferred from the second reactor to the third reactor through a transfer pipe.

[00203] The polymerization reagent is transferred from the second reactor to the third reactor, and a solution in which dichlorodimethylsilane is dissolved as a coupling agent is injected into the third reactor [coupling agent: active Li=1:1 mol.]. The temperature of the third reactor is maintained at 65°C.

[00204] After that, the solution of IR1520 (BASF Co.) is injected into the polymerization solution discharged from the third reactor, in which 30% of the mass is dissolved. IR1520, as an antioxidant at a speed of 170 g/hour and mix. The polymerization reagent thus obtained is placed in steam-heated hot water and agitated to remove solvents to obtain a modified conjugated diene-based polymer.

[00205] Comparative Example 3

[00206] In the first reactor of continuous reactors, where three reactors are connected in series, injected with a solution of styrene, in which 60% of the mass. styrene dissolved in n-hexane, at a rate of 6.58 kg/hour, a solution of 1,3-butadiene, in which 60% of the mass. 1,3-butadiene is dissolved in n-hexane, at a rate of 9.58 kg/hour, n-hexane at a rate of 47.66 kg/hour, a solution of 1,2-butadiene, in which 2.0% of the mass. 1,2-butadiene is dissolved in n-hexane, at a rate of 10 g/hour, a solution in which 10% of the mass. 2,2-di(2-tetrahydrofuryl)propane is dissolved in n-hexane, as a polar additive, at a rate of 10.0 g/h, and a solution of n-butyl lithium, in which 15% of the mass. n-butyllithium dissolved in n-hexane as a polymerization initiator at a rate of 39.0 g/h. In this case, the temperature of the first reactor is maintained at 55°C, and when the polymerization conversion rate reaches 48%, the polymerization reagent is transferred from the first reactor to the second reactor through a transfer pipe.

[00207] Then a solution of 1,3-butadiene is injected into the second reactor, in which 60% of the mass. 1,3-butadiene dissolved in n-hexane, at a rate of 0.50 kg/hour. In this case, the temperature in the second reactor is maintained at 65°C, and when the polymerization conversion rate reaches 95% or more, the polymerization reagent is transferred from the second reactor to the third reactor through a transfer pipe.

[00208] The polymerization agent is transferred from the second reactor to the third reactor, and a solution in which dichlorodimethylsilane is dissolved as a coupling agent is injected into the third reactor [coupling agent: active Li=1:1 mol.]. The temperature of the third reactor is maintained at 65°C.

[00209] After that, the solution of IR1520 (BASF Co.) is injected into the polymerization solution discharged from the third reactor, in which 30% of the mass is dissolved. IR1520, as an antioxidant at a speed of 167 g/hour and mix. The polymerization reagent thus obtained is placed in steam-heated hot water and agitated to remove solvents to obtain a modified conjugated diene-based polymer.

[00210] Comparative Example 4

[00211] A modified conjugated diene-based polymer is obtained by carrying out the same procedure as in Example 1, except for maintaining the temperature of the third reactor at 75°C and transferring the polymerization reagent from the first reactor to the second reactor through a transfer pipe when the conversion rate at polymerization reaches 70% in example 1.

[00212] Comparative Example 5

[00213] A conjugated diene-based polymer is obtained by carrying out the same procedure as in example 1, except for the absence of injection into the third reactor of a solution in which N, N-bis (3- (diethoxy (methyl) silyl) propyl) is dissolved methyl-1-amine, as in example 1.

[00214] Comparative Example 6

[00215] A modified conjugated diene-based polymer is obtained by carrying out the same procedure as in example 1, except for continuous injection into the first reactor in example 1 of a solution of n-butyllithium, in which 15% of the mass is dissolved. n-butyllithium in n-hexane, instead of the modification initiator obtained in Preparation Example 1, at a rate of 39.0 g/hr.

[00216] Reference Example 1

[00217] A modified conjugated diene-based polymer is obtained by carrying out the same procedure as in comparative example 1, except for injecting 8 mol. 3-(dimethoxy(methyl)silyl)-N, N-diethylpropan-1-amine relative to 1 mol. active lithium of the modification initiator in comparative example 1 (modifier: active Li=8:1 mol.).

[00218] Reference Example 2

[00219] A modified conjugated diene-based polymer is obtained by carrying out the same procedure as in comparative example 1, except for injecting 0.2 mol. 3-(dimethoxy(methyl)silyl)-N, N-diethylpropan-1-amine) relative to 1 mol. active lithium of the modification initiator in comparative example 1 (modifier: active Li=0.2:1 mol.).

[00220] Experimental Example 1

[00221] For each of the modified or unmodified conjugated diene-based polymers obtained in the Examples, Comparative Examples, and Reference Examples, the styrene unit content and the vinyl content of each polymer, the weight average molecular weight (Mw, ×10 ³ g/mol), are measured, number average molecular weight (Mn, ×10 ³ g/mol), molecular weight distribution (PPD, MWD), binding number (N.S.), Mooney viscosity (VM (MV)), Mooney stress relaxation coefficient, factor compression, Si content, and N content. The results are shown in Table 1 and Table 2 below.

[00222] 1) Styrene unit and vinyl content (wt. %)

[00223] The styrene unit (SM) and the vinyl content of each polymer are measured and analyzed using a Varian VNMRS 500 MHz NMR instrument.

[00224] When measuring the NMR spectrum, 1,1,2,2-tetrachloroethanol is used as the solvent, and the styrene unit and the vinyl content are calculated by calculating the solvent peak as 5.97 ppm. and considering signals 7.2-6.9 ppm. as a random styrene peak, 6.9-6.2 ppm as block styrene peak, 5.8-5.1 ppm as a 1,4-vinyl peak and 5.1-4.5 ppm. as a 1,2-vinyl peak.

[00225] 2) Weight average molecular weight (Mw, ×10 ³ g/mol), number average molecular weight (Mn, ×10 ³ g/mol), molecular weight distribution (PPD, MWD) and binding number (N.S. )

[00226] Gel Permeation Chromatography (GPC) measures the weight average molecular weight (Mw) and the number average molecular weight (Mn) and obtain a molecular weight distribution curve. In addition, the molecular weight distribution (PPD, MWD, Mw/Mn) is calculated from each weight average molecular weight and number average molecular weight thus measured. Specifically, GPC was performed using two PLgel Olexis columns (Polymer Laboratories Co.) and one PLgel mixed-C column (Polymer Laboratories Co.) in combination, and with polystyrene (PS) as the standard GPC material for calculating molecular weight. masses. The solvent for measurement in GPC is prepared by mixing tetrahydrofuran with 2% of the mass. amine compound. In this case, the molecular weight distribution curves thus obtained are shown in FIG. 1-5.

[00227] In addition, the binding number is calculated by collecting a portion of the polymerization reagent before injecting the modifier or coupling agent in each of the examples and comparative examples and determining the peak molecular weight (MP ₁ ) of the polymer, then by determining the peak molecular weight (Mp ₂ ) of each modified polymer based on a conjugated diene and calculated according to the following mathematical formula 3:

[00228] Mathematical formula 3

Binding number (N.S.) = Mp ₂ /Mp _1.

[00229] 3) Mooney Viscosity and Mooney Stress Relaxation Coefficient

[00230] Mooney Viscosity (MV (MV), (ML 1+4, at 100°C) MU) is measured with an MV-2000 instrument (Alpha Technologies Co.) using a Large rotor with a rotor speed of 2 ± 0 .02 rpm at 100°C. In this case, the test sample used is kept at room temperature (23±3°C) for 30 minutes or longer, 27±3 g of the sample is taken and placed in the die cavity, and then the press platen is operated for measurement.

[00231] After measuring the Mooney viscosity, the magnitude of the gradient (absolute value) of change in Mooney viscosity shown upon release of torque is determined, and the Mooney stress relaxation coefficient is obtained from the absolute value.

[00232] 4) Si content

[00233] The Si content is determined using the ICP analysis method, which uses inductively coupled plasma optical emission spectroscopy (ICP-OES; Optima 7300DV). In particular, the measurement is carried out by adding approximately 0.7 g of the test sample to a platinum (Pt) crucible and adding approximately 1 ml of conc. sulfuric acid (98 wt.%, grade: for electronic devices), heating at 300°C for 3 hours, calcining the sample in an electric oven (Thermo Scientific, Lindberg Blue M) according to the following program from stages 1-3:

[00234] 1) stage 1: start temperature 0°C, speed (t-pa/hour) 180°C/hour, temperature (hold time) 180°C (1 hour)

[00235] 2) stage 2: initial temperature 180°C, speed (t-pa/hour) 85°C/hour, temperature (hold time) 370°C (2 hours)

[00236] 3) stage 3: initial temperature 370°C, speed (t-pa/hour) 47°C/hour, temperature (hold time) 510°C (3 hours),

[00237] adding to the residue 1 ml of conc. nitric acid (48% wt.) and 20 μl conc. hydrofluoric acid (50 wt.%), sealing the platinum crucible and shaking for 30 minutes or more, adding 1 ml of boric acid to the sample, storing at 0°C for 2 hours or more, diluting in 30 ml of ultrapure water, and carrying out calcination.

[00238] 5) N content

[00239] The N content is measured using the NSX analysis method using a trace nitrogen quantitative analyzer (NSX-2100H). Specifically, the quantitative trace nitrogen analyzer (autosampler, horizontal oven, PMT, and nitrogen detector) is turned on, set the quantities of carrier gas flowing so that Ar is 250 ml/min, O ₂ is 350 ml/min, and the ozonizer is 300 ml /min, the heater is set to 800°C and the analyzer is held for approximately 3 hours to stabilize. After stabilization of the analyzer, a calibration curve is obtained in the calibration intervals of 5 ppm, 10 ppm, 50 ppm, 100 ppm and 500 ppm using a nitrogen standard (AccuStandard S-22750-01-5 ml), get the area corresponding to each concentration and a straight line is obtained using the ratio of concentration versus area. Then, a ceramic boat containing 20 mg of the test sample is placed on the autosampler of the analyzer and measurements are taken to obtain an area. The N content is calculated using the sample area thus obtained and the calibration curve.

[00240] 6) Compression factor (g')

[00241] The compression factor is determined as follows. The sample is injected into a light scattering GPC instrument (Viscotek TDAmax, Malvern Co.) equipped with a light scattering detector in which two columns packed with polystyrene gel as a filler and a viscometer are connected, and the absolute molecular weight is obtained from the light scattering detector. , the true viscosity [ƞ] relative to the absolute molecular weight is obtained from the light scattering detector and the viscometer, the true viscosity [ƞ] ₀ of the linear polymer relative to the absolute molecular weight is calculated by mathematical formula 2 below, and the average value of the true viscosity ratio ([ƞ]/ [ƞ] ₀ ) corresponding to each absolute molecular weight is represented as a compression factor. In this case, measurements are made using a mixed solution of tetrahydrofuran and N,N,N',N'-tetramethylethylenediamine (adjusted by mixing 20 ml of N,N,N',N'-tetramethylethylenediamine with 1 liter of tetrahydrofuran) as eluent, and PL Olexix (Agilent Co.) as a column under oven temperature conditions of 40°C and a THF flow rate of 1.0 ml/min. The test sample is prepared by dissolving 15 mg of polymer in 10 ml of THF.

[00103] Mathematical formula 2

[ƞ] ₀₌ 10 ^-3.883 Μ ^0.771 .

[00104] In the mathematical formula 2, M represents the absolute molecular weight.

[00244] Table 1

Chapter Example Reference Example Comparative Example one 2 3 four 5 one 2 one 2 four 5 6 Reaction conditions Initiator a a b c a a a a d a a d modifier or binding agent A B A A C C C C D A - A Temperature of the first reactor (°C) fifty fifty fifty fifty fifty 50→80 50→80 50→80 55 75 fifty fifty First Reactor Polymerization Conversion Rate (%) 43 43 43 43 43 Period. Period. Period. 47 70 45 43 NMR
(% mass) CM eighteen eighteen eighteen eighteen eighteen eighteen eighteen eighteen eighteen eighteen eighteen eighteen Vinyl 47 47 47 47 47 47 47 47 47 47 47 47 GPC Mw (×10 ³ g/mol) 464 471 454 464 442 314 498 494 471 575 444 453 Mn (×10 ³ g/mol) 305 308 295 298 289 273 380 341 310 311 300 287 PPD 1.52 1.53 1.54 1.56 1.53 1.15 1.31 1.45 1.52 1.85 1.48 1.58 Ch.S. 1.7 1.8 1.8 1.7 1.7 1.0 2.0 1.8 1.55 1.5 - 1.6 Molecular weight distribution curve MIND MIND MIND MIND MIND MIND MIND bm MIND MIND MIND MIND Mooney Viscosity (VM) 56 56 54 53 55 45 62 59 57 64 52 60 Mooney stress relaxation coefficient 1.133 1.126 1.180 1.142 1.171 1.068 1.058 1.065 1.038 0.635 1.487 1.129 Compression factor (g') 1.082 1.070 1.132 1.067 1.064 1.069 1.053 1.063 1.075 0.599 1.456 1.075 Si content (ppm) 225 225 215 210 110 110 fifty 115 25 123 - 215 N content (ppm) 112 170 169 160 111 110 52 110 - 85 60 62

BM - bimodal

UM - unimodal

Period. - periodic

[00245] Table 2

Chapter Example Comparative Example 6 7 3 Reaction conditions Initiator a a d modifier or binding agent A B D Temperature of the first reactor (°C) fifty fifty 55 First Reactor Polymerization Conversion Rate (%) 43 41 46 NMR
(% mass) CM 39 39 39 Vinyl 25 25 25 GPC Mw (×10 ³ g/mol) 506 492 479 Mn (×10 ³ g/mol) 320 306 313 PPD 1.58 1.61 1.53 Ch.S. 1.7 1.7 1.5 Molecular weight distribution curve Unimodal Unimodal Unimodal Mooney Viscosity (VM) 55 54 58 Mooney stress relaxation coefficient 1.232 1.192 0.982 Compression factor (g') 1,200 1.133 0.947 Si content (ppm) 220 223 thirty N content (ppm) 112 170 -

[00246] In Table 1 and Table 2 above, the specific materials used as initiator, modifier, and coupling agent are the following materials.

[00247] * Initiator a: modification initiator obtained in Obtaining Example 1;

[00248] * Initiator b: modification initiator obtained in Obtaining Example 2;

[00249] * Initiator c: modification initiator obtained in Obtaining Example 3;

[00250] * Initiator d: n-butyllithium;

[00251] * Modifier A: N,N-bis(3-(diethoxy(methyl)silyl)propyl)methyl-1-amine;

[00252] *Modifier B: 3,3'-(1,1,3,3-tetramethoxy-disiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine);

[00253] * Modifier C: 3-(dimethoxy(methyl)silyl)-N, N-diethylpropan-1-amine;

[00254] * Coupling agent D: dichlorodimethylsilane.

[00255] As shown in Table 1 and Table 2 above, the modified conjugated diene based polymers of Examples 1-7 according to embodiments of the present invention are found to have a unimodal gel permeation chromatography molecular weight distribution curve (see FIG. 1 and FIG. 2), MWD (molecular weight distribution) of 1.0 to less than 1.7, Si content and N content of 50 ppm or more, Mooney stress relaxation coefficient of 0.7 or more, and contraction factor of 1 ,0 or more. In contrast, the unmodified or modified conjugated diene-based polymers of Comparative Examples 1-5 were found to have a bimodal GPC molecular weight distribution curve (see FIG. 3), a Mooney stress relaxation coefficient of less than 0.7, a contraction factor of less than 1.0, the Si content is less than 50 ppm, and the N content is less than 50 ppm. In particular, Comparative Example 4, in which continuous polymerization is carried out, but the polymerization conversion ratio of the first reactor deviates from the range of the present invention, was found to have a SPD value greater than 1.7, a Mooney stress relaxation coefficient, and a compression factor less than 0.7, respectively, which are significantly lower values when compared to the examples.

[00256] In addition, Comparative Example 1, which uses the same modification initiator and modifier as in Example 5 of the present invention, but the polymer is obtained by a batch polymerization method, shows a bimodal shape of the molecular weight distribution curve by gel permeation chromatography (see. FIG 3). However, the molecular weight distribution curve could be controlled so that it shows a unimodal shape, although the method of periodic polymerization is used, as in reference examples 1 and 2 (see FIG. 4 and FIG. 5), but in this case, the binding numbers of the polymers are 1.0 and 2.0, respectively, and are present only in the case where all the polymers are not bound by the modifier (Reference Example 1), and in the case where all the polymers are bound by the modifier (Reference Example 2), and, therefore, the polymers have a structure and properties different from the unimodal polymer according to the continuous polymerization process of the present invention. As confirmed in Table 4 to be described later, processability, tensile properties, and viscoelastic properties can be found to be inferior to those of Example 5.

[00257] Meanwhile, the polymer of Comparative Example 5 was prepared under the same conditions as in Example 1, except for not using the modifier proposed in the embodiment of the present invention, and the modified conjugated diene-based polymer of Comparative Example 6 was prepared under those the same conditions as in Example 1, except for the initiator used for polymerization, that is, obtained by using the modifier and the modification initiator proposed in the present invention, and the polymer thus obtained does not include functional groups derived from the modifier and modification initiator at the same time. Accordingly, as confirmed in Table 4 below, the filler compounding properties are worse, and the tensile properties and viscoelastic properties are significantly poorer when compared with the properties of the examples.

[00258] Experimental Example 2

[00259] For a comparative analysis of the physical properties of rubber compositions comprising modified or unmodified copolymers of examples, comparative examples and reference examples, and molded articles made from them, tensile mechanical properties and viscoelastic properties were determined, and the results are presented in the following table 4 and table 5.

[00260] 1) Preparation of rubber specimens for testing

[00261] Blending is carried out using each of the modified or unmodified conjugated diene-based polymers of Examples, Comparative Examples, and Reference Examples as the starting rubber under the blending conditions listed in Table 3 below. per 100 wt.h. original rubber material.

[00262] Table 3

Chapter raw material Quantity (wt.h.) First mixing stage Rubber 100 Silica 70 Coupling agent (X50S) 11.2 Process oil 37.5 Zinc white 3 Stearic acid 2 Antioxidant 2 Antioxidant 2 Wax one Second mixing stage Sulfur 1.5 Rubber Vulcanization Accelerator 1.75 Vulcanization accelerator 2

[00263] Specifically, the rubber test specimen is mixed with a first mixing step and a second mixing step. In the first mixing step, the parent rubber, silica (filler), organic binder, process oil, zinc oxide, stearic acid, antioxidant, antioxidant and wax are mixed using a Banbury mixer equipped with a temperature control device. In this case, the initial temperature of the mixing equipment is controlled at 70°C, and after mixing is completed, the first compounded mixture is obtained at a discharge temperature of 145 to 155°C. In the second mixing step, the first compounded mixture is cooled to room temperature, and the first compounded mixture, sulfur, a rubber vulcanization accelerator and a vulcanization accelerator are added to a mixer and mixed at a temperature of 100°C or less, a second compounded mixture is obtained. Then, the rubber test specimen was cured at 160° C. for 20 minutes.

[00264] 2) Tensile properties

[00265] Tensile properties are measured by fabricating each test specimen and measuring the tensile strength at break and the breaking stress at 300% elongation (300% modulus) for each specimen in accordance with ASTM 412 standard for tensile test methods. Specifically, tensile properties were measured using a Universal Test Machine 4204 (Instron Co.) at a speed of 50 cm/min at room temperature.

[00266] 3) Viscoelastic properties

[00267] The viscoelastic properties are captured by measuring the viscoelastic behavior under thermodynamic strain at each measurement temperature (-60 to 60°C) at a frequency of 10 Hz using a dynamic mechanical analyzer (GABO Co.) in a film tension model and setting a tan δ value. Each of the obtained values of Examples 1 to 5 is indexed by setting the obtained value of Comparative Example 2 to 100. Each of the obtained values of Examples 6 and 7 is indexed by setting the final value of Comparative Example 3 to 100. In this case, if the value of tan δ at low temperature is 0 °C rises, the wet skid resistance becomes better, and if the tan δ value at a high temperature of 60°C rises, the hysteresis loss decreases and the low running resistance (fuel consumption) becomes better.

[00268] 4) Processability characteristics

[00269] By measuring the Mooney viscosity (BM, (ML 1+4, at 100°C) MU) of the compound of the secondary mixture obtained during the preparation of 1) rubber sample, the processing characteristics of each polymer are subjected to a comparative analysis, and in this case than the lower the measured Mooney viscosity value, the better the processability characteristics.

[00270] In particular, using the MV-2000 (Alpha Technologies Co.) using the Large Rotor with a rotor speed of 2±0.02 rpm at 100°C, each compound of the secondary mixture is stored at room temperature (23±3° C) for 30 minutes or longer, 27 ± 3 g is taken and placed in the matrix cuvette, and then the press plate is operated for 4 minutes to take the measurement.

[00271] Table 4

Chapter Example Reference Example Comparative Example one 2 3 four 5 one 2 one 2 four 5 6 Tensile properties Tensile strength (kg-s/cm ² ) 188 189 191 188 187 180 180 178 185 183 185 186 300% modulus (kg-s/cm ² ) 98 98 97 97 98 72 75 80 70 80 77 84 Viscoelastic properties tan δ (at 0°C) 103 101 102 101 102 99 101 100 100 100 102 99 tan δ (at 60°C) 134 133 135 132 132 110 105 129 100 123 115 119 Processability characteristics 81 80 80 81 82 97 92 92 72 89 80 81

[00272] Table 4 indexes (%) the obtained viscoelastic property values of Examples 1-5, Comparative Example 1, Comparative Examples 4-6, and Reference Examples 1 and 2, and is presented based on the measured viscoelastic property values of Comparative Example 2.

[00273] Table 5

Chapter Example Comparative Example 6 7 3 Tensile properties Tensile strength (kg-s/cm ² ) 185 186 185 300% modulus (kg-s/cm ² ) 114 116 85 Viscoelastic properties tan δ (at 0°C) 101 102 100 tan δ (at 60°C) 132 134 100 Processability characteristics 82 83 75

[00274] In Table 5, the obtained values of Examples 6 and 7 are indexed (%) and are presented based on the measured values of the viscoelastic properties of Comparative Example 3.

[00275] As can be seen from Table 4 and Table 5, the tensile properties, viscoelastic properties, and processability characteristics of Examples 1-7 according to embodiments of the present invention are all excellent in balance when compared to Comparative Examples 1-6.

[00276] However, with regard to viscoelastic properties, it is generally known that increasing the tan δ value at 0°C simultaneously with the tan δ value at 60°C is very difficult. Accordingly, when compared with Comparative Examples 1-6, Examples 1-7, which show the same or better level of tan δ value at 0°C and a significantly improved tan δ value at 60°C, were confirmed to have very excellent viscoelastic properties.

[00277] In addition, as shown in Table 4, in the case where the polymer is obtained by batch polymerization but shows a unimodal molecular weight distribution curve as in Reference Examples 1 and 2, it was found that the inherent poorer processability characteristics for batch polymerization did not are improved, and the excellent compounding properties that could be obtained by batch polymerization are not achieved. Here, the inherent poorer processability characteristics for batch polymerization can be confirmed by the results of Comparative Example 1, in which conventional batch polymerization is carried out and a bimodal shape of the molecular weight distribution curve is obtained. Specifically, in Reference Example 1, the Mooney viscosity of the compounded mixture increased by 18% when compared to Example 5, exhibited significantly reduced processability characteristics, and showed greatly reduced 300% modulus and tan δ value at 60°C to about 30%, respectively. In addition, in Reference Example 2, the Mooney viscosity of the compounded mixture increases by 14% and the processability characteristics are significantly deteriorated compared to Example 5. Meanwhile, the tensile properties (300% modulus) and viscoelastic properties (tan δ value at 60°) are noticeably fall, as in reference example 1.

Claims (60)

1. A modified conjugated diene based polymer having a unimodal molecular weight distribution curve by Gel Permeation Chromatography (GPC), and molecular weight distribution (MPD; MWD) from 1.0 to less than 1.7, and containing a functional group derived from a modification initiator at one end and a functional group derived from a modifier represented by the following formula 2 or formula 3 at the other end, where the modification initiator is the reaction product of a compound represented by the following formula 1 and an organometallic compound: Formula 1

, in formula 1: R ₁ -R ₃ each independently represent a hydrogen atom; R ₄ is a single bond; R ₅ is a functional group represented by the following formula 1a or formula 1b; and "n" is equal to 1, Formula 1a

, in formula 1a: R ₆ is a substituted or unsubstituted alkylene group of 1-20 carbon atoms with a substituent, where the substituent is an alkyl group of 1-10 carbon atoms, a cycloalkyl group of 5-10 carbon atoms, or an aryl group of 6-20 carbon atoms; R ₇ and R ₈ are each independently an unsubstituted alkylene group of 1-20 carbon atoms; R ₉ is an alkyl group of 1-30 carbon atoms, or an aryl group of 6 carbon atoms; and X represents an N atom; Formula 1b

, in formula 1b: R ₁₀ is an unsubstituted alkylene group of 1-20 carbon atoms; and R ₁₁ and R ₁₂ each independently represent an alkyl group of 1-30 carbon atoms; Formula 2

, in formula 2: R ₂₀ is an alkylene group of 1-10 carbon atoms; R ₂₁ and R ₂₂ each independently represent an alkyl group of 1-10 carbon atoms; R ₂₃ is a single bond; R ₂₄ is an alkyl group of 1-10 carbon atoms; "a" means integer 2, "c" means an integer 1 or 2, and "b" means an integer from 1 to 2, where b+c=3, Formula 3

, in formula 3 A ₁ and A ₂ are each independently an alkylene group of 1-20 carbon atoms; R ₂₅ -R ₂₈ each independently represent an alkyl group of 1-20 carbon atoms; and L ₁ -L ₄ each independently represent an alkyl group of 1-20 carbon atoms. 2. The modified conjugated diene polymer according to claim 1, wherein in formula 1a, R ₇ and R ₈ are each independently an unsubstituted alkylene group of 1-10 carbon atoms; and in formula 1b, R ₁₀ is an unsubstituted alkylene group of 1-10 carbon atoms, and R ₁₁ and R ₁₂ each independently represent an alkyl group of 1-10 carbon atoms. 3. The modified conjugated diene based polymer according to claim 1, wherein in formula 2: R ₂₀ is an alkylene group of 1-5 carbon atoms; R ₂₁ and R ₂₂ each independently represent an alkyl group of 1-5 carbon atoms; R ₂₃ is a single bond; and R ₂₄ is an alkyl group of 1-5 carbon atoms. 4. The modified conjugated diene based polymer according to claim 1, wherein in formula 3, A ₁ and A ₂ are each independently an alkylene group of 1-10 carbon atoms; R ₂₅ -R ₂₈ each independently represent an alkyl group of 1-10 carbon atoms; and L ₁ -L ₄ each independently represent an alkyl group of 1-10 carbon atoms. 5. The modified conjugated diene based polymer according to claim 1, wherein the modified conjugated diene based polymer has a number average molecular weight (Mn) of 1,000 to 2,000,000 g/mol and a weight average molecular weight (Mw) of 1,000 to 3,000,000 g/mol. 6. The modified conjugated diene based polymer according to claim 1, wherein the modified conjugated diene based polymer has a Si content and an N content of 50 ppm or more based on total weight, respectively. 7. The modified conjugated diene based polymer according to claim 1, wherein the modified conjugated diene based polymer has a Mooney stress relaxation coefficient, which is measured at 100° C., from 0.7 to 3.0. 8. The modified conjugated diene based polymer according to claim 1, wherein the modified conjugated diene based polymer has a compression factor, which is obtained by measurement with a light scattering gel permeation chromatography method equipped with a viscometer, from 1.0 to 3.0. 9. The modified conjugated diene based polymer according to claim 1, wherein the modified conjugated diene based polymer has a binding number (N.S.) of 1<N.S.<F, where F is the number of functional groups of the modifier. 10. A rubber composition for a tire element or rubber products containing a modified conjugated diene-based polymer according to claim 1 and a filler. 11. The rubber composition according to claim 10, in which the rubber composition contains from 0.1 to 200 wt.h. filler based on 100 wt.h. modified polymer based on a conjugated diene. 12. The rubber composition according to claim 10, in which the rubber composition contains from 20 to 60 wt.h. process oil based on 100 wt.h. modified polymer based on a conjugated diene.

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