KR20210151003A - Modified conjugated diene polymer, preparing method thereof and rubber composition comprising the same - Google Patents

Abstract

The present invention relates to a modified conjugated diene polymer having excellent compatibility with filler, and excellent processability, tensile strength, and viscoelastic properties; a method for manufacturing same; and a rubber composition comprising the same. The modified conjugated diene polymer comprises a conjugated diene-based monomer-derived repeating unit; and a modifier-derived functional group represented by chemical formula 1.

Description

Modified conjugated diene-based polymer, manufacturing method thereof, and rubber composition comprising the same

The present invention relates to a modified conjugated diene-based polymer having excellent affinity with a filler and excellent processability, tensile strength and viscoelastic properties, a method for preparing the same, and a rubber composition comprising the same.

In response to the recent demand for fuel economy reduction in automobiles, a conjugated diene-based polymer having low running resistance, excellent abrasion resistance and tensile properties, and adjustment stability typified by wet skid resistance is required as a rubber material for tires.

In order to reduce the running resistance of the tire, there is a method of reducing the hysteresis loss of the vulcanized rubber, and rebound elasticity of 50°C to 80°C, Tanδ, Goodrich heat, etc. are used as evaluation indicators of the vulcanized rubber. That is, a rubber material having a large rebound elasticity at the above temperature or a small Tanδ or Goodrich heat generation is preferable.

As a rubber material having a small hysteresis loss, natural rubber, polyisoprene rubber, polybutadiene rubber, etc. are known, but these have a problem of low wet skid resistance. Accordingly, recently, conjugated diene-based (co)polymers such as styrene-butadiene rubber (hereinafter referred to as SBR) or butadiene rubber (hereinafter referred to as BR) have been manufactured by emulsion polymerization or solution polymerization and are used as rubber for tires. .

When the BR or SBR is used as a rubber material for a tire, a filler such as silica or carbon black is usually blended together to obtain the required physical properties of the tire. However, the affinity of the BR or SBR with the filler is not good, so there is a problem in that physical properties including abrasion resistance, crack resistance or workability are rather deteriorated.

Accordingly, as a method for increasing the dispersibility of SBR and fillers such as silica or carbon black, a method of modifying the polymerization active site of a conjugated diene-based polymer obtained by anionic polymerization using organolithium with a functional group capable of interacting with the filler has been proposed. . For example, a method of modifying the polymerizable end of a conjugated diene-based polymer with a tin-based compound, introducing an amino group, or modifying with an alkoxysilane derivative has been proposed.

In addition, in a living polymer obtained by coordination polymerization using a catalyst composition containing a neodymium compound as a method for improving the dispersibility of BR and fillers such as silica or carbon black, the living active terminal is modified with a specific modifier. This was developed. However, in the case of the terminal-modified polymer, the affinity with the filler is improved and compounding properties, such as tensile properties and viscoelastic properties, are improved, but on the other hand, compounding processability is greatly reduced, so there is a problem in poor processability.

JP 5172663 B2

An object of the present invention is to provide a modified conjugated diene-based polymer having improved mechanical properties such as tensile properties and abrasion resistance by having a high molecular weight, and improved compounding properties such as viscoelastic properties by including a functional group derived from a modifier.

Another object of the present invention is to provide a method for producing the modified conjugated diene-based polymer.

Another object of the present invention is to provide a rubber composition comprising the modified conjugated diene-based polymer.

In order to solve the above problems, the present invention provides a repeating unit derived from a conjugated diene-based monomer; And it provides a modified conjugated diene-based polymer comprising a functional group derived from a modifier represented by the following formula (1).

[Formula 1]

In Formula 1,

R ₁ is an alkyl group having 1 to 10 carbon atoms,

,

및

로 이루어진 군에서 선택된 어느 하나 이상을 포함하는 탄소수 1 내지 10의 알킬렌기이고, R ₂ is

,

and

It is an alkylene group having 1 to 10 carbon atoms including at least one selected from the group consisting of

Wherein R ₃ is an alkylene group having 1 to 10 carbon atoms,

wherein R ₄ to R ₉ are each independently an alkyl group having 1 to 20 carbon atoms, wherein two of R ₄ to R ₉ may be connected to each other to form a heterocycle together with N,

X is the following formula (a) or formula (b),

[Formula a]

In the above formula (a),

R ₁₀ to R ₁₅ are each independently an alkyl group having 1 to 20 carbon atoms, wherein two of R ₁₀ to R ₁₅ may be connected to each other to form a heterocycle together with N,

[Formula b]

In the above formula (b),

R ₁₆ is an alkyl group having 1 to 10 carbon atoms.

In addition, the present invention comprises the steps of preparing an active polymer by polymerizing a conjugated diene-based monomer in the presence of a catalyst composition comprising a neodymium compound in a hydrocarbon solvent; and reacting the active polymer with the modifier represented by Formula 1;

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

The modified conjugated diene-based polymer according to the present invention includes a functional group derived from a modifier represented by Formula 1, so that it has excellent affinity with a filler and improved compounding properties. and excellent wet road resistance.

Hereinafter, the present invention will be described in more detail to help the understanding of the present invention.

The terms or words used in the description and claims of the present invention should not be construed as being limited to their ordinary or dictionary meanings, and the inventor appropriately defines the concept of the term in order to best describe his invention. Based on the principle that it can be done, it should be interpreted as meaning and concept consistent with the technical idea of the present invention.

The term 'alkyl group' used in the present invention may mean a monovalent aliphatic saturated hydrocarbon, and linear alkyl groups such as methyl, ethyl, propyl and butyl and isopropyl, sec-butyl ), tert-butyl, and neo-pentyl, such as branched alkyl groups, may be included.

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

The term 'heterocycle' used in the present invention may mean including both a cycloalkyl group or an aryl group in which a carbon atom in a cycloalkyl group or an aryl group is substituted with one or more hetero atoms.

The terms 'derived unit' and 'derived functional group' used in the present invention may indicate a component, structure, or substance itself derived from a substance.

Hereinafter, the present invention will be described in detail.

The present invention provides a modified conjugated diene-based polymer having a high molecular weight and excellent mechanical properties such as tensile properties and abrasion resistance, and excellent compounding properties such as viscoelastic properties by including a functional group derived from a modifier.

Specifically, the modified conjugated diene-based polymer of the present invention includes a repeating unit derived from a conjugated diene-based monomer; and a denaturant-derived functional group represented by the following formula (1).

[Formula 1]

In Formula 1,

R ₁ is an alkyl group having 1 to 10 carbon atoms,

,

및

로 이루어진 군에서 선택된 어느 하나 이상을 포함하는 탄소수 1 내지 10의 알킬렌기이고, R ₂ is

,

and

It is an alkylene group having 1 to 10 carbon atoms including at least one selected from the group consisting of

Wherein R ₃ is an alkylene group having 1 to 10 carbon atoms,

wherein R ₄ to R ₉ are each independently an alkyl group having 1 to 20 carbon atoms, wherein two of R ₄ to R ₉ may be connected to each other to form a heterocycle together with N,

X is the following formula (a) or formula (b),

[Formula a]

In the above formula (a),

R ₁₀ to R ₁₅ are each independently an alkyl group having 1 to 20 carbon atoms, wherein two of R ₁₀ to R ₁₅ may be connected to each other to form a heterocycle together with N,

[Formula b]

In the above formula (b),

R ₁₆ is an alkyl group having 1 to 10 carbon atoms.

The modifier according to the present invention may be the compound represented by Formula 1 itself, or may include other compounds capable of modifying the conjugated diene-based polymer together with the compound represented by Formula 1 above.

Here, the 'conjugated diene-based monomer-derived repeating unit' may mean a repeating unit formed during polymerization of the conjugated diene-based monomer, and the modifier-derived functional group represented by Formula 1 includes a repeating unit derived from the conjugated diene-based monomer A functional group derived from the modifier represented by Formula 1 may be present in the polymer chain, and the functional group derived from the modifier represented by Formula 1 may be present at at least one end of the polymer chain.

The modifier represented by Formula 1 according to the present invention can easily modify the conjugated diene-based polymer at a high denaturation rate by including a reactive functional group, a filler affinity functional group, and a solvent affinity functional group for the conjugated diene-based polymer. It is possible to improve the abrasion resistance, low fuel consumption characteristics, and workability of a rubber composition and molded articles such as tires manufactured therefrom.

Specifically, the modifier represented by Formula 1 includes an ester functional group as a reactive functional group for the polymer in the molecule, and the reactive functional group exhibits high reactivity with respect to the active site of the conjugated diene-based polymer, thereby highly modifying the conjugated diene-based polymer. As a result, the functional group substituted by the modifier can be introduced into the conjugated diene-based polymer in a high yield.

In addition, it includes an amine group and an alkyl chain, and the amine group reacts with the end of the conjugated diene-based polymer to be converted into a primary or secondary amino group, thereby further improving affinity with a filler, particularly carbon black. In addition, the alkyl chain can increase the affinity for the polymerization solvent to increase the solubility of the modifier, thereby improving the rate of modification of the conjugated diene-based polymer.

In addition, the modifier chain may include hetero atoms such as N, O, and S, thereby increasing the polarity of the modifier and improving interaction with the filler, thereby preparing a modified conjugated diene-based polymer having excellent compounding properties.

In Formula 1, R ₁ may be an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 3 carbon atoms, an alkyl group having 1 or 2 carbon atoms, such as an ethyl group.

,

및

로 이루어진 군에서 선택된 어느 하나 이상을 포함하는 탄소수 1 내지 10의 알킬렌기이다. 구체적으로, 상기 R₂는

,

및

로 이루어진 군에서 선택된 어느 하나 이상을 포함하고, 동일한 종류를 2개 이상 포함하는 것도 가능하며, 이와 동시에, 탄소수 1 내지 6의 알킬렌기, 탄소수 2 내지 6의 알킬렌기, 탄소수 3 및 4의 알킬렌기일 수 있다. 여기서, 상기 R₃는 탄소수 1 내지 10의 알킬렌기, 탄소수 1 내지 6의 알킬렌기, 2 내지 4의 알킬렌기, 예컨대 에틸렌기일 수 있다.In Formula 1, R ₂ is

,

and

It is an alkylene group having 1 to 10 carbon atoms including at least one selected from the group consisting of. Specifically, the R ₂ is

,

and

Including any one or more selected from the group consisting of, it is also possible to include two or more of the same type, and at the same time, an alkylene group having 1 to 6 carbon atoms, an alkylene group having 2 to 6 carbon atoms, and alkylene having 3 and 4 carbon atoms. it can be a gimmick Here, R ₃ may be an alkylene group having 1 to 10 carbon atoms, an alkylene group having 1 to 6 carbon atoms, an alkylene group having 2 to 4 carbon atoms, such as an ethylene group.

In Formula 1, R ₄ to R ₉ may each independently be an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 4 carbon atoms, such as methyl. Here, _{two of R 4} to R ₉ may be connected to each other to form a 5-ring heterocycle together with N, for example _{, one of R 4} to R ₆ and one of R ₇ to R ₉ may be connected to each other to —Si A 5-ring heterocycle including -N-Si- may be formed.

In Formula 1, X is Formula a or Formula b. In Formula (a), R ₁₀ to R ₁₅ may each independently be an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 4 carbon atoms, such as methyl. Here, _{two of R 10} to R ₁₅ may be connected to each other to form a 5-ring heterocycle together with N, for example _{, one of R 10} to R ₁₂ and one of R ₁₃ to R ₁₅ may be connected to each other to —Si A 5-ring heterocycle including -N-Si- may be formed. In Formula (b), R ₁₆ may be an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 3 carbon atoms, an alkyl group having 1 or 2 carbon atoms, such as an ethyl group.

Specifically, the modifier represented by Formula 1 may be a compound represented by any one of Formulas 1-1 to 1-3, but is not limited thereto.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In addition, the modified conjugated diene-based polymer may be a butadiene homopolymer such as polybutadiene, or a diene-based copolymer such as a butadiene-isoprene copolymer.

As a specific example, the modified conjugated diene-based polymer may contain 80 to 100% by weight of 1,3-butadiene monomer-derived units, and 20% by weight or less of other conjugated diene-based monomer-derived units that are optionally copolymerizable with 1,3-butadiene. There is an effect that the content of 1,4-cis bonds in the polymer is not lowered within the above range. In this case, the 1,3-butadiene monomer includes 1,3-butadiene or derivatives thereof, such as 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, or 2-ethyl-1,3-butadiene. and other conjugated diene-based monomers copolymerizable with 1,3-butadiene include 2-methyl-1,3-pentadiene, 1,3-pentadiene, 3-methyl-1,3-pentadiene, 4 -methyl-1,3-pentadiene, 1,3-hexadiene, or 2,4-hexadiene may be mentioned, and any one or two or more compounds of these may be used.

In addition, the modified conjugated diene-based polymer of the present invention may be a lanthanum-based rare earth element catalyzed modified conjugated diene-based polymer. That is, the modified conjugated diene-based polymer may be a conjugated diene-based polymer including an organometallic moiety activated from a catalyst composition including a neodymium compound.

The modified conjugated diene-based polymer may have a weight average molecular weight (Mw) of 1.0 × 10 ⁵ g/mol to 10.0 × 10 ⁵ g/mol, and a number average molecular weight (Mn) of 1.0 × 10 ⁵ g/mol to 6.0 × 10 ^{may be 5} g/mol, and when applied to a rubber composition within this range, it has excellent tensile properties and excellent processability. It has an excellent effect.

The weight average molecular weight may specifically be 3.0 × 10 ⁵ g/mol to 9.0 × 10 ⁵ g/mol, or 4.0 × 10 ⁵ g/mol to 8.0 × 10 ⁵ g/mol, and the number average molecular weight (Mn) is 2.0 × 10 ⁵ g/mol to 5.0 × 10 ⁵ g/mol, 2.5 × 10 ⁵ g/mol to 4.5 × 10 ⁵ g/mol.

In addition, the modified conjugated diene-based polymer may have a molecular weight distribution (Mw/Mn) of 1.0 to 4.0, specifically 1.5 to 3.5, or 2.0 to 3.0.

In the present invention, the molecular weight distribution of the modified conjugated diene-based polymer may be calculated from the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn). In this case, the number average molecular weight (Mn) is a common average of individual polymer molecular weights calculated by measuring the molecular weights of n polymer chains, obtaining the sum of these molecular weights, and dividing by n, and the weight average molecular weight (Mw) is a polymer The molecular weight distribution of the composition is shown. All molecular weight averages can be expressed in grams per mole (g/mol). In addition, the weight average molecular weight and the number average molecular weight may mean a polystyrene equivalent molecular weight analyzed by gel permeation chromatography (GPC), respectively.

When the modified conjugated diene-based polymer according to an embodiment of the present invention simultaneously satisfies the weight average molecular weight (Mw) and number average molecular weight conditions along with the molecular weight distribution described above, tensile properties for the rubber composition when applied to the rubber composition; It is excellent in viscoelasticity and workability, and there is an effect of excellent balance of physical properties between them.

In addition, the present invention provides a method for producing the modified conjugated diene-based polymer. The preparation method comprises the steps of preparing an active polymer by polymerizing a conjugated diene-based monomer in the presence of a catalyst composition containing a neodymium compound in a hydrocarbon solvent (step 1); and reacting the active polymer with a modifier represented by Formula 1 below (step 2).

[Formula 1]

In Formula 1, R ₁ , R ₂ , and X are the same as defined above.

Step 1 is a step of preparing an active polymer including an organometallic moiety by polymerizing the conjugated diene-based monomer, and may be performed by polymerizing the conjugated diene-based monomer in the presence of a catalyst composition including a neodymium compound in a hydrocarbon solvent.

In the present invention, the organometallic moiety in the active polymer including the organometallic moiety may be an activated organometallic moiety (an activated organometallic moiety at the end of the molecular chain) of the conjugated diene-based polymer, among which anionic polymerization or When an activated organometallic moiety of the conjugated diene-based polymer is obtained by coordination anion polymerization, the organometallic moiety may represent an activated organometallic moiety at the end.

The conjugated diene-based monomer is not particularly limited, for example, 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl The group consisting of -1,3-butadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene and 2,4-hexadiene, etc. It may be at least one selected from

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

The catalyst composition may be used in an amount such that the amount of the neodymium compound is 0.03 to 0.10 mmol relative to 100 g of the total of the conjugated diene-based monomers, specifically, the neodymium compound is 0.05 to 0.09 mmol, or 0.06 to 0.08 mmol, compared to 100 g of the total of the conjugated diene-based monomers It can be used in an amount that makes this possible.

The neodymium compound is a carboxylate salt thereof (eg, neodymium acetate, neodymium acrylate, neodymium methacrylate, neodymium gluconate, neodymium citrate, neodymium fumarate, neodymium lactate, neodymium maleate, neodymium oxalate, neodymium 2 -ethylhexanoate, neodymium neodecanoate, etc.); Organophosphates (e.g., neodymium dibutyl phosphate, neodymium dipentyl phosphate, neodymium dihexyl phosphate, neodymium diheptyl phosphate, neodymium dioctyl phosphate, neodymium bis(1-methyl heptyl) phosphate, neodymium bis(2-ethylhexyl) phosphate, or neodymium didecyl phosphate, etc.); organic phosphonates (e.g., neodymium butyl phosphonate, neodymium pentyl phosphonate, neodymium hexyl phosphonate, neodymium heptyl phosphonate, neodymium octyl phosphonate, neodymium (1-methyl heptyl) phosphonate, neodymium (2-ethylhexyl) phosphonate, neodymium disyl phosphonate, neodymium dodecyl phosphonate, or neodymium octadecyl phosphonate); organic phosphinates (e.g., neodymium butylphosphinate, neodymium pentylphosphinate, neodymium hexyl phosphinate, neodymium heptyl phosphinate, neodymium octyl phosphinate, neodymium (1-methyl heptyl) phosphinate, or neodymium (2-ethylhexyl) phosphinate, etc.); carbamates (eg, neodymium dimethyl carbamate, neodymium diethyl carbamate, neodymium diisopropyl carbamate, neodymium dibutyl carbamate, or neodymium dibenzyl carbamate, etc.); dithiocarbamate (eg, neodymium dimethyldithiocarbamate, neodymium diethyldithiocarbamate, neodymium diisopropyl dithiocarbamate, or neodymium dibutyldithiocarbamate); xanthogenates (eg, neodymium methyl xanthogen, neodymium ethyl xanthogen, neodymium isopropyl xanthogen, neodymium butyl xanthogen, or neodymium benzyl xanthogen, etc.); β-diketonates (eg, neodymium acetylacetonate, neodymium trifluoroacetyl acetonate, neodymium hexafluoroacetyl acetonate or neodymium benzoyl acetonate, etc.); alkoxides or allyloxides (eg, neodymium methoxide, neodymium ethoxide, neodymium isopropoxide, neodymium phenoxide or neodymium nonyl phenoxide, etc.); halides or pseudohalides (such as neodymium fluoride, neodymium chloride, neodymium bromide, neodymium iodide, neodymium cyanide, neodymium cyanate, neodymium thiocyanate, or neodymium azide); oxyhalides (eg, neodymium oxyfluoride, neodymium oxy chloride, or neodymium oxy bromide, etc.); or an organic neodymium compound comprising one or more rare earth-carbon bonds (eg, Cp ₃ Ln, Cp ₂ LnR, Cp ₂ LnCl, CpLnCl ₂ , CpLn(cyclooctatetraene), (C ₅ Me ₅ ) ₂ LnR , LnR ₃ , Ln(allyl) ₃ , or Ln(allyl) ₂ Cl, etc., wherein Ln is a rare earth metal element, and R is a hydrocarbyl group), and any one or a mixture of two or more thereof may include

Specifically, the neodymium compound may be a compound represented by the following formula (2).

[Formula 2]

In Formula 2,

R _a to R _c are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms,

However, R _a to R _c are not all hydrogen at the same time.

Specifically, the neodymium compound is Nd(2-ethylhexanoate) ₃ , Nd(2,2-dimethyl decanoate) ₃ , Nd(2,2-diethyl decanoate) ₃ , Nd(2,2) -dipropyl decanoate) ₃ , Nd (2,2-dibutyl decanoate) ₃ , Nd (2,2-dihexyl decanoate) ₃ , Nd (2,2-dioctyl decanoate) ₃ , Nd(2-ethyl-2-propyl decanoate) ₃ , Nd(2-ethyl-2-butyl decanoate) ₃ , Nd(2-ethyl-2-hexyl decanoate) ₃ , Nd(2- Propyl-2-butyl decanoate) ₃ , Nd(2-propyl-2-hexyl decanoate) ₃ , Nd(2-propyl-2-isopropyl decanoate) ₃ , Nd(2-butyl-2- Hexyl decanoate) ₃ , Nd(2-hexyl-2-octyl decanoate) ₃ , Nd(2,2-diethyl octanoate) ₃ , Nd(2,2-dipropyl octanoate) ₃ , Nd(2,2-dibutyl octanoate) ₃ , Nd(2,2-dihexyl octanoate) ₃ , Nd(2-ethyl-2-propyl octanoate) ₃ , Nd(2-ethyl-2 -Hexyl octanoate) ₃ , Nd (2,2-diethyl nonanoate) ₃ , Nd (2,2-dipropyl nonanoate) ₃ , Nd (2,2-dibutyl nonanoate) ₃ , One selected from the group consisting of Nd(2,2-dihexyl nonanoate) ₃ , Nd(2-ethyl-2-propyl nonanoate) ₃ and Nd(2-ethyl-2-hexyl nonanoate) ₃ may be more than

In addition, as another example, considering the excellent solubility in solvents, conversion to catalytically active species, and thus the catalytic activity improvement effect without concerns about oligomerization, the neodymium compound is more specifically, R _{a in Formula 2} It is an alkyl group having 4 to 12 carbon atoms, and R _b and R _c are each independently hydrogen or an alkyl group having 2 to 8 carbon atoms, with the proviso that R _b and R _c may be a neodymium-based compound other than hydrogen at the same time.

As a more specific example, in Formula 2, R _a is an alkyl group having 6 to 8 carbon atoms, R _b and R _c may each independently be hydrogen or an alkyl group having 2 to 6 carbon atoms, wherein R _b and R _c are It may not be hydrogen at the same time, and specific examples thereof include Nd(2,2-diethyl decanoate) ₃ , Nd(2,2-dipropyl decanoate) ₃ , Nd(2,2-dibutyl decanoate) ) ₃ , Nd(2,2-dihexyl decanoate) ₃ , Nd(2,2-dioctyl decanoate) ₃ , Nd(2-ethyl-2-propyl decanoate) ₃ , Nd(2- Ethyl-2-butyl decanoate) ₃ , Nd(2-ethyl-2-hexyl decanoate) ₃ , Nd(2-propyl-2-butyl decanoate) ₃ , Nd(2-propyl-2-hexyl) Decanoate) ₃ , Nd (2-propyl-2-isopropyl decanoate) ₃ , Nd (2-butyl-2-hexyl decanoate) ₃ , Nd (2-hexyl-2-octyl decanoate) ₃ , Nd(2-t-butyl decanoate) ₃ , Nd(2,2-diethyl octanoate) ₃ , Nd(2,2-dipropyl octanoate) ₃ , Nd(2,2-di Butyl octanoate) ₃ , Nd(2,2-dihexyl octanoate) ₃ , Nd(2-ethyl-2-propyl octanoate) ₃ , Nd(2-ethyl-2-hexyl octanoate) ₃ , Nd(2,2-diethyl nonanoate) ₃ , Nd(2,2-dipropyl nonanoate) ₃ , Nd(2,2-dibutyl nonanoate) ₃ , Nd(2,2-di Hexyl nonanoate) ₃ , Nd(2-ethyl-2-propyl nonanoate) ₃ and Nd(2-ethyl-2-hexyl nonanoate) ₃ may be at least one selected from the group consisting of, among them, Neodymium-based compounds are Nd(2,2-diethyl decanoate) ₃ , Nd(2,2-dipropyl decanoate) ₃ , Nd(2,2-dibutyl decanoate) ₃ , Nd(2, 2-dihexyl decanoate) ₃ , and Nd(2,2-dioctyl decanoate) ₃ may be at least one selected from the group consisting of.

More specifically, in Formula 2, R _a may be an alkyl group having 6 to 8 carbon atoms, and R _b and R _c may each independently be an alkyl group having 2 to 6 carbon atoms.

As such, the neodymium compound represented by Formula 2 includes a carboxylate ligand including an alkyl group of various lengths of 2 or more carbon atoms as a substituent at the α (alpha) position, thereby inducing a steric change around the neodymium central metal between the compounds It is possible to block the agglomeration phenomenon, and thus, there is an effect of suppressing oligomerization. In addition, such a neodymium-based compound has a high solubility in a solvent, and a ratio of neodymium located in a central portion having difficulty in conversion to a catalytically active species is reduced, thereby increasing the conversion rate to a catalytically active species.

The solubility of the neodymium compound may be about 4 g or more per 6 g of the non-polar solvent at room temperature (25° C.). The solubility of the neodymium-based compound refers to the degree of clear dissolution without turbidity, and by exhibiting such high solubility, excellent catalytic activity can be exhibited.

The neodymium compound may be used in the form of a reactant with a Lewis base. This reactant has the effect of improving the solubility of the neodymium compound in the solvent by the Lewis base and storing it in a stable state for a long period of time. The Lewis base may be used, for example, in a ratio of 30 moles or less, or 1 to 10 moles relative to 1 mole of the rare earth element. The Lewis base may be, for example, acetylacetone, tetrahydrofuran, pyridine, N,N-dimethylformamide, thiophene, diphenyl ether, triethylamine, an organophosphorus compound, or monovalent or divalent alcohol.

Meanwhile, the catalyst composition may further include at least one of an alkylating agent, a halide, and a conjugated diene-based monomer together with the neodymium compound. That is, the catalyst composition according to an embodiment of the present invention may include a neodymium compound and further include at least one of an alkylating agent, a halide, and a conjugated diene-based monomer.

Hereinafter, the (a) alkylating agent, (b) halide, and (c) conjugated diene-based monomer will be separately described.

(a) alkylating agent

The alkylating agent is an organometallic compound capable of transferring a hydrocarbyl group to another metal, and may serve as a co-catalyst. The alkylating agent is not particularly limited as long as it is used as an alkylating agent in the production of a diene-based polymer. For example, it is soluble in a polymerization solvent, such as an organoaluminum compound, an organomagnesium compound, or an organolithium compound, and forms a metal-carbon bond. It may be an organometallic compound containing.

Specifically, as the organoaluminum compound, trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, tripentyl Alkyl aluminum, such as aluminum, trihexyl aluminum, tricyclohexyl aluminum, and trioctylaluminum; diethylaluminum hydride, di-n-propylaluminum hydride, diisopropylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride (DIBAH), di-n-octylaluminum hydride, Diphenylaluminum hydride, di-p-tolylaluminum hydride, dibenzylaluminum hydride, phenylethylaluminum hydride, phenyl-n-propylaluminum hydride, phenylisopropylaluminum hydride, phenyl-n-butylaluminum hydride Ride, phenylisobutylaluminum hydride, phenyl-n-octylaluminum hydride, p-tolylethylaluminum hydride, p-tolyl-n-propylaluminum hydride, p-tolylisopropylaluminum hydride, p-tolyl- n-butylaluminum hydride, p-tolylisobutylaluminum hydride, p-tolyl-n-octylaluminum hydride, benzylethylaluminum hydride, benzyl-n-propylaluminum hydride, benzylisopropylaluminum hydride, benzyl dihydrocarbylaluminum hydride such as -n-butylaluminum hydride, benzylisobutylaluminum hydride or benzyl-n-octylaluminum hydride; Hydrocarbylaluminum dihydride such as ethylaluminum dihydride, n-propylaluminum dihydride, isopropylaluminum dihydride, n-butylaluminum dihydride, isobutylaluminum dihydride or n-octylaluminum dihydride, etc. A hydride etc. are mentioned. Examples of the organic magnesium compound include alkyl magnesium compounds such as diethyl magnesium, di-n-propyl magnesium, diisopropyl magnesium, dibutyl magnesium, dihexyl magnesium, diphenyl magnesium, or dibenzyl magnesium, and the like. Examples of the organolithium compound include alkyl lithium compounds such as n-butyllithium.

In addition, the organoaluminum compound may be aluminoxane. The aluminoxane may be prepared by reacting a trihydrocarbyl aluminum-based compound with water, and specifically may be a linear aluminoxane of the following Chemical Formula 3a or a cyclic aluminoxane of the following Chemical Formula 3b.

[Formula 3a]

[Formula 3b]

In Formulas 3a and 3b,

R is a monovalent organic group bonded to an aluminum atom through a carbon atom, and may be a hydrocarbyl group, and x and y are each independently an integer of 1 or more, specifically 1 to 100, more specifically 2 to 50 It can be an integer.

More specifically, the aluminoxane is methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethylaluminoxane, n-propylaluminoxane, isopropylaluminoxane, butylaluminoxane, isobutylaluminoxane, n-pentyl Aluminoxane, neopentylaluminoxane, n-hexylaluminoxane, n-octylaluminoxane, 2-ethylhexylaluminoxane, cyclohexylaluminoxane, 1-methylcyclopentylaluminoxane, phenylaluminoxane or 2,6-dimethylphenyl aluminoxane and the like, and any one or a mixture of two or more thereof may be used.

In addition, the modified methylaluminoxane may be a compound in which the methyl group of methylaluminoxane is substituted with a modifying group (R), specifically, a hydrocarbon group having 2 to 20 carbon atoms, specifically, a compound represented by the following formula (4).

[Formula 4]

In Formula 4, R is as defined above, and m and n may be each independently an integer of 2 or more. In addition, in Formula 4, Me represents a methyl group.

Specifically, in Formula 4, R is an alkyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkenyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, It may be an arylalkyl group having 7 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an allyl group or an alkynyl group having 2 to 20 carbon atoms, and more specifically, an ethyl group, isobutyl group, hexyl group or octyl group having 2 carbon atoms. to 10, and more specifically, may be an isobutyl group.

More specifically, the modified methylaluminoxane may be obtained by substituting about 50 to 90 mol% of the methyl groups of the methylaluminoxane with the aforementioned hydrocarbon groups. When the content of the substituted hydrocarbon group in the modified methylaluminoxane is within the above range, the catalytic activity may be increased by promoting alkylation.

Such modified methylaluminoxane may be prepared according to a conventional method, and specifically may be prepared using trimethylaluminum and alkylaluminum other than trimethylaluminum. In this case, the alkyl aluminum may be triisobutyl aluminum, triethyl aluminum, trihexyl aluminum or trioctyla aluminum, and any one or a mixture of two or more thereof may be used.

In addition, the catalyst composition according to an embodiment of the present invention may include 1 to 200 moles, 1 to 100 moles, or 3 to 20 moles of the alkylating agent relative to 1 mole of the neodymium compound. If the amount of the alkylating agent exceeds 200 moles, it is difficult to control the catalytic reaction during the preparation of the polymer, and there is a risk that the excessive amount of the alkylating agent may cause side reactions.

(b) halides

The halide is not particularly limited, but may include, for example, a simple halogen, an interhalogen compound, a hydrogen halide, an organic halide, a non-metal halide, a metal halide, or an organometal halide, and any of these One or a mixture of two or more may be used. Among them, any one or a mixture of two or more selected from the group consisting of organic halides, metal halides, and organometallic halides may be used as the halide in consideration of the excellent effect of improving catalytic activity and thus improving reactivity.

Examples of the halogen alone include fluorine, chlorine, bromine or iodine.

Examples of the interhalogen compound include iodine monochloride, iodine monobromide, iodine trichloride, iodine pentafluoride, iodine monofluoride or iodine trifluoride.

In addition, the hydrogen halide may include hydrogen fluoride, hydrogen chloride, hydrogen bromide or hydrogen iodide.

In addition, as the organic halide, t-butyl chloride (t-BuCl), t-butyl bromide, allyl chloride, allyl bromide, benzyl chloride, benzyl bromide, chloro-di-phenylmethane, bromo-di-phenylmethane, tri Phenylmethyl chloride, triphenylmethyl bromide, benzylidene chloride, benzylidene bromide, methyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, trimethylchlorosilane (TMSCl), benzoyl chloride, benzoyl bromide, propyi Onyl chloride, propionyl bromide, methyl chloroformate, methyl bromoformate, iodomethane, diiodomethane, triiodomethane (also called 'iodoform'), tetraiodomethane, 1-io Dopropane, 2-iodopropane, 1,3-diiodopropane, t-butyl iodide, 2,2-dimethyl-1-iodopropane (also called 'neopentyl iodide'), allyl iodine Odide, iodobenzene, benzyl iodide, diphenylmethyl iodide, triphenylmethyl iodide, benzylidene iodide (also called 'benzal iodide'), trimethylsilyl iodide, triethyl Silyl iodide, triphenylsilyl iodide, dimethyldiiodosilane, diethyldiiodosilane, diphenyldiiodosilane, methyltriiodosilane, ethyltriiodosilane, phenyltriiodosilane, benzoyl iodide, propionyl iodide or methyl iodoformate; and the like.

In addition, as the non-metal halide, phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, phosphorus oxychloride, phosphorus oxybromide, boron trifluoride, boron trichloride, boron tribromide, silicon tetrafluoride, silicon tetrachloride (SiCl ₄ ), silicon tetrabromide , arsenic trichloride, arsenic tribromide, selenium tetrachloride, selenium tetrabromide, tellurium tetrachloride, tellurium tetrabromide, silicon tetraiodide, arsenic triiodide, tellurium tetraiodide, boron triiodide, phosphorus triiodide, phosphorus oxyiodide or selenium tetraiodide, etc. can be heard

In addition, as the metal halide, tin tetrachloride, tin tetrabromide, aluminum trichloride, aluminum tribromide, antimony trichloride, antimony pentachloride, antimony tribromide, aluminum trifluoride, gallium trichloride, gallium tribromide, gallium trifluoride, indium trichloride, Indium tribromide, indium trifluoride, titanium tetrachloride, titanium tetrabromide, zinc dichloride, zinc dibromide, zinc difluoride, aluminum triiodide, gallium triiodide, indium triiodide, titanium tetraiodide, zinc iodide, tetraiodide germanium, tin tetraiodide, tin iodide, antimony triiodide, or magnesium iodide.

In addition, as the organometallic halide, dimethyl aluminum chloride, diethyl aluminum chloride, dimethyl aluminum bromide, diethyl aluminum bromide, dimethyl aluminum fluoride, diethyl aluminum fluoride, methyl aluminum dichloride, ethyl aluminum dichloride, methyl aluminum dichloride Bromide, ethylaluminum dibromide, methylaluminum difluoride, ethylaluminum difluoride, methylaluminum sesquichloride, ethylaluminum sesquichloride (EASC), isobutylaluminum sesquichloride, methylmagnesium chloride, methylmagnesium bromide, ethyl Magnesium chloride, ethylmagnesium bromide, n-butylmagnesium chloride, n-butylmagnesium bromide, phenylmagnesium chloride, phenylmagnesium bromide, benzylmagnesium chloride, trimethyltin chloride, trimethyltin bromide, triethyltin chloride, triethyltin bromide, di -t-butyltin dichloride, di-t-butyltin dibromide, di-n-butyltin dichloride, di-n-butyltin dibromide, tri-n-butyltin chloride, tri-n-butyltin bromide , methylmagnesium iodide, dimethylaluminum iodide, diethylaluminum iodide, di-n-butylaluminum iodide, diisobutylaluminum iodide, di-n-octylaluminum iodide, methylaluminum Diiodide, ethylaluminum diiodide, n-butylaluminum diiodide, isobutylaluminum diiodide, methylaluminum sesquiiodide, ethylaluminum sesquiiodide, isobutylaluminum sesquiiodide, ethylmagnesium iodide Odide, n-butylmagnesium iodide, isobutylmagnesium iodide, phenylmagnesium iodide, benzylmagnesium iodide, trimethyltin iodide, triethyltin iodide, tri-n-butyltin iodide odide, di-n-butyltin diiodide, or di-t-butyltin diiodide;

In addition, the catalyst composition according to an embodiment of the present invention contains the halide in an amount of 1 mole to 20 moles, more specifically 1 mole to 5 moles, and more specifically 2 moles to 3 moles, based on 1 mole of the neodymium compound. may include If the halide is included in a molar ratio of more than 20, it is not easy to remove the catalytic reaction, and there is a fear that an excessive amount of the halide may cause a side reaction.

In addition, the catalyst composition according to an embodiment of the present invention may include a non-coordinating anion-containing compound or a non-coordinating anion precursor compound instead of or together with the halide.

Specifically, in the compound containing the non-coordinating anion, the non-coordinating anion is a sterically bulky anion that does not form a coordination bond with the active center of the catalyst system due to steric hindrance, and is a tetraarylborate anion or tetraaryl fluoride. borate anion, and the like. In addition, the compound containing the non-coordinating anion may include a carbonium cation such as a triaryl carbonium cation together with the non-coordinating anion; It may include an ammonium cation such as an N,N-dialkyl anilinium cation, or a counter cation such as a phosphonium cation. More specifically, the compound containing the non-coordinating anion is triphenyl carbonium tetrakis (pentafluoro phenyl) borate, N,N-dimethylanilinium tetrakis (pentafluoro phenyl) borate, triphenyl carbonium tetra kiss[3,5-bis(trifluoromethyl)phenyl]borate, or N,N-dimethylanilinium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, or the like.

In addition, as the non-coordinating anion precursor, a compound capable of forming a non-coordinating anion under reaction conditions, such as a triaryl boron compound (BE ₃ , where E is a pentafluorophenyl group or a 3,5-bis (trifluoromethyl) phenyl group, etc.) the same strong electron-withdrawing aryl group).

(c) conjugated diene-based monomers

In addition, the catalyst composition may further include a conjugated diene-based monomer, and a portion of the conjugated diene-based monomer used in the polymerization reaction is mixed with the catalyst composition for polymerization in advance to perform pre-polymerization or pre-polymerization. By using it in the form of a premix catalyst composition, it is possible not only to improve the catalyst composition activity, but also to stabilize the active polymer to be prepared.

In the present invention, the "preforming" means a catalyst composition including a neodymium compound, an alkylating agent and a halide, that is, diisobutylaluminum hydride (DIBAH) in a catalyst system. In order to reduce the possibility of generating active species in the catalyst composition, a small amount of a conjugated diene-based monomer such as 1,3-butadiene is added. have. In addition, "premix (premix)" may mean a state in which each compound is uniformly mixed without polymerization in the catalyst composition system.

In this case, the conjugated diene-based monomer used in the preparation of the catalyst composition may be used in an amount within the total amount of the conjugated diene-based monomer used in the polymerization, for example, 1 per mole of the neodymium compound. It may be used in an amount of from 10 moles to 100 moles, specifically from 10 moles to 50 moles, or from 20 moles to 50 moles.

The catalyst composition according to an embodiment of the present invention includes at least one of the aforementioned neodymium compound and alkylating agent, halide and conjugated diene-based monomers in an organic solvent, specifically, a neodymium compound, an alkylating agent and a halide, and optionally a conjugated diene-based monomer. It can be prepared by mixing the monomers. In this case, the organic solvent may be a non-polar solvent that is not reactive with the components of the catalyst composition. Specifically, the non-polar solvent is n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, isopentane, isohexane, isopentane, isooctane, 2,2-dimethylbutane, cyclo linear, branched or cyclic aliphatic hydrocarbons having 5 to 20 carbon atoms, such as pentane, cyclohexane, methylcyclopentane or methylcyclohexane; a mixed solvent of aliphatic hydrocarbons having 5 to 20 carbon atoms, such as petroleum ether or petroleum spirits, or kerosene; Alternatively, it may be an aromatic hydrocarbon-based solvent such as benzene, toluene, ethylbenzene, and xylene, and any one or a mixture of two or more thereof may be used. More specifically, the non-polar solvent may be a linear, branched or cyclic aliphatic hydrocarbon having 5 to 20 carbon atoms or a mixed solvent of aliphatic hydrocarbons, and more specifically, n-hexane, cyclohexane, or a mixture thereof. can

In addition, the organic solvent may be appropriately selected according to the constituent components constituting the catalyst composition, in particular, the type of the alkylating agent.

Specifically, in the case of alkylaluminoxane such as methylaluminoxane (MAO) or ethylaluminoxane as an alkylating agent, since it is not easily dissolved in an aliphatic hydrocarbon-based solvent, an aromatic hydrocarbon-based solvent may be appropriately used.

In addition, when modified methylaluminoxane is used as the alkylating agent, an aliphatic hydrocarbon-based solvent may be appropriately used. In this case, since it is possible to implement a single solvent system together with an aliphatic hydrocarbon-based solvent such as hexane, which is mainly used as a polymerization solvent, it may be more advantageous for the polymerization reaction. In addition, the aliphatic hydrocarbon-based solvent may promote catalytic activity, and reactivity may be further improved by such catalytic activity.

Meanwhile, the organic solvent may be used in an amount of 20 moles to 20,000 moles, more specifically, 100 moles to 1,000 moles, based on 1 mole of the neodymium compound.

Meanwhile, the polymerization in step 1 may be performed as a continuous polymerization in a polymerization reactor including at least two reactors, or may be performed in a batch reactor.

In addition, the polymerization may be an elevated temperature polymerization, an isothermal polymerization, or a constant temperature polymerization (adiabatic polymerization).

Here, the constant temperature polymerization refers to a polymerization method comprising the step of polymerization with heat of reaction by itself without optionally applying heat after the catalyst composition is added. , and the isothermal polymerization refers to a polymerization method in which heat is applied after the catalyst composition is added to increase heat, or heat is taken away to maintain a constant temperature of the reactant.

In addition, the polymerization may be carried out using coordination anionic polymerization or may be carried out by radical polymerization, specifically bulk polymerization, solution polymerization, suspension polymerization or emulsion polymerization, and more specifically solution polymerization. .

The polymerization may be carried out in a temperature range of -20 °C to 200 °C, specifically 50 °C to 150 °C, more specifically 10 °C to 120 °C or 60 °C to 90 °C for 15 minutes to It may be performed for 3 hours. If the polymerization temperature exceeds 200 ℃, it is difficult to sufficiently control the polymerization reaction, there is a risk that the cis-1,4 bond content of the resulting conjugated diene-based polymer may be lowered, and if the temperature is less than -20 ℃, polymerization There is a possibility that the reaction rate and efficiency may be lowered.

In addition, the method for producing the modified conjugated diene-based polymer according to an embodiment of the present invention includes a reaction terminator for completing the polymerization reaction such as polyoxyethylene glycol phosphate after preparing the active polymer; Alternatively, the polymerization may be terminated by further using an additive such as an antioxidant such as 2,6-di-t-butylparacresol. In addition, additives for facilitating solution polymerization together with the reaction terminator, for example, an additive such as a chelating agent, a dispersing agent, a pH adjusting agent, an oxygen scavenger or an oxygen scavenger may be optionally further used.

Step 2 is a step of preparing a modified conjugated diene-based polymer including a functional group by modifying the active polymer, and may be performed by reacting the active polymer with a modifier represented by Chemical Formula 1.

The modifier is 0.01 parts by weight or more, 0.02 parts by weight or more, 0.03 parts by weight or more, 0.04 parts by weight or more, 0.05 parts by weight or more, 0.60 parts by weight or less, 0.50 parts by weight or less, 0.30 parts by weight or less, based on 100 parts by weight of the conjugated diene-based monomer. , may be used in an amount of 0.20 parts by weight or less.

In addition, the modifier may be used in an amount of 0.5 mol or more, 1 mol or more, 2 mol or more, 10 mol or less, 8 mol or less relative to 1 mol of the neodymium compound in the catalyst composition. Specifically, the modifier may be used in an amount of 2 to 8 moles relative to 1 mole of the neodymium compound in the catalyst composition.

In addition, the denaturation reaction may be performed at 0° C. to 90° C. for 1 minute to 5 hours.

After completion of the above-described modification reaction, a solution of 2,6-di-t-butyl-p-cresol (BHT) in isopropanol or the like may be added to the polymerization reaction system to stop the polymerization reaction.

In the manufacturing method, after step 2, a modified conjugated diene-based polymer may be obtained through a solvent removal treatment such as steam stripping or vacuum drying treatment to lower the partial pressure of the solvent through supply of water vapor. In addition, an unmodified active polymer may be included in the reaction product obtained as a result of the above-mentioned reaction together with the above-mentioned modified conjugated diene polymer.

Furthermore, the present invention provides a rubber composition comprising the conjugated diene-based polymer and a molded article prepared from the rubber composition.

The rubber composition may include 0.1 wt% or more and 100 wt% or less of the modified conjugated diene-based polymer, specifically 10 wt% to 100 wt%, and more specifically 20 wt% to 90 wt%. If the content of the modified conjugated diene-based polymer is less than 0.1% by weight, as a result, the improvement effect of abrasion resistance and crack resistance of a molded article manufactured using the rubber composition, such as a tire, may be insignificant.

In addition, the rubber composition may further include other rubber components as needed in addition to the modified conjugated diene-based polymer, wherein the rubber component may be included in an amount of 90% by weight or less based on the total weight of the rubber composition. Specifically, it may be included in an amount of 1 to 900 parts by weight based on 100 parts by weight of the modified conjugated diene-based copolymer.

The rubber component may be natural rubber or synthetic rubber, for example, the rubber component may include natural rubber (NR) containing cis-1,4-polyisoprene; Modified natural rubbers such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber that are modified or refined of the general natural rubber; 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, or a synthetic rubber such as halogenated butyl rubber, and any one or a mixture of two or more thereof may be used.

In addition, the rubber composition may include 20 to 90 parts by weight of a filler based on 100 parts by weight of the modified conjugated diene-based polymer, and the filler may be silica-based, carbon black, or a combination thereof. Specifically, the filler may be carbon black.

The carbon black-based filler is not particularly limited, but may have, for example, a nitrogen adsorption specific surface area (N2SA, measured in accordance with JIS K 6217-2:2001) of 20 m 2 /g to 250 m 2 /g. In addition, the carbon black may have a dibutyl phthalate oil absorption (DBP) of 80 cc/100g to 200 cc/100g. When the nitrogen adsorption specific surface area of the carbon black exceeds 250 m ² /g, the processability of the rubber composition may decrease, and if it is less than 20 m 2 /g, the reinforcing performance by the carbon black may be insignificant. In addition, when the DBP oil absorption amount of the carbon black exceeds 200 cc/100g, there is a fear that the processability of the rubber composition is reduced, and when it is less than 80 cc/100g, the reinforcing performance by the carbon black may be insignificant.

In addition, the silica is not particularly limited, but may be, for example, wet silica (hydrous silicic acid), dry silica (silicic anhydride), calcium silicate, aluminum silicate or colloidal silica. Specifically, the silica may be wet silica having the most remarkable effect of improving fracture properties and coexisting effects of wet grip properties. In addition, the silica has a nitrogen adsorption specific surface area (nitrogen surface area per gram, NSA) of 120 m / g to 180 m / g, and a cetyl trimethyl ammonium bromide (CTAB) adsorption specific surface area of 100 m / g to 200 m / g can be If the nitrogen adsorption specific surface area of the silica is less than 120 m 2 /g, there is a fear that the reinforcing performance by silica may be lowered, and if it exceeds 180 m / g, there is a fear that the processability of the rubber composition may decrease. In addition, if the CTAB adsorption specific surface area of the silica is less than 100 m 2 /g, the reinforcing performance by the silica filler may decrease, and if it exceeds 200 m / g, there is a fear that the processability of the rubber composition may decrease.

On the other hand, when silica is used as the filler, a silane coupling agent may be used together to improve reinforcing properties and low heat generation.

Specifically, the silane coupling agent is bis(3-triethoxysilylpropyl)tetrasulfide, bis(3-triethoxysilylpropyl)trisulfide, bis(3-triethoxysilylpropyl)disulfide, bis (2-triethoxysilylethyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, bis(2-trimethoxysilylethyl)tetrasulfide, 3-mercaptopropyltrimethoxysilane , 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfur Feed, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-trimethoxysilyl Propylbenzothiazolyltetrasulfide, 3-triethoxysilylpropylbenzolyltetrasulfide, 3-triethoxysilylpropylmethacrylate monosulfide, 3-trimethoxysilylpropylmethacrylate monosulfide, bis (3-diethoxymethylsilylpropyl)tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide or dimethoxymethylsilylpropylbenzothiazolyl tetrasulfide and the like, and any one or a mixture of two or more thereof may be used. More specifically, in consideration of the reinforcing improvement effect, the silane coupling agent may be bis(3-triethoxysilylpropyl)polysulfide or 3-trimethoxysilylpropylbenzothiazyltetrasulfide.

In addition, the rubber composition according to an embodiment according to the present invention may be crosslinkable with sulfur, and thus may further include a vulcanizing agent.

The vulcanizing agent may be specifically sulfur powder, and may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the rubber component. When included in the above content range, it is possible to secure the required elastic modulus and strength of the vulcanized rubber composition, and at the same time to obtain low fuel economy.

In addition, the rubber composition according to an embodiment of the present invention, in addition to the above components, various additives commonly used in the rubber industry, specifically, a vulcanization accelerator, a process oil, a plasticizer, an anti-aging agent, an anti-scorch agent, zinc white ), stearic acid, a thermosetting resin, or a thermoplastic resin may be further included.

The vulcanization accelerator is not particularly limited, and specifically, M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazyl sulfenamide), etc. A thiazole-based compound of , or a guanidine-based compound such as DPG (diphenylguanidine) may be used. The vulcanization accelerator may be included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the rubber component.

In addition, the process oil acts as a softener in the rubber composition. Specifically, it may be a paraffinic, naphthenic, or aromatic compound. More specifically, when considering tensile strength and abrasion resistance, aromatic process oil price, hysteresis loss And in consideration of low-temperature characteristics, a naphthenic or paraffin-based process oil may be used. The process oil may be included in an amount of 100 parts by weight or less based on 100 parts by weight of the rubber component.

In addition, the antioxidant is specifically N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, 6- and oxy-2,2,4-trimethyl-1,2-dihydroquinoline, or a high-temperature condensate of diphenylamine and acetone. The antioxidant may be used in an amount of 0.1 to 6 parts by weight based on 100 parts by weight of the rubber component.

The rubber composition according to an embodiment of the present invention can be obtained by kneading using a kneader such as a Banbury mixer, a roll, an internal mixer, etc. according to the above formulation, and also has low heat generation and wear resistance by a vulcanization process after molding processing. This excellent rubber composition can be obtained.

Accordingly, the rubber composition may be used for each member of the tire such as a tire tread, under tread, side wall, carcass coated rubber, belt coated rubber, bead filler, cheffer, or bead coated rubber, vibration proof rubber, belt conveyor, hose, etc. It may be useful in the manufacture of various industrial rubber products of

A molded article manufactured using the rubber composition may include a tire or a tire tread.

Example

Hereinafter, the present invention will be described in more detail by way of Examples. However, the following examples are provided to illustrate the present invention, and the scope of the present invention is not limited thereto.

Preparation Example 1: Preparation of the compound of Formula 1-1

[Formula 1-1]

Preparation Example 2: Preparation of the compound of Formula 1-2

Ethyl 4-(bis(2-((((E)-4-methylpentan-2-ylidene)amino)ethyl)amino)butanoate was prepared with reference to WO 2018-084546 A1 EtOH (400 ml ) to a solution of ethyl 4-(bis(2-((((E)-4-methylpentan-2-ylidene)amino)ethyl)amino)butanoate (120 g) in SOCl ₂ (20 ml) The reaction mixture is refluxed at 0°C overnight.The resulting solution is cooled to room temperature.Volatile solvent is evaporated under reduced pressure.Ethyl 4-(bis(2-aminoethyl)amino)buta prepared by washing the _{solid with Et 2 O} Noate hydrochloride was used without further purification.

To a solution of ethyl 4-(bis(2-aminoethyl)amino)butanoate hydrochloride (64 g) _{in CH 2} Cl ₂ (400 ml) at 0° C. _{Et 3} N (120 g) and 1,2-bis( Chlorodimethylsilyl)ethane (93 g) was added. The reaction mixture was warmed to room temperature and stirred overnight. The resulting solution was filtered off and the residue was diluted with fresh n-hexane and filtered again. The volatile solution was removed under reduced pressure to yield the title compound.

¹ H-NMR (500 MHz, CDCl ₃ ): δ 4.11 (q, 2H), 3.21-3.18 (m, 4H), 2.71 (m, 4H), 2.55 (m, 2H), 2.50-2.39 (m, 2H) , 1.39-1.21 (m, 6H), 1.10 (m, 4H), 0.10 (m, 24H)

[Formula 1-2]

Preparation Example 3: Preparation of the compound of Formula 1-3

[Formula 1-3]

Example 1

After putting 800 g of 1,3-butadiene and 5.4 kg of n-hexane in a 20L autoclave reactor, the temperature inside the reactor was raised to 70°C. Neodymium versatate (Neodymium versatate, Solvay) was added in n-hexane solvent, diisobutylaluminum hydride (DIBAH), and diethylaluminum chloride (DEAC) were added to the neodymium versatate:DIBAH:DEAC=1:16: A catalyst composition was prepared by sequentially adding them to a molar ratio of 2.4 and mixing them. After introducing the catalyst composition to the reactor, polymerization was performed for 30 minutes.

After the addition of 0.05 phm of the denaturant of [Formula 1-2] prepared in Preparation Example 1, the denaturation reaction was performed at 70° C. for 30 minutes.

Thereafter, the reaction was terminated by adding a hexane solution containing 1.0 g of a polymerization terminator and a solution in which the antioxidant WINGSTAY (Eliokem SAS, France) was dissolved in hexane at 30% by weight, and the resulting heavy content was heated with steam. The solvent was removed by putting it in hot water and stirring, and then roll drying was performed to remove the remaining amount of solvent and water to prepare a modified butadiene polymer.

Example 2

A modified butadiene polymer was prepared in the same manner as in Example 1, except that the content of the modifier was changed as shown in Table 1 below.

Example 3

A modified butadiene polymer was prepared in the same manner as in Example 1, except that the modifier of [Formula 1-1] was used instead of the modifier of [Formula 1-2].

Example 4

A modified butadiene polymer was prepared in the same manner as in Example 3, except that the content of the modifier was changed as shown in Table 1 below.

Example 5

A modified butadiene polymer was prepared in the same manner as in Example 1, except that the modifier of [Formula 1-3] was used instead of the modifier of [Formula 1-2].

Comparative Example 1

After putting 800 g of 1,3-butadiene and 5.4 kg of n-hexane in a 20L autoclave reactor, the temperature inside the reactor was raised to 70°C. After the catalyst composition was added thereto, polymerization was performed for 30 minutes. In this case, the catalyst composition is prepared by adding neodymium versatate (Solvay Co.) to n-hexane solvent, diisobutylaluminum hydride (DIBAH), and diethylaluminum chloride (DEAC) to the neodymium versatate:DIBAH: DEAC=1:16:2.4 was added sequentially so that the molar ratio was mixed and prepared. Thereafter, the reaction was terminated by adding a hexane solution containing 1.0 g of a polymerization terminator and a solution in which the antioxidant WINGSTAY (Eliokem SAS, France) was dissolved in hexane at 30% by weight, and the resulting heavy content was heated with steam. The solvent was removed by putting it in hot water and stirring, and then roll drying was performed to remove the remaining amount of solvent and water to prepare a modified butadiene polymer.

division Example comparative example One 2 3 4 5 One denaturant Formula 1-2 Formula 1-2 Formula 1-1 Formula 1-1 Formula 1-3 not used Denaturant dosage (phm) 0.05 0.10 0.05 0.10 0.05 -

* phm: parts by weight based on 100 parts by weight of the conjugated diene-based monomer

Experimental Example 1

For the polymers of Examples and Comparative Examples, each physical property was measured in the following manner, and the results are shown in Table 1 below.

(1) Mooney viscosity (ML1+4, @100℃) and -S/R

For each polymer, Mooney viscosity was measured at 100° C. with a Rotor Speed of 2±0.02 rpm using a Monsanto MV2000E with a large rotor. At this time, the sample used was left at room temperature (23±3° C.) for more than 30 minutes, and then 27±3 g was collected, filled in the die cavity, and the Mooney viscosity was measured while applying a torque by operating the platen.

When the Mooney viscosity is measured, the change in Mooney viscosity appearing as the torque is released was observed for 1 minute, and the -S/R value was determined from the slope value.

division Example comparative example One 2 3 4 5 One rate of metamorphosis 29 28 22 23 27 - Mooney viscosity
(100℃ MV) before metamorphosis 32 33 32 33 33 43 after metamorphosis 50 49 50 48 51 - △MV 18 16 18 15 19 - -S/R before metamorphosis 0.804 0.800 0.805 0.801 0.805 0.585 after metamorphosis 0.771 0.790 0.781 0.800 0.791 -

Experimental Example 2

After preparing a rubber composition and a rubber specimen using the polymers of Examples and Comparative Examples, Mooney viscosity, tensile stress, 300% modulus, abrasion resistance, and viscoelastic properties were measured in the following manner, respectively. The results are shown in Table 3 below.

Specifically, the rubber composition contains 70 parts by weight of carbon black, 22.5 parts by weight of process oil (TDAE oil), 2 parts by weight of antioxidant (TMDQ), 3 parts by weight of zinc oxide (ZnO), and It was prepared by mixing 2 parts by weight of stearic acid.

Then, 2 parts by weight of sulfur, 2 parts by weight of a vulcanization accelerator (CZ) and 0.5 parts by weight of a vulcanization accelerator (DPG) were added to each rubber composition, and gently mixed at 50 rpm for 1.5 minutes at 50 ° C. Using a roll at 50 ° C. to prepare a sheet-shaped vulcanization formulation, and vulcanize the vulcanization formulation at 160° C. for 25 minutes to prepare a rubber specimen.

(1) Tensile properties

After vulcanizing each rubber composition at 150° C. for t90 minutes, according to ASTM D412, the tensile strength of the vulcanized product (tensile strength, kg f/cm ² ) and the modulus at 300% elongation (M-300%, kg f/cm ^{2 )} ) was measured.

Based on the measured value of Comparative Example 1, it was calculated and indexed by Equation 1 below.

[Equation 1]

Index = (measured value/reference value) × 100

(2) wear resistance

Each rubber specimen was subjected to a DIN abrasion test according to ASTM D5963, and expressed as a DIN wt loss index (loss volume indes: ARIA (Abrasion resistance index, Method A)). The result value of Comparative Example 1 was indexed to 100 and shown.

Based on the measured value of Comparative Example 1, it was calculated and indexed by Equation 2 below.

[Equation 2]

Index = (reference value/measurement value) × 100

(3) Viscoelastic properties

The most important property of Tanδ for low fuel consumption characteristics was measured using DMTS 500N from Gabo, Germany, at a frequency of 10 Hz, Prestrain 3%, and Dynamic Strain 3% at -60°C to 60°C (Tanδ). At this time, the Tanδ value at 0°C indicates road resistance, and the Tanδ value at 60°C indicates the rolling resistance characteristic (fuel efficiency).

Based on the measured value of Comparative Example 1, it was calculated and indexed by Equation 2 below.

[Equation 2]

Index = (reference value/measurement value) × 100

division Example comparative example One 2 3 4 5 One tensile properties M-300% (kg f/cm ² ) 91 92 89 85 88 84 M-300% index 108 110 106 101 105 100 wear resistance loss weight(mg) 26.7 26.5 27.1 26.8 27.6 28.7 DIN index 107 108 106 107 104 100 Viscoelastic properties Tanδ @ 50~70℃ 0.151 0.150 0.155 0.154 0.148 0.180 Tanδ @ 50~70℃ index 116 117 116 117 122 100

As shown in Table 3, Examples 1 to 5 prepared as rubber specimens using the modified conjugated diene-based polymer according to the present invention exhibited superior tensile properties and abrasion resistance compared to Comparative Examples. In addition, it was confirmed that the rolling resistance was improved and the fuel efficiency was good.

Claims (10)

a repeating unit derived from a conjugated diene-based monomer; and
Modified conjugated diene-based polymer comprising a functional group derived from a modifier represented by the following formula (1):
[Formula 1]

In Formula 1,
R ₁ is an alkyl group having 1 to 10 carbon atoms,
R ₂ is

,

and

It is an alkylene group having 1 to 10 carbon atoms including at least one selected from the group consisting of
Wherein R ₃ is an alkylene group having 1 to 10 carbon atoms,
wherein R ₄ to R ₉ are each independently an alkyl group having 1 to 20 carbon atoms, wherein two of R ₄ to R ₉ may be connected to each other to form a heterocycle together with N,
X is the following formula (a) or formula (b),
[Formula a]

In the above formula (a),
R ₁₀ to R ₁₅ are each independently an alkyl group having 1 to 20 carbon atoms, wherein two of R ₁₀ to R ₁₅ may be connected to each other to form a heterocycle together with N,
[Formula b]

In the above formula (b),
R ₁₆ is an alkyl group having 1 to 10 carbon atoms.
The method according to claim 1,
In Formula 1,
R ₁ is an alkyl group having 1 to 6 carbon atoms,
R ₂ is

,

and

It is an alkylene group having 1 to 6 carbon atoms including at least one selected from the group consisting of
R ₃ is an alkylene group having 1 to 6 carbon atoms,
R ₄ to R ₉ are each independently an alkyl group having 1 to 6 carbon atoms, wherein two of R ₄ to R ₉ are connected to each other to form a 5-ring heterocycle together with N,
R ₁₀ to R ₁₅ are each independently an alkyl group having 1 to 6 carbon atoms, wherein two of R ₄ to R ₉ are connected to each other to form a 5-ring heterocycle together with N,
R ₁₆ is a modified conjugated diene-based polymer having 1 to 6 carbon atoms.
The method according to claim 1,
The modifier represented by Formula 1 is a modified conjugated diene-based polymer that is a compound represented by any one of Formulas 1-1 to 1-3.
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

The method according to claim 1,
A modified conjugated diene-based polymer having a weight average molecular weight of 100,000 to 1,000,000 g/mol.
The method according to claim 1,
A modified conjugated diene-based polymer having a molecular weight distribution of 1.0 to 4.0.
preparing an active polymer by polymerizing a conjugated diene-based monomer in the presence of a catalyst composition including a neodymium compound in a hydrocarbon solvent; and
A method for producing the modified conjugated diene-based polymer of claim 1, comprising the step of reacting the active polymer with a modifier represented by the following formula (1):
[Formula 1]

In Formula 1,
R ₁ is an alkyl group having 1 to 10 carbon atoms,
R ₂ is

,

and

It is an alkylene group having 1 to 10 carbon atoms including at least one selected from the group consisting of
Wherein R ₃ is an alkylene group having 1 to 10 carbon atoms,
wherein R ₄ to R ₉ are each independently an alkyl group having 1 to 20 carbon atoms, wherein two of R ₄ to R ₉ may be connected to each other to form a heterocycle together with N,
X is the following formula (a) or formula (b),
[Formula a]

In the above formula (a),
R ₁₀ to R ₁₅ are each independently an alkyl group having 1 to 20 carbon atoms, wherein two of R ₁₀ to R ₁₅ may be connected to each other to form a heterocycle together with N,
[Formula b]

In the above formula (b),
R ₁₆ is an alkyl group having 1 to 10 carbon atoms.
7. The method of claim 6,
The catalyst composition is a method for producing a modified conjugated diene-based polymer comprising 0.03 to 0.10 mmol of the neodymium compound relative to 100 parts by weight of the conjugated diene-based monomer.
7. The method of claim 6,
The modifier is 0.01 to 0.60 parts by weight based on 100 parts by weight of the conjugated diene-based monomer.
7. The method of claim 6,
The modifier is a method for producing a modified conjugated diene-based polymer in an amount of 0.5 to 10 moles relative to 1 mole of the neodymium compound.
7. The method of claim 6,
The neodymium compound is a method for producing a modified conjugated diene-based polymer, which is a compound represented by the following formula 2:
[Formula 2]

In Formula 2,
R _a to R _c are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms,
However, R _a to R _c are not all hydrogen at the same time.