Preparation method for catalyst composition

Abstract

The present invention relates to a method for preparing a catalyst composition for manufacturing a conjugated diene-based polymer, comprising the steps of: reacting a functionalizing agent represented by Formula 1 with an alkylating agent to produce a functionalized alkylating agent (S1); and reacting the functionalized alkylating agent, a neodymium compound, and a halogen compound (S2).

Description

Technology Field

[0001] The present invention relates to a method for preparing a catalyst composition for manufacturing conjugated diene-based polymers. Background Technology

[0003] Recently, in response to the demand for lower fuel consumption in automobiles, conjugated diene polymers are required as rubber materials for tires that possess low driving resistance, excellent wear resistance and tensile properties, and handling stability represented by wet skid resistance.

[0004] Meanwhile, in conjugated diene polymers, linearity and branching significantly influence the physical properties of the polymer. Specifically, as linearity decreases or branching increases, the dissolution rate and viscosity characteristics of the polymer increase, and as a result, the processability of the polymer is improved. However, if the degree of branching of the polymer is excessively high, the molecular weight distribution becomes broad, and consequently, the mechanical properties of the polymer that affect the wear resistance, crack resistance, or rebound characteristics of the rubber composition actually deteriorate. Furthermore, the linearity and branching of conjugated diene polymers, particularly butadiene-based polymers, are largely dependent on the content of cis 1,4-bonds contained within the polymer. As the content of cis 1,4-bonds in the conjugated diene polymer increases, linearity increases, and as a result, the polymer possesses excellent mechanical properties, which can improve the wear resistance, crack resistance, and rebound characteristics of the rubber composition.

[0005] Accordingly, various methods for manufacturing conjugated diene polymers are being researched and developed to increase linearity by increasing the content of cis-1,4 bonds in the conjugated diene polymer, while simultaneously ensuring appropriate processability.

[0006] Specifically, a method for producing butadiene-based polymers has been developed using a polymerization catalyst of a complex metal composed of a rare earth metal compound such as neodymium and an alkylating agent of Group I to Group III, specifically methylaluminoxane. However, the polymers obtained by the above method have a problem in that the improvement effect on physical properties is still insufficient because the cis-1,4 bond content is not sufficiently high and the vinyl content is not sufficiently low.

[0007] In another method, a method was developed to produce a butadiene-based polymer with a high cis-1,4 bond content using a polymerization catalyst comprising a rare earth metal compound, an alkylating agent of Group I to Group III, and an ionic compound composed of non-coordinating anions and cations. Although the above method utilizes Nd(OCOCCl3)3 as the rare earth metal compound, the polymerization activity of the metal compound is low and the vinyl bond content of the butadiene polymer is high; therefore, the improvement in physical properties of the rubber composition containing the butadiene-based polymer produced by the above method was insufficient compared to the conventional rubber composition containing the butadiene-based polymer. Furthermore, the butadiene-based polymer produced by the above method has a high vinyl bond content and a wide molecular weight distribution.

[0008] As another method, a method was developed to produce butadiene-based polymers with a high cis-1,4 bond content using a polymerization catalyst composed of a rare earth metal salt containing a halogen atom and aluminoxan. However, in this method as well, there is a problem in that the polymerization activity of the neodymium salt is low and industriality is low because special catalysts such as bis(trichloroacetic acid)(versatic acid) neodymium salt are used.

[0009] Accordingly, there is a need to develop a method for manufacturing conjugated diene polymers that can exhibit high linearity while also demonstrating excellent processability. Prior art literature

[0011] (Patent Document 0001) JP 3175350 B2 The problem to be solved

[0012] The present invention was devised to solve the problems of the prior art described above, and aims to provide a method for preparing a catalyst composition that is easy to manufacture for producing conjugated diene polymers capable of modifying polymers and possessing excellent catalytic activity. means of solving the problem

[0014] To solve the above problem, the present invention provides a method for preparing a catalyst composition comprising the steps of: reacting a functionalizing agent represented by the following chemical formula 1 with an alkylating agent to produce a functionalized alkylating agent (S1); and reacting the functionalized alkylating agent, a neodymium compound, and a halogen compound (S2).

[0015] [Chemical Formula 1]

[0016] (X1) a -N-(X2) 3-a

[0017] In the above chemical formula 1,

[0018] a is an integer of 1 or 2, and

[0019] X1 and X2 are each independently a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, -OR a , -SiR b R c R d Selected from the group consisting of covalent functional groups, or X1 and X2 have two adjacent functional groups connected to each other to form a heterocyclic compound, provided that at least one of X1 and X2 comprises a covalent functional group,

[0020] The above R a , R b , R c and R dEach is independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a covalent functional group, and -NR'R", and R' and R" are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, and a covalent functional group, and

[0021] The above-mentioned covalent functional group is a functional group containing a carbon-carbon double bond. Effects of the invention

[0023] The method for preparing a catalyst composition according to the present invention involves reacting a functionalizing agent represented by Formula 1 with an alkylating agent to produce a functionalizing agent, and then reacting a neodymium compound and a halogen compound to produce a conjugated diene polymer having excellent polymerization activity and high linearity, as well as excellent processability and physical properties. Specific details for implementing the invention

[0025] Hereinafter, the present invention will be described in more detail to aid in understanding the invention.

[0026] Terms and words used in this specification and claims should not be interpreted as being limited to their ordinary or dictionary meanings, but should be interpreted in a meaning and concept consistent with the technical spirit of the invention, based on the principle that the inventor can appropriately define the concept of the terms to best describe his invention.

[0027] Unless otherwise defined, the terms and measurement methods used in the present invention may be defined as follows.

[0028] [Term]

[0029] In the present invention, the term 'catalytic composition' includes a simple mixture of components, various complexes caused by physical or chemical attraction, or chemical reaction products of components.

[0030] In the present invention, the term 'monovalent hydrocarbon group' may refer to a monovalent atomic group in which carbon and hydrogen are bonded, such as a monovalent alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, or an aryl group containing one or more unsaturated bonds, and the minimum number of carbon atoms of a substituent represented as a monovalent hydrocarbon may be determined according to the type of each substituent.

[0031] In the present invention, the term 'alkyl group' may mean a monovalent aliphatic saturated hydrocarbon and may include linear alkyl groups such as methyl, ethyl, propyl, and butyl; and branched alkyl groups such as isopropyl, sec-butyl, tert-butyl, and neo-pentyl.

[0032] In the present invention, the term 'alkenyl group' may refer to a monovalent aliphatic unsaturated hydrocarbon containing one or more double bonds.

[0033] In the present invention, the term 'alkynyl group' may refer to a monovalent aliphatic unsaturated hydrocarbon containing one or more triple bonds.

[0034] In the present invention, the term 'alkylene group' may refer to divalent aliphatic saturated hydrocarbons such as methylene, ethylene, propylene, and butylene.

[0035] In the present invention, the term 'heterocyclic group' may mean an aliphatic cyclic hydrocarbon group, an aromatic cyclic hydrocarbon group, or a combination thereof in which a carbon atom is substituted with one or more heteroatoms.

[0037] Method for preparing a catalyst composition

[0038] The present invention provides a method for preparing a catalyst composition that is applied during the production of a polymer and has excellent catalytic activity, while also being able to modify the polymer to improve its physical properties.

[0039] A manufacturing method according to one embodiment of the present invention is characterized by comprising: a step (S1) of preparing a functionalized alkylating agent by reacting a functionalizing agent represented by the following chemical formula 1 with an alkylating agent; and a step (S2) of reacting the functionalized alkylating agent, a neodymium compound, and a halogen compound:

[0040] [Chemical Formula 1]

[0041] (X1) a -N-(X2) 3-a

[0042] In the above chemical formula 1,

[0043] a is an integer of 1 or 2, and

[0044] X1 and X2 are each independently a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, -OR a , -SiR b R c R d Selected from the group consisting of covalent functional groups, or X1 and X2 have two adjacent functional groups connected to each other to form a heterocyclic compound, provided that at least one of X1 and X2 comprises a covalent functional group,

[0045] The above R a , R b , R c and R dEach is independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a covalent functional group, and -NR'R", and R' and R" are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, and a covalent functional group, and

[0046] The above-mentioned covalent functional group is a functional group containing a carbon-carbon double bond.

[0048] (S1) Step

[0049] The above step (S1) is a step of producing a functionalized alkylating agent comprising a unit derived from the functionalizing agent and a unit derived from the alkylating agent by reacting a functionalizing agent and an alkylating agent, wherein 5 to 20 moles or 6 to 17 moles of an alkylating agent are reacted with 1 mole of the functionalizing agent. Additionally, the reaction of the above step (S1) may be carried out by mixing at a temperature of 0°C to 60°C for 1 to 8 hours for easier production of the functionalized alkylating agent.

[0050] Meanwhile, in one embodiment of the present invention, the functionalized alkylating agent may be produced through a reaction mechanism as shown in Reaction Scheme 1 below.

[0051] [Reaction Equation 1]

[0052]

[0053] The above reaction formula 1 represents the process of manufacturing a functionalized alkylating agent (F-Al) by an aluminum hydride addition reaction using an example of a functionalizing agent (2a) and an example of an alkylating agent (DIBAH).

[0055] As another example, the functionalized alkylating agent prepared in step (S1) may be prepared by reacting a functionalizing agent represented by Chemical Formula 1 with an alkylating agent, and may include a unit derived from the functionalizing agent and a unit derived from the alkylating agent.

[0056] Functional vaporizer

[0057] The above-mentioned functionalizing agent is an amine-based compound comprising one or more covalent functional groups containing carbon-carbon double bonds, wherein the covalent functional groups are functional groups containing carbon-carbon double bonds, such as vinyl groups, allyl groups, metaallyl groups, or (meth)acrylic groups, and can react with an alkylating agent to form a functionalized alkylating agent in which the functionalizing agent and the alkylating agent are combined. Typically, since the alkylating agent is present in a larger amount than the main catalyst in the catalyst composition, it can be used in polymer manufacturing to have excellent catalytic activity while acting more easily on polymer modification.

[0058] Specifically, the above-mentioned functional agent may be a compound represented by Chemical Formula 1.

[0059] [Chemical Formula 1]

[0060] (X1) a -N-(X2) 3-a

[0061] In the above chemical formula 1,

[0062] a is an integer of 1 or 2, and

[0063] X1 and X2 are each independently a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, -OR a , -SiR b R c R d Selected from the group consisting of covalent functional groups, or X1 and X2 have two adjacent functional groups connected to each other to form a heterocyclic compound, provided that at least one of X1 and X2 comprises a covalent functional group,

[0064] The above Ra , R b , R c and R d Each is independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a covalent functional group, and -NR'R", and R' and R" are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, and a covalent functional group, and

[0065] The above-mentioned covalent functional group is a functional group containing a carbon-carbon double bond.

[0066] Also, in the above chemical formula 1, when a=2, multiple X1s may each be the same or different. Likewise, in the above chemical formula 1, when 3-a>1, i.e., 2, multiple X2s may each be the same or different.

[0067] Specifically, in the above Chemical Formula 1, X1 and X2 are each independently a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, -OR a , -SiR b R c R d and is selected from the group consisting of covalent functional groups, or two adjacent functional groups among X1 and X2 may be connected to each other to form a heterocycle. In this case, the R a , R b, R c , and R dEach can be independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a covalent functional group, and -NR'R", and R' and R" can each be independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, and a covalent functional group.

[0068] At this time, the monovalent hydrocarbon group may specifically be a linear or branched alkyl group having 1 to 20 carbon atoms, such as a methyl group, an ethyl group, or a propyl group; a cycloalkyl group having 3 to 20 carbon atoms, such as a cyclopropyl group, a cyclobutyl group, or a cyclopentyl group; an aryl group having 6 to 20 carbon atoms, such as a phenyl group; and as a combination group thereof, an arylalkyl group having 7 to 20 carbon atoms or an alkylaryl group having 7 to 20 carbon atoms.

[0069] Additionally, the above-mentioned covalent functional group may be an alkenyl group or a (meth)acryl group, wherein the alkenyl group may specifically be an alkenyl group having 2 to 20 carbon atoms, more specifically an alkenyl group having 2 to 12 carbon atoms, and even more specifically an alkenyl group having 2 to 6 carbon atoms. More specifically, the above-mentioned covalent functional group may be selected from the group consisting of vinyl groups, allyl groups, methallyl groups, butenyl groups, pentenyl groups, hexenyl groups, and (meth)acryl groups, and considering the significant improvement effect on catalytic activity and polymerization reactivity when applied to a catalyst composition, the above-mentioned covalent functional group may be an allyl group. Meanwhile, in the present invention, the term (meth)acryl group includes acryl and methacryl groups.

[0070] In addition, X1 and X2 may each be independently substituted with one or more substituents selected from the group consisting of a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms.

[0071] More specifically, X1 and X2 are each independently selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxy group, a vinyl group, an allyl group, a meta-allyl group, a (meth)acryl group, an amino group (-NH2), an alkylamino group, an allylamino group, an alkylallylamino group, a silyl group (-SiH3), an alkylsilyl group, a dialkylsilyl group, a trialkylsilyl group, an allylsilyl group, a diallylsilyl group, a trialylsilyl group, an alkylallylsilyl group, an alkyldiallylsilyl group, a dialkylallylsilyl group, a (diallylamino)silyl group, a (diallylamino)alkylsilyl group, a (diallylamino)dialkylsilyl group, and an alkyldi(diallylamino)silyl group; or two adjacent functional groups among X1 and X2 may be connected to each other to form a heterocyclic compound. At this time, the alkyl group may be a straight-chain or branched alkyl group having 1 to 20 carbon atoms, more specifically a straight-chain or branched alkyl group having 1 to 6 carbon atoms, and the alkoxy group may be a straight-chain or branched alkoxy group having 1 to 20 carbon atoms, more specifically a straight-chain or branched alkoxy group having 1 to 6 carbon atoms. However, in the above formula 1, at least one of X1 and X2 may be a covalent functional group containing an intramolecular double bond, such as a vinyl group, an allyl group, a metaallyl group, or a (meth)acrylic group.

[0072] More specifically, the functionalizing agent may be selected from the group consisting of a vinyl group, an allyl group, a metaallyl group, a mono-, di-, or tri-alkylsilyl group, a (diallylamino)alkylsilyl group, a (diallylamino)dialkylsilyl group, and an alkyldi(diallylamino)silyl group in the above formula 1, or X1 and X2 may be compounds in which two adjacent functional groups are connected to each other to form a heterocyclic compound, wherein at least one of X1 and X2 is selected from the group consisting of a vinyl group, an allyl group, a metaallyl group, a (diallylamino)alkylsilyl group, a (diallylamino)dialkylsilyl group, and a dialkyldi(diallylamino)alkylsilyl group, and the alkyl group is an alkyl group having 1 to 6 carbon atoms.

[0073] More specifically, in the above functionalizing agent, X1 and X2 in Chemical Formula 1 are each independently -SiR b R c R d Alternatively, it may be a covalent functional group, or X1 and X2 may be a compound in which two adjacent functional groups are connected to each other to form a heterocycle. In this case, the R b, R c , and R d The group is as previously defined, and more specifically, each may independently be an alkyl group having 1 to 6 carbon atoms or -NR'R (wherein R' and R" are each independently covalent functional groups such as vinyl, allyl, or metaallyl groups).

[0074] As another example, the above functional vaporizer may be any one or more mixtures selected from the group consisting of compounds of the following chemical formulas 2a to 2l.

[0075]

[0076] In the above chemical formulas 2a to 2l, Me is a methyl group, TMS is a trimethylsilyl group, TES is a triethylsilyl group, and Me is a methyl group.

[0078] alkylating agent

[0079] In addition, the above-mentioned alkylating agent is an organometallic compound capable of transferring a hydrocarbyl group to another metal and acting as a co-catalyst; any agent commonly used as an alkylating agent in the industry may be used without special restrictions, but, for example, it may be an organometallic compound or a boron-containing compound that is soluble in a non-polar solvent, specifically a non-polar hydrocarbon solvent, and comprises a bond between a cationic metal, such as a Group 1, Group 2, or Group 3 metal, and carbon. More specifically, the above-mentioned alkylating agent may be any one or more mixtures selected from the group consisting of organoaluminum compounds, organomagnesium compounds, and organolithium compounds.

[0080] Specifically, the alkylating agent may include an organoaluminum compound represented by the following chemical formula 4.

[0081] [Chemical Formula 4]

[0082] Al(R) z (X) 3-z

[0083] In the above chemical formula 4,

[0084] R is each independently a hydrocarbyl group; or a heterohydrocarbyl group comprising at least one heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom, a boron atom, a silicon atom, a sulfur atom, and a phosphorus atom within the hydrocarbyl group structure, X is each independently selected from the group consisting of a hydrogen atom, a halogen group, a carboxyl group, an alkoxy group, and an aryloxy group, and z is an integer from 1 to 3.

[0085] More specifically, the organoaluminum compound is 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, phenylisobutylaluminum hydride, phenyl-n-octylaluminum hydride, p-tolylethylaluminum hydride, p-tolyl-n-propylaluminum hydride, p-tolylisopropylaluminum Examples include dihydrocarbylaluminum hydrides such as hydride, p-tolyl-n-butylaluminum hydride, p-tolyl-isobutylaluminum hydride, p-tolyl-n-octylaluminum hydride, benzylethylaluminum hydride, benzyl-n-propylaluminum hydride, benzylisopropylaluminum hydride, benzyl-n-butylaluminum hydride, benzylisobutylaluminum hydride, or benzyl-n-octylaluminum hydride; and hydrocarbylaluminum dihydrides such as ethylaluminum dihydride, n-propylaluminum dihydride, isopropylaluminum dihydride, n-butylaluminum dihydride, isobutylaluminum dihydride, or n-octylaluminum dihydride.

[0086] In addition, the above-mentioned organoaluminum compound may be aluminoxan.

[0087] The above aluminoxan can be prepared by reacting water with a trihydrocarbyl aluminum-based compound, and specifically, it may be a straight-chain aluminoxan of the following chemical formula 5a or a cyclic aluminoxan of the following chemical formula 5b:

[0088] [Chemical Formula 5a]

[0089]

[0090] [Chemical Formula 5b]

[0091]

[0092] In the above chemical formulas 5a and 5b, R is a monovalent organic group bonded to an aluminum atom through a carbon atom, and is the same as the previously defined R, and x and y can each be an integer of 1 or more, specifically 1 to 100, more specifically 2 to 50.

[0093] More specifically, the aluminoxan may be methylaluminoxan (MAO), modified methylaluminoxan (MMAO), ethylaluminoxan, n-propylaluminoxan, isopropylaluminoxan, butylaluminoxan, isobutylaluminoxan, n-pentylaluminoxan, neopentylaluminoxan, n-hexylaluminoxan, n-octylaluminoxan, 2-ethylhexylaluminoxan, cyclohexylaluminoxan, 1-methylcyclopentylaluminoxan, phenylaluminoxan, or 2,6-dimethylphenylaluminoxan, etc., and any one or more of these may be used.

[0094] In addition, in the above aluminoxan compound, the modified methylaluminoxan is one in which the methyl group of methylaluminoxan is substituted with a modifying group (R), specifically a hydrocarbon group having 2 to 20 carbon atoms, and specifically may be a compound of the following chemical formula 6.

[0095] [Chemical Formula 6]

[0096]

[0097] In the above chemical formula 6, R is as previously defined, and m and n may each be integers greater than or equal to 2. Also, in the above chemical formula 2, Me represents a methyl group.

[0098] More specifically, in the above formula 6, R may be a linear or branched 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, 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; more specifically, it may be a linear or branched alkyl group having 2 to 10 carbon atoms, such as an ethyl group, an isobutyl group, a hexyl group, or an octyl group, and even more specifically, it may be an isobutyl group.

[0099] More specifically, the modified methylaluminoxane may be one in which about 50 mol% to 90 mol% of the methyl groups of methylaluminoxane are substituted with the hydrocarbon groups mentioned above. When the content of the substituted hydrocarbon groups in the modified methylaluminoxane is within the above range, alkylation can be promoted to increase catalytic activity.

[0100] Such modified methylaluminoxan can be manufactured according to conventional methods, specifically using trimethylaluminum and alkylaluminum other than trimethylaluminum. In this case, the alkylaluminum may be triisobutylaluminum, triethylaluminum, trihexylaluminum, or trioctylaluminum, and any one or a mixture of two or more of these may be used.

[0101] Meanwhile, the organomagnesium compound as the alkylating agent comprises at least one magnesium-carbon bond and is a magnesium compound soluble in a nonpolar solvent, specifically a nonpolar hydrocarbon-based solvent. Specifically, the organomagnesium compound may be a compound of the following chemical formula 7a:

[0102] [Chemical Formula 7a]

[0103] Mg(R)2

[0104] In the above chemical formula 7a, R is independently the same as the previously defined R as a monovalent organic group.

[0105] More specifically, the organic magnesium compounds of the above chemical formula 7a may include alkyl magnesium compounds such as diethyl magnesium, di-n-propyl magnesium, diisopropyl magnesium, dibutyl magnesium, dihexyl magnesium, diphenyl magnesium, or dibenzyl magnesium.

[0106] In addition, the above organomagnesium compound may be a compound of the following chemical formula 7b:

[0107] [Chemical Formula 7b]

[0108] RMgX

[0109] In the above chemical formula 7b, R is a monovalent organic group and is the same as the previously defined R, and X is selected from the group consisting of a hydrogen atom, a halogen group, a carboxyl group, an alkoxy group, and an aryloxy group.

[0110] More specifically, the organic magnesium compound of the above formula 7b is a hydrocarbyl magnesium hydride such as methyl magnesium hydride, ethyl magnesium hydride, butyl magnesium hydride, hexyl magnesium hydride, phenyl magnesium hydride, benzyl magnesium hydride, etc.; a hydrocarbyl magnesium halide such as methyl magnesium chloride, ethyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, phenyl magnesium chloride, benzyl magnesium chloride, methyl magnesium bromide, ethyl magnesium bromide, butyl magnesium bromide, hexyl magnesium bromide, phenyl magnesium bromide, benzyl magnesium bromide, etc.; It may be hydrocarbyl magnesium carboxylates such as methyl magnesium hexanoate, ethyl magnesium hexanoate, butyl magnesium hexanoate, hexyl magnesium hexanoate, phenyl magnesium hexanoate, benzyl magnesium hexanoate; hydrocarbyl magnesium alkoxides such as methyl magnesium ethoxide, ethyl magnesium ethoxide, butyl magnesium ethoxide, hexyl magnesium ethoxide, phenyl magnesium ethoxide, benzyl magnesium ethoxide; or hydrocarbyl magnesium aryloxides such as methyl magnesium phenoxide, ethyl magnesium phenoxide, butyl magnesium phenoxide, hexyl magnesium phenoxide, phenyl magnesium phenoxide, benzyl magnesium phenoxide.

[0111] In addition, as the above-mentioned alkylating agent, an R-Li alkyllithium compound may be used (wherein R is a straight-chain or branched alkyl group having 1 to 20 carbon atoms, and more specifically, a linear alkyl group having 1 to 8 carbon atoms). More specifically, examples include methyllithium, ethyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, t-butyllithium, isobutyllithium, pentyllithium, isopentyllithium, etc., and any one or a mixture of two or more of these may be used.

[0112] Among the compounds mentioned above, the alkylating agent usable in the present invention may specifically be DIBAH, which can serve as a molecular weight regulator during polymerization.

[0113] In addition, the alkylating agent may be modified methylaluminoxan, in that the catalytic activity and reactivity can be further improved by using a single commercial solvent of an aliphatic hydrocarbon system as the solvent system used in the preparation of the catalyst composition.

[0115] (S2) Step

[0116] The above step (S2) is a step for preparing a catalyst composition by reacting the functionalized alkylating agent with a neodymium compound and a halogen compound, wherein the reaction may be carried out with 5 to 20 moles or 6 to 17 moles of the functionalized alkylating agent for every 1 mole of neodymium.

[0117] Additionally, the reaction of step (S2) above may be carried out using one or more selected from the group consisting of diene monomers and aliphatic hydrocarbon solvents.

[0118] As another example, the reaction of step (S2) above can be carried out by mixing a functionalized alkylating agent, a neodymium compound and a halogen compound, and optionally a diene monomer and an organic solvent according to a conventional method.

[0119] For example, a pre-mixed catalyst composition can be prepared by sequentially or simultaneously adding a functionalized alkylating agent, a neodymium compound, a halogen compound, and optionally a diene monomer in an organic solvent, and then mixing.

[0120] As another example, a prepolymerization type catalyst composition can be prepared by mixing a functionalized alkylating agent, a neodemium compound, and a halogen compound in an organic solvent, and then adding a diene monomer to prepolymerize.

[0121] At this time, in order to promote the generation of catalytic active species, the mixing and polymerization process may be performed in a temperature range of 0°C to 60°C, and heat treatment may be performed in parallel to satisfy the above temperature conditions.

[0122] More specifically, the above step (S2) can be performed by mixing a functionalized alkylating agent, a neodymium compound, an organic solvent, and optionally a diene monomer, followed by a first heat treatment at a temperature of 10°C to 60°C, and then adding a halogen compound to the resulting mixture and performing a second heat treatment at a temperature range of 0°C to 60°C.

[0124] Neodymium compounds

[0125] In addition, the above-mentioned neodymium compound serves as a main catalyst component that is activated by an alkylating agent to form a catalytically active species, such as a neodymium-containing carboxylate (e.g., neodymium acetate, neodymium acrylate, neodymium methacrylate, neodymium acetate, neodymium gluconate, neodymium citrate, neodymium fumarate, neodymium sulfate, neodymium maleate, neodymium oxalate, neodymium 2-ethylhexanoate, neodymium neodecanoate, etc.), an organic phosphate (e.g., neodymium dibutyl phosphate, neodymium dipentyl phosphate, neodymium dihexyl phosphate, neodymium diheptyl phosphate, neodymium dioctyl phosphate, neodymium bis(1-methylheptyl) phosphate, neodymium bis(2-ethylhexyl) phosphate, or neodymium didecyl Phosphates, 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, etc.), organic phosphinates (e.g., neodymium butyl phosphinate, neodymium pentyl phosphinate, neodymium hexyl phosphinate, neodymium heptyl phosphinate, neodymium octyl phosphinate, neodymium (1-methyl heptyl) phosphinate or neodymium (2-ethylhexyl) phosphinate, etc.), carbamate (e.g., Neodymium dimethyl carbamate, neodymium diethyl carbamate, neodymium diisopropyl carbamate, neodymium dibutyl carbamate or neodymium dibenzyl carbamate, etc.), dithiocarbamates (e.g., neodymium dimethyl dithiocarbamate, neodymium diethyl dithiocarbamate, neodymium diisopropyl dithiocarbamate or neodymium dibutyl dithiocarbamate, etc.), xantogenates (e.g., neodymium methyl xantogenate, neodymium ethyl xantogenate, neodymium isopropyl xantogenate, neodymium butyl xantogenate, or neodymium benzyl xantogenate, etc.),β-diketonates (e.g., neodymium acetylacetonate, neodymium trifluoroacetylacetonate, neodymium hexafluoroacetylacetonate or neodymium benzoyl acetonate, etc.), alkoxides or allyl oxides (e.g., neodymium methoxide, neodymium ethoxide, neodymium isopropoxide, neodymium phenoxide or neodymium nonyl phenoxide, etc.), halides or pseudo-halides (neodymium fluoride, neodymium chloride, neodymium bromide, neodymium iodide, neodymium cyanide, neodymium cyanate, neodymium thiocyanate, or neodymium azide, etc.), oxyhalides (e.g., neodymium oxyfluoride, neodymium oxychloride, or neodymium oxybromide, etc.), or one or more Examples include organo-rare earth metal compounds containing rare earth metal-carbon bonds (e.g., Cp3Ln, Cp2LnR, Cp2LnCl, CpLnCl2, CpLn(cyclooctatetraene), (C5Me5)2LnR, LnR3, Ln(allyl)3, or Ln(allyl)2Cl, etc., wherein Ln is neodymium and R is a hydrocarbyl group as previously defined), and may include any one or more of these.

[0126] More specifically, the neodymium compound may be a compound represented by the following chemical formula 3.

[0127] [Chemical Formula 3]

[0128]

[0129] In the above chemical formula 3, R1 to R3 are each independently hydrogen atoms or linear or branched alkyl groups having 1 to 12 carbon atoms.

[0130] More specifically, the rare earth metal compound may be a neodymium compound in which R1 in Chemical Formula 3 is a linear or branched alkyl group having 6 to 12 carbon atoms, and R2 and R3 are each independently hydrogen atoms or linear or branched alkyl groups having 2 to 6 carbon atoms, provided that R2 and R3 are not simultaneously hydrogen atoms; more specifically, it may be a neodymium compound in which R1 in Chemical Formula 3 is a linear or branched alkyl group having 6 to 8 carbon atoms, and R2 and R3 are each independently linear or branched alkyl groups having 2 to 6 carbon atoms.

[0131] As such, when the neodymium compound of Chemical Formula 3 contains a carboxylate ligand comprising an alkyl group of various lengths with two or more carbon atoms as a substituent at the α position, it can induce steric changes around the neodymium central metal to block aggregation between compounds, and as a result, inhibit oligomerization, thereby increasing the conversion rate to active species. Such a neodymium compound has high solubility in polymerization solvents.

[0132] More specifically, the above rare earth metal compound is 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, Nd(2,2-dihexyl nonanoate)3, Nd(2-ethyl-2-propyl nonanoate)3 and Nd(2-ethyl-2-hexyl It may be any one or more mixtures selected from the group consisting of nonanoates)3. Additionally, considering the excellent solubility in polymerization solvents without concerns regarding oligomerization, the conversion rate to catalytic active species, and the resulting excellent effect of improving catalytic activity, the neodymium compound may be any one or more mixtures selected from the group consisting of 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.

[0134] Halogen compounds

[0135] In addition, the above halogen compound is not particularly limited in type, but any compound commonly used as a halogenating agent in the manufacture of diene-based polymers may be used without special restrictions.

[0136] Specifically, the above halogen compounds may include halogen elements, interhalogen compounds, hydrogen halides, organic halides, nonmetallic halides, metal halides, or organometallic halides, and any one or more of these may be used. Among these, considering the excellent effect of enhancing catalytic activity and consequently improving reactivity, any one or more of the above halogen compounds selected from the group consisting of organic halides, metal halides, and organometallic halides may be used.

[0137] More specifically, the above halogen elements may include fluorine, chlorine, bromine, or iodine.

[0138] In addition, specific examples of the above-mentioned halogen compounds include iodine monochloride, iodine monobromide, iodine trichloride, iodine pentafluoride, iodine monofluoride, or iodine trifluoride.

[0139] In addition, the above-mentioned hydrogen halides may specifically include hydrogen fluoride, hydrogen chloride, hydrogen bromide, or hydrogen iodide.

[0140] In addition, the above organic halides specifically include t-butyl chloride (t-BuCl), t-butyl bromide, allyl chloride, allyl bromide, benzyl chloride, benzyl bromide, chloro-diphenylmethane, bromo-diphenylmethane, triphenylmethyl chloride, triphenylmethyl bromide, benzylidene chloride, benzylidene bromide, methyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, trimethylchlorosilane (TMSCl), benzoyl chloride, benzoyl bromide, propionyl chloride, propionyl bromide, methyl chloroformate, methyl bromoformate, iodomethane, diiodomethane, triiodomethane (also called 'iodoform'), tetraiodomethane, 1-iodopropane, 2-iodopropane, Examples include 1,3-diiodopropane, t-butyl iodide, 2,2-dimethyl-1-iodopropane (also called 'neopentyl iodide'), allyl iodide, iodobenzene, benzyl iodide, diphenylmethyl iodide, triphenylmethyl iodide, benzylidene iodide (also called 'benzal iodide'), trimethylsilyl iodide, triethylsilyl iodide, triphenylsilyl iodide, dimethyldiiodosilane, diethyldiiodosilane, diphenyldiiodosilane, methyltriiodosilane, ethyltriiodosilane, phenyltriiodosilane, benzoyl iodide, propionyl iodide, or methyl iodoformate.

[0141] In addition, the above non-metallic halides may specifically include phosphorus trichloride, phosphorus tribromide, phosphorus chloride, phosphorus oxychloride, phosphorus oxybromide, boron trifluoride, boron trichloride, boron tribromide, silicon tetrafluoride, silicon tetrachloride (SiCl4), 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.

[0142] In addition, the metal halide mentioned above may specifically include tin tetrachloride, tin tetrabromide, aluminum trichloride, aluminum tribromide, antimony trichloride, antimony chloride, 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 triiodide, zinc diiodide, germanium tetraiodide, tin tetraiodide, tin diiodide, antimony triiodide, or magnesium diiodide.

[0143] In addition, the organometallic halides specifically include dimethylaluminum chloride, diethylaluminum chloride, dimethylaluminum bromide, diethylaluminum bromide, dimethylaluminum fluoride, diethylaluminum fluoride, methylaluminum dichloride, ethylaluminum dichloride, methylaluminum dibromide, ethylaluminum dibromide, methylaluminum difluoride, ethylaluminum difluoride, methylaluminum sesquichloride, ethylaluminum sesquichloride (EASC), isobutylaluminum sesquichloride, methyl magnesium chloride, methyl magnesium bromide, ethyl magnesium chloride, ethyl magnesium bromide, n-butyl magnesium chloride, n-butyl magnesium bromide, phenyl magnesium chloride, phenyl magnesium bromide, benzyl magnesium 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 Examples include sesquiiodide, isobutylaluminum sesquiiodide, ethyl magnesium iodide, n-butyl magnesium iodide, isobutyl magnesium iodide, phenyl magnesium iodide, benzyl magnesium iodide, trimethyltin iodide, triethyltin iodide, tri-n-butyltin iodide, di-n-butyltin diiodide, or di-t-butyltin diiodide.

[0144] In addition, a catalyst composition for producing a conjugated diene polymer according to one 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 halogen compound.

[0145] Specifically, in the compound containing the above-mentioned non-coordinating anion, the non-coordinating anion is a stereochemically bulky anion that does not form a coordinate bond with the active center of the catalytic system due to steric hindrance, and may be a tetraarylborate anion or a tetraarylborate fluoride anion. In addition, the compound containing the above-mentioned non-coordinating anion may include, together with the above-mentioned non-coordinating anion, a carbonium cation such as a triaryl carbonium cation; an ammonium cation such as an N,N-dialkylanilinium cation; or a phosphonium cation. More specifically, the compound containing the above-mentioned non-coordinating anion may be triphenyl carbonium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenyl carbonium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, or N,N-dimethylanilinium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, etc.

[0146] In addition, as the above-mentioned non-coordinating anion precursor, a compound capable of forming a non-coordinating anion under reaction conditions may be a triaryl boron compound (BR3, where R is a strongly electron-withdrawing aryl group such as a pentafluorophenyl group or a 3,5-bis(trifluoromethyl)phenyl group).

[0148] diene monomer

[0149] When using the above-mentioned diene monomer, the diene monomer may be used in an amount such that it is included in the catalyst composition being prepared in an amount of 1 to 100 moles or 20 to 50 moles per mole of neodymium compound.

[0150] In addition, the above-mentioned diene monomer may be used without special restrictions as long as it is commonly used in the manufacture of conjugated diene polymers. Specifically, the above-mentioned diene monomer may include 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, or 2,4-hexadiene, and any one of these or a mixture of two or more of them may be used.

[0152] organic solvent

[0153] When using the above organic solvent, the organic solvent may be used in an amount of 20 to 20,000 moles or 100 to 1,000 moles per mole of neodymium compound.

[0154] The above organic solvent may be a non-polar solvent that is not reactive with the components used in the preparation of the catalyst composition, for example, linear, branched, or cyclic aliphatic hydrocarbons having 5 to 20 carbon atoms, such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, isopentane, isohexane, isopentane, isooctane, 2,2-dimethylbutane, cyclopentane, 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; or an aromatic hydrocarbon-based solvent such as benzene, toluene, ethylbenzene, xylene, etc., and any one or more of these may be used. More specifically, the nonpolar 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.

[0155] In addition, the above organic solvent can be appropriately selected depending on the type of constituent material of the catalyst composition, particularly the alkylating agent.

[0156] Specifically, when alkylaluminoxanes such as methylaluminoxane (MAO) or ethylaluminoxane are used as alkylating agents, aromatic hydrocarbon solvents can be appropriately used because they are not easily dissolved in aliphatic hydrocarbon solvents.

[0157] In addition, when modified methylaluminoxane is used as an alkylating agent, an aliphatic hydrocarbon solvent may be appropriately used. In this case, since a single solvent system can be implemented together with an aliphatic hydrocarbon 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 solvent can promote catalytic activity, and reactivity can be further improved through this catalytic activity.

[0159] In one embodiment of the present invention, the above manufacturing method can produce a catalyst composition containing a functionalized alkylating agent by reacting a functionalizing agent represented by Formula 1 with an alkylating agent to produce a functionalized alkylating agent, and then reacting a neodymium compound with a halogen compound. This catalyst composition can produce a conjugated diene polymer having excellent polymerization activity and easily modifying the polymer to have high linearity, as well as excellent processability and physical properties.

[0161] Catalyst composition

[0162] According to one embodiment of the present invention, a catalyst composition is provided that includes an alkylating agent functionalized by the above manufacturing method, which has excellent catalytic activity and can be used in the manufacture of a polymer to easily modify the polymer.

[0163] A catalyst composition according to one embodiment of the present invention comprises a functionalized alkylating agent; a neodymium compound; and a halogen compound, wherein the functionalized alkylating agent may comprise a functionalizing agent-derived unit and an alkylating agent-derived unit represented by the following chemical formula 1:

[0164] [Chemical Formula 1]

[0165] (X1) a -N-(X2) 3-a

[0166] In the above chemical formula 1, a, X1, and X2 are as defined above, and the specific descriptions of the functionalizing agent, alkylating agent, neodymium compound, and halogen compound are as defined above.

[0168] In addition, the catalyst composition may contain 5 to 20 moles or 6 to 17 moles of a functionalized alkylating agent per 1 mole of the neodymium compound, and in this case, the catalytic reaction can be easily controlled without fear of side reactions caused by an excess amount of alkylating agent, and the catalytic activity is excellent, and the polymer can be easily modified when applied to the manufacture of the polymer.

[0169] In addition, the catalyst composition may contain 1 to 20 moles or 2 to 6 moles of a halogen compound per 1 mole of the neodymium compound, and in this case, excellent catalytic activity may be achieved without the difficulty of generating catalytic active species or the risk of side reactions caused by an excess amount of halogen compound.

[0170] As another example, the catalyst composition may further include a diene monomer and an organic solvent in addition to the components described above, as needed. In this case, the diene monomer may be included in an amount of 1 to 100 moles or 20 to 50 moles per 1 mole of the neodymium compound, and the organic solvent may be included in an amount of 20 to 20,000 moles or 100 to 1,000 moles per 1 mole of the neodymium compound.

[0172] Conjugated diene polymer

[0173] In addition, the present invention provides a conjugated diene polymer comprising a functional group derived from a functionalizing agent, manufactured using the above catalyst composition, and a method for manufacturing the same.

[0174] A conjugated diene polymer according to one embodiment of the present invention may be produced by polymerizing a conjugated diene monomer according to a conventional method for producing conjugated diene polymers, except for using the catalyst composition described above.

[0175] Specifically, the conjugated diene polymer comprises repeating units derived from conjugated diene monomers, wherein, if the conjugated diene polymer is a butadiene copolymer, it may comprise repeating units derived from other conjugated diene monomers along with repeating units derived from conjugated diene monomers.

[0176] More specifically, the conjugated diene polymer may comprise 80% to 100% by weight of repeating units derived from 1,3-butadiene monomers and optionally 20% by weight or less of repeating units derived from conjugated diene monomers other than those copolymerizable with 1,3-butadiene, and within the above range, the cis 1,4- linkage content may be controlled to within the range described below. At this time, the 1,3-butadiene monomer may include 1,3-butadiene or its derivatives such as 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, or 2-ethyl-1,3-butadiene, and conjugated diene monomers other than those copolymerizable with the 1,3-butadiene may 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, and any one or more of these compounds may be used.

[0178] In addition, the conjugated diene polymer may have a cis-1,4 bond content of the conjugated diene portion measured by Fourier transform infrared spectroscopy (FT-IR) of 96 weight% or more, specifically 97 weight% or more, and more specifically 98 weight% or more. Accordingly, when applied to a rubber composition, the wear resistance, crack resistance, and ozone resistance of the rubber composition may be improved.

[0179] In addition, the conjugated diene polymer may have a 1,2-vinyl bond content of the conjugated diene portion measured by Fourier transform infrared spectroscopy of 4 weight% or less, specifically 3 weight% or less, and more specifically 2 weight% or less. If the 1,2-vinyl bond content in the polymer exceeds 4 weight%, there is a risk that the wear resistance, crack resistance, and ozone resistance of the rubber composition containing it will deteriorate.

[0180] In addition, the conjugated diene polymer according to one embodiment of the present invention may have a Mooney viscosity (MV) of 20 or more and 100 or less at 100°C, specifically 30 or more and 80 or less, 35 or more and 75 or less, or 40 or more and 70 or less. The conjugated diene polymer according to the present invention may have excellent processability by having a Mooney viscosity within the aforementioned range.

[0181] In the present invention, the Mooney viscosity was measured using a Mooney viscometer, for example, the Large Rotor of the Monsanto MV2000E, under conditions of 100°C and a Rotor Speed ​​of 2 ± 0.02 rpm. Specifically, after leaving the polymer at room temperature (23 ± 5°C) for more than 30 minutes, 27 ± 3 g was collected and filled into the die cavity, and the Mooney viscosity was measured while applying torque by operating the platen.

[0182] In addition, the conjugated diene polymer may have a molecular weight distribution (Mw / Mn) of 2.0 to 3.5, and more specifically, may have a molecular weight distribution of 2.5 to 3.5, 2.5 to 3.2, or 2.6 to 3.0.

[0183] In the present invention, the molecular weight distribution of a conjugated diene polymer can 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 the common average of the individual polymer molecular weights calculated by measuring the molecular weights of n polymer molecules, finding the sum of these molecular weights, and dividing by n, and the weight-average molecular weight (Mw) represents the molecular weight distribution of the polymer composition. All molecular weight averages can be expressed in grams per mole (g / mol). Additionally, the weight-average molecular weight and the number-average molecular weight may each refer to the polystyrene equivalent molecular weight analyzed by gel permeation chromatography (GPC).

[0184] The conjugated diene polymer according to one embodiment of the present invention satisfies the molecular weight distribution condition described above, while having a weight-average molecular weight (Mw) of 3 x 10 5 Up to 1.5 x 10 6 It can be g / mol, and the number average molecular weight (Mn) is 1.0 x 10 5 Up to 5.0 X 10 5 It may be g / mol, and when applied to a rubber composition within this range, it exhibits excellent tensile properties and superior processability. This improves the workability of the rubber composition, making mixing easier, and results in excellent mechanical properties and property balance of the rubber composition. The weight-average molecular weight is, for example, 5 x 10⁻⁶ 5 Up to 1.2 x 10 6 g / mol, or 5 x 10⁻⁶ 5 Up to 8 x 10 5 It can be g / mol, and the number-average molecular weight is, for example, 1.5 x 10⁻⁶ 5 Up to 3.5 x 10 5g / mol, or 2.0 x 10⁻⁶ 5 Up to 2.7 x 10 5 It can be g / mol.

[0185] More specifically, when the conjugated diene polymer according to one embodiment of the present invention simultaneously satisfies the conditions of weight-average molecular weight (Mw) and number-average molecular weight along with the molecular weight distribution described above, when applied to a rubber composition, it exhibits excellent tensile properties, viscoelasticity, and processability, and has the effect of having an excellent balance of physical properties among them.

[0187] In addition, the method for preparing the conjugated diene polymer according to one embodiment of the present invention may be performed by including the step of polymerizing a conjugated diene monomer in the presence of the catalyst composition in a hydrocarbon solvent.

[0188] The above hydrocarbon solvent is not particularly limited, but may be one or more selected from the group consisting of, for example, n-pentane, n-hexane, n-heptane, isooctane, cyclohexane, toluene, benzene, and xylene.

[0189] The above catalyst composition may be used in an amount such that the neodymium compound is 0.1 mmol to 0.5 mmol based on a total of 100 g of conjugated diene monomers, and specifically, the neodymium compound may be used in an amount such that it is 0.1 mmol to 0.4 mmol, more specifically 0.1 mmol to 0.25 mmol based on a total of 100 g of conjugated diene monomers.

[0191] Rubber composition

[0192] Furthermore, the present invention provides a rubber composition comprising the conjugated diene polymer and a molded article manufactured from the rubber composition.

[0193] The rubber composition according to one embodiment of the present invention may contain a conjugated diene polymer in an amount of 0.1% by weight or more and 100% by weight or less, specifically 10% by weight to 100% by weight, and more specifically 20% by weight to 90% by weight. If the content of the conjugated diene polymer is less than 0.1% by weight, the improvement effect on wear resistance and crack resistance of a molded article, such as a tire, manufactured using the rubber composition may be negligible.

[0194] In addition, the rubber composition may further include other rubber components as needed in addition to the conjugated diene-based polymer, wherein the rubber components may be included in an amount of 90% by weight or less relative to the total weight of the rubber composition. Specifically, it may be included in an amount of 1 to 900 parts by weight per 100 parts by weight of the modified conjugated diene-based copolymer.

[0195] The above rubber component may be natural rubber or synthetic rubber, for example, the above rubber component may be natural rubber (NR) containing cis-1,4-polyisoprene; modified natural rubber such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), hydrogenated natural rubber, etc., which is obtained by modifying or purifying the above general natural rubber; It may be synthetic rubber such as styrene-butadiene copolymer (SBR), polybutadiene (BR), polyisoprene (IR), butyl rubber (IIR), ethylene-propylene copolymer, polyisobutylene-co-isoprene, neoprene, poly(ethylene-co-propylene), poly(styrene-co-butadiene), poly(styrene-co-isoprene), poly(styrene-co-isoprene-co-butadiene), poly(isoprene-co-butadiene), poly(ethylene-co-propylene-co-diene), polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, butyl halogenated rubber, etc., and any one or more of these may be used.

[0196] In addition, the rubber composition may comprise 0.1 to 150 parts by weight of a filler per 100 parts by weight of a conjugated diene polymer, and the filler may be silica-based, carbon black, or a combination thereof. Specifically, the filler may be carbon black.

[0197] The above carbon black-based filler is not particularly limited, but, for example, may have a nitrogen adsorption specific surface area (N2SA, measured in accordance with JIS K 6217-2:2001) of 20 m² / g to 250 m² / g. In addition, the above carbon black may have a dibutyl phthalate oil absorption capacity (DBP) of 80 cc / 100g to 200 cc / 100g. The nitrogen adsorption specific surface area of ​​the above carbon black is 250 m² 2 If it exceeds / g, there is a risk that the processability of the rubber composition will deteriorate, and 20 m 2 If it is less than / g, the reinforcing performance by carbon black may be negligible. In addition, if the DBP oil absorption amount of the carbon black exceeds 200 cc / 100g, there is a risk that the processability of the rubber composition will be reduced, and if it is less than 80 cc / 100g, the reinforcing performance by carbon black may be negligible.

[0199] In addition, the silica is not specifically limited, but may be, for example, wet silica (hydrated silica), dry silica (anhydrous silica), calcium silicate, aluminum silicate, or colloidal silica. Specifically, the silica may be wet silica, which exhibits the most significant effects in improving fracture characteristics and achieving wet grip. Furthermore, the silica may have a nitrogen adsorption surface area per gram (N2SA) of 120 m² / g to 180 m² / g and a CTAB (cetyl trimethyl ammonium bromide) adsorption specific surface area of ​​100 m² / g to 200 m² / g. If the nitrogen adsorption specific surface area of ​​the silica is less than 120 m² / g, there is a risk that the reinforcing performance by the silica will be reduced, and if it exceeds 180 m² / g, there is a risk that the processability of the rubber composition will be reduced. In addition, if the CTAB adsorption specific surface area of ​​the silica is less than 100 m² / g, there is a risk that the reinforcing performance by the silica filler will be reduced, and if it exceeds 200 m² / g, there is a risk that the processability of the rubber composition will be reduced.

[0200] Meanwhile, when silica is used as the above-mentioned filler, a silane coupling agent may be used together to improve reinforcement and low heat generation.

[0201] Specifically, the above silane coupling agents include bis(3-triethoxysilylpropyl)tetrasulfide, bis(3-triethoxysilylpropyl)trisulfide, bis(3-triethoxysilylpropyl)disulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, bis(2-trimethoxysilylethyl)tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, Examples include 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-trimethoxysilylpropylbenzothiazolyltetrasulfide, 3-triethoxysilylpropylbenzothiazolyltetrasulfide, 3-triethoxysilylpropylmethacrylate monosulfide, 3-trimethoxysilylpropylmethacrylate monosulfide, bis(3-diethoxymethylsilylpropyl)tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, or dimethoxymethylsilylpropylbenzothiazolyltetrasulfide, and any one or a mixture of two or more of these may be used. More specifically, considering the effect of improving reinforcement, the silane coupling agent may be bis(3-triethoxysilylpropyl)polysulfide or 3-trimethoxysilylpropylbenzothiazyltetrasulfide.

[0203] In addition, the rubber composition according to one embodiment of the present invention may be sulfur-crosslinkable and, accordingly, may further include a vulcanizing agent.

[0204] The above vulcanizing agent may specifically be sulfur powder and may be included in an amount of 0.1 to 10 parts by weight per 100 parts by weight of rubber component. When included within the above content range, the necessary elastic modulus and strength of the vulcanized rubber composition can be secured, and at the same time, low fuel consumption can be obtained.

[0205] In addition, a rubber composition according to one embodiment of the present invention may further include, in addition to the above-mentioned components, various additives commonly used in the rubber industry, specifically vulcanization accelerators, process oils, plasticizers, anti-aging agents, anti-scotch agents, zinc white, stearic acid, thermosetting resins, or thermoplastic resins.

[0206] The above vulcanization accelerator is not particularly limited, and specifically, thiazole compounds such as M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), and CZ (N-cyclohexyl-2-benzothiazylsulfenamide), or guanidine compounds such as DPG (diphenylguanidine) may be used. The above vulcanization accelerator may be included in an amount of 0.1 to 5 parts by weight per 100 parts by weight of the rubber component.

[0207] In addition, the process oil acts as a softener in the rubber composition and, specifically, may be a paraffinic, naphthenic, or aromatic compound; more specifically, an aromatic process oil may be used when considering tensile strength and wear resistance, and a naphthenic or paraffinic process oil may be used when considering hysteresis loss and low-temperature characteristics. The process oil may be included in an amount of 100 parts by weight or less per 100 parts by weight of the rubber component, and when included in the above amount, it can prevent a decrease in the tensile strength and low heat generation (low fuel consumption) of the vulcanized rubber.

[0208] In addition, specific examples of the above-mentioned anti-aging agents include N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, or high-temperature condensation products of diphenylamine and acetone. The above-mentioned anti-aging agent may be used in an amount of 0.1 to 6 parts by weight per 100 parts by weight of the rubber component.

[0210] A rubber composition according to one embodiment of the present invention can be obtained by mixing using a mixer such as a Banbury mixer, a roll mixer, or an internal mixer according to the above formulation, and a rubber composition with low heat generation and excellent wear resistance can be obtained by a vulcanization process after molding.

[0211] Accordingly, the above rubber composition can be useful for manufacturing various components of a tire, such as tire treads, undertreads, sidewalls, carcass coating rubber, belt coating rubber, bead fillers, choppers, or bead coating rubber, or various industrial rubber products such as anti-vibration rubber, belt conveyors, and hoses.

[0213] A molded article manufactured using the above rubber composition may include a tire or a tire tread.

[0215] Examples

[0216] The present invention will be explained in more detail below through examples and experimental examples. However, the following examples and experimental examples are intended to illustrate the present invention and do not limit the scope of the present invention solely to these examples.

[0217] Preparation Example 1. Preparation of 1-allyl-2,2,5,5-tetramethyl-1,2,5-azadisilolidine

[0218]

[0219] Allylamine (0.7 ml, 9.29 mmol) was dissolved in dichloromethane (CH2Cl2), and trimethylamine (Et3N) (4.5 ml, 32.5 mmol) was added. While stirring the resulting solution, a dichloromethane solution of 1,2-bis(chlorodimethylsilyl)ethane (2 g, 9.29 mmol) was added. The resulting mixture was stirred overnight for 12 hours at room temperature (23±5℃). After the reaction was complete, all volatile substances were removed by vacuum treatment, and the resulting residue was extracted with hexane. After removing the solvent, a yellow oil was obtained. For further purification, the residue was distilled under reduced pressure (suction, about 100°C) to obtain 1-allyl-2,2,5,5-tetramethyl-1,2,5-azadisiloridin as a colorless oil.

[0220] 1 H NMR (500 MHz, CDCl3) 5.86-5.78 (m, 1H), 5.04-4.91 (m, 2H), 3.19 (d, J = 5.35 Hz, 2H), 0.61 (m, 4H), 0.00 (s, 12H).

[0222] Preparation Example 2. Preparation of N-allylhexamethyldisilanamine

[0223]

[0224] Et3N (25.6 ml, 183.75 mmol) was added at 0°C to a solution prepared by dissolving allylamine (3.9 ml, 52.5 mmol) in CH2Cl2. After stirring the reaction solution for 10 minutes, TMSCl (13.3 ml, 105 mmol) was added at the same temperature. The resulting reaction mixture was stirred for 2 hours at atmosphere temperature (23±5°C), filtered, and the volatile solvent removed by evaporation. Hexane was added to the residue and filtered again. After the removal of hexane, the residue was subjected to suction distillation (approx. 110 o N-allylhexamethyldisilanamine (MAA) of colorless oil was obtained by purification with C).

[0225] 1 H NMR (500 MHz, CDCl3) 5.73-5.67 (m, 1H), 5.03 (d, J = 17.1 Hz, 1H), 4.91 (d, J = 5.3 Hz, 1H), 3.35 (d, J = 2.2 Hz, 2H), 0.00 (s, 18H).

[0227] Preparation Example 3. Preparation of N,N-diallyltrimethylsilanamine

[0228]

[0229] Et3N (6.46 ml, 46.35 mmol) was added at 0°C to a solution prepared by dissolving N,N-diallylamine (3.8 ml, 30.9 mmol) in CH2Cl2. After stirring the reaction solution for 10 minutes, TMSCl (3.9 ml, 30.9 mmol) was added at the same temperature. The resulting reaction mixture was stirred for 2 hours at ambient temperature (23±5°C), filtered, and the volatile solvent was removed by evaporation. Hexane was added to the residue and filtered again. After the removal of hexane, the residue was purified by suction distillation (approx. 100°C) to obtain colorless oil of N,N-diallyltrimethylsilanamine.

[0230] 1 H NMR (500 MHz, CDCl3) 5.65-5.57 (m, 2H), 5.05-4.95 (m, 4H), 3.24 (d, J = 5.7 Hz, 4H), 0.00 (s, 9H).

[0232] Example 1

[0233] In a hexane solvent, the functionalizing agent prepared in Preparation Example 1 and diisobutylaluminum hydride (DIBAH) were added and mixed at 30°C for 8 hours to prepare a functionalized alkylating agent (functionalizing agent:DIBAH = 1:1 mol). Subsequently, a neodymium compound of Nd(2,2-diethyl decanoate)3 and diethylaluminum chloride (DEAC) were sequentially added and mixed to prepare a catalyst composition (functionalized alkylating agent:Nd:DEAC = 10:1:3 mol).

[0235] Example 2

[0236] A catalyst composition was prepared in the same manner as in Example 1, except that the functional vaporizer prepared in Example 2 was used instead of the functional vaporizer prepared in Example 1 in a hexane solvent.

[0238] Example 3

[0239] A catalyst composition was prepared in the same manner as in Example 1, except that the functional vaporizer prepared in Example 3 was used instead of the functional vaporizer prepared in Example 1 in a hexane solvent.

[0241] Comparative Example 1

[0242] A catalyst composition was prepared by sequentially adding and mixing a neodymium compound of Nd(2,2-diethyl decanoate)3, diisobutylaluminum hydride (DIBAH), and diethylaluminum chloride (DEAC) in a hexane solvent (Nd:DIBAH:DEAC=1:10:2.4 mol).

[0244] Comparative Example 2

[0245] A neodymium (Nd) compound of Nd(2,2-diethyl decanoate)3 was added in a hexane solvent at a concentration of 40 wt%, followed by the addition of the functionalizing agent prepared in Preparation Example 1 (Nd:functionalizing agent = 1:1 mol), followed by the sequential addition of diisobutylaluminum hydride (DIBAH) and diethylaluminum chloride (DEAC) in a molar ratio of neodymium compound:DIBAH:DEAC = 1:10:2.4, and then mixed to prepare a catalyst composition.

[0247] Experimental Example 1

[0248] Butadiene polymers were prepared using the catalyst compositions prepared in Examples 1 to 3 and Comparative Examples 1 and 2, and the catalytic activity and properties of the prepared polymers were compared and analyzed.

[0249] (1) Preparation of polymer

[0250] 4.7 kg of a hexane solution in which 1,3-butadiene was dissolved at 60 wt% was placed in a reactor under vacuum, and the internal temperature of the reactor was raised to 70°C. After adding each catalyst composition prepared in the above examples and comparative examples, polymerization was carried out for 60 minutes. Subsequently, HPSS (IC CHEMICAL) as a polymerization inhibitor and IR1520 (BASF) as an antioxidant were added at 0.10 parts by weight and 0.30 parts by weight, respectively, relative to 100 parts by weight of the monomer to terminate the reaction, the solvent was removed by steam stripping, and the butadiene polymer was prepared by drying for 4 minutes using a 6-inch Hot Roll (110°C).

[0252] (2) Microstructure analysis

[0253] The cis 1,4-bond and 1,2-vinyl bond content in each polymer was measured using Varian VNMRS 500 MHz NMR, and 1,1,2,2-tetrachloroethane D2 (Cambridge Isotope) was used as the solvent.

[0255] (3) Mooney dots

[0256] Mooney viscosity (ML1+4, @100℃) (MU) was measured using a large rotor with a Monsanto MV2000E at 100℃ under conditions of a rotor speed of 2±0.02 rpm. The sample used was left at room temperature (23±3℃) for at least 30 minutes, then 27±3g was collected and filled into the die cavity, and the Mooney viscosity was measured while applying torque by operating the platen.

[0258] (4) Polymer conversion rate (%)

[0259] The catalytic activity of each catalyst composition was confirmed by measuring the conversion rate of each polymer, and excellent catalytic activity can be confirmed through the high polymer conversion rate.

[0260] The polymer conversion rate was calculated by transferring a fixed amount of polymer to an aluminum dish through a valve connected to the outlet of the polymerization reactor and measuring its weight, removing volatile components on a hot plate, and then measuring the polymer weight to determine the total solid content (%), and finally calculating the percentage of the polymer (solid content) weight in the final polymer relative to the weight of the input monomer.

[0262] (5) Modification rate (%)

[0263] Each polymer was dissolved in cyclohexane and stored in a sample (prepared at 1.0 mg / ml) mobile phase reservoir, and tetrahydrofuran (THF) was stored in another mobile phase reservoir. The mobile phase reservoirs were each connected to a dual-head pump, and first, the solution from the mobile phase reservoir containing the dissolved polymer was injected into a column packed with silica adsorbent through the pump and an injector with a loop volume of 100 µL. At this time, the pump pressure was 450 psi and the injection flow rate was 0.7 ml / min. Subsequently, after confirming that no unmodified butadiene polymer units within the polymer were detected by the detector (ELSD, Waters), the tetrahydrofuran was injected into the column via the pump at 5 minutes from the start of injection. At this time, the pump pressure was 380 psi and the injection flow rate was 0.7 ml / min. It was confirmed that modified butadiene polymer units within the polymer were no longer detected by the detector following the injection of tetrahydrofuran, and the injection of the second solvent was terminated. Subsequently, the denaturation rate (%) was calculated from the detected chromatogram results according to the following Equation 1.

[0264] [Mathematical Formula 1]

[0265]

[0266] In the above mathematical formula 1, the peak area of ​​the unmodified polymer unit is the peak area of ​​the chromatogram for the first solution transferred to the detector, and the peak area of ​​the modified polymer unit is the peak area of ​​the chromatogram for the second solution transferred to the detector.

[0267] division Examples Comparative example 1 2 3 1 2 Microstructure (wt%) cis 1,4-linkage 96.7 97.2 96.3 97.1 97.0 1,2-vinyl linkage 0.3 0.3 0.3 0.4 0.3 Mooney viscosity (ML1+4, @100℃) 41 38 42 50 49 Polymerization conversion rate (%) 71 69 65 64 62 Modification rate (%) 21 20 19 0 7

[0268] As shown in Table 1 above, the polymer prepared using the catalyst compositions of Examples 1 to 3 exhibited excellent catalytic activity and simultaneously showed a modification rate of 19 to 21%, thereby confirming that it was modified into a functional vaporizer represented by Chemical Formula 1.

[0269] In addition, the polymer produced using the catalyst composition of Comparative Example 2, which was prepared using a method other than the manufacturing method presented in the present invention but using a functionalizing agent, showed a significantly reduced modification rate compared to Examples 1 to 3, and through this, it was confirmed that the catalyst composition prepared by the manufacturing method according to the present invention is effective for polymer modification.

[0271] Experimental Example 2

[0272] After preparing rubber compositions and rubber specimens using each polymer prepared in Experimental Example 1 above, the 300% modulus, wear resistance, and viscoelastic properties (driving resistance) were measured, respectively, in the following manner. The results are shown in Table 2 below.

[0274] (1) Preparation of rubber composition and rubber specimen

[0275] Specifically, each rubber composition was prepared by combining 100 parts by weight of each polymer with 70 parts by weight of carbon black, 22.5 parts by weight of process oil, 2 parts by weight of anti-aging agent (TMDQ), 3 parts by weight of zinc oxide (ZnO), and 2 parts by weight of stearic acid. Subsequently, 2 parts by weight of sulfur, 2 parts by weight of vulcanization accelerator (CZ), and 0.5 parts by weight of vulcanization accelerator (DPG) were added to each rubber composition and lightly mixed at 50 rpm for 1.5 minutes at 50°C, followed by using a roll at 50°C to obtain a sheet-shaped vulcanized compound. The obtained vulcanized compound was vulcanized at 160°C for 25 minutes to produce a rubber specimen.

[0277] (2) 300% modulus (kg·f / cm²) 2 )

[0278] After vulcanizing each of the above rubber compositions at 150°C for 90 minutes, the modulus (M-300%) at 300% elongation of the vulcanized material was measured in accordance with ASTM D412.

[0280] (3) Viscoelastic properties (Tanδ @ 50~70℃ Avg.)

[0281] The most important Tan δ property for fuel efficiency characteristics was measured using a German Gabo DMTS 500N at a frequency of 10 Hz, Prestrain 3%, and Dynamic Strain 3%, and the average value was presented. In this case, the Tan δ value at 50–70°C represents driving resistance, that is, fuel efficiency.

[0283] (4) Wear resistance (DIN wear test)

[0284] For each rubber specimen, a DIN abrasion test was performed in accordance with ASTM D5963, and the loss weight (mg) and the measured value of Comparative Example 1 were used as the basis for the DIN loss index (loss volume index): ARIA (Abration resistance index, Method A). A higher value indicates superior performance.

[0285] division Examples Comparative example 1 2 3 1 2 Wear resistance Weight loss (mg) 16 14 18 23 20 DIN Index (%) 144 164 128 100 115 Tensile properties M-300%(kgf / cm 2 ) 98 99 96 87 94 M-300% Index(%) 113 114 109 100 108 Viscoelastic properties Tanδ @ 50~70℃(Avg.) 0.136 0.138 0.140 0.161 0.149 Tanδ @ 50~70℃Index(%) 118 117 115 100 108

[0286] In Table 2 above, the index values ​​were calculated using Equation 2 or Equation 3 based on the measured values ​​of Comparative Example 1, and the wear resistance and viscoelastic properties were calculated using Equation 3, while the tensile properties were calculated using Equation 2.

[0287] [Mathematical Formula 2]

[0288] Index=(Measurement Value / Reference Value)X100

[0289] [Mathematical Formula 3]

[0290] Index=(Reference Value / Measurement Value)X100

[0292] Through Table 2 above, it was confirmed that the polymer prepared using the catalyst compositions of Examples 1 to 3 prepared by the manufacturing method of the present invention exhibits significantly superior wear resistance, tensile properties, and viscoelastic properties compared to the polymer prepared using the catalyst compositions of Comparative Example 1 and Comparative Example 2.

[0293] Specifically, the polymer prepared using the catalyst compositions of Examples 1 to 3 showed a 300% modulus and viscoelastic properties that were both significantly improved by more than 10% compared to the polymer prepared using the catalyst composition of Comparative Example 1 without using a functionalizing agent, and at the same time exhibited significantly improved abrasion resistance of about 30% to 60% or more.

[0294] In addition, the polymer prepared using the catalyst compositions of Examples 1 to 3 exhibited significantly improved wear resistance, while also showing improved 300% modulus and viscoelastic properties compared to the polymer prepared using the catalyst composition of Comparative Example 2, which was prepared using a functionalizing agent but not the method of the present invention.

[0296] From the above results, it can be confirmed that the manufacturing method according to the present invention can produce a catalyst composition that includes a functionalized alkylating agent, which has excellent catalytic activity, and can easily modify the polymer to produce a polymer having excellent tensile properties, wear resistance, and viscoelastic properties in a balanced manner, by reacting a functionalized alkylating agent represented by Formula 1 with an alkylating agent to produce a functionalized alkylating agent, and then reacting a neodymium compound and a halogen compound.

Claims

Claim 1 A method for preparing a catalyst composition comprising the steps of: reacting a functionalizing agent represented by the following chemical formula 1 with an alkylating agent to produce a functionalized alkylating agent (S1); and reacting the functionalized alkylating agent, a neodymium compound, and a halogen compound (S2): [Chemical Formula 1](X1) a -N-(X2) 3-a In the above chemical formula 1, a is an integer of 1 or 2, and X1 and X2 are each independently a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, -OR a , -SiR b R c R d Selected from the group consisting of and covalent functional groups, or X1 and X2 have two adjacent functional groups connected to each other to form a heterocyclic compound, wherein at least one of X1 and X2 includes a covalent functional group, and R a , R b , R c and R d Each is independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a covalent functional group, and -NR'R", and R' and R" are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, and a covalent functional group, and the covalent functional group is a functional group comprising a carbon-carbon double bond. Claim 2 A method for preparing a catalyst composition according to claim 1, wherein the covalent functional group is selected from the group consisting of alkenyl groups having 2 to 20 carbon atoms and (meth)acrylic groups. Claim 3 A method for preparing a catalyst composition according to claim 1, wherein the covalent functional group is selected from the group consisting of vinyl group, allyl group, metaallyl group, butenyl group, pentenyl group, hexenyl group and (meth)acryl group. Claim 4 In claim 1, in the above chemical formula 1, X1 and X2 are each independently a monovalent hydrocarbon group having 1 to 10 carbon atoms, -OR a , -SiR b R c R d Selected from the group consisting of and covalent functional groups, or X1 and X2 have two adjacent functional groups connected to each other to form a heterocyclic compound, wherein at least one of X1 and X2 includes a covalent functional group, and R a , R b , R c and R d A method for preparing a catalyst composition, wherein each is independently selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylaryl group having 7 to 10 carbon atoms, an arylalkyl group having 7 to 10 carbon atoms, a covalent functional group, and -NR'R", and R' and R" are each independently selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylaryl group having 7 to 10 carbon atoms, an arylalkyl group having 7 to 10 carbon atoms, and a covalent functional group. Claim 5 In claim 1, the functionalizing agent wherein X1 and X2 in Formula 1 are each independently covalent functional groups or -SiR b R c R d or, comprising a compound in which two adjacent functional groups among X1 and X2 are connected to each other to form a heterocycle, wherein R b, R c and R d A method for preparing a catalyst composition in which each is independently an alkyl group having 1 to 6 carbon atoms or -NR'R", and said R' and R" are each independently covalent functional groups. Claim 6 A method for preparing a catalyst composition according to claim 1, wherein the functional vaporizing agent comprises one or more mixtures selected from the group consisting of compounds of the following chemical formulas 2a to 2l: In the above chemical formulas 2a to 2l, Me is a methyl group, TMS is a trimethylsilyl group, TES is a triethylsilyl group, and Me is a methyl group. Claim 7 Method for preparing a catalyst composition according to claim 1, wherein the neodymium compound is a compound represented by the following chemical formula 3: [Chemical Formula 3] In the above chemical formula 3, R1 to R3 are each independently hydrogen atoms or linear or branched alkyl groups having 1 to 12 carbon atoms. Claim 8 A method for preparing a catalyst composition according to claim 1, wherein the alkylating agent comprises an organoaluminum compound of the following chemical formula 4: [Chemical Formula 4]Al(R) z (X) 3-z In the above chemical formula 4, R is each independently a hydrocarbyl group; or a heterohydrocarbyl group comprising at least one heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom, a boron atom, a silicon atom, a sulfur atom, and a phosphorus atom within the hydrocarbyl group structure, X is each independently selected from the group consisting of a hydrogen atom, a halogen group, a carboxyl group, an alkoxy group, and an aryloxy group, and z is an integer from 1 to 3. Claim 9 A method for preparing a catalyst composition according to claim 1, comprising 5 to 20 moles of a functionalized alkylating agent per 1 mole of the neodymium compound. Claim 10 A method for preparing a catalyst composition according to claim 1, wherein step (S2) is further performed using one or more selected from the group consisting of a diene monomer and an aliphatic hydrocarbon solvent. Claim 11 A method for preparing a catalyst composition according to claim 1, wherein in step (S1), 5 to 20 moles of an alkylating agent are reacted with 1 mole of a functionalizing agent. Claim 12 A method for preparing a catalyst composition according to claim 1, wherein the reaction in step (S1) is performed by mixing at a temperature of 0°C to 60°C for 1 to 8 hours. Claim 13 A method for preparing a catalyst composition according to claim 1, wherein in step (S2), 5 to 20 moles of a functionalized alkylating agent are reacted with 1 mole of neodymium.

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