WO2016209046A1 - Catalyst composition for preparing conjugated diene polymer and conjugated diene polymer prepared by means of same - Google Patents

Abstract

The present invention provides a catalyst composition for preparing a conjugated diene polymer and a conjugated diene polymer prepared by means of same, the conjugated diene polymer comprising a functional group agent in the following chemical formula (1) as well as a rare earth metal compound, an alkylating agent and a halogen compound, showing excellent catalyst activity and polymerization reactivity, and having high linearity and excellent processability. Chemical formula (1): (X₁)_a-Sn-(X₂)_4-a, wherein a, X₁ and X₂ are as defined in the description.

Description

Catalyst composition for producing conjugated diene polymer and conjugated diene polymer prepared using the same

Citation with Related Applications

This application claims the benefit of priority based on Korean Patent Application No. 2015-0089906 dated June 24, 2015 and Korean Patent Application No. 2015-0184236 dated December 22, 2015. The contents are included as part of this specification.

Technical Field

The present invention relates to a catalyst composition for producing a conjugated diene polymer and a conjugated diene polymer prepared using the same.

As the demand for rubber compositions increases in various manufacturing fields such as tires, impact polystyrene, shoe soles, and golf balls, synthetic rubbers, which are synthetic rubbers, especially butadiene-based polymers The value is increasing.

On the other hand, in the conjugated diene polymer, linearity and degree of branching have a great influence on the physical properties of the polymer. Specifically, the lower the linearity or the greater the branching, the higher the dissolution rate and viscosity characteristics of the polymer, and as a result the processability of the polymer is improved. However, when the degree of branching of the polymer is too large, the molecular weight distribution is widened, so that the mechanical properties of the polymer affecting the abrasion resistance, crack resistance, or repulsion property of the rubber composition are rather deteriorated. In addition, the linearity and degree of branching of conjugated diene-based polymers, particularly butadiene-based polymers, are highly dependent on the content of cis 1,4-bonds contained in the polymer. The higher the content of the cis 1,4-bond in the conjugated diene-based polymer, the higher the linearity. As a result, the polymer may have excellent mechanical properties, thereby improving wear resistance, crack resistance, and repulsion property of the rubber composition.

Accordingly, various methods for preparing conjugated diene-based polymers for increasing the content of cis-1,4 bonds in the conjugated diene-based polymer to increase linearity and to have appropriate processability have been studied.

Specifically, a method for preparing butadiene-based polymers has been developed using a polymerization catalyst of a rare metal metal compound such as neodymium and an alkylating agent of Groups I to III, specifically, methylaluminoxane. However, the polymer obtainable by the above method does not have a sufficiently high cis-1,4 bond content, and also has a low vinyl content.

Alternatively, a high butadiene-based polymer having a cis-1,4 bond content using a polymerization catalyst comprising a rare earth metal compound, an alkylating agent of Groups I to III, and an ionic compound consisting of a non-coordinating anion and a cation. A method of manufacturing was developed. The method uses Nd (OCOCCl ₃ ) ₃ as the rare earth metal compound, but the rubber containing the butadiene-based polymer produced by the method because the polymerization activity of the metal compound is low and the vinyl bond content of the butadiene polymer is large. The composition was insufficient in the improvement of physical properties compared with the rubber composition containing the conventional butadiene type polymer. In addition, the butadiene-based polymer prepared by the above method has a high vinyl bond content and a wide molecular weight distribution.

As another method, a method for producing a butadiene polymer having a high cis-1,4 bond content using a polymerization catalyst consisting of a rare earth metal salt composed of a halogen atom-containing component and an aluminoxane has been developed. However, also in this method, since a special catalyst such as bis (trichloroacetic acid) (versartic acid) neodymium salt is used, there is a problem that the polymerization activity of the neodymium salt is low and the industrial performance is low.

Accordingly, there is a demand for the development of a method for producing a conjugated diene polymer that can exhibit excellent linearity while having high linearity.

The first problem to be solved by the present invention is to provide a catalyst composition having excellent catalytic activity and easy to prepare a conjugated diene polymer having high linearity and excellent processability.

In addition, a second problem to be solved by the present invention is to provide a conjugated diene polymer prepared using the catalyst composition and a method for producing the same.

In addition, a third problem to be solved by the present invention is to provide a rubber composition comprising a conjugated diene-based polymer prepared by using the catalyst composition and a tire component prepared therefrom.

That is, according to one embodiment of the present invention, a catalyst composition for preparing a conjugated diene-based polymer including a functionalizing agent, a rare earth metal compound, an alkylating agent, and a halogen compound of Formula 1 is provided:

[Formula 1]

(X ₁ ) _a -Sn- (X ₂ ) _4-a

In Chemical Formula 1,

a is an integer of 1 to 3,

X ₁ and X ₂ are each independently selected from the group consisting of a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, -OR _a , -NR _b R _c , -SiR _d R _e R _f and a covalent functional group; In this case, R _a , R _{b ,} R _c , R _d , R _e and R _f are each independently 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 aralkyl group having 7 to 20 carbon atoms, -SiR'R "R"'and a covalent functional group, and each of R', R "and R"'is independent 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 aralkyl group having 7 to 20 carbon atoms, and a covalent functional group. is selected from the group, with the proviso that X ₁ and X _2, at least one of which contains a covalently linked functional groups, Lorca

The covalent functional group is a functional group including a carbon-carbon double bond.

In addition, according to another embodiment of the present invention is prepared using the catalyst composition, provides a conjugated diene-based polymer having a Mooney viscosity of 10MU to 90MU, polydispersity of 3.4 or less at 100 ℃.

In addition, according to another embodiment of the present invention, it provides a method for producing a conjugated diene polymer comprising the step of polymerizing a conjugated diene monomer using the catalyst composition.

Furthermore, according to another embodiment of the present invention, there is provided a rubber composition comprising the conjugated diene-based polymer and a tire part manufactured using the same.

The catalyst composition for conjugated diene-based polymerization according to the present invention includes a functionalizing agent capable of providing a covalently bonded functional functional group in the preparation of the conjugated diene-based polymer, thereby exhibiting high catalytic activity and polymerization reactivity and using the conjugated diene-based polymerization. When preparing a diene polymer, it is possible to prepare a conjugated diene polymer having high linearity and excellent processability and physical properties.

The following drawings, which are attached to this specification, illustrate preferred embodiments of the present invention, and together with the contents of the present invention serve to further understand the technical spirit of the present invention, the present invention is limited to the matters described in such drawings. It should not be construed as limited.

1 is a graph illustrating a change in Mooney viscosity (ML1 + 4) according to vulcanization of rubber specimens prepared using the conjugated diene-based polymer in Example 1. FIG.

FIG. 2 is a graph illustrating a change in Mooney viscosity (ML1 + 4) according to vulcanization of rubber specimens prepared using the conjugated diene-based conjugated diene-based polymer prepared in Example 2. FIG.

3 is a graph illustrating a change in Mooney viscosity (ML1 + 4) according to vulcanization of rubber specimens prepared using the conjugated diene-based conjugated diene-based polymer prepared in Comparative Example 1. FIG.

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

The terms or words used in this specification and claims are not to be construed as limiting in their usual or dictionary meanings, and the inventors may appropriately define the concept of terms in order to best explain their invention in the best way possible. It should be interpreted as meaning and concept corresponding to the technical idea of the present invention based on the principle that the present invention.

As used herein, the term "preforming" means prepolymerization in the catalyst composition for preparing conjugated diene polymers. Specifically, a catalyst composition for preparing a conjugated diene polymer containing a rare earth metal compound, an alkylating agent including an aluminum compound, and a halogen compound is diisobutyl aluminum hydride (hereinafter referred to as diisobutyl aluminum hydride (DIBAH)) as the aluminum compound. When it contains, in order to reduce the possibility of generating a variety of catalytically active species, including a small amount of monomers such as butadiene together. Accordingly, prior to the polymerization reaction for preparing the conjugated diene polymer, butadiene is pre-polymerized in the catalyst composition for preparing the conjugated diene polymer, which is referred to as prepolymerization.

In addition, the term "premixing" as used herein refers to a state in which each component is uniformly mixed without polymerization in the catalyst composition.

In addition, the term "catalyst composition" as used herein is intended to encompass a simple mixture of components, chemical reactants of various complexes or components caused by physical or chemical attraction.

In the present invention, in the preparation of the catalyst composition for forming a conjugated diene-based polymer, by using a functionalizing agent including a covalent functional group such as an intramolecular allyl group, the catalytic activity and the reactivity of the catalyst composition are improved and high A conjugated diene-based polymer having excellent linearity and physical properties can be prepared.

Catalyst composition

The catalyst composition for conjugated diene polymerization according to an embodiment of the present invention includes (a) a functionalizing agent, (b) a rare earth metal compound, (c) an alkylating agent, and (d) a halogen compound. Hereinafter, each component will be described in detail.

(a) functionalizing agent

In the catalyst composition for conjugated diene polymerization according to an embodiment of the present invention, the functionalizing agent is a tin (Sn) -based compound including at least one covalent functional group including a carbon-carbon double bond. Specifically, the covalent functional group is a functional group including a carbon-carbon double bond such as a vinyl group, an allyl group, a metaallyl group, or a (meth) acrylic group, and reacts with a neodymium compound activated by an alkylating agent in the catalyst composition. It is possible to improve catalytic activity by increasing the reactivity while stabilizing the catalytically active species.

In addition, the functionalizer includes Sn as a central element, thereby increasing the activity of the catalyst composition, and can improve the processability of the conjugated diene polymer produced using the same.

Specifically, the functionalizing agent may be a compound of Formula 1:

[Formula 1]

(X ₁ ) _a -Sn- (X ₂ ) _4-a

In Chemical Formula 1,

a is an integer of 1 to 3,

X ₁ and X ₂ are each independently selected from the group consisting of a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, -OR _a , -NR _b R _c , -SiR _d R _e R _f and a covalent functional group; In this case, R _a , R _{b ,} R _c , R _d , R _e and R _f are each independently 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 aralkyl group having 7 to 20 carbon atoms, -SiR'R "R"'and a covalent functional group, and each of R', R "and R"'is independent 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 aralkyl group having 7 to 20 carbon atoms, and a covalent functional group. Selected from the group provided that at least one of X ₁ and X ₂ comprises a covalent functional group,

The covalent functional group is a functional group including a carbon-carbon double bond.

In Formula 1, when a> 1, a plurality of X ₁ may be the same or different. Similarly, in the case of 4-a> 1 in Formula 1, a plurality of X ₂ may be the same or different.

Specifically in Formula 1, X ₁ and X ₂ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, -OR _a , -NR _b R _c , -SiR _d R _e R _f and a covalent functional group It may be selected from the group consisting of, wherein R _a , R _{b ,} R _c , R _d , R _e and R _f are each independently a hydrogen atom, an alkyl group of 1 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms , An aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, -SiR'R "R"', and a covalent functional group. R ', R "and R"' each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkylaryl group having 7 to 12 carbon atoms, and 7 carbon atoms Aralkyl group of 12 to 12 and may be selected from the group consisting of covalent functional groups It was, in even more specifically may be an alkyl group having 1 to 8 carbon atoms.

In addition, the hydrocarbon group is specifically a linear or branched alkyl group having 1 to 20 carbon atoms such as methyl group, ethyl group or propyl group; Cycloalkyl groups having 3 to 20 carbon atoms such as a cyclopropyl group, a cyclobutyl group or a cyclopentyl group; C6-C20 aryl groups, such as a phenyl group; And as a combination group thereof, it may be an arylalkyl group having 7 to 20 carbon atoms or an alkylaryl group having 7 to 20 carbon atoms.

In addition, the covalent functional group may be an alkenyl group or a (meth) acryl group, wherein the alkenyl group is specifically an alkenyl group having 2 to 20 carbon atoms, more specifically an alkenyl group having 2 to 12 carbon atoms, and more specifically It may be 2 to 6 alkenyl group. More specifically, the covalent functional group may be selected from the group consisting of vinyl group, allyl group, metaallyl group (methallyl), butenyl group, pentenyl group, hexenyl group, and (meth) acryl group, in the catalyst composition Given the significant improvement in catalytic activity and polymerization reactivity in the application, the covalent functional groups may be allyl groups. In the present invention, the (meth) acryl group is meant to include an acryl group and a methacryl group.

Meanwhile, X ₁ and X ₂ are each independently composed of a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a linear or branched alkoxy group having 1 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms. It may be substituted with one or more substituents selected from the group.

More specifically, X ₁ and X ₂ are each independently a hydrogen atom, an alkyl group, an alkoxy group, a vinyl group, an allyl group, a metaallyl group, a (meth) acryl group, an amino group (-NH ₂ ), an alkylamino group, an allylamino group , Alkylallylamino group, alkylsilylamino group, silyl group (-SiH ₃ ), alkylsilyl group, dialkylsilyl group, trialkylsilyl group, allylsilyl group, diallyl silyl group, triallyl silyl group, alkyl allyl silyl group, It may be selected from the group consisting of an alkyldiallylsilyl group and a dialkylallylsilyl group, wherein the alkyl group is a linear or branched alkyl group having 1 to 20 carbon atoms, more specifically, a linear or branched alkyl group having 1 to 6 carbon atoms. The alkoxy group may be a linear or branched alkoxy group having 1 to 20 carbon atoms, more specifically, a linear or branched alkoxy group having 1 to 6 carbon atoms. However, in Chemical Formula 1, X ₁ and X ₂ are at least one covalently bonded functional group including an intramolecular double bond, such as a vinyl group, allyl group, metaallyl group, or (meth) acryl group.

Even more specifically, the functionalizing agent may be selected from the group consisting of compounds of the formula 2a to 2n:

In Formulas 2a to 2n, Me is a methyl group, Ph is a phenyl group, OEt is an ethoxy group, and TMS is a trimethylsilyl group.

The improvement effect on workability may be increased so that the number of allyl groups in the functionalizing agent can be increased. Accordingly, X ₁ and X ₂ may be each independently selected from the group consisting of a linear or branched alkyl group having 1 to 6 carbon atoms, vinyl group, allyl group, and metaallyl group, wherein X ₁ and X ₂ are At least one may be a vinyl group, allyl group or metaallyl group.

The functionalizing agent of Chemical Formula 1 may be used using a conventional synthetic reaction. In one example, the functionalizing agent of Chemical Formula 1 may be prepared by a reaction as in Scheme 1 below. Scheme 1 below is only an example for describing the present invention and the present invention is not limited thereto.

Scheme 1

(b) rare earth metal compounds

In the catalyst composition for conjugated diene polymerization according to an embodiment of the present invention, the rare earth metal compound is activated by an alkylating agent, and then reacts with a reactive group of the functionalizing agent to form a catalytically active species for polymerization of the conjugated diene. Form.

Such rare earth metal compounds can be used without particular limitation as long as they are usually used in the production of conjugated diene polymers. Specifically, the rare earth metal compound may be any one or two or more of the rare earth metals having an atomic number of 57 to 71, such as lanthanum, neodymium, cerium, gadolinium, or praseodymium, and more specifically, neodymium, lanthanum, and gadoli. It may be a compound containing any one or two or more selected from the group consisting of 윰.

In addition, the rare earth metal compound is a rare earth metal-containing carboxylate (for example, neodymium acetate, neodymium acrylate, neodymium methacrylate, neodymium acetate, neodymium gluconate, neodymium citrate, neodymium fumarate, neodymium lactate, Neodymium maleate, neodymium oxalate, neodymium 2-ethylhexanoate, neodymium neodecanoate, etc.), 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 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, etc.), Organic phosphinates (e.g., neodymium butylphosphinate, neodymium pentylphosphinate, neodymium hexyl phosphinate, neodymium heptyl phosphinate, neodymium octyl phosphinate, neodymium (1-methylheptyl) phosphate 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 and the like), dithio carbamate (for example, neodymium dimethyldithiocarbamate, neodymium diethyldithiocarbamate, neodymium di Propyl dithio carbamate or neodymium dibutyldithiocarbamate, etc.), xanthogenates (e.g., neodymium methyl xanthogenate, neodymium ethyl xanthogenate, neodymium isopropyl xanthogenate, neodymium Butyl xanthogenate, or neodymium benzyl xanthate, etc.), β-diketonate (e.g., neodymium acetylacetonate, neodymium trifluoroacetyl acetonate, neodymium hexafluoroacetyl acetonate or neodymium benzoyl aceto , 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. Organic rare earth metal compounds comprising, for example, Cp ₃ Ln, Cp ₂ LnR, Cp ₂ LnCl, CpLnCl ₂ , CpLn (cyclooctatetraene), (C ₅ Me ₅ ) ₂ LnR, LnR ₃ , Ln (allyl _{3) 3,} or Ln (allyl) ₂ Cl, etc., wherein wherein Ln is a rare earth metal element, R is a hydrocarbyl group as defined above) and the like, may include any one or a mixture of two or more of these have.

More specifically, the rare earth metal compound may be a neodymium compound of Formula 3:

[Formula 3]

In Formula 3, R ₁ to R ₃ are each independently a hydrogen atom, or a linear or branched alkyl group having 1 to 12 carbon atoms.

As such, when the neodymium compound of Formula 3 includes a carboxylate ligand including an alkyl group having various lengths of 2 or more carbon atoms in the α position, the neodymium compound may induce a steric change around the neodymium center metal to block entanglement between compounds. As a result, the oligomerization is suppressed and the conversion rate to the active species is high. Such neodymium compounds have high solubility in polymerization solvents.

More specifically, in the rare earth metal compound, in Formula 3, R ₁ is a linear or branched alkyl group having 6 to 12 carbon atoms, and R ₂ and R ₃ are each independently a hydrogen atom, or a linear or branched carbon group having 2 to 6 carbon atoms. Alkyl groups, provided that R ₂ and R ₃ are not neodymium compounds at the same time.

More specifically, in the neodymium compound of Formula 3, R ₁ is a linear or branched alkyl group having 6 to 8 carbon atoms, and R ₂ and R ₃ are each independently a linear or branched alkyl group having 2 to 6 carbon atoms. Can be. As such, R ₁ has an alkyl group of 6 or more, and both R ₂ and R ₃ have an alkyl group of 2 or more carbon atoms, thereby further improving the efficiency reduction of conversion into catalytic active species without fear of oligomerization in the polymerization process. It is possible to exhibit better catalytic activity.

The neodymium compound may be specifically 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 nonanoate) ₃ It may be any one or a mixture of two or more selected from the group consisting of. In addition, considering the excellent solubility in the polymerization solvent, the conversion rate to the catalytic active species and thus the effect of improving the catalytic activity without concern for oligomerization, the neodymium 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 , and Nd (2,2 -Dioctyl decanoate) ₃ or any one or two or more mixtures selected from the group consisting of:

In addition, the neodymium compound may have a solubility of about 4 g or more per 6 g of nonpolar solvent at room temperature (23 ± 5 ° C.). In the present invention, the solubility of the neodymium compound means the degree of clear dissolution without turbidity. By exhibiting such high solubility, it is possible to exhibit excellent catalytic activity.

(c) alkylating agents

In the catalyst composition for conjugated diene polymerization according to an embodiment of the present invention, the alkylating agent serves as a promoter as an organometallic compound capable of transferring a hydrocarbyl group to another metal. The alkylating agent can be used without particular limitation as long as it is generally used as an alkylating agent in the preparation of the diene polymer.

Specifically, the alkylating agent is an organometallic compound or a boron-containing compound which is soluble in a nonpolar solvent, specifically a nonpolar hydrocarbon solvent, and which includes a bond between a cationic metal such as a Group 1, Group 2 or Group 3 metal and carbon. Can be. More specifically, the alkylating agent may be any one or a mixture of two or more selected from the group consisting of an organoaluminum compound, an organic magnesium compound, and an organolithium compound.

In the alkylating agent, the organoaluminum compound may specifically be a compound of Formula 4 below.

[Formula 4]

Al (R) _z (X) _{3 -z}

In Chemical Formula 4,

R is each independently a monovalent organic group bonded to an aluminum atom via a carbon atom, each having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and a cycloalkyl having 3 to 20 carbon atoms. Hydrocarbyl groups such as alkenyl groups, aryl groups having 6 to 20 carbon atoms, arylalkyl groups having 7 to 20 carbon atoms, alkylaryl groups having 7 to 20 carbon atoms, alkynyl groups having 2 to 32 carbon atoms, and the like; Or a heterohydrocarbyl group including one or more hetero atoms selected from the group consisting of nitrogen atoms, oxygen atoms, boron atoms, silicon atoms, sulfur atoms, and phosphorus atoms by replacing carbon in the hydrocarbyl group structure,

Each X is independently selected from the group consisting of a hydrogen atom, a halogen group, a carboxyl group, an alkoxy group, and an aryloxy group,

z is an integer of 1 to 3.

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 Lide, phenyl-n-butylaluminum hydride, phenylisobutylaluminum hydride, phenyl-n-octylaluminum hydride, p-tolylethylaluminum hydride, p-tolyl-n-propylaluminum hydride, p-tolyliso Propyl aluminum hydride, p-tolyl-n-butylaluminum hydride, p-tolyl iso portion Aluminum hydride, p-tolyl-n-octylaluminum hydride, benzylethylaluminum hydride, benzyl-n-propylaluminum hydride, benzylisopropylaluminum hydride, benzyl-n-butylaluminum hydride, benzylisobutylaluminum Dihydrocarbyl aluminum hydrides such as hydride or benzyl-n-octyl aluminum hydride; Hydrocarbyl aluminum such as ethylaluminum dihydride, n-propylaluminum dihydride, isopropylaluminum dihydride, n-butylaluminum dihydride, isobutylaluminum dihydride, or n-octylaluminum dihydride Dihydride and the like.

In addition, the organoaluminum compound may be aluminoxane.

The aluminoxane may be prepared by reacting water with a trihydrocarbyl aluminum compound, and specifically, may be a linear aluminoxane of Formula 5a or a cyclic aluminoxane of Formula 5b:

[Formula 5a]

[Formula 5b]

In 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 R, and x and y are each independently an integer of 1 or more, specifically 1 to 100, more Specifically, it may be an integer of 2 to 50.

More specifically, the aluminoxane is methyl aluminoxane (MAO), modified methyl aluminoxane (MMAO), ethyl aluminoxane, n-propyl aluminoxane, isopropyl aluminoxane, butyl aluminoxane, isobutyl aluminoxane, n-pentyl Aluminoxane, neopentyl aluminoxane, n-hexyl aluminoxane, n-octyl aluminoxane, 2-ethylhexyl aluminoxane, cyclohexyl aluminoxane, 1-methylcyclopentyl aluminoxane, phenyl aluminoxane or 2,6-dimethylphenyl Aluminoxane and the like, and any one or a mixture of two or more thereof may be used.

In addition, in the aluminoxane compound, the modified methylaluminoxane is a methyl group of methylaluminoxane is substituted with a modification group (R), specifically, a hydrocarbon group having 2 to 20 carbon atoms, specifically, the compound of formula (6) have:

[Formula 6]

In Formula 6, R is as defined above, m and n may each be an integer of 2 or more. In addition, Me in the formula (2) means a methyl group (methyl group).

More specifically, in Formula 6, R is 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, and 6 to C carbon atoms. It may be an aryl group of 20, an aralkyl group of 7 to 20 carbon atoms, an alkylaryl group of 7 to 20 carbon atoms, an allyl group or an alkynyl group of 2 to 20 carbon atoms, more specifically, an ethyl group, isobutyl group, hexyl group or jade It may be a linear or branched alkyl group having 2 to 10 carbon atoms such as a tilyl group, and more specifically, isobutyl group.

More specifically, the modified methyl aluminoxane may be substituted with about 50 mol% to 90 mol% of the methyl group of methyl aluminoxane with the aforementioned hydrocarbon group. When the content of the substituted hydrocarbon group in the modified methylaluminoxane is within the above range, it is possible to promote the alkylation to increase the catalytic activity.

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

On the other hand, the organic magnesium compound as the alkylating agent is a magnesium compound containing at least one magnesium-carbon bond and soluble in a nonpolar solvent, specifically a nonpolar hydrocarbon solvent. Specifically, the organic magnesium compound may be a compound of Formula 7a:

[Formula 7a]

Mg (R) ₂

In the general formula (7a), each R is independently the same as R defined above as a monovalent organic group.

More specifically, the organic magnesium compound of Formula 7a may be an alkylmagnesium compound such as diethylmagnesium, di-n-propylmagnesium, diisopropylmagnesium, dibutylmagnesium, dihexylmagnesium, diphenylmagnesium, or dibenzylmagnesium. Can be mentioned.

In addition, the organic magnesium compound may be a compound of Formula 7b:

[Formula 7b]

RMgX

In Formula 7b, R is a monovalent organic group, the same as R defined above, 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.

More specifically, the organic magnesium compound represented by Chemical Formula 7b may include hydrocarbyl magnesium hydride such as methyl magnesium hydride, ethyl magnesium hydride, butyl magnesium hydride, hexyl magnesium hydride, phenyl magnesium hydride and benzyl magnesium hydride; 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 Hydrocarbyl magnesium halides such as magnesium bromide; Hydrocarbyl magnesium carboxylates such as methyl magnesium hexanoate, ethyl magnesium hexanoate, butyl magnesium hexanoate, hexyl magnesium hexanoate, phenyl magnesium hexanoate and benzyl magnesium hexanoate; Hydrocarbyl magnesium alkoxides such as methyl magnesium ethoxide, ethyl magnesium ethoxide, butyl magnesium ethoxide, hexyl magnesium ethoxide, phenyl magnesium ethoxide and benzyl magnesium ethoxide; Or hydrocarbyl magnesium aryloxide, such as methyl magnesium phenoxide, ethyl magnesium phenoxide, butyl magnesium phenoxide, hexyl magnesium phenoxide, phenyl magnesium phenoxide, benzyl magnesium phenoxide, and the like.

As the alkylating agent, an alkyl lithium of R—Li (wherein R is a linear or branched alkyl group having 1 to 20 carbon atoms, more specifically a linear alkyl group having 1 to 8 carbon atoms) may be used as the organolithium compound. More specifically, methyllithium, ethyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, t-butyllithium, isobutyllithium, pentyllithium, isopentlilithium, etc. may be mentioned, Mixtures of two or more may be used.

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

In addition, the alkylating agent may be modified methylaluminoxane in that the solvent system used in the preparation of the catalyst composition may be a single solvent having an aliphatic hydrocarbon system to further improve the catalytic activity and reactivity.

(d) halogen compounds

In the catalyst composition for conjugated diene polymerization according to an embodiment of the present invention, the halogen compound is not particularly limited in kind, but can be used without particular limitation as long as it is used as a halogenating agent in the production of a diene polymer.

Specifically, the halogen compound may be a halogen group, an interhalogen compound, hydrogen halide, organic halide, nonmetal halide, metal halide or organometal halide, and any one or two of them. Mixtures of the above may be used. In consideration of the excellent catalytic activity and excellent reactivity, the halogen compound may be any one or a mixture of two or more selected from the group consisting of organic halides, metal halides and organometallic halides.

More specifically, the halogen alone may be fluorine, chlorine, bromine or iodine.

In addition, examples of the interhalogen compound include iodine monochloride, iodine monobromide, iodine trichloride, iodine pentafluoride, iodine monofluoride or iodine trifluoride.

Moreover, as said hydrogen halide, hydrogen fluoride, hydrogen chloride, hydrogen bromide, or hydrogen iodide is mentioned specifically ,.

In addition, the organic halide is specifically t-butyl chloride (t-BuCl), t-butyl bromide, allyl chloride, allyl bromide, benzyl chloride, benzyl bromide, chloro-di-phenylmethane, bromo-di-phenylmethane , 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-io Dopropane, 2-iodopropane, 1,3-diiodopropane, t-butyl iodide, 2,2-dimethyl-1-iodopropane ('neo Yl iodide), allyl iodide, iodobenzene, benzyl iodide, diphenylmethyl iodide, triphenylmethyl iodide, benzylidene iodide (also referred to as 'benzal iodide' Trimethylsilyl iodide, triethylsilyl iodide, triphenylsilyl iodide, dimethyldiiodosilane, diethyldiiodosilane, diphenyldiiodosilane, methyltriiodosilane, ethyl Triiodosilane, phenyltriiodosilane, benzoyl iodide, propionyl iodide, methyl iodoformate and the like.

In addition, the non-metal halide specifically includes phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, phosphorus oxychloride, phosphorus oxybromide, boron trifluoride, boron trichloride, boron tribromide, silicon tetrafluoride, silicon tetrachloride (SiCl ₄ ), Silicon bromide, arsenic trichloride, arsenic tribromide, selenium tetrachloride, selenium tetrabromide, tellurium tetrachloride, telluride tetrabromide, silicon iodide trifluoride, tellurium iodide, boron trichloride, boron triiode, phosphorus iodide or phosphorus iodide Selenium and the like.

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

In addition, the organometallic halide is specifically dimethylaluminum chloride, diethylaluminum chloride, dimethylaluminum bromide, diethylaluminum bromide, dimethylaluminum fluoride, diethylaluminum fluoride, methylaluminum dichloride, ethylaluminum dichloride, methyl Aluminum dibromide, ethylaluminum dibromide, methylaluminum difluoride, ethylaluminum difluoride, methylaluminum sesquichloride, ethylaluminum sesquichloride (EASC), isobutylaluminum sesquichloride, methylmagnesium chloride, methylmagnesium bromide , Ethylmagnesium chloride, ethylmagnesium bromide, n-butylmagnesium chloride, n-butylmagnesium bromide, phenylmagnesium chloride, phenylmagnesium bromide, benzylmagnesium Lauride, 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 Iodide, diisobutyl aluminum iodide, di-n-octyl aluminum iodide, methyl aluminum di iodide, ethyl aluminum di iodide, n-butyl aluminum di iodide, isobutyl aluminum di iodide, methyl aluminum ses Quiniodide, ethylaluminum sesquiiodide, isobutylaluminum sesquiiodide, ethylmagnesium iodide, n-butylmagnesium Odide, isobutylmagnesium iodide, phenylmagnesium iodide, benzyl magnesium iodide, trimethyltin iodide, triethyltin iodide, tri-n-butyltin iodide, di-n-butyl Tin diiodide, di-t-butyltin diiodide, and the like.

In addition, the catalyst composition for producing a conjugated diene polymer 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 halogen compound.

Specifically, in the compound containing the non-coordinating anion, the non-coordinating anion is a steric 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 a tetraaryl fluoride Borate anions and the like. Further, the compound containing the non-coordinating anion may include a carbonium cation such as triaryl carbonium cation together with the above non-coordinating anion; It may include an ammonium cation such as an N, N-dialkyl aninium 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 and the like.

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

The catalyst composition for forming a conjugated diene polymer according to an embodiment of the present invention may further include a diene monomer in addition to the above components.

The diene monomer may be mixed with a polymerization catalyst to form a premixing catalyst, or a preforming catalyst may be formed by polymerization with components in the polymerization catalyst, specifically, an alkylating agent such as DIBAH. It may be formed. In this way, the prepolymerization can not only improve the catalytic activity, but also more stabilize the conjugated diene polymer.

Specifically, the diene monomer may be used without particular limitation as long as it is generally used in the preparation of conjugated diene polymer. Specifically, the diene monomer is 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 the like, and any of these Or mixtures of two or more may be used.

The catalyst composition for forming a conjugated diene polymer according to an embodiment of the present invention may further include a reaction solvent in addition to the above components.

Specifically, the reaction solvent may be a nonpolar solvent which is not reactive with the above catalyst components. Specifically, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, isopentane, isohexane, isopentane, isooctane, 2,2-dimethylbutane, cyclopentane, cyclohexane Linear, branched, or cyclic aliphatic hydrocarbons having 5 to 20 carbon atoms such as methylcyclopentane or methylcyclohexane; Mixed solvents of aliphatic hydrocarbons having 5 to 20 carbon atoms such as petroleum ether, petroleum spirits, kerosene, and the like; Or an aromatic hydrocarbon solvent such as benzene, toluene, ethylbenzene, xylene, or the like, and any one or a mixture of two or more thereof may be used. More specifically, the nonpolar solvent may be a linear, branched or cyclic aliphatic hydrocarbon or aliphatic hydrocarbon having 5 to 20 carbon atoms, and more specifically n-hexane, cyclohexane, or a mixture thereof. Can be.

In addition, the reaction solvent may be appropriately selected depending on the kind of constituent materials constituting the catalyst composition, especially the alkylating agent.

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

In addition, when modified methylaluminoxane is used as the alkylating agent, an aliphatic hydrocarbon solvent may be appropriately used. In this case, since it is possible to implement a single solvent system 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 the catalytic activity, and the catalytic activity can further improve the reactivity.

The components in the catalyst composition as described above form catalytically active species through interaction with each other. Accordingly, the catalyst composition according to an embodiment of the present invention may include an optimal combination of the components of the above components to exhibit higher catalytic activity and excellent polymerization reactivity during the polymerization reaction for forming the conjugated diene-based polymer. .

Specifically, the catalyst composition may be included in an amount of 20 equivalents or less, more specifically, 0.0001 equivalents to 20 equivalents of the functionalizing agent based on 1 equivalent of the rare earth metal compound. If the content of the functionalizing agent exceeds 20 equivalents, there is a fear that the unreacted functionalizing agent remains and cause side reactions. More specifically, the functionalizing agent may be included in an amount of 1 to 10 equivalents based on 1 equivalent of the rare earth metal compound.

In addition, the catalyst composition may have 5 to 200 moles of the alkylating agent described above with respect to 1 mole of the rare earth metal compound, and if the content of the alkylating agent is less than 5 molar ratio, the activation effect on the rare earth metal compound is insignificant. It is not easy to control the catalytic reaction, and there is a fear that excess alkylating agent causes side reactions. More specifically, the catalyst composition may include 5 moles to 20 moles of the alkylating agent described above with respect to 1 mole of the rare earth metal compound, and may include 5 moles to 10 moles in consideration of remarkable effect of improving workability.

In addition, the catalyst composition may include 1 mol to 20 mol of the above halogen compound with respect to 1 mol of the rare earth metal compound, and more specifically 2 mol to 6 mol. If the content of the halogen compound is less than 1 molar ratio, the production of catalytically active species may be insufficient, resulting in a decrease in catalytic activity. If the content of the halogen compound exceeds 20 molar ratio, control of the catalytic reaction is not easy, and excess halogen compounds may cause side reactions. It may cause.

In addition, when the catalyst composition further comprises the diene monomer described above, the catalyst composition may specifically include 1 to 100 equivalents, more specifically 20 to 50 equivalents of diene monomer, based on 1 equivalent of the rare earth metal compound. It may further comprise an equivalent.

In addition, when the catalyst composition further includes the reaction solvent, the catalyst composition may further include a reaction solvent in an amount of 20 mol to 20,000 mol with respect to 1 mol of the rare earth metal compound, and more specifically, 100 mol to 1,000 mol. It may include.

The catalyst composition having the configuration as described above can be prepared by mixing the functionalizing agent, rare earth metal compound, alkylating agent, halogen compound, and optionally conjugated diene monomer and reaction solvent according to a conventional method.

For example, in the case of the premixed catalyst composition, the functionalizing agent, the rare earth metal compound, the alkylating agent, the halogen compound, and optionally the conjugated diene monomer may be prepared by sequentially or simultaneously adding and mixing the reaction solvent.

As another example, the prepolymerized catalyst composition may be prepared by mixing a functionalizing agent, a rare earth metal compound, an alkylating agent and a halogen compound in a reaction solvent, followed by prepolymerization by adding a conjugated diene monomer.

In this case, in order to promote the production of catalytically active species, the mixing and polymerization process may be carried out at a temperature range of 0 ℃ to 60 ℃, in which case heat treatment may be performed in parallel to meet the above temperature conditions.

More specifically, the catalyst composition is subjected to a first heat treatment at a temperature of 10 ° C. to 60 ° C. after mixing of the rare earth metal compound, the alkylating agent, the reaction solvent, and optionally the conjugated diene monomer, and adding the halogen compound to the resulting mixture. By the second heat treatment in the temperature range of 0 ℃ to 60 ℃.

In the catalyst composition prepared by the above production method, catalytically active species are produced by the interaction of the components.

As such, the catalyst composition according to the present invention can produce catalytically active species having superior catalytic activity and polymerization reactivity due to the use of the functionalizing agent. As a result, it is possible to prepare conjugated diene-based polymers having higher linearity and processability.

Specifically, the catalyst composition having the composition as described above may exhibit catalytic activity of 10,000 kg [polymer] / mol [Nd] · h or more during the polymerization of 5 minutes to 60 minutes within the temperature range of 20 ° C. to 90 ° C. . In the present invention, the catalytic activity is a value obtained from the molar ratio of the rare earth metal compound to the total amount of the conjugated diene polymer produced.

Conjugate Dien  polymer

According to another embodiment of the present invention there is provided a conjugated diene polymer prepared using the catalyst composition described above and a method of preparing the same.

The conjugated diene polymer according to one embodiment of the present invention may be prepared by polymerizing a conjugated diene monomer according to a conventional conjugated diene polymer manufacturing method except using the catalyst composition for conjugated diene polymerization described above.

In this case, the polymerization may be carried out by various polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization or emulsion polymerization, and may also be performed by a batch method, a continuous method, or a semi-continuous method. More specifically, it may be appropriately selected from the above-described polymerization methods according to the kind of functionalizing agent used in the catalyst composition. For example, when the functionalizing agent included in the catalyst composition is a Sn-based compound, it may be performed by the Andrew bottle type polymerization method.

Specifically, when prepared by solution polymerization, the conjugated diene polymer according to an embodiment of the present invention may be carried out by adding a diene monomer to the above-mentioned polymerization catalyst in a polymerization solvent and reacted.

The conjugated diene monomer may be used without particular limitation as long as it is generally used in the preparation of conjugated diene polymer. The diene monomer is specifically 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 the like, or any one of these Mixtures of two or more may be used. More specifically, the diene monomer may be 1,3-butadiene.

In addition, other monomers copolymerizable with the diene monomer may be further used in consideration of the physical properties of the diene polymer finally prepared during the polymerization reaction.

The other monomers are specifically styrene, p-methyl styrene, α-methylstyrene, 1-vinylnaphthalene, 3-vinyltoluene, ethylvinylbenzene, divinylbenzene, 4-cyclohexyl styrene, 2,4,6-trimethyl Aromatic vinyl monomers such as styrene and the like, and any one or a mixture of two or more thereof may be used. The other monomers may be used in an amount of 20% by weight or less based on the total weight of the monomers used in the polymerization reaction.

In this case, the diene monomer is not used in the total amount of the diene polymer is used in the preparation of the non-polar solvent, but a part of the total amount is dissolved in the polymerization solvent and polymerized, at least once, depending on the polymerization conversion rate, Specifically, two or more times, more specifically, may be divided into two to four times.

In addition, the polymerization solvent may be a nonpolar solvent, which is the same solvent that can be used in the preparation of the catalyst for polymerization.

The concentration of the monomer in the use of the polymerization solvent is not particularly limited, but may be 3% to 80% by weight, more specifically 10% to 30% by weight.

In addition, molecular weight modifiers such as trimethylaluminum, diisobutylaluminum hydride or trimethyl silane during the polymerization reaction; A reaction terminator for completing a polymerization reaction such as polyoxyethylene glycol phosphate; Or additives such as antioxidants such as 2,6-di-t-butylparacresol may be used. In addition, additives, such as chelating agents, dispersants, pH regulators, deoxygenants, and oxygen scavengers, which typically facilitate solution polymerization, may optionally be further used.

In addition, the polymerization reaction may be carried out at a temperature of 0 ℃ to 200 ℃, more specifically 20 ℃ to 100 ℃.

In addition, the polymerization reaction may be performed for 5 minutes to 3 hours in the above temperature range until the conjugated diene-based polymer 100% conversion, specifically, may be performed for 10 minutes to 2 hours.

As a result of the above polymerization reaction, a conjugated diene polymer is produced.

The conjugated diene-based polymer specifically comprises a rare earth metal catalyzed conjugated diene-based polymer comprising an active organometallic site derived from a catalyst comprising the rare earth metal compound described above, more specifically 1,3-butadiene monomer units. Rare earth metal catalyzed butadiene-based polymers, more specifically neodymium catalyzed butadiene-based polymers comprising 1,3-butadiene monomer units. In addition, the conjugated diene-based polymer may be a polybutadiene consisting of only 1,3-butadiene monomer.

The conjugated diene-based polymer produced by the polymerization reaction may be dissolved in a polymerization solvent or obtained in precipitated form. If dissolved in the polymerization solvent, it may be precipitated by adding a lower alcohol such as methyl alcohol, ethyl alcohol or steam. Accordingly, the method for preparing a conjugated diene-based polymer according to an embodiment of the present invention may further include a precipitation and separation process for the conjugated diene-based polymer prepared after the polymerization reaction, wherein, the precipitated conjugated diene-based polymer Filtration, separation and drying processes can be carried out according to conventional methods.

As described above, according to the method for preparing a conjugated diene polymer according to an embodiment of the present invention, a conjugated diene polymer having a high linearity and processability can be manufactured by using a functionalizing agent in the preparation of the catalyst composition.

Specifically, the conjugated diene-based polymer may include a functional group derived from the functionalizing agent in the molecule.

The conjugated diene polymer may also be a rare earth metal catalyzed diene polymer comprising an active organic metal moiety derived from a catalyst comprising the rare earth metal compound, more particularly a rare earth metal comprising 1,3-butadiene monomer units. Catalyzed butadiene-based polymers, and more particularly neodymium catalyzed butadiene-based polymers.

In addition, the conjugated diene-based polymer according to an embodiment of the present invention has a polydispersity (PDI) of 3.4 or less, which is a ratio (Mw / Mn) between a weight average molecular weight (Mw) and a number average molecular weight (Mn). It may have a narrow molecular weight distribution. When the PDI of the conjugated diene-based polymer exceeds 3.4, there is a fear that mechanical properties such as wear resistance and impact resistance when applied to the rubber composition. More specifically, considering the remarkable effect of improving the mechanical properties of the polymer according to the polydispersity control, the polydispersity of the conjugated diene-based polymer may be 3.2 or less.

In addition, the conjugated diene-based polymer according to an embodiment of the present invention, the weight average molecular weight (Mw) is 300,000g / mol to 1,200,000g / mol, specifically may be 400,000g / mol to 1,000,000g / mol. . In addition, the conjugated diene-based polymer according to an embodiment of the present invention, the number average molecular weight (Mn) is 100,000g / mol to 700,000g / mol, specifically may be 120,000g / mol to 500,000g / mol.

When the weight average molecular weight of the conjugated diene polymer is less than 300,000 g / mol or the number average molecular weight is less than 100,000 g / mol, the elastic modulus of the vulcanizate is lowered, the hysteresis loss is increased, and the wear resistance may be deteriorated. Moreover, when a weight average molecular weight exceeds 1,200,000 g / mol or a number average molecular weight exceeds 700,000 g / mol, workability will fall, the workability of the rubber composition containing the said conjugated diene type polymer will worsen, and kneading will become difficult. It may be difficult to sufficiently improve the physical properties of the rubber composition. In the present invention, the weight average molecular weight and the number average molecular weight are polystyrene reduced molecular weights analyzed by gel permeation chromatography (GPC), respectively.

More specifically, the conjugated diene-based polymer according to an embodiment of the present invention, when applied to the rubber composition in consideration of a good balance of mechanical properties, elastic modulus and workability for the rubber composition, the weight with the polydispersity described above It is preferable to simultaneously satisfy the average molecular weight and number average molecular weight conditions. Specifically, the conjugated diene polymer has a ratio (Mw / Mn) of a weight average molecular weight (Mw) and a number average molecular weight (Mn) of 3.4 or less, and a weight average molecular weight (Mw) of 300,000 g / mol to 1,200,000 g / mol The number average molecular weight (Mn) is 100,000 g / mol to 700,000 g / mol, more specifically, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) is 3.2 or less, the weight The average molecular weight (Mw) may be 400,000 g / mol to 1,000,000 g / mol, and the number average molecular weight (Mn) may be 120,000 g / mol to 500,000 g / mol.

In addition, the conjugated diene-based polymer exhibits high linearity due to the use of functionalizing agents in its preparation. In general, the higher the linearity, the lower the degree of branching and the higher the solution viscosity. Specifically, when the solution viscosity (SV) is divided into the Mooney viscosity (MV) and the value is corrected as the linearity (SV / MV), the linearity of the conjugated diene polymer according to the embodiment of the present invention ( SV / MV) may be 1 to 15, more specifically 3 to 13.

In addition, the conjugated diene polymer may have a Mooney viscosity (ML1 + 4) at 100 ° C of 10 MU to 90 MU, specifically 20 MU to 80 MU. In addition, the conjugated diene polymer may have a solution viscosity of 100 cP to 600 cP, specifically, 120 cP to 500 cP.

In the present invention, the Mooney viscosity may be measured using a Mooney viscometer, for example, Rotor Speed 2 ± 0.02rpm, Large Rotor at 100 ° C. with Monsanto MV2000E. At this time, the sample used can be measured at room temperature (23 ± 3 ℃) for more than 30 minutes, collected 27 ± 3g, filled into the die cavity and operated by platen, and the unit of Mooney viscosity is MU. (Mooney unit). In the present invention, the solution viscosity (SV) was carried out in the same manner as the Mooney viscosity measurement, but the viscosity of the polymer in 5% toluene at 20 ℃ was measured.

More specifically, when considering the remarkable effect of the improvement according to the Mooney viscosity and solution viscosity control, the conjugated diene polymer according to an embodiment of the present invention has a Mooney viscosity (MV) at 100 ℃ 20MU to 80MU The solution viscosity (SV) may be 100 cP to 600 cP, and the linearity (SV / MV) may be 3 to 13.

In addition, the conjugated diene-based polymer according to an embodiment of the present invention has a cis content in the conjugated diene-based polymer measured by Fourier transform infrared spectroscopy, specifically, the content of cis-1,4 bond is 95% or more, More specifically, it may be 96% or more. In addition, the content of the vinyl bond in the conjugated diene-based polymer may be 1% or less. As such, when the cis-1,4 bond content in the polymer is high, linearity may be increased to improve wear resistance and crack resistance of the rubber composition when blended into the rubber composition.

In addition, the conjugated diene-based polymer according to an embodiment of the present invention has a pseudo-living (pseudo-living) characteristics. Accordingly, the end of the polymer may be modified through a modification process of functionalizing the functional group with a functional functional group such as a functional group having an interaction with an inorganic filler such as carbon black or silica. In this case, the method for preparing a conjugated diene-based polymer according to an embodiment of the present invention may further include a step of modifying the conjugated diene-based polymer prepared as a result of the polymerization reaction using a modifier.

The modification process may be performed according to a conventional modification method except using the conjugated diene polymer according to the present invention.

In addition, as the modifier, a compound capable of imparting the functional group to the polymer when reacting with the conjugated diene-based polymer or increasing the molecular weight by coupling may be used. Specifically, an azacyclopropane group, a ketone group, Carboxyl group, thiocarboxyl group, carbonate, carboxylic acid anhydride, carboxylic acid metal salt, acid halide, urea group, thiourea group, amide group, thioamide group, isocyanate group, thioisocyanate group, halogenated isocyano group, epoxy group, thioepoxy group, imine group and An active proton containing at least one functional group selected from the group consisting of MZ bonds, wherein M is selected from the group consisting of Sn, Si, Ge, and P, and Z is a halogen atom; It may not contain onium salt. More specifically, the terminal modifiers are alkoxysilanes, imine-containing compounds, esters, ester-carboxylate metal complexes, alkyl ester carboxylate metal complexes, aldehydes or ketones, amides, isocyanates, isothiocyanates, imines and epoxys. It may be any one or a mixture of two or more selected from the group consisting of. As an example, the denaturant may be (E) -N, N-dimethyl-4-((undecylimino) methyl) benzeneamine ((E) -N, N-dimethyl-4-((undecylimino) methyl) benzenamine) Can be. In the modification process, the terminal denaturant may be used in an amount of 0.01 equivalents to 200 equivalents, more specifically 0.1 equivalents to 150 equivalents based on 1 equivalent of the rare earth metal compound.

Conjugated diene-based polymers prepared through denaturation processes, such as those described above, include a denaturant-derived functional group in the polymer, specifically at the end thereof. , Carboxylic acid anhydride, carboxylic acid metal salt, acid halide, urea group, thiourea group, amide group, thioamide group, isocyanate group, thioisocyanate group, halogenated isocyano group, epoxy group, thioepoxy group, imine group and MZ bond M may be selected from the group consisting of Sn, Si, Ge, and P, and Z is a halogen atom. By including such a modifier-derived functional group, it exhibits excellent affinity for inorganic fillers such as carbon black or silica used in the preparation of the rubber composition, thereby increasing their dispersibility and further improving the physical properties of the resulting rubber composition. . Accordingly, according to another embodiment of the present invention provides the modified conjugated diene-based polymer.

Rubber composition

According to another embodiment of the present invention there is provided a rubber composition comprising the conjugated diene-based polymer.

Specifically, the rubber composition may include 10 wt% to 100 wt% of the conjugated diene-based polymer and 90 wt% or less of the rubber component. When the content of the conjugated diene-based polymer is less than 10% by weight, the effect of improving wear resistance, crack resistance and ozone resistance of the rubber composition may be insignificant.

In addition, the rubber component is specifically natural rubber (NR); Or styrene-butadiene copolymer (SBR), hydrogenated SBR, polybutadiene (BR) with low cis-1,4-bond content, hydrogenated BR, polyisoprene (IR), butyl rubber (IIR), ethylene-propylene Ethylene propylene rubber, Ethylene propylene diene rubber, 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 It may be a synthetic rubber such as rubber, silicone rubber, epichlorohydrin rubber and the like, and any one or a mixture of two or more thereof may be used.

In addition, the rubber composition may further comprise at least 10 parts by weight of the filler with respect to 100 parts by weight of the rubber component. In this case, the filler may be carbon black, starch, silica, aluminum hydroxide, magnesium hydroxide, clay (hydrated aluminum silicate), or the like, and any one or a mixture of two or more thereof may be used.

In addition to the above-mentioned rubber components and fillers, the rubber composition includes a compounding agent commonly used in the rubber industry, such as a vulcanizing agent, a vulcanization accelerator, an anti-aging agent, an anti-scoring agent, a softening agent, a zinc oxide, a stearic acid or a silane coupling agent. It can select and mix | blend suitably within the range which does not impair the objective.

Such a rubber composition is prepared using a catalyst composition comprising a functionalizing agent to include a conjugated diene-based polymer having excellent linearity and processability, thereby improving the balance without any bias in terms of wearability, viscoelasticity and processability. Can be represented.

Accordingly, the rubber composition may be used for passenger cars, trucks (tracks), bus tires (for example, tire treads, side wheels, subtreads, bead fillers, braking members, etc.), elastic parts of tire stock, O-rings, profiles It is useful in the manufacture of various rubber moldings, such as gaskets, membranes, hoses, belts, soles, dustproof rubbers or window seals.

Hereinafter, the present invention will be described in detail with reference to Examples. However, embodiments according to the present invention can be modified in many different forms, the scope of the present invention should not be construed as limited to the embodiments described below. The embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.

[Production of Functionalizing Agent]

Production Example  One: Allyltributylstanan ( allyltributylstannane Manufacturing

To a vein prepared by dissolving n Bu ₃ SnCl (35 g, 30 ml, 110 mmol) in THF at 0 ° C., a solution of allylmagnesium bromide (allylMgBr) (65 ml, 129 mmol, 2.0 M in THF) was slowly added. . The reaction mixture was stirred at room temperature (23 ± 5 ° C.) for 2 hours and then refluxed for 12 hours overnight. The resulting solution was quenched with ice water and then extracted with diethyl ether (Et ₂ O). The ether solution was dried over Na ₂ SO ₄ and then volatile solvents were removed under reduced pressure. The residue was purified via silica gel neutralized with Et ₃ N, and an eluent of Et ₂ O: Hx (mixed volume ratio = 1: 20 to 1:10) to give allyltributylstanan as a functionalizing agent.

¹ H NMR (500 MHz, CDCl ₃ ) 5.98-5.88 (m, 1H), 4.88 (d, J = 16.8 Hz, 1H), 4.64 (d, J = 9.9 Hz, 1H), 1.78 (dt, J = 8.6 , 30.2 Hz, 2H), 1.53-1.44 (m, 8H), 1.34-1.26 (m, 8H), 0.94-0.80 (m, 18H).

Production Example  2: Diallyldibutylstanan ( diallyldibutylstannane Manufacturing

To a solution prepared by dissolving n Bu ₂ SnCl ₂ (3 g, 9.87 mmol) in Et ₂ O at room temperature (23 ± 5 ° C.), an allylMgBr (1.0 M, 30 mmol, 30 ml in Et ₂ O) solution was added dropwise It was. The reaction mixture was stirred at rt for 2 h. After completion of the reaction, the resulting solution was quenched with NaCl and extracted with diethyl ether (Et ₂ O). The resulting organic layer was extracted with Et ₂ O and dried over MgSO ₄ . The volatile solvent was removed under reduced pressure and the residue was purified through silica gel neutralized with Et ₃ N and Et ₂ O to give diallyldibutylstanan as colorless oil as functionalizing agent (3.07 g, 99% yield). ).

¹ H NMR (500 MHz, CDCl ₃ ) 5.96-5.89 (2H, m), 4.81 (2H, d, J = 20 Hz), 4.68 (2H, d, J = 10 Hz), 1.89-1.80 (8H, m ), 1.54-1.28 (13H, m), 0.95-0.89 (12H, m).

Production Example  3: Triallylbutylstanan ( triallylbutylstannane Manufacturing

Mg (16 g, 693 mmol) and allyl bromide (allylBr) (52 ml, 600 mmol) were reacted in THF (500 ml) to prepare a THF solution of AllylMgBr. After stirring the reaction solution overnight, THF solution of n BuSnCl ₃ (51.3 g, 182 mmol) was added dropwise to the THF solution of AllylMgBr over 2 hours. The reaction mixture was stirred at room temperature for 0.5 hours and then refluxed for 12 hours overnight. The resulting solution was cooled to room temperature, poured into ice water, extracted with diethyl ether (Et ₂ O), and dried over Na ₂ SO ₄ . The organic layer was removed under reduced pressure, and the resulting residue was purified through silica gel neutralized with Et ₃ N, and an eluent of Et ₂ O: normal hexane (Hx) (mixed volume ratio = 1: 10) to form tri-functionalizer. Allylbutylstanan was obtained (3.07 g, 99% yield).

¹ H NMR (500 MHz, CDCl ₃ ) 5.97-5.88 (m, 3H), 4.84 (dd, J = 11.1, 27.9 Hz, 3H), 4.71 (dd, J = 10.3, 20.4 Hz, 3H), 1.88 (dt , J = 8.55, 31.1 Hz, 3H), 1.58-1.43 (m, 1H), 1.34-1.27 (m, 1H), 1.06-1.02 (m, 1H), 0.90 (t, J = 7.3 Hz, 2H).

Production Example  4: Tetraallylstanan ( tetraallylstannane Manufacturing

Allyl magnesium bromide (2.0 M, 48.4 mmol, 24.2 ml in THF) in a solution prepared by dissolving SnCl ₄ (3 g, 11.5 mmol) in toluene (30 ml) at room temperature (23 ± 5 ° C.) The solution was added. The reaction mixture was stirred at rt for 2 h and refluxed for 12 h overnight. After the reaction was completed, the mixture was cooled to room temperature, poured into water, and extracted with diethyl ether (Et ₂ O). Combined ethereal extracts were washed with water and dried over anhydrous Na ₂ SO ₄ Dried over and concentrated under reduced pressure. The residue was filtered over silica gel using hexane eluent to afford tetraallylstanan as a colorless oil.

¹ H NMR (500 MHz, CDCl ₃ ) 5.97-5.89 (m, 4H), 4.90 (dd, J = 5.0, 25.0 Hz 4H), 4.76 (dd, J = 10.0, 25.0 Hz, 4H), 1.91 (td, J = 30, 20 Hz, 8H).

Production Example  5: Triallylphenylstanan ( triallylphenylstannane Manufacturing

To a solution prepared by dissolving PhSnCl ₃ (3 g, 9.93 mmol) in Et ₂ O at 0 ° C., an allylMgCl solution (16.4 ml, 32.8 mmol, 2.0 M in THF) was added. The reaction mixture was stirred at rt overnight for 12 h. After completion of the reaction, the resulting solution was poured into ice cubes, extracted with Et ₂ O, and dried over Na ₂ SO ₄ . The ether solution was evaporated under reduced pressure and the residue was purified by eluent (mixed volume ratio = 1: 10) silica gel chromatography of Et ₂ O: Hx to give triallylphenylstanan as a functionalizing agent.

¹ H NMR (500 MHz, CDCl ₃ ) 7.42-7.26 (m, 5H), 5.95-5.81 (m, 3H), 4.83 (dd, J = 11.8, 28.5 Hz, 3H), 4.70 (dd, J = 12.6, 22.8 Hz, 3H), 2.02 (dt, J = 8.5, 33.2 Hz, 6H).

[Production of conjugated diene polymer]

Example 1

In a hexane solvent, a neodymium compound of Nd (2,2-diethyl decanoate) ₃ (concentration in hexane = 40 wt%) and a functionalizing agent (i) of the following chemical structure prepared in Preparation Example 2 (DAT, 5 equivalents based on 1 equivalent of neodymium compound) was added, and then diisobutylaluminum hydride (DIBAH) and diethylaluminum chloride (DEAC) were sequentially added in a molar ratio of neodymium compound: DIBAH: DEAC = 1: 10: 2.4. And then mixed to prepare a catalyst composition.

After alternately adding vacuum and nitrogen to a completely dried organic reactor, 4.7 kg (1,3-butadiene content = 500 g) of a 1,3-butadiene / hexane mixed solution was put into a vacuum reactor, and the catalyst composition prepared above was After the addition, the polymerization reaction was carried out at 70 ° C. for 60 minutes to prepare a butadiene polymer.

(i)

(i)

Example  2

In the same manner as in Example 1, except that (ii) (TAT, 5 equivalents based on 1 equivalent of neodymium compound) of the following chemical structure prepared in Preparation Example 4 was used as the functionalizing agent in Example 1. The butadiene polymer was prepared.

(ii)

(ii)

Example 3

Nd (2,2-diethyl decanoate) _{3 in} a mixed solution of hexane and 1,3-butadiene (pBD) Neodymium compound (concentration in hexane = 40% by weight) and the functionalizing agent (i) (1 equivalent based on 1 equivalent of neodymium compound), diisobutylaluminum hydride (DIBAH), and diethylaluminum chloride (DEAC) A catalyst composition was prepared by sequentially adding a molar ratio of: DIBAH: DEAC = 1: 9.2: 2.4 and then mixing. In this case, the 1,3-butadiene was used in 33 equivalents based on 1 equivalent of the neodymium compound.

A butadiene polymer was prepared in the same manner as in Example 1, except that the prepared catalyst composition was used.

Comparative Example 1

In a hexane solvent, a neodymium compound of Nd (2,2-diethyl decanoate) ₃ , diisobutylaluminum hydride (DIBAH) and diethylaluminum chloride (DEAC) were added to a neodymium compound: DIBAH: DEAC = 1: 10.1: In order to prepare a molar ratio of 2.4 and then mixed to prepare a polymerization catalyst.

A butadiene polymer was prepared in the same manner as in Example 1, except that the prepared polymerization catalyst was used.

Comparative Example 2

Butadiene polymer prepared in the same manner as in Example 1 except for using nickel octoate (Nickel octoate) in place of the Nd-based catalyst, and no functionalizing agent (BR1208) ™, manufactured by LG Chem).

Experimental Example 1

The use of the butadiene-based polymer was evaluated to improve the catalytic activity and the conversion rate according to the use of the functionalizing agent according to the present invention.

Specifically, 89 mg (0.054 mmol) of a neodymium compound of Nd (2,2-diethyl decanoate) ₃ in hexane, the functionalizing agent described in Table 1 (usage: the content of Table 1 below based on 1 equivalent of the neodymium compound) , Diisobutylaluminum hydride (DIBAH) (0.12ml, 0.675mmol) and diethylaluminum chloride (DEAC) (0.13ml, 0.130mmol) were sequentially added and mixed to prepare a catalyst composition. After vacuum and nitrogen were alternately added to the completely dried reactor, 150 g of 1,3-butadiene / hexane mixed solution (1,3-butadiene content = 22.5 g) was added to a vacuum reactor, and the catalyst composition prepared above was After addition, the butadiene polymer was prepared by carrying out a polymerization reaction at 70 ° C. for the polymerization time shown in Table 1 below.

Functional vaporizer Polymerization time Conversion rate Kinds usage Example 4

(iii)

(iii) 5 equivalents 30 minutes 100% Example 5

(i) 5 equivalents 30 minutes 91% Example 6

(iv) 5 equivalents 30 minutes 95% Example 7

(ii) 5 equivalents 30 minutes 98% Example 8

(v) 5 equivalents 30 minutes 49% Example 9 50 minutes 59% Example 10 90 mins 65% Example 11

(vi) 5 equivalents 30 minutes 10% Example 12

(vii) 5 equivalents 30 minutes 25%

As a result, the use of the functionalizing agent according to the present invention enabled the conversion to butadiene polymer, and the longer the polymerization time, the higher the conversion to butadiene polymer. In addition, when reacted for the same polymerization time with the same amount of use, all functional groups bound to Sn are polymerizable functional groups, or functional functionalizers containing alkyl groups together with one or more polymerizable reactive functional groups (Examples 4 to 7). It showed higher conversion compared with the functionalizing agent (Examples 8-11) which has an aryl group or an alkoxy group. Similarly, in the case of a functionalizing agent containing an allyl group as a polymerizable functional group (Example 5) even though it contains an alkyl group, the functionalizing agent containing an allyl group bonded through oxygen as a hetero atom (Example 12) High conversion.

Experimental Example  2

Rubber samples were prepared using the butadiene polymers prepared in Examples 1 and 2 and Comparative Example 1, and the Mooney viscosity (ML1 + 4) change was observed according to vulcanization.

Specifically, based on 100 parts by weight of the butadiene-based polymer prepared in Examples 1, 2 and Comparative Example 1 as the raw material rubber 70 parts by weight of graphite, 22.5 parts by weight of process oil, 2 parts by weight of the antioxidant (TMDQ) Each rubber compound was prepared by combining 3 parts by weight of zinc oxide (ZnO) and 2 parts by weight of stearic acid. 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 the prepared rubber compound, and vulcanized at 160 ° C. for 25 minutes to prepare a rubber specimen.

Rubber specimens made only of the polymers prepared in each of Examples 1, 2 and Comparative Example 1, rubber specimens (CMB) prepared using such rubber formulations, and sulfur addition to the rubber formulations After vulcanization, the rubber specimens (FMB) were measured using a Rotor Speed 2 ± 0.02 rpm and a Large Rotor at 100 ° C. using Monsanto MV2000E to measure the Mooney viscosity (ML1 + 4). At this time, the sample used was allowed to stand at room temperature (23 ± 3 ℃) for more than 30 minutes, collected 27 ± 3g and filled in the die cavity and measured by operating the platen (Platen). The results are shown in FIGS.

As shown in Figures 1 to 3, the polymers of Examples 1 and 2 showed the highest Mooney viscosity when pre-vulcanized rubber (CMB), after which the Mooney viscosity decreased. In addition, the polymer of Example 2 has a small difference in Mooney viscosity between Raw and FMB. On the other hand, the polymer of Comparative Example 1 increased the Mooney latex toward Raw-CMB-FMB. From these results, it can be confirmed that the polymers of Examples 1 and 2 have excellent processability compared to Comparative Example 1.

Experimental Example  3

Various physical properties of the butadiene polymers prepared in Examples 1 to 3 and Comparative Examples 1 and 2 were measured by the following methods, and the results are shown in Table 2.

1) Microstructure Analysis

Fourier transform infrared spectroscopy and nuclear magnetic resonance spectroscopy were used to measure cis-1,4 bond, vinyl bond and trans bond in the butadiene polymer.

2) weight average molecular weight (Mw), number average molecular weight (Mn), and polydispersity (PDI)

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the butadiene polymer prepared by gel permeation chromatography (GPC) were measured, and polydispersity (PDI, Mw / Mn) was calculated therefrom. It was.

Specifically, the prepared butadiene-based polymer was dissolved in THF for 30 minutes under 40 ° C., respectively, and then loaded on a gel permeation chromatography to flow. In this case, two columns of PLgel Olexis brand name and one PLgel mixed-C column of Polymer Laboratories were combined. The newly replaced columns were all mixed bed type columns, and polystyrene was used as the gel permeation chromatography standard material (GPC Standard material).

3) Viscosity Characteristics

Mooney Viscosity (MV, (ML1 + 4, @ 100 ° C) (MU): To a butadiene-based polymer, Mooney Viscosity (MV) was obtained using Rotor Speed 2 ± 0.02rpm, Large Rotor at 100 ° C with MV2000E from Monsanto. The samples used were allowed to stand at room temperature (23 ± 3 ° C.) for 30 minutes or longer, and then 27 ± 3 g were taken and filled into the die cavity, and platen was operated to apply a torque to measure the Mooney viscosity.

-S / R value: -S / R value was determined from the change inclination value of the Mooney viscosity which appears as a torque loosens in the measurement of the Mooney viscosity.

Solution Viscosity (SV) The viscosity of the polymer in 5% toluene was measured at 20 ° C.

Comparative Example 1 Comparative Example 2 Example 1 Example 2 Example 3 Functional Vaporizer (Content) - - DAT (5eq) TAT (5eq) DAT (1eq) + pBD (33eq) catalyst Nd system Ni series Nd system Nd system Nd system IR Microstructure (cis / vinyl / trans) (weight ratio) 96.4 / 0.5 / 3.1 96.2 / 2.0 / 1.8 97.2 / 0.5 / 2.3 97.2 / 0.5 / 2.3 ND GPC Mn g / mol 2.49E + 05 1.57E + 05 2.06E + 05 1.93E + 05 ND Mw g / mol 8.47E + 05 7.78E + 05 6.28E + 05 5.82E + 05 ND Mw / Mn - 3.41 4.96 3.05 3.02 ND MV ML1 + 4 (@ 100 ° C) MU 44.8 43.2 43.9 40.9 43.7 -S / R - 0.5502 0.7651 0.8395 0.6568 0.6944 Solution viscosity (SV) 276.0 280.0 369.5 182.4 134.4 SV / MV 6.16 6.48 8.42 4.46 3.08

In Table 2, ND means 'not measured', and eq means equivalents.

As a result, the butadiene polymers of Examples 1 to 3 prepared by using the functionalizing agent in terms of microstructure had a cis bond content in the polymer of 97% or more, a vinyl bond content of 0.5% or less, and Example 1 Butadiene polymer of 3 to 3 showed high linearity with -S / R value of 0.65 or more. In terms of molecular weight distribution, the butadiene polymers of Examples 1 to 3 produced using the functionalizing agent exhibited a low PDI of 3.05 or less, more specifically 3.02 to 3.05, showing a narrow molecular weight distribution. In addition, in terms of viscosity characteristics, the butadiene polymers of Examples 1 to 3 prepared using the functionalizing agent had an SV / MV of 3.08 to 8.42.

In addition, the copolymer of Example 3 prepared using the catalyst composition to which 1,3-butadiene was further added as a conjugated diene monomer at the time of preparation of a catalyst composition is compared with Examples 1 and 2 using the same functionalizing agent. Significantly lower solution viscosity and SV / MV. From this, the improvement of workability at the time of manufacture of a rubber composition can be anticipated.

On the other hand, the butadiene polymer of Comparative Example 1 prepared in the same manner as in Example 1, except that no functionalizing agent was used, compared to Examples 1 to 3 using the functionalizing agent, a broader molecular weight distribution and more Low -S / R values were shown. For this reason, the butadiene polymer of Comparative Example 1 exhibited a decrease in processability as shown in Table 4 below.

In addition, the butadiene polymer of Comparative Example 2 prepared by using a nickel-based catalyst, which does not use a functionalizing agent, has a higher content of vinyl in the polymer and shows a wider molecular weight distribution than those of Examples 1 to 3. It was.

Experimental Example 4

Rubber samples were prepared in the same manner as in Experiment 1 using the butadiene polymers prepared in Examples 1 to 3 and Comparative Examples 1 and 2. Abrasion properties, viscoelasticity and workability were measured for the rubber specimens produced in the following manner, and the results are shown in Table 3.

1) wear characteristics

Loss volume index: ARI _A (Abrasion resistance index, Method A) Measured according to the method specified in ASTM D5963 test standard and expressed as an index value. In this case, the higher the value, the better the wear performance.

 2) viscoelastic properties

A TA dynamic mechanical analyzer was used. Tan δ values were measured by varying the strain at a frequency of 10 Hz and each measurement temperature (-70 ° C. to 70 ° C.) in the torsion mode. The Payne effect is expressed as the difference between the minimum and maximum values at 0.28% to 40% of the strain. The smaller the Faye effect, the better the dispersibility of the filler such as silica. The higher the low temperature 0 [deg.] C. Tan δ value, the better the wet road resistance. The lower the high temperature 50 [deg.] C. to 70 [deg.] C. value, the lower the hysteresis loss.

3) Machinability

In the same manner as in Experimental Example 1, the surface of the vulcanized rubber sheet (FMB) prepared using the butadiene polymer prepared in Examples 1 to 3 and Comparative Examples 1 and 2 was photographed using a digital camera (sheet Width = 20cm).

Based on the observations, the better the surface state of the sheet and the edge part is neat, the closer to 1, and the surface state is rough and the edge is not flat. Was evaluated.

Comparative Example 1 Comparative Example 2 Example 1 Example 2 Example 3 Functional Vaporizer (Content) - - DAT (5eq) TAT (5eq) DAT (1eq) + pBD catalyst Nd system Ni series Nd system Nd system Nd system Tanδ @ 0 ℃ 0.209 (112%) 0.208 (115%) 0.186 (104%) 0.210 (117%) 0.185 avg. Tanδ @ 50 ℃ ~ 70 ℃ 0.164 (85%) 0.162 (88%) 0.144 (98%) 0.166 (85%) 0.147 Loss volume index 100 89 109 101 107 Machinability 4 One One One 2

In Table 3, eq means equivalents.

As a result, it can be seen that the butadiene polymers of Examples 1 to 3 prepared using the catalyst composition including the functionalizing agent have better wear characteristics by showing a higher loss volume index than those of Comparative Examples 1 and 2. have.

In addition, the butadiene polymers of Examples 1 to 3 prepared by using a catalyst composition containing a functionalizing agent in terms of viscoelasticity exhibited a similar level of low-temperature 0 ° C Tan δ values compared to Comparative Examples 1 and 2, thereby providing equivalent levels It can be seen that the wet road surface resistance of. In addition, since the Tan δ value at a high temperature of 50 ℃ to 70 ℃ shows a lower value than the comparative examples 1 and 2, it can be confirmed that the hysteresis loss is less, the low rolling resistance of the tire, that is, the low fuel efficiency is more improved.

In addition, in the case of the vulcanized rubber specimens of the butadiene polymer of Comparative Example 1 prepared using the catalyst composition containing no functionalizing agent, the surface roughness of both sides of the sheet was largely observed. In contrast, the FMB sheet prepared using the butadiene polymers of Examples 1 to 3 according to the present invention exhibited smooth surface properties. Particularly, in Examples 1 and 2 prepared using a Sn-based functionalizing agent, a smooth surface equal to or higher than the FMB sheet manufactured using the nickel catalyzed butadiene polymer of Comparative Example 2, which is known to have excellent workability. Characteristics. From this, it can be expected that the butadiene polymer according to the present invention exhibits excellent processability in the production of tires and the like.

From the above experimental results, it can be seen that the rubber composition comprising the butadiene polymer according to the present invention has a better balance without any bias in terms of wear, viscoelasticity and processability compared to the rubber composition of the comparative example.

Claims (18)

A functionalizing agent of the formula (1), Rare earth metal compounds, Alkylating agents, and Halogen compound Catalyst composition for producing a conjugated diene-based polymer comprising: [Formula 1] (X ₁ ) _a -Sn- (X ₂ ) _4-a In Chemical Formula 1, a is an integer of 1 to 3, X ₁ and X ₂ are each independently selected from the group consisting of a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, -OR _a , -NR _b R _c , -SiR _d R _e R _f and a covalent functional group; Provided that at least one of X ₁ and X ₂ includes a covalent functional group, wherein R _a , R _{b ,} R _c , R _d , R _e and R _f are each independently a hydrogen atom, having 1 to 20 carbon atoms An alkyl group, a cycloalkyl group of 3 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkylaryl group of 7 to 20 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, -SiR'R "R"'and a covalent functional group R ', R "and R"' are each independently selected from 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, and having 7 to 20 carbon atoms. An alkylaryl group, an aralkyl group having 7 to 20 carbon atoms, and a covalent functional group, Lorca The covalent functional group is a functional group including a carbon-carbon double bond. The method of claim 1, The covalently bonded functional group is selected from the group consisting of alkenyl group and (meth) acryl group having 2 to 20 carbon atoms catalyst composition for producing a conjugated diene polymer. The method of claim 1, The covalent functional group is a catalyst composition for producing a conjugated diene-based polymer is selected from the group consisting of a vinyl group, allyl group, metaallyl group, butenyl group, pentenyl group, hexenyl group and (meth) acryl group. The method of claim 1, X ₁ and X ₂ are each independently selected from the group consisting of a linear or branched alkyl group having 1 to 6 carbon atoms, a vinyl group, an allyl group and a metaallyl group, provided that at least one of X ₁ and X ₂ is a vinyl group A catalyst composition for producing a conjugated diene polymer, which is selected from the group consisting of allyl group and metaallyl group. The method of claim 1, The functionalizing agent is a catalyst composition for producing a conjugated diene-based polymer comprising any one or a mixture of two or more selected from the group consisting of a compound of formula 2a to 2n:

In Formulas 2a to 2n, Me is a methyl group, nBu is an n-butyl group, Ph is a phenyl group, TMS is a trimethylsilyl group, and OEt is an ethoxy group. The method of claim 1, The rare earth metal compound is a catalyst composition for producing a conjugated diene-based polymer comprising a neodymium compound of formula (3): [Formula 3]

In Formula 3, R ₁ to R ₃ are each independently a hydrogen atom, or a linear or branched alkyl group having 1 to 12 carbon atoms. The method of claim 6, Wherein the neodymium compound includes a neodymium compound in which Formula ₁ is a linear or branched alkyl group having 6 to 8 carbon atoms, and R ₂ and R ₃ are each independently a linear or branched alkyl group having 2 to 6 carbon atoms. Catalyst composition for producing conjugated diene polymer. The method of claim 1, The neodymium compound may be 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 Ate) 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-no nano-benzoate) _3, Nd (2,2- dibutyl no nano this ) From _3, Nd (2,2- dihexyl no nano-benzoate) _3, Nd (2- ethyl-2-propyl-no nano-benzoate) ₃ and the group consisting of Nd (2- ethyl-2-hexyl-no nano-benzoate) ₃ A catalyst composition for producing a conjugated diene-based polymer comprising any one or a mixture of two or more selected. The method of claim 1, The alkylating agent is a catalyst composition for producing a conjugated diene-based polymer comprising an organoaluminum compound of formula (4): [Formula 4] Al (R) _z (X) _{3 -z} In Chemical Formula 4, Each R independently represents a hydrocarbyl group; Or a heterohydrocarbyl group including at least one hetero atom 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 in a hydrocarbyl group structure, Each X is independently selected from the group consisting of a hydrogen atom, a halogen group, a carboxyl group, an alkoxy group, and an aryloxy group, x is an integer of 1-3. The method of claim 1, A catalyst composition for producing a conjugated diene-based polymer comprising a functionalizing agent in an amount of 20 equivalents or less based on 1 equivalent of the rare earth metal compound. The method of claim 1, A catalyst composition for producing a conjugated diene-based polymer comprising an alkylating agent in an amount of 5 to 200 moles per 1 mole of the rare earth metal compound. The method of claim 1, A catalyst composition for producing a conjugated diene polymer, comprising a halogen compound in an amount of 1 to 20 moles per 1 mole of the rare earth metal compound. The method of claim 1, A catalyst composition for producing a conjugated diene polymer further comprising any one or both selected from the group consisting of diene monomers and aliphatic hydrocarbon solvents. Prepared using the catalyst composition according to claim 1, A conjugated diene polymer having a Mooney viscosity of 10 MU to 90 MU and a polydispersity of 3.4 or less at 100 ° C. The method of claim 14, A conjugated diene-based polymer comprising a functional group derived from a functionalizing agent of formula 1 in a polymer: [Formula 1] (X ₁ ) _a -Sn- (X ₂ ) _4-a In Chemical Formula 1, a is an integer of 1 to 3, X ₁ and X ₂ are each independently selected from the group consisting of a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, -OR _a , -NR _b R _c , -SiR _d R _e R _f and a covalent functional group; At least one of X ₁ and X ₂ includes a covalent functional group, and R _a , R _{b ,} R _c , R _d , R _e and R _f each independently represent a hydrogen atom and 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 aralkyl group having 7 to 20 carbon atoms, -NR'R "and a covalent functional group; , R 'and R "are each independently a hydrogen atom, an alkyl group of 1 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkylaryl group of 7 to 20 carbon atoms, 7 to 20 carbon atoms Aralkyl group and a covalent functional group of The covalent functional group is a functional group including a carbon-carbon double bond. A method for producing a conjugated diene polymer comprising the step of polymerizing a conjugated diene monomer using the catalyst composition according to claim 1. A rubber composition comprising the conjugated diene polymer according to claim 14. Tire parts produced using the rubber composition according to claim 17.

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