KR102019841B1

KR102019841B1 - Method for preparing modified conjugated diene polymer and the modified conjugated diene polymer prepared by same

Info

Publication number: KR102019841B1
Application number: KR1020150184242A
Authority: KR
Inventors: 박현웅; 김동희; 강석연; 안정헌; 김수화; 박수환
Original assignee: 주식회사 엘지화학
Priority date: 2015-12-22
Filing date: 2015-12-22
Publication date: 2019-09-10
Also published as: KR20170074679A

Abstract

The present invention relates to a method for preparing a modified conjugated diene-based polymer and a modified conjugated diene-based polymer prepared thereby, specifically polymerizing the conjugated diene monomer in the presence of a catalyst composition comprising a functionalizing agent to form an active organic metal moiety. Preparing a conjugated diene-based polymer having (step 1); And reacting the conjugated diene-based polymer having the active organometallic portion with a denaturant (step 2).

Description

Method for preparing modified conjugated diene-based polymer and modified conjugated diene-based polymer produced by the present invention TECHNICAL FIELD

The present invention relates to a method for producing a modified conjugated diene-based polymer having improved blendability and physical properties, and a modified conjugated diene-based polymer produced thereby.

Recently, as interest in energy saving and environmental issues increases, automobiles are required to have lower fuel consumption. As one of the methods for realizing this, a method of lowering the heat generation property in a tire by using an inorganic filler such as silica or carbon black in the rubber composition for tire formation has been proposed. However, since the dispersion of the above-mentioned inorganic filler in the rubber composition is not easy, there is a problem in that physical properties of the rubber composition, including wear resistance, crack resistance, or processability, are lowered.

A method for improving the dispersibility of inorganic fillers such as silica and carbon black in the rubber composition by solving such a problem, wherein the functional group capable of interacting the polymerization active site of the conjugated diene-based polymer obtained by anionic polymerization using organic lithium with the inorganic filler A method of metamorphosis was developed. Specifically, a method of modifying the polymerization active terminal of the conjugated diene polymer with a tin compound, introducing an amino group, or modifying with an alkoxysilane derivative has been proposed.

However, even when the rubber composition was prepared using the modified conjugated diene-based polymer modified by the above-described method, the compounding processability could not be sufficiently secured, and there was a problem of showing a high Mooney viscosity. In addition, the initial vulcanization time is also short, there is a problem that the physical properties of the rubber composition is produced or non-uniform.

Japanese Patent Publication No. 1994-057767 (registered on March 3, 1993)

The first problem to be solved by the present invention is a modified conjugated diene system which can improve the initial vulcanization time of the modified conjugated diene-based polymer, improving the processability while maintaining the physical properties of the rubber composition comprising the modified conjugated diene-based polymer It is to provide a method for producing a polymer.

Another object of the present invention is to provide a modified conjugated diene polymer prepared according to the modified conjugated diene polymer production method.

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

That is, according to one embodiment of the present invention, a step of preparing a conjugated diene-based polymer having an active organic metal site by polymerizing the conjugated diene-based monomer in the presence of a catalyst composition comprising a functionalizing agent (step 1); And reacting the conjugated diene-based polymer having the active organometallic portion with a modifier (step 2).

In addition, according to another embodiment of the present invention, there is provided a modified conjugated diene-based polymer prepared according to the method for producing the modified conjugated diene-based polymer.

Furthermore, according to another embodiment of the present invention, there is provided a rubber composition comprising the modified conjugated diene-based polymer and a tire component prepared therefrom.

The rubber composition according to the present invention includes a modified conjugated diene-based polymer prepared using a functionalizing agent, whereby the pattern viscosity of the rubber composition can be reduced to improve workability, and the affinity improves affinity with the filler due to the modifying agent. Physical properties can be improved.

In addition, in the vulcanization reaction of the rubber composition comprising the modified conjugated diene-based polymer, the physical properties of the rubber composition may be uniformly represented by the initial vulcanization reaction at an appropriate rate.

1 is a photograph of visual observation of a rubber specimen prepared according to Example 1, Comparative Example 1.

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 being limited to their ordinary or dictionary meanings, and the inventors may appropriately define the concept of terms in order to best describe their invention. 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, when the catalyst composition for producing a conjugated diene polymer containing a rare earth metal compound, an aluminum compound, and a halogen compound contains diisobutyl aluminum hydride (hereinafter referred to as diisobutyl aluminum hydride (DIBAH)) as the aluminum compound. In order to reduce the possibility of generating various catalytically active species, monomers such as butadiene are included together in a small amount. 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.

denaturalization Conjugated diene system Manufacturing method of polymer

Method for producing a modified conjugated diene polymer according to an embodiment of the present invention, the step of preparing a conjugated diene polymer having an active organic metal site by polymerizing the conjugated diene monomer in the presence of a catalyst composition comprising a functionalizing agent ( Step 1); And reacting the conjugated diene-based polymer having the active organometallic portion with a modifier (step 2).

Hereinafter, a method for preparing a modified conjugated diene polymer according to the present invention will be described in detail for each step.

Step 1: Having an Active Organometallic Site Conjugate Diene Preparation of Polymer

In the method for producing a modified conjugated diene-based polymer according to an embodiment of the present invention, step 1 is a conjugated diene-based polymer having an active organic metal site by polymerizing the conjugated diene monomer in the presence of a catalyst composition comprising a functionalizing agent Manufacturing step.

1. Catalyst Composition

The catalyst composition according to an embodiment of the present invention may include (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

The functionalizing agent according to an embodiment of the present invention is a compound containing 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, allyl group, metaallyl group, or (meth) acrylic group, and reacts with a neodymium compound activated by an alkylating agent in the catalyst composition. In order to stabilize the catalytically active species and increase reactivity, catalytic activity can be improved.

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

[Formula 1]

(X ₁ ) _a -M _1- (X ₂ ) _ma

In Chemical Formula 1,

a is an integer of 0 to 3,

m is the valence number of M ₁ ,

M ₁ is selected from the group consisting of Group 14 elements and Group 15 elements,

X ₁ and X ₂ are each independently selected from the group consisting of a hydrogen atom, an alkyl group, -NR'R ", -SiR'R" R '", a functional group of Formula 2 and a covalent functional group (wherein R' , R ″ and R ′ ″ are each independently selected from the group consisting of a hydrogen atom, an alkyl group and a covalent functional group), provided that at least one of X ₁ and X ₂ comprises a covalent functional group,

[Formula 2]

-[YM _2- (Z) _n-1 ]

In Chemical Formula 2,

n is the valence number of M ₂ ,

M ₂ is selected from the group consisting of Group 14 elements and Group 15 elements,

Y is a hydrocarbylene group unsubstituted or substituted with a covalent functional group,

Z is selected from the group consisting of a hydrogen atom, an alkyl group, -NR'R ", -SiR'R" R '"and a covalent functional group (wherein R', R" and R '"are each independently hydrogen Selected from the group consisting of atoms, alkyl groups and covalent functional groups),

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. Likewise, when ma> 1 in Formula 1, a plurality of X ₂ and a plurality of Z in n-1> 1 in Formula 2 may be the same or different.

Specifically, in Chemical Formulas 1 and 2, 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 having 2 to 12 carbon atoms. And may be more specifically an alkenyl group having 2 to 6 carbon atoms. More specifically, the covalent functional group may be selected from the group consisting of vinyl group, allyl group, metaallyl group, butenyl group, pentenyl group, hexenyl group and (meth) acryl group, and when applied to the catalyst composition, the catalyst Given the significant improvement in activity and polymerization reactivity, the covalent functional group may be an allyl group.

In addition, in Chemical Formulas 1 and 2, M ₁ and M ₂ may be each independently selected from the group consisting of Si, Sn and N. Accordingly, when M ₁ and M ₂ are Si or Sn, the valence number m of M ₁ and the valence number n of M ₂ are 4, respectively, and when M ₁ and M ₂ are N, the valence of M ₁ The number m and the valence number n of M _{2 become} 3, respectively.

In Formula 1, X ₁ and X ₂ are each independently a hydrogen atom, an alkyl group, a vinyl group, an allyl group, a metaallyl group, an alkenyl group, a (meth) acryl group, an amino group (-NH ₂ ), or an alkylamino group. , Allylamino group, alkylallylamino group, silyl group (-SiH ₃ ), alkylsilyl group, dialkylsilyl group, trialkylsilyl group, allylsilyl group, diallyl silyl group, triallyl silyl group, alkyl allyl silyl group, alkyl It may be selected from the group consisting of a diallyl silyl group, a dialkyl allyl silyl group, and a functional group represented by Formula 2, wherein the alkyl group is a linear or branched alkyl group having 1 to 20 carbon atoms, more specifically, 1 to 6 carbon atoms. It may be a straight chain or branched alkyl group. In addition, the alkylene group may be a straight or branched alkylene group having 2 to 20 carbon atoms, more specifically, a straight or branched alkylene group having 2 to 8 carbon atoms.

In Formula 2, Y may specifically be an alkylene group or an alkylene group in which at least one hydrogen atom in a molecule is substituted with a covalent functional group, wherein the covalent functional group is as defined above, and the alkyl The rene group may be an alkylene group having 1 to 20 carbon atoms, more specifically, an alkylene group having 1 to 8 carbon atoms.

In Chemical Formula 2, Z represents a hydrogen atom, an alkyl group, a vinyl group, an allyl group, a metaallyl group, an alkenyl group, a (meth) acryl group, an amino group (-NH ₂ ), an alkylamino group, an allylamino group, and an alkylallylamino group. , Silyl group (-SiH ₃ ), alkylsilyl group, dialkylsilyl group, trialkylsilyl group, allylsilyl group, diallylsilyl group, triallylsilyl group, alkylallylsilyl group, alkyldiallylsilyl group, and di It may be selected from the group consisting of an alkyl allyl silyl group, wherein the alkyl group may be 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. In addition, the alkylene group may be a straight or branched alkylene group having 2 to 20 carbon atoms, more specifically, a straight or branched alkylene group having 2 to 8 carbon atoms.

In the functionalizing agent, its function and improvement effect may vary depending on the type and number of central elements (M ₁ and M ₂ ). Accordingly, the functionalizer is more specifically, a Sn-based compound of Formula 1-1 including Sn as a central element (M ₁ ); Si-based compound of Formula 1-2 including Si as the central element (M ₁ ); N-based compound of formula 1-3 including N as central element (M ₁ ), and two central elements (M ₁ and M ₂ ) connected by an intramolecular bridge group (Y) 4 may be a composite metal compound:

[Formula 1-1]

(X ₁ ) _a -Sn- (X ₂ ) _4-a

[Formula 1-2]

(X ₁ ) _a -Si- (X ₂ ) _4-a

[Formula 1-3]

(X ₁ ) _a -N- (X ₂ ) _3-a

[Formula 1-4]

(X ₁ ) _a -M ₁ -([YM _2- (Z) _n-1 ]) _ma

In Formulas 1-1 to 1-4, a, m, n, M ₁ , M ₂ , X ₁ , X ₂ , Y and Z are as defined above.

As in Chemical Formula 1-1, in the case of the functionalizing agent containing Sn as the central element (M ₁ ), it is possible to improve the processability of the conjugated diene-based polymer.

In addition, as in Chemical Formula 1-2, in the case of a functionalizing agent containing Si as the central element (M ₁ ), it is possible to produce a conjugated diene polymer having a narrow molecular weight distribution.

In addition, as shown in the above formula 1-3, in the case of the functionalizing agent containing N as the central element (M ₁ ), the exothermic rate in the polymerization reactor increases during the polymerization reaction, and as a result it can exhibit better catalytic activity have. In addition, when the N-based functionalizing agent is premixed with a butadiene monomer, the viscosity of the polymerized cement decreases, and a continuous polymerization process is possible.

In addition, as shown in Formula 1-4, when it contains two central elements (M ₁ and M ₂ ) connected by a bridge group (Y) conjugated diene having excellent physical properties to increase the structural stability of the catalytically active species The preparation of polymers is possible.

Even more specifically, the functionalizing agent may be selected from the group consisting of compounds of the general formula 1a to 1w:

In Formulas 1a to 1w, Me means methyl group, nBu means n-butyl group, TMS means trimethylsilyl group, and TES means triethylsilyl group.

The functionalizing agent of Formula 1 may be obtained commercially, or may be prepared and used according to a conventional method. 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

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

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, and the like, oxyhalide (e.g., neodymium oxyfluoride, neodymium oxychloride, or neodymium oxy bromide, etc.), or one or more rare earth metal-carbon bonds 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 below.

[Formula 3]

(In Formula 3, R _{One To} R _{3 Are} each independently a hydrogen atom, or a linear or branched alkyl group having 1 to 12 carbon atoms)

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 minute carbon atom having 2 to 6 carbon atoms. It may be a topographic alkyl group, provided that R ₂ and R ₃ are neodymium compounds which are not hydrogen atoms at the same time.

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, the rare earth metal compound may include Nd (2-ethylhexanoate) ₃ , Nd (2,2-diethyl decanoate) ₃ , Nd (2,2-dipropyl decanoate) ₃ , Nd ( 2,2-dibutyl decanoate) ₃ , Nd (2,2-dihexyl decanoate) ₃ , Nd (2,2-dioctyl decanoate) ₃ , Nd (2-ethyl-2-propyl de Decanoate) ₃ , Nd (2-ethyl-2-butyl decanoate) ₃ , Nd (2-ethyl-2-hexyl decanoate) ₃ , Nd (2-propyl-2-butyl decanoate) ₃ , Nd (2-propyl-2-hexyl decanoate) ₃ , Nd (2-propyl-2-isopropyl decanoate) ₃ , Nd (2-butyl-2-hexyl decanoate) ₃ , Nd (2- Hexyl-2-octyl decanoate) ₃ , Nd (2-t-butyl decanoate) ₃ , Nd (2,2-diethyl octanoate) ₃ , Nd (2,2-dipropyl octanoate) ₃ , Nd (2,2-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- di The nano titeu furnace) _3, Nd (2,2- dipropyl no nano-benzoate) _3, Nd (2,2- dibutyl no nano-benzoate) _3, Nd (2,2- dihexyl no nano-benzoate) _3, Nd (2-ethyl-2-propyl nonanoate) ₃ and Nd (2-ethyl-2-hexyl nonanoate) ₃ or any mixture of two or more. 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 rare earth metal 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

The alkylating agent according to an embodiment of the present invention 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]

AlR _x X _3- _x

(In 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, allyl groups, or alkynyl groups having 2 to 32 carbon atoms; 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 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,

x is an integer from 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 hydrogen; 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 via 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 substituted with a methyl group of methylaluminoxane by a modifier, specifically, a hydrocarbon group having 2 to 20 carbon atoms, and specifically, may be a compound represented by Formula 6 below:

[Formula 6]

(In Chemical Formula 6, R is as defined above, and m and n may each be an integer of 2 or more. Also, in Chemical Formula 2, Me represents a 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 to 90 mole% of the methyl group of methyl aluminoxane as described above. 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]

MgR ₂

(In Formula 7a, R is independently the same as R as previously defined as 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 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 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 the catalyst compositions to form a premixing catalyst, or specifically, a preforming catalyst may be formed by polymerization with an alkylating agent such as DIBAH. 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, 2,4-hexadiene, and the like. One or more than one mixture may be used.

The catalyst composition 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 reactivity can be further improved by the catalytic activity.

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 30 equivalents or less, specifically 20 equivalents or less, of the functionalizing agent based on 1 equivalent of the rare earth metal compound.

In addition, the catalyst composition has an activation effect on the rare earth metal compound when the alkylating agent is 5 to 200 molar ratio with respect to 1 mole of the rare earth metal compound and the content of the alkylating agent is less than 5 molar ratio. Reaction control is not easy, and there exists a possibility that an excess alkylating agent may cause side reaction. More specifically, the catalyst composition may include 5 to 20 molar ratios of the alkylating agent with respect to 1 mole of the rare earth metal compound, and may include 5 to 10 molar ratios in consideration of the remarkable effect of improving workability.

In addition, the catalyst composition may include the halogen compound in an amount of 1 to 20 molar ratio with respect to 1 mole of the rare earth metal compound, and more specifically, may include 2 to 6 molar ratio. 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 comprise 1 to 50 equivalents, more specifically 20 to 35 equivalents of diene monomer relative to 1 equivalent of the rare earth metal compound. It may further include.

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 to 20,000 moles per 1 mole of the rare earth metal compound, and more specifically, in a molar ratio of 100 to 1,000 moles. 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 performed at a temperature range of -30 ° C to 130 ° C, in which case the 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 −20 ° C. to 60 ° C. after mixing a rare earth metal compound, an alkylating agent, a reaction solvent, and optionally a conjugated diene monomer, and the resulting mixture contains a halogen compound. It can be prepared by the second heat treatment in the temperature range of -20 ℃ to 60 ℃ by addition.

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 better polymerization reactivity than the prior art 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.

2. Conjugate Diene polymer

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

In this case, the polymerization may be carried out by bulk polymerization, solution polymerization, suspension polymerization or emulsion polymerization, and may also be carried out 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.

Specifically, when prepared by solution polymerization, the conjugated diene polymer according to one embodiment of the present invention may be carried out by adding a diene monomer to the catalyst composition described above in a polymerization solvent.

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 conjugated diene-based monomer is not used in the total amount of the amount used for preparing the conjugated diene-based polymer in a nonpolar solvent, but a part of the total amount is dissolved in the polymerization solvent and polymerized, and then, once according to the polymerization conversion rate. Above, specifically, two or more times, more specifically, may be divided into 2 to 4 times.

In addition, the polymerization solvent may be a nonpolar solvent, which may be the same as the reaction solvent usable in the preparation of the catalyst composition.

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 agents, chelating agents, dispersants, pH adjusting agents, deoxygenants, and oxygen scavengers, which typically facilitate solution polymerization, may optionally be further used.

In addition, the polymerization may be carried out at a temperature of -30 ℃ to 130 ℃, more specifically 0 ℃ to 100 ℃.

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, step 1 of the modified conjugated diene-based polymer manufacturing method according to an embodiment of the present invention may be used to prepare a conjugated diene-based polymer having high linearity and processability by using a functionalizing agent in the preparation of the catalyst composition. Can be.

Specifically, the conjugated diene-based polymer may include a functional group derived from a functionalizing agent of Formula 1 in a molecule.

[Formula 1]

(X ₁ ) _a -M _1- (X ₂ ) _ma

(In Formula 1,

a is an integer of 0 to 3,

m is the valence number of M ₁ ,

[Formula 2]

-[YM _2- (Z) _n-1 ]

In Chemical Formula 2,

n is the valence number of M ₂ ,

Z is selected from the group consisting of a hydrogen atom, an alkyl group, -NR'R ", -SiR'R" R '"and a covalent functional group (wherein R', R" and R '"are each independently hydrogen Atom, alkyl group and covalent functional group), wherein the covalent functional group is a functional group including a carbon-carbon double bond)

Stage 2: Degeneration Conjugate Diene Preparation of Polymer

In the method of preparing a modified conjugated diene-based polymer according to an embodiment of the present invention, step 2 is a step of reacting the conjugated diene-based polymer having the active organic metal moiety with a modifier.

1. Denaturers

The denaturant according to an embodiment of the present invention is a conjugated diene-based polymer, specifically, in a conjugated diene-based polymer having an active organic metal moiety, to the conjugated diene-based polymer through substitution or addition reaction with the active organometallic moiety. The polymer is modified by imparting functional functionality.

In the present invention, the active site of the conjugated diene polymer may be an active site of the conjugated diene polymer (active site at the molecular chain end), an active site in the main chain or an active site in the side chain. When the active site of the conjugated diene polymer is obtained by polymerization, it may be an active terminal.

For example, the denaturant may be represented by the following Formula 8.

[Formula 8]

(In Formula 8,

Cy is 6 to 6 carbon atoms unsubstituted or substituted with one or more substituents selected from the group consisting of a halogen group, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms. When the aromatic divalent hydrocarbon group is 20, and the substituents are plural, two or more substituents may be linked to each other to form an aliphatic or aromatic ring. More specifically, Cy may be a phenylene group.

In addition, in Formula 8, R ¹ is a heteroalkyl group having 1 to 20 carbon atoms or a heterocycle group having 2 to 20 carbon atoms, specifically selected from the group consisting of N, S and O in a functional group, and more specifically, a carboxylic acid ester. Group, an alkoxy group, an amino group, or an epoxy group, and more specifically, an amino group (-NR ¹¹ R ¹² , wherein R ¹¹ and R ¹² are each independently a hydrocarbon group having 1 to 20 carbon atoms, specifically, 1 to 10 carbon atoms). Linear or branched alkyl group, a cycloalkyl group having 3 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms.

In Formula 8, R ² is an aliphatic monovalent hydrocarbon group having 11 to 30 carbon atoms, specifically, an undecyl group, a dodecyl group, a tridecyl group, and a tetradecyl group. ), Pentadecyl group, hexadecyl group, heptadecyl (heptadecyl), octadecyl group, octadecyl group, nonadecyl (nonadecyl, icosyl group), such as 11 to 20 carbon atoms It may be a linear aliphatic monovalent hydrocarbon group.

More specifically, the denaturing agent may be represented by (E) -4-((dodecylimino) methyl) -N, N-dimethylaniline ((E) -4-((dodecylimino) methyl) -N of Formula 8a, N-dimethylaniline).

[Formula 8a]

The denaturant may be used in a stoichiometric amount or more with respect to the active site of the conjugated diene-based polymer, specifically, the denaturant may be used per mole of neodymium compound used in the preparation of the conjugated diene-based polymer having the active site. It may be used in a 0.1 to 20 molar ratio, more specifically 0.5 to 10 molar ratio.

On the other hand, in the method for producing a modified conjugated diene-based polymer according to an embodiment of the present invention, the modification reaction of step 2 may be carried out by a solution reaction or a solid phase reaction, specifically, by a solution reaction Can be.

In addition, the modification reaction may be performed using a batch reactor, or may be continuously performed using a device such as a multistage continuous reactor or an in-line mixer.

In addition, the modification reaction may be carried out at the same temperature and pressure conditions as the conventional polymerization reaction, specifically, may be carried out at a temperature of 0 ℃ to 100 ℃.

After completion of the above modification reaction, an isopropanol solution of 2,6-di-t-butyl-p-cresol (BHT) or the like can be added to the polymerization reaction system to stop the polymerization reaction. Thereafter, the modified conjugated diene-based polymer may be obtained through desolvent treatment or vacuum drying such as steam stripping to lower the partial pressure of the solvent through supply of steam. In addition, the reaction product obtained as a result of the above-described modification reaction may include a conjugated diene polymer having an active organometallic moiety that is not modified, together with the above-described modified conjugated diene polymer. The content of the conjugated diene-based polymer having an active organometallic moiety included in the reaction product may vary depending on the modification rate of the modified conjugated diene polymer.

Accordingly, the method for preparing a modified conjugated diene-based polymer according to an embodiment of the present invention may further include a precipitation and separation process for the prepared modified conjugated diene-based polymer. Filtration, separation and drying of the precipitated modified conjugated diene-based polymer may be carried out according to a conventional method.

By the method for preparing a modified conjugated diene-based polymer according to an embodiment of the present invention as described above, a modified conjugated diene polymer containing an inorganic filler affinity functional group and a solvent affinity functional group at the same time, having a high modification rate is prepared do. The modified conjugated diene polymer exhibits good affinity for the inorganic filler when applied to the rubber composition, including intramolecular inorganic filler affinity functional groups. As a result, when applied to the rubber composition, it is possible to improve the physical properties and processability of the rubber composition, including wear resistance.

2. Degeneration Conjugate Diene polymer

The modified conjugated diene-based polymer according to an embodiment of the present invention is prepared by modifying the conjugated diene-based polymer having the active organometallic moiety obtained in step 1 with the modifier of the formula (8).

Specifically, since the modified conjugated diene-based polymer is manufactured using a conjugated diene-based polymer polymerized under a catalyst composition including a functionalizing agent, the pattern viscosity of the rubber composition including the modified conjugated diene-based polymer decreases. Processability can be improved.

In addition, since the modified conjugated diene-based polymer is prepared using a modifier, affinity with the filler may be improved, and thus physical properties may be improved.

In addition, the modified conjugated diene-based polymer is modified by using the modifier of the formula (8) comprising an inorganic filler affinity functional group and a solvent-affinity functional group at the same time, the functional group derived from the modifier at the polymerization active terminal of the conjugated diene-based polymer Include.

In the above-described denaturing agent comprising an intramolecular tertiary amino group, an imino group and a linear aliphatic hydrocarbon group, the tertiary amino group improves the affinity with the filler in the rubber composition, and the imino group is used with the conjugated diene polymer terminal. The reaction can be converted to a secondary amino group to further improve affinity with the inorganic filler. In addition, the alkyl group increases the affinity for the polymerization solvent to increase the solubility of the denaturant, as a result can improve the modification rate for the conjugated diene polymer. As such, the denaturant has an optimized structure capable of maximizing affinity for inorganic fillers and solvents, thereby efficiently producing a modified conjugated diene-based polymer that can improve the abrasion resistance, low fuel efficiency and workability of the rubber composition with good balance. can do. In the present invention, the solubility of the denaturant means the degree to which the denaturant is dissolved clearly without turbidity.

Specifically, the modified conjugated diene polymer may have a cis-1,4 bond content of 95% or more, more specifically 98% or more of the conjugated diene portion measured by Fourier Transform Infrared Spectroscopy (FT-IR). As described above, since the cis-1,4 bond content and the vinyl bond content in the 1,3-butadiene monomer unit are higher than those of the conventional butadiene-based polymer, the elongation crystallinity is remarkably high, and as a result, rubber when blended into the rubber composition Abrasion resistance, crack resistance and ozone resistance of the composition can be improved. In addition, the modified conjugated diene-based polymer may have a vinyl content of 5% or less, more specifically 2% or less, as measured by Fourier transform infrared spectroscopy. When the vinyl content in the polymer is greater than 5%, the stretch crystallinity is insufficient, which may deteriorate the wear resistance, crack resistance, and ozone resistance of the rubber composition including the same.

In the present invention, the cis-1,4 bond content and the vinyl content in the polymer by FT-IR are obtained by the bisulfide carbon solution of a conjugated diene-based polymer prepared at a concentration of 5 mg / mL by blanking carbon disulfide in the same cell. After measuring the FT-IR transmittance spectrum, the maximum peak value (a, baseline) around 1130 cm ⁻¹ of the measurement spectrum, the minimum peak value (b) near 967 cm ⁻¹ indicating trans-1,4 binding, and vinyl bond Each content was determined using a minimum peak value (c) near 911 cm ⁻¹ , and a minimum peak value d near 736 cm ⁻¹ representing a cis-1,4 bond.

In addition, the modified conjugated diene-based polymer may have a molecular weight distribution (MWD) of 2.5 to 3.5, specifically, a molecular weight distribution of 2.8 to 3.2 by the specific production method. When the molecular weight distribution of the modified conjugated diene-based polymer is less than 2.5, the workability of the rubber composition including the diene-based polymer is deteriorated, so that kneading is difficult, so that the physical properties of the rubber composition are not sufficiently improved, and the molecular weight distribution of the modified conjugated diene-based polymer is When it exceeds 3.5, there is a possibility that physical properties such as hysteresis loss of the rubber composition are lowered.

In the present invention, the molecular weight distribution (MWD) is characterized by the ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn), also called polydispersity. The number average molecular weight is a common average of individual polymer molecular weights calculated by measuring the molecular weights of n polymer molecules, calculating the sum of these molecular weights, and dividing by n. The weight average molecular weight describes the molecular weight distribution of the polymer composition and can be calculated according to the following formula (1).

[Equation 1]

In Formula 1, N _i is the number of molecules having a molecular weight M _i . All molecular weight averages can be expressed in grams per mole (g / mol).

In addition, the modified conjugated diene-based polymer has a weight average molecular weight (Mw) of 5X10 ⁵ g / mol to 1.2X10 ⁶ g / mol, more specifically 6X10 ⁵ g / mol to 1.0X10 under conditions that satisfy the above molecular weight distribution. specifically, ⁶ g / mol, more addition number-average molecular weight (Mn) of 1.5X10 ⁵ g / mol to about 4.5X10 ⁵ g / mol, it may be one of 2.0X10 ⁵ g / mol to about 3.2X10 ⁵ g / mol.

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 . If the weight average molecular weight of the butadiene-based polymer is less than 500,000 g / mol or the number average molecular weight is less than 150,000 g / mol, the elastic modulus of the vulcanizate is lowered, which not only increases hysteresis loss but also deteriorates wear resistance. When the amount exceeds 1,200,000 g / mol or the number average molecular weight exceeds 450,000 g / mol, the workability of the rubber composition containing the modified conjugated diene-based polymer deteriorates and kneading becomes difficult, resulting in physical properties of the rubber composition. Not enough to improve

In addition, the modified conjugated diene-based polymer may have a Mooney viscosity (MV) at 100 ℃ 40 to 70, more specifically 45 to 65. For polymers of the same structure, the solution viscosity increases proportionally as the Mooney viscosity increases. That is, as the solution viscosity or the Mooney viscosity increases, the branching degree in the conjugated diene polymer is increased.

According to one embodiment of the present invention, the Mooney viscosity may be measured using Rotor Speed 2 ± 0.02rpm, Large Rotor at 100 ° C. with Monsanto MV2000E, for example. The sample used at this time can be measured by leaving the platen operating after placing 27 ± 3g in the die cavity after leaving at room temperature (23 ± 3 ℃) for more than 30 minutes.

Polymer Compositions and Rubber Compositions

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

Specifically, the polymer composition may be a conjugated diene-based polymer having an active organometallic moiety obtained by polymerizing a conjugated diene-based monomer using a catalyst composition, and a conjugated diene-based polymer having the active organometallic moiety as a modifier of Formula 8. It includes a modified conjugated diene-based polymer prepared by modification.

More specifically, the polymer composition may comprise a conjugated diene-based polymer having the active organometallic portion and the modified conjugated diene-based polymer in a weight ratio of 0.01: 99.99 to 90:10, and more specifically, in a weight ratio of 10:90 to 40:60. It may include.

The conjugated diene-based polymer having the active organometallic moiety is prepared using a catalyst composition including a functionalizing agent, and may include a functional group derived from the functionalizing agent in the polymer.

In addition, the modified conjugated diene-based polymer is the same as described above.

The polymer composition may be prepared by mixing the conjugated diene-based polymer having the active organometallic moiety and the modified conjugated diene-based polymer, or obtained as a result of the modification reaction in the preparation of the modified conjugated diene-based polymer. May be a reaction product. When the polymer composition is a reaction product obtained as a result of the modification reaction, the content ratio of the conjugated diene-based polymer having the active organic metal moiety included in the reaction product to the modified conjugated diene-based polymer is a modification rate of the modified conjugated diene polymer. The modification rate may be variously changed by appropriately controlling the modification process conditions for the conjugated diene-based polymer having the active organometallic site and the process for producing the conjugated diene-based polymer having the active organometallic moiety.

By simultaneously including the conjugated diene-based polymer having the active organometallic portion and the modified conjugated diene-based polymer as described above, the physical properties of the rubber composition such as wear resistance and processability can be more easily controlled according to its use, and as a result Rubber compositions and molded articles having excellent physical properties can be prepared.

On the other hand, the rubber composition according to another embodiment of the present invention includes the modified conjugated diene-based polymer.

Specifically, the rubber composition may include 10% by weight or more, more specifically 10 to 100% by weight of the modified conjugated diene-based polymer. When the content of the modified 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.

The rubber composition may further include a conjugated diene polymer having the active organometallic portion together with the modified conjugated diene polymer. At this time, the conjugated diene polymer having the active organometallic moiety is the same as described in the polymer composition.

In addition, the rubber composition may further include a rubber component in an amount of 90% by weight or less based on the total weight of the rubber composition together with the modified conjugated diene-based polymer. More specifically, the rubber component may further include 1 to 900 parts by weight based on 100 parts by weight of the modified conjugated diene-based polymer.

In addition, the rubber component may be natural rubber or synthetic rubber, and specifically, the rubber component may include natural rubber (NR) including cis-1,4-polyisoprene; Modified natural rubbers such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber obtained by modifying or refining the general natural rubber; Styrene-butadiene copolymer (SBR), polybutadiene (BR), polyisoprene (IR), butyl rubber (IIR), ethylene-propylene copolymer, polyisobutylene-co-isoprene, neoprene, poly (ethylene-co- Propylene), poly (styrene-co-butadiene), poly (styrene-co-isoprene), poly (styrene-co-isoprene-co-butadiene), poly (isoprene-co-butadiene), poly (ethylene-co-propylene Co-diene), polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, butyl rubber, halogenated butyl rubber, etc., and any one or a mixture of two or more thereof may be used. have.

The rubber composition may further include 10 parts by weight or more, more specifically 10 to 120 parts by weight of a filler, based on 100 parts by weight of the modified conjugated diene polymer. If the content of the filler is 10 parts by weight or more, the effect of improving reinforcement and other physical properties is sufficiently exhibited. If the content of the filler is 100 parts by weight or less, workability and the like are good. In addition, considering the improved effects such as reinforcement and processability, the content of the filler may be 20 to 80 parts by weight.

In addition, the filler may be specifically carbon black or silica, and any one or a mixture of two or more thereof may be used. More specifically, the filler may be carbon black.

In the filler, the carbon black is not particularly limited. Specifically, the carbon black has a nitrogen adsorption specific surface area (measured based on N 2 SA, JIS K 6217-2: 2001) of 20 to 250 m 2 / g. It may be. In addition, the carbon black may have a dibutyl phthalate oil absorption (DBP) of 80cc / 100g to 200cc / 100g. When the nitrogen adsorption specific surface area of the carbon black exceeds 250 m ² / g, the workability of the rubber composition for tires may be deteriorated, and when it is less than 20 m ² / g, the reinforcing performance by the carbon black as a filler may be deteriorated. In addition, when the DBP oil absorption of the carbon black exceeds 200cc / 100g, the workability of the rubber composition may be lowered. If the DBP oil absorption of the carbon black is less than 80cc / 100g, the reinforcing performance by the carbon black as a filler may be disadvantageous.

In addition, the silica may be specifically wet silica (silicate silicate), dry silica (silicate anhydrous), calcium silicate, aluminum silicate or colloidal silica. More specifically, the filler may be a wet silica having the most remarkable effect of improving the breaking property and wet grip.

In addition, the silica may have a nitrogen adsorption specific surface area (N 2 SA) of 120 to 180 m 2 / g and a CTAB (cetyl trimethyl ammonium bromide) adsorption specific surface area of 100 to 200 m 2 / g. When the nitrogen adsorption specific surface area of the silica is less than 120 m 2 / g, the reinforcing performance by silica as a filler may be deteriorated. When the nitrogen adsorption specific surface area is more than 180 m 2 / g, the workability of the rubber composition may be deteriorated. In addition, when the CTAB adsorption specific surface area of the silica is less than 100 m 2 / g, the reinforcing performance by silica, which is a filler, may be deteriorated, and when it exceeds 200 m 2 / g, the workability of the rubber composition may be deteriorated.

In addition, the rubber composition may include an inorganic filler of at least one metal, metal oxide or metal hydroxide selected from aluminum, magnesium, titanium, calcium and zirconium. More specifically, the inorganic filler is γ-alumina, α-alumina, alumina-hydrate (Al ₂ O ₃ · H ₂ 0), aluminum hydroxide [Al (OH) ₃ ], aluminum carbonate [Al ₂ (CO ₃ ) ₂ ], Magnesium hydroxide [Mg (OH) ₂ ], magnesium oxide (MgO), magnesium carbonate (MgCO 3), talc (3MgO.4SiO ₂ .H ₂ O), attapalzite (5Mg0.8SiO ₂ .9H ₂ O), Titanium bag (TiO ₂ ), titanium black, calcium oxide (CaO), calcium hydroxide [Ca (OH) ₂ ], aluminum magnesium oxide (Mg0Al ₂ O ₃ ), clay (Al ₂ O ₃ · 2SiO ₂ ), kaolin ( Al ₂ O ₃ · 2Si0 ₂ · 2H ₂ O), pyrophyllite (Al ₂ O ₃ · 4Si0 ₂ · H ₂ O), bentonite (Al ₂ O ₃ · 4Si0 ₂ · 2H ₂ O), aluminum silicate (Al ₂ SiO ₅ , Al ₄ · ₃ SiO ₄ · 5H ₂ O, etc.), magnesium silicate (Mg ₂ SiO ₄ , MgSiO ₃ Etc.), calcium silicate (such as Ca ₂ · SiO ₄ ), magnesium silicate (Al ₂ O ₃ · CaO · 2SiO _2, etc.), magnesium calcium silicate (CaMgSiO ₄ ), calcium carbonate (CaCO ₃ ), zirconium oxide (ZrO ₂ ), Zirconium hydroxide [ZrO (OH) ₂ nH ₂ O], zirconium carbonate [Zr (CO ₃ ) ₂ ], or crystalline aluminosilicate and the like, and any one or a mixture of two or more thereof may be used.

In addition, when the carbon black and the inorganic filler are mixed and used, the mixing weight ratio may be 95: 5 to 5:95 when considering the improvement effect on the performance.

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

Specific examples of the silane coupling agent include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis (3-triethoxysilylpropyl) disulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane , 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasul Feed, 3-triethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilyl Propylbenzothiazolyl tetrasulfide, 3-triethoxysilylpropylbenzolyl tetrasulfide, 3-triethoxysilylpropyl methacrylate Monosulfide, 3-trimethoxysilylpropylmethacrylate monosulfide, bis (3-diethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, dimethoxymethylsilylpropylbenzothiazolyl tetrasulfide, and the like, and any one or a mixture of two or more thereof may be used. More specifically, in consideration of the reinforcing improvement effect, the silane coupling agent may be bis (3-triethoxysilylpropyl) polysulfide or 3-trimethoxysilylpropylbenzothiazyl tetrasulfide.

In the rubber composition according to one embodiment of the present invention, since a modified polymer having a high affinity with silica is introduced into the molecular active site as a rubber component, the compounding amount of the silane coupling agent is usually used. Can be further reduced. Specifically, the silane coupling agent may be used in 1 to 20 parts by weight based on 100 parts by weight of silica. When used in the above range, the gelation of the rubber component can be prevented while the effect as a coupling agent is sufficiently exhibited. More specifically, the silane coupling agent may be used in 5 to 15 parts by weight based on 100 parts by weight of silica.

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

The vulcanizing agent may be specifically sulfur powder.

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

In addition, the rubber composition according to an embodiment of the present invention, in addition to the components described above, various additives commonly used in the rubber industry, specifically, vulcanization accelerators, process oils, plasticizers, anti-aging agents, anti-scoring agents, zinc white (zinc white) ), Stearic acid, a thermosetting resin, or a thermoplastic resin may be further included.

The said vulcanization accelerator is not specifically limited, Specifically, M (2-mercapto benzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2- benzothiazyl sulfenamide), etc. Thiazole compounds, or guanidine compounds such as DPG (diphenylguanidine) can be used. The vulcanization accelerator may be included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the rubber component.

In addition, the process oil acts as a softener in the rubber composition, specifically, may be a paraffinic, naphthenic, or aromatic compound, and more specifically, aromatic process oil, hysteresis loss in consideration of tensile strength and wear resistance. And naphthenic or paraffinic process oils may be used when considering low temperature properties. The process oil may be included in an amount of 100 parts by weight or less with respect to 100 parts by weight of the rubber component, when included in the content, it is possible to prevent the degradation of the tensile strength, low heat generation (low fuel consumption) of the vulcanized rubber.

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

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

Accordingly, the rubber composition may be used for tire members such as tire treads, under treads, sidewalls, carcass coated rubbers, belt coated rubbers, bead fillers, pancreapers, or bead coated rubbers, dustproof rubbers, belt conveyors, hoses, and the like. Useful for the production of various industrial rubber products.

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.

< Example 1> denaturation Conjugate Diene Preparation of Polymer

In hexane solvent, Nd (2,2-diethyl decanoate) ₃ The neodymium compound and the functionalizing agent (MAA, neodymium compound 1 equivalent standard equivalent) of the formula 1c are added, and then diisobutylaluminum hydride (DIBAH) and diethylaluminum chloride (DEAC) are added to the neodymium compound: DIBAH: DEAC The catalyst composition was prepared by sequentially adding a molar ratio of = 1: 10: 2.4 and then mixing.

After vacuum and nitrogen were alternately added to the completely dried organic reactor, 4.7 kg of a 1,3-butanediene / hexane mixed solution was added to the reactor in a vacuum state, and the catalyst composition prepared above was added, followed by 60 at 70 ° C. The butadiene polymer was prepared by performing a polymerization reaction for a minute.

[Formula 1c]

Stage 2: Degeneration Conjugate Diene Preparation of Polymer

(E) -4-((dodecylimino) methyl) -N, N-dimethylaniline ((E) -4-((dodecylimino) methyl) -N of Formula 8a to the polymerization solution containing the butadiene polymer , N-dimethylaniline) was added to the nucleic acid solution containing 1.4mmol denaturant and denatured at 70 ℃ for 30 minutes. After addition of a hexane solution containing 1.0 g of a polymerization terminator and a nucleic acid solution containing 1.0 g of an antioxidant, a modified butadiene polymer was prepared by precipitating and separating the resultant reaction product.

[Formula 8a]

Comparative Example 1 No Functional Vaporizers Added

In hexane solvent, Nd (2,2-diethyl decanoate) ₃ The neodymium compound, diisobutylaluminum hydride (DIBAH), and diethylaluminum chloride (DEAC) were sequentially added in a molar ratio of neodymium compound: DIBAH: DEAC = 1: 10.1: 2.4, followed by mixing to prepare a catalyst composition.

Except for using the catalyst composition, a modified butadiene polymer was prepared in the same manner as in Example 1.

<Comparative Example 2> Addition of functionalizing agent and denaturing agent

< Experimental Example 1>

Using the modified butadiene polymer prepared in Example 1 and Comparative Example 1 and the butadiene polymer of Comparative Example 2 to prepare a polymer composition and a rubber composition, the Mooney viscosity (ML1 + 4) change was observed.

Specifically, a polymer composition prepared only of the polymer and a rubber composition as described below were prepared.

60 parts by weight of carbon black, 15 parts by weight of process oil, and zinc oxide (ZnO) based on 100 parts by weight of the modified butadiene polymer prepared in Example 1 and Comparative Example 1 or the butadiene polymer of Comparative Example 2 as raw material rubber Each rubber composition was prepared by combining 3 parts by weight and 2 parts by weight of stearic acid, and 1.5 parts by weight of sulfur and 0.9 parts by weight of vulcanization accelerator (TBBS).

For each of the polymer compositions and rubber compositions of Example 1, Comparative Examples 1 and 2, the Mooney viscosity (ML1 + 4) was measured using a Rotor Speed 2 ± 0.02 rpm, Large Rotor at 100 ° C. with Monsanto MV2000E. At this time, the sample used was allowed to stand at room temperature (23 ± 3 ℃) for 30 minutes or more and collected 27 ± 3g and filled in the die cavity and measured by operating the platen (Platen). The results are shown in Table 1.

In addition, the rubber composition using a Rotor Speed 2 ± 0.02 rpm, Large Rotor at 125 ° C with Monsanto MV2000E, the initial vulcanization time (scorch time, t5) was measured, and the results are shown in Table 1. At this time, the sample used was allowed to stand at room temperature (23 ± 3 ℃) for 30 minutes or more and collected 27 ± 3g was filled inside the die cavity and measured by operating the platen (Platen).

In this case, the initial vulcanization time, when measuring for 60 minutes at 125 ℃ using the Mooney viscometer, means the time required until the measured torque value "minimum torque value + 5 point" (t5).

Mooney viscosity (Mu) Of rubber composition
Initial Vulcanization Time (Min) Example 1 Polymer composition 43 30 Rubber composition 65 (Δ22) Comparative Example 1 Polymer composition 45 20 Rubber composition 77 (Δ32) Comparative Example 2 Polymer composition 45 40 Rubber composition 57 (Δ12)

As shown in Table 1, the variation in Mooney viscosity was 51% in Example 1, 71% in Comparative Example 1, and 26% in Comparative Example 2, and Mooney viscosity increased most in Comparative Example 1. It can be seen that it has the highest Mooney viscosity value. On the other hand, in the case of Comparative Example 2, the Mooney viscosity is the smallest increase to 26%, thereby showing the lowest Mooney viscosity.

Accordingly, since the rubber composition of Example 1 prepared according to the present invention exhibits an appropriate level of Mooney viscosity of 22 Mu, which is excellent in processability, it is possible to increase the physical properties of the rubber specimen prepared through excellent mixing with the filler. can do.

In addition, in the case of Comparative Example 1, the initial vulcanization time takes 20 minutes, it can be seen that Example 1 takes 30 minutes, Comparative Example 2 takes 40 minutes. Accordingly, in the case of a rubber composition using a modified butadiene polymer prepared by using a functionalizing agent and a modifying agent together as in the present invention, since the vulcanization reaction time is controlled to an appropriate time of 30 extra, excessively fast initial as in Comparative Example 1 Due to the vulcanization reaction time, it is possible to solve the problem of exhibiting uneven physical properties or inferior in process due to too long initial vulcanization rate as in Comparative Example 2.

Experimental Example 2

Using the butadiene polymer prepared in Example 1 and Comparative Examples 1, 2 was carried out in the same manner as in Experimental Example 1 to prepare a rubber composition.

The rubber composition was vulcanized in the form of a plate to prepare a rubber specimen. The hardness, 300% modulus, tensile strength, and elongation rate of the rubber specimen were measured in the following manner at a temperature of 23 ° C. Shown in

1) Hardness-The sheet prepared by the above method is placed on a Shore-A Hardness Tester of Cogenix, and Shore-A hardness after 5 seconds is measured.

2) Tensile strength-After the specimen is manufactured using ASTM D412 fixture, it is left at 23 ℃ for 24 hours and then experimented at 500 mm / min using INSTRON's 4465 Model (ASTM D638)

3) Elongation-After the specimen was prepared using ASTM D412 fixture, it was left at 23 ° C for 24 hours and then experimented at 500 mm / min using INSTRON's 4465 Model (ASTM D638).

Hardness (shore A) 300% modulus (kgf / cm ² ) Tensile strength (kgf / cm ² ) % Elongation Example 1 61 106 168 411 Comparative Example 1 61 101 165 416 Comparative Example 2 61 101 148 387

As shown in Table 2, in the case of Example 1 it can be seen that the hardness, 300% modulus, tensile strength and elongation properties are all excellent.

Specifically, the 300% modulus, tensile strength and elongation characteristics, it is shown that Example 1 is up to 5%, 13.5%, 6.2% increase compared to Comparative Example 2, Example 1 and Comparative Example 1 is shown to be at a similar level Can be.

Experimental Example 3

The rubber composition was vulcanized in a plate-like form for cylinder type, viscoelastic properties, and surface observation for observing wear characteristics, and rubber specimens were prepared. The wear properties, viscoelasticity, and processability of the rubber specimens were measured in the following manner, 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. In the torsion mode, the strain was changed at a frequency of 10 Hz and each measurement temperature (-70 to 70 ° C.) to measure the Tan δ value. The higher the low temperature 0 [deg.] C. Tan δ value, the better the wet road resistance. The lower the high temperature 50 to 70 [deg.] C. tan value, the lower the hysteresis loss, and the lower rolling resistance of the tire, that is, the lower fuel efficiency.

Volume loss index Tan δ Example 1 109 0.128 Comparative Example 1 110 0.128 Comparative Example 2 100 0.141

As shown in Table 3, it can be seen that both the wear characteristics and the viscoelastic properties of Example 1 are excellent.

Specifically, the wear characteristics of Example 1 are 9%, viscoelastic properties are 9% improved compared to Comparative Example 2, it can be seen that Example 1 and Comparative Example 1 are shown at a similar level. Through this, it can be seen that not only the tensile strength characteristics of the rubber specimens shown in Experimental Example 2, but also the wear characteristics and the viscoelastic characteristics were maintained at a similar level in Example 1 and Comparative Example 1.

< Experimental Example 4>

Using the butadiene polymer prepared in Example 1 and Comparative Example 1 was carried out in the same manner as in Experimental Example 1 to prepare a rubber composition. The rubber composition was mixed in an internal mixer according to ASTM D3189, and molded into a plate shape having a thickness of 2 mm and a width of 150 mm, and then visually observed to be formed into the plate shape. Table 4 shows.

Surface roughness Polish Continuity of sheet edge Example 1 100 100 100 Comparative Example 1 82 79 65

In the above table, the numerical value for Example 1 is assumed to be 100, and the relative value of Comparative Example 1 with respect to Example 1 is shown.

As can be seen in Figure 1 and Table 4, it can be seen that in Example 1 is superior to Comparative Example 1 in the surface roughness, gloss, the degree of continuity of the sheet edge. Specifically, Example 1 is 21% superior to Comparative Example 1 in terms of surface roughness characteristics, Example 1 is 26.5% superior to Comparative Example 1 in case of gloss, and Example 1 is comparative example in case of sheet edges. It can be seen that 53.8% is higher than 1.

Through this, it can be seen that the blendability of the rubber composition of Example 1 is superior to the blendability of the rubber composition of Comparative Example 1.

As a result, in the case of using the modified conjugated diene-based polymer prepared using the functionalizing agent and the modifying agent of the present invention through Experimental Examples 1 to 4, while the processability of the rubber composition is improved, the rubber prepared from the rubber composition It can be seen that the specimen is maintained at excellent levels of physical properties.

Claims

Polymerizing the conjugated diene monomer in the presence of a catalyst composition comprising a functionalizing agent to prepare a conjugated diene polymer having an active organometallic moiety (step 1); And
Reacting the conjugated diene-based polymer having the active organometallic moiety with a modifier (step 2);
The functionalizing agent is represented by the following formula (1), a method for producing a modified conjugated diene polymer.
[Formula 1]
(X ₁ ) _a -M _1- (X ₂ ) _ma
(In Formula 1,
a is an integer of 0 to 3,
m is the valence number of M ₁ ,
M ₁ is selected from the group consisting of Group 14 elements and Group 15 elements,
X ₁ and X ₂ are each independently selected from the group consisting of a hydrogen atom, an alkyl group, -NR'R ", -SiR'R" R '", a functional group of Formula 2 and a covalent functional group (wherein R' , R ″ and R ′ ″ are each independently selected from the group consisting of a hydrogen atom, an alkyl group and a covalent functional group), provided that at least one of X ₁ and X ₂ comprises a covalent functional group,
[Formula 2]
-[YM _2- (Z) _n-1 ]
In Chemical Formula 2,
n is the valence number of M ₂ ,
M ₂ is selected from the group consisting of Group 14 elements and Group 15 elements,
Y is a C2-C20 alkylene group substituted with a C2-C20 alkylene group or a covalent functional group,
Z is selected from the group consisting of a hydrogen atom, an alkyl group, -NR'R ", -SiR'R" R '"and a covalent functional group (wherein R', R" and R '"are each independently hydrogen Selected from the group consisting of an atom, an alkyl group, and a covalent functional group), wherein the covalent functional group is a functional group including a carbon-carbon double bond.

delete

The method of claim 1,
The covalent functional group is a method for producing a modified conjugated diene polymer that is selected from the group consisting of alkenyl group and (meth) acryl group having 2 to 20 carbon atoms.

The method of claim 1,
The covalently bonded functional group is selected from the group consisting of vinyl group, allyl group, metaallyl group, butenyl group, pentenyl group, hexenyl group and (meth) acryl group.

The method of claim 1,
The M ₁ and M ₂ are each independently selected from the group consisting of Si, Sn and N method of producing a modified conjugated diene polymer.

delete

The method of claim 1,
The functionalizing agent is a method for producing a modified conjugated diene-based polymer comprising any one or two or more compounds selected from the group consisting of compounds of the formula 1-1 to 1-4.
[Formula 1-1]
(X ₁ ) _a -Sn- (X ₂ ) _4-a
[Formula 1-2]
(X ₁ ) _a -Si- (X ₂ ) _4-a
[Formula 1-3]
(X ₁ ) _a -N- (X ₂ ) _3-a
[Formula 1-4]
(X ₁ ) _a -M ₁ -([YM _2- (Z) _n-1 ]) _ma
(In Chemical Formulas 1-1 to 1-4,
a is an integer of 0 to 3,
m is the valence number of M ₁ , n is the valence number of M ₂ ,
M ₁ and M ₂ are each independently selected from the group consisting of Group 14 elements and Group 15 elements,
X ₁ and X ₂ are each independently selected from the group consisting of a hydrogen atom, an alkyl group, -NR'R ", -SiR'R" R '", and a covalent functional group (wherein R', R" and R '"Are each independently selected from the group consisting of a hydrogen atom, an alkyl group and a covalent functional group), provided that at least one of X ₁ and X ₂ comprises a covalent functional group, and said covalent functional group is carbon-carbon Functional group containing hepatic double bonds)

The method of claim 1,
The functionalizing agent is a method for producing a modified conjugated diene-based polymer comprising any one or a mixture of two or more selected from the group consisting of a compound of formula 1a to 1w.

(In Formulas 1a to 1w, Me means methyl group, nBu means n-butyl group, TMS means trimethylsilyl group, and TES means triethylsilyl group.)

The method of claim 1,
The catalyst composition is a method for producing a modified conjugated diene polymer, characterized in that it further comprises one or more selected from the group consisting of a rare earth metal compound, an alkylating agent, and a halogen compound.

The method of claim 9,
The rare earth metal compound is a compound containing one or two or more rare earth metals selected from the group consisting of neodymium, lanthanum and gadolidone, a modified conjugated diene-based polymer manufacturing method.

The method of claim 9,
The rare earth metal compound is a carboxylate, organophosphate, phosphate, organic phosphonate, phosphonate, organic phosphinate, carbamate, dithiocarbamate, xanthogenate, β containing a rare earth metal -Diketonates, alkoxides, allyl oxides, halides, pseudo halides, oxyhalides and any one or two or more mixtures selected from the group consisting of organic rare earth metal compounds comprising at least one rare earth metal-carbon bond Method for producing a modified conjugated diene polymer.

The method of claim 9,
The rare earth metal compound is a method for producing a modified conjugated diene-based polymer comprising a neodymium compound of formula (3).
[Formula 3]

The method of claim 12,
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 alkyl group having 2 to 6 carbon atoms, Provided that the R ₂ and R ₃ simultaneously contain neodymium compounds which are not hydrogen atoms.

The method of claim 9,
The rare earth metal compound is Nd (2-ethylhexanoate) ₃ , Nd (2,2-diethyl decanoate) ₃ , Nd (2,2-dipropyl decanoate) ₃ , Nd (2,2- Dibutyl decanoate) ₃ , Nd (2,2-dihexyl decanoate) ₃ , Nd (2,2-dioctyl decanoate) ₃ , Nd (2-ethyl-2-propyl decanoate) ₃ , Nd (2-ethyl-2-butyl decanoate) ₃ , Nd (2-ethyl-2-hexyl decanoate) ₃ , Nd (2-propyl-2-butyl decanoate) ₃ , Nd (2- Propyl-2-hexyl decanoate) ₃ , Nd (2-propyl-2-isopropyl decanoate) ₃ , Nd (2-butyl-2-hexyl decanoate) ₃ , Nd (2-hexyl-2- Octyl decanoate) ₃ , Nd (2-t-butyl 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- A process for producing a modified conjugated diene-based polymer comprising one or a mixture of two or more selected from the group consisting of propyl nonanoate) ₃ and Nd (2-ethyl-2-hexyl nonanoate) ₃ .

The method of claim 9,
The alkylating agent may be an organometallic compound comprising a bond between a cationic metal and carbon selected from the group consisting of Group 1, Group 2 and Group 3 metals; Boron-containing compounds; Or a method for producing a modified conjugated diene polymer comprising a mixture thereof.

The method of claim 9,
The alkylating agent is a method for producing a modified conjugated diene-based polymer comprising an organoaluminum compound of formula (4).
[Formula 4]
AlR _x X _3- _x
(In 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, and x is an integer of 1 to 3)

The method of claim 9,
The alkylating agent is a method for producing a modified conjugated diene-based polymer comprising any one or a mixture of two or more selected from the group consisting of aluminoxane and modified aluminoxane.

The method of claim 9,
The halogen compound is a modified conjugated diene-based polymer prepared by any one or two or more selected from the group consisting of a halogen group, an interhalogen compound, hydrogen halide, organic halides, base metal halides, metal halides and organometallic halides Way.

The method of claim 9,
A method for producing a modified conjugated diene-based polymer comprising a functionalizing agent in an amount of 30 equivalents or less with respect to 1 equivalent of the rare earth metal compound.

The method of claim 9,
A method for producing a modified 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 9,
A method for producing a modified conjugated diene-based polymer comprising a halogen compound in an amount of 1 to 20 moles with respect to 1 mole of the rare earth metal compound.

The method of claim 9,
The catalyst composition is a method for producing a modified conjugated diene polymer further comprises any one or both selected from the group consisting of a diene monomer and a reaction solvent.

The method of claim 22,
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 Any one or more selected from the group consisting of -methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, and 2,4-hexadiene Method for producing a modified conjugated diene-based polymer comprising a.

The method of claim 22,
The reaction solvent is a method for producing a modified conjugated diene-based polymer comprising any one or a mixture of two or more selected from the group consisting of linear, branched or cyclic aliphatic hydrocarbon having 5 to 20 carbon atoms.

The method of claim 1,
The modifying agent is a method for producing a modified conjugated diene polymer, characterized in that represented by the following formula (8).
[Formula 8]

(In Formula 8, Cy is substituted with one or more substituents selected from the group consisting of a halogen group, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms, or Unsubstituted aromatic divalent hydrocarbon group having 6 to 20 carbon atoms, R ¹ is a functional group containing at least one hetero atom selected from the group consisting of N, S and O, and R ² is an aliphatic carbon having 11 to 30 Monovalent hydrocarbon group)

The method of claim 25,
In Formula 8, Cy is a phenylene group, R ¹ is —NR ¹¹ R ¹² , wherein R ¹¹ and R ¹² are each independently a hydrocarbon group having 1 to 20 carbon atoms, and R ² is a linear having 11 to 20 carbon atoms. A method for producing a modified conjugated diene polymer which is an aliphatic monovalent hydrocarbon group.

The method of claim 1,
The denaturing agent is (E) -4-((dodecylimino) methyl) -N, N-dimethylaniline ((E) -4-((dodecylimino) methyl) -N, N-dimethylaniline) Method of Making Polymers.

The method of claim 1,
After performing the step 1, a modified conjugated diene-based polymer manufacturing method comprising a functional group derived from the functionalizing agent of formula 1 in the conjugated diene-based polymer.
[Formula 1]
(X ₁ ) _a -M _1- (X ₂ ) _ma
(In Formula 1,
a is an integer of 0 to 3,
m is the valence number of M ₁ ,
M ₁ is selected from the group consisting of Group 14 elements and Group 15 elements,
X ₁ and X ₂ are each independently selected from the group consisting of a hydrogen atom, an alkyl group, -NR'R ", -SiR'R" R '", a functional group of Formula 2 and a covalent functional group (wherein R' , R ″ and R ′ ″ are each independently selected from the group consisting of a hydrogen atom, an alkyl group and a covalent functional group), provided that at least one of X ₁ and X ₂ comprises a covalent functional group,
[Formula 2]
-[YM _2- (Z) _n-1 ]
In Chemical Formula 2,
n is the valence number of M ₂ ,
M ₂ is selected from the group consisting of Group 14 elements and Group 15 elements,
Y is a hydrocarbylene group unsubstituted or substituted with a covalent functional group,
Z is selected from the group consisting of a hydrogen atom, an alkyl group, -NR'R ", -SiR'R" R '"and a covalent functional group (wherein R', R" and R '"are each independently hydrogen Atom, alkyl group and covalent functional group), wherein the covalent functional group is a functional group including a carbon-carbon double bond)

A modified conjugated diene-based polymer prepared according to the method for producing a modified conjugated diene-based polymer according to any one of claims 1, 3 to 5, and 7 to 28.

A rubber composition comprising the modified conjugated diene-based polymer according to claim 29.

The method of claim 30,
Based on 100 parts by weight of the modified conjugated diene polymer,
A rubber composition further comprising 1 to 900 parts by weight of the rubber component and 10 to 120 parts by weight of the filler.

The method of claim 31, wherein
Wherein said filler is carbon black.

The method of claim 30,
A rubber composition that is sulfur crosslinkable.

Tire parts produced using the rubber composition according to claim 30.