阅读说明：本技术 改性共轭二烯类聚合物 (Modified conjugated diene polymer ) 是由 白根昇 李鲁美 李羲承 文珉植 金鲁马 于 2020-11-27 设计创作，主要内容包括：本发明涉及一种改性共轭二烯类聚合物,更具体地,一种通过连续聚合制备的改性共轭二烯类聚合物,由此该改性共轭二烯类聚合物具有特定的聚合物结构、分子量分布和形状,具有优异的加工性能和窄的分子量分布,根据凝胶渗透色谱法(GPC),具有单峰形状的分子量分布曲线,并具有1.0至小于1.7的分子量分布(PDI；MWD),并且该改性共轭二烯类聚合物包含在一个末端的来自由式1表示的改性剂的官能团和在另一个末端的来自改性引发剂的官能团。(The present invention relates to a modified conjugated diene-based polymer, and more particularly, to a modified conjugated diene-based polymer prepared by continuous polymerization, whereby the modified conjugated diene-based polymer has a specific polymer structure, molecular weight distribution and shape, has excellent processability and narrow molecular weight distribution, has a molecular weight distribution curve of a monomodal shape according to Gel Permeation Chromatography (GPC), and has a molecular weight distribution (PDI; MWD) of 1.0 to less than 1.7, and comprises a functional group derived from a modifier represented by formula 1 at one end and a functional group derived from a modification initiator at the other end.)

1. A modified conjugated diene polymer having:

a molecular weight distribution curve of a single peak shape according to Gel Permeation Chromatography (GPC), and

a molecular weight distribution (PDI; MWD) of from 1.0 to less than 1.7,

wherein the modified conjugated diene-based polymer comprises a functional group derived from a modifier represented by the following formula 1 at one end and a functional group derived from a modification initiator at the other end:

[ formula 1]

In the formula 1, the first and second groups,

R₁to R₈Each independently an alkyl group of 1 to 20 carbon atoms,

L₁and L₂Each independently an alkylene group of 1 to 20 carbon atoms,

n is an integer from 2 to 4.

2. The modified conjugated diene polymer according to claim 1, wherein R is represented by formula 1₁To R₈Each independently an alkyl group of 1 to 10 carbon atoms.

3. The modified conjugated diene polymer according to claim 1, wherein R is represented by formula 1₁To R₈Each independently an alkyl group of 1 to 6 carbon atoms.

4. The modified conjugated diene polymer according to claim 1, wherein R is represented by formula 1₁To R₄Is methyl or ethyl, R₅To R₈Is an alkyl group of 1 to 10 carbon atoms.

5. The modified conjugated diene polymer according to claim 1, wherein the modifier represented by formula 1 is one or more selected from the following formulae 1a to 1 e:

[ formula 1a ]

[ formula 1b ]

[ formula 1c ]

[ formula 1d ]

[ formula 1e ]

In formulae 1a to 1e, Me is methyl and Et is ethyl.

6. The modified conjugated diene-based polymer according to claim 1, wherein the modification initiator is one or more compounds selected from the group consisting of:

a compound represented by the following formula 2 a;

a reaction product of a compound selected from the group consisting of compounds represented by the following formulae 2b to 2e and an organometallic compound; and

a compound represented by the following formula 2 f:

[ formula 2a ]

In the formula 2a, the first and second groups,

R_a1to R_a7Each independently is a hydrogen atom; alkyl of 1 to 20 carbon atoms; cycloalkyl of 3 to 20 carbon atoms; aryl of 6 to 20 carbon atoms; arylalkyl of 7 to 20 carbon atoms; an alkylaryl group of 7 to 20 carbon atoms; or a heteroatom-containing alkyl group of 1 to 20 carbon atoms, and

m is an integer of 0 to 3,

[ formula 2b ]

In the formula 2b, the first and second groups,

X_b1is N or O at X_b1In the case of O, R_b7Or R_b8In the absence of the presence of the agent,

R_b1to R_b5Each independently is a hydrogen atom; alkyl of 1 to 20 carbon atoms; cycloalkyl of 3 to 20 carbon atoms; aryl of 6 to 20 carbon atoms; arylalkyl of 7 to 20 carbon atoms; or an alkylaryl group of 7 to 20 carbon atoms; or two adjacent substituents may be linked to form an aliphatic or aromatic ring,

R_b6is a single bond; or an alkylene group of 1 to 12 carbon atoms,

R_b7and R_b8Each independently an alkyl group of 1 to 14 carbon atoms or an aryl group of 6 to 14 carbon atoms,

[ formula 2c ]

In the formula 2c, the reaction mixture is,

R_clto R_c3Each independently is a hydrogen atom; alkyl of 1 to 30 carbon atoms; alkenyl of 2 to 30 carbon atoms; alkynyl of 2 to 30 carbon atoms; heteroalkyl of 1 to 30 carbon atoms, heteroalkenyl of 2 to 30 carbon atoms; heteroalkynyl of 2 to 30 carbon atoms; cycloalkyl of 5 to 30 carbon atoms; aryl of 6 to 30 carbon atoms; or a heterocyclic group of 3 to 30 carbon atoms,

R_c4is a single bond; an alkylene group of 1 to 20 carbon atoms which is substituted or unsubstituted with a substituent; cycloalkylene of 5 to 20 carbon atoms substituted or unsubstituted with a substituent; or an arylene group of 6 to 20 carbon atoms which is substituted or unsubstituted with a substituent, wherein the substituent is an alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 5 to 10 carbon atoms or an aryl group of 6 to 20 carbon atoms,

R_c5is an alkyl group of 1 to 30 carbon atoms; alkenyl of 2 to 30 carbon atoms; alkynyl of 2 to 30 carbon atoms; heteroalkyl of 1 to 30 carbon atoms; heteroalkenyl of 2 to 30 carbon atoms; heteroalkynyl of 2 to 30 carbon atoms; cycloalkyl of 5 to 30 carbon atoms; aryl of 6 to 30 carbon atoms; a heterocyclic group of 3 to 30 carbon atoms; or a functional group represented by the following formula 2c-1 or formula 2c-2, and

k is an integer of 1 to 5, at least one R_c5Is a functional group represented by formula 1a or formula 1b, and when k is an integer of 2 to 5, a plurality of R_c5Which may be the same or different from each other,

[ formula 2c-1]

In the formula 2c-1, the compound,

R_c6is an alkylene group of 1 to 20 carbon atoms which is substituted or unsubstituted with a substituent; cycloalkylene of 5 to 20 carbon atoms substituted or unsubstituted with a substituent; or an arylene group of 6 to 20 carbon atoms which is substituted or unsubstituted with a substituent, wherein the substituent is an alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 5 to 10 carbon atoms or an aryl group of 6 to 20 carbon atoms,

R_c7and R_c8Each independently an alkylene group of 1 to 20 carbon atoms which is substituted by an alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 5 to 10 carbon atoms or an aryl group of 6 to 20 carbon atoms, or which is unsubstituted,

R_c9is a hydrogen atom; alkyl of 1 to 30 carbon atoms; alkenyl of 2 to 30 carbon atoms; alkynyl of 2 to 30 carbon atoms; heteroalkyl of 1 to 30 carbon atoms; heteroalkenyl of 2 to 30 carbon atoms; heteroalkynyl of 2 to 30 carbon atoms; cycloalkyl of 5 to 30 carbon atoms; aryl of 6 to 30 carbon atoms; or a heterocyclic group of 3 to 30 carbon atoms,

X_c1is N, O or S atom at X_c1In the case of O or S, R_c9In the absence of the presence of the agent,

[ formula 2c-2]

In the formula 2c-2, the compound,

R_c10is an alkylene group of 1 to 20 carbon atoms which is substituted or unsubstituted with a substituent; cycloalkylene of 5 to 20 carbon atoms substituted or unsubstituted with a substituent; or an arylene group of 6 to 20 carbon atoms which is substituted or unsubstituted with a substituent, wherein the substituent is an alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 5 to 10 carbon atoms or an aryl group of 6 to 20 carbon atoms,

R_c11and R_c12Each independently an alkyl group of 1 to 30 carbon atoms; alkenyl of 2 to 30 carbon atoms; alkynyl of 2 to 30 carbon atoms; heteroalkyl of 1 to 30 carbon atoms; heteroalkenyl of 2 to 30 carbon atoms; heteroalkynyl of 2 to 30 carbon atoms; cycloalkyl of 5 to 30 carbon atoms; aryl of 6 to 30 carbon atoms; or a heterocyclic group of 3 to 30 carbon atoms,

[ formula 2d ]

In the formula 2d, the first and second groups,

R_d1to R_d5Each independently is a hydrogen atom; alkyl of 1 to 30 carbon atoms; alkenyl of 2 to 30 carbon atoms; alkynyl of 2 to 30 carbon atoms; heteroalkyl of 1 to 30 carbon atoms; heteroalkenyl of 2 to 30 carbon atoms; heteroalkynyl of 2 to 30 carbon atoms; cycloalkyl of 5 to 30 carbon atoms; aryl of 6 to 30 carbon atoms; or a heterocyclic group of 3 to 30 carbon atoms,

R_d6is an alkylene group of 1 to 20 carbon atoms substituted with an alkyl group of 1 to 30 carbon atoms, an alkenyl group of 2 to 30 carbon atoms, an alkynyl group of 2 to 30 carbon atoms, a heteroalkyl group of 1 to 30 carbon atoms, a heteroalkenyl group of 2 to 30 carbon atoms, a heteroalkynyl group of 2 to 30 carbon atoms, a cycloalkane of 5 to 30 carbon atomsAryl of 6 to 30 carbon atoms or heterocyclyl of 3 to 30 carbon atoms, or the alkylene group is unsubstituted,

X_d1is a functional group represented by the following formula 2d-1 or formula 2d-2,

[ formula 2d-1]

In the formula 2d-1, the metal oxide,

R_d7and R_d8Each independently an alkylene group of 1 to 20 carbon atoms which is substituted by an alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 5 to 10 carbon atoms or an aryl group of 6 to 20 carbon atoms, or which is unsubstituted,

R_d9is a hydrogen atom; alkyl of 1 to 30 carbon atoms; alkenyl of 2 to 30 carbon atoms; alkynyl of 2 to 30 carbon atoms; heteroalkyl of 1 to 30 carbon atoms; heteroalkenyl of 2 to 30 carbon atoms; heteroalkynyl of 2 to 30 carbon atoms; cycloalkyl of 5 to 30 carbon atoms; aryl of 6 to 30 carbon atoms; or a heterocyclic group of 3 to 30 carbon atoms,

X_d2is N, O or S at X_d2In the case of O or S, R_d9In the absence of the presence of the agent,

[ formula 2d-2]

In the formula 2d-2, the metal oxide,

R_d11and R_d12Each independently an alkyl group of 1 to 30 carbon atoms; alkenyl of 2 to 30 carbon atoms; alkynyl of 2 to 30 carbon atoms; heteroalkyl of 1 to 30 carbon atoms; heteroalkenyl of 2 to 30 carbon atoms; heteroalkynyl of 2 to 30 carbon atoms; cycloalkyl of 5 to 30 carbon atoms; aryl of 6 to 30 carbon atoms; or a heterocyclic group of 3 to 30 carbon atoms,

[ formula 2e ]

In the formula 2e, the first and second groups,

R_e1is an alkenyl group of 2 to 10 carbon atoms,

[ formula 2f ]

In the formula 2f, the first and second groups,

R_f1、R_f2and R_f5Each independently an alkyl group of 1 to 20 carbon atoms; cycloalkyl of 3 to 20 carbon atoms; aryl of 6 to 20 carbon atoms; arylalkyl of 7 to 20 carbon atoms; or an alkylaryl group of from 7 to 20 carbon atoms,

R_f3and R_f4Each independently an alkylene group of 1 to 20 carbon atoms or an arylene group of 6 to 20 carbon atoms,

p is an integer of 1 to 5.

7. The modified conjugated diene-based polymer according to claim 1, wherein the modified conjugated diene-based polymer has a number average molecular weight (Mn) of 1,000 to 2,000,000g/mol and a weight average molecular weight (Mw) of 1,000 to 3,000,000 g/mol.

8. The modified conjugated diene-based polymer according to claim 1, wherein the Si content and the N content of the modified conjugated diene-based polymer are each 50ppm or more on a weight basis.

9. The modified conjugated diene-based polymer according to claim 1, wherein the Mooney stress relaxation ratio of the modified conjugated diene-based polymer measured at 100 ℃ is from 0.7 to 3.0.

10. The modified conjugated diene-based polymer according to claim 1, wherein the coupling number (C.N) of the modified conjugated diene-based polymer satisfies 1< C.N < F, where F is the number of functional groups of the modifier.

Technical Field

[ Cross-reference to related applications ]

This application claims benefit based on priority of korean patent application No.10-2019-0157390, filed on 29/11/2019, the entire contents of which are incorporated herein by reference.

[ technical field ]

The present invention relates to a modified conjugated diene-based polymer having excellent processability and good tensile strength and viscoelastic properties.

Background

In accordance with recent demand for automobiles with low fuel consumption rates, conjugated diene-based polymers having modulation stability represented by wet skid resistance and low rolling resistance as well as excellent abrasion resistance and tensile properties are required as rubber materials for tires.

In order to reduce the rolling resistance of a tire, there is a method of reducing the hysteresis loss of a vulcanized rubber, and rebound resilience, tan δ, Goodrich heat generation (Goodrich heating) and the like at 50 ℃ to 80 ℃ are used as evaluation indexes of the vulcanized rubber. That is, it is desirable to use a rubber material having high resilience at the above-mentioned temperature or having a low tan δ value or Goodrich heat generation.

Natural rubber, polyisoprene rubber or polybutadiene rubber is known as a rubber material having a low hysteresis loss, but these rubbers have a limitation of low wet skid resistance. Therefore, recently, conjugated diene-based polymers or copolymers such as styrene-butadiene rubber (hereinafter referred to as "SBR") and butadiene rubber (hereinafter referred to as "BR") are produced by emulsion polymerization or solution polymerization for use as rubber for tires. Among these polymerization methods, the solution polymerization has the greatest advantage over the emulsion polymerization that the vinyl structure content and styrene content, which determine the physical properties of the rubber, can be arbitrarily adjusted, and the molecular weight and physical properties thereof can be controlled by coupling or modification. Therefore, SBR prepared by solution polymerization is widely used as a rubber material for tires, since the structure of SBR or BR finally prepared is easily changed, and the movement of chain ends can be reduced and the coupling force with fillers such as silica and carbon black can be increased by the coupling or modification of the chain ends.

If solution-polymerized SBR is used as the rubber material for tires, since the glass transition temperature of the rubber is raised by increasing the vinyl content in SBR, physical properties required for tires such as rolling resistance and braking force can be controlled, and fuel consumption can be reduced by appropriately adjusting the glass transition temperature. The solution-polymerized SBR is prepared by using an anionic polymerization initiator, and is used by coupling or modifying chain ends of the polymer thus formed using various modifying agents. For example, U.S. Pat. No.4,397,994 discloses a method of coupling living anions at the ends of polymer chains obtained by polymerizing styrene-butadiene using an alkyllithium as a monofunctional initiator in a nonpolar solvent using a coupling agent such as a tin compound.

Meanwhile, the polymerization of SBR or BR may be carried out by batch polymerization or continuous polymerization. According to the batch polymerization, the polymer thus produced has a narrow molecular weight distribution and is advantageous in improvement of physical properties, but there are problems of low productivity and deterioration of processability. According to the continuous polymerization, the polymerization is continuously carried out, and is advantageous in terms of excellent productivity and improvement of processability, but there are problems that the molecular weight distribution is wide and physical properties are deteriorated. Therefore, research into improving productivity, processability, and physical properties simultaneously in the process of preparing SBR or BR is continuously required.

[ Prior art documents ]

[ patent document ]

(patent document 1) US 4397994A

(patent document 2) JP 1994-271706A

Disclosure of Invention

Technical problem

The present invention is designed to solve the above-mentioned problems of the conventional art, and an object of the present invention is to provide a modified conjugated diene-based polymer which is prepared by continuous polymerization and has excellent processability, good physical properties such as tensile properties, and excellent viscoelastic properties.

Technical scheme

In order to solve the above-mentioned task, according to one embodiment of the present invention, there is provided a modified conjugated diene-based polymer having: a molecular weight distribution curve of a monomodal shape according to Gel Permeation Chromatography (GPC), and a molecular weight distribution (PDI; MWD) of 1.0 to less than 1.7, wherein the modified conjugated diene-based polymer comprises a functional group derived from a modifier represented by formula 1 below at one terminal and a functional group derived from a modification initiator at the other terminal.

[ formula 1]

In formula 1, R₁To R₈Each independently an alkyl group of 1 to 20 carbon atoms; l is₁And L₂Each independently an alkylene group of 1 to 20 carbon atoms; n is an integer from 2 to 4.

Advantageous effects

The modified conjugated diene-based polymer according to the present invention is prepared by continuous polymerization with controlled polymerization conversion and has a molecular weight distribution curve of a single peak shape according to gel permeation chromatography and a narrow molecular weight distribution of less than 1.7, and thus, the modified conjugated diene-based polymer may have excellent processability as well as good tensile properties and viscoelastic properties.

In addition, the modified conjugated diene-based polymer according to the present invention contains a functional group derived from a modification initiator at one end and a functional group derived from a modifier at the other end, thereby further improving viscoelastic properties.

Drawings

The accompanying drawings, which are included to provide a further understanding of the inventive concepts, illustrate embodiments of the present disclosure and together with the description serve to explain the principles of the disclosure. However, the inventive concept should not be construed as being limited to these figures.

Fig. 1 shows a molecular weight distribution curve according to Gel Permeation Chromatography (GPC) of the modified conjugated diene-based polymer of example 1 according to an embodiment of the present invention;

fig. 2 shows a molecular weight distribution curve according to Gel Permeation Chromatography (GPC) of the modified conjugated diene-based polymer of comparative example 1 according to an embodiment of the present invention;

fig. 3 shows a molecular weight distribution curve according to Gel Permeation Chromatography (GPC) of the modified conjugated diene-based polymer of comparative example 10 according to an embodiment of the present invention;

fig. 4 shows a molecular weight distribution curve according to Gel Permeation Chromatography (GPC) of the modified conjugated diene-based polymer of comparative example 11 according to an embodiment of the present invention.

Detailed Description

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

It should be understood that the words or terms used in the specification and claims of this invention should not be construed as meanings defined in commonly used dictionaries. It should also be understood that these words or terms should be interpreted as having meanings consistent with their meanings in the technical idea of the present invention based on the principle that the inventor can appropriately define the meanings of the words or terms to best explain the invention.

Definition of terms

The term "alkyl" in the present invention may refer to a monovalent aliphatic saturated hydrocarbon, and may include: straight chain alkyl groups such as methyl, ethyl, propyl and butyl; branched alkyl groups such as isopropyl, sec-butyl, tert-butyl and neopentyl; and a cyclic saturated hydrocarbon, or a cyclic unsaturated hydrocarbon group containing one or two or more unsaturated bonds.

The term "alkylene" used in the present invention may refer to a divalent aliphatic saturated hydrocarbon such as methylene, ethylene, propylene and butylene.

The terms "unit from … …" and "functional group from … …" as used herein may refer to a moiety or a structure from a substance, or the substance itself.

The term "single bond" as used herein may refer to a single covalent bond per se, excluding individual atoms or molecular groups.

Measuring method

In the present disclosure, "weight average molecular weight (Mw)", "Molecular Weight Distribution (MWD)" and "unimodal property" are obtained by measuring weight average molecular weight (Mw) and number average molecular weight (Mn) by Gel Permeation Chromatography (GPC) (PL GPC220, Agilent Technologies) to obtain a molecular weight distribution curve, and calculating molecular weight distribution (PDI, MWD, Mw/Mn) from the respective molecular weights thus measured.

-a column: two PLgel oxides (Polymer Laboratories Co.) and one PLgel mixed-C (Polymer Laboratories Co.) were used in combination

-a solvent: using a mixture of tetrahydrofuran and 2% by weight of an amine compound

-flow rate: 1ml/min

-sample concentration: 1-2mg/ml (diluted in THF)

-injection amount: 100 μ l

Column temperature: 40 deg.C

-a detector: refractive index

-standard: polystyrene (calibrated by cubic function)

In the present disclosure, mooney stress relaxation is measured at 100 ℃ using a large rotor at a rotor speed of 2 ± 0.02rpm compared to MV2000 using Alpha Technologies co. Specifically, the polymer was left at room temperature (23. + -. 5 ℃ C.) for 30 minutes or more, 27. + -.3 g was collected and put into a cavity, and then, the platen was operated and the Mooney viscosity was measured while applying a torque. Further, after the mooney viscosity was measured, a value of a slope of a change in mooney viscosity exhibited when the torque was released was measured, and the mooney stress relaxation ratio was obtained as an absolute value thereof.

In the present disclosure, the "Si content" is measured by an ICP analysis method, and is measured by using inductively coupled plasma emission spectrometry (ICP-OES; Optima 7300 DV). By using inductively coupled plasma emission spectroscopy, measurements were made by: about 0.7g of the sample was added to a platinum (Pt) crucible, about 1mL of concentrated sulfuric acid (98 wt%, electronic grade) was added thereto, heated at 300 ℃ for 3 hours, and the sample was incinerated in an electric furnace (Thermo Scientific, Lindberg Blue M) by the following procedure of steps 1 to 3:

1) step 1: the initial temperature was 0 ℃, the rate (temperature/hour) was 180 ℃/hour, the temperature (holding time) was 180 ℃ (1 hour),

2) step 2: the initial temperature was 180 ℃, the rate (temperature/hour) was 85 ℃/hour, the temperature (hold time) was 370 ℃ (2 hours),

3) and step 3: the initial temperature was 370 ℃, the rate (temperature/hour) was 47 ℃/hour, the temperature (hold time) was 510 ℃ (3 hours),

to the residue were added 1mL of concentrated nitric acid (48 wt%) and 20 μ l of concentrated hydrofluoric acid (50 wt%), the platinum crucible was sealed and shaken for 30 minutes or more, 1mL of boric acid was added to the sample, stored at 0 ℃ for 2 hours or more, diluted in 30mL of ultrapure water, and incinerated. Further, the sample is in a state where the solvent is removed by placing the sample in hot water heated by steam and stirring, and it is also necessary to remove the remaining monomer and the remaining modifier. If oil is added, it is also necessary to remove the oil by extraction before measurement.

In the present disclosure, the "N content" may be measured by, for example, an NSX analysis method, and the measurement by the NSX analysis method may use a trace amount of nitrogenThe quantitative analyzer (NSX-2100H). Specifically, the quantitative analyzer for trace nitrogen (autosampler, horizontal furnace, PMT) was turned on&Nitrogen detector) the carrier gas flow rate was set to: 250ml/min for Ar and 250ml/min for O₂350ml/min, 300ml/min for the ozone generator, the heater was set to 800 ℃, and the analyzer was left to stand for about 3 hours to stabilize. After the analyzer was stabilized, calibration curves were prepared for the calibration curve ranges of 5ppm, 10ppm, 50ppm, 100ppm and 500ppm using nitrogen standards (AccuStandard S-22750-01-5ml) to obtain areas corresponding to the respective concentrations. Then, a straight line is made using the ratio of the concentration to the area. Thereafter, the ceramic boat containing 20mg of the sample was placed in an autosampler of an analyzer and measured to obtain an area. The N content was calculated by using the area of the sample thus obtained and a calibration curve.

In this case, the sample used for the NSX analysis method is a modified conjugated diene-based polymer sample from which the solvent is removed by placing the sample in hot water heated by steam and stirring, and may be a sample from which the residual monomer and the residual modifier are removed. Further, if oil is added to the sample, the sample may be the sample after the oil is extracted (removed).

Modified conjugated diene polymer

The present invention provides a modified conjugated diene-based polymer prepared by continuous polymerization and having excellent processability, a narrow molecular weight distribution and excellent physical properties.

The modified conjugated diene-based polymer according to one embodiment of the present invention is characterized by having a molecular weight distribution curve of a monomodal shape according to Gel Permeation Chromatography (GPC) and having a molecular weight distribution (PDI; MWD) of 1.0 to less than 1.7, wherein the modified conjugated diene-based polymer comprises a functional group derived from a modifier represented by formula 1 below at one end and a functional group derived from a modification initiator at the other end.

[ formula 1]

In formula 1, R₁To R₈Each independently an alkyl group of 1 to 20 carbon atoms; l is₁And L₂Each independently an alkylene group of 1 to 20 carbon atoms; n is an integer from 2 to 4.

According to an embodiment of the present invention, the modified conjugated diene-based polymer may include a repeating unit derived from a conjugated diene-based monomer, a functional group derived from a modification initiator, and a functional group derived from a modifier. The repeating unit derived from the conjugated diene-based monomer may refer to a repeating unit formed from the conjugated diene-based monomer during polymerization, and the functional group derived from the modification initiator and the functional group derived from the modifying agent may refer to a functional group derived from the modification initiator and a functional group derived from the modifying agent, respectively, present at the terminal of the polymer chain.

In addition, according to another embodiment of the present invention, the modified conjugated diene-based polymer may be a copolymer comprising a repeating unit derived from a conjugated diene-based monomer, a repeating unit derived from an aromatic vinyl monomer, a functional group derived from a modification initiator, and a functional group derived from a modifier. Here, the repeating unit derived from the aromatic vinyl monomer may refer to a repeating unit formed from the aromatic vinyl monomer during polymerization.

According to an embodiment of the present invention, the conjugated diene monomer may be one or more selected from the group consisting of 1, 3-butadiene, 2, 3-dimethyl-1, 3-butadiene, piperylene, 3-butyl-1, 3-octadiene, isoprene, 2-phenyl-1, 3-butadiene and 2-halo-1, 3-butadiene (halo means a halogen atom).

The aromatic vinyl monomer may include, for example, one or more selected from the group consisting of styrene, α -methylstyrene, 3-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- (p-methylphenyl) styrene, 1-vinyl-5-hexylnaphthalene, 3- (2-pyrrolidinylethyl) styrene, 4- (2-pyrrolidinylethyl) styrene and 3- (2-pyrrolidinyl-1-methylethyl) - α -methylstyrene.

In another embodiment, the modified conjugated diene-based polymer may be a copolymer further comprising a repeating unit derived from a diene-based monomer having 1 to 10 carbon atoms together with the repeating unit derived from a conjugated diene-based monomer. The repeating unit derived from a diene-based monomer may be a repeating unit derived from a diene-based monomer different from the conjugated diene-based monomer, and the diene-based monomer different from the conjugated diene-based monomer may be, for example, 1, 2-butadiene. If the modified conjugated diene-based polymer is a copolymer further containing a diene-based monomer, the modified conjugated diene-based polymer may contain more than 0% by weight to 1% by weight, more than 0% by weight to 0.1% by weight, more than 0% by weight to 0.01% by weight, or more than 0% by weight to 0.001% by weight of a repeating unit derived from a diene-based monomer, within which range the effect of preventing gel formation can be achieved.

According to an embodiment of the present invention, the copolymer may be a random copolymer, in which case an excellent balance effect between physical properties may be achieved. Random copolymers may refer to the arrangement of repeat units forming the copolymer in a disorder.

The modified conjugated diene-based polymer according to one embodiment of the present invention may have a number average molecular weight (Mn) of 1,000 to 2,000,000g/mol, 10,000 to 1,000,000g/mol, or 100,000 to 800,000g/mol, a weight average molecular weight (Mw) of 1,000 to 3,000,000g/mol, 10,000 to 2,000,000g/mol, or 100,000 to 2,000,000g/mol, and a peak average molecular weight (Mp) of 1,000 to 3,000,000g/mol, 10,000 to 2,000,000g/mol, or 100,000 to 2,000,000 g/mol. Within these ranges, excellent effects of rolling resistance and wet skid resistance can be obtained.

In another embodiment, the molecular weight distribution (PDI; MWD; Mw/Mn) of the modified conjugated diene-based polymer is a ratio of a weight average molecular weight (Mw) to a number average molecular weight (Mn), which may be 1.0 to less than 1.7, particularly preferably, 1.1 to less than 1.7, and within the range, an excellent effect of a balance between tensile properties, viscoelastic properties and physical properties may be obtained.

Meanwhile, the modified conjugated diene-based polymer has a molecular weight distribution curve of a monomodal shape according to Gel Permeation Chromatography (GPC), which conforms to the molecular weight distribution exhibited by a polymer prepared by continuous polymerization, and it can be said that the modified conjugated diene-based polymer has uniform properties. That is, the modified conjugated diene-based polymer according to one embodiment of the present invention is prepared by continuous polymerization, thereby having a molecular weight distribution curve having a monomodal shape and a molecular weight distribution of 1.0 to less than 1.7.

In general, in the case where the conjugated diene-based polymer is produced by a batch polymerization method and subjected to a modification reaction, the molecular weight distribution curve of the modified conjugated diene-based polymer thus produced has multiple peaks, which is a bimodal or more peak molecular weight distribution curve. In particular, in the case of batch polymerization, polymerization reaction is initiated after the entire raw materials are injected, and chain growth can be simultaneously performed at a plurality of initiation points due to many initiators, and thus the molecular weight of the polymer chain thus produced can be constant, and a unimodal shape having a significantly narrow molecular weight distribution can be obtained. However, in the case of the modification reaction by injecting a modifier, there are two cases of "unmodified" and "modified and coupled", and therefore, two groups having a large difference in molecular weight are formed in the polymer chain, and as a result, a multimodal molecular weight distribution curve having two or more peaks in the molecular weight distribution curve is formed. Meanwhile, in the continuous polymerization method according to an embodiment of the present invention, unlike batch polymerization, initiation of the reaction and injection of the raw material are continuously performed, and the generation point of the initiation point is different at the time of initiating the reaction. Therefore, the initiation point of polymerization differs, including the initial stage of the reaction, the intermediate stage of the reaction, the final stage of the reaction, and the like, and after the completion of the polymerization reaction, polymer chains having different molecular weights are produced. Therefore, a specific peak does not dominate in a curve showing a molecular weight distribution which is broad in the form of a single peak, and although chains whose polymerization is initiated are coupled in the final stage of the reaction, the molecular weight thereof may be similar to that of chains whose polymerization is initiated in the initial stage, and thus, the diversity of the molecular weight distribution may remain the same, and in general, a single peak distribution curve may be maintained.

In the case of producing and modifying a polymer by a batch polymerization method, the modification conditions may be controlled so as to have a unimodal shape, but in this case, it is necessary that all the polymers are not coupled, or that all the polymers are coupled, otherwise, a unimodal molecular weight distribution curve cannot be exhibited.

In addition, in the case where the molecular weight distribution curve of the entire polymer coupled like the modified conjugated diene-based polymer shows a monomodal distribution although prepared by the batch polymerization method as described above, only polymers having the same level of molecular weight are present, and the processability is poor, and the compounding property is lowered since functional groups that can interact with fillers such as silica and carbon black are reduced by the coupling. In contrast, in the case where the entire polymer is not coupled, functional groups at the polymer terminal, which are required to interact with fillers such as silica and carbon black during processing, preferably interact with each other, thereby causing a phenomenon of preventing interaction with the fillers and significantly deteriorating processability. Finally, in the case where control is performed to have a molecular weight distribution curve of a single-peak shape when a polymer is produced by a batch polymerization method, the processability and compounding properties of the modified conjugated diene-based polymer thus produced may be deteriorated, and in particular, the processability may be significantly deteriorated.

Meanwhile, the coupling of the modified conjugated diene-based polymer can be confirmed by the coupling number (C.N), which is a numerical value depending on the number of functional groups that can be coupled with the polymer present in the modifying agent. That is, the coupling number represents the ratio of a polymer composed only of terminal modification without coupling between polymer chains to a polymer in which a plurality of polymer chains are coupled with one modifier, and may have a range of 1. ltoreq. C.N. ltoreq.F, where F refers to the number of functional groups in the modifier that can react with the living polymer terminals. In other words, the modified conjugated diene-based polymer having a coupling number of 1 means that all the polymer chains are not coupled, and the modified conjugated diene-based polymer having a coupling number of F means that all the polymer chains are coupled.

Thus, the modified conjugated diene-based polymer according to one embodiment of the present invention may have a molecular weight distribution curve in a monomodal shape, and the coupling number may be more than 1 and less than the number of functional groups of the modifier used (1. ltoreq. C.N. ltoreq.F).

In another embodiment, the Si content of the modified conjugated diene-based polymer may be 50ppm or more, 100ppm to 10,000ppm or 100ppm to 5,000ppm on a weight basis, within which range a rubber composition comprising the modified conjugated diene-based polymer has an effect of exhibiting excellent mechanical properties such as tensile properties and viscoelastic properties. The Si content may refer to the content of Si atoms present in the modified conjugated diene-based polymer. Meanwhile, the Si atom may be derived from a functional group derived from the modifier.

In another embodiment, the N content of the modified conjugated diene-based polymer may be 50ppm or more, 100ppm to 10,000ppm or 100ppm to 5,000ppm on a weight basis, within which range a rubber composition comprising the modified conjugated diene-based polymer has an effect of exhibiting excellent mechanical properties such as tensile properties and viscoelastic properties. The N content may refer to the content of nitrogen atoms present in the modified conjugated diene-based polymer, and in this case, the nitrogen atoms may be derived from the functional group derived from the modifying agent. Further, the N atom may include an N atom derived from a functional group derived from the modification initiator, as the case may be.

In another embodiment, the modified conjugated diene-based polymer may have a mooney stress relaxation ratio measured at 100 ℃ of 0.7 or more, 0.7 to 3.0, 0.7 to 2.5, or 0.7 to 2.0.

Here, the mooney stress relaxation ratio represents a change in stress exhibited as a response to the same amount of strain, and can be measured using a mooney viscometer.

Meanwhile, the mooney stress relaxation ratio can be used as an index of the branched structure of the corresponding polymer. For example, in the case of comparing polymers having the same mooney viscosity, as the degree of branching increases, the mooney stress relaxation ratio decreases, which can be used as an index of the degree of branching.

In addition, the modified conjugated diene-based polymer may have a mooney viscosity at 100 ℃ of 30 or more, 40 to 150, or 40 to 140, and in the range, excellent effects of processability and productivity may be obtained.

In addition, the vinyl content of the modified conjugated diene-based polymer may be 5% by weight or more, 10% by weight or more, or 10% by weight to 60% by weight. Here, the vinyl content may mean the amount of the 1, 4-addition but 1, 2-addition conjugated diene monomer based on 100% by weight of the conjugated diene copolymer composed of the monomer having a vinyl group and the aromatic vinyl monomer.

Meanwhile, the modifier according to the present invention may be a modifier for modifying one end of the conjugated diene-based polymer, and a specific example may be a modifier having affinity with silica. The modifier having affinity with silica may refer to a modifier that includes a functional group having affinity with silica in a compound used as the modifier, and may refer to a functional group that has excellent affinity with a filler, particularly, a silica-based filler, and is capable of causing interaction between the silica-based filler and the functional group derived from the modifier.

The modifier according to one embodiment of the present invention is represented by formula 1 below, can easily introduce a functional group tertiary amine group having affinity with a filler, and can perform modification.

[ formula 1]

In formula 1, R₁To R₈Each independently an alkyl group of 1 to 20 carbon atoms; l is₁And L₂Each independently an alkylene group of 1 to 20 carbon atoms; n is an integer from 2 to 4.

Specifically, in formula 1, R₁To R₄May each independently be a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, in which case R is substituted₁To R₄May each be independently substituted with one or more substituents selected from: alkyl of 1 to 10 carbon atoms, cycloalkyl of 3 to 10 carbon atoms, alkoxy of 1 to 10 carbon atoms, cycloalkoxy of 4 to 10 carbon atoms, aryl of 6 to 12 carbon atoms, aryloxy of 6 to 12 carbon atoms, alkanoyloxy of 2 to 12 carbon atoms (R)_aCOO-, wherein R_aIs an alkyl group of 1 to 9 carbon atoms), an aralkyloxy group of 7 to 13 carbon atoms, an arylalkyl group of 7 to 13 carbon atoms, and an alkylaryl group of 7 to 13 carbon atoms. More specifically, R₁To R₄May be a substituted or unsubstituted alkyl group of 1 to 10 carbon atoms, more specifically, R₁To R₄May each independently be a substituted or unsubstituted alkyl group of 1 to 6 carbon atoms.

In addition, in formula 1, R₅To R₈May each independently be a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, specifically, a substituted or unsubstituted alkyl group of 1 to 10 carbon atoms, more specifically, a substituted or unsubstituted alkyl group of 1 to 6 carbon atoms. If substituted, R₅To R₈Can be represented by the above R₁To R₄Substituted with the substituent(s). At R₅To R₈In the case of groups other than alkyl groups but hydrolysable groups, N-R₅R₆And N-R₇R₈The bonds will hydrolyze to N-H in the presence of water, thereby adversely affecting the processability of the polymer.

More specifically, the compound represented by formula 1 may be the following formula 1: wherein R is₁To R₄Is methyl or ethyl, and R₅To R₈Is an alkyl group of 1 to 10 carbon atoms.

Amino groups contained in formula 1, i.e., -NR₅R₆and-NR₇R₈Tertiary amino groups may be preferred. In the case of using the compounds of the invention as modifiers, the tertiary amino groups lead to even better processability.

At R₅To R₈In the case of binding to a protecting group for protecting an amino group or binding to hydrogen, the effect according to the present invention may be difficult to achieve. In the case of binding with hydrogen, the anion reacts with hydrogen during modification, thereby losing reactivity and failing to perform its own modification reaction. In the case of bonding with a protecting group, the modification reaction may proceed, but in the state of being bonded to the terminal of the polymer, during subsequent processing, deprotection reaction may proceed due to hydrolysis, resulting in a primary or secondary amino group. The deprotected primary or secondary amino groups can cause a phenomenon of crumbling of the compounded mixture during compounding and can be a factor that reduces processability.

In addition, in formula 1, L₁And L₂May each independently be a substituted or unsubstituted alkylene group of 1 to 20 carbon atoms. More specifically, L₁And L₂May each independently be an alkylene group of 1 to 10 carbon atoms, more specifically, an alkylene group of 1 to 6 carbon atoms, such as a methylene group, an ethylene group and a propylene group.

The closer the distance between the Si atom and the N atom in the molecule, the better the effect can be exhibited, but in the case where Si and N are directly bonded, the bond is easily broken. Therefore, the bond between Si and N is broken during subsequent processing, and secondary amino groups generated due to water are likely to be lost during subsequent processing. In addition, in the finally prepared modified conjugated diene-based polymer, it is difficult to couple with the silica filler due to the lack of an amino group which promotes bonding with the silica filler, and therefore, the dispersing effect of the dispersant is lowered. As described above, L is L in consideration of excellent improvement effect according to the bond length between Si and N₁And L₂May more preferably each independently be an alkylene group of 1 to 3 carbon atoms, such as methylene, ethylene and propylene, more specifically, propylene. Furthermore, L₁And L₂Can be referred to as R₁To R₄The substituents specified.

More specifically, the compound represented by formula 1 may be one or more selected from compounds represented by the following formulae 1a to 1 e.

[ formula 1a ]

[ formula 1b ]

[ formula 1c ]

[ formula 1d ]

[ formula 1e ]

In formulae 1a to 1e, Me is methyl and Et is ethyl.

In the modifier of the invention, in the compound represented by formula 1, an alkoxysilane structure is bonded to the activated terminal of the conjugated diene-based polymer, and at the same time, the Si — O — Si structure and three or more amino groups bonded at the terminal exhibit affinity with a filler such as silica, and therefore, when compared with a conventional modifier containing one amino group in the molecule, coupling of the filler with the modified conjugated diene-based polymer can be promoted. Further, since the degree of coupling of the activated terminal of the conjugated diene-based polymer is uniform, if a change in the molecular weight distribution before and after the coupling is observed, the molecular weight distribution does not increase but is constant after the coupling as compared with before the coupling. Therefore, the physical properties of the modified conjugated diene-based polymer itself are not deteriorated, the filler aggregation in the rubber composition can be prevented, and the dispersibility of the filler is improved, thereby improving the processability of the rubber composition, in particular, the fuel consumption property, the wear property and the braking property of the tire in a balanced manner.

The modifier represented by formula 1 may be prepared by a condensation reaction represented by the following reaction 1.

[ reaction 1]

In reaction 1, R₁To R₈、L₁To L₂And n is the same as defined in formula 1, and R' are optional substituents that do not affect the condensation reaction. For example, R 'and R' may each independently be from R₁To R₄Is the same.

The reaction is performed under acid conditions, and any acid used for the condensation reaction may be used without limitation. The optimum acid can be selected by one skilled in the art based on a variety of process variables, including the type of reactor in which the reaction is conducted, the starting materials, the reaction temperature, and the like.

Meanwhile, the modification initiator according to an embodiment of the present invention may be one or more compounds selected from the group consisting of: a compound represented by the following formula 2 a; a reaction product of a compound selected from the group consisting of compounds represented by the following formulae 2b to 2e and an organometallic compound; and a compound represented by the following formula 2 f.

For example, a compound represented by the following formula 2a may be applied as a modification initiator without reacting with an organometallic compound, and may be a compound represented below.

[ formula 2a ]

In formula 2a, R_a1To R_a7Each independently is a hydrogen atom; alkyl of 1 to 20 carbon atoms;cycloalkyl of 3 to 20 carbon atoms; aryl of 6 to 20 carbon atoms; arylalkyl of 7 to 20 carbon atoms; an alkylaryl group of 7 to 20 carbon atoms; or a heteroatom-containing heteroalkyl group of 1 to 20 carbon atoms, and m is an integer of 0 to 3.

Specifically, in formula 2a, R_a1To R_a7May each independently be a hydrogen atom; alkyl of 1 to 20 carbon atoms; cycloalkyl of 3 to 20 carbon atoms; aryl of 6 to 20 carbon atoms; arylalkyl of 7 to 20 carbon atoms; an alkylaryl group of 7 to 20 carbon atoms; alkoxy of 1 to 20 carbon atoms; alkoxyalkyl having 2 to 20 carbon atoms; aryloxy of 6 to 20 carbon atoms; or an aryloxyalkyl group of 7 to 20 carbon atoms.

More specifically, in formula 2a, R_a1May be an alkyl group of 1 to 10 carbon atoms, more preferably, an alkyl group of 1 to 5 carbon atoms, and R_a2To R_a7May each independently be a hydrogen atom or an alkyl group of 1 to 10 carbon atoms, preferably a hydrogen atom or an alkyl group of 1 to 5 carbon atoms.

More preferably, the modification initiator represented by formula 2a may be a compound represented by formula 2aa below.

[ formula 2aa ]

In the formula 2aa, m is an integer of 0 to 3.

In another embodiment, the compound represented by the following formula 2b may be used in the type of compound produced by the reaction with the organometallic compound, and may be the compound represented below.

[ formula 2b ]

In formula 2b, X_b1Is N or O and is at X_b1In the case of O, R_b7Or R_b8Is absent, R_b1To R_b5Each independently is a hydrogen atom; alkyl of 1 to 20 carbon atoms; cycloalkyl of 3 to 20 carbon atoms; aryl of 6 to 20 carbon atoms; arylalkyl of 7 to 20 carbon atoms; or an alkylaryl group of 7 to 20 carbon atoms; or two adjacent substituents may be linked to form an aliphatic or aromatic ring, R_b6Is a single bond or alkylene of 1 to 12 carbon atoms, R_b7And R_b8Each independently an alkyl group of 1 to 14 carbon atoms or an aryl group of 6 to 14 carbon atoms.

Specifically, in the compound represented by formula 2b, X_b1Is N or O and is at X_b1In the case of O, R_b7Or R_b8Is absent, R_b1To R_b5Each independently is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms, R_b6Is a single bond or alkylene of 1 to 6 carbon atoms, R_b7And R_b8Each independently an alkyl group of 1 to 10 carbon atoms.

More specifically, the compound represented by formula 2b may be a compound represented by formula 2ba to formula 2bd below.

[ formula 2ba ]

[ formula 2bb ]

[ formula 2bc ]

[ formula 2bd ]

In another embodiment, the compound represented by formula 2c below may be used in the type of compound produced by the reaction with an organometallic compound, and may be the compound represented below.

[ formula 2c ]

In formula 2c, R_clTo R_c3May each independently be a hydrogen atom; alkyl of 1 to 30 carbon atoms; alkenyl of 2 to 30 carbon atoms; alkynyl of 2 to 30 carbon atoms; heteroalkyl of 1 to 20 carbon atoms, heteroalkenyl of 2 to 30 carbon atoms; heteroalkynyl of 2 to 30 carbon atoms; cycloalkyl of 5 to 30 carbon atoms; aryl of 6 to 30 carbon atoms; or a heterocyclic group of 3 to 30 carbon atoms.

R_c4May be a single bond; an alkylene group of 1 to 20 carbon atoms which is substituted or unsubstituted with a substituent; cycloalkylene of 5 to 20 carbon atoms substituted or unsubstituted with a substituent; or an arylene group of 6 to 20 carbon atoms substituted or unsubstituted with a substituent, wherein the substituent may be an alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 5 to 10 carbon atoms, or an aryl group of 6 to 20 carbon atoms.

R_c5Alkyl groups which may be 1 to 30 carbon atoms; alkenyl of 2 to 30 carbon atoms; alkynyl of 2 to 30 carbon atoms; heteroalkyl of 1 to 30 carbon atoms; heteroalkenyl of 2 to 30 carbon atoms; heteroalkynyl of 2 to 30 carbon atoms; cycloalkyl of 5 to 30 carbon atoms; aryl of 6 to 30 carbon atoms; a heterocyclic group of 3 to 30 carbon atoms; or a functional group represented by the following formula 2c-1 or formula 2c-2, and k may be an integer of 1 to 5, at least one R_c5May be a functional group represented by formula 2c-1 or formula 2c-2, and in the case where k is an integer of 2 to 5, a plurality of R' s_c5May be the same or different.

[ formula 2c-1]

In the formula 2c-1, R_c6Is an alkylene group of 1 to 20 carbon atoms which is substituted or unsubstituted with a substituent; cycloalkylene of 5 to 20 carbon atoms substituted or unsubstituted with a substituent; or an arylene group of 6 to 20 carbon atoms substituted or unsubstituted with a substituent, wherein the substituent is an alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 5 to 10 carbon atoms or an aryl group of 6 to 20 carbon atoms, R_c7And R_c8Each independently an alkylene group of 1 to 20 carbon atoms which is substituted by an alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 5 to 10 carbon atoms or an aryl group of 6 to 20 carbon atoms, or which is unsubstituted, R_c9Is a hydrogen atom; alkyl of 1 to 30 carbon atoms; alkenyl of 2 to 30 carbon atoms; alkynyl of 2 to 30 carbon atoms; heteroalkyl of 1 to 30 carbon atoms; heteroalkenyl of 2 to 30 carbon atoms; heteroalkynyl of 2 to 30 carbon atoms; cycloalkyl of 5 to 30 carbon atoms; aryl of 6 to 30 carbon atoms; or a heterocyclic group of 3 to 30 carbon atoms, X_c1Is N, O or S atom at X_c1In the case of O or S, R_c9May not be present.

[ formula 2c-2]

In the formula 2c-2, R_c10Is an alkylene group of 1 to 20 carbon atoms which is substituted or unsubstituted with a substituent; cycloalkylene of 5 to 20 carbon atoms substituted or unsubstituted with a substituent; or an arylene group of 6 to 20 carbon atoms substituted or unsubstituted with a substituent, wherein the substituent is an alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 5 to 10 carbon atoms or an aryl group of 6 to 20 carbon atoms, R_c11And R_c12May each independently be an alkyl group of 1 to 30 carbon atoms; alkenyl of 2 to 30 carbon atoms; alkynyl of 2 to 30 carbon atoms; heteroalkyl of 1 to 30 carbon atoms; heteroalkenyl of 2 to 30 carbon atoms; heteroalkynyl of 2 to 30 carbon atoms; cycloalkyl of 5 to 30 carbon atoms; aryl of 6 to 30 carbon atoms; or a heterocyclic group of 3 to 30 carbon atoms.

In particular, in the general formulaIn the compound represented by 2c, R_clTo R_c3May each independently be a hydrogen atom; alkyl of 1 to 10 carbon atoms; alkenyl of 2 to 10 carbon atoms; or alkynyl of 2 to 10 carbon atoms, R_c4May be a single bond; or alkylene of 1 to 10 carbon atoms which is substituted or unsubstituted by a substituent, R_c5Alkyl groups which may be 1 to 10 carbon atoms; alkenyl of 2 to 10 carbon atoms; alkynyl of 2 to 10 carbon atoms; or a functional group represented by formula 2c-1 or formula 2c-2, in formula 2c-1, R_c6May be an unsubstituted alkylene group of 1 to 10 carbon atoms, R_c7And R_c8May each independently be an unsubstituted alkylene group of 1 to 10 carbon atoms, R_c9Alkyl groups which may be 1 to 10 carbon atoms; cycloalkyl of 5 to 20 carbon atoms; aryl of 6 to 20 carbon atoms; or a heterocyclic group of 3 to 20 carbon atoms, and in the formula 2c-2, R_c10Is unsubstituted alkylene of 1 to 10 carbon atoms, R_c11And R_c12May each independently be an alkyl group of 1 to 10 carbon atoms; cycloalkyl of 5 to 20 carbon atoms; aryl of 6 to 20 carbon atoms; or a heterocyclic group of 3 to 20 carbon atoms.

More specifically, the compound represented by formula 2c may be a compound represented by formula 2ca to formula 2cc below.

[ formula 2ca ]

[ formula 2cb ]

[ formula 2cc ]

In another embodiment, the compound represented by formula 2d below may be used in the type of compound produced by the reaction with an organometallic compound, and may be the compound represented below.

[ formula 2d ]

In formula 2d, R_d1To R_d5Each independently is a hydrogen atom; alkyl of 1 to 30 carbon atoms; alkenyl of 2 to 30 carbon atoms; alkynyl of 2 to 30 carbon atoms; heteroalkyl of 1 to 30 carbon atoms, heteroalkenyl of 2 to 30 carbon atoms; heteroalkynyl of 2 to 30 carbon atoms; cycloalkyl of 5 to 30 carbon atoms; aryl of 6 to 30 carbon atoms; or a heterocyclic group of 3 to 30 carbon atoms, R_d6Is an alkylene group of 1 to 20 carbon atoms, which is substituted with an alkyl group of 1 to 30 carbon atoms; alkenyl of 2 to 30 carbon atoms; alkynyl of 2 to 30 carbon atoms; heteroalkyl of 1 to 30 carbon atoms; heteroalkenyl of 2 to 30 carbon atoms; heteroalkynyl of 2 to 30 carbon atoms; cycloalkyl of 5 to 30 carbon atoms; aryl of 6 to 30 carbon atoms; or heterocyclyl having 3 to 30 carbon atoms, or the alkylene group is unsubstituted, X_d1May be a functional group represented by the following formula 2d-1 or formula 2 d-2.

[ formula 2d-1]

In the formula 2d-1, R_d7And R_d8Each independently an alkylene group of 1 to 20 carbon atoms which is substituted by an alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 5 to 10 carbon atoms or an aryl group of 6 to 20 carbon atoms, or which is unsubstituted, R_d9Is a hydrogen atom; alkyl of 1 to 30 carbon atoms; alkenyl of 2 to 30 carbon atoms; alkynyl of 2 to 30 carbon atoms; heteroalkyl of 1 to 30 carbon atoms; heteroalkenyl of 2 to 30 carbon atoms; heteroalkynyl of 2 to 30 carbon atoms; cycloalkyl of 5 to 30 carbon atoms; aryl of 6 to 30 carbon atoms; or a heterocyclic group of 3 to 30 carbon atoms, X_d2Is N, O or S at X_d2Is O or SIn the case of R_d9May not be present.

[ formula 2d-2]

In the formula 2d-2, R_d11And R_d12May each independently be an alkyl group of 1 to 30 carbon atoms; alkenyl of 2 to 30 carbon atoms; alkynyl of 2 to 30 carbon atoms; heteroalkyl of 1 to 30 carbon atoms; heteroalkenyl of 2 to 30 carbon atoms; heteroalkynyl of 2 to 30 carbon atoms, cycloalkyl of 5 to 30 carbon atoms; aryl of 6 to 30 carbon atoms; or a heterocyclic group of 3 to 30 carbon atoms.

Specifically, in the compound represented by formula 2d, R_d1To R_d5May each independently be a hydrogen atom; alkyl of 1 to 10 carbon atoms; alkenyl of 2 to 10 carbon atoms; or alkynyl of 2 to 10 carbon atoms, R_d6May be an unsubstituted alkylene group of 1 to 10 carbon atoms, X_d1May be a functional group represented by the formula 2d-1 or the formula 2d-2, in the formula 2d-1, R_d7And R_d8May each independently be an unsubstituted alkylene group of 1 to 10 carbon atoms, R_d9Is an alkyl group of 1 to 10 carbon atoms; cycloalkyl of 5 to 20 carbon atoms; aryl of 6 to 20 carbon atoms; or a heterocyclic group of 3 to 20 carbon atoms, X_d2Is N, in the formula 2d-2, R_d11And R_d12May each independently be an alkyl group of 1 to 10 carbon atoms; cycloalkyl of 5 to 20 carbon atoms; aryl of 6 to 20 carbon atoms; or a heterocyclic group of 3 to 20 carbon atoms.

More specifically, the compound represented by formula 2d may be a compound represented by formula 2da or formula 2db below.

[ formula 2da ]

[ formula 2db ]

In the case where the compounds represented by formulae 2b to 2d are selected, a pretreatment for reaction with an organometallic compound may be required, and here, the organometallic compound may be one or more selected from the group consisting of an organolithium compound, an organosodium compound, an organopotassium compound, an organorubidium compound and an organocesium compound. Specifically, the organometallic compound may be one or more selected from methyllithium, ethyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, n-decyllithium, tert-octyllithium, phenyllithium, 1-naphthyllithium, n-eicosyllithium, 4-butylphenyl-lithium, 4-tolyllithium, cyclohexyllithium, 3, 5-di-n-heptylcyclohexyllithium, and 4-cyclopentyllithium.

In another embodiment, the compound represented by formula 2e below may be used in the type of compound produced by the reaction with an organometallic compound, and may be the compound represented below.

[ formula 2e ]

In the formula 2e, the first and second groups,

R_e1is an alkenyl group of 2 to 10 carbon atoms.

Specifically, the compound represented by formula 2e may be a compound represented by the following formula 2ea, i.e., 1-vinylimidazole; 1-vinyl-1H-imidazole.

[ formula 2ea ]

For example, the compound represented by the following formula 2f may be used as a modification initiator without reacting with an organometallic compound, and may be a compound represented below.

[ formula 2f ]

In formula 2f, R_f1、R_f2And R_f5Each independently an alkyl group of 1 to 20 carbon atoms; cycloalkyl of 3 to 20 carbon atoms; aryl of 6 to 20 carbon atoms; arylalkyl of 7 to 20 carbon atoms; or alkylaryl groups of 7 to 20 carbon atoms, R_f3And R_f4Each independently an alkylene group of 1 to 20 carbon atoms or an arylene group of 6 to 30 carbon atoms, and p is an integer of 1 to 5.

Specifically, in formula 2f, R_f1、R_f2And R_f5May each independently be an alkyl group of 1 to 10 carbon atoms; cycloalkyl of 3 to 10 carbon atoms; aryl of 6 to 10 carbon atoms; arylalkyl of 7 to 10 carbon atoms; or alkylaryl of 7 to 10 carbon atoms, R_f3And R_f4May each independently be an alkylene group of 1 to 10 carbon atoms or an arylene group of 6 to 10 carbon atoms, and n is an integer of 1 to 3.

More specifically, in formula 2f, R_f1、R_f2And R_f5May each independently be an alkyl group of 1 to 6 carbon atoms, R_f3And R_f4May each independently be an alkylene group of 1 to 6 carbon atoms, and n may be an integer of 1 to 3.

More specifically, the modification initiator represented by formula 2f may be a compound represented by formula 2fa below.

[ formula 2fa ]

As described above, the modified conjugated diene-based polymer according to one embodiment of the present invention has a specific structure and may have a unique molecular weight distribution pattern and shape. Such a polymer structure can be represented by physical properties such as a mooney stress relaxation ratio and a coupling number, a molecular weight distribution profile and a shape can be represented by a PDI value, a shape of a molecular weight distribution curve and a coupling number, and modification of both terminals by a modifier and a modification initiator can affect the structure, the molecular weight distribution profile and the shape thereof. The parameters indicating the structure of such a polymer and the properties relating to the molecular weight distribution can be satisfied by the production method to be described later. Although the production by this production method is preferable in order to satisfy the above properties, the effects sought to be achieved in the present invention can be accomplished only if all of the above properties are satisfied.

Method for preparing modified conjugated diene polymer

In addition, the invention provides a preparation method of the modified conjugated diene polymer.

The method for producing a modified conjugated diene-based polymer according to one embodiment of the present invention comprises: polymerizing a conjugated diene-based monomer, or a conjugated diene-based monomer and an aromatic vinyl monomer in a hydrocarbon solvent in the presence of a modification initiator to prepare a living polymer into which a functional group derived from the modification initiator is introduced (S1); and reacting or coupling the living polymer prepared in the step (S1) with a modifier represented by formula 1 below (S2), wherein the step (S1) is continuously performed in two or more polymerization reactors, and the polymerization conversion rate in the first reactor of the polymerization reactors may be 50% or less.

[ formula 1]

In formula 1, the respective substituents and indices are the same as defined above.

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

In addition, the conjugated diene-based monomer and the aromatic vinyl-based monomer are the same as defined above.

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

The polymerization of step (S1) may be, for example, anionic polymerization, specifically, living anionic polymerization in which an anionic living moiety is formed at the polymerization terminal by a propagation reaction of an anion. Further, the polymerization of step (S1) may be heating polymerization, isothermal polymerization, or constant temperature polymerization (adiabatic polymerization). Here, the isothermal polymerization refers to a polymerization method including a step of performing polymerization using heat generated by the reaction itself without optionally supplying heat after adding a polymerization initiator, and the heating polymerization refers to a polymerization method including adding a polymerization initiator and then increasing the temperature by optionally supplying heat. Isothermal polymerization refers to a polymerization method in which the temperature of a polymer is kept constant by adding heat or removing heat by supplying heat after a polymerization initiator is added.

In addition, according to an embodiment of the present invention, the polymerization of step (S1) may be performed by a diene-based compound containing 1 to 10 carbon atoms in addition to the conjugated diene-based monomer, and in this case, an effect of preventing gel formation on the wall side of the reactor during long-time operation may be achieved. The diene-based compound may include, for example, 1, 2-butadiene.

The polymerization of step (S1) may be performed at a temperature ranging from-20 ℃ to 80 ℃,0 ℃ to 70 ℃, or 10 ℃ to 70 ℃ below 80 ℃. Within the range, the molecular weight distribution of the polymer is controlled to be narrow, and the effect of improving physical properties is excellent.

The living polymer prepared by the step (S1) may refer to a polymer in which a polymer anion is coupled with an organometallic cation.

According to an embodiment of the present invention, the preparation method of the modified conjugated diene-based polymer may be performed by a continuous polymerization method in a plurality of reactors including two or more polymerization reactors and one modification reactor. In a specific embodiment, the step (S1) may be continuously performed in two or more polymerization reactors including the first reactor, and the number of polymerization reactors may be flexibly determined according to reaction conditions and environments. A continuous polymerization process may refer to a reaction process in which reactants are continuously supplied into a reactor and reaction products produced therefrom are continuously discharged. By the continuous polymerization method, productivity and processability can be excellent, and the effect of excellent uniformity of the polymer thus produced can be obtained.

In addition, according to an embodiment of the present invention, if the living polymer is continuously produced in the polymerization reactor, the polymerization conversion rate in the first reactor may be 50% or less, 10% to 50% or 20% to 50%, and within the range, the occurrence of a side reaction may be suppressed in forming the polymer after initiating the polymerization reaction, and the polymer having a linear structure may be induced during the polymerization. Therefore, the molecular weight distribution of the polymer can be controlled to be narrow, and an excellent improvement effect of physical properties can be obtained.

In this case, the polymerization conversion rate may be controlled according to the reaction temperature, the residence time in the reactor, and the like.

The polymerization conversion can be determined, for example, by measuring the solid concentration in a polymer solution phase containing the polymer during polymerization of the polymer. In a specific embodiment, a cylindrical container is installed at the outlet of each polymerization reactor in order to get the polymer solution, so that the cylindrical container is filled with a certain amount of the polymer solution. Then, the cylindrical container is separated from the reactor, the weight (a) of the cylinder filled with the polymer solution is measured, the polymer solution filled in the cylindrical container is transferred to an aluminum container, for example, an aluminum pan, the weight (B) of the cylindrical container from which the polymer solution is removed is measured, the aluminum container containing the polymer solution is dried in an oven at 140 ℃ for 30 minutes, the weight (C) of the polymer after drying is measured, and calculation is performed according to the following mathematical formula 1:

[ mathematical formula 1]

Meanwhile, the polymer polymerized in the first reactor may be sequentially transferred to the polymerization reactor before the modification reactor, and polymerization may be performed until the final polymerization conversion rate becomes 95% or more. After the polymerization in the first reactor, the polymerization conversion of the second reactor, or each reactor from the second reactor to the polymerization reactor before the modification reactor, may be appropriately controlled to control the molecular weight distribution.

Meanwhile, in the step (S1), the residence time of the polymer in the first reactor during the preparation of the living polymer may be 1 to 40 minutes, 1 to 30 minutes, or 5 to 30 minutes, and within the range, the control of the polymerization conversion rate is easy, and thus, the molecular weight distribution of the polymer may be controlled to be narrow, and the effect of improving the physical properties may be excellent.

The term "polymerization reactant" used in the present invention may refer to an intermediate of a polymer type under polymerization in each reactor during the performance of step (S1), or may refer to a polymer of which polymerization conversion rate under polymerization in the reactor is less than 95% after completion of step (S1) or step (S2) and before obtaining a living polymer or a modified conjugated diene-based polymer.

According to an embodiment of the present invention, the molecular weight distribution (PDI, polydispersity index; MWD, Mw/Mn) of the living polymer prepared in the step (S1) may be less than 1.5, from 1.0 to less than 1.5, or from 1.1 to less than 1.5, and within the range, the molecular weight distribution of the modified conjugated diene-based polymer prepared by modification reaction or coupling with the modifier is narrow, and the effect of improving physical properties may be excellent.

Meanwhile, the polymerization of step (S1) may be performed by including a polar additive, and the polar additive may be added in a ratio of 0.001g to 50g, 0.001g to 10g, or 0.005g to 0.1g, based on a total of 100g of the monomers. In another embodiment, the polar additive may be added in a ratio of 0.001g to 10g, 0.005g to 5g, or 0.005g to 4g, based on 1mmol of the polymerization initiator in total.

The polar additive may be, for example, one or more selected from tetrahydrofuran, 2-bis (2-tetrahydrofuryl) propane, diethyl ether, cyclopentyl ether, dipropyl ether, ethylene glycol methyl ether, ethylene glycol dimethyl ether, diethylene glycol, dimethyl ether, t-butoxyethoxyethane, bis (3-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine, N' -tetramethylethylenediamine, sodium menthol and 2-ethyltetrahydrofuryl ether, and may preferably be 2, 2-bis (2-tetrahydrofuryl) propane, triethylamine, tetramethylethylenediamine, sodium menthol or 2-ethyltetrahydrofuryl ether. If the polar additive is contained, and if the conjugated diene-based monomer, or the conjugated diene-based monomer and the aromatic vinyl-based monomer are copolymerized, the difference in the reaction rates thereof can be compensated for, and an effect of causing easy formation of a random copolymer can be achieved.

According to an embodiment of the present invention, the reaction or coupling of step (S2) may be performed in a modification reactor, and in this case, the modifying agent may be used in an amount of 0.01mmol to 10mmol based on 100g of the total monomer. In another embodiment, the modifier may be used in a molar ratio of 1:0.1 to 10, 1:0.1 to 5, or 1:0.1 to 1:3, based on 1mol of the polymerization initiator of step (S1).

In addition, according to an embodiment of the present invention, the modifier may be injected into the modification reactor, and the step (S2) may be performed in the modification reactor. In another embodiment, the modifier may be injected into a transfer part for transferring the living polymer prepared in the step (S1) to the modification reactor for performing the step (S2), and in the transfer part, the reaction or coupling may be performed by mixing the living polymer with the modifier.

The method for producing a modified conjugated diene-based polymer according to an embodiment of the present invention is a method for satisfying the properties of the above-described modified conjugated diene-based polymer. The effects intended to be achieved by the present invention can be achieved if the above properties are satisfied as described above, but at least in the production process, it is required to satisfy the polymerization conversion rate in the course of transportation from the first reactor to the second reactor, and the physical properties of the modified conjugated diene-based polymer according to the present invention can be achieved by variously controlling other polymerization conditions.

Rubber composition

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

The rubber composition may contain 10% by weight or more, 10% by weight to 100% by weight, or 20% by weight to 90% by weight of the modified conjugated diene-based polymer, within which the mechanical properties such as tensile strength and abrasion resistance are excellent, and an effect of excellent balance between physical properties may be obtained.

In addition, the rubber composition may contain other rubber components as needed in addition to the modified conjugated diene-based polymer, and in this case, the content of the rubber component may be 90% by weight or less based on the total weight of the rubber composition. In a specific embodiment, the content of the rubber component may be 1 part by weight to 900 parts by weight based on 100 parts by weight of the modified conjugated diene-based copolymer.

The rubber component may be, for example, natural rubber or synthetic rubber, and may be specifically Natural Rubber (NR) including cis-1, 4-polyisoprene; modified natural rubber obtained by modifying or purifying conventional natural rubber, such as Epoxidized Natural Rubber (ENR), deproteinized natural rubber (DPNR) and hydrogenated natural rubber; and synthetic rubbers such as styrene-butadiene copolymer (SBR), polybutadiene (BR), polyisoprene (IR), butyl rubber (IIR), ethylene-propylene copolymer, polyisobutylene-isoprene copolymer, chloroprene rubber, poly (ethylene-propylene) copolymer, poly (styrene-butadiene) copolymer, poly (styrene-isoprene-butadiene) copolymer, poly (ethylene-propylene-diene) copolymer, polysulfide rubber, acrylic rubber, polyurethane rubber, silicone rubber, epichlorohydrin rubber, and halogenated butyl rubber, and any one of them or a mixture of two or more of them may be used.

The rubber composition may contain 0.1 to 200 parts by weight or 10 to 120 parts by weight of the filler, based on 100 parts by weight of the modified conjugated diene-based polymer of the present invention. The filler may be, for example, a silica-based filler, specifically, wet silica (hydrated silicate), dry silica (anhydrous silicate), calcium silicate, aluminum silicate, or colloidal silica. Preferably, the filler may be wet silica having the most remarkable improvement effect of the deterioration property and the compatible effect of the wet-road adhesion. Further, the rubber composition may further contain a carbon-based filler, if necessary.

In another embodiment, if silica is used as the filler, a silane coupling agent may be used together to improve the reinforcement and low heat release properties. Specific examples of the silane coupling agent may include: bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis (3-triethoxysilylpropyl) disulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, and mixtures thereof, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropylbenzothiazolyl tetrasulfide, 3-triethoxysilylpropylbenzoyl tetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis (3-diethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide or dimethoxymethylsilylpropylbenzothiazolyl tetrasulfide, and any one of them or a mixture of two or more of them may be used. Preferably, in view of the property-enhancing improvement effect, bis (3-triethoxysilylpropyl) polysulfide or 3-trimethoxysilylpropylbenzothiazolyl tetrasulfide may be used.

In addition, in the rubber composition according to one embodiment of the invention, since the modified conjugated diene-based polymer in which a functional group having high affinity with silica is introduced into an active site is used as a rubber component, the blending amount of the silane coupling agent can be smaller than that in the conventional case. Therefore, the silane coupling agent may be used in an amount of 1 to 20 parts by weight or 5 to 15 parts by weight, based on 100 parts by weight of the silica. Within the above amount range, the effect as a coupling agent can be sufficiently exhibited, and the effect of preventing gelation of the rubber component can be obtained.

The rubber composition according to one embodiment of the present invention may be sulfur-crosslinkable and, therefore, may further contain a vulcanizing agent. The vulcanizing agent may specifically be sulfur powder, and may be contained in an amount of 0.1 to 10 parts by weight, based on 100 parts by weight of the rubber component. Within the above range, the elasticity and strength required for the vulcanized rubber composition can be secured, and at the same time, an excellent low fuel consumption rate can be obtained.

The rubber composition according to one embodiment of the present invention may further contain various additives used in the conventional rubber industry, in particular, a vulcanization accelerator, a processing oil, an antioxidant, a plasticizer, an age resistor, an anti-scorching agent, zinc white, stearic acid, a thermosetting resin or a thermoplastic resin, in addition to the above components.

The vulcanization accelerator may include, for example, thiazole compounds such as 2-mercaptobenzothiazole (M), dibenzothiazyl Disulfide (DM) and N-cyclohexyl-2-benzothiazylsulfenamide (CZ); or a guanidine compound such as Diphenylguanidine (DPG), and may be contained in an amount of 0.1 to 5 parts by weight, based on 100 parts by weight of the rubber component.

The processing oil acts as a softener in the rubber composition and may include, for example, paraffins, naphthenes, or aromatics. In view of tensile strength and abrasion resistance, aromatic processing oils may be used; naphthenic or paraffinic process oils may be used in view of hysteresis loss and low temperature performance. The content of the processing oil may be 100 parts by weight or less based on 100 parts by weight of the rubber component. Within the above range, the tensile strength and low heat release performance (low fuel consumption rate) of the vulcanized rubber can be prevented from deteriorating.

The antioxidant may include, for example, 2, 6-di-t-butyl-p-cresol, dibutylhydroxytoluene, 2, 6-bis ((dodecylthio) methyl) -4-nonylphenol, or 2-methyl-4, 6-bis ((octylthio) methyl) phenol, and may be used in an amount of 0.1 parts by weight to 6 parts by weight, based on 100 parts by weight of the rubber component.

The age resistor may include, for example, N-isopropyl-N '-phenyl-p-phenylenediamine, N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine, 6-ethoxy-2, 2, 4-trimethyl-1, 2-dihydroquinoline, or a condensate of diphenylamine and acetone at a high temperature, and may be contained 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 one embodiment of the present invention can be obtained by mixing according to the mixing formulation using a mixing device such as a banbury mixer, a roll and an internal mixer. By the vulcanization process after the molding process, a rubber composition having low heat release properties and good abrasion resistance can be obtained.

Thus, the rubber composition can be used for manufacturing various members of a tire, such as a tire tread, a tread base, a sidewall, a carcass coating rubber, a belt coating rubber, a bead filler, a chafer and a bead coating rubber, or for manufacturing rubber products in various industries, such as a vibration damping rubber, a conveyor belt and a hose.

In addition, the present invention provides a tire manufactured using the rubber composition.

The tire may be a tire or include a tire tread.

Examples

Hereinafter, the present invention will be described in detail with reference to examples. Embodiments according to the present invention may be modified into various other types, and the scope of the present invention should not be limited to the embodiments described below. The embodiments of the present invention are provided to fully explain the present invention to those skilled in the art.

Preparation of example 1

(1) Preparation of the Compound represented by formula 2aa-1

10.11ml (91.46mmol) of N-methylaniline were dissolved in 284ml of methyl tert-butyl ether (MTBE) and the temperature was lowered to-20 ℃ and then 42.83ml (23% by weight, 105.18mmol) of an N-butyllithium hexane solution were slowly added thereto. The reaction solution was stirred for about 180 minutes while slowly raising the temperature to room temperature. If the reaction solution became light yellow, the temperature was again lowered to-20 ℃ and carbon dioxide was injected for about 20 minutes, followed by stirring for about one hour while raising the temperature to room temperature, to prepare a reaction product in a white slurry state. The temperature was again lowered to-20 ℃ and 9.27ml (114.33mmol) of Tetrahydrofuran (THF) and 62.4ml (18 wt%, 114.33mmol) of a solution of tert-butyllithium pentane were successively added and the reaction was carried out to prepare the reaction product as a dark yellow slurry. Then, after stirring at-10 ℃ for about 2 hours, the solvent was removed and washing was performed with hexane about three times under an argon atmosphere to prepare 14.9g (yield 99% or more) of the compound represented by the following formula 2aa-1 as a yellow solid. 20mg of the compound represented by formula 2aa-1 thus prepared was poured into a mixed solvent of aqueous HCl/hexane (1ml/1ml), a deprotection reaction was performed, and NMR was measured to confirm its preparation.

[ formula 2aa-1]

¹H NMR (500MHz, pyridine) < delta > 7.51(m,1H),7.19(m,1H),6.99(m,1H),3.33(s, 3H).

(2) Preparation of the Compound represented by formula 2aa-2

Next, 1.49g (9.15mmol) of the compound represented by formula 2aa-1 was added to a closed system autoclave reactor capable of performing a reaction at high temperature/high pressure, and 1.56g (22.87mmol) of isoprene and 2.11g (11.43mmol) of bis (tetrahydrofuryl) propane (DTHFP) were injected in a cyclohexane solvent, followed by performing a reaction at 8 bar and 100 ℃ for 24 hours. After the reaction was completed, the solvent was removed by vacuum concentration, and filtration was performed with hexane to remove the unreacted compound represented by formula 2aa-1 and obtain the compound represented by formula 2aa-2 below dissolved in the filtrate. 20mg of the compound represented by formula 2aa-2 was poured into a mixed solvent of aqueous HCl/hexane (1ml/1ml), a deprotection reaction was performed, and NMR was measured to confirm that the compound represented by formula 2aa-2 was produced.

[ formula 2aa-2]

¹H NMR(500MHz,CDCl₃):δ7.07-7.01(m,2H),6.65-6.63(m,2H),5.75(m,1H),5.20(m,1H),4.0(s,1H),3.21(d,2H),3.09(s,1H),2.00(m,4H),1.82(s,6H),1.70(s,3H)。

Preparation of example 2

Two vacuum dried 2L stainless steel pressure vessels were prepared. Into the first pressure vessel were charged 516g of cyclohexane, 217.6g of a compound represented by the following formula 2bd, and 108g of tetramethylethylenediamine to prepare a first reaction solution. Meanwhile, 258g of 2.5M n-butyllithium and 472g of cyclohexane were charged into the second pressure vessel to prepare a second reaction solution. In this case, the molar ratio of the compound represented by formula 2bd, n-butyllithium and tetramethylethylenediamine was 1:1: 1. The pressure of each pressure vessel was maintained at 4 bar, and the first reaction solution and the second reaction solution were injected into the continuous reactor through the first continuous channel at an injection rate of 1.0g/min and the second continuous channel at an injection rate of 1.0g/min, respectively, using mass flow meters. In this case, the temperature of the continuous reactor was maintained at 25 ℃, the internal pressure was maintained at 2 bar using a back pressure regulator, and the residence time in the reactor was controlled within 10 minutes to prepare a modified initiator. After the reaction was completed, the conversion of the compound represented by formula 2bd was confirmed to be 99% or more by gas chromatography analysis, confirming that the modification initiator was prepared.

[ formula 2bd ]

Preparation of example 3

Two vacuum dried 2L stainless steel pressure vessels were prepared. Into the first pressure vessel were charged 6,922g of cyclohexane, 120g of a compound represented by the following formula 2ca, and 60g of tetramethylethylenediamine to prepare a first reaction solution. Meanwhile, 180g of 2.0M n-butyllithium and 6,926g of cyclohexane were charged into the second pressure vessel to prepare a second reaction solution. In this case, the molar ratio of the compound represented by formula 2ca, n-butyllithium and tetramethylethylenediamine was 1:1: 1. The pressure of each pressure vessel was maintained at 7 bar, and the first reaction solution and the second reaction solution were injected into the continuous reactor through the first continuous channel at an injection rate of 1.0g/min and the second continuous channel at an injection rate of 1.0g/min, respectively, using mass flow meters. In this case, the temperature of the continuous reactor was maintained at-10 ℃, the internal pressure was maintained at 3 bar using a back pressure regulator, and the residence time in the reactor was controlled within 10 minutes to prepare a modified initiator. After the reaction was completed, analysis by gas chromatography confirmed that the conversion of the compound represented by formula 2ca was 99% or more, confirming that the modification initiator was prepared.

[ formula 2ca ]

Preparation of example 4

Two vacuum dried 2L stainless steel pressure vessels were prepared. Into the first pressure vessel were charged 516g of cyclohexane, 100g of a compound represented by the following formula 2db, and 105g of tetramethylethylenediamine to prepare a first reaction solution. Meanwhile, 248g of 2.5M n-butyllithium and 472g of cyclohexane were charged into the second pressure vessel to prepare a second reaction solution. In this case, the molar ratio of the compound represented by the formula 2db, n-butyllithium and tetramethylethylenediamine was 1:1: 1. The pressure of each pressure vessel was maintained at 4 bar, and the first reaction solution and the second reaction solution were injected into the continuous reactor through the first continuous channel at an injection rate of 1.0g/min and the second continuous channel at an injection rate of 1.0g/min, respectively, using mass flow meters. In this case, the temperature of the continuous reactor was maintained at 0 ℃, the internal pressure was maintained at 2 bar using a back pressure regulator, and the residence time in the reactor was controlled within 10 minutes to prepare a modified initiator. After the reaction was completed, the conversion of the compound represented by formula 2db was confirmed to be 99% or more by gas chromatography analysis, confirming that the modification initiator was prepared.

[ formula 2db ]

Preparation of example 5

Two vacuum dried 2L stainless steel pressure vessels were prepared. Into the first pressure vessel were charged 6,922g of cyclohexane, 52.2g of a compound represented by the following formula 2ea, and 60g of tetramethylethylenediamine to prepare a first reaction solution. Meanwhile, 180g of 2.0M n-butyllithium and 6,926g of cyclohexane were charged into the second pressure vessel to prepare a second reaction solution. In this case, the molar ratio of the compound represented by formula 2ea, n-butyllithium and tetramethylethylenediamine was 1:1: 1. The pressure of each pressure vessel was maintained at 7 bar, and the first reaction solution and the second reaction solution were injected into the continuous reactor through the first continuous channel at an injection rate of 1.0g/min and the second continuous channel at an injection rate of 1.0g/min, respectively, using mass flow meters. In this case, the temperature of the continuous reactor was maintained at-10 ℃, the internal pressure was maintained at 3 bar using a back pressure regulator, and the residence time in the reactor was controlled within 10 minutes to prepare a modified initiator. After the reaction was completed, the conversion of the compound represented by formula 2ea was confirmed to be 99% or more by gas chromatography analysis, confirming that the modification initiator was prepared.

[ formula 2ea ]

Preparation of example 6

To the flask were added 60g of cyclohexane, 2.04g (0.02mol) of N, N' -dimethylpropane-1, 3-diamine and 6.93g (0.044mol) of 1-bromo-3-chloropropane, and reacted by stirring at 60 ℃ for 4 hours. 1.39g (0.2mol) of Li was added thereto and stirred at 40 ℃ for 12 hours, and unreacted materials were removed. 2.72g (0.04mol) of isoprene was added and stirred at 40 ℃ for 1 hour to prepare a compound represented by the following formula 2 fa. The active Li concentration of the thus-prepared compound was measured by a titration method using diphenylacetic acid, and the active Li concentration thus measured was 0.55M (to the extent of 83% compared to the calculated active Li concentration (0.66M)).

[ formula 2fa ]

Example 1

To the first reactor among the continuous reactors connected in series of three reactors, a styrene solution in which 60% by weight of styrene was dissolved in n-hexane at a rate of 1.92kg/h, a 1, 3-butadiene solution in which 60% by weight of 1, 3-butadiene was dissolved in n-hexane at a rate of 11.80kg/h, n-hexane at a rate of 47.73kg/h, a 1, 2-butadiene solution in which 2.0% by weight of 1, 2-butadiene was dissolved in n-hexane at a rate of 40g/h, a solution in which 10% by weight of 2,2- (di (2-tetrahydrofuryl) propane was dissolved in n-hexane as a polar additive at a rate of 53g/h, and a solution in which 10% by weight of the compound represented by formula 2aa-2 prepared in preparation example 1 was dissolved in n-hexane as a modification initiator were injected at a rate of 185.0g/h In this case, the temperature of the first reactor was maintained at 50 ℃, and when the polymerization conversion rate reached 39%, the polymerization reactant was transferred from the first reactor to the second reactor through the transfer pipe.

Then, a 1, 3-butadiene solution in which 60% by weight of 1, 3-butadiene was dissolved in n-hexane was injected into the second reactor at a rate of 2.95 kg/h. In this case, the temperature of the second reactor was maintained at 65 ℃, and when the polymerization conversion rate reached 95% or more, the polymerization reactant was transferred from the second reactor to the third reactor through the transfer pipe.

The polymerization reactant was transferred from the second reactor to the third reactor, and a solution in which 20% by weight of a compound represented by formula 1a below was dissolved as a modifier was continuously injected into the third reactor (the molar ratio of [ modifier ]: act.li ] was 1: 1). The temperature of the third reactor was maintained at 70 ℃.

Thereafter, to the polymerization solution discharged from the third reactor, an IR1520(BASF Co.) solution having 30% by weight of an antioxidant dissolved therein was injected at a rate of 167g/h and stirred. The thus-obtained polymer was poured into hot water heated with steam and stirred to remove the solvent, thereby preparing a conjugated diene-based polymer modified at both ends.

[ formula 1a ]

Example 2

A conjugated diene-based polymer having both ends modified was prepared by carrying out the same method as in example 1, except that in example 1, the polymerization reactant was transferred from the first reactor to the second reactor through a transfer pipe when the polymerization conversion rate reached 41%, and a solution in which 20% by weight of a compound represented by formula 1b below was dissolved as a modifier was continuously supplied to the third reactor (molar ratio of [ modifier ]: [ act.li ]: 1).

[ formula 1b ]

Example 3

A conjugated diene-based polymer having both ends modified was prepared by carrying out the same method as in example 1, except that in example 1, the polymerization reactant was transferred from the first reactor to the second reactor through a transfer pipe when the polymerization conversion rate reached 40%, and a solution in which 20% by weight of a compound represented by the following formula 1c was dissolved as a modifier was continuously supplied to the third reactor (molar ratio of [ modifier ]: [ act.li ]: 1).

[ formula 1c ]

Example 4

A conjugated diene-based polymer having both ends modified was prepared by carrying out the same method as in example 1, except that in example 1, the polymerization reactant was transferred from the first reactor to the second reactor through a transfer pipe when the polymerization conversion rate reached 40%, and a solution in which 20% by weight of a compound represented by formula 1d below was dissolved as a modifier was continuously supplied to the third reactor (molar ratio of [ modifier ]: [ act.li ]: 1).

[ formula 1d ]

Example 5

A conjugated diene-based polymer modified at both ends was prepared by carrying out the same method as in example 1, except that a solution in which 10% by weight of the modification initiator prepared in preparation example 2 was dissolved as a modification initiator in n-hexane was injected at a rate of 165 g/h.

Example 6

A conjugated diene-based polymer modified at both ends was prepared by carrying out the same method as in example 1, except that a solution in which 10% by weight of the modification initiator prepared in preparation example 3 was dissolved as a modification initiator in n-hexane was injected at a rate of 185 g/h.

Example 7

To the first reactor of the continuous reactors connected in series of three reactors, a styrene solution in which 60% by weight of styrene was dissolved in n-hexane was injected at a rate of 3.58kg/h, a 1, 3-butadiene solution in which 60% by weight of 1, 3-butadiene was dissolved in n-hexane at a rate of 10.47kg/h, n-hexane at a rate of 47.59kg/h, a 1, 2-butadiene solution in which 2.0% by weight of 1, 2-butadiene was dissolved in n-hexane at a rate of 40g/h, a solution in which 10% by weight of 2,2- (di (2-tetrahydrofuryl) propane was dissolved in n-hexane as a polar additive at a rate of 127g/h, and a solution in which 10% by weight of the modification initiator prepared in preparation example 4 was dissolved in n-hexane as a modification initiator at a rate of 130g/h, the temperature of the first reactor was maintained at 50 ℃, and when the polymerization conversion rate reached 41%, the polymerization reactant was transferred from the first reactor to the second reactor through the transfer pipe.

Then, a 1, 3-butadiene solution in which 60% by weight of 1, 3-butadiene was dissolved in n-hexane was injected into the second reactor at a rate of 2.62 kg/h. In this case, the temperature of the second reactor was maintained at 65 ℃, and when the polymerization conversion rate reached 95% or more, the polymerization reactant was transferred from the second reactor to the third reactor through the transfer pipe.

The polymerization reactant was transferred from the second reactor to the third reactor, and a solution in which 20% by weight of a compound represented by formula 1a below was dissolved as a modifier was continuously injected into the third reactor (the molar ratio of [ modifier ]: act.li ] was 1: 1). The temperature of the third reactor was maintained at 70 ℃.

Thereafter, to the polymerization solution discharged from the third reactor, an IR1520(BASF Co.) solution having 30% by weight of an antioxidant dissolved therein was injected at a rate of 167g/h and stirred. The thus-obtained polymer was poured into hot water heated with steam and stirred to remove the solvent, thereby preparing a conjugated diene-based polymer modified at both ends.

[ formula 1a ]

Example 8

A conjugated diene-based polymer having both ends modified was prepared by performing the same method as in example 7, except that in example 7, the polymerization reactant was transferred from the first reactor to the second reactor through a transfer pipe when the polymerization conversion rate reached 43%, and a solution in which 20 wt% of the compound represented by the following formula 1b was dissolved as a modifier in n-hexane was continuously supplied to the third reactor (molar ratio of [ modifier ]: [ act.li ]: 1).

[ formula 1b ]

Example 9

A conjugated diene-based polymer having both ends modified was prepared by carrying out the same method as in example 7, except that in example 7, a solution in which 20% by weight of a compound represented by the following formula 1c was dissolved as a modifier in n-hexane was continuously supplied to a third reactor (molar ratio of [ modifier ]: act.li ] 1: 1).

[ formula 1c ]

Example 10

A conjugated diene-based polymer having both ends modified was prepared by carrying out the same method as in example 7, except that in example 7, a solution in which 20% by weight of a compound represented by the following formula 1e was dissolved as a modifier in n-hexane was continuously supplied to a third reactor (molar ratio of [ modifier ]: act.li ] 1: 1).

[ formula 1e ]

Example 11

A conjugated diene-based polymer modified at both ends was prepared by carrying out the same method as in example 7, except that a solution in which 10% by weight of the modification initiator prepared in preparation example 5 was dissolved as a modification initiator in n-hexane was injected at a rate of 121 g/h.

Example 12

A conjugated diene-based polymer having both terminals modified was produced by carrying out the same method as in example 1, except that in example 1, a solution in which 10% by weight of the compound represented by formula 2fa produced in production example 6 was dissolved as a modification initiator in n-hexane was injected at a rate of 265.0g/h, and a polymerization reactant was transferred from the first reactor to the second reactor through a transfer pipe when the polymerization conversion rate reached 41%.

Comparative example 1

Into a 20L autoclave reactor, 100g of styrene, 880g of 1, 3-butadiene, 5000g of n-hexane and 0.89g of 2, 2-bis (2-tetrahydrofuryl) propane as a polar additive were injected, and the internal temperature of the reactor was raised to 50 ℃. When the internal temperature of the reactor reached 50 ℃, 5.5mmol of the compound represented by formula 2aa-2 prepared in preparation example 1 was injected as a modification initiator, and an adiabatic reaction with heating was performed. After about 20 minutes, 20g of 1, 3-butadiene were injected to end-cap the ends of the polymer chains with butadiene. After 5 minutes, 5.5mmol of the compound represented by formula 1a was injected as a modifier, and reacted for 15 minutes. Then, the polymerization reaction was quenched with ethanol, and 45ml of a solution in which 0.3 wt% of IR1520(BASF Co.) antioxidant was dissolved in n-hexane was added thereto. The thus-obtained polymer was poured into hot water heated with steam and stirred to remove the solvent, thereby preparing a conjugated diene-based polymer modified at both ends.

Comparative example 2

A single terminal-modified conjugated diene-based polymer was produced by carrying out the same process as in example 4, except that in example 4, an n-butyllithium solution in which 10% by weight of n-butyllithium was dissolved in n-hexane in place of the modification initiator was injected at a rate of 75.0g/h, the temperature of the first reactor was maintained at 55 ℃, and the polymerization reactant was transferred from the first reactor to the second reactor through a transfer pipe when the polymerization conversion rate reached 45%.

Comparative example 3

A conjugated diene-based polymer having both terminals modified was prepared by carrying out the same process as in example 1, except that in example 1, the temperature of the first reactor was maintained at 75 ℃, the temperature of the second reactor was maintained at 80 ℃, the temperature of the third reactor was maintained at 80 ℃ and the polymerization reactant was transferred from the first reactor to the second reactor through the transfer pipe when the polymerization conversion rate reached 68%.

Comparative example 4

A single terminal-modified conjugated diene-based polymer was prepared by carrying out the same method as in example 1, except that in example 1, the polymerization reactant was transferred from the first reactor to the second reactor through the transfer pipe when the polymerization conversion rate reached 42%, and the reaction was carried out without injecting the modifier into the third reactor.

Comparative example 5

A single terminal-modified conjugated diene-based polymer was produced by carrying out the same process as in example 1, except that in example 1, a solution of n-butyllithium in which 10% by weight of the compound of production example 1 was dissolved in n-hexane as a modification initiator was continuously injected into the first reactor at a rate of 75.0g/h, instead of the n-butyllithium solution, and the polymerization reactant was transferred from the first reactor to the second reactor through a transfer pipe when the polymerization conversion rate reached 41%.

Comparative example 6

A single terminal-modified conjugated diene-based polymer was prepared by performing the same method as in example 9, except that in example 9, a solution of n-butyllithium in which 10% by weight of n-butyllithium was dissolved in n-hexane instead of the compound prepared in preparation example 3 as a modification initiator was continuously injected into the first reactor at a rate of 75.0g/h, the temperature of the first reactor was maintained at 55 ℃, a polymerization reactant was transferred from the first reactor to the second reactor through a transfer pipe when the polymerization conversion rate reached 49%, and a solution in which 20% by weight of the compound represented by formula 1d was dissolved in n-hexane as a modifier was continuously injected into the third reactor (the molar ratio of [ modifier ]: [ act.li ]: 1).

Comparative example 7

A conjugated diene-based polymer having both ends modified was prepared by carrying out the same method as in example 5, except that in example 5, the polymerization reactant was conveyed from the first reactor to the second reactor through a conveying pipe when the polymerization conversion rate reached 41%, and a solution in which 20% by weight of a compound represented by the following formula i was dissolved as a modifier in n-hexane was continuously injected into the third reactor (molar ratio of [ modifier ]: [ act.li ]: 1).

[ formula i ]

In formula i, Me is methyl.

Comparative example 8

A conjugated diene-based polymer having both ends modified was prepared by carrying out the same method as in example 6, except that in example 6, the polymerization reactant was conveyed from the first reactor to the second reactor through a conveying pipe when the polymerization conversion rate reached 41%, and a solution in which 20% by weight of a compound represented by the following formula ii was dissolved as a modifier in n-hexane was continuously supplied to the third reactor (molar ratio of [ modifier ]: [ act.li ]: 1).

[ formula ii ]

In formula ii, TMS is trimethylsilyl and Me is methyl.

Comparative example 9

A conjugated diene-based polymer having both ends modified was prepared by performing the same method as in example 5, except that in example 5, a polymerization reactant was transferred from the first reactor to the second reactor through a transfer pipe when the polymerization conversion rate reached 41%, a solution in which 10 wt% of the modification initiator prepared in preparation example 4 was dissolved as a modification initiator in n-hexane was injected at a rate of 130g/h, and a solution in which 20 wt% of the compound represented by the following formula iii was dissolved as a modifier in n-hexane was continuously supplied to the third reactor (the molar ratio of [ modifier ]: [ act.li ]: 1).

[ formula iii ]

In formula iii, TMS is trimethylsilyl and Me is methyl.

Comparative example 10

A conjugated diene-based polymer modified at both ends was prepared by carrying out the same process as in comparative example 1, except that 28mmol of 3- (dimethoxy (methyl) silyl) -N, N-diethylpropane-1-amine was injected as a modifier in comparative example 1.

Comparative example 11

A conjugated diene-based polymer modified at both ends was prepared by carrying out the same process as in comparative example 1, except that in comparative example 1, 1.6mmol of 3- (dimethoxy (methyl) silyl) -N, N-diethylpropane-1-amine was injected as a modifier.

Experimental example 1

The following physical properties were measured for each of the single-terminal or both-terminal modified conjugated diene-based polymers prepared in examples and comparative examples, and the results are shown in the following tables 1 and 2.

1) Styrene Unit content and vinyl content (% by weight)

Styrene unit (SM) content and vinyl content in each polymer were measured and analyzed using a Varian VNMRS 500MHz NMR.

When NMR was measured, 1,2, 2-tetrachloroethane was used as a solvent, and the styrene unit content and the vinyl group content were calculated by calculating that the peak of the solvent was 5.97ppm, and 7.2 to 6.9ppm was considered as a random styrene peak, 6.9 to 6.2ppm was a block styrene peak, 5.8 to 5.1ppm was a 1, 4-vinyl peak, and 5.1 to 4.5ppm was a 1, 2-vinyl peak. A sample was prepared by dissolving 10mg of the polymer in 1mL of 1,1,2, 2-tetrachloroethane.

^{3 3}2) Weight average molecular weight (Mw,. times.10 g/mol), number average molecular weight (Mn,. times.10 g/mol), peak-to-peak molecular weight ³(maximum peak molecular weight) (Mp,. times.10 g/mol), number of couplings (C.N) and molecular weight distribution (PDI, MWD)

the weight average molecular weight (Mw), the number average molecular weight (Mn), and the peak molecular weight (Mp) were measured by Gel Permeation Chromatography (GPC) (PL GPC220, Agilent Technologies) under the following conditions, and a molecular weight distribution curve was obtained. Further, the molecular weight distribution (PDI, MWD, Mw/Mn) was calculated from the respective molecular weights thus measured. In this case, the molecular weight distribution curves thus obtained are shown in fig. 1 to 4.

-a column: two PLgel oxides (Polymer Laboratories Co.) and one PLgel mixed-C (Polymer Laboratories Co.) were used in combination

-a solvent: using a mixture of tetrahydrofuran and 2% by weight of an amine compound

-flow rate: 1ml/min

-sample concentration: 1-2mg/ml (diluted in THF)

-injection amount: 100 μ l

Column temperature: 40 deg.C

-a detector: refractive index

-standard: polystyrene (calibrated by cubic function)

In addition, the coupling number is obtained as follows: in each of examples and comparative examples, a part was collected before the injection of the modifier or the coupling agentPolymer, peak molecular weight (Mp) of the resulting polymer₁) To obtain the peak molecular weight (Mp) of each of the modified conjugated diene polymers₂) And is calculated according to the following mathematical formula 2:

[ mathematical formula 2]

Coupling number (C.N) ═ Mp₂/Mp₁

3) Mooney viscosity and Mooney stress relaxation ratio

Mooney viscosity (MV, (ML1+4, @100 ℃) MU) was measured at 100 ℃ using a large rotor at a rotor speed of 2. + -. 0.02rpm using MV-2000(Alpha Technologies Co.). In this case, the sample used was left at room temperature (23 ± 3 ℃) for 30 minutes or more, and 27 ± 3g of the sample was collected and put into the cavity, and then, the platen was operated for 4 minutes for measurement.

After the mooney viscosity was measured, a value of a slope of a change in mooney viscosity exhibited when the torque was released was measured, and a mooney stress relaxation ratio was obtained.

4) Si content

The Si content was measured by an ICP analysis method using inductively coupled plasma emission spectrometry (ICP-OES; Optima 7300 DV). Specifically, the measurement was performed as follows: about 0.7g of the sample was added to a platinum (Pt) crucible and about 1ml of concentrated sulfuric acid (98 wt%, electronic grade) was added thereto, heated at 300 ℃ for 3 hours, and the sample was incinerated in an electric furnace (Thermo Scientific, Lindberg Blue M) by the following procedure of steps 1 to 3:

1) step 1: the initial temperature was 0 ℃, the rate (temperature/hour) was 180 ℃/hour, the temperature (holding time) was 180 ℃ (1 hour),

2) step 2: the initial temperature was 180 ℃, the rate (temperature/hour) was 85 ℃/hour, the temperature (hold time) was 370 ℃ (2 hours),

3) and step 3: the initial temperature was 370 ℃, the rate (temperature/hour) was 47 ℃/hour, the temperature (hold time) was 510 ℃ (3 hours),

to the residue were added 1mL of concentrated nitric acid (48 wt%) and 20 μ l of concentrated hydrofluoric acid (50 wt%), the platinum crucible was sealed and shaken for 30 minutes or more, 1mL of boric acid was added to the sample, stored at 0 ℃ for 2 hours or more, diluted in 30mL of ultrapure water, and incinerated.

5) Content of N

The N content was measured by the NSX analysis method using a quantitative analyzer for trace nitrogen (NSX-2100H). Specifically, the quantitative analyzer for trace nitrogen (autosampler, horizontal furnace, PMT) was turned on&Nitrogen detector) the carrier gas flow was set such that Ar was 250ml/min, O₂350ml/min, 300ml/min ozone generator, heater set to 800 ℃, and analyzer left for about 3 hours for stabilization. After the analyzer was stabilized, calibration curves were prepared using nitrogen standards (AccuStandard S-22750-01-5ml) over the calibration curve ranges of 5ppm, 10ppm, 50ppm, 100ppm and 500ppm, giving areas corresponding to the respective concentrations. Then, a straight line is formed by using the ratio of the concentration to the area. Thereafter, the ceramic boat containing 20mg of the sample was placed in an autosampler of an analyzer and measured to obtain an area. Using the area of the sample thus obtained and the calibration curve, the N content was calculated.

[ Table 1]

[ Table 2]

In tables 1 and 2, PI means an initiator, M means a modifier or a coupling agent, and specific substances of the initiator, the modifier and the coupling agent are shown in the following table 3.

[ Table 3]

Referring to tables 1 and 2, it can be confirmed that the modified conjugated diene-based polymers of examples 1 to 12 prepared according to the embodiment of the present invention satisfy all the ranges of the required physical properties. Specifically, the molecular weight distribution curve has a unimodal shape, and at the same time, the PDI value is less than 1.7, it can be expected that the processability will be remarkably excellent and the compounding property will be excellent. All of the mooney stress relaxation ratios are 0.7 or more, preferably, 0.8 or more, and it is expected that the linearity will be excellent.

In contrast, it was confirmed that comparative example 3, in which the polymerization conversion rate was not controlled when transferred from the first reactor to the second reactor, exhibited a high PDI value and a mooney stress relaxation ratio of a specific value or less, and the balance or linearity of physical properties exhibited unsatisfactory results.

In addition, the conventional modified conjugated diene-based polymer obtained by applying the batch polymerization as in comparative example 1 has a PDI value of less than 1.7, but has a molecular weight distribution curve of a bimodal shape, and it can be expected that the processability will be poor. In the results of the batch polymerization, as in comparative example 10 and comparative example 11, a molecular weight distribution curve of a unimodal shape can be exhibited, but this corresponds to an extreme case having a minimum value or a maximum value of the coupling number, and as found from the above explanation or evaluation results explained later, such a modified conjugated diene-based polymer by the batch polymerization causes deterioration of compounding property.

Fig. 1 to 4 show molecular weight distribution curves of example 1, comparative example 10, and comparative example 11, and it can be confirmed that the respective shapes of the molecular weight distribution curves are the same as described above.

Experimental example 2

In order to comparatively analyze the physical properties of the rubber compositions comprising each of the both-terminal or single-terminal modified conjugated diene-based copolymers prepared in examples and comparative examples and the molded articles made from the rubber compositions, the tensile properties and viscoelastic properties were measured, respectively, and the results are shown in the following tables 5 and 6.

1) Preparation of rubber test specimens

Using the modified conjugated diene polymers of examples and comparative examples as raw material rubbers, compounding was performed under the compounding conditions shown in table 4 below. The raw materials in table 4 are represented by parts by weight based on 100 parts by weight of the raw rubber.

[ Table 4]

Specifically, the rubber sample was obtained by kneading in the first stage and the second stage. In the first-stage mixing, a raw material rubber, silica (filler), an organosilane coupling agent (X50S, Evonik), a processing oil (TADE oil), zinc oxide (ZnO), stearic acid, an antioxidant (tmq (rd)) (2,2, 4-trimethyl-1, 2-dihydroquinoline polymer), an antiaging agent (6PPD ((dimethylbutyl) -N-phenyl-phenylenediamine), and a wax (microcrystalline wax) were mixed using a banbury mixer equipped with a temperature control device, in which case the initial temperature of the mixing device was controlled to 70 ℃, and after completion of mixing, a first mixed mixture was obtained at a discharge temperature of 145 ℃ to 155 ℃ Sulfonamide)) was added to the compounding apparatus and mixed at a temperature of 100 ℃ or less to give a second compounded mixture. Then, a rubber sample was formed by performing a curing process at 160 ℃ for 20 minutes.

2) Tensile Properties

Tensile properties were measured as follows: according to ASTM 412 tensile test method, each specimen was manufactured and the tensile strength when each specimen was broken and the tensile stress when each specimen was stretched by 300% (300% modulus) were measured. Specifically, tensile properties were measured at 50cm/min at room temperature using a Universal Test machine 4204 tensile tester (Instron co.).

3) Viscoelastic property

Viscoelastic properties were determined by measuring the viscoelastic behavior of the thermodynamic deformation at various measurement temperatures (-60 ℃ to 60 ℃) at a frequency of 10Hz in the film stretching mode with a dynamic mechanical analyzer (GABO Co.) and obtaining tan δ values. According to the obtained values, if the index value of tan δ is increased at a low temperature of 0 ℃, the wet skid resistance becomes better, and if the index value of tan δ is decreased at a high temperature of 60 ℃, the hysteresis loss is decreased, and the low rolling resistance (fuel consumption rate) becomes better.

4) Processability (M-Y-Y

The processability of the individual polymers was comparatively analyzed by measuring the Mooney viscosity (MV, (ML1+4 @100 ℃ C.) MU) of the second compounded mixture obtained in 1) the process for preparing rubber samples, in which case the lower the Mooney viscosity measurement, the better the processability.

Specifically, each second compounded mixture was left at room temperature (23 ± 3 ℃) for 30 minutes or more at 100 ℃ with MV-2000(Alpha Technologies Co.) using a large rotor at a rotor speed of 2 ± 0.02rpm, and 27 ± 3g was collected, put into a mold cavity, and then, the press plate was operated for 4 minutes.

[ Table 5]

In table 5, the results of viscoelastic properties of examples 1 to 6, example 12, comparative examples 1 to 4, and comparative examples 7 to 11 are indicated and shown based on the measured value of comparative example 5. Higher values indicate better results.

Referring to table 5, as expected by measuring physical properties of the polymer in experimental example 1, examples 1 to 6 and example 12 exhibited significantly excellent tensile strength and modulus, and for viscoelastic properties, it was confirmed that the tan δ value at a low temperature was at a slightly increased level, and the tan δ value at a high temperature was significantly increased, and it was confirmed that the fuel consumption rate was significantly improved without loss of wet skid resistance.

In addition, it was confirmed that, as in comparative example 10 and comparative example 11, in the case where the polymers produced by the batch polymerization had a molecular weight distribution curve of a single peak shape, poor processability inherent to the batch polymerization itself was exhibited, and excellent compounding performance that could be achieved as an advantage of the batch polymerization was not achieved. Meanwhile, in comparative example 1 in which the same coupling number range as in example was applied, poor processability inherent in batch polymerization could be confirmed.

In addition, in the case of comparative example 3, which shows the results obtained by not applying the production method of the present invention, it can be found that the ranges of the PDI value and the mooney stress relaxation ratio are not satisfied, and that the poor viscoelasticity is noted as compared with the examples. Further, in the same manner, in the case of comparative examples 2,4, 5, 7 to 9 to which the modifier and/or the modification initiator according to the present invention was not applied, viscoelastic properties were poor or processability was poor.

[ Table 6]

In table 6, the results of viscoelastic properties of examples 7 to 11 are indicated (%) based on the measured values of comparative example 6 and are shown. Higher values indicate better results.

Table 6 shows the result set evaluated by changing the content of the comonomer in the set of table 5, and it can be confirmed from table 6 that the effect is not changed although the content of the monomer is changed, and the same result as the improved result of the physical properties as confirmed in table 5 is exhibited.