RU2815196C1 - Modified polymer based on conjugated diene, method of its production and rubber composition containing it - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to a modified conjugated diene-based polymer, a method of its preparation, as well as a rubber composition comprising it. The modified conjugated diene polymer comprises a first chain containing a repeating unit based on a conjugated diene, a second chain containing a repeating unit derived from a compound represented by the formula, and a unit derived from an alkoxysilane-based modifier. The first and second chains are connected through a link obtained from a modifier.

EFFECT: modified polymer has excellent processability, good tensile strength and viscoelasticity.

13 cl, 5 tbl, 7 ex

Description

Field of technology

Cross reference to related applications

This application claims priority under Republic of Korea Patent Application No. 10-2019-0113004 filed on September 11, 2019 and Republic of Korea Patent Application No. 110-2020-0116307 and Republic of Korea Patent Application No. 10-2020-0116305 , filed September 10, 2020, the contents of which are incorporated herein by reference in their entirety.

The present invention relates to a modified conjugated diene polymer having excellent processability and good tensile strength and viscoelastic properties, a method for producing the same, and a rubber composition including the polymer.

According to the current demand for low fuel consumption vehicles, a conjugated diene polymer is required as a rubber material for tires, which has modulation stability represented by skid resistance on wet road surfaces, as well as low rolling resistance and excellent abrasion resistance and performance properties. stretching

To reduce the rolling resistance of tires, there is a method for reducing the hysteresis loss of vulcanized rubber, and rebound elasticity at a temperature of 50°C to 80°C, tan δ, Goodrich heat generation or the like is used as the evaluation index of vulcanized rubber. That is, it is desirable to use a rubber material having high rebound elasticity at the above temperature or low tan δ or Goodrich heat generation value.

Natural rubbers, polyisoprene rubbers or polybutadiene rubbers are known as low hysteresis loss rubber materials, but such rubbers are limited by low slip resistance on wet road surfaces. Thus, recently, polymers or copolymers based on conjugated diene, such as styrene butadiene rubbers (hereinafter referred to as "BSR") and butadiene rubbers (hereinafter referred to as "BDK"), are prepared by emulsion polymerization or solution polymerization, for use as rubber for tires. Among these polymerization methods, the greatest advantage of solution polymerization over emulsion polymerization is that the vinyl structure content and styrene content, which determine the physical properties of the rubber, can be arbitrarily adjusted, and its molecular weight and physical properties can be adjusted by combination or modification. Thus, SBR produced by solution polymerization is widely used as a rubber material for tires because the structure of the resulting SBR or BdR is easy to change, and the movement of chain end groups can be reduced and the bonding force with filler such as silica and carbon black, by combining or modifying chain end groups.

If SBR (styrene butadiene rubber) obtained by solution polymerization is used as the rubber material, since the glass transition temperature of rubber increases with the vinyl content of SBR, the physical properties such as rolling resistance and braking force required for tires can be adjusted, and Fuel consumption can be reduced by appropriately regulating the glass transition temperature. Solution polymerized BSA is prepared using an anionic polymerization initiator and is used by combining or modifying the chain end groups of the polymer thus obtained to introduce a functional group into the end group, using various modifiers. For example, US 4,397,994 discloses a method of coupling the active end-chain anions of a polymer obtained by polymerizing butadiene and styrene using an alkyl lithium, which is a monofunctional polymerization initiator in a non-polar solvent, using a coupling agent such as a tin compound.

In addition, to introduce a functional group modifier at the end group of a polymer chain, a widely known technique is to use an aminoalkoxysilane-based modifier, including an alkoxysplane group and an amino group in the molecule, to simultaneously increase the dispersibility and reactivity of the filler. However, if the amount of amino groups in the modifier is increased, problems arise in that the solubility in the hydrocarbon solvent used to prepare the polymer may decrease and a simple modification reaction may become difficult.

Description of the invention

The present invention is designed to solve the above problems of conventional technology and aims to provide a modified conjugated diene polymer including a second chain containing a repeating unit derived from the compound represented by Formula 1 and a unit derived from an alkoxysilane modifier in the polymer, and having excellent affinity for the filler.

It is further an object of the present invention to provide a method for producing a modified conjugated diene polymer comprising a first polymer chain modified with a modifier and a second chain derived from a macromonomer, wherein the first chain and the second chain are connected through a unit derived from the modifier by including the step reacting a macromonomer comprising a repeating unit derived from the compound represented by Formula 1 after a modification reaction.

The present invention also provides a rubber composition comprising a modified conjugated diene polymer.

To solve the above objects, according to an embodiment of the present invention, there is provided a modified conjugated diene polymer, comprising: a first chain containing a repeating unit derived from a conjugated diene monomer; a second chain containing a repeating unit derived from a compound represented by the following formula 1 and a functional group derived from an alkoxysilane-based modifier, wherein the first chain and the second chain are connected by a unit derived from the modifier:

Formula 1

in formula 1

each of R _1a -R _1c independently represents a hydrogen atom; an alkyl group containing from 1 to 20 carbon atoms; an alkenyl group containing from 2 to 20 carbon atoms; an alkynyl group containing from 2 to 20 carbon atoms; a heteroalkyl group containing from 1 to 20 carbon atoms; a heteroalkenyl group containing from 2 to 20 carbon atoms; a heteroalkynyl group containing from 2 to 20 carbon atoms; a cycloalkyl group containing from 5 to 20 carbon atoms; an aryl group containing from 6 to 20 carbon atoms or a heterocyclic group containing from 3 to 20 carbon atoms,

R _1d represents a single bond, substituted by a substituent or an unsubstituted alkylene group containing from 1 to 20 carbon atoms; a substituted or unsubstituted cycloakylene group containing from 5 to 20 carbon atoms, or a substituted or unsubstituted arylene group containing from 6 to 20 carbon atoms, where the substituent is an alkyl group containing from 1 to 10 carbon atoms; a cycloalkyl group containing from 5 to 10 carbon atoms, or an aryl group containing from 6 to 20 carbon atoms, and

R _1e represents an alkyl group containing from 1 to 20 carbon atoms; an alkenyl group containing from 2 to 20 carbon atoms; an alkynyl group containing from 2 to 20 carbon atoms; a heteroalkyl group containing from 1 to 20 carbon atoms; a heteroalkenyl group containing from 2 to 20 carbon atoms; a heteroalkynyl group containing from 2 to 20 carbon atoms; a cycloalkyl group containing from 5 to 20 carbon atoms; an aryl group containing from 6 to 20 carbon atoms; a heterocyclic group containing from 3 to 20 carbon atoms, or a substituent represented by the following formula 1a:

Formula 1a

in formula 1a

R _1f represents a single bond, substituted by a substituent or an unsubstituted alkylene group containing from 1 to 20 carbon atoms; a substituted or unsubstituted cycloakylene group containing from 5 to 20 carbon atoms, or a substituted or unsubstituted arylene group containing from 6 to 20 carbon atoms, where the substituent is an alkyl group containing from 1 to 10 carbon atoms; a cycloalkyl group containing from 5 to 10 carbon atoms, or an aryl group containing from 6 to 20 carbon atoms, and

each of R _1g -R _1h independently represents an alkyl group containing from 1 to 20 carbon atoms; an alkenyl group containing from 2 to 20 carbon atoms; an alkynyl group containing from 2 to 20 carbon atoms; a heteroalkyl group containing from 1 to 20 carbon atoms; a heteroalkenyl group containing from 2 to 20 carbon atoms; a heteroalkynyl group containing from 2 to 20 carbon atoms; a cycloalkyl group containing from 5 to 20 carbon atoms; an aryl group containing from 6 to 20 carbon atoms, or a heterocyclic group containing from 3 to 20 carbon atoms; or R _1g and R _1h are connected to each other to form a heterocyclic group containing from 2 to 10 carbon atoms, together with N.

In addition, the present invention provides a method for producing a modified conjugated diene polymer, comprising: polymerizing (S1) a conjugated diene monomer or a conjugated diene monomer and a vinyl aromatic compound monomer in the presence of a polymerization initiator in a hydrocarbon solvent to obtain a first active chains; (S2) reacting the first active chain with an alkoxysilane-based modifier to obtain a first modified active chain; and (S3) reacting the first modified active chain and a macromonomer containing a repeating unit derived from a compound represented by the following formula 1:

Formula 1

in formula 1

each of R _1a -R _1c independently represents a hydrogen atom; an alkyl group containing from 1 to 20 carbon atoms; an alkenyl group containing from 2 to 20 carbon atoms; an alkynyl group containing from 2 to 20 carbon atoms; a heteroalkyl group containing from 1 to 20 carbon atoms; a heteroalkenyl group containing from 2 to 20 carbon atoms; a heteroalkynyl group containing from 2 to 20 carbon atoms; a cycloalkyl group containing from 5 to 20 carbon atoms; an aryl group containing from 6 to 20 carbon atoms or a heterocyclic group containing from 3 to 20 carbon atoms,

R _1d represents a single bond, substituted by a substituent or an unsubstituted alkylene group containing from 1 to 20 carbon atoms; a substituted or unsubstituted cycloakylene group containing from 5 to 20 carbon atoms, or a substituted or unsubstituted arylene group containing from 6 to 20 carbon atoms, where the substituent is an alkyl group containing from 1 to 10 carbon atoms; a cycloalkyl group containing from 5 to 10 carbon atoms, or an aryl group containing from 6 to 20 carbon atoms, and

R _1e represents an alkyl group containing from 1 to 20 carbon atoms; an alkenyl group containing from 2 to 20 carbon atoms; an alkynyl group containing from 2 to 20 carbon atoms; a heteroalkyl group containing from 1 to 20 carbon atoms; a heteroalkenyl group containing from 2 to 20 carbon atoms; a heteroalkynyl group containing from 2 to 20 carbon atoms; a cycloalkyl group containing from 5 to 20 carbon atoms; an aryl group containing from 6 to 20 carbon atoms; a heterocyclic group containing from 3 to 20 carbon atoms; or a substituent represented by the following formula 1a:

Formula 1a

in formula 1a

R _1f represents a single bond, substituted by a substituent or an unsubstituted alkylene group containing from 1 to 20 carbon atoms; a substituted or unsubstituted cycloalkylene group containing from 5 to 20 carbon atoms, or a substituted or unsubstituted arylene group containing from 6 to 20 carbon atoms, where the substituent is an alkyl group containing from 1 to 10 carbon atoms; a cycloalkyl group containing from 5 to 10 carbon atoms, or an aryl group containing from 6 to 20 carbon atoms, and

each of R _1g and R _1h independently represents an alkyl group containing from 1 to 20 carbon atoms; an alkenyl group containing from 2 to 20 carbon atoms; an alkynyl group containing from 2 to 20 carbon atoms; a heteroalkyl group containing from 1 to 20 carbon atoms; a heteroalkenyl group containing from 2 to 20 carbon atoms; a heteroalkynyl group containing from 2 to 20 carbon atoms; a cycloalkyl group containing from 5 to 20 carbon atoms; an aryl group containing from 6 to 20 carbon atoms, or a heterocyclic group containing from 3 to 20 carbon atoms; or R _1g and R _1h are connected to each other to form a heterocyclic group containing from 2 to 10 carbon atoms, together with N.

The present invention also provides a rubber composition comprising a modified conjugated diene polymer and a filler.

The modified conjugated diene polymer according to the present invention is produced by a production method including the step of reacting the modified first active chain after carrying out the modification reaction and a macromonomer including a repeating unit derived from the compound represented by Formula 1, and may include a functional group derived from the compound represented by Formula 1 in the molecular chain of the polymer is separate from the functional group derived from the modifier, whereby it can have excellent affinity for the excipient.

In addition, the method for producing a modified conjugated diene polymer according to the present invention includes a step of reacting a macromonomer including a repeating unit obtained from a compound represented by Formula 1 after a modification reaction, and the modified conjugated diene polymer can be obtained with a high degree of modification by introducing a functional group derived from the compound represented by Formula 1, for example, an amino group, into the polymer separately from the modifier.

Moreover, the rubber composition of the present invention includes a modified conjugated diene polymer and can exhibit excellent tensile properties and viscoelastic properties.

Best Mode for Carrying Out the Invention

In the following, the present invention is described in more detail for a better understanding of the present invention.

It is to be understood that the words or terms used in the specification and claims of this invention are not to be interpreted as having the meaning as defined in commonly used dictionaries, but rather that the words or terms are to be interpreted as having a meaning consistent with their meaning according to the technical spirit of the invention based on on the principle that the inventor can correctly define the meaning of words or terms to best explain the invention.

Terms

The term "macromonomer" as used herein means a monomer unit of two or more repeating units derived from a polymerization-reactive monomer and may be connected to a polymer chain or reactive compound through an end group.

The term "polymer" as used herein refers to a polymeric compound obtained by polymerizing monomers of the same type or different types. Thus, the general term "polymer" refers to a polymer derived from one type of monomer, but includes the commonly used homopolymer and copolymer.

The term "first chain (main chain)" as used herein can mean the molecular chain of the main skeleton forming the polymer, and can mean a chain substantially comprising repeating units of a conjugated diene monomer or a conjugated diene monomer and a conjugated diene monomer. vinyl aromatic compound, and the term “second chain (minor chain)” may mean a chain containing fewer repeat units than the first chain and substantially comprising a repeat unit of the compound represented by Formula 1.

The term "substituted" as used herein can mean that the hydrogen of a functional group, group of atoms, or compound is replaced by a particular substituent. If the hydrogen of a functional group, group of atoms or compound is replaced by a particular substituent, then one or many, including two or more substituents may be present depending on the number of hydrogen atoms present in the functional group, group of atoms or compound, and if multiple substituents are present, each of the substituents may be the same or they may be different.

The term "vinyl group content" as used herein refers to the percentage by weight (or weight) of butadiene included in the polymer chain at positions 1 and 2, based on conjugated diene monomer groups (butadiene, etc.) in polymer (based on the total weight of polymerized butadiene).

The term "monovalent hydrocarbon group" as used herein can mean a monovalent group of atoms obtained by bonding carbon and hydrogen in a monovalent alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkyl group including one or more unsaturated bonds, and aryl group. The minimum number of carbon atoms in a monovalent hydrocarbon substituent may be determined according to the type of each substituent.

The term "divalent hydrocarbon group" as used herein may mean a divalent atomic group obtained by bonding carbon and hydrogen in a divalent alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, a cycloalkylene group including one or more unsaturated bonds, and arylene group. The minimum number of carbon atoms in a divalent hydrocarbon substituent may be determined according to the type of each substituent.

The term "alkyl group" as used herein may mean a monovalent aliphatic saturated hydrocarbon and may include a linear alkyl group such as methyl, ethyl, propyl and butyl; a branched alkyl group such as isopropyl, sec-butyl, t-butyl and neo-pentyl, and a cyclic saturated hydrocarbon group or a cyclic unsaturated hydrocarbon group including one or two or more unsaturated bonds.

The term "alkylene group" as used herein can mean a divalent aliphatic saturated hydrocarbon such as methylene, ethylene, propylene and butylene.

The term "cycloalkyl group" as used herein may mean a cyclic saturated hydrocarbon.

The term "aryl group" as used herein can mean an aromatic hydrocarbon and can include both a monocyclic aromatic hydrocarbon in which a single ring is formed and a polycyclic aromatic hydrocarbon in which two or more rings are linked.

The term "aralkyl" as used herein is also referred to as arylalkyl, and can mean the combination of an alkyl group and an aryl group formed by replacing the hydrogen atom attached to the carbon constituting the alkyl group with an aryl group.

The term "single bond" as used herein can mean a single covalent bond by itself, without including a separate atomic or molecular group.

The terms “unit derived,” “repeating unit derived,” and “functional group derived” as used herein can express a component or structure derived from a particular material, or the material itself.

It is further understood that the terms “comprising,” “comprising,” and “having,” and their derivatives as used herein, whether or not such terms are specifically disclosed, do not exclude the presence or addition of possible components, steps, or processes. For the avoidance of any doubt, all components claimed using the term "including" may include additional additives, excipients or compounds, including polymer or other materials, unless otherwise described. In contrast, the term "consisting essentially of ~" excludes the use of possible components, and also excludes possible other components, stages, or processes from the scope of a possible explanation. The term “consisting of ~” excludes possible components, steps or processes that are not specifically described or illustrated.

Measurement methods and conditions

Herein, “1,2-vinyl bond content” is measured and analyzed using a Varian VNMRS 500 MHz NMR spectrometer, and the 1,2-vinyl bond content of the polymer as a whole is calculated and measured using 1,1,2,2-tetrachloroethane as solvent during NMR measurement, and calculating 6.0 ppm as solvent peak, 7.2-6.9 ppm as random styrene peaks, 6.9-6.2 ppm as block styrene peaks, 5.8 -5.1 ppm as 1,4-vinyl and 1,2-vinyl peaks and 5.1-4.5 ppm as 1,2-vinyl peaks.

Herein, “weight average molecular weight (Mw)”, “number average molecular weight (Mn)” and “molecular weight distribution (MWD)” are measured by gel permeation chromatography (GPC) and measured by examining the molecular weight distribution curve. Molecular weight distribution (MWD, MWD, Mw/Mn) is calculated based on each molecular weight measured. Specifically, GPC uses two PLgel Olexis columns (Polymer laboratories Co.) and one PLgel mixed-C column (Polymer Laboratories Co.) in combination, and uses polystyrene (PS) as the standard GPC material for molecular weight calculations, and use tetrahydrofuran mixed with an amine compound in an amount of 2 wt. % as a solvent for GPC measurements.

In this specification, "N content" can be measured, for example, by the trace nitrogen analysis method (NSX), and when measured by the NSX analysis method, a quantitative trace nitrogen analyzer (NSX-2100H) can be used. For example, in the case of using a quantitative trace nitrogen analyzer, turn on a quantitative trace nitrogen analyzer (autosampler, horizontal oven, PMT&Nitrogen detector), the amount of carrier gas flow is set to 250 ml/min for argon Ar, 350 ml/min for oxygen O ₂ and 300 ml/min for the ozonizer, the heater is set to 800°C, and the analyzer is kept for approximately 3 hours to stabilize. Once the analyzer has stabilized, a calibration curve is plotted for the 5 ppm, 10 ppm, 50 ppm, 100 ppm and 500 ppm calibration curve ranges based on the nitrogen standard (AccuStandard S-22750-01-5 mL) and the area corresponding to each concentration is obtained. Then, using the ratios of concentrations to areas, a straight line is drawn. The ceramic boat containing 20 mg of sample is then placed in the analyzer's automatic dispenser and measured to obtain the area. Using the area of the sample thus obtained and the calibration curve, the N content is calculated. In this case, the sample is a modified conjugated diene polymer from which the solvents are removed by placing the sample in hot water heated by steam and stirred, and may represent a sample from which the remaining monomers, remaining modifiers and oil are removed.

Herein, “Si content” is measured using inductively coupled plasma optical emission spectroscopy (ICP-OES; Optima 7300DV) as the ICP analytical method. Specifically, the measurement is carried out by placing 0.7 g of sample in a platinum (Pt) crucible, adding approximately 1 ml of concentrated sulfuric acid (98 wt.%, electronic purity), heating at 300°C for 3 hours, burning sample in an electric oven (Thermo Scientific, Lindberg Blue M) according to the following program from stages 1-3:

1) stage 1: initial temperature 0°C, speed (temperature/h) 180°C/h, temperature (holding time) 180°C (1 h),

2) stage 2: initial temperature 180°C, speed (temperature/hour) 85°C/hour, temperature (holding time) 370°C (2 hours), and

3) stage 3: initial temperature 370°C, speed (temperature/hour) 47°C/hour, temperature (holding time) 510°C (3 hours),

adding 1 ml of concentrated nitric acid (48 wt.%) and 20 ml of concentrated hydrofluoric acid (50 wt.%) to the residue, sealing the platinum crucible and shaking for 30 minutes or more, adding 1 ml of boric acid to the sample, holding at temperature 0°C for 2 hours or more, diluted in 30 ml ultrapure water and burned.

Modified polymer based on conjugated diene

The present invention provides a modified conjugated diene polymer having excellent filler affinity and consequently providing a rubber composition having excellent processability, tensile properties and viscoelastic properties.

The modified conjugated diene polymer according to an embodiment of the present invention includes a first chain containing repeating units derived from a conjugated diene monomer; a second chain comprising a repeating unit derived from a compound represented by the following formula 1 and a unit derived from an alkoxysilane based modifier, wherein the first chain and the second chain are connected by a unit derived from the modifier:

Formula 1

in formula 1

each of R _1a -R _1c independently represents a hydrogen atom; an alkyl group containing from 1 to 20 carbon atoms; an alkenyl group containing from 2 to 20 carbon atoms; an alkynyl group containing from 2 to 20 carbon atoms; a heteroalkyl group containing from 1 to 20 carbon atoms; a heteroalkenyl group containing from 2 to 20 carbon atoms; a heteroalkynyl group containing from 2 to 20 carbon atoms; a cycloalkyl group containing from 5 to 20 carbon atoms; an aryl group containing from 6 to 20 carbon atoms, or a heterocyclic group containing from 3 to 20 carbon atoms,

R _1d represents a single bond, substituted by a substituent or an unsubstituted alkylene group containing from 1 to 20 carbon atoms; a substituted or unsubstituted cycloalkylene group containing from 5 to 20 carbon atoms, or a substituted or unsubstituted arylene group containing from 6 to 20 carbon atoms, where the substituent is an alkyl group containing from 1 to 10 carbon atoms; a cycloalkyl group containing from 5 to 10 carbon atoms, or an aryl group containing from 6 to 20 carbon atoms, and

R _1e represents an alkyl group containing from 1 to 20 carbon atoms; an alkenyl group containing from 2 to 20 carbon atoms; an alkynyl group containing from 2 to 20 carbon atoms; a heteroalkyl group containing from 1 to 20 carbon atoms; a heteroalkenyl group containing from 2 to 20 carbon atoms; a heteroalkynyl group containing from 2 to 20 carbon atoms; a cycloalkyl group containing from 5 to 20 carbon atoms; an aryl group containing from 6 to 20 carbon atoms; a heterocyclic group containing from 3 to 20 carbon atoms, or a substituent represented by the following formula 1a:

Formula 1a

in formula 1a

R _1f represents a single bond, substituted by a substituent or an unsubstituted alkylene group containing from 1 to 20 carbon atoms; a substituted or unsubstituted cycloalkylene group containing from 5 to 20 carbon atoms, or a substituted or unsubstituted arylene group containing from 6 to 20 carbon atoms, where the substituent is an alkyl group containing from 1 to 10 carbon atoms; a cycloalkyl group containing from 5 to 10 carbon atoms, or an aryl group containing from 6 to 20 carbon atoms, and

each of R _1g and R _1h independently represents an alkyl group containing from 1 to 20 carbon atoms; an alkenyl group containing from 2 to 20 carbon atoms; an alkynyl group containing from 2 to 20 carbon atoms; a heteroalkyl group containing from 1 to 20 carbon atoms; a heteroalkenyl group containing from 2 to 20 carbon atoms; a heteroalkynyl group containing from 2 to 20 carbon atoms; a cycloalkyl group containing from 5 to 20 carbon atoms; an aryl group containing from 6 to 20 carbon atoms; or a heterocyclic group containing from 3 to 20 carbon atoms; or each R _1g and R _1h are connected to each other to form a heterocyclic group containing from 2 to 10 carbon atoms, together with N.

The modified conjugated diene polymer according to an embodiment of the present invention can be produced by a method as described below, comprising the step of reacting a macromonomer comprising a repeating unit derived from the compound represented by Formula 1 with a modified active first chain after a modification reaction, thereby making it may have a structure similar to a graft copolymer comprising a first chain containing a repeating unit derived from a conjugated diene monomer and a second chain derived from a macromonomer linked to a unit derived from an alkoxysilane modifier that is linked to at least one end group of the first chain. That is, in a modified polymer based on a conjugated diene, the first chain and the second chain are connected by a link obtained from the modifier.

As described above, if all the functional groups are extensively distributed on one end group of the modified conjugated diene polymer and react with silica, only one end group of the polymer can be connected to the silica, and the other end group can be in a free state, and, Accordingly, similar to the conventional single end group modified polymer, the filler dispersibility and flocculation prevention effects can be excellent, and the processability can be remarkably improved. In addition, on one end group connected to the functional group, a second chain derived from the macromonomer and a unit derived from the modifier are included, and the effects upon interaction with the filler can be achieved at the same or better level than that of a conventional polymer modified on both end groups, and thus the tensile properties and viscoelastic properties can become excellent.

In addition, typically a remaining group derived from the modifier, such as an alkoxy group (-OR, where R is a hydrocarbon group) or a hydroxyl group (-OH), is present in the modified conjugated diene polymer, and over time the remaining group condensation reaction, hydrolysis reaction, etc. may occur, and storage stability may deteriorate, Mooney viscosity may increase, molecular weight distribution may increase, and the superior compounding properties of the modified conjugated diene polymer may not be maintained, and therefore when used in a rubber compound, problems arise due to the lack of the required properties. However, since the modified conjugated diene polymer according to an embodiment of the present invention is prepared by the method described hereinafter, it is possible to obtain a structure in which the second chain derived from the macromonomer is linked to an alkoxy group representing a residual group derived from the modifier, present in the polymer, and as a result, the residual group derived from the modifier may not be present in the polymer, or the amount of such groups may be reduced, unlike the traditional production method.

In addition, the modified conjugated diene polymer in accordance with an embodiment of the present invention is prepared by the process described later herein and may have the advantage of introducing more functional groups than would be the case if only a multifunctional modifier were used. In particular, in view of the active polymer and the alkoxy group of the modifier, the coupling of one modifier molecule to two or more polymer chains is difficult due to the steric hindrance of the polymer and, although three or more chains can be attached, a modified polymer to which three or more chains are attached more chains, should be small. However, according to the production method of the present invention, regardless of steric hindrance, a second chain derived from a macromonomer can be attached to the residual alkoxy group of the modifier attached to the polymer chain, and more functional groups can be introduced into the polymer chain.

That is, there are limitations when introducing functional groups into one modifier molecule, and although it does not matter how many functional groups are introduced, there is a difference in the absolute number of functional groups compared to the case of attaching a chain containing a functional group to a residual alkoxy group without any effect spatial difficulty, as in the present invention.

Accordingly, the modified conjugated diene polymer of the present invention has excellent storage stability over time and can continuously maintain excellent compounding properties initially or over time, and can have excellent tensile properties and viscoelastic properties in contrast to from a conventional polymer modified on the basis of a single end group.

First chain containing a repeating unit derived from a conjugated diene monomer

According to an embodiment of the present invention, the first chain, which is the main skeleton of the modified conjugated diene polymer, contains a repeating unit derived from a conjugated diene monomer, and the conjugated diene monomer may be one or more monomers 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-halogen-1, 3-butadiene (halogen means halogen atom).

In addition, the first chain may also further comprise a repeating unit derived from a vinyl aromatic monomer, and the vinyl aromatic monomer may be one or more monomers selected from the group consisting of styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinyl naphthalene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene, 1-vinyl-5-hexylnaphthalene, 3-(2-pyrrolidinethyl)styrene, 4-(2-pyrrolidinethyl) styrene and 3-(2-pyrrolidine-1-methylethyl)-α-methylstyrene.

In yet another embodiment, the first chain of the modified conjugated diene polymer may be a copolymer further comprising a repeat unit derived from a diene monomer containing 1 to 10 carbon atoms together with a repeat unit derived from a conjugated diene monomer . The repeating unit derived from a diene monomer may be a repeating unit derived from a diene monomer other than a conjugated diene monomer, and the diene monomer other than a conjugated diene monomer may be, for example , 1,2-butadiene. If the modified conjugated diene polymer is a copolymer further comprising a diene monomer, the modified conjugated diene polymer may contain a repeat unit derived from the diene monomer in an amount of greater than 0 wt. % up to 1 wt. %, from more than 0 wt. % up to 0.1 wt. %, from more than 0 wt. % up to 0.01 wt. % or more than 0 wt. % up to 0.001 wt. %, and in this range, gelling prevention effects can be achieved.

According to an embodiment of the present invention, if repeating units derived from two or more monomers are included in a first chain that forms the backbone of a modified conjugated diene polymer, the first chain may be a random copolymer chain, in which case the effects can be achieved excellent balance between physical properties. Random copolymer can mean a random arrangement of repeating units that form the copolymer.

A second chain including a repeating unit derived from a compound represented by Formula 1. Moreover, according to an embodiment of the present invention, the modified conjugated diene polymer further includes a second chain in addition to the first chain, and the second chain is derived from a macromolecule containing a repeating unit derived from the compound represented by Formula 1, and the main unit may be a repeating unit derived from the compound represented by Formula 1.

Specifically, in Formula 1, each of R _1a -R _1c independently represents a hydrogen atom; an alkyl group containing from 1 to 10 carbon atoms; an alkenyl group containing from 2 to 10 carbon atoms; an alkynyl group containing from 2 to 10 carbon atoms; a heteroalkyl group containing from 1 to 10 carbon atoms; a heteroalkenyl group containing from 2 to 10 carbon atoms; a heteroalkynyl group containing from 2 to 10 carbon atoms; a cycloalkyl group containing from 5 to 10 carbon atoms; an aryl group containing from 6 to 10 carbon atoms, or a heterocyclic group containing from 3 to 10 carbon atoms, R _1d represents a single bond or an unsubstituted alkylene group containing from 1 to 10 carbon atoms, and R _1e represents an alkyl group, containing from 1 to 10 carbon atoms; an alkenyl group containing from 2 to 10 carbon atoms; an alkynyl group containing from 2 to 10 carbon atoms; a heteroalkyl group containing from 1 to 10 carbon atoms; a heteroalkenyl group containing from 2 to 10 carbon atoms; a heteroalkynyl group containing from 2 to 10 carbon atoms; a cycloalkyl group containing from 5 to 10 carbon atoms; an aryl group containing from 6 to 10 carbon atoms; a heterocyclic group containing from 3 to 10 carbon atoms, or a substituent represented by formula 1a, and in formula 1a, R _1f represents a single bond or an unsubstituted alkylene group containing from 1 to 10 carbon atoms, and each of R _1g and R _1h independently of each other represent an alkyl group containing from 1 to 10 carbon atoms; an alkenyl group containing from 2 to 10 carbon atoms; an alkynyl group containing from 2 to 10 carbon atoms; a heteroalkyl group containing from 1 to 10 carbon atoms; a heteroalkenyl group containing from 2 to 10 carbon atoms; a heteroalkynyl group containing from 2 to 10 carbon atoms; a cycloalkyl group containing from 5 to 10 carbon atoms; an aryl group containing from 6 to 10 carbon atoms; or a heterocyclic group containing from 3 to 10 carbon atoms, or R _1g and R _1h can be combined with each other to form a heterocyclic group containing from 2 to 10 carbon atoms, together with N.

In another embodiment in Formula 1, R _1a -R _1c each independently represents a hydrogen atom or an alkyl group containing from 1 to 6 carbon atoms, R _1d represents a single bond or an unsubstituted alkylene group containing from 1 to 6 carbon atoms, and R _1e represents an alkyl group containing from 1 to 10 carbon atoms or a substituent represented by formula 1a, and in formula 1a, R _1f represents a single bond or an unsubstituted alkylene group containing from 1 to 6 carbon atoms, and each R _1g and R _1h independently represents an alkyl group containing from 1 to 10 carbon atoms, or R _1g and R _1h can be connected to each other to form a heterocyclic group containing from 2 to 6 carbon atoms, together with N.

More specifically, the compound represented by Formula 1 may be the compounds represented by Formulas 1-1-1-3 below.

Formula 1-1

Formula 1-2

Formula 1-3

In addition, the modified conjugated diene polymer may have an interconnected type of first chain and second chain through a unit derived from an alkoxysilane modifier, and the second chain may be linked to the modifier as a center.

According to an embodiment of the present invention, the modifier may be a modifier having an affinity for silica. By silica-affinity modifier is meant a modifier containing a functional group having silica affinity in the compound used as a modifier, and by silica-affinity functional group is meant a functional group having excellent affinity to the excipient , in particular, to a silica-based filler, and allowing interaction between the silica-based filler and the functional group derived from the modifier.

Specifically, according to an embodiment of the present invention, the alkoxysilane modifier may be an amine-containing alkoxysilane modifier or an amine-free alkoxysilane modifier, and the amine-containing alkoxysilane modifier may be a compound represented by formula 2 below.

Formula 2

In Formula 2, R ¹ may be a single bond or an alkylene group containing 1 to 10 carbon atoms, R ² and R ³ may each independently be an alkyl group containing 1 to 10 carbon atoms, R ⁴ may be hydrogen , an epoxy group, an alkyl group containing from 1 to 10 carbon atoms, an allyl group containing from 2 to 10 carbon atoms, a monosubstituted, disubstituted or trisubstituted alkylsilyl group with alkyl groups containing from 1 to 10 carbon atoms, or a heterocyclic group containing from 2 to 10 carbon atoms, R ²¹ may be a single bond, an alkylene group containing 1 to 10 carbon atoms, or -[R ⁴² O]j-, where R ⁴² may be an alkylene group containing 1 to 10 carbon atoms carbon, each of a and m independently may be an integer selected from 1 to 3, n may be an integer from 0 to 2, and j may be an integer selected from 1 to 30.

In a specific embodiment, the compound represented by Formula 2 may be a compound selected from the group consisting of N,N-bis(3-(dimethoxy(methyl)silyl)propyl)-methyl-1-amine, N,N-bis( 3-(diethoxy(methyl)silyl)propyl)-methyl-1-amine, N,N-bis(3-(trimethoxysilyl)propyl)-methyl-1-amine, N,N-bis(3-(triethoxysilyl)propyl )-methyl-1-amine, tri(trimethoxysilyl)amine, tri(3-(trimethoxysilyl)propyl)amine, N,N-bis(3-(diethoxy(methyl)silyl)propyl)-1,1,1-trimethylsilanamine , N-(3-(1H-1,2,4-triazol-1-yl)propyl)-3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)propan-1-amine, 3-(trimethoxysilyl )-N-(3-(trimethoxysilyl)propyl)-N-(3-(1-(3-(trimethoxysilyl)propyl)-1H-1,2,4-triazol-3-yl)propyl)propan-1- amine, N-allyl-N-(3-(trimethoxysilyl)propyl)prop-2-en-1-amine, N,N-bis(oxiran-2-yl-methyl)-3-(trimethoxysilyl)propan-1- amine, 1,1,1-trimethyl-N-(3-(triethoxysilyl)propyl)-N-(trimethylsilyl)silanamine and N,N-bis(3-(triethoxysilyl)silanamine)propyl)-2,5,8, 11,14-pentaoxahexadecane-16-amine.

In yet another embodiment, the compound represented by Formula 2 may be one or more compounds selected from the compounds represented by Formulas 2-1-2-6 below.

Formula 2-1

Formula 2-2

Formula 2-3

Formula 2-4

Formula 2-5

Formula 2-6

In formulas 2-1-2-6, Me is the methyl group and Et is the ethyl group.

In another embodiment, the amine containing alkoxysilane modifier may include a compound represented by Formula 3 below.

Formula 3

In Formula 3, each of R5, R6 and R9 may independently represent an alkylene group containing from 1 to 10 carbon atoms, each of ^R7 , ^R8 , ^R10 and ^R11 may independently represent an alkyl group containing from 1 to 10 carbon atoms, R ¹² may represent hydrogen or an alkyl group containing from 1 to 10 carbon atoms, each of b and c independently may represent 1, 2 or 3, where the condition b+c≥4 may be satisfied, and A may represent yourself or wherein R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ can each independently represent hydrogen or an alkyl group containing from 1 to 10 carbon atoms.

In a specific embodiment, the compound represented by Formula 3 may be a compound selected from the group consisting of N-(3-(1H-imidazol-1-yl)propyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl )propyl)propan-1-amine and 3-(4,5-dihydro-1H-imidazol-1-yl)-N,N-bis(3-(triethoxysilyl)propyl)propan-1-amine.

In another embodiment, the amine-containing alkoxysilane modifier may include a compound represented by Formula 4 below.

Formula 4

In Formula 4, each of A ¹ and A ² independently may represent a divalent hydrocarbon group containing from 1 to 20 carbon atoms, which contains or does not contain an oxygen atom; each of R ¹⁷ -R ²⁰ independently may represent a monovalent hydrocarbon group containing from 1 to 20 carbon atoms; each of L ¹ -L ⁴ independently may be a monosubstituted, disubstituted or trisubstituted alkylsilyl group with alkyl groups containing from 1 to 10 carbon atoms, or a monovalent hydrocarbon group containing from 1 to 20 carbon atoms, where each of L1 and L2, and also L3 and L4 may be combined with each other to form a ring of 1 to 5 carbon atoms, and if L1 and L2, and L3 and L4 are combined with each other to form a ring, the ring so formed may contain from 1 to 3 heteroatoms, which are one or more heteroatoms selected from the group consisting of N, O and S.

In a specific embodiment, the compound represented by Formula 4 may be a compound selected from the group consisting of 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropane- 1-amine), 3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine), 3,3'-(1,1, 3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N ,N-diethylpropan-1-amine), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dipropylpropan-1-amine), 3,3'- (1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3- diyl)bis(N,N-diethylpropan-1-amine), 3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dipropylpropan-1-amine), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dipropylpropan-1-amine), 3,3'-(1,1,3,3-tetramethoxydisiloxane -1,3-diyl)bis(N,N-diethylmethane-1-amine), 3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-diethylmethane- 1-amine), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-diethylmethane-1-amine), 3,3'-(1,1, 3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dimethylmethane-1-amine), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N ,N-dipropylmethane-1-amine), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dimethylmethane-1-amine), 3,3'- (1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dipropylmethane-1-amine), 3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3- diyl)bis(N,N-dimethylmethane-1-amine), 3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dipropylmethane-1-amine), N,N'-((1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl)silanamine ), N,N'-((1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl )silanamine), N,N'-((1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N- (trimethylsilyl)silanamine), N,N'-((1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl- N-phenylsilanamine), N,N'-((1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N -phenylsilanamine), N,N'-((1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N- phenylsilanamine), 1,3-bis(3-(1H-imidazol-1-yl)propyl)-1,1,3,3-tetramethoxydisiloxane, 1,3-bis(3-(1H-imidazol-1-yl) propyl)-1,1,3,3-tetraethoxydisiloxane and 1,3-bis(3-(1H-imidazol-1-yl)propyl)-1,1,3,3-tetrapropoxydisiloxane.

More specifically, the compound represented by Formula 4 may be the compound represented by Formula 4-1 below.

Formula 4-1

In Formula 4-1, Me represents a methyl group.

In yet another embodiment, the amine-containing alkoxysilane modifier may include a compound represented by Formula 5 below.

Formula 5

In Formula 5, each of R _b2 -R _b4 independently represents an alkylene group containing from 1 to 10 carbon atoms, each of R _b5 -R _b8 independently represents an alkyl group containing from 1 to 10 carbon atoms, each of R _b13 - R _b14 independently represents an alkylene group containing from 1 to 10 carbon atoms, each of R _b15 -R _b18 independently represents an alkyl group containing from 1 to 10 carbon atoms, and each of m ₁ , m ₂ , m ₃ and independently represents an integer from 1 to 3.

Specifically, the compound represented by Formula 5 may be the compound represented by Formula 5-1 below.

Formula 5-1

In Formula 5-1, Et represents an ethyl group.

In yet another embodiment, the amine-containing alkoxysilane modifier may include a compound represented by Formula 6 below.

Formula 6

In Formula 6, R _e1 and R _e2 are each independently an alkylene group containing 1 to 10 carbon atoms, each R _e3 -R _e6 is independently hydrogen, an alkyl group containing 1 to 10 carbon atoms, or -R _e7 SiR _e8 R _e9 R _e10 , where at least one of R _e3 -R _e6 is -R _e7 SiR _e8 R _e9 R _e10 , where R _e7 represents a single bond or an alkylene group containing from 1 to 10 carbon atoms, each of R _e8 -R _e10 independently represents an alkyl group containing from 1 to 10 carbon atoms or an alkoxy group containing from 1 to 10 carbon atoms, wherein at least one of R _e8 -R _e10 is an alkoxy group containing from 1 to 10 atoms carbon.

In particular, the compound represented by Formula 6 may be the compound represented by Formula 6-1 below.

Formula 6-1

In Formula 6-1, Me represents a methyl group.

In yet another embodiment, the amine-containing alkoxysilane modifier may include a compound represented by Formula 7 below.

Formula 7

In Formula 7, R _h1 and R _h2 each independently represent an alkyl group containing from 1 to 10 carbon atoms or an alkoxy group containing from 1 to 10 carbon atoms, R _h3 represents a single bond or an alkylene group containing from 1 to 10 atoms carbon, and A ₃ represents -Si(R _h4 R _h5 R _h6 ) or -N[Si(R _h7 R _h8 R _h9 )] ₂ , where each of R _h4 -R _h9 independently represents an alkyl group containing from 1 up to 10 carbon atoms or an alkoxy group containing from 1 to 10 carbon atoms.

In particular, the compound represented by Formula 7 may be the compound represented by Formula 7-1 or Formula 7-2 below

Formula 7-1

Formula 7-2

In Formulas 7-1 and 7-2, Me represents a methyl group.

In another embodiment, the non-amine alkoxysilane modifier may be a compound represented by Formula 8 below.

Formula 8

In Formula 8, X represents O or S, each of R _f1 and R _f2 independently represents a single bond or an alkylene group containing from 1 to 10 carbon atoms, each of R _f3 -R _f8 independently represents hydrogen, an alkyl group containing from 1 to 10 carbon atoms, an alkoxy group containing from 1 to 10 carbon atoms, an aryl group containing from 6 to 10 carbon atoms, a cycloalkyl group containing from 5 to 10 carbon atoms or an aralkyl group containing from 7 to 14 carbon atoms, and p is an integer 0 or 1, where if p is 0, R _f1 is an alkyl group containing from 1 to 10 carbon atoms or an alkoxy group containing from 1 to 10 carbon atoms.

In particular, the compound represented by Formula 8 may be the compound represented by Formula 8-1 or Formula 8-2 below.

Formula 8-1

Formula 8-2

In yet another embodiment, the amine-free alkoxysilane modifier may be the compound represented by Formula 9 below.

Formula 9

In Formula 9, R _g1 -R _g4 each independently represents hydrogen, an alkyl group containing 1 to 10 carbon atoms, an alkoxy group containing 1 to 10 carbon atoms, an aryl group containing 6 to 12 carbon atoms, or -R _g5 Si(OR _g6 )r(R _g7 ) _3-r , where at least one of R _g1 -R _g4 is -R _g5 Si(OR _g6 )r(R _g7 ) _3-r , where R _g5 is a single bond or an alkylene group containing from 1 to 10 carbon atoms, each of R _g6 and R _g7 independently represents an alkyl group containing from 1 to 10 carbon atoms, g is from 1 to 3, and Y is C or N, where if Y is N, R _g4 is missing.

In particular, the compound represented by Formula 9 may be the compound represented by Formula 9-1 below.

Formula 9-1

In formula 9-1, Me is the methyl group.

In another embodiment, the amine-free alkoxysilane modifier may be the compound represented by Formula 10 below.

Formula 10

In Formula 10, R _g1 -R _g3 each independently represents an alkyl group containing 1 to 10 carbon atoms or an alkoxy group containing 1 to 10 carbon atoms, R _g4 represents an alkoxy group containing 1 to 10 carbon atoms, and q is an integer from 2 to 100.

Specifically, in Formula 10, R _g1 -R _g3 each independently represents an alkyl group containing 1 to 6 carbon atoms or an alkoxy group containing 1 to 6 carbon atoms, R _g4 represents an alkoxy group containing 1 to 6 carbon atoms , and q is an integer from 2 to 50.

The main parameter of a modified polymer based on a conjugated diene

In addition, the modified conjugated diene polymer according to an embodiment of the present invention may have a polymer N content of 150 ppm or more on a weight basis as determined by NSX (Nitrogen Analyzer) analysis, and may have a polymer Si content of 180 ppm or more on a weight basis. mass according to ICP analysis (inductively coupled plasma mass spectrometry method).

In particular, the modified conjugated diene polymer may have a Si content of the polymer on a weight basis, as determined by ICP analysis, of 180 ppm or more, preferably 190 ppm or more, more preferably 200 ppm or more.

The Si content may be derived from the modifier, and the Si content is due to the functional group present in the modified conjugated diene polymer, which is expected to improve the affinity for the filler and may be a major factor while improving processability.

According to an embodiment of the present invention, the modified conjugated diene polymer has a polymer N content according to NSX analysis of 150 ppm or more, preferably 160 ppm or more, more preferably 170 ppm or more. The modified conjugated diene polymer may have a relatively high N atom content due to a production method providing the presence of an additional functional group derived from the compound represented by Formula 1, such as an amine group, and may have a structure in which the functional group derived from the compound represented by Formula 1 is connected to the first polymer chain through a unit derived from a modifier, which in turn is connected to at least one end group of the first chain, which markedly improves the affinity for the filler, for example, silica, and dispersibility during preparation mixture and achieves excellent viscoelastic properties and, at the same time, significantly improved workability.

Moreover, due to such a high content of N atoms, the modified conjugated diene polymer according to an embodiment of the present invention may have a molar ratio (N/Si) of N atoms to Si atoms of 0.75 or more. Generally, the modifier modified polymer may include a Si atom and a N atom due to a modification polymerization initiator, a modified monomer, etc., but as described above, since the polymer according to an embodiment of the present invention includes a repeating unit derived from the compound represented by formula 1, the N content may be relatively high, and as a consequence, the molar ratio of N atom to Si atom may be 0.75 or more, preferably 0.77 or more, or 0.78 or more, more preferably 0.8 or more , optimally 0.9 or more. In this way, the workability effects due to improved dispersibility during the preparation of the mixture can be optimized.

Moreover, according to an embodiment of the present invention, the modified conjugated diene polymer may have a Mooney Viscosity Change Ratio (MVR) according to Mathematical Formula 1 of 20% or less.

Mathematical formula 1

In mathematical formula 1, MVR is the change coefficient of Mooney viscosity, MV _f is the Mooney viscosity at 100°C after keeping the polymer at 25°C for 30 days, and MVi is the initial Mooney viscosity of the polymer at 100 °C.

The Mooney viscosity change factor may be a measure indicating the increase in Mooney viscosity occurring during storage after preparation as well as processability, and the polymer of the present invention may have improved processability, in addition to excellent storage stability due to the low coefficient changes in Mooney viscosity, even when stored for a long time, due to the structural characteristics with the specific bond structure of the second chain containing the repeating unit derived from the compound represented by formula 1, the unit derived from the modifier and the first polymer chain.

The Mooney viscosity change rate is the change rate between the initial Mooney viscosity of the polymer and the Mooney viscosity of the polymer after storage for 30 days at room temperature, and the present invention provides a polymer with this value being 20% or less, preferably 15% or less. Here, the Mooney viscosity is the Mooney viscosity at a temperature of 100° C. and can be measured by a conventional method used in the art.

General information

In yet another embodiment, the modified conjugated diene polymer according to an embodiment of the present invention may have a number average molecular weight (Mn) of 1000 g/mol to 2,000,000 g/mol, 10,000 g/mol to 1,000,000 g/mol, or 100,000 g /mol to 800000 g/mol, mass average molecular weight (Mw) from 1000 g/mol to 3000000 g/mol, from 10000 g/mol to 2000000 g/mol or from 100000 g/mol to 2000000 g/mol and peak mass average molecular weight mass (Mp) from 1000 g/mol to 300000 g/mol, from 10000 g/mol to 2000000 g/mol or from 100000 g/mol to 2000000 g/mol. Within these limits, excellent rolling resistance and skid resistance effects on wet road surfaces can be achieved. In another embodiment, the modified conjugated diene polymer may have a molecular weight distribution (MWD; MWD; Mw/Mn) of 1.0 to 3.0, or 1.1 to 2.5, or 1.1 to 2 ,0, and within these limits, excellent effects of tensile properties, viscoelastic properties and balance between physical properties can be achieved.

In addition, the modified conjugated diene polymer may have a Mooney viscosity at 100° C. of 30 or more, 40 to 150, or 40 to 140, and at such values excellent processability and performance effects can be achieved.

Herein, Mooney viscosity can be measured using a Mooney viscometer. In particular, Mooney viscosity can be measured using the MV-2000E viscometer from Monsanto Co. using a large rotor at a rotor speed of 2±0.02 rpm at a temperature of 100°C. In this case, the polymer was kept at room temperature (23±5°C) for 30 minutes or more, and 27±3 g of polymer was taken out and placed in the die cavity, and then the rotor was driven by applying torque to measure it.

In addition, the content of vinyl groups in the modified conjugated diene-based polymer can be 5 wt. % or more, 10 wt. % or more or 10 wt. % up to 60 wt. %. In this case, the content of vinyl groups may not mean the amount of 1,4-attached, but the amount of 1,2-attached monomer based on the conjugated diene per 100 mass. % copolymer based on a conjugated diene, consisting of a monomer containing a vinyl group and a monomer based on a vinyl aromatic compound.

Method for producing a modified polymer based on a conjugated diene

In addition, the present invention provides a method for producing a modified polymer based on a conjugated diene

A method for producing a modified conjugated diene polymer according to an embodiment of the present invention includes polymerizing (S1) a conjugated diene monomer or a conjugated diene monomer and a vinyl aromatic compound monomer in the presence of a polymerization initiator in a hydrocarbon solvent to obtain an active first chain; reacting (S2) the active first chain with an alkoxysilane-based modifier to obtain a modified active first chain; and reacting (S3) the modified active first chain and a macromonomer comprising a repeating unit derived from the compound represented by Formula 1 below.

Formula 1

In Formula 1, R _1a -R _1c are the same as defined above, and the modifier is the same as explained above.

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

The polymerization initiator is not particularly limited and may be, for example, one or more polymerization initiators selected from the group consisting of methyl lithium, ethyl lithium, propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, hexyllithium, n-decyl lithium , tert-octyllithium, phenyllithium, 1-naphthyllithium, n-eicosyllithium, 4-butylphenyllithium, 4-tolyllithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium, naphthylsodium, naphthylpotassium, lithium alkoxide, sodium alkoxide, alkoxide potassium, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide and lithium isopropylamide.

According to an embodiment of the present invention, the polymerization initiator can be used in an amount of 0.01 mmol to 10 mmol, 0.05 mmol to 5 mmol, 0.1 mmol to 2 mmol, 0.1 mmol to 1 mmol, or 0.15 to 0.8 mmol per 100 g of monomer. Here, 100 g of monomer may represent the total amount of a conjugated diene monomer or a conjugated diene monomer and a vinyl aromatic monomer.

Stage S1

The polymerization of step (S1) may be, for example, an anionic polymerization, and in particular a living anionic polymerization in which the anionic active moiety is included at the end of the polymerization by propagating the polymerization reaction with anions. In addition, the polymerization of step (S1) may be a heating polymerization, an isothermal polymerization, or a constant temperature polymerization (adiabatic polymerization). Here, constant temperature polymerization means a polymerization method including a polymerization step using self-generated heat of reaction without applying additional heat after adding a polymerization initiator, and heating polymerization means a polymerization method including introducing a polymerization initiator and then increasing the temperature by applying additional heat. Isothermal polymerization means a polymerization method in which the temperature of the polymer is kept constant by increasing heat by applying heat or removing heat after adding a polymerization initiator.

Moreover, according to the embodiment of the present invention, the polymerization of step (S1) can be carried out by further adding a diene-based compound containing 1 to 10 carbon atoms in addition to the conjugated diene-based monomer, in which case preventing effects can be achieved formation of a gel on the reactor wall during operation for a long time. The diene-based compound may be, for example, 1,2-butadiene.

The polymerization of step (S1) can be performed in a temperature range, for example, 80°C or less, -20°C to 80°C, 0°C to 80°C, 0°C to 70°C, or 10°C C to 70°C, and in this range, the molecular weight distribution of the polymer is adjusted so that it is narrow, and the effects of improving physical properties were excellent.

The active first chain obtained in step (S1) may be a polymer in which a polymer anion and an organometallic cation are paired.

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

The polar additive may be, for example, one or more additives selected from the group consisting of tetrahydrofuran, 2,2-di(2-tetrahydrofuryl)propane, diethyl ether, cyclopentyl ether, dipropyl ether, ethylene methyl ether, ethylene dimethyl ether, diethyl glycol, dimethyl ether, tert-butoxyethoxyethane, bis(3-dimethylaminoethyl)ether, (dimethylaminoethyl)ethyl ether, trimethylamine, triethylamine, tripropylamine, N,N,N',N'-tetramethylethylenediamine, sodium mentholate and 2-ethyltetrahydrofuryl ether, preferably 2 ,2-di(2-tetrahydrofuryl)propane, triethylamine, tetramethylethylenediamine, sodium mentholate or 2-ethyltetrahydrofuryl ether. If a polar additive is included and if a conjugated diene monomer and a vinyl aromatic compound-based monomer are copolymerized, the difference in their reaction rates can be compensated for, and effects causing easy formation of a random copolymer can be achieved.

Stage S2

Step (S2) is a step of reacting the active first chain with a modifier to obtain a modified active first chain, and here the reaction may be a modification reaction or a coupling reaction, in which case the modifier may be used in an amount of 0.01 mmol to 10 mmol per 100 g of monomer. In another embodiment, the modifier can 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 1 mole of polymerization initiator in step (S1).

Stage S3

Moreover, step (S3) is a step of reacting the active first chain with a macromonomer including a repeating unit derived from the compound represented by Formula 1 to obtain a modified conjugated diene polymer. In this case, the macromonomer may further include a unit derived from a conjugated diene monomer.

Moreover, the production method according to an embodiment of the present invention may further include the step of producing a macromonomer to step (S3), and the macromonomer can be obtained by carrying out a low degree polymerization reaction of a compound represented by Formula 1 or a compound represented by Formula 1 and a monomer at based on a conjugated diene in the presence of a lithium compound in a hydrocarbon solvent. In this case, the polymerization reaction may be a living anionic polymerization with the formation of an anionic active moiety on the end group of the polymer by propagation of the polymerization reaction by anions, and the macromonomer may be a living anionic end group, one of the end groups of which is capable of acting as a monomer.

As used herein, the organolithium compound may be an alkyl lithium compound and, in particular, may be methyllithium, ethyl lithium, propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, hexyllithium, n-decyllithium, tert-octyllithium, phenyllithium, 1-naphthyllithium, n-eicosyllithium, 4-butylphenyllithium, 4-tolyllithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium or 4-cyclopentyllithium, more specifically n-butyllithium.

In one embodiment, the macromonomer can be prepared by Reaction 1 below and may be a compound with the structure represented by Formula M below.

Reaction 1

In Reaction 1, R _1e is the same as defined in Formula 1, R-Li is an alkyl lithium compound, and R is an alkyl group derived from alkyl lithium.

In addition, the macromonomer may include from 1 to 80, from 1 to 60, or from 1 to 50 repeating units derived from the compound represented by formula 1, and, for example, in formula M, r may be from 1 to 80, from 1 to 60 or from 1 to 50. In this case, an excellent balance of processability, tensile properties and viscoelastic properties of a modified conjugated diene polymer including a second chain derived from a macromonomer can be obtained.

Meanwhile, step (S3) may be to obtain a modified conjugated diene polymer by reacting the modified active polymer and the macromonomer, i.e. a functional group derived from the modifier in the modified active polymer, and a living anionic end group of the macromonomer.

Specifically, the first modified active polymer chain obtained in step (S2) includes a functional group derived from the modifier, and the functional group derived from the modifier includes an alkoxy group that has not reacted with the polymer chain but remains, and accordingly through the reaction of the living anionic end group of the macromonomer and the alkoxy group, a modified conjugated diene polymer can be obtained.

In addition, the macromonomer can be used in an amount of 0.1 to 4.0 mol, 0.1 to 2.0 mol, or 0.5 to 1.5 mol per 1 mol of polymerization initiator.

Meanwhile, as a conventional method for introducing an additional functional group into a polymer, the active polymer was modified with a modifier, and a condensation reaction was used to react the condensation-capable compound with the Si-O bond of the modifier. However, if such a condensation reaction is used, the bond between the material containing the additional functional group and the modified active polymer is formed as -Si-O-Si, and there is a possibility of hydrolysis occurring during the subsequent stripping step, washing or storage step, and, accordingly, there are problems of bond separation around the condensation bound part and finally loss of the functional group.

In contrast, in the modified conjugated diene polymer obtained by the production method of the present invention, the living end group of the macromonomer reacts with the Si-O-R group of the modifier to form a Si-C bond, and this bond is a bond not subject to hydrolysis reaction , as a condensation bond, and is not subject to separation. Accordingly, the benefits may be that storage stability is improved and defects do not occur due to loss of the originally introduced functional group.

Rubber compound

Among other things, the present invention provides a rubber composition including a modified conjugated diene polymer.

A modified polymer based on a conjugated diene can be included in the rubber mixture in an amount of 10 wt. % or more, from 10 wt. % up to 100 wt. % or from 20 wt. % up to 90 wt. %, and at such values the mechanical properties such as tensile strength and abrasion resistance are excellent and an excellent balance effect between the physical properties can be achieved.

In addition, if necessary, another rubber component can be additionally included in the rubber composition in addition to the modified conjugated diene polymer, in which case the rubber component can be included in an amount of 90 wt. % or less based on the total weight of the rubber compound. In a specific embodiment, the rubber component can be included in an amount of 1 part by weight. up to 900 mass.h. based on 100 parts by mass. a modified polymer based on a conjugated diene.

The rubber component may be, for example, natural rubber or synthetic rubber, and in particular may be a natural rubber (NR) including cis-1,4-polyisoprene; modified natural rubber, which is obtained by modifying or refining ordinary natural rubber such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR) and hydrogenated natural rubber, and synthetic rubber such as styrene butadiene rubber (SBR), polybutadiene ( BdK), polyisoprene (IR), butyl rubber (IRU), ethylene-propylene copolymer, polyisobutylene-isoprene copolymer, neoprene, ethylene-propylene copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-isoprene-butadiene copolymer, isoprene-copolymer butadiene, ethylene-propylene-diene copolymer, polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber and halogenated butyl rubber, and any one of these or mixtures of two or more of them can be used.

The rubber mixture may include filler in an amount of 0.1 parts by weight. up to 200 mass.h. or from 10 parts by mass up to 120 parts by mass based on 100 parts by mass. modified conjugated diene polymer of the present invention. The filler may be, for example, a silica-based filler, in particular wet silica (hydrated silicate), dry silica (anhydrous silicate), calcium silicate, aluminum silicate or colloidal silica. Preferably, the filler may be wet silica, which has the most significant improving effect on degradation characteristics and a compatible effect on improving wet grip. In addition, the rubber composition may further include a carbon-based filler, if desired.

In yet another embodiment, if silica is used as the filler, a silane coupling agent can be used together to improve the reinforcing and low exothermic properties. Specific examples of the silane coupling agent may include bis(3-triethoxysilylpropyl) tetrasulfide, bis(3-triethoxysilylpropyl) trisulfide, bis(3-triethoxysilylpropyl) disulfide, bis(2-triethoxysilylpropyl) tetrasulfide, bis(3-trimethoxysilylpropyl) tetrasulfide, bis(2 -trimethoxysilylethyl)tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamo yltetrasulfide, 2-trimethoxylylethyl-N,N-dimethylthiocarbamoyltetrasulfide , 3-trimethoxylylpropylbenzothiazoletetrasulfide, 3-trimethoxylylpropylbenzenetetrasulfide, 3-trimethoxylylpropylmethacrylate monosulfide, 3-trimethoxypropylmethacrylate monosulfide, bis(3-diethoxymethylsilpropyl)tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilpropyl-N,N-dimethyl thiocarbamoyltetrasulfide or dimethoxymethylsilylpropylbenzothiazoletetrasulfide, and either one or a mixture of the two or more. Preferably, bis(3-trimethoxylylpropyl)polysulfide or 3-trimethoxylylpropylbenzothiazyltetrasulfide can be used from the viewpoint of the effect of improving reinforcement properties.

Moreover, in the rubber composition according to the embodiment of the present invention, since a modified conjugated diene polymer in which a functional group having high affinity for silica is introduced into the active part is used as the rubber component, the amount of silane coupling agent added to the mixture may be less than usual. Thus, it is possible to use a silane coupling agent in an amount of 1 part by weight. up to 20 parts by mass or from 5 parts by mass up to 15 parts by mass based on 100 parts by mass. silicon dioxide. Within the above amount limits, the effects as a binding agent can be sufficiently exerted, and the prevention of gelling effects of the rubber component can be achieved.

The rubber composition in accordance with an embodiment of the present invention may be crosslinkable sulfur and thus may further include a vulcanizing agent. The vulcanizing agent may in particular be sulfur powder and may be included in an amount of from 0.1 to 10 parts by weight. based on 100 parts by mass. rubber component. Within the above values, the elasticity and strength required for a vulcanized rubber compound can be achieved, and at the same time, excellent low fuel consumption can be achieved.

The rubber composition in accordance with an embodiment of the present invention may further include various additives used in the conventional rubber industry in addition to the above components, in particular, vulcanization accelerator, process oil, antioxidant, plasticizer, antioxidant, anti-vulcanization agent, zinc white, stearic acid, thermosetting resin or thermoplastic resin.

The vulcanization accelerator may include, for example, thiazole-based compounds such as 2-mercaptobenzothiazole (M), dibenzothiazyl disulfide (DM) and N-cyclohexyl-2-benzothiazyl sulfenamide (CS), or guanidine-based compounds such as diphenylguanidine (DPG), in an amount from 0.1 to 5 parts by mass. based on 100 parts by mass. rubber component.

The process oil acts as a plasticizer in the rubber composition and may include, for example, a paraffin-based compound, a naphthenic compound, or an aromatic compound. Aromatic process oil can be used taking into account tensile strength and wear resistance, and naphthene or paraffin based process oil can be used taking into account hysteresis loss and low temperature properties. Process oil can be included in an amount of 100 parts by weight. or less per 100 parts by mass. rubber component. Within the above limits, deterioration of the tensile strength and low exothermic properties (low fuel consumption coefficient) of vulcanized rubber can be prevented.

The antioxidant may include, for example, 2,6-di-tert-butylparacresol, dibutylhydroxytoluenyl, 2,6-bis((dodecylthio)methyl)-4-nonylphenol or 2-methyl-4,6-bis((octylthio)methyl)phenol , and it can be used in an amount of 0.1 to 6 parts by mass. based on 100 parts by mass. rubber component.

The antioxidant 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 the condensation product of diphenylamine and acetone at high temperature, in an amount of 0.1 parts by weight. up to 6 parts by mass based on 100 parts by mass. rubber component.

The rubber compound according to an embodiment of the present invention can be produced by mixing using a mixing device such as a Banbury mixer, rollers and a closed mixer, in accordance with the mixture preparation procedure. By vulcanization after molding, a rubber compound with low exothermic properties and good abrasive properties can be obtained.

Therefore, the rubber composition may be suitable for the manufacture of each tire element such as tire tread, undertread, sidewall, carcass rubber, belt cover rubber, bead filler, bead tape and bead cover rubber or in the production of rubber products in various industries such as such as vibration resistant rubber, conveyor belt and hose.

In addition, the present invention provides a tire obtained using a rubber compound.

The tire may include a tire or tire tread.

Examples

The present invention is described in more detail below with reference to embodiments. However, embodiments in accordance with the present invention can be modified into various other forms, and the scope of the present invention should not be considered limited to the embodiments described below. Embodiments of the present invention are provided for a more complete understanding of the present invention by one skilled in the art.

Experiment No. 1

Receipt example 1

To a 500 mL round bottom flask, add 100 mL of tetrahydrofuran and 1 g of n-butyllithium (10 wt.% in n-hexane), add 4-(dimethylamino)styrene (product number: 476382, Sigma-Aldrich) (at a ratio of 3 mol per 1 mol [active Li]), followed by reaction at 10°C for 30 minutes to prepare a solution containing the macromonomer (15.6 mmol/L). Through gas chromatography analysis, 4-(dimethylamino)styrene was not detected after the reaction, and the reaction was guaranteed to proceed.

Receipt example 2

A solution containing macromonomer (15.6 mmol/L) was prepared in the same way as in Preparation Example 1, except for the reaction of N,N-dimethylvinylbenzylamine (product number: 185582, Sigma-Aldrich) (at a ratio of 3 mol to 1 mol [active Li]) instead of 4-(dimethylamino)styrene in Preparation Example 1. Through gas chromatography analysis, N,N-dimethylvinylbenzylamine was not detected after the reaction, and the reaction was guaranteed to proceed.

Example 1

3 kg of n-hexane, 215 g of styrene, 745 g of 1,3-butadiene and 1.29 g of 2,2-bis(2-oxoranyl)propane were introduced into a 20 L autoclave reactor as a polar additive, then 3,2 g n-butyllithium (10 wt.% in n-hexane), the internal temperature of the reactor was brought to 60°C and an adiabatic reaction was carried out with heating. After approximately 30 minutes, 39 g of 1,3-butadiene was introduced to cap the polymer end groups with butadiene. After approximately 10 minutes, tris(3-(trimethoxysilyl)propyl)amine was added as a modifier and reacted for 15 minutes (molar ratio [DTP]:[act. Li] = 1.5:1, molar ratio [modifier] :[act. Li]=1:1). Then, the solution containing the macromonomer prepared in Preparation Example 1 was added, and the reaction was carried out for 15 minutes (molar ratio [act. Li]:[macromonomer]=1:1), and the reaction was terminated using ethanol. 33 g of solution was added there, in which 30 wt. % Wingstay K antioxidant dissolved in hexane. The polymer thus obtained was introduced into hot water heated by steam and stirred to remove solvents, and then roll-dried to remove remaining solvents and water to obtain a modified styrene-butadiene copolymer.

Example 2

A modified styrene-butadiene copolymer was prepared by the same method as in Example 1, except that the solution containing the macromonomer obtained in Preparation Example 2 was added as the macromonomer in Example 1 (molar ratio [act. Li]:[macromonomer]=1 :1).

Example 3

A modified butadiene-styrene copolymer was prepared in the same manner as in Example 1, except that bis(methyldimethoxysilylpropyl)-N-methylamine (product number: SIB1645.0; Gelest) was used instead of tris(3-(trimethoxysilyl)propyl) as a modifier. amine used in example 1 (molar ratio [modifier]:[act. Li]=1:1).

Example 4

A modified butadiene-styrene copolymer was prepared in the same way as in example 1, with the exception of using 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-) as a modifier dimethylpropan-1-amine (NC CHEM) instead of tris(3-(trimethoxysilyl)propyl)amine used in Example 1.

Comparative example 1

3 kg of n-hexane, 215 g of styrene, 745 g of 1,3-butadiene and 1.29 g of 2,2-bis(2-oxoranyl)propane were introduced into a 20-liter autoclave reactor as a polar additive, then n-butyllithium was introduced (10 wt.% in n-hexane), the internal temperature of the reactor was brought to 60°C and an adiabatic reaction was carried out with heating. After approximately 30 minutes, 39 g of 1,3-butadiene was introduced to cap the polymer end groups with butadiene. After approximately 10 minutes, tris(3-(trimethoxysilyl)propyl)amine was added as a modifier and reacted for 15 minutes (molar ratio [DTP]:[act. Li] = 1.5:1, molar ratio [modifier] :[act. Li]=1:1). The reaction was then terminated using ethanol. 33 g of solution was added to it, in which 30 wt. % Wingstay K antioxidant dissolved in hexane. The polymer thus obtained was introduced into hot water, heated with steam and stirred to remove solvents, and then roll-dried to remove remaining solvents and water to obtain a modified styrene-butadiene copolymer.

Comparative example 2

A modified butadiene-styrene copolymer was prepared in the same manner as in Comparative Example 1, except that the solution containing the macromonomer prepared in Example 1 was used instead of the n-butyllithium used in Comparative Example 1, so that the amount of macromonomer introduced was as follows: the same as the amount of n-butyllithium in Comparative Example 1, when carrying out an adiabatic reaction with heating and without a subsequent modification reaction (molar ratio [DTP]:[act. Li]=1.5:1, molar ratio [modifier]: [act. Li]=1:1).

Comparative example 3

A modified butadiene-styrene copolymer was prepared in the same manner as in Comparative Example 1, except that the solution containing the macromonomer prepared in Example 1 was used instead of the n-butyllithium used in Comparative Example 1, so that the amount of macromonomer introduced was as follows: the same as the amount of n-butyllithium in Comparative Example 1, and carrying out an adiabatic reaction with heating.

Evaluation of polymer properties

For each of the modified butadiene-styrene copolymers obtained in the examples and comparative examples, the content of styrene and vinyl units in each polymer, mass average molecular weight (Mw, x10 ³ g/mol), number average molecular weight (Mn, x10 ³ g/mol) were measured ), molecular weight distribution (MWD, MWD), Mooney viscosity (MB), Si content and N content, respectively. The results are presented in Table 1 below.

1) Content of styrene and vinyl units (wt.%)

The content of styrene (SM) and vinyl units in each polymer was measured and analyzed using an NMR spectrometer, VNMRS from Varian at 500 MHz.

For NMR measurements, 1,1,2,2-tetrachloroethane was used as the solvent, and the styrene and vinyl contents were calculated by calculating the solvent peak as 5.97 ppm and considering 7.2–6.9 ppm as the random styrene peaks, 6. 9-6.2 ppm as block styrene peaks, 5.8-5.1 ppm as 1,4-vinyl peaks and 5.1-4.5 ppm as 1,2-vinyl peaks.

2) Mass average molecular weight (Mw, x10 ³ g/mol), number average molecular weight (Mn, x10 ³ g/mol) and molecular weight distribution (PPD, MWD)

Through gel permeation chromatography (GPC) analysis, the weight average molecular weight (Mw) and number average molecular weight (Mn) were measured and a molecular weight distribution curve was obtained.

In addition, the molecular weight distribution (MWD, MWD, Mw/Mn) was calculated for each molecular weight measured in this way. Specifically, GPC was performed using two PLgel Olexis columns (Polymer Laboratories Co.) and one PLgel mixed-C column (Polymer Laboratories Co.) in combination, and polystyrene (PS) as the standard GPC material for molecular weight calculations. The solvent for GPC measurements was prepared by mixing tetrahydrofuran with 2 wt. % amine compound.

3) Mooney viscosity

Mooney viscosity (VM, (ML1+4, @100°C) MU) was measured using an MV-2000 (ALPHA Technologies Co.) using a large rotor at a rotor speed of 2 ± 0.02 rpm at a temperature of 100° WITH. In this case, the sample used was kept at room temperature (23±3°C) for 30 minutes or more, and a sample weighing 27±3 g was taken and placed in a mold and then subjected to a press plate for 4 minutes to take measurements.

4) Si content

Si content was measured by ICP analysis using inductively coupled plasma optical emission spectroscopy (ICP-ESO; Optima 7300DV). Specifically, the measurement was performed by placing a sample weighing approximately 0.7 g in a platinum (Pt) crucible and adding approximately 1 ml of concentrated sulfuric acid (98 wt.%, electronic purity), heating at 300°C for 3 hours , burning the sample in an electric oven (Thermo Scientific, Lindberg Blue M) according to the following program of stages 1-3:

1) stage 1: initial temperature 0°C, speed (temperature/hour) 180°C/hour, temperature (holding time) 180°C (1 hour)

2) stage 2: initial temperature 180°C, speed (temperature/hour) 85°C/hour, temperature (holding time) 370°C (2 hours)

3) stage 3: initial temperature 370°C, speed (temperature/hour) 47°C/hour, temperature (holding time) 510°C (3 hours),

adding 1 ml of concentrated nitric acid (48 wt%) and 20 μl of concentrated hydrofluoric acid (50 wt%) to the residue, sealing the platinum crucible and shaking for 30 minutes or more, adding 1 ml of boric acid to the sample, holding at temperature 0°C for 2 hours or more, dilute in 30 ml of ultra-high purity water and carry out combustion.

5) N content

N content was measured by NSX analysis using a quantitative trace nitrogen analyzer (NSX-2100H). Specifically, a quantitative trace nitrogen analyzer (autosampler, horizontal oven, PMT and nitrogen detector) was turned on, the carrier gas flow rate was set to 250 ml/min for Ar, 350 ml/min for _O2 and 300 ml/min for the ozonator , the heater was set to 800°C and the analyzer was allowed to stabilize for approximately 3 hours. After stabilizing the analyzer, a calibration curve was obtained for the 5 ppm, 10 ppm, 50 ppm, 100 ppm and 500 ppm calibration curve ranges using a nitrogen standard (standard S-22750-01-5 ml), and the area corresponding to each concentration was obtained. A straight line was then drawn using the concentration to area ratios. The ceramic boat with 20 mg of sample was then placed into the analyzer's autosampler and measured to obtain the area. Using the area of the sample thus obtained and the calibration curve, the N content was calculated.

As shown in Table 1 above, the N content of Examples 1 to 4 increased markedly in contrast to Comparative Example 1 and Comparative Example 2. Here, Comparative Example 1 corresponded to a polymer prepared without reacting with the macromonomer of the present invention, and Comparative Example 2 corresponded to a polymer prepared using the macromonomer proposed in the present invention as a modification polymerization initiator, but without the use of a modifier. From the noticeable increase in N content in the polymers of Examples 1 to 4 in contrast to Comparative Example 1 and Comparative Example 2, it can be assumed that the modified conjugated diene polymer of the present invention includes a second chain containing a repeating unit derived from the compound represented by formula 1, and a unit derived from an alkoxysilane-based modifier containing an amine.

Evaluation of rubber molded product properties

To compare and analyze the physical properties of the rubber compounds including the modified styrene-butadiene copolymers obtained in the Examples and Comparative Examples and the molded articles obtained therefrom, the tensile properties and viscoelastic properties were respectively measured, and the results are shown in Table 3 below.

1) Obtaining a rubber sample

Mixing was carried out using each of the modified styrene-butadiene copolymers of the Examples, Comparative Examples and Reference Examples as the starting rubber under the mixing conditions shown in Table 2 below. The starting materials in Table 2 are presented in parts by weight per 100 parts by weight. original rubber.

Specifically, to prepare a rubber sample, mixing was carried out in the first mixing stage and in the second mixing stage. In the first mixing step, the starting rubber, silica (filler), organic silane coupling agent (X50S, Evonik), process oil (TADE oil), zinc oxide (ZnO), stearic acid, antioxidant (TMQ (RD); 2.2) were mixed ,4-trimethyl-1,2-dihydroquinoline polymer), antioxidant (6PPD ((dimethylbutyl)-N-phenylphenylenediamine) and wax (microcrystalline wax) using a Banbury mixer equipped with a temperature control device. In this case, the initial temperature in the mixing the device was maintained at 70 ° C, and after mixing was completed, the first mixture of components was obtained at a discharge temperature of 145 ° C to 155 ° C. In the second stage of mixing, the first mixture of components was cooled to room temperature, and sulfur, a vulcanization accelerator, was added to the first mixture of components rubber (diphenylguanidine (DPG)) and a vulcanization accelerator (N-cyclohexyl-2-benzothiazylsulfenamide (CS)) into a mixing device and mixed at a temperature of 100°C or less to obtain a second mixture of components. Then, a rubber sample was obtained by curing at 160°C for 20 minutes.

2) Tensile properties

To measure the tensile properties, each test specimen was prepared and the tensile stress was measured at 300% elongation (300% modulus) of each specimen in accordance with ASTM 412 Tensile Test Procedure. Specifically, the tensile properties were measured using a 4204 Universal Testing Machine for Tensile tests (Instron Co.) at a speed of 50 cm/min at room temperature.

3) Viscoelastic properties

The viscoelastic properties were confirmed by measuring the viscoelastic behavior under thermodynamic deformation at each specific measurement temperature (-60°C to 60°C) at a frequency of 10 Hz using a dynamometer analyzer (from GABO Co.) in film tension mode and providing a tan δ value. From the results obtained, it follows that if the value of tan δ at a low temperature of 0°C increases, the skid resistance on wet road surfaces becomes better, and if the value of tan δ at a high temperature of 60°C decreases, the hysteresis loss decreases and the rolling resistance (coefficient fuel consumption) is getting better. The obtained values in Table 3 are expressed as a score (%) based on the value obtained for Comparative Example 1, and hence, a higher numerical value corresponds to better results.

4) Machinability properties

By measuring the Mooney viscosity (VM, (ML1+4, @100°C) MU) of the first mixture of components obtained in step (1) of obtaining a rubber sample, the processability properties of each polymer were compared and analyzed, and in this case, the lower the measured Mooney viscosity value, the better the machinability properties. The obtained values in Table 3 are presented as scores (%) based on the value obtained for Comparative Example 1, and hence, a higher numerical value means better results.

In particular, when using MV-2000 (ALPHA Technologies Co.) using a large rotor at a rotor speed of 2 ± 0.02 rpm at a temperature of 100 ° C, each first mixture of components was kept at room temperature (23 ± 3 ° C) for 30 minutes or more, and a mixture weighing 27 ± 3 g was taken and placed in a mold and then subjected to a press platen for 4 minutes to take measurements.

As shown in Table 3, it was confirmed that the modified styrene-butadiene copolymers of Examples 1 to 4, in which the reaction with the macromonomer was carried out after completion of the modification reaction using a modifier according to an embodiment of the present invention, showed excellent processability properties and, at the same time, , excellent tensile properties and viscoelastic properties compared with Comparative Examples 1-3. In particular, Examples 1-4 showed markedly improved tensile properties and processability properties, while exhibiting equivalent or better viscoelastic properties compared to Comparative Example 3. In this case, Comparative Example 3 corresponds to a modified styrene-butadiene copolymer prepared by the same in the same manner as in example 1, except for the use of the macromonomer in example 1 as a modification initiator, but without performing the step of interaction with the macromonomer after the modification reaction.

Although the production methods of Example 1 and Comparative Example 3 are different and the content of Si and N in the polymers is the same, due to the marked difference in the effects of Example 1 and Comparative Example 3, it can be assumed that the modified conjugated diene polymer of the present invention is a copolymer , with a structure different from Comparative Example 3, for example, with a structure similar to a graft copolymer, by attaching a second chain including a repeating unit derived from the compound represented by Formula 1 derived from a macromonomer with a modified polymeric first chain through a unit derived from modifier. It can be confirmed that the tensile properties, viscoelastic properties and machinability properties were noticeably superior when the properties were balanced due to this difference in structure (see Table 1 and Table 3).

Experiment No. 2

Receipt example 3

100 ml of tetrahydrofuran and 1 g of n-butyllithium (10 wt.% in n-hexane) were added to a 500 ml round-bottom flask, then N,N-dimethyl-1-(4-vinylphenyl)methanamine was added (molar ratio 3.0 mol per 1 mol [act. Li]), then the reaction was carried out at a temperature of 10°C for 30 min to prepare a solution containing the macromonomer (15.6 mmol/L). Using GC analysis, the completion of the reaction was confirmed as N,N-dimethyl-1-(4-vinylphenyl)methanamine was not detected after the reaction.

Example 5

3 kg of n-hexane, 215 g of styrene, 745 g of 1,3-butadiene and 1.29 g of 2,2-bis(2-oxoranyl)propane were introduced into a 20 L autoclave reactor as a polar additive, then 3,2 g n-butyllithium (10 wt.% solution in n-hexane), the internal temperature of the reactor was brought to 60°C and an adiabatic reaction was carried out with heating. After approximately 30 minutes, 39 g of 1,3-butadiene was introduced, capping the end groups of the polymer with butadiene. After approximately 10 minutes, tetramethoxysilane (tetramethyl orthosilicate) was added as a modifier and reacted for 15 minutes (molar ratio [DTP]:[act. Li]=1.5:1, molar ratio [modifier]:[act. Li] =0.7:1). Then, the solution containing the macromonomer prepared in Preparation Example 3 was added, and the reaction was carried out for 15 minutes (molar ratio [act. Li]:[macromonomer]=1:1), and the reaction was terminated using ethanol. 33 g of solution was added there, in which 30 wt. % Wingstay K antioxidant was dissolved in hexane. The polymer thus obtained was introduced into hot water heated by steam and stirred to remove solvents, and then roll-dried to remove remaining solvents and water to obtain a modified styrene-butadiene copolymer.

Example 6

The modified butadiene-styrene copolymer was prepared in the same way as in example 5, except that the modifier used in example 5 was used as hexamethoxydisiloxane (hexamethyl diorthosilicate) instead of tetramethoxysilane (molar ratio [modifier]:[act. Li] = 0.7: 1).

Example 7

The modified butadiene-styrene copolymer was prepared in the same way as in example 5, with the exception of the use of 3,3,7,7-tetramethoxy-5,5-bis((trimethoxysilyl)methyl)-2,8-dioxa- 3,7-disilanonane instead of tetramethoxysilane used in example 5 (molar ratio [modifier]:[act. Li]=0.7:1).

Comparative example 4

The modified styrene-butadiene copolymer was prepared in the same manner as in Example 5, except that the solution containing the macromonomer prepared in Example 3 was used instead of the n-butyllithium used in Example 5, so that the amount of macromonomer added was the same as that used in Example 5. as well as the amount of n-butyllithium in Example 5, when carrying out the adiabatic reaction with heating, without carrying out the subsequent reaction of adding a modifier and macromonomer and carrying out the reaction, and interrupting the reaction after blocking with butadiene.

Comparative Example 5

3 kg of n-hexane, 215 g of styrene, 745 g of 1,3-butadiene and 1.29 g of 2,2-bis(2-oxoranyl)propane were introduced into a 20 L autoclave reactor as a polar additive, then 3,2 g n-butyllithium (10 wt.% solution in n-hexane), the internal temperature of the reactor was brought to 60°C and an adiabatic reaction was carried out with heating. After approximately 30 minutes, 39 g of 1,3-butadiene was introduced to cap the polymer end groups with butadiene. After approximately 30 minutes, hexamethoxydisiloxane was introduced as a modifier and the reaction was carried out for 15 minutes (molar ratio [DTP]:[act. Li]=1.5:1, molar ratio [modifier]:[act. Li]=0, 7:1). The reaction was then terminated using ethanol. 33 g of solution was added to it, in which 30 wt. % Wingstay K Antioxidant in Hexane. The polymer thus obtained was introduced into hot water heated by steam and stirred to remove solvents, and then roll-dried to remove remaining solvents and water to obtain a modified styrene-butadiene copolymer.

Comparative Example 6

A modified styrene-butadiene copolymer was prepared in the same manner as in Comparative Example 5, except that 3,3,7,7-tetramethoxy-5,5-bis((trimethoxysilyl)methyl)-2,8-dioxa was used as a modifier -3,7-disilanonane instead of hexamethoxydisiloxane in Comparative Example 5 (molar ratio [DTP]:[act. Li]=1.5:1, molar ratio [modifier]:[act. Li]=0.7:1).

Comparative example 7

A modified styrene-butadiene copolymer was prepared in the same manner as in Comparative Example 4, except that tetramethoxysilane was added as a modifier and reacted for 15 minutes after capping the polymer with butadiene and reacted for approximately 10 minutes (molar ratio [modifier ]:[act. Li]=0.7:1).

Comparative Example 8

The modified butadiene-styrene copolymer was prepared in the same way as in comparative example 7, except for the introduction of 3,3,7,7-tetramethoxy-5,5-bis((trimethoxysilyl)methyl)-2,8-dioxa as a modifier -3,7-disilanonane instead of the tetramethoxysilane used in Comparative Example 7 (molar ratio [DTP]:[active Li]=1.5:1, molar ratio [modifier]:[active Li]=0.7:1 ).

Evaluation of polymer properties

For each of the modified butadiene-style copolymers obtained in the Examples and Comparative Examples, the content of styrene and vinyl units in each polymer, mass average molecular weight (Mw, x10 ³ g/mol), number average molecular weight (Mn, x10 ³ g/mol) , molecular weight distribution (MWD, MWD), Mooney viscosity (MV), Si content and N content were determined, respectively, by the same method as in experiment No. 1. The results are presented in Table 4 below.

As shown in Table 4 above, in Examples 5 to 7, Si and N atoms were present in the polymer molecule, and the N content was greatly increased in contrast to Comparative Example 4. Meanwhile, in Comparative Examples 5 and 6, no atoms were detected in the polymer N. In this case, Comparative Example 4 corresponded to the polymer obtained without using the modifier proposed in the present invention, and Comparative Examples 5 and 6 corresponded to polymers obtained without using the macromonomer proposed in the present invention. From the presence of N atoms and Si atoms in the polymer and the noticeable increase in N content in the polymers in Examples 5-7 in contrast to Comparative Example 4, it can be assumed that the modified conjugated diene polymer according to the present invention includes a second chain containing a repeating unit , obtained from the compound represented by formula 1, and a unit obtained from a modifier based on an amine-containing alkoxysilane.

Evaluation of rubber molded product properties

To compare and analyze the physical properties of the rubber compounds including the modified styrene-butadiene copolymers obtained in the Examples and Comparative Examples and the molded articles obtained therefrom, the tensile properties and viscoelastic properties, respectively, were measured by the same method as in Experiment No. 1 and the results are presented in Table 5 below. In addition, a rubber molded product (sample) was prepared in the same manner as in Experiment No. 1.

In Table 5 above, the obtained values of the viscoelastic properties are expressed as an index (%) based on Comparative Example 4, and the machinability properties are expressed as an index based on the obtained values for Comparative Example 5, the higher the values, the better the properties.

As can be seen from Table 5, it was confirmed that the modified styrene-butadiene polymers of Examples 5-7, which were obtained by reacting with a macromonomer after a modification reaction using a modifier in accordance with an embodiment of the present invention, showed excellent processability properties and, at the same time , excellent tensile properties and viscoelastic properties when compared with Comparative Examples 4-8.

In particular, Examples 5-7 showed equal or better tensile properties, improved viscoelastic properties and markedly improved processability properties when compared with Comparative Examples 7 and 8. In this case, Comparative Examples 7 and 8 were the same modified styrene-butadiene copolymers, obtained in the same way as in example 5 and example 7, except that the macromonomer was used as the modification initiator in examples 5-7.

Despite the difference in production methods in Examples 5 and 7 from Comparative Examples 7 and 8 and the same level of Si and N in the polymers, due to the noticeable difference in the effects of Examples 5 and 7 from Comparative Examples 7 and 8, it can be assumed that the modified polymer based on The conjugated diene of the present invention is a copolymer with a structure different from Comparative Examples 7 and 8, for example, with a structure similar to a graft copolymer by connecting a second chain including a repeating unit derived from a compound represented by Formula 1 derived from a macromonomer with modified by the first polymer chain by means of a unit derived from a modifier. It can be confirmed that the tensile properties, viscoelastic properties and machinability properties were more noticeably superior when the properties were balanced due to the difference in the structures (see Table 4 and Table 5).

Claims (46)

1. A modified polymer based on a conjugated diene, including: a first chain containing a repeating unit derived from a conjugated diene monomer; a second chain containing a repeating unit derived from a compound represented by the following formula 1 and a unit derived from an alkoxysilane based modifier, where the first chain and the second chain are connected by a link obtained from the modifier: Formula 1 in formula 1 R _1a -R _1c represent hydrogen atoms, R _1d represents a single bond, and R _1e is a substituent represented by the following formula 1a: Formula 1a in formula 1a R _1f represents a single bond, substituted by a substituent or an unsubstituted alkylene group containing from 1 to 20 carbon atoms; a substituted or unsubstituted cycloakylene group containing from 5 to 20 carbon atoms, or a substituted or unsubstituted arylene group containing from 6 to 20 carbon atoms, where the substituent is an alkyl group containing from 1 to 10 carbon atoms; a cycloalkyl group containing from 5 to 10 carbon atoms, or an aryl group containing from 6 to 20 carbon atoms, and each of R _1g and R _1h independently represents an alkyl group containing from 1 to 20 carbon atoms; an alkenyl group containing from 2 to 20 carbon atoms; an alkynyl group containing from 2 to 20 carbon atoms; a heteroalkyl group containing from 1 to 20 carbon atoms; a heteroalkenyl group containing from 2 to 20 carbon atoms; a heteroalkynyl group containing from 2 to 20 carbon atoms; a cycloalkyl group containing from 5 to 20 carbon atoms; an aryl group containing from 6 to 20 carbon atoms, or a heterocyclic group containing from 3 to 20 carbon atoms, or R _1g and R _1h are connected to each other to form a heterocyclic group containing from 2 to 10 carbon atoms, together with N . 2. A modified polymer based on a conjugated diene according to claim 1, in which in formula 1a R _1f represents a single bond or an unsubstituted alkylene group containing from 1 to 10 carbon atoms; each of R _1g and R _1h independently represents an alkyl group containing from 1 to 10 carbon atoms; an alkenyl group containing from 2 to 10 carbon atoms; an alkynyl group containing from 2 to 10 carbon atoms; a heteroalkyl group containing from 1 to 10 carbon atoms; a heteroalkenyl group containing from 2 to 10 carbon atoms; a heteroalkynyl group containing from 2 to 10 carbon atoms; a cycloalkyl group containing from 5 to 10 carbon atoms; an aryl group containing from 6 to 10 carbon atoms, or a heterocyclic group containing from 3 to 10 carbon atoms, or R _1g and R _1h are connected to each other to form a heterocyclic group containing from 2 to 10 carbon atoms, together with N . 3. Modified polymer based on conjugated diene according to claim 1, in which in formula 1a R _1f represents a single bond or an unsubstituted alkylene group containing from 1 to 6 carbon atoms, and each of R _1g and R _1h independently represents an alkyl group containing from 1 to 10 carbon atoms, or R _1g and R _1h are connected to each other to form a heterocyclic group containing from 2 to 6 carbon atoms, together with N. 4. The modified conjugated diene polymer of claim 1, wherein the first chain further includes a repeating unit derived from a vinyl aromatic compound monomer. 5. The modified conjugated diene polymer according to claim 1, wherein the second chain further includes a unit derived from a conjugated diene monomer. 6. A modified polymer based on a conjugated diene according to claim 1, where the modified polymer based on a conjugated diene has a number average molecular weight (Mn) from 1000 g/mol to 2000000 g/mol, a mass average molecular weight (Mw) from 1000 g/mol to 3,000,000 g/mol and peak weight-average molecular weight (Mp) from 1000 g/mol to 3,000,000 g/mol. 7. A method for producing a modified polymer based on a conjugated diene according to claim 1, including: polymerizing (S1) a conjugated diene monomer or a conjugated diene monomer and a vinyl aromatic compound monomer in the presence of a polymerization initiator in a carbon solvent to produce an active first chain; subjecting (S2) to reacting the active first chain with an alkoxysilane modifier to produce a modified active first chain, and carrying out (S3) the reaction of a modified active first chain and a macromonomer including a repeating unit obtained from a compound represented by the following formula 1: Formula 1 in formula 1 R _1a -R _1c represent hydrogen atoms, R _1d represents a single bond, and R _1e is the substituent represented by the following formula 1a: Formula 1a in formula 1a R _1f represents a single bond, substituted by a substituent or an unsubstituted alkylene group containing from 1 to 20 carbon atoms; a substituted or unsubstituted cycloakylene group containing from 5 to 20 carbon atoms; or a substituted or unsubstituted arylene group containing from 6 to 20 carbon atoms, where the substituent is an alkyl group containing from 1 to 10 carbon atoms; a cycloalkyl group containing from 5 to 10 carbon atoms, or an aryl group containing from 6 to 20 carbon atoms, and each of R _1g and R _1h independently represents an alkyl group containing from 1 to 20 carbon atoms; an alkenyl group containing from 2 to 20 carbon atoms; an alkynyl group containing from 2 to 20 carbon atoms; a heteroalkyl group containing from 1 to 20 carbon atoms; a heteroalkenyl group containing from 2 to 20 carbon atoms; a heteroalkynyl group containing from 2 to 20 carbon atoms; a cycloalkyl group containing from 5 to 20 carbon atoms; an aryl group containing from 6 to 20 carbon atoms, or a heterocyclic group containing from 3 to 20 carbon atoms, or R _1g and R _1h are connected to each other to form a heterocyclic group containing from 2 to 10 carbon atoms, together with N. 8. A method for producing a modified conjugated diene polymer according to claim 7, wherein the macromonomer further includes a unit derived from a conjugated diene monomer. 9. A method for producing a modified conjugated diene polymer according to claim 7, wherein the macromonomer is produced by a low degree polymerization reaction of a compound represented by Formula 1 or a compound represented by Formula 1 and a conjugated diene monomer in the presence of an organolithium compound in a hydrocarbon solvent . 10. A method for producing a modified polymer based on a conjugated diene according to claim 7, in which the modifier is used in an amount from 0.1 mol to 10 mol per 1 mol of polymerization initiator. 11. A method for producing a modified polymer based on a conjugated diene according to claim 7, in which the macromonomer is used in an amount from 0.1 to 2.0 mol per 1 mol of polymerization initiator. 12. Rubber mixture, including a modified polymer based on a conjugated diene according to claim 1 and a filler. 13. Rubber mixture according to claim 12, including from 0.1 parts by weight. up to 200 parts by weight filler per 100 parts by weight. a modified polymer based on a conjugated diene.