KR20220048452A - Oil-extended conjugated diene-based polymer, preparation method thereof and rubber composition comprising the same - Google Patents

Abstract

The present invention relates to an oil-extended conjugated diene-based polymer having excellent processability, abrasion resistance, viscoelastic properties, and aging properties, a preparation method thereof, and a rubber composition comprising the same. The present invention provides the oil-extended conjugated diene-based polymer which comprises: a polymer chain including a repeating unit derived from a conjugated diene-based monomer; and a unit derived from vegetable oil, wherein at least one of the polymer chains is coupled with the unit derived from vegetable oil and the polymer chain has a weight average molecular weight of 100,000 g/mol or more, the preparation method thereof, and the rubber composition comprising the same.

Description

Oil-extended conjugated diene-based polymer, manufacturing method thereof, and rubber composition comprising the same

The present invention relates to a dielectric conjugated diene-based polymer having excellent wear resistance, viscoelastic properties and aging properties, a method for preparing the same, and a rubber composition comprising the same.

In response to the recent demand for fuel economy reduction in automobiles, a conjugated diene-based polymer having low running resistance, excellent abrasion resistance and tensile properties, and adjustment stability typified by wet road resistance is required as a rubber material for tires.

In order to reduce the running resistance of the tire, there is a method of reducing the hysteresis loss of the vulcanized rubber, and rebound elasticity of 50°C to 80°C, tan δ, Goodrich heat, etc. are used as evaluation indicators of the vulcanized rubber. That is, a rubber material having a large rebound elasticity at the above temperature or a small tan δ and Goodrich heat generation is preferable.

As a rubber material with a small hysteresis loss, natural rubber, polyisoprene rubber, polybutadiene rubber, etc. are known, but these have a problem of small wet road resistance. Accordingly, recently, conjugated diene-based polymers or copolymers such as styrene-butadiene rubber (hereinafter referred to as SBR) or butadiene rubber (hereinafter referred to as BR) have been manufactured by emulsion polymerization or solution polymerization and are used as rubber for tires. . Among them, the greatest advantage of solution polymerization compared to emulsion polymerization is that the content of vinyl structure and styrene content defining rubber properties can be arbitrarily adjusted, and molecular weight and physical properties can be controlled by coupling or modification. that it can Therefore, it is easy to change the structure of the final manufactured SBR or BR, and it is possible to reduce the movement of the chain ends by bonding or modifying the chain ends, and to increase the binding force with fillers such as silica or carbon black. It is widely used as a rubber material for

When this solution-polymerized SBR is used as a rubber material for a tire, by increasing the vinyl content in the SBR, the glass transition temperature of the rubber can be increased to adjust the required physical properties of the tire such as running resistance and braking force, as well as lower the glass transition temperature. By properly adjusting it, fuel consumption can be reduced. The solution polymerization SBR is prepared by using an anionic polymerization initiator, and is used by bonding or modifying the chain ends of the formed polymer using various modifiers. For example, U.S. Patent No. 4,397,994 discloses a technique in which an active anion at the chain end of a polymer obtained by polymerizing styrene-butadiene in a non-polar solvent using alkyllithium, a monofunctional initiator, is combined using a binder such as a tin compound. did

In addition, oil-extended SBR (oil-extended SBR) has been developed and used for the purpose of improving the processability of solution-polymerized SBR.

The oilfield SBR is generally prepared by preparing SBR by emulsion polymerization or solution polymerization, adding petroleum oil before removing the solvent, and then removing the solvent, and the petroleum oil remains in the polymer. Improves the machinability of SBR. In order to obtain a number of beneficial properties, such oil SBR is easily compounded with other rubbers and additives when applied to a rubber composition containing the same, is not easily decomposed during processing, and provides superior properties to the final product. It is used in various fields.

However, in the case of petroleum oil, it is necessary to develop a product that can be applied to various industries because it is environmentally friendly while having the effective characteristics of oil field SBR because it causes various environmental problems.

US 4397994 A KR 10-2020-0031529 A

The present invention has been devised to solve the problems of the prior art, and includes a polymer chain having a weight average molecular weight of 100,000 g/mol or more and a plant oil-derived unit including repeating units derived from a conjugated diene-based monomer, and at least one of the polymer chains An object of the present invention is to provide a dielectric conjugated diene-based polymer having excellent processability, abrasion resistance, running resistance and aging properties coupled with a vegetable oil-derived unit.

In addition, an object of the present invention is to provide a method for producing a dielectric conjugated diene-based polymer, comprising the step of reacting an active polymer with vegetable oil before termination of polymerization.

In addition, an object of the present invention is to provide a rubber composition excellent in processability, abrasion resistance and viscoelastic properties, including the dielectric conjugated diene-based polymer.

According to one embodiment of the present invention for solving the above problems, the present invention provides a polymer chain comprising a repeating unit derived from a conjugated diene-based monomer; and a vegetable oil-derived unit, wherein at least one of the polymer chains is coupled to a vegetable oil-derived unit, and the polymer chain has a weight average molecular weight of 100,000 g/mol or more.

In addition, the present invention comprises the steps of preparing an active polymer by polymerizing a conjugated diene-based monomer or a conjugated diene-based monomer and an aromatic vinyl-based monomer in a hydrocarbon solvent in the presence of an organolithium compound (S1); reacting the active polymer with vegetable oil (S2); And it provides a method for producing the dielectric conjugated diene-based polymer comprising the step (S3) of terminating the reaction.

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

(1) The present invention provides a polymer chain comprising a repeating unit derived from a conjugated diene-based monomer; and a vegetable oil-derived unit, wherein at least one of the polymer chains is coupled to a vegetable oil-derived unit, and the polymer chain has a weight average molecular weight of 100,000 g/mol or more.

(2) The present invention provides the dielectric conjugated diene-based polymer according to (1) above, wherein the Mooney viscosity measured at 100° C. is 50 or more.

(3) The present invention provides a dielectric conjugated diene-based polymer in which the coupling efficiency defined by the following formula (1) is 10% or more in (1) or (2):

[Equation 1]

Coupling Efficiency (%)=[CA/WA]×100

In Equation 1 above,

CA is the molecular weight area of the polymer in which the polymer chain and the vegetable oil-derived unit are coupled to each other in the molecular weight distribution obtained by gel permeation chromatography (GPC), and WA is the total molecular weight area of the dielectric conjugated diene-based polymer.

(4) The present invention provides a dielectric conjugated diene-based polymer according to any one of (1) to (3), wherein the vegetable oil-derived unit is included in an amount of 0.1% to 50% by weight based on the total weight of the polymer. .

(5) The present invention according to any one of (1) to (4), wherein the vegetable oil is soybean oil, rapeseed oil, canola oil, sunflower oil, linseed oil, rice bran oil, palm oil, olive oil, peanut oil, palm oil, cottonseed oil and coconut oil It provides a dielectric conjugated diene-based polymer that is at least one selected from the group consisting of.

(6) The present invention according to any one of (1) to (5), wherein the vegetable oil is an epoxidized vegetable oil, and the epoxidized vegetable oil is epoxidized soybean oil, epoxidized rapeseed oil, epoxidized canola oil, epoxidized sunflower oil, epoxidized linseed oil, epoxidized rice bran oil, epoxidized palm oil, epoxidized olive oil, epoxidized peanut oil, epoxidized palm oil, epoxidized cottonseed oil, and epoxidized coconut oil, which is at least one selected from the group consisting of a dielectric conjugated diene-based polymer to provide.

(7) The present invention provides a dielectric conjugated diene-based polymer according to any one of (1) to (6), wherein the polymer chain further includes a repeating unit derived from an aromatic vinyl-based monomer.

(8) The present invention provides a dielectric conjugated diene-based polymer according to any one of (1) to (7), which contains a functional group including at least one of an N atom and an Si atom.

(9) The present invention comprises the steps of preparing an active polymer by polymerizing a conjugated diene-based monomer or a conjugated diene-based monomer and an aromatic vinyl-based monomer in a hydrocarbon solvent in the presence of an organolithium compound (S1); reacting the active polymer with vegetable oil (S2); And it provides a method for producing the dielectric conjugated diene-based polymer comprising the step (S3) of terminating the reaction.

(10) The present invention provides a method for producing a dielectric conjugated diene-based polymer according to (9), wherein the vegetable oil is used in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the total monomer.

(11) The present invention according to (9) or (10), wherein the vegetable oil is soybean oil, rapeseed oil, canola oil, sunflower oil, linseed oil, rice bran oil, palm oil, olive oil, peanut oil, palm oil, cottonseed oil, coconut oil, epoxidized Soybean oil, epoxidized rapeseed oil, epoxidized canola oil, epoxidized sunflower oil, epoxidized linseed oil, epoxidized rice bran oil, epoxidized palm oil, epoxidized olive oil, epoxidized peanut oil, epoxidized palm oil, epoxidized cottonseed oil and epoxidized coconut oil It provides a method for producing a dielectric conjugated diene-based polymer that is at least one selected from the group.

(12) The present invention according to any one of (9) to (11) above, further comprising the step of reacting or coupling the active polymer with a modifier after step (S1) and before step (S2), wherein the modifier provides a method for producing a dielectric conjugated diene-based polymer, which is a compound including a functional group including at least one of an N atom and a Si atom in a molecule.

(13) The present invention relates to the dielectric conjugated diene-based polymer; And it provides a rubber composition comprising a filler.

(14) The present invention provides a rubber composition according to (13), wherein the filler is at least one selected from a silica-based filler and a carbon black-based filler.

The dielectric conjugated diene-based polymer according to the present invention has excellent abrasion resistance and excellent running resistance and aging properties because a polymer chain having a weight average molecular weight of 100,000 g/mol or more and a vegetable oil-derived unit are coupled.

The method for producing a dielectric conjugated diene-based polymer according to the present invention comprises a step of reacting an active polymer having activity with vegetable oil before polymerization is terminated, whereby a plant oil-derived unit is coupled to one end of a polymer chain. A diene-based polymer can be easily prepared.

In addition, since the rubber composition according to the present invention includes the dielectric conjugated diene-based polymer, it is easy to mix and has excellent wear resistance, and excellent running resistance and aging properties.

The following drawings attached to the present specification illustrate specific embodiments of the present invention, and serve to further understand the technical spirit of the present invention together with the above-described contents of the present invention, so the present invention is limited to the matters described in those drawings should not be construed as limited.
1 shows the molecular weight distribution curve of the dielectric styrene-butadiene copolymer of Example 1 according to an embodiment of the present invention by gel permeation chromatography (GPC).
2 shows a molecular weight distribution curve of the dielectric styrene-butadiene copolymer of Example 2 according to an embodiment of the present invention by gel permeation chromatography (GPC).
3 shows a molecular weight distribution curve of the styrene-butadiene copolymer of Comparative Example 1 according to an embodiment of the present invention by gel permeation chromatography (GPC).

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

The terms or words used in the description and claims of the present invention should not be construed as being limited to their ordinary or dictionary meanings, and the inventor must properly understand the concept of the term in order to best describe his invention. Based on the principle that can be defined, it should be interpreted as meaning and concept consistent with the technical idea of the present invention.

[Definition of Terms]

As used herein, the term 'alkyl group' may refer to a monovalent aliphatic saturated hydrocarbon, and may include a linear alkyl group such as methyl, ethyl, propyl, and butyl; It may mean including all branched alkyl groups such as isopropyl, sec-butyl, tert-butyl, and neopentyl.

As used herein, the term 'alkylene group' may refer to a divalent aliphatic saturated hydrocarbon such as methylene, ethylene, propylene, and butylene.

As used herein, the terms 'derived unit', 'derived repeating unit' and 'derived functional group' may refer to a component, structure, or material itself derived from a certain material.

As used herein, the term 'coupling bond' may mean that the polymer chain and the vegetable oil-derived unit form a covalent bond by a coupling reaction between the polymer chain and the vegetable oil-derived unit.

As used herein, the term 'coupling efficiency' may mean a ratio of a molecular weight area of a coupling-bonded polymer to a total molecular weight area of a polymer in a molecular weight distribution obtained by gel permeation chromatography.

[Measuring conditions]

In the present specification, 'weight average molecular weight (Mw)', 'number average molecular weight (Mn)' and 'molecular weight distribution (MWD)' are GPC (Gel permeation chromatograph) (PL GPC220, Agilent Technologies), and the weight average molecular weight under the following conditions (Mw) and number average molecular weight (Mn) were measured, and molecular weight distribution (PDI, MWD, Mw/Mn) was calculated and obtained from each of the measured molecular weights.

- Column: A combination of two PLgel Olexis (Polymer Laboratories) columns and one PLgel mixed-C (Polymer Laboratories) column is used.

- Solvent: tetrahydrofuran mixed with 2 wt% of an amine compound

- Flow rate: 1 ml/min

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

- Injection volume: 100 μl

- Column temperature: 40℃

- Detector: Refractive index

- Standard: Polystyrene (corrected by cubic function)

In this specification, 'Mooney viscosity' was measured using MV-2000 (ALPHA Technologies, Inc.) at 100°C with a rotor speed of 2±0.02 rpm and a Large Rotor, and the sample used at this time was room temperature (23±3°C). After leaving for 30 minutes or longer, 27±3 g was collected, filled in the die cavity, and the platen was operated to measure for 4 minutes.

In the present specification, 'coupling efficiency' may be obtained by Equation 1 below.

[Equation 1]

Coupling Efficiency (%)=[CA/WA]×100

In Equation 1 above,

CA is the molecular weight area of the polymer in which the polymer chain and the vegetable oil-derived unit are coupled to each other in the molecular weight distribution obtained by gel permeation chromatography (GPC), and WA is the total molecular weight area of the dielectric conjugated diene-based polymer.

Oil-extended, Conjugated Diene Polymer

The present invention provides a dielectric conjugated diene-based polymer having excellent wear resistance, running resistance and aging properties.

The dielectric conjugated diene-based polymer according to an embodiment of the present invention includes a polymer chain including a repeating unit derived from a conjugated diene-based monomer; and a vegetable oil-derived unit, wherein at least one of the polymer chains is coupled to a vegetable oil-derived unit, and the polymer chain has a weight average molecular weight of 100,000 g/mol or more.

In general, oil-extended rubber is a rubber manufactured by mixing petroleum-based oil with synthetic rubber to improve flexibility, elasticity, and compounding properties of synthetic rubber such as a conjugated diene-based polymer. However, petroleum-based oil has many environmental problems as it is not an environmentally friendly material, and since environmental problems have recently become an issue, the need for developing an environmentally friendly material for rubber is also increasing.

In addition, as an issue of such environmental problems, a technique for producing synthetic rubber through a stripping process step by adding natural oil instead of petroleum oil when mixing synthetic rubber, or by adding after completion of polymerization of rubber, has been attempted. , in this case, the abrasion resistance of the synthetic rubber is improved, but there is a problem in that the fuel efficiency characteristics are lowered, and there is a problem in that the long-term property maintenance characteristics are not good due to the migration phenomenon.

However, the oil-dielectric conjugated diene-based polymer according to the present invention is prepared by reacting an active polymer with vegetable oil before termination of polymerization using vegetable oil derived from plants, which is an eco-friendly material, thereby having a structure in which a polymer chain and a plant oil-derived unit are combined. It can be environmentally friendly and have excellent flexibility, elasticity, compounding properties and abrasion resistance.

The dielectric conjugated diene-based polymer includes a polymer chain including a repeating unit derived from a conjugated diene-based monomer, and the polymer chain may have a weight average molecular weight of 100,000 g/mol or more. If the weight average molecular weight of the polymer chain is less than 100,000 g/mol, the mechanical properties of the dielectric conjugated diene-based polymer including the same may be reduced, and the running resistance is reduced due to the increase in the number of polymer chain ends due to the formation of a large number of low molecular weight polymer chains. There may be problems with degradation.

As another example, the polymer chain may have a weight average molecular weight of 150,000 or more and 2,000,000 g/mol or less, or 200,000 or more and 1,500,000 g/mol or less. In this case, abrasion resistance, aging properties, and running resistance may be excellent without a problem of deterioration in processability due to excessive increase in molecular weight of the final polymer.

In addition, the repeating unit derived from the conjugated diene-based monomer may mean a repeating unit formed during polymerization of the conjugated diene-based monomer.

In addition, the polymer chain may further include a repeating unit derived from an aromatic vinylic monomer, and in this case, the dielectric conjugated diene-based polymer may be a copolymer comprising a repeating unit derived from a conjugated diene-based monomer and a repeating unit derived from an aromatic vinyl monomer. there is. Here, the repeating unit derived from the aromatic vinyl monomer may mean a repeating unit formed during polymerization of the aromatic vinyl monomer.

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

The aromatic vinyl monomer is, for example, styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene, 1 -Vinyl-5-hexylnaphthalene, 3- (2-pyrrolidino ethyl) styrene (3- (2-pyrrolidino ethyl) styrene), 4- (2-pyrrolidino ethyl) styrene (4- (2-pyrrolidino ethyl) )styrene) and 3-(2-pyrrolidino-1-methyl ethyl)-methylstyrene (3-(2-pyrrolidino-1-methyl ethyl)methylstyrene) may be at least one selected from the group consisting of.

As another example, the dielectric conjugated diene-based polymer may be a copolymer further comprising a repeating unit derived from a diene-based monomer having 1 to 10 carbon atoms together with the repeating unit derived from the conjugated diene-based monomer. The repeating unit derived from the diene-based monomer may be a repeating unit derived from a diene-based monomer different from the conjugated diene-based monomer, and the diene-based monomer different from the conjugated diene-based monomer may be, for example, 1,2-butadiene. . When the modified conjugated diene-based polymer is a copolymer further comprising a diene-based monomer, the modified conjugated diene-based polymer contains more than 0% by weight to 1% by weight of the repeating unit derived from the diene-based monomer, more than 0% by weight to 0.1% by weight, It may be included in an amount of more than 0% by weight to 0.01% by weight, or more than 0% by weight to 0.001% by weight, and has an effect of preventing gel formation within this range.

According to an embodiment of the present invention, the copolymer may be a random copolymer, and in this case, an excellent balance between physical properties is obtained. The random copolymer may mean that repeating units constituting the copolymer are disorderly arranged.

As another example, the dielectric conjugated diene-based polymer may include a functional group including at least one of an N atom and a Si atom. In this case, the dielectric conjugated diene-based polymer has excellent processability and abrasion resistance and has superior viscoelastic properties. There is a further improvement effect.

For example, the functional group may be an amino group, an amide group, an imino group, an imidazole group, a pyrimidyl group, a cyclic amino group, or a silyl group unsubstituted or substituted with a substituent, wherein the substituent is an alkyl group having 1 to 20 carbon atoms, and a carbon number A cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heteroalkyl group having 2 to 20 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms. there is.

In another example, the functional group is an alkylamino group, an allylamino group, an alkylallylamino group, an alkylaminosilyl group, an alkylaminoalkylsilyl group, a trialkoxysilyl group, an alkylalkoxysilyl group, an alkylaminoalkoxysilyl group, a di(alkylsilyl)amino group. And it may be at least one selected from the group consisting of a di (alkylamino) silyl group.

As another example, the functional group may further include a ketone group, an epoxy group, an ether group, or an ester group in addition to the functional group including at least one of an N atom and a Si atom.

On the other hand, the functional group is derived from the modifier by the manufacturing method described below of modifying or coupling reaction using a modifier, and the modifier is not particularly limited as long as it is a compound capable of providing the above functional group. can

In addition, the oil-extended conjugated diene-based polymer includes a plant oil-derived unit, and specifically, the oil-extended conjugated diene-based polymer may include a vegetable oil-derived unit in an amount of 0.1% to 50% by weight based on the total weight of the polymer. Specifically, the dielectric conjugated diene-based polymer may include a vegetable oil-derived unit in an amount of 5 wt% to 40 wt%, 10 wt% to 40 wt%, or 20 wt% to 35 wt%, based on the total weight of the polymer. In this case, the flexibility, elasticity, and abrasion resistance of the dielectric conjugated diene-based polymer are more excellent.

Here, the content of the vegetable oil-derived unit in the oil-extended conjugated diene-based polymer can be calculated from the input amount of vegetable oil used in the preparation of the polymer, for example, the weight% of the vegetable oil input relative to 100% by weight of the total monomer used in the preparation of the polymer is vegetable oil in the polymer It may be the content of the derived unit.

The vegetable oil is not particularly limited and may be included in the present invention as long as it is a vegetable oil, but specifically selected from the group consisting of soybean oil, rapeseed oil, canola oil, sunflower oil, flax oil, rice bran oil, palm oil, olive oil, peanut oil, palm oil, cottonseed oil and coconut oil It may be one or more types.

As another example, the vegetable oil may be an epoxidized vegetable oil, and the epoxidized vegetable oil is not particularly limited and may be included in the present invention as long as it is an epoxidized vegetable oil, specifically, epoxidized soybean oil, epoxidized rapeseed oil, epoxidized canola oil, It may be at least one selected from the group consisting of epoxidized sunflower oil, epoxidized linseed oil, epoxidized rice bran oil, epoxidized palm oil, epoxidized olive oil, epoxidized peanut oil, epoxidized palm oil, epoxidized cottonseed oil, and epoxidized coconut oil. .

More specifically, in terms of more advantageously achieving the desired effect, the vegetable oil may be soybean oil or epoxidized soybean oil.

Meanwhile, in the present invention, 'epoxidized vegetable oil' is an organic compound obtained from an epoxidation reaction of vegetable oil, and the degree of epoxidation (epoxidation rate) may be different depending on the type of the vegetable oil. In general, vegetable oil is a triglyceride molecule represented by the following formula (1).

[Formula 1]

In Formula 1, R ₁ to R ₃ are each a radical of an ester derived from a fatty acid, and each is an unsaturated or saturated hydrocarbon group.

Here, the relative ratios of R ₁ to R ₃ may vary depending on the type of vegetable oil, and may be exemplarily shown in Table 1 below.

vegetable oil Saturation (wt%, R ₁ ) monounsaturated (wt%, R ₂ ) polyunsaturated (wt%, R ₃ ) soybean oil 17 23 60 sunflower oil 10 45 40 canola oil 7 63 28 flax oil 10 45 40 olive oil 14 73 11 peanut oil 17 46 32 cottonseed oil 26 18 52 palm oil 49 37 9 olive oil 14 73 11

On the other hand, epoxidation of vegetable oil is performed while an oxygen atom is added to an unsaturated bond in a molecule of vegetable oil and an epoxide is generated, and the degree of epoxidation may be affected by the ratio of unsaturated bonds in the vegetable oil.

As another example, in consideration of the degree of epoxidation and the effect of controlling the degree of epoxidation, the epoxidized vegetable oil according to the present invention is at least one selected from epoxidized soybean oil, epoxidized sunflower oil, epoxidized linseed oil and epoxidized cottonseed oil, more preferably The epoxidized vegetable oil may be at least one selected from epoxidized soybean oil and epoxidized cottonseed oil, and most preferably, epoxidized soybean oil.

As another example, in the dielectric conjugated diene-based polymer according to an embodiment of the present invention, at least one of the polymer chains may be coupled to a vegetable oil-derived unit.

Specifically, the dielectric conjugated diene-based polymer is prepared by adding and reacting vegetable oil to the active polymer before the end of polymerization, and the ester of the triglyceride molecule of the vegetable oil and the anion of the active polymer react, so that the polymer chain and the plant oil-derived unit are covalently bonded may be formed, and at least one of the polymer chains may have a structure in which a coupling bond is coupled to a plant oil-derived unit. As another example, depending on the degree of coupling, the dielectric conjugated diene-based polymer may have a linear structure, a branched structure, and a star-type structure with increased molecular weight by coupling two or more polymer chains to a vegetable oil-derived unit.

As another example, in the dielectric conjugated diene-based polymer according to an embodiment of the present invention, at least one polymer chain forms a coupling bond with a vegetable oil-derived unit, so that the molecular weight distribution curve by gel permeation chromatography is bimodal. In this case, the dielectric conjugated diene-based polymer may be a batch polymer prepared by batch polymerization.

In the case of a dielectric conjugated diene-based polymer obtained by mixing vegetable oil after the completion of polymerization of the conventional polymer, the polymer does not have an anionic activity capable of reacting, so it cannot react or combine with vegetable oil. The polymer chain unit and the vegetable oil-derived unit are present in a mixture state. As a result, in the case of the conventional dielectric conjugated diene-based polymer, no matter what polymerization method is used, whether batch or continuous, the molecular weight between the polymer chains is constant or distributed in a wide range, so there is no polymer chain with a different molecular weight. It has a unimodal shape in the molecular weight distribution curve measured by the graph.

On the other hand, in the dielectric conjugated diene-based polymer according to an embodiment of the present invention, whether the coupling bond between the polymer chain and the vegetable oil-derived unit can be confirmed by Mooney viscosity. Specifically, the dielectric conjugated diene-based polymer may have a Mooney viscosity measured at 100° C. of 50 or more, 50 to 150, or 60 to 140.

As another example, the dielectric conjugated diene-based polymer may have a Mooney viscosity increase rate defined by Equation 2 below 120% or more, or 130% or more, or 130% or more and 150% or less.

[Equation 2]

Mooney viscosity increase rate (%)=[MV2/MV1]×100

In Equation 2, MV1 is the Mooney viscosity measured at 100° C. of the conjugated diene-based polymer, and MV2 is the Mooney viscosity measured at 100° C. of the dielectric conjugated diene-based polymer.

That is, the Mooney viscosity increase rate represents the Mooney viscosity change rate of the oil-extended conjugated diene-based polymer prepared by reacting with vegetable oil of the present invention compared to the general conjugated diene-based polymer prepared without reacting with vegetable oil. In the conjugated diene-based polymer, it can be predicted that at least one of the polymer chains forms a coupling bond with a vegetable oil-derived unit.

As another example, the dielectric conjugated diene-based polymer according to an embodiment of the present invention may have a coupling efficiency defined by the following Equation 1 of 10% or more, or 30% or more. In addition, the upper limit of the coupling efficiency is not particularly limited, but may be 80% or less, or 70% or less in terms of realization of excellent properties in a balanced manner in abrasion resistance, running resistance, and aging properties. As another example, the coupling efficiency may be 10% or more, 10% or more and 80% or less, 10% or more and 70% or less, or 30% or more and 70% or less. , it can be confirmed that the polymer chain and the vegetable oil-derived unit are coupled.

[Equation 1]

Coupling Efficiency (%)=[CA/WA]×100

In Equation 1 above,

CA is the molecular weight area of the polymer in which the polymer chain and the vegetable oil-derived unit are coupled to each other in the molecular weight distribution obtained by gel permeation chromatography (GPC), and WA is the total molecular weight area of the dielectric conjugated diene-based polymer.

Here, CA prepares the active polymer during the manufacturing process of the polymer and collects some polymers before reacting with vegetable oil to obtain the peak molecular weight area (Mp ₁ A) by gel chromatography of the polymer, and then finally prepared dielectric conjugate It can be obtained by subtracting the area of Mp ₁ A from the molecular weight distribution area of the diene-based polymer.

In another example, the dielectric conjugated diene-based polymer may include a polymer chain including a repeating unit derived from a conjugated diene-based monomer; and a vegetable oil-derived unit, wherein at least one of the polymer chains is coupled to a vegetable oil-derived unit, and the polymer chain has a weight average molecular weight of 100,000 g/mol or more, and when it meets the coupling efficiency of the above range Abrasion resistance, running resistance, and aging properties have a better effect in a balanced way.

On the other hand, the dielectric conjugated diene-based polymer according to an embodiment of the present invention has a number average molecular weight (Mn) of 100,000 g/mol to 3,000,000 g/mol, 200,000 g/mol to 2,000,000 g/mol, or 200,000 g/mol to 1,000,000 g/mol, and a weight average molecular weight (Mw) of 100,000 g/mol to 5,000,000 g/mol, 300,000 g/mol to 3,000,000 g/mol, or 300,000 g/mol to 2,000,000 g/mol, Within the range, there is an excellent effect of running resistance and wet road resistance.

In addition, the dielectric conjugated diene-based polymer may have a molecular weight distribution of 1.1 or more and 2.5 or less, and has excellent processability within this range.

In addition, the dielectric conjugated diene-based polymer may have a vinyl content of 5 wt% or more, 10 wt% or more, or 10 wt% to 60 wt%. Here, the vinyl content means the content of the 1,2-added conjugated diene-based monomer, not the 1,4-added, based on 100% by weight of the conjugated diene-based copolymer consisting of a monomer having a vinyl group and an aromatic vinyl-based monomer. can

As described above, the dielectric conjugated diene-based polymer according to an embodiment of the present invention has a specific structure and molecular weight, and the specific structure of the dielectric conjugated diene-based polymer has properties such as molecular weight distribution curve shape, Mooney viscosity, and coupling efficiency. It can be expressed as, and by satisfying the above specific structure and the above physical properties, the technical task of the present invention can be more preferably implemented. In addition, such a dielectric conjugated diene-based polymer may be preferably satisfied by the manufacturing method described later.

Method for producing dielectric conjugated diene-based polymer

In addition, the present invention provides a method for producing the dielectric conjugated diene-based polymer.

The method for producing the dielectric conjugated diene-based polymer according to the present invention comprises the steps of preparing an active polymer by polymerizing a conjugated diene-based monomer or a conjugated diene-based monomer and an aromatic vinyl-based monomer in a hydrocarbon solvent in the presence of an organolithium compound (S1) ; reacting the active polymer with vegetable oil (S2); and terminating the reaction (S3).

Here, the conjugated diene-based monomer, the aromatic vinyl-based monomer and the vegetable oil used in the manufacturing method are the same as described above.

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

According to an embodiment of the present invention, the organolithium compound is 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 based on 100 g of the total monomer. can be used as In addition, the organolithium compound is not particularly limited, but for example, methyllithium, ethyllithium, propyllithium, n-butyllithium, s-butyllithium, t-butyllithium, hexyllithium, n-decyllithium, t-octyllithium , phenyllithium, 1-naphthyllithium, n-eicosyllithium, 4-butylphenyllithium, 4-tolylylithium, cyclohexyllithium, 3-5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium, It may be at least one selected from the group consisting of lithium alkoxide, lithium sulfonate, lithium amide and lithium isopropylamide.

(S1) step

The polymerization in step (S1) may be, for example, anionic polymerization, and as a specific example, living anionic polymerization having an anionic active site at the polymerization end by an anion-based growth polymerization reaction. In addition, the polymerization in step (S1) may be an elevated temperature polymerization, isothermal polymerization, or constant temperature polymerization (adiabatic polymerization), and the constant temperature polymerization includes the step of polymerization by its own heat of reaction without optionally applying heat after the organolithium compound is added. may mean a polymerization method in which the temperature rise polymerization may refer to a polymerization method in which the temperature is increased by optionally applying heat after the organolithium compound is added, and the isothermal polymerization is heat after the organolithium compound is added. It may refer to a polymerization method in which the temperature of the polymer is maintained constant by increasing heat by adding or taking heat away.

In addition, according to an embodiment of the present invention, the polymerization in step (S1) may be carried out by further including a diene-based compound having 1 to 10 carbon atoms in addition to the conjugated diene-based monomer, and in this case, it is applied to the reactor wall during long-term operation. It has the effect of preventing the formation of a gel. An example of the diene-based compound may be 1,2-butadiene.

The polymerization of step (S1) may be carried out in a temperature range of, for example, less than 80 ℃, -20 ℃ to 80 ℃, 0 ℃ to 80 ℃, 0 ℃ to 70 ℃ or 10 ℃ to 70 ℃, within this range By narrowing the molecular weight distribution of the polymer, there is an excellent effect of improving physical properties.

The active polymer prepared by the step (S1) may refer to a polymer in which a polymer anion and an organometallic cation are bound.

Meanwhile, the polymerization in step (S1) may be carried out including a polar additive, and the polar additive is added in a proportion of 0.001 g to 50 g, 0.001 g to 10 g, or 0.005 g to 0.1 g based on 100 g of the total monomer. can do. As another example, the polar additive may be added in a proportion of 0.001 g to 10 g, 0.005 g to 5 g, or 0.005 g to 4 g based on 1 mmol of the total organolithium compound.

The polar additive is, for example, tetrahydrofuran, 2,2-di(2-tetrahydrofuryl)propane, diethyl ether, cycloamyl ether, dipropyl ether, ethylene methyl ether, ethylene dimethyl ether, diethyl glycol, dimethyl ether , tertiary butoxyethoxyethane, bis (3-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine, N,N,N',N'-tetramethyl It may be at least one selected from the group consisting of ethylenediamine, sodium mentholate, and 2-ethyl tetrahydrofurfuryl ether, preferably triethylamine, tetramethylethylenediamine, sodium It may be mentholate (sodium mentholate) or 2-ethyl tetrahydrofurfuryl ether (2-ethyl tetrahydrofurfuryl ether), and when the polar additive is included, a conjugated diene-based monomer, or a conjugated diene-based monomer and an aromatic vinyl-based monomer are copolymerized In this case, there is an effect of inducing the formation of a random copolymer easily by compensating for the difference in their reaction rate.

(S2) step

The step (S2) is a step of performing a coupling reaction between the polymer chain and the plant oil-derived unit, and may be performed by reacting the active polymer with the vegetable oil, specifically, the vegetable oil is the total monomer used in the step (S1). It may be used in an amount of 0.1 to 50 parts by weight based on 100 parts by weight. Specifically, the vegetable oil may be used in an amount of 5 to 40 parts by weight, 10 to 40 parts by weight, or 20 to 35 parts by weight, based on 100 parts by weight of the total monomer, wherein the monomer is a conjugated diene-based monomer or It may be a conjugated diene-based monomer and an aromatic vinyl-based monomer.

In addition, the reaction is not particularly limited as long as the reaction can occur because the active polymer and vegetable oil are easily mixed, for example, 90° C. or less, -20° C. to 80° C., 0° C. to 80° C. or 30° C. to 80° C. It can be carried out by mixing in the temperature range of

As another example, in the aspect that the combination of the polymer chain and the vegetable oil-derived unit can easily occur without the problem of reaction degradation due to the increase in the viscosity of the vegetable oil, it is carried out by mixing in a temperature range of 30 ° C or higher, or 30 ° C or higher and 90 ° C or lower. it could be

In addition, the manufacturing method according to the present invention may further include the step of reacting or coupling the active polymer and the modifier before performing the step (S2) after the step (S1), wherein the modifier is N in the molecule It may be a compound including a functional group including at least one of an atom and a Si atom.

The modifier may be used in an amount of 0.01 mmol to 10 mmol based on 100 g of the total monomer. As another example, the modifier may be used in a molar ratio of 1:0.1 to 10, 1:0.1 to 5, or 1:0.1 to 1:3 based on 1 mole of the organolithium compound in step (S1).

Meanwhile, the modifier may be applied to the present invention without particular limitation as long as it is a compound capable of providing the functional group so that the dielectric conjugated diene-based polymer may include the aforementioned functional group.

Illustratively, the 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 having 1 to 10 carbon atoms, R ² and R ³ may each independently be an alkyl group having 1 to 10 carbon atoms, and R ⁴ is hydrogen, an epoxy group, or an alkylene group having 1 to 10 carbon atoms. It may be a monosubstituted, disubstituted or trisubstituted alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms, an allyl group having 2 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a heterocyclic group having 2 to 10 carbon atoms, R ²¹ may be a single bond, an alkylene group having 1 to 10 carbon atoms, or -[R ⁴² O] _j -, R ⁴² may be an alkylene group having 1 to 10 carbon atoms, and a and m are each independently from 1 to 3 It may be an integer selected from, n may be an integer from 0 to 2, and j may be an integer selected from 1 to 30.

As a specific example, the compound represented by Formula 2 is N,N-bis(3-(dimethoxy(methyl)silyl)propyl)-methyl-1-amine(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-(diethoxy(methyl)silyl) )propyl)-methyl-1-amine), N,N-bis(3-(trimethoxysilyl)propyl)-methyl-1-amine(N,N-bis(3-(trimethoxysilyl)propyl)-methyl- 1-amine), N,N-bis(3-(triethoxysilyl)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, N-bis (3- (diethoxy (methyl) silyl) propyl) -1,1,1-trimethlysilanamine), N- (3-(1H-1,2,4-triazol-1-yl)propyl)-3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)propan-1-amine ( N-(3-(1H-1,2,4-triazole-1-yl)propyl)-3-(trimethoxysilyl)-N-(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(3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)-N-(3-(1-(3-(trimehtoxysilyl)propyl)-1H-1,2,4- triazol-3-yl)propyl)propan-1-amine), N-allyl-N-(3-(trimethoxysilyl)prop Phil)prop-2-en-1amine (N-allyl-N-(3-(trimethoxysilyl)propyl)prop-2-en-1-amine), N,N-bis(oxiran-2-ylmethyl) )-3-(trimethoxysilyl)propan 1-amine (N,N-bis(oxiran-2-ylmethyl)-3-(trimethoxysilyl)propan-1-amine), 1,1,1-trimethyl-N- (3- (triethoxysilyl) propyl) -N- (trimethylsilyl) silanamine (1,1,1-trimethyl-N- (3- (triethoxysilyl) propyl) -N- (trimethylsilyl) silanamine) and N; N-bis(3-(triethoxysilyl)propyl)-2,5,8,11,14-pentaoxahexadecan-16-amine (N,N-bis(3-(triethoxysilyl)propyl)-2, 5,8,11,14-pentaoxahexadecan-16-amine) may be one selected from the group consisting of.

As another example, the modifier may include a compound represented by the following formula (3).

[Formula 3]

또는

일 수 있으며, 이 때, R¹³, R¹⁴, R¹⁵ 및 R¹⁶은 각각 독립적으로 수소, 또는 탄소수 1 내지 10의 알킬기일 수 있다.In Formula 3, R ⁵ , R ⁶ and R ⁹ may each independently be an alkylene group having 1 to 10 carbon atoms, and R ⁷ , R ⁸ , R ¹⁰ and R ¹¹ are each independently an alkyl group having 1 to 10 carbon atoms. may be, R ¹² may be hydrogen or an alkyl group having 1 to 10 carbon atoms, b and c are each independently 1, 2 or 3, and may be b+c≥4, and A is

or

may be, and in this case, R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ may each independently be hydrogen or an alkyl group having 1 to 10 carbon atoms.

As a specific example, the compound represented by Formula 3 is N-(3-(1H-imidazol-1-yl)propyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl Propan-1-amine (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 (3-(4,5-dihydro-1H-imidazol) It may be one selected from the group consisting of -1-yl)-N,N-bis(3-(triethoxysilyl)propyl)propan-1-amine).

As another example, the modifier may include a compound represented by the following formula (4).

[Formula 4]

In Formula 4, A ¹ and A ² may each independently be a divalent hydrocarbon group having 1 to 20 carbon atoms including or not including an oxygen atom, and R ¹⁷ to R ²⁰ are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms. may be a hydrocarbon group, and L ¹ to L ⁴ are each independently a monosubstituted, disubstituted or trisubstituted alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms, or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or L ¹ and L ² and L ³ and L ⁴ may be connected to each other to form a ring having 1 to 5 carbon atoms, and when L ¹ and L ² and L ³ and L ⁴ are connected to each other to form a ring, a ring formed may include 1 to 3 at least one hetero atom selected from the group consisting of N, O and S.

As a specific example, the compound represented by Formula 4 is 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine)( 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine), 3,3'-(1,1,3,3-tetra Ethoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-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-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine), 3,3'-(1,1,3,3-tetra Methoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-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-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dimpropylpropan-1-amine), 3,3'-(1,1,3,3-tetra Ethoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-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-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-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dipropylpropan-1-amine), 3,3'-(1,1,3,3-tetrapropoxy Cydisiloxane-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-diethylmethan-1-amine) (3 ,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-diethylmethan-1-amine), 3,3'-(1,1,3,3-tetrae Toxydisiloxane-1,3-diyl)bis(N,N-diethylmethan-1-amine)(3,3′-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N ,N-diethylmethan-1-amine), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-diethylmethan-1-amine) (3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-diethylmethan-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-dimethylmethan-1-amine), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dipropylmethan-1-amine) ( 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dipropylmethan-1-amine), 3,3'-(1,1,3,3-tetra Propoxydisiloxane-1,3-diyl)bis(N,N-dimethylmethan-1-amine)(3,3′-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N ,N-dimethylmethan-1-amine), 3,3'-(1,1,3, 3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dipropylmethan-1-amine)(3,3′-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl) )bis(N,N-dipropylmethan-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-dimethylmethan-1-amine), 3,3'-(1,1,3 ,3-Tetraethoxydisiloxane-1,3-diyl)bis(N,N-dipropylmethane-1-amine)(3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-) diyl)bis(N,N-dipropylmethan-1-amine), N,N'-((1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(propane-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-(trimethylsilyl)silanamine), N,N'-((1,1,3,3-tetraethoxydisiloxane-1,3-diyl) Bis(propane-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-tetraprotoxy) Cydisiloxane-1,3-diyl)bis(propane-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(propane-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilaneamine(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(propane-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilaneamine (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(propane-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilaneamine (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-tetramethoxydisiloxane), 1,3- Bis(3-(1H-imidazol-1-yl)propyl)1,1,3,3-tetraethoxydisiloxane(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 (1,3- It may be one selected from the group consisting of bis(3-(1H-imidazol-1-yl)propyl)-1,1,3,3-tetrapropoxydisiloxane).

As another example, the modifier may include a compound represented by the following Chemical Formula 5.

[Formula 5]

In Formula 5, R _b2 to R _b4 are each independently an alkylene group having 1 to 10 carbon atoms, R _b5 to R _b8 are each independently an alkyl group having 1 to 10 carbon atoms, and R _b13 and R _b14 are each independently a carbon number an alkylene group of 1 to 10, R _b15 to R _b18 are each independently an alkyl group having 1 to 10 carbon atoms, and m _{1 ,} m ₂ , m ₃ and m ₄ are each independently an integer of 1 to 3.

As another example, the modifier may include a compound represented by the following Chemical Formula 5.

[Formula 5]

In Formula 5, R _e1 and R _e2 are each independently an alkylene group having 1 to 10 carbon atoms, and _Re3 to R _e6 are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, or -R _e7 SiR _e8 R _e9 R _e10 However, at least one of _Re3 to _Re6 is —R _e7 SiR _e8 Re9 _{Re9 Re10} , wherein _Re7 is a single bond or an alkylene group having 1 to 10 carbon atoms, and _Re8 to _Re10 are independently of each other 1 carbon number an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, wherein at least one of R _e8 to R _e10 is an alkoxy group having 1 to 10 carbon atoms.

As another example, the modifier may include a compound represented by the following formula (6).

[Formula 12]

In Formula 6, R _h1 and R _h2 are each independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, R _h3 is a single bond or an alkylene group having 1 to 10 carbon atoms, A ₃ is -Si (R _h4 R _h5 R _h6 ) or —N[Si(R _h7 R _h8 R _h9 )] ₂ , wherein R _h4 to R _h9 are each independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. am.

As another example, the method for producing the dielectric conjugated diene-based polymer according to an embodiment of the present invention may be performed by batch polymerization or continuous polymerization using a plurality of reactors including two or more reactors.

(S3) step

Step (S3) is a step to prepare a dielectric conjugated diene-based polymer by terminating the reaction, and may be performed by adding a polymerization terminator after step (S2) to terminate polymerization activity.

Here, the polymerization terminator is not particularly limited, and a compound commonly used to terminate polymerization activity may be used in a conventional amount.

rubber composition

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

The rubber composition may include the dielectric conjugated diene-based polymer in an amount of 10 wt% or more, 10 wt% to 100 wt%, or 20 wt% to 90 wt%, within this range, tensile strength, abrasion resistance, etc. It has excellent mechanical properties and excellent balance between the physical properties.

In addition, the rubber composition may further include other rubber components as needed in addition to the dielectric conjugated diene-based polymer, wherein the rubber component may be included in an amount of 90% by weight or less based on the total weight of the rubber composition. As a specific example, the other rubber component may be included in an amount of 1 to 900 parts by weight based on 100 parts by weight of the dielectric conjugated diene-based polymer.

The rubber component may be, for example, natural rubber or synthetic rubber, and specific examples thereof include natural rubber (NR) including cis-1,4-polyisoprene; Modified natural rubbers such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber that are modified or refined of the general natural rubber; Styrene-butadiene copolymer (SBR), polybutadiene (BR), polyisoprene (IR), butyl rubber (IIR), ethylene-propylene copolymer, polyisobutylene-co-isoprene, neoprene, poly(ethylene-co-) propylene), poly(styrene-co-butadiene), poly(styrene-co-isoprene), poly(styrene-co-isoprene-co-butadiene), poly(isoprene-co-butadiene), poly(ethylene-co-propylene) -co-diene), polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, or a synthetic rubber such as halogenated butyl rubber, and any one or a mixture of two or more thereof may be used.

The rubber composition may include, for example, 0.1 parts by weight to 200 parts by weight, or 10 parts by weight to 120 parts by weight of a filler based on 100 parts by weight of the dielectric conjugated diene-based polymer of the present invention. The filler may be, for example, a silica-based filler, and specific examples include wet silica (hydrous silicic acid), fumed silica (silicic anhydride), calcium silicate, aluminum silicate or colloidal silica, and preferably, the effect of improving fracture properties and wet It may be wet silica that has the best effect of compatibility with wet grip. In addition, the rubber composition may further include a carbon-based filler if necessary.

As another example, when silica is used as the filler, a silane coupling agent for improving reinforcing properties and low heat generation may be used together, and as a specific example, the silane coupling agent is bis(3-triethoxysilylpropyl)tetrasulfide , bis(3-triethoxysilylpropyl)trisulfide, bis(3-triethoxysilylpropyl)disulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(3-trimethoxysilyl) propyl) tetrasulfide, bis(2-trimethoxysilylethyl)tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-Mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide Feed, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-trimethoxysilylpropylbenzothiazolyltetrasulfide, 3-triethoxysilylpropylbenzolyltetrasulfide, 3-triethoxysilylpropylmethacrylate monosulfide, 3-trimethoxysilylpropylmethacrylate monosulfide, bis(3-diethoxymethylsilylpropyl)tetrasulfide, 3-mercaptopropyldimethoxymethyl It may be silane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide or dimethoxymethylsilylpropylbenzothiazolyltetrasulfide, and any one or a mixture of two or more thereof may be used. Preferably, in consideration of the reinforcing improvement effect, it may be bis(3-triethoxysilylpropyl)polysulfide or 3-trimethoxysilylpropylbenzothiazyltetrasulfide.

In addition, in the rubber composition according to an embodiment of the present invention, as a rubber component, a dielectric conjugated diene-based polymer in which a functional group with high affinity for silica is introduced is used as a rubber component. may be reduced than the case, and accordingly, the silane coupling agent may be used in an amount of 1 to 20 parts by weight, or 5 to 15 parts by weight, based on 100 parts by weight of silica, and the effect as a coupling agent within this range is It has the effect of preventing the gelation of the rubber component while being sufficiently exhibited.

The rubber composition according to an embodiment of the present invention may be crosslinkable with sulfur, and may further include a vulcanizing agent. The vulcanizing agent may be specifically sulfur powder, and may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the rubber component, and within this range, the vulcanized rubber composition has a low fuel efficiency while securing the required elasticity modulus and strength. It has an excellent effect.

The rubber composition according to an embodiment of the present invention includes, in addition to the above components, various additives commonly used in the rubber industry, specifically, a vulcanization accelerator, process oil, antioxidant, plasticizer, anti-aging agent, scorch inhibitor, zinc white), stearic acid, a thermosetting resin, or a thermoplastic resin may be further included.

The vulcanization accelerator is, for example, a thiazole-based compound such as M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazyl sulfenamide), or DPG A guanidine-based compound such as (diphenylguanidine) may be used, and may be included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the rubber component.

The process oil acts as a softener in the rubber composition, and may be, for example, a paraffinic, naphthenic, or aromatic compound. Naphthenic or paraffinic process oils may be used. The process oil may be included in an amount of 100 parts by weight or less based on 100 parts by weight of the rubber component, for example, and has an effect of preventing deterioration of the tensile strength and low heat generation (low fuel efficiency) of the vulcanized rubber within this range.

The antioxidant is, for example, 2,6-di-t-butylparacresol, dibutylhydroxytoluenyl, 2,6-bis((dodecylthio)methyl)-4-nonylphenol (2,6-bis( (dodecylthio)methyl)-4-nonylphenol) or 2-methyl-4,6-bis((octylthio)methyl)phenol (2-methyl-4,6-bis((octylthio)methyl)phenol), It may be used in an amount of 0.1 to 6 parts by weight based on 100 parts by weight of the rubber component.

The antioxidant is, for example, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, 6-ethoxy-2 ,2,4-trimethyl-1,2-dihydroquinoline, or a high-temperature condensate of diphenylamine and acetone, etc., may be used in an amount of 0.1 to 6 parts by weight based on 100 parts by weight of the rubber component.

The rubber composition according to an embodiment of the present invention can be obtained by kneading using a kneader such as a Banbury mixer, a roll, an internal mixer, etc. according to the compounding prescription, and has low heat generation and wear resistance by a vulcanization process after molding processing. This excellent rubber composition can be obtained.

Accordingly, the rubber composition may be used for each member of the tire such as a tire tread, under tread, side wall, carcass coated rubber, belt coated rubber, bead filler, cheffer, or bead coated rubber, vibration proof rubber, belt conveyor, hose, etc. It may be useful in the manufacture of various industrial rubber products of

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

The tire may include a tire or a tire tread.

Example

Hereinafter, in order to describe the present invention in detail, examples will be described in detail. However, the embodiment according to the present invention may be modified in various other forms, and the scope of the present invention should not be construed as being limited to the embodiment described in detail below. The embodiments of the present invention are provided to more completely explain the present invention to those of ordinary skill in the art.

Example 1

In a 20 L autoclave reactor, 700 g of n-hexane, 32 g of styrene, 118 g of 1,3-butadiene and 0.21 g of 2,2-bis(2-oxolanyl)propane as a polar additive were added, followed by n-butyl Lithium 86.5 g (0.2wt% in n-hexane) was added, the internal temperature of the reactor was adjusted to 50° C., and an adiabatic temperature rising reaction was performed. An adiabatic temperature increase reaction was performed at 60° C. for an additional 30 minutes. In this case, after the reaction, a portion of the polymer was collected and used as a sample for measuring the polymer chain weight average molecular weight. Then, 15 g of epoxidized soybean oil was added and mixed at 70° C. for 20 minutes. The reaction was stopped using ethanol, and 3 g of a solution in which an antioxidant, Wingstay K, was dissolved in hexane at 30 wt% was added. The resulting polymer was put into hot water heated with steam, stirred to remove the solvent, and then roll-dried to remove the remaining solvent and water to prepare an oil-extended styrene-butadiene copolymer.

Example 2

A dielectric styrene-butadiene copolymer was prepared in the same manner as in Example 1, except that soybean oil was used instead of epoxidized soybean oil in Example 1.

Example 3

Dielectric styrene-butadiene was carried out in the same manner as in Example 1, except that in Example 1, 0.02 g of 2,2-bis(2-oxolanyl)propane was added and an adiabatic temperature increase reaction was performed for 50 minutes. A copolymer was prepared.

Example 4

A dielectric butadiene polymer was prepared in the same manner as in Example 1, except that in Example 1, 150 g of 1,3-butadiene was added without using styrene.

Example 5

Dielectric styrene-butadiene was carried out in the same manner as in Example 4, except that in Example 4, 0.02 g of 2,2-bis(2-oxolanyl)propane was added and an adiabatic temperature increase reaction was performed for 50 minutes. A copolymer was prepared.

Comparative Example 1

In a 20 L autoclave reactor, 700 g of n-hexane, 32 g of styrene, 118 g of 1,3-butadiene and 0.21 g of 2,2-bis(2-oxolanyl)propane as a polar additive were added, followed by n-butyl Lithium 86.5 g (0.2wt% in n-hexane) was added, the internal temperature of the reactor was adjusted to 50° C., and an adiabatic temperature rising reaction was performed. An adiabatic temperature increase reaction was performed at 60° C. for an additional 30 minutes. Thereafter, the reaction was stopped using ethanol, and 3 g of a solution in which an antioxidant, Wingstay K, was dissolved in hexane at 30% by weight was added. The resulting polymer was put into hot water heated by steam, stirred to remove the solvent, and then roll-dried to remove the remaining solvent and water to prepare a styrene-butadiene copolymer.

Comparative Example 2

In Example 1, 2,2-bis(2-oxolanyl)propane was added at 0.4 g and n-butyllithium was added at 385 g (0.2 wt% in n-hexane) to conduct adiabatic temperature rise reaction. Except for that, in the same manner as in Example 1, a dielectric styrene-butadiene copolymer was prepared.

Comparative Example 3

In a 20 L autoclave reactor, 700 g of n-hexane, 32 g of styrene, 118 g of 1,3-butadiene and 0.21 g of 2,2-bis(2-oxolanyl)propane as a polar additive were added, followed by n-butyl Lithium 86.5 g (0.2wt% in n-hexane) was added, the internal temperature of the reactor was adjusted to 50° C., and an adiabatic temperature rising reaction was performed. An adiabatic temperature increase reaction was performed at 60° C. for an additional 30 minutes. Thereafter, the reaction was stopped using ethanol, and 3 g of a solution in which an antioxidant, Wingstay K, was dissolved in hexane at 30% by weight was added. 15 g of soybean oil was added to the resulting polymer, mixed, put in hot water heated with steam, stirred to remove the solvent, and then roll-dried to remove the remaining solvent and water to prepare an oil-extended styrene-butadiene copolymer.

Experimental Example 1

The weight average molecular weight, molecular weight distribution, styrene unit and vinyl content, and Mooney viscosity of the dielectric conjugated diene-based polymers prepared in Examples and Comparative Examples were measured. The results are shown in Table 2 below.

1) Styrene units and vinyl content (wt%)

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

For NMR measurement, 1,1,2,2-tetrachloroethane was used as the solvent, and the solvent peak was calculated as 5.97 ppm, 7.2~6.9 ppm is random styrene, 6.9~6.2 ppm is block styrene, and 5.8~5.1 ppm is 1,4-vinyl and 1,2-vinyl, 5.1 to 4.5 ppm were calculated as 1,2-vinyl peaks to calculate the styrene unit and vinyl content.

2) Weight average molecular weight (Mw, X10 ³ g/mol), molecular weight distribution (PDI, MWD) and coupling efficiency

The weight average molecular weight (Mw) and number average molecular weight (Mn) were measured with a gel permeation chromatograph (GPC) (PL GPC220, Agilent Technologies) under the following conditions, a molecular weight distribution curve was obtained, and molecular weight distribution (PDI, MWD, Mw) /Mn) was calculated and obtained from each of the measured molecular weights. In this case, molecular weight distribution curves are shown in FIGS. 1 to 3 .

- Column: A combination of two PLgel Olexis (Polymer Laboratories) columns and one PLgel mixed-C (Polymer Laboratories) column is used.

- Solvent: tetrahydrofuran mixed with 2 wt% of an amine compound

- Flow rate: 1 ml/min

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

- Injection volume: 100 μl

- Column temperature: 40℃

- Detector: Refractive index

- Standard: Polystyrene (corrected by cubic function)

In addition, the coupling efficiency (%) is obtained by collecting a portion of the polymer before reacting with vegetable oil to obtain a peak molecular weight area (Mp ₁ A) by gel chromatography of the polymer, and then the molecular weight distribution of the finally prepared dielectric conjugated diene-based polymer CA was obtained by subtracting the area of Mp ₁ A from the area and calculated by Equation 1 below.

[Equation 1]

Coupling Efficiency (%)=[CA/WA]×100

In Equation 1 above,

CA is the molecular weight area of the polymer in which the polymer chain and the vegetable oil-derived unit are coupled to each other in the molecular weight distribution obtained by gel permeation chromatography (GPC), and WA is the total molecular weight area of the dielectric conjugated diene-based polymer.

3) Mooney viscosity

The Mooney viscosity (MV, (ML1+4, @100°C) MU) was measured using MV-2000 (ALPHA Technologies) at 100°C at 100°C using a Rotor Speed of 2±0.02 rpm, a Large Rotor. After the sample was left at room temperature (23±3° C.) for more than 30 minutes, 27±3 g was collected, filled in the die cavity, and the platen was operated for measurement for 4 minutes.

In Table 2, 1) Mw1 is the weight average molecular weight of the polymer chain before adding vegetable oil, and 2) Mw2 is the weight average molecular weight of the finally prepared polymer.

1, 2 and Table 2, the dielectric styrene-butadiene copolymer or dielectric butadiene polymer of Examples 1 to 5 is a polymer chain having a weight average molecular weight of 1000,000 g/mol or more and a vegetable oil-derived unit. structure was confirmed.

Specifically, in Comparative Examples 1, 1 and 2 prepared by batch polymerization, the molecular weight distribution curve of Comparative Example 1 was in a unimodal form, whereas Examples 1 and 2 were in a bimodal form, respectively. It can be confirmed that at least one polymer chain in the dielectric conjugated diene-based polymer of the present invention and a vegetable oil-derived unit are coupled to each other to include a coupled polymer chain structure (refer to FIGS. 1 to 3 ).

In addition, in Examples 1 to 5, all of the Mooney viscosities measured at 100° C. were 50 or more, and compared to Comparative Example 1, which is a conventional styrene-butadiene copolymer, all of them showed a greatly increased Mooney viscosity by about 140% or more. In the case of the dielectric styrene-butadiene copolymer of Example 3, Mooney viscosity was rather decreased compared to Comparative Example 1. Through this increase in Mooney viscosity, it can be predicted that the dielectric conjugated diene-based polymer according to the present invention has a structure in which a polymer chain and a plant oil-derived unit are combined by being prepared by reacting an active polymer with vegetable oil before termination of polymerization. On the other hand, through the decrease in Mooney viscosity of Comparative Example 3, it can be predicted that the oil-existing styrene-butadiene copolymer of Comparative Example 3 has a polymer chain and vegetable oil in the form of a mixture, so that the vegetable oil acts as an oil and the Mooney viscosity decreases.

In addition, in Examples 1 to 5, it can be confirmed that all coupling efficiencies are 50% or more.

From these results, it can be confirmed that the dielectric conjugated diene polymer of the present invention has a completely different microstructure from the dielectric conjugated diene polymer obtained by mixing vegetable oil after completion of polymerization.

Experimental Example 2

In order to comparatively analyze the physical properties of the rubber composition containing each modified conjugated diene-based copolymer prepared in the Examples and Comparative Examples and molded articles prepared therefrom, abrasion resistance, running resistance (fuel efficiency) and aging properties were measured respectively. The results are shown in Table 5 below.

1) Preparation of rubber specimens of Examples 1 to 4 and Comparative Examples 2 to 4

Each copolymer was formulated as a raw rubber under the compounding conditions shown in Table 2 below. The raw materials in Table 3 are each part by weight based on 100 parts by weight of the raw rubber.

division Raw material Content (parts by weight) 1st stage kneading Rubber 100 silica 70 Coupling agent (X50S) 11.2 fair oil 27.5 Zincizing agent 3 stearic acid 2 antioxidant 2 anti-aging agent 2 wax One 2nd stage kneading sulfur 1.5 rubber accelerator 1.75 vulcanization accelerator 2

Specifically, the rubber specimen is kneaded through the first stage kneading and the second stage kneading. In the first stage kneading, raw rubber, silica (filler), organosilane coupling agent (X50S, Evonik), process oil (TDAE oil), zinc oxide (ZnO), stearic acid, , antioxidant (TMQ(RD) (2,2,4-trimethyl-1,2-dihydroquinoline polymer), antioxidant (6PPD ((dimethylbutyl)-N-phenyl-phenylenediamine) and wax (Microcrystaline Wax) ) was kneaded.At this time, the initial temperature of the kneader was controlled to 70 ° C., and after the mixing was completed, a first blend was obtained at a discharge temperature of 145 ° C. In the second stage of kneading, the first blend was cooled to room temperature, Add the primary compound, sulfur, rubber accelerator (DPG (diphenylguanidine)) and vulcanization accelerator (CZ (N-cyclohexyl-2-benzothiazylsulfenamide)) to a kneader, and mix at a temperature of 100° C. or less. A tea blend was obtained, and then, a rubber specimen was prepared through a curing process at 160° C. for 20 minutes.

2) Preparation of rubber specimens of Comparative Examples 1-1 and 1-2

The copolymer prepared in Comparative Example 1 was used as a raw rubber and blended under the compounding conditions shown in Table 4 below. The raw materials in Table 4 below are each part by weight based on 100 parts by weight of the raw rubber.

division Raw material Content (parts by weight) 1st stage kneading Rubber 100 silica 70 Coupling agent (X50S) 11.2 Process oil (Comparative Example 1-1) or Soybean oil (Comparative Example 1-2) 37.5 Zincizing agent 3 stearic acid 2 antioxidant 2 anti-aging agent 2 wax One 2nd stage kneading sulfur 1.5 rubber accelerator 1.75 vulcanization accelerator 2

Specifically, the rubber specimen is kneaded through the first stage kneading and the second stage kneading. In the first stage kneading, using a Banbari mixer equipped with a temperature control device, raw rubber, silica (filler), organosilane coupling agent (X50S, Evonik), process oil (TDAE oil) or soybean oil, zinc oxide (ZnO), Stearic acid, antioxidant (TMQ(RD) (2,2,4-trimethyl-1,2-dihydroquinoline polymer), antioxidant (6PPD ((dimethylbutyl)-N-phenyl-phenylenediamine) and wax ( Microcrystaline Wax) was kneaded.At this time, the initial temperature of the kneader was controlled to 70° C., and after completion of mixing, a first formulation was obtained at a discharge temperature of 145° C. In the second stage of kneading, the first formulation was cooled to room temperature. Then, the primary compound, sulfur, rubber accelerator (DPG (diphenylguanidine)) and vulcanization accelerator (CZ (N-cytlohexyl-2-benzothiazylsulfenamide)) were added to the kneader, and at a temperature of 100° C. or less A secondary formulation was obtained by mixing, and then, a rubber specimen was prepared through a curing process at 160° C. for 20 minutes.

3) Wear resistance

For each rubber specimen, a DIN abrasion test was performed according to ASTM D5963, and DIN loss index (loss volume indes): ARIA (Abration resistance index, Method A) based on the measured value of Comparative Example 1-1 ), and the higher the number, the better.

4) Driving resistance (fuel efficiency)

For the viscoelastic properties, the tan δ value was confirmed by measuring the viscoelastic behavior against dynamic deformation at a frequency of 10 Hz and each measurement temperature (-60°C to 60°C) in Film Tension mode using a dynamic mechanical analyzer (GABO). The lower the high temperature 60℃ tan δ value, the less the hysteresis loss and the better the running resistance (fuel efficiency). Therefore, the higher the number, the better.

5) aging properties

The aging properties were confirmed by a 300% change in modulus before and after heat aging of each rubber specimen, and it can be confirmed that the aging properties are excellent from the fact that there is no change before and after aging.

Specifically, each rubber specimen was left at 100°C for 24 hours to undergo heat aging, and for each rubber specimen, before and after aging, according to the tensile test method of ASTM 412, using a Universal Test Machine 4204 (Instron) tensile tester. Tensile stress was measured when it was stretched to 300% by pulling at a speed of 50 cm/min at room temperature. At this time, when the 300% modulus after aging was lowered compared to the 300% modulus before aging, it was marked with ×, and when the 300% modulus before and after aging was maintained the same without deterioration, it was marked with ○.

As can be seen in Table 5, Examples 1 to 5 were significantly superior in abrasion resistance, running resistance, and aging properties in a well-balanced manner compared to Comparative Examples 1-1 to 3 in comparison.

Specifically, Examples 1 to 5 showed excellent running resistance compared to Comparative Example 1-1 and at the same time improved aging properties and significantly improved abrasion resistance to a level of 120 to 150%, and exhibited superior wear resistance compared to Comparative Example 1-2 and aging physical properties This is improved and driving resistance is greatly improved to about 106% to 116%. Through this, the oil-dielectric conjugated diene-based polymer according to the present invention exists in a form in which the vegetable oil-derived unit in the polymer is bonded to the polymer chain, so abrasion resistance, running resistance and aging that cannot be realized in the prior art of mixing conventional process oil or vegetable oil with rubber It was confirmed that excellent properties could be realized at the same time as physical properties.

In addition, Examples 1 to 5 have improved aging properties compared to Comparative Example 2, and at the same time, the abrasion resistance was significantly improved by about 140% to 170%, and the driving resistance by about 119% to 131%, and the aging properties were improved compared to Comparative Example 3 At the same time, it was confirmed that the driving resistance was significantly improved to about 106% to 117%.

Through this, the dielectric conjugated diene-based polymer according to the present invention includes a polymer chain having a weight average molecular weight of 100,000 g/mol or more and a vegetable oil-derived unit, and at least one of the polymer chains has a structure coupled to a vegetable oil-derived unit. It was confirmed that excellent properties could be realized at the same time in abrasion resistance, running resistance, and aging properties, which could not be realized in a dielectric conjugated diene-based polymer that does not satisfy these characteristics.

Claims (14)

a polymer chain comprising a repeating unit derived from a conjugated diene-based monomer; and a plant oil-derived unit,
At least one of the polymer chains is coupled to a plant oil-derived unit,
The polymer chain is a dielectric conjugated diene-based polymer having a weight average molecular weight of 100,000 g/mol or more.
According to claim 1,
A dielectric conjugated diene-based polymer having a Mooney viscosity of 50 or more measured at 100°C.
According to claim 1,
A dielectric conjugated diene-based polymer having a coupling efficiency of 10% or more as defined by the following Equation 1:
[Equation 1]
Coupling Efficiency (%)=[CA/WA]×100
In Equation 1 above,
CA is the molecular weight area of a polymer in which a polymer chain and a vegetable oil-derived unit are coupled to each other in the molecular weight distribution obtained by gel permeation chromatography (GPC), and WA is the total molecular weight area of the dielectric conjugated diene-based polymer.
According to claim 1,
The vegetable oil-derived unit is a dielectric conjugated diene-based polymer included in an amount of 0.1% to 50% by weight based on the total weight of the polymer.
According to claim 1,
The vegetable oil is at least one selected from the group consisting of soybean oil, rapeseed oil, canola oil, sunflower oil, linseed oil, rice bran oil, palm oil, olive oil, peanut oil, palm oil, cottonseed oil and coconut oil.
According to claim 1,
The vegetable oil is an epoxidized vegetable oil,
The epoxidized vegetable oil is epoxidized soybean oil, epoxidized rapeseed oil, epoxidized canola oil, epoxidized sunflower oil, epoxidized linseed oil, epoxidized rice bran oil, epoxidized palm oil, epoxidized olive oil, epoxidized peanut oil, epoxidized palm oil, epoxidized A dielectric conjugated diene-based polymer of at least one selected from the group consisting of cottonseed oil and epoxidized coconut oil.
According to claim 1,
The polymer chain is a dielectric conjugated diene-based polymer further comprising a repeating unit derived from an aromatic vinyl-based monomer.
According to claim 1,
A dielectric conjugated diene-based polymer comprising a functional group including at least one of an N atom and an Si atom.
preparing an active polymer by polymerizing a conjugated diene-based monomer or a conjugated diene-based monomer and an aromatic vinyl-based monomer in the presence of an organolithium compound in a hydrocarbon solvent (S1);
reacting the active polymer with vegetable oil (S2); and
A method for producing the dielectric conjugated diene-based polymer of claim 1 comprising the step (S3) of terminating the reaction.
10. The method of claim 9,
The vegetable oil is a method for producing a dielectric conjugated diene-based polymer to be used in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the total monomer.
10. The method of claim 9,
The vegetable oil is soybean oil, rapeseed oil, canola oil, sunflower oil, linseed oil, rice bran oil, palm oil, olive oil, peanut oil, palm oil, cottonseed oil, coconut oil, epoxidized soybean oil, epoxidized rapeseed oil, epoxidized canola oil, epoxidized sunflower oil, epoxidized Flax oil, epoxidized rice bran oil, epoxidized palm oil, epoxidized olive oil, epoxidized peanut oil, epoxidized palm oil, epoxidized cottonseed oil, and epoxidized coconut oil is at least one selected from the group consisting of a method for producing a dielectric conjugated diene-based polymer .
10. The method of claim 9,
After the step (S1), further comprising the step of reacting or coupling the active polymer and the modifier before the step (S2),
The method for producing a dielectric conjugated diene-based polymer, wherein the modifier is a compound including a functional group including at least one of an N atom and an Si atom in a molecule.
The dielectric conjugated diene-based polymer of claim 1; and a rubber composition comprising a filler.
14. The method of claim 13,
The filler is a rubber composition of at least one selected from a silica-based filler and a carbon black-based filler.

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