Method for producing a polymer composition and polymer composition

Abstract

The present invention relates to a method for producing a polymer composition, and to a method for producing a polymer composition capable of preventing the yellowing phenomenon of a branched conjugated diene polymer with an improved degree of branching, and to a polymer composition produced thereby.

Description

Technical Field

[0001] The present invention claims the benefit of priority based on Korean Patent Application No. 10-2022-0081775 filed on July 4, 2022, and all the contents disclosed in the document of the Korean patent application are incorporated herein by reference in their entirety.

[0002] The present invention relates to a method for manufacturing a polymer composition and a polymer composition manufactured thereby.

Background Art

[0003] In recent years, as interest in energy conservation and environmental issues has increased, there has been a demand for lower fuel consumption in automobiles. As one method for achieving this, a method has been proposed to increase the cis bond content of polybutadiene in a rubber composition for tire formation.

[0004] Polybutadiene can be manufactured using a Ziegler-Natta catalyst. The Ziegler-Natta catalyst can be manufactured by activating an organometallic compound, for example, an organonickel compound, with an alkylaluminum compound and a fluorine compound, and the manufactured catalyst is reacted with a 1,3-butadiene monomer to manufacture polybutadiene.

[0005] U.S. Patent No. 7,081,504 (Patent Document 1) and U.S. Patent No. 5,451,646 (Patent Document 2) disclose a method for manufacturing polybutadiene that improves processability by introducing an alkylated diphenylamine compound and a para-styrenated diphenylamine compound during the manufacture of polybutadiene to adjust the molecular weight of polybutadiene and improve the degree of branching when manufacturing polybutadiene with a high cis bond content.

[0006] However, as in Patent Documents 1 and 2, the alkylated diphenylamine compound and para-styrenated diphenylamine compound introduced during the production of polybutadiene remain in the polybutadiene, and amine compounds such as the alkylated diphenylamine compound and para-styrenated diphenylamine compound remaining in the polybutadiene also cause yellowing of the rubber composition.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0008] The problem to be solved by the present invention is to improve the yellowing phenomenon of a branched conjugated diene polymer with an improved degree of branching. That is, the present invention aims to provide a method for producing a polymer composition capable of preventing the yellowing phenomenon of a conjugated diene polymer produced from a catalyst composition containing a diphenylamine compound by mixing a compound containing a t-butylphenol group with a branched conjugated diene polymer in order to solve the problems mentioned in the background art of the above invention.

[0009] Further, the present invention aims to provide a polymer composition produced by the method for producing the polymer composition, containing a branched conjugated diene polymer, having excellent processability, and having an improved yellowing phenomenon.

Means for Solving the Problems

[0010] In order to solve the above problems, the present invention provides a method for producing a polymer composition and a polymer composition. (1) The present invention provides a method for producing a polymer composition, which includes a step (S10) of polymerizing a conjugated diene monomer in the presence of a catalyst composition containing an organometallic compound, an organoaluminum compound, a fluorine-based compound, and a diphenylamine-based compound to produce a branched conjugated diene polymer, and a step (S20) of mixing a compound containing a t-butylphenol group with the monomer before polymerization in the step (S10), the polymerization solution during polymerization, or the branched conjugated diene polymer after polymerization.

[0011] (2) In the present invention, there is provided a method for producing the polymer composition according to (1) above, wherein the organometallic compound is an organonickel compound.

[0012] (3) In the present invention, there is provided a method for producing the polymer composition according to (1) or (2) above, wherein the organometallic compound is at least one selected from the group consisting of nickel benzoate, nickel acetate, nickel naphthenate, nickel octanoate, nickel neodecanoate, bis(α-furyldioxime)nickel, nickel palmitate, nickel stearate, nickel acetylacetonate, nickel salicylaldehyde, bis(cyclopentadiene)nickel, bis(salicylaldehyde)ethylenediimine nickel, cyclopentadienyl-nickel nitrosyl, bis(π-allylnickel), bis(π-cycloocta-1,5-diene)nickel, bis(π-allylnickel trifluoroacetate), and nickel tetracarbonyl.

[0013] (4) In the present invention, there is provided a method for producing the polymer composition according to any one of (1) to (3) above, wherein the organoaluminum compound is an alkylaluminum compound represented by the following Chemical Formula 1.

[0014] [Chemical Formula 1] AlR 1 R 2 R 3

[0015] In the Chemical Formula 1, R 1 ~R 3is independently hydrogen or an alkyl group having 1 to 12 carbon atoms, and R 1 ~R 3 are not all hydrogen.

[0016] (5) In the present invention, there is provided a method for producing a polymer composition according to any one of (1) to (4) above, wherein the fluorine-based compound is at least one selected from the group consisting of hydrogen fluoride and boron trifluoride.

[0017] (6) In the present invention, there is provided a method for producing a polymer composition according to any one of (1) to (5) above, wherein the diphenylamine-based compound is a compound represented by the following chemical formula 2.

[0018] [Chemical formula]

[0019] In the chemical formula 2, R 4 and R 5 are each independently an alkyl group having 2 to 18 carbon atoms which is substituted or unsubstituted with an aryl group having 6 to 30 carbon atoms.

[0020] (7) In the present invention, there is provided a method for producing a polymer composition according to any one of (1) to (6) above, wherein the compound containing a t-butylphenol group is t-butylcatechol, butylhydroxytoluene, or a mixture thereof.

[0021] (8) In the present invention, there is provided a method for producing a polymer composition according to any one of (1) to (7) above, wherein in the step (S20), the compound containing a t-butylphenol group is mixed at a content of 0.0001 part by weight to 0.005 part by weight with respect to 100 parts by weight of the conjugated diene-based monomer or the branched conjugated diene-based polymer.

[0022] (9) The present invention provides a polymer composition containing a metal-catalyzed branched conjugated diene-based polymer and a compound containing a t-butylphenol group.

[0023] (10) In the present invention, the content of the compound containing a t-butylphenol group is 0.0001 to 0.005 parts by weight with respect to 100 parts by weight of the metal-catalyzed branched conjugated diene polymer, and the polymer composition according to (9) above is provided.

Effect of the Invention

[0024] The polymer composition produced by the method for producing a polymer composition of the present invention contains a branched conjugated diene polymer, is excellent in processability, and has an improved yellowing phenomenon.

Mode for Carrying Out the Invention

[0025] Hereinafter, the present invention will be described in more detail so that the present invention can be easily understood. The terms and words used in the description and claims of the present invention should not be construed as being limited to their ordinary or dictionary meanings. The inventors should interpret them in a meaning and concept consistent with the technical idea of the present invention in accordance with the principle that they can appropriately define the concept of the terms in order to explain their invention in the best way.

[0026] The present invention relates to a method for producing a polymer composition and a polymer composition produced thereby. Regarding the branched conjugated diene polymer, the entire contents described in U.S. Patent No. 7,081,504 (Patent Document 1) and U.S. Patent No. 5,451,646 (Patent Document 2) are incorporated as they are. Therefore, even if there are matters not described in the description of the present invention regarding the production of the branched conjugated diene polymer, the matters described in U.S. Patent No. 7,081,504 (Patent Document 1) and U.S. Patent No. 5,451,646 (Patent Document 2) all correspond to matters regarding the branched conjugated diene polymer of the present invention, and regarding the production of the branched conjugated diene polymer of the present invention, the matters described in U.S. Patent No. 7,081,504 (Patent Document 1) and U.S. Patent No. 5,451,646 (Patent Document 2) can be applied as they are.

[0027] Hereinafter, in addition to the contents disclosed in U.S. Patent No. 7,081,504 (Patent Document 1) and U.S. Patent No. 5,451,646 (Patent Document 2), the technical features of the present invention for solving the problems of U.S. Patent No. 7,081,504 (Patent Document 1) and U.S. Patent No. 5,451,646 (Patent Document 2) will be described in detail below.

[0028] Method for producing a polymer composition The present invention provides a method for producing a polymer composition. According to one embodiment of the present invention, the method for producing the polymer composition includes a step (S10) of polymerizing a conjugated diene monomer in the presence of a catalyst composition containing an organometallic compound, an organoaluminum compound, a fluorine-based compound, and a diphenylamine-based compound to produce a branched conjugated diene polymer, and a step (S20) of mixing a compound containing a t-butylphenol group with the monomer before polymerization, the polymerization solution during polymerization, or the branched conjugated diene polymer after polymerization in the step (S10).

[0029] According to one embodiment of the present invention, the step (S10) is a step for producing a branched conjugated diene polymer, and may be performed by polymerizing a conjugated diene monomer in the presence of a catalyst composition.

[0030] According to one embodiment of the present invention, the catalyst composition may include an organometallic compound activated with an organoaluminum compound and a fluorine-based compound for polymerizing a conjugated diene monomer, and a diphenylamine-based compound for inducing the branching of a conjugated diene polymer. Here, the branching of a conjugated diene polymer means inducing the formation of a branched chain having a branch formed on the main chain formed from a conjugated diene monomer, and the branched conjugated diene polymer is for distinguishing from a linear conjugated diene polymer and means a conjugated diene polymer containing a branched chain.

[0031] According to one embodiment of the present invention, the organometallic compound may be an organonickel compound. Specifically, the organometallic compound may be nickel benzoate, nickel acetate, nickel naphthenate, nickel octanoate, nickel neodecanoate, bis(α-furyldioxime)nickel, nickel palmitate, nickel stearate, nickel acetylacetonate, nickel salicylaldehyde, bis(cyclopentadiene)nickel, bis(salicylaldehyde)ethylenediimine nickel, cyclopentadienyl-nickel nitrosyl, bis(π-allylnickel), bis(π-cycloocta-1,5-diene)nickel, bis(π-allylnickel trifluoroacetate), and nickel tetracarbonyl, and more specifically, it may be nickel octanoate.

[0032] According to one embodiment of the present invention, the organoaluminum compound is for activating the organometallic compound, and may be an alkylaluminum compound represented by the following Chemical Formula 1.

[0033] [Chemical Formula 1] AlR 1 R 2 R 3

[0034] In Chemical Formula 1, R 1 ~R 3 are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms, and R 1 ~R 3 are not all hydrogen.

[0035] According to one embodiment of the present invention, the organoaluminum compound may be an alkylaluminum such as trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum; a dihydrocarbylaluminum hydride such as diethylaluminum hydride, di-n-propylaluminum hydride, diisopropylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride (DIBAH), di-n-octylaluminum hydride, diphenylaluminum hydride, di-p-tolylaluminum hydride, dibenzylaluminum hydride, phenylethylaluminum hydride, phenyl-n-propylaluminum hydride, phenylisopropylaluminum hydride, phenyl-n-butylaluminum hydride, phenylisobutylaluminum hydride, phenyl-n-octylaluminum hydride, p-tolylethylaluminum hydride, p-tolyl-n-propylaluminum hydride, p-tolylisopropylaluminum hydride, p-tolyl-n-butylaluminum hydride, p-tolylisobutylaluminum hydride, p-tolyl-n-octylaluminum hydride, benzylethylaluminum hydride, benzyl-n-propylaluminum hydride, benzylisopropylaluminum hydride, benzyl-n-butylaluminum hydride, benzylisobutylaluminum hydride, or benzyl-n-octylaluminum hydride; or a hydrocarbylaluminum dihydride such as ethylaluminum dihydride, n-propylaluminum dihydride, isopropylaluminum dihydride, n-butylaluminum dihydride, isobutylaluminum dihydride, or n-octylaluminum dihydride.

[0036] According to one embodiment of the present invention, the fluorine-based compound is for activating the organometallic compound, and may be one or more selected from the group consisting of hydrogen fluoride and boron trifluoride. The fluorine-based compound may be in the form of a complex as necessary, and the complex may include an ether-based compound, an alcohol-based compound, a ketone-based compound, an ester-based compound, a nitrile-based compound, an amine-based compound, and water that contain atoms or radicals capable of providing electrons to or sharing electrons with hydrogen fluoride or boron trifluoride.

[0037] According to one embodiment of the present invention, in the catalyst composition, the molar ratio of the organometallic compound: organoaluminum compound may be 1:0.3 to 300, the molar ratio of the organometallic compound: fluorine-based compound may be 1:0.5 to 200, and the molar ratio of the organoaluminum compound: fluorine-based compound may be 1:0.7 to 7.

[0038] According to one embodiment of the present invention, the diphenylamine-based compound may be a compound represented by the following Chemical Formula 2.

[0039]

Chemical Formula

[0040] In Chemical Formula 2, R 4 and R 5 are each independently an alkyl group having 2 to 18 carbon atoms which is substituted or unsubstituted with an aryl group having 6 to 30 carbon atoms.

[0041] According to one embodiment of the present invention, the R 4 and R 5may each independently be present at the ortho, meta, or para position, and may be an alkyl group having 2 or more, 3 or more, 4 or more carbon atoms, which may or may not be substituted with an aryl group having 6 to 30 carbon atoms, or may be an alkyl group having 18 or less, 16 or less, 14 or less, or 12 or less carbon atoms, which may or may not be substituted with an aryl group having 6 to 30 carbon atoms. Specifically, the above R 4 and R 5 may each independently be present at the para position. Further, when the alkyl group is substituted with an aryl group having 6 to 30 carbon atoms, the alkyl group may be an alkyl group having 2 carbon atoms. More specifically, the alkyl group having 2 carbon atoms substituted with the aryl group having 6 to 30 carbon atoms may be a styrene derivative. That is, the diphenylamine-based compound may be a diphenylamine compound alkylated with an alkyl group having 2 to 18 carbon atoms or a para-styrenated diphenylamine compound.

[0042] According to one embodiment of the present invention, the content of the diphenylamine-based compound may be 0.25 parts by weight to 1.5 parts by weight, or 0.5 parts by weight to 0.75 parts by weight with respect to 100 parts by weight of the conjugated diene-based monomer.

[0043] According to one embodiment of the present invention, the step (S10) may be performed by polymerizing the conjugated diene-based monomer in a hydrocarbon solvent in the presence of the catalyst composition.

[0044] According to one embodiment of the present invention, the hydrocarbon solvent may be at least one selected from the group consisting of n-pentane, n-hexane, n-heptane, isooctane, cyclohexane, toluene, benzene, and xylene.

[0045] According to one embodiment of the present invention, the conjugated diene monomer may be one or more selected from the group consisting of 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, and 2,4-hexadiene, and specifically may be 1,3-butadiene.

[0046] According to one embodiment of the present invention, the polymerization in the step (S10) may be carried out using coordination anion polymerization, and the polymerization environment may be bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization, and specifically may be solution polymerization.

[0047] According to one embodiment of the present invention, the polymerization in the step (S10) may be carried out at a temperature of -20°C or higher, -10°C or higher, 0°C or higher, 10°C or higher, 20°C or higher, 30°C or higher, 40°C or higher, 50°C or higher, or 60°C or higher, and may also be carried out at a temperature of 200°C or lower, 150°C or lower, 120°C or lower, or 90°C or lower. When within this range, the polymerization reaction can be smoothly controlled, and the cis-1,4 bond content of the produced conjugated diene polymer can be ensured.

[0048] According to one embodiment of the present invention, the polymerization in the step (S10) may be carried out for 15 minutes or longer, 20 minutes or longer, 30 minutes or longer, 40 minutes or longer, 50 minutes or longer, or 1 hour or longer, and may also be carried out for 3 hours or shorter, 2 hours 30 minutes or shorter, or 2 hours or shorter.

[0049] According to one embodiment of the present invention, the conjugated diene polymer formed by the polymerization in the step (S10) may be a living polymer containing sites activated by a catalyst composition.

[0050] According to an embodiment of the present invention, the method for producing the polymer composition may include a step (S11) of reacting the living polymer with a modifier. The modifier may be a known modifier that can be used during the production of a conjugated diene polymer using a catalyst composition containing an organometallic compound.

[0051] According to an embodiment of the present invention, the step (S20) may be performed by mixing a compound containing a t-butylphenol group with the monomer before polymerization, the polymerization solution during polymerization, or the branched conjugated diene polymer after polymerization in the step (S10). At this time, the mixing method of the compound containing a t-butylphenol group is not particularly limited, and it may be premixed and added to the monomer or solvent in the step (S10), added during polymerization in the step (S10), directly added and mixed into the solution of the branched conjugated diene polymer produced in the step (S10), mixed during solvent removal in the step (S10), mixed after obtaining the branched conjugated diene polymer produced in the step (S10) in the rubber phase, or mixed and added during rubber compounding after obtaining the branched conjugated diene polymer produced in the step (S10) in the rubber phase. That is, the step (S20) does not necessarily have to be performed after the step (S10), and may be performed simultaneously with the step (S10) or at an appropriate time after the step (S10) as needed.

[0052] According to an embodiment of the present invention, any compound having a t-butyl group as a substituent on the phenol group is applicable as the compound containing a t-butylphenol group. At this time, the t-butyl group may be present at the ortho, meta, or para position. In addition, the compound containing a t-butylphenol group may further contain other substituents (up to 4) in addition to the t-butyl group on the phenol group. At this time, the other substituents may be alkyl groups having 1 to 30, 1 to 20, or 1 to 10 carbon atoms. Specifically, the compound containing a t-butylphenol group may be t-butylcatechol, butylhydroxytoluene, or a mixture thereof.

[0053] According to one embodiment of the present invention, in the step (S20), the compound containing a t-butylphenol group may be mixed in an amount of 0.0001 to 0.005 parts by weight based on 100 parts by weight of the conjugated diene monomer or branched conjugated diene polymer. Specifically, in the step (S20), the compound containing a t-butylphenol group may be 0.0001 parts by weight or more, 0.0005 parts by weight or more, 0.001 parts by weight or more, 0.0015 parts by weight or more, 0.002 parts by weight or more, 0.0025 parts by weight or more, 0.003 parts by weight or more, 0.0035 parts by weight or more, or 0.004 parts by weight or more based on 100 parts by weight of the branched conjugated diene polymer, and may also be 0.005 parts by weight or less, or 0.004 parts by weight or less. When within this range, there is an effect that the physical properties of the polymer composition are not deteriorated and the yellowing phenomenon can be significantly improved.

[0054] Polymer composition The present invention provides a polymer composition. According to one embodiment of the present invention, the polymer composition may include a metal-catalyzed branched conjugated diene polymer and a compound containing a t-butylphenol group.

[0055] According to one embodiment of the present invention, the polymer composition may include a metal-catalyzed branched conjugated diene polymer. Specifically, the metal-catalyzed branched conjugated diene polymer is a branched conjugated diene polymer produced in the step (S10) of the method for producing the polymer composition, and may be a metal-catalyzed branched conjugated diene polymer.

[0056] According to one embodiment of the present invention, the metal-catalyzed branched conjugated diene polymer may include a conjugated diene monomer unit. The conjugated diene monomer unit means a repeating unit formed by the polymerization of a conjugated diene monomer.

[0057] According to one embodiment of the present invention, the metal-catalyzed branched conjugated diene polymer may contain 80% by weight or more, 85% by weight or more, 90% by weight or more, 95% by weight or more, or 100% by weight of 1,3-butadiene monomer units, and may selectively contain 20% by weight or less, 15% by weight or less, 10% by weight or less, or 5% by weight or less of other conjugated diene monomer units copolymerizable with 1,3-butadiene. When within this range, a decrease in the cis-1,4 bond content in the conjugated diene polymer can be prevented. The 1,3-butadiene monomer may be 1,3-butadiene or a derivative thereof such as 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, or 2-ethyl-1,3-butadiene, and the other conjugated diene monomer copolymerizable with 1,3-butadiene may be 2-methyl-1,3-pentadiene, 1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 1,3-hexadiene, or 2,4-hexadiene, etc.

[0058] According to one embodiment of the present invention, the metal-catalyzed branched conjugated diene polymer may be a conjugated diene polymer catalyzed from a catalyst composition containing an organometallic compound. That is, the conjugated diene polymer may be a conjugated diene polymer containing an activated organometallic site from a catalyst composition containing an organonickel compound.

[0059] According to one embodiment of the present invention, the metal-catalyzed branched conjugated diene polymer has a weight average molecular weight (Mw) of 1.0×10 5 g / mol or more, 2.0×10 5 g / mol or more, 3.0×10 5 g / mol or more, 4.0×10 5 g / mol or more, 5.0×10 5 g / mol or more, 6.0×10 5 g / mol or more, 7.0×10 5 g / mol or more, 8.0×10 5 g / mol or more, or 9.0×10 5 g / mol or more, and also, 1.0×10 6less than g / mol, 9.0×10 5 less than g / mol, 8.0×10 5 less than g / mol, 7.0×10 5 less than g / mol, 6.0×10 5 less than g / mol, 5.0×10 5 less than g / mol, 4.0×10 5 less than g / mol, or 3.0×10 5 g / mol or less may also be acceptable. Further, the conjugated diene polymer has a number average molecular weight (Mn) of 1.0×10 5 g / mol or more, 2.0×10 5 g / mol or more, 3.0×10 5 g / mol or more, 4.0×10 5 g / mol or more, or 5.0×10 5 g / mol or more may also be acceptable. Also, 6.0×10 5 g / mol or less, 5.0×10 5 g / mol or less, 4.0×10 5 g / mol or less, 3.0×10 5 g / mol or less, 2.0×10 5 g / mol or less, or 1.0×10 5 g / mol or less may also be acceptable. When within this range, when applied to the polymer composition, it has the effects of excellent tensile properties, excellent processability, easy kneading due to improved workability of the polymer composition, and excellent mechanical properties and property balance of the polymer composition.

[0060] According to one embodiment of the present invention, the metal-catalyzed branched conjugated diene polymer may have a molecular weight distribution (Mw / Mn) of 1.0 or more, 1.5 or more, 2.0 or more, 2.1 or more, 2.2 or more, or 2.3 or more, and may also be 4.0 or less, 3.5 or less, 3.0 or less, or 2.5 or less. The molecular weight distribution can be calculated from the ratio (Mw / Mn) of the number average molecular weight (Mn) to the weight average molecular weight (Mw). At this time, the number average molecular weight (Mn) is the common average of the individual polymer molecular weights calculated by measuring the molecular weights of n polymer chains, obtaining the sum of these molecular weights, and dividing by n, and the weight average molecular weight (Mw) represents the molecular weight distribution of the polymer composition. The average of the total molecular weight can be expressed in grams per mole (g / mol). Further, the weight average molecular weight and the number average molecular weight may each mean the polystyrene-equivalent molecular weight analyzed by gel permeation chromatography (GPC).

[0061] According to one embodiment of the present invention, when the metal-catalyzed branched conjugated diene polymer simultaneously satisfies the conditions of the weight average molecular weight (Mw) and the number average molecular weight together with the molecular weight distribution, when applied to a polymer composition, it has excellent tensile properties, viscoelasticity, and processability with respect to the polymer composition, and has the effect of excellent physical property balance among them.

[0062] According to one embodiment of the present invention, the metal-catalyzed branched conjugated diene polymer may have a cis-1,4 bond content of 95.0% by weight or more, 95.5% by weight or more, 96.0% by weight or more, 96.5% by weight or more, 97.0% by weight or more, or 97.5% by weight or more, and may also be 100.0% by weight or less, 99.5% by weight or less, or 99.0% by weight or less.

[0063] According to one embodiment of the present invention, the metal-catalyzed branched conjugated diene polymer may have a Mooney viscosity (ML1+4, @100 °C) of 30 or more, 35 or more, 40 or more, or 45 or more, and may also be 70 or less, 65 or less, 60 or less, 55 or less, or 50 or less.

[0064] According to one embodiment of the present invention, the polymer composition may contain 0.1% by weight or more, 10% by weight or more, or 20% by weight or more of the metal-catalyzed branched conjugated diene polymer, and may also contain 100% by weight or less, 95% by weight or less, or 90% by weight or less. When within this range, it is possible to sufficiently ensure the abrasion resistance and crack resistance of molded articles produced using the polymer composition, such as tires.

[0065] According to one embodiment of the present invention, the compound containing the t-butylphenol group may be the same as that described in the method for producing the aforementioned polymer composition, and the compound containing the t-butylphenol group may exist in the form of a derivative derived from the compound containing the t-butylphenol group in the polymer composition.

[0066] According to one embodiment of the present invention, the content of the compound containing the t-butylphenol group is 0.0001 part by weight or more, 0.0005 part by weight or more, 0.001 part by weight or more, 0.0015 part by weight or more, 0.002 part by weight or more, 0.0025 part by weight or more, 0.003 part by weight or more, 0.0035 part by weight or more, or 0.004 part by weight or more with respect to 100 parts by weight of the metal-catalyzed branched conjugated diene polymer, and may also be 0.005 part by weight or less, or 0.004 part by weight or less. When within this range, there is an effect that the physical properties of the polymer composition are not deteriorated and the yellowing phenomenon can be significantly improved.

[0067] Rubber composition The present invention provides a rubber composition. According to one embodiment of the present invention, the rubber composition may contain the polymer composition.

[0068] According to one embodiment of the present invention, in addition to the polymer composition, the rubber composition may further contain other rubber components as necessary. At this time, the rubber component may be contained in a content of 90% by weight or less based on the total weight of the rubber composition. Specifically, it may be contained in an amount of 1 part by weight to 900 parts by weight based on 100 parts by weight of the polymer composition.

[0069] According to one embodiment of the present invention, the rubber component may be natural rubber or synthetic rubber. For example, the rubber component may include natural rubber (NR) containing cis-1,4-polyisoprene; modified natural rubbers such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber obtained by modifying or purifying 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, halogenated butyl rubber, etc. Any one or a mixture of two or more of these may be used.

[0070] According to one embodiment of the present invention, the rubber composition may contain a filler in an amount of 20 parts by weight or more and 90 parts by weight or less based on 100 parts by weight of the polymer composition. The filler may be a silica-based filler, a carbon black-based filler, or a combination thereof. Specifically, the filler may be a carbon black-based filler.

[0071] According to one embodiment of the present invention, the carbon black-based filler has a nitrogen adsorption specific surface area (N2SA, measured according to JIS K6217-2:2001) of 20 m 2 / g to 250 m 2It may also be within this range. When it is within this range, the processability of the rubber composition is excellent, and the reinforcing performance by the filler can be sufficiently ensured. Further, the carbon black-based filler may have a dibutyl phthalate oil absorption amount (DBP) of 80 cc / 100 g to 200 cc / 100 g. When it is within this range, the processability of the rubber composition is excellent, and the reinforcing performance by the filler can be sufficiently ensured.

[0072] According to one embodiment of the present invention, the silica-based filler may be wet silica (hydrated silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate, colloidal silica, or the like. Specifically, the silica-based filler may be wet silica that has the most remarkable effect of improving the fracture characteristics and the combined effect of wet grip. Further, the silica-based filler has a nitrogen adsorption specific surface area (nitrogen surface area per gram, N2SA) of 120 m 2 / g to 180 m 2 / g, and the CTAB (cetyl trimethyl ammonium bromide) adsorption specific surface area may be 100 m 2 / g to 200 m 2 / g. When it is within this range, the processability of the rubber composition is excellent, and the reinforcing performance by the filler can be sufficiently ensured.

[0073] According to one embodiment of the present invention, when a silica-based filler is used as the filler, a silane coupling agent may be used together for improving reinforcement and low heat generation properties. The silane coupling agent may be bis(3-triethoxysilylpropyl)tetrasulfide, bis(3-triethoxysilylpropyl)trisulfide, bis(3-triethoxysilylpropyl)disulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, bis(2-trimethoxysilylethyl)tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropylbenzothiazolyl tetrasulfide, 3-triethoxysilylpropylbenzolyl tetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis(3-diethoxymethylsilylpropyl)tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, or dimethoxymethylsilylpropylbenzothiazolyl tetrasulfide, etc. Specifically, considering the improvement effect of reinforcement, the silane coupling agent may be bis(3-triethoxysilylpropyl)polysulfide or 3-trimethoxysilylpropylbenzothiazyl tetrasulfide.

[0074] According to one embodiment of the present invention, the rubber composition may be sulfur crosslinkable, and thus may further contain a vulcanizing agent. Specifically, the vulcanizing agent may be sulfur powder, and may be contained in an amount of 0.1 part by weight to 10 parts by weight based on 100 parts by weight of the rubber component. When within this range, it is possible to ensure the required elastic modulus and strength of the vulcanized rubber composition and to ensure low fuel consumption.

[0075] According to one embodiment of the present invention, in addition to the above components, the rubber composition may further contain various additives commonly used in the rubber industry, specifically, a vulcanization accelerator, a process oil, a plasticizer, an antioxidant, an anti-scorch agent, zinc white, stearic acid, a thermosetting resin, or a thermoplastic resin, etc.

[0076] According to one embodiment of the present invention, the vulcanization accelerator is not particularly limited. Specifically, thiazole-based compounds such as M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazylsulfenamide), or guanidine-based compounds such as DPG (diphenylguanidine) may be used. The vulcanization accelerator may be contained in an amount of 0.1 part by weight to 5 parts by weight based on 100 parts by weight of the rubber component.

[0077] According to one embodiment of the present invention, the process oil acts as a softening agent in the rubber composition. Specifically, it may be a paraffinic, naphthenic, or aromatic compound. More specifically, considering the tensile strength and abrasion resistance, an aromatic process oil may be used, and considering the hysteresis loss and low-temperature properties, a naphthenic or paraffinic process oil may be used. The process oil may be contained in a content of 100 parts by weight or less based on 100 parts by weight of the rubber component. When within this range, it is possible to prevent a decrease in the tensile strength and low heat generation (low fuel consumption) of the vulcanized rubber.

[0078] According to one embodiment of the present invention, the anti-aging agent may be 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. The anti-aging agent may be used in an amount of 0.1 to 6 parts by weight based on 100 parts by weight of the rubber component.

[0079] According to one embodiment of the present invention, the rubber composition can be obtained by kneading using a kneader such as a Banbury mixer, a roll, or an internal mixer according to the above formulation, and after molding, a rubber composition with low heat generation and excellent abrasion resistance can be obtained through a vulcanization process.

[0080] According to one embodiment of the present invention, the rubber composition is useful for manufacturing various members of a tire such as a tire tread, an undertread, a sidewall, a carcass coating rubber, a belt coating rubber, a bead filler, a chafer, or a bead coating rubber, and various industrial rubber products such as dust rubber, belt conveyors, and hoses. Specifically, the molded product manufactured using the rubber composition may include a tire or a tire tread.

[0081] Hereinafter, the examples of the present invention will be described in detail so that those having ordinary knowledge in the technical field to which the present invention pertains can easily implement it. However, the present invention may be realized in various different forms and is not limited to the examples described herein.

[0082] [Production Example] [Production Example 1: Production of Catalyst Composition] A catalyst composition was produced in the same manner as in Examples 10 to 22 described in U.S. Patent No. 7,081,504 (Patent Document 1).

[0083] [Examples] [Example 1] After charging 500 g of 1,3-butadiene and 4.2 kg of n-hexane into a 20 L autoclave reactor, the internal temperature of the reactor was raised to 70°C. After charging the catalyst composition prepared in Production Example 1 into the reactor, polymerization was carried out. When the polymerization conversion rate reached 98% or more, a solution of 1.0 g of a polymerization terminator in n-hexane and a solution of antioxidant Irganox 1520 (manufactured by BASF) dissolved in n-hexane at 30% by weight were added to terminate the reaction. A solution of t-butylcatechol (TBC) dissolved in n-hexane at 0.5% by weight was added so that the content of t-butylcatechol (TBC) was 1 ppm with respect to the content of 1,3-butadiene charged into the reactor. The obtained polymer was put into warm water heated with steam, stirred to remove the solvent, and then roll-dried to remove the remaining solvent and water to produce a butadiene polymer composition.

[0084] [Example 2] In Example 1 above, a butadiene polymer composition was produced in the same manner as in Example 1, except that a solution of t-butylcatechol dissolved in n-hexane at 0.5% by weight was charged so that the content of t-butylcatechol (TBC) was 5 ppm instead of 1 ppm with respect to the content of 1,3-butadiene charged into the reactor.

[0085] [Example 3] In Example 1 above, a butadiene polymer composition was produced in the same manner as in Example 1, except that a solution of t-butylcatechol dissolved in n-hexane at 0.5% by weight was charged so that the content of t-butylcatechol (TBC) was 15 ppm instead of 1 ppm with respect to the content of 1,3-butadiene charged into the reactor.

[0086] [Example 4] In Example 1, a solution in which 0.5% by weight of t-butylcatechol was dissolved in n-hexane was charged in such a manner that the content of t-butylcatechol (TBC) was 20 ppm instead of 1 ppm with respect to the content of 1,3-butadiene charged into the reactor. A butadiene polymer composition was produced in the same manner as in Example 1 except for the above.

[0087] [Example 5] In Example 1, a solution in which 0.5% by weight of t-butylcatechol was dissolved in n-hexane was charged in such a manner that the content of t-butylcatechol (TBC) was 40 ppm instead of 1 ppm with respect to the content of 1,3-butadiene charged into the reactor. A butadiene polymer composition was produced in the same manner as in Example 1 except for the above.

[0088] [Example 6] 500 g of 1,3-butadiene and 4.2 kg of n-hexane were charged into a 20 L autoclave reactor, and then the internal temperature of the reactor was raised to 70°C. After charging the catalyst composition produced in Production Example 1 into the reactor, polymerization was carried out. When the polymerization conversion rate reached 98% or more, a solution of 1.0 g of a polymerization terminator in n-hexane and a solution of an antioxidant Irganox 1520 (manufactured by BASF) dissolved in n-hexane at 30% by weight were added to terminate the reaction. A solution of butylhydroxytoluene (BHT) dissolved in n-hexane at 10% by weight was added so that the content of butylhydroxytoluene (BHT) was 10 ppm with respect to the content of 1,3-butadiene charged into the reactor. The obtained polymer was put into warm water heated with steam, stirred to remove the solvent, and then roll-dried to remove the remaining solvent and water to produce a butadiene polymer composition.

[0089] [Example 7] After charging 500 g of 1,3-butadiene and 4.2 kg of n-hexane into a 20 L autoclave reactor, the internal temperature of the reactor was raised to 70°C. A solution in which t-butylcatechol (TBC) was dissolved at 0.5% by weight in n-hexane was added to the reactor such that the content of t-butylcatechol (TBC) was 10 ppm with respect to the content of 1,3-butadiene charged into the reactor. Next, after charging the catalyst composition produced in Production Example 1, polymerization was carried out. When the polymerization conversion rate reached 98% or more, a solution of 1.0 g of a polymerization terminator in n-hexane and a solution in which the antioxidant Irganox 1520 (manufactured by BASF) was dissolved at 30% by weight in n-hexane were added to terminate the reaction. The resulting polymer was put into warm water heated with steam, stirred to remove the solvent, and then roll-dried to remove the remaining solvent and water to produce a butadiene polymer composition.

[0090] [Example 8] In Example 7 above, a butadiene polymer composition was produced in the same manner as in Example 1, except that a solution in which t-butylcatechol was dissolved at 0.5% by weight in n-hexane was charged such that the content of t-butylcatechol (TBC) was 20 ppm instead of 10 ppm with respect to the content of 1,3-butadiene charged into the reactor.

[0091] [Comparative Example 1] After charging 500 g of 1,3-butadiene and 4.2 kg of n-hexane into a 20 L autoclave reactor, the internal temperature of the reactor was raised to 70°C. After charging the catalyst composition produced in Production Example 1 into the reactor, polymerization was carried out. When the polymerization conversion rate reached 98% or more, a solution of 1.0 g of a polymerization terminator in n-hexane and a solution in which the antioxidant Irganox 1520 (manufactured by BASF) was dissolved at 30% by weight in n-hexane were added to terminate the reaction. The resulting polymer was put into warm water heated with steam, stirred to remove the solvent, and then roll-dried to remove the remaining solvent and water to produce a butadiene polymer composition.

[0092] <Experimental Example 1: Physical Property Evaluation of Polymer Composition> For the butadiene polymer compositions produced in Examples 1 to 6 and Comparative Example 1, the Mooney viscosity and cis-1,4 bond content were measured by the following methods and shown in Table 1 below.

[0093] * Mooney viscosity (ML1+4, @100 °C): For each polymer, the Mooney viscosity was measured at 100 °C under the condition of Rotor Speed 2 ± 0.02 rpm using the Large Rotor of Monsanto's MV2000E. The sample used at this time was left standing at room temperature (23 ± 3 °C) for 30 minutes or more, then 27 ± 3 g was taken and filled inside the die cavity, and the platen was operated to measure the Mooney viscosity while applying torque.

[0094] * Cis-1,4 bond content: The cis-1,4 bond content in the conjugated diene part was measured by Fourier transform infrared spectroscopy (FT-IR). Specifically, after measuring the FT-IR transmittance spectrum of a carbon disulfide solution of a conjugated diene polymer prepared to a concentration of 5 mg / mL with carbon disulfide in the same cell as a blank, the maximum peak value (a, baseline) near 1130 cm -1 in the vicinity, the minimum peak value (b) near 967 cm indicating the trans-1,4 bond, the minimum peak value (c) near 911 cm -1 indicating the vinyl bond, and the minimum peak value (d) near 736 cm -1 indicating the cis-1,4 bond were used to determine the respective contents. -1 in the vicinity.

[0095]

Table 1

[0096] As shown in Table 1 above, in Examples 1 to 8, even when a compound containing a t-butylphenol group was mixed into the polymer composition during or after the production of the polymer, compared with Comparative Example 1 in which no compound containing a t-butylphenol group was mixed into the butadiene polymer, it was confirmed that the cis-1,4 bond content of the butadiene polymer was not affected, the influence on the Mooney viscosity was not significant, and the Mooney viscosity was maintained at an equivalent level.

[0097] <Experimental Example 2: Measurement of Y / I (yellow index)> After thinning 20 g of the polymer compositions produced in Examples 1 to 8 and Comparative Example 1 with a roll mill at a 2.0 mm interval, 5 g was cut into a square shape and placed in a test piece mold, and pressure bonding was performed at a temperature of 140 °C to produce a test piece with a thickness of 5 mm. Thereafter, Y / I was measured for the produced test piece using a colorimeter (Ultrascan Pro, Hunterlab), and the results are shown in Table 2 below.

[0098] <Experimental Example 3: Measurement of antioxidant content> After completely dissolving the polymer compositions produced in Examples 1 to 8 and Comparative Example 1 in chloroform, methanol was added to precipitate the polymer components. Thereafter, the filtrate was filtered to produce a sample. A calibration curve was created by injecting a standard sample of the antioxidant into an HPLC / UV instrument, the sample produced above was injected, and the content of the antioxidant in the polymer composition was calculated using the calibration curve and is shown in Table 2 below.

[0099]

Table 2

[0100] As shown in Table 2 above, for the polymer compositions produced in Examples 1 to 8, compared with the polymer composition produced in Comparative Example 1, even after 6 weeks had passed, Y / I did not increase rapidly and was maintained at an appropriate level, and it was confirmed that the antioxidant also remained at a high content.

[0101] Also, as can be confirmed from Examples 2 to 4 in which a compound containing a t-butylphenol group was mixed after the polymerization was completed, and Examples 7 and 8 in which a compound containing a t-butylphenol group was mixed before the polymerization was started, it was confirmed that the yellowing phenomenon was improved regardless of the timing of the addition of the compound containing a t-butylphenol group.

[0102] From such results, it was confirmed that the polymer composition produced by the method for producing a polymer composition of the present invention contains a branched conjugated diene polymer, is excellent in processability, and has an improved yellowing phenomenon.

Claims

1. A step (S10) of polymerizing a conjugated diene monomer in the presence of a catalyst composition containing an organometallic compound, an organoaluminum compound, a fluorine-based compound, and a diphenylamine-based compound to produce a branched conjugated diene polymer; A step (S20) of mixing a monomer before polymerization, a polymerization solution during polymerization, or a branched conjugated diene polymer after polymerization in the step (S10) with a compound containing a t-butylphenol group; A method for producing a polymer composition, comprising:

2. The method for producing a polymer composition according to claim 1, wherein the organometallic compound is an organonickel compound.

3. The method for producing a polymer composition according to claim 1, wherein the organometallic compound is selected from the group consisting of nickel benzoate, nickel acetate, nickel naphthenate, nickel octanoate, nickel neodecanoate, bis(α-furyldioxime)nickel, nickel palmitate, nickel stearate, nickel acetylacetonate, nickel salicylaldehyde, bis(cyclopentadiene)nickel, bis(salicylaldehyde)ethylenediimine nickel, cyclopentadienyl-nickel nitrosyl, bis(π-allylnickel), bis(π-cycloocta-1,5-diene)nickel, bis(π-allylnickel trifluoroacetate), and nickel tetracarbonyl.

4. The method for producing a polymer composition according to claim 1, wherein the organoaluminum compound is an alkylaluminum compound represented by the following Chemical Formula 1. [Chemical Formula 1] AlR 1 R 2 R 3 In the Chemical Formula 1, R 1 to R 3 each independently represents hydrogen or an alkyl group having 1 to 12 carbon atoms, and R 1 to R 3 are not all hydrogen.

5. The method for producing a polymer composition according to claim 1, wherein the fluorine-based compound is at least one selected from the group consisting of hydrogen fluoride and boron trifluoride.

6. The method for producing a polymer composition according to claim 1, wherein the diphenylamine-based compound is a compound represented by the following Chemical Formula 2. 【Chemical Formula 3】 In the Chemical Formula 2, R 4 and R 5 is each independently an alkyl group having 2 to 18 carbon atoms which is substituted or unsubstituted with an aryl group having 6 to 30 carbon atoms.

7. The method for producing a polymer composition according to claim 1, wherein the compound containing a t-butylphenol group is t-butylcatechol, butylhydroxytoluene, or a mixture thereof.

8. In the step (S20), the compound containing a t-butylphenol group is mixed in an amount of 0.0001 to 0.005 parts by weight based on 100 parts by weight of the conjugated diene monomer or the branched conjugated diene polymer. The method for producing a polymer composition according to claim 1.

9. A polymer composition comprising a metal-catalyzed branched conjugated diene polymer and a compound containing a t-butylphenol group.

10. The content of the compound containing a t-butylphenol group is 0.0001 to 0.005 parts by weight based on 100 parts by weight of the metal-catalyzed branched conjugated diene polymer. The polymer composition according to claim 9.

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