Method for producing copolymer having improved oil retainability

Abstract

The present invention relates to a method for producing a copolymer, the method comprising a process in which a monomer that contains a 1,3-diene structure and has 4 to 20 carbon atoms is polymerized in a solvent in the presence of an anionic polymerization initiator.

Description

Method for producing copolymers with improved oil retention properties

[0001] The present invention relates to a method for producing copolymers with improved oil retention properties.

[0002] In recent years, copolymers such as styrene-based elastomers have been used in areas such as grips and gel materials to achieve good tactile feel, high flexibility, or elasticity.

[0003] For example, in fields such as grips (sports, toys, stationery, etc.) and oil gel materials (mats, toys, etc.), formulation designs to improve oil retention have been widely studied from the perspective of suppressing changes in physical properties or stickiness due to oil bleeding over time, or interfacial peeling of coextruded or two-color molded parts. There is also a demand for new production methods for copolymers with good oil retention. The good oil retention of copolymers means that the formulation remains unchanged from the initial production stage, reducing changes in physical properties over time. Furthermore, reduced oil bleeding can suppress changes in the touch, stickiness on the surface, and interfacial peeling of two-color molded parts.

[0004] SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a method for producing a copolymer having improved oil retention properties.

[0005] According to one aspect of the present invention, a method for producing a copolymer can include polymerizing a monomer containing a 1,3-diene structure and having 4 to 20 carbon atoms in a solvent in the presence of an anionic polymerization initiator to produce the copolymer. The temperature change during polymerization can be less than 15°C.

[0006] According to another aspect of the present invention, a method for producing a copolymer may include polymerizing a monomer containing a 1,3-diene structure and having 4 to 20 carbons in a solvent in the presence of an anionic polymerization initiator, and cooling the temperature during polymerization so that the consistency of the copolymer may be 6 mol % or less.

[0007] In some embodiments, the cooling may include maintaining a temperature change during the polymerization of less than 15° C. In some embodiments, the temperature change during the polymerization may be less than 10° C. In some embodiments, the temperature change during the polymerization may be 8° C. or less.

[0008] In some embodiments, the polymerization initiation temperature may be from 10 to 90° C. In some embodiments, the polymerization initiation temperature may be from 40 to 70° C.

[0009] In some embodiments, the monomer may include butadiene. In some embodiments, the monomer may include isoprene. In some embodiments, the monomer may include 7,11-dimethyl-3-methylene-1,6,10-dodecatriene (β-farnesene).

[0010] In some embodiments, the only monomers polymerized in the polymerization may consist of butadiene. In some embodiments, the only monomers polymerized in the polymerization may consist of isoprene. In some embodiments, the only monomers polymerized in the polymerization may consist of 7,11-dimethyl-3-methylene-1,6,10-dodecatriene (β-farnesene).

[0011] In some embodiments, the process may further include hydrogenating the copolymer, thereby producing an α-olefin random copolymer.

[0012] In some embodiments, the copolymer may be an ethylene-1-butene copolymer.

[0013] In some embodiments, the copolymer may have a weight average molecular weight of 10,000 to 500,000 Da.

[0014] In some embodiments, the copolymer may have a content of vinyl bond structural units of 5 to 85 mol % relative to the total molar amount of conjugated diene (1,3-diene structure) monomer units incorporated in 3,4-bond, 1,4-bond, and 1,2-bond modes of the conjugated diene monomer.

[0015] According to another aspect of the present invention, a method for producing a block copolymer may include polymerizing a first aromatic vinyl compound to produce a polymerized first aromatic vinyl compound, and producing the copolymer according to the method disclosed herein, thereby producing the block copolymer comprising the polymerized first aromatic vinyl compound and the copolymer. The solvent may contain the polymerized first aromatic vinyl compound. In some embodiments, the method for producing the block copolymer may include polymerizing a first aromatic vinyl compound to produce a polymerized first aromatic vinyl compound; and producing the copolymer according to a method for producing a copolymer, which may include polymerizing a monomer comprising a 1,3-diene structure and having 4 to 20 carbon atoms in a solvent in the presence of an anionic polymerization initiator to produce the copolymer, thereby producing the block copolymer comprising the polymerized first aromatic vinyl compound and the copolymer. Furthermore, in the method for producing a block copolymer, the method for producing a copolymer may include each of the above-described embodiments disclosed herein. The solvent may contain the polymerized first aromatic vinyl compound. In some embodiments, the method for producing the block copolymer may include polymerizing a first aromatic vinyl compound to produce a polymerized first aromatic vinyl compound; and producing a copolymer according to a copolymer production method that may include polymerizing a monomer having a 1,3-diene structure and 4 to 20 carbon atoms in a solvent in the presence of an anionic polymerization initiator and cooling the temperature during polymerization so that the consistency of the copolymer may be 6 mol % or less, thereby producing the block copolymer comprising the polymerized first aromatic vinyl compound and the copolymer. Also, in the method for producing the block copolymer, the method for producing the copolymer may include any of the embodiments disclosed herein above. The solvent may contain the polymerized first aromatic vinyl compound.

[0016] According to another aspect of the present invention, a method for producing a triblock copolymer includes producing the block copolymer according to the method disclosed herein. According to another aspect of the present invention, a method for producing a triblock copolymer can include producing the block copolymer according to the method disclosed herein, and subsequently polymerizing a second aromatic vinyl compound after the block copolymer is obtained, thereby producing the triblock copolymer comprising the polymerized first aromatic vinyl compound, the copolymer, and the polymerized second aromatic vinyl compound. In some embodiments, a method for producing a triblock copolymer can include using a coupling reaction of the block copolymer to produce the triblock copolymer. Specifically, in some embodiments, the method for producing the triblock copolymer may include: producing the block copolymer comprising the polymerized first aromatic vinyl compound and the copolymer according to the method disclosed herein; producing the block copolymer comprising the polymerized second aromatic vinyl compound and the copolymer according to a method similar to the method disclosed herein; and coupling the block copolymer comprising the polymerized first aromatic vinyl compound and the copolymer and the block copolymer comprising the second aromatic vinyl compound and the copolymer by a coupling reaction, thereby producing the triblock copolymer comprising the polymerized first aromatic vinyl compound, the copolymer, and the polymerized second aromatic vinyl compound. The coupling reaction may also include a coupling reaction using a coupling agent described below. In this specification, "producing the block copolymer comprising a second aromatic vinyl compound polymerized according to a method similar to the method disclosed in this specification and the copolymer" specifically refers to the same as in the above-mentioned description of the method for producing the block copolymer comprising the polymerized first aromatic vinyl compound and the copolymer, except that "the first aromatic vinyl compound" is replaced with "the second aromatic vinyl compound."The first aromatic vinyl compound and the second aromatic vinyl compound may be the same or different.

[0017] In some embodiments, the method for producing the triblock copolymer may include producing the block copolymer according to a method for producing a copolymer that may include polymerizing a first aromatic vinyl compound to produce a polymerized first aromatic vinyl compound, and polymerizing a monomer comprising a 1,3-diene structure and having 4 to 20 carbon atoms in a solvent in the presence of an anionic polymerization initiator to produce the copolymer, thereby producing a block copolymer comprising the polymerized first aromatic vinyl compound and the copolymer. The solvent may contain the polymerized first aromatic vinyl compound.

[0018] In some embodiments, the method for producing the triblock copolymer may include: polymerizing a first aromatic vinyl compound to produce a polymerized first aromatic vinyl compound; and polymerizing a monomer having a 1,3-diene structure and 4 to 20 carbon atoms in a solvent in the presence of an anionic polymerization initiator to produce a copolymer, thereby producing a block copolymer comprising the polymerized first aromatic vinyl compound and the copolymer; and subsequently polymerizing a second aromatic vinyl compound after the block copolymer is obtained, thereby producing the triblock copolymer comprising the polymerized first aromatic vinyl compound, the copolymer, and the polymerized second aromatic vinyl compound. The solvent may contain the polymerized first aromatic vinyl compound.

[0019] In some embodiments, the method for producing the triblock copolymer includes: producing a block copolymer according to a method for producing a block copolymer, which may include polymerizing a first aromatic vinyl compound to produce a polymerized first aromatic vinyl compound, and polymerizing a monomer comprising a 1,3-diene structure and having 4 to 20 carbon atoms in a solvent in the presence of an anionic polymerization initiator to produce a copolymer, thereby producing a block copolymer comprising the polymerized first aromatic vinyl compound and the copolymer, wherein the solvent may contain the polymerized first aromatic vinyl compound; and and producing a block copolymer according to a method for producing a block copolymer, which may include polymerizing a second aromatic vinyl compound to produce a polymerized second aromatic vinyl compound, and polymerizing a monomer having a 1,3-diene structure and 4 to 20 carbon atoms in a solvent in the presence of an anionic polymerization initiator to produce a copolymer, thereby producing a block copolymer comprising the polymerized second aromatic vinyl compound and the copolymer (the solvent may contain the polymerized second aromatic vinyl compound); and coupling the block copolymer comprising the polymerized first aromatic vinyl compound and the copolymer and the block copolymer comprising a second aromatic vinyl compound and the copolymer by a coupling reaction, thereby producing the triblock copolymer comprising the polymerized first aromatic vinyl compound, the copolymer, and the polymerized second aromatic vinyl compound.

[0020] In some embodiments, the method for producing the triblock copolymer may include: polymerizing a first aromatic vinyl compound to produce a polymerized first aromatic vinyl compound; and producing a copolymer according to a copolymer production method that may include polymerizing a monomer comprising a 1,3-diene structure and having 4 to 20 carbon atoms in a solvent in the presence of an anionic polymerization initiator and cooling the temperature during polymerization such that the consistency of the copolymer may be 6 mol % or less, thereby producing the block copolymer comprising the polymerized first aromatic vinyl compound and the copolymer. The solvent may contain the polymerized first aromatic vinyl compound.

[0021] In some embodiments, the method for producing the triblock copolymer may include: polymerizing a first aromatic vinyl compound to produce a polymerized first aromatic vinyl compound; and producing a copolymer according to a copolymer production method that may include polymerizing a monomer having a 1,3-diene structure and 4 to 20 carbon atoms in a solvent in the presence of an anionic polymerization initiator and cooling the temperature during polymerization so that the consistency of the copolymer may be 6 mol % or less, thereby producing the block copolymer comprising the polymerized first aromatic vinyl compound and the copolymer; and subsequently polymerizing a second aromatic vinyl compound after the block copolymer is obtained, thereby producing the triblock copolymer comprising the polymerized first aromatic vinyl compound, the copolymer, and the polymerized second aromatic vinyl compound. The solvent may contain the polymerized first aromatic vinyl compound.

[0022] In some embodiments, the method for producing the triblock copolymer may include: polymerizing a first aromatic vinyl compound to produce a polymerized first aromatic vinyl compound; and producing a copolymer according to a copolymer production method that may include polymerizing a monomer comprising a 1,3-diene structure and having 4 to 20 carbon atoms in a solvent in the presence of an anionic polymerization initiator, and cooling the temperature during polymerization such that the consistency of the copolymer may be 6 mol % or less, thereby producing the block copolymer comprising the polymerized first aromatic vinyl compound and the copolymer; (The solvent may contain the polymerized first aromatic vinyl compound); and The method may include: polymerizing a second aromatic vinyl compound to produce a polymerized second aromatic vinyl compound; and producing a copolymer according to a copolymer production method that may include polymerizing a monomer having a 1,3-diene structure and 4 to 20 carbon atoms in a solvent in the presence of an anionic polymerization initiator to produce a copolymer, thereby producing a block copolymer comprising the polymerized second aromatic vinyl compound and the copolymer (the solvent may contain the polymerized second aromatic vinyl compound); and coupling the block copolymer comprising the polymerized first aromatic vinyl compound and the copolymer and the block copolymer comprising a second aromatic vinyl compound and the copolymer by a coupling reaction, thereby producing the triblock copolymer comprising the polymerized first aromatic vinyl compound, the copolymer, and the polymerized second aromatic vinyl compound. The coupling reaction may also include a coupling reaction using a coupling agent described below. The first aromatic vinyl compound and the second aromatic vinyl compound may be the same or different.

[0023] In some embodiments, the first aromatic vinyl compound and the second aromatic vinyl compound are each independently selected from the group consisting of styrene, α-methylstyrene, 4-methylstyrene, o-methylstyrene, m-methylstyrene, β-methylstyrene, 2,6-dimethylstyrene, 2,4-dimethylstyrene, α-methyl-o-methylstyrene, α-methyl-m-methylstyrene, α-methyl-p-methylstyrene, β-methyl-o-methylstyrene, β-methyl-m-methylstyrene, β-methyl-p-methylstyrene, 2,4,6-trimethylstyrene, α-methyl-2,6-dimethylstyrene, α-methyl-2,4-dimethylstyrene, 3-methyl-2,6-dimethylstyrene, f-methyl-2,4-dimethylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, 2,6-dichlorostyrene, 2,4-dichlorostyrene, α ... The compound may include a compound selected from the group consisting of o-o-chlorostyrene, α-chloro-m-chlorostyrene, α-chloro-p-chlorostyrene, β-chloro-o-chlorostyrene, β-chloro-m-chlorostyrene, β-chloro-p-chlorostyrene, 2,4,6-trichlorostyrene, α-chloro-2,6-dichlorostyrene, α-chloro-2,4-dichlorostyrene, β-chloro-2,6-dichlorostyrene, β-chloro-2,4-dichlorostyrene, o-t-butylstyrene, m-t-butylstyrene, p-butylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-chloromethylstyrene, m-chloromethylstyrene, p-chloromethylstyrene, o-bromomethylstyrene, m-bromomethylstyrene, p-bromomethylstyrene, a styrene derivative substituted with a silyl group, indene, and vinylnaphthalene.

[0024] In some embodiments, each of the first aromatic vinyl compound and the second aromatic vinyl compound can include styrene.

[0025] In some embodiments, the triblock copolymer may have a content of vinyl bond structural units of 5 to 85 mol % relative to the total molar amount of conjugated diene (1,3-diene structure) monomer units incorporated in the bonding modes of 3,4-bonds, 1,4-bonds, and 1,2-bonds of the conjugated diene monomers.

[0026] In some embodiments, the triblock copolymer may have a styrene content of 5 to 70 wt %, based on the total weight of the triblock copolymer.

[0027] In some embodiments, the triblock copolymer can have a glass transition temperature (Tg) of -60°C to 25°C as measured by DSC at 10°C / min.

[0028] In some embodiments, the triblock copolymer may have an MFR at 230° C. and 2.16 kg, measured according to SO1133, of less than or equal to 250 g / 10 min.

[0029] In some embodiments, the triblock copolymer is a hydrogenated triblock copolymer, and the hydrogenated triblock copolymer may have a peak crystallization temperature (Tc) of -8°C to 4°C as measured by DSC at 10°C / min.

[0030] In some embodiments, the first aromatic vinyl compound and the second aromatic vinyl compound can be polymerized by ionic polymerization.

[0031] In some embodiments, the anionic polymerization initiator may include at least one initiator selected from the group consisting of alkali metals, alkaline earth metals, lanthanide rare earth metals, and compounds containing earth metals and lanthanide rare earth metals. In some embodiments, the anionic polymerization initiator may include at least one initiator selected from the group consisting of alkali metals, compounds containing alkali metals, and organic alkali metal compounds. In some embodiments, the anionic polymerization initiator may include at least one alkali metal selected from the group consisting of lithium, sodium, and potassium. In some embodiments, the anionic polymerization initiator may include at least one alkaline earth metal selected from the group consisting of beryllium, magnesium, calcium, strontium, and barium. In some embodiments, the anionic polymerization initiator may include at least one lanthanide rare earth metal selected from the group consisting of lanthanum and neodymium. In some embodiments, the anionic polymerization initiator may include at least one organolithium compound selected from the group consisting of methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium, stilbenelithium, dilithiomethane, dilithionaphthalene, and 1,4-dilithiobutane. In some embodiments, the anionic polymerization initiator may include at least one organolithium compound selected from the group consisting of dilithiobutane, 1,4-dilithio-2-ethylcyclohexane, 1,3,5-trilithiobenzene, sodium naphthalene, and potassium naphthalene.

[0032] In some embodiments, the solvent may include at least one selected from the group consisting of saturated aliphatic hydrocarbons, saturated alicyclic hydrocarbons, and aromatic hydrocarbons. In some embodiments, the solvent may include at least one selected from the group consisting of cyclopentane, cyclohexane, and methylcyclohexane. In some embodiments, the solvent may include at least one saturated aliphatic hydrocarbon selected from the group consisting of n-pentane, isopentane, n-hexane, n-heptane, and isooctane. In some embodiments, the solvent may include at least one selected from the group consisting of pentane, benzene, toluene, and xylene.

[0033] In some embodiments, the solvent may further comprise a Lewis base. In some embodiments, the solvent may further comprise at least one Lewis base selected from the group consisting of dibutyl ether, diethyl ether, tetrahydrofuran, dioxane, tetramethylethylenediamine, hexamethyltriethylenetetramine, 1,2-diethoxypropane, ditetrahydrofurylpropane, ethylene glycol diethyl ether, pyridine, tertiary amines, alkali metal alkoxides, and phosphine compounds. In some embodiments, the amount of the Lewis base may be in the range of 0.01 to 1,000 molar equivalents relative to 1 mol of the anionic polymerization initiator.

[0034] In some embodiments, the method may further include adding a polymerization terminator to the solvent. In some embodiments, the polymerization terminator may include an alcohol.

[0035] In some embodiments, the method may further include precipitating the triblock copolymer in another solvent.

[0036] In some embodiments, the method may further include washing the polymerization reaction solution with water, separating, and drying.

[0037] Another aspect of the present invention can relate to triblock copolymers produced by the methods disclosed herein.

[0038] According to aspects of the present invention, a method for producing a copolymer having excellent oil retention properties and suitable for 2K molding, grip, and oil gel applications is provided.

[0039] These and other embodiments, features, and advantages of the present invention will be more readily understood by those of ordinary skill in the art upon reading the following detailed description.

[0040] According to the present invention, a method for producing a copolymer having improved oil retention properties can be provided.

[0041] 1 is a diagram of the calculation of vinyl content (VC) and consistency; 2 is a diagram of the polymer sheet layout for oil retention testing and oil retention for the hydrogenated triblock polymers tested; 3 is a diagram of the polymer sheet layout for oil retention testing.

[0042] The present invention will now be described in more detail.

[0043] In the context of this specification, all publications, patent applications, patents, and other references cited herein are expressly incorporated herein by reference in their entirety for all purposes, as if fully set forth, unless otherwise indicated.

[0044] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. In case of conflict, the present specification, including definitions, will control.

[0045] Unless expressly indicated, trademarks are shown in capital letters.

[0046] Unless otherwise stated, all percentages, parts, ratios, etc. are by weight.

[0047] Unless otherwise specified, pressures expressed in psi are gauge pressures and pressures expressed in kPa are absolute pressures. However, pressure differences are expressed as absolute values ​​(e.g., Pressure 1 is 25 psi higher than Pressure 2).

[0048] When an amount, concentration, or other value or parameter is given as a range or as a list of upper and lower limits, this should be understood to specifically disclose all ranges formed from any pair of any upper and lower range limits, regardless of whether the ranges are separately disclosed. When a range of numerical values ​​is recited herein, unless otherwise specified, the range is intended to include its endpoints, and all integers and fractions within the range. It is not intended that the scope of the present disclosure be limited to the specific values ​​recited when defining the range.

[0049] When the term "about" is used, it is used to mean that a particular effect or result may be obtained within a certain tolerance, and one of ordinary skill in the art would know how to obtain the tolerance. When the term "about" is used to describe a value or an endpoint of a range, the disclosure should be understood to include the specific value or endpoint referred to.

[0050] As used herein, the words "comprises," "comprising," "includes," "including," "has," "having," or other variants thereof are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that includes a list of elements is not necessarily limited to only those elements but may include other elements that are not expressly listed or that are inherent to such process, method, article, or apparatus.

[0051] The transitional phrase "consisting of" excludes any element, step, or ingredient not specified in the claim and closes the claim to the inclusion of materials other than those recited, except for impurities ordinarily incident thereto. When the phrase "consist of" appears in the body of a claim rather than immediately following the preamble, it limits the claim to only the elements set forth in that body and does not exclude other elements from the claim as a whole.

[0052] The transitional phrase "consisting essentially of" limits the scope of the claim to the specified materials or steps and to those materials or steps that do not materially affect the basic and novel characteristic(s) of the claimed invention. A "consisting essentially of" claim occupies a middle ground between a closed claim written in the "consisting of" format and a fully open claim drafted in the "comprising" format. Additives and minor impurities at levels appropriate for any additive as defined herein are not excluded from the composition by the term "consisting essentially of."

[0053] Furthermore, unless expressly stated to the contrary, "or" and "and / or" refer to inclusive rather than exclusive. For example, a condition A or B, or a condition A and / or B, is satisfied by any one of the following: A being true (i.e., present) and B being false (i.e., not present), A being false (i.e., not present) and B being true (i.e., present), and both A and B being true (i.e., present).

[0054] The use of "a" or "an" to describe various elements and components herein is merely for convenience and to give a general sense of the disclosure. The description should be read to include one or at least one, and the singular also includes the plural unless it is clear that it is meant otherwise.

[0055] As used herein, the terms "predominant portion" or "predominantly" mean more than 50% of a reference material, unless otherwise defined herein. Unless specified, percentages are on a molar basis when referring to molecules (such as hydrogen and ethylene), and are otherwise on a mass or weight basis (such as for additive content).

[0056] As used herein, unless otherwise defined, the terms "substantial portion" or "substantially" mean all or nearly all or the vast majority as would be understood by one of ordinary skill in the art in the context in which it is used. It is intended to allow for some reasonable variation from 100% that would normally occur in an industrial or commercial scale situation.

[0057] The terms "depleted" or "reduced" are synonymous with less than that originally present. For example, removing a substantial portion of a material from a stream results in a material-depleted stream that is substantially depleted of that material. In contrast, the terms "enriched" or "increased" are synonymous with more than that originally present.

[0058] The term "number average molecular weight" or "Mn" means number average molecular weight, and the term "weight average molecular weight" or "Mw" means weight average molecular weight, as determined by gel permeation chromatography (GPC) based on a standard polystyrene calibration curve.

[0059] The crystallization peak temperature (Tc) is determined herein using a differential scanning calorimeter (DSC) and is defined as the peak top temperature of the exothermic peak observed when a sample is heated from 30° C. to 200° C. at a heating rate of 10° C. / min and then cooled to −60° C. at a cooling rate of 10° C. / min. The measurement is as shown in the Examples.

[0060] The glass transition temperature (Tg) as used herein is determined using a differential scanning calorimeter (DSC), more specifically, is a value measured by the method shown in the examples.

[0061] Also, the term "elastomer" has its ordinary meaning, ie, a material having elastic properties, as understood by those skilled in the relevant art.

[0062] The term "substantially homogeneous mixture" means that the components of the mixture are substantially uniformly distributed throughout the mixture by weight. The mixture may have discrete domains (of the same or different size) of one component within a continuous domain of another component, where the discrete domains are substantially uniformly distributed (by weight) within the continuous domain. This is intended to be a level of homogeneity achievable by typical industrial mixing equipment operated under commercially applicable conditions, as recognized by those skilled in the relevant art.

[0063] As used herein, the term "copolymer" refers to a polymer containing copolymerized units resulting from the copolymerization of two or more comonomers. In this regard, a copolymer may be described herein with reference to its constituent comonomers or the amounts of its constituent comonomers, e.g., "a copolymer containing butadiene and 15 mol % comonomer" or similar descriptions. Such descriptions may be considered informal in that they do not refer to the comonomers as copolymerized units, in that they do not involve conventional nomenclature for copolymers, such as that of the International Union of Pure and Applied Chemistry (IUPAC), in that they do not use product-by-process terminology, or for other reasons. However, as used herein, a description of a copolymer with reference to its constituent comonomers or the amounts of its constituent comonomers means that the copolymer contains copolymerized units of the specified comonomers (in the specified amounts, if specified). It therefore follows, by corollary, that a copolymer is not the product of a reaction mixture containing a specified comonomer in a specified amount, unless expressly stated in limited circumstances.

[0064] For convenience, many elements of the invention may be discussed separately, lists of options may be provided, and numerical values ​​may be ranges, but for purposes of this disclosure, this should not be considered a limitation on the scope of the disclosure or support of this disclosure for any claim of any combination of any such separate components, list items, or ranges. Unless otherwise expressly stated, each and every combination contemplated by this disclosure should be considered to be expressly disclosed for all purposes.

[0065] Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present disclosure, suitable methods and materials are described herein. Therefore, the materials, methods, and examples herein are illustrative only and, except as specifically stated, are not intended to be limiting.

[0066] The present invention relates to a method for producing copolymers with excellent oil retention properties suitable for grip and oil gel applications, as further detailed below.

[0067] Polymerization of Monomers Comprising a 1,3-Diene Structure In one embodiment, the method of the present disclosure can include polymerizing a monomer comprising a 1,3-diene structure and having 4 to 20 carbons in a solvent in the presence of an anionic polymerization initiator to produce a copolymer, wherein the temperature change during the polymerization is less than 15°C.

[0068] In another aspect, the methods of the present disclosure may include polymerizing a monomer comprising a 1,3-diene structure and having 4 to 20 carbons in a solvent in the presence of an anionic polymerization initiator, and cooling the temperature during the polymerization to achieve a copolymer consistency of 6 mol% or less. In some embodiments, the cooling may include maintaining a temperature change during the polymerization of less than 15°C. In some embodiments, the cooling may include maintaining a temperature change during the polymerization of 14°C or less, 13°C or less, 12°C or less, 11°C or less, 10°C or less, 9°C or less, 8°C or less, 7°C or less, 6°C or less, 5°C or less, 4°C or less, or 3°C or less.

[0069] The temperature change may refer to the difference between the minimum and maximum temperatures measured throughout the polymerization, including the beginning and end of the polymerization. The temperature during the polymerization may be measured by a temperature sensor that may be in contact with the polymerization mixture. Other methods and / or tools not described in this disclosure but understood by those skilled in the art may also be used.

[0070] In some embodiments, the temperature change during the polymerization can be less than 14°C, less than 13°C, less than 12°C, less than 11°C, less than 10°C, less than 9°C, less than 8°C, less than 7°C, less than 6°C, less than 5°C, less than 4°C, less than 3°C, or less than 2°C, and / or greater than 0°C, more than 1°C, more than 2°C, more than 3°C, more than 4°C, more than 5°C, more than 6°C, or more than 7°C. In some embodiments, the temperature change during the polymerization can be less than 10°C. In some embodiments, the temperature change during the polymerization can be 8°C or less. The temperature change can be controlled by a thermostat attached to a cooling device that cools the polymerization mixture. Other methods and / or tools not described in this disclosure but understood by those skilled in the art can also be used. As mentioned above, the lower and upper limits described herein can be combined in any combination. For example, in some embodiments, the temperature change during the polymerization can be 0°C or more and less than 15°C, 0°C or more and less than 12°C, 0°C or more and less than 10°C, 0°C or more and less than 9°C, 0°C or more and less than 8°C, 0°C or more and less than 7°C, 0°C or more and less than 6°C, 0°C or more and less than 5°C, 0°C or more and less than 4°C, 0°C or more and less than 3°C, 1°C or more and less than 15°C, 1°C or more and less than 12°C, 1°C or more and less than 10°C, 1°C or more and less than 9°C, 1°C or more and less than 8°C, 1°C or more and less than 7°C, 1°C or more and less than 6°C, 1°C or more and less than 5°C, 1°C or more and less than 4°C, or 1°C or more and less than 3°C.

[0071] In some embodiments, the initiation temperature of the polymerization can be from 10° C. to 90° C. In some embodiments, the initiation temperature of the polymerization can be from 40° C. to 70° C. For example, the initiation temperature of the polymerization can be at least 10° C., at least 15° C., at least 20° C., at least 25° C., at least 30° C., at least 35° C., at least 40° C., at least 45° C., at least 50° C., at least 55° C., or at least 60° C., and / or no greater than 70° C., no greater than 65° C., no greater than 55° C., no greater than 45° C., no greater than 35° C., no greater than 25° C., or no greater than 15° C.

[0072] The polymerization may be carried out for at least about 1 hour, at least about 2 hours, at least about 3 hours, at least about 4 hours, at least about 5 hours, at least about 6 hours, at least about 7 hours, at least about 8 hours, at least about 9 hours, at least about 10 hours, at least about 12 hours, at least about 15 hours, at least about 20 hours, or at least about 24 hours, and / or for up to 36 hours, 30 hours, 24 hours, 20 hours, 16 hours, 12 hours, 10 hours, 8 hours, 7 hours, 6 hours, 5 hours, 4 hours, 3 hours, 2 hours, or 1.5 hours. As noted above, the lower and upper limits may be combined in any manner. For example, in some embodiments, the polymerization may be carried out for 1 to 36 hours, 2 to 24 hours, or 3 to 20 hours.

[0073] The monomer may have at least 4, at least 5, at least 6, at least 7, at least 8, at least 9, at least 10, at least 11, at least 12, at least 13, at least 14, at least 15, at least 16, at least 17, at least 18, or at least 19 carbons, and / or no more than 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, or 5 carbons. As noted above, the lower and upper limits can be combined in any manner. For example, in some embodiments, the monomer may have 4 to 18, 4 to 16, or 4 to 15 carbons.

[0074] In some embodiments, each C═C in the 1,3-diene structure may independently be part of a cyclic structure or an aliphatic chain. The monomer may be unsubstituted or substituted with one or more moieties selected from the group consisting of hydroxyl, amino, alkylamino, arylamino, alkoxy, aryloxy, nitro, cyano, sulfonic acid, sulfate, phosphonic acid, phosphate, or phosphonate. One or more hydrogen atoms bonded to carbon atoms in the monomer may be substituted with one or more halogen atoms, such as fluorine, chlorine, bromine, and / or iodine, such as trifluoromethyl, difluoromethyl, fluorochloromethyl, etc., so long as the substituent(s) do not interfere with the objectives and effects of the present invention. In addition, the hydrocarbon chain may be interrupted by heteroatoms such as N or O, so long as the heteroatoms do not interfere with the objectives and effects of the present invention.

[0075] In some embodiments, the monomer may include at least one of butadiene, isoprene, 2,3-dimethyl-butadiene, 1,3-pentadiene, 1,3-hexadiene, myrcene, and 7,11-dimethyl-3-methylene-1,6,10-dodecatriene (β-farnesene), as long as the objectives and advantages of the present invention are not hindered. In some embodiments, a mixture of monomers may be used, and the polymerization form of the copolymer may be random or block, and is not particularly limited. In some embodiments, the monomer may include butadiene. In some embodiments, the monomer may include isoprene. In some embodiments, the monomer may include 7,11-dimethyl-3-methylene-1,6,10-dodecatriene (β-farnesene). The content of the monomer relative to the total amount of monomers polymerized in the polymerization may be at least 40 mol%, at least 50 mol%, at least 60 mol%, at least 70 mol%, at least 80 mol%, or at least 90 mol%, and / or no more than 99 mol%, no more than 90 mol%, no more than 80 mol%, no more than 70 mol%, no more than 60 mol%, or no more than 50 mol%. In some embodiments, the only monomer polymerized in the polymerization consists of butadiene. In some embodiments, the only monomer polymerized in the polymerization consists of isoprene. In some embodiments, the only monomer polymerized in the polymerization consists of 7,11-dimethyl-3-methylene-1,6,10-dodecatriene (β-farnesene). As mentioned above, the lower and upper limits can be combined in any manner. For example, in some embodiments, the content of the monomer relative to the total amount of monomers polymerized in the polymerization may be 40 to 99 mol %, 50 to 90 mol %, or 60 to 80 mol %.

[0076] Furthermore, the copolymer may contain structural units derived from other polymerizable monomers, for example, structural units derived from aromatic vinyl compounds such as styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene, etc., so long as the objectives and effects of the present invention are not impaired. "Derived from other polymerizable monomers" means that the structural units are structural units formed as a result of polymerization of other polymerizable monomers. The content of structural units derived from other polymerizable monomers in the copolymer is preferably about 10% by mass or less, about 5% by mass or less, about 3% by mass or less, and / or 0% by mass, based on the total mass of the copolymer.

[0077] <Vinyl Content (VC)> There is no particular limitation on the bonding form of the monomers in the copolymer. For example, the monomers can be incorporated into the copolymer via 1,2- or 3,4-bonds to introduce pendant vinyl groups into the copolymer. In some embodiments, the monomers can be incorporated into the copolymer via 1,4-bonds to introduce unsaturation into the polymer backbone. Only one of these bonding forms may be present, or two or more may be present. Furthermore, any of these bonding forms may be present in any ratio.

[0078] The vinyl content (VC) can be the ratio of monomer units incorporated via 1,2-bonds and 3,4-bonds to the total molar amount of conjugated diene (1,3-diene structure) monomer units incorporated via 3,4-bonds, 1,4-bonds, and 1,2-bonds in the conjugated diene monomer. A conjugated diene incorporated via 3,4-bonds, 1,4-bonds, and 1,2-bonds in the conjugated diene monomer can have a 1,3-diene structure. The ratio of monomer units incorporated via 1,2-bonds and 3,4-bonds to the total molar amount of conjugated diene (1,3-diene structure) monomer units incorporated via 3,4-bonds, 1,4-bonds, and 1,2-bonds in the conjugated diene monomer is synonymous with the content of vinyl bond structural units. The vinyl content can be determined by the ratio of the total molar amount of conjugated diene (1,3-diene structure) monomer units incorporated via 1,2-bonds and 3,4-bonds in the conjugated diene monomer. １ It can be determined using H-NMR analysis.

[0079] From the viewpoint of oil retention, the amount of 1,2-bonds and 3,4-bonds is 1 mol % or more, 2 mol % or more, 3 mol % or more, 5 mol % or more relative to the total moles of repeating units in the copolymer (i.e., the total moles of conjugated diene (1,3-diene structure) monomer units incorporated in the conjugated diene monomer in the bonding modes of 3,4-bonds, 1,4-bonds, and 1,2-bonds; the same applies hereinafter in this specification). The content may be 7 mol% or more, 10 mol% or more, 15 mol% or more, 20 mol% or more, 25 mol% or more, 30 mol% or more, 35 mol% or more, 40 mol% or more, or 45 mol% or more, and / or 10 mol% or less, 15 mol% or less, 20 mol% or less, 25 mol% or less, 30 mol% or less, 35 mol% or less, 40 mol% or less, 45 mol% or less, or 50 mol% or less. In some embodiments, the monomer may include butadiene, and the amount of 1,2-bonds and 3,4-bonds may be 30 mol% or more, 31 mol% or more, 32 mol% or more, 33 mol% or more, 34 mol% or more, 35 mol% or more, 36 mol% or more, 37 mol% or more, 38 mol% or more, 39 mol% or more, 40 mol% or more, 41 mol% or more, 42 mol% or more, 43 mol% or more, 44 mol% or more, or 45 mol% or more, and / or 43 mol% or less, 44 mol% or less, 45 mol% or less, 46 mol% or less, 47 mol% or less, 48 ​​mol% or less, 49 mol% or less, or 50 mol% or less, based on the total moles of repeat units in the copolymer.In some embodiments, the monomers may include isoprene, β-farnesene, and / or a mixture comprising isoprene and butadiene, and the amount of 1,2-linkages and 3,4-linkages, based on the total moles of repeat units in the copolymer, may be 1 mol% or more, 2 mol% or more, 3 mol% or more, 4 mol% or more, 5 mol% or more, 6 mol% or more, 7 mol% or more, 8 mol% or more, 9 mol% or more, The amount of 1,2-bonds and 3,4-bonds may be 10 mol% or more, 11 mol% or more, 12 mol% or more, 13 mol% or more, 14 mol% or more, or 15 mol% or more, and / or 8 mol% or less, 9 mol% or less, 10 mol% or less, 11 mol% or less, 12 mol% or less, 13 mol% or less, 14 mol% or less, 15 mol% or less, 16 mol% or less, 17 mol% or less, 18 mol% or less, 19 mol% or less, or 20 mol% or less. Herein, the amount of 1,2-bonds and 3,4-bonds is measured in accordance with the method described in the Examples of the copolymer before hydrogenation. １ In some embodiments, the amount of 1,4-linkages may be less than 97 mol%, less than 95 mol%, less than 93 mol%, less than 90 mol%, less than 85 mol%, less than 80 mol%, less than 75 mol%, less than 70 mol%, less than 65 mol%, less than 60 mol%, less than 55 mol%, less than 50 mol%, less than 45 mol%, less than 40 mol%, less than 35 mol%, less than 30 mol%, less than 25 mol%, less than 20 mol%, less than 15 mol%, less than 10 mol%, or less than 5 mol%, based on the total moles of repeat units in the copolymer.

[0080] Consistency: As used herein, "consistency" refers to the difference between the maximum and minimum vinyl content (VC) measured among multiple segments of a copolymer. VC is the percentage of the vinyl content of a block copolymer. １ H-NMR analysis can be used to measure and can be obtained for multiple segments (e.g., 10 segments) in the copolymer. See, for example, Figure 1.

[0081] During the polymerization of monomers containing 1,3-diene structures, polymerization mixture samples can be taken periodically and analyzed for VC and conversion of 1,3-diene structures. For example, polymerization mixture samples can be taken every 1 minute, 2 minutes, 3 minutes, 4 minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, 10 minutes, 12 minutes, 15 minutes, 18 minutes, or 20 minutes. Prior to analysis, methanol can be added to the sample to stop the polymerization process.

[0082] The conversion may be defined as the percentage of monomer that is polymerized during the polymerization. １ It can be determined by H-NMR analysis or by measuring the weight of the polymer isolated after removing the solvent and any unreacted monomers.

[0083] The VC for segments with approximately the same conversion interval can be used in the consistency analysis. For example, in the case of 10 segments, the first through tenth segments may have conversions of about 10%, about 20%, about 30%, about 40%, about 50%, about 60%, about 70%, about 80%, about 90%, and about 100%, respectively, with an interval of about 10%. The interval can be about 5% (for 20 segments), 10% (for 10 segments), 20% (for 5 segments), or 25% (for 4 segments). For example, an interval of about 5% may be 5±0.1%, 5±0.2%, 5±0.3%, 5±0.4%, or 5±0.5%, an interval of about 10% may be 10±0.1%, 10±0.2%, 10±0.3%, 10±0.4%, or 10±0.5%, an interval of about 20% may be 20±0.1%, 20±0.2%, 20±0.3%, 20±0.4%, or 20±0.5%, and an interval of about 25% may be 25±0.1%, 25±0.2%, 25±0.3%, 25±0.4%, or 25±0.5%.

[0084] In some embodiments, in view of desired oil retention, the copolymer consistency can be 6 mol% or less, 5.5 mol% or less, 5 mol% or less, 4.5 mol% or less, 4 mol% or less, 3.5 mol% or less, 3 mol% or less, 2.5 mol% or less, 2 mol% or less, 1.5 mol% or less, or 1 mol% or less, and / or 0 mol% or more.

[0085] Hydrogenation of the Copolymer In some embodiments, the process according to the present disclosure may further comprise hydrogenating the copolymer, thereby producing an α-olefin random copolymer. As used herein, an α-olefin is an α-olefin having the chemical formula C ｘ H ２ｘ Alkenes (also known as olefins) are organic compounds distinguished by having a double bond in the initial or alpha (α) position. See, for example, Petrochemicals in Nontechnical Language, 3rd Edition, Donald L. Burdick and William L. Leffler.

[0086] In some embodiments, the copolymer may include an ethylene-1-butene copolymer. In some embodiments, the copolymer may be an ethylene-1-butene copolymer. In some embodiments, the copolymer may have a weight average molecular weight of 10,000 to 500,000 Da. For example, the weight average molecular weight may be at least 10,000 Da, at least 50,000 Da, at least 100,000 Da, at least 150,000 Da, at least 200,000 Da, at least 300,000 Da, or at least 400,000 Da, and / or no more than 500,000 Da, no more than 450,000 Da, no more than 350,000 Da, no more than 250,000 Da, no more than 200,000 Da, no more than 150,000 Da, no more than 100,000 Da, no more than 80,000 Da, or no more than 40,000 Da. As mentioned above, the lower and upper limits may be combined in any manner. For example, in some embodiments, the weight average molecular weight can be 10,000 to 450,000 Da, 50,000 to 350,000 Da, or 100,000 to 250,000 Da.

[0087] In some embodiments, the copolymer may have a content of vinyl bond structural units of 5 to 85 mol % relative to the total molar amount of conjugated diene (1,3-diene structure) monomer units incorporated in 3,4-bond, 1,4-bond, and 1,2-bond modes of the conjugated diene monomer. In some embodiments, the copolymer may have a content of vinyl bonded structural units of at least 5 mol%, at least 10 mol%, at least 15 mol%, at least 20 mol%, at least 30 mol%, at least 40 mol%, at least 50 mol%, at least 60 mol%, at least 70 mol%, or at least 80 mol%, and / or 85 mol% or less, 75 mol% or less, 65 mol% or less, 55 mol% or less, 45 mol% or less, 35 mol% or less, 25 mol% or less, 20 mol% or less, 15 mol% or less, or 10 mol% or less, based on the total molar amount of conjugated diene (1,3-diene structure) monomer units incorporated in 3,4-bonded, 1,4-bonded, and 1,2-bonded bonding modes of the conjugated diene monomer. In some embodiments, when the copolymer is formed from butadiene, the content of vinyl-bonded structural units refers to the content of 1,2-bonded structural units (e.g., pendant vinyl bonds). In some embodiments, when the copolymer is formed from isoprene, the content of vinyl-bonded structural units refers to the total content of 1,2-bonded structural units and 3,4-bonded structural units. As mentioned above, the lower and upper limits can be arbitrarily combined. For example, in some embodiments, the copolymer can have a vinyl-bonded structural unit content of 5 to 85 mol %, 5 to 75 mol %, 5 to 65 mol %, or 5 to 55 mol %, based on the total molar amount of conjugated diene (1,3-diene structure) monomer units incorporated in the bonding modes of 3,4-bonds, 1,4-bonds, and 1,2-bonds of the conjugated diene monomer.In some embodiments, for example, when the copolymer is formed from butadiene, the copolymer may have a vinyl bond structural unit content of 5 to 85 mol%, 10 to 70 mol%, 20 to 60 mol%, or 30 to 55 mol%, relative to the total molar amount of conjugated diene (1,3-diene structure) monomer units incorporated in 3,4-, 1,4-, and 1,2-bonded bonding modes of the conjugated diene monomer. In some embodiments, for example, when the copolymer is formed from a monomer including isoprene, the copolymer may have a vinyl bond structural unit content of 5 to 45 mol%, 5 to 35 mol%, 5 to 25 mol%, or 5 to 15 mol%, relative to the total molar amount of conjugated diene (1,3-diene structure) monomer units incorporated in 3,4-, 1,4-, and 1,2-bonded bonding modes of the conjugated diene monomer. In some embodiments, for example, when the copolymer may be formed from β-farnesene, the copolymer may have a content of vinyl bond structural units of 5 to 45 mol %, 5 to 35 mol %, 5 to 25 mol %, or 5 to 15 mol %, relative to the total molar amount of conjugated diene (1,3-diene structure) monomer units incorporated in 3,4-bond, 1,4-bond, and 1,2-bond bonding modes of the conjugated diene monomer.

[0088] The copolymer may have at least about 30 mol%, at least about 40 mol%, at least about 50 mol%, at least about 60 mol%, at least about 70 mol%, at least about 80 mol%, at least about 90 mol%, at least about 95 mol%, or at least about 96 mol%, and / or up to 100 mol% of the carbon-carbon double bonds in the structural units derived from the monomer containing the 1,3-diene structure hydrogenated, which value is sometimes referred to as the hydrogenation rate.

[0089] In the hydrogenation, the content of carbon-carbon double bonds in the structural units derived from the monomer containing a 1,3-diene structure in the copolymer is １ It can be measured by H-NMR analysis, and the hydrogenation rate can be obtained from the measured value.

[0090] The hydrogenation of the copolymer can be carried out after polymerization, or once the copolymer has been isolated after polymerization.

[0091] In some embodiments, in isolating the copolymer after polymerization, the resulting polymerization reaction solution may be poured into a poor solvent for the copolymer, such as methanol, to coagulate the copolymer, or the copolymer may be isolated by pouring the polymerization reaction solution into hot water together with steam to remove the solvent by azeotropy (steam stripping) and then drying.

[0092] In some embodiments, when the polymerization and the hydrogenation are carried out successively without isolating the copolymer, the α-olefin random copolymer can be isolated by pouring the hydrogenation reaction solution into a poor solvent for the α-olefin random copolymer, such as methanol, to solidify the α-olefin random copolymer, or by pouring the hydrogenation reaction solution into hot water together with steam to azeotropically remove the solvent (steam stripping), followed by drying and isolating the α-olefin random copolymer.

[0093] The copolymer can be hydrogenated in the presence of a hydrogenation catalyst such as Raney nickel; a heterogeneous catalyst in which a metal such as platinum (Pt), palladium (Pd), ruthenium (Ru), rhodium (Rh), or nickel (Ni) is supported on a support such as carbon, alumina, or diatomaceous earth; a Ziegler-based catalyst consisting of a combination of a transition metal compound (nickel octylate, nickel naphthenate, nickel acetylacetonate, cobalt octylate, cobalt naphthenate, cobalt acetylacetonate, etc.), an organoaluminum compound such as triethylaluminum or triisobutylaluminum, and an organolithium compound; or a metallocene-based catalyst consisting of a bis(cyclopentadienyl) transition metal compound such as titanium, zirconium, or hafnium, and an organometallic compound such as lithium, sodium, potassium, aluminum, zinc, or magnesium. The reaction can be carried out at a reaction temperature of about 20° C. to about 200° C., under a hydrogen pressure of about 0.1 MPa to about 20 MPa, for a time period of about 0.1 to 100 hours.

[0094] Methods of Producing Block and Triblock Copolymers Another aspect of the present disclosure relates to a method of producing a block copolymer, which may include polymerizing a first aromatic vinyl compound to produce a polymerized first aromatic vinyl compound and producing a copolymer according to the methods disclosed herein, thereby producing a block copolymer comprising the polymerized first aromatic vinyl compound and the copolymer, wherein the solvent contains the polymerized aromatic vinyl compound.

[0095] The polymerized first aromatic vinyl compound can be produced by polymerizing the first aromatic vinyl compound using an alkyllithium compound or a dilithium compound as an initiator. Examples of alkyllithium compounds include methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, and pentyllithium. Examples of dilithium compounds include naphthalenedilithium and dithiohexylbenzene.

[0096] In some embodiments, the polymerized first aromatic vinyl compound may correspond to polymer block (a), which may contain about 50% by weight or more, about 80% by weight or more, about 90% by weight or more, about 95% by weight or more, or substantially 100% by weight of the polymerized first aromatic vinyl compound. The polymer block (a) may be composed of only one type of first aromatic vinyl compound, or may be composed of two or more types of first aromatic vinyl compounds.

[0097] In some embodiments, the polymer block (a) may contain structural units derived from a copolymerizable monomer other than the first aromatic vinyl compound, for example, a conjugated diene such as isoprene, butadiene, 2,3-dimethyl-butadiene, 1,3-pentadiene, 1,3-hexadiene, β-farnesene, myrcene, etc., so long as the objectives and effects of the present invention are not hindered. The content of the structural units derived from the copolymerizable monomers in the polymer block (a) is preferably about 10% by mass or less, about 5% by mass or less, about 3% by mass or less, or substantially 0% by mass, based on the total mass of the polymer block (a).

[0098] The content of the polymer block (a) in the block copolymer can be at least about 5 wt%, at least about 10 wt%, at least about 15 wt%, at least about 20 wt%, at least about 25 wt%, at least about 30 wt%, at least about 35 wt%, at least about 40 wt%, at least about 45 wt%, at least about 50 wt%, at least about 55 wt%, at least about 60 wt%, or at least about 65 wt%, and / or about 70 wt% or less, 65 wt% or less, 60 wt% or less, 55 wt% or less, 50 wt% or less, 45 wt% or less, 40 wt% or less, 35 wt% or less, 30 wt% or less, 25 wt% or less, 20 wt% or less, 15 wt% or less, or 10 wt% or less, based on the total weight of the block copolymer. １ The content of the polymer block (a) in the block copolymer can be obtained from H-NMR analysis. As described above, the lower limit and the upper limit can be arbitrarily combined. For example, in some embodiments, the content of the polymer block (a) in the block copolymer can be 5 to 70 wt %, 10 to 65 wt %, or 15 to 60 wt %, based on the total weight of the block copolymer.

[0099] In some embodiments, the block copolymer may include the polymer block (a) and a polymer block (b) corresponding to a copolymer produced by a method disclosed herein (e.g., polymerizing a monomer having a 1,3-diene structure and 4 to 20 carbon atoms). The bond between the polymer block (a) and the polymer block (b) in the block copolymer may be linear, branched, radial, or any combination thereof.

[0100] For example, when the polymer block (a) is represented by "A" and the polymer block (b) is represented by "B", a diblock copolymer represented by "A-B", a triblock copolymer represented by "A-B-A", a tetrablock copolymer represented by "A-B-A-B", a pentablock copolymer represented by "A-B-A-B-A" and "B-A-B-A-B", (A-B) ｎ X-type copolymers (X represents a coupling agent residue, and n represents an integer of 3, 4, 5, 6, 7, 8, 9, 10, 12, 15, or 20 or more) are exemplified.

[0101] Herein, when the same type of polymer blocks can be linearly bonded via a bifunctional coupling agent or the like, the entirety of the bonded polymer blocks can be treated as one polymer block. Accordingly, including the above examples, polymer blocks that can be originally represented strictly as "Y-X-Y" (where "X" represents a coupling residue and "Y" represents a polymer block), can be represented as "Y" as a whole, unless it is particularly necessary to distinguish them from a single polymer block "Y". This type of polymer block containing a coupling agent residue will be treated as above in this specification. For example, a block copolymer containing a coupling agent residue that should be represented strictly as "A-B-X-B-A" (where "X" represents a coupling agent residue) will be represented as "A-B-A" and treated as an example of a triblock copolymer.

[0102] Examples of coupling agents include polyhydric epoxy compounds such as divinylbenzene, epoxidized 1,2-polybutadiene, epoxidized soybean oil, and 1,3-bis(N,N-glycidylaminomethyl)cyclohexane; halogen compounds such as dimethyldichlorosilane, dimethyldibromosilane, trichlorosilane, methyltrichlorosilane, tetrachlorosilane, and tetrachlorotin; ester compounds such as methyl benzoate, ethyl benzoate, phenyl benzoate, diethyl oxalate, diethyl malonate, diethyl adipate, dioctyl adipate, dimethyl phthalate, diethyl phthalate, dimethyl isophthalate, and dimethyl terephthalate; carbonate ester compounds such as dimethyl carbonate, diethyl carbonate, and diphenyl carbonate; and alkoxysilane compounds such as dimethyldimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, bis(trimethoxysilyl)hexane, and bis(triethoxysilyl)ethane.

[0103] In some embodiments, the block copolymer can be hydrogenated by the hydrogenation procedures disclosed herein. In some embodiments, the hydrogenated block copolymer can have a crystallization peak temperature (Tc) of about −8° C., about −5° C., about −4° C., about −3° C., about −2.5° C., about −2° C., about −1.5° C., about −1° C., about −0.5° C., about 0° C., about 0.5° C., about 1° C., about 1.5° C., about 2° C., about 2.5° C., to about 3° C., about 3.5° C., or about 4° C. In some embodiments, the hydrogenated block copolymer can have a crystallization peak temperature (Tc) of 4° C. or lower, 3.5° C. or lower, 3° C. or lower, 2.5° C. or lower, 2° C. or lower, 1.5° C. or lower, 1° C. or lower, 0.5° C. or lower, 0° C. or lower, −0.5° C. or lower, or −1° C. or lower. As noted above, the lower and upper limits can be combined in any manner. For example, in some embodiments, the hydrogenated block copolymer may have a peak crystallization temperature (Tc) of -8°C to 4°C, -5°C to 4°C, or -4°C to 4°C.

[0104] In some embodiments, the weight average molecular weight (Mw) of the hydrogenated block copolymer can be from 10,000 to 500,000 Da. For example, the weight average molecular weight can be at least 10,000 Da, at least 50,000 Da, at least 100,000 Da, at least 150,000 Da, at least 200,000 Da, at least 300,000 Da, or at least 400,000 Da, and / or no more than 500,000 Da, no more than 450,000 Da, no more than 350,000 Da, no more than 250,000 Da, no more than 200,000 Da, no more than 150,000 Da, no more than 100,000 Da, no more than 80,000 Da, or no more than 40,000 Da. In some embodiments, the weight average molecular weight (Mw) of the hydrogenated block copolymer can be from about 50,000 Da, or about 60,000 Da, or about 65,000 Da, or about 70,000 Da, to about 500,000 Da, or about 400,000 Da, or about 300,000 Da, or about 115,000 Da. As noted above, the lower and upper limits can be combined in any manner. For example, in some embodiments, the weight average molecular weight (Mw) of the hydrogenated block copolymer can be from 50,000 to 450,000 Da, from 100,000 to 400,000 Da, or from 150,000 to 350,000 Da.

[0105] The molecular weight distribution (Mw / Mn) of the hydrogenated block copolymer can be 1.5 or less, 1.4 or less, 1.3 or less, 1.2 or less, or 1.1 or less, or can be from about 1.01 to about 1.5, or to about 1.3, or to about 1.2, or to about 1.1, or to about 1.05.

[0106] In some embodiments, the hydrogenated block copolymer may have one or more functional groups, such as a carboxyl group, a hydroxyl group, an acid anhydride group such as maleic anhydride, an amino group, and / or an epoxy group, in the main chain and / or side chain, as long as the effects of the present invention are not significantly impaired.

[0107] According to another aspect of the present disclosure, a method for producing a triblock copolymer comprises producing the block copolymer according to the methods disclosed herein. Another aspect of the present disclosure relates to a method for producing a triblock copolymer, which may include producing the block copolymer according to the methods disclosed herein, and subsequently polymerizing a second aromatic vinyl compound after the block copolymer is obtained, thereby producing a triblock copolymer comprising the polymerized first aromatic vinyl compound, the copolymer, and the polymerized second aromatic vinyl compound. Another aspect of the present disclosure may include a method for producing a triblock copolymer, the method comprising: producing the block copolymer comprising the polymerized first aromatic vinyl compound and the copolymer according to the method disclosed herein; producing the block copolymer comprising the polymerized second aromatic vinyl compound and the copolymer according to a method similar to the method disclosed herein; and coupling the block copolymer comprising the polymerized first aromatic vinyl compound and the copolymer and the block copolymer comprising the second aromatic vinyl compound and the copolymer by a coupling reaction, thereby producing the triblock copolymer comprising the polymerized first aromatic vinyl compound, the copolymer, and the polymerized second aromatic vinyl compound. The coupling reaction may also include a coupling reaction using the above-mentioned coupling agent. The first aromatic vinyl compound and the second aromatic vinyl compound may be the same or different from each other.

[0108] In some embodiments, the polymerized second aromatic vinyl compound may correspond to polymer block (c). In some embodiments, the triblock copolymer may include the aforementioned polymer block (a) and polymer block (c), which may contain structural units derived from the second aromatic vinyl compound in an amount of about 50% by weight or more, about 80% by weight or more, about 90% by weight or more, about 95% by weight or more, or substantially 100% by weight. The polymer block (c) may be composed of only one second aromatic vinyl compound, or may be composed of two or more second aromatic vinyl compounds. The polymer block (c) may be the same as or different from the polymer block (a) in terms of the structure of the structural units and / or the polymer chain length.

[0109] In some embodiments, the polymer block (c) may contain structural units derived from a copolymerizable monomer other than the second aromatic vinyl compound, for example, a conjugated diene such as isoprene, butadiene, 2,3-dimethyl-butadiene, 1,3-pentadiene, 1,3-hexadiene, β-farnesene, myrcene, etc., so long as the objectives and effects of the present invention are not hindered. The content of the structural units derived from the copolymerizable monomers in the polymer block (c) is preferably about 10% by mass or less, about 5% by mass or less, about 3% by mass or less, or substantially 0% by mass, based on the total mass of the polymer block (c).

[0110] In some embodiments, the first aromatic vinyl compound and the second aromatic vinyl compound are each independently selected from the group consisting of styrene, α-methylstyrene, 4-methylstyrene, o-methylstyrene, m-methylstyrene, β-methylstyrene, 2,6-dimethylstyrene, 2,4-dimethylstyrene, α-methyl-o-methylstyrene, α-methyl-m-methylstyrene, α-methyl-p-methylstyrene, β-methyl-o-methylstyrene, β-methyl-m-methylstyrene, β-methyl-p-methylstyrene, 2,4,6-trimethylstyrene, α-methyl-2,6-dimethylstyrene, α-methyl-2,4-dimethylstyrene, 3-methyl-2,6-dimethylstyrene, f-methyl-2,4-dimethylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, 2,6-dichlorostyrene, 2,4-dichlorostyrene, α ... The aromatic vinyl compounds may include compounds selected from the group consisting of o-o-chlorostyrene, α-chloro-m-chlorostyrene, α-chloro-p-chlorostyrene, β-chloro-o-chlorostyrene, β-chloro-m-chlorostyrene, β-chloro-p-chlorostyrene, 2,4,6-trichlorostyrene, α-chloro-2,6-dichlorostyrene, α-chloro-2,4-dichlorostyrene, β-chloro-2,6-dichlorostyrene, β-chloro-2,4-dichlorostyrene, o-t-butylstyrene, m-t-butylstyrene, p-butylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-chloromethylstyrene, m-chloromethylstyrene, p-chloromethylstyrene, o-bromomethylstyrene, m-bromomethylstyrene, p-bromomethylstyrene, styrene derivatives substituted with a silyl group, indene, and vinylnaphthalene. The aromatic vinyl compounds may be used alone or in combination of two or more.

[0111] In some embodiments, each of the first aromatic vinyl compound and the second aromatic vinyl compound can include styrene.

[0112] In some embodiments, the triblock copolymer may have a content of vinyl bond structural units of 5 to 85 mol % relative to the total molar amount of conjugated diene (1,3-diene structure) monomer units incorporated in the bonding modes of 3,4-bonds, 1,4-bonds, and 1,2-bonds of the conjugated diene monomers. In some embodiments, the triblock copolymer may have a content of vinyl bond structural units of at least 5 mol%, at least 10 mol%, at least 15 mol%, at least 20 mol%, at least 30 mol%, at least 40 mol%, at least 50 mol%, at least 60 mol%, at least 70 mol%, or at least 80 mol%, and / or 85 mol% or less, 75 mol% or less, 65 mol% or less, 55 mol% or less, 45 mol% or less, 35 mol% or less, 25 mol% or less, 20 mol% or less, 15 mol% or less, or 10 mol% or less, based on the total molar amount of conjugated diene (1,3-diene structure) monomer units incorporated in the conjugated diene monomer via 3,4-bonds, 1,4-bonds, and 1,2-bonds. As mentioned above, the lower and upper limits can be combined arbitrarily. For example, in some embodiments, the triblock copolymer may have a vinyl bond structural unit content of 5 to 85 mol%, 5 to 75 mol%, 5 to 65 mol%, or 5 to 55 mol%, based on the total molar amount of conjugated diene (1,3-diene structure) monomer units incorporated in the bonding modes of 3,4-bonds, 1,4-bonds, and 1,2-bonds of the conjugated diene monomer. In some embodiments, for example, when the polymer block (b) in the triblock copolymer may be formed from butadiene, the triblock copolymer may have a vinyl bond structural unit content of 5 to 85 mol%, 10 to 70 mol%, 20 to 60 mol%, or 30 to 55 mol%, based on the total molar amount of conjugated diene (1,3-diene structure) monomer units incorporated in the bonding modes of 3,4-bonds, 1,4-bonds, and 1,2-bonds of the conjugated diene monomer.In some embodiments, for example, when the polymer block (b) in the triblock copolymer can be formed from a monomer containing isoprene, the triblock copolymer can have a content of vinyl bond structural units of 5 to 45 mol %, 5 to 35 mol %, 5 to 25 mol %, or 5 to 15 mol % relative to the total molar amount of conjugated diene (1,3-diene structure) monomer units incorporated in the bonding modes of 3,4-bonds, 1,4-bonds, and 1,2-bonds of the conjugated diene monomers. In some embodiments, for example, when the polymer block (b) in the triblock copolymer can be formed from β-farnesene, the triblock copolymer can have a content of vinyl bond structural units of 5 to 45 mol %, 5 to 35 mol %, 5 to 25 mol %, or 5 to 15 mol % relative to the total molar amount of conjugated diene (1,3-diene structure) monomer units incorporated in the bonding modes of 3,4-bonds, 1,4-bonds, and 1,2-bonds of the conjugated diene monomers.

[0113] In some embodiments, the triblock copolymer can have a styrene content of 5 to 70 wt%, based on the total weight of the triblock copolymer. For example, the styrene content can be at least 5 wt%, at least 10 wt%, at least 15 wt%, at least 20 wt%, at least 25 wt%, at least 30 wt%, at least 35 wt%, at least 40 wt%, at least 45 wt%, at least 50 wt%, at least 55 wt%, at least 60 wt%, or at least 65 wt%, and / or no more than 70 wt%, no more than 65 wt%, no more than 60 wt%, no more than 55 wt%, no more than 50 wt%, no more than 45 wt%, no more than 40 wt%, no more than 35 wt%, no more than 30 wt%, no more than 25 wt%, no more than 20 wt%, no more than 15 wt%, or no more than 10 wt%. As noted above, the lower and upper limits can be combined in any manner. For example, in some embodiments, the triblock copolymer can have a styrene content of from 10 to 65 weight percent, from 15 to 60 weight percent, or from 20 to 55 weight percent, based on the total weight of the triblock copolymer.

[0114] In some embodiments, the triblock copolymer may have a glass transition temperature (Tg) of from −60° C. to 25° C., as measured by DSC at 10° C. / min. The Tg may be at least −60° C., at least −50° C., at least −40° C., at least −30° C., at least −20° C., at least −10° C., at least 0° C., at least 5° C., at least 10° C., at least 15° C., or at least 20° C., and / or 25° C. or less, 20° C. or less, 15° C. or less, 10° C. or less, 5° C. or less, 0° C. or less, −10° C. or less, or −20° C. or less.

[0115] In some embodiments, the triblock copolymer may have a melt flow rate (MFR) at 230° C. and 2.16 kg of 250 g / 10 min or less, as measured according to ISO 1133. The MFR may be 250 g / 10 min or less, 100 g / 10 min or less, 50 g / 10 min or less, 20 g / 10 min or less, 10 g / 10 min or less, 5 g / 10 min or less, 3 g / 10 min or less, 1 g / 10 min or less, 0.5 g / 10 min or less, 0.1 g / 10 min or less, and / or greater than 100 g / 10 min, greater than 50 g / 10 min, greater than 20 g / 10 min, greater than 10 g / 10 min, greater than 5 g / 10 min, greater than 3 g / 10 min, greater than 1 g / 10 min, greater than 0.5 g / 10 min, greater than 0.1 g / 10 min, or greater than 0 g / 10 min. In some embodiments, the MFR may be less than 0.1 g / 10 min or no flow, i.e., in some embodiments, the MFR may be 0 g / 10 min or more and 0.1 g / 10 min or less.

[0116] In some embodiments, the first aromatic vinyl compound and the second aromatic vinyl compound can be polymerized by ionic polymerization.

[0117] In some embodiments, the triblock copolymer may be hydrogenated by the hydrogenation procedures disclosed herein. In some embodiments, the hydrogenated triblock copolymer may comprise the following repeat units:

[0118] (wherein i, k, l, m, and n are positive integers)

[0119] In some embodiments, the hydrogenated triblock copolymer may have a crystallization peak temperature (Tc) of about −8° C., about −5° C., about −4° C., about −3° C., about −2.5° C., about −2° C., about −1.5° C., about −1° C., about −0.5° C., about 0° C., about 0.5° C., about 1° C., about 1.5° C., about 2° C., or about 2.5° C., to about 3° C., about 3.5° C., or about 4° C. In some embodiments, the hydrogenated triblock copolymer may have a crystallization peak temperature (Tc) of 4° C. or lower, 3.5° C. or lower, 3° C. or lower, 2.5° C. or lower, 2° C. or lower, 1.5° C. or lower, 1° C. or lower, 0.5° C. or lower, 0° C. or lower, −0.5° C. or lower, or −1° C. or lower. As mentioned above, the lower and upper limits may be combined in any manner. For example, in some embodiments, the hydrogenated triblock copolymer may have a peak crystallization temperature (Tc) of -8°C to 4°C, -5°C to 4°C, or -4°C to 4°C.

[0120] In some embodiments, the weight average molecular weight (Mw) of the hydrogenated triblock copolymer can be from 10,000 Da to 500,000 Da. For example, the weight average molecular weight can be at least 10,000 Da, at least 50,000 Da, at least 100,000 Da, at least 150,000 Da, at least 200,000 Da, at least 300,000 Da, or at least 400,000 Da, and / or no more than 500,000 Da, no more than 450,000 Da, no more than 350,000 Da, no more than 250,000 Da, no more than 200,000 Da, no more than 150,000 Da, no more than 100,000 Da, no more than 80,000 Da, or no more than 40,000 Da. In some embodiments, the weight average molecular weight (Mw) of the hydrogenated triblock copolymer can be from about 50,000 Da, or about 60,000 Da, or about 65,000 Da, or about 70,000 Da, to about 500,000 Da, or about 400,000 Da, or about 300,000 Da, or about 115,000 Da. As noted above, the lower and upper limits can be combined in any manner. For example, in some embodiments, the weight average molecular weight (Mw) of the hydrogenated triblock copolymer can be from 50,000 to 450,000 Da, from 100,000 to 400,000 Da, or from 150,000 to 350,000 Da.

[0121] The molecular weight distribution (Mw / Mn) of the hydrogenated triblock copolymer can be 1.5 or less, 1.4 or less, 1.3 or less, 1.2 or less, or 1.1 or less, or from about 1.01 to about 1.5, or to about 1.3, or to about 1.2, or to about 1.1, or to about 1.05.

[0122] In some embodiments, the hydrogenated triblock copolymer may have one or more functional groups, such as a carboxyl group, a hydroxyl group, an acid anhydride group such as maleic anhydride, an amino group, and / or an epoxy group, in the main chain and / or side chain, as long as the effects of the present invention are not significantly impaired.

[0123] In some embodiments, the compound comprising the hydrogenated triblock copolymer and oil (hydrogenated triblock copolymer / oil=100 phr / 200 phr) has １３ C DD / MAS The ion exchange rate may have a full width at half height as measured by NMR of greater than 0.65 ppm, greater than 0.66 ppm, greater than 0.67 ppm, greater than 0.68 ppm, greater than 0.69 ppm, greater than 0.70 ppm, greater than 0.71 ppm, greater than 0.72 ppm, greater than 0.73 ppm, greater than 0.74 ppm, greater than 0.75 ppm, or greater than 0.76 ppm, and / or less than 0.78 ppm, less than 0.77 ppm, less than 0.76 ppm, less than 0.75 ppm, less than 0.74 ppm, less than 0.73 ppm, less than 0.72 ppm, less than 0.71 ppm, less than 0.70 ppm, less than 0.69 ppm, less than 0.68 ppm, less than 0.67 ppm, or less than 0.66 ppm. The method for measuring the half-width is further described in the Examples. As described above, the lower limit and the upper limit can be combined in any manner. For example, in some embodiments, the half-width can be greater than 0.65 ppm and less than 0.78 ppm, greater than 0.66 ppm and less than 0.78 ppm, or greater than 0.67 ppm and less than 0.78 ppm.

[0124] A compound containing the hydrogenated triblock copolymer, oil, and polypropylene (PP) (hydrogenated triblock copolymer / oil / PP=100 phr / 100 phr / 40 phr) can be formed into a sheet, for example, as shown in FIG. 2, and sandwiched between two random polypropylene (PP, 2 mm thick, Flint Hills, "13T25A") plates to test for oil retention. In some embodiments, when testing a sheet having a composition of hydrogenated triblock copolymer / oil / PP=100 / 100 / 40, the oil retention may be less than 2.0 wt.%, less than 1.9 wt.%, less than 1.8 wt.%, less than 1.7 wt.%, less than 1.6 wt.%, less than 1.5 wt.%, less than 1.4 wt.%, less than 1.3 wt.%, less than 1.2 wt.%, or less than 1.1 wt.%, and / or more than 0.1 wt.%, more than 0.2 wt.%, more than 0.3 wt.%, more than 0.4 wt.%, more than 0.5 wt.%, more than 0.6 wt.%, more than 0.7 wt.%, more than 0.8 wt.%, or more than 0.9 wt.%, based on the total weight of the sheet, as further described in the examples. In some embodiments, when a compound comprising the hydrogenated triblock copolymer, oil, and PP (hydrogenated triblock copolymer / oil / PP=100 / 200 / 20) can be formed into a sheet, the sheet can be tested, and the oil retention can be less than 5.0 wt.%, less than 4.9 wt.%, less than 4.8 wt.%, less than 4.7 wt.%, less than 4.6 wt.%, less than 4.5 wt.%, less than 4.4 wt.%, less than 4.3 wt.%, less than 4.2 wt.%, less than 4.1 wt.%, less than 4.0 wt.%, less than 3.9 wt.%, less than 3.8 wt.%, less than 3.7 wt.%, less than 3.6 wt.%, or less than 3.5 wt.%, and / or more than 3.0 wt.%, more than 3.1 wt.%, more than 3.2 wt.%, or more than 3.3 wt.%, based on the total weight of the sheet.

[0125] Anionic Polymerization Initiator The copolymer can be produced, for example, by an anionic polymerization method requiring an anionic polymerization initiator. In some embodiments, the anionic polymerization initiator can include at least one initiator selected from the group consisting of alkali metals, alkaline earth metals, lanthanide rare earth metals, and compounds containing earth metals and lanthanide rare earth metals. In some embodiments, the anionic polymerization initiator can include at least one initiator selected from the group consisting of alkali metals, compounds containing alkali metals, and organic alkali metal compounds. In some embodiments, the anionic polymerization initiator can include at least one alkali metal selected from the group consisting of lithium, sodium, and potassium. In some embodiments, the anionic polymerization initiator can include at least one alkaline earth metal selected from the group consisting of beryllium, magnesium, calcium, strontium, and barium.

[0126] In some embodiments, the anionic polymerization initiator may include at least one lanthanoid rare earth metal selected from the group consisting of lanthanum and neodymium. In some embodiments, the anionic polymerization initiator may include at least one organolithium compound selected from the group consisting of methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium, stilbenelithium, dilithiomethane, dilithionaphthalene, and 1,4-dilithiobutane. In some embodiments, the anionic polymerization initiator may include an organolithium compound. In some embodiments, the anionic polymerization initiator may include at least one organolithium compound selected from the group consisting of dilithiobutane, 1,4-dilithio-2-ethylcyclohexane, 1,3,5-trilithiobenzene, sodium naphthalene, and potassium naphthalene.

[0127] <Solvent> Polymerization of the monomers may be carried out in the presence of a solvent. The solvent is not particularly limited as long as it is inert to the initiator and does not adversely affect the polymerization. In some embodiments, the solvent may include at least one selected from the group consisting of saturated aliphatic hydrocarbons, saturated alicyclic hydrocarbons, and aromatic hydrocarbons. In some embodiments, the solvent may include at least one selected from the group consisting of cyclopentane, cyclohexane, and methylcyclohexane. In some embodiments, the solvent may include at least one saturated aliphatic hydrocarbon selected from the group consisting of n-pentane, isopentane, n-hexane, n-heptane, and isooctane. In some embodiments, the solvent may include at least one saturated aliphatic hydrocarbon such as hexane, cyclohexane, heptane, octane, and decane. In some embodiments, the solvent may include at least one selected from the group consisting of pentane, benzene, toluene, and xylene.

[0128] Lewis Base: A Lewis base may be used as a co-catalyst in the polymerization. In some embodiments, the solvent may further comprise a Lewis base. In some embodiments, the solvent may further comprise at least one Lewis base selected from the group consisting of dibutyl ether, diethyl ether, tetrahydrofuran, dioxane, tetramethylethylenediamine, hexamethyltriethylenetetramine, 1,2-diethoxypropane, ditetrahydrofurylpropane, ethylene glycol diethyl ether, pyridine, tertiary amines, alkali metal alkoxides, and phosphine compounds. Examples of Lewis bases include ethers such as dimethyl ether, diethyl ether, and tetrahydrofuran; glycol ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether; and amines such as triethylamine, N,N',N'-tetramethylethylenediamine, and N-methylmorpholine. In some embodiments, the Lewis base may comprise tetrahydrofuran and / or tetramethylethylenediamine. In some embodiments, the Lewis base may be tetrahydrofuran. In some embodiments, the Lewis base may be tetramethylethylenediamine.

[0129] In some embodiments, the amount of Lewis base is in the range of 0.01 to 1,000 molar equivalents relative to 1 mole of anionic polymerization initiator, hi some embodiments, the amount of Lewis base is at least 0.01 molar equivalent, at least 0.1 molar equivalent, at least 0.5 molar equivalent, at least 2 molar equivalents, at least 5 molar equivalents, at least 10 molar equivalents, at least 20 molar equivalents, at least 50 molar equivalents, at least 100 molar equivalents, at least 200 molar equivalents, at least 300 molar equivalents, at least 500 molar equivalents, at least 700 molar equivalents, at least 800 molar equivalents, at least 900 molar equivalents, at least 100 molar equivalents, at least 200 molar equivalents, at least 300 molar equivalents, at least 500 molar equivalents, at least 700 molar equivalents, at least 800 molar equivalents, at least 1 ... The amount of Lewis base may be 1,000 molar equivalents, or at least 900 molar equivalents, and / or 1,000 molar equivalents or less, 950 molar equivalents or less, 850 molar equivalents or less, 750 molar equivalents or less, 550 molar equivalents or less, 350 molar equivalents or less, 250 molar equivalents or less, 150 molar equivalents or less, 75 molar equivalents or less, 40 molar equivalents or less, 30 molar equivalents or less, 25 molar equivalents or less, 15 molar equivalents or less, 7 molar equivalents or less, 5 molar equivalents or less, 3 molar equivalents or less, or 1 molar equivalent or less, relative to 1 mol of anionic polymerization initiator. As mentioned above, the lower and upper limits can be arbitrarily combined. For example, the amount of Lewis base may be 0.1 to 950 molar equivalents, 0.5 to 850 molar equivalents, or 2 to 750 molar equivalents relative to 1 mol of anionic polymerization initiator.

[0130] In some embodiments, the method may include adding a polymerization terminator to the solvent. The addition of the polymerization terminator may occur prior to hydrogenation of the copolymer, the block copolymer, and / or the triblock copolymer. In some embodiments, the polymerization terminator may include an active hydrogen compound such as an alcohol, a carboxylic acid, or water. In some embodiments, the polymerization terminator may include an alcohol.

[0131] In some embodiments, the method of preparation may further include precipitating the triblock copolymer in another solvent.

[0132] In some embodiments, the production method may further include washing the polymerization reaction solution with water, separating, and drying.

[0133] Another aspect of the present disclosure relates to triblock copolymers produced by the methods disclosed herein. In some embodiments, the triblock copolymers can be incorporated into formulations that may include, for example, paraffin oil, process oil, bio-based oil, tackifiers, fillers, additives, and polyolefins such as polyethylene and polypropylene.

[0134] The present invention will be explained in more detail with reference to examples, but the scope of the present invention is not limited to these examples.

[0135] [Preparation of Hydrogenated Triblock Copolymer] [Example 1] 50 kg of cyclohexane as a solvent and 0.024 kg of 10.5 wt % sec-butyllithium (cyclohexane solution) as an initiator were placed in a nitrogen-purged, dried pressure vessel, and the temperature was raised to 50°C. 1 kg of styrene was added thereto, and the solution was polymerized for 60 minutes. Thereafter, at the same temperature, 0.98 kg of THF as a Lewis base was added, followed by 4.8 kg of butadiene over a period of 300 minutes, and the reaction was continued for another 30 minutes. During the polymerization of butadiene, the vessel was appropriately cooled so that the temperature fluctuations were within 2°C (i.e., 50±2°C) as measured by a temperature controller (LT370, Chino Corporation), as listed in Table 1. Polymerization mixture samples were periodically taken. １The 1,3-diene conversion and the VC of each segment were measured by H-NMR. Furthermore, 1 kg of styrene was added at the same temperature and polymerized for 60 minutes, after which the polymerization was terminated with methanol to obtain a reaction solution containing a polystyrene-polybutadiene-polystyrene triblock copolymer. A Ziegler hydrogenation catalyst formed from nickel octylate and trimethylaluminum was added to this reaction solution under a hydrogen atmosphere, and the hydrogenation reaction was carried out at 80°C for 5 hours under a hydrogen pressure of 1 MPa. After cooling and depressurization, the hydrogenation catalyst was removed by washing with water, and the residue was concentrated and dried under vacuum to obtain a hydrogenated product of a polystyrene-poly(ethylene / butylene)-polystyrene triblock copolymer (hereinafter referred to as "hydrogenated triblock copolymer" or "SEBS").

[0136] [Examples 2 to 5 and Comparative Examples 1 to 3] Hydrogenated triblock copolymers of Examples 2 to 5 and Comparative Examples 1 to 3 were prepared in the same manner as in Example 1, except that only the diene polymerization conditions shown in Table 1 were different.

[0137]

[0138] [Properties of Hydrogenated Triblock Copolymers] The chemical structures of the obtained hydrogenated triblock copolymers were evaluated according to the following methods, and the results are summarized in Table 2. The hydrogenated triblock copolymers in Examples 1 to 5, which were prepared according to the disclosed methods, had a consistency of 4.8 mol% or less and a crystallization temperature of 3.6°C or less. In contrast, the hydrogenated triblock copolymers in Comparative Examples 1 to 3, which were prepared over a wider diene polymerization temperature range, had a consistency of 6.5 mol% or more and a higher crystallization temperature of 4.7°C or more.

[0139]

[0140] <Consistency and Total Vinyl Content> The vinyl content (VC) is the ratio of conjugated diene monomer units incorporated via 1,2-bonds and 3,4-bonds to the total molar amount of conjugated diene monomer units incorporated in the bonding modes of 3,4-bonds, 1,4-bonds, and 1,2-bonds of the conjugated diene monomer before hydrogenation. VC is calculated by dividing the VC of the triblock copolymer before hydrogenation by the total molar amount of the conjugated diene monomer units incorporated via 1,2-bonds and 3,4-bonds. １ The total vinyl content was measured using H-NMR spectroscopy. During the polymerization of butadiene, samples of the polymerization mixture were taken every 2 minutes, and after adding methanol to the sample to quench the polymerization process, the samples were analyzed. Here, the total vinyl content is the content of vinyl bond structural units relative to the total molar amount of conjugated diene (1,3-diene structure) monomer units incorporated in the conjugated diene monomer in the bonding modes of 3,4-bonds, 1,4-bonds, and 1,2-bonds.

[0141] The VC was calculated for each of the 10 segments in the diene polymer block (polymer block (B)). For example, see FIG. 1. The first to tenth segments are: １ As obtained from H-NMR analysis, the conversion rates were about 10%, about 20%, about 30%, about 40%, about 50%, about 60%, about 70%, about 80%, about 90%, and about 100%. The ten sections had approximately the same mass. That is, for the polymerization mixture sample collected as described above, the VC value obtained by analyzing a sample at the time when the butadiene conversion reached about 10% was designated as the VC value of the first section. Similarly, the VC values ​​obtained by analyzing the polymerization mixture sample at the time when the butadiene conversion reached about 20%, about 30%, about 40%, about 50%, about 40%, about 50%, about 60%, about 70%, about 80%, about 90%, and about 100% were designated as the VC values ​​of the second, third, fourth, fifth, sixth, seventh, eighth, ninth, and tenth sections, respectively. Consistency was achieved by taking the difference between the maximum and minimum VC measured for the 10 sections of the diene polymer block, and the VC value obtained by analyzing the last sample of the polymerization mixture, i.e., the VC value of the 10th section, was taken as the total VC value.

[0142] <Amount of vinyl bond in polymer block (B)> A non-hydrogenated triblock copolymer was dissolved in CDCl ３ Dissolved in １ Analysis was performed by H-NMR measurement [apparatus: "AVANCE 400 NanoBay" (available from Bruker Corporation), measurement temperature: 30°C]. The amount of vinyl bonds was calculated from the ratio of the peak area corresponding to 1,2-bond units in the butadiene structural units to the total peak area of ​​structural units derived from butadiene. The amount of vinyl bonds corresponds to each vinyl content (VC) in the explanation section of the evaluation method for "consistency and total vinyl content" above, and the VC value of the 10th section corresponds to the total vinyl content described above.

[0143] <Measurement of Crystallization Peak Temperature (Tc) and Glass Transition Temperature (Tg)> Using differential scanning calorimetry (DSC), the crystallization peak temperature (Tc) was determined from the exothermic peak observed during the temperature drop in Step 4 below. The glass transition temperature (Tg) can also be determined from the endothermic peak observed during the temperature rise in Step 3 below.

[0144] Apparatus: DSC Q2000 (manufactured by TA Instruments) Heating rate: 10°C / min Heating rate: 10°C / min Nitrogen flow rate: 50 mL / min Temperature profile 1st time: Equilibrate at 30°C → 200°C (hold for 3 minutes) 2nd time: 200°C → -60°C (hold for 3 minutes) 3rd time: -60°C → 200°C (hold for 3 minutes) 4th time: 200°C → -60°C.

[0145] <Styrene content> The hydrogenated triblock copolymer was ３ Dissolved in １ The polymer was analyzed by H-NMR measurement [apparatus: "AVANCE 400 NanoBay" (available from Bruker), measurement temperature: 30°C], and the styrene content was calculated from the peak intensity derived from styrene.

[0146] <Hydrogenation rate of polymer block (B)> The hydrogenated triblock copolymer was ３ Dissolved in １Analysis was performed by H-NMR measurement [apparatus: "AVANCE 400 NanoBay" (available from Bruker), measurement temperature: 30°C]. The hydrogenation rate was calculated from the ratio of the peak area derived from hydrogenated butadiene to the peak area derived from residual olefins of butadiene.

[0147] <Weight-average molecular weight (Mw)> The weight-average molecular weight (Mw) of the hydrogenated triblock copolymer, expressed relative to polystyrene, was determined by gel permeation chromatography (GPC) under the conditions described below. In addition, the Mw of only the polymer block (a) was measured by the same procedure before adding the conjugated diene compound.

[0148] (GPC measurement device and measurement conditions) Device: GPC device "HLC-8020" (available from Tosoh Corporation) Separation column: Two columns of "TSKgel (registered trademark) G4000HX" (available from Tosoh Corporation) were connected in series. Eluent: tetrahydrofuran Eluent flow rate: 0.7 mL / min Sample concentration: 5 mg / 10 mL Column temperature: 40°C Detector: differential refractive index (RI) detector Calibration curve: prepared using standard polystyrene.

[0149] Extrusion and Injection Molding of Hydrogenated Triblock Copolymer Blended with Oil: The hydrogenated triblock copolymer was extruded in a 27 mm Leistritz twin-screw extruder equipped with 11 barrel zones, a 52:1 L / D ratio, a gear pump, a screen changer, and a 6-hole die. Pellets were made through a Gala underwater cutter and spin dryer system using water at approximately 50°F to 60°F. Oil (Krystol 550, Petro-Canada Lubricants Inc.) and homopolypropylene (P4G2Z, Flint Hills) were added to the hydrogenated triblock copolymer crumb using a high-intensity mixer, which generated shear and heat in the hydrogenated triblock copolymer to facilitate the incorporation and homogenization of the oil throughout and between batches. For half-width NMR studies, 100 parts by weight of the hydrogenated triblock copolymer was mixed with 200 parts by weight of oil. For oil retention evaluation, formulations were prepared according to the compositions shown in Table 3.

[0150] Sample plaques for oil retention and half-width NMR studies were obtained by injection molding using a Toyo Machinery & Metal Co., Ltd. (TOYO) Si-90-6 apparatus equipped with an F200HDU high-speed injection unit. Injection screw conditions ranged from 200°C to 230°C, and mold temperatures ranged from 20°C to 45°C. A mold insert equipped with a single gate system was used to prepare sheets measuring 2 mm thick by 125 mm long by 125 mm wide, from which test samples were die-cut into 1" x 2" (1 inch x 2 inches) shapes to ensure uniformity. Test conditions are described herein, and the results of the oil retention and half-width NMR evaluations are summarized in Tables 3 and 4, respectively. In Table 3, Examples 1A to 5A contained the hydrogenated triblock copolymers described in Examples 1 to 5, respectively, and Comparative Examples 1A to 3A contained the hydrogenated triblock copolymers described in Comparative Examples 1 to 3, respectively. The oil retention evaluation results are also illustrated in Figure 2. Examples 1A to 5A, which contained the hydrogenated triblock copolymers of Examples 1 to 5, respectively, had oil retention of 1.7 wt % or less (at SEBS / oil / PP = 100 / 100 / 40) and 4.7 wt % or less (at SEBS / oil / PP = 100 / 200 / 20). Comparative Examples 1A to 3A had oil retention of 2.0 wt % or more (at SEBS / oil / PP = 100 / 100 / 40) and 5.1 wt % or more (at SEBS / oil / PP = 100 / 200 / 20). Thus, the hydrogenated triblock copolymers of Examples 1 to 5 imparted significantly lower oil retention in Examples 1A to 5A compared to the hydrogenated triblock copolymers of Comparative Examples 1 to 3.

[0151]

[0152] <Oil Retention> An injection-molded RCP PP plaque with an MFR of 25 was used as a substrate. The side of the RCP PP plaque without the ejector pin was used as the test surface. Four rectangular plaque samples were cut out from the sample plaque to be tested using a film die, and all four plaque samples were weighed together. This weight was W １The RCP PP plaques were placed on a metal oil holder. These plaques were placed individually (not stacked) on the RCP PP plaques, positioned to avoid contact with adjacent plaques. See Figure 3 for an example. Another RCP PP plaque was placed on top of the plaque with the injector pin mark facing away from the plaque. A metal weight plate was placed on top of the RCP PP / four plaques / RCP PP specimen set to prevent warping of the plaques. The specimen fixture was placed in an oven set at 80°C and removed from the oven after 500 hours. The metal plate was left on top of the specimen set, and the specimen set was allowed to cool on the counter for a total of one hour. For the final 15 minutes, the metal plate was removed from the top of the specimen set to facilitate the cooling process. The four specimens were then weighed together after removing the top RCP PP plaque. This weight was calculated as W ２ The weight of the four plates was checked again to ensure that the weight of the sample had not changed and that the sample had cooled completely. The weight loss was calculated using the following formula: Weight Loss in % = {(W １ -W ２ ) / W １}×100%.

[0153] In Table 4, Examples 1B through 5B contained the hydrogenated triblock copolymers described in Examples 1 through 5, respectively, and Comparative Examples 1B through 3B contained the hydrogenated triblock copolymers described in Comparative Examples 1 through 3, respectively.

[0154]

[0155] <Half-width-NMR> The half-width-NMR was calculated by the following steps. １３CDD / MAS NMR spectra were acquired under the following conditions. For each spectral peak after Fourier transformation, waveform separation analysis was performed by optimizing the peak shape generated by a Lorentzian waveform, a Gaussian waveform, or a mixture of both. In the optimization calculation, the optimal value was calculated by the nonlinear least-squares method using the center position, height, and half-width-NMR as variable parameters. Peaks between 13 ppm and 15 ppm were selected, and half-width-NMR was calculated.

[0156] Equipment: JNM-ECZ500R (JEOL RESONANCE Inc.) Measurement method: DD / MAS Measurement nuclear frequency: 124.50 MHz ( １３ C nucleus) Sample tube: Zirconia 3.2 mmφ Sample rotation frequency: 10 kHz Spectral width: 62.5 kHz Pulse width: 2.76 microseconds (90° pulse) Pulse repetition time: 10 seconds Number of measurement points: 2048 Measurement temperature: 31°C

[0157] As described above, the above-described manufacturing method can be used to produce copolymers with improved oil retention. The triblock copolymers obtained by the above-described manufacturing method can be incorporated into formulations that may contain, for example, paraffin oil, process oil, bio-based oil, tackifiers, fillers, additives, and polyolefins such as polyethylene and polypropylene. Also, according to one aspect of the present invention, a method for manufacturing copolymers suitable for 2K molding, grip, and oil gel applications is provided.

[0158] 1 1st section (segment) 2 2nd section (segment) 3 3rd section (segment) 4 4th section (segment) 5 5th section (segment) 6 6th section (segment) 7 7th section (segment) 8 8th section (segment) 9 9th section (segment) 10 10th section (segment) 11 ethylene-butylene block 21 styrene block 22 random copolymer block 23 vinyl bond structure 30 styrene-ethylene-butylene-styrene block copolymer (SEBS) 40 formula for calculating consistency 51 Evaluation results of each example sample and each comparative example sample having a composition of SEBS / oil / PP = 100 phr / 100 phr / 40 phr (relationship between consistency and oil retention) 52 Evaluation results of each example sample and each comparative example sample having a composition of SEBS / oil / PP = 100 phr / 200 phr / 20 phr (relationship between consistency and oil retention) 53 Random polypropylene (rPP) plaque / four flat plate samples / schematic diagram of a sample set for oil retention test in which random polypropylene (rPP) plaques are stacked 61 Polypropylene (PP) plaque 62 Rectangular plate-shaped sample

Claims

1. A method for producing a copolymer comprising the steps of: The method includes polymerizing a monomer having a 1,3-diene structure and 4 to 20 carbons in a solvent in the presence of an anionic polymerization initiator to produce a copolymer; A method for producing a copolymer, wherein the temperature change during said polymerization is less than 15°C.

2. A method for producing a copolymer comprising the steps of: polymerizing a monomer having a 1,3-diene structure and 4 to 20 carbon atoms in a solvent in the presence of an anionic polymerization initiator; cooling the temperature during said polymerization so that the consistency of said copolymer is 6 mol % or less; A method for producing a copolymer comprising:

3. 3. The process of claim 2, wherein said cooling comprises maintaining a temperature change during said polymerization of less than 15°C.

4. The method according to claim 1 or 2, wherein the polymerization initiation temperature is 10 to 90° C.

5. The method according to claim 1 or 2, wherein the monomer comprises butadiene.

6. The method of claim 1 or 2, wherein the monomer comprises isoprene.

7. The method according to claim 1 or 2, wherein the monomer comprises 7,11-dimethyl-3-methylene-1,6,10-dodecatriene (β-farnesene).

8. 3. The process of claim 1 or 2, wherein the only monomer polymerized in the polymerization comprises butadiene.

9. 3. The process of claim 1 or 2, wherein the only monomer polymerized in the polymerization consists of isoprene.

10. The process of claim 1 or 2, wherein the only monomer polymerized in the polymerization consists of 7,11-dimethyl-3-methylene-1,6,10-dodecatriene (β-farnesene).

11. The process of claim 1 or 2, further comprising hydrogenating the copolymer, thereby producing an α-olefin random copolymer.

12. The process according to claim 1 or 2, wherein the copolymer is an ethylene-1-butene copolymer.

13. The method according to claim 1 or 2, wherein the copolymer has a weight average molecular weight of 10,000 to 500,000 Da.

14. The method according to claim 1 or 2, wherein the copolymer has a content of vinyl bond structural units of 5 to 85 mol % based on the total molar amount of conjugated diene (1,3-diene structure) monomer units incorporated in the bonding modes of 3,4-bonds, 1,4-bonds, and 1,2-bonds of the conjugated diene monomer.

15. 1. A method for producing a block copolymer, comprising the steps of: polymerizing the first vinyl aromatic compound to produce a polymerized first vinyl aromatic compound; Producing the copolymer according to the process of claim 1 or 2, thereby producing the block copolymer comprising the polymerized first aromatic vinyl compound and the copolymer; Including, The method of claim 1, wherein the solvent contains the polymerized first aromatic vinyl compound.

16. A method for producing a triblock copolymer, comprising the steps of: A method of making the block copolymer comprising producing the block copolymer according to the method of claim 15.

17. A method for producing a triblock copolymer, comprising the steps of: Producing the block copolymer according to the method of claim 15; and polymerizing a second aromatic vinyl compound successively after the block copolymer is obtained, thereby producing the triblock copolymer comprising the polymerized first aromatic vinyl compound, the copolymer, and the polymerized second aromatic vinyl compound; The method of claim 16, comprising:

18. The first aromatic vinyl compound and the second aromatic vinyl compound are each independently selected from the group consisting of styrene, α-methylstyrene, 4-methylstyrene, o-methylstyrene, m-methylstyrene, β-methylstyrene, 2,6-dimethylstyrene, 2,4-dimethylstyrene, α-methyl-o-methylstyrene, α-methyl-m-methylstyrene, α-methyl-p-methylstyrene, β-methyl-o-methylstyrene, β-methyl-m-methylstyrene, β-methyl-p-methylstyrene, 2,4,6-trimethylstyrene, α-methyl-2,6-dimethylstyrene, α-methyl-2,4-dimethylstyrene, 3-methyl-2,6-dimethylstyrene, f-methyl-2,4-dimethylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, 2,6-dichlorostyrene, 2,4-dichlorostyrene, α-chloro-o-chlorostyrene, 16. The method of claim 15, comprising a compound selected from the group consisting of α-chloro-m-chlorostyrene, α-chloro-p-chlorostyrene, β-chloro-o-chlorostyrene, β-chloro-m-chlorostyrene, β-chloro-p-chlorostyrene, 2,4,6-trichlorostyrene, α-chloro-2,6-dichlorostyrene, α-chloro-2,4-dichlorostyrene, β-chloro-2,6-dichlorostyrene, β-chloro-2,4-dichlorostyrene, o-t-butylstyrene, m-t-butylstyrene, p-butylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-chloromethylstyrene, m-chloromethylstyrene, p-chloromethylstyrene, o-bromomethylstyrene, m-bromomethylstyrene, p-bromomethylstyrene, styrene derivatives substituted with a silyl group, indene, and vinylnaphthalene.

19. The method of claim 15, wherein the first aromatic vinyl compound and the second aromatic vinyl compound each comprise styrene.

20. The method according to claim 16, wherein the triblock copolymer has a vinyl bond structural unit content of 5 to 85 mol% based on the total molar amount of conjugated diene (1,3-diene structure) monomer units incorporated in the bonding modes of 3,4-bonds, 1,4-bonds, and 1,2-bonds of the conjugated diene monomer.

21. The method of claim 16, wherein the triblock copolymer has a styrene content of 5 to 70% by weight, based on the total weight of the triblock copolymer.

22. 17. The method of claim 16, wherein the triblock copolymer is a hydrogenated triblock copolymer, and the hydrogenated triblock copolymer has a crystallization peak temperature (Tc) of -8°C to 4°C measured by DSC at 10°C / min.

23. The method of claim 15, wherein the first and second aromatic vinyl compounds are polymerized by ionic polymerization.

24. 3. The method of claim 1, wherein the anionic polymerization initiator comprises at least one initiator selected from the group consisting of alkali metals, alkaline earth metals, lanthanide rare earth metals, and compounds containing earth metals and lanthanide rare earth metals.

25. 25. The method of claim 24, wherein the anionic polymerization initiator comprises at least one initiator selected from the group consisting of alkali metals, compounds containing alkali metals, and organic alkali metal compounds.

26. 25. The method of claim 24, wherein the anionic polymerization initiator comprises at least one alkali metal selected from the group consisting of lithium, sodium, and potassium.

27. 25. The method of claim 24, wherein the anionic polymerization initiator comprises at least one alkaline earth metal selected from the group consisting of beryllium, magnesium, calcium, strontium, and barium.

28. 25. The method of claim 24, wherein the anionic polymerization initiator comprises at least one lanthanide rare earth metal selected from the group consisting of lanthanum and neodymium.

29. The method of claim 24, wherein the anionic polymerization initiator comprises at least one organic alkali metal compound selected from the group consisting of methyl lithium, ethyl lithium, n-butyl lithium, sec-butyl lithium, t-butyl lithium, hexyl lithium, phenyl lithium, stilbene lithium, dilithiomethane, dilithionaphthalene, and 1,4-dilithiobutane.

30. The method of claim 24, wherein the anionic polymerization initiator comprises an organolithium compound.

31. 25. The method of claim 24, wherein the anionic polymerization initiator comprises at least one organolithium compound selected from the group consisting of dilithiobutane, 1,4-dilithio-2-ethylcyclohexane, 1,3,5-trilithiobenzene, sodium naphthalene, and potassium naphthalene.

32. The method according to claim 1 or 2, wherein the solvent comprises at least one selected from the group consisting of saturated aliphatic hydrocarbons, saturated alicyclic hydrocarbons, and aromatic hydrocarbons.

33. The method according to claim 1 or 2, wherein the solvent comprises at least one selected from the group consisting of cyclopentane, cyclohexane, and methylcyclohexane.

34. The method according to claim 1 or 2, wherein the solvent comprises at least one saturated aliphatic hydrocarbon selected from the group consisting of n-pentane, isopentane, n-hexane, n-heptane, and isooctane.

35. The method according to claim 1 or 2, wherein the solvent comprises at least one selected from the group consisting of pentane, benzene, toluene, and xylene.

36. The method of claim 1 or 2, wherein the solvent further comprises a Lewis base.

37. 3. The method according to claim 1, wherein the solvent further comprises at least one Lewis base selected from the group consisting of dibutyl ether, diethyl ether, tetrahydrofuran, dioxane, tetramethylethylenediamine, hexamethyltriethylenetetramine, 1,2-diethoxypropane, ditetrahydrofurylpropane, and ethylene glycol diethyl ether; pyridine; tertiary amines; alkali metal alkoxides; and phosphine compounds.

38. The method according to claim 36, wherein the amount of the Lewis base is in the range of 0.01 to 1,000 molar equivalents per 1 mol of the anionic polymerization initiator.

39. The process according to claim 1 or 2, further comprising adding a polymerization terminator to the solvent.

40. The method of claim 39 , wherein the polymerization terminator comprises an alcohol.

41. The method of claim 16 further comprising precipitating the triblock copolymer in another solvent.

42. The method according to claim 1 or 2, further comprising washing the polymerization reaction solution with water, separating and drying the same.

43. A triblock copolymer produced by the process of claim 16.