Method for hydrogenating an aromatic polymer, hydrogenated block copolymer, and use thereof

Abstract

The present invention discloses a method for hydrogenating an aromatic polymer, which comprises contacting an aromatic polymer with a hydrogenation reagent in the presence of a hydrogenation catalyst to hydrogenate at least a part of the aromatic rings in the aromatic polymer, the hydrogenation catalyst comprising an alumina carrier and a platinum element, a group 14 element, and a rare earth metal element supported on the carrier. The present invention also provides a hydrogenated block copolymer, a hydrogenated pentablock copolymer, and a hydrogenated heptablock copolymer. The hydrogenation method of the present invention can effectively hydrogenate the aromatic rings in the aromatic polymer and obtain a high degree of aromatic ring hydrogenation, while having little effect on the structure of the polymer, and the molecular chains of the aromatic polymer are hardly decomposed before and after the hydrogenation reaction. The hydrogenated block copolymer of the present invention has a high degree of hydrogenation, and also has high light transmittance, low haze, and excellent impact toughness.

Description

Detailed Description of the Invention

[0001] [Cross - Reference to Related Applications] This application claims the benefit of Chinese Patent Application No. 202110560968.X, filed on May 19, 2021, the content of which is incorporated herein by reference.

[0002] [Technical Field] The present invention relates to a method for hydrogenating aromatic polymers. The present invention also relates to hydrogenated block copolymers, hydrogenated pentablock copolymers, and hydrogenated heptablock copolymers, and their uses.

[0003] [Background Art] General unsaturated polymer materials usually contain unsaturated double bonds (such as benzene ring double bonds, diolefin double bonds, etc.), and their heat resistance, ultraviolet resistance, and yellowing resistance are poor. Hydrogenation of unsaturated polymers is a means to rapidly and effectively improve their performance.

[0004] Polystyrene is the most widely used thermoplastic at present, with many advantages such as high water resistance, corrosion resistance, transparency, easy coloring, and easy processing and molding. It is widely applied in various fields such as electronic communication, molds, food packaging, and daily necessities. When the benzene ring double bond in polystyrene is hydrogenated, fully saturated polycyclohexylethylene (PVCH) is obtained. Compared with polystyrene (PS), fully saturated PVCH has a significantly improved glass transition temperature, which increases from around 105 °C to 147 °C. Also, its heat resistance, ultraviolet resistance and other properties are significantly improved. Moreover, it maintains the high light transmittance of PS. However, polystyrene has insufficient toughness after hydrogenation and is prone to breakage. Other transparent monovinyl aromatic hydrocarbon polymers are styrene-butadiene resins, which are styrene-butadiene block copolymers with a high styrene content. In order to improve the toughness of styrene-butadiene resins, highly transparent impact-resistant styrene-butadiene resins with both high transparency and impact resistance have been developed by researchers. However, due to the large amount of butadiene unsaturated double bonds contained in styrene-butadiene resins, they are not excellent in heat resistance, ultraviolet resistance, and yellowing resistance during outdoor use.

[0005] For the hydrogenation of conjugated diolefin unsaturated double bonds in polymers, homogeneous nickel, cobalt-based catalyst systems or metallocene-based catalyst systems can be used. However, the hydrogenation of unsaturated double bonds in aromatic rings is more difficult than that of diolefin double bonds. Usually, heterogeneous catalysts are employed, and strict process conditions such as high temperature and high pressure are required.

[0006] For example, Elias H G and Etter O (Glass Temperature of Hydrogenated Polystyrene, Journal of Macromolecular Science-Chemistry, 1967, 1(5): 943-953) hydrogenated polystyrene using a Raney nickel catalyst at a pressure of 200-270 °C and 210-260 atm for 24 hours to achieve a hydrogenation degree of 42-100%, but serious degradation occurred in the polymer. Also, for example, Gehlsen et al. (MD Gehlsen, Weimann P A, Bates F S, et al., Synthesis and Characterization of Poly(vinylcyclohexane) Derivatives, Journal of Polymer Science Part B Polymer Physics, 1995, 33(10): 1527-1536) hydrogenated a polystyrene cyclohexane solution using Pd / BaSO4 as a catalyst at a pressure of 140 °C and 35 atm and reacted for 12 hours so that the mass ratio of the catalyst / polymer was 2.5 / 1 to obtain fully hydrogenated PVCH, but the polymer was partially chain-cut and decomposed (Tg = 140 °C). Zhou Hongyong et al. (Zhou Hongyong et al., Manufacture of Magnetic Nanoruthenium Catalyst and Catalytic Performance for Hydrogenation Catalyst of Polystyrene, Polymer Materials Science and Engineering, 2011, 27(011): 73-76) supported metal Ru on a magnetic nanocarrier to manufacture a magnetic nanocatalyst and used it in the hydrogenation reaction of polystyrene. When the reaction temperature is 120 °C or higher, the hydrogen pressure is 8 MPa, and the reaction time is 5 h, the hydrogenation degree of polystyrene reaches 90% or more, but polystyrene decomposes after hydrogenation, and small molecules such as benzene, toluene, cyclohexane, and methylcyclohexane are generated.

[0007] To solve the problem that the polymer is easily decomposed during the hydrogenation of the polymer, US5700878 discloses a method for hydrogenating an aromatic polymer, which includes contacting the aromatic polymer with a hydrogenating agent in the presence of a metal hydrogenation catalyst supported on silica, and hydrogenating at least 80% of the aromatic polymer. Silica is at least 10m2 has a surface area of / g, and for the pore size distribution, at least 98% of the pore volume is determined from pores with a pore diameter larger than 600 Å when measured with a mercury porosimeter, and the pore volume measured with a mercury porosimeter for pores with a pore diameter less than 600 Å as a result of measurement by the nitrogen desorption method is less than 2% of the total pore volume. However, the hydrogenation catalyst used in this method has a large noble metal loading amount and a large amount of catalyst used, so the cost is high. Furthermore, from the experimental data of the examples described in the patent specification, the molecular weight of the hydrogenated polymer obtained by performing a hydrogenation reaction on polystyrene and poly-α-methylstyrene using the disclosed method is relatively clearly lower than that of the non-hydrogenated polymer, suggesting that the polymer is decomposed by the hydrogenation reaction.

[0008] Therefore, in order to hydrogenate a highly transparent monovinyl aromatic hydrocarbon polymer, it is necessary to solve problems such as the low hydrogenation activity of the catalyst, the easy decomposition of the hydrogenation product, and the lack of balance between impact toughness and heat resistance of the hydrogenation product.

[0009] [Summary of the Invention] [Problems to be Solved by the Invention] One object of the present invention is to provide a method for hydrogenating an aromatic polymer that can not only hydrogenate aromatic rings in the aromatic polymer but also effectively suppress the decomposition of polymer molecular chains during hydrogenation.

[0010] Another object of the present invention is to provide a hydrogenated block copolymer. The hydrogenated block copolymer according to the present invention not only has a high degree of aromatic ring hydrogenation and a high degree of conjugated diolefin hydrogenation but also can achieve a balance between transparency and impact toughness.

[0011] [Means for Solving the Problems] According to a first aspect of the present invention, the present invention provides a method for hydrogenating an aromatic polymer, wherein the aromatic polymer contains an aromatic ring, and the method includes contacting the aromatic polymer with a hydrogenation reagent in the presence of a hydrogenation catalyst to hydrogenate at least a part of the aromatic rings in the aromatic polymer to obtain a hydrogenated aromatic polymer. The hydrogenation catalyst contains a carrier that is alumina, and a platinum element, a Group 14 element, and a rare earth metal element supported on the carrier. In the hydrogenation catalyst, the molar ratio of the Group 14 element to the platinum element is 10 or less.

[0012] According to a second aspect of the present invention, the present invention provides a hydrogenated aromatic polymer produced by the method according to the first aspect of the present invention.

[0013] According to a third aspect of the present invention, the present invention provides a hydrogenated block copolymer containing a monovinyl aromatic hydrocarbon structural unit derived from a monovinyl aromatic hydrocarbon and a conjugated diolefin structural unit derived from a conjugated diolefin. In the hydrogenated block copolymer, the hydrogenation degree of the aromatic rings in the monovinyl aromatic hydrocarbon structural unit is 98 mol% or more, and the hydrogenation degree of the unsaturated double bonds in the conjugated diolefin structural unit is 99 mol% or more. The hydrogenated block copolymer has a notched impact strength of 20 to 30 kJ / m 2 and an elongation at break of 200 to 400% and a light transmittance of 88 to 92% and a haze of 1 to 5.

[0014] According to a fourth aspect of the present invention, the present invention provides a pentablock copolymer having a structure represented by Formula II. In the hydrogenated pentablock copolymer, the hydrogenation degree of the aromatic rings in the monovinyl aromatic hydrocarbon structural unit is 98 mol% or more, and the hydrogenation degree of the unsaturated double bonds in the conjugated diolefin structural unit is 99 mol% or more. S51-(S52 / B51)-B52-(S53 / B53)-S54 (Formula II) (In Formula II, the S51 block and the S54 block are each independently a homopolymer segment of a monovinyl aromatic hydrocarbon, the S52 / B51 block and the S53 / B53 block are each independently a random copolymer segment of a monovinyl aromatic hydrocarbon and a conjugated diolefin, and the B52 block is a homopolymer segment of a conjugated diolefin.)

[0015] According to a fifth aspect of the present invention, the present invention is a heptablock copolymer having a structure represented by Formula III, and provides a hydrogenated heptablock copolymer in which the degree of hydrogenation of the aromatic ring in the monovinyl aromatic hydrocarbon structural unit is 98 mol% or more, and the degree of hydrogenation of the unsaturated double bond in the conjugated diolefin structural unit is 99 mol% or more. S71-(S72 / B71)-B72-(S73 / B73)-B74-(S75 / B75)-S76 (Formula III) (In Formula III, the S71 block and the S76 block are each independently a homopolymer segment of a monovinyl aromatic hydrocarbon, the S72 / B71 block, the S73 / B73 block, and the S75 / B75 block are each independently a random copolymer segment of a monovinyl aromatic hydrocarbon and a conjugated diolefin, and the B72 block and the B74 block are each independently a homopolymer segment of a conjugated diolefin.)

[0016] According to a sixth aspect of the present invention, the present invention provides the use of the hydrogenated block copolymer according to the third aspect of the present invention, the hydrogenated pentablock copolymer according to the fourth aspect of the present invention, or the hydrogenated heptablock copolymer according to the fifth aspect of the present invention in the manufacture of a packaging material or an optoelectronic product.

[0017] [Advantages of the Invention] The method for hydrogenating an aromatic polymer according to the present invention can not only effectively hydrogenate the aromatic rings in the aromatic polymer and obtain a high degree of aromatic ring hydrogenation, but also has little influence on the polymer structure, and the molecular chains of the aromatic polymer before and after the hydrogenation reaction are hardly decomposed.

[0018] The hydrogenated block copolymer, hydrogenated pentablock copolymer and hydrogenated heptablock copolymer according to the present invention have a high degree of hydrogenation (the degree of hydrogenation is about 100%), have the characteristics of high light transmittance and low haze, and are excellent in impact toughness and heat resistance, and can balance impact toughness and heat resistance well. The hydrogenated block copolymer, hydrogenated pentablock copolymer and hydrogenated heptablock copolymer according to the present invention are extremely promising for commercialization in fields such as the manufacture of packaging materials (especially packaging materials in the medical and health fields) and optoelectronic product materials (especially materials for cameras and display screens of optoelectronic products).

[0019] [Embodiments for Carrying out the Invention] Hereinafter, specific embodiments of the present invention will be described in detail. It should be understood that the specific embodiments described in this specification are used only for explaining and interpreting the present invention, and not for limiting the present invention.

[0020] The endpoints and any values within the ranges disclosed in this specification are not limited to these exact ranges or values, but are to be understood as including values close to these ranges or values. In the case of numerical ranges, between the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values, they can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed in this specification.

[0021] In the present invention, the term "monovinyl aromatic hydrocarbon" means a compound in which one of the hydrogens on the aromatic ring is substituted with a vinyl group. For example, the monovinyl aromatic hydrocarbon may be one or more selected from the compounds represented by Formula I. [Chemical Formula] (In formula I, R1 is a substituted or unsubstituted aryl group having 6 to C 20 and specific examples thereof include, but are not limited to, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, o-ethylphenyl group, m-ethylphenyl group, p-ethylphenyl group, o-t-butylphenyl group, m-t-butylphenyl group, p-t-butylphenyl group, p-dodecylphenyl group, 2,4-di-n-butylphenyl group, p-n-propylphenyl group, and 2,4-diethylphenyl group.)

[0022] Preferably, the monovinyl aromatic hydrocarbon is one or more selected from the group consisting of styrene, 2-methylstyrene, 4-methylstyrene, 4-tert-butylstyrene, 4-methylstyrene, 3,5-diethylstyrene, 3,5-di-n-butylstyrene, 4-n-propylstyrene, and 4-dodecylstyrene. More preferably, the monovinyl aromatic hydrocarbon is one or more selected from the group consisting of styrene, 2-methylstyrene, 4-methylstyrene, and α-methylstyrene.)

[0023] In the present invention, the term "conjugated diolefin" means an unsaturated chain hydrocarbon containing a conjugated double bond (i.e., -C=C-C=C-) in its molecular structure, and may be various conjugated diolefins generally used in the art, and is not particularly limited. For example, the conjugated diolefin may be one or more selected from the group consisting of C4 to C8 conjugated diolefins.)

[0024] Preferably, the conjugated diolefin may be one or more selected from the group consisting of butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, and 2,3-dimethylbutadiene. More preferably, the conjugated diolefin is butadiene, isoprene, or a combination thereof.)

[0025] In the present invention, the term "structural unit derived from ××××" means a structural unit formed by the addition polymerization of the monomer (i.e., ××××). For example, a structural unit derived from a monovinyl aromatic hydrocarbon is a structural unit formed by the addition polymerization of a monovinyl aromatic hydrocarbon.

[0026] In the present invention, the term "content of pendant group" means the content of a structural unit derived from a conjugated diolefin containing an ethylenic pendant group (i.e., the pendant group contains a C=C bond), based on the total amount of structural units derived from the conjugated diolefin in the copolymer. Specifically, when the conjugated diolefin is butadiene, the ethylenic pendant group means the pendant group in the structural unit formed by 1,2-polymerization from butadiene (i.e.,

Chemical formula

[0027] In the present invention, the term "styrene non-block" (which can also be expressed as "St non-block") means the content of styrene structural units derived from styrene in the random copolymer segment. In the present invention, the styrene non-block content of the polymer is measured using nuclear magnetic resonance hydrogen spectroscopy.

[0028] In the present invention, the term "end block" means a block located at both ends of a polymer molecular chain, and may also be referred to as a "terminal block". The term "internal block" means a block directly bonded to an end block, that is, the end block and the internal block are linked in a covalent bond form by one of their respective terminal atoms.

[0029] In the present invention, the term "homopolymer segment" means that the structural units in this block are obtained from substantially the same monomer. In the present invention, at least 99% by weight or more of the structural units in the homopolymer segment are obtained from the same monomer. In the present invention, the term "random copolymer segment" means that the structural units in this block are derived from two or more types of monomers, and different types of structural units are randomly distributed.

[0030] In the present invention, the term "bond" means that two blocks are covalently bonded through their respective terminal atoms.

[0031] In the present invention, the term "hydrogenation" has the same meaning as the term "hydrogen addition", and means that a carbon-carbon unsaturated bond including an unsaturated bond of an aromatic ring and a carbon-carbon unsaturated bond of a non-aromatic ring such as a carbon-carbon double bond of a non-aromatic ring is hydrogenated. In the present invention, the term "degree of hydrogenation" has the same meaning as the term "degree of hydrogen addition", and means the change rate between the content of carbon-carbon unsaturated bonds in the polymer after hydrogen addition and the content of carbon-carbon unsaturated bonds in the polymer before hydrogen addition, and can be calculated using the following formula. Degree of hydrogenation = (1 - molar content of carbon-carbon unsaturated bonds in the polymer after hydrogen addition / molar content of carbon-carbon unsaturated bonds in the polymer before hydrogen addition) × 100%.

[0032] The term "degree of hydrogenation of aromatic ring" means the change rate between the content of carbon-carbon unsaturated bonds derived from aromatic rings in the polymer after hydrogenation and the content of carbon-carbon unsaturated bonds derived from aromatic rings in the polymer before hydrogenation, and can be calculated using the following formula. Degree of hydrogenation of aromatic ring = (1 - molar content of carbon-carbon unsaturated bonds derived from aromatic rings in the polymer after hydrogenation / molar content of carbon-carbon unsaturated bonds derived from aromatic rings in the polymer before hydrogenation) × 100%.

[0033] The term "degree of hydrogenation of conjugated diolefin" is the change rate between the content of carbon-carbon unsaturated double bonds derived from conjugated diolefin structural units in the polymer after hydrogenation and the content of carbon-carbon unsaturated double bonds derived from conjugated diolefin structural units in the polymer before hydrogenation, and can be calculated using the following formula. Degree of hydrogenation of conjugated diolefin = (1 - molar content of carbon-carbon unsaturated double bonds derived from conjugated diolefin in the polymer after hydrogenation / molar content of carbon-carbon unsaturated double bonds derived from conjugated diolefin in the polymer before hydrogenation) × 100%

[0034] In the present invention, the number average molecular weight (M n ), weight average molecular weight (M w ), and molecular weight distribution index (M w / M n ) of the polymer were measured in g / mol using gel permeation chromatography with monodisperse polystyrene as the standard.

[0035] In the present invention, unless otherwise specified, all the pressures are gauge pressures.

[0036] In the present invention, the term "at least one kind" represents one kind or two or more kinds. In the present invention, the term "optional" means not essential, and can be understood as "including or not including", "containing or not containing". 1. Aromatic polymer

[0037] In the present invention, the aromatic polymer refers to a polymer containing an aromatic ring and a structural unit having an aromatic ring. As a typical example of the aromatic ring, a benzene ring can be mentioned. The aromatic ring in the aromatic polymer is derived from the aromatic structural unit of an aromatic monomer containing an aromatic ring. As a typical example of the structural unit having an aromatic ring, a monovinyl aromatic hydrocarbon structural unit derived from a monovinyl aromatic hydrocarbon may be included, but is not limited thereto.

[0038] Based on the total amount of the aromatic polymer, the content of the aromatic structural unit derived from the aromatic monomer containing an aromatic ring in the aromatic polymer is 40% by weight or more, preferably 50% by weight or more, more preferably 70% by weight or more. In one preferred embodiment, based on the total amount of the aromatic polymer, the content of the aromatic structural unit in the aromatic polymer is 65 to 85% by weight, for example, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, or 85% by weight.

[0039] The aromatic polymer may contain only aromatic structural units, or may contain non-aromatic structural units having no aromatic structural units and aromatic rings. The non-aromatic structural units may be selected from structural units containing an unsaturated bond and structural units not containing an unsaturated bond. As a typical example of the non-aromatic structural unit, a conjugated diolefin structural unit derived from a conjugated diolefin is included.

[0040] When the aromatic polymer contains a conjugated diolefin structural unit, based on the total amount of the aromatic polymer, the content of the conjugated diolefin structural unit is preferably 60% by weight or less, and may be, for example, 5 to 60% by weight. More preferably, based on the total amount of the aromatic polymer, the content of the conjugated diolefin structural unit is 50% by weight or less, and may be, for example, 10 to 50% by weight. Even more preferably, based on the total amount of the aromatic polymer, the content of the conjugated diolefin structural unit is 15 to 35% by weight, for example, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, or 35% by weight. The conjugated diolefin is preferably butadiene and / or isoprene. When the aromatic polymer contains a conjugated diolefin structural unit derived from a conjugated diolefin, based on the total amount of the conjugated diolefin structural unit derived from the conjugated diolefin, the content of the pendant group is preferably 40 to 60% by weight, for example, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, or 60% by weight.

[0041] When the aromatic polymer contains a conjugated diolefin structural unit, the sequence order of the aromatic structural unit and the conjugated diolefin structural unit in the polymer molecular chain may be determined according to the specific use requirements of the hydrogenated aromatic polymer, and may be random, block, or graft.

[0042] In one preferred embodiment, the aromatic polymer is a block copolymer containing structural units derived from monovinyl aromatic hydrocarbons and structural units derived from conjugated diolefins. Here, the aromatic polymer contains at least two homopolymer segments of monovinyl aromatic hydrocarbons (i.e., homopolymer segments formed mainly by the polymerization of monovinyl aromatic hydrocarbons), at least one homopolymer segment of conjugated diolefins (i.e., homopolymer segments formed mainly by the polymerization of conjugated diolefins), and at least two random copolymer segments of monovinyl aromatic hydrocarbons and conjugated diolefins (i.e., random copolymer segments formed by the random copolymerization of monovinyl aromatic hydrocarbons and conjugated diolefins). The two end blocks of the aromatic polymer are each independently a homopolymer segment of monovinyl aromatic hydrocarbons. The blocks directly connected to the end blocks are internal blocks, and the internal blocks are each independently a random copolymer segment of monovinyl aromatic hydrocarbons and conjugated diolefins. When the block copolymer contains at least three random copolymer segments of monovinyl aromatic hydrocarbons and conjugated diolefins and at least two homopolymer segments of conjugated diolefins, the homopolymer segments of conjugated diolefins and the random copolymer segments of monovinyl aromatic hydrocarbons and conjugated diolefins are arranged at intervals, and the two terminal groups of the homopolymer segment of conjugated diolefins are each directly connected to one random copolymer segment of monovinyl aromatic hydrocarbons and conjugated diolefins.

[0043] In this preferred embodiment, based on the total amount of the aromatic polymer, the content of the structural unit derived from monovinyl aromatic hydrocarbon may be 40 to 95% by weight, and the content of the structural unit derived from conjugated diolefin may be 5 to 60% by weight. In the aromatic polymer, based on the total amount of the structural unit derived from monovinyl aromatic hydrocarbon, the content of the structural unit derived from monovinyl aromatic hydrocarbon in the random copolymer segment may be 15 to 20% by weight, preferably 17 to 18.5% by weight. In this preferred embodiment, in the aromatic polymer, based on the total amount of the conjugated diolefin structural unit, the content of the pendant group may be 40 to 60% by weight.

[0044] In this preferred embodiment, the conjugated diolefin structural unit in the homopolymer segment of the conjugated diolefin and the conjugated diolefin structural unit in the random copolymer segment may be the same or different. Preferably, the homopolymer segment of the conjugated diolefin contains a homopolymer segment of one first conjugated diolefin and at least one homopolymer segment of a second conjugated diolefin. The structural unit in the homopolymer segment of the first conjugated diolefin is derived from the first conjugated diolefin, the structural unit in the homopolymer segment of the second conjugated diolefin is derived from the second conjugated diolefin, and the first conjugated diolefin and the second conjugated diolefin are different. More preferably, the homopolymer segment of the first conjugated diolefin is directly bonded to one internal block, the first conjugated diolefin is isoprene, and the conjugated diolefin in the random copolymer segment of the second conjugated diolefin and the monovinyl aromatic hydrocarbon and the conjugated diolefin is butadiene. Based on the total amount of the hydrogenated block copolymer, the content of the isoprene structural unit derived from isoprene is preferably 0.5 to 10% by weight, more preferably 1 to 5% by weight, still more preferably 2 to 4% by weight, and the content of the butadiene structural unit derived from butadiene is preferably 5 to 40% by weight, more preferably 10 to 35% by weight, still more preferably 15 to 30% by weight.

[0045] In a more preferred embodiment, the aromatic polymer is a pentablock copolymer having a structure represented by Formula II. S51-(S52 / B51)-B52-(S53 / B53)-S54 (Formula II) (In Formula II, the S51 block and the S54 block are end blocks and are each independently a homopolymer segment of a monovinyl aromatic hydrocarbon. The S52 / B51 block and the S53 / B53 block are internal blocks and are each independently a random copolymer segment of a monovinyl aromatic hydrocarbon and a conjugated diolefin. The B52 block is a homopolymer segment of a conjugated diolefin.)

[0046] In the pentablock copolymer represented by Formula II, the monovinyl aromatic hydrocarbon structural units in the S51 block, the S52 / B51 block, the S53 / B53 block, and the S54 block are represented as S51 monovinyl aromatic hydrocarbon structural units, S52 monovinyl aromatic hydrocarbon structural units, S53 monovinyl aromatic hydrocarbon structural units, and S54 monovinyl aromatic hydrocarbon structural units, respectively. These may be the same or different and may each be one or more selected from the group consisting of styrene, 2-methylstyrene, 4-methylstyrene, and α-methylstyrene. Preferably, the monovinyl aromatic hydrocarbon structural units in the S51 block, the S52 / B51 block, the S53 / B53 block, and the S54 block are the same and are all styrene structural units derived from styrene. In Formula II, when all of the monovinyl aromatic hydrocarbon structural units in the S51 block, the S52 / B51 block, the S53 / B53 block, and the S54 block are styrene structural units derived from styrene, based on the total amount of the styrene structural units in the hydrogenated block copolymer, the content of the styrene non-block is preferably 15 to 20% by weight, more preferably 17 to 18.5% by weight.

[0047] In the pentablock copolymer represented by Formula II, the conjugated diolefin structural unit in the B52 block is derived from B52 conjugated diolefin, the conjugated diolefin structural unit in the S52 / B51 block is derived from B51 conjugated diolefin, and the conjugated diolefin structural unit in the S53 / B53 block is derived from B53 conjugated diolefin. The B52 conjugated diolefin, the B51 conjugated diolefin, and the B53 conjugated diolefin may be the same or different, and each may be at least one selected from the group consisting of butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, and 2,3-dimethylbutadiene. Preferably, the B52 conjugated diolefin is different from the B51 conjugated diolefin and the B53 conjugated diolefin, and the B51 conjugated diolefin and the B53 conjugated diolefin are preferably the same.

[0048] More preferably, the B52 conjugated diolefin is isoprene, and the B51 conjugated diolefin and the B53 conjugated diolefin are butadiene. Based on the total amount of the pentablock copolymer, the content of the isoprene structural unit derived from isoprene is preferably 0.5 to 10% by weight, more preferably 1 to 5% by weight, and still more preferably 2 to 4% by weight. The content of the butadiene structural unit derived from butadiene is preferably 5 to 40% by weight, more preferably 10 to 35% by weight, and still more preferably 15 to 30% by weight. Based on the total amount of the isoprene-derived structural units in the pentablock copolymer, the content of the isoprene structural unit containing a vinyl pendant group (i.e., the content of the pendant group) is preferably 50 to 60% by weight, more preferably 50 to 57% by weight. Based on the total amount of the butadiene-derived structural units in the pentablock copolymer, the content of the butadiene structural unit containing a vinyl pendant group (i.e., the content of the pendant group) is preferably 40 to 60% by weight, more preferably 45 to 55% by weight.

[0049] Based on the total amount of the pentablock copolymer represented by Formula II, the content of the monovinyl aromatic hydrocarbon structural unit derived from the monovinyl aromatic hydrocarbon is preferably 40 to 95% by weight, more preferably 50 to 90% by weight, still more preferably 65 to 85% by weight, and the content of the conjugated diolefin structural unit derived from the conjugated diolefin is preferably 5 to 60% by weight, more preferably 10 to 50% by weight, still more preferably 15 to 35% by weight. The monovinyl aromatic hydrocarbon structural unit includes the monovinyl aromatic hydrocarbon structural unit in the S51 block, the monovinyl aromatic hydrocarbon structural unit in the S54 block, the monovinyl aromatic hydrocarbon structural unit in the S52 / B51 block, and the monovinyl aromatic hydrocarbon structural unit in the S53 / B53 block, and the conjugated diolefin structural unit includes the conjugated diolefin structural unit in the S52 / B51 block, the conjugated diolefin structural unit in B52, and the conjugated diolefin structural unit in the S53 / B53 block.

[0050] In the pentablock copolymer represented by Formula II, the number average molecular weight of the S51 block is preferably 5,000 to 50,000, the number average molecular weight of the S52 / B51 block is preferably 20,000 to 50,000, the number average molecular weight of the S53 / B53 block is preferably 20,000 to 50,000, and the number average molecular weight of the B52 block is preferably 2,000 to 20,000. In the aromatic polymer represented by Formula II, the ratio of the number average molecular weight of the S51 block to the number average molecular weight of the S54 block is preferably 1:2 to 10, more preferably 1:2 to 6. In the pentablock copolymer represented by Formula II, the ratio of the number average molecular weight of the S52 / B51 block to the number average molecular weight of the S53 / B53 block is preferably 1:0.9 to 1.25.

[0051] The number average molecular weight of the pentablock copolymer represented by Formula II is preferably 50,000 to 220,000, more preferably 80,000 to 200,000. The molecular weight distribution index (M w / M n ) of the pentablock copolymer represented by Formula II is preferably 1.05 to 1.2.

[0052] In another preferred embodiment, the aromatic polymer is a heptablock copolymer having a structure represented by Formula III. S71-(S72 / B71)-B72-(S73 / B73)-B74-(S75 / B75)-S76 (Formula III) (In Formula III, the S71 block and the S76 block are end blocks and are each independently a homopolymerization segment of a monovinyl aromatic hydrocarbon. The S72 / B71 block, the S73 / B73 block, and the S75 / B75 block are each independently a random copolymerization segment of a monovinyl aromatic hydrocarbon and a conjugated diolefin. Here, the S72 / B71 block and the S75 / B75 block are internal blocks, and the B72 block and the B74 block are each independently a homopolymerization segment of a conjugated diolefin.)

[0053] In the heptablock copolymer represented by formula III, the monovinyl aromatic hydrocarbon structural units in the S71 block, S72 / B71 block, S73 / B73 block, S75 / B75 block and S76 block are represented as S71 monovinyl aromatic hydrocarbon structural units, S72 monovinyl aromatic hydrocarbon structural units, S73 monovinyl aromatic hydrocarbon structural units, and S75 monovinyl aromatic hydrocarbon structural units, respectively, and may be the same or different, and each may be one or more selected from the group consisting of styrene, 2-methylstyrene, 4-methylstyrene, and α-methylstyrene. Preferably, the monovinyl aromatic hydrocarbon structural units in the S71 block, S72 / B71 block, S73 / B73 block, S75 / B75 block and S76 block are the same and are all styrene structural units derived from styrene. In the heptablock copolymer represented by formula III, when the monovinyl aromatic hydrocarbon structural units in the S71 block, S72 / B71 block, S73 / B73 block, S75 / B75 block and S76 block are all styrene structural units derived from styrene, based on the total amount of styrene structural units in the heptablock copolymer, the content of the styrene non-block is preferably 15 to 20% by weight, more preferably 17 to 18.5% by weight.

[0054] In the heptablock copolymer represented by Formula III, the conjugated diolefin structural unit in the B72 block is derived from the B72 conjugated diolefin, the conjugated diolefin structural unit in the S72 / B71 block is derived from the B71 conjugated diolefin, the conjugated diolefin structural unit in the S73 / B73 block is derived from the B73 conjugated diolefin, the conjugated diolefin structural unit in the B74 block is derived from the B74 conjugated diolefin, the conjugated diolefin structural unit in the S75 / B75 block is derived from the B75 conjugated diolefin, and the B72 conjugated diolefin, the B71 conjugated diolefin, the B73 conjugated diolefin, the B74 conjugated diolefin, and the B75 conjugated diolefin may be the same or different, and each may be at least one selected from the group consisting of butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, and 2,3-dimethylbutadiene. Preferably, the B72 conjugated diolefin is different from the B71 conjugated diolefin, the B73 conjugated diolefin, the B74 conjugated diolefin, and the B75 conjugated diolefin, and the B71 conjugated diolefin, the B73 conjugated diolefin, the B74 conjugated diolefin, and the B75 conjugated diolefin are preferably the same.

[0055] More preferably, in the heptablock copolymer represented by Formula III, the B72 conjugated diolefin is isoprene, and the B71 conjugated diolefin, the B73 conjugated diolefin, the B74 conjugated diolefin, and the B75 conjugated diolefin are butadiene. Based on the total amount of the heptablock copolymer, the content of the isoprene structural unit derived from isoprene is preferably 0.5 to 10% by weight, more preferably 1 to 5% by weight, and still more preferably 2 to 4% by weight. The content of the butadiene structural unit derived from butadiene is preferably 5 to 40% by weight, more preferably 10 to 35% by weight, and still more preferably 15 to 30% by weight. Still more preferably, based on the total amount of the structural units derived from isoprene in the aromatic polymer, the content of the isoprene structural unit containing a vinyl pendant group is preferably 40 to 60% by weight, more preferably 45 to 55% by weight. Based on the total amount of the structural units derived from butadiene in the aromatic polymer, the content of the butadiene structural unit containing a vinyl pendant group is preferably 40 to 60% by weight, more preferably 45 to 55% by weight.

[0056] In the heptablock copolymer represented by the formula III, based on the total amount of the aromatic polymer, the content of the monovinyl aromatic hydrocarbon structural unit derived from the monovinyl aromatic hydrocarbon is preferably 40 to 95% by weight, more preferably 50 to 90% by weight, and still more preferably 65 to 85% by weight, and the content of the conjugated diolefin structural unit derived from the conjugated diolefin is preferably 5 to 60% by weight, more preferably 10 to 50% by weight, and still more preferably 15 to 35% by weight. The monovinyl aromatic hydrocarbon structural unit includes the monovinyl aromatic hydrocarbon structural unit in the S71 block, the monovinyl aromatic hydrocarbon structural unit in the S76 block, the monovinyl aromatic hydrocarbon structural unit in the S72 / B71 block, the monovinyl aromatic hydrocarbon structural unit in the S73 / B73 block, and the monovinyl aromatic hydrocarbon structural unit in the S75 / B75 block, and the conjugated diolefin structural unit includes the conjugated diolefin structural unit in the S72 / B71 block, the conjugated diolefin structural unit in the B72 block, the conjugated diolefin structural unit in the S73 / B73 block, the conjugated diolefin structural unit in the B74 block, and the conjugated diolefin structural unit in the S75 / B75 block.

[0057] In the heptablock copolymer represented by Formula III, the number average molecular weight of the S71 block is preferably from 5,000 to 50,000, the number average molecular weight of the S72 / B71 block is preferably from 20,000 to 50,000, the number average molecular weight of the B72 block is preferably from 2,000 to 20,000, the number average molecular weight of the S73 / B73 block is preferably from 5,000 to 50,000, the number average molecular weight of the B74 block is preferably from 2,000 to 20,000, the number average molecular weight of the S75 / B75 block is preferably from 5,000 to 50,000, and the number average molecular weight of the S76 block is preferably from 10,000 to 50,000. In the heptablock copolymer represented by Formula III, the ratio of the number average molecular weight of the S71 block to the number average molecular weight of the S76 block is preferably from 1:1.5 to 5, more preferably from 1.6 to 3. In the heptablock copolymer represented by Formula III, the ratio of the number average molecular weight of the S72 / B71 block, the number average molecular weight of the S73 / B73 block, and the number average molecular weight of S75 / B75 is preferably from 1:1 to 1.2:1 to 1.25. In the heptablock copolymer represented by Formula III, the ratio of the number average molecular weight of the B72 block to the number average molecular weight of the B74 block is preferably from 1:0.9 to 1.2.

[0058] In the heptablock copolymer represented by Formula III, the number average molecular weight (M n ) of the heptablock copolymer is preferably from 50,000 to 200,000, more preferably from 120,000 to 190,000. The molecular weight distribution index (M w / M n ) of the heptablock copolymer is preferably from 1.05 to 1.2.

[0059] The aromatic polymer may be produced by a conventional method.

[0060] When the aromatic polymer is a block copolymer, it may be produced by sequentially charging monomers by an anionic polymerization method. Specifically, under the conditions of anionic polymerization, the polymerization monomers are sequentially charged into a solution containing an organolithium initiator and an optional polarity regulator to obtain the block copolymer.

[0061] The organic lithium initiator may be various organic lithium initiators that can initiate the polymerization of the polymerization monomer and are commonly used in the field of anionic polymerization. The organic lithium initiator is preferably an organic monolithium compound, more preferably a compound represented by Formula IV. R2Li (Formula IV) (In Formula IV, R2 is an alkyl group having 1 to C 10 such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an s-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, an isopentyl group, a t-pentyl group, a neopentyl group, a hexyl group (including various isomers of the hexyl group), a heptyl group (including various isomers of the heptyl group), an octyl group (including various isomers of the octyl group), a nonyl group (including various isomers of the nonyl group), or a decyl group (including various isomers of the decyl group).)

[0062] Specific examples of the organic lithium initiator may include, but are not limited to, one or more of ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, s-butyllithium, t-butyllithium, and isobutyllithium.

[0063] Preferably, the organic lithium initiator is one or more selected from the group consisting of n-butyllithium, s-butyllithium, isobutyllithium, and t-butyllithium. More preferably, the organic lithium initiator is n-butyllithium.

[0064] The usage amount of the organic lithium initiator may be determined according to the expected molecular weight of the first block (i.e., the starting end block) of the block copolymer. Generally, based on 1 g of the monomer for forming the first block, the usage amount of the organic lithium initiator may be 0.03 to 0.2 mmol (millimole), preferably 0.04 to 0.15 mmol.

[0065] The polarity regulator may be a compound containing an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom in its molecular structure. The polarity regulator is preferably at least one selected from the group consisting of ethyl ether, dibutyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, diglyme, dioxane, crown ether, tetrahydrofurfuryl ethyl ether, triethylamine, tetramethylethylenediamine, hexamethylphosphoric triamide, potassium tert-butoxide, potassium tert-amyloxide, potassium lauryl alcohol, potassium alkylbenzenesulfonate, and sodium alkylbenzenesulfonate. The amount of the polarity regulator used may be appropriately determined according to specific polymerization conditions. Generally, the molar ratio of the polarity regulator to the organolithium initiator may be 0.1 to 40:1, preferably 0.2 to 20:1, and the organolithium initiator is in terms of lithium element.

[0066] The block copolymer preferably employs solution polymerization. In the present invention, the type of the solvent used for solution polymerization is not particularly limited, and the solvent may be a solvent commonly used for solution polymerization, as long as it is in a liquid state and inert under the conditions of the polymerization reaction (that is, it does not participate in the polymerization reaction and does not react with the polymer obtained by the reaction). Preferably, the solvent is at least one selected from the group consisting of cyclohexane, methylcyclohexane, n-hexane, cyclooctane, cycloheptane, acetone, n-butanone, decalin, and tetrahydrofuran. The amount of the solvent used may be determined according to the amount of the polymerization monomer. Generally, due to the amount of the solvent used, the concentration of the monomer is in the range of 5 to 40% by weight.

[0067] When producing the block copolymer, the order of adding the monomers is determined by the sequence structure of each block in the expected block copolymer. Taking the pentablock copolymer described above as an example, the pentablock copolymer may be produced by a method including the following steps. (5-1) Under the conditions of anionic polymerization, in the presence of at least one solvent, contact S51 monovinyl aromatic hydrocarbon with an organolithium initiator and a polarity regulator to carry out a homopolymerization reaction to form a reaction mixture containing an S51 block. (5-2) Under the conditions of anionic polymerization, add S52 monovinyl aromatic hydrocarbon and B51 conjugated diolefin to the reaction mixture containing the S51 block, and carry out a random copolymerization reaction to obtain a reaction mixture containing an S51 block and an S52 / B51 block. (5-3) Under the conditions of anionic polymerization, add B52 conjugated diolefin to the reaction mixture containing the S51 block and S52 / B51, and carry out a homopolymerization reaction to obtain a reaction mixture containing an S51 block, an S52 / B51 block, and a B52 block. (5-4) Under the conditions of anionic polymerization, add S53 monovinyl aromatic hydrocarbon and B53 conjugated diolefin to the reaction mixture containing the S51 block, S52 / B51 block, and B52 block, and carry out a random copolymerization reaction to obtain a reaction mixture containing an S51 block, an S52 / B51 block, a B52 block, and an S53 / B53 block. (5-5) Under the conditions of anionic polymerization, add S54 monovinyl aromatic hydrocarbon to the reaction mixture containing the S51 block, S52 / B51 block, B52 block, and S53 / B53 block, and carry out a homopolymerization reaction to obtain a reaction mixture containing the pentablock copolymer.

[0068] The polymerization reaction can be carried out under the conditions of a general anionic polymerization reaction. Generally, the temperature of the polymerization reaction in each step may be 40 to 90 °C. The temperature of the polymerization reaction in each step may be the same or different. Preferably, the temperature of the polymerization reaction in each step is the same, that is, the polymerization reaction in each step is carried out at the same temperature. According to the production method of the present invention, the duration of the polymerization reaction in each step is such that all or almost all of the monomers introduced in that step can react, and the conversion rate of the monomers in the polymerization reaction in each step is usually 99% or more. Generally, the duration of the polymerization reaction in each step may be 0.5 to 1.2 hours.

[0069] After the final stage of the polymerization reaction is completed, at least one terminator can be added to terminate the active chains. The terminator may be various substances capable of terminating active chains commonly used in the field of anionic polymerization, and may be, for example, at least one selected from the group consisting of water, alcohol, and acid. The terminator is preferably at least one selected from the group consisting of isopropanol, methanol, and water. The present invention does not particularly limit the amount of the polymerization terminator used, as long as the amount of the polymerization terminator is sufficient to inactivate the active centers. In actual operation, the amount of the polymerization terminator used may be determined according to the amount of the anionic polymerization initiator used.

[0070] By purifying and separating the obtained reaction mixture by a conventional method, a block copolymer can be obtained. Specifically, the obtained reaction mixture can be centrifuged, filtered, decanted, or hot water agglomerated to obtain a block copolymer, or the obtained mixture can be stripped to remove the solvent to obtain a block copolymer.

[0071] As will be understood by those skilled in the art, the above-mentioned heptablock copolymer may be produced by adding one random copolymerization reaction step and one homopolymerization reaction step that are sequentially performed based on the method for producing the pentablock copolymer. In this specification, the specific production method of the heptablock copolymer will not be described in detail.

[0072] The aromatic polymer may contain one or more than two kinds of auxiliaries. The auxiliaries may include antioxidants. In the present invention, the type of the antioxidant is not particularly limited, and various antioxidants commonly used in the art may be used. For example, the antioxidant may be a phenolic and / or amine antioxidant. Specifically, the antioxidant may be one or more selected from the group consisting of 4,6-bis(octylthiomethyl)-o-cresol, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tris(2,4-di-tert-butylphenyl) phosphite, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,6-di-tert-butyl-p-cresol, tert-butylcatechol, and 2,2'-methylenebis(4-methyl-6-tert-butylphenol). When pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and tris(2,4-di-tert-butylphenyl) phosphite are used in combination, the content of tris(2,4-di-tert-butylphenyl) phosphite is preferably 50% by weight or less. When octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and tris(2,4-di-tert-butylphenyl) phosphite are used in combination, the content of tris(2,4-di-tert-butylphenyl) phosphite is preferably 50% by weight or less. The usage amount of the antioxidant may be the normal usage amount in the art. For example, based on 100 parts by weight of the aromatic polymer, the usage amount of the antioxidant may be 0.005 to 2 parts by weight, preferably 0.1 to 1 part by weight. 2. Hydrogenation method

[0073] The hydrogenation method of the aromatic polymer according to the present invention includes the step of contacting the aromatic polymer with a hydrogenation reagent in the presence of a hydrogenation catalyst to hydrogenate at least a part of the aromatic rings in the aromatic polymer to obtain a hydrogenated aromatic polymer.

[0074] The hydrogenation catalyst contains a carrier which is alumina, and a platinum element, a Group 14 element, and a rare earth metal element supported on the carrier.

[0075] In the hydrogenation catalyst, in terms of elements, the molar ratio of the Group 14 element to the platinum element is 10 or less, preferably 8 or less. In the hydrogenation catalyst, in terms of elements, the molar ratio of the Group 14 element to the platinum element is 1 or more. In one preferred embodiment, in the hydrogenation catalyst, in terms of elements, the molar ratio of the Group 14 element to the platinum element is 3 to 7:1, for example, 3:1, 3.1:1, 3.2:1, 3.3:1, 3.4:1, 3.5:1, 3.6:1, 3.7:1, 3.8:1, 3.9:1, 4:1, 4.1:1, 4.2:1, 4.3:1, 4.4:1, 4.5:1, 4.6:1, 4.7:1, 4.8:1, 4.9:1, 5:1, 5.1:1, 5.2:1, 5.3:1, 5.4:1, 5.5:1, 5.6:1, 5.7:1, 5.8:1, 5.9:1, 6:1, 6.1:1, 6.2:1, 6.3:1, 6.4:1, 6.5:1, 6.6:1, 6.7:1, 6.8:1, 6.9:1, or 7:1. The Group 14 element may be at least one element selected from the group consisting of carbon (C), silicon (Si), germanium (Ge), tin (Sn), and lead (Pb), but is preferably at least one element selected from the group consisting of Si, Ge, and Sn. In one particularly preferred embodiment, the Group 14 element is Sn.

[0076] In the hydrogenation catalyst, in terms of elements, the molar ratio of the rare earth metal element to the platinum element is preferably 1 to 6:1, for example, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2:1, 2.1:1, 2.2:1, 2.3:1, 2.4:1, 2.5:1, 2.6:1, 2.7:1, 2.8:1, 2.9:1, 3:1, 3.1:1, 3.2:1, 3.3:1, 3.4:1, 3.5:1, 3.6:1, 3.7:1, 3.8:1, 3.9:1, 4:1, 4.1:1, 4.2:1, 4.3:1, 4.4:1, 4.5:1, 4.6:1, 4.7:1, 4.8:1, 4.9:1, 5:1, 5.1:1, 5.2:1, 5.3:1, 5.4:1, 5.5:1, 5.6:1, 5.7:1, 5.8:1, 5.9:1, or 6:1. Preferably, in terms of elements, the molar ratio of the rare earth metal element to the platinum element is 1.5 to 5:1. The rare earth metal element is at least one element selected from the group consisting of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, preferably at least one element selected from the group consisting of La, Ce, and Pr, more preferably La, Ce, or a combination thereof. In one particularly preferred embodiment, the rare earth metal element is Ce.

[0077] In one preferred embodiment, the hydrogenation catalyst further contains an alkali metal element and an alkaline earth metal element. The alkali metal element may be at least one element selected from the group consisting of lithium (Li), sodium (Na), potassium (K), rubidium (Rb), and cesium (Cs), preferably at least one element selected from the group consisting of Li, Na, and K, and more preferably K. The alkaline earth metal element may be at least one element selected from the group consisting of beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), and barium (Ba), preferably Mg, Ca, or a combination thereof, and more preferably Mg. In this preferred embodiment, in the hydrogenation catalyst, the molar ratio of the alkali metal element to the platinum element in terms of elements is preferably 7 to 20:1, for example, 7:1, 7.5:1, 8:1, 8.5:1, 9:1, 9.5:1, 10:1, 10.5:1, 11:1, 11.5:1, 12:1, 12.5:1, 13:1, 13.5:1, 14:1, 14.5:1, 15:1, 15.5:1, 16:1, 16.5:1, 17:1, 17.5:1, 18:1, 18.5:1, 19:1, 19.5:1, or 20:1. In this preferred embodiment, in the hydrogenation catalyst, the molar ratio of the alkaline earth metal element to the platinum element in terms of elements is preferably 10 to 35:1, for example, 10:1, 10.5:1, 11:1, 11.5:1, 12:1, 12.5:1, 13:1, 13.5:1, 14:1, 14.5:1, 15:1, 15.5:1, 16:1, 16.5:1, 17:1, 17.5:1, 18:1, 18.5:1, 19:1, 19.5:1, 20:1, 20.5:1, 21:1, 21.5:1, 22:1, 22.5:1, 23:1, 23.5:1, 24:1, 24.5:1, 25:1, 25.5:1, 26:1, 26.5:1, 27:1, 27.5:1, 28:1, 28.5:1, 29:1, 29.5:1, 30:1, 30.5:1, 31:1, 31.5:1, 32:1, 32.5:1, 33:1, 33.5:1, 34:1, 34.5:1, or 35:1.

[0078] In one preferred embodiment, the hydrogenation catalyst further contains a Group 4 metal element, a halogen group element, or a combination thereof. The Group 4 metal element may be titanium (Ti), zirconium (Zr), or a combination thereof, but preferably Zr. The halogen group element may be at least one element selected from the group consisting of fluorine (F), chlorine (Cl), bromine (Br), and iodine (I), but preferably Cl. In this preferred embodiment, in the hydrogenation catalyst, in terms of elements, the molar ratio of the Group 4 metal element to the platinum element is preferably 2 to 10:1, for example, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, 8:1, 8.5:1, 9:1, 9.5:1, or 10:1. In this preferred embodiment, in the hydrogenation catalyst, in terms of elements, the molar ratio of the Group 4 metal element to the platinum element is preferably 4 to 6:1. In this preferred embodiment, in the hydrogenation catalyst, in terms of elements, the molar ratio of the halogen group element to the platinum element is preferably 2 to 8:1, for example: 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, or 8:1. In this preferred embodiment, in the hydrogenation catalyst, in terms of elements, the molar ratio of the halogen group element to the platinum element is more preferably 4 to 6:1.

[0079] In a particularly preferred embodiment, in the hydrogenation catalyst, the hydrogenation catalyst contains a platinum element, a Group 14 element, a Group 4 metal element, a rare earth metal element, a halogen group element, an alkali metal element, and an alkaline earth metal element, the Group 14 element is Sn, the Group 4 metal element is Zr, the rare earth metal element is Ce, the halogen group element is Cl, the alkali metal element is K, and the alkaline earth metal element is Mg.

[0080] Based on the total amount of the hydrogenation catalyst, the content of the platinum element is, in terms of elemental conversion, 0.1 to 0.8% by weight, for example, 0.1% by weight, 0.2% by weight, 0.3% by weight, 0.4% by weight, 0.5% by weight, 0.6% by weight, 0.7% by weight, or 0.8% by weight. Preferably, based on the total amount of the hydrogenation catalyst, the content of the platinum element is, in terms of elemental conversion, 0.2 to 0.8% by weight.

[0081] In the hydrogenation catalyst, the alumina is preferably γ-alumina.

[0082] The specific surface area of the hydrogenation catalyst is preferably 100 to 400 m 2 / g, more preferably 200 to 350 m 2 / g, even more preferably 250 to 320 m 2 / g. The average pore diameter of the hydrogenation catalyst is preferably 5 to 40 nm, more preferably 10 to 20 nm, even more preferably 15 to 20 nm.

[0083] The hydrogenation catalyst can be obtained by supporting each component in the catalyst on a carrier and optionally calcining it. However, each component in the catalyst may also be supported on the carrier by a conventional method such as a liquid phase method. Specific examples of the liquid phase method include, but are not limited to, one or a combination of two or more of the impregnation method and the spray method.

[0084] Each component in the hydrogenation catalyst may be supported on the carrier by two or more supporting steps, or each component in the hydrogenation catalyst may be simultaneously supported on the carrier. In one preferred embodiment, each component in the hydrogenation catalyst is supported on the carrier by two or more supporting steps. In this preferred embodiment, preferably, first, the rare earth metal element is supported on the carrier, and then, the platinum element and the Group 14 element are supported on the carrier. When the hydrogenation catalyst contains a Group 4 metal element, a halogen group element, or a combination thereof, preferably, the Group 4 metal element, the halogen group element, or a combination thereof is supported on the carrier together with the platinum element and the Group 14 element. When the hydrogenation catalyst contains an alkali metal element and an alkaline earth metal element, preferably, prior to supporting the platinum element and the Group 14 element, the alkali metal element and the alkaline earth metal element are supported on the carrier containing the rare earth metal element.

[0085] When each component in the catalyst is supported using a liquid phase method, after the supporting is completed, the carrier may be dried to remove the liquid phase supported on the carrier. The temperature of the drying may be 50 to 200 °C, preferably 80 to 150 °C, and the duration of the drying may be 1 to 10 hours, preferably 2 to 8 hours. The drying may be carried out at normal pressure (i.e., 1 standard atmosphere), or may be carried out under conditions of reduced pressure. The drying may be carried out in an oxidizing atmosphere (e.g., air atmosphere), or may be carried out in an inert atmosphere (e.g., an atmosphere combined with one or more of nitrogen gas, argon gas, and helium gas).

[0086] When manufacturing the hydrogenation catalyst, after the supporting is completed, calcination may or may not be carried out, but it is preferable to carry out calcination. The calcination may be carried out under normal conditions. Specifically, the temperature of the calcination may be 400 to 650 °C, preferably 400 to 600 °C, and the duration of the calcination may be 1 to 10 hours, preferably 2 to 8 hours. The calcination is preferably carried out in an oxidizing atmosphere, for example, in an air atmosphere.

[0087] The hydrogenation catalyst is preferably produced by a method including the following steps. (a) A solution containing a rare earth metal element precursor is brought into contact with a carrier to obtain a second carrier, and at least a part of the solvent in the second carrier is removed to obtain a first intermediate carrier. (b) Optionally, the first intermediate carrier is brought into contact with a solution containing an alkali metal element precursor and an alkaline earth metal element precursor to obtain a third carrier, and at least a part of the solvent in the third carrier is removed to obtain a second intermediate carrier. (c) The first intermediate carrier or the second intermediate carrier is brought into contact with a solution containing a platinum precursor, a Group 14 element precursor, an optional Group 4 metal element precursor, and an optional halogen group element precursor to obtain a fourth carrier, and at least a part of the solvent in the fourth carrier is removed to obtain a third intermediate carrier. (d) The third intermediate carrier is calcined.

[0088] In the present invention, the precursors in steps (a), (b), and (c) are not particularly limited, and each may independently be a soluble compound of the above components, for example, a soluble salt. The term "soluble" means directly soluble in a solvent (e.g., water) or soluble in a solvent (e.g., water) in the presence of a co-solvent. Specifically, the platinum element precursor is preferably chloroplatinic acid, the Group 14 element precursor is a chloride and / or nitrate of a Group 14 element, preferably stannous chloride, tin chloride, or a combination thereof, the Group 4 metal element precursor may be a chloride, nitrate, or a combination thereof of a Group 4 element, but is preferably zirconium nitrate, zirconyl nitrate, or a combination thereof, the rare earth metal element precursor may be a chloride of a rare earth metal, a rare earth metal nitrate, or a combination thereof. The alkali metal element precursor may be a chloride of an alkali metal, a nitrate of an alkali metal, or a combination thereof. The alkaline earth metal element precursor may be a chloride of an alkaline earth metal, a nitrate of an alkaline earth metal, or a combination thereof. The halogen group element precursor may be at least one selected from the group consisting of halogen-containing compounds, for example, HCl, HBr, HI, and HF.

[0089] In the present invention, the concentrations of the solutions in step (a), step (b), and step (c) are not particularly limited and may be determined according to the water absorption rate of the carrier and the target content of each component.

[0090] The solvents of the solutions in step (a), step (b), and step (c) are each independently at least one selected from the group consisting of water, hydrochloric acid, and organic solvents. The organic solvent is preferably an alcohol, and preferred examples thereof include one or more selected from the group consisting of ethanol, isopropanol, and butanol, but are not limited thereto. Preferably, the solvents of the solutions in step (a) and step (b) are water. In one preferred embodiment, the solvent of the solution in step (c) is ethanol. According to this preferred embodiment, it is advantageous for the uniform dispersion of the catalyst components and the stabilization of the catalytic activity. In a more preferred embodiment, the solvent of the solution in step (c) is a mixed solution of hydrochloric acid and ethanol, where the volume ratio of hydrochloric acid to ethanol is preferably 1:1 to 5. According to this more preferred embodiment, it is more advantageous for the uniform dispersion of the catalyst components and the stabilization of the catalytic activity.

[0091] The hydrogenation catalyst is reduced before being used in the hydrogenation reaction. The reduction is carried out in a hydrogen-containing atmosphere, more preferably in a hydrogen-containing atmosphere. The temperature of the reduction is preferably 400 to 550 °C. The duration of the reduction is preferably 1 to 10 hours. The reduction may be carried out outside the hydrogenation reactor or in situ in the hydrogenation reactor. Preferably, the hydrogenation catalyst is reduced in situ in the hydrogenation reactor.

[0092] When performing a hydrogenation reaction using a conventional heterogeneous powder catalyst, since the catalytic activity of the catalyst is low, usually, the amount of the catalyst used is 100 to 800% of the weight of the polymer. Since the catalyst used in the hydrogenation method according to the present invention has high reaction activity, the amount of the hydrogenation catalyst used can be significantly reduced. In the hydrogenation method according to the present invention, with respect to 100 parts by weight of the aromatic polymer, the amount of the hydrogenation catalyst used may be 1 to 20 parts by weight, preferably 2 to 10 parts by weight, and more preferably 2.5 to 5 parts by weight.

[0093] In the method according to the present invention, in the presence of at least one solvent, an aromatic polymer is brought into contact with a hydrogenation catalyst. The solvent is a solvent capable of dissolving both the aromatic polymer and the hydrogenated aromatic polymer produced in the hydrogenation reaction. Specific examples of the solvent may include, but are not limited to, at least one selected from the group consisting of cyclohexane, methylcyclohexane, n - hexane, cyclooctane, cycloheptane, acetone, n - butanone, decalin, and tetrahydrofuran.

[0094] When performing a hydrogenation reaction using a conventional heterogeneous powder catalyst, since the catalytic activity of the catalyst is low, there is a limitation on the concentration of the polymer solution. If the concentration of the polymer solution is too high, the hydrogenation efficiency decreases, and usually, the concentration of the polymer solution is 5% by weight or less. Since the hydrogenation catalyst used in the present invention has high reaction activity, it enables a reaction at a high polymer concentration. In the hydrogenation method according to the present invention, depending on the amount of the solvent used, the concentration of the obtained polymer reaches 20% by weight, preferably 5 to 15% by weight.

[0095] In the hydrogenation method according to the present invention, the temperature of the hydrogenation reaction may be 50 to 200°C, preferably 120 to 180°C, and more preferably 120 to 150°C.

[0096] In the hydrogenation method according to the present invention, the hydrogenation reagent may be a normal hydrogenation reagent. In one preferred embodiment, the hydrogenation reagent is hydrogen gas. When hydrogen gas is used as the hydrogenation reagent, the pressure of the hydrogen gas may be 0.1 to 10 MPa, preferably 0.5 to 5 MPa, and the pressure is gauge pressure.

[0097] In the hydrogenation method according to the present invention, the hydrogenation catalyst can be recycled. Generally, after the hydrogenation reaction is completed, the hydrogenation reaction mixture may be subjected to solid-liquid separation to recover the hydrogenation catalyst. The recovered hydrogenation catalyst may be recycled to the hydrogenation reaction. Preferably, the recovered hydrogenation catalyst is sequentially washed and dried before being recycled to the hydrogenation reaction.

[0098] In the hydrogenation method according to the present invention, the degree of hydrogenation of the aromatic ring is high. In the hydrogenation method according to the present invention, the degree of hydrogenation of the aromatic ring may be 95 mol% or more, preferably 97 mol% or more, more preferably 98 mol% or more, still more preferably 99 mol% or more, even more preferably 100 mol%. In the hydrogenation method according to the present invention, when the aromatic polymer contains a conjugated diolefin structural unit, the degree of hydrogenation of the conjugated diolefin structural unit may be 97 mol% or more, preferably 99 mol% or more, more preferably 100 mol%.

[0099] In the hydrogenation method according to the present invention, the decomposition of the aromatic polymer during the hydrogenation reaction is small. In the hydrogenation method according to the present invention, the number average molecular weight of the aromatic polymer as the hydrogenation reaction raw material is M n 1, and the number average molecular weight of the hydrogenated aromatic polymer as the hydrogenation reaction product is M n 2. Defining [(M n 1 - M n 2) / M n 1]×100% as the decomposition rate, the decomposition rate is 2.5% or less, preferably 1.5% or less, more preferably 1% or less, still more preferably 0.5% or less, even more preferably 0.3% or less, particularly preferably 0.1% or less. 3. Hydrogenated block copolymer

[0100] The present invention provides a hydrogenated block copolymer, the block copolymer containing a monovinyl aromatic hydrocarbon structural unit derived from a monovinyl aromatic hydrocarbon and a conjugated diolefin structural unit derived from a conjugated diolefin. The hydrogenated block copolymer is formed by hydrogenating the block copolymer, and the hydrogenated block copolymer contains a hydrogenated monovinyl aromatic hydrocarbon structural unit and a hydrogenated conjugated diolefin structural unit. In the hydrogenated block copolymer, the degree of hydrogenation of the aromatic ring in the monovinyl aromatic hydrocarbon structural unit is 98 mol% or more, preferably 99 mol% or more, more preferably 100 mol%, and the degree of hydrogenation of the unsaturated double bond in the conjugated diolefin structural unit is 99 mol% or more, preferably 99.5 mol% or more, more preferably 100 mol%.

[0101] In the hydrogenated block copolymer according to the present invention, the block copolymer contains at least two homopolymerization segments of a monovinyl aromatic hydrocarbon, at least one homopolymerization segment of a conjugated diolefin, and at least two random copolymerization segments of a monovinyl aromatic hydrocarbon and a conjugated diolefin. The two end blocks of the block copolymer are each independently a homopolymerization segment of a monovinyl aromatic hydrocarbon, and the block directly bonded to the end block is an internal block, and the internal block is each independently a random copolymerization segment of a monovinyl aromatic hydrocarbon and a conjugated diolefin. When the block copolymer contains at least three random copolymerization segments of a monovinyl aromatic hydrocarbon and a conjugated diolefin and at least two homopolymerization segments of a conjugated diolefin, the homopolymerization segments of the conjugated diolefin and the random copolymerization segments of a monovinyl aromatic hydrocarbon and a conjugated diolefin are arranged at intervals, and the two terminal groups of the homopolymerization segment of the conjugated diolefin are each directly bonded to one random copolymerization segment of a monovinyl aromatic hydrocarbon and a conjugated diolefin.

[0102] In the hydrogenated block copolymer according to the present invention, based on the total amount of the block copolymer, the content of the structural unit derived from monovinyl aromatic hydrocarbon may be 40 to 95% by weight, and the content of the structural unit derived from conjugated diolefin may be 5 to 60% by weight, preferably 50% by weight or less, for example, it may be 10 to 50% by weight, more preferably 15 to 35% by weight, for example, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, or 35% by weight. Based on the total amount of the structural unit derived from monovinyl aromatic hydrocarbon in the block copolymer, the content of the structural unit derived from monovinyl aromatic hydrocarbon in the random copolymer segment may be 15 to 20% by weight, preferably 17 to 18.5% by weight. In the block copolymer, based on the total amount of the conjugated diolefin structural unit, the content of the pendant group may be 40 to 60% by weight.

[0103] In this preferred embodiment, the conjugated diolefin structural units in the homopolymer segment of the conjugated diolefin and the conjugated diolefin structural units in the random copolymer segment may be the same or different. Preferably, the homopolymer segment of the conjugated diolefin contains a homopolymer segment of one first conjugated diolefin and at least one homopolymer segment of a second conjugated diolefin. The structural units in the homopolymer segment of the first conjugated diolefin are derived from the first conjugated diolefin, the structural units in the homopolymer segment of the second conjugated diolefin are derived from the second conjugated diolefin, and the first conjugated diolefin and the second conjugated diolefin are different. More preferably, the homopolymer segment of the first conjugated diolefin is directly bonded to one internal block, the first conjugated diolefin is isoprene, and the conjugated diolefin in the random copolymer segment of the second conjugated diolefin and the monovinyl aromatic hydrocarbon and the conjugated diolefin is butadiene. Based on the total amount of the hydrogenated block copolymer, the content of isoprene structural units derived from isoprene is preferably 0.5 to 10% by weight, more preferably 1 to 5% by weight, still more preferably 2 to 4% by weight, and the content of butadiene structural units derived from butadiene is preferably 5 to 40% by weight, more preferably 10 to 35% by weight, still more preferably 15 to 30% by weight.

[0104] In the hydrogenated block copolymer according to the present invention, the notched impact strength of the hydrogenated block copolymer is 20 to 30 kJ / m 2 , preferably 21 to 25 kJ / m 2 . The elongation at break of the hydrogenated block copolymer is 200 to 400%, preferably 250 to 380%, more preferably 260 to 350%. The light transmittance of the hydrogenated block copolymer is 88 to 92%, preferably 90 to 92%. The haze of the hydrogenated block copolymer is 1 to 5, preferably 1 to 2. In the block copolymer according to the present invention, the Vicat softening point of the hydrogenated block copolymer is 110 to 150 °C, preferably 115 to 130 °C.

[0105] In the present invention, the notched impact strength is the notched impact strength of a simply supported beam measured based on the method specified in ISO179-1-2000, obtained from a test using a pendulum impact tester Ceast Resil Impactor6957. The dimensions of the adopted spline are 80mm×10mm×4mm, the notched remaining width dimension is 8±0.2mm, and the elongation at break is obtained using a material tensile testing machine INSTRON 5567 according to the method specified in ASTM D638-03. The dimensions of the adopted spline are 170mm×10mm×4mm. The light transmittance and haze are measured using an EEL57D type haze meter based on the method specified in ASTM D1033-2007. In the present invention, the Vicat softening point is measured using an Instron-HV6M type Vicat softening point temperature measuring device, with a heating rate of 50°C / h and a load of 50N.

[0106] The present invention also provides a hydrogenated pentablock copolymer, which is formed by hydrogenating the pentablock copolymer, where the pentablock copolymer is a pentablock copolymer having a structure represented by Formula II. S51-(S52 / B51)-B52-(S53 / B53)-S54 (Formula II) (In Formula II, the S51 block and the S54 block are end blocks, and each independently is a homopolymerization segment of a monovinyl aromatic hydrocarbon. The S52 / B51 block and the S53 / B53 block are internal blocks, and each independently is a random copolymerization segment of a monovinyl aromatic hydrocarbon and a conjugated diolefin. The B52 block is a homopolymerization segment of a conjugated diolefin.)

[0107] In the pentablock copolymer represented by Formula II, the monovinyl aromatic hydrocarbon structural units in the S51 block, S52 / B51 block, S53 / B53 block, and S54 block are represented as S51 monovinyl aromatic hydrocarbon structural units, S52 monovinyl aromatic hydrocarbon structural units, S53 monovinyl aromatic hydrocarbon structural units, and S54 monovinyl aromatic hydrocarbon structural units, respectively, and may be the same or different, and each may be one or more selected from the group consisting of styrene, 2-methylstyrene, 4-methylstyrene, and α-methylstyrene. Preferably, the monovinyl aromatic hydrocarbon structural units in the S51 block, S52 / B51 block, S53 / B53 block, and S54 block are the same and are all styrene structural units derived from styrene. In Formula II, when the monovinyl aromatic hydrocarbon structural units in the S51 block, S52 / B51 block, S53 / B53 block, and S54 block are all styrene structural units derived from styrene, based on the total amount of styrene structural units in the hydrogenated block copolymer, the content of the styrene non-block is preferably 15 to 20% by weight, more preferably 17 to 18.5% by weight.

[0108] In the pentablock copolymer represented by Formula II, the conjugated diolefin structural units in the B52 block are derived from B52 conjugated diolefin, the conjugated diolefin structural units in the S52 / B51 block are derived from B51 conjugated diolefin, the conjugated diolefin structural units in the S53 / B53 block are derived from B53 conjugated diolefin, and the B52 conjugated diolefin, the B51 conjugated diolefin, and the B53 conjugated diolefin may be the same or different, and each may be at least one selected from the group consisting of butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, and 2,3-dimethylbutadiene. Preferably, the B52 conjugated diolefin is different from the B51 conjugated diolefin and the B53 conjugated diolefin, and the B51 conjugated diolefin and the B53 conjugated diolefin are preferably the same.

[0109] More preferably, the B52 conjugated diolefin is isoprene, and the B51 conjugated diolefin and the B53 conjugated diolefin are butadiene. Based on the total amount of the pentablock copolymer, the content of the isoprene structural unit derived from isoprene is preferably 0.5 to 10% by weight, more preferably 1 to 5% by weight, still more preferably 2 to 4% by weight, and the content of the butadiene structural unit derived from butadiene is preferably 5 to 40% by weight, more preferably 10 to 35% by weight, still more preferably 15 to 30% by weight. Based on the total amount of the isoprene-derived structural units in the pentablock copolymer, the content of the isoprene structural unit containing a vinyl pendant group (i.e., the content of the pendant group) is preferably 50 to 60% by weight, more preferably 50 to 57% by weight. Based on the total amount of the butadiene-derived structural units in the pentablock copolymer, the content of the butadiene structural unit containing a vinyl pendant group (i.e., the content of the pendant group) is preferably 40 to 60% by weight, more preferably 45 to 55% by weight.

[0110] Based on the total amount of the pentablock copolymer represented by Formula II, the content of the monovinyl aromatic hydrocarbon structural unit derived from the monovinyl aromatic hydrocarbon is preferably 40 to 95% by weight, more preferably 50 to 90% by weight, still more preferably 65 to 85% by weight, and the content of the conjugated diolefin structural unit derived from the conjugated diolefin is preferably 5 to 60% by weight, more preferably 10 to 50% by weight, still more preferably 15 to 35% by weight. The monovinyl aromatic hydrocarbon structural unit includes the monovinyl aromatic hydrocarbon structural unit in the S51 block, the monovinyl aromatic hydrocarbon structural unit in the S54 block, the monovinyl aromatic hydrocarbon structural unit in the S52 / B51 block, and the monovinyl aromatic hydrocarbon structural unit in the S53 / B53 block, and the conjugated diolefin structural unit includes the conjugated diolefin structural unit in the S52 / B51 block, the conjugated diolefin structural unit in B52, and the conjugated diolefin structural unit in the S53 / B53 block.

[0111] In the pentablock copolymer represented by Formula II, the number average molecular weight of the S51 block is preferably from 5,000 to 50,000, the number average molecular weight of the S52 / B51 block is preferably from 20,000 to 50,000, the number average molecular weight of the S53 / B53 block is preferably from 20,000 to 50,000, and the number average molecular weight of the B52 block is preferably from 2,000 to 20,000. In the aromatic polymer represented by Formula II, the ratio of the number average molecular weight of the S51 block to the number average molecular weight of the S54 block is preferably from 1:2 to 10, more preferably from 1:2 to 6. In the pentablock copolymer represented by Formula II, the ratio of the number average molecular weight of the S52 / B51 block to the number average molecular weight of the S53 / B53 block is preferably from 1:0.9 to 1.25.

[0112] The number average molecular weight of the pentablock copolymer represented by Formula II is preferably from 50,000 to 220,000, more preferably from 80,000 to 200,000. The molecular weight distribution index (M w / M n ) of the pentablock copolymer represented by Formula II is preferably from 1.05 to 1.2.

[0113] In the hydrogenated pentablock copolymer according to the present invention, the hydrogenated pentablock copolymer contains a hydrogenated monovinyl aromatic hydrocarbon structural unit and a hydrogenated conjugated diolefin structural unit. In the hydrogenated block copolymer, the degree of hydrogenation of the aromatic ring in the monovinyl aromatic hydrocarbon structural unit is 98 mol% or more, preferably 99 mol% or more, more preferably 100 mol%, and the degree of hydrogenation of the unsaturated double bond in the conjugated diolefin structural unit is 99 mol% or more, preferably 99.5 mol% or more, more preferably 100 mol%.

[0114] In the hydrogenated pentablock copolymer according to the present invention, the notched impact strength of the hydrogenated block copolymer is 20 to 30 kJ / m 2 , preferably 21 to 25 kJ / m 2It is as follows. The elongation at break of the hydrogenated block copolymer is 200 to 400%, preferably 250 to 380%, more preferably 260 to 350%. The light transmittance of the hydrogenated block copolymer is 88 to 92%, preferably 90 to 92%. The haze of the hydrogenated block copolymer is 1 to 5, preferably 1 to 2. In the hydrogenated pentablock copolymer according to the present invention, the Vicat softening point of the hydrogenated pentablock copolymer is 110 to 150 °C, preferably 115 to 130 °C.

[0115] The present invention further provides a hydrogenated heptablock copolymer, and the heptablock copolymer is a heptablock copolymer having a structure represented by Formula III. S71-(S72 / B71)-B72-(S73 / B73)-B74-(S75 / B75)-S76 (Formula III) (In Formula III, the S71 block and the S76 block are end blocks, and each independently is a homopolymerization segment of a monovinyl aromatic hydrocarbon. The S72 / B71 block, the S73 / B73 block, and the S75 / B75 block are each independently a random copolymerization segment of a monovinyl aromatic hydrocarbon and a conjugated diolefin. Here, the S72 / B71 block and the S75 / B75 block are internal blocks, and the B72 block and the B74 block are each independently a homopolymerization segment of a conjugated diolefin.)

[0116] In the heptablock copolymer represented by Formula III, the monovinyl aromatic hydrocarbon structural units in the S71 block, S72 / B71 block, S73 / B73 block, S75 / B75 block, and S76 block are represented as S71 monovinyl aromatic hydrocarbon structural units, S72 monovinyl aromatic hydrocarbon structural units, S73 monovinyl aromatic hydrocarbon structural units, and S75 monovinyl aromatic hydrocarbon structural units, respectively. They may be the same or different, and each may be one or more selected from the group consisting of styrene, 2-methylstyrene, 4-methylstyrene, and α-methylstyrene. Preferably, the monovinyl aromatic hydrocarbon structural units in the S71 block, S72 / B71 block, S73 / B73 block, S75 / B75 block, and S76 block are the same and are all styrene structural units derived from styrene. In the heptablock copolymer represented by Formula III, when the monovinyl aromatic hydrocarbon structural units in the S71 block, S72 / B71 block, S73 / B73 block, S75 / B75 block, and S76 block are all styrene structural units derived from styrene, based on the total amount of styrene structural units in the heptablock copolymer, the content of the styrene non-block is preferably 15 to 20% by weight, more preferably 17 to 18.5% by weight.

[0117] In the heptablock copolymer represented by Formula III, the conjugated diolefin structural unit in the B72 block is derived from the B72 conjugated diolefin, the conjugated diolefin structural unit in the S72 / B71 block is derived from the B71 conjugated diolefin, the conjugated diolefin structural unit in the S73 / B73 block is derived from the B73 conjugated diolefin, the conjugated diolefin structural unit in the B74 block is derived from the B74 conjugated diolefin, and the conjugated diolefin structural unit in the S75 / B75 block is derived from the B75 conjugated diolefin. The B72 conjugated diolefin, the B71 conjugated diolefin, the B73 conjugated diolefin, the B74 conjugated diolefin, and the B75 conjugated diolefin may be the same or different, and each is at least one selected from the group consisting of butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, and 2,3-dimethylbutadiene. Preferably, the B72 conjugated diolefin is different from the B71 conjugated diolefin, the B73 conjugated diolefin, the B74 conjugated diolefin, and the B75 conjugated diolefin, and the B71 conjugated diolefin, the B73 conjugated diolefin, the B74 conjugated diolefin, and the B75 conjugated diolefin are preferably the same.

[0118] In the heptablock copolymer represented by Formula III, more preferably, the B72 conjugated diolefin is isoprene, and the B71 conjugated diolefin, the B73 conjugated diolefin, the B74 conjugated diolefin, and the B75 conjugated diolefin are butadiene. Based on the total amount of the heptablock copolymer, the content of the isoprene structural unit derived from isoprene is preferably 0.5 to 10% by weight, more preferably 1 to 5% by weight, still more preferably 2 to 4% by weight, and the content of the butadiene structural unit derived from butadiene is preferably 5 to 40% by weight, more preferably 10 to 35% by weight, still more preferably 15 to 30% by weight. Still more preferably, based on the total amount of the structural units derived from isoprene in the heptablock copolymer represented by Formula III, the content of the isoprene structural unit containing a vinyl pendant group is preferably 40 to 60% by weight, more preferably 45 to 55% by weight, and based on the total amount of the structural units derived from butadiene in the heptablock copolymer represented by Formula III, the content of the butadiene structural unit containing a vinyl pendant group is preferably 40 to 60% by weight, more preferably 45 to 55% by weight.

[0119] In the heptablock copolymer represented by the formula III, based on the total amount of the heptablock copolymer, the content of the monovinyl aromatic hydrocarbon structural unit derived from the monovinyl aromatic hydrocarbon is preferably 40 to 95% by weight, more preferably 50 to 90% by weight, and still more preferably 65 to 85% by weight. The content of the conjugated diolefin structural unit derived from the conjugated diolefin is preferably 5 to 60% by weight, more preferably 10 to 50% by weight, and still more preferably 15 to 35% by weight. The monovinyl aromatic hydrocarbon structural unit includes the monovinyl aromatic hydrocarbon structural unit in the S71 block, the monovinyl aromatic hydrocarbon structural unit in the S76 block, the monovinyl aromatic hydrocarbon structural unit in the S72 / B71 block, the monovinyl aromatic hydrocarbon structural unit in the S73 / B73 block, and the monovinyl aromatic hydrocarbon structural unit in the S75 / B75 block. The conjugated diolefin structural unit includes the conjugated diolefin structural unit in the S72 / B71 block, the conjugated diolefin structural unit in the B72 block, the conjugated diolefin structural unit in the S73 / B73 block, the conjugated diolefin structural unit in the B74 block, and the conjugated diolefin structural unit in the S75 / B75 block.

[0120] In the heptablock copolymer represented by Formula III, the number average molecular weight of the S71 block is preferably 5,000 to 50,000, the number average molecular weight of the S72 / B71 block is preferably 20,000 to 50,000, the number average molecular weight of the B72 block is preferably 2,000 to 20,000, the number average molecular weight of the S73 / B73 block is preferably 5,000 to 50,000, the number average molecular weight of the B74 block is preferably 2,000 to 20,000, the number average molecular weight of the S75 / B75 block is preferably 5,000 to 50,000, and the number average molecular weight of the S76 block is preferably 10,000 to 50,000. In the heptablock copolymer represented by Formula III, the ratio of the number average molecular weight of the S71 block to the number average molecular weight of the S76 block is preferably 1:1.5 to 5, more preferably 1.6 to 3. In the heptablock copolymer represented by Formula III, the ratio of the number average molecular weight of the S72 / B71 block, the number average molecular weight of the S73 / B73 block, and the number average molecular weight of S75 / B75 is preferably 1:1 to 1.2:1 to 1.25. In the heptablock copolymer represented by Formula III, the ratio of the number average molecular weight of the B72 block to the number average molecular weight of the B74 block is preferably 1:0.9 to 1.2.

[0121] In the heptablock copolymer represented by Formula III, the number average molecular weight of the heptablock copolymer is preferably 50,000 to 200,000, more preferably 120,000 to 190,000. The molecular weight distribution index (M w / M n ) of the heptablock copolymer is preferably 1.05 to 1.2.

[0122] In the hydrogenated heptablock copolymer according to the present invention, the hydrogenated heptablock copolymer contains a hydrogenated monovinyl aromatic hydrocarbon structural unit and a hydrogenated conjugated diolefin structural unit. In the hydrogenated heptablock copolymer, the degree of hydrogenation of the aromatic ring in the monovinyl aromatic hydrocarbon structural unit is 98 mol% or more, preferably 99 mol% or more, more preferably 99.5 mol%, and the degree of hydrogenation of the unsaturated double bond in the conjugated diolefin structural unit is 99 mol% or more, preferably 99.5 mol% or more, more preferably 100 mol%.

[0123] In the hydrogenated heptablock copolymer according to the present invention, the notched impact strength of the hydrogenated heptablock copolymer is 20 - 30 kJ / m 2 , preferably 21 - 25 kJ / m 2 . The elongation at break of the hydrogenated heptablock copolymer is 200 - 400%, preferably 250 - 350%, more preferably 260 - 320%. The light transmittance of the hydrogenated heptablock copolymer is 88 - 92%, preferably 90 - 92%. The haze of the hydrogenated heptablock copolymer is 1 - 5, preferably 1 - 2. In the hydrogenated heptablock copolymer according to the present invention, the Vicat softening point of the hydrogenated heptablock copolymer is 110 - 150 °C, preferably 120 - 140 °C.

[0124] In the hydrogenated block copolymer according to the present invention, the hydrogenated pentablock copolymer and the hydrogenated heptablock copolymer can be obtained by hydrogenating the corresponding block copolymer by the hydrogenation method of the present invention.

[0125] In the hydrogenated block copolymer according to the present invention, the hydrogenated pentablock copolymer and the hydrogenated heptablock copolymer can be applied to the production of packaging materials or optoelectronic products.

[0126] Hereinafter, the present invention will be described with reference to examples, but it does not limit the scope of the present invention.

[0127] In the following examples and comparative examples, the relevant performance parameters can be tested by the following methods.

[0128] (1) Hydrogenation degree and microstructure of the polymer Determined using nuclear magnetic resonance hydrogen spectrum ( 1 1H-NMR). 1 The 1H-NMR test was performed on a BRUKER AVANCEDRX400MHz NMR instrument. Deuterated chloroform was used as the solvent, and the sample was prepared into a solution with a concentration of 1-2 wt% at room temperature. Tetramethylsilane was used as the internal standard. The operating frequency was 400.13MHz, the spectral width was 8012.82Hz, the number of data points was 32K, the pulse angle was 30°, the pulse width was 6μs, the pulse delay was 5s, and the number of sampling times was 64.

[0129] (2) Molecular weight and molecular weight distribution index (M w w / M n ) Measured using an alliance-2690 type gel permeation chromatograph from Waters, USA. The column was of the PL Mixed-C type with a 5μm packing agent. Chromatographically pure tetrahydrofuran (THF) was used as the solvent, and narrow distribution polystyrene was used as the standard sample. The polymer sample was prepared into a solution with a mass concentration of 1mg / mL. The sample injection volume was 100.00μL, the flow rate was 1mL / min, and the test temperature was 40.0°C.

[0130] (3) Light transmittance and haze Measured using an EEL57D type haze meter according to the method specified in ASTM D1033-2007.

[0131] (4) Notched impact strength of a simple supported beam Measured with a pendulum impact tester Ceast Resil Impactor6957 according to the method specified in ISO179-1-2000. The dimensions of the adopted spline were 80mm×10mm×4mm, and the notch remaining width size was 8±0.2mm.

[0132] (5) Elongation at break in tension It was measured using an INSTRON 5567 material tensile testing machine in accordance with the method specified in ASTM D638-03. The dimensions of the adopted spline were 170 mm × 10 mm × 4 mm.

[0133] (6) Vicat softening point It was measured using an In stron-HV6M type Vicat softening point temperature measuring device. The heating rate was 50 °C / h and the load was 50 N.

[0134] (7) Composition of the hydrogenation catalyst The composition of the hydrogenation catalyst was measured using a Rigaku ZSX PrimuslV type fluorescent X-ray analyzer.

[0135] (8) Specific surface area and average pore diameter of the hydrogenation catalyst The specific surface area and average pore diameter of the hydrogenation catalyst were measured using an ASAP 2020 type physical adsorption device purchased from Micromeritics Instrument Corporation using the N2 adsorption method.

[0136] In the following production, unless otherwise specified, the usage amount of each precursor and the concentration of each precursor solution are determined based on the weight of the hydrogenation catalyst and the content of each element in the hydrogenation catalyst. In the following production, unless otherwise specified, the weight of the produced hydrogenation catalyst was all 10 g. In the following production examples, unless otherwise specified, the γ-alumina support used had a specific surface area of 350 m 2 / g and an average pore diameter of 20 nm.

[0137] Production Examples 1 to 7 are used for the production of the hydrogenation catalyst. Production Example 1

[0138] In this production example, a hydrogenation catalyst having the composition shown in Table 1 was produced. (1) The γ-alumina support was immersed in an equal volume using a cerium nitrate solution, and the immersed support was dried at 120 °C in an air atmosphere for 8 hours to obtain an alumina support containing cerium element. (2) Using a solution containing potassium nitrate and magnesium nitrate, the alumina support containing cerium element obtained in step (1) was immersed in an equal volume, and the immersed support was dried at 120 °C in an air atmosphere for 8 hours to obtain a catalyst intermediate carrying cerium element, potassium element, and magnesium element. (3) Using a hydrochloric acid ethanol solution (the volume ratio of hydrochloric acid to absolute ethanol is 1:2) containing chloroplatinic acid, tin chloride, and zirconium dichloride, the catalyst intermediate obtained in step (2) was immersed in an equal volume to carry platinum element, tin element, and zirconium element on the support. The immersed support was dried at 120 °C in an air atmosphere for 8 hours, and then calcined at 600 °C in an air atmosphere for 6 hours to obtain a hydrogenation catalyst. The specific surface area of the hydrogenation catalyst was 300 m 2 / g, and the average pore diameter was 17.6 nm. Production Example 2

[0139] In this production example, a hydrogenation catalyst having the composition shown in Table 1 was produced. A hydrogenation catalyst was produced by the same method as in Production Example 1 except that the usage amount of the precursor was changed, and a hydrogenation catalyst with a different composition was obtained. The specific surface area of the hydrogenation catalyst was 295 m 2 / g, and the average pore diameter was 18.2 nm. Production Example 3

[0140] In this production example, a hydrogenation catalyst having the composition shown in Table 1 was produced. A hydrogenation catalyst was produced by the same method as in Production Example 1 except that the usage amount of the precursor was changed, and a hydrogenation catalyst with a different composition was obtained. The specific surface area of the hydrogenation catalyst was 290 m 2 / g, and the average pore diameter was 18.5 nm. Production Example 4

[0141] In this production example, a hydrogenation catalyst having the composition shown in Table 1 was produced. Without performing step (2), the alumina carrier containing cerium element produced in step (1) was subjected to step (3), and was immersed in an equal volume using a hydrochloric acid ethanol solution containing chloroplatinic acid, tin chloride and zirconium chloride. Also, except for adjusting the usage amount of the precursor, a hydrogenation catalyst was produced by the same method as in Production Example 1, and a hydrogenation catalyst was obtained. The hydrogenation catalyst had a specific surface area of 280 m 2 / g and an average pore diameter of 18.7 nm. Production Example 5

[0142] In this production example, a hydrogenation catalyst having the composition shown in Table 1 was produced. Except for changing the usage amount of the precursor, a hydrogenation catalyst was produced by the same method as in Production Example 1, and a hydrogenation catalyst having a different composition was obtained. The hydrogenation catalyst had a specific surface area of 280 m 2 / g and an average pore diameter of 18.9 nm. Production Comparative Example 1 (Not of the present invention)

[0143] The γ-alumina carrier used in step (1) of Production Example 1 was immersed in an equal volume in a nickel nitrate solution under the same conditions as in step (3) of Production Example 1. After immersion, the carrier was dried at 120 °C in an air atmosphere for 8 hours to obtain a catalyst supporting nickel element. Based on the total amount of the catalyst, in terms of elements, the nickel content in the catalyst was 10% by weight. Production Comparative Example 2 (Not of the present invention)

[0144] In this production comparative example, a catalyst having the composition shown in Table 1 was produced. Except for changing the usage amount of the precursor, a hydrogenation catalyst was produced by the same method as in Production Example 1, and a hydrogenation catalyst having a different composition was obtained. The hydrogenation catalyst had a specific surface area of 230 m 2 / g and an average pore diameter of 18.2 nm. Production Comparative Example 3 (Not of the present invention)

[0145] In this production comparative example, a catalyst having the composition shown in Table 1 was produced. A hydrogenation catalyst was produced by the same method as in Production Example 1, except that stannous chloride was not contained in the immersion liquid used in step (3). The obtained hydrogenation catalyst had a specific surface area of 230 m 2 / g and an average pore diameter of 18.3 nm. Production Example 6

[0146] In this production example, a catalyst having the composition shown in Table 1 was produced. A hydrogenation catalyst was produced by the same method as in Production Example 1, except that HCl was not contained in the immersion liquid used in step (3) and the same volume of absolute ethanol was used instead of HCl. The obtained hydrogenation catalyst had a specific surface area of 280 m 2 / g and an average pore diameter of 18.2 nm. Production Example 7

[0147] In this production example, a catalyst having the composition shown in Table 1 was produced. A hydrogenation catalyst was produced by the same method as in Production Example 1, except that zirconium dichloride was not contained in the immersion liquid used in step (3). The obtained hydrogenation catalyst had a specific surface area of 280 m 2 / g and an average pore diameter of 18.3 nm.

[0148]

Table 1

[0149] Examples 1 to 19 are used to illustrate the present invention. Example 1

[0150] (1) Production of block copolymer (1-1) 800 g of cyclohexane, 60 mg of tetrahydrofurfuryl ethyl ether (ETE), and 38 g of styrene were added to a 2 L stainless steel stirring kettle, the temperature was raised to 50°C, 1.6 mmol of n-butyllithium initiator was added, and polymerization was carried out at 50°C for 30 minutes to obtain a styrene homopolymer. The conversion rate of styrene was 99% or more. (1-2) The temperature of the stirring kettle was maintained at 50 °C, 30 g of butadiene and 22 g of styrene were added to the stirring kettle, and the reaction was carried out for 40 minutes to randomly copolymerize butadiene and styrene. The conversion rate of butadiene was 99% or more, and the conversion rate of styrene was 99% or more. (1-3) The temperature of the stirring kettle was maintained at 50 °C, 6 g of isoprene was added to the stirring kettle, and the reaction was carried out for 40 minutes. The conversion rate of isoprene was 99% or more. (1-4) The temperature of the stirring kettle was maintained at 50 °C, 30 g of butadiene and 22 g of styrene were added to the stirring kettle, and the reaction was carried out for 30 minutes to randomly copolymerize butadiene and styrene. The conversion rate of butadiene was 99% or more, and the conversion rate of styrene was 99% or more. (1-5) The temperature of the stirring kettle was maintained at 50 °C, 92 g of styrene was added to the stirring kettle, and the reaction was further carried out for 30 minutes. The conversion rate of styrene was 99% or more. (1-6) 0.25 g of isopropanol was added to the stirring kettle, and the reaction was stopped at 50 °C to obtain a block copolymer. An antioxidant 1076 was added to the obtained rubber solution in an amount of 1% by weight of the total weight of the monomers charged in each step of the reaction, and mixed for 10 minutes to obtain a rubber solution containing a block copolymer. The concentration of the block copolymer in the rubber solution was adjusted to 10% by weight. The structural parameters of the block copolymer are shown in Table 2, and the structure of the block copolymer is S51-S52 / B51-B52-S53 / B53-S54, where S51, S52, S53 and S54 are all structural units derived from styrene, B51 and B53 are all structural units derived from butadiene, and B52 is a structural unit derived from isoprene. (2) Production of hydrogenated block copolymer The hydrogenation catalyst produced in Production Example 1 was reduced to obtain a reduced catalyst, and the reduced catalyst was used in the hydrogenation reaction. The reduction was carried out in a hydrogen gas atmosphere, the reduction temperature was 450 °C, and the reduction duration was 2 hours. 200 g of a rubber solution containing the block copolymer produced in step (1) and 1 g of the hydrogenated catalyst after reduction were added to a 0.5 L high-pressure reactor with a stirring function, and the hydrogenation reaction was carried out at a reaction temperature of 150 °C, a hydrogen gas pressure of 3 MPa, a reaction time of 1 h, and a stirring rotation speed of 800 rpm. After the hydrogenation reaction was completed, the hydrogenation reaction product was centrifuged to obtain a reaction mixture containing the hydrogenated block copolymer. The reaction mixture was filtered to separate the hydrogenated catalyst. The separated hydrogenated catalyst was washed with n-hexane and vacuum dried, and then recycled to the hydrogenation reaction. As a result of measurement, the hydrogenation catalyst had a hydrogenation activity reduction rate of 2% or less after being recycled 5 times (based on the hydrogenation activity when used for the first time). The liquid phase obtained by filtration was collected, the solvent was removed, and the hydrogenated block copolymer according to the present invention was obtained. The structure and performance parameters of the hydrogenated block copolymer are shown in Table 3. Example 2

[0151] (1) Production of block copolymer (1-1) 800 g of cyclohexane, 60 mg of ETE, and 19 g of styrene were added to a 2 L stainless steel stirring kettle, the temperature was raised to 50 °C, 2.4 mmol of n-butyllithium initiator was added, and polymerization was carried out at 50 °C for 30 minutes to obtain a styrene homopolymer. The conversion rate of styrene was 99% or more. (1-2) While maintaining the temperature of the stirring kettle at 50 °C, 30 g of butadiene and 22 g of styrene were added to the stirring kettle and reacted for 40 minutes to randomly copolymerize butadiene and styrene. The conversion rate of butadiene was 99% or more, and the conversion rate of styrene was 99% or more. (1-3) While maintaining the temperature of the stirring kettle at 50 °C, 6 g of isoprene was added to the stirring kettle and reacted for 40 minutes. The conversion rate of isoprene was 99% or more. (1-4) While maintaining the temperature of the stirring kettle at 50 °C, 30 g of butadiene and 22 g of styrene were added to the stirring kettle and reacted for 30 minutes to randomly copolymerize butadiene and styrene. The conversion rate of butadiene was 99% or more, and the conversion rate of styrene was 99% or more. (1-5) The temperature of the stirring kettle was maintained at 50 °C, 111 g of styrene was added to the stirring kettle, and the reaction was further carried out for 30 minutes. The conversion rate of styrene was 99% or more. (1-6) 0.25 g of isopropanol was added to the stirring kettle, the reaction was stopped at 50 °C, and a block copolymer was obtained. Antioxidant 1076 was added to the obtained rubber solution in an amount of 1% by weight based on the total weight of the monomers charged in each step of the reaction, and the mixture was stirred for 10 minutes to obtain a rubber solution containing a block copolymer. The concentration of the block copolymer in the rubber solution was adjusted to 10% by weight. The structural parameters of the block copolymer are shown in Table 2, and the structure of the block copolymer is S51-S52 / B51-B52-S53 / B53-S54, where S51, S52, S53, and S54 are all structural units derived from styrene, B51 and B53 are all structural units derived from butadiene, and B52 is a structural unit derived from isoprene. (2) Production of hydrogenated block copolymer A hydrogenated block copolymer was produced in the same manner as in Example 1, except that the rubber solution containing the block copolymer produced in step (1) of Example 2 was used. The structure and performance parameters of the produced hydrogenated block copolymer are shown in Table 3. Example 3

[0152] (1) Production of block copolymer (1-1) 800 g of cyclohexane, 50 mg of ETE, and 38 g of styrene were added to a 2 L stainless steel stirring kettle, the temperature was raised to 50 °C, 2.4 mmol of n-butyllithium initiator was added, and polymerization was carried out at 50 °C for 30 minutes to obtain a styrene homopolymer. The conversion rate of styrene was 99% or more. (1-2) The temperature of the stirring kettle was maintained at 50 °C, 30 g of butadiene and 22 g of styrene were added to the stirring kettle, and the reaction was carried out for 40 minutes to randomly copolymerize butadiene and styrene. The conversion rate of butadiene was 99% or more, and the conversion rate of styrene was 99% or more. (1-3) The temperature of the stirring kettle was maintained at 50 °C, 6 g of isoprene was added to the stirring kettle, and the reaction was carried out for 40 minutes. The conversion rate of isoprene was 99% or more. (1-4) The temperature of the stirring kettle was maintained at 50 °C, 30 g of butadiene and 22 g of styrene were added to the stirring kettle, and the reaction was carried out for 30 minutes to randomly copolymerize butadiene and styrene. The conversion rate of butadiene was 99% or more, and the conversion rate of styrene was 99% or more. (1-5) The temperature of the stirring kettle was maintained at 50 °C, 111 g of styrene was added to the stirring kettle, and the reaction was further carried out for 30 minutes. The conversion rate of styrene was 99% or more. (1-6) 0.25 g of isopropanol was added to the stirring kettle, and the reaction was stopped at 50 °C to obtain a block copolymer. Antioxidant 1076 was added to the obtained rubber solution in an amount of 1% by weight of the total weight of the monomers introduced into the reaction in each step, and mixed for 10 minutes to obtain a rubber solution containing a block copolymer. The concentration of the block copolymer in the rubber solution was adjusted to 10% by weight. The structural parameters of the block copolymer are shown in Table 2, and the structure of the block copolymer is S51-S52 / B51-B52-S53 / B53-S54, where S51, S52, S53, and S54 are all structural units derived from styrene, B51 and B53 are all structural units derived from butadiene, and B52 is a structural unit derived from isoprene. (2) Production of hydrogenated block copolymer A hydrogenated block copolymer was produced in the same manner as in Example 1, except that the rubber solution containing the block copolymer produced in step (1) of Example 3 was used. The structure and performance parameters of the produced hydrogenated block copolymer are shown in Table 3. Example 4

[0153] (1) Production of block copolymer Instead of styrene in steps (1-1), (1-2), and (1-4), 2-vinyltoluene (2-EMB) of the same weight was used respectively, and instead of styrene in step (1-5), α-methylstyrene (AMS) of the same weight was used. A block copolymer was produced in the same manner as in Example 1 except for this. The structural parameters of the produced block copolymer are shown in Table 2, and the structure of the block copolymer is S51-S52 / B51-B52-S53 / B53-S54, where S51, S52, and S53 are all structural units derived from 2-vinyltoluene, S54 is a structural unit derived from α-methylstyrene, B51 and B53 are all structural units derived from butadiene, and B52 is a structural unit derived from isoprene. (2) Production of hydrogenated block copolymer A hydrogenated block copolymer was produced in the same manner as in Example 1 except that a rubber solution containing the block copolymer produced in step (1) of Example 4 was used. The structure and performance parameters of the produced hydrogenated block copolymer are shown in Table 3. Example 5

[0154] (1) Production of block copolymer A block copolymer was produced in the same manner as in Example 1 except that isoprene of the same weight was used respectively instead of butadiene in steps (1-2) and (1-4). The structural parameters of the produced block copolymer are shown in Table 2, and the structure of the block copolymer is S51-S52 / B51-B52-S53 / B53-S54, where S51, S52, S53, and S54 are all structural units derived from styrene, and B51, B53, and B52 are all structural units derived from isoprene. (2) Production of hydrogenated block copolymer A hydrogenated block copolymer was produced in the same manner as in Example 1 except that a rubber solution containing the block copolymer produced in step (1) of Example 5 was used. The structure and performance parameters of the produced hydrogenated block copolymer are shown in Table 3. Comparative Example 1 (not of the present invention)

[0155] In step (2), the hydrogenation catalyst was changed to the same weight of nickel element-supported catalyst produced in Production Comparative Example 1. As the reduction conditions of the nickel element-supported hydrogenation catalyst, in a hydrogen gas atmosphere, the catalyst precursor containing nickel was reduced at 500 °C for 6 h to obtain the hydrogenation catalyst after reduction. A block copolymer was produced in the same manner as in Example 1 except for this, and a hydrogenated block copolymer was produced by the hydrogenation reaction of the block copolymer. The structure and performance parameters of the produced hydrogenated block copolymer are shown in Table 3. Comparative Example 2 (not of the present invention)

[0156] In step (2), a block copolymer was produced in the same manner as in Example 1 except that the hydrogenation catalyst was changed to the same weight of hydrogenation catalyst produced in Production Comparative Example 2, and a hydrogenated block copolymer was produced by the hydrogenation reaction of the block copolymer. The structure and performance parameters of the produced hydrogenated block copolymer are shown in Table 3. Comparative Example 3 (not of the present invention)

[0157] In step (2), a block copolymer was produced in the same manner as in Example 1 except that the hydrogenation catalyst was changed to the same weight of hydrogenation catalyst produced in Production Comparative Example 3, and a hydrogenated block copolymer was produced by the hydrogenation reaction of the block copolymer. The structure and performance parameters of the produced hydrogenated block copolymer are shown in Table 3. Example 6

[0158] In step (2), a block copolymer was produced in the same manner as in Example 1 except that the hydrogenation catalyst was changed to the same weight of hydrogenation catalyst produced in Production Example 6, and a hydrogenated block copolymer was produced by the hydrogenation reaction of the block copolymer. The structure and performance parameters of the produced hydrogenated block copolymer are shown in Table 3. Example 7

[0159] In step (2), a block copolymer was produced in the same manner as in Example 1, except that the hydrogenation catalyst was changed to the same weight of the hydrogenation catalyst produced in Production Example 7, and a hydrogenated block copolymer was produced by the hydrogenation reaction of the block copolymer. The structure and performance parameters of the produced hydrogenated block copolymer are shown in Table 3. Example 8

[0160] (1) Production of block copolymer (1-1) 800 g of cyclohexane, 100 mg of tetrahydrofuran (THF), and 38 g of styrene were added to a 2 L stainless steel stirring kettle, the temperature was raised to 50 °C, 2.4 mmol of n-butyllithium initiator was added, and polymerization was carried out at 50 °C for 30 minutes to obtain a styrene homopolymer. The conversion rate of styrene was 99% or more. (1-2) While maintaining the temperature of the stirring kettle at 50 °C, 30 g of butadiene was added to the stirring kettle and reacted for 40 minutes. The conversion rate of butadiene was 99% or more. (1-3) While maintaining the temperature of the stirring kettle at 50 °C, 22 g of styrene was added to the stirring kettle and reacted for 40 minutes. The conversion rate of styrene was 99% or more. (1-4) While maintaining the temperature of the stirring kettle at 50 °C, 30 g of butadiene was added to the stirring kettle and reacted for 30 minutes. The conversion rate of butadiene was 99% or more. (1-5) While maintaining the temperature of the stirring kettle at 50 °C, 92 g of styrene was added to the stirring kettle and further reacted for 30 minutes. The conversion rate of styrene was 99% or more. (1-6) 0.25 g of isopropanol was added to the stirring kettle, the reaction was stopped at 50 °C to obtain a block copolymer. An antioxidant 1076 was added to the obtained rubber solution in an amount of 1% by weight of the total weight of the monomers introduced into the reaction in each step, and mixed for 10 minutes to obtain a rubber solution containing a block copolymer, and the concentration of the block copolymer in the rubber solution was adjusted to 10% by weight. The structural parameters of the block copolymer are shown in Table 2. (2) Production of hydrogenated block copolymer A hydrogenated block copolymer was produced in the same manner as in Example 1, except that a rubber solution containing the block copolymer produced in step (1) of Example 8 was used. The structural and performance parameters of the produced hydrogenated block copolymer are shown in Table 3. Example 9

[0161] (1) Production of block copolymer (1-1) 800 g of cyclohexane, 100 mg of tetrahydrofuran (THF), and 38 g of styrene were added to a 2 L stainless steel stirring kettle, the temperature was raised to 50 °C, 2.4 mmol of n-butyllithium initiator was added, and polymerization was carried out at 50 °C for 30 minutes to obtain a styrene homopolymer. The conversion rate of styrene was 99% or more. (1-2) While maintaining the temperature of the stirring kettle at 50 °C, 30 g of butadiene was added to the stirring kettle and reacted for 40 minutes. The conversion rate of butadiene was 99% or more. (1-3) While maintaining the temperature of the stirring kettle at 50 °C, 30 g of butadiene and 22 g of styrene were added to the stirring kettle and reacted for 40 minutes to randomly copolymerize butadiene and styrene. The conversion rate of butadiene was 99% or more, and the conversion rate of styrene was 99% or more. (1-4) While maintaining the temperature of the stirring kettle at 50 °C, 92 g of styrene was added to the stirring kettle and reacted for an additional 30 minutes. The conversion rate of styrene was 99% or more. (1-5) Finally, 0.25 g of isopropanol was added to the stirring kettle, and the reaction was stopped at 50 °C to obtain a block copolymer. An antioxidant 1076 was added to the obtained rubber solution in an amount of 1% by weight of the total weight of the monomers charged in each step of the reaction, and mixed for 10 minutes to obtain a rubber solution containing a block copolymer, and the concentration of the block copolymer in the rubber solution was adjusted to 10% by weight. The structural parameters of the block copolymer are shown in Table 2. (2) Production of hydrogenated block copolymer A hydrogenated block copolymer was produced in the same manner as in Example 1, except that a rubber solution containing the block copolymer produced in step (1) of Example 9 was used. The structural and performance parameters of the produced hydrogenated block copolymer are shown in Table 3. Example 10

[0162] (1) Production of block copolymer (1-1) 800 g of cyclohexane, 60 mg of tetrahydrofurfuryl ethyl ether (ETE), and 30 g of isoprene were added to a 2 L stainless steel stirring kettle. The temperature was raised to 50°C, and 1.6 mmol of n-butyllithium initiator was added. Polymerization was carried out at 50°C for 30 minutes to obtain an isoprene homopolymer. The conversion rate of isoprene was 99% or more. (1-2) While maintaining the temperature of the stirring kettle at 50°C, 30 g of butadiene and 22 g of styrene were added to the stirring kettle and reacted for 40 minutes to randomly copolymerize butadiene and styrene. The conversion rate of butadiene was 99% or more, and the conversion rate of styrene was 99% or more. (1-3) While maintaining the temperature of the stirring kettle at 50°C, 6 g of isoprene was added to the stirring kettle and reacted for 40 minutes. The conversion rate of isoprene was 99% or more. (1-4) While maintaining the temperature of the stirring kettle at 50°C, 30 g of butadiene and 22 g of styrene were added to the stirring kettle and reacted for 30 minutes to randomly copolymerize butadiene and styrene. The conversion rate of butadiene was 99% or more, and the conversion rate of styrene was 99% or more. (1-5) While maintaining the temperature of the stirring kettle at 50°C, 92 g of styrene was added to the stirring kettle and reacted for an additional 30 minutes. The conversion rate of styrene was 99% or more. (1-6) Finally, 0.25 g of isopropanol was added to the stirring kettle, and the reaction was stopped at 50°C to obtain a block copolymer. An antioxidant 1076 was added to the obtained rubber solution in an amount of 1% by weight of the total weight of the monomers introduced into the reaction of each step, and mixed for 10 minutes to obtain a rubber solution containing a block copolymer. The concentration of the block copolymer in the rubber solution was adjusted to 10% by weight. The structural parameters of the block copolymer are shown in Table 2. (2) Production of hydrogenated block copolymer A hydrogenated block copolymer was produced in the same manner as in Example 1, except that a rubber solution containing the block copolymer produced in Step (1) of Example 10 was used. The structure and performance parameters of the produced hydrogenated block copolymer are shown in Table 3. Example 11

[0163] (1) Production of block copolymer (1-1) 800 g of cyclohexane, 60 mg of ethyltetrahydrofurfuryl ether (ETE), and 38 g of styrene were added to a 2 L stainless steel stirring kettle, the temperature was raised to 50 °C, 1.6 mmol of n-butyllithium initiator was added, and polymerization was carried out at 50 °C for 30 minutes to obtain a styrene homopolymer. The conversion rate of styrene was 99% or more. (1-2) While maintaining the temperature of the stirring kettle at 50 °C, 30 g of butadiene and 22 g of styrene were added to the stirring kettle and reacted for 40 minutes to randomly copolymerize butadiene and styrene. The conversion rate of butadiene was 99% or more, and the conversion rate of styrene was 99% or more. (1-3) While maintaining the temperature of the stirring kettle at 50 °C, 20 g of styrene was added to the stirring kettle and reacted for 40 minutes. The conversion rate of styrene was 99% or more. (1-4) While maintaining the temperature of the stirring kettle at 50 °C, 30 g of butadiene and 22 g of styrene were added to the stirring kettle and reacted for 30 minutes to randomly copolymerize butadiene and styrene. The conversion rate of butadiene was 99% or more, and the conversion rate of styrene was 99% or more. (1-5) While maintaining the temperature of the stirring kettle at 50 °C, 92 g of styrene was added to the stirring kettle and reacted for an additional 30 minutes. The conversion rate of styrene was 99% or more. (1-6) 0.25 g of isopropanol was added to the stirring kettle, the reaction was stopped at 50 °C to obtain a block copolymer. An antioxidant 1076 was added to the obtained rubber solution in an amount of 1% by weight of the total weight of the monomers introduced into the reaction in each step, and mixed for 10 minutes to obtain a rubber solution containing a block copolymer, and the concentration of the block copolymer in the rubber solution was adjusted to 10% by weight. The structural parameters of the block copolymer are shown in Table 2. (2) Production of hydrogenated block copolymer A hydrogenated block copolymer was produced in the same manner as in Example 1, except that a rubber solution containing the block copolymer produced in step (1) of Example 11 was used. The structure and performance parameters of the produced hydrogenated block copolymer are shown in Table 3. Example 12

[0164] (1) Production of block copolymer (1-1) 800 g of cyclohexane, 60 mg of tetrahydrofurfuryl ethyl ether (ETE), and 38 g of styrene were added to a 2 L stainless steel stirring kettle, the temperature was raised to 50 °C, 1.6 mmol of n-butyllithium initiator was added, and polymerization was carried out at 50 °C for 30 minutes to obtain a styrene homopolymer. The conversion rate of styrene was 99% or more. (1-2) The temperature of the stirring kettle was maintained at 50 °C, 6 g of isoprene was added to the stirring kettle, and the reaction was carried out for 40 minutes. The conversion rate of isoprene was 99% or more. (1-3) The temperature of the stirring kettle was maintained at 50 °C, 30 g of butadiene and 22 g of styrene were added to the stirring kettle, and the reaction was carried out for 40 minutes to randomly copolymerize butadiene and styrene. The conversion rate of butadiene was 99% or more, and the conversion rate of styrene was 99% or more. (1-4) The temperature of the stirring kettle was maintained at 50 °C, 30 g of butadiene and 22 g of styrene were added to the stirring kettle, and the reaction was carried out for 30 minutes to randomly copolymerize butadiene and styrene. The conversion rate of butadiene was 99% or more, and the conversion rate of styrene was 99% or more. (1-5) The temperature of the stirring kettle was maintained at 50 °C, 92 g of styrene was added to the stirring kettle, and the reaction was carried out for an additional 30 minutes. The conversion rate of styrene was 99% or more. (1-6) 0.25 g of isopropanol was added to the stirring kettle, the reaction was stopped at 50 °C to obtain a block copolymer. An antioxidant 1076 was added to the obtained rubber solution in an amount of 1% by weight of the total weight of the monomers introduced into the reaction of each step, and mixed for 10 minutes to obtain a rubber solution containing a block copolymer, and the concentration of the block copolymer in the rubber solution was adjusted to 10% by weight. The structural parameters of the block copolymer are shown in Table 2. (2) Production of Hydrogenated Block Copolymer A hydrogenated block copolymer was produced in the same manner as in Example 1, except that a rubber solution containing the block copolymer produced in step (1) of Example 12 was used. The structure and performance parameters of the produced hydrogenated block copolymer are shown in Table 3. Example 13

[0165] In step (2), a block copolymer was produced in the same manner as in Example 1, except that the hydrogenation catalyst was changed to the same weight of the hydrogenation catalyst produced in Production Example 2, and a hydrogenated block copolymer was produced by the hydrogenation reaction of the block copolymer. The structure and performance parameters of the produced hydrogenated block copolymer are shown in Table 3. Example 14

[0166] In step (2), a block copolymer was produced in the same manner as in Example 1, except that the hydrogenation catalyst was changed to the same weight of the hydrogenation catalyst produced in Production Example 3, and a hydrogenated block copolymer was produced by the hydrogenation reaction of the block copolymer. The structure and performance parameters of the produced hydrogenated block copolymer are shown in Table 3. Example 15

[0167] In step (2), a block copolymer was produced in the same manner as in Example 1, except that the hydrogenation catalyst was changed to the same weight of the hydrogenation catalyst produced in Production Example 4, and a hydrogenated block copolymer was produced by the hydrogenation reaction of the block copolymer. The structure and performance parameters of the produced hydrogenated block copolymer are shown in Table 3. Example 16

[0168] In step (2), a block copolymer was produced in the same manner as in Example 1, except that the hydrogenation catalyst was changed to the same weight of the hydrogenation catalyst produced in Production Example 5, and a hydrogenated block copolymer was produced by the hydrogenation reaction of the block copolymer. The structure and performance parameters of the produced hydrogenated block copolymer are shown in Table 3. Example 17

[0169] (1) Production of block copolymer A heptablock copolymer was produced by a method similar to that of Example 1. The structure of the heptablock copolymer is S71-(S72 / B71)-B72-(S73 / B73)-B74-(S75 / B75)-S76, where the S71 block and the S76 block are homopolymer segments of styrene, the S72 / B71 block, the S73 / B73 block, and the S75 / B75 block are random copolymer segments of styrene and butadiene, the B72 block is a homopolymer segment of isoprene, and B74 is a homopolymer segment of butadiene. As a result of measurement, based on the total amount of the heptablock copolymer, the content of styrene structural units was 75.2% by weight, the content of butadiene structural units was 22.3% by weight, the content of isoprene structural units was 2.5% by weight, and the content of styrene non-blocks was 18.1% by weight. Based on the total amount of conjugated diolefin structural units in the heptablock copolymer, the content of pendant groups was 48.4% by weight. Based on the total amount of butadiene structural units in the heptablock copolymer, the content of 1,2-PB structural units was 48.2% by weight. Based on the total amount of isoprene structural units in the heptablock copolymer, the content of 3,4-IP structural units was 50.1% by weight, and 1,2-IP structural units were not detected. Here, the number average molecular weight of the S71 block was 25,000, the number average molecular weight of the S72 / B71 block was 31,000, the number average molecular weight of the B72 block was 4,000, the number average molecular weight of the S73 / B73 block was 33,000, the number average molecular weight of the B74 block was 6,000, the number average molecular weight of the S75 / B75 block was 36,000, and the number average molecular weight of the S76 block was 43,000. (2) Production of hydrogenated heptablock copolymer The hydrogenation catalyst produced in Production Example 1 was reduced to obtain a reduced catalyst, and the reduced catalyst was used in the hydrogenation reaction. The reduction was carried out in a hydrogen gas atmosphere, the reduction temperature was 450 °C, and the reduction duration was 10 hours. 200 g of a rubber solution containing the heptablock copolymer produced in step (1) and 0.5 g of the hydrogenated catalyst after reduction were added to a 0.5 L high-pressure reactor with a stirring function, and the hydrogenation reaction was carried out at a reaction temperature of 150 °C, a hydrogen gas pressure of 3 MPa, a reaction time of 2 h, and a stirring rotation speed of 600 rpm. After the hydrogenation reaction was completed, the hydrogenation reaction product was centrifuged to obtain a reaction mixture containing the hydrogenated heptablock copolymer. The reaction mixture was filtered to separate the hydrogenated catalyst. The separated hydrogenated catalyst was washed with n-hexane, vacuum dried, and recycled for the hydrogenation reaction. The liquid phase obtained by filtration was collected, the solvent was removed, and the hydrogenated heptablock copolymer according to the present invention was obtained. The structural parameters and performance parameters of the hydrogenated heptablock copolymer are shown in Table 3. Example 18

[0170] (1) Production of block copolymer A heptablock copolymer was produced by a method similar to that of Example 1. The structure of the heptablock copolymer is S71-(S72 / B71)-B72-(S73 / B73)-B74-(S75 / B75)-S76, where the S71 block and the S76 block are homopolymer segments of styrene, the S72 / B71 block, the S73 / B73 block, and the S75 / B75 block are random copolymer segments of styrene and butadiene, the B72 block is a homopolymer segment of isoprene, and B74 is a homopolymer segment of butadiene. As a result of the measurement, based on the total amount of the heptablock copolymer, the content of the styrene structural unit is 80.5% by weight, the content of the butadiene structural unit is 16.7% by weight, the content of the isoprene structural unit is 2.8% by weight, and the content of the styrene non-block is 17.5% by weight. Based on the total amount of the conjugated diolefin structural units in the heptablock copolymer, the content of the pendant group is 46.1% by weight. Based on the total amount of the butadiene structural units in the heptablock copolymer, the content of the 1,2-PB structural unit is 45.6% by weight. Based on the total amount of the isoprene structural units in the heptablock copolymer, the content of the 3,4-IP structural unit is 48.5% by weight, and the 1,2-IP structural unit was not detected. The number average molecular weight of the S71 block is 16,000, the number average molecular weight of the S72 / B71 block is 23,000, the number average molecular weight of the B72 block is 3,800, the number average molecular weight of the S73 / B73 block is 25,000, the number average molecular weight of the B74 block is 3,600, the number average molecular weight of the S75 / B75 block is 26,000, and the number average molecular weight of the S76 block is 45,000. (2) Production of hydrogenated heptablock copolymer The hydrogenation catalyst produced in Production Example 1 was reduced to obtain a reduced catalyst, and the reduced catalyst was used in the hydrogenation reaction. The reduction was carried out in a hydrogen gas atmosphere, the reduction temperature was 450 °C, and the reduction duration was 10 hours. 200 g of a rubber solution containing the block copolymer produced in step (1) and 0.5 g of the reduced hydrogenation catalyst were added to a 0.5 L high-pressure reactor equipped with a stirring function, and the hydrogenation reaction was carried out at a reaction temperature of 150 °C, a hydrogen gas pressure of 3 MPa, a reaction time of 2 h, and a stirring rotation speed of 600 rpm. After the hydrogenation reaction was completed, the hydrogenation reaction product was centrifuged to obtain a reaction mixture containing a hydrogenated heptablock copolymer. The reaction mixture was filtered to separate the hydrogenation catalyst. The separated hydrogenation catalyst was washed with n - hexane and vacuum - dried, and then recycled to the hydrogenation reaction. The liquid phase obtained by filtration was collected, the solvent was removed, and the hydrogenated heptablock copolymer according to the present invention was obtained. The structural parameters and performance parameters of the hydrogenated heptablock copolymer are shown in Table 3. Example 19

[0171] (1) Production of polystyrene 800 g of cyclohexane and 200 g of styrene were added to a 2 L stainless - steel stirring kettle. The temperature was raised to 50 °C, and 1.6 mmol of n - butyllithium initiator was added. Polymerization was carried out at 50 °C for 50 minutes to obtain polystyrene. (2) Production of hydrogenated polystyrene The hydrogenation catalyst produced in Production Example 1 was reduced to obtain a reduced catalyst, and the reduced catalyst was used in the hydrogenation reaction. The reduction was carried out in a hydrogen gas atmosphere. The reduction temperature was 450 °C, and the reduction duration was 2 hours. 200 g of a rubber solution containing the polystyrene produced in step (1) and 1 g of the reduced hydrogenation catalyst were added to a 0.5 L high - pressure reactor with a stirring function. The hydrogenation reaction was carried out at a reaction temperature of 150 °C, a hydrogen gas pressure of 3 MPa, a reaction time of 1 h, and a stirring rotation speed of 800 rpm. After the hydrogenation reaction was completed, the hydrogenation reaction product was centrifuged to obtain a reaction mixture containing hydrogenated polystyrene. The reaction mixture was filtered to separate the hydrogenation catalyst. The separated hydrogenation catalyst was washed with n - hexane and vacuum - dried, and then recycled to the hydrogenation reaction. As a result of measurement, after the hydrogenation catalyst was recycled 5 times, the reduction rate of its hydrogenation activity was 2% or less (based on the hydrogenation activity used for the first time). The liquid phase obtained by filtration was collected, the solvent was removed, and the hydrogenated polystyrene according to the present invention was obtained. The structural parameters of the hydrogenated polystyrene are shown in Table 3. From the experimental results in Table 3, in the method for hydrogenating an aromatic polymer according to the present invention, not only can the aromatic polymer be effectively hydrogenated to obtain a high degree of hydrogen addition (the degree of hydrogenation reaches 95 mol% or more, preferably, the degree of hydrogen addition is about 100 mol%), but also it is found that the molecular weight of the polymer hardly decreases before and after the hydrogenation reaction, and it is suggested that in the hydrogenation reaction, the molecular chains of the polymer are hardly decomposed.

[0172] The hydrogenated block copolymer according to the present invention has high light transmittance and low haze, ensures the transparency of the material, and is excellent in impact strength, and is suitable for fields such as packaging materials (especially packaging materials in the medical and health fields) and optoelectronic product materials (especially materials for cameras and display screens of optoelectronic products).

[0173] As described above, the preferred embodiments of the present invention have been described in detail, but the present invention is not limited thereto. Without departing from the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention, including combining each of the technical features in any other appropriate manner, and these simple modifications and combinations should also be regarded as the disclosure content of the present invention and all belong to the patent scope of the present invention.

[0174] [Table 2]

[0175] [Table 3]

Claims

1. A method for hydrogenating an aromatic polymer, wherein the aromatic polymer contains an aromatic ring, comprising the step of contacting the aromatic polymer with a hydrogenation reagent in the presence of a hydrogenation catalyst to hydrogenate at least a part of the aromatic rings in the aromatic polymer to obtain a hydrogenated aromatic polymer, wherein the hydrogenation catalyst contains a carrier which is alumina, and a platinum element, a Group 14 element, and a rare earth metal element supported on the carrier, and in the hydrogenation catalyst, in terms of elemental conversion, the molar ratio of the Group 14 element to the platinum element is 10 or less, the Group 14 element is tin, and the rare earth metal element is cerium, a method for hydrogenating an aromatic polymer.

2. The method according to claim 1, wherein in the hydrogenation catalyst, in terms of elemental conversion, the molar ratio of the Group 14 element to the platinum element is 8 or less.

3. The method according to claim 1, wherein in the hydrogenation catalyst, in terms of elemental conversion, the molar ratio of the Group 14 element to the platinum element is 1 or more.

4. The method according to claim 1, wherein in the hydrogenation catalyst, in terms of elemental conversion, the molar ratio of the Group 14 element to the platinum element is 3 to 7:

1.

5. The method according to claim 1, wherein in the hydrogenation catalyst, in terms of elemental conversion, the molar ratio of the rare earth metal element to the platinum element is 1 to 6:

1.

6. The method according to claim 1, wherein the hydrogenation catalyst further contains an alkali metal element and an alkaline earth metal element.

7. In the hydrogenation catalyst, in terms of elemental conversion, the molar ratio of the alkali metal element to the platinum element is 7 to 20:1, and in the hydrogenation catalyst, in terms of elemental conversion, the molar ratio of the alkaline earth metal element to the platinum element is 10 to 35:1, the method according to claim 6.

8. The method according to claim 6, wherein the alkali metal element is potassium and the alkaline earth metal element is magnesium.

9. The method according to claim 1, wherein the hydrogenation catalyst further contains a Group 4 metal element, a halogen group element, or a combination thereof.

10. In the hydrogenation catalyst, the molar ratio of the Group 4 metal element to the platinum element is 2 to 10:1 in terms of elements, In the hydrogenation catalyst, the molar ratio of the halogen group element to the platinum element is 2 to 8:1 in terms of elements, according to the method of claim 9.

11. The method according to claim 9, wherein the Group 4 metal element is zirconium and the halogen group element is chlorine.

12. The method according to claim 1, wherein the content of the platinum element is 0.1 to 0.8% by weight based on the total amount of the hydrogenation catalyst.

13. The method according to claim 1, wherein the alumina is γ-alumina.

14. The specific surface area of the hydrogenation catalyst is 100 to 400 m2 / g, and the average pore diameter of the hydrogenation catalyst is 5 to 40 nm, according to the method of claim 1.

15. The method according to claim 1, wherein the content of the aromatic structural unit derived from the aromatic monomer containing an aromatic ring in the aromatic polymer is 40% by weight or more based on the total amount of the aromatic polymer.

16. The method according to claim 15, wherein the content of the aromatic structural unit in the aromatic polymer is 65 to 85% by weight based on the total amount of the aromatic polymer.

17. The aromatic structural unit is a monovinyl aromatic hydrocarbon structural unit derived from a monovinyl aromatic hydrocarbon, and the monovinyl aromatic hydrocarbon is one or more selected from the group consisting of compounds represented by Formula I, according to the method of claim 15. 【Chemical Formula 1】 (In Formula I, R1 is a substituted or unsubstituted aryl having 6 to 20 carbon atoms.)

18. The method according to claim 17, wherein the monovinyl aromatic hydrocarbon is one or more selected from the group consisting of styrene, vinyltoluene, α-methylstyrene, 4-t-butylstyrene, 4-methylstyrene, 3,5-diethylstyrene, 3,5-di-n-butylstyrene, 4-n-propylstyrene, and 4-dodecylstyrene.

19. The method according to claim 17, wherein the monovinyl aromatic hydrocarbon is one or more selected from the group consisting of styrene, 2-methylstyrene, 4-methylstyrene, and α-methylstyrene.

20. The method according to claim 1, wherein the aromatic polymer contains a conjugated diolefin structural unit derived from a conjugated diolefin, and the content of the conjugated diolefin structural unit is 60% by weight or less based on the total amount of the aromatic polymer.

21. The method according to claim 20, wherein the content of the conjugated diolefin structural unit is 10 to 50% by weight based on the total amount of the aromatic polymer.

22. The conjugated diolefin is butadiene, isoprene, or a combination thereof, and in the aromatic polymer, the degree of hydrogenation of the conjugated diolefin is 97 mol% or more. The method according to claim 20.

23. The aromatic polymer contains at least two homopolymerization segments of monovinyl aromatic hydrocarbons, at least one homopolymerization segment of conjugated diolefins, and at least two random copolymerization segments of monovinyl aromatic hydrocarbons and conjugated diolefins. The two end blocks of the aromatic polymer are each independently a homopolymerization segment of a monovinyl aromatic hydrocarbon. The block directly bonded to the end block is an internal block, and the internal block is each independently a random copolymerization segment of a monovinyl aromatic hydrocarbon and a conjugated diolefin. Based on the total amount of the aromatic polymer, the content of the monovinyl aromatic hydrocarbon structural unit derived from monovinyl aromatic hydrocarbon is 40 to 95% by weight, and the content of the conjugated diolefin structural unit derived from conjugated diolefin is 5 to 60% by weight. In the random copolymer segment, the content of the monovinyl aromatic hydrocarbon structural unit derived from monovinyl aromatic hydrocarbon is 15 to 20% by weight. The method according to claim 1, wherein in the aromatic polymer, based on the total amount of the conjugated diolefin structural units, the content of the pendant groups is 40 to 60% by weight.

24. The method according to claim 1, wherein the aromatic polymer is one or more selected from the group consisting of a pentablock copolymer having a structure represented by formula II and a heptablock copolymer having a structure represented by formula III. S51-(S52 / B51)-B52-(S53 / B53)-S54 (Formula II) (In formula II, the S51 block and the S54 block are each independently a homopolymer segment of monovinyl aromatic hydrocarbon. The S52 / B51 block and the S53 / B53 block are each independently a random copolymer segment of monovinyl aromatic hydrocarbon and conjugated diolefin. The B52 block is a homopolymer segment of conjugated diolefin. The conjugated diolefin in the B52 block is isoprene, and the conjugated diolefins in the B51 block and the B53 block are butadiene. The number average molecular weight of the S51 block is 0.5×10⁴ to 5×10⁴, the ratio of the number average molecular weight of the S51 block to the number average molecular weight of the S54 block is 1:2 to 10, the number average molecular weight of the S52 / B51 block is 2×10⁴ to 5×10⁴, the ratio of the number average molecular weight of the S52 / B51 block to the number average molecular weight of the S53 / B53 block is 1:0.9 to 1.25, and the number average molecular weight of the B52 block is 0.2×10⁴ to 2×10⁴.) S71-(S72 / B71)-B72-(S73 / B73)-B74-(S75 / B75)-S76 (Formula III) (In Formula III, the S71 block and the S76 block are each independently a homopolymer segment of a monovinyl aromatic hydrocarbon, the S72 / B71 block, the S73 / B73 block, and the S75 / B75 block are each independently a random copolymer segment of a monovinyl aromatic hydrocarbon and a conjugated diolefin, the B72 block and the B74 block are each independently a homopolymer segment of a conjugated diolefin, the conjugated diolefin in the B72 block is isoprene, and the conjugated diolefins in the B71 block, the B73 block, and the B75 block are butadiene, the number average molecular weight of the S71 block is 5,000 to 50,000, the ratio of the number average molecular weight of the S71 block to the number average molecular weight of the S76 block is 1:1.5 to 5, the number average molecular weight of the S72 / B71 block is 20,000 to 50,000, the ratio of the number average molecular weight of the S72 / B71 block, the number average molecular weight of the S73 / B73 block, and the number average molecular weight of the S75 / B75 is 1:1 to 1.2:1 to 1.25, the number average molecular weight of the B72 block is 2,000 to 20,000, and the ratio of the number average molecular weight of the B72 block to the number average molecular weight of the B74 block is 1:0.9 to 1.2.)

25. The temperature of the contact is 50 to 200 °C, The amount of the hydrogenation catalyst used is 1 to 20 parts by weight with respect to 100 parts by weight of the aromatic polymer. The method according to claim 1.

26. The hydrogenation reagent is hydrogen gas, The pressure of the hydrogen gas is 0.1 to 10 MPa, and the pressure is gauge pressure. The method according to claim 1.

27. The degree of hydrogenation of the aromatic ring is 95 mol% or more, Let the number average molecular weight of the aromatic polymer be M ｎas 1, and the number average molecular weight of the hydrogenated aromatic polymer as M ｎ as 2, [(M ｎ 1 - M ｎ 2) / M ｎ 1] × 100% is defined as the decomposition rate, and the decomposition rate is 2.5% or less. The method according to claim 1.

28. A hydrogenated pentablock copolymer, The pentablock copolymer is a pentablock copolymer having a structure represented by formula II, In the hydrogenated pentablock copolymer, the degree of hydrogenation of the aromatic ring in the monovinyl aromatic hydrocarbon structural unit is 98 mol% or more, and the degree of hydrogenation of the unsaturated double bond in the conjugated diolefin structural unit is 99 mol% or more. Hydrogenated pentablock copolymer. S51-(S52 / B51)-B52-(S53 / B53)-S54 (Formula II) (In formula II, the S51 block and the S54 block are each independently a homopolymer segment of a monovinyl aromatic hydrocarbon, The S52 / B51 block and the S53 / B53 block are each independently a random copolymer segment of a monovinyl aromatic hydrocarbon and a conjugated diolefin, The B52 block is a homopolymer segment of a conjugated diolefin.)

29. The conjugated diolefin structural unit in the B52 block is derived from B52 conjugated diolefin, the conjugated diolefin structural unit in the S52 / B51 block is derived from B51 conjugated diolefin, and the conjugated diolefin structural unit in the S53 / B53 block is derived from B53 conjugated diolefin. The B52 conjugated diolefin is isoprene, the B51 conjugated diolefin and the B53 conjugated diolefin are butadiene, Based on the total amount of the pentablock copolymer, the content of the isoprene structural unit derived from isoprene is 5 to 20% by weight, and the content of the butadiene structural unit derived from butadiene is 5 to 40% by weight, Based on the total amount of isoprene structural units derived from isoprene in the pentablock copolymer, the content of isoprene structural units containing vinyl pendant groups is 50 to 60% by weight, and based on the total amount of structural units derived from butadiene in the pentablock copolymer, the content of butadiene structural units containing vinyl pendant groups is 40 to 60% by weight. The hydrogenated pentablock copolymer according to claim 28.

30. The monovinyl aromatic hydrocarbon is one or more selected from the group consisting of compounds represented by Formula I. The hydrogenated pentablock copolymer according to claim 28. 【Chemical Formula 2】 (In Formula I, R １ is a substituted or unsubstituted aryl of C ６ to C ２０ .)

31. The monovinyl aromatic hydrocarbon is one or more selected from the group consisting of styrene, 2-methylstyrene, 4-methylstyrene, and α-methylstyrene. The hydrogenated pentablock copolymer according to claim 30.

32. The number average molecular weight of the S51 block is 0.5×10⁴ to 5×10⁴, the ratio of the number average molecular weight of the S51 block to the number average molecular weight of the S54 block is 1:2 to 10, the number average molecular weight of the S52 / B51 block is 2×10⁴ to 5×10⁴, the ratio of the number average molecular weight of the S52 / B51 block to the number average molecular weight of the S53 / B53 block is 1:0.9 to 1.25, the number average molecular weight of the B52 block is 0.2×10⁴ to 2×10⁴, and the number average molecular weight of the hydrogenated block copolymer is 5×10⁴ to 22×10⁴. The hydrogenated pentablock copolymer according to claim 28.

33. A hydrogenated heptablock copolymer, The heptablock copolymer is a heptablock copolymer having a structure represented by Formula III, In the hydrogenated heptablock copolymer, the degree of hydrogenation of the aromatic ring in the monovinyl aromatic hydrocarbon structural unit is 98 mol% or more, and the degree of hydrogenation of the unsaturated double bond in the conjugated diolefin structural unit is 99 mol% or more. Hydrogenated heptablock copolymer. S71-(S72 / B71)-B72-(S73 / B73)-B74-(S75 / B75)-S76 (Formula III) (In Formula III, the S71 block and the S76 block are each independently a homopolymer segment of a monovinyl aromatic hydrocarbon, The S72 / B71 block, the S73 / B73 block, and the S75 / B75 block are each independently a random copolymer segment of a monovinyl aromatic hydrocarbon and a conjugated diolefin, The B72 block and the B74 block are each independently a homopolymer segment of a conjugated diolefin.)

34. The conjugated diolefin structural unit in the B72 block is derived from B72 conjugated diolefin, the conjugated diolefin structural unit in the S72 / B71 block is derived from B71 conjugated diolefin, the conjugated diolefin structural unit in the S73 / B73 block is derived from B73 conjugated diolefin, and the conjugated diolefin structural unit in the S75 / B75 block is derived from B75 conjugated diolefin. The B72 conjugated diolefin is isoprene, and the B71 conjugated diolefin, the B73 conjugated diolefin, and the B75 conjugated diolefin are butadiene, Based on the total amount of the heptablock copolymer, the content of the isoprene structural unit derived from isoprene is 0.5 to 10% by weight, and the content of the butadiene structural unit derived from butadiene is 5 to 40% by weight, Based on the total amount of isoprene structural units derived from isoprene in the heptablock copolymer, the content of isoprene structural units containing vinyl pendant groups is 40 to 60% by weight. Based on the total amount of butadiene structural units derived from butadiene in the heptablock copolymer, the content of butadiene structural units containing vinyl pendant groups is 40 to 60% by weight. The hydrogenated heptablock copolymer according to claim 33.

35. The monovinyl aromatic hydrocarbon is one or more selected from the group consisting of compounds represented by Formula I. The hydrogenated heptablock copolymer according to claim 33. 【Chemical Formula 3】 (In Formula I, R １ is a substituted or unsubstituted aryl of C ６ to C ２０ .)

36. The monovinyl aromatic hydrocarbon is one or more selected from the group consisting of styrene, 2-methylstyrene, 4-methylstyrene, and α-methylstyrene. The hydrogenated heptablock copolymer according to claim 35.

37. The number average molecular weight of the S71 block is 0.5×10⁴ to 5×10⁴, the ratio of the number average molecular weight of the S71 block to the number average molecular weight of the S76 block is 1:1.5 to 5, the number average molecular weight of the S72 / B71 block is 2×10⁴ to 5×10⁴, and the ratio of the number average molecular weight of the S72 / B71 block, the number average molecular weight of the S73 / B73 block, and the number average molecular weight of the S75 / B75 is 1:1 to 1.2:1 to 1.

25. The number average molecular weight of the B72 block is 0.2×10⁴ to 2×10⁴, the ratio of the number average molecular weight of the B72 block to the number average molecular weight of the B74 block is 1:0.9 to 1.2, and the number average molecular weight of the hydrogenated heptablock copolymer is 5×10⁴ to 20×10⁴. The hydrogenated heptablock copolymer according to claim 33.

38. Use of the hydrogenated pentablock copolymer according to any one of claims 28 to 32 in the manufacture of a packaging material or an optoelectronic product. Use of the hydrogenated heptablock copolymer according to any one of claims 33 to 37 in the manufacture of a packaging material or an optoelectronic product.

Images