Hydrogenation methods for aromatic polymers and hydrogenated block copolymers and their applications

Abstract

This invention discloses a method for hydrogenating aromatic polymers. The method includes contacting the aromatic polymer with a hydrogenating agent in the presence of a hydrogenating catalyst to hydrogenate at least a portion of the aromatic rings in the aromatic polymer. The hydrogenating catalyst contains a support and platinum, a Group IVA element, and a rare earth metal element supported on the support. The support is alumina. This invention also provides hydrogenated block copolymers, hydrogenated pentablock copolymers, and hydrogenated heptblock copolymers. The hydrogenation method of this invention not only effectively hydrogenates the aromatic rings in aromatic polymers to obtain a high degree of aromatic ring hydrogenation, but also has minimal impact on the polymer structure; the molecular chains of the aromatic polymer remain essentially undegraded before and after the hydrogenation reaction. The hydrogenated block copolymers of this invention not only have a high degree of hydrogenation but also exhibit high light transmittance, low haze, and excellent impact toughness.

Description

[0001] This application claims the benefit of Chinese patent application 202110560968.X, filed on May 19, 2021, the contents of which are incorporated herein by reference. Technical Field

[0002] This invention relates to a method for hydrogenating aromatic polymers, and also to hydrogenated block copolymers, hydrogenated pentablock copolymers and hydrogenated heptblock copolymers and their applications. Background Technology

[0003] Common unsaturated polymer materials usually contain unsaturated double bonds (such as benzene ring double bonds, diene double bonds, etc.), which have poor heat resistance, UV resistance, and yellowing resistance. Hydrogenation of unsaturated polymers is a quick and effective way to improve their performance.

[0004] Polystyrene is currently the most widely used thermoplastic, possessing numerous advantages such as water resistance, corrosion resistance, high transparency, easy coloring, and easy processing and molding. It is widely used in various fields including electronics and communications, mold making, food packaging, and daily necessities. Hydrogenation of the benzene ring double bonds in polystyrene yields fully saturated polycyclohexylethylene (PVCH). Compared to polystyrene (PS), fully saturated PVCH has a significantly higher glass transition temperature, increasing from approximately 105℃ to 147℃. Its heat resistance and UV resistance are also significantly improved, while maintaining the high light transmittance of PS. However, hydrogenated polystyrene lacks sufficient toughness and is more prone to breakage.

[0005] Another transparent monovinyl aromatic polymer is styrene-butadiene resin (SBR), a styrene-butadiene block copolymer with a high styrene content. To improve the toughness of SBR, researchers have developed a highly transparent, impact-resistant SBR that combines high transparency with impact resistance. However, due to the large number of unsaturated butadiene double bonds in SBR, its heat resistance, UV resistance, and yellowing resistance are poor when used outdoors.

[0006] The hydrogenation of unsaturated double bonds in conjugated dienes in polymers can be achieved using homogeneous nickel-cobalt catalyst systems or metallocene catalyst systems. However, the hydrogenation of unsaturated double bonds in aromatic rings is more difficult than that of diene double bonds, typically requiring heterogeneous catalysts and demanding process conditions such as high temperature and high pressure.

[0007] Elias HG and Etter O (Glass Temperature of Hydrogenated Polystyrene, Journal of Macromolecular Science-Chemistry, 1967, 1(5): 943-953) used Raney Ni catalyst to hydrogenate polystyrene at 200-270℃ and 210-260 atm pressure. After 24 hours of reaction, the degree of hydrogenation could reach 42-100%, but the polymer underwent severe degradation.

[0008] For example, Gehlsen et al. (MD Gehlsen, Weimann PA, Bates FS, et al., Synthesis and Characterization of Poly(vinylcyclohexane) Derivatives, Journal of Polymer Science Part B Polymer Physics, 1995, 33(10): 1527-1536) used Pd / BaSO4 as a catalyst to hydrogenate polystyrene cyclohexane solution at 140℃ and 35 atm pressure. The catalyst / polymer mass ratio was 2.5 / 1, and the reaction lasted for 12 hours to obtain fully hydrogenated PVCH. The polymer underwent partial chain scission degradation (Tg = 140℃).

[0009] Zhou Hongyong et al. (Zhou Hongyong et al., Preparation of magnetic ruthenium nanocatalysts and their catalytic performance in the hydrogenation of polystyrene, Polymer Materials Science and Engineering, 2011, 27(011): 73-76) prepared magnetic nanocatalysts by loading metallic Ru onto magnetic nanocarriers and used them for the hydrogenation reaction of polystyrene. At a reaction temperature above 120℃, a hydrogen pressure of 8MPa, and a reaction time of 5h, the degree of hydrogenation of polystyrene could reach over 90%. However, after hydrogenation, polystyrene degraded, producing small molecules such as benzene, toluene, cyclohexane, and methylcyclohexane.

[0010] To address the issue of polymer degradation during hydrogenation, US5700878 discloses a method for hydrogenating aromatic polymers, comprising: contacting an aromatic polymer with a hydrogenating agent in the presence of a metal hydrogenation catalyst supported on silica, thereby hydrogenating at least 80% of the aromatic polymer, wherein the surface area of ​​the silica in the metal hydrogenation catalyst is at least 10 m². 2The pore size distribution, measured by a mercury porosimeter, shows that at least 98% of the pore volume is determined by pores with a diameter greater than 600 angstroms, while the volume of pores with a diameter less than 600 angstroms, measured by a mercury porosimeter, is less than 2% of the total pore volume when measured by nitrogen desorption. However, this method uses a hydrogenation catalyst with a large loading of noble metals and a large amount of catalyst, resulting in high costs. Furthermore, experimental data from the embodiments described in the patent specification show that the molecular weight of the hydrogenated polymer obtained by hydrogenating polystyrene and polyα-methylstyrene using the disclosed method is significantly lower than that of the unhydrogenated polymer, indicating that the hydrogenation reaction leads to polymer degradation.

[0011] Therefore, hydrogenation of highly transparent monovinyl aromatic polymers still needs to address issues such as low catalyst hydrogenation activity, easy degradation of hydrogenation products, and the inability of hydrogenation products to simultaneously achieve impact resistance, toughness, and heat resistance. Summary of the Invention

[0012] One object of the present invention is to provide a method for hydrogenating aromatic polymers, which can not only hydrogenate the aromatic rings in the aromatic polymers, but also effectively inhibit the degradation of polymer molecular chains during the hydrogenation process.

[0013] Another object of the present invention is to provide a hydrogenated block copolymer that not only has a high degree of aromatic ring hydrogenation and conjugated diene hydrogenation, but also achieves a good balance between transparency and impact toughness.

[0014] According to a first aspect of the present invention, a method for hydrogenating an aromatic polymer containing aromatic rings is provided. The method comprises contacting the aromatic polymer with a hydrogenating agent in the presence of a hydrogenating catalyst to hydrogenate at least a portion of the aromatic rings in the aromatic polymer, thereby obtaining a hydrogenated aromatic polymer.

[0015] The hydrogenation catalyst contains a support and platinum, Group IVA elements, and rare earth metal elements supported on the support. The support is alumina. In the hydrogenation catalyst, the molar ratio of the Group IVA elements to platinum is not higher than 10.

[0016] According to a second aspect of the present invention, the present invention provides a hydrogenated aromatic polymer prepared by the method described in the first aspect of the present invention.

[0017] According to a third aspect of the present invention, a hydrogenated block copolymer is provided, the block copolymer comprising a monovinyl aromatic structural unit derived from a monovinyl aromatic hydrocarbon and a conjugated diene structural unit derived from a conjugated diene, wherein the degree of hydrogenation of the aromatic ring in the monovinyl aromatic structural unit is 98 mol% or more, and the degree of hydrogenation of the unsaturated double bond in the conjugated diene structural unit is 99 mol% or more, wherein the notched impact strength of the hydrogenated block copolymer is 20-30 kJ / m. 2 The elongation at break is 200-400%, the light transmittance is 88-92%, and the haze is 1-5.

[0018] According to a fourth aspect of the present invention, a hydrogenated pentablock copolymer is provided, wherein the pentablock copolymer is a pentablock copolymer having the structure shown in Formula II:

[0019] S51-(S52 / B51)-B52-(S53 / B53)-S54 (Formula II)

[0020] In Formula II, the S51 block and the S54 block are each independently a homopolymer segment of a monovinyl aromatic hydrocarbon.

[0021] The S52 / B51 and S53 / B53 blocks are each independently random copolymer segments of monovinyl aromatic hydrocarbons and conjugated dienes.

[0022] The B52 block is a homopolymer segment of a conjugated diene;

[0023] In the hydrogenated pentablock copolymer, the degree of hydrogenation of the aromatic ring in the monovinyl aromatic structural unit is 98 mol% or more, and the degree of hydrogenation of the unsaturated double bond in the conjugated diene structural unit is 99 mol% or more.

[0024] According to a fifth aspect of the present invention, a hydrogenated heptblock copolymer is provided, wherein the block copolymer is a heptblock copolymer having the structure shown in Formula III:

[0025] S71-(S72 / B71)-B72-(S73 / B73)-B74-(S75 / B75)-S76 (Formula III)

[0026] In Formula III, the S71 block and the S76 block are each independently a homopolymer segment of a monovinyl aromatic hydrocarbon.

[0027] The S72 / B71 block, S73 / B73 block, and S75 / B75 block are each independently random copolymer segments of monovinyl aromatic hydrocarbons and conjugated dienes.

[0028] The B72 block and the B74 block are each independently homopolymer segments of the conjugated diene;

[0029] In the hydrogenated heptblock copolymer, the degree of hydrogenation of the aromatic ring in the monovinyl aromatic structural unit is 98 mol% or more, and the degree of hydrogenation of the unsaturated double bond in the conjugated diene structural unit is 99 mol% or more.

[0030] According to a sixth aspect of the present invention, the present invention provides the use of the hydrogenated block copolymers described in the third aspect of the present invention, the hydrogenated pentablock copolymers described in the fourth aspect of the present invention, or the hydrogenated heptaboles described in the fifth aspect of the present invention in the preparation of packaging materials or optoelectronic products.

[0031] The hydrogenation method for aromatic polymers according to the present invention not only effectively hydrogenates the aromatic rings in aromatic polymers to obtain a high degree of aromatic ring hydrogenation, but also has minimal impact on the polymer structure, with the molecular chains of the aromatic polymer remaining essentially undegraded before and after the hydrogenation reaction. The hydrogenated block copolymers, hydrogenated pentablock copolymers, and hydrogenated heptblock copolymers according to the present invention have a high degree of hydrogenation (approaching 100%), exhibiting not only high light transmittance and low haze, but also excellent impact toughness and heat resistance, achieving a good balance between impact toughness and heat resistance. The hydrogenated block copolymers, hydrogenated pentablock copolymers, and hydrogenated heptblock copolymers according to the present invention have promising commercial prospects in packaging materials (especially medical and health packaging materials) and in the manufacture of optoelectronic product materials (especially materials for cameras, displays, etc. in optoelectronic products). Detailed Implementation

[0032] The following provides a detailed description of specific embodiments of the present invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.

[0033] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0034] In this invention, the term "monovinyl aromatic hydrocarbon" refers to a compound formed by replacing one hydrogen atom on an aromatic ring with a vinyl group. For example, the monovinyl aromatic hydrocarbon may be one or more compounds selected from those shown in Formula I.

[0035]

[0036] In Equation I, R1 is C6-C 20Specific examples of substituted or unsubstituted aryl groups may include, but are not limited to: phenyl, o-tolyl, m-tolyl, p-tolyl, o-ethylphenyl, m-ethylphenyl, p-ethylphenyl, o-tert-butylphenyl, m-tert-butylphenyl, p-tert-butylphenyl, p-dodecylphenyl, 2,4-di-n-butylphenyl, p-n-propylphenyl, and 2,4-diethylphenyl.

[0037] Preferably, the monovinyl aromatic hydrocarbon is selected from one or more of 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 selected from one or more of the group consisting of styrene, 2-methylstyrene, 4-methylstyrene, and α-methylstyrene.

[0038] In this invention, the term "conjugated diene" refers to an unsaturated chain hydrocarbon containing a conjugated double bond (i.e., -C=C=C-) in its molecular structure. It can be any conjugated diene commonly used in the art, without particular limitation. For example, the conjugated diene can be one or more of the group consisting of C4-C8 conjugated dienes. Preferably, the conjugated diene is one or more of the group consisting of butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, and 2,3-dimethylbutadiene. More preferably, the conjugated diene is butadiene, isoprene, or a combination thereof.

[0039] In this invention, "structural unit derived from ××××" refers to a structural unit formed by addition polymerization of the monomer (i.e., ××××). For example, a structural unit derived from monovinyl aromatic hydrocarbons refers to a structural unit formed by addition polymerization of monovinyl aromatic hydrocarbons.

[0040] In this invention, the term "side group content" refers to the content of structural units derived from a conjugated diene containing olefinic side groups (i.e., side groups containing C=C bonds) in the copolymer, based on the total amount of structural units derived from the conjugated diene. Specifically, when the conjugated diene is butadiene, olefinic side groups refer to structural units formed by 1,2-polymerization of butadiene (i.e., The side groups in the polymer are denoted as 1,2-PB; when the conjugated diene is isoprene, the olefinic side group refers to the side group in the structural unit formed by isoprene through 1,2-polymerization and / or 3,4-polymerization (the side group formed by 1,2-polymerization is denoted as 1,2-IP, and the side group formed by 3,4-polymerization is denoted as 3,4-IP). In this invention, the side group content of the polymer is determined by proton nuclear magnetic resonance spectroscopy.

[0041] In this invention, the term "styrene nonblock" (also referred to as "St nonblock") refers to the content of styrene structural units derived from styrene in the random copolymer segment. In this invention, the styrene nonblock content of the polymer is determined by proton nuclear magnetic resonance spectroscopy.

[0042] In this invention, the term "terminal block" refers to a block located at the two ends of a polymer molecular chain, and can also be called "terminal block"; the term "internal block" refers to a block that is directly bonded to the terminal block, that is, the terminal block and the internal block are connected together by a covalent bond through one of their respective terminal atoms.

[0043] In this invention, the term "homogeneous segment" refers to a block in which the structural units are substantially derived from the same monomer. Specifically, in this invention, at least 99% by weight of the structural units in the homopolymer segment are derived from the same monomer. In this invention, the term "random copolymer segment" refers to a block in which the structural units are derived from two or more monomers, and the different types of structural units are randomly distributed.

[0044] In this invention, the term "bonding" refers to two blocks being connected together by covalent bonds through their respective end atoms.

[0045] In this invention, the terms "hydrogenation" and "hydrogenation" have the same meaning, referring to the hydrogenation of carbon-carbon unsaturated bonds. These carbon-carbon unsaturated bonds include unsaturated bonds in aromatic rings and carbon-carbon unsaturated bonds in non-aromatic rings, such as carbon-carbon double bonds. In this invention, the terms "degree of hydrogenation" and "degree of hydrogenation" have the same meaning, referring to the rate of change of the content of carbon-carbon unsaturated bonds in the polymer after hydrogenation compared to the content of carbon-carbon unsaturated bonds in the polymer before hydrogenation, which can be calculated using the following formula:

[0046] Degree of hydrogenation = (1 - molar content of carbon-carbon unsaturated bonds in the polymer after hydrogenation / molar content of carbon-carbon unsaturated bonds in the polymer before hydrogenation) × 100%.

[0047] The term "degree of hydrogenation of the aromatic ring" refers to the rate of change in the content of carbon-carbon unsaturated bonds from the aromatic ring in the polymer after hydrogenation compared to the content of carbon-carbon unsaturated bonds from the aromatic ring in the polymer before hydrogenation. It can be calculated using the following formula:

[0048] Degree of hydrogenation of aromatic ring = (1 - molar content of carbon-carbon unsaturated bonds from aromatic ring in the polymer after hydrogenation / molar content of carbon-carbon unsaturated bonds from aromatic ring in the polymer before hydrogenation) × 100%.

[0049] The term "degree of hydrogenation of conjugated dienes" refers to the rate of change in the content of carbon-carbon unsaturated double bonds from the conjugated diene structural units in the hydrogenated polymer compared to the content of carbon-carbon unsaturated double bonds from the conjugated diene structural units in the unhydrogenated polymer. It can be calculated using the following formula:

[0050] Degree of hydrogenation of conjugated diene = (1 - molar content of carbon-carbon unsaturated double bonds from conjugated diene in the hydrogenated polymer / molar content of carbon-carbon unsaturated double bonds from conjugated diene in the unhydrogenated polymer) × 100%.

[0051] In this invention, the number-average molecular weight (M) of the polymer n ), weight-average molecular weight (M w ) and molecular weight distribution index (M w / M n Monodisperse polystyrene was used as a standard, and the determination was performed by gel permeation chromatography, expressed in g / mol.

[0052] In this invention, unless otherwise specified, all pressures are gauge pressures.

[0053] In this invention, the term "at least one" means one or more. In this invention, the term "optional" means not essential and can be understood as "including or not including," or "containing or not containing."

[0054] 1. Aromatic polymers

[0055] In this invention, an aromatic polymer containing an aromatic ring refers to a polymer containing a structural unit with an aromatic ring, a typical example of which is a benzene ring. The aromatic ring in the aromatic polymer originates from an aromatic structural unit of an aromatic monomer containing an aromatic ring. Typical examples of the structural unit with an aromatic ring may include, but are not limited to, monovinyl aromatic structural units derived from monovinyl aromatic hydrocarbons.

[0056] Based on the total amount of the aromatic polymer, the content of aromatic structural units derived from aromatic monomers containing aromatic rings in the aromatic polymer can be 40% by weight or more, preferably 50% by weight or more, and more preferably 70% by weight or more. In a preferred embodiment, based on the total amount of the aromatic polymer, the content of aromatic structural units in the aromatic polymer is 65-85% 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.

[0057] The aromatic polymer may contain only aromatic structural units, or it may contain aromatic structural units and non-aromatic structural units without aromatic rings. The non-aromatic structural units may be selected from structural units containing unsaturated bonds and structural units without unsaturated bonds. Typical examples of non-aromatic structural units include conjugated diene structural units derived from conjugated dienes.

[0058] When the aromatic polymer contains conjugated diene structural units, the content of the conjugated diene structural units is preferably no more than 60% by weight, based on the total amount of the aromatic polymer, for example, 5-60% by weight. More preferably, the content of the conjugated diene structural units is no more than 50% by weight, based on the total amount of the aromatic polymer, for example, 10-50% by weight. Even more preferably, the content of the conjugated diene structural units is 15-35% by weight, based on the total amount of the aromatic polymer, 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 diene is preferably butadiene and / or isoprene. When the aromatic polymer contains conjugated diene structural units derived from conjugated dienes, the side group content is preferably 40-60% by weight, based on the total amount of conjugated diene structural units derived from conjugated dienes, 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.

[0059] When the aromatic polymer contains conjugated diene structural units, the arrangement order of the aromatic structural units and the conjugated diene structural units in the polymer molecular chain can be selected according to the specific application requirements of the hydrogenated aromatic polymer, and can be random, block, or grafted.

[0060] In a preferred embodiment, the aromatic polymer is a block copolymer containing structural units derived from monovinyl aromatic hydrocarbons and structural units derived from conjugated dienes. The aromatic polymer contains at least two homopolymer segments of monovinyl aromatic hydrocarbons (i.e., homopolymer segments formed essentially by the polymerization of monovinyl aromatic hydrocarbons), at least one homopolymer segment of a conjugated diene (i.e., homopolymer segments formed essentially by the polymerization of a conjugated diene), and at least two random copolymer segments of monovinyl aromatic hydrocarbons and conjugated dienes (i.e., random copolymer segments formed by the random copolymerization of monovinyl aromatic hydrocarbons and conjugated dienes). Each of the two end blocks of the aromatic polymer is independently a homopolymer segment of monovinyl aromatic hydrocarbons, and the block directly bonded to the end blocks is an end block, each of which is independently a random copolymer segment of monovinyl aromatic hydrocarbons and conjugated dienes. When the block copolymer contains at least three random copolymer segments of monovinyl aromatic hydrocarbons and conjugated dienes and at least two homopolymer segments of conjugated dienes, the homopolymer segments of the conjugated dienes are arranged alternately with the random copolymer segments of monovinyl aromatic hydrocarbons and conjugated dienes, and each of the two end groups of the homopolymer segment of the conjugated dienes is directly bonded to one random copolymer segment of monovinyl aromatic hydrocarbons and conjugated dienes.

[0061] In this preferred embodiment, based on the total amount of the aromatic polymer, the content of structural units derived from monovinyl aromatic hydrocarbons can be 40-95% by weight, and the content of structural units derived from conjugated dienes can be 5-60% by weight. Based on the total amount of structural units derived from monovinyl aromatic hydrocarbons in the aromatic polymer, the content of structural units derived from monovinyl aromatic hydrocarbons in the random copolymer segment can be 15-20% by weight, preferably 17-18.5% by weight. In this preferred embodiment, in the aromatic polymer, based on the total amount of conjugated diene structural units, the side group content can be 40-60% by weight.

[0062] In this preferred embodiment, the conjugated diene structural units in the homopolymer segment of the conjugated diene and the conjugated diene structural units in the random copolymer segment can be the same or different. Preferably, the homopolymer segment of the conjugated diene contains a homopolymer segment of a first conjugated diene and at least one homopolymer segment of a second conjugated diene, wherein the structural units in the homopolymer segment of the first conjugated diene are derived from the first conjugated diene, and the structural units in the homopolymer segment of the second conjugated diene are derived from the second conjugated diene, and the first conjugated diene is different from the second conjugated diene. More preferably, the homopolymer segment of the first conjugated diene is directly bonded to an endopeptide segment, wherein the first conjugated diene is isoprene, and the second conjugated diene and the conjugated diene in the random copolymer segment of the monovinyl aromatic hydrocarbon and the conjugated diene are butadiene. Based on the total amount of the hydrogenated block copolymer, the content of isoprene structural units derived from isoprene is preferably 0.5-10% by weight, more preferably 1-5% by weight, and even more preferably 2-4% by weight; the content of butadiene structural units derived from butadiene is preferably 5-40% by weight, more preferably 10-35% by weight, and even more preferably 15-30% by weight.

[0063] In a more preferred embodiment, the aromatic polymer is a pentablock copolymer having the structure shown in Formula II:

[0064] S51-(S52 / B51)-B52-(S53 / B53)-S54 (Formula II)

[0065] In Formula II, S51 and S54 are end blocks, each independently representing a homopolymer segment of a monovinyl aromatic hydrocarbon; S52 / B51 and S53 / B53 are end blocks, each independently representing a random copolymer segment of a monovinyl aromatic hydrocarbon and a conjugated diene; and B52 is a homopolymer segment of a conjugated diene.

[0066] In the pentablock copolymer shown in Formula II, the monovinyl aromatic structural units in the S51 block, S52 / B51 block, S53 / B53 block, and S54 block are represented as S51 monovinyl aromatic structural unit, S52 monovinyl aromatic structural unit, S53 monovinyl aromatic structural unit, and S54 monovinyl aromatic structural unit, respectively. These units can be the same or different, and each unit can be one or more selected from the group consisting of styrene, 2-methylstyrene, 4-methylstyrene, and α-methylstyrene. Preferably, the monovinyl aromatic structural units in the S51 block, S52 / B51 block, S53 / B53 block, and S54 block are the same, all being styrene structural units derived from styrene. In Formula II, when the monovinyl aromatic structural units in the S51 block, S52 / B51 block, S53 / B53 block, and S54 block are all styrene structural units derived from styrene, the content of non-block styrene is preferably 15-20% by weight, more preferably 17-18.5% by weight, based on the total amount of styrene structural units in the hydrogenated block copolymer.

[0067] In the pentablock copolymer shown in Formula II, the conjugated diene structural unit in the B52 block is derived from the B52 conjugated diene, the conjugated diene structural unit in the S52 / B51 block is derived from the B51 conjugated diene, and the conjugated diene structural unit in the S53 / B53 block is derived from the B53 conjugated diene. The B52, B51, and B53 conjugated dienes can be the same or different, and each can 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 diene is different from the B51 and B53 conjugated dienes, and the B51 and B53 conjugated dienes are preferably the same.

[0068] More preferably, the B52 conjugated diene is isoprene, and the B51 and B53 conjugated dienes are butadiene. Based on the total amount of the pentablock copolymer, the content of isoprene structural units derived from isoprene is preferably 0.5-10% by weight, more preferably 1-5% by weight, and even more preferably 2-4% by weight; the content of butadiene structural units derived from butadiene is preferably 5-40% by weight, more preferably 10-35% by weight, and even more preferably 15-30% 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 side groups (i.e., side group content) is preferably 50-60% by weight, more preferably 50-57% by weight. Based on the total amount of butadiene structural units derived from butadiene in the pentablock copolymer, the content of butadiene structural units containing vinyl side groups (i.e., side group content) is preferably 40-60% by weight, more preferably 45-55% by weight.

[0069] Based on the total amount of the pentablock copolymer shown in Formula II, the content of monovinyl aromatic structural units derived from monovinyl aromatics is preferably 40-95% by weight, more preferably 50-90% by weight, and even more preferably 65-85% by weight; the content of conjugated diene structural units derived from conjugated dienes is preferably 5-60% by weight, more preferably 10-50% by weight, and even more preferably 15-35% by weight. The monovinyl aromatic structural units include monovinyl aromatic structural units in the S51 block, the S54 block, the S52 / B51 block, and the S53 / B53 block; the conjugated diene structural units include conjugated diene structural units in the S52 / B51 block, the B52 block, and the S53 / B53 block.

[0070] In the pentablock copolymer shown in Formula II, the number-average molecular weight of the S51 block is preferably 0.5 million 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 0.2 million to 20,000. In the aromatic polymer shown in 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 1:2-10, more preferably 1:2-6. In the pentablock copolymer shown in 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 1:0.9-1.25.

[0071] The number-average molecular weight of the pentablock copolymer shown in Formula II is preferably 50,000 to 220,000, more preferably 80,000 to 200,000. The molecular weight distribution index (Mi) of the pentablock copolymer shown in Formula II is... w / M n The preferred value is 1.05-1.2.

[0072] In another, more preferred embodiment, the aromatic polymer is a heptblock copolymer having the structure shown in Formula III:

[0073] S71-(S72 / B71)-B72-(S73 / B73)-B74-(S75 / B75)-S76 (Formula III)

[0074] In Formula III, the S71 and S76 blocks are end blocks, each independently representing a homopolymer segment of a monovinyl aromatic hydrocarbon; the S72 / B71, S73 / B73, and S75 / B75 blocks are each independently representing a random copolymer segment of a monovinyl aromatic hydrocarbon and a conjugated diene, wherein the S72 / B71 and S75 / B75 blocks are end blocks; and the B72 and B74 blocks are each independently representing a homopolymer segment of a conjugated diene.

[0075] In the seven-block copolymer shown in Formula III, the monovinyl aromatic structural units in blocks S71, S72 / B71, S73 / B73, S75 / B75, and S76 are respectively represented as S71 monovinyl aromatic structural unit, S72 monovinyl aromatic structural unit, S73 monovinyl aromatic structural unit, and S75 monovinyl aromatic structural unit. These units can be the same or different, and each can be selected from one or more of the group consisting of styrene, 2-methylstyrene, 4-methylstyrene, and α-methylstyrene. Preferably, the monovinyl aromatic structural units in blocks S71, S72 / B71, S73 / B73, S75 / B75, and S76 are the same, all being styrene structural units derived from styrene. In the heptapole copolymer represented by Formula III, when the monovinyl aromatic 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, the content of non-block styrene is preferably 15-20% by weight, more preferably 17-18.5% by weight, based on the total amount of styrene structural units in the heptapole copolymer.

[0076] In the heptadecanoe copolymer shown in Formula III, the conjugated diene structural unit in the B72 block is derived from the B72 conjugated diene, the conjugated diene structural unit in the S72 / B71 block is derived from the B71 conjugated diene, the conjugated diene structural unit in the S73 / B73 block is derived from the B73 conjugated diene, the conjugated diene structural unit in the B74 block is derived from the B74 conjugated diene, and the conjugated diene structural unit in the S75 / B75 block is derived from the B75 conjugated diene. The B72 conjugated diene, the B71 conjugated diene, the B73 conjugated diene, the B74 conjugated diene, and the B75 conjugated diene 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 diene is different from the B71 conjugated diene, the B73 conjugated diene, the B74 conjugated diene, and the B75 conjugated diene, and the B71 conjugated diene, the B73 conjugated diene, the B74 conjugated diene, and the B75 conjugated diene are preferably the same.

[0077] More preferably, in the heptablock copolymer represented by Formula III, the B72 conjugated diene is isoprene, and the B71, B73, B74, and B75 conjugated dienes are butadiene. Based on the total amount of the heptablock copolymer, the content of isoprene structural units derived from isoprene is preferably 0.5-10% by weight, more preferably 1-5% by weight, and even more preferably 2-4% by weight; the content of butadiene structural units derived from butadiene is preferably 5-40% by weight, more preferably 10-35% by weight, and even more preferably 15-30% by weight. More preferably, based on the total amount of isoprene-derived structural units in the aromatic polymer, the content of isoprene structural units containing vinyl side groups is preferably 40-60% by weight, more preferably 45-55% by weight; based on the total amount of butadiene-derived structural units in the aromatic polymer, the content of butadiene structural units containing vinyl side groups is preferably 40-60% by weight, more preferably 45-55% by weight.

[0078] In the heptablock copolymer shown in Formula III, based on the total amount of aromatic polymer, the content of monovinyl aromatic structural units derived from monovinyl aromatics is preferably 40-95% by weight, more preferably 50-90% by weight, and even more preferably 65-85% by weight; the content of conjugated diene structural units derived from conjugated dienes is preferably 5-60% by weight, more preferably 10-50% by weight, and even more preferably 15-35% by weight. The monovinyl aromatic structural unit includes monovinyl aromatic structural units in the S71 block, the S76 block, the S72 / B71 block, the S73 / B73 block, and the S75 / B75 block; the conjugated diene structural unit includes conjugated diene structural units in the S72 / B71 block, the B72 block, the S73 / B73 block, the B74 block, and the S75 / B75 block.

[0079] In the heptabolic copolymer shown in Formula III, the number-average molecular weight of the S71 block is preferably 0.5 million 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 0.2 million to 20,000, the number-average molecular weight of the S73 / B73 block is preferably 0.5 million to 50,000, the number-average molecular weight of the B74 block is preferably 0.2 million to 20,000, the number-average molecular weight of the S75 / B75 block is preferably 0.5 million to 50,000, and the number-average molecular weight of the S76 block is preferably 10,000 to 50,000. In the heptabolic copolymer shown in Formula III, the ratio of the number-average molecular weight of the S71 block to that of the S76 block is preferably 1:1.5-5, more preferably 1.6-3. In the heptabolic copolymer shown in Formula III, the ratio of the number-average molecular weights of the S72 / B71 block, the S73 / B73 block, and the S75 / B75 block is preferably 1:1-1.2:1-1.25. In the heptabolic copolymer shown in Formula III, the ratio of the number-average molecular weight of the B72 block to the B74 block is preferably 1:0.9-1.2.

[0080] In the heptablock copolymer represented by Formula III, the number-average molecular weight (M) of the heptablock copolymer is... n The molecular weight distribution index (M0.05) is preferably between 50,000 and 200,000, more preferably between 120,000 and 190,000. The molecular weight distribution index (M0.05) of the heptblock copolymer is... w / M n The preferred value is 1.05-1.2.

[0081] The aromatic polymer can be prepared using conventional methods.

[0082] When the aromatic polymer is a block copolymer, it can be prepared by anionic polymerization through the sequential addition of monomers. Specifically, under anionic polymerization conditions, the monomers can be sequentially added to a solution containing an organolithium initiator and optionally a polarity modifier to obtain the block copolymer.

[0083] The organolithium initiator can be any organolithium initiator commonly used in anionic polymerization that can initiate the polymerization of the monomers. Preferably, the organolithium initiator is an organolithium monolithium compound, more preferably a compound represented by Formula IV.

[0084] R2Li (Formula IV)

[0085] In equation IV, R2 is C1-C 10 Alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, hexyl (including various isomers of hexyl), heptyl (including various isomers of heptyl), octyl (including various isomers of octyl), nonyl (including various isomers of nonyl), or decyl (including various isomers of decyl).

[0086] Specific examples of the organolithium initiator may include, but are not limited to, one or more of the following: ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, and isobutyl lithium.

[0087] Preferably, the organolithium initiator is one or more selected from the group consisting of n-butyllithium, sec-butyllithium, isobutyllithium, and tert-butyllithium. More preferably, the organolithium initiator is n-butyllithium.

[0088] The amount of the organolithium initiator can be determined based on the expected molecular weight of the first block (i.e., the initial end block) of the block copolymer. Generally, the amount of the organolithium initiator can be 0.03-0.2 mmol (millimoles) relative to 1 g of monomer used to form the first block, preferably 0.04-0.15 mmol.

[0089] The polarity modifier can be a compound containing oxygen, nitrogen, sulfur, or phosphorus atoms in its molecular structure. Preferably, the polarity modifier is selected from at least one group consisting of diethyl ether, dibutyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dioxane, crown ether, tetrahydrofurfuryl ethyl ether, triethylamine, tetramethylethylenediamine, hexamethylphosphoric triamine, potassium tert-butoxide, potassium tert-pentoxide, potassium lauryl alcohol, potassium alkylbenzene sulfonate, and sodium alkylbenzene sulfonate. The amount of the polarity modifier can be appropriately selected according to the specific polymerization conditions. Generally, the molar ratio of the polarity modifier to the organolithium initiator can be 0.1-40:1, preferably 0.2-20:1, where the organolithium initiator is calculated based on elemental lithium.

[0090] The block copolymer is preferably produced by solution polymerization. This invention does not particularly limit the type of solvent used in solution polymerization; the solvent can be any commonly used solvent in solution polymerization, as long as it is liquid under the polymerization reaction conditions and is inert (i.e., does not participate in the polymerization reaction or react with the resulting polymer). Preferably, the solvent is at least one selected from the group consisting of cyclohexane, methylcyclohexane, n-hexane, cyclooctane, cycloheptane, acetone, n-butanone, decahydronaphthalene, and tetrahydrofuran. The amount of solvent used can be selected based on the amount of monomer. Generally, the amount of solvent used results in a monomer concentration in the range of 5-40% by weight.

[0091] In preparing block copolymers, the order of monomer addition depends on the desired sequence structure of each block in the block copolymer. Taking the pentablock copolymer described above as an example, the pentablock copolymer can be prepared using a method including the following steps:

[0092] (5-1) Under anionic polymerization conditions, in the presence of at least one solvent, S51 monovinyl aromatic hydrocarbon is contacted with an organolithium initiator and a polarity modifier to carry out a homopolymerization reaction to form a reaction mixture containing S51 blocks.

[0093] (5-2) Under anionic polymerization conditions, S52 monovinyl aromatic hydrocarbon and B51 conjugated diene are added to the reaction mixture containing S51 block to carry out random copolymerization reaction to obtain a reaction mixture containing S51 block and S52 / B51 block.

[0094] (5-3) Under anionic polymerization conditions, B52 conjugated diene was added to the reaction mixture containing S51 block and S52 / B51 to carry out homopolymerization reaction to obtain a reaction mixture containing S51 block, S52 / B51 block and B52 block.

[0095] (5-4) Under anionic polymerization conditions, S53 monovinyl aromatic hydrocarbon and B53 conjugated diene were added to the reaction mixture containing S51 block, S52 / B51 block and B52 block to carry out random copolymerization reaction to obtain a reaction mixture containing S51 block, S52 / B51 block, B52 block and S53 / B53 block.

[0096] (5-5) Under anionic polymerization conditions, S54 monovinyl aromatic hydrocarbon is added to a reaction mixture containing S51 block, S52 / B51 block, B52 block and S53 / B53 block, and homopolymerization is carried out to obtain a reaction mixture containing the pentablock copolymer.

[0097] The polymerization reaction can be carried out under conventional anionic polymerization conditions. Generally, the temperature of each polymerization step can be 40-90°C. The temperatures of each polymerization step can be the same or different. Preferably, the temperatures of each polymerization step are the same, that is, each polymerization step is carried out at the same temperature. According to the preparation method of the present invention, the duration of each polymerization step is such that all or substantially all of the monomers added in that step react, and the conversion rate of monomers in each polymerization step is usually above 99%. Generally, the duration of each polymerization step can be 0.5-1.2 hours.

[0098] After the final polymerization reaction is completed, at least one terminator can be added to terminate the active chain. The terminator can be any substance commonly used in anionic polymerization that can terminate the active chain, such as at least one selected from the group consisting of water, alcohol, and acid. Preferably, the terminator is at least one selected from the group consisting of isopropanol, methanol, and water. This invention does not particularly limit the amount of the polymerization terminator, as long as the amount is sufficient to deactivate the active center. In actual operation, the amount of polymerization terminator can be determined based on the amount of anionic polymerization initiator.

[0099] The obtained reaction mixture can be purified and separated using conventional methods to obtain the block copolymer. Specifically, the obtained reaction mixture can be centrifuged, filtered, decanted, or coagulated in hot water to obtain the block copolymer; alternatively, the obtained mixture can be stripped to remove the solvent, thereby obtaining the block copolymer.

[0100] Those skilled in the art will understand that the heptagonal copolymer described above can be prepared by adding a random copolymerization step and a homopolymerization step sequentially to the preparation method of the pentablock copolymer. This article will not provide a detailed description of the specific preparation method of the heptagonal copolymer.

[0101] The aromatic polymer may contain one or more additives. The additives may include antioxidants. This invention does not particularly limit the type of antioxidant, and it can be any antioxidant conventional in the art. 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-dioctylthiomethyl-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'-methylene-bis(4-methyl-6-tert-butylphenol). When pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] is used in combination with tris(2,4-di-tert-butylphenyl) phosphite, the content of tris(2,4-di-tert-butylphenyl) phosphite is preferably not higher than 50% by weight; 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 not higher than 50% by weight. The amount of the antioxidant can be the conventional amount used in the art. For example, based on 100 parts by weight of aromatic polymer, the amount of the antioxidant can be 0.005-2 parts by weight, preferably 0.1-1 parts by weight.

[0102] 2. Hydrogenation method

[0103] The method for hydrogenating an aromatic polymer according to the present invention includes contacting an aromatic polymer with a hydrogenating agent in the presence of a hydrogenating catalyst to hydrogenate at least a portion of the aromatic rings in the aromatic polymer to obtain a hydrogenated aromatic polymer.

[0104] The hydrogenation catalyst contains a support and platinum, Group IVA elements, and rare earth metals supported on the support, wherein the support is alumina.

[0105] In the hydrogenation catalyst, the molar ratio of the Group IVA element to platinum is not higher than 10, preferably not higher than 8. In the hydrogenation catalyst, the molar ratio of the Group IVA element to platinum is not less than 1. In a preferred embodiment, the molar ratio of the Group IVA element to platinum in the hydrogenation catalyst is 3-7:1, 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.

[0106] The Group IVA element can be at least one element selected from the group consisting of carbon (C), silicon (Si), germanium (Ge), tin (Sn), and lead (Pb), preferably at least one element selected from the group consisting of Si, Ge, and Sn. In a particularly preferred embodiment, the Group IVA element is Sn.

[0107] In the hydrogenation catalyst, the molar ratio of the rare earth metal element to the platinum element is preferably 1-6:1, 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, the molar ratio of the rare earth metal element to the platinum element is 1.5-5:1.

[0108] The rare earth metal element may be 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, and more preferably La, Ce, or a combination thereof. In a particularly preferred embodiment, the rare earth metal element is Ce.

[0109] In a preferred embodiment, the hydrogenation catalyst further comprises 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, the molar ratio of alkali metal element to platinum element in the hydrogenation catalyst is preferably 7-20:1, for example, it can be 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, the molar ratio of alkaline earth metal elements to platinum elements in the hydrogenation catalyst is preferably 10-35:1, for example, it can be 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, 2... 0.5:1, 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.

[0110] In a preferred embodiment, the hydrogenation catalyst further comprises a Group IVB metal, a halogen, or a combination thereof. The Group IVB metal may be titanium (Ti), zirconium (Zr), or a combination thereof, preferably Zr. The halogen may be at least one element selected from the group consisting of fluorine (F), chlorine (Cl), bromine (Br), and iodine (I), preferably Cl. In this preferred embodiment, the molar ratio of the Group IVB metal to platinum in the hydrogenation catalyst, based on elemental composition, is preferably 2-10:1, 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, the molar ratio of the Group IVB metal to platinum in the hydrogenation catalyst, based on elemental composition, is preferably 4-6:1. In this preferred embodiment, the molar ratio of the halogen to the platinum element in the hydrogenation catalyst is preferably 2-8:1, 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, the molar ratio of the halogen to the platinum element in the hydrogenation catalyst is more preferably 4-6:1.

[0111] In a particularly preferred embodiment, the hydrogenation catalyst contains platinum, a Group IVA element, a Group IVB metal element, a rare earth metal element, a halogen element, an alkali metal element, and an alkaline earth metal element, wherein the Group IVA element is Sn, the Group IVB metal element is Zr, the rare earth metal element is Ce, the halogen element is Cl, the alkali metal element is K, and the alkaline earth metal element is Mg.

[0112] Based on the total amount of the hydrogenation catalyst, the platinum content can be 0.1-0.8 wt%, for example, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, or 0.8 wt%, where the platinum element is calculated as an element. Preferably, based on the total amount of the hydrogenation catalyst, the platinum content is 0.2-0.8 wt%, where the platinum element is calculated as an element.

[0113] In the hydrogenation catalyst, the alumina is preferably γ-alumina.

[0114] The specific surface area of ​​the hydrogenation catalyst is preferably 100-400 m². 2 / g, more preferably 200-350m 2 / g, further preferably 250-320m 2 / g. The average pore size of the hydrogenation catalyst is preferably 5-40 nm, more preferably 10-20 nm, and even more preferably 15-20 nm.

[0115] The hydrogenation catalyst can be obtained by loading the components of the catalyst onto a support and optionally calcining them. Conventional methods can be used to load the components of the catalyst onto the support, such as liquid-phase methods. Specific examples of the liquid-phase methods may include, but are not limited to, one or more combinations of impregnation and spraying methods.

[0116] The components of the hydrogenation catalyst can be loaded onto the support through two or more loading steps, or the components of the hydrogenation catalyst can be loaded onto the support simultaneously. In a preferred embodiment, the components of the hydrogenation catalyst are loaded onto the support through two or more loading steps. In this preferred embodiment, it is preferable to first load the rare earth metal elements onto the support, and then load the platinum element and the Group IVA element onto the support.

[0117] When the hydrogenation catalyst contains a Group IVB metal element, a halogen element, or a combination thereof, it is preferable that the Group IVB metal element, the halogen element, or a combination thereof, along with platinum and a Group IVA element, are simultaneously supported on a support.

[0118] When the hydrogenation catalyst contains alkali metal elements and alkaline earth metal elements, it is preferable to load the alkali metal elements and alkaline earth metal elements on a support containing rare earth metal elements before loading platinum elements and Group IVA elements.

[0119] When loading the components in the catalyst using a liquid-phase method, the support can be dried after loading to remove the liquid phase. The drying temperature can be 50-200°C, preferably 80-150°C; the drying duration can be 1-10 hours, preferably 2-8 hours. The drying can be carried out at atmospheric pressure (i.e., 1 standard atmosphere) or under reduced pressure. The drying can be carried out in an oxidizing atmosphere (e.g., air) or in an inactive atmosphere (e.g., an atmosphere formed by one or more of nitrogen, argon, and helium).

[0120] In preparing the hydrogenation catalyst, after loading, calcination may or may not be performed, but calcination is preferred. The calcination can be carried out under conventional conditions. Specifically, the calcination temperature can be 400-650°C, preferably 400-600°C; the calcination duration can be 1-10 hours, preferably 2-8 hours. The calcination is preferably carried out in an oxidizing atmosphere, such as in air.

[0121] The hydrogenation catalyst is preferably prepared by a method comprising the following steps:

[0122] (a) A solution containing a rare earth metal element precursor is contacted with a support to obtain a second support, and at least part of the solvent in the second support is removed to obtain a first intermediate support.

[0123] (b) Optionally, the first intermediate support is contacted with a solution containing an alkali metal element precursor and an alkaline earth metal element precursor to obtain a third support, and at least part of the solvent in the third support is removed to obtain a second intermediate support.

[0124] (c) The first intermediate support or the second intermediate support is contacted with a solution containing a platinum precursor, a Group IVA element precursor, an optional Group IVB metal element precursor, and an optional halogen element precursor to obtain a fourth support, and at least part of the solvent in the fourth support is removed to obtain a third intermediate support.

[0125] (d) The third intermediate carrier is calcined.

[0126] This invention does not specifically limit the precursors described in steps (a), (b), and (c), and each can be an independent soluble compound of the aforementioned components, such as 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 precursor is preferably chloroplatinic acid; the Group IVA element precursor can be a chloride and / or nitrate of the IVA element, preferably stannous chloride, stannous chloride, or a combination thereof; the Group IVB metal element precursor can be a chloride, nitrate, or a combination thereof of the IVB element, preferably zirconium nitrate, zirconium oxynitrate, or a combination thereof; the rare earth metal element precursor can be a chloride of a rare earth metal, a nitrate of a rare earth metal, or a combination thereof. The alkali metal element precursor can be a chloride of an alkali metal, a nitrate of an alkali metal, or a combination thereof. The alkaline earth metal element precursor can be a chloride of an alkaline earth metal, a nitrate of an alkaline earth metal, or a combination thereof. The halogen precursor is a halogen-containing compound, for example, it can be at least one selected from the group consisting of HCl, HBr, HI and HF.

[0127] The present invention does not have a particular limitation on the concentration of the solution described in steps (a), (b) and (c), and can determine it according to the water absorption rate of the carrier and the target content of each component.

[0128] The solvent for the solutions described in steps (a), (b), and (c) is 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 include, but are not limited to, one or more of the group consisting of ethanol, isopropanol, and butanol. Preferably, the solvent for the solutions described in steps (a) and (b) is water. In a preferred embodiment, the solvent for the solution described in step (c) is ethanol. This preferred embodiment facilitates uniform dispersion of the catalyst components and stabilizes catalyst activity. In a more preferred embodiment, the solvent for the solution described in step (c) is a mixed solution of hydrochloric acid and ethanol, wherein the volume ratio of hydrochloric acid to ethanol is preferably 1:1-5. This more preferred embodiment further facilitates uniform dispersion of the catalyst components and stabilizes catalyst activity.

[0129] Before being used in the hydrogenation reaction, the hydrogenation catalyst is reduced. The reduction is carried out in a hydrogen-containing atmosphere, more preferably in a hydrogen atmosphere. The reduction temperature is preferably 400-550°C. The reduction duration is preferably 1-10 hours. The reduction can be carried out outside the hydrogenation reactor or in situ within the hydrogenation reactor. Preferably, the hydrogenation catalyst is reduced in situ within the hydrogenation reactor.

[0130] Traditional heterogeneous powder catalysts used in hydrogenation reactions often have low catalytic activity, requiring a catalyst dosage typically ranging from 100% to 800% of the polymer weight. The hydrogenation method according to the present invention utilizes a catalyst with high reactivity, significantly reducing the amount of hydrogenation catalyst required. According to the hydrogenation method of the present invention, the amount of hydrogenation catalyst relative to 100 parts by weight of the aromatic polymer can be 1-20 parts by weight, preferably 2-10 parts by weight, and more preferably 2.5-5 parts by weight.

[0131] According to the method of the present invention, an aromatic polymer is contacted with a hydrogenation catalyst in the presence of at least one solvent. The solvent may be a solvent capable of dissolving both the aromatic polymer and the hydrogenated aromatic polymer generated by 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, decahydronaphthalene, and tetrahydrofuran.

[0132] Traditional heterogeneous powder catalysts for hydrogenation reactions suffer from low catalytic activity, limiting the effectiveness of the hydrogenation process. Excessive polymer concentration leads to low efficiency, typically below 5% by weight. The hydrogenation catalyst used in this invention exhibits high reactivity, enabling the reaction to proceed at higher polymer concentrations. According to the hydrogenation method of this invention, the amount of solvent used achieves a polymer concentration of 20% by weight, preferably 5-15% by weight.

[0133] According to the hydrogenation method of the present invention, the temperature of the hydrogenation reaction can be 50-200°C, preferably 120-180°C, and more preferably 120-150°C.

[0134] According to the hydrogenation method of the present invention, the hydrogenation reagent can be a commonly used hydrogenation reagent. In a preferred embodiment, the hydrogenation reagent is hydrogen gas. When hydrogen gas is used as the hydrogenation reagent, the pressure of the hydrogen gas can be 0.1-10 MPa, preferably 0.5-5 MPa, and the pressure is gauge pressure.

[0135] According to the hydrogenation method of the present invention, the hydrogenation catalyst can be recycled. Generally, after the hydrogenation reaction is completed, the hydrogenation reaction mixture can be subjected to solid-liquid separation to recover the hydrogenation catalyst. The recovered hydrogenation catalyst can be recycled for hydrogenation reactions. Preferably, the recovered hydrogenation catalyst is washed and dried sequentially before being recycled for hydrogenation reactions.

[0136] According to the hydrogenation method of the present invention, the degree of hydrogenation of the aromatic ring is high. According to the hydrogenation method of the present invention, the degree of hydrogenation of the aromatic ring can be 95 mol% or more, preferably 97 mol% or more, more preferably 98 mol% or more, further preferably 99 mol% or more, and even more preferably 100 mol%. According to the hydrogenation method of the present invention, when the aromatic polymer contains a conjugated diene structural unit, the degree of hydrogenation of the conjugated diene structural unit can be 97 mol% or more, preferably 99 mol% or more, and more preferably 100 mol%.

[0137] According to the hydrogenation method of the present invention, the aromatic polymer undergoes minimal degradation during the hydrogenation reaction. According to the hydrogenation method of the present invention, the number-average molecular weight of the aromatic polymer used as a raw material for the hydrogenation reaction is defined as M. n 1. The number-average molecular weight of the hydrogenated aromatic polymer, which is a product of the hydrogenation reaction, is defined as M. n 2, [(M n 1-M n 2) / M n1]×100% is defined as the degradation rate, which is not higher than 2.5%, preferably not higher than 1.5%, more preferably not higher than 1%, further preferably not higher than 0.5%, even more preferably not higher than 0.3%, and particularly preferably not higher than 0.1%.

[0138] 3. Hydrogenated block copolymers

[0139] This invention provides a hydrogenated block copolymer comprising a monovinyl aromatic structural unit derived from a monovinyl aromatic hydrocarbon and a conjugated diene structural unit derived from a conjugated diene. The hydrogenated block copolymer is formed by hydrogenating the block copolymer, and comprises hydrogenated monovinyl aromatic structural units and hydrogenated conjugated diene structural units. In the hydrogenated block copolymer, the degree of hydrogenation of the aromatic ring in the monovinyl aromatic 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 diene structural unit is 99 mol% or more, preferably 99.5 mol% or more, more preferably 100 mol%.

[0140] According to the hydrogenated block copolymer of the present invention, the block copolymer contains at least two homopolymer segments of monovinyl aromatic hydrocarbons, at least one homopolymer segment of a conjugated diene, and at least two random copolymer segments of monovinyl aromatic hydrocarbons and conjugated dienes. Each of the two end blocks of the block copolymer is independently a homopolymer segment of a monovinyl aromatic hydrocarbon, and the block directly bonded to the end blocks is an end block, each of the end blocks being independently a random copolymer segment of a monovinyl aromatic hydrocarbon and a conjugated diene. When the block copolymer contains at least three random copolymer segments of monovinyl aromatic hydrocarbons and conjugated dienes and at least two homopolymer segments of conjugated dienes, the homopolymer segments of the conjugated dienes are arranged alternately with the random copolymer segments of the monovinyl aromatic hydrocarbons and conjugated dienes, and each of the two end groups of the homopolymer segments of the conjugated dienes is directly bonded to one random copolymer segment of a monovinyl aromatic hydrocarbon and a conjugated diene.

[0141] According to the hydrogenated block copolymer of the present invention, based on the total amount of the block copolymer, the content of structural units derived from monovinyl aromatic hydrocarbons can be 40-95% by weight, and the content of structural units derived from conjugated dienes can be 5-60% by weight, preferably not more than 50% by weight, for example, 10-50% by weight, more preferably 15-35% 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 structural units derived from monovinyl aromatic hydrocarbons in the block copolymer, the content of structural units derived from monovinyl aromatic hydrocarbons in the random copolymer segment can be 15-20% by weight, preferably 17-18.5% by weight. In the block copolymer, based on the total amount of conjugated diene structural units, the side group content can be 40-60% by weight.

[0142] In this preferred embodiment, the conjugated diene structural units in the homopolymer segment of the conjugated diene and the conjugated diene structural units in the random copolymer segment can be the same or different. Preferably, the homopolymer segment of the conjugated diene contains a homopolymer segment of a first conjugated diene and at least one homopolymer segment of a second conjugated diene, wherein the structural units in the homopolymer segment of the first conjugated diene are derived from the first conjugated diene, and the structural units in the homopolymer segment of the second conjugated diene are derived from the second conjugated diene, and the first conjugated diene is different from the second conjugated diene. More preferably, the homopolymer segment of the first conjugated diene is directly bonded to an endopeptide segment, wherein the first conjugated diene is isoprene, and the second conjugated diene and the conjugated diene in the random copolymer segment of the monovinyl aromatic hydrocarbon and the conjugated diene are butadiene. Based on the total amount of the hydrogenated block copolymer, the content of isoprene structural units derived from isoprene is preferably 0.5-10% by weight, more preferably 1-5% by weight, and even more preferably 2-4% by weight; the content of butadiene structural units derived from butadiene is preferably 5-40% by weight, more preferably 10-35% by weight, and even more preferably 15-30% by weight.

[0143] The hydrogenated block copolymer according to the present invention has a notched impact strength of 20-30 kJ / m. 2 The preferred value is 21-25 kJ / m 2The hydrogenated block copolymer has an elongation at break of 200-400%, preferably 250-380%, more preferably 260-350%. The light transmittance of the hydrogenated block copolymer is 88-92%, preferably 90-92%. The haze of the hydrogenated block copolymer is 1-5, preferably 1-2. According to the block copolymer of the present invention, the Vicat softening point of the hydrogenated block copolymer is 110-150°C, preferably 115-130°C.

[0144] In this invention, the notched impact strength is the notched impact strength of a simply supported beam determined according to the method specified in ISO 179-1-2000, and is obtained by testing with a Ceast Resil Impactor 6957 pendulum impact testing machine. The specimen size used is 80mm × 10mm × 4mm, and the remaining width of the notch is 8 ± 0.2mm. The elongation at break is obtained according to the method specified in ASTM D638-03, and is obtained by testing with an INSTRON 5567 tensile testing machine. The specimen size used is 170mm × 10mm × 4mm. The light transmittance and haze are obtained according to the method specified in ASTM D1033-2007, and are obtained by testing with an EEL57D haze meter.

[0145] In this invention, the Vicat softening point was obtained using an Instron-HV6M Vicat softening point temperature measuring instrument, with a heating rate of 50℃ / h and a load of 50N.

[0146] The present invention also provides a hydrogenated pentablock copolymer, wherein the hydrogenated pentablock copolymer is formed by hydrogenating the pentablock copolymer, wherein the pentablock copolymer is a pentablock copolymer having the structure shown in Formula II:

[0147] S51-(S52 / B51)-B52-(S53 / B53)-S54 (Formula II)

[0148] In Formula II, S51 and S54 are end blocks, each independently representing a homopolymer segment of a monovinyl aromatic hydrocarbon; S52 / B51 and S53 / B53 are end blocks, each independently representing a random copolymer segment of a monovinyl aromatic hydrocarbon and a conjugated diene; and B52 is a homopolymer segment of a conjugated diene.

[0149] In the pentablock copolymer shown in Formula II, the monovinyl aromatic structural units in the S51 block, S52 / B51 block, S53 / B53 block, and S54 block are represented as S51 monovinyl aromatic structural unit, S52 monovinyl aromatic structural unit, S53 monovinyl aromatic structural unit, and S54 monovinyl aromatic structural unit, respectively. These units can be the same or different, and each unit can be one or more selected from the group consisting of styrene, 2-methylstyrene, 4-methylstyrene, and α-methylstyrene. Preferably, the monovinyl aromatic structural units in the S51 block, S52 / B51 block, S53 / B53 block, and S54 block are the same, all being styrene structural units derived from styrene. In Formula II, when the monovinyl aromatic structural units in the S51 block, S52 / B51 block, S53 / B53 block, and S54 block are all styrene structural units derived from styrene, the content of non-block styrene is preferably 15-20% by weight, more preferably 17-18.5% by weight, based on the total amount of styrene structural units in the hydrogenated block copolymer.

[0150] In the pentablock copolymer shown in Formula II, the conjugated diene structural unit in the B52 block is derived from the B52 conjugated diene, the conjugated diene structural unit in the S52 / B51 block is derived from the B51 conjugated diene, and the conjugated diene structural unit in the S53 / B53 block is derived from the B53 conjugated diene. The B52, B51, and B53 conjugated dienes can be the same or different, and each can 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 diene is different from the B51 and B53 conjugated dienes, and the B51 and B53 conjugated dienes are preferably the same.

[0151] More preferably, the B52 conjugated diene is isoprene, and the B51 and B53 conjugated dienes are butadiene. Based on the total amount of the pentablock copolymer, the content of isoprene structural units derived from isoprene is preferably 0.5-10% by weight, more preferably 1-5% by weight, and even more preferably 2-4% by weight; the content of butadiene structural units derived from butadiene is preferably 5-40% by weight, more preferably 10-35% by weight, and even more preferably 15-30% 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 side groups (i.e., side group content) is preferably 50-60% by weight, more preferably 50-57% by weight. Based on the total amount of butadiene structural units derived from butadiene in the pentablock copolymer, the content of butadiene structural units containing vinyl side groups (i.e., side group content) is preferably 40-60% by weight, more preferably 45-55% by weight.

[0152] Based on the total amount of the pentablock copolymer shown in Formula II, the content of monovinyl aromatic structural units derived from monovinyl aromatics is preferably 40-95% by weight, more preferably 50-90% by weight, and even more preferably 65-85% by weight; the content of conjugated diene structural units derived from conjugated dienes is preferably 5-60% by weight, more preferably 10-50% by weight, and even more preferably 15-35% by weight. The monovinyl aromatic structural units include monovinyl aromatic structural units in the S51 block, the S54 block, the S52 / B51 block, and the S53 / B53 block; the conjugated diene structural units include conjugated diene structural units in the S52 / B51 block, the B52 block, and the S53 / B53 block.

[0153] In the pentablock copolymer shown in Formula II, the number-average molecular weight of the S51 block is preferably 0.5 million 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 0.2 million to 20,000. In the aromatic polymer shown in 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 1:2-10, more preferably 1:2-6. In the pentablock copolymer shown in 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 1:0.9-1.25.

[0154] The number-average molecular weight of the pentablock copolymer shown in Formula II is preferably 50,000 to 220,000, more preferably 80,000 to 200,000. The molecular weight distribution index (Mi) of the pentablock copolymer shown in Formula II is... w / M n The preferred value is 1.05-1.2.

[0155] In the hydrogenated pentablock copolymer according to the present invention, the hydrogenated pentablock copolymer contains hydrogenated monovinyl aromatic structural units and hydrogenated conjugated diene structural units. In the hydrogenated block copolymer, the degree of hydrogenation of the aromatic ring in the monovinyl aromatic 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 diene structural unit is 99 mol% or more, preferably 99.5 mol% or more, more preferably 100 mol%.

[0156] The hydrogenated pentablock copolymer according to the present invention has a notched impact strength of 20-30 kJ / m. 2 The preferred value is 21-25 kJ / m 2 The hydrogenated block copolymer has an elongation at break of 200-400%, preferably 250-380%, more preferably 260-350%. The light transmittance of the hydrogenated block copolymer is 88-92%, preferably 90-92%. The haze of the hydrogenated block copolymer is 1-5, preferably 1-2. According to the invention, the hydrogenated pentablock copolymer has a Vicat softening point of 110-150°C, preferably 115-130°C.

[0157] The present invention further provides a hydrogenated heptblock copolymer, wherein the heptblock copolymer is a heptblock copolymer having the structure shown in Formula III:

[0158] S71-(S72 / B71)-B72-(S73 / B73)-B74-(S75 / B75)-S76 (Formula III)

[0159] In Formula III, the S71 and S76 blocks are end blocks, each independently representing a homopolymer segment of a monovinyl aromatic hydrocarbon; the S72 / B71, S73 / B73, and S75 / B75 blocks are each independently representing a random copolymer segment of a monovinyl aromatic hydrocarbon and a conjugated diene, wherein the S72 / B71 and S75 / B75 blocks are end blocks; and the B72 and B74 blocks are each independently representing a homopolymer segment of a conjugated diene.

[0160] In the seven-block copolymer shown in Formula III, the monovinyl aromatic structural units in blocks S71, S72 / B71, S73 / B73, S75 / B75, and S76 are respectively represented as S71 monovinyl aromatic structural unit, S72 monovinyl aromatic structural unit, S73 monovinyl aromatic structural unit, and S75 monovinyl aromatic structural unit. These units can be the same or different, and each can be selected from one or more of the group consisting of styrene, 2-methylstyrene, 4-methylstyrene, and α-methylstyrene. Preferably, the monovinyl aromatic structural units in blocks S71, S72 / B71, S73 / B73, S75 / B75, and S76 are the same, all being styrene structural units derived from styrene. In the heptapole copolymer represented by Formula III, when the monovinyl aromatic 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, the content of non-block styrene is preferably 15-20% by weight, more preferably 17-18.5% by weight, based on the total amount of styrene structural units in the heptapole copolymer.

[0161] In the heptadecanoe copolymer shown in Formula III, the conjugated diene structural unit in the B72 block is derived from the B72 conjugated diene, the conjugated diene structural unit in the S72 / B71 block is derived from the B71 conjugated diene, the conjugated diene structural unit in the S73 / B73 block is derived from the B73 conjugated diene, the conjugated diene structural unit in the B74 block is derived from the B74 conjugated diene, and the conjugated diene structural unit in the S75 / B75 block is derived from the B75 conjugated diene. The B72 conjugated diene, the B71 conjugated diene, the B73 conjugated diene, the B74 conjugated diene, and the B75 conjugated diene 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 diene is different from the B71 conjugated diene, the B73 conjugated diene, the B74 conjugated diene, and the B75 conjugated diene, and the B71 conjugated diene, the B73 conjugated diene, the B74 conjugated diene, and the B75 conjugated diene are preferably the same.

[0162] In the heptablock copolymer represented by Formula III, more preferably, the B72 conjugated diene is isoprene, and the B71, B73, B74, and B75 conjugated dienes are butadiene. Based on the total amount of the heptablock copolymer, the content of isoprene structural units derived from isoprene is preferably 0.5-10% by weight, more preferably 1-5% by weight, and even more preferably 2-4% by weight; the content of butadiene structural units derived from butadiene is preferably 5-40% by weight, more preferably 10-35% by weight, and even more preferably 15-30% by weight. More preferably, based on the total amount of isoprene-derived structural units in the heptablock copolymer of Formula III, the content of isoprene structural units containing vinyl side groups is preferably 40-60% by weight, more preferably 45-55% by weight; based on the total amount of butadiene-derived structural units in the heptablock copolymer of Formula III, the content of butadiene structural units containing vinyl side groups is preferably 40-60% by weight, more preferably 45-55% by weight.

[0163] In the heptablock copolymer shown in Formula III, based on the total amount of the heptablock copolymer, the content of monovinyl aromatic structural units derived from monovinyl aromatics is preferably 40-95% by weight, more preferably 50-90% by weight, and even more preferably 65-85% by weight; the content of conjugated diene structural units derived from conjugated dienes is preferably 5-60% by weight, more preferably 10-50% by weight, and even more preferably 15-35% by weight. The monovinyl aromatic structural unit includes monovinyl aromatic structural units in the S71 block, the S76 block, the S72 / B71 block, the S73 / B73 block, and the S75 / B75 block; the conjugated diene structural unit includes conjugated diene structural units in the S72 / B71 block, the B72 block, the S73 / B73 block, the B74 block, and the S75 / B75 block.

[0164] In the heptabolic copolymer shown in Formula III, the number-average molecular weight of the S71 block is preferably 0.5 million 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 0.2 million to 20,000, the number-average molecular weight of the S73 / B73 block is preferably 0.5 million to 50,000, the number-average molecular weight of the B74 block is preferably 0.2 million to 20,000, the number-average molecular weight of the S75 / B75 block is preferably 0.5 million to 50,000, and the number-average molecular weight of the S76 block is preferably 10,000 to 50,000. In the heptabolic copolymer shown in Formula III, the ratio of the number-average molecular weight of the S71 block to that of the S76 block is preferably 1:1.5-5, more preferably 1.6-3. In the heptabolic copolymer shown in Formula III, the ratio of the number-average molecular weights of the S72 / B71 block, the S73 / B73 block, and the S75 / B75 block is preferably 1:1-1.2:1-1.25. In the heptabolic copolymer shown in Formula III, the ratio of the number-average molecular weight of the B72 block to the B74 block is preferably 1:0.9-1.2.

[0165] 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 (M0.05) of the heptablock copolymer is... w / M n The preferred value is 1.05-1.2.

[0166] In the hydrogenated heptablock copolymer according to the present invention, the hydrogenated heptablock copolymer contains hydrogenated monovinyl aromatic structural units and hydrogenated conjugated diene structural units. In the hydrogenated heptablock copolymer, the degree of hydrogenation of the aromatic ring in the monovinyl aromatic 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 diene structural unit is 99 mol% or more, preferably 99.5 mol% or more, more preferably 100 mol%.

[0167] The hydrogenated heptablock copolymer according to the present invention has a notched impact strength of 20-30 kJ / m. 2 The preferred value is 21-25 kJ / m 2 The hydrogenated heptablock copolymer has an elongation at break of 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. According to the present invention, the hydrogenated heptablock copolymer has a Vicat softening point of 110-150°C, preferably 120-140°C.

[0168] The hydrogenated block copolymers, hydrogenated pentablock copolymers, and hydrogenated heptblock copolymers according to the present invention can be obtained by hydrogenating the corresponding block copolymers using the hydrogenation method of the present invention.

[0169] The hydrogenated block copolymers, hydrogenated pentablock copolymers, and hydrogenated heptblock copolymers according to the present invention are suitable for preparing packaging materials or optoelectronic products.

[0170] The present invention will be described below with reference to the embodiments, but this does not limit the scope of the invention.

[0171] In the following examples and comparative examples, the performance parameters involved were obtained through testing using the following methods:

[0172] (1) Degree of hydrogenation and microstructure of polymer

[0173] Using nuclear magnetic resonance hydrogen spectroscopy (NMR) 1 Determined by H-NMR, 1 H-NMR measurements were performed on a BRUKER AVANCED RTX 400MHz NMR spectrometer. Deuterated chloroform was used as the solvent. The samples were prepared into 1-2% by weight solutions at room temperature, with tetramethylsilane as an internal standard. The NMR spectrometer operated at a frequency of 400.13MHz, a spectral width of 8012.82Hz, a data point of 32K, a pulse angle of 30°, a pulse width of 6μs, a pulse delay of 5s, and 64 samplings.

[0174] (2) Molecular weight and molecular weight distribution index (M w / M n )

[0175] The determination was performed using a Waters Alliance-2690 gel permeation chromatograph with a PL Mixed-C column (5 μm packing material) and chromatographically pure tetrahydrofuran (THF) as the solvent. Narrow-distribution polystyrene was used as the standard. The polymer sample was prepared into a solution with a mass concentration of 1 mg / mL, and the injection volume was 100.00 μL. The flow rate was 1 mL / min, and the test temperature was 40.0℃.

[0176] (3) Light transmittance and haze

[0177] The haze was measured using an EEL57D haze meter, following the method specified in ASTM D1033-2007.

[0178] (4) Notched impact strength of simply supported beam

[0179] The impact was measured using a Ceast Resil Impactor 6957 pendulum impact testing machine, according to the method specified in ISO 179-1-2000. The specimen size was 80 mm × 10 mm × 4 mm, and the remaining notch width was 8 ± 0.2 mm.

[0180] (5) Elongation at break

[0181] The tensile testing was performed using an INSTRON 5567 tensile testing machine, following the method specified in ASTM D638-03, with a sample size of 170 mm × 10 mm × 4 mm.

[0182] (6) Vicat softening point

[0183] The temperature was measured using an Instron-HV6M Vicat softening point thermometer at a heating rate of 50℃ / h and a load of 50N.

[0184] (7) Hydrogenation catalyst composition

[0185] The composition of the hydrogenation catalyst was determined using a Rigaku ZSX PrimuslV X-ray fluorescence spectrometer from Japan.

[0186] (8) Specific surface area and average pore size of hydrogenation catalyst

[0187] The specific surface area and average pore size of the hydrogenation catalyst were determined using the N2 adsorption method on an ASAP 2020 physical adsorption instrument purchased from Mack Company, USA.

[0188] In the following preparation processes, unless otherwise specified, the amounts of each precursor and the concentrations 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 preparation processes, unless otherwise specified, the weight of the prepared hydrogenation catalyst is 10 g. In the following preparation examples, unless otherwise specified, the specific surface area of ​​the γ-alumina support used is 350 m². 2 / g, with an average pore size of 20nm.

[0189] Preparation Examples 1-7 were used to prepare hydrogenation catalysts.

[0190] Preparation Example 1

[0191] This preparation example is used to prepare a hydrogenation catalyst having the composition shown in Table 1.

[0192] (1) The γ-alumina support was impregnated with an equal volume of cerium nitrate solution, and the impregnated support was dried in air at 120°C for 8 hours to obtain an alumina support containing cerium.

[0193] (2) The alumina support containing cerium obtained in step (1) was impregnated with an equal volume of solution containing potassium nitrate and magnesium nitrate. The impregnated support was dried in air at 120°C for 8 hours to obtain a catalyst intermediate loaded with cerium, potassium and magnesium.

[0194] (3) The catalyst intermediate obtained in step (2) was impregnated in equal volumes with a hydrochloric acid-ethanol solution containing chloroplatinic acid, tin chloride, and zirconium chloride (hydrochloric acid to anhydrous ethanol volume ratio of 1:2). Platinum, tin, and zirconium elements were then loaded onto a support. The impregnated support was dried in air at 120°C for 8 hours and then calcined in air at 600°C for 6 hours to obtain the hydrogenation catalyst. The specific surface area of ​​this hydrogenation catalyst was 300 m². 2 / g, with an average pore size of 17.6nm.

[0195] Preparation Example 2

[0196] This preparation example is used to prepare a hydrogenation catalyst having the composition shown in Table 1.

[0197] The hydrogenation catalyst was prepared using the same method as in Example 1, except that the amount of precursor was varied to obtain hydrogenation catalysts with different compositions. The specific surface area of ​​this hydrogenation catalyst was 295 m². 2 / g, with an average pore size of 18.2nm.

[0198] Preparation Example 3

[0199] This preparation example is used to prepare a hydrogenation catalyst having the composition shown in Table 1.

[0200] The hydrogenation catalyst was prepared using the same method as in Example 1, except that the amount of precursor was varied to obtain hydrogenation catalysts with different compositions. The specific surface area of ​​this hydrogenation catalyst was 290 m². 2 / g, with an average pore size of 18.5nm.

[0201] Preparation Example 4

[0202] This preparation example is used to prepare a hydrogenation catalyst having the composition shown in Table 1.

[0203] The hydrogenation catalyst was prepared using the same method as in Example 1, except that step (2) was omitted. Instead, the cerium-containing alumina support prepared in step (1) was directly used in step (3) for impregnation with an equal volume of hydrochloric acid-ethanol solution containing chloroplatinic acid, tin chloride, and zirconium chloride. The amount of precursor was adjusted to obtain the hydrogenation catalyst. The specific surface area of ​​this hydrogenation catalyst was 280 m². 2 / g, with an average pore size of 18.7nm.

[0204] Preparation Example 5

[0205] This preparation example is used to prepare a hydrogenation catalyst having the composition shown in Table 1.

[0206] The hydrogenation catalyst was prepared using the same method as in Preparation Example 1, except that the amount of precursor was varied to obtain hydrogenation catalysts with different compositions. The specific surface area of ​​this hydrogenation catalyst was 280 m². 2 / g, with an average pore size of 18.9nm.

[0207] Preparation of Comparative Example 1 (not of this invention)

[0208] The γ-alumina support used in step (1) of Preparation Example 1 was impregnated with nickel nitrate solution under the same conditions as in step (3) of Preparation Example 1. The impregnated support was dried in air at 120°C for 8 hours to obtain a catalyst loaded with nickel. Based on the total amount of catalyst, the nickel content in the catalyst was 10% by weight.

[0209] Preparation of Comparative Example 2 (not of this invention)

[0210] This comparative example was used to prepare catalysts with the compositions shown in Table 1.

[0211] The hydrogenation catalyst was prepared using the same method as in Preparation Example 1, except that the amount of precursor was varied to obtain hydrogenation catalysts with different compositions. The specific surface area of ​​this hydrogenation catalyst was 230 m². 2 / g, with an average pore size of 18.2nm.

[0212] Preparation of Comparative Example 3 (not of this invention)

[0213] This comparative example was used to prepare catalysts with the compositions shown in Table 1.

[0214] The hydrogenation catalyst was prepared using the same method as in Example 1, except that the impregnation solution used in step (3) did not contain tin chloride, and the resulting hydrogenation catalyst had a specific surface area of ​​230 m². 2 / g, with an average pore size of 18.3nm.

[0215] Preparation Example 6

[0216] This preparation example is used to prepare a catalyst having the composition shown in Table 1.

[0217] The hydrogenation catalyst was prepared using the same method as in Example 1, except that the impregnation solution used in step (3) did not contain HCl; instead, an equal volume of anhydrous ethanol was used to replace HCl. The resulting hydrogenation catalyst had a specific surface area of ​​280 m². 2 / g, with an average pore size of 18.2nm.

[0218] Preparation Example 7

[0219] This preparation example is used to prepare a catalyst having the composition shown in Table 1.

[0220] The hydrogenation catalyst was prepared using the same method as in Example 1, except that the impregnation solution used in step (3) did not contain zirconium chloride, and the resulting hydrogenation catalyst had a specific surface area of ​​280 m². 2 / g, with an average pore size of 18.3nm.

[0221] Table 1

[0222]

[0223] Note: Based on the total amount of hydrogenation catalyst, expressed in elements.

[0224] Examples 1-19 are used to illustrate the present invention.

[0225] Example 1

[0226] (1) Preparation of block copolymers

[0227] (1-1) In a 2L stainless steel stirred tank, add 800g cyclohexane, 60mg tetrahydrofurfuryl ethyl ether (ETE) and 38g styrene, raise the temperature to 50℃, add 1.6mmol n-butyllithium initiator, and polymerize at 50℃ for 30 minutes to obtain styrene homopolymer. The conversion rate of styrene is over 99%.

[0228] (1-2) Keep the temperature of the stirred tank at 50℃, add 30g butadiene and 22g styrene to the stirred tank, react for 40 minutes to allow butadiene and styrene to undergo random copolymerization, with the conversion rate of butadiene being over 99% and the conversion rate of styrene being over 99%.

[0229] (1-3) Keep the temperature of the stirred tank at 50℃, add 6g of isoprene, react for 40 minutes, and the conversion rate of isoprene is over 99%.

[0230] (1-4) Keep the temperature of the stirred tank at 50℃, add 30g butadiene and 22g styrene to the stirred tank, react for 30 minutes to allow butadiene and styrene to undergo random copolymerization, with the conversion rate of butadiene being over 99% and the conversion rate of styrene being over 99%.

[0231] (1-5) Keep the temperature of the stirred tank at 50℃, add 92g of styrene, and continue the reaction for 30 minutes. The conversion rate of styrene is over 99%.

[0232] (1-6) Add 0.25g of isopropanol to the stirred tank and terminate the reaction at 50℃ to obtain a block copolymer; add antioxidant 1076 to the obtained adhesive solution, the amount of antioxidant 1076 added is 1% by weight of the total weight of the monomers added in each step of the reaction, mix for 10 minutes to obtain an adhesive solution containing the block copolymer, and adjust the concentration of the block copolymer in the adhesive solution to 10% by weight. The structural parameters of the block copolymer are shown in Table 2. The structure of the block copolymer is: S51-S52 / B51-B52-S53 / B53-S54, where S51, S52, S53 and S54 are structural units derived from styrene, B51 and B53 are structural units derived from butadiene, and B52 is a structural unit derived from isoprene.

[0233] (2) Preparation of hydrogenated block copolymers

[0234] The hydrogenation catalyst prepared in Preparation Example 1 was reduced to obtain a reduced catalyst. The reduced catalyst was used in a hydrogenation reaction. The reduction was carried out in a hydrogen atmosphere at a temperature of 450°C for a duration of 2 hours.

[0235] In a 0.5L high-pressure reactor with a stirrer, 200g of the block copolymer solution prepared in step (1) and 1g of the reduced hydrogenation catalyst were added to carry out a hydrogenation reaction. The reaction temperature was 150℃, the hydrogen pressure was 3MPa, the reaction time was 1h, and the stirring speed was 800rpm.

[0236] After the hydrogenation reaction is completed, the hydrogenation product is centrifuged to obtain a reaction mixture containing the hydrogenated block copolymer. The reaction mixture is filtered to separate the hydrogenation catalyst, which is then washed with hexane, dried under vacuum, and recycled for the hydrogenation reaction. It was determined that after five cycles, the hydrogenation activity of the hydrogenation catalyst decreased by less than 2% (based on the hydrogenation activity at the time of the first use). The filtered liquid phase is collected and the solvent is removed to obtain the hydrogenated block copolymer according to the present invention. The structure and performance parameters of the hydrogenated block copolymer are listed in Table 3.

[0237] Example 2

[0238] (1) Preparation of block copolymers

[0239] (1-1) In a 2-liter stainless steel stirred tank, add 800g cyclohexane, 60mg ETE and 19g styrene, raise the temperature to 50℃, add 2.4mmol n-butyllithium initiator, and polymerize at 50℃ for 30 minutes to obtain styrene homopolymer. The conversion rate of styrene is over 99%.

[0240] (1-2) Keep the temperature of the stirred tank at 50℃, add 30g butadiene and 22g styrene to the stirred tank, react for 40 minutes to allow butadiene and styrene to undergo random copolymerization, with the conversion rate of butadiene being over 99% and the conversion rate of styrene being over 99%.

[0241] (1-3) Keep the temperature of the stirred tank at 50℃, add 6g of isoprene, react for 40 minutes, and the conversion rate of isoprene is over 99%.

[0242] (1-4) Keep the temperature of the stirred tank at 50℃, add 30g butadiene and 22g styrene to the stirred tank, react for 30 minutes to allow butadiene and styrene to undergo random copolymerization, with the conversion rate of butadiene being over 99% and the conversion rate of styrene being over 99%.

[0243] (1-5) Keep the temperature of the stirred tank at 50℃, add 111g of styrene, and continue the reaction for 30 minutes. The conversion rate of styrene is over 99%.

[0244] (1-6) Add 0.25g of isopropanol to the stirred tank and terminate the reaction at 50℃ to obtain a block copolymer; add antioxidant 1076 to the obtained adhesive solution, the amount of antioxidant 1076 added is 1% by weight of the total weight of the monomers added in each step of the reaction, mix for 10 minutes to obtain an adhesive solution containing the block copolymer, and adjust the concentration of the block copolymer in the adhesive solution to 10% by weight. The structural parameters of the block copolymer are shown in Table 2. The structure of the block copolymer is: S51-S52 / B51-B52-S53 / B53-S54, where S51, S52, S53 and S54 are structural units derived from styrene, B51 and B53 are structural units derived from butadiene, and B52 is a structural unit derived from isoprene.

[0245] (2) Preparation of hydrogenated block copolymers

[0246] The hydrogenated block copolymer was prepared using the same method as in Example 1, except that the block copolymer-containing solution prepared in step (1) of Example 2 was used. The structure and performance parameters of the hydrogenated block copolymer are listed in Table 3.

[0247] Example 3

[0248] (1) Preparation of block copolymers

[0249] (1-1) In a 2-liter stainless steel stirred tank, add 800g cyclohexane, 50mg ETE and 38g styrene, raise the temperature to 50℃, add 2.4mmol n-butyllithium initiator, and polymerize at 50℃ for 30 minutes to obtain styrene homopolymer. The conversion rate of styrene is over 99%.

[0250] (1-2) Keep the temperature of the stirred tank at 50℃, add 30g butadiene and 22g styrene to the stirred tank, react for 40 minutes to allow butadiene and styrene to undergo random copolymerization, with the conversion rate of butadiene being over 99% and the conversion rate of styrene being over 99%.

[0251] (1-3) Keep the temperature of the stirred tank at 50℃, add 6g of isoprene, react for 40 minutes, and the conversion rate of isoprene is over 99%.

[0252] (1-4) Keep the temperature of the stirred tank at 50℃, add 30g butadiene and 22g styrene to the stirred tank, react for 30 minutes to allow butadiene and styrene to undergo random copolymerization, with the conversion rate of butadiene being over 99% and the conversion rate of styrene being over 99%.

[0253] (1-5) Keep the temperature of the stirred tank at 50℃, add 111g of styrene, and continue the reaction for 30 minutes. The conversion rate of styrene is over 99%.

[0254] (1-6) Add 0.25g of isopropanol to the stirred tank and terminate the reaction at 50℃ to obtain a block copolymer; add antioxidant 1076 to the obtained adhesive solution, the amount of antioxidant 1076 added is 1% by weight of the total weight of the monomers added in each step of the reaction, mix for 10 minutes to obtain an adhesive solution containing the block copolymer, and adjust the concentration of the block copolymer in the adhesive solution to 10% by weight. The structural parameters of the block copolymer are shown in Table 2. The structure of the block copolymer is: S51-S52 / B51-B52-S53 / B53-S54, where S51, S52, S53 and S54 are structural units derived from styrene, B51 and B53 are structural units derived from butadiene, and B52 is a structural unit derived from isoprene.

[0255] (2) Preparation of hydrogenated block copolymers

[0256] The hydrogenated block copolymer was prepared using the same method as in Example 1, except that the block copolymer-containing solution prepared in step (1) of Example 3 was used. The structure and performance parameters of the hydrogenated block copolymer are listed in Table 3.

[0257] Example 4

[0258] (1) Preparation of block copolymers

[0259] Block copolymers were prepared using the same method as in Example 1, except that styrene in steps (1-1), (1-2), and (1-4) was replaced with an equal weight of 2-vinyltoluene (2-EMB), and styrene in step (1-5) was replaced with an equal weight of α-methylstyrene (AMS). The structural parameters of the obtained block copolymers are shown in Table 2. The structure of the block copolymers is: S51-S52 / B51-B52-S53 / B53-S54, where S51, S52, and S53 are structural units derived from 2-vinyltoluene, S54 is a structural unit derived from α-methylstyrene, B51 and B53 are structural units derived from butadiene, and B52 is a structural unit derived from isoprene.

[0260] (2) Preparation of hydrogenated block copolymers

[0261] The hydrogenated block copolymer was prepared using the same method as in Example 1, except that the block copolymer-containing solution prepared in step (1) of Example 4 was used. The structure and performance parameters of the hydrogenated block copolymer are listed in Table 3.

[0262] Example 5

[0263] (1) Preparation of block copolymers

[0264] Block copolymers were prepared using the same method as in Example 1, except that butadiene in steps (1-2) and (1-4) was replaced with an equal weight of isoprene. The structural parameters of the obtained block copolymers are shown in Table 2. The structure of the block copolymers is: S51-S52 / B51-B52-S53 / B53-S54, where S51, S52, S53 and S54 are structural units derived from styrene, and B51, B53 and B52 are structural units derived from isoprene.

[0265] (2) Preparation of hydrogenated block copolymers

[0266] The hydrogenated block copolymer was prepared using the same method as in Example 1, except that the block copolymer-containing solution prepared in step (1) of Example 5 was used. The structure and performance parameters of the hydrogenated block copolymer are listed in Table 3.

[0267] Comparative Example 1 (not the present invention)

[0268] Block copolymers were prepared using the same method as in Example 1, and hydrogenation reactions were carried out on the block copolymers to prepare hydrogenated block copolymers. The difference was that in step (2), the hydrogenation catalyst was replaced by a nickel-supported catalyst prepared in Comparative Example 1 in equal weight. The reduction conditions of the nickel-supported hydrogenation catalyst were as follows: the nickel-containing catalyst precursor was reduced at 500°C for 6 hours in a hydrogen atmosphere to obtain the reduced hydrogenation catalyst. The structure and performance parameters of the prepared hydrogenated block copolymers are listed in Table 3.

[0269] Comparative Example 2 (not the present invention)

[0270] Block copolymers were prepared using the same method as in Example 1, and hydrogenation reactions were carried out on the block copolymers to prepare hydrogenated block copolymers. The difference was that in step (2), the hydrogenation catalyst was replaced by the hydrogenation catalyst prepared in Comparative Example 2 in equal weight. The structure and performance parameters of the hydrogenated block copolymers were listed in Table 3.

[0271] Comparative Example 3 (not the present invention)

[0272] Block copolymers were prepared using the same method as in Example 1, and hydrogenation reactions were carried out on the block copolymers to prepare hydrogenated block copolymers. The difference was that in step (2), the hydrogenation catalyst was replaced by the hydrogenation catalyst prepared in Comparative Example 3 in equal weight. The structure and performance parameters of the hydrogenated block copolymers were listed in Table 3.

[0273] Example 6

[0274] Block copolymers were prepared using the same method as in Example 1, and hydrogenation reactions were carried out on the block copolymers to prepare hydrogenated block copolymers. The difference was that in step (2), the hydrogenation catalyst was replaced by an equal weight of the hydrogenation catalyst prepared in Example 6. The structure and performance parameters of the hydrogenated block copolymers were listed in Table 3.

[0275] Example 7

[0276] Block copolymers were prepared using the same method as in Example 1, and hydrogenation reactions were carried out on the block copolymers to prepare hydrogenated block copolymers. The difference was that in step (2), the hydrogenation catalyst was replaced by an equal weight of the hydrogenation catalyst prepared in Example 7. The structure and performance parameters of the hydrogenated block copolymers were listed in Table 3.

[0277] Example 8

[0278] (1) Preparation of block copolymers

[0279] (1-1) In a 2-liter stainless steel stirred tank, add 800g cyclohexane, 100mg tetrahydrofuran (THF) and 38g styrene, raise the temperature to 50℃, add 2.4mmol n-butyllithium initiator, and polymerize at 50℃ for 30 minutes to obtain styrene homopolymer. The conversion rate of styrene is over 99%.

[0280] (1-2) Keep the temperature of the stirred tank at 50℃, add 30g of butadiene, react for 40 minutes, and the conversion rate of butadiene is over 99%;

[0281] (1-3) Keep the temperature of the stirred tank at 50℃, add 22g of styrene, react for 40 minutes, and the conversion rate of styrene is over 99%;

[0282] (1-4) Keep the temperature of the stirred tank at 50℃, add 30g of butadiene, react for 30 minutes, and the conversion rate of butadiene is over 99%;

[0283] (1-5) Keep the temperature of the stirred tank at 50℃, add 92g of styrene, and continue the reaction for 30 minutes. The conversion rate of styrene is over 99%.

[0284] (1-6) Add 0.25g of isopropanol to the stirred tank and terminate the reaction at 50℃ to obtain a block copolymer; add antioxidant 1076 to the obtained adhesive solution, the amount of antioxidant 1076 added is 1% by weight of the total weight of the monomers added in each step of the reaction, mix for 10 minutes to obtain an adhesive solution containing the block copolymer, and adjust the concentration of the block copolymer in the adhesive solution to 10% by weight, wherein the structural parameters of the block copolymer are shown in Table 2.

[0285] (2) Preparation of hydrogenated block copolymers

[0286] The hydrogenated block copolymer was prepared using the same method as in Example 1, except that the block copolymer-containing solution prepared in step (1) of Example 8 was used. The structure and performance parameters of the hydrogenated block copolymer are listed in Table 3.

[0287] Example 9

[0288] (1) Preparation of block copolymers

[0289] (1-1) In a 2-liter stainless steel stirred tank, add 800g cyclohexane, 100mg tetrahydrofuran (THF) and 38g styrene, raise the temperature to 50℃, add 2.4mmol n-butyllithium initiator, and polymerize at 50℃ for 30 minutes to obtain styrene homopolymer. The conversion rate of styrene is over 99%.

[0290] (1-2) Keep the temperature of the stirred tank at 50℃, add 30g of butadiene, react for 40 minutes, and the conversion rate of butadiene is over 99%;

[0291] (1-3) Keep the temperature of the stirred tank at 50℃, add 30g butadiene and 22g styrene to the stirred tank, react for 40 minutes to allow butadiene and styrene to undergo random copolymerization, with the conversion rate of butadiene being over 99% and the conversion rate of styrene being over 99%.

[0292] (1-4) Keep the temperature of the stirred tank at 50°C, add 92g of styrene, and continue the reaction for 30 minutes. The conversion rate of styrene is over 99%.

[0293] (1-5) Finally, 0.25g of isopropanol was added to the stirred tank and the reaction was terminated at 50℃ to obtain the block copolymer. Antioxidant 1076 was added to the obtained adhesive solution. The amount of antioxidant 1076 added was 1% by weight of the total weight of the monomers added in each step of the reaction. After mixing for 10 minutes, an adhesive solution containing the block copolymer was obtained. The concentration of the block copolymer in the adhesive solution was adjusted to 10% by weight. The structural parameters of the block copolymer are shown in Table 2.

[0294] (2) Preparation of hydrogenated block copolymers

[0295] The hydrogenated block copolymer was prepared using the same method as in Example 1, except that the block copolymer-containing solution prepared in step (1) of Example 9 was used. The structure and performance parameters of the hydrogenated block copolymer are listed in Table 3.

[0296] Example 10

[0297] (1) Preparation of block copolymers

[0298] (1-1) In a 2L stainless steel stirred tank, add 800g cyclohexane, 60mg tetrahydrofurfuryl ethyl ether (ETE) and 30g isoprene, raise the temperature to 50℃, add 1.6mmol n-butyllithium initiator, and polymerize at 50℃ for 30 minutes to obtain isoprene homopolymer. The conversion rate of isoprene is over 99%.

[0299] (1-2) Keep the temperature of the stirred tank at 50℃, add 30g butadiene and 22g styrene to the stirred tank, react for 40 minutes to allow butadiene and styrene to undergo random copolymerization, with the conversion rate of butadiene being over 99% and the conversion rate of styrene being over 99%.

[0300] (1-3) Keep the temperature of the stirred tank at 50℃, add 6g of isoprene, react for 40 minutes, and the conversion rate of isoprene is over 99%.

[0301] (1-4) Keep the temperature of the stirred tank at 50℃, add 30g butadiene and 22g styrene to the stirred tank, react for 30 minutes to allow butadiene and styrene to undergo random copolymerization, with the conversion rate of butadiene being over 99% and the conversion rate of styrene being over 99%.

[0302] (1-5) Keep the temperature of the stirred tank at 50℃, add 92g of styrene, and continue the reaction for 30 minutes. The conversion rate of styrene is over 99%.

[0303] (1-6) Finally, 0.25g of isopropanol was added to the stirred tank and the reaction was terminated at 50℃ to obtain the block copolymer. Antioxidant 1076 was added to the obtained adhesive solution. The amount of antioxidant 1076 added was 1% by weight of the total weight of the monomers added in each step of the reaction. After mixing for 10 minutes, an adhesive solution containing the block copolymer was obtained. The concentration of the block copolymer in the adhesive solution was adjusted to 10% by weight. The structural parameters of the block copolymer are shown in Table 2.

[0304] (2) Preparation of hydrogenated block copolymers

[0305] The hydrogenated block copolymer was prepared using the same method as in Example 1, except that the block copolymer-containing solution prepared in step (1) of Example 10 was used. The structure and performance parameters of the hydrogenated block copolymer are listed in Table 3.

[0306] Example 11

[0307] (1) Preparation of block copolymers

[0308] (1-1) In a 2L stainless steel stirred tank, add 800g cyclohexane, 60mg ethyl tetrahydrofurfuryl ether (ETE) and 38g styrene, raise the temperature to 50℃, add 1.6mmol n-butyllithium initiator, and polymerize at 50℃ for 30 minutes to obtain styrene homopolymer. The conversion rate of styrene is over 99%.

[0309] (1-2) Keep the temperature of the stirred tank at 50℃, add 30g butadiene and 22g styrene to the stirred tank, react for 40 minutes to allow butadiene and styrene to undergo random copolymerization, with the conversion rate of butadiene being over 99% and the conversion rate of styrene being over 99%.

[0310] (1-3) Keep the temperature of the stirred tank at 50℃, add 20g of styrene, react for 40 minutes, and the conversion rate of styrene is over 99%;

[0311] (1-4) Keep the temperature of the stirred tank at 50℃, add 30g butadiene and 22g styrene to the stirred tank, react for 30 minutes to allow butadiene and styrene to undergo random copolymerization, with the conversion rate of butadiene being over 99% and the conversion rate of styrene being over 99%.

[0312] (1-5) Keep the temperature of the stirred tank at 50℃, add 92g of styrene, and continue the reaction for 30 minutes. The conversion rate of styrene is over 99%.

[0313] (1-6) Add 0.25g of isopropanol to the stirred tank and terminate the reaction at 50℃ to obtain a block copolymer; add antioxidant 1076 to the obtained adhesive solution, the amount of antioxidant 1076 added is 1% by weight of the total weight of the monomers added in each step of the reaction, mix for 10 minutes to obtain an adhesive solution containing the block copolymer, and adjust the concentration of the block copolymer in the adhesive solution to 10% by weight, wherein the structural parameters of the block copolymer are shown in Table 2.

[0314] (2) Preparation of hydrogenated block copolymers

[0315] The hydrogenated block copolymer was prepared using the same method as in Example 1, except that the block copolymer-containing solution prepared in step (1) of Example 11 was used. The structure and performance parameters of the hydrogenated block copolymer are listed in Table 3.

[0316] Example 12

[0317] (1) Preparation of block copolymers

[0318] (1-1) In a 2L stainless steel stirred tank, add 800g cyclohexane, 60mg tetrahydrofurfuryl ethyl ether (ETE) and 38g styrene, raise the temperature to 50℃, add 1.6mmol n-butyllithium initiator, and polymerize at 50℃ for 30 minutes to obtain styrene homopolymer. The conversion rate of styrene is over 99%.

[0319] (1-2) Keep the temperature of the stirred tank at 50℃, add 6g of isoprene, react for 40 minutes, and the conversion rate of isoprene is over 99%.

[0320] (1-3) Keep the temperature of the stirred tank at 50℃, add 30g butadiene and 22g styrene to the stirred tank, react for 40 minutes to allow butadiene and styrene to undergo random copolymerization, with the conversion rate of butadiene being over 99% and the conversion rate of styrene being over 99%.

[0321] (1-4) Keep the temperature of the stirred tank at 50℃, add 30g butadiene and 22g styrene to the stirred tank, react for 30 minutes to allow butadiene and styrene to undergo random copolymerization, with the conversion rate of butadiene being over 99% and the conversion rate of styrene being over 99%.

[0322] (1-5) Keep the temperature of the stirred tank at 50℃, add 92g of styrene, and continue the reaction for 30 minutes. The conversion rate of styrene is over 99%.

[0323] (1-6) Add 0.25g of isopropanol to the stirred tank and terminate the reaction at 50℃ to obtain a block copolymer; add antioxidant 1076 to the obtained adhesive solution, the amount of antioxidant 1076 added is 1% by weight of the total weight of the monomers added in each step of the reaction, mix for 10 minutes to obtain an adhesive solution containing the block copolymer, and adjust the concentration of the block copolymer in the adhesive solution to 10% by weight, wherein the structural parameters of the block copolymer are shown in Table 2.

[0324] (2) Preparation of hydrogenated block copolymers

[0325] The hydrogenated block copolymer was prepared using the same method as in Example 1, except that the block copolymer-containing solution prepared in step (1) of Example 12 was used. The structure and performance parameters of the hydrogenated block copolymer are listed in Table 3.

[0326] Example 13

[0327] Block copolymers were prepared using the same method as in Example 1, and hydrogenation reactions were carried out on the block copolymers to prepare hydrogenated block copolymers. The difference was that in step (2), the hydrogenation catalyst was replaced by an equal weight of the hydrogenation catalyst prepared in Example 2. The structure and performance parameters of the hydrogenated block copolymers were listed in Table 3.

[0328] Example 14

[0329] Block copolymers were prepared using the same method as in Example 1, and hydrogenation reactions were carried out on the block copolymers to prepare hydrogenated block copolymers. The difference was that in step (2), the hydrogenation catalyst was replaced by an equal weight of the hydrogenation catalyst prepared in Example 3. The structure and performance parameters of the hydrogenated block copolymers were listed in Table 3.

[0330] Example 15

[0331] Block copolymers were prepared using the same method as in Example 1, and hydrogenation reactions were carried out on the block copolymers to prepare hydrogenated block copolymers. The difference was that in step (2), the hydrogenation catalyst was replaced by an equal weight of the hydrogenation catalyst prepared in Example 4. The structure and performance parameters of the hydrogenated block copolymers were listed in Table 3.

[0332] Example 16

[0333] Block copolymers were prepared using the same method as in Example 1, and hydrogenation reactions were carried out on the block copolymers to prepare hydrogenated block copolymers. The difference was that in step (2), the hydrogenation catalyst was replaced by an equal weight of the hydrogenation catalyst prepared in Preparation Example 5. The structure and performance parameters of the prepared hydrogenated block copolymers are listed in Table 3.

[0334] Example 17

[0335] (1) Preparation of block copolymers

[0336] A heptablock copolymer was prepared using a method similar to that in Example 1. The structure of the heptablock copolymer is S71-(S72 / B71)-B72-(S73 / B73)-B74-(S75 / B75)-S76, wherein 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 the B74 block is a homopolymer segment of butadiene.

[0337] Based on the total amount of the heptablock copolymer, the content of styrene structural units was 75.2% by weight, butadiene structural units were 22.3% by weight, isoprene structural units were 2.5% by weight, and non-block styrene was 18.1% by weight. Based on the total amount of conjugated diene structural units in the heptablock copolymer, the side group content 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 no 1,2-IP structural units were detected.

[0338] The number-average molecular weight of the S71 block is 25,000, the number-average molecular weight of the S72 / B71 block is 31,000, the number-average molecular weight of the B72 block is 4,000, the number-average molecular weight of the S73 / B73 block is 33,000, the number-average molecular weight of the B74 block is 6,000, the number-average molecular weight of the S75 / B75 block is 36,000, and the number-average molecular weight of the S76 block is 43,000.

[0339] (2) Preparation of hydrogenated heptablock copolymers

[0340] The hydrogenation catalyst prepared in Preparation Example 1 was reduced to obtain a reduced catalyst. The reduced catalyst was used in a hydrogenation reaction. The reduction was carried out in a hydrogen atmosphere at a temperature of 450°C for a duration of 10 hours.

[0341] In a 0.5L high-pressure reactor with a stirrer, 200g of the heptabolic copolymer solution prepared in step (1) and 0.5g of the reduced hydrogenation catalyst were added to carry out a hydrogenation reaction. The reaction temperature was 150℃, the hydrogen pressure was 3MPa, the reaction time was 2h, and the stirring speed was 600rpm.

[0342] After the hydrogenation reaction is completed, the hydrogenation product is centrifuged to obtain a reaction mixture containing the hydrogenated heptablock copolymer. The reaction mixture is filtered to separate the hydrogenation catalyst. The separated hydrogenation catalyst is washed with n-hexane and dried under vacuum, and then recycled for the hydrogenation reaction. The filtered liquid phase is collected and the solvent is removed to obtain the hydrogenated heptablock copolymer according to the present invention. The structural and performance parameters of the hydrogenated heptablock copolymer are listed in Table 3.

[0343] Example 18

[0344] (1) Preparation of block copolymers

[0345] A heptablock copolymer was prepared using a method similar to that in Example 1. The structure of the heptablock copolymer is: S71-(S72 / B71)-B72-(S73 / B73)-B74-(S75 / B75)-S76, wherein 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 the B74 block is a homopolymer segment of butadiene.

[0346] Based on the total amount of the heptablock copolymer, the content of styrene structural units was 80.5% by weight, butadiene structural units were 16.7% by weight, isoprene structural units were 2.8% by weight, and non-block styrene was 17.5% by weight. Based on the total amount of conjugated diene structural units in the heptablock copolymer, the side group content was 46.1% by weight. Based on the total amount of butadiene structural units in the heptablock copolymer, the content of 1,2-PB structural units was 45.6% by weight. Based on the total amount of isoprene structural units in the heptablock copolymer, the content of 3,4-IP structural units was 48.5% by weight, and no 1,2-IP structural units were detected.

[0347] The number-average molecular weights of the S71 block are 16,000, the S72 / B71 block is 23,000, the B72 block is 3,800, the S73 / B73 block is 25,000, the B74 block is 3,600, the S75 / B75 block is 26,000, and the S76 block is 45,000.

[0348] (2) Preparation of hydrogenated heptablock copolymers

[0349] The hydrogenation catalyst prepared in Preparation Example 1 was reduced to obtain a reduced catalyst. The reduced catalyst was used in a hydrogenation reaction. The reduction was carried out in a hydrogen atmosphere at a temperature of 450°C for a duration of 10 hours.

[0350] In a 0.5L high-pressure reactor with a stirrer, 200g of the block copolymer solution prepared in step (1) and 0.5g of the reduced hydrogenation catalyst were added to carry out a hydrogenation reaction. The reaction temperature was 150℃, the hydrogen pressure was 3MPa, the reaction time was 2h, and the stirring speed was 600rpm.

[0351] After the hydrogenation reaction is completed, the hydrogenation product is centrifuged to obtain a reaction mixture containing the hydrogenated heptablock copolymer. The reaction mixture is filtered to separate the hydrogenation catalyst. The separated hydrogenation catalyst is washed with n-hexane and dried under vacuum, and then recycled for the hydrogenation reaction. The filtered liquid phase is collected and the solvent is removed to obtain the hydrogenated heptablock copolymer according to the present invention. The structural and performance parameters of the hydrogenated heptablock copolymer are listed in Table 3.

[0352] Example 19

[0353] (1) Preparation of polystyrene

[0354] In a 2L stainless steel stirred tank, 800g of cyclohexane and 200g of styrene were added, the temperature was raised to 50℃, 1.6mmol of n-butyllithium initiator was added, and polystyrene was obtained by polymerization at 50℃ for 50 minutes.

[0355] (2) Preparation of hydrogenated polystyrene

[0356] The hydrogenation catalyst prepared in Preparation Example 1 was reduced to obtain a reduced catalyst. The reduced catalyst was used in a hydrogenation reaction. The reduction was carried out in a hydrogen atmosphere at a temperature of 450°C for a duration of 2 hours.

[0357] In a 0.5L high-pressure reactor with a stirrer, 200g of the polystyrene-containing adhesive prepared in step (1) and 1g of the reduced hydrogenation catalyst were added to carry out a hydrogenation reaction. The reaction temperature was 150℃, the hydrogen pressure was 3MPa, the reaction time was 1h, and the stirring speed was 800rpm.

[0358] After the hydrogenation reaction is completed, the hydrogenation product is centrifuged to obtain a reaction mixture containing hydrogenated polystyrene. The reaction mixture is filtered to separate the hydrogenation catalyst, which is then washed with n-hexane, dried under vacuum, and recycled for the hydrogenation reaction. It was determined that after five cycles, the hydrogenation activity of the hydrogenation catalyst decreased by less than 2% (based on the hydrogenation activity at the time of the first use). The filtered liquid phase is collected and the solvent is removed to obtain the hydrogenated polystyrene according to the present invention. The structural parameters of the hydrogenated polystyrene are listed in Table 3.

[0359] As can be seen from the experimental results in Table 3, the hydrogenation method for aromatic polymers according to the present invention can not only effectively hydrogenate aromatic polymers to obtain a high degree of hydrogenation (a degree of hydrogenation reaching 95 mol% or more, and in preferred cases, the degree of hydrogenation can be close to 100 mol%), but also the molecular weight of the polymer remains essentially unchanged before and after the hydrogenation reaction, indicating that the polymer undergoes minimal molecular chain degradation during the hydrogenation process. The hydrogenated block copolymers according to the present invention exhibit high light transmittance and low haze, ensuring material transparency while also possessing excellent impact strength, making them suitable for packaging materials (especially packaging materials in the medical and health field) and optoelectronic product materials (especially materials for cameras, displays, etc. in optoelectronic products).

[0360] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

[0361]

[0362]

Claims

1. A method for hydrogenating an aromatic polymer, said aromatic polymer containing an aromatic ring, the method comprising contacting the aromatic polymer with a hydrogenating agent in the presence of a hydrogenating catalyst to hydrogenate at least a portion of the aromatic ring in the aromatic polymer to obtain a hydrogenated aromatic polymer, said aromatic polymer containing a conjugated diene structural unit derived from a conjugated diene. The hydrogenation catalyst contains a support and platinum, Group IVA elements, and rare earth metal elements supported on the support. The support is alumina. In the hydrogenation catalyst, the molar ratio of the Group IVA elements to the platinum elements is not higher than 10 (based on elemental composition).

2. The method according to claim 1, wherein, In the hydrogenation catalyst, the molar ratio of the Group IVA element to the platinum element is not higher than 8 (based on elemental composition).

3. The method according to claim 1 or 2, wherein, In the hydrogenation catalyst, the molar ratio of the Group IVA element to the platinum element is not less than 1 (based on elemental composition).

4. The method according to claim 1, wherein, In the hydrogenation catalyst, the molar ratio of the Group IVA element to the platinum element is 3-7:1 (based on elemental composition).

5. The method according to any one of claims 1, 2, and 4, wherein, The element in Group IVA is tin.

6. The method according to claim 1, wherein, In the hydrogenation catalyst, the molar ratio of the rare earth metal element to the platinum element is 1-6:1 (based on elemental composition).

7. The method according to claim 1, wherein, In the hydrogenation catalyst, the molar ratio of the rare earth metal element to the platinum element is 1.5-5:1 (based on elemental composition).

8. The method according to any one of claims 1, 6, and 7, wherein, The rare earth metal element is cerium.

9. The method according to claim 1, wherein, The hydrogenation catalyst also contains alkali metal elements and alkaline earth metal elements.

10. The method according to claim 9, wherein, In the hydrogenation catalyst, the molar ratio of the alkali metal element to the platinum element is 7-20:1 (based on elemental composition).

11. The method according to claim 9, wherein, In the hydrogenation catalyst, the molar ratio of the alkaline earth metal element to the platinum element is 10-35:1 (based on elemental composition).

12. The method according to claim 9 or 10, wherein, The alkali metal element is potassium.

13. The method according to claim 9 or 11, wherein, The alkaline earth metal element is magnesium.

14. The method according to claim 1, wherein, The hydrogenation catalyst also contains a Group IVB metal, a halogen, or a combination thereof.

15. The method according to claim 14, wherein, In the hydrogenation catalyst, the molar ratio of the Group IVB metal element to the platinum element is 2-10:1 (based on elemental composition).

16. The method of claim 14, wherein, In the hydrogenation catalyst, the molar ratio of the Group IVB metal element to the platinum element is 4-6:1 (based on elemental composition).

17. The method according to claim 14, wherein, In the hydrogenation catalyst, the molar ratio of the halogen element to the platinum element is 2-8:1 (based on elemental composition).

18. The method according to claim 14, wherein, In the hydrogenation catalyst, the molar ratio of the halogen element to the platinum element is 4-6:1 (based on elemental composition).

19. The method according to any one of claims 14-16, wherein, The group IVB metal element is zirconium.

20. The method according to any one of claims 14, 17, and 18, wherein, The halogen element is chlorine.

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

22. The method according to claim 1, wherein, Based on the total amount of the hydrogenation catalyst, the platinum content is 0.2-0.8% by weight.

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

24. The method according to claim 1, wherein, The specific surface area of ​​the hydrogenation catalyst is 100-400 m². 2 / g; the average pore size of the hydrogenation catalyst is 5-40nm.

25. The method according to claim 1, wherein, The specific surface area of ​​the hydrogenation catalyst is 200-350 m². 2 / g; the average pore size of the hydrogenation catalyst is 10-20nm.

26. The method according to claim 1, wherein, Based on the total amount of the aromatic polymer, the content of aromatic structural units derived from aromatic monomers containing aromatic rings in the aromatic polymer is 40% by weight or more.

27. The method according to claim 1, wherein, Based on the total amount of the aromatic polymer, the content of aromatic structural units derived from aromatic monomers containing aromatic rings in the aromatic polymer is 50% by weight or more.

28. The method according to claim 1, wherein, Based on the total amount of the aromatic polymer, the content of aromatic structural units derived from aromatic monomers containing aromatic rings in the aromatic polymer is 70% by weight or more.

29. The method according to claim 1, wherein, Based on the total amount of the aromatic polymer, the content of aromatic structural units in the aromatic polymer is 65-85% by weight.

30. The method according to any one of claims 26-29, wherein, The aromatic structural unit is a monovinyl aromatic structural unit derived from a monovinyl aromatic hydrocarbon, wherein the monovinyl aromatic hydrocarbon is one or more selected from the group consisting of compounds represented by formula I. In Equation I, R1 is C6-C 20 The substituted or unsubstituted aryl group.

31. The method according to claim 30, wherein, The monovinyl aromatic hydrocarbon is selected from one or more of the group consisting of styrene, α-methylstyrene, 4-tert-butylstyrene, 4-methylstyrene, 3,5-diethylstyrene, 3,5-di-n-butylstyrene, 4-n-propylstyrene and 4-dodecylstyrene.

32. The method according to claim 30, wherein, The monovinyl aromatic hydrocarbon is vinyltoluene.

33. The method according to claim 30, wherein, The monovinyl aromatic hydrocarbon is selected from one or more of the group consisting of styrene, 2-methylstyrene and 4-methylstyrene.

34. The method according to any one of claims 1 and 26-29, wherein, Based on the total amount of the aromatic polymer, the content of the conjugated diene structural unit is no more than 60% by weight.

35. The method according to any one of claims 1 and 26-29, wherein, Based on the total amount of the aromatic polymer, the content of the conjugated diene structural unit is 10-50% by weight.

36. The method according to any one of claims 1 and 26-29, wherein, Based on the total amount of the aromatic polymer, the content of the conjugated diene structural unit is 15-35% by weight.

37. The method according to any one of claims 1 and 26-29, wherein, The conjugated diene is butadiene, isoprene, or a combination thereof.

38. The method according to claim 1, wherein, In the aromatic polymer, the degree of hydrogenation of the conjugated diene is 97 mol% or more.

39. The method according to claim 1, wherein, In the aromatic polymer, the degree of hydrogenation of the conjugated diene is 99 mol% or more.

40. The method according to claim 1, wherein, The aromatic polymer contains at least two homopolymer segments of monovinyl aromatic hydrocarbons, at least one homopolymer segment of a conjugated diene, and at least two random copolymer segments of monovinyl aromatic hydrocarbons and conjugated dienes. Each of the two end blocks of the aromatic polymer is an independent homopolymer segment of monovinyl aromatic hydrocarbons, and the block directly bonded to the end blocks is an end block. Each end block is an independent random copolymer segment of monovinyl aromatic hydrocarbons and conjugated dienes.

41. The method according to claim 40, wherein, Based on the total amount of the aromatic polymer, the content of monovinyl aromatic structural units derived from monovinyl aromatics is 40-95% by weight, the content of conjugated diene structural units derived from conjugated dienes is 5-60% by weight, and the content of monovinyl aromatic structural units derived from monovinyl aromatics in the random copolymer segment is 15-20% by weight.

42. The method according to claim 41, wherein, In the aromatic polymer, the side group content is 40-60% by weight, based on the total amount of conjugated diene structural units.

43. The method according to claim 1, wherein, The aromatic polymer is one or more selected from the group consisting of pentablock copolymers having the structure shown in Formula II and heptblock copolymers having the structure shown in 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 a monovinyl aromatic hydrocarbon; The S52 / B51 and S53 / B53 blocks are each independently random copolymer segments of monovinyl aromatic hydrocarbons and conjugated dienes. The B52 block is a homopolymer segment of a conjugated diene; 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, S73 / B73 block, and S75 / B75 block are each independently random copolymer segments of monovinyl aromatic hydrocarbons and conjugated dienes. The B72 block and the B74 block are each independently homopolymer segments of the conjugated diene.

44. The method according to claim 43, wherein, The conjugated diene in the B52 block is isoprene, while the conjugated diene in the B51 and B53 blocks is butadiene.

45. The method according to claim 43 or 44, wherein, The number-average molecular weight of the S51 block is 0.5 million to 50,000, and the ratio of the number-average molecular weight of the S51 block to that of the S54 block is 1:2-10; the number-average molecular weight of the S52 / B51 block is 20,000 to 50,000, and the ratio of the number-average molecular weight of the S52 / B51 block to that of the S53 / B53 block is 1:0.9-1.25; the number-average molecular weight of the B52 block is 0.2 million to 20,000.

46. ​​The method according to claim 43, wherein, The conjugated diene in the B72 block is isoprene, while the conjugated diene in the B71 block, the B73 block, and the B75 block is butadiene.

47. The method according to claim 43 or 46, wherein, The number-average molecular weight of the S71 block is 5,000 to 50,000, and the ratio of the number-average molecular weight of the S71 block to that of the S76 block is 1:1.5-5; the number-average molecular weight of the S72 / B71 block is 20,000 to 50,000, and the ratio of the number-average molecular weight of the S72 / B71 block, the S73 / B73 block, and the S75 / B75 block is 1:1-1.2:1-1.25; 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 that of the B74 block is 1:0.9-1.

2.

48. The method according to claim 1, wherein, The contact temperature is 50-200℃.

49. The method according to claim 1, wherein, The contact temperature is 120-150℃.

50. The method according to any one of claims 1, 48, and 49, wherein, The amount of the hydrogenation catalyst is 1-20 parts by weight relative to 100 parts by weight of the aromatic polymer.

51. The method according to any one of claims 1, 48, and 49, wherein, The amount of the hydrogenation catalyst is 2-10 parts by weight relative to 100 parts by weight of the aromatic polymer.

52. The method according to any one of claims 1, 48, and 49, wherein, The amount of the hydrogenation catalyst is 2.5-5 parts by weight relative to 100 parts by weight of the aromatic polymer.

53. The method according to any one of claims 1, 48, and 49, wherein, The hydrogenating agent is hydrogen gas.

54. The method according to claim 53, wherein, The pressure of the hydrogen gas is 0.1-10 MPa, and the pressure is gauge pressure.

55. The method according to claim 53, wherein, The pressure of the hydrogen gas is 0.5-5 MPa, and the pressure is gauge pressure.

56. The method according to any one of claims 1, 2, 4, 6, 7, 9-11, 14-16, 21-29, 38-44, 48, and 49, wherein, The degree of hydrogenation of the aromatic ring is 95 mol% or more.

57. The method according to any one of claims 1, 2, 4, 6, 7, 9-11, 14-16, 21-29, 38-44, 48, and 49, wherein, The degree of hydrogenation of the aromatic ring is 97 mol% or more.

58. The method according to any one of claims 1, 2, 4, 6, 7, 9-11, 14-16, 21-29, 38-44, 48, and 49, wherein, The degree of hydrogenation of the aromatic ring is 98 mol% or more.

59. The method according to any one of claims 1, 2, 4, 6, 7, 9-11, 14-16, 21-29, 38-44, 48, and 49, wherein, The degree of hydrogenation of the aromatic ring is 99 mol% or more.

60. The method according to any one of claims 1, 2, 4, 6, 7, 9-11, 14-16, 21-29, 38-44, 48, and 49, wherein, The degree of hydrogenation of the aromatic ring is 100 mol%.

61. The method according to any one of claims 1, 2, 4, 6, 7, 9-11, 14-16, 21-29, 38-44, 48, and 49, wherein, The number-average molecular weight of the aromatic polymer is M. n 1. The number-average molecular weight of the hydrogenated aromatic polymer is M. n 2, [(M n 1-M n 2) / M n 1]×100% is defined as the degradation rate, which is not higher than 2.5%.

62. The method according to claim 61, wherein, The degradation rate is no higher than 1.5%.

63. The method according to claim 61, wherein, The degradation rate is no higher than 1%.

64. The method according to claim 61, wherein, The degradation rate is no higher than 0.5%.

65. The method according to claim 61, wherein, The degradation rate is no higher than 0.3%.

66. The method according to claim 61, wherein, The degradation rate is no higher than 0.1%.

67. A hydrogenated aromatic polymer prepared by the method of any one of claims 1-66.

68. A hydrogenated block copolymer, said block copolymer comprising a monovinyl aromatic structural unit derived from a monovinyl aromatic hydrocarbon and a conjugated diene structural unit derived from a conjugated diene, wherein the degree of hydrogenation of the aromatic ring in the monovinyl aromatic structural unit is 98 mol% or more, and the degree of hydrogenation of the unsaturated double bond in the conjugated diene structural unit is 99 mol% or more, characterized in that, The notched impact strength of this hydrogenated block copolymer is 20-30 kJ / m. 2 The elongation at break is 200-400%, the light transmittance is 88-92%, and the haze is 1-5. The number-average molecular weight of the aromatic polymer used as a raw material for hydrogenation is defined as M. n 1. The number-average molecular weight of the hydrogenated aromatic polymer, which is the product of the hydrogenation reaction, is defined as M. n 2, [(M n 1-M n 2) / M n 1]×100% is defined as the degradation rate, which is not higher than 2.5%. The aromatic polymer used as the raw material for the hydrogenation reaction is the block copolymer, and the hydrogenated aromatic polymer used as the product of the hydrogenation reaction is the hydrogenated block copolymer.

69. The hydrogenated block copolymer according to claim 68, wherein, The Vicat softening point of this hydrogenated block copolymer is 110-150℃.

70. The hydrogenated block copolymer according to claim 68, wherein, The block copolymer contains at least two homopolymer segments of monovinyl aromatic hydrocarbons, at least one homopolymer segment of a conjugated diene, and at least two random copolymer segments of monovinyl aromatic hydrocarbons and conjugated dienes. Each of the two end blocks of the block copolymer is an independent homopolymer segment of monovinyl aromatic hydrocarbons, and the block directly bonded to the end blocks is an end block. Each end block is an independent random copolymer segment of monovinyl aromatic hydrocarbons and conjugated dienes.

71. The hydrogenated block copolymer according to claim 70, wherein, Based on the total amount of the block copolymer, the content of monovinyl aromatic structural units derived from monovinyl aromatics is 40-95% by weight, the content of conjugated diene structural units derived from conjugated dienes is 5-60% by weight, and the content of monovinyl aromatic structural units derived from monovinyl aromatics in the random copolymer segment is 15-20% by weight.

72. The hydrogenated block copolymer according to claim 71, wherein, In the block copolymer, the side group content is 40-60% by weight, based on the total amount of conjugated diene structural units.

73. The hydrogenated block copolymer according to claim 68, wherein, The block copolymer contains at least three random copolymer segments of monovinyl aromatic hydrocarbons and conjugated dienes and at least two homopolymer segments of conjugated dienes, wherein the homopolymer segments of the conjugated dienes are arranged alternately with the random copolymer segments of the monovinyl aromatic hydrocarbons and conjugated dienes.

74. The hydrogenated block copolymer according to claim 73, wherein, The homopolymer segment of the conjugated diene contains a homopolymer segment of a first conjugated diene and at least one homopolymer segment of a second conjugated diene, wherein the structural units in the homopolymer segment of the first conjugated diene are derived from the first conjugated diene, and the structural units in the homopolymer segment of the second conjugated diene are derived from the second conjugated diene, wherein the first conjugated diene is different from the second conjugated diene.

75. The hydrogenated block copolymer according to claim 74, wherein, The homopolymer segment of the first conjugated diene is directly bonded to an intramolecular segment. The first conjugated diene is isoprene, and the conjugated diene in the random copolymer segment of the second conjugated diene and the monovinyl aromatic hydrocarbon and the conjugated diene is butadiene.

76. The hydrogenated block copolymer according to claim 75, wherein, Based on the total amount of the block copolymer, the content of isoprene-derived structural units is 0.5-10% by weight, and the content of butadiene-derived structural units is 5-40% by weight.

77. A hydrogenated pentablock copolymer, wherein, The pentablock copolymer is a pentablock copolymer having the structure shown in Formula II: 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 and S53 / B53 blocks are each independently random copolymer segments of monovinyl aromatic hydrocarbons and conjugated dienes. The B52 block is a homopolymer segment of a conjugated diene; In the hydrogenated pentablock copolymer, the degree of hydrogenation of the aromatic ring in the monovinyl aromatic structural unit is ≥98 mol%, and the degree of hydrogenation of the unsaturated double bond in the conjugated diene structural unit is ≥99 mol%. The notched impact strength of the hydrogenated pentablock copolymer is 20-30 kJ / m. 2 The elongation at break is 200-400%, the light transmittance is 88-92%, and the haze is 1-5. The number-average molecular weight of the aromatic polymer used as a raw material for hydrogenation is defined as M. n 1. The number-average molecular weight of the hydrogenated aromatic polymer, which is the product of the hydrogenation reaction, is defined as M. n 2, [(M n 1-M n 2) / M n 1]×100% is defined as the degradation rate, which is not higher than 2.5%. The aromatic polymer used as the raw material for the hydrogenation reaction is the pentablock copolymer, and the hydrogenated aromatic polymer used as the product of the hydrogenation reaction is the hydrogenated pentablock copolymer.

78. The hydrogenated pentablock copolymer according to claim 77, wherein, The conjugated diene structural unit in the B52 block is derived from the B52 conjugated diene, the conjugated diene structural unit in the S52 / B51 block is derived from the B51 conjugated diene, and the conjugated diene structural unit in the S53 / B53 block is derived from the B53 conjugated diene. The B52 conjugated diene is isoprene, and the B51 and B53 conjugated dienes are butadiene.

79. The hydrogenated pentablock copolymer according to claim 78, wherein, Based on the total amount of the pentablock copolymer, the content of isoprene structural units derived from isoprene is 5-20% by weight, and the content of butadiene structural units derived from butadiene is 5-40% by weight.

80. The hydrogenated pentablock copolymer according to claim 78 or 79, wherein, Based on the total amount of isoprene structural units derived from isoprene in the pentablock copolymer, the content of isoprene structural units containing vinyl side groups is 50-60% by weight; based on the total amount of butadiene structural units derived from butadiene in the pentablock copolymer, the content of butadiene structural units containing vinyl side groups is 40-60% by weight.

81. The hydrogenated pentablock copolymer according to any one of claims 77-79, wherein, The monovinyl aromatic hydrocarbon is one or more selected from the group consisting of compounds represented by formula I. In Equation I, R1 is C6-C 20 The substituted or unsubstituted aryl group.

82. The hydrogenated pentablock copolymer according to any one of claims 77-79, wherein, The monovinyl aromatic hydrocarbon is selected from one or more of the group consisting of styrene, 2-methylstyrene and 4-methylstyrene.

83. The hydrogenated pentablock copolymer according to any one of claims 77-79, wherein, The number-average molecular weight of the S51 block is 0.5 million to 50,000, and the ratio of the number-average molecular weight of the S51 block to that of the S54 block is 1:2-10; the number-average molecular weight of the S52 / B51 block is 20,000 to 50,000, and the ratio of the number-average molecular weight of the S52 / B51 block to that of the S53 / B53 block is 1:0.9-1.25; the number-average molecular weight of the B52 block is 0.2 million to 20,000.

84. The hydrogenated pentablock copolymer according to any one of claims 77-79, wherein, The number-average molecular weight of the hydrogenated block copolymer is between 50,000 and 220,000.

85. A hydrogenated heptblock copolymer, wherein, The heptablock copolymer is a heptablock copolymer having the structure shown in 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 each independently a homopolymer segment of a monovinyl aromatic hydrocarbon. The S72 / B71 block, S73 / B73 block, and S75 / B75 block are each independently random copolymer segments of monovinyl aromatic hydrocarbons and conjugated dienes. The B72 block and the B74 block are each independently homopolymer segments of the conjugated diene; In the hydrogenated heptablock copolymer, the degree of hydrogenation of the aromatic ring in the monovinyl aromatic structural unit is ≥98 mol%, and the degree of hydrogenation of the unsaturated double bond in the conjugated diene structural unit is ≥99 mol%. The notched impact strength of the hydrogenated heptablock copolymer is 20-30 kJ / m. 2 The elongation at break is 200-400%, the light transmittance is 88-92%, and the haze is 1-5. The number-average molecular weight of the aromatic polymer used as a raw material for hydrogenation is defined as M. n 1. The number-average molecular weight of the hydrogenated aromatic polymer, which is the product of the hydrogenation reaction, is defined as M. n 2, [(M n 1-M n 2) / M n 1]×100% is defined as the degradation rate, which is not higher than 2.5%. The aromatic polymer used as the raw material for the hydrogenation reaction is the heptabolic copolymer, and the hydrogenated aromatic polymer used as the product of the hydrogenation reaction is the hydrogenated heptabolic copolymer.

86. The hydrogenated heptblock copolymer according to claim 85, wherein, The conjugated diene structural unit in the B72 block is derived from the B72 conjugated diene; the conjugated diene structural unit in the S72 / B71 block is derived from the B71 conjugated diene; the conjugated diene structural unit in the S73 / B73 block is derived from the B73 conjugated diene; and the conjugated diene structural unit in the S75 / B75 block is derived from the B75 conjugated diene. The B72 conjugated diene is isoprene, and the B71, B73, and B75 conjugated dienes are butadiene.

87. The hydrogenated heptblock copolymer according to claim 86, wherein, Based on the total amount of the heptablock copolymer, the content of isoprene structural units derived from isoprene is 0.5-10% by weight, and the content of butadiene structural units derived from butadiene is 5-40% by weight.

88. The hydrogenated heptblock copolymer according to claim 86 or 87, wherein, Based on the total amount of isoprene structural units derived from isoprene in the heptablock copolymer, the content of isoprene structural units containing vinyl side groups is 40-60% 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 side groups is 40-60% by weight.

89. The hydrogenated heptblock copolymer according to any one of claims 85-87, wherein, The monovinyl aromatic hydrocarbon is one or more selected from the group consisting of compounds represented by formula I. In Equation I, R1 is C6-C 20 The substituted or unsubstituted aryl group.

90. The hydrogenated heptblock copolymer according to any one of claims 85-87, wherein, The monovinyl aromatic hydrocarbon is selected from one or more of the group consisting of styrene, 2-methylstyrene and 4-methylstyrene.

91. The hydrogenated heptblock copolymer according to any one of claims 85-87, wherein, The number-average molecular weight of the S71 block is 5,000 to 50,000, and the ratio of the number-average molecular weight of the S71 block to that of the S76 block is 1:1.5-5. The number-average molecular weight of the S72 / B71 block is 20,000 to 50,000, and the ratio of the number-average molecular weight of the S72 / B71 block, the S73 / B73 block, and the S75 / B75 block is 1:1-1.2:1-1.

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 that of the B74 block is 1:0.9-1.

2.

92. The hydrogenated heptblock copolymer according to any one of claims 85-87, wherein, The number-average molecular weight of this hydrogenated heptblock copolymer is between 50,000 and 200,000.

93. The use of the hydrogenated block copolymer of any one of claims 68-76, the hydrogenated pentablock copolymer of any one of claims 77-84, or the hydrogenated heptabole of any one of claims 85-92 in the preparation of packaging materials or optoelectronic products.

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