Novel block copolymers and uses thereof

Abstract

Hydrogenated block copolymers comprising a polymer block A and a polymer block B are disclosed. Prior to hydrogenation, polymer block A has a first vinyl aromatic compound, polymer block B contains monomers a) a styrenic compound having a radical reactive group, b) at least one conjugated diene, and optionally (c) a second vinyl aromatic compound which is the same or different from the first vinyl aromatic compound. The repeating units of monomer a) constitute 10-70 wt% of the total block copolymer and 10-80 wt% of the total weight of block B. After hydrogenation, the RU of the polymerized units derived from monomer b) is 0-1.5 meq / g hydrogenated block copolymer. The hydrogenated block copolymers exhibit reactivity and higher flow properties prior to curing, and after curing, exhibit excellent mechanical properties, improved flame retardancy, and good solvent resistance.

Description

Technical Field

[0001] This disclosure relates to novel reactive block copolymers and their uses. Background Technology

[0002] Many applications, such as adhesives, sealants, coatings, tires, the automotive industry, the construction industry, the electrical and electronics industry, and medical devices, require elastic materials with good mechanical properties, low viscosity during processing, and low reactivity. Additionally, excellent solvent resistance and high-temperature resistance are desirable. Under certain operating conditions, some applications require materials with high flowability and good strength during production, in addition to flame retardancy in the final application. Good mechanical properties in terms of strength and impact resistance, as well as weather resistance or ozone resistance, are also desirable. Existing thermoplastic materials may not meet these requirements.

[0003] In addition to excellent mechanical properties and improved flame retardancy, excellent solvent resistance and high-temperature mechanical properties after exposure to curing, there is a continued need for polymer compositions that exhibit reactivity and higher flowability. Invention Overview

[0005] In one aspect, this disclosure relates to a hydrogenated block copolymer comprising, substantially consisting of, or consisting of at least one polymer block A and at least one polymer block B. Prior to hydrogenation, each block A is a polymer of a first vinyl aromatic compound, and each block B is a copolymer block of a monomer that is: (a) a styrene compound having a radical reactive group, (b) at least one conjugated diene, and optionally (c) a second vinyl aromatic compound that is the same as or different from the first vinyl aromatic compound. The peak molecular weight (Mp) of block A is 3-60 kg / mol, and the peak molecular weight (Mp) of block B is 20-200 kg / mol. The polymeric units derived from (a) constitute 10-80 wt% of the total weight of the hydrogenated block copolymer and 10-70 wt% of the total weight of block B. The residual olefinic unsaturation of the polymeric units derived from monomer (b) is 0-1.5 meq / g of the hydrogenated block copolymer. The hydrogenated block copolymers have i) a peak DMA of 10 rad / s tanD (tangent delta) with a maximum temperature of -30 to 80 °C, ii) a gel content of >50 wt% of the total weight of the hydrogenated block copolymer after curing, as measured by the peroxide-cured gel test (PCGT), and iii) an aromatic block index of 20-80%.

[0006] In the second aspect, monomer (a) is p-methylstyrene, and monomer (b) is selected from isoprene, butadiene, and combinations thereof. Block B has a corrected 1,4-diene unit content of 10-55%, and the hydrogenated block copolymer has one or more of the following characteristics: i) dielectric constant (Dk) less than 2.6 at 1 GHz, ii) dielectric constant (Dk) less than 2.6 at 10 GHz, iii) loss tangent (Df) less than 0.002 at 1 GHz, iv) loss tangent (Df) less than 0.002 at 10 GHz, and v) solution viscosity <2000 cP at 25 °C in 25 wt% toluene.

[0007] In the third aspect, the (a) p-methylstyrene in the B block is 10-50 wt%.

[0008] In the fourth aspect, block A contains polymerized p-methylstyrene units.

[0009] Attached Figure Description

[0010] Figure 1 This is a graph showing the dynamic mechanical analysis (DMA) performance including elastic modulus (G') and tanD (tanδ). Summary of the Invention

[0011] The following terms used in this specification will have the following meanings.

[0012] "Aromatic block" or "aromatic block index" refers to the percentage of aromatic groups with two adjacent aromatic units in a block copolymer. The aromatic block index is calculated based on the 1D H-1NMR spectrum of the block copolymer and is given by the following formula: Aromatic block index = 100 * Integral 2 / Integral 1; where Integral 1 is determined by integrating the H-1NMR spectrum from 7.5 ppm to 6.0 ppm and dividing the result by N, where N is the average number of protons directly attached to the aromatic ring, for example, 5 for unsubstituted aromatic groups (phenyl ring), 4 for monosubstituted aromatic groups (e.g., p-methylstyrene), and 3 for disubstituted aromatic groups (e.g., dimethylstyrene). Integral 2 is determined by integrating the H-1NMR spectrum from the signal minimum (6.9–6.6 ppm) to 6.0 ppm and dividing by 2. In practice, Integral 2 is determined by integrating the spectral area covering the steepest valley region between the 6.9–6.6 ppm low-field chemical shift and the 6.0 ppm high-field chemical shift. When calculating the peak areas of Integral 1 and Integral 2, the peak areas generated by solvent protons are not included.

[0013] "Molecular weight" refers to the styrene equivalent molecular weight of a polymer or block copolymer, expressed in kg / mol. Molecular weight can be measured using gel permeation chromatography (GPC) with a polystyrene calibration standard, for example, according to ASTM 5296. The chromatograph is calibrated using a commercially available polystyrene molecular weight standard. The molecular weight of the polymer measured using a GPC thus calibrated is the styrene equivalent molecular weight. The detector can be a combination of a UV and a refractive index detector. The molecular weights expressed herein are measured at the peak of the GPC trace, commonly referred to as the "peak molecular weight," and designated Mp.

[0014] "pMeS" refers to p-methylstyrene, and "St" refers to styrene.

[0015] A "radical reactive group" is a chemical group that can form or be induced to form a free radical. Free radicals can be formed by any known means, including thermal, photochemical, or chemical methods. For example, a benzyl carbon with at least one hydrogen substituent can be a radical reactive group. The benzyl carbon group can also be substituted, provided it has one benzyl hydrogen atom. Another example of a radical reactive group is a cyclobutane ring, which can, for example, be photochemically activated to form a free radical. Other examples of radical reactive groups include allyl groups, which can form allyl radicals.

[0016] "Corrected 1,4-diene unit content" or "C14DUC" refers to a polymer block having repeating units derived from butadiene (Bd), isoprene (Ip), or combinations thereof, mathematically given by the following equation (1) based on the following parameters: the total diene content of Bd wt% (Bw) in the polymer block, the wt% of 1,4-addition units (B14) of Bd (B14) in the Bd unit of the polymer block, the total diene content of Ip wt% (Iw) in the polymer block, and the wt% of 1,4-addition units (I14) of Ip in the Ip unit of the polymer block.

[0017] C14DUC=(Bw*B14 / 100)+Iw*(I14-40) / 100 (1)

[0018] The polymerization of conjugated dienes is based on polymeric units formed by addition at two double bonds (producing 1,4-addition units) and one double bond (producing side vinyl groups).

[0019] "Residual olefin unsaturation," or RU, refers to the amount of unreduced olefin C=C groups in the polymerized diene unit after the block copolymer is hydrogenated to HSBC, expressed in milliequivalents per gram (meq / g). RU is measured by ozone titration or 1H NMR spectroscopy of HSBC.

[0020] The "peroxide-cured gel test" or "PCGT" refers to a test that measures the gel content of a cured composition, expressed in wt%, based on hydrogenated block copolymers (HSBCs). PCGT is measured using a rotorless rheometer by mixing HSBC with 0.5 wt% BIPB (bis-(tert-butylperoxyisopropyl)benzene) initiator and curing at 180°C for 30 minutes. The gel content is calculated as follows: first, the initial weight (Wi) of the cured sample is measured; then, the sample is immersed in toluene for 1 day; the solution containing the sample is filtered, and the weight of the swollen gel after filtration is recorded (Ws); the swollen gel is then vacuum-dried at 60°C until constant weight or dry weight (Wd) is achieved. The gel content (gel %) is calculated using the following formula: gel % = 100 * Wd / Wi. The swelling ratio is calculated using the following formula: swelling ratio = Ws / Wd.

[0021] "Coupling efficiency," or CE, is the ratio (expressed as a percentage) of the sum of the integrated peak areas of coupled substances with one or more arms (i.e., n>1) to the sum of the integrated peak areas of coupled and uncoupled arms (n=1 and n>1). CE is determined by GPC based on peak surface integration.

[0022] "Branching degree" or DOB refers to the average number of arms in a coupled compound. DOB is calculated from the GPC peak area of ​​each coupled compound having 2 arms, 3 arms, 4 arms...i arms. The DOB value is calculated using the following mathematical expression: DOB = [GPC area of ​​2*2-arm compound + GPC area of ​​3*3-arm compound + GPC area of ​​4*4-arm compound + ...i*i-arm compound] / [GPC area of ​​all coupled compounds].

[0023] In some embodiments, the hydrogenated block copolymers involved in this disclosure refer to hydrogenated styrene-based block copolymers (HSBCs) with pMeS in the intermediate blocks and compositions containing HSBCs. Before curing, the HSBC-based compositions exhibit high flowability, and after curing, the cured compositions exhibit excellent weather resistance compared to the uncured compositions.

[0024] Hydrogenated styrene-based block copolymers (HSBCs): HSBCs are hydrogenated forms of styrene-based block copolymers (SBCs), wherein the SBC, prior to hydrogenation, has at least one polymer block A and at least one polymer block B. In the SBC, i.e., prior to hydrogenation, each A block is a rigid block of a first vinyl aromatic compound, and each B block is a copolymer block of a monomer comprising (a) a styrene compound having a radical-reactive group, (b) at least one conjugated diene, and optionally (c) a second vinyl aromatic compound that is the same as or different from the first vinyl aromatic compound.

[0025] In some embodiments, the first vinyl aromatic compound used to construct polymer block A can be any aromatic compound having at least one vinyl group linked thereto. Non-limiting classes of suitable compounds include styrene and substituted styrene, vinyl naphthalene and substituted vinyl naphthalene, vinyl indene, vinyl anthracene, 1,1-diphenylethylene, and mixtures thereof. Some specific examples include vinyl aromatic compounds having 8-20 carbon atoms, such as o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 2,4-dimethylstyrene, α-methylstyrene, vinyl naphthalene, vinyl toluene, and vinyl xylene, or mixtures thereof.

[0026] In some embodiments, the styrene compound having a radical reactive group (i.e., monomer (a)) may be a substituted styrene of formula (I), a vinylbenzocyclobutene of formula (II), a vinyl dihydroindene of formula (III), a vinyl tetrahydronaphthalene of formula (IV), or any combination thereof.

[0027] Table 1. Structure of various (a) monomers

[0028]

[0029]

[0030] In some embodiments, the monomer (a) of formula (I) is selected from o-methylstyrene, p-methylstyrene, o-ethylstyrene, p-ethylstyrene, o-isopropylstyrene, p-isopropylstyrene, o-methyl-α-methylstyrene, p-methyl-α-methylstyrene, o-ethyl-α-methylstyrene, p-ethyl-α-methylstyrene, o-isopropyl-α-methylstyrene, p-isopropyl-α-methylstyrene, and mixtures thereof.

[0031] In some embodiments, the first vinyl aromatic monomer includes pMeS, p-methyl-α-methylstyrene, or a mixture thereof.

[0032] In some embodiments, the monomer (b) conjugated diene in block (B) is selected from butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1-phenyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 3-butyl-1,3-octadiene, farnesene, myrcene, pentadiene, cyclohexadiene, and mixtures thereof.

[0033] In some embodiments, the optional monomer (c) second vinyl aromatic compound in block (B), when present, can be any aromatic compound having at least one vinyl group linked thereto. Non-limiting classes of suitable compounds include styrene and substituted styrene, vinylnaphthalene and substituted vinylnaphthalene, vinylindene, vinylanthracene, 1,1-diphenylethylene, and mixtures thereof. Other examples include vinyl aromatic compounds having 8-20 carbon atoms, such as o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 2,4-dimethylstyrene, α-methylstyrene, vinylnaphthalene, vinyltoluene, vinylxylene, and mixtures thereof.

[0034] In some embodiments, the peak molecular weight (Mp) of block A is 3-60 kg / mol, or 5-50 kg / mol, or 10-45 kg / mol, or 15-40 kg / mol, or 20-35 kg / mol, or >10 kg / mol or <50 kg / mol.

[0035] In some embodiments, the Mp of block B is 20-200 kg / mol, or 30-180 kg / mol, or 40-160 kg / mol, or 50-140 kg / mol, or 60-120 kg / mol, or >20 kg / mol or <160 kg / mol.

[0036] In some embodiments, polymeric units derived from monomer (a) account for 10-80 wt%, or 15-75 wt%, or 20-70 wt%, or 25-60 wt%, or 30-65 wt%, or >15 wt%, or <75 wt%, of the total weight of polymeric blocks B based on HSBC.

[0037] In some embodiments, the polymeric units derived from monomer (a) account for 10-70 wt%, or 15-65 wt%, or 20-60 wt%, or 25-55 wt%, or 30-50 wt%, or >15 wt%, or <65 wt%, based on the total weight of HSBC.

[0038] In some implementations, after SBC hydrogenation, the RU of the obtained HSBC is 0-1.5 meq, or 0.01-1.4 meq, or 0.02-1.3 meq, 0.05-1.2 meq, or 0.1-1.1 meq, or 0.2-1.0 meq, or 0.025-0.8 meq, or >0 meq, or <1.0 meq.

[0039] In some embodiments, the HSBC containing block B has 10-50 wt% polymeric units derived from pMeS, or 15-45 wt%, or 20-40 wt%, or >15 wt%, or <60 wt%, based on the total weight of the HSBC.

[0040] In some embodiments, the corrected 1,4-diene unit content of the HSBC containing block B is 10-70 wt%, or 15-65 wt%, or 20-60 wt%, or 25-55 wt%, or >15 wt%, or <65 wt%, based on the total weight of the HSBC. In some embodiments, the corrected 1,4-diene unit content of block B is 10-60 wt%, or 15-55 wt%, or 20-50 wt%, or 25-45 wt%, or >15 wt%, or <55 wt%, based on the total weight of the B block.

[0041] In some embodiments, HSBC has a structure in which monomer (a) is p-methylstyrene and monomer (b) is selected from isoprene, butadiene, and combinations thereof.

[0042] In some embodiments, an HSBC having at least one block A and at least one block B includes one or more structures selected from: AB, ABA, (AB). n X, ABAB, (BAB) n X, (BA) n X and (ABA) n X, where X is a coupling agent (CA) residue and n is 1-30.

[0043] In some embodiments, the HSBC includes block A, block B, and block C, wherein block C contains a conjugated diene monomer selected from butadiene, isoprene, and mixtures thereof. In some embodiments, block C is hydrogenated.

[0044] Preparation method: SBC precursors can be prepared by anionic polymerization using methods known in the art. The polymerization initiator is typically an organometallic compound, such as an organolithium compounds, including ethyl lithium, propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, phenyl lithium, hexylbiphenyl lithium, hexamethylene dilithium, butadiene lithium, isoprene lithium, 1,1-diphenylhexyl lithium, or polystyrene lithium.

[0045] In some embodiments, the amount of initiator is 0.002-5 mol%, or 0.005-4.5 mol%, or 0.01-4 mol%, or 0.015-3.8 mol%, or 0.02-3.5 mol%, based on the total mol% of the monomers to be polymerized.

[0046] In some embodiments, the solvent used for anionic polymerization is selected from aliphatic, alicyclic, or aromatic hydrocarbons having 4-12 carbon atoms, such as pentane, hexane, heptane, cyclopentane, cyclohexane, methylcyclohexane, decahydronaphthalene, isooctane, benzene, alkylbenzenes such as toluene, xylene, ethylbenzene, and mixtures thereof.

[0047] In some embodiments, in anionic polymerization, a coupling agent is used for polymer chain termination. The coupling agent is, for example, a bifunctional or polyfunctional compound, such as divinylbenzene, a halogenated aliphatic or aryl aliphatic hydrocarbon, such as 1,2-dibromoethane, bis(chloromethyl)benzene, or silicon tetrachloride, dialkyl- or diaryl dichloride, alkyl- or aryl trichloride, tin tetrachloride, alkylmethoxysilane, alkylethoxysilane, polyfunctional aldehydes, such as dialdehyde terephthalate, ketones, esters, acid anhydrides, or epoxides. In some embodiments, the coupling agent is selected from methyltrimethoxysilane (MTMS), tetramethoxysilane (TMOS), divinylbenzene (DVB), dimethyl adipate, and mixtures thereof.

[0048] HSBC is obtained by hydrogenating SBC precursors using a known hydrogenation catalyst (e.g., a catalyst based on nickel, cobalt, titanium, or a mixture thereof).

[0049] In some embodiments, after hydrogenation, >80 mol% or >85 mol% or >88 mol% or >90 mol% or >92 mol% or >95 mol% or >98 mol% or >99 mol% of the intrachain double bonds and side chain vinyl groups present in the polymerization units derived from (b) conjugated diene monomers are reduced.

[0050] In some embodiments, after hydrogenation, <50 wt%, <40 wt%, 30 wt%, <20 wt%, <10 wt%, or <5 wt% of the aromatic double bond is reduced.

[0051] Functionalization of HSBCs: In some embodiments, HSBCs are functionalized by substituting monomer (a) with a functional group (e.g., halogen) to provide halogen-functionalized HSBCs. This can be achieved by reacting with a halogen in the presence of light (e.g., a 500-watt tungsten bulb) or a chemical radical initiator (e.g., azobis(isobutyronitrile)), as is known in the art, e.g., U.S. Patent 5,654,379, which is incorporated herein by reference. Halogenation selectively occurs on the benzyl carbon atom of the radical reactive portion present in the styrene compound (i.e., monomer (a)). For example, in the case of an HSBC where monomer (a) is pMeS, bromination yields a bromomethyl-functionalized HSBC. Halogen-functionalized HSBCs can be valuable starting materials for generating a variety of functionalized HSBCs by reacting with nucleophiles. Substituting the highly reactive and versatile electrophile benzyl bromide with other functional groups can be achieved through nucleophilic substitution reactions to introduce the desired functional group.

[0052] HSBC-based curable compositions: In some embodiments, the curable composition is prepared from a mixture comprising 1-99.9 wt% HSBC and 0.1-5 wt% curing initiator by weight of the total weight of the curable composition.

[0053] The curing initiator can be a thermal initiator or a photochemical initiator. Non-limiting examples of thermal initiators include peroxides, such as diisobutyl peroxide, ditert-butyl peroxide, dicumyl peroxide, tert-butylcumyl peroxide, α,α-bis(tert-butylperoxy)diisopropylbenzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane (DBPH), 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl-4-4-bis(tert-butylperoxy)valerate, benzoyl peroxide, lauroyl peroxide, dilauryl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyn-3, diaryl peroxide, ketone peroxide, peroxydicarbonate, peroxy ester, dialkyl peroxide, hydroperoxide, peroxy ketal, and mixtures thereof. In some implementations, the 1-hour half-life temperature of the peroxide is >100°C and <200°C.

[0054] In some embodiments, the photoinitiator may be selected from monomolecular (Type I) and bimolecular (Type II) photoinitiators. Examples of Type I initiators include benzophenones, combinations thereof including tertiary amines, alkylbenzophenones, 4,4'-bis(dimethylamino)benzophenone (Mischel ketone), anthrones, halobenzophenones, and mixtures thereof. Non-limiting examples of Type II initiators include benzoin, benzoin derivatives, especially benzoin ethers, benzoin ketals, acylphosphine oxides, especially 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, diacylphosphine oxide, phenyl-glyoxylates, camphorquinone, α-aminoalkylphenyl ketones, α,α-dialkoxyacetophenones, α-hydroxyalkylphenyl ketones, and mixtures thereof.

[0055] In some embodiments, the curable composition further comprises one or more curing aids, flame retardants, and solvents that facilitate mixing of the components. The solvent is then evaporated to obtain the curable composition for curing.

[0056] Examples of curing aids that may be used include one or more components selected from: 1,2-bis(vinylphenyl)ethylene, butadiene liquid rubber, divinyl aromatic compounds, triallyl cyanurate, triallyl isocyanurate, vinyl-functionalized polyphenylene ethers (e.g., SA-9000), bismaleimide aromatic resins, monofunctional or polyfunctional acrylate or methacrylate monomers, plasticizers, tackifying resins, styrene block copolymers comprising one or more polydiene blocks, and combinations thereof. Examples of suitable curing aids include divinylbenzene, 1,2-bis(vinylphenyl)ethane, ethylene glycol methacrylate (EGDMA), trimethylolpropane trimethacrylate (TMpTMA), triallyl isocyanurate, triallyl cyanurate, diethylene glycol diacrylate, neophenyl glycol diacrylate, and mixtures thereof.

[0057] In some embodiments, the solvent is selected from aliphatic hydrocarbons, aromatic hydrocarbons, or combinations thereof. Suitable examples of aliphatic hydrocarbons include C6-C6 hydrocarbons. 12 Saturated hydrocarbons, such as cyclohexane, methylcyclohexane, n-hexane, heptane, octane, and dodecane. Aromatic hydrocarbons can have 7-10 carbon atoms, such as toluene, xylene, and mesitylene.

[0058] In some embodiments, the curable composition further comprises additives, such as other resins, plasticizers, redox coupling agents, fillers, fibers, antioxidants, flame retardants, foaming agents, surface treatment agents, viscosity modifiers, wetting agents, degassing agents, toughening agents, adhesion promoters, dyes, pigments, colorants, heat stabilizers, light stabilizers, lubricants, flow modifiers, drip delay agents, anti-blocking agents, antistatic agents, flow promoters, processing aids, substrate adhesives, release agents, low-ripple additives, stress-relieving additives, waxes, anti-drip agents, etc., in amounts of 0.5–50 wt%, or 1–45 wt%, or 2–40 wt%, or 5–30 wt%, or 8–25 wt%, or >1 wt%, or <45 wt%, based on the total weight of the curable composition.

[0059] Exemplary fillers include one or more inorganic silicates, such as andalusite, sillimanite, kyanite, mullite, pyrophyllite, or gibbsite; and minerals such as calcium silicate, silica, surface-treated silica, or quartz powder; metal sulfates, such as barium sulfate; metal oxides, such as zinc oxide, titanium dioxide, zeolite, leucite, potassium feldspar, biotite, gypsum, anhydrite, or barite; and calcium minerals such as talc or chalk (CaCO3) and metal hydroxides. In some embodiments, the filler is selected from calcium carbonate, mica, magnesium hydroxide, aluminum hydroxide, and mixtures thereof.

[0060] In some embodiments, the flame retardant is selected from halogenated compounds, non-halogenated compounds, intumescent non-halogenated compounds, phosphorus-containing compounds, nitrogen-containing compounds, bromine-containing compounds, and mixtures thereof.

[0061] In some embodiments, the plasticizer is any one of paraffin oil, naphthenic oil, natural oil, hydrogenated naphthenic oil, low molecular weight polyolefin, low molecular weight styrene-butadiene block, or combinations thereof. In some embodiments, the rubber may be selected from natural rubber, synthetic rubber, and mixtures thereof. Non-limiting examples include natural rubber, ethylene-propylene-diene-monomer rubber (EPDM), ethylene / α-olefin rubber (EPR), styrene / butadiene rubber (SBR), acrylonitrile / butadiene rubber (NBR), chloroprene rubber, polybutadiene rubber (BR), synthetic polyisoprene rubber (IR), isobutylene-isoprene rubber (IIR), etc.

[0062] In some embodiments, the curable composition includes other polymers. Non-limiting examples include polybutadiene, 1,2-polybutadiene, polyisoprene, polybutadiene-polyisoprene copolymer, polybutadiene-polystyrene-polydivinylbenzene terpolymer, poly(phenylene ether) (PPE), curable cyclic olefins or copolymers thereof, polyacrylates, polydicyclopentadiene, styrene-isoprene-styrene copolymers, butadiene-acrylonitrile copolymers, acrylonitrile-styrene resins, acrylonitrile-butadiene-styrene resins, polyesters, styrene block copolymers, hydrogenated styrene block copolymers, polyolefins, polytetrafluoroethylene (PTFE), polyetherimide (PEI), maleimide resins, cyanate ester resins, epoxy resins, phenolic resins, benzoxazine resins, polyamide resins, polyimide resins, polyphenylene sulfide, polyacetal, polysulfone, polyesterimide, polyethersulfone, polyetherketone, fluoropolymers, other rubber polymers, and mixtures thereof.

[0063] In some embodiments, the curable composition contains a tackifying resin selected from one or more natural or modified rosin, rosin esters (including those prepared using polyols), polyterpene resins, phenol-modified terpene resins, aromatic resins, aliphatic petroleum resins (e.g., those prepared using C5 or C9 hydrocarbon streams obtained from petroleum cracking / refining), or any hydrogenated form or combination thereof.

[0064] In some embodiments, a curable composition comprising HSBC, a peroxide initiator, and one or more curing aids can be dynamically cured in the molten phase. This can be valuable for the preparation of thermoplastic vulcanizates. In the dynamic curing mode, the curable composition remains in the molten state. During curing, dynamic curing imposes significant deformation and stress on the composition. High deformation and stress disrupt the gel formed during curing, resulting in the formation of dispersed microgels into the thermoplastic phase, which is commonly referred to as a thermoplastic vulcanizate.

[0065] In some embodiments, the curable composition comprises (a) 5-99 wt% HSBC, (b) 0.1-5 wt% at least one curing agent, (c) 5-94 wt% one or more curing aids, and optionally (d) 0.1-20 wt% additives, based on the total weight of the curable composition.

[0066] In some embodiments, the curable composition comprises i) at least one rubber of 5-95 phr, ii) 5-50 phr of HSBC or a functionalized form of HSBC, iii) 50-200 phr of filler, iv) 0.1-20 phr of curing agent, such as peroxide, v) up to 70 phr of plasticizer or resin, and vi) up to 15 phr of anti-degradation agent, wherein the amounts of components (ii) to (vi) are based on 100 parts of component (i).

[0067] In some embodiments, HSBC can also be blended with crystalline polyolefins (e.g., crystalline polypropylene) at a ratio of 1:99 to 99:1 to provide blends for different end uses. In some embodiments, the blend also contains a flame retardant. An example is a blend of 10-50 wt% HSBC, 1-20 wt% crystalline polyolefin, and 20-50 wt% flame retardant.

[0068] Preparation method of HSBC-based curable compositions: In some embodiments, HSBC and other components may first be mixed with a solvent. The mixture is then shaped as desired, and the solvent is evaporated. In some embodiments, HSBC-containing curable compositions are prepared by premixing the composition using suitable equipment (e.g., Henschel mixer, V-type mixer, ribbon mixer, etc.). The premixed composition can then be extruded into granules.

[0069] Curing method for HSBC-based compositions: Thermoplastic vulcanizate (TPV) compositions can be prepared, for example, by a method comprising the following steps: introducing a molten thermoplastic vulcanizate containing HSBC and a radical source, wherein the thermoplastic vulcanizate comprises a cured rubber dispersed within a thermoplastic matrix having HSBC. This method is suitable for continuous production, for example, by (i) dynamically vulcanizing the rubber in a first stage of the process to form a molten thermoplastic vulcanizate, (ii) maintaining the thermoplastic vulcanizate in the molten state until a second stage, and (iii) introducing the molten thermoplastic vulcanizate and a radical source in a second stage of the process to form a modified thermoplastic vulcanizate.

[0070] In some embodiments, curing and / or crosslinking can be achieved using an electron beam (e.g., a series of cathodes generating a high concentration of electrons) or by irradiation with halogen elements. Electron beam treatment can be performed using an electron accelerator, such as any of electrostatic direct current (DC), motorized DC, radio frequency (RF) linear accelerators (LINACS), magnetically inductive LINAC, and continuous wave (CW) machines. Crosslinking can be carried out at suitable temperatures, such as room temperature, or from ambient temperature to 60°C. The cured composition can be processed in a melt to form molding compounds, melt films, and hot melt adhesives.

[0071] Performance of HSBC: In some embodiments, the viscosity of HSBC in a 25 wt% solution in toluene at 25°C is 50-2000 cP, or 70-1800 cP, or 100-1600 cP, or 150-1500 cP, or 200-1200 cP, or 300-1100 cP, or 400-1000 cP, or >100 cP, or <1000 cP, or <2000 cP.

[0072] In some implementations, the Dk of the HSBC at 1 GHz is 1-2.6, or 1.2-2.5, or 1.4-2.4, or 1.6-2.2 or <2.6.

[0073] In some implementations, the Dk of the HSBC at 10 GHz is 1-2.6, or 1.2-2.5, or 1.4-2.4, or 1.6-2.2 or <2.6.

[0074] In some implementations, the Df of the HSBC at 1 GHz is 0-0.002, or 0.0001-0.0022, or 0.0005-0.0024, or 0.0008-0.0026, or 0.001-0.0028 or <0.002.

[0075] In some implementations, the Df of the HSBC at 10 GHz is 0-0.002, or 0.0001-0.0022, or 0.0005-0.0024, or 0.0008-0.0026, or 0.001-0.0028 or <0.002.

[0076] It's important to note that lower Dk and Df values ​​generally indicate better performance in applications such as electronic devices. Furthermore, there are slight differences in Dk and Df measurements at 1 GHz and 10 GHz, but these small differences can be significant depending on the application.

[0077] In some implementations, the maximum temperature of the HSBC Dynamic Mechanics Analyzer (DMA) 10 rad / s tanD peak is -30 to 80°C, or -20 to 75°C, or -10 to 60°C, or 0 to 50°C.

[0078] In some embodiments, the aromatic block index of HSBC, as measured by 1D 1H-NMR spectroscopy, is 20-80%, or 25-75%, or 30-70%, or 35-65%, or 40-60%, or 40-75%, or >40% or <70%.

[0079] In some implementations, the DMA cross temperature (T-cross) of the HSBC is 100-300°C, or 120-280°C, or 140-250°C, or 160-220°C, or 180-200°C, or >110°C, or <220°C.

[0080] Properties of HSBC-based compositions: Before curing, HSBC-containing compositions exhibit good flow properties. After curing, the cured compositions possess excellent mechanical properties. The cured compositions exhibit improved flame retardancy, excellent solvent resistance, and improved mechanical properties at high temperatures. These physical properties make them valuable for high-performance applications.

[0081] In some embodiments, prior to curing, the viscosity of the composition in a 25 wt% solution in toluene at 25°C is 10-1000 cP, or 50-1900 cP, or 100-1800 cP, or 150-1600 cP, or 200-1400 cP, or 250-1200 cP, or >100 cP, or <1000 cP, or <2000 cP.

[0082] The properties of the cured compositions described in this article are for a “base” composition having 100 parts HSBC and 0.5 parts peroxide (BIPB or DCP) after curing at 180°C for 2 hours and then compression molding.

[0083] In some embodiments, the base composition has a Dk of 0.2-4, or 0.4-3.8, or 0.6-3.6, or 0.8-3.4, or 1-3.2, 1.2-3, or 1.4-2.8, or 1.6-2.6, <3.5, or <2.6 at 1 GHz; or a Dk of 0.2-4, or 0.4-3.8, or 0.6-3.6, or 0.8-3.4, or 1-3.2, 1.2-3, or 1.4-2.8, or 1.6-2.6, <3.5, or <2.6 at 10 GHz.

[0084] In some embodiments, the base composition has a Df of <0.002, or <0.0025, or <0.003, or <0.0035, or <0.004, or <0.0045, or <0.005 at 1 GHz; or a Df of <0.002, or <0.0025, or <0.003, or <0.0035, or <0.004, or <0.0045, or <0.005 at 10 GHz.

[0085] In some embodiments, the DMA cross temperature (T cross) of the base composition is 200-500°C, or 220-450°C, or 240-430°C, or 250-400°C, or >300°C or <400°C.

[0086] In some embodiments, the base composition further comprises at least one flame retardant of grade V0, as measured according to the UL94 vertical burning test method.

[0087] In some embodiments, the gel content (based on PCGT) of the cured composition (HSBC having 0.5 wt% BIPB) is >40 wt%, or >45 wt%, or >50 wt%, or >55 wt%, or >60 wt%, or >65 wt%, or >70 wt%, or >80 wt%, or >90 wt%, relative to the total weight of the cured composition after solvent removal.

[0088] Applications: In some embodiments, compositions containing HSBC can be injection molded or extruded using conventional plastics processing equipment, with or without a curing agent. In some embodiments, HSBC is used in the manufacture of adhesives (e.g., solvent-based adhesives and melt adhesives), flame-retardant articles, hot melt adhesives, meltblown films, thermoplastic vulcanizates, tires, and flexographic printing plates. Other applications include automotive or transportation, tires, sealants, damping layers in films, buildings, structures, footwear, industrial equipment, healthcare, medical devices, sports equipment, handles, prosthetic components, and bulletproof equipment.

[0089] In some embodiments, compositions containing HSBC are used to manufacture copper-clad laminates by combining desired components such as HSBC, diene polymers, curing initiators, flame retardants, and optional additives.

[0090] In some embodiments, cured compositions containing HSBC are used to manufacture sealant articles (e.g., seals for rotating shafts), laminated diaphragm sealant articles for diaphragm pumps, dynamic seals, static seals, O-rings, co-extruded hoses, hoses for handling chemicals or fuels, and foam articles.

[0091] In some implementations, HSBC-based thermoplastic vulcanizates (TPVs) can be used to manufacture extruded articles with desired surface appearances, such as weatherproof seals, hoses, belts, gaskets, molding articles, protective covers, elastic fibers, vehicle components such as weatherproof seals, braking components such as cups, coupling discs and diaphragm cups, protective covers for constant velocity universal joints and rack and pinion joints, tubing, gaskets, hydraulic or pneumatic parts, O-rings, pistons, valves, valve seats, valve guides, drive belts (including V-belts), toothed belts with cut-off ribs, and other elastomeric polymer-based components or elastomeric polymers combined with other materials, such as metal / plastic composites.

[0092] A variety of technologies can be used to manufacture articles from HSBC-based compositions, such as foaming (for producing foam products), coating, injection molding, extrusion, co-extrusion, blow molding, hot melt spraying, lamination with other materials, compression molding, and solution spraying. Example

[0093] Use the following testing method.

[0094] The molecular weight of the polymer was determined according to ASTM 5296 by gel permeation chromatography (GPC) using polystyrene calibration standards.

[0095] Proton NMR methods are used to determine the total aromatic content ArC, such as pMeS content, expressed in wt%, and Ru, expressed in meq of residual olefinic unsaturation per gram of HSBC.

[0096] The Brinell viscosity is measured at 25°C using the ASTM D-2196 test method and is expressed in centipoises (cP) or millipascals per second (mPa·s).

[0097] According to ASTM 4065, the viscoelastic behavior of polymer samples was measured by dynamic mechanical analysis (DMA) using plate / plate geometry and an angular frequency of 10 rad / s, while applying a temperature scan of +2°C per minute. The rubber tanD peak temperature (tanD maxT) corresponds to the temperature at which the tanD peak of the glass-rubber transition reaches its maximum value. The final crossover temperature (T-cross) corresponds to the temperature at which the more elastic behavior observed in the rubbery plateau region transitions to the more viscous behavior observed at higher temperatures. The T-cross is the temperature at which the elastic modulus and viscous modulus are equal, i.e., tanD = 1.

[0098] Temperature scanning experiments were conducted in the temperature range of -40 to 300 °C at a heating rate of +2 °C / min and 10 rad / s, where the storage modulus (G'), loss modulus (G”), and loss factor (tanδ) are functions of temperature. The tanδ peak temperature of the rubber is considered to be the Tg of the rubber phase in this paper.

[0099] Curing of the composition was achieved using MDR. The sample was introduced into a machine mold at a preset temperature of 110°C (or the copolymer's highest Tg, if higher), forming a plate with a thickness of 0.7 mm. The mold was closed under vacuum and held at this temperature for 2 minutes. The mold temperature was then increased to 180°C. Under vacuum, the sample was held at 180°C for 30 minutes to achieve curing. The maximum torque value of the MDR during the curing step at 180°C (expressed in dN.m) was recorded and correlated with the maximum torque recorded during this curing period. The time required to reach 90% of the maximum torque value was recorded as "tc90" and expressed in minutes and seconds.

[0100] The gel content and swelling ratio per PCGT of the cured samples were analyzed.

[0101] Samples with a thickness of 2 mm were used for UL94 testing.

[0102] The dielectric properties (dielectric constant and loss factor) of the HSBC and cured composition were measured at high frequencies on parallel plate samples at 23°C and 50% humidity, according to the method of IPC-TM-650 2.5.5.9 at 1 GHz and / or according to the method of IEC61189-2-721-2015 at 10 GHz.

[0103] Tensile stress-strain characteristics were measured according to ASTM D412 using a dumbbell “C” and a crosshead displacement velocity of 500 mm / min.

[0104] Shore A hardness is measured on a 3x2mm plate with a 10-second dwell time, according to ASTM D2240.

[0105] Unless otherwise specified, all reported melt flow rates (MFR) are measured according to ASTM D1238 at a load of 2.16 kg and a temperature of 230 °C.

[0106] The components used in the embodiments include:

[0107] DCP: Dicumyl peroxide;

[0108] BIPB: Bis(2-tert-butylperoxyisopropyl)benzene;

[0109] TAC: Trienyl cyanurate;

[0110] TAIC: Triallyl isocyanurate;

[0111] NORYL SA9000 resin is a modified low molecular weight polyphenylene ether oligomer with vinyl end groups, derived from SABIC.

[0112] NISSO-PB(B-3000): 1,2-polybutadiene homopolymer, derived from Nippon Soda.

[0113] POLYFLON MpA FA-5601 (flame retardant additive), obtained from DAIKIN.

[0114] FP-2500S (nitrogen-phosphorus based flame retardant), obtained from Adeka.

[0115] The samples were prepared by two methods: i) in the first method, HSBC or a thermoplastic elastomer composition prepared therefrom was pressed into a 2 mm plate under high pressure at 180 °C; and ii) in the second method, a layer of the curable composition was obtained by preparing a curable composition in a solvent and pouring it into a tray, followed by vacuum drying at 60 °C for 4 hours. The samples could be further dried at temperatures higher than the HSBC Tg, but without reaching conditions that would lead to premature curing.

[0116] Example 1: Preparation of polymer 1

[0117] In a stainless steel reactor, 6 L of purified and dried cyclohexane, 62 mL of 0.45 M sec-butyllithium, and 241.5 g of dried pMeS were added at 65 °C. The reaction was allowed to proceed for 21 minutes, and a sample was taken (first reaction). Then, 68.7 g of 1,3-butadiene and 5.8 mL of 1,2-diethoxypropane were added, and the reaction was allowed to proceed for 15 minutes. A small sample was taken (second reaction), and 488.5 g of 1,3-butadiene and 197.4 g of pMeS were added at 88 minutes and 11 minutes, respectively, and the reaction was allowed to proceed for 11 minutes. A small sample was taken (third reaction), and 6.7 g of 1,3-butadiene was added. 1.6 mL of methyltrimethoxysilane (MTMS) was added at 2–12 minute intervals, and the temperature was raised to 70 °C. The reaction was allowed to proceed for 40 minutes, and then terminated with 0.8 mL of 2-ethylhexanol (fourth reaction).

[0118] The peak molecular weights (Mp) of the first, second, third, and fourth samples were 8.9, 14.6, 57.5, and 118.4 kg / mol, respectively, corresponding to each complete polymerization stage.

[0119] The polymer solution was sampled and transferred to a hydrogenation reactor, where the poly(1,3-butadiene) block was hydrogenated to a conversion of 99 mol% over 5 hours at 40 bar and 75 °C using a homogeneous cobalt catalyst. The solution was washed to remove the catalyst and stabilized with an antioxidant. The polymer was recovered from the solution by steam condensation, and the product was then milled and dried at 50–80 °C.

[0120] Examples 2-5

[0121] Polymers 2, 3, 4 and 5 were prepared based on the steps in Example 1, but with different amounts of the components.

[0122] 600-900 kg of purified and dried cyclohexane was loaded into a reactor along with 2-3 kg of a 10-15 wt% sec-butyllithium solution. 30-50 kg of dried pMeS was added to the reactor at 40-50 °C. The reaction was allowed to proceed for 50-60 minutes, and a sample was taken. Then, 10-30 kg of 1,3-butadiene and 900-1100 ml of 1,2-diethoxypropane were added, and the reaction was allowed to proceed for 5-9 minutes. Subsequently, 75-125 kg of 1,3-butadiene was added over 60-120 minutes, followed by 25-45 kg of pMeS over 12-18 minutes. The reaction was allowed to proceed for 12-18 minutes. A small sample was taken, and 1.2-3 kg of 1,3-butadiene was added. For polymers 2, 3, and 4, 80-270 kg of MTMS was subsequently added at 60-70 °C. For polymer 5, 200-250 kg of tetramethoxysilane (TMOS) was added at a temperature of 60-70 °C. In each case, the reaction was allowed to proceed for 30-90 minutes, and then terminated by adding 8-11 ml of methanol. These polymers were hydrogenated using the same method as in Example 1. The RU levels in the products obtained from the hydrogenation step are reported in Table 2.

[0123] Molecular weight data are shown in Tables 2 and 3. Polymers 1, 3, and 4 exhibit high levels of hydrogenation in the polymerized diene units, resulting in RU levels below 0.3 meq / g. This high level of hydrogenation leads to good tolerance in outdoor applications, particularly in terms of thermal oxidation and UV weathering resistance.

[0124] Example 6 is a linear poly(p-methylstyrene) with an Mp of 23 kg / mol.

[0125] Example 7 is a hydrogenated block copolymer with a rigid poly(p-methylstyrene) block at the end and a hydrogenated polybutadiene rubber block at the center.

[0126] Example 8 is a hydrogenated block copolymer with a rigid polystyrene block at the end and a hydrogenated polybutadiene-styrene rubber central block.

[0127] Examples 6-8 all lack segment B.

[0128] In Table 4, Examples 2-5 demonstrate that HSBC exhibits low viscosity in both melt and solution forms. Example 5 shows a very low solution viscosity. Example 7, despite having a relatively low Mp, exhibits significantly higher viscosity in both melt and solution forms, making this polymer less satisfactory for a wide range of applications.

[0129] The mechanical properties of the prepared polymers are summarized in Table 5. Examples 3 and 4 show high tensile strengths equal to or higher than 20 MPa and DMA rubber transition temperatures above -30°C. Example 7 shows a low DMA Tg below -30°C, which is less ideal for applications such as copper-clad laminates.

[0130] In Table 6, according to ASTM D1238, the melt flow rate (MFR) of the homopolymer polypropylene (PP) used at a load of 2.16 kg and a temperature of 230 °C is 12 g / 10 min. Example 9 demonstrates ideal flame retardancy with a UL-94 V-0 rating. Example 10 is based on polymer 8 without block B, which has a flame retardancy rating of only UL-94 V-2, with longer burning times t1 and t2.

[0131] Table 7 shows the curing agents used, the MDR properties measured during curing, and the solvent resistance of the HSBC after curing, where the gel percentage and swelling ratio were calculated by PCGT. All polymers were cured for 30 minutes at 180°C in the presence of peroxide in the absence of air in an MFDR machine. Examples 13-15 show high curing efficiency with high gel content even at very low peroxide contents such as 0.5 wt% or 1 wt%. Example 16 further demonstrates that low swelling can be achieved after curing with higher peroxide contents. Examples 17, 19, and 20 were not properly cured and resulted in very low gel contents, exhibiting unsatisfactory weak solvent resistance after curing. Example 14 shows a Dk of 2.31 and a Df of 0.0006 measured at 10 GHz.

[0132] In Table 8, the cured compositions of Examples 12 and 15 exhibited excellent elastic modulus retention above 100°C and below 250°C. However, Example 20 showed a significant decrease in elastic modulus above 150°C. The modulus achieved at 200°C was close to that obtained on the uncured corresponding HSBC polymer 8. All examples showed good thermal degradation behavior, with a TGA loss temperature close to 400°C for 10% TGA.

[0133] Table 9 shows examples of compositions that can be effectively cured, as indicated by the significant maximum torque generated during MDR curing. The use of a curing aid reduces the swelling of cured samples in toluene, as shown by the significant change in the swelling ratio of cured samples containing the curing aid. The cured compositions of Examples 23, 27, 29, and 30 exhibit very low swelling in solution. The data also indicate that the use of a curing aid can increase the gel content. The cured compositions of Examples 22, 23, 28, and 29 have Dk values ​​of 2.39, 2.38, 2.32, and 2.4, and Df values ​​of 0.0007, 0.0013, 0.0008, and 0.0019, respectively, measured at 10 GHz.

[0134] Figure 1 The DMA of polymer 4 and composition Example 15, prepared by curing with 1% DCP, is shown. Both examples exhibit similar properties at temperatures below 100°C. The two samples behave very differently above 100°C. Above 100°C, the elastic modulus G' of polymer 4 decreases sharply by more than two decimals with increasing temperature between 100-200°C. This indicates a rapid loss of cohesion with increasing temperature. Above 100°C, the tanD of polymer 4 increases rapidly at temperatures above 130°C, reaching values ​​above 1. This indicates that the polymer 4 sample becomes more viscous than elastic above 130°C, becoming a viscous melt polymer. On the other hand, the cured composition containing polymer 4 (Example 15) shows an elastic modulus G' stable at around 50-100 kPa up to 250°C. Above 100°C, the cured composition maintains a tanD below 1, exhibiting superior elastic behavior.

[0135] Table 10 shows the properties of HSBC (polymers 4 and 5) and the cured compositions of HSBC obtained therefrom using 0.5% BIPB (Example 14). Dielectric measurements of the samples were performed at 1 GHz and 10 GHz at 23°C and 50% humidity.

[0136] The dielectric properties of the cured compositions based on polymer 4 are shown in Table 11. Dielectric properties were measured at 10 GHz. For Example 34, which contains a cured composition with a higher content of polymer 4, lower Dk and Df values ​​were observed.

[0137] Table 2. HSBC Structure and Composition Description

[0138]

[0139] 1 The Mp of the 1st arm in the B block of the block copolymer is twice that of the 2nd arm.

[0140] 2 FS: Full-sequence block copolymers, therefore they are uncoupled polymers.

[0141] 3 Polymer 6 was not hydrogenated.

[0142] NA means not applicable.

[0143] Table 3. Exemplary HSBC Structure and Composition Description

[0144]

[0145] 1 Coupling agent. 2 Before hydrogenation. NA indicates not applicable.

[0146] Table 4. Viscosity properties of exemplary HSBCs

[0147]

[0148] 1 The Mp of the 1-arm of the coupled block copolymer or twice the Mp of the fully sequenced block copolymer

[0149] Table 5. Mechanical properties of exemplary HSBCs

[0150]

[0151] Table 6. Performance of flame retardant compositions containing HSBC

[0152]

[0153] Table 7. Curing characterization and properties of the cured compositions in solvents.

[0154]

[0155] (a): The gel content is too low to be measured.

[0156] Table 8. High-temperature properties of cured HSBC

[0157]

[0158] Table 9. Curing characterization and solvent properties of curing compositions containing curing aids

[0159]

[0160] Table 10. Dielectric properties of HSBC and cured HSBC

[0161]

[0162] Table 11. Dielectric properties of HSBC cured compositions

[0163]

[0164] As used herein, the term “comprising / including” means an element or step identified after the term, but any such element or step is not exhaustive, and embodiments may include other elements or steps. Although the terms “comprising” and “including” have been used herein to describe various aspects, the terms “substantially consisting of” and “consisting of” may be used in place of “comprising” and “including” to provide a more specific aspect of this disclosure, and are also disclosed therein.

Claims

1. A hydrogenated block copolymer comprising at least one polymer block A and at least one Polymer block B, Prior to hydrogenation, each block A is a polymer of a first vinyl aromatic compound, and each block B is a copolymer block of the following monomer units: (a) A styrene compound having a radical reactive group, having the following formula (I) or (II): Where R1 = R 1 = H, R2 = H, R2' = H; (b) at least one conjugated diene; and optionally (c) A second vinyl aromatic compound that is the same as or different from the first vinyl aromatic compound; The peak molecular weight Mp of each block A is 3-60 kg / mol, and the peak molecular weight Mp of each block B is 20-200 kg / mol; and The polymeric units derived from monomer unit (a) comprise 10-70 wt% of the total weight of the hydrogenated block copolymer and 15-75 wt% of the total weight of block B; Among them, after hydrogenation, the residual olefinic unsaturation degree of the polymeric unit derived from monomer unit (b) is 0-1.5 meq / g of hydrogenated block copolymer; and The hydrogenated block copolymer has: i) The peak maximum temperature of DMA at 10 r / s tanD is -30 to 80℃; ii) The gel content after curing is >50 wt% of the total weight of the hydrogenated block copolymer, as measured by a peroxide-cured gel test; iii) The aromatic segment index is 20-80%; and iv) The viscosity of a 25 wt% solution in toluene at 25 °C is <2000 cP.

2. The hydrogenated block copolymer according to claim 1, wherein: The monomer unit (a) is p-methylstyrene, and the monomer unit (b) is selected from isoprene, butadiene, and combinations thereof; Block B has a corrected 1,4-diene unit content of 10-55%; and The hydrogenated block copolymer has one or more of the following characteristics: i) The dielectric constant Dk at 1 GHz is <2.

6. ii) The dielectric constant Dk at 10 GHz is <2.

6. iii) The loss tangent Df at 1 GHz is <0.002, and iv) The loss tangent Df at 10 GHz is <0.

002.

3. The hydrogenated block copolymer according to any one of claims 1-2, wherein block A comprises polymerized p-methylstyrene units, the monomer unit (a) in block B is p-methylstyrene, and the wt% of p-methylstyrene in (a) of block B is 15-50 wt%.

4. The hydrogenated block copolymer according to claim 1, wherein the styrene compound is vinylbenzocyclobutene.

5. The hydrogenated block copolymer according to any one of claims 1-2, wherein: The corrected 1,4-diene unit content of block B is 10-50%; Hydrogenated block copolymers with a residual olefinic unsaturation of 0-0.3 meq / g derived from monomer unit (b); and The hydrogenated block copolymer has an aromatic block index of 40-75% and a solution viscosity of <1000 cP in toluene at 25°C at 25 wt%.

6. The hydrogenated block copolymer according to any one of claims 1-2, wherein the DMA cross temperature of the hydrogenated block copolymer is 100-300°C. o C.

7. The hydrogenated block copolymer according to any one of claims 1-2, wherein the hydrogenated block copolymer comprises one or more of the following structures: AB, ABA, (AB-) n X, ABAB, (BAB-) n X, (BA-) n X, and (ABA-) n X, where X is a coupling agent residue and n is 1-30.

8. The hydrogenated block copolymer according to any one of claims 1-2, further comprising a functional group of a radical reactive group of a styrene compound attached to the monomer unit (a).

9. A curable composition comprising: (a) 1-99 wt% of the hydrogenated block copolymer of any one of claims 1-8, (b) 0.1-5 wt% of an initiator selected from thermal initiators and photochemical initiators, based on the total weight of the composition.

10. The curable composition according to claim 9, further comprising: One or more curing aids selected from 1,2-bis(vinylphenyl)ethylene, divinyl aromatic compounds, triallyl cyanurate, triallyl isocyanurate, vinyl-functionalized polyphenylene ether, bismaleimide aromatic resins, mono- or polyfunctional acrylate or methacrylate monomers, and combinations thereof. Flame retardants; and Solvents, selected from aliphatic hydrocarbons, aromatic hydrocarbons, and combinations thereof.

11. The curable composition according to any one of claims 9-10, further comprising a polyolefin, wherein the curable composition is cured in a molten phase.

12. A blend comprising: 99-1 wt% of the hydrogenated block copolymer of any one of claims 1-8, 1-99 wt% crystalline polyolefins, and Optional 20-50 wt% flame retardant.

13. The blend according to claim 12, comprising: 10-50 wt% of a hydrogenated block copolymer, 1-20 wt% of a crystalline polyolefin, and 20-50 wt% of a flame retardant, wherein the blend has a flame retardancy rating of V0 according to the UL94 vertical burning test method.

14. A cured composition obtained by curing the blend of claim 12.

15. A curable composition comprising 100 parts of the hydrogenated block copolymer of any one of claims 1-8 and 0.5 parts of a peroxide initiator, wherein at 180°C... o After C curing for 2 hours and after compression molding, Dk at 1 GHz is <3.5 and Df at 1 GHz is <0.

003.

16. A curable composition comprising 100 parts of the hydrogenated block copolymer of any one of claims 1-8 and 0.5 parts of a peroxide initiator, at 180°C o After C curing for 2 hours and after compression molding, Dk at 10 GHz was <2.6 and Df at 10 GHz was <0.003.

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