Novel block copolymers and their uses

Abstract

To provide a hydrogenated block copolymer comprising a polymer block A and a polymer block B.SOLUTION: Prior to hydrogenation, a polymer block A has a first vinyl aromatic compound, and a polymer block B contains monomers: 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 repeat units of the monomer a) forms 10-70 wt.% of the total block copolymer, and 10-80 wt.% of the total weight of the block B. After hydrogenation, the polymerized units derived from the monomer b) has a RU of 0-1.5 meq per gram of the hydrogenated block copolymer. The hydrogenated block copolymer exhibits reactivity and higher flow properties before curing, and shows, after curing, excellent mechanical properties, improved flame resistance, and excellent solvent resistance.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to novel reactive block copolymers and their uses. [Background technology]

[0002] Many applications require elastomeric materials with low viscosity and reactivity during processing, along with excellent mechanical performance, such as adhesives, sealants, coatings, tires, the automotive, construction, electrical, electronics, and medical devices. Furthermore, it is desirable for these materials to have excellent solvent and high temperature resistance. Under certain operating conditions, some applications require high flow and high strength materials during manufacturing, along with flame resistance in the end use. Excellent mechanical performance in terms of strength and impact resistance, as well as weathering or ozone resistance, is also desirable. Existing thermoplastic materials may not be able to meet these requirements. Summary of the Invention [Problem to be solved by the invention]

[0003] There is a continuing need for polymer compositions that exhibit excellent mechanical performance and improved flame resistance after exposure to cure, excellent solvent resistance and mechanical performance at high temperatures, as well as reactivity and higher flow properties. [Means for solving the problem]

[0004] In a first aspect, the present disclosure relates to a hydrogenated block copolymer comprising, consisting essentially 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) a styrene compound having a radically 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. Block A has a peak molecular weight (Mp) of 3 to 60 kg / mol, and block B has a peak molecular weight (Mp) of 20 to 200 kg / mol. Polymerized units derived from (a) constitute 10 to 80 wt% of the total weight of the hydrogenated block copolymer, and 10 to 70 wt% of the total weight of block B. Polymerized units derived from monomer (b) have a residual olefinic unsaturation of 0 to 1.5 meq per gram of hydrogenated block copolymer. The hydrogenated block copolymer has i) a tangent delta peak maximum temperature of -30 to 80°C at DMA 10 rad / s, ii) after cure, a gel content of >40 wt% of the total weight of the hydrogenated block copolymer as measured by the Peroxide Cure Gel Test (PCGT), and iii) an aromatic blockiness index of 20 to 80%.

[0005] In a second embodiment, monomer (a) is paramethylstyrene, and monomer (b) is selected from the group consisting of isoprene, butadiene, and combinations thereof. Block B has a corrected 1,4-diene unit content of 10 to 55%, and the hydrogenated block copolymer has one or more of: i) a dielectric constant (Dk) of <2.6 at 1 GHz, ii) a dielectric constant (Dk) of <2.6 at 10 GHz, iii) a loss tangent (Df) of <0.002 at 1 GHz, iv) a loss tangent (Df) of <0.002 at 10 GHz, and v) a solution viscosity of <2000 cP at 25 wt% in toluene at 25°C.

[0006] In a third embodiment, the weight percentage of (a) paramethylstyrene in the B block is 10 to 50% by weight.

[0007] In a fourth embodiment, block A comprises polymerized paramethylstyrene units. [Brief explanation of the drawings]

[0008] [Figure 1] 1 is a graph showing dynamic mechanical analysis (DMA) performance including modulus (G') and tangent delta (tan delta). DETAILED DESCRIPTION OF THE INVENTION

[0009] As used herein, the following terms have the following meanings:

[0010] "Aromatic blockiness" or "aromatic blockiness index" refers to the percentage of aromatic groups in a block copolymer that have two adjacent aromatic units. The aromatic blockiness index is calculated based on the H-I NMR spectrum of the block copolymer and is given by the formula: aromatic blockiness index = 100 × integral 2 / integral 1, where integral 1 is determined by integrating the H-I NMR spectrum from 7.5 ppm to 6.0 ppm and dividing the resulting value by "N," where "N" is the average number of protons directly bonded to the aromatic ring, e.g., 5 for unsubstituted aromatic groups (phenyl rings), 4 for monosubstituted aromatic groups such as paramethylstyryl groups, and 3 for disubstituted aromatic groups such as dimethylstyryl groups. Integral 2 is determined by integrating the H-I NMR spectrum from the signal minimum of 6.9 ppm to 6.6 ppm down to 6.0 ppm and dividing by 2. In practice, integral 2 is found by integrating the area of ​​the spectrum from the signal minimum covering the region of the steepest valley between the downfield chemical shift of 6.9-6.6 ppm and the upfield chemical shift of 6.0 ppm. When calculating the peak areas for integral 1 and integral 2, the peak areas arising from solvent protons are not included.

[0011] "Molecular weight" refers to the styrene equivalent molecular weight in kg / mol of a polymer or block copolymer. Molecular weight can be measured, for example, by gel permeation chromatography (GPC) using polystyrene calibration standards, performed according to ASTM 5296. The chromatograph is calibrated using commercially available polystyrene molecular weight standards. The molecular weight of a polymer measured using a GPC so calibrated is the styrene equivalent molecular weight. The detector can be a combination of an ultraviolet detector and a refractive index detector. Molecular weights expressed herein are measured at the peak of the GPC trace, commonly referred to as the "peak molecular weight," and are designated as Mp.

[0012] "pMeS" refers to paramethylstyrene and "St" refers to styrene.

[0013] A "radical reactive group" refers to a chemical group that can form or be induced to form a free radical species. Free radical species can be formed by any known means, including thermal, photochemical, or chemical reagents. For example, a benzylic carbon having at least one hydrogen substituent can be a radical reactive group. The benzylic carbon group can also be substituted as long as it has one benzylic hydrogen atom. Another example of a radical reactive group is a cyclobutane ring, which can be activated, for example, photochemically, to form a free radical species. Another example of a radical reactive group is an allyl group, which can form an allyl free radical.

[0014] "Corrected 1,4-diene unit content" or "C14DUC" refers to a polymer block having repeat units derived from butadiene (Bd), isoprene (Ip), or a combination thereof, and is determined by the parameters of the weight percent (Bw) of Bd content in the total dienes in the polymer block, the weight percent (B14) of 1,4-addition units of Bd among the Bd units in the polymer block, the weight percent (Iw) of Ip content in the total dienes in the polymer block, and the weight percent (I14) of 1,4-addition units of Ip among the Ip units in the polymer block, expressed as follows: C14DUC=(Bw×B14 / 100)+Iw×(I14-40) / 100 (1) Polymerization of conjugated dienes produces polymerized units based on addition across both double bonds (giving 1,4-addition units) and one double bond (giving pendant vinyl groups).

[0015] "Residual olefinic unsaturation" or RU refers to the amount of olefinic C=C groups in polymerized diene units in milliequivalents per gram (meq / g) that have not been reduced after the block copolymer has been hydrogenated to HSBC. RU is measured by ozone titration or from the H NMR spectrum of the HSBC.

[0016] The "Peroxide-Cure Gel Test" or "PCGT" refers to a test that measures the gel content of a cured composition based on a hydrogenated block copolymer (HSBC), expressed as a weight percent. PCGT is measured by mixing HSBC with 0.5 wt. % BIPB (bis-(t-butylperoxyisopropyl)benzene) initiator and curing at 180°C for 30 minutes using a moving die rheometer (MDR). The gel content is calculated by first measuring the initial weight (W) of the cured sample before immersing the sample in toluene for 1 day. The solution containing the sample is then filtered, and the weight of the filtered swollen gel (Ws) is recorded. The swollen gel is then dried under vacuum at 60°C until a constant weight is reached or until a dry weight (Wd) is reached. The gel content (gel%) is calculated using the formula: gel% = 100 × Wd / W. The swelling ratio is calculated using the formula: swelling ratio = Ws / Wd.

[0017] "Coupling efficiency" or CE refers to the ratio (expressed as a percentage) of the sum of the integrated peak areas of coupled species with more than one arm (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 from the integration of the peak areas.

[0018] "Degree of branching" or DOB refers to the average number of arms of a coupling species. DOB is calculated from the GPC peak areas of individual coupling species with 2 arms, 3 arms, 4 arms, ..., i arms. DOB values ​​are calculated using the formula: DOB = [GPC area of ​​2 x 2-arm species + GPC area of ​​3 x 3-arm species + GPC area of ​​4 x 4-arm species + ... GPC area of ​​i x i-arm species] / [GPC area of ​​all coupling species].

[0019] The present disclosure in embodiments is directed to hydrogenated block copolymers, herein referred to as hydrogenated styrenic block copolymers (HSBCs) containing pMeS in the midblock, and compositions thereof comprising HSBC. HSBC-based compositions have high flow rates before curing, and after curing, the cured compositions have superior weatherability compared to the uncured compositions.

[0020] Hydrogenated styrene block copolymer (HSBC): HSBC is a hydrogenated form of a styrenic block copolymer (SBC), which, 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 monomers comprising (a) a styrene compound having a radically 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.

[0021] In embodiments, the first vinyl aromatic compound used to construct polymer block A can be any aromatic compound having at least one vinyl group attached thereto. Non-limiting classes of compounds suitable for use include styrene and substituted styrenes, vinyl naphthalene and substituted vinyl naphthalenes, vinyl indenes, vinyl anthracenes, 1,1-diphenylethylenes, and mixtures thereof. Some specific examples include vinyl aromatic compounds having 8 to 20 carbon atoms, such as o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 2,4-dimethylstyrene, alpha-methylstyrene, vinyl naphthalene, vinyl toluene, and vinyl xylene, or mixtures thereof.

[0022] In embodiments, the styrenic compound having a radical reactive group, i.e., monomer (a), can be a substituted styrene of formula (I), a vinylbenzocyclobutene of formula (II), a vinyldihydroindene of formula (III), a vinyltetrahydronaphthalene of formula (IV), or any combination thereof.

[0023] [Table 1]

[0024] In an embodiment, monomer (a) of formula (I) is selected from o-methylstyrene, p-methylstyrene, o-ethylstyrene, p-ethylstyrene, o-isopropylstyrene, para-isopropylstyrene, o-methyl-α-methylstyrene, p-methyl-α-methylstyrene, o-ethyl-α-methylstyrene, p-ethyl-α-methylstyrene, o-isopropyl-α-methylstyrene, para-isopropyl-α-methylstyrene and mixtures thereof.

[0025] In embodiments, the first vinyl aromatic monomer comprises pMeS, p-methyl-α-methylstyrene, or a mixture thereof.

[0026] In embodiments, (b) the copolymer block of monomers in block (B) comprising a conjugated diene monomer is selected from the group consisting of 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, piperylene, cyclohexadiene, and mixtures thereof.

[0027] In embodiments, the copolymer block of monomers in block (B) optionally includes (c) a second vinyl aromatic compound. If present, the second vinyl aromatic compound can be any aromatic compound having at least one vinyl group attached thereto. Non-limiting classes of compounds suitable for use include styrene and substituted styrenes, vinyl naphthalene and substituted vinyl naphthalenes, vinyl indenes, vinyl anthracenes, 1,1-diphenylethylenes, and mixtures thereof. Other examples include vinyl aromatic compounds having 8 to 20 carbon atoms, such as o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 2,4-dimethylstyrene, α-methylstyrene, vinyl naphthalene, vinyl toluene, vinyl xylene, and mixtures thereof.

[0028] In embodiments, block A has a peak molecular weight (Mp) of 3 to 60 kg / mol, or 5 to 50 kg / mol, or 10 to 45 kg / mol, or 15 to 40 kg / mol, or 20 to 35 kg / mol, or >10 kg / mol, or <50 kg / mol.

[0029] In embodiments, block B has an Mp of 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.

[0030] In embodiments, the polymerized units derived from monomer (a) constitute 10 to 80 wt %, or 15 to 75 wt %, or 20 to 70 wt %, or 25 to 60 wt %, or 30 to 65 wt %, or >15 wt %, or <75 wt %, based on the total weight of polymer block B of HSBC.

[0031] In embodiments, the polymerized units derived from monomer (a) comprise 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 the HSBC.

[0032] In an embodiment, after hydrogenation of the SBC, the resulting HSBC has an RU per gram of HSBC of 0-1.5 meq, or 0.01-1.4 meq, or 0.02-1.3 meq, or 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.

[0033] In embodiments, the HSBC comprising block B has 10 to 50 wt %, or 15 to 45 wt %, or 20 to 40 wt %, or >15 wt %, or <60 wt % of polymerized units derived from (a)pMeS, based on the total weight of the HSBC.

[0034] In embodiments, the HSBC comprising block B has a corrected 1,4-diene unit content of 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 embodiments, block B has a corrected 1,4-diene unit content of 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 blocks.

[0035] In an embodiment, the HSBC has a structure where monomer (a) is paramethylstyrene and monomer (b) is selected from the group consisting of isoprene, butadiene, and combinations thereof.

[0036] In embodiments, an HSBC having at least one block A and at least one block B is represented by the following: 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 to 30.

[0037] In an embodiment, the HSBC comprises a block A, a block B, and a block C, wherein block C comprises a conjugated diene monomer selected from butadiene, isoprene, and mixtures thereof. In an embodiment, block C is hydrogenated.

[0038] Preparation Process SBC precursors can be prepared by anionic polymerization using processes known in the art. The polymerization initiator is generally an organometallic compound, such as an organolithium compound such as ethyllithium, propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, phenyllithium, hexylbiphenyllithium, hexamethylenedilithium, butadienelithium, isoprenyllithium, 1,1-diphenylhexyllithium, or polystyryllithium.

[0039] In embodiments, the initiator is used in an amount of 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.

[0040] In embodiments, the solvent for the anionic polymerization is selected from the group consisting of aliphatic, alicyclic, or aromatic hydrocarbons having 4 to 12 carbon atoms, such as pentane, hexane, heptane, cyclopentane, cyclohexane, methylcyclohexane, decalin, isooctane, benzene, alkylbenzenes such as toluene, xylene, ethylbenzene, and mixtures thereof.

[0041] In an embodiment, in anionic polymerization, polymer chain termination is carried out using a coupling agent, such as a difunctional or polyfunctional compound, such as divinylbenzene, aliphatic or araliphatic hydrocarbon halides, such as 1,2-dibromoethane, bis(chloromethyl)benzene, or silicon tetrachloride, dialkyl or diaryl silicon dichlorides, alkyl or aryl silicon trichlorides, tin tetrachloride, alkyl silicon methoxides, alkyl silicon ethoxides, polyfunctional aldehydes, such as terephthalic acid dialdehyde, ketones, esters, anhydrides, or epoxides. In an embodiment, the coupling agent is selected from methyltrimethoxysilane (MTMS), tetramethoxysilane (TMOS), divinylbenzene (DVB), dimethyl adipate, and mixtures thereof.

[0042] HSBC can be obtained by hydrogenating SBC precursors using known hydrogenation catalysts, for example catalysts based on nickel, cobalt, titanium or mixtures thereof.

[0043] In 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 in-chain double bonds and pendant vinyl groups present in the polymerized units derived from (b) conjugated diene monomer are reduced.

[0044] In embodiments, after hydrogenation, <50% by weight, or <40% by weight, or <30% by weight, or <20% by weight, or <10% by weight, or <5% by weight of the arene double bonds are reduced.

[0045] HSBC Functionalization In embodiments, HSBC is functionalized by substituting monomer (a) with a functional group, e.g., a halogen, to yield a halogen-functionalized HSBC. This can be achieved by reaction with a halogen or a chemical free radical initiator, e.g., azobis(isobutyronitrile), in the presence of light (e.g., a 500-watt tungsten bulb), as known in the art, e.g., U.S. Pat. No. 5,654,379, incorporated herein by reference. Halogenation occurs selectively at the benzylic carbon atom of the radical-reactive moiety present in the styrene compound, i.e., monomer (a). For example, in the case of HSBC where monomer (a) is pMeS, bromination yields bromomethyl-functionalized HSBC. Halogen-functionalized HSBC can be a valuable starting material for generating diverse functionalized HSBCs by reaction with nucleophiles. Substitution of other functional groups on benzylic bromine, a highly active and versatile electrophile, can be achieved by nucleophilic substitution reactions to introduce desired functionality.

[0046] Curable compositions based on HSBC In an embodiment, the curable composition is prepared from a mixture comprising 1 to 99.9 wt % of HSBC and 0.1 to 5 wt % of a curing initiator, based on the total weight of the curable composition.

[0047] The curing initiator can be either a thermal initiator or a photoinitiator. Non-limiting examples of thermal initiators include peroxides such as diisobutyl peroxide, di-tert-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, α,α-bis(tert-butylperoxy)diisopropylbenzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane (DBPH), 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl-4,4-bis(tert-butylperoxy)valerate, benzoyl peroxide, lauroyl peroxide, dilauroyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, diaryl peroxides, ketone peroxides, peroxydicarbonates, peroxyesters, dialkyl peroxides, hydroperoxides, peroxyketals, and mixtures thereof. In an embodiment, the peroxide has a 1 hour half-life temperature of >100°C and <200°C.

[0048] In embodiments, the photoinitiator can be selected from unimolecular (Type I) and bimolecular (Type II) photoinitiators. Examples of Type I initiators include benzophenone in combination with a tertiary amine, alkylbenzophenones, 4,4'-bis(dimethylamino)benzophenone (Michler's ketone), anthrone, halogenated benzophenones, and mixtures thereof. Non-limiting examples of Type II initiators include benzoin, benzoin derivatives, particularly benzoin ethers, benzil ketals, acylphosphine oxides, particularly 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bisacylphosphine oxides, phenyl-glyoxyl esters, camphorquinone, alpha-aminoalkylphenones, alpha,alpha-dialkoxyacetophenones, alpha-hydroxyalkylphenones, and mixtures thereof.

[0049] In embodiments, the curable composition further comprises one or more co-curatives, a flame retardant, and a solvent to aid in mixing of the components, which is subsequently evaporated to provide the curable composition for curing.

[0050] Examples of useful co-curing agents include one or more members selected from 1,2-bis(vinylphenyl)ethylene, butadiene-based liquid rubber, divinylaromatic compounds, triallyl cyanurate, triallyl isocyanurate, vinyl-functionalized polyphenylene oxide such as NORYL® SA-9000, bismaleimide aromatic resins, mono- or polyfunctional acrylate or methacrylate monomers, plasticizers, tackifying resins, and styrene block copolymers containing one or more polydiene blocks, and combinations thereof. Suitable examples of co-curing agents include divinylbenzene, 1,2-bis(vinylphenyl)ethane, ethylene glycol methacrylate (EGDMA), trimethylolpropane trimethacrylate (TMPTMA), triallyl isocyanurate, triallyl cyanurate, diethylene glycol diacrylate, neophenylene glycol diacrylate, and mixtures thereof.

[0051] In an embodiment, the solvent is selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, or combinations thereof. Suitable examples of aliphatic hydrocarbons include C6 to C8 12 Saturated hydrocarbons include, for example, cyclohexane, methylcyclohexane, n-hexane, heptane, octane, and dodecane. Aromatic hydrocarbons can have 7 to 10 carbon atoms, such as toluene, xylene, and mesitylene.

[0052] In embodiments, the curable composition further comprises additives such as other resins, plasticizers, redox couples, fillers, fibers, antioxidants, flame retardants, blowing agents, surfactants, viscosity modifiers, wetting agents, degassing agents, toughening agents, adhesion promoters, dyes, pigments, colorants, heat stabilizers, light stabilizers, lubricants, flow improvers, drip retardants, antiblocking agents, antistatic agents, flow promoters, processing aids, substrate adhesives, mold release agents, low shrinkage agents, stress relief additives, waxes, anti-drip agents in an amount 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.

[0053] Exemplary fillers include one or more inorganic silicates such as andalusite, sillimanite, kyanite, mullite, pyrophyllite, or allophane, and the minerals calcium silicate, silica, surface-treated silica, and ground quartz; 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 (CaCO), metal hydroxides. In embodiments, the filler is selected from calcium carbonate, mica, magnesium hydroxide, aluminum hydroxide, and mixtures thereof.

[0054] In embodiments, the flame retardant is selected from halogenated compounds, non-halogenated compounds, non-halogenated intumescent compounds, phosphorus-containing compounds, nitrogen-containing compounds, bromine-containing compounds, and mixtures thereof.

[0055] In embodiments, the plasticizer is either a paraffinic oil, a naphthenic oil, a natural oil, a hydrotreated naphthenic oil, a low molecular weight polyolefin, a low molecular weight styrene-butadiene block, or a combination thereof. In embodiments, the rubber can be selected from natural rubber, synthetic rubber, and mixtures thereof. Non-limiting examples include natural rubber, ethylene-propylene-diene monomer rubber (EPDM), ethylene / alpha-olefin rubber (EPR), styrene / butadiene rubber (SBR), acrylonitrile / butadiene rubber (NBR), polychloroprene rubber, polybutadiene rubber (BR), synthetic polyisoprene rubber (IR), isobutylene-isoprene rubber (IIR), and the like.

[0056] In embodiments, the curable composition includes other polymers, non-limiting examples of which include polybutadiene, 1,2-polybutadiene, polyisoprene, polybutadiene-polyisoprene copolymers, polybutadiene-polystyrene-polydivinylbenzene terpolymers, poly(phenylene ether)s (PPEs), 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), polyetherimides (PEI), maleimide resins, cyanate ester resins, epoxy resins, phenolic resins, benzoxazine resins, polyamide resins, polyimide resins, polyphenylene sulfide, polyacetals, polysulfones, polyesterimides, polyethersulfones, polyetherketones, fluororesins, other rubber polymers, and mixtures thereof.

[0057] In embodiments, the curable composition comprises a tackifying resin selected from one or more natural or modified rosins, rosin esters including those made using polyols, polyterpene resins, phenol-modified terpene resins, aromatic resins, aliphatic petroleum resins such as those made using C5 or C9 hydrocarbon streams obtained from petroleum cracking / refining or any hydrogenated form, or combinations of the foregoing.

[0058] In embodiments, a curable composition comprising HSBC, a peroxide initiator, and one or more co-curatives can be dynamically cured in the melt phase. This aspect can be valuable for preparing thermoplastic vulcanizates. In the dynamic cure mode, the curable composition is maintained in a molten state. Dynamic cure imposes significant deformation and stress on the composition during curing. The high deformation and stress destroy the gel formed during curing, resulting in dispersed microgels in the thermoplastic phase, forming what is commonly referred to as a thermoplastic vulcanizate.

[0059] In embodiments, the curable composition comprises, based on the total weight of the curable composition, (a) 5 to 99 wt % HSBC, (b) 0.1 to 5 wt % of at least one curing agent, (c) 5 to 94 wt % of one or more co-curing agents, and optionally (d) 0.1 to 20 wt % of additives.

[0060] In an embodiment, the curable composition comprises i) 5 to 95 phr of at least one rubber, ii) 5 to 50 phr of HSBC or functionalized forms of HSBC, iii) 50 to 200 phr of filler, iv) 0.1 to 20 phr of a curing agent, such as a peroxide, v) up to 70 phr of a plasticizer or resin, and vi) up to 15 phr of an antidegradant, the amounts of components (ii) through (vi) being based on 100 parts of component (i).

[0061] In embodiments, HSBC can also be mixed with a crystalline polyolefin, such as crystalline polypropylene, in a ratio of 1:99 to 99:1 HSBC to crystalline polyolefin to provide blends for various end uses. In embodiments, the blend further comprises a flame retardant. An example is a blend of 10-50 wt% HSBC, 1-20 wt% crystalline polyolefin, and 20-50 wt% flame retardant.

[0062] Preparation process of HSBC-based curable compositions In embodiments, HSBC and other ingredients can be first mixed with a solvent. The mixture is processed into the desired shape, followed by evaporation of the solvent. In embodiments, the curable composition containing HSBC is prepared by pre-blending the composition using a suitable device, such as a Henschel mixer, V-blender, or ribbon blender. The pre-blended composition can then be extruded into pellets.

[0063] Process of hardening composition based on HSBC Thermoplastic vulcanizate (TPV) compositions can be made, for example, by a process that includes introducing a molten thermoplastic vulcanizate containing HSBC and a free radical source, where the thermoplastic vulcanizate includes cured rubber dispersed within a thermoplastic matrix with HSBC. This process can be adapted for continuous production by, for example, (i) dynamically vulcanizing the rubber in a first stage of the process to form a molten thermoplastic vulcanizate, (ii) maintaining the thermoplastic vulcanizate in a molten state until a second stage, and (iii) introducing the molten thermoplastic vulcanizate and a free radical source to the second stage of the process to form a modified thermoplastic vulcanizate.

[0064] In embodiments, curing and / or crosslinking can be achieved by irradiation with an electron beam, e.g., using an array of cathodes generating a high concentration of electrons, or using elemental halogens. Electron beam treatment can be carried out using any of the following electron accelerators: electrostatic direct current (DC), electrodynamic DC, radio frequency (RF) linear accelerators (LINACS), magnetic induction LINAC, and continuous wave (CW) instruments. Crosslinking can be carried out at a suitable temperature, e.g., room temperature or from ambient to 60°C. The cured composition can be processed in the molten state to form molding compounds, molten films, and hot melt adhesives.

[0065] HSBC Characteristics In embodiments, the HSBC has a solution viscosity at 25% by weight in toluene at 25°C of 50-2000 cP, or 70-1800 cP, or 100-1600 cP, or 150-1500 cP, or 200-1200, or 300-1100 cP, or 400-1000 cP, or >100 cP, or <1000 cP, or <2000 cP.

[0066] In embodiments, the HSBC has a Dk at 1 GHz of 1 to 2.6, or 1.2 to 2.5, or 1.4 to 2.4, or 1.6 to 2.2, or <2.6.

[0067] In embodiments, the HSBC has a Dk at 10 GHz of 1 to 2.6, or 1.2 to 2.5, or 1.4 to 2.4, or 1.6 to 2.2, or <2.6.

[0068] In embodiments, the HSBC has a Df of 0 to 0.002, or 0.0001 to 0.0022, or 0.0005 to 0.0024, or 0.0008 to 0.0026, or 0.001 to 0.0028, or <0.002 at 1 GHz.

[0069] In embodiments, the HSBC has a Df at 10 GHz of 0 to 0.002, or 0.0001 to 0.0022, or 0.0005 to 0.0024, or 0.0008 to 0.0026, or 0.001 to 0.0028, or <0.002.

[0070] Note that lower values ​​of Dk and Df result in better performance in applications such as electronics. Furthermore, there is a small difference in the measurements of Dk and Df at 1 GHz versus 10 GHz, but in some applications this small difference can be very important.

[0071] In an embodiment, the HSBC has a tangent delta peak maximum temperature at 10 rad / s dynamic mechanical analyzer (DMA) of -30 to 80°C, or -20 to 75°C, or -10 to 60°C, or 0 to 50°C.

[0072] In embodiments, the HSBC has an aromatic blockiness index, as measured by 1D1H-NMR spectroscopy, of 20-80%, or 25-75%, or 30-70%, or 35-65%, or 40-60%, or 40-75%, or >40%, or <70%.

[0073] In embodiments, the HSBC has a DMA crossover temperature (T-crossover) of 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.

[0074] Properties of HSBC-based compositions Before curing, compositions containing HSBC have good flow properties. After curing, the cured compositions have excellent mechanical performance. The cured compositions have improved flame resistance, excellent solvent resistance, and high temperature mechanical performance. These physical properties make the cured compositions valuable for their high performance in a variety of applications.

[0075] In embodiments, the composition, prior to curing, has a solution viscosity at 25% by weight in toluene at 25°C of 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.

[0076] Herein, the properties of the cured composition refer to a "base" composition having 100 parts HSBC, 0.5 parts peroxide (BIPB or DCP) after curing at 180°C for 2 hours and then compression molding.

[0077] In embodiments, the base composition has a Dk at 1 GHz of 0.2 to 4, or 0.4 to 3.8, or 0.6 to 3.6, or 0.8 to 3.4, or 1 to 3.2, 1.2 to 3, or 1.4 to 2.8, or 1.6 to 2.6, or <3.5, or <2.6; or at 10 GHz of 0.2 to 4, or 0.4 to 3.8, or 0.6 to 3.6, or 0.8 to 3.4, or 1 to 3.2, 1.2 to 3, or 1.4 to 2.8, or 1.6 to 2.6, <3.5, or <2.6.

[0078] In embodiments, the base composition has a Df at 1 GHz of <0.002, or <0.0025, or <0.003, or <0.0035, or <0.004, or <0.0045, or <0.005, or has a Df at 10 GHz of <0.002, or <0.0025, or <0.003, or <0.0035, or <0.004, or <0.0045, or <0.005.

[0079] In embodiments, the base composition has a DMA crossover temperature (Tcrossover) of 200-500°C, or 220-450°C, or 240-430°C, or 250-400°C, or >300°C, or <400°C.

[0080] In an embodiment, the base composition further comprises at least one flame retardant with a V0 rating as measured according to the UL94 vertical flame test method.

[0081] In embodiments, the cured composition (HSBC with 0.5 wt. % BIPB) has a gel content based on PCGT of >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. %, based on the total weight of the cured composition after removal of solvent.

[0082] Purpose In embodiments, compositions containing HSBC can be injection molded or extruded using conventional plastics processing equipment, with or without a curing agent. In embodiments, HSBC is used to make adhesives, such as solvent-based and hot-melt adhesives, flame-retardant articles, hot-melt adhesives, melt-blown films, thermoplastic vulcanizates, tires, and flexographic plates. Other applications include automotive or transportation, tires, sealants, damping layers in films, building, construction, shoes, industrial equipment, health care, medical devices, sporting equipment, grips, artificial joint parts, and ballistic protection equipment.

[0083] In embodiments, compositions comprising HSBC are used to make copper clad laminates by combining the necessary ingredients, such as HSBC, diene-based polymer, curing initiator, flame retardant, and optional additives.

[0084] In embodiments, cured compositions comprising HSBC are used to make sealant articles, such as seals for rotating shafts, laminated diaphragm sealant articles for diaphragm pumps, dynamic seals, static seals, O-rings, coextruded hoses, hoses for handling chemicals or fuels, and foam articles.

[0085] In embodiments, HSBC-based thermoplastic vulcanizates (TPVs) can be used to produce extruded articles with desirable surface appearances, such as vehicle parts such as weather seals, hoses, belts, gaskets, moldings, boots, elastic fibers, weather seals, brake parts such as cups, coupling discs and diaphragm cups, boots for constant velocity joints and rack and pinion joints, tubing, sealing gaskets, hydraulic or pneumatic equipment parts, O-rings, pistons, valves, valve seats, valve guides, V-belts, power transmission belts including toothed belts with truncated ribs, and other elastomeric polymer based parts or elastomeric polymers combined with other materials such as metal / plastic combinations.

[0086] A variety of techniques can be used to manufacture articles from HSBC-based compositions, including foaming (for making foamed articles), coating, injection molding, extrusion, co-extrusion, blow molding, hot melt spraying, lamination with other materials, compression molding, and solution spraying. [Example]

[0087] The following test methods are used:

[0088] The molecular weight of the polymer is determined by gel permeation chromatography (GPC) according to ASTM 5296 using polystyrene calibration standards.

[0089] Proton NMR methods are used to determine the total aromatic content ArC, eg, pMeS content expressed in weight percent and RU, expressed in meq of residual olefinic unsaturation per gram of HSBC.

[0090] Brookfield viscosity is measured using the ASTM D-2196 test method at 25°C and is expressed in centipoise (cP) or millipascal seconds (mPa.s).

[0091] The viscoelastic behavior of polymer samples is measured by dynamic mechanical analysis (DMA) according to ASTM 4065 using a parallel plate geometry and an angular frequency of 10 rad / s, imposing a temperature sweep of +2°C per minute. The rubber tangent delta peak temperature (tanDmaxT) is the temperature at which the tangent delta peak, corresponding to the glass-to-rubber transition, reaches its maximum value. The final crossover temperature (Tcrossover) is the temperature corresponding to the transition from more elastic behavior observed in the rubbery plateau zone to more viscous behavior observed at higher temperatures. Tcrossover is the temperature at which the elastic and viscous moduli are equal, i.e., tan delta is 1.

[0092] Temperature sweep experiments are performed from -40 to 300 °C with a heating ramp of +2 °C / min and 10 rad / s to obtain the storage modulus (G'), loss modulus (G"), and loss factor (tan δ) as a function of temperature. The tangent delta peak temperature of the rubber is herein referred to as the T of the rubber phase. g It is considered to be.

[0093] Curing of the composition is achieved using an MDR. Samples are heated to 110°C (or the maximum T of the copolymer if higher). g ) to form a 0.7 mm thick plate. The mold is closed under vacuum and held at that temperature for 2 minutes. The mold temperature is then increased to reach 180°C. The sample is held under vacuum at 180°C for 30 minutes to achieve cure. The maximum torque value of the MDR (expressed in dN.m) is recorded during the curing step at 180°C and corresponds to the maximum torque recorded during that cure period. The time required to reach 90% of the maximum torque value is recorded as "tc90" and is expressed in minutes and seconds.

[0094] The cured samples are analyzed for gel content and swelling ratio per PCGT.

[0095] UL94 testing uses a 2mm thick specimen.

[0096] The dielectric performance of HSBC and cured compositions is measured at high frequency, dielectric constant and loss tangent according to IPC-TM-6502.5.5.9 method at 1 GHz and / or IEC 61189-2-721-2015 method at 10 GHz, parallel plate, on samples at 23°C and 50% humidity.

[0097] Tensile stress-strain properties are measured according to ASTM D412 using a dumbbell "C" and a crosshead displacement rate of 500 mm / min.

[0098] Shore A hardness with a 10 second dwell time is measured on a 3 x 2 mm plate according to ASTM D2240.

[0099] Unless otherwise specified, all reported melt flow rates (MFR) are measured according to ASTM D1238 at 230°C under a 2.16 kg load.

[0100] The ingredients used in the examples are as follows:

[0101] DCP: dicumyl peroxide, BIPB: Di(2-Tert-butylperoxyisopropyl)benzene; TAC: triallyl cyanurate; TAIC: triallyl isocyanurate; NORYL SA9000 resin is a low molecular weight modified polyphenylene ether oligomer with vinyl end groups available from SABIC.

[0102] NISSO-PB (B-3000): 1,2-polybutadiene homopolymer available from Nippon Soda Polyflon MPA FA-5601 (flame retardant additive), available from Daikin Industries, FP-2500S (nitrogen-phosphorus flame retardant) available from Adeka.

[0103] The samples were prepared in two ways: i) In the first method, HSBC or a thermoplastic elastomer composition made from HSBC was compressed into a 2 mm plate under high pressure at 180°C; ii) In the second method, a layer of the curable composition was obtained by preparing the curable composition in a solvent, pouring it into a tray, and subsequently drying it under vacuum at 60°C for 4 hours. The samples were prepared using HSBCT. g Further drying at temperatures above 1000 K may be possible without reaching conditions that result in premature curing.

[0104] Example 1 - Preparation of Polymer 1 To a stainless steel reactor were added 6 liters of purified and dried cyclohexane, 62 ml of 0.45M sec-BuLi, and 241.5 g of dried pMeS at 65 °C. The reaction was allowed to proceed for 21 minutes, and a sample was taken (first). Next, 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), and 488.5 g of 1,3-butadiene and 197.4 g of pMeS were added at 88 and 11 minutes, respectively, and the reaction was allowed to proceed for 11 minutes. A small sample was taken (third), and 6.7 g of 1,3-butadiene was added. 1.6 ml of methyltrimethoxysilane (MTMS) was added at intervals of 2 to 12 minutes, and the temperature was raised to 70 °C. The reaction was allowed to proceed for 40 minutes, and then quenched with 0.8 ml of 2-ethylhexanol (fourth).

[0105] 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, which correspond to the complete polymerization stage.

[0106] A sample was taken, and the polymer solution was transferred to a hydrogenation reactor, where the poly-1,3-butadiene block was hydrogenated to a conversion level of 99 mol% using a homogeneous cobalt catalyst at 40 barg and 75°C for 5 hours. The solution was washed to remove the catalyst and stabilized with an antioxidant. The polymer was recovered from the solution by steam coagulation, after which the product was crushed and dried at 50-80°C.

[0107] Examples 2-5 (Polymer 2, Polymer 3, Polymer 4, and Polymer 5) were produced based on the procedure of Example 1, but using different amounts of components. 600-900 kg of purified and dried cyclohexane was charged to a reactor along with 2-3 kg of a 10-15 wt % solution of sec-BuLi. 30-50 kg of dry pMeS was added to the reactor at a temperature range of 40-50°C. The reaction was allowed to proceed for 50-60 minutes, and a sample was taken. Next, 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. This was followed by the addition of 75-125 kg of 1,3-butadiene over 60-120 minutes, and 25-45 kg of pMeS over 12-18 minutes. The reaction was allowed to proceed for 12-18 minutes, and a small sample was taken, and 1.2-3 kg of 1,3-butadiene was added. For polymers 2, 3, and 4, this was followed by the addition of 80-270 kg of MTMS at a temperature of 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, after which it was stopped by adding 8-11 ml of methanol. These polymers were hydrogenated using the same procedure as in Example 1. The RU levels of the products obtained in the hydrogenation step are reported in Table 2.

[0108] Molecular weight data are shown in Tables 2 and 3. Polymer 1, Polymer 3, and Polymer 4 exhibit high levels of hydrogenation in the polymerized diene units, resulting in RU levels of less than 0.3 meq / g. This high level of hydrogenation provides good resistance for applications under outdoor conditions, especially with respect to thermal oxidation and UV weathering resistance.

[0109] Example 6 is a linear poly(paramethylstyrene) having an Mp of 23 kg / mol. Example 7 is a hydrogenated block copolymer having terminal poly(paramethylstyrene) rigid blocks and a hydrogenated polybutadiene central rubbery block. Example 8 is a hydrogenated block copolymer having terminal polystyrene rigid blocks and a hydrogenated poly(butadiene-co-styrene) rubbery central block. Examples 6, 7, and 8 all lack a "Block B."

[0110] In Table 4, Examples 2-5 show that HSBC has low viscosity in both the melt and in solution. Example 5 shows a very low solution viscosity. Example 7, despite having a relatively low Mp, has a significantly higher viscosity in both the melt and in solution, making this polymer less than satisfactory for various applications.

[0111] The mechanical properties of the prepared polymers are summarized in Table 5. Examples 3 and 4 show high tensile strengths of 20 MPa or more and DMA rubber transition temperatures above -30°C. Example 7 shows low DMAT values ​​below -30°C. g , which is not very desirable for applications such as copper clad laminates.

[0112] In Table 6, the homopolypropylene (PP) used has a melt flow rate (MFR) of 12 g / 10 min at 230°C and a load of 2.16 kg according to ASTM D1238. Example 9 shows desirable flame resistance with a UL-94V-0 rating. Example 10, based on polymer 8 without block B, shows only a UL-94V-2 rating with longer burn times t1 and t2.

[0113] Table 7 shows the curing agents used, the MDR properties measured during cure, and the solvent resistance of HSBC after cure; gel % and swelling ratio are calculated by PCGT. All polymers were cured in the presence of peroxide in an MDR instrument at 180°C for 30 minutes in the absence of air. Examples 13-15 demonstrate high cure 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 at higher peroxide contents. Examples 17, 19, and 20 did not cure properly, resulting in very low gel content and undesirably poor solvent resistance after cure. Example 14 exhibits a Dk of 2.31 and a Df of 0.0006 measured at 10 GHz.

[0114] In Table 8, cured composition Examples 12 and 15 show excellent modulus retention from above 100°C up to 250°C, except for Example 20, which shows a significant drop in modulus above 150°C. The modulus reached at 200°C is close to that obtained for the corresponding uncured HSBC Polymer 8. All examples show good thermal degradation behavior with TGA 10% loss temperatures close to 400°C.

[0115] Table 9 shows examples of compositions that can be cured efficiently, as indicated by the significant maximum torque generated during MDR curing. The use of a co-curing agent allows for reduced swelling of the cured samples in toluene, as indicated by the significant change in the swelling ratio of the cured samples containing the co-curing agent. Cured compositions Examples 23, 27, 29, and 30 exhibited very low swelling in solution. The data also show that higher gel content can be achieved by using a co-curing agent. The cured compositions of Examples 22, 23, 28, and 29 exhibit Dk values ​​of 2.39, 2.38, 2.32, and 2.4, respectively, and Df values ​​of 0.0007, 0.0013, 0.0008, and 0.0019, respectively, measured at 10 GHz.

[0116] Figure 1 shows the DMA of Polymer 4 and the composition of Example 15 made from Polymer 4 cured with 1% DCP. Both examples show similar performance at temperatures below 100°C. The behavior of both samples is very different above 100°C. Above 100°C, the elastic modulus G' of Polymer 4 decreases significantly by more than 20 between 100°C and 200°C, indicating a rapid loss of cohesion with increasing temperature. Above 100°C, the tangent delta of Polymer 4 increases rapidly, reaching values ​​above 1 at temperatures above 130°C. This indicates that the Polymer 4 sample becomes more viscous than elastic above 130°C and turns into a viscous molten polymer. On the other hand, the cured composition containing Polymer 4 (Example 15) shows a stabilized elastic modulus G' of approximately 50-100 kPa up to 250°C. Above 100°C, the cured composition maintains a tangent delta of less than 1, indicating predominantly elastic behavior.

[0117] Table 10 shows the properties of HSBC (Polymers 4 and 5) and the cured composition of HSBC obtained therefrom using 0.5% BIPB (Example 14). Dielectric measurements were performed on the samples at 1 GHz and 10 GHz at 23°C and 50% humidity.

[0118] The dielectric properties of the cured compositions based on Polymer 4 are shown in Table 11. The dielectric properties were measured at 10 GHz. Lower Dk and Df values ​​were observed for Example 34, which contained a cured composition with a higher amount of Polymer 4.

[0119] [Table 2]

[0120] As used herein, the term "comprising" means including the elements or steps identified after the term, but such elements or steps are not exhaustive and embodiments may include other elements or steps. Although the terms "comprising" and "including" are used herein to describe various aspects, more specific aspects of the disclosure can and are disclosed by using the terms "consisting essentially of" and "consisting of" instead of "comprising" and "including."

[0121] [Table 3]

[0122] [Table 4]

[0123] [Table 5]

[0124] [Table 6]

[0125] [Table 7]

[0126] [Table 8]

[0127] [Table 9]

[0128] [Table 10]

[0129] Table 11

Claims

1. A hydrogenated block copolymer comprising at least one polymer block A and at least one polymer block B, Before hydrogenation, each block A is a polymer of a first vinyl aromatic compound; Each block B is (a) a styrene compound having a radical reactive group and represented by any one of formulas (I) to (IV) or a combination thereof; [In the formula, R1 = H or CH3; R2=H, and R2' = H or a monovalent alkyl group. (b) at least one conjugated diene; is a copolymer block of monomer units of each block A has a peak molecular weight (Mp) of 3 to 60 kg / mol, and each block B has a peak molecular weight (Mp) of 20 to 200 kg / mol; the polymerized units derived from the monomer unit (a) constitute 10 to 70 wt % of the total weight of the hydrogenated block copolymer and 10 to 80 wt % of the total weight of the block B; After hydrogenation, the polymerized units derived from monomer unit (b) have 0 to 1.5 meq of residual olefinic unsaturation per gram of hydrogenated block copolymer; The hydrogenated block copolymer is i) Tangent delta peak maximum temperature between -30 and 80°C at DMA 10 rad / s; ii) after curing, a gel content of >40 wt. % of the total weight of the hydrogenated block copolymer; The gel content is measured by the peroxide cured gel test (PCGT), in which the hydrogenated block copolymer is mixed with 0.5 wt % of bis-(t-butylperoxyisopropyl)benzene initiator, cured at 180°C for 30 minutes, weighed to obtain the initial weight (Wi), soaked in toluene for 1 day, filtered, and dried under vacuum at 60°C to a constant weight (Wd), with the gel content calculated as Wd / Wi ​​x 100; and iii) having an aromatic blockiness index of 20 to 80%; Hydrogenated block copolymer.

2. Each block B comprises (c) a second vinyl aromatic compound that is the same as or different from the first vinyl aromatic compound in block A.

10. The hydrogenated block copolymer of claim 1, further comprising:

3. The monomer unit (a) is paramethylstyrene and the monomer unit (b) is selected from the group consisting of isoprene, butadiene, and combinations thereof; Block B has a corrected 1,4-diene unit content of 10 to 55%; The corrected 1,4-diene unit content (C14DUC) is calculated by the following formula (1): C14DUC=(Bw×B14 / 100)+Iw×(I14-40) / 100 (1) [In the formula, Bw is the weight % of butadiene units in the total diene units of the block, B14 is the weight % of 1,4-addition units in the butadiene units, Iw is the weight % of isoprene units in the total diene units of the block, and I14 is the weight % of 1,4-addition units in the isoprene units. The hydrogenated block copolymer is i) a dielectric constant (Dk) of <2.6 at 1 GHz; ii) a dielectric constant (Dk) of <2.6 at 10 GHz; iii) a loss tangent (Df) of <0.002 at 1 GHz; iv) a loss tangent (Df) of <0.002 at 10 GHz; and v) a solution viscosity of <2000 cP at 25 wt % in toluene at 25°C having one or more of: The hydrogenated block copolymer of claim 1 .

4. 4. The hydrogenated block copolymer of claim 1, wherein block A comprises polymerized para-methylstyrene units, monomer unit (a) of the B block is para-methylstyrene, and the weight percentage of (a) para-methylstyrene in the B block is 10 to 50 wt %, based on the total weight of the hydrogenated block copolymer.

5. Block B has a corrected 1,4-diene unit content of up to 50%; the polymerized units derived from monomer unit (b) have 0 to 0.3 meq of residual olefinic unsaturation per gram of hydrogenated block copolymer; the hydrogenated block copolymer has an aromatic blockiness index of 40% to 75% and a solution viscosity at 25 wt% in toluene at 25°C of <1000 cP; The hydrogenated block copolymer according to any one of claims 1 to 3.

6. The hydrogenated block copolymer of any one of claims 1 to 3, wherein the hydrogenated block copolymer has a DMA crossover temperature of 100 to 300°C.

7. The hydrogenated block copolymer may be AB, ABA, (AB-) ｎ X, A-B-A-B, (B-A-B-) ｎ X, (B-A-) ｎ X and (A-B-A-) ｎ 4. The hydrogenated block copolymer of claim 1, comprising one or more structures of X, where X is a coupling agent residue and n is 1 to 30.

8. The hydrogenated block copolymer of any one of claims 1 to 3, further comprising a functional group bonded to the radical reactive group of the styrene compound of the monomer unit (a).

9. 1. A curable composition comprising: (a) 1 to 99 wt. % of the hydrogenated block copolymer of any one of claims 1 to 3, and (b) 0.1 to 5 wt. % of an initiator selected from thermal initiators and photoinitiators, based on the total weight of the composition. A curable composition comprising:

10. one or more co-curing agents selected from 1,2-bis(vinylphenyl)ethylene, butadiene-based liquid rubbers, divinyl aromatic compounds, triallyl cyanurate, triallyl isocyanurate, vinyl-functionalized polyphenylene oxide, bismaleimide aromatic resins, mono- or polyfunctional acrylate or methacrylate monomers, plasticizers, tackifying resins, styrene block copolymers containing one or more polydiene blocks, and combinations thereof; flame retardants, and a solvent selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, and combinations thereof; The curable composition of claim 9 further comprising:

11. 11. The curable composition of claim 9 or 10, further comprising a polyolefin, wherein the curable composition is cured in the melt phase.

12. 99 to 1 wt. % of the hydrogenated block copolymer of any one of claims 1 to 3, and 1 to 99% by weight of a crystalline polyolefin A blend containing

13. 13. The blend of claim 12, comprising 10 to 50 wt. % of the hydrogenated block copolymer, 1 to 20 wt. % of the crystalline polyolefin, and 20 to 50 wt. % of the flame retardant, wherein the blend has a V0 rating according to the UL 94 vertical flame test method.

14. A cured composition obtainable by curing the blend of claim 12 or 13.

15. 4. A curable composition comprising 100 parts of the hydrogenated block copolymer of any one of claims 1 to 3 and 0.5 parts of a peroxide initiator, wherein the curable composition, after curing at 180°C for 2 hours and compression molding, has a Dk of <3.5 at 1 GHz and a Df of <0.003 at 1 GHz.

16. 4. A curable composition comprising 100 parts of the hydrogenated block copolymer of any one of claims 1 to 3 and 0.5 parts of a peroxide initiator, wherein the curable composition, after curing at 180°C for 2 hours and compression molding, has a Dk of <2.6 at 10 GHz and a Df of <0.003 at 10 GHz.

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