Fully hydrogenated branched styrenic block copolymer

Abstract

To provide a fully hydrogenated branched block copolymer (f-HbBC).SOLUTION: The f-HbBC comprises a mixture of radial block copolymers having a general structure of (S-B)nX(s-B)m, (s-B)zX, and mixtures thereof. Prior to hydrogenation, each block S and "s" is a polymer block of a vinyl aromatic monomer, and the block B is a polymer block of a conjugated diene monomer. The mixture of radial block copolymers comprises at least 70 wt.% of a poly(vinylcyclohexane) content, and less than 30 wt.% of a hydrogenated polymer block of a conjugated diene monomer. One or more radial block copolymers in the mixture have a molecular weight of at least 120 kg / mol, and at least 60% of radial block copolymers in the mixture have a molecular weight greater than 100 kg / mol. The mixture contains less than 40 wt.% of the (s-B)zX structure. The f-HbBC has Tg higher than 145°C and a polydispersity index greater than 1.20.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present disclosure relates to fully hydrogenated branched block copolymers, their preparation methods and uses. [Background technology]

[0002] Branched multimodal (or multimodal) polymers, including asymmetric branched polymers having high and low molecular weight (MW) portions of monovinyl-substituted aromatic blocks designed for articles with low haze, high flexural modulus, and high hardness, are known in the art. Vinyl aromatic polymers have higher glass transition temperatures (T) than their corresponding unhydrogenated polymers. g To further strengthen these materials, hydrogenated block copolymers of vinyl aromatics and conjugated dienes have been developed. However, the higher T g And polymeric materials having relatively low haze values ​​remain desirable. Summary of the Invention [Problem to be solved by the invention]

[0003] (Summary) There remains a need for block copolymers, especially fully hydrogenated branched block copolymers, with high hydrogenation levels and improved processability, mechanical and optical properties. [Means for solving the problem]

[0004] In one embodiment, the present disclosure provides (SB) n X(sB) m , (sB) zThe present invention relates to a fully hydrogenated branched block copolymer (f-HbBC) comprising, consisting essentially of, or consisting of a mixture of radial block copolymers having the general structure of X and mixtures thereof. Prior to hydrogenation, each block S and "s" is independently a polymer block of a vinyl aromatic monomer, each block B is a polymer block of a conjugated diene monomer, and X is a residue of a coupling agent, where m>n, n≧1, m=1-20, z=2-4, and m+n≧3. After hydrogenation, the radial block copolymer exhibits multiple peaks in a GPC curve. The mixture comprises at least 70% by weight poly(vinylcyclohexane) content and less than 30% by weight hydrogenated polymer blocks of conjugated diene monomers, based on the total weight of the mixture. At least 60% of the radial block copolymers in the mixture have a molecular weight (M) of >100 kg / mol. p ), and the remainder have molecular weights (M p At least 30% of the radial block copolymers in the mixture have a molecular weight (M) of at least 100 kg / mol. p ), and the remainder have molecular weights (M p ) Less than 40% by weight of the mixture is (sB) z X. f-HbBC has a polydispersity index of >1.20, a glass transition temperature (T g ), MFR >0.1g / 10min measured at 260°C with a load of 5 kg, and at least 20kJ / m2 measured at 25°C 2 It has an unnotched Charpy impact strength of

[0005] In a second embodiment, the mixture (sB) z (SB) for radial block copolymers having the structure of X n X(sB) m The weight ratio of the radial block copolymer having the structure is 1:1 to 20:1.

[0006] In a third embodiment, the at least one radial block copolymer has a molecular weight (M p ).

[0007] In a fourth embodiment, the mixture of radial block copolymers comprises 60-80% of >100 kg / mol molecular weight (M p ) and 20-40% of the radial block copolymers have a molecular weight (M p ) radial block copolymers. [Brief description of the drawings]

[0008] [Figure 1] FIG. 1 is a gel permeation chromatography (GPC) curve of one embodiment of f-HbBC having a mixture of radial block copolymers, with different structures represented by multiple modes (peaks) in the GPC curve. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] The following terms are used throughout this specification.

[0010] "Consisting essentially of" means that the claimed composition contains primarily the specified material, but allows for additional ingredients that do not materially affect the novel features or function of the claimed invention, if any, in amounts of <30%, or <20%, or <10%.

[0011] "At least one of [a group, such as A, B, and C]" or "any of [a group, such as A, B, and C]" means a single member of the group, more than one member of the group, or a combination of members of the group. For example, at least one of A, B, and C includes, for example, only A, only B, or only C, as well as A and B, A and C, B and C; or A, B and C, or any and all other combinations of A, B, and C. In another example, at least one of A and B means only A, only B, and A and B.

[0012] A list of embodiments presented as "A, B, or C" should be interpreted as including embodiments of A only, B only, C only, "A or B," "A or C," "B or C," or "A, B, or C."

[0013] "Either A, B, or C" means one option among A, B, or C.

[0014] "Any of A, B, and C" means one or more of the options A, B, and C.

[0015] "Vinyl content" means the content of conjugated dienes that have polymerized via 1,2-addition in the case of butadiene, or 3,4-addition in the case of isoprene, resulting in monosubstituted olefin or vinyl groups adjacent to the polymer backbone. Vinyl content may be measured by proton NMR.

[0016] The "coupling efficiency", designated as %CE, is calculated using the values ​​of weight percent coupled polymer and weight percent uncoupled polymer. The weight percent of coupled and uncoupled polymer is measured using the output of a differential refractive index detector. The intensity of the signal at a particular elution volume is proportional to the amount of material of the molecular weight corresponding to the polystyrene standard detected in that elution volume. The area under the curve spanning the MW range corresponding to the coupled polymer represents the weight percent of the coupled polymer, and similarly for the uncoupled polymer. The %CE is given by 100 x (weight percent coupled polymer / weight percent coupled polymer + weight percent uncoupled polymer). Coupling efficiency can also be measured by calculating the data from the GPC and dividing the integrated area under the GPC curve of all coupled polymers (including 2-arm, 3-arm, 4-arm, etc. copolymers) by the integrated area under the GPC curve of both coupled and uncoupled polymers.

[0017] "Hydrogenation level" refers to the percentage of original unsaturated bonds that become saturated upon hydrogenation. The hydrogenation level of hydrogenated vinyl aromatic polymers can be measured using proton NMR. The hydrogenation level of hydrogenated diene polymers can be measured using proton NMR.

[0018] The "polystyrene content" or PSC of a block copolymer means the weight percent of vinyl aromatic, e.g., polystyrene, in the block copolymer, calculated by dividing the sum of the molecular weights of all vinyl aromatic blocks by the molecular weight of the entire block copolymer. PSC can be measured using any suitable method, such as proton NMR.

[0019] "Poly(vinylcyclohexane) content" or "PVCH content" means the weight percent of vinylcyclohexane in a block copolymer. Vinylcyclohexane is formed within the block copolymer by hydrogenation of the vinyl aromatic blocks. PVCH content is calculated by summing the molecular weights of all vinylcyclohexane blocks divided by the molecular weight of the entire block copolymer. PVHC content may be measured by proton NMR.

[0020] "Molecular weight" or MW means the styrene equivalent molecular weight in kg / mol of a polymer block or block copolymer. MW may be measured by gel permeation chromatography (GPC) using polystyrene calibration standards, for example as performed according to ASTM D5296. The GPC detector can be an ultraviolet or refractive index detector or a combination of these. The chromatograph is calibrated using commercially available polystyrene molecular weight standards. The MW of a polymer measured using a GPC so calibrated is the styrene equivalent molecular weight or apparent molecular weight. The MW given herein is measured at the peak of the GPC trace and is generally expressed as the M p The styrene equivalent "peak molecular weight" is expressed as

[0021] The "polydispersity index" or PDI of a polymer is the degree of distribution of the molecular weights of the polymer as a measure of the range of sizes of the polymer chains. PDI is calculated by dividing the weight average molecular weight (M w ) and number average molecular weight (M n ) is calculated as the ratio of PDI=M w / M n .

[0022] "Radial" means, and is used interchangeably with, a star-shaped, symmetrically branched, or dissimilarly branched, or asymmetrically branched configuration.

[0023] The present disclosure relates to fully hydrogenated branched block copolymers (f-HbBCs) that are characterized by, among other features, excellent high temperature resistance and optical properties (e.g., haze <10%).

[0024] (Fully Hydrogenated Branched Block Copolymer (f-HbBC)) f-HbBC is (SB) n X(sB) m , (sB) z X and mixtures of radial block copolymers having the general structure of mixtures of these, i.e., some radial copolymers are (SB) n X(sB) m Some have the structure (sB) z X, where X is a residue of a coupling agent. The designations "n", "m" and "z" refer to the number of "arms" or "branches" in each of the structures. In embodiments, m>n, (m+n) is ≧3, and z ranges from 2 to 4, and n≧1, m>0, m≧n. In embodiments, (m+n) is ≧3, and z ranges from 3 to 4.

[0025] In some embodiments, each of (SB) n X(sB) m Or (sB) z X independently has a number of arms (branches) ranging from 2 to 25, or 2 to 20, or 2 to 15, or 2 to 10, or 2 to 7.

[0026] In some embodiments, the structure (SB) n X(sB) m The radial block copolymers having the formula: have m=n, the value of which ranges from 1-20, or 2-15, or 3-10, or 4-8.

[0027] In some embodiments, the structure (SB) n X(sB) m is present in an amount of 50-80, or 50-70, or 55-65, or >50, or <75 wt%, based on the total weight of the radial block copolymer, and n=1-2, m=1-3, with the proviso that m+n=2-4.

[0028] In some embodiments, the f-HbBC is a distribution of other arms, e.g., (sB) 4 , (sB) 3 , (sB) 2 etc., and the uncoupled arms (eg, SB and / or sB) in an amount of 15-25, or 15-20, or 10-15, or 8-12, or <25% by weight based on the total weight of the f-HbBC.

[0029] In some embodiments, structure (sB) where z=2 to 4 z The radial block copolymer having X is present in an amount of 20-40, or 20-35, or 20-30, or <40, or <35, or <30 weight percent based on the total weight of the radial block copolymer.

[0030] In some embodiments, the combination (SB) n X(sB) m and (sB) z The radial block copolymer having the X structure is present in an amount of >70, or >75, or 70-85, or 75-85, or 70-80 weight percent based on the total weight of the radial block copolymer.

[0031] In some embodiments, f-HbBC is in the range of 1:1 to 20:1, or 1.5:1 to 15:1, or 1.8:1 to 10:1, or 2:1 to 5:1, or 2.2:1 to 4:1, or >1 or >1.5. m (sB) z (SB) for X n X(sB) by weight.

[0032] In embodiments, prior to hydrogenation, each block S and "s" is independently a polymer block of a vinyl aromatic monomer and each block B is a polymer block of a conjugated diene monomer.

[0033] In embodiments, the vinyl aromatic monomer is selected from the group consisting of styrene, ortho-methylstyrene, para-methylstyrene, para-ethylstyrene, para-n-propylstyrene, para-iso-propylstyrene, para-tert-butylstyrene, 2,4-dimethylstyrene, alpha-methylstyrene, vinylnaphthalene, vinyltoluene, vinylxylene, isomers of para-decylstyrene, isomers of para-dodecylstyrene, and mixtures thereof.

[0034] In embodiments, the conjugated diene monomer is selected from the group consisting of isoprene, 1,3-butadiene, 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.

[0035] In embodiments, the radial block copolymer blend comprises a poly(vinylcyclohexane) (PVCH) content in an amount of at least 70 or >75 or >80 or >85 or <95 or 70-95 or 70-85 or 70-80 weight percent based on the total weight of the blend. The PVCH content is the result of hydrogenation of blocks S and "s". In embodiments, the radial block copolymer blend comprises hydrogenated polymer blocks of conjugated diene monomers in an amount of <30 or <25 or <20 or 5-30 or 10-25 or 15-30 or 1-20 weight percent based on the total weight of the blend.

[0036] In embodiments, the f-HbBC has a coupling efficiency (CE) of 70-90%, or 72-85%, or 70-80%, or >70%, or <90%.

[0037] In embodiments, the mixture of radial block copolymers has a molecular weight (M) of at least 120, or >130, or >140, or >145, or from 120 to 250, or from 130 to 220, or from 140 to 200 kg / mol as measured by GPC and / or h-NMR. p ), the remainder having a molecular weight (M p ).

[0038] In embodiments, the mixture of radial block copolymers has a molecular weight (M) of >100, or >105, or >110, or >120, or >140, or from 100 to 700, or from 120 to 680 kg / mol. p In embodiments, the mixture of radial block copolymers comprises at least 60% or >65% or >68% or >70% or 60-80% radial block copolymers having a molecular weight (M) of <100 kg / mol or <95 or <90, <85 or <80, 5-100, 6-90, 10-85, or 5-80 kg / mol. p ) in an amount of ≦40% or <35% or <32% or <30% or 20-40%.

[0039] In some embodiments, block S is selected from the group consisting of block “s” and block “s” with molecular weight (M p ) higher molecular weight (M p In some embodiments, the block S has a molecular weight (M) of 100-150, or 105-145, or 110-140, or 100-140, or 110-150, or 110-130, or 110-120 kg / mol prior to hydrogenation. p In some embodiments, block "s" has a molecular weight (M) of 5-15, or 6-14, or 7-12, or 8-11, or >5, or <13 kg / mol prior to hydrogenation. p ).

[0040] In embodiments, the f-HbBC has a vinyl content of 30-80, or 35-75, or 40-70, or 45-65, or 50-60, or >35, or <75% by weight based on the total weight of the f-HbBC, before and after hydrogenation. It should be noted that the vinyl content does not change significantly due to the hydrogenation process (e.g., changes by <10% compared to the value before hydrogenation).

[0041] In some embodiments, f-HbBC is fully hydrogenated, i.e., each block S and "s" has a hydrogenation level of >90%, or >92%, or >95%, or >97%, or >98%, or >99%, or up to 100%. After hydrogenation, the polymerized blocks S and "s" become poly(vinylcyclohexane) (PVCH). Each block B has a hydrogenation level of >90%, or >92%, or >95%, or >97%, or >98%, or >99%, or up to 100%.

[0042] In embodiments, the f-HbBC has a total polystyrene content (PSC) before hydrogenation and a total PVCH content after hydrogenation of at least 70 or >75 or >80 or >85 or <95 or 70-95 or 70-85 or 70-80 wt%.

[0043] In some embodiments, the f-HbBC has a molecular weight (M p ).

[0044] In embodiments, the f-HbBC has a polydispersity index (PDI) as measured by GPC of >1.20, or >1.40, or >1.50, or >1.70, or >1.80, or between 1.20 and 3.0, or between 1.30 and 2.80, or between 1.50 and 2.50, or between 1.60 and 2.0.

[0045] (Method of preparing f-HbBC) f-HbBC can be prepared by the sequential (or consecutive) polymerization of monomers in solution (in a solvent) in the presence of an initiator, stepwise addition of monomers and initiator, followed by coupling of the resulting block copolymer with a coupling agent, and a final hydrogenation step.

[0046] It should be noted that f-HbBC may also be prepared by making the radial block copolymers separately according to the process steps described above and then blending or mixing them together in solution or solid form to form an f-HbBC with similar properties to an f-HbBC in which all the radial block copolymers were made in situ in one pot.

[0047] In some embodiments, the f-HbBC structure (SB) n X(sB) m Block(S) n First, the desired M block is formed by a step-growth polymerization in a reaction with one or more polymerization initiators, optionally with the addition of vinyl aromatic monomers. p At the same time, ((sB) mThe second initiator feed is added after polymerization of the first styrene feed, but before or simultaneously with the addition of the second styrene feed.

[0048] After essentially all of the styrene monomer has been consumed and a polystyrene block of the desired molecular weight has been obtained, a conjugated diene monomer is introduced. Polymerization continues and the vinyl aromatic / (alpha-alkylstyrene) copolymer block segment is reacted with the conjugated diene monomer (and in turn, optionally a vinyl aromatic monomer) to form intermediate block copolymers having structures (SB) and (sB). At this point, coupling is utilized by introduction of a suitable coupling agent to produce a coupled polymer mixture (SB). n X(sB) m and (sB) z This can lead to the formation of X.

[0049] The process conditions for the sequential polymerization steps are similar to those used in anionic polymerization, preferably from -30°C to 150°C, or 10°C to 100°C, or 30°C to 90°C, in an inert atmosphere, e.g., nitrogen, or at a pressure of 0.5 to 65 bar. The polymerization reaction can last from 5 minutes to 5 hours or <12 hours, depending on factors including temperature, monomer concentration, molecular weight of the polymer, etc.

[0050] After completion of the coupling reaction, the polymerization reaction mixture is optionally treated with a proton donor terminating agent, such as water, carbon dioxide, hydrogen, an alcohol, a phenol, or a linear saturated aliphatic mono- or di-carboxylic acid, to react with the polymer initiator prior to hydrogenation.

[0051] In embodiments, the polymerization is typically carried out in the presence of a solvent, such as an ether, benzene, toluene, xylene, ethylbenzene cyclohexane, methylcyclohexane, etc. In embodiments, a mixed solvent system is used with a saturated hydrocarbon and a linear or cyclic ether.

[0052] In embodiments, the amount of solvent used in the polymerization step is from 50 to 90 weight percent, based on the total weight of the monomer / solvent mixture.

[0053] In some embodiments, copolymerization modifiers are used to increase the vinyl content in the polymer to a desired level. Modifiers serve to improve the efficiency of comonomer incorporation during copolymerization. Examples include polar modifiers such as dimethyl ether, diethyl ether, ethyl methyl ether, ethyl propyl ether, etc., and chelating polar modifiers such as, but not limited to, diethoxypropane (DEP), 1,2-dioxy-ethane (dioxo), 1,2-dimethoxy-ethane, and ortho-dimethoxy-benzene (ODMB), etc. The amount of modifier required depends on the type, for example, non-chelating polar modifiers such as diethyl ether (DEE) are typically most effective at relatively high levels of 2-20 or 4-8 wt.% based on the weight of the solvent plus modifier. If a chelating polar modifier such as DEP or ODMB is used, it is used in a lower amount of 50-1000 ppm, or 400-1000 ppm, or 500-700 ppm.

[0054] Examples of polymerization initiators include organomonoalkali metal compounds "RM" where R is an alkyl, cycloalkyl or aryl group containing 4 to 8 carbon atoms, such as n-butyl, and M is an alkali metal, such as lithium, including alkyllithium compounds and other organolithium compounds, such as s-butyllithium, n-butyllithium, t-butyllithium, amyllithium, and the like, including diinitiators such as the di-sec-butyllithium adduct of m-diisopropenylbenzene. In embodiments, the initiator is s-butyllithium and / or n-butyllithium. In embodiments, the initiator is used in an amount of 0.002 to 5, or 0.005 to 4.5, or 0.01 to 4, or 0.015 to 3.8, or 0.02 to 3.5 weight percent based on the total weight percent of the monomers being polymerized.

[0055] Examples of coupling agents include, among others, di- or multivinylarene compounds, di- or multiepoxides, di- or multiisocyanates, di- or multialkoxysilanes, di- or multiimines, di- or multialdehydes, di- or multiketones, alkoxytin compounds, di- or multihalides, such as silicon halides and halosilanes, mono-, di- or multianhydrides, di- or multiesters, such as esters of monoalcohols with polycarboxylic acids, diesters which are esters of monohydric alcohols with dicarboxylic acids, diesters which are esters of monobasic acids with polyalcohols, such as glycerol, and mixtures of two or more such compounds. The coupling agent may be selected from divinylbenzene, dichloroethane, dibromobutane, and esters of carboxylic acids.

[0056] Examples of silane-based coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrippropoxysilane, vinyltributoxysilane, vinylethoxydimethoxysilane, vinylethoxydipropoxysilane, propenylethoxydimethoxysilane, propenylethoxydipropoxysilane, or mixtures thereof. In embodiments, the coupling agent is a tetra-alkoxysilane, such as tetra-methoxysilane, and tetra-ethoxysilane, or a tri-alkoxysilane, such as methyltrimethoxysilane.

[0057] Other examples of coupling agents include polyepoxides, polyisocyanates, polyamines, polyaldehydes, polyhalides, polyanhydrides, polyketones, polyoxyesters, polyesters, and mixtures thereof. In embodiments, the coupling agent is selected from epoxidized vegetable oils, such as epoxidized soybean oil, such as acrylated epoxidized soybean oil, epoxidized linseed oil, and mixtures thereof.

[0058] In embodiments, the coupling agent is used in an amount of from 1 to 15, or from 2 to 14, or from 3 to 12, or from 5 to 10, based on the total weight of the monomers polymerized.

[0059] After the sequential polymerization, the polymer is hydrogenated in the presence of a hydrogenation catalyst at a temperature of <350° C. or <250° C. or <100° C. or >50° C. and a hydrogenation pressure of 500-900 or <1000 or >450 psig.

[0060] In embodiments, the hydrogenation reaction is carried out in the same solvent or a different solvent than that used in the polymerization reaction. Typically, the polymer solution obtained from the polymerization step is further diluted with additional solvent prior to hydrogenation to a weight of polymer in solvent of 5 to 50 or 10 to 40 weight percent, based on the total weight of the solution before hydrogenation.

[0061] In embodiments, hydrogenation occurs in the absence of a catalytic modifier until >90% of the aliphatic unsaturation has been reduced and <30% of the aromatic unsaturation has been reduced. At this point, in embodiments, a catalytic modifier, such as a Lewis base, a weak organic acid, an alcohol, an amine, or the like, is added and hydrogenation continues at elevated temperatures of 100-200° C. or 175-225° C. and pressures of ≧1000, 1100-2000, or 1200-1800 psig until >40% or >75% of the aromatic unsaturation has been reduced. After completion of the hydrogenation step, >95% or >98% or >99% of the aliphatic unsaturation has been reduced and at least 40% of the aromatic unsaturation has been reduced. In embodiments, a hydrogenation level of >95% of each block B, S, and “s” is independently obtained.

[0062] After the hydrogenation period is over, the catalyst residues can be removed either by extraction, precipitation, filtration or other means. The hydrogenation mixture is then processed to recover the f-HbBC, such as by flashing off the solvent or coagulating the polymer with steam and / or hot water.

[0063] Examples of hydrogenation catalysts include transition metal catalysts, such as nickel, cobalt, or combinations thereof. The catalyst can be any heterogeneous catalyst present as dispersed submicron or colloidal particles, or a homogeneous catalyst. In some embodiments, the catalyst is prepared by combining a nickel or cobalt carboxylate or alkoxide with an alkyl or hydride of a metal selected from Groups IA, II-A, and III-B of the Periodic Table of the Elements ("cocatalyst"). In some embodiments, the catalyst is formed by reacting a cobalt or nickel carboxylate with another metal alkyl, such as Li alkyl, including n-butyllithium and sec-butyllithium, or a metal hydride, such as lithium hydride and lithium aluminum hydride. The reaction results in the formation of submicron particles that remain suspended in the solvent indefinitely, like a colloidal suspension.

[0064] Examples of aluminum alkyl compounds are those of formula R n ALY 3-nwherein R is C 1 ~C 10 Or C 2 ~C 8 and Y is hydrogen or R 2 where R 2 is different from R 1 ~C 10 and n is 1 to 3. In embodiments, the aluminum alkyl compound is a trialkylaluminum compound. In embodiments, the aluminum alkyl compound has a molar ratio of aluminum to cobalt of 1:1 to 20:1, or 1:1 to 5:1, or 1:1 to 2:1.

[0065] Examples of soluble nickel or cobalt compounds include nickel carboxylates, such as nickel octanoate, nickel stearate, nickel decanoate, nickel acetylacetanoate, nickel naphthenate, nickel octanoate; and cobalt carboxylates, such as cobalt stearate, cobalt octanoate, and cobalt versatate. In some embodiments, the catalyst used is a cobalt and nickel (nick) catalyst, such as a mixture of cobalt carboxylates and nickel carboxylates. In some embodiments, a cobalt catalyst is used, and the amount of cobalt is at least 10%, or 25-75%, or at least 50%, based on the total molar amount of metal present in the hydrogenation catalyst.

[0066] In embodiments, the hydrogenation catalyst is prepared by contacting a Group 8-10 metal compound with one or more aluminum alkyls in a suitable solvent at a temperature of 20-100° C. for 1-120 minutes. Suitable solvents include aliphatic hydrocarbons such as hexane, heptane, octane, etc., alicyclic hydrocarbons such as cyclopentane, cyclohexane, etc., alkyl-substituted alicyclic hydrocarbons such as methylcyclopentane, methylcyclohexane, methylcyclooctane, etc., aromatic hydrocarbons such as benzene, hydroaromatic hydrocarbons such as decalin, tetralin, etc., alkyl-substituted aromatic hydrocarbons such as toluene, xylene, etc.

[0067] (Characteristics of f-HbBC) In some embodiments, f-HbBC has a T of >145° C., or >150° C., or >155° C., or >160° C., or 145-200° C., or 150-190° C., or 155-180° C., or 160-190° C. as measured by DMA according to ASTM 4065. g has.

[0068] In embodiments, the f-HbBC has a melt flow rate (MFR) of >0.1 or >0.5 or <10 or 0.1-35 or 0.5-25 or 1-20 or 1.5-15 or 0.5-10 g / 10 min as measured according to ASTM D1238 at 260° C. with a 5 kg load.

[0069] In embodiments, the f-HbBC has a VICAT softening point of >125°C, or >130°C, or 125-180°C, or 130-160°C, or 125-150°C, as measured according to ASTM D1525.

[0070] In embodiments, the f-HbBC has a flexural modulus of at least 1500, or >1600, or >1700, or 1500-3000, or 1550-2500, or 1600-2200, or 1650-2000, or 1600-1850 MPa as measured according to ASTM D790.

[0071] In some embodiments, the f-HbBC is at least 20, or 20-50, or 25-45, or 30-40, or 20-40, or 30-50 kJ / m as measured at 25° C. according to ASTM E23. 2 It has an unnotched Charpy impact of 0.01 mm.

[0072] In embodiments, the f-HbBC has a shrinkage (machine direction) after injection molding measured according to ASTM D955 of <4%, or <3.5%, or <3%, or <2.5%, or <2%, or 0.5-4%, or 0.6-2%.

[0073] In some embodiments, a film is prepared from the f-HbBC, hi some embodiments, the film has a thickness of 10 μm to 5 mm, or 50 μm to 3 mm, or 100 μm to 2 mm, or 1 mm to 4 mm.

[0074] In embodiments, the film has a haze measured according to ASTM D1003 of <15%, or <12%, or <10%, or <8%.

[0075] (Application) With its high optical and high temperature resistance properties, f-HbBC is particularly useful for many applications, such as optical films, lenses used in cameras, mobile phones, projectors, sensors, lighting applications such as high brightness LEDs used in TV backlighting, LCDs, traffic lights and automotive lights, and general lighting purposes. f-HbBC is also suitable for organic thin-film solar cell applications, which require excellent UV resistance. f-HbBC's high T g The high molecular weight of f-HbBC makes it suitable for high power lens applications. f-HbBC may also be used as a modifier for other polymers such as polypropylene, polyethylene, cyclic olefin polymers and copolymers, polyamides, etc. in many transparent medical device and packaging applications. Other applications include fabricated products, thermoformed products, extrusions, injection molded products, films, and foams. EXAMPLES

[0076] The following examples are intended to be non-limiting.

[0077] Example measurement methods include: Glass transition temperature (T g ) was measured by dynamic mechanical analysis (DMA) in tensile vibration mode using a TA Instruments DMA Q800 at a frequency of 1 Hz and a strain amplitude of 1% according to ASTM 4065. The T g The tan δ peak at the highest temperature represents the T g It is thought that.

[0078] The radial block copolymers in f-HbBC may be confirmed by using GPC and proton NMR. A typical GPC column is from Polymer Laboratories (PL-GPC) with a temperature range of 30-220°C and contains a multi-heater oven to control the temperature to within 0.05°C. The radial block copolymers can be seen by multiple peaks in the GPC curve (e.g., molecular weight, amount, etc.).

[0079] Ingredients used in the examples include: CE-1 is a pentablock copolymer (polycyclohexylethylene-ethylene-1-butene-polycyclohexylethylene) having 65 mol% hydrogenated polystyrene (hydrogenation level >99%) and 35 mol% hydrogenated conjugated diene polymer blocks (hydrogenation level >99%) disclosed in JP 2021-042329 A.

[0080] CE-2 is a multimodal branched block copolymer of styrene and butadiene disclosed in US Pat. No. 3,639,517.

[0081] Example 1 - Non-hydrogenated branched block copolymer precursor A non-hydrogenated branched block copolymer (or precursor polymer) was prepared as follows: 458 lbs. of cyclohexane and 89 lbs. of styrene were charged to a reactor vessel. 0.77 lbs. of an approximately 12 weight percent solution of s-butyllithium in cyclohexane was added to initiate polymerization. An additional 60 lbs. of styrene was added at a rate to maintain the reaction temperature below 60° C. After polymerization of the styrene was complete, an additional 4.65 lbs. of the s-butyllithium solution was added. The resulting solution was mixed with 77 lbs. of styrene along with a 41 lbs. cyclohexane flush to produce a population of high molecular weight chains by chain extension of the initial polystyrene block and a population of low molecular weight chains resulting from reaction with a second feed initiator.

[0082] After polymerization of the styrene feed was complete, 75 lbs. of butadiene was added and polymerized to produce a population of high molecular weight, high polystyrene content chains (SB) and lower molecular weight, lower polystyrene content chains (sB). These chains were coupled by adding 1 lb. of epoxidized soybean oil, followed by 0.03 lbs. of methanol to ensure complete termination.

[0083] Example 2 - f-HbBC Polymer 90 grams of the precursor polymer prepared in Example 1 was dissolved in cyclohexane to give a 10 wt% solution. The polymer solution and 6-9 grams of cobalt hydrogenation catalyst in cyclohexane solution were charged to a reactor. The temperature and pressure were gradually increased to 200°C and 80 psig over a 16 hour period while 27 grams of additional catalyst were added until the polystyrene conversion was >97%. The solution was contacted with acidic water to extract the metals and then neutralize. 0.05 wt% of each of the antioxidants Irganox 1010 and Irgafos 168 were added and f-HbBC((SB) n X(sB) m and (sB) z The mixture of X; n ≥ 1, m + n ≥ 3, z = 2-4) was recovered by precipitation and dried in a vacuum oven. Residual diene and polystyrene unsaturations were < 2% and < 3%, respectively.

[0084] GPC analysis of f-HbBC is shown in Figure 1, which shows that 71% of the radial block copolymers had a molecular weight of >100 kg / mol (M p ), with 29% of the radial block copolymers having a molecular weight (M p ).

[0085] The composition details of f-HbBC are shown in Table 1. Table 2 compares the properties of f-HbBC and comparative examples.

[0086] [Table 1]

[0087] The f-HbBC is compared to prior art block polymers, pentablock (CE-1) and multimodal branched block copolymers (CE-2).

[0088] [Table 2]

[0089] As shown, the f-HbBC of Example 2 had much better Charpy impact (unnotched) and T g and still maintains a low haze value. g is the theoretical maximum T of homopolystyrene. g It is known that the temperature cannot exceed 105°C.

[0090] As used herein, the term "comprising" means including the elements or steps identified after the term, but that any such elements or steps are not exhaustive and that certain embodiments may include other elements or steps. Although the terms "comprising" and "including" have been used herein to describe various aspects, the terms "consisting essentially of" and "consisting of" may be used in place of "comprising" and "including" to provide more specific aspects of the present disclosure and are similarly disclosed.

Claims

1. (S-B) ｎ X(s-B) ｍ , (s-B) ｚ X, and mixtures of radial block copolymers having the general structure of mixtures thereof, Prior to hydrogenation, each block S and "s" is independently a polymer block of a vinyl aromatic monomer; Each block B is a polymer block of a conjugated diene monomer, X is a residue of a coupling agent; m>n, n≧1, m=1 to 20, z=2 to 4, and m+n≧3; After hydrogenation, The radial block copolymer exhibits multiple peaks in a GPC curve; the mixture comprises at least 70 weight percent poly(vinylcyclohexane) content and less than 30 weight percent hydrogenated polymer blocks of conjugated diene monomers, based on the total weight of the mixture; At least 60% of the radial block copolymers in the mixture have a molecular weight (M ｐ ), with the remainder having a molecular weight (M ｐ ) At least 30% of the radial block copolymers in the mixture have a molecular weight (M ｐ ), with the remainder having a molecular weight (M ｐ ) Less than 40% by weight of the mixture is (s-B) ｚ X has the general structure: The fully hydrogenated branched block copolymer is A polydispersity index of 1.20 to 3.0; Glass transition temperature (T ｇ ), an MFR of 0.1 to 35 g / 10 min measured at 260° C. and a load of 5 kg; and 20-50 kJ / m when measured at 25°C ２ Unnotched Charpy impact strength having Fully hydrogenated branched block copolymer.

2. The mixture is (s-B) 1:1 to 20:1 ｚ (S-B) for a radial block copolymer having the structure of X ｎ X(s-B) ｍ 2. The fully hydrogenated branched block copolymer of claim 1 having a weight ratio of radial block copolymer having the structure:

3. At least one radial block copolymer has a molecular weight (M ｐ 3. The fully hydrogenated branched block copolymer of claim 1 or 2, wherein

4. Molecular weight (M ｐ )>100 kg / mol radial block copolymers having at least one block S and a molecular weight (M ｐ 3. The fully hydrogenated branched block copolymer according to claim 1 or 2, wherein the radial block copolymer having a molecular weight of 1000 to 10000 kg / mol does not have any block S.

5. 3. The fully hydrogenated branched block copolymer of claim 1 or 2, wherein the fully hydrogenated branched block copolymer has a polydispersity index of 1.20 to 3.

0.

6. The radial block copolymer comprises 50 to 80 weight percent (SB), based on the total weight of the radial block copolymer. ｎ X(s-B) ｍ and 20 to 40% by weight of (s-B). ｚ 3. The fully hydrogenated branched block copolymer of claim 1 or 2, comprising X.

7. The radial block copolymer comprises 70 to 85 weight percent (S-B), based on the total weight of the radial block copolymer. ｎ X(s-B) ｍ And (s-B) ｚ 3. The fully hydrogenated branched block copolymer of claim 1 or 2, comprising an X structure.

8. 3. The fully hydrogenated branched block copolymer of claim 1 or 2, wherein each block S, "s", and B is independently hydrogenated to a level of >95% as measured by proton NMR, and the fully hydrogenated branched block copolymer has a poly(vinylcyclohexane) content of 70 to 95%.

9. 3. The fully hydrogenated branched block copolymer of claim 1 or 2, further comprising other arm distributions selected from (s-B)4, (s-B)3, (s-B)2 and mixtures thereof, and uncoupled arms selected from S-B, s-B and mixtures thereof, in an amount of 15 to 25 weight percent based on the total weight of the fully hydrogenated branched block copolymer.

10. The block S has a molecular weight (M ｐ ), with block "s" having a molecular weight (M ｐ 3. The fully hydrogenated branched block copolymer of claim 1 or 2, wherein

11. 3. The fully hydrogenated branched block copolymer of claim 1 or 2 having, prior to hydrogenation, a polystyrene content of from 70 to 95%.

12. 3. The fully hydrogenated branched block copolymer of claim 1 or 2, wherein the coupling agent is selected from the group consisting of polyepoxides, polyisocyanates, polyamines, polyaldehydes, polyhalides, polyanhydrides, polyketones, polyoxyesters, polyesters, and mixtures thereof, and the fully hydrogenated branched block copolymer has a coupling efficiency of 70-90%.

13. Glass transition temperature (T ｇ 3. The fully hydrogenated branched block copolymer of claim 1 or 2, wherein

14. 3. The fully hydrogenated branched block copolymer of claim 1 or 2, when formed into a film having a thickness in the range of 1 mm to 4 mm, exhibiting a haze of <15% as measured by ASTM D1003.

15. Flexural modulus of 1500 to 3000 MPa, VICAT softening point of 125-180°C; 20 to 50 kJ / m ２ Unnotched Charpy impact, A melt flow index of 0.1 to 35 g / 10 min measured at 260° C. under a 5 kg load, and <4% shrinkage after injection molding (machine direction) 3. The fully hydrogenated branched block copolymer of claim 1 or 2, having at least one of:

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