Thermoplastic polymer compositions

Abstract

To provide improved thermoplastic polymer compositions with enhanced impact strength and a balance of other mechanical properties, achieved through the incorporation of a suitable SBC as an impact modifier.SOLUTION: The disclosure relates to a thermoplastic polymer composition comprising: an epoxidized product of a hydrogenated styrenic block copolymer (HSBC), an engineering thermoplastic, optionally an oil extended HSBC, and optional additives. The HSBC includes at least one block "S" composed of vinyl aromatic units and at least one block "R" composed of hydrogenated diene units. The epoxidized HSBC contains 1 to 35 wt.% epoxy functional groups and has a residual unsaturation (RU) of 0.05 to 20 meq / g. This thermoplastic polymer composition offers improved impact resistance and processability and is suitable for producing molded articles.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to thermoplastic polymer compositions, methods of preparation and uses thereof. [Background technology]

[0002] Engineering thermoplastics have advantageous properties including heat resistance, chemical resistance, electrical insulation, dimensional stability, etc., and can be used in many applications, such as automotive, oil field, and air conditioning. Engineering thermoplastics are also finding increasing use in the electrical and electronics industries. However, despite their interesting properties, these polymers are limited by their inherently brittle nature.

[0003] Impact modifiers are recognized for their ability to balance toughness, stiffness, and processability of inherently rigid polymers. Various impact modifiers are known in the art for blending with engineering thermoplastics to improve mechanical properties. Styrenic block copolymers (SBCs) have been utilized as impact modifiers. Modifications of the SBCs can be finely tuned to facilitate blending with specific classes of engineering thermoplastics. Summary of the Invention [Problem to be solved by the invention]

[0004] There remains a need for improved thermoplastic polymer compositions having an improved balance of impact strength and other mechanical properties achieved by the incorporation of suitable SBCs as impact modifiers. [Means for solving the problem]

[0005] (Summary of the Invention) In one aspect, the present disclosure relates to a thermoplastic polymer composition comprising, consisting essentially of, or consisting of (a) 2 to 40 weight percent of an epoxidation product of a hydrogenated styrenic block copolymer (HSBC), (b) 60 to 98 weight percent of an engineering thermoplastic, and (c) 10 weight percent or less of at least one additive, all weight percentages being based on the total weight of the thermoplastic polymer composition. HSBC can be any of SR, SRS, SRSR, (SRS) n X, (SR) n The general structure is selected from the group consisting of polyamide, polyphenylene oxide, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyphthalamide, polyimide, polyetherimide, liquid crystal polymer, polycarbonate, polymethyl methacrylate, acrylonitrile butadiene styrene, polyoxymethylene, styrene-acrylonitrile, polyether ketone, polyether ether ketone, polyketone, polysulfone, and mixtures thereof. Each block "S" is composed of vinyl aromatic units, each block "R" is composed of hydrogenated diene units, X is the residue of a coupling agent, and n is greater than or equal to 2. The epoxidized hydrogenated styrene block copolymer (e-HSBC) contains 1 to 35 wt.% epoxy functional groups based on the total weight of the blocks "R" and has a residual unsaturation (RU) of 0.05 to 20 meq / g. The engineering thermoplastic is selected from the group consisting of polyamide, polyphenylene oxide, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyphthalamide, polyimide, polyetherimide, liquid crystal polymer, polycarbonate, polymethyl methacrylate, acrylonitrile butadiene styrene, polyoxymethylene, styrene-acrylonitrile, polyether ketone, polyether ether ketone, polyketone, polysulfone, and mixtures thereof. In an embodiment, the thermoplastic polymer composition further comprises (d) up to 20 wt. % of an oil-extended hydrogenated styrenic block copolymer.

[0006] In a second embodiment, the thermoplastic polymer composition has a notched Izod impact strength of 2 KJ / m or less, measured at 21°C according to ASTM D256. 2 and a flexural modulus measured in accordance with ASTM D790 of greater than 1.5 GPa.

[0007] In a third embodiment, the thermoplastic polymer composition has a tensile strength at break greater than 40 GPa, an elongation at yield greater than 4%, and an elongation at break greater than 4%, all measured according to ASTM D638.

[0008] In a fourth embodiment, the block "R" is selected from E / B, EP / MB, and E / B / EP / MB, where each E / B block is composed of ethylene ("E") and butylene ("B") units, each EP / MB block is composed of ethylene-propylene (EP) and methylene-butylene (MB) units, and each E / B / EP / MB block is composed of ethylene ("E"), butylene ("B"), ethylene-propylene (EP) and methylene-butylene (MB) units. DETAILED DESCRIPTION OF THE INVENTION

[0009] The following terms may have the following meanings:

[0010] "Consisting essentially of" means that the claimed composition contains primarily the specified material, and may have additional ingredients that do not materially affect the novel properties or function of the claimed invention, and such additional ingredients, if present, are in amounts of less than 30%, or less than 20%, or less than 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 from the group, more than one member from the group, or a combination of members from the group. For example, at least one of A, B, and C includes, for example, A only, B only, or C only, as well as A and B, A and C, B and C; or any and all other combinations of A, B, and C or A, B, and C.

[0012] A list of embodiments expressed as "A, B, or C" is to be interpreted as including the 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" refers to one choice from A, B, or C.

[0014] "Any of A, B and C" refers to one or more choices from A, B and C.

[0015] "Butylene unit content" refers to the content of butylene units ("B") in the hydrogenated block copolymer in weight percent. Butylene units are obtained / formed by polymerization of 1,3-butadiene monomers via 1,2-addition, followed by hydrogenation. 1,3-butadiene monomers can also be polymerized via 1,4-addition, which upon hydrogenation results in ethylene units ("E"). Both butylene units and ethylene units can be part of the hydrogenated block copolymer, which may also contain vinyl aromatic units and / or ethylene-propylene units, in any order. The butylene unit content is 1 HNMR and 13 It can be measured by CNMR.

[0016] "Coupling efficiency (CE)" refers to the weight of coupled polymer molecules divided by the total weight of both coupled and uncoupled polymer molecules, expressed as a percentage (%). CE can be used to determine the amount of diblocks or, more generally, the content of "uncoupled arms" in the overall block copolymer. For example, if the coupling efficiency is 80%, the polymer may contain 20% by weight of diblock or uncoupled arms and 80% by weight of triblock and multiarm species.

[0017] "Vinyl aromatic unit content" or VAC of a block copolymer refers to the weight percent of polymerized vinyl aromatic monomer, e.g., styrene, para-methylstyrene, etc., in the block copolymer, and is calculated by dividing the sum of the molecular weights of all vinyl aromatic units by the total molecular weight of the block copolymer. VAC can be determined by proton nuclear magnetic resonance spectroscopy ( 1 HNMR) and 13It can be measured using C NMR. VAC is sometimes used interchangeably with PSC or polystyrene content.

[0018] "Molecular weight" or M w refers to the styrene equivalent molecular weight in kg / mol of the polymer block or block copolymer. M w can be measured by gel permeation chromatography (GPC) using polystyrene calibration standards, as performed in accordance with ASTM 5296. The GPC detector may be an ultraviolet detector or a refractive index detector, or a combination thereof. The chromatograph is calibrated using commercially available polystyrene molecular weight standards. The M of a polymer measured using such a calibrated GPC is w is the styrene equivalent molecular weight or apparent molecular weight. w is measured at the peak of the GPC trace and is usually called the styrene equivalent "peak molecular weight", M p It is expressed as:

[0019] "HSBC" refers to hydrogenated styrene block copolymers. HSBC is derived from the polymerization of 1,3-butadiene and / or isoprene with vinyl aromatic monomers. In HSBC, a significant proportion of the double bonds from the 1,3-butadiene and / or isoprene units are hydrogenated to achieve hydrogenation levels of over 80%, 90%, or even 99%. However, aromatic bonds are hydrogenated to levels ranging from 0% to 15%.

[0020] "Hydrogenation level" refers to the level (in percentage) of saturation of double bonds (e.g., olefinic, aromatic, etc.) in a block copolymer; 1 It can be measured by HNMR.

[0021] "Residual unsaturation" or RU refers to the level of unsaturation, i.e., carbon-carbon double bonds, per gram of block copolymer. RU is 1 It can be measured using HNMR or ozonolysis titration.

[0022] "Unit" refers to a structural building block derived from one or more polymerized monomers and represents a repeating entity that forms part of a polymer or copolymer chain. Unlike "monomers," which are individual molecules before polymerization, "units" are transformed versions of monomers after they have undergone the polymerization process.

[0023] The "polydispersity index" or PDI is the weight average molecular weight (M w ) number average molecular weight (M n ), sometimes referred to as the molecular weight distribution. PDI is used to indicate the molecular weight distribution of the polymer chains in a given polymer.

[0024] Epoxidized HSBC (e-HSBC) or epoxy-grafted HSBC or epoxy-functionalized HSBC are terms used interchangeably to describe compositions in which epoxy groups are grafted onto the backbone of a hydrogenated styrenic block copolymer (HSBC) or onto vinyl groups adjacent to the backbone.

[0025] "Oil-extended HSBC" or OE-HSBC refers to an HSBC polymer material (or HSBC) prepared by combining a specific amount of HSBC with a predetermined amount of oil (the weight ratio of HSBC to oil may be 1:5 to 5:1), mixing the ingredients, and allowing the mixture to soak for a set period of time (e.g., 24 hours at room temperature) to allow the HSBC to absorb the oil. This mixture, designated OE-HSBC, is used in formulations to improve their processability.

[0026] The present disclosure relates to a thermoplastic polymer composition containing an epoxidation product of a hydrogenated styrenic block copolymer (HSBC), an engineering thermoplastic, optionally an oil-extended hydrogenated styrenic block copolymer (OE-HSBC), and optional additives, which exhibits enhanced impact resistance and improved processability, making it suitable for the production of molded articles.

[0027] Epoxidized Hydrogenated Styrene Block Copolymer (e-HSBC): e-HSBC can be obtained by epoxidizing or grafting HSBC with an epoxidizing agent, whereby all or some of the available unsaturated double bonds of the diene units of HSBC are epoxidized. 1 Standard analytical methods, including HNMR, can be used to detect / analyze the e-HSBC structure. The hydrogenation level of HSBC is 50-90% before epoxidation to form e-HSBC.

[0028] HSBC may be either a triblock, tetrablock, pentablock or mixtures thereof; and either a linear or branched (multi-arm) block copolymer comprising at least one block "S" composed of vinyl aromatic units; and at least one rubbery block "R" (block "R") composed of hydrogenated diene units and optionally vinyl aromatic units. The vinyl aromatic units are derived from polymerized vinyl aromatic monomers, while the hydrogenated diene units, prior to hydrogenation, are derived from polymerized diene monomers.

[0029] In embodiments, the vinyl aromatic monomer is selected from the group consisting of styrene, para-methylstyrene, para-ethylstyrene, para-n-propylstyrene, para-iso-propylstyrene, para-n-butylstyrene, para-sec-butylstyrene, para-iso-butylstyrene, para-t-butylstyrene, isomers of para-decylstyrene, isomers of para-dodecylstyrene, ortho-substituted styrenes, meta-substituted styrenes, alpha-methylstyrene, 1,1-diphenylethylene, and mixtures thereof.

[0030] In embodiments, the 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.

[0031] In embodiments, the block "R" is selected from poly(isoprene-r-butadiene) and poly(butadiene-r-styrene), where -r- refers to a random copolymer, e.g., "poly(isoprene-r-butadiene)" refers to a polyisoprene-butadiene random copolymer.

[0032] In an embodiment, each block "R" is a block selected from E / B, EP / MB, E / B / EP / MB and combinations thereof.

[0033] In an embodiment, the block "R" is a block E / B composed of ethylene ("E") and butylene ("B") units, where those units are hydrogenated 1,4-butadiene and hydrogenated 1,2-butadiene units, respectively.

[0034] In an embodiment, the block "R" is a block EP / MB composed of ethylene-propylene (EP) units and methylene-butylene (MB) units. Each EP unit is a hydrogenated 1,4-isoprene unit, and each MB unit is a hydrogenated 3,4-isoprene unit and / or a hydrogenated 1,2-isoprene unit. In an embodiment, the methylene-butylene (MB) units are present in the block EP / MB in an amount of less than 10% by weight, or less than 8% by weight, or less than 5% by weight, relative to the total weight of the block EP / MB.

[0035] In an embodiment, the block "R" is a block E / B / EP / MB composed of ethylene ("E"), butylene ("B"), ethylene-propylene (EP) and methylene-butylene (MB) units.

[0036] In an embodiment, HSBC is SR, SRS, SRSR, (SRS) n X, (SR) n X and mixtures thereof, where X is the residue of a coupling agent and n≧2 or 1-20 or 1-10 or 1-7.

[0037] In embodiments, the coupling agent includes a difunctional or polyfunctional compound such as divinylbenzene, an aliphatic or araliphatic hydrocarbon halide such as 1,2-dibromoethane, bis(chloromethyl)benzene, silicon tetrachloride, dialkyl or diaryl silicon dichloride, alkyl or aryl silicon trichloride, tin tetrachloride, alkyl silicon methoxide, alkyl silicon ethoxide, a polyfunctional aldehyde such as terephthaldialdehyde, a ketone, an ester, an anhydride, or an epoxide. In embodiments, the coupling agent is selected from methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, dimethyl adipate, gamma-glycidoxypropyltrimethoxysilane, and mixtures thereof. In embodiments, the coupling efficiency (CE) of the HSBC is greater than 10%, greater than 20%, or between 10 and 100%, or between 20 and 95%, or between 70 and 95%, or greater than 90%, or between 80 and 98%, or between 85 and 95%.

[0038] In embodiments, the content of butylene units ("B") in each block E / B is 15 to 80% by weight, or 20 to 75% by weight, or 25 to 70% by weight, or 30 to 65% by weight, or 15 to 65% by weight, or 30 to 80% by weight, or 25 to 40% by weight, or 50 to 70% by weight, or more than 20% by weight, or more than 25% by weight, or more than 30% by weight, or less than 80% by weight, relative to the total weight of the blocks E / B.

[0039] In embodiments, the e-HSBC comprises a mixture of different epoxidized block copolymers, such as a mixture of e-USBC (epoxidized non-hydrogenated SBC) and e-HSBC or a mixture of different e-HSBCs.

[0040] In embodiments, the e-HSBC comprises a mixture of different e-HSBCs, with a first e-HSBC having a low butylene unit ("B") content and a second e-HSBC having a high butylene unit ("B") content. By low butylene unit ("B") content, we mean an e-HSBC having a butylene unit ("B") content of less than 45% by weight, or less than 40% by weight, or less than 42% by weight, or less than 38% by weight, or more than 10% by weight, or 10-45% by weight, or 20-42% by weight, or 25-45% by weight. By high butylene unit ("B") content, we mean an e-HSBC having a butylene unit ("B") content of more than 45% by weight, or more than 48% by weight, or more than 50% by weight, or less than 80% by weight, or 45-80% by weight, or 48-75% by weight, or 50-70% by weight. In an embodiment, the mixture of the first e-HSBC and the second e-HSBC has a weight ratio in the range of 1:10 to 10:1, or 1:8 to 8:1, or 1:5 to 5:1, or 1:3 to 3:1.

[0041] In embodiments, the hydrogenation level of each block "S" in the e-HSBC is less than 30%, or less than 20%, or less than 10%, or less than 5% relative to the total double bonds present in the block "S".

[0042] In an embodiment, M of each block "S" p is 5 to 50 kg / mol, or 10 to 45 kg / mol, or 15 to 40 kg / mol, or 20 to 35 kg / mol, or 5 to 30 kg / mol, or 20 to 50 kg / mol, or 3 to 20 kg / mol, or 5 to 15 kg / mol, or 4 to 12 kg / mol, or 3 to 10 kg / mol, or less than 60 kg / mol, or less than 50 kg / mol, or less than 15 kg / mol, or more than 3 kg / mol, or more than 10 kg / mol.

[0043] In an embodiment, HSBC's pis 100 to 500 kg / mol, or 150 to 450 kg / mol, or 200 to 400 kg / mol, or 100 to 300 kg / mol, or 220 to 350 kg / mol, or 220 to 500 kg / mol, or 20 to 300 kg / mol, or 30 to 250 kg / mol, or 40 to 200 kg / mol, or 50 to 150 kg / mol, or 20 to 120 kg / mol, or 40 to 110 kg / mol, or less than 280 kg / mol, or more than 30 kg / mol.

[0044] In an embodiment, the sum of the VACs of the HSBC is 10-50% by weight, or 15-45% by weight, or 20-40% by weight, or 25-35% by weight, or 10-35% by weight, or 25-50% by weight, or less than 50% by weight, or more than 15% by weight, based on the total weight of the HSBC.

[0045] In embodiments, the hydrogenation level of the diene units in each block "R" is greater than 50%, or greater than 55%, or greater than 60%, or greater than 65%, or greater than 80%, or greater than 85%, or greater than 90%, or greater than 95%, or greater than 98%, or greater than 99%, or 100% or less than 90%, or 50-90%, or 55-85%, or 60-80%, or 65-90%, or 50-75%, or 80-99%, or 85-98%, or 90-99%.

[0046] In an embodiment, the residual unsaturation (RU) of the HSBC is less than 20 meq / g, or less than 15 meq / g, or less than 10 meq / g, or less than 8 meq / g, or less than 5 meq / g, or less than 0.4 meq / g, or less than 0.3 meq / g, or less than 0.2 meq / g, or greater than 0.001 meq / g, or greater than 0.01 meq / g, or between 0.01 and 20 meq / g, or between 0.1 and 10 meq / g, or between 0.5 and 8 meq / g, or between 1 and 5 meq / g, or between 0 and 0.5 meq / g, or between 0 and 0.2 meq / g, or between 0.001 and 0.2 meq / g.

[0047] In embodiments, the residual unsaturation (RU) of the e-HSBC is less than 20 meq / g, or less than 15 meq / g, or less than 10 meq / g, or less than 8 meq / g, or less than 5 meq / g, or greater than 0.01 meq / g, or between 0.05 and 20 meq / g, or between 0.1 and 10 meq / g, or between 0.5 and 8 meq / g, or between 1 and 5 meq / g.

[0048] In embodiments, HSBC is epoxidized using known methods, such as treatment with hydrogen peroxide in the presence of a peracid (e.g., peracetic acid), acetic acid, and sulfuric acid, or hydrogen peroxide in combination with a low molecular weight fatty acid, such as formic acid.

[0049] In embodiments, peracids used as functionalizing / epoxidizing agents include percarboxylic acids such as performic acid, peracetic acid, perpropionic acid, 3-chloroperbenzoic acid, potassium monopersulfate, and mixtures thereof.

[0050] In embodiments, the e-HSBC has epoxy functionality in an amount of 1 to 35, or 3 to 30, or 4 to 25, or 3 to 22 weight percent based on the total weight of diene units in the "R" block.

[0051] In embodiments, the degree of epoxidation of the e-HSBC is 100% or less, or 15-99%, or 10-92%, or 40-80%, or 55-95%, or 60-85%, or greater than 50% relative to the polymer blocks that are subjected to functionalization (i.e., epoxidation).

[0052] In embodiments, the diene units in each block "R" are epoxidized at the aliphatic double bond. The amount of epoxy functionality in the e-HSBC is 0.05 to 20 mmol / g, or 0.1 to 15 mmol / g, or 0.5 to 12 mmol / g, or 1 to 10 mmol / g, or 1.5 to 8 mmol / g, or greater than 0.1 mmol / g or less than 20 mmol / g, based on the amount of HSBC per gram. The amount of epoxy functionality in the e-HSBC can be determined by titration or 1 It can be measured by 1 H NMR.

[0053] In embodiments, the e-HSBC is present in an amount of 2 to 40, or 10 to 40, or 5 to 40, or 5 to 35, or 10 to 35, or 5 to 32 wt %, based on the total weight of the thermoplastic polymer composition.

[0054] (Engineering Thermoplastic): In an embodiment, the engineering thermoplastic is selected from the group consisting of polyamide (PA), polyphenylene oxide (PPO), polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyphthalamide (PPA), polyimide (PI), polyetherimide (PEI), liquid crystal polymer (LCP), polycarbonate (PC), polymethyl methacrylate (PMMA), acrylonitrile butadiene styrene (ABN), polyoxymethylene (POM), styrene-acrylonitrile (SAN), polyether ketone (PEK), polyether ether ketone (PEEK), polyketone (PK), polysulfone (PSU), polyphenylene sulfide (PPS), and mixtures thereof.

[0055] In an embodiment, the engineering thermoplastic is a blend of two engineering thermoplastics selected from PPO and PPS, PA and PPS, PA and PET, PA and PPO, PA and PTT, and PA and PBT. The blend may be such that the weight ratio of the two engineering thermoplastics ranges from 1:5 to 5:1, or 1:3 to 3:1, or 1:1.

[0056] In an embodiment, the engineering thermoplastic is a blend of two engineering thermoplastics selected from either PPO and PPS; and PA and PTT.

[0057] Engineering thermoplastics may be either virgin or recycled materials or a mixture thereof. Examples of recycled materials include recycled PET (r-PET) obtained from post-consumer (PCR) items (e.g., bottles, containers, etc.) or from post-industrial recycled materials (PIR).

[0058] In embodiments, the engineering thermoplastic is added to the thermoplastic polymer composition in an amount of 60-98, or 60-90, or 60-95, or 65-95, or 65-90, or 68-95 weight percent based on the total weight of the thermoplastic polymer composition.

[0059] (Polyamide (PA)): In embodiments, the engineering thermoplastic is a PA selected from the group consisting of aliphatic PA, aromatic PA, copolymers, and mixtures thereof. Examples of PA include polyphthalamide (PPA), polyarylamide (PAA), poly(metaxylylene adipamide), amorphous semi-aromatic PA, and poly(paraphenylene terephthalamide), etc.

[0060] (Polyphthalamide (PPA)): In an embodiment, the engineering thermoplastic is a PPA obtained by polycondensation between at least one diacid and at least one diamine. The PPA may be a block copolymer or a random copolymer.

[0061] In embodiments, the PPA has at least 45 mole %, or at least 50 mole %, or at least 55 mole % of the diacid portion of the repeat units in the PPA that are terephthalic acid and / or isophthalic acid, based on the total molar amount of the PPA. Other suitable diacids can be selected from adipic acid, sebacic acid, dodecanedioic acid, and mixtures thereof.

[0062] In embodiments, the diamine is an aliphatic diamine having 4 to 14 or 6 to 12 carbon atoms. Examples of suitable diamines include hexamethylenediamine, nonamethylenediamine, 2-methyl-octamethylenediamine, 2-methylpentamethylenediamine, decamethylenediamine, and mixtures thereof.

[0063] In embodiments, the PPA has a carbon to amide (C / CONH) molar ratio of at least 8.1, or greater than 8.2, or greater than 8.4, or greater than 9, or 8-15, or 8.1-14, or 8.5-13, or 9-12.

[0064] In embodiments, the PPA is selected from the group consisting of PPA6T / 6I; PPA6T / 66; PPA6T / 6; PPA6T / 61 / 66; PPA10,T / 10,I; PPA10,T; PPA9,T; and mixtures thereof. For example, in the term "6T / x," x represents one or more comonomers.

[0065] In embodiments, the PPA comprises one or more units of 2-methylpentamethylene adipamide, hexamethylene sebacamide, hexamethylene azelamide, hexamethylene dodecamethylamide, hexamethylene cyclohexane dicarboxylamide, dodeca-methylene adipamide, hexamethylene terephthalamide units, hexamethylene adipamide units, hexamethylene isophthalamide units, and mixtures thereof.

[0066] In embodiments, the PPA comprises hexamethylene terephthalamide units or hexamethylene terephthalamide units and hexamethylene adipamide units, and optionally hexamethylene isophthalamide units. The hexamethylene terephthalamide units may be present in an amount of at least 50 mol %, or 40-90 mol %, or 10-50 mol % hexamethylene adipamide units and 0-30 mol % hexamethylene isophthalamide units.

[0067] In embodiments, the melting point of the PPA is greater than 290° C., or greater than 295° C., or greater than 300° C., or greater than 310° C., or less than 380° C. In embodiments, the glass transition temperature of the PPA is greater than 80° C., or greater than 90° C., or greater than 100° C., or less than 220° C.

[0068] In embodiments, the PPA has an inherent viscosity greater than 0.4, or greater than 0.6, or greater than 0.8, or less than 2.0, measured at 30° C. in a 60 / 40 phenol / tetrachloroethylene mixture at a concentration of 0.4 g / dl.

[0069] Polyphenylene Oxide (PPO): In an embodiment, the engineering thermoplastic is PPO, including oligomers, polymers, and mixtures thereof.

[0070] Examples of PPOs include poly(2,6-dimethyl-1,4-phenylene) ether; poly(2,3,6-trimethyl-1,4-phenylene) ether; poly(2,6-diethyl-1,4-phenylene) ether; poly(2-methyl-6-propyl-1,4-phenylene) ether; poly(2,6-dipropyl-1,4-phenylene) ether; poly(2-ethyl-6-propyl-1,4-phenylene) ether; poly(2,6-dilauryl-1,4-phenylene) ether; poly(2,6-diphenyl-1,4-phenylene) ether; poly(2,6-dimethoxy-1,4-phenylene) ether; poly(2,6-diethoxy-1,4-phenylene) poly(2-ethoxy-1,4-phenylene) ether; poly(2-methoxy-6-ethoxy-1,4-phenylene) ether; poly(2-ethyl-6-stearyloxy-1,4-phenylene) ether; poly(2,6-dichloro-1,4-phenylene) ether; poly(2-methyl-6-phenyl-1,4-phenylene) ether; poly(2,6-dibenzyl-1,4-phenylene) ether; poly(2-ethoxy-1,4-phenylene) ether; poly(2-chloro-1,4-phenylene) ether; poly(2,6-dibromo-1,4-phenylene) ether; poly(3-bromo-2,6-dimethyl-1,4-phenylene) ether; copolymers and mixtures thereof.

[0071] In embodiments, the engineering thermoplastic has a number average molecular weight (M n ) is 0.500 to 7 or 0.750 to 4 kg / mol, and the weight average molecular weight (M w ) is 0.500 to 15 or 1.5 to 9 kg / mol.

[0072] In an embodiment, the intrinsic viscosity of the PPO oligomer is 0.03 to 1, or 0.35 to 1, or 0.25 to 0.70, or 0.35 to 0.55, or 0.35 to 0.50, or 0.03 to 0.13, or 0.05 to 0.10, or 0.10 to 0.15 dL / g, measured in chloroform using an Ubbelohde viscometer at 25°C.

[0073] In an embodiment, the number average molecular weight (M n ) is 5 to 75, or 3 to 40, or 10 to 50 kg / mol. In an embodiment, the polydispersity index (PDI) of the PPO is 1 to 7, or 2 to 5.

[0074] In an embodiment, the intrinsic viscosity of the PPO is greater than 0.10 dL / g, or greater than 0.20 dL / g, or less than 4 dL / g, or 0.1 to 0.9 dL / g, or 0.2 to 0.6 dL / g, or 0.29 to 0.48 dL / g, measured in chloroform using an Ubbelohde viscometer at 25°C.

[0075] The PPO may be functionalized with hydroxyl, vinyl, isocyanate, anhydride, carboxylic acid, carboxyl ester, urethane, amino, phosphino, epoxy, silane, acrylate, methacrylate, and combinations thereof. In embodiments, the PPO has 1.2 to 2.8 phenolic hydroxy groups per molecule. The PPO may have a polydispersity index of 1.2 to 3 and an intrinsic viscosity of 0.03 to 0.2 deciliters per gram.

[0076] Polyethylene Terephthalate (PET): In embodiments, the engineering thermoplastic is PET obtained with an acid component (e.g., terephthalic acid) or its ester-forming derivatives and a glycol component (e.g., ethylene glycol) or its ester-forming derivatives.

[0077] PET can be obtained by using any additional alkylene glycol apart from ethylene glycol. Examples of alkylene glycols include 1,2-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, hexamethylene glycol, octamethylenediol, nonylmethylene glycol, decamethylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2-methyl-octanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, dibutylene glycol, tributylene glycol, poly(oxy)ethylene glycol, polytetramethylene glycol, 1,4-cyclohexanedimethanol or 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 1,1-cyclohexanedimethanol, 2-methyl- ... Examples of 1,3-alicyclic diols include 2,2-hexanediol, cyclohexanediol, cyclodecanediol, tricyclodecane dimethanol, 2,2-norbornane dimethanol, 3-methyl-2,2-norbornane dimethanol, 2,3-norbornane dimethanol, 2,5-norbornane dimethanol, 2,6-norbornane dimethanol, adamantane dicarboxylmethanol, 1,3-dimethyl-5,7-adamantane dicarboxylmethanol, 1,3-adamantane-diol, and 5,7-dimethyladamantane-diol; bis(4-ω-hydroxyalkyl)phenyl, bis(ω-hydroxyalkyloxy)naphthalene, 2,2-bis(4-ω-hydroxyalkyloxyphenyl)propane, and bis(4-ω-hydroxyalkyloxyphenyl)one diols containing an aromatic benzene group, and mixtures thereof.

[0078] Examples of dicarboxylic acids include phthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenyletherdicarboxylic acid, diphenylsulfonedicarboxylic acid, dicarboxyphenoxyethane, diphenylketonedicarboxylic acid, cyclopentanedicarboxylic acid, 2,3-furandicarboxymethyl acid, 2,4-furandicarboxylic acid, 2,5-furandicarboxylic acid, 3,4-furandicarboxylic acid, hexahydroterephthalic acid, cyclodecanedicarboxylic acid, ditricyclodecanoic acid, tricyclodecanealicyclic dicarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, trimellitic acid, trimesic acid, pyromellitic acid, tricarballylic acid, gallic acid, and mixtures thereof.

[0079] In embodiments, the PET comprises ethylene terephthalate units in an amount greater than 80 mol %, or greater than 85 mol %, or greater than 90 mol %, based on the total number of moles of PET, with the remainder being C3-C6 glycol (e.g., propylene glycol, hexamethylene glycol, tetramethylene glycol, etc.) and / or dicarboxylic acid (e.g., isophthalic acid, naphthalene-2,6-dicarboxylic acid, etc.) units.

[0080] In an embodiment, the intrinsic viscosity of the PET measured in ortho-chlorophenol at 35° C. is 0.4 to 0.9 or 0.45 to 0.8.

[0081] In an embodiment, the PET is recycled PET (r-PET). In an embodiment, the thermoplastic polymer composition comprises a blend of virgin PET and r-PET in a weight ratio of 1:10-10:1, or 1:8-8:1, or 1:5-5:1, or 1:3-3:1, or 1:1.

[0082] (Polytrimethylene terephthalate (PTT)): In an embodiment, the engineering thermoplastic is PTT obtained by polycondensation reaction between terephthalic acid (or its dimethyl ester, dimethyl terephthalate) and 1,3-propanediol. The polymerization involves an esterification reaction (or transesterification reaction) followed by polycondensation under vacuum to form chains of the desired molecular weight.

[0083] In an embodiment, the tensile strength at yield of the PTT measured according to ISO 527-1 / -2 is greater than 20 MPa, or greater than 30 MPa, or less than 80 MPa, or between 20 and 80 MPa, or between 25 and 70 MPa, or between 30 and 60 MPa.

[0084] In embodiments, the elongation at break of the PTT measured according to ISO 527-1 / -2 is greater than 5%, or greater than 10% or less than 70%, or between 5 and 70%, or between 10 and 50%, or between 5 and 25%.

[0085] In an embodiment, the PTT elongation at yield measured according to ISO 527-1 / -2 is greater than 1%, or greater than 3% or less than 25%, or between 1 and 25%, or between 2 and 15%, or between 3 and 10%.

[0086] In embodiments, the tensile modulus of the PTT measured according to ISO 527-1 / -2 is greater than 0.5 GPa, or greater than 1.0 GPa or less than 10 GPa, or between 0.5 and 10 GPa, or between 1 and 5 GPa.

[0087] In an embodiment, the flexural modulus of the PTT measured according to ISO 178 is greater than 0.5 GPa, or greater than 1.0 GPa or less than 10 GPa, or between 0.5 and 10 GPa, or between 1 and 5 GPa.

[0088] In an embodiment, the notched Izod impact strength of the PTT measured according to ISO 180 / 1A is 5 kJ / m 2 Over 10kJ / m 2 Over 50kJ / m 2 Less than or 5 to 50 kJ / m 2 or 10 to 30 kJ / m2 is.

[0089] In an embodiment, the notched Charpy impact strength of the PTT measured in accordance with ISO 180 / 1eA is 1 kJ / m 2 Over 1.5kJ / m 2 Over 20kJ / m 2 Less than or 1 to 20 kJ / m 2 or 1.5 to 10 kJ / m 2 is.

[0090] (Polyphenylene sulfide (PPS)): In embodiments, the engineering thermoplastic is PPS, including those having relatively low molecular weights as described in U.S. Pat. No. 3,354,129 and those having relatively high molecular weights as described in U.S. Pat. No. 3,919,177. PPS may be a linear or branched polymer depending on the desired properties. Substantially linear PPS having a relatively high molecular weight is preferred for applications requiring the toughness of higher molecular weight PPS.

[0091] In embodiments, the PPS is a low molecular weight PPS (“LMWPPS”), having a number average molecular weight (M n In an embodiment, the weight average molecular weight (M w ) is 2 to 40, 20 to 35, or 30 to 34 kg / mol.

[0092] In an embodiment, the PPS is M n In embodiments, the M of the HMWPPS is 11 to 100, or 25 to 50, or 27 to 35 kg / mol. w is 55 to 150, 80 to 120, or 85 to 100 kg / mol.

[0093] In embodiments, the PPS is filled / reinforced with a material such as glass or a filler in an amount of less than 65 wt %, or 10-50 wt %, or 20-45 wt % of its total weight. Examples of fillers include minerals such as calcium carbonate, calcium sulfate, talc, and mica. Examples of glass fillers include commercially available glass fillers, such as borosilicate glass or aluminum silicate glass, and glass fibers and glass beads as reinforcing materials for polymer blends. The PPS may be unfilled unless otherwise specified.

[0094] (Optional Oil-Extended Hydrogenated Styrenic Block Copolymer (OE-HSBC)): In embodiments, the thermoplastic polymer composition further comprises an oil-extended HSBC, which is obtained by combining a hydrogenated styrenic block copolymer (HSBC') with a suitable amount of at least one oil. The HSBC' for use in making the OE-HSBC may be the same as or different from the HSBC precursor for use in making the e-HSBC, and the description above regarding HSBC is as described with respect to the HSBC precursor prior to epoxidation to produce the e-HSBC.

[0095] In an embodiment, the OE-HSBC has a weight ratio of HSBC' to oil in the range of 1:5 to 5:1, or 1:4 to 4:1, or 1:3 to 3:1, or 1:2 to 2:1, or 1:1.

[0096] In embodiments, the oil is selected from the group consisting of hydrocarbon oils, vegetable oils, synthetic oils, and mixtures thereof. Examples of oils include naphthenic oil, mineral oil, soybean oil, cottonseed oil, castor oil, palm oil, linseed oil, coconut oil, sunflower oil, corn oil, olive oil, peanut oil, rapeseed oil, sesame oil, rice bran oil, jetropha oil, polyalphaolefins, silicone oil, and mixtures thereof.

[0097] In embodiments, the oil is transesterified or epoxidized with a degree of epoxidation of 2 to 10% or 3 to 8%.

[0098] In an embodiment, the OE-HSBC has the general structure SE / BS with an RU of 0.001-0.2 meq / g, a butylene unit ("B") content of 30-50, a total VAC of 20-40 wt. %, and M of the block "S". p is 15 to 40 kg / mol, and M of the block copolymer p is 220-350 kg / mol and the hydrogenation level of the diene units in each block "R" is 85-98%.

[0099] In embodiments, the OE-HSBC, if added, is in an amount of up to 20 wt %, or 1-20, or 3-18, or 5-15, or 1-12 wt %, based on the total weight of the thermoplastic polymer composition.

[0100] (Optional Impact Modifier): In embodiments, the thermoplastic polymer composition further comprises an impact modifier other than e-HSBC and / or OE-HSBC. Examples of suitable impact modifiers include ethylene-propylene diene polymers (EPDM) optionally functionalized with epoxy, anhydride, ortho-ester, oxazoline, sulfonate, or phosphonate groups; elastomeric copolymers such as carboxylated ethylene-propylene rubber, silicone rubber, ethylene-acrylic rubber, ethylene-propylene copolymer rubber, ethylene-propylene-diene terpolymer rubber, poly(butyl acrylate), styrene block copolymer (SBC), and mixtures thereof.

[0101] In embodiments, the additional impact modifier, if present, is in an amount up to 20 wt %, or 0.1 to 10, or 0.5 to 5, or 1 to 3 wt %, based on the total weight of the thermoplastic polymer composition.

[0102] Optional Additives: In embodiments, the thermoplastic polymer composition further comprises at least one additive selected from the group consisting of activators, curing agents, stabilizers, neutralizing agents, thickeners, coalescing agents, slip agents, mold release agents, antimicrobial agents, antioxidants, antiozonants, color changing pH indicators, tackifiers, crosslinkers, UV absorbers, catalysts, fillers, fibers, flame retardants, viscosity modifiers, wetting agents, defoamers, toughening agents, heat stabilizers, light stabilizers, lubricants, flow control agents, drip retardants, antistatic agents, processing aids, dyes, pigments, colorants, plasticizers, glidants, and mixtures thereof.

[0103] In embodiments, the additives are used in an amount of up to 10 wt. %, or 0.1 to 10, or 0.1 to 5, or 0.5 to 5, based on the total weight of the thermoplastic polymer composition.

[0104] (Thermoplastic polymer composition): In embodiments, the thermoplastic polymer composition comprises, based on the total weight of the thermoplastic polymer composition, (a) 60 to 98 wt. % of an engineering thermoplastic, (b) 2 to 40 wt. % of e-HSBC, (c) 20 wt. % or less of an OE-HSBC, and (d) 10 wt. % or less of at least one additive; or (a) 68 to 95 wt. % of an engineering thermoplastic, (b) 5 to 32 wt. % of e-HSBC, (c) 20 wt. % or less of an OE-HSBC, and (d) 10 wt. % or less of at least one additive.

[0105] Preparation of Thermoplastic Polymer Compositions: The compositions can be prepared by mixing the components in the required amounts using known processing equipment, for example, a mixer or by melt-kneading using an extruder or kneader, and, if necessary, compounding / pelletizing for further processing into molded articles.

[0106] In embodiments, the thermoplastic polymer composition is prepared using a twin screw extruder at a temperature above 200°C, or above 230°C, or from 200 to 350°C, or from 220 to 340°C.

[0107] Once prepared, the thermoplastic polymer compositions can be used to make articles by known methods, such as injection molding, blow molding, extrusion, or other known means.

[0108] Properties: The thermoplastic polymer compositions exhibit a balance of properties, including toughness, stiffness, and processability for use in high performance applications.

[0109] In an embodiment, the thermoplastic polymer composition has a notched Izod impact strength of 2 KJ / m, measured at 21°C according to ASTM D256. 2 Over 50KJ / m 2 Less than or 2 to 50KJ / m 2 or 3 to 45 KJ / m 2 or 4 to 40 KJ / m 2 or 5 to 35 KJ / m 2 or 2 to 35 KJ / m 2 or 5 to 50 KJ / m 2 is.

[0110] In embodiments, the thermoplastic polymer composition has a flexural modulus measured according to ASTM D790 of greater than 1.5 GPa, or greater than 2 GPa, or less than 10 GPa, or from 1.5 to 10 GPa, or from 1.8 to 8 GPa, or from 2.0 to 6 GPa, or from 1.5 to 6 GPa, or from 2.0 to 10 GPa.

[0111] In embodiments, the thermoplastic polymer composition has a tensile strength at break measured according to ASTM D638 of greater than 40 GPa, or greater than 50 GPa, or less than 150 GPa, or 40-150 GPa, or 45-120 GPa, or 50-100 GPa, or 40-80 GPa.

[0112] In embodiments, the thermoplastic polymer composition has an elongation at yield measured according to ASTM D638 of greater than 4% or less than 30%, or 4-30%, or 5-25%, or 6-20%, or 4-15%, or 6-30%.

[0113] In embodiments, the elongation at break of the thermoplastic polymer composition measured according to ASTM D638 is greater than 4% or less than 30%, or 4-30%, or 5-25%, or 6-20%, or 4-15%, or 6-30%.

[0114] Applications: Thermoplastic polymer compositions can be used to form articles such as electronic components, e.g., connectors, bobbins, coils, relays, etc. Other applications include automotive underhood parts, automotive fuel lines, switches and brushes, electrical fittings, thermal equipment, motor parts for home appliances, computer parts, fax machine gears and guards, pumps, and housings. Other applications exist, for example, in aerospace, military, recreational vehicle, and electrical applications. [Example]

[0115] The following specific examples are intended to be non-limiting.

[0116] The following test methods are used:

[0117] The synthesis of e-SBC was confirmed by proton nuclear magnetic resonance spectroscopy (H NMR; Varian 500 MHz spectrometer, 23 °C) using CD212 as the solvent.

[0118] The following ingredients were used in the examples:

[0119] PPA-1 has a density of 1.350 g / cm 3 , T g 123℃, melting point 313℃, tensile strength 83MPa, tensile modulus 2.8GPa, tensile elongation 11%, notched Izod 13kJ / m 2 It is a polyphthalamide manufactured by Syensqo.

[0120] PET-1 is recycled polyethylene terephthalate manufactured by Burcham International as Burcham 80 IV r-PET.

[0121] PTT-1 has a tensile strength at yield of 35 MPa, an elongation at break of 15%, an elongation at yield of 5%, a tensile modulus of 1.6 GPa, a flexural modulus of 1.6 GPa, and a notched Izod impact strength of 18 kJ / m 2 and notched Charpy impact strength of 2.2 kJ / m 2 The polymer is polytrimethylene terephthalate (PTT) manufactured by DuPont.

[0122] PA-1 is a polyamide-6 manufactured by Bridgeport.

[0123] PPS-1 has a melting point of 285°C and a T g The material is a polyphenylene sulfide manufactured by Fortron, with a melting point of 90°C, a tensile strength at break of 90 MPa, and a flexural strength of 3800 MPa.

[0124] PPO-1 is a T g The polyphenylene oxide is manufactured by SABIC and has a melting point of 214°C and an intrinsic viscosity of 0.33 dl / g.

[0125] HSBC-1 has a MFR of 6g / 10min at 230℃ / 5kg load, a VAC of 30wt%, a butylene unit ("B") content of 35-60wt%, and M of block "S". p is 7 kg / mol, block copolymer M p The polymer is a poly(styrene-ethylene / butylene-styrene) (SE / BS) copolymer with a ρ of 77 kg / mol and an RU in the range of 2.4 to 3.9 meq / g.

[0126] HSBC-2 has a MFR of less than 1g / 10min at 230℃ / 5kg load, a VAC of 33wt%, a butylene unit ("B") content of 41wt%, and M of block "S". p is 27 kg / mol, block copolymer M p The copolymer is a poly(styrene-ethylene / butylene-styrene) (SE / BS) copolymer with a σ of 270 kg / mol and an RU of 0.15 meq / g.

[0127] Example 1 Preparation of e-HSBC. HSBC-1 was dissolved in cyclohexane at 25°C, and performic acid, which was separately prepared from formic acid and hydrogen peroxide (1.0:0.5 molar), was added to the solution. The performic acid was introduced in six equal portions throughout the epoxidation reaction. The reaction was carried out at 50°C for 8 hours, after which the reaction mixture was neutralized with 10% aqueous sodium bicarbonate solution. The product was precipitated in methanol. 1 Epoxy content was measured using H NMR spectroscopy. Various HSBC-1 samples with different butylene unit ("B") contents and RU were used to achieve the amounts of epoxy functionality shown in Table 1.

[0128] Example 2 Preparation of OE-HSBC. 100 g of HSBC-2 was combined with 134 g of Drake oil 34 (mineral oil). The mixture was homogenized by shaking the container and then allowed to stand at 25° C. for 24 hours. The resulting oil-extended HSBC (OE-HSBC-2a) was used to prepare the composition.

[0129] [Table 1]

[0130] (Examples 3 to 19) Thermoplastic polymer compositions were prepared by compounding the components using a stationary microcompounder, Xplore™ MC40, and injection molding. During compounding, the extrusion melt temperature was maintained between 260 and 330°C. CEx-1 to CEx-5 are comparative examples. Tables 2 to 4 show the compositions and their properties.

[0131] [Table 2]

[0132] [Table 3]

[0133] [Table 4]

[0134] 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. 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" have been used herein to describe various aspects, the terms "consisting essentially of" and "consisting of" can be used in place of the terms "comprising" and "including" to provide more specific aspects of the present disclosure and are also disclosed.

Claims

1. 1. A thermoplastic polymer composition comprising: (a) 2 to 40 wt. % epoxidation product of a hydrogenated styrene block copolymer, wherein the hydrogenated styrene block copolymer is S-R, S-R-S, S-R-S-R, (S-R-S) ｎ X, (S-R) ｎ X and mixtures thereof; each block "S" is composed of vinyl aromatic units; each block "R" is composed of hydrogenated diene units; X is a residue of a coupling agent, and n≧2; The epoxidized hydrogenated styrene block copolymer is containing 1 to 35% by weight of epoxy functional groups relative to the total weight of the blocks "R"; The residual unsaturation (RU) is 0.05 to 20 meq / g. epoxidation products of hydrogenated styrene block copolymers; (b) 60 to 98 weight percent of an engineering thermoplastic selected from the group consisting of polyamide, polyphenylene oxide, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyphthalamide, polyimide, polyetherimide, liquid crystal polymer, polycarbonate, polymethyl methacrylate, acrylonitrile butadiene styrene, polyoxymethylene, styrene-acrylonitrile, polyether ketone, polyether ether ketone, polyketone, polysulfone, and mixtures thereof; and (c) up to 10 wt. % of at least one additive; and (d) 20% by weight or less of an oil-extended hydrogenated styrene block copolymer Including, All weight percentages are based on the total weight of the thermoplastic polymer composition. Thermoplastic polymer compositions.

2. Block "R" is selected from E / B, EP / MB and E / B / EP / MB; each block E / B is composed of ethylene ("E") and butylene ("B") units; each block EP / MB is composed of ethylene-propylene (EP) units and methylene-butylene (MB) units; each block E / B / EP / MB is composed of ethylene ("E") units, butylene ("B") units, ethylene-propylene (EP) units and methylene-butylene (MB) units; The thermoplastic polymer composition of claim 1.

3. 3. The thermoplastic polymer composition of claim 2, wherein the block "R" is E / B with a butylene unit ("B") content of 30 to 65% by weight relative to the total weight of the block "R".

4. Notched Izod impact strength of 2 KJ / m measured at 21°C according to ASTM D256 ２ 3. The thermoplastic polymer composition of claim 1 or 2, wherein the thermoplastic polymer composition has a modulus of elasticity greater than 1.5 GPa as measured according to ASTM D790.

5. 3. The thermoplastic polymer composition of claim 1 or 2, having a tensile strength at break greater than 40 GPa, an elongation at yield greater than 4%, and an elongation at break greater than 4%, all measured according to ASTM D638.

6. 3. The thermoplastic polymer composition of claim 1 or 2, wherein the engineering thermoplastic is selected from the group consisting of polyamide, polyphenylene oxide, polyethylene terephthalate, polytrimethylene terephthalate, and polybutylene terephthalate.

7. 3. The thermoplastic polymer composition of claim 1 or 2, wherein the engineering thermoplastic is a blend of two engineering thermoplastics selected from the group consisting of polyphenylene oxide and polyphenylene sulfide, polyamide and polyphenylene sulfide, polyamide and polyethylene terephthalate, polyamide and polyphenylene oxide, polyamide and polytrimethylene terephthalate, and polyamide and polybutylene terephthalate, in a weight ratio of 1:5 to 5:

1.

8. a blend of two engineering thermoplastics selected from polyphenylene oxide and polyphenylene sulfide, and polyamide and polytrimethylene terephthalate; the polyphenylene oxide has an intrinsic viscosity of greater than 0.10 dl / g; The polyphenylene sulfide has a tensile strength at break of more than 50 MPa; The polytrimethylene terephthalate has a tensile strength at yield of more than 20 MPa; The thermoplastic polymer composition of claim 7.

9. the epoxidized hydrogenated styrene block copolymer is a mixture of a first epoxidized hydrogenated styrene block copolymer and a second epoxidized hydrogenated styrene block copolymer; the first epoxidized hydrogenated styrenic block copolymer has a butylene unit (“B”) content of less than 45 wt. %; the second hydrogenated styrenic block copolymer has a butylene unit (“B”) content greater than 45 wt. %; a weight ratio of the first epoxidized hydrogenated styrenic block copolymer to the second epoxidized hydrogenated styrenic block copolymer in the mixture ranging from 1:10 to 10:1; The thermoplastic polymer composition of claim 1 or 2.

10. The molecular weight of the block "S" (M ｐ ) is 5 to 50 kg / mol, and the molecular weight (M ｐ 3. The thermoplastic polymer composition according to claim 1, wherein the molecular weight of the polymer is 100 to 500 kg / mol.

11. The hydrogenated styrene block copolymer a vinyl aromatic unit content (VAC) of 10 to 50 wt. %; The residual unsaturation (RU) is 0.1 to 10 meq / g. The thermoplastic polymer composition of claim 1 or 2.

12. The thermoplastic polymer composition of claim 1 or 2, wherein the oil-extended hydrogenated styrene block copolymer is present in an amount of 1 to 20 wt %.

13. 13. The thermoplastic polymer composition of claim 12, wherein the oil-extended hydrogenated styrenic block copolymer comprises a hydrogenated styrenic block copolymer dissolved in an oil selected from the group consisting of hydrocarbon oils, vegetable oils, synthetic oils, and mixtures thereof, and wherein the weight ratio of the hydrogenated styrenic block copolymer to oil ranges from 1:5 to 5:

1.

14. The hydrogenated styrene block copolymer has the general structure SE / BS, the hydrogenated styrene block copolymer a residual unsaturation (RU) of 0.001 to 0.2 meq / g; a butylene unit ("B") content of 30 to 50; the total content of vinyl aromatic units is 20 to 40% by weight; The thermoplastic polymer composition of claim 13.

15. The hydrogenated styrene block copolymer The molecular weight of the block "S" (M ｐ ) is 15 to 40 kg / mol, The molecular weight (M ｐ ) is 220 to 350 kg / mol; The thermoplastic polymer composition of claim 13.

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