Thermoplastic compositions, methods for manufacturing the same, and articles prepared therefrom

Abstract

The thermoplastic composition contains a specific amount of poly (methyl methacrylate) and a radially hydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene having a specific alkenyl aromatic compound content. The invention also provides a method for preparing the composition and an article prepared from the composition.

Description

[0001] Related applications

[0002] This application claims priority to and the benefit of European patent application No. 23150475.4, filed on January 5, 2023, the contents of which are incorporated herein by reference in their entirety. Technical Field

[0003] The present disclosure relates to thermoplastic compositions, particularly thermoplastic compositions having a low dielectric constant, a low dissipation factor, and good mechanical properties, methods for making the same, and articles comprising the same. Background Art

[0004] Impact-modified compositions are meaningful for providing a balance of desired characteristics (comprising shock strength, flowability, chemical resistance and dielectric properties). One class of impact-modified compositions is based on poly(methyl methacrylate). For example, core-shell impact modifiers have been mixed with poly(methyl methacrylate) to attempt to provide enhanced shock strength without affecting optical properties. However, dielectric properties are not tunable, and therefore such blends are limited in application. In particular, applications in electronic devices require certain dielectric properties.

[0005] Therefore, it would be advantageous to provide an impact modified poly(methyl methacrylate) composition having a low dielectric constant and a low dissipation factor.It would be a further advantage to provide a composition having high impact resistance. Summary of the Invention

[0006] One aspect of the present disclosure is a thermoplastic composition comprising: 70 to 99 weight percent poly(methyl methacrylate); and 1 to 30 weight percent of a radially hydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene, having an alkenyl aromatic compound content of 10 to 20 weight percent based on the total weight of the hydrogenated block copolymer; wherein the weight percent of each component is based on the total weight of the thermoplastic composition; wherein the combined amount of the poly(methyl methacrylate) and the hydrogenated block copolymer is at least 90 weight percent; and wherein a molded sample of the thermoplastic composition exhibits one or more of the following: a dielectric constant, Dk, of 2.45 to 2.75 at 1.9 GHz; a dielectric loss, Df, of less than 0.01 at 1.9 GHz; a transmittance greater than 90% at a thickness of 2 mm or 3 mm according to ASTM D1003; a haze of less than 4% at a thickness of 2 mm according to ASTM D1003; and a haze of less than 8% at a thickness of 3 mm according to ASTM D100.

[0007] Another aspect of the present disclosure is a method for making a thermoplastic composition comprising melt mixing the components of the composition.

[0008] Another aspect of the present disclosure is an article comprising the composition.

[0009] The above described and other features are exemplified by the following detailed description. DETAILED DESCRIPTION

[0010] The present inventors have unexpectedly discovered that thermoplastic compositions comprising specific amounts of poly(methyl methacrylate) and specific non-polar impact modifiers can provide a desired combination of properties. In particular, the compositions can provide good impact strength, optical properties, and dielectric properties.

[0011] Thus, one aspect of the present disclosure is a thermoplastic composition. The composition comprises poly(methyl methacrylate). Poly(methyl methacrylate), also known as "PMMA," comprises repeating units derived from the polymerization of methyl methacrylate. Poly(methyl methacrylate) can be obtained by free radical polymerization. Preferably, the poly(methyl methacrylate) is a methyl methacrylate homopolymer and excludes repeating units derived from other monomers from the polymer.

[0012] The weight average molecular weight (Mw) of the poly(methyl methacrylate) can vary over a wide range, with the Mw generally being matched to the intended use and processing mode of the composition. In one aspect, the Mw of the poly(methyl methacrylate) can be from 20,000 to 1,000,000 grams per mole (g / mol), or from 50,000 to 500,000 g / mol, or from 80,000 to 300,000 g / mol, as determined according to ASTM D5296-11. In one aspect, the poly(methyl methacrylate) can have a mass fraction of 6 cubic centimeters per 10 minutes (cm3) at 230°C, 3.8 kilograms (kg), as measured according to ISO 1133 or ASTM D1238. 3 / 10min) to 18cm 3 / 10 of the melt volume flow rate (MVR).

[0013] The poly(methyl methacrylate) can be present in the composition in an amount of 70 to 99 weight percent, based on the total weight of the composition. Within this range, the poly(methyl methacrylate) can be present in an amount of 75 to 99 weight percent, or 77 to 98 weight percent, or 70 to 95 weight percent, or 78 to 99 weight percent, or 80 to 99 weight percent, or 80 to 95 weight percent, or 78 to 92 weight percent, or 85 to 98 weight percent, each based on the total weight of the composition.

[0014] In addition to poly(methyl methacrylate), the thermoplastic composition comprises a hydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene. The hydrogenated block copolymer is a non-polar impact modifier that, without wishing to be bound by theory, is believed to contribute to the desired combination of properties achieved by the compositions of the present invention. For simplicity, this component will be referred to as the "hydrogenated block copolymer."

[0015] The present inventors have discovered that a desired combination of properties can be achieved when the hydrogenated block copolymer comprises 10 to 20 weight percent poly(alkenyl aromatic) content and 80 to 90 weight percent hydrogenated poly(conjugated diene) content, based on the weight of the hydrogenated block copolymer. In one aspect, the hydrogenated block copolymer can have an alkenyl aromatic content of 10 to 15 weight percent, based on the total weight of the hydrogenated block copolymer. The hydrogenated block copolymers of the present disclosure further have a radial structure.

[0016] In one aspect, the hydrogenated block copolymer may have a molecular weight greater than 0.91 g / cm 3 , or greater than or equal to 0.92g / cm 3 , or greater than or equal to 0.93g / cm 3 proportion.

[0017] In one aspect, the hydrogenated block copolymer has a weight average molecular weight of 40,000 to 400,000 g / mol. The number average molecular weight and weight average molecular weight can be determined by gel permeation chromatography based on comparison with a polystyrene standard. In one aspect, the hydrogenated block copolymer has a weight average molecular weight of 200,000 to 400,000 g / mol or 220,000 to 350,000 g / mol. In one aspect, the hydrogenated block copolymer has a weight average molecular weight of 40,000 to 200,000 g / mol or 40,000 to 180,000 g / mol or 40,000 to 150,000 g / mol.

[0018] The alkenyl aromatic monomer used to prepare the hydrogenated block copolymer may have a structure according to formula (6):

[0019]

[0020] Among them, R 5 and R 6 Each independently represents a hydrogen atom, C 1-8 Alkyl or C 2-8 Alkenyl; R 7 and R 11 Each independently represents a hydrogen atom, C 1-8 an alkyl group, a chlorine atom or a bromine atom; and R 8 、R 9 and R10 Each independently represents a hydrogen atom, C 1-8 Alkyl or C 2-8 Alkenyl, or R 8 and R 10 Together with the central aromatic ring, it forms a naphthyl group, or R 9 and R 10 Together with the central aromatic ring, a naphthyl group is formed. Specific alkenyl aromatic monomers include, for example, styrene, chlorostyrenes such as p-chlorostyrene, methylstyrenes such as α-methylstyrene and p-methylstyrene, and tert-butylstyrenes such as 3-tert-butylstyrene and 4-tert-butylstyrene. In one aspect, the alkenyl aromatic monomer is styrene.

[0021] The conjugated diene used to prepare the hydrogenated block copolymer can be C 4-20 Conjugated dienes. Suitable conjugated dienes include, for example, 1,3-butadiene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and the like, and combinations thereof. In one aspect, the conjugated diene is 1,3-butadiene, 2-methyl-1,3-butadiene, or a combination thereof. In another aspect, the conjugated diene is 1,3-butadiene.

[0022] The hydrogenated block copolymer is a copolymer comprising (A) at least one block derived from an alkenyl aromatic compound and (B) at least one block derived from a conjugated diene, wherein the aliphatic unsaturated group content in block (B) is at least partially reduced by hydrogenation. In one aspect, the aliphatic unsaturation in the (B) block is reduced by at least 50%, or at least 70%. The arrangement of blocks (A) and (B) can be a radially remote block structure with or without branches. In one aspect, the hydrogenated block copolymer is a diblock copolymer, a triblock copolymer, or a combination thereof.

[0023] In one aspect, the hydrogenated block copolymer does not include monomer residues other than alkenyl aromatic compounds and conjugated dienes. In one aspect, the hydrogenated block copolymer is composed of blocks derived from alkenyl aromatic compounds and conjugated dienes. It does not include grafting formed by these or any other monomers. It also consists of carbon and hydrogen atoms and therefore does not include heteroatoms. In one aspect, the hydrogenated block copolymer includes residues of one or more acid functionalizing agents such as maleic anhydride. In one aspect, the hydrogenated block copolymer includes polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer.

[0024] Methods for preparing hydrogenated block copolymers are known in the art and many hydrogenated block copolymers are commercially available.

[0025] The hydrogenated block copolymer can be present in the thermoplastic composition in an amount of 1 to 30 weight percent, based on the total weight of the composition. Within this range, the hydrogenated block copolymer can be present in an amount of 1 to 25 weight percent, or 2 to 23 weight percent, or 5 to 30 weight percent, or 1 to 22 weight percent, or 1 to 20 weight percent, or 5 to 20 weight percent, or 8 to 22 weight percent, or 2 to 15 weight percent, each based on the total weight of the thermoplastic composition.

[0026] In one aspect, the impact modifier other than the hydrogenated block copolymer can be minimized (i.e., present in an amount less than 1 weight percent) or excluded from the thermoplastic composition. For example, homopolystyrene, high impact polystyrene or core-shell impact modifier can be excluded from the composition. In one aspect, the hydrogenated block copolymer with an alkenyl aromatic compound content greater than 20 weight percents can be minimized or excluded from the composition. For example, the hydrogenated block copolymer with an alkenyl aromatic compound content greater than 20 weight percents can be present in an amount of 5 weight percents or less, or 1 weight percent or less, or 0.5 weight percent or less, or 0.1 weight percent or less. In one aspect, the hydrogenated block copolymer with an alkenyl aromatic compound content greater than 20 weight percents is excluded from the composition. In one aspect, the hydrogenated block copolymer with a linear structure can be excluded from the composition.

[0027] The combined amount of the poly(methyl methacrylate) and the hydrogenated block copolymer is at least 90 weight percent, or at least 92 weight percent, or at least 95 weight percent, or at least 97 weight percent, or at least 99 weight percent. In other words, the composition can contain 10 weight percent or less, or 8 weight percent or less, or 5 weight percent or less, or 3 weight percent or less, or 1 weight percent or less of components other than poly(methyl methacrylate) and the hydrogenated block copolymer having an alkenyl aromatic content of 10 to 20 weight percent.

[0028] In a specific aspect, the thermoplastic composition can comprise 75 to 99 weight percent, or 77 to 98 weight percent, of poly(methyl methacrylate); and 1 to 25 weight percent, or 2 to 23 weight percent, of a radial hydrogenated block copolymer, wherein the radial hydrogenated block copolymer has an alkenyl aromatic content of 10 to 15 weight percent, based on the total weight of the radial hydrogenated block copolymer. The radial hydrogenated block copolymer can be a poly(styrene-ethylene / butylene-styrene) radial triblock copolymer.

[0029] The thermoplastic composition may optionally further comprise an additive composition. The additive composition comprises one or more additives. The additive can be, for example, a stabilizer, a release agent, a lubricant, a processing aid, an anti-drip agent, a nucleating agent, a UV blocker, a dye, a pigment, an antioxidant, an antistatic agent, a foaming agent, mineral oil, a metal deactivator, an antitack agent or a combination thereof. In one aspect, the additive composition can comprise an antioxidant. When present, based on the gross weight of the composition, such additive is typically used in an amount of 0.1 to 10 weight percent.

[0030] Antioxidant additives may include organic phosphites such as tris(nonylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, distearylpentaerythritol diphosphite; alkylated monophenols or polyphenols; alkylation reaction products of polyphenols with dienes, such as tetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane; butylation reaction products of p-cresol or dicyclopentadiene; alkylated hydroquinones; hydroxylated thiodiphenyl ethers; alkylene-bisphenols; benzyl compounds; β-(3,5-di-tert-butyl)-4-hydroxyhydrocinnamate; -4-hydroxyphenyl)-propionic acid ester with a monohydric alcohol or polyhydric alcohol; β-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acid ester with a monohydric alcohol or polyhydric alcohol; ester of a thioalkyl or thioaryl compound, such as distearylthiopropionate, dilaurylthiopropionate, ditridecylthiodipropionate, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate; β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid amide, or a combination thereof. The antioxidant can be used in an amount of 0.01 to 0.5 weight percent, or 0.01 to 0.1 weight percent, based on the total weight of the composition.

[0031] Composition can be minimized or excluded alternatively other component that is not specifically described in this article.For example, composition comprises and is less than 5 weight percents or is less than 2 weight percents or is less than 1 weight percent or is less than 0.1 weight percent of the thermoplastic polymer except the aforementioned polymer of the present composition.In one aspect, composition can minimize or exclude homopolystyrene, rubber-modified polystyrene or core-shell impact modifier.

[0032] The composition according to the present disclosure can exhibit a combination of desired properties. For example, a molded sample of the composition can exhibit a dielectric constant Dk of 2.45 to 2.75 at 1.9 gigahertz (GHz). A molded sample of the composition can exhibit a dielectric loss Df of less than 0.01 at 1.9 GHz. According to ASTM D1003, at a thickness of 2 mm or 3 mm, the molded sample of the composition can exhibit a transmittance greater than 90%. According to ASTM D1003, at a thickness of 2 mm, the molded sample of the composition can exhibit a haze of less than 4%. According to ASTM D1003, the molded sample of the composition can exhibit a turbidity of less than 8% at a thickness of 3 mm. The molded sample of the composition can exhibit a notched Izod impact strength of at least 15 joules / meter (J / m) at room temperature, 0°C, -30°C, or -40°C, each determined according to ASTM D648. The molded sample of the composition can exhibit one or more of the aforementioned properties. In one aspect, the molded sample of the composition exhibits each of the aforementioned properties.

[0033] In a specific aspect, the thermoplastic composition of the present disclosure can comprise 75 to 99 weight percent poly(methyl methacrylate); and 1 to 25 weight percent radial poly(styrene-ethylene / butylene-styrene) triblock copolymer having a styrene content of 10 to 15 weight percent, based on the total weight of the radial hydrogenated block copolymer; wherein the amount of poly(methyl methacrylate) and radial poly(styrene-ethylene / butylene-styrene) triblock copolymer totals at least 95 weight percent, based on the total weight of the composition; and wherein a molded sample of the thermoplastic composition exhibits one or more of the following: a dielectric constant, Dk, of 2.45 to 2.75 at 1.9 GHz; a dielectric loss, Df, of less than 0.01 at 1.9 GHz; a transmittance greater than 90% at a thickness of 2 mm or 3 mm according to ASTM D1003; a haze of less than 4% at a thickness of 2 mm according to ASTM D1003; and a haze of less than 8% at a thickness of 3 mm according to ASTM D1003.

[0034] For example, the compositions of the present disclosure can be made by melt blending the components of the composition. Conventional equipment such as a ribbon blender, a HENSCHEL TM Mixer, Banbury TMThe components of the composition can be mixed or blended using a mixer, a tumbler, or the like, and the blended composition can then be melt blended or melt kneaded. Common equipment such as single-screw extruders, twin-screw extruders, multi-screw extruders, co-kneaders, etc. can be used for melt blending or melt kneading. For example, the composition of the present invention can be prepared by melt blending the components in a twin-screw extruder at a temperature of 50 to 210° C. The extrudate can be immediately quenched and pelletized in a water bath. As required, the pellets thus prepared can be a quarter inch long or less. Such pellets can be used for subsequent molding, shaping, or forming.

[0035] The shaped, formed or molded articles comprising the composition represent another aspect of the present disclosure. By various methods, such as injection molding, extrusion, rotational molding, blow molding and thermoforming, the composition can be molded into useful molded articles. The article can be a consumer product. In some aspects, the article can be an automotive component. In some aspects, the article can be a consumer electronics housing. Exemplary articles include but are not limited to external automotive parts (grilles, mirror housings, columns, spoilers, logos, roof rails, frames, decorations, fenders, etc.), interior automotive parts (decorative parts, electronic housings, dashboard parts, navigation systems, housing frames, etc.), storage boxes, personal device parts, household appliance parts, furniture, electrical housings (e.g., robot vacuum cleaners, drones, etc.) and consumer electronic devices (e.g., for laptop computers, phones, tablets, batteries, wireless charging, AR / VR goggles, etc.) Equipment housings or parts). Exemplary multilayer products include but are not limited to top cover layers in sheet form, top or middle layers in multilayer assemblies (e.g., for electronic devices, photovoltaic devices, (O) LEDs), films for insert molding or in-mold decoration, top layers for composite materials, etc. In some aspects, the article can be an automotive bumper, an automotive exterior part, an automotive reflector housing, an automotive wheel cover, an automotive dashboard or trim, an automotive glove box, automotive door hardware or other interior trim, an automotive exterior light, an automotive part in the engine compartment, an agricultural tractor or device part, a vehicle window or part thereof, a construction equipment vehicle or device part, a marine or personal watercraft part, an all-terrain vehicle or all-terrain vehicle part, plumbing equipment, a valve or pump, an air conditioning heating or cooling part, a furnace or heat pump part, a computer housing, a computer housing or business machine housing or part, a monitor housing or part, a computer router, a desktop printer, a large office / industrial printer, an electronic part, a projector part, an electronic display part, a copier part, a scanner part, an electronic printer toner cartridge, a handheld electronic device housing, a handheld device housing, a hair dryer, an iron, a coffee maker, a toaster, a washing machine or laundry machine parts, microwave ovens, ovens, power tools, electrical components, electrical enclosures, lighting parts, parts for lighting fixtures, dental instruments, medical instruments, medical or dental lighting parts, aircraft parts, train or track parts, seat assemblies, sidewalls, ceiling parts, cookware, medical instrument trays, animal cages, fibers, laser-welded medical devices, optical fibers, lenses (automatic and non-automatic), cell phone parts, greenhouse parts, sunroom parts, fire helmets, safety shields, safety glasses, air pump parts, humidifier housings, thermostatic control housings, air conditioner drain pans, outdoor cabinets, telecommunications housings or infrastructure, Simple Network Detection System (SNIDS) equipment, network interface devices, smoke detectors, parts or equipment in plenum spaces, medical scanners, X-ray equipment, parts for medical applications or devices, electrical boxes or housings, and electrical connectors, construction or agricultural equipment, and turbine blades.

[0036] In other aspects, the article is a component of an aircraft interior or train interior, an access panel, an access door, an air damper, a gas regulator, an air grille, a handrail, a luggage storage door, a balcony component, a cabinet wall, a ceiling panel, a door pull, a door handle, a duct housing, a housing for an electronic device, an equipment housing, an equipment panel, a floor panel, a food cart, a food tray, a galley surface, a handle, a television housing, a light panel, a magazine rack, a telephone housing, a partition, a trolley part, a seat back, a seat component, a fence component, Seat shells, brackets, side walls, speaker housings, storage compartments, storage housings, toilet seats, tray tables, trays, decorative panels, window trim, window slides, balcony components, balers, ceiling panels, covers for life jackets, covers for storage bins, dust covers for windows, layers for electrochromic devices, lenses for televisions, electronic displays, gauges or instrument panels, lamp covers, light diffusers, light tubes, light pipes, reflectors, partitions, railings, refrigerator doors, shower doors, sink bowls, cart containers, cart side panels or windows.

[0037] As described herein, the present inventors have unexpectedly discovered that compositions comprising specific amounts of the components described herein can provide certain advantageous properties. In particular, a combination of high mechanical strength, good dielectric properties, and good optical properties can be achieved. Thus, the present disclosure provides significant improvements.

[0038] The present disclosure is further illustrated by the following examples, which are non-limiting.

[0039] Example

[0040] The materials used in the following examples are provided in Table 1.

[0041] Table 1

[0042]

[0043] On Coperion ZSK-26Mc twin-screw extruder, prepare composition by mixing, all components are fed into main throat.Composition is melt-kneaded, extruded, cooled and granulated by water bath.For the comparative example using PMMA-1, PMMA-2 or 1M-PMMA separately, these compositions are injection molded as is.Typical extrusion profile is shown in Table 2.

[0044] Table 2

[0045]

[0046]

[0047] After drying the extruded pellets at 120° C. for 3 hours using a Sumitomo DEMAG SE180EV injection molding machine or a FANUC S-2000i injection molding machine, the extruded pellets were molded into test specimens. Typical molding conditions are shown in Table 3.

[0048] Table 3

[0049] Molding parameters unit value Pre-drying time Hour 4 Pre-drying temperature ℃ 80 Zone 1 temperature ℃ 200 Zone 2 temperature ℃ 210 Zone 3 temperature ℃ 210 Nozzle temperature ℃ 220 mold temperature ℃ 30

[0050] Molded samples of the compositions were evaluated according to the following test methods. Specific gravity was determined according to ASTM D792. Melt flow rate (MFR) was determined according to ASTM D638 at 230°C under a 2.16 kg load. Tensile properties were characterized according to ASTM D790 at a temperature of 23°C and a test speed of 50 mm / min. Flexural properties were characterized according to ASTM D256 at a temperature of 23°C on a 127 x 12.7 x 3.2 millimeter (mm) bar at a test speed of 1.27 millimeters / minute (mm / min). Heat deflection temperature (HDT) was determined according to ASTM D648 using a 127 x 12.7 x 3.2 mm bar under a load of 1.82 megapascals (MPa). Notched Izod impact strength (NII) was determined according to ASTM D648 on 63.5 x 12.7 x 3.2 mm rods at 23° C., 0° C., -30° C., or -40° C. under a load of 5.0 lbf. Unnotched Izod impact strength was determined according to ASTM D648 on 63.5 x 12.7 x 3.2 mm rods at 23° C., 0° C., -30° C., or -40° C. under a load of 5 lbf. Dielectric constant (Dk) and dielectric loss (Df) were measured on 100 x 100 x 2 mm panels at 1.9 GHz using a QWED split dielectric resonator and an Agilent PNA network analyzer. Haze and transmittance were measured according to ASTM D1003 on 100 x 100 x 2 or 100 x 100 x 3 mm panels. Yellowness index (YI) is measured according to ASTM E313 on 100 x 100 x 2 or 100 x 100 x 3 mm panels. Pencil hardness is measured using a PPH-1 model, a 1 kg load, a 45° angle, a Mitsubishi pencil, and a 100 x 100 x 2 mm plaque. Hardness is reported as the hardest pencil that does not scratch the surface. The pencil hardness scale from softer to harder is 2B, B, HB, F, H, 2H, 3H, etc.

[0051] Table 4 shows the compositions and properties of Examples 1 to 7 and Comparative Examples 1 to 10. The amount of each component is provided in weight percent (wt %) based on the total weight of the composition.

[0052] Table 4

[0053]

[0054]

[0055] Comparative Example 1 shows the performance of PMMA-1. Examples 1-4 show the compositions of PMMA-1 and different amounts of SEBS-1. As shown in Table 4, compared to Comparative Example 1, a decrease in Dk and Df was observed for each of Examples 1-4. An increase in impact strength was observed. Unexpectedly, the compositions of Examples 1-4 maintained high transparency (e.g., greater than 90%) and low haze. Relative to Comparative Example 3 (which is a commercially available impact-modified PMMA), a decrease in Dk and Df was observed for each of Examples 1-4 compared to Comparative Example 3. It was observed that various mechanical properties have a certain dependence on the amount of SEBS contained in the composition. Compared to Comparative Examples 4-6, it can be seen that the use of SEBS with a lower polystyrene content as in Examples 1-4 can provide good transparency and haze.

[0056] Comparative Example 2 illustrates the performance of PMMA-2. Examples 5-7 show compositions of PMMA-1 and varying amounts of SEBS-1. As shown in Table 4, compared to Comparative Example 2, a decrease in Dk and Df was observed in each of Examples 5-7. Increased impact strength was also observed. Surprisingly, the compositions of Examples 1-4 maintained high transparency (e.g., greater than 90%) and low haze.

[0057] Comparative example 7-10 shows a composition suitable with the composition of embodiment 1-4, except that, linear block copolymer (SEBS-3) is used instead of radial block copolymer (SEBS-1). The SEBS-3 block copolymer used in comparative example 7-10 has the same styrene content as the SEBS-1 radial block copolymer used in embodiment 1-4. As shown in Table 4, when using radial block copolymer, compared with the composition of embodiment 1-4, the composition of comparative example 7-10 all shows significantly higher turbidity and yellowness under 2 and 3 millimeters of thickness. Compared with the composition of embodiment 1-4, the composition of comparative example 7-10 also shows the transmittance reduced. Therefore it can be seen that even when styrene content is identical, using the hydrogenated block copolymer with linear structure can not achieve identical optical performance.

[0058] Thus, when including specific hydrogenated block copolymers having specific structures and alkenyl aromatic compound contents, compositions according to the present disclosure can advantageously provide a desired combination of dielectric, mechanical, and optical properties. Thus, the present disclosure provides significant improvements.

[0059] The present invention further encompasses the following aspects.

[0060] Aspect 1: A thermoplastic composition comprising: 70 to 99 weight percent poly(methyl methacrylate); and 1 to 30 weight percent of a radially hydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene, having an alkenyl aromatic compound content of 10 to 20 weight percent based on the total weight of the hydrogenated block copolymer; wherein the weight percent of each component is based on the total weight of the thermoplastic composition; wherein the combined amount of poly(methyl methacrylate) and the hydrogenated block copolymer is at least 90 weight percent; and wherein a molded sample of the thermoplastic composition exhibits one or more of the following: a dielectric constant Dk of 2.45 to 2.75 at 1.9 GHz; a dielectric loss Df of less than 0.01 at 1.9 GHz; a transmittance greater than 90% at a thickness of 2 mm or 3 mm according to ASTM D1003; a haze of less than 4% at a thickness of 2 mm according to ASTM D1003; and a haze of less than 8% at a thickness of 3 mm according to ASTM D100.

[0061] Aspect 2: The thermoplastic composition according to aspect 1, wherein the hydrogenated block copolymer is a poly(styrene-ethylene / butylene-styrene) triblock copolymer.

[0062] Aspect 3: The thermoplastic composition according to aspect 1 or 2, wherein the hydrogenated block copolymer has an alkenyl aromatic content of 10 to 15 weight percent based on the total weight of the hydrogenated block copolymer.

[0063] Aspect 4: The thermoplastic composition of any of aspects 1 to 3, comprising 75 to 99 weight percent poly(methyl methacrylate).

[0064] Aspect 5: The thermoplastic composition of any one of aspects 1 to 4, comprising 1 to 25 weight percent of the hydrogenated block copolymer.

[0065] Aspect 6: The thermoplastic composition of any one of aspects 1 to 5, comprising 75 to 99 weight percent, or 77 to 98 weight percent, of poly(methyl methacrylate); and 1 to 25 weight percent, or 2 to 23 weight percent of the hydrogenated block copolymer, wherein the hydrogenated block copolymer has an alkenyl aromatic content of 10 to 15 weight percent based on the total weight of the hydrogenated block copolymer.

[0066] Aspect 7: The thermoplastic composition according to aspect 6, wherein the hydrogenated block copolymer is a poly(styrene-ethylene / butylene-styrene) triblock copolymer.

[0067] Aspect 8: The thermoplastic composition according to any one of aspects 1 to 7, further comprising an additive composition.

[0068] Aspect 9: The thermoplastic composition according to any one of aspects 1 to 8, further comprising an antioxidant.

[0069] Aspect 10: The thermoplastic composition of any one of aspects 1 to 9, wherein the combined amount of the poly(methyl methacrylate) and the hydrogenated block copolymer is at least 92 weight percent, or at least 95 weight percent, or at least 97 weight percent, or at least 99 weight percent, based on the total weight of the composition.

[0070] Aspect 11: The thermoplastic composition of any of aspects 1 to 10, wherein the composition does not include an impact modifier other than the hydrogenated block copolymer.

[0071] Aspect 12: The thermoplastic composition of any of Aspects 1 to 11, wherein a molded sample of the thermoplastic composition exhibits one or more of the following: a dielectric constant Dk of 2.45 to 2.75 at 1.9 GHz; a dielectric loss Df of less than 0.01 at 1.9 GHz; a transmittance greater than 90% at a thickness of 2 mm or 3 mm; a haze of less than 4% at a thickness of 2 mm; and a haze of less than 8% at a thickness of 3 mm.

[0072] Aspect 13: The thermoplastic composition according to aspect 1, comprising 75 to 99 weight percent poly(methyl methacrylate); and 1 to 25 weight percent poly(styrene-ethylene / butylene-styrene) triblock copolymer, the poly(styrene-ethylene / butylene-styrene) triblock copolymer having a styrene content of 10 to 15 weight percent, based on the total weight of the hydrogenated block copolymer; wherein the combined amount of poly(methyl methacrylate) and poly(styrene-ethylene / butylene-styrene) triblock copolymer is at least 95 weight percent, based on the total weight of the composition; and wherein a molded sample of the thermoplastic composition exhibits one or more of the following: a dielectric constant Dk of 2.45 to 2.75 at 1.9 GHz; a dielectric loss Df of less than 0.01 at 1.9 GHz; a transmittance greater than 90% at a thickness of 2 mm or 3 mm; a haze of less than 4% at a thickness of 2 mm; and a haze of less than 8% at a thickness of 3 mm.

[0073] Aspect 14: A method for making the thermoplastic composition of any of aspects 1 to 13, comprising melt mixing the components of the composition.

[0074] Aspect 15: An article comprising the composition of any one of aspects 1 to 13.

[0075] Alternatively, the compositions, methods, and articles may comprise, consist of, or consist essentially of any suitable material, step, or component disclosed herein. The compositions, methods, and articles may additionally or alternatively be formulated so as to be free of or essentially free of any material (or species), step, or component that is otherwise not necessary to achieve the function or purpose of the compositions, methods, and articles.

[0076] All ranges disclosed herein include endpoints, and endpoints can be combined independently of each other. "Combination" includes blends, mixtures, alloys, reaction products, etc. The terms "first", "second", etc. do not represent any order, quantity or importance, but are used to distinguish one element from another. Unless otherwise specified herein or clearly contradicted by the context, the terms "one" and "a kind of" and "the" do not represent quantity restrictions, but are interpreted as covering the singular and plural. Unless otherwise explicitly stated, "or" means "and / or". Mentioning "an aspect" throughout the specification means that the specific elements described in conjunction with the aspect are included in at least one aspect described herein, and may or may not be present in other aspects. The term "combination thereof" as used in this article includes one or more listed elements and is open, allowing the presence of one or more unnamed similar elements. In addition, it should be understood that the elements described can be combined in any suitable manner in various aspects.

[0077] Unless specified to the contrary herein, all test standards are the most current standards in effect as of the filing date of this application, or, if priority is claimed, the filing date of the earliest priority application in which the test standards appear.

[0078] Unless otherwise defined, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. All cited patents, patent applications, and other references are incorporated herein by reference in their entirety. However, if a term in this application contradicts or conflicts with a term in an incorporated reference, the term from this application takes precedence over the conflicting term from the incorporated reference.

[0079] Compounds are described using standard nomenclature. For example, any position not substituted by any indicator group is understood to have its valency filled by a bond or hydrogen atom as indicated. A dash ("-") that is not between two letters or symbols is used to indicate the point of attachment of a substituent. For example, -CHO connects through the carbon of a carbonyl group.

[0080] As used in this article, the term "alkyl", whether used alone or as a prefix, suffix or fragment of another term, refers to a residue that only contains carbon and hydrogen. The residue can be aliphatic or aromatic, straight chain, cyclic, bicyclic, branched, saturated or unsaturated. It can also contain a combination of aliphatic, aromatic, straight chain, cyclic, bicyclic, branched, saturated and unsaturated hydrocarbon parts. However, when the alkyl residue is described as substituted, it can optionally contain heteroatoms on and above the carbon and hydrogen members of the substituent residue. Therefore, when specifically described as substituted, the alkyl residue can also contain one or more carbonyls, amino, hydroxyl groups, etc., or it can contain heteroatoms in the main chain of the alkyl residue. The term "alkyl" refers to a branched or straight chain, saturated aliphatic alkyl group, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl and n-hexyl and sec-hexyl. "Alkenyl" refers to a straight or branched monovalent hydrocarbon radical having at least one carbon-carbon double bond (e.g., vinyl (-HC=CH2)). "Alkoxy" refers to an alkyl radical attached via an oxygen (i.e., alkyl-O-), such as methoxy, ethoxy, and sec-butoxy. "Alkylene" refers to a straight or branched, saturated, divalent aliphatic hydrocarbon radical (e.g., methylene (-CH2-) or propylene (-(CH2)3-)). "Cycloalkylene" refers to a divalent cyclic alkylene radical, -C n H 2n-x , where x is the number of hydrogens replaced by cyclization. "Cycloalkenyl" refers to a monovalent group having one or more rings and one or more carbon-carbon double bonds in the ring, wherein all ring members are carbon (e.g., cyclopentyl and cyclohexyl). "Aryl" refers to an aromatic hydrocarbon group containing a specified number of carbon atoms, such as phenyl, cycloheptatrienone, indanyl, or naphthyl. "Arylene" refers to a divalent aryl group. "Alkylenarylene" refers to an arylene group substituted by an alkyl group. "Arylalkylene" refers to an alkylene group substituted by an aryl group (e.g., benzyl). The prefix "halo" refers to a group or compound comprising one or more fluorine, chlorine, bromine, or iodine substituents. There may be a combination of different halogen atoms (e.g., bromine and fluorine) or only chlorine atoms. The prefix "hetero" refers to a compound or group comprising at least one ring member of a heteroatom (e.g., 1, 2, or 3 heteroatoms), wherein the heteroatoms are each independently N, O, S, Si, or P. "Substituted" means that the compound or group is substituted with at least one (e.g., 1, 2, 3, or 4) substituents, each of which is independently C 1-9 Alkoxy, C 1-9 Haloalkoxy, nitro (-NO2), cyano (-CN), C 1-6 Alkylsulfonyl (-S(=O)2-alkyl), C 6-12Arylsulfonyl (-S(=O)2-aryl), thiol (-SH), thiocyanate (-SCN), toluenesulfonyl (CH3C6H4SO2-), C 3-12 Cycloalkyl, C 2-12 Alkenyl, C 5-12 Cycloalkenyl, C 6-12 Aryl, C 7-13 Arylalkylene, C 4-12 Heterocycloalkyl, and C 3-12 A heteroaryl group replaces a hydrogen atom provided that the normal valence of the substituted atom is not exceeded. The number of carbon atoms indicated in the group does not include any substituents. For example, -CH2CH2CN is a C2 alkyl group substituted with a nitrile.

[0081] While particular embodiments have been described, presently unforeseen or possibly unforeseen alternatives, modifications, variations, improvements, and substantial equivalents may occur to the applicant or others skilled in the art. Accordingly, the appended claims as filed and as they may be amended are intended to encompass all such alternatives, modifications, variations, improvements, and substantial equivalents.

Claims

1. A thermoplastic composition comprising: 70 to 99 weight percent poly(methyl methacrylate); and 1 to 30 weight percent of a radially hydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene, the conjugated diene having an alkenyl aromatic compound content of 10 to 20 weight percent, preferably 10 to 15 weight percent, based on the total weight of the hydrogenated block copolymer; in, The weight percentage of each component is based on the total weight of the thermoplastic composition; wherein the combined amount of poly(methyl methacrylate) and the hydrogenated block copolymer is at least 90 weight percent; and wherein a molded sample of the thermoplastic composition exhibits one or more of the following: Dielectric constant Dk of 2.45 to 2.75 at 1.9 GHz; Dielectric loss Df less than 0.01 at 1.9 GHz; Greater than 90% transmittance at 2 mm or 3 mm thickness according to ASTM D1003; Less than 4% haze at a thickness of 2 mm according to ASTM D1003; and Less than 8% haze at 3 mm thickness according to ASTM D1003.

2. The thermoplastic composition according to claim 1, wherein The radially hydrogenated block copolymer is a poly(styrene-ethylene / butylene-styrene) triblock copolymer.

3. The thermoplastic composition of any one of claims 1 to 2, comprising 75 to 99 weight percent poly(methyl methacrylate).

4. The thermoplastic composition of any one of claims 1 to 3, comprising 1 to 25 weight percent of the radially hydrogenated block copolymer.

5. The thermoplastic composition according to any one of claims 1 to 4, comprising: 75 to 99 weight percent, or 77 to 98 weight percent, of poly(methyl methacrylate); and 1 to 25 weight percent, or 2 to 23 weight percent, of the radially hydrogenated block copolymer, wherein the hydrogenated block copolymer has an alkenyl aromatic content of 10 to 15 weight percent based on the total weight of the hydrogenated block copolymer.

6. The thermoplastic composition according to claim 5, wherein The radially hydrogenated block copolymer is a poly(styrene-ethylene / butylene-styrene) triblock copolymer.

7. The thermoplastic composition according to any one of claims 1 to 6, further comprising an additive composition.

8. The thermoplastic composition according to any one of claims 1 to 7, further comprising an antioxidant.

9. The thermoplastic composition according to any one of claims 1 to 8, wherein The combined amount of poly(methyl methacrylate) and the radially hydrogenated block copolymer is at least 92 weight percent, or at least 95 weight percent, or at least 97 weight percent, or at least 99 weight percent, based on the total weight of the composition.

10. The thermoplastic composition according to any one of claims 1 to 9, wherein The composition does not contain an impact modifier other than the radially hydrogenated block copolymer.

11. The thermoplastic composition according to any one of claims 1 to 10, wherein The composition does not include a linear hydrogenated block copolymer.

12. The thermoplastic composition according to any one of claims 1 to 11, wherein The radially hydrogenated block copolymer has a molecular weight greater than or equal to 0.92 g / cm 3 proportion.

13. The thermoplastic composition according to claim 1, comprising: 75 to 99 weight percent poly(methyl methacrylate); and 1 to 25 weight percent of a poly(styrene-ethylene / butylene-styrene) triblock copolymer having a styrene content of 10 to 15 weight percent, based on the total weight of the hydrogenated block copolymer; in, The combined amount of poly(methyl methacrylate) and poly(styrene-ethylene / butylene-styrene) triblock copolymer is at least 95 weight percent, based on the total weight of the composition.

14. A process for making the thermoplastic composition of any one of claims 1 to 13, the process comprising melt mixing the components of the composition.

15. An article comprising the composition of any one of claims 1 to 13.

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