IMPROVED HYDROGENATED POLY(VINYLCYCLOHEXANE) (PVCH) POLYMER

BACKGROUND OF THE INVENTION

A. Field of the Invention

[0001] The invention generally concerns a composition, and a method for making the same, that includes a poly(vinyl cyclohexane) (PVCH) polymer having a degree of hydrogenation greater than 97 % and/or a yellowness index (YI) of less than 3.25. In certain aspects, the PVCH polymer can be an amorphous polymer or an atactic polymer.

B. Description of Related Art

[0002] Hydrogenation of amorphous vinyl aromatic polymer compositions (e.g., poly(vinylcyclohexane) (PVCH) polymers) can improve their physical properties, such as thermal and mechanical properties, and oxidative stability. However, it can be difficult to obtain a high degree of hydrogenation. Also, the resulting polymeric composition can suffer in that it can have a yellowness index (YI) unsuitable for transparent/optically clear applications.

[0003] Various attempts to produce polymers with suitable attributes such as a low YI have been described. For example, International Application Publication No. WO 00/69956 to Blaha et al. entitled “Hydrogenated vinyl aromatic polymer compositions containing stabilizers” describes the use of stabilizer additive packages containing amines and UV absorbers to produce poly(vinylcyclohexane) homopolymers having a stable YI. These stabilizer packages can oftentimes be inefficient from a cost perspective and may not reduce the YI to an acceptable level for use in applications that require a high degree of transparency.

SUMMARY OF THE INVENTION

[0004] A discovery has been made that provides a solution to at least one or more of the problems associated with the YI index of PVCH polymer compositions. In one aspect, the discovery can include a composition that has a poly(vinylcyclohexane) (PVCH) polymer having a degree of hydrogenation greater than 97 % and a YI of less than 3.25. The YI can be measured in accordance with ASTM E313 with a molded plaque having a thickness of 3.25 mm comprising the composition. Such polymers can be used in polymeric compositions that rely on a high degree of transparency.

[0005] In one aspect of the present invention, the PVCH polymer can preferably be an amorphous polymer and/or an atactic polymer. In other aspects, the PVCH polymer can be a semicrystalline polymer. The PVCH polymer of the present invention can have a degree of hydrogenation 98 % or greater, preferably 99% or greater, more preferably 99.5% or greater, or most preferably 100%. PVCH polymer compositions of the present invention can have a YI of less than 3.25, preferably 3.0 or less, more preferably 2.75 or less, or most preferably 0.1 to 3, or 1 to 2.75. The PVCH polymer composition of the present invention can have a weight average molecular weight (MW) greater than 30,000 D, preferably 80,000 D to 500,000 D, as measured using gel permeation chromatography (GPC) using polystyrene as a standard. The polymer resin compositions of the present invention can include 95 wt. % or more, preferably 97 wt. % or more, or more preferably 99 wt. % or more of the PVCH polymer. In one aspect, the polymeric resins or composition of the present invention can have or has any one of, any combination of, or all of the following properties: a tensile modulus of at least 2000 MPa, preferably 2000 MPa to 4000 MPa, as measured in accordance with ASTM D638; a tensile strength of at least 25 MPa, preferably 25 MPa to 60 MPa, as measured in accordance with ASTM D638; a tensile elongation of at least 1%, preferably 1 % to 3 %, as measured in accordance with ASTM D638; a flexural modulus of at least 2500 MPa, preferably 2500 MPa to 3500 MPa, as measured in accordance with ASTM D790; a flexural strength of at least 90 MPa, preferably 90 MPa to 140 MPa, as measured in accordance with ASTM D790; a notched Izod impact strength of at least 15 J/m, preferably 15 J/m to 40 J/m, as measured in accordance with ASTM D256; a heat deflection temperature of at least 125 °C at 0.45 MPa, preferably 125 °C to 135 °C at 0.45 MPa, as measured in accordance with ASTM D648; a light transmission equal to or greater than 80 %, preferably 90 % to 95%, as measured in accordance with ASTM DI 003; a haze value of 5 % or less, preferably 0.5 % to 4 %, more preferably 0.5% to 3% as measured in accordance with ASTM DI 003; and/or a glass transition temperature 140 °C to 150 °C, as measured using differential scanning calorimetry (DSC) at 5 °C/min. In some aspects, a polymeric composition of the present invention can be a molded composition (e.g., an extrusion molded, injection molded, compression molded, rotational molded, blow molded, injection blow molded, 3-D printed, or thermoformed article). In certain preferred instances, a polymeric composition of the present invention can be transparent. [0006] A polymeric composition of the present invention can be included in or formed into an article of manufacture. Non-limiting examples of article of manufacture include a film, sheet, a packing film, a forming film, a protective packaging, a shrink sleeve and/or a label, a shrink film, a twist wrap, a sealant film, bag, a coating, a lidding film, a lab ware, a cuvette, a test tube, a Eppendorf tube, a laboratory container, a beaker, a flask, a jar, a bottle, a funnel, a pipette tip, a well plate, a microtiter plate, a syringe, a medical packing film and/or component, a medical tray, a blister pack, a medical component container, a food packing film, a food container, an automotive part, an electrical device part, an electronic device part, an industrial device part, a cover window of an optical device, an optical component of an electronic device, a flash light lens, a camera lens, a sensor lens, an illumination lens, a safety glass lens, an ophthalmic corrective lens, an imaging lens, a semiconductor container, a laser-direct structured electronic connector, a 5G antenna cover, a pre-fillable syringe, a sample vial, an UV-visible spectroscopy cuvette, a biochip, a contact lens mold, a virtual reality lens, a vehicle rear-view camera lens, an electronic display light-guiding plates, a RADAR/LiDAR sensor, or a face shield.

[0007] Methods of preparing polymeric compositions of the present invention are also described. The methods can include hydrogenating a solution comprising an amorphous polystyrene polymer in the presence of a hydrogenation catalyst to obtain a solution comprising a crude amorphous poly(vinylcyclohexane) polymer (PVCH) having a degree of hydrogenation (e.g., greater than 97 %) to produce a PVCH polymer composition. The hydrogenation catalyst can be a low porosity / attrition resistant catalyst, preferably a platinum containing catalyst, more preferably a Pt/CaCO,', Pt/AbOs or Pt/SiCh catalyst. Hydrogenation conditions can include a temperature of 120 °C to 200 °C and a ft pressure of 3.4 MPa to 13.8 MPa (500 to 2000 psig). In some aspects, the crude amorphous PVCH polymer composition can be isolated (e.g., precipitated from the solution) and then further refined. Refining can include any one of, any combination of, or all of: (1) treating a solution of crude PVCH polymer composition with activated carbon black; (2) re-precipitating the crude PVCH polymer composition at least one time; and (3) processing the crude PVCH polymer composition under mild conditions, preferably in the presence of stabilizers, or a combination thereof. After refining the crude PVCH polymer, it can be further hydrogenated to produce the polymer composition of the present invention. Treating the solution of the composition with activated carbon black can include contacting a solution comprising the crude poly(vinylcyclohexane) polymer and a non-polar solvent (e.g., cyclohexane or decahydronaphthalene) with the activated carbon black at 22 °C to 25 °C at atmospheric pressure.

[0008] Methods of reducing the YI of a composition comprising a poly(vinylcyclohexane) polymer are also described. One method can include contacting the composition with activated carbon black, metal deactivators, or a combination thereof, to remove impurities from the composition and reduce the YI of the composition. Such a treatment can produce a composition having a yellowness index of less than 3.25, as measured in accordance with ASTM E313 with a molded plaque having a thickness of 3.25 mm comprising the composition. The PVCH polymer of the composition can have a degree of hydrogenation greater than 97 %, preferably 98% or greater, more preferably 99% or greater, more preferably 99.9% or greater and up to 100%.

[0009] In certain aspects of the invention, 22 embodiments are described. Embodiment l is a composition comprising an amorphous poly(vinylcyclohexane) (PVCH) polymer having a degree of hydrogenation greater than 97 %, wherein the composition has a yellowness index of less than 3.25, as measured in accordance with ASTM E313 with a molded plaque having a thickness of 3.25 mm comprising the composition. Embodiment 2 is the composition of embodiment 1, wherein the amorphous PVCH polymer has a degree of hydrogenation greater than 98 %, preferably 99% or greater, more preferably 99.5% or greater, or most preferably 100%. Embodiment 3 is the composition of any one of embodiments 1 to 2, wherein the composition has a yellowness index (YI) of 3.24 or less, preferably 3.00 or less, more preferably 2.75 or less, most preferably 0.5 to 3, or 1 to 2.75. Embodiment 4 is the composition of any one of embodiments 1 to 3, wherein the amorphous PVCH polymer has a weight average molecular weight (Mw) greater than 30,000 D, preferably 80,000 D to 500,000 D, as measured using gel permeation chromatography (GPC) using polystyrene as a standard. Embodiment 5 is the composition of any one of embodiments 1 to 4, wherein the composition contains greater than 95 wt. %, preferably greater than 97 wt. %, or more preferably greater than 99 wt. % of the amorphous PVCH polymer. Embodiment 6 is the composition of any one of embodiments 1 to 5, wherein the composition has any one of, any combination of, or all of the following properties: a tensile modulus of at least 2000 MPa, preferably 2000 MPa to 4000 MPa, as measured in accordance with ASTM D638; a tensile strength of at least 25 MPa, preferably 25 MPa to 60 MPa, as measured in accordance with ASTM D638; a tensile elongation of at least 1%, preferably 1 % to 3 %, as measured in accordance with ASTM D638; a flexural modulus of at least 2500 MPa, preferably 2500 MPa to 3500 MPa, as measured in accordance with ASTM D790; a flexural strength of at least 90 MPa, preferably 90 MPa to 140 MPa, as measured in accordance with ASTM D790; a notched Izod impact strength of at least 15 J/m, preferably 15 J/m to 40 J/m, as measured in accordance with ASTM D256; a heat deflection temperature of at least 125 °C at 0.45 MPa, preferably 125 °C to 135 °C at 0.45 MPa, as measured in accordance with ASTM D648; a light transmission equal to or greater than 80 %, preferably 90 % to 95%, as measured in accordance with ASTM DI 003; a haze value of 5% or less, preferably 0.5% to 4%, more preferably 0.5% to 3% as measured in accordance with ASTM DI 003; and/or a glass transition temperature 140 °C to 150 °C, as measured using differential scanning calorimetry (DSC) at 5 °C/min. Embodiment 7 is the composition of any one of embodiments 1 to 6, wherein the composition has: a tensile strength of 37 MPa to 45 MPa, as measured in accordance with ASTM D638; a notched Izod impact strength of 20 J/m to 30 J/m, as measured in accordance with ASTM D256; a light transmission of 92 % to 97 %, measured in accordance with ASTM DI 003; and a haze value of 2 % to 4 %, as measured in accordance with ASTM DI 003. Embodiment 8 is the composition of any one of embodiments 1 to 7, wherein the composition is a molded composition. Embodiment 9 is the composition of embodiment 8, wherein the composition is an extrusion molded, injection molded, compression molded, rotational molded, blow molded, injection blow molded, 3-D printed, or thermoformed article. Embodiment 10 is the composition of any one of embodiments 1 to 9, wherein the composition is transparent. Embodiment 11 is the composition of any one of embodiments 1 to 10, wherein the composition is comprised in an article of manufacture. Embodiment 12 is the composition of embodiment 11, wherein the article of manufacture is a film, sheet, packing film, forming film, protective packaging, shrink sleeve and/or label, shrink film, twist wrap, sealant film, bag, coating, lidding film, lab ware, cuvette, test tube, Eppendorf tube, laboratory container, beaker, flask, jar, bottle, funnel, pipette tip, well plate, microtiter plate, syringe, medical packing film and/or component, a medical tray, a blister pack, a medical component container, a food packing film, a food container, an automotive part, an electrical device part, an electronic device part, an industrial device part, a cover window of an optical device, an optical component of an electronic device, a flash light lens, a camera lens, a sensor lens, an illumination lens, a safety glass lens, an ophthalmic corrective lens, an imaging lens, a semiconductor container, a laser-direct structured electronic connector, a 5G antenna cover, a pre-fillable syringe, a sample vial, a UV-visible spectroscopy cuvette, a biochip, a contact lens mold, a virtual reality lens, a vehicle rear-view camera lens, an electronic display light-guiding plates, a RADAR/LiDAR sensor, or a face shield.

[0010] Embodiment 13 is a method of preparing the composition of any one of embodiments 1 to 10, the method comprising: hydrogenating an amorphous polystyrene solution in the presence of a hydrogenation catalyst to obtain a solution comprising a crude amorphous poly(vinylcyclohexane) (PVCH) polymer having a degree of hydrogenation greater than 97 %; refining the crude amorphous PVCH polymer to obtain the composition of any one of embodiments 1 to 10, wherein refining comprises one of more of: treating the solution of the crude amorphous PVCH polymer with activated carbon black; precipitating and/or re-precipitating the crude amorphous PVCH polymer at least one time; and processing the crude amorphous PVCH polymer under mild conditions, preferably in the presence of stabilizers, and optionally further hydrogenating the precipitated and/or refined crude amorphous PVCH polymer. Embodiment 14 is the method of embodiment 13, wherein the hydrogenation catalyst is a low porosity / attrition resistant catalyst. Embodiment 15 is the method of any one of embodiments 13 to 14, wherein the catalyst is a platinum containing catalyst, more preferably a Pt/CaCCh', Pt/AbOs or Pt/SiCb catalyst, preferably a Pt/AbOs catalyst. Embodiment 16 is the method of any one of embodiments 13 to 15, wherein the hydrogenation of the amorphous polystyrene is performed at 120 °C to 200 °C and 3.4 MPa to 13.8 MPa of H2 pressure. Embodiment 17 is the method of any one of embodiments 13 to 16 wherein treating the solution of the composition with activated carbon black comprises contacting a cyclohexane solution of the crude amorphous poly(vinylcyclohexane) polymer with the activated carbon black at 20 °C to 30 °C at atmospheric pressure. Embodiment 18 is the method of any one of embodiments 13 to 17, wherein the crude PVCH polymer composition is isolated (e.g., by precipitated) prior to refining. Embodiment 19 is the method of any one of embodiments 13 to 18, wherein the isolated or refined crude PVCH polymer composition is further hydrogenated to produce the polymer composition of the present invention.

[0011] Embodiment 20 is a method of reducing the yellowing index (YI) of a composition comprising an amorphous poly(vinylcyclohexane) (PVCH) polymer, the method comprising contacting the composition with activated carbon black, metal deactivators or a combination thereof to remove impurities from the composition and reduce the YI of the composition. Embodiment 21 is the method of embodiment 10, wherein the composition has a yellowness index of less than 3.25, as measured in accordance with ASTM E313 with a molded plaque having a thickness of 3.25 mm comprising the composition. Embodiment 22 is the method of any one of embodiments 20 to 21, wherein the amorphous PVCH polymer has a degree of hydrogenation greater than 97 %, preferably 98%, more preferably 99%, more preferably 99.9%.

[0012] Other embodiments of the invention are discussed throughout this application. Any embodiment discussed with respect to one aspect of the invention applies to other aspects of the invention as well and vice versa. Each embodiment described herein is understood to be embodiments of the invention that are applicable to other aspects of the invention. It is contemplated that any embodiment or aspect discussed herein can be combined with other embodiments or aspects discussed herein and/or implemented with respect to any method or composition of the invention, and vice versa. Furthermore, compositions of the invention can be used to achieve methods of the invention.

[0013] The following includes definitions of various terms and phrases used throughout this specification and the claims.

[0014] “Yellow Index (YI)” refers to a number calculated from spectrophotometric data that describes the change in color of a test sample from clear or white to yellow. YI can be determined using standard methodology such as ASTM E313 with a molded plaque having a thickness of 3.25 mm comprising a polymer composition of the present invention.

[0015] “Amorphous” polymers include amorphous regions where molecules are arranged randomly. Amorphous polymers generally do not include crystalline regions where molecules are arranged in a more uniform pattern. “Semi-crystalline” polymers refers to polymers having both amorphous regions and crystalline regions.

[0016] The term “atactic polymer” refers to a polymer or polymer structure in which the repeating units have no regular stereochemical configuration; having a random sequence of stereochemical groups.

[0017] The phrase “hydrogenation activity” refers to as a measured rate of polymer hydrogenation, in the unit of moles of aromatic rings per hour per gram of catalytic metal at a specific reaction temperature, pressure, and polymer concentration. [0018] The phrase “mild conditions” refers to conditions which result in no more than a 50% loss in molecular weight. More preferably no more than a 25% loss; most preferably, no more than a 2% loss. Non-limiting examples include lower shear in processing such as one or more of extrusion and molding, lower temperature of processing, lower residence time in the processing, lower oxygen and/or completely inert atmosphere during processing optionally along with stabilizers.

[0019] The terms “about” or “approximately” are defined as being close to as understood by one of ordinary skill in the art. In one non-limiting embodiment, the terms are defined to be within 10%, preferably within 5%, more preferably within 1%, and most preferably within 0.5%.

[0020] The terms “wt.%,” “vol.%,” or “mol.%” refers to a weight percentage of a component, a volume percentage of a component, or molar percentage of a component, respectively, based on the total weight, the total volume of material, or total moles, that includes the component. In a non-limiting example, 10 grams of component in 100 grams of the material is 10 wt.% of component.

[0021] The term “substantially” and its variations are defined to include ranges within 10%, within 5%, within 1%, or within 0.5%.

[0022] The terms “inhibiting” or “reducing” or “preventing” or “avoiding” or any variation of these terms, when used in the claims and/or the specification includes any measurable decrease or complete inhibition to achieve a desired result.

[0023] The term “effective,” as that term is used in the specification and/or claims, means adequate to accomplish a desired, expected, or intended result.

[0024] The use of the words “a” or “an” when used in conjunction with any of the terms “comprising,” “including,” “containing,” or “having” in the claims, or the specification, may mean “one,” but it is also consistent with the meaning of “one or more,” “at least one,” and “one or more than one.”

[0025] The words “comprising” (and any form of comprising, such as “comprise” and “comprises”), “having” (and any form of having, such as “have” and “has”), “including” (and any form of including, such as “includes” and “include”) or “containing” (and any form of containing, such as “contains” and “contain”) are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.

[0026] The compositions of the present invention can “comprise,” “consist essentially of,” or “consist of’ particular ingredients, components, compositions, etc. disclosed throughout the specification. With respect to the transitional phrase “consisting essentially of,” in one nonlimiting aspect, a basic and novel characteristic of the compositions of the present invention contain a PVCH polymer, preferably an amorphous (e.g., atactic) polymer, having a degree of hydrogenation greater than 97 % and a yellowness index of less than 3.25.

[0027] Other objects, features and advantages of the present invention will become apparent from the following figures, detailed description, and examples. It should be understood, however, that the figures, detailed description, and examples, while indicating specific embodiments of the invention, are given by way of illustration only and are not meant to be limiting. Additionally, it is contemplated that changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description. In further embodiments, features from specific embodiments may be combined with features from other embodiments. For example, features from one embodiment may be combined with features from any of the other embodiments. In further embodiments, additional features may be added to the specific embodiments described herein.

BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Advantages of the present invention may become apparent to those skilled in the art with the benefit of the following detailed description and upon reference to the accompanying drawings.

[0029] FIG. 1 is a schematic of an embodiment of a process to prepare PVCH polymer compositions of the present invention that includes a reactor unit and a refining unit.

[0030] FIG. 2 is a schematic of an embodiment of a carbon black refining process of the present invention that can be used to produce a PVCH polymer composition of the present invention. [0031] FIG. 3 is a schematic of an embodiment of re-precipitation refining process to produce a PVCH polymer composition of the present invention.

[0032] FIG. 4. is a schematic of an embodiment of more than one refining process and further hydrogenation process to produce a PVCH polymer composition of the present invention.

[0033] While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings. The drawings may not be to scale.

DETAILED DESCRIPTION OF THE INVENTION

[0034] At least one solution to some of the problems associated with the yellowing of polymeric compositions that include poly(vinylcyclohexane) polymers has been discovered. The solution can include a cost-effective composition that includes PVCH having a degree of hydrogenation greater than 97% and a YI of less than 3.25. Such a composition can be used in transparent and/or optical clear applications.

[0035] These and other non-limiting aspects of the present invention are discussed in further detail in the following sections.

A. Polymeric Compositions

[0036] The polymeric compositions of the present invention can include a PVCH polymer, preferably an amorphous PVCH polymer. In one aspect, the PVCH polymer is atactic. The PVCH polymer can have a degree of hydrogenation greater than 97%. For example, the degree of hydrogenation can include 97.1%, 97.2%, 97.3%, 97.4%, 97.5%, 97.6%, 97.8%, 97.9%, 98%, 98.1%, 98.2%, 98.3%, 98.4%, 98.5%, 98.6%, 98.7%, 98.8%, 98.9%, 99.0%, 99.1%, 99.2%, 99.3%, 99.4%, 99.5%, 99.6%, 99.7%, 99.8%, 99.9%, 100% or any value or range there between. Non-limiting examples of ranges include 97.1 to 100%, 98% to 100%, 98.5% to 100% or the like. The PVCH polymer of the present invention can have a weight average molecular weight (MW) (as measured using gel permeation chromatography (GPC) using polystyrene as a standard) of greater than 30,000 D, preferably 80,000 D to 500,000 D, or any range or value there between. Non-limiting examples of molecular weight values include 30,000 D, 35,000 D, 40,000 D, 50,000 D, 60,000 D, 70,000 D, 80,000 D, 90,000 D, 100,000 D, 150,000 D, 200,000 D, 250,000 D, 300,000 D, 350,000 D, 400,000 D, 450,000 D, 500,000 D, or any value there between. Nonlimiting examples of MW ranges include 30,000 D to 500,000 D, 50,000 D to 500,000 D, 80, 000 D to 500,000 D, 100,000 D to 500,000 D and any range there between.

[0037] The polymer compositions of the present invention can have a YI of less than 3.25. For example, the YI can be 0.1, 0.5, 0.55, 0.60, 0.65, 0.75, 0.80, 0.85, 0.90, 0.95, 1.0, 1.05, 1.1, 1.15, 1.20, 1.25, 1.30, 1.35, 1.40, 1.45, 1.5, 1.55, 1.60, 1.65, 1.70, 1.75, 1.80, 1.85, 1.90, 1.95, 2.0, 2.5, 2.60, 2.65, 2.70, 2.75, 2.80, 2.85, 2.90, 2.95, 3.0, 3.05, 3.10, 3.15, 3.20, 3.24 or any value or range there between.

[0038] The polymer compositions of the present invention can have a total metals (e.g., iron, copper, and the like) of less than 30 ppm, preferably less than 20 ppm, more preferably less than 10 ppm, most preferably less than 1 ppm.

[0039] The polymer compositions of the present invention can have a variety of properties. Non-limiting examples of properties include tensile modulus, tensile strength, tensile elongation, a flexural modulus; a flexural strength a heat deflection temperature, a light transmission value, a haze value, and a glass transition value. The polymer compositions can have one, all, or a combination of the above properties. The composition of the present invention can be transparent.

[0040] Tensile modulus of the polymer compositions of the present invention can be at least 2000 MPa, or 2000 MPa, 2100 MPa, 2200 MPa, 2300 MPa, 2400 MPa, 2500 MPa, 2600 MPa, 2700 MPa, 2800 MPa, 2900 MPa, 3000 MPa, 3100 MPa, 3200 MPa, 3300 MPa, 3400 MPa, 3500 MPa, 3600 MPa, 3700 MPa, 3800 MPa, 3900 MPa, 4000 MPa, or any value there between, or any range there between (e.g., 2000 MPa to 4000 MPa, 2100 MPa to 3900 MPa, 2200 MPa to 3800 MPa, 2500 MPa to 3500 MPa, and the like). Tensile modulus can be measured in accordance with ASTM D638.

[0041] Tensile strength of the polymer compositions of the present invention can be at least 25 MPa, or 25 MPa, 26 MPa, 27 MPa, 28 MPa, 29 MPa, 30 MPa, 31 MPa, 32 MPa, 33 MPa, 34 MPa, 35 MPa, 36 MPa, 37 MPa, 38 MPa, 39 MPa, 40 MPa, 41 MPa, 42 MPa, 43 MPa, 44 MPa, 45 MPa, 46 MPa, 47 MPa, 48 MPa, 49 MPa, 50 MPa, 51 MPa, 52 MPa, 53 MPa, 54 MPa, 55 MPa, 56 MPa, 57 MPa, 58 MPa, 59 MPa, 60 MPa and any value there between or any range there between (e.g., 25 MPa to 60 MPa, 30 MPa to 55 MPa, 40 MPa, to 50 MPa and the like). Tensile strength can be can be measured in accordance with ASTM D638.

[0042] Tensile elongation of the polymer compositions of the present invention can be 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 3.9%, or any value or range there between or any range there between, preferably 1 % to 3 %. Tensile elongation can be can be measured in accordance with ASTM D638.

[0043] Flexural modulus of the polymer compositions of the present invention can beat least 2500 MPa, or 2500 MPa, 2600 MPa, 2700 MPa, 2800 MPa, 2900 MPa, 3000 MPa, 3100 MPa, 3200 MPa, 3300 MPa, 3400 MPa, 3500 MPa or any value there between, or any range there between (e.g., 2500 MPa to 3500 MPa). Flexural modulus can be measured in accordance with ASTM D790.

[0044] Flexural strength of the polymer compositions of the present invention can be at least 90 MPa, or 90 MPa, 95 MPa, 100 MPa, 110 MPa, 115 MPa, 120 MPa, 125 MPa, 130 MPa, 135 MPa, 140 MPa, or any value there between or any range there between (e.g., 90 MPa to 140 MPa, 100 MPa to 135 MPa, 105 to 125 MPa and the like). Flexural strength can be measured in accordance with ASTM D790.

[0045] Notched Izod impact strength of the polymer compositions of the present invention can be, at least 15 J/m, or 15 J/m, 16 J/m, 17 J/m, 18 J/m, 19 J/m, 20 J/m, 21 J/m, 22 J/m, 23 J/m, 24 J/m, 25 J/m, 26 J/m, 27 J/m 28 J/m, 29 J/m, 30 J/m, 31 J/m, 32 J/m, 33 J/m, 34 J/m, 35 J/m, 36 J/m, 37 J/m, 38 J/m, 39 J/m, 40 J/m or any value there between or any range there between (e.g., 15 J/m to 40 J/m, 20 J/m to 40 J/m, or 25 J/m to 35 J/m and the like). Notched Izod impact strength can be measured in accordance with ASTM D256.

[0046] Heat deflection temperature of the polymer compositions of the present invention can be at least 125 °C at 0.45 MPa, or 125 °C, 126 °C, 127 °C, 128 °C, 129 °C, 130 °C, 131 °C, 131 °C, 132 °C, 133 °C, 134 °C, 135 °C or any value there between at 0.45 MPa or any range there between at 0.45 MPa (e.g., 125 °C to 135 °C, 125 °C to 130 °C, and the like at 0.45 MPa). Heat deflection temperatures can be measured in accordance with ASTM D648.

[0047] Light transmission of the polymer compositions of the present invention can be equal to or greater than 80 % or 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, or any value there between, or any range there between (e.g., 80% to 95%, 85 to 95%, 90 % to 95%, and the like). Light transmission can be measured in accordance with ASTM D1003.

[0048] The haze value of the polymer compositions of the present invention can be 5% or less, or less than 5%, 4.5%, 4.0%, 3.5%, 3.0%, 2.5%, 2.0%, 1.5%, 1.0%, 0.5% or 0.1% or any value there between or any range there between (e.g., 0.1% to 5%, 0.5 % to 4 %, 0.5% to 3% and the like). Haze values can be measured in accordance with ASTM DI 003.

[0049] A glass transition temperature of the polymer compositions of the present invention can range from 140 °C to 150 °C, or 140 °C, 141 °C, 142 °C, 143 °C, 144 °C, 145 °C, 146 °C, 147 °C, 148 °C, 149 °C, 150°C or any value or range there between. Glass transition temperatures can be measured using DSC at 5 °C/min.

[0050] In some aspects of the present invention, the polymer compositions have a tensile modulus of at least 2000 MPa, preferably 2000 MPa to 4000 MPa, a tensile strength of at least 25 MPa, preferably 25 MPa to 60 MPa, a tensile elongation of at least 1%, preferably 1 % to 3 %, a flexural modulus of at least 2500 MPa, preferably 2500 MPa to 3500 MPa, a flexural strength of at least 90 MPa, preferably 90 MPa to 140 MPa, a notched Izod impact strength of at least 15 J/m, preferably 15 J/m to 40 J/m, a heat deflection temperature of at least 125 °C at 0.45 MPa, preferably 125 °C to 135 °C at 0.45 MPa, a light transmission equal to or greater than 80 %, preferably 90 % to 95%, a haze value of 5 % or less, preferably 0.5 % to 4 %, more preferably 0.5% to 3%, and a glass transition temperature 140 °C to 150 °C.

[0051] The polymer compositions of the present invention can include additives, other polymers, fillers, or a combination thereof. Non-limiting additive include a metal deactivator, an antioxidant, a heat stabilizer, a flow modifier, an impact modifier, a fire retardant, a mold release agent, a coupling agent, a UV absorber, light stabilizer, a hindered amine light stabilizer, or any combination thereof. Non-limiting examples of antioxidants include sterically hindered phenolic compounds, aromatic amines, a phosphite compound, a thiol compound. Non-limiting examples of hindered phenolic compounds include benzenepropanoic acid (CAS No. 1444299-84-4), 3,5- bis(l,l-dimethylethyl)-4-hydrox-octadecyl ester (CAS No. 73754-27-5); l,2-bis(3,5-di-tert-butyl- 4-hydroxy hydrocinnamoyl)hydrazide (CAS No. 32687-78-8); 2,6-di-/cv7-butyl-4-methylphenol (CAS No. 128-37-0), pentaerythritol-tetrakis(3-(3,5-di-/c77-butyl-4-hydroxypheny l)propionate (CAS No. 6683-19-8), octadecyl 3-(3',5'-di-/c77-butyl-4-hydroxyphenyl)propionate (CAS No. 2082-79-3), l,3,5-trimethyl-2,4,6-tris-(3,5-di-/er/-butyl-4-hydroxybenzy l)benzene (CAS No. 1709-70-2), 2,2'-thiodiethylenebis(3,5-di-/c77-butyl-4-hydroxyphenyl)pro pionate (CAS No. 41484-35-9), calcium bis(ethyl 3,5-di-/c77-butyl-4-hydroxybenzylphosphonate) (CAS No. 65140- 91-2), l,3,5-tris(3',5'-di-/er/-butyl-4'-hydroxybenzyl)-isocyanurat e (CAS No. 27676-62-6), 1,3,5- tris(4-/er/-butyl-3-hydroxy-2,6-dimethylbenzyl)-l,3,5-triazi ne-2,4,6-(lH,3H,5H)-trione (CAS No. 40601-76-1), 3, 3-bis(3-/c77-butyl-4-hydroxyphenyl)ethylene butyrate (CAS No. 32509-66-3), 4,4'-thiobis(2-/er/-butyl-5-methylphenol) (CAS No. 96-69-5), 2,2'-methylene-bis-(6-(l-methyl- cyclohexyl)-para-cresol) (CAS No. 77-62-3), 3,3'-bis(3,5-di-/er/-butyl-4-hydroxyphenyl)-N,N'- hexamethylenedipropionamide (CAS No. 23128-74-7), 2,5,7,8-tetramethyl-2-(4',8',12'- trimethyltridecyl)-chroman-6-ol (CAS No. 10191-41-0), 2,2-ethylidenebis(4,6-di-/c77- butylphenol) (CAS No. 35958-30-6), l,l,3-tris(2-methyl-4-hydroxy-5'-/er/-butylphenyl)butane (CAS No. 1843-03-4), 3,9-bis(l,l-dimethyl-2-(beta-(3-ter/-butyl-4-hydroxy-5- methylphenyl)propionyloxy)ethyl)-2,4,8,10-tetraoxaspiro[5.5] undecane (CAS No. 90498-90-1;),

1.6-hexanediyl-bis(3,5-bis(l,l-dimethylethyl)-4-hydroxybe nzene)propanoate) (CAS No. 35074- 77-2), 2,6-di-/er/-butyl-4-nonylphenol (CAS No. 4306-88-1), 4,4'-butylidenebis(6-/c77-butyl-3- methylphenol (CAS No. 85-60-9); 2,2'-methylene bis(6-/er/-butyl-4-methylphenol) (CAS No. 119-47-1), triethylenglycol-bis-(3-/c77-butyl-4-hydroxy-5-methylphenyl) propionate (CAS No. 36443-68-2), a mixture of Cn to C15 linear and branched alkyl esters of 3 -(3 ',5'-di-/c77-butyl -4'- hydroxyphenyl)propionic acid (CAS No. 171090-93-0), 2,2'-thiobis(6-ter/-butyl-/?ara-cresol) (CAS No. 90-66-4), diethyl-(3,5-di-tert-butyl-4-hydroxybenzyl)phosphate (CAS No. 976-56-7),

4.6-bis (octylthiomethyl)-ortAo-cresol (CAS No. 110553-27-0), benzenepropanoic acid, octyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl)propanoate (CAS No. 125643-61-0), l,l,3-tris[2-methyl-4-[3- (3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]-5-/c77-buty lphenyl]butane (CAS No. 180002- 86-2), mixed styrenated phenols (CAS No. 61788-44-1), butylated, octylated phenols (CAS No. 68610-06-0), butylated reaction product of p-cresol and di cyclopentadiene (CAS No. 68610-51-5) or any combination thereof.

[0052] Non-limiting examples of phosphite antioxidants include one of tris(2,4-di-/c77- butylphenyl)phosphite (CAS No. 31570-04-4), tris(2,4-di-/c77-butylphenyl)phosphate (CAS No. 95906-11-9), bis(2,4-di-ter/-butylphenyl)pentaerythritol diphosphite (CAS No. 26741-53-7); and tetrakis (2,4-di-butylphenyl)-4,4'-biphenylene diphosphonite (CAS No. 119345-01-6), and bis (2,4-dicumylphenyl)pentaerythritol diphosphite (CAS No. 154862-43-8), or any combination thereof.

[0053] Non-limiting examples of UV stabilizers include hindered amine light stabilizers, hydroxybenzophenones, hydroxyphenyl benzotriazoles, cyanoacrylates, oxanilides, hydroxyphenyl triazines, and combinations thereof. Non-limiting examples of hindered amine light stabilizers include dimethyl succinate polymer with 4-hydroxy-2,2,6,6-tetramethyl-l- piperidine ethanol (CAS No. 65447-77-0); poly[[6-((l,l,3,3-tetramethylbutyl)amino)-l,3,5- triazine2,4diyl] [(2,2,6, 6-tetramethyl-4-piperidyl)imino]hexamethylene[2, 2,6, 6-tetramethyl-4- piperidyl)imino]] (CAS No. 70624-18-9); and l,5,8,12-Tetrakis[4,6-bis(N-butyl-N-l,2,2,6,6- pentamethyl-4-piperidylamino)-l,3,5-triazin-2-yl]-l,5,8,12-t etraazadodecane (CAS No. 106990- 43-6).

[0054] Non-limiting examples of heat stabilizers include phenothiazine (CAS No. 92-84-2), /2-methoxyphenol (CAS No. 150-76-5); benzhydrol (CAS No. 91-01-1); 2,5-di-tert-butyl-l,4- benzoquinone (CAS No. 2460-77-7); diisopropylamine (CAS No 108-18-9), and distearyl thiodipropionate (CAS No. 693-36-7), or any combination thereof.

[0055] Non-limiting examples of antioxidants include a mixture of at least two of 1,3,5- trimethyl-2,4,6-tris-(3,5-di-tert-butyl-4-hydroxybenzyl) benzene sold under the trade name of Irganox® 1330 (BASF, Germany), tris[2,4-bis(2-methyl-2-propanyl)phenyl] phosphite sold under the trade name of Irgafos® 168 (BASF, Germany), pentaerythritol -tetrakis (3 -(3, 5 -di -tert-butyl -4- hydroxyphenyl) propionate sold under the trade name Irganox® 1010 (BASF, Germany), 1,5,8,12- Tetrakis[4, 6-bis(N-butyl-N-l, 2,2,6, 6-pentamethyl-4-piperidylamino)- 1,3, 5-triazin-2-yl]-l, 5, 8,12- tetraazadodecane sold under the trade name of Chimassorb 119 (BASF, Germany) is used. [0056] Non-limiting examples of metal deactivators include 3-(3,5-ditert-butyl-4- hydroxyphenyl)-N'-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propa noyl]propanehydrazide sold under the tradename Irganox® MD-1024 (BASF), 2-[[2-[2-[3-(3,5-ditert-butyl-4- hydroxyphenyl)propanoyloxy]ethylamino]-2-oxoacetyl]amino]eth yl 3-(3,5-ditert-butyl-4- hydroxyphenyl)propanoate sold under the tradename Naugard XL-1 (SI Group, USA), oxalyl bis(benzylidenehydrazide) sold under the tradename OABH (Eastman Chemical USA).

[0057] The polymer compositions of the present invention can include additional polymers such that a polymer blend is obtained. Non-limiting examples of additional polymers can include syndiotactic PVCH polymers, isotactic PVCH polymers, polypropylene polymers, polyethylene polymers, polycarbonate polymers, polyester polymers, thermoset polymers, thermoplastic polymers, elastomers, or any combination or blend thereof.

[0058] Thermoset polymers are polymers that cure irreversibly. Thermoset polymers are malleable prior to heating and capable of forming a mold. Non-limiting examples of thermoset polymers that can be included in the composition of the present invention include epoxy resins, epoxy vinylesters, alkyds, amino-based polymers (e.g., polyurethanes, urea-formaldehyde), diallyl phthalate, phenolics polymers, polyesters, unsaturated polyester resins, dicyclopentadiene, polyimides, silicon polymers, cyanate esters of polycyanurates, thermosetting polyacrylic resins, bakelite, Duroplast, benzoxazines, or co-polymers thereof, or blends thereof.

[0059] Thermoplastic polymers have polymeric matrices that have the ability to become pliable or moldable above a specific temperature and solidify below the temperature. Non-limiting examples of thermoplastic polymers that can be included in the composition of the present invention include polyethylene terephthalate (PET), a polycarbonate (PC) family of polymers, polybutylene terephthalate (PBT), poly(l,4-cyclohexylidene cyclohexane-l,4-dicarboxylate) (PCCD), glycol modified polycyclohexyl terephthalate (PCTG), poly(phenylene oxide) (PPO), polypropylene (PP), polyethylene (PE), polyvinyl chloride (PVC), polystyrene (PS), polymethyl methacrylate (PMMA), polyethyleneimine or polyetherimide (PEI) and their derivatives, thermoplastic elastomer (TPE), terephthalic acid (TP A) elastomers, poly(cyclohexanedimethylene terephthalate) (PCT), polyethylene naphthalate (PEN), polyamide (PA), polysulfone sulfonate (PSS), sulfonates of polysulfones, polyether ether ketone (PEEK), polyether ketone ketone (PEKK), acrylonitrile butyldiene styrene (ABS), polyphenylene sulfide (PPS), co-polymers thereof, or blends thereof. In addition to these, other thermoplastic polymers known to those of skill in the art, and those hereinafter developed, can also be used in the context of the present invention.

[0060] Fillers can include particles, powders, fibers, or a combination thereof. Non-limiting examples of fillers include glass, polymer beads, and/or minerals. Non-limiting examples of minerals include silica, clays, treated clays, calcium carbonate, clays, intercalated clays, kaolin, talc, alumina trihydrate, wollastonite, dolomite, barium sulfate, magnesium hydroxide, diatomaceious earth magnetite/hematite, halloysite, zinc oxide, and titanium dioxide. Nonlimiting examples of fibers include glass fibers, carbon fibers, aramid fibers, thermoplastic fibers, ceramic fibers, basalt fibers, steel fibers, and/or the like. Non-limiting examples of thermoplastic fibers include polyethylene fibers, polyester fibers, polyamide fibers

[0061] The polymer compositions of the present invention can include lwt.% to 99 wt.% additional polymers, 0 wt.% to 40 wt.%, fillers, and/or 0.01 to 5 wt.% additives, with the balance being the PVCH having a degree of hydrogenation greater than 97 % and/or a YI index of less than 3.25. An amount of additives range from 0.01 wt.% to 5 wt.%, or 0.01 wt.%, 0.02 wt.%, 0.03 wt.%, 0.04 wt.%, 0.05% wt., 0.06 wt.%, 0.07 wt.%, 0.08 wt.%, 0.09 wt.%, 0.1 wt.%, 0.5 wt.%, 0.75 wt.%, 1 wt.%, 2 wt.%, 3 wt.%, 4 wt.%, or 5 wt.% or any range or value there between. In certain aspects, the addition of the additives, fillers, and/or additional polymers does not increase the YI of the composition.

[0062] In some aspects, the composition of the present invention is a molded composition (e.g., an extrusion molded, injection molded, compression molded, rotational molded, blow molded, injection blow molded, 3-D printed, or thermoformed article). In some aspects, the compositions of the present invention are formed into sheets or films.

B. Methods of Preparing the Composition of the Present Invention

[0063] FIG. 1 depicts a schematic of a process for preparing a polymer composition of present invention. System 100 can include reactor 102 and refining unit 104. Reactor 102 can include inlet conduit 106 for a polystyrene reactant feed, preferably an amorphous polystyrene, inlet conduit 108 for H2 reactant feed, reaction zone 110 that is configured to be in fluid communication with the inlet conduits 104 and 106, and outlet conduit 112 configured to be in fluid communication with the reaction zone 110 and configured to remove the product stream (e.g., hydrogenated or partially hydrogenated aromatic containing polymer) from the reaction zone. Reactor 102 can be any reactor suitable for performing polymer hydrogenations (e.g., a batch reactor or continuous reactor). Reactor 102 can include one or more heating and/or cooling devices (e.g., insulation, electrical heaters, jacketed heat exchangers in the wall) or controllers (e.g., computers, flow valves, automated values, etc.) that can be used to control the reaction temperature and pressure of the reaction mixture. While only one reactor is shown, it should be understood that multiple reactors can be housed in one unit or a plurality of reactors housed in one heat transfer unit. In some embodiments, a series of physically separated reactors with interstage cooling/heating devices, including heat exchangers, furnaces, fired heaters, and the like can be used. The reaction zone 110 can include the hydrogenation catalyst 114.

Hydrogenation catalyst

[0064] The hydrogenation catalyst can be a low pore volume catalyst as described herein. In some instances, the catalyst can be commercial catalyst having the properties described herein. The hydrogenation catalyst can include a low pore volume support (pore volume less than 0.4 cm ³ /g) and a catalytic metal. The catalyst can have a specific surface area of at least 5 m ² /g to 45 m ² /g, or 5 m ² /g to 40 m ² /g, or 5 m ² /g to 20 m ² /g or 5 m ² /g, 10 m ² /g, 15 m ² /g, 20 m ² /g, 25 m ² /g, 30 m ² /g, 35 m ² /g, 40 m ² /g, or 45 m ² /g, or any value or range there between. The pore volume of the catalyst can be 0.01 cm ³ /g to 0.35 cm ³ /g, or 0.03 cm ³ /g to 0.3 cm ³ /g, or 0.05 cm ³ /g to 0.25 cm ³ /g, or 0.01, 0.03, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35 cm ³ /g, or any value or range there between. The median particle diameter of the catalyst can be less than 300 microns, preferably less than 150 microns or 300, 250, 200, 150, 100, 50, 25, 15, 10, 1 microns or less, but greater than 0.1 micron. The catalyst has at least 50% of its pores having diameters of less than 100 nm. The support can be alumina (AI2O3), titania (TiCh), silica (SiCh), calcium carbonate, or mixtures, or combinations thereof. In a preferred instance, the catalyst is a Pt/AhCh catalyst. The support can be in powder form. The support can have a specific surface area of at least 5 m ² /g to 80 m ² /g, 5 m ² /g to 60 m ² /g, 5 m ² /g to 45 m ² /g, or 5 m ² /g to 40 m ² /g, or 5 m ² /g to 20 m ² /g or 5 m ² /g, 10 m ² /g, 15 m ² /g, 20 m ² /g, 25 m ² /g, 30 m ² /g, 35 m ² /g, 40 m ² /g, 45 m ² /g, 50 m ² /g, 55 m ² /g, 60 m ² /g, 65 m ² /g, 70 m ² /g, 75 m ² /g, or 80 m ² /g, or any value or range there between. The pore volume of the support can be 0.01 cm ³ /g to 0.35 cm ³ /g, or 0.03 cm ³ /g to 0.3 cm ³ /g, or 0.05 cm ³ /g to 0.25 cm ³ /g, or 0.01, 0.03, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35 cm ³ /g, or any value or range there between. The median particle diameter of the support can be less than 300 microns, preferably less than 150 microns or 300, 250, 200, 150, 100, 50, 25, 15, 10, 1 microns or less, but greater than 0.1 micron. The support has at least 50% of its pores having diameters of less than 100 nm. Based on the total weight of the catalyst, the catalyst can include 99.1 wt.% to 99.95 wt.%, 99.75 wt.% to 99.5 wt.% or any range or value there between (e.g., 99.1, 99.2, 99.3, 99.4, 99.5, 99.6, 99.7, 99.8, 99.9, 99.95 wt.%). The amount of support will balance the amount of catalytic metal used.

[0065] The catalyst include catalytic particles, preferably nanoparticles that include platinum (Pt), palladium (Pd), ruthenium (Ru) or any combination thereof. The total amount of catalytic metal, based on the total weight of catalyst, can range from 0.05 wt.% to 0.9 wt.%, or 0.2 to 0.6 wt.%, or 0.25 to 0.5 wt.%, or 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, wt.% or any range or value there between. In a preferred instance, the total amount of catalytic metal can be about 0.25 to 0.5 wt.%.

[0066] The catalyst can be made using catalyst preparation methodology known to a person with skill in performing catalyst synthesis (e.g., a chemist or an engineer). Depending on the support material, a base or acid may be employed during the process of producing the catalyst. More than one method of reducing the catalyst precursor to a nanoparticle can also be used. Nonlimiting examples of preparing the catalyst are described below.

SiCh and TiCh supports, Catalytic Metal and H2 Reduction

[0067] A catalytic metal precursor can be dissolved in deionized water to form a catalytic metal precursor solution. Catalytic metal precursors can be obtained as a metal nitrate, a metal amine, a metal chloride, a metal coordination complex, a metal sulfate, a metal phosphate hydrate, metal complex, or any combination thereof. These metals or metal compounds can be purchased from any chemical supplier such as Millipore Sigma (St. Louis, Missouri, USA), Alfa-Aesar (Ward Hill, Massachusetts, USA), and Strem Chemicals (Newburyport, Massachusetts, USA). A nonlimiting example of a metal precursor compound is tetraammineplatinum(II) chloride, tetraamineplatinum(II) nitrate, tetraamineplatinum(II) hydroxide, tetraaminepalladium(II) chloride, tetraaminepalladium(II) nitrate, hexaammineruthenium(III) chloride, or hexaammineruthenium(II) chloride. The catalytic metal precursor solution can be added to a composition that includes a known quantity of support (e.g., SiCh or TiCh), water, and a base (e.g., ammonium hydroxide or sodium hydroxide) to form a catalytic metal precursor/support composition. Support materials can be obtained from commercial suppliers such as Millipore Sigma, Alfa-Aesar, Cristal, Evonik, and the like. In some embodiments, the water suspension of catalyst supports can be added to the metal precursor solution. The catalytic metal precursor/support composition can be agitated for a period of time (e.g., 0.5 to 24 hours) at ambient temperature (e.g., 20 °C to 35 °C). The catalytic metal precursor/support composition can be separated from the water using known separation techniques (e.g., filtration, centrifugation, and the like) and washed sufficiently with deionized water to remove any residual base. Residual water in the filtered catalytic metal precursor/support composition can be removed by drying the catalytic metal precursor/support composition at a temperature of 80 °C to 100 °C, or about 95 °C. Once dried, the dried catalytic metal precursor/support composition can be subjected to reducing conditions to convert the catalytic metal precursor to metal nanoparticles. Reducing conditions can include using H2 balanced with N2 with at a desired flowrate (e.g., 450 to 600 standard cubic centimeter per min) at a desired temperature. For example, a temperature rate of 5 to 10 °C /min from 20 °C to 400 °C and kept at 400 °C for 0.5 to 1 hr before cooling to room temperature to produce the catalysts of the present invention.

SiCh and TiCh supports, Catalytic Metal and Solution Reduction

[0068] A catalytic metal precursor described in the SiCh and TiCh Metal and H2 Reduction section above can be dissolved in deionized water to form a catalytic metal precursor solution. The catalytic metal precursor solution can be added to a composition that includes a known quantity of support (e.g., SiCh or TiCh), water, and a base (e.g., ammonium hydroxide or sodium hydroxide), and agitated for a period of time (e.g., 0.5 to 24 hours) at ambient temperature (e.g., 20 °C to 35 °C) to form a catalytic metal precursor/support composition. In some embodiments, the water suspension of catalyst supports can be added to the metal precursor solution. A reducing agent such as sodium borohydride or formaldehyde dissolved in deionized water can be added dropwise into catalyst precursor/support composition and the resulting mixture can then be stirred for a desired amount of time (e.g., 1 hr to 24 hrs). A molar reducing agent to Pt ratio can be 1 : 1, 2: 1, 3: 1, 4: 1, 5: 1 or any value or range there between. The solid catalyst/support material can be separated from the slurry and washed with deionized water to remove excess materials (e.g., three times with deionized water). The washed solid catalyst/support material can be dried in an oven at 95 °C to produce the Pt/TiCb catalyst of the present invention.

AI2O3 Support, Catalytic Metal, and H2 Reduction

[0069] A catalytic metal precursor can be dissolved in deionized water to form a catalytic metal precursor solution. Catalytic metal precursors can be obtained as a metal nitrate, a metal amine, a metal chloride, a metal coordination complex, a metal sulfate, a metal phosphate hydrate, metal complex, or any combination thereof. Non-limiting examples of metal precursor compounds include chloroplatinic acid, potassium hexachloroplatinate(IV), potassium tetrachloroplatinate(II), sodium hexachloroplatinate(IV), sodium tetrachloroplatinate (II), potassium hexachloropalladate(IV), potassium tetrachloropalladate(II), sodium hexachloropalladate(IV), sodium tetrachloropalladate(II), or ammonium hexachlororuthenate(IV). These metals or metal compounds can be purchased from any chemical supplier such as Millipore Sigma (St. Louis, Missouri, USA), Alfa-Aesar (Ward Hill, Massachusetts, USA), and Strem Chemicals (Newburyport, Massachusetts, USA). The catalytic metal precursor solution can be added to a composition that includes a known quantity of AI2O3, water, and a mineral acid (e.g., hydrochloric acid or nitric acid) and, then, agitated for a period of time (e.g., 0.5 to 24 hours) at ambient temperature (e.g., 20 °C to 35 °C) to form a catalytic metal precursor/ AI2O3 composition. It should be understood that the order of addition of the catalyst and support solutions can be reversed. AI2O3 can be obtained from commercial suppliers such as Alfa-Aesar, Millipore Sigma, and the like. The catalytic metal precursor/ AI2O3 composition can be separated from the water using known separation techniques (e.g., filtration, centrifugation, and the like) and washed sufficiently with deionized water to remove any residual acid. Water in the filtered catalytic metal precursor/ Al 2O3 composition can be removed by drying the catalytic metal precursor/ AI2O3 composition at a temperature of 80 °C to 100 °C, or about 95 °C. Once dried, the dried catalytic metal precursor/ AI2O3 composition can be subjected to reducing conditions to convert the catalytic metal precursor to metal nanoparticles. Reducing condition can include using H2 balanced N2 with at a desired flowrate (e.g., 450 to 600 standard cubic centimeter per min) at a desired temperature. For example, a temperature rate of 5 to 10 °C /min from 20 °C to 400 °C and kept at 400 °C for 0.5 to 1 hr before cooling to room temperature to produce the AI2O3 supported catalysts of the present invention. [0070] Referring back to FIG. 1, the polystyrene reactant feed can enter reaction zone 108 via feed conduit 106. The reactant feed can be a mixture of solvent (e.g., cyclohexane or decahydronaphthalene) and amorphous polystyrene. A mass ratio of solvent to polymer can be 4: 1, 9:1, 19: 1 or any range or value there between. The H2 reactant feed can enter reactor 102 after purging the reactor with nitrogen via hydrogen conduit 108. The pressure of reactor 102 can be maintained with the H2 reactant feed. The temperature and pressure can be varied depending on the reaction to be performed and is within the skill of a person performing the reaction (e.g., an engineer or chemist). Temperatures can range from 120 °C to about 200 °C, 140 °C to 190 °C, 150 °C to 180 °C, or any value or range there between. H2 pressures can range from about 3.4 MPa to 13.8 MPa or 3.45, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.8 or any range or value there between.

[0071] The crude product stream can be removed from reaction zone 110 via crude product outlet 112. The crude product stream can include the crude amorphous PVCH polymer composition. In a preferred aspect, the produced crude PVCH polymer composition can be an atactic PVCH polymer composition or an amorphous PVCH polymer composition. The produced crude PVCH polymer composition can be absent lower molecular weight polymers due to polymer scission. The hydrogenation activity can be at greater than 10 moles of aromatic rings per hour per gram of catalytic metal (e.g., Pt, Pd, and/or Ru) at the reaction temperature of 140 °C, and greater than 20 mole of aromatic rings per hour per gram of catalytic metal at 160 °C at a pressure of 3.4 to 7 MPa, and polymer concentration of 1 wt.% to 30 wt.%, preferably 5 wt.% to 25 wt.%, more preferably 5wt.% to 10 wt.%. Hydrogenation level can be at least 97%, at least 97.5%, at least 98%, at least 98.5%, at least 99%, at least 99.5%, or 100% or any range or value there between.

[0072] The crude PVCH stream can exit reaction zone 110 and enter precipitation/refining unit 104 via crude product conduit 112. In precipitation/ refining unit 104, the crude PVCH can be precipitated and/or refined to produce the PVCH polymer composition of the present invention.

[0073] In some aspects, the crude PVCH composition can be isolated prior to refining. One method of isolation can include precipitation of the crude PVCH composition. Precipitation can include adding the crude PVCH polymer composition solution into an anti-solvent at a temperature of 20 °C to 30 °C, preferably 22 to 25 °C at atmospheric pressure. Non-limiting examples of the anti-solvent can include acetone, methyl ethyl ketone, or similar polar solvents. The ratio of antisolvent to polymer solution can be 1.5: 1, 2: 1, or 2.5: 1. In some instances, the precipitated polymer can be isolated using techniques known in the art by chemists and/or engineers (e.g. filtration, centrifugation, and the like). The isolated polymer composition can be washed with the antisolvent (e.g., 1, 2, 3, 4 or more times) and then dried under vacuum at 120 °C to 130 °C to produce a crude PVCH polymer composition. The composition can be in the form of a resin. In other instances, the crude PVCH polymer composition solution is used in the refining steps.

[0074] In some instances, the crude PVCH polymer composition can be isolated by removing the solvent using distillation techniques known in the art to produce a crude PVCH polymer composition. In other instances, the solvent can be partially removed using distillation techniques known in the art and then the anti-solvent can be added to the concentration polymer solution. Hereinafter crude PVCH polymer composition can include isolated crude PVCH polymer composition, a solution of the crude PVCH polymer composition, or a mixture thereof.

[0075] Refining of the crude PVCH polymer composition can be performed using the following refining methods in any order or in combination with each other: 1) a solution crude PVCH polymer composition crude can be treated with carbon black; 2) at least one re-precipitation of the crude PVCH polymer composition; or 3) processing the crude PVCH polymer composition under mild conditions, preferably in the presence of stabilizers to produce the polymer composition of the present invention.

[0076] In some instance, the isolated crude PVCH polymer composition and/or the refined crude PVCH polymer composition can be further hydrogenated to a level of at least 99% to produce the PVCH polymer composition of the present invention.

[0077] Before the refining process, some additional polymers (e.g., isotactic and syndiotactic PVCH, or any polymer (e.g., a thermoplastic polymer) that is soluble in a PVCH solution) and/or additives (e.g., antioxidants, metal deactivators, and the like) may be added to the hydrogenated PVCH polymer composition solution prior to the refining step(s). In some instances, polymers, additives and fillers are added after the refining step to produce the composition of the present invention. Refining with carbon black

[0078] The crude PVCH polymer composition (e.g., isolated crude PVCH polymer composition, a solution of the crude PVCH polymer composition, or a mixture thereof), a reprecipitated PVCH polymer composition, a mildly processed crude PVCH polymer composition, or a combination of the compositions can be refined by treating a solution of the crude PVCH polymer composition(s) with carbon black to produce the polymer composition of the present invention. Referring to FIG. 2, refining unit 104 can include a batch or continuous reactor 202, filtration unit 204, and/or solvent removal unit 206. A refining solvent (e.g., cyclohexane or decalin) can enter reactor via solvent inlet 208 and mixed with the crude PVCH/solvent at a temperature of 20 °C to 40 °C at a pressure of 1 to 2 atm to dissolve the crude PVCH in the solvent, forming a PVCH solution. In some aspects, the crude PVCH solution from reactor 102 (See, FIG. 1) enters reactor 202 via inlet 208, and further solvent dissolution is not necessary. In some aspects, reactor 202, filtration unit 204 and solvent removal unit 206 are the same unit. Carbon black can be added to crude PVCH /solvent solution via inlet 210 and the solution agitated at 100 to 1000 rpm, at a temperature of 20 °C to 40 °C, for 1 to 2 hours to form PVCH / carbon black / solvent composition 212. The ratio of carbon black to crude PVCH can be 1 :20 or 1 : 10. In some instances, metal deactivators and/or antioxidants can be added to the carbon black/PVCH polymer solution. In particular, copper and/or iron metal activators. Non-limiting examples of commercial metal deactivator compositions include 3-(3,5-ditert-butyl-4-hydroxyphenyl)-N'-[3-(3,5-ditert- butyl-4-hydroxyphenyl)propanoyl]propanehydrazide sold under the tradename Irganox® MD- 1024 (BASF), 2-[[2-[2-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]e thylamino]-2- oxoacetyl]amino]ethyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate sold under the tradename Naugard XL-1 (SI Group, USA), oxalyl bis(benzylidenehydrazide) sold under the tradename OABH (Eastman Chemical USA).

[0079] Carbon black/PVCH/ solvent composition 212 can exit reactor 202 and enter filtration unit 204 via filtration conduit 214. In filtration unit 204, the carbon black can be removed using filtration techniques known in the art (e.g., centrifugation, vacuum filtration, gravity filtration, and the like). After removal of the carbon black, the filtered PVCH polymer composition solution can exit filtration unit 204 via filtration exit conduit 216 and enter solvent removal unit 206. The solvent (e.g., cyclohexane) can be removed from the solution in solvent removal unit 206 using known solvent removal techniques (e.g., distillation, evaporation, filtration, centrifugation, or the like) to produce the PVCH polymer composition. The carbon black treated PVCH polymer composition can be analyzed for yellowness and/or impurities (e.g., trace metals). If the PVCH polymer composition meets the standard for yellowness (e.g., YI is less than 3.25), it can exit refining unit 104 via conduit 218 to be further processed (e.g., pelletized, molded, formed into a film or sheet), stored, transported, or a combination thereof.

Refining by re-precipitation

[0080] The crude PVCH polymer composition, carbon black treated PVCH polymer composition, or mildly processed PVCH polymer composition, or a combination of the compositions can be further refined by one or more re-precipitations. Referring FIG. 3, solvent can enter refining unit 104 via inlet conduit 304. The crude PVCH polymer composition, isolated crude PVCH polymer composition, carbon black treated PVCH polymer composition, and/or processed crude PVCH polymer composition or a combination of the compositions can enter refining unit 104 via inlet conduit 302 and be dissolved in the solvent to form solution 306. The ratio of solvent to polymer can range from 4: 1, 9: 1, or 19: 1. Non-limiting examples solvent include cyclohexane and/or decahydronaphthalene (decalin). Dissolution conditions can include temperature and pressure. Dissolution temperature can be 20 to 30 °C, preferably 22 to 25 °C at atmospheric pressure. The crude PVCH polymer/solvent can be agitated for 1 to 2 hours or until complete dissolution is achieved. After dissolution, the mixture is stirred an additional 1 hour, and then poured into an anti-solvent. Non-limiting examples of the anti-solvent can include acetone, methyl ethyl ketone, or similar polar solvents. The ratio of anti-solvent to polymer solution can be 1.5: 1, 2: 1, or 2.5: 1. The precipitated polymer can be isolated using techniques known in the art by chemists and/or engineers (e.g. filtration, centrifugation, and the like). The isolated polymer can be washed with the anti-solvent (e.g., 1, 2, 3, and 4 or more times) and then dried under vacuum at 120 °C to 130 °C. In some instances, the solvent can be removed using distillation techniques known in the art to produce a crude PVCH polymer composition as previously described. In other instances, the solvent can be removed using distillation techniques known in the art and the antisolvent added to the concentration polymer solution. These processes can be repeated multiple times or until the desired YI of less than 3.25 is achieved. In some aspects, the crude PVCH polymer composition is isolated (e.g., by precipitation) and then re-precipitated until the desired YI of less than 3.25 is achieved.

Refining by processing under mild conditions in the presence of stabilizers.

[0081] The crude PVCH polymer composition (e.g., isolated crude PVCH polymer composition, a solution of the crude PVCH polymer composition or a mixture thereof), carbon black treated PVCH polymer composition, re-precipitated PVCH polymer composition, or a combination thereof can be further refined by processing the compositions under mild conditions to produce the polymer composition of the present invention having a YI of less than 3.24. For example, lower shear in processing such as extrusion and molding, lower temperature of processing, lower residence time in the processing, lower oxygen or completely inert atmosphere during processing than used in conventional polymer processing. Processing under such conditions results in no more than a 50% loss in molecular weight, more preferably no more than a 25% loss; most preferably, no more than a 2% loss. Furthermore, processing under mild conditions inhibits yellowing or additional yellowing from occurring. In some instances, stabilizers can be added during the processing. Non-limiting examples of stabilizers include antioxidants, light stabilizers, acid scavengers, metal deactivators, heat stabilizers, flame retardants, biocides, and the like. The YI after processing is less than 3.25, preferably 3.0 or less.

Further hydrogenation

[0082] The carbon black treated PVCH polymer composition, crude PVCH polymer composition (e.g., isolated crude PVCH polymer composition, a solution of the crude PVCH polymer composition or a mixture thereof), mildly processed crude PVCH polymer composition, or a combination of the compositions can be further hydrogenation as shown in System 400 of FIG. 4, the crude PVCH polymer composition, carbon black treated PVCH polymer composition, precipitated or re-precipitated PVCH polymer composition, and/or processed crude PVCH polymer composition or a combination of compositions exit refining unit 104 and enter hydrogenation unit 102 via conduit 402 and undergo further hydrogenation as described above.

C. Methods of reducing the YI of a PVCH polymer composition [0083] In another aspect of the present invention, methods of reducing the YI of a composition that includes a PVCH polymer are contemplated. The polymer compositions that include PVCH can have a YI that needs to be lowered for a desired application or article of manufacture. Nonlimiting examples of such compositions include commercially available PVCH polymer or manufactured resins containing PVCH. Such a PVCH polymer composition can have a YI index greater than 3. In other instances, the YI can be less than 3, but needs further refinement. The method includes contacting the composition with activated carbon black, metal deactivators, or a combination thereof to remove impurities from the composition using the method described in refining process Bl above. After removal of the solvent and carbon black, the composition can have a YI of less than the original YI value, preferably less than 3.25, more preferably 3.0 or less. In some instances, the composition includes PVCH having a degree of hydrogenation greater than 97% (97.5%, 98%, 98.5%, 99%, 99.5%, 99.9% or any value or range there between). If the composition does not include PVCH having a degree of hydrogenation of greater than 97%, refining steps Bl and B2 can be performed.

D. Articles of Manufacture

[0084] In some aspects, the composition of the present invention is a molded composition (e.g., an extrusion molded, injection molded, compression molded, rotational molded, blow molded, injection blow molded, 3-D printed, or thermoformed article). In other instances, the compositions of the present invention are formed into films or sheets.

[0085] The composition of the present invention can be used to produce articles of manufacture. In some instances, these articles of manufacture are transparent and/or have a YI of less than 3.25, preferably 3.0 or less. Non-limiting examples of article of manufacture include a film, a sheet, a packing film, a forming film, a protective packaging, a shrink sleeve and/or label, a shrink film, a twist wrap, a sealant film, bag, a coating, a lidding film, lab ware, a cuvette, a test tube, an Eppendorf tube, a laboratory container, a beaker, a flask, a jar, a bottle, a funnel, a pipette tip, a well plate, a microtiter plate, a syringe, a medical packing film and/or component, a medical tray, a blister pack, a medical component container, a food packing film, a food container, an automotive part, an electrical device part, an electronic device part, an industrial device part, a cover window of an optical device, an optical component of an electronic device, a flash light lens, a camera lens, a sensor lens, an illumination lens, a safety glass lens, an ophthalmic corrective lens, an imaging lens, a semiconductor container, a laser-direct structured electronic connector, a 5G antenna cover, a pre-fillable syringe, a sample vial, a UV-visible spectroscopy cuvette, a biochip, a contact lens mold, a virtual reality lens, a vehicle rear-view camera lens, an electronic display light-guiding plates, a RADAR/LiDAR sensor, or a face shield. Preferred articles of manufacture include semiconductor containers, laser-direct structured electronic connectors, 5G antenna covers, syringes that are to be pre-filled, sample vials, cuvettes for UV-visible spectroscopy, biochips, contact lens molds, virtual reality lenses, rear-view camera lenses for automotive applications, light-guiding plates for electronic displays, RADAR/LiDAR sensor, and face shields.

[0086] It has been observed that, in particular, the use of a sterically-hindered phenol, such as Irganox 1010 as a non-limiting example; and, a hydrolytically stable phosphite processing stabilizer, such as Irgafos 168 as a non-limiting example, are particularly useful when the hydrogenated aromatic polymers (such as a PVCH polymer having a degree of saturation of greater than 97% when produced from polystyrene starting material) are used to produce articles subject to gamma-irradiation. Gamma-irradiation (and other forms or irradiation) are known to cause yellowing of polymer materials and the present invention can be used to eliminate or lessen such problems. Such irradiation techniques are commonly used on such articles for sterilization purposes. Such articles are commonly found in the medical and pharmaceutical fields; nonlimiting examples include syringes, medical packing films and/or components, medical trays, blister packs, medical component containers, and the like. Food packaging articles are other examples of materials subject to gamma-irradiation for which the present invention has applicability. Non-limiting examples include food packing films and food containers. The inventors have found that PVCH powder (produced from hydrogenation of polystyrene), when stabilized with 1250 ppm Irganox 1010 and 1250 ppm Irgafos 168 works particularly well, and can be used both with and without the other components and processing techniques described herein. When this stabilized PVCH was molded into a color chip plaque and subjected to 50 kGy gamma irradiation, measurement of the Yellowness index (YI) before and after 4 days of gamma irradiation showed a change in YI of only about 2 units, which is quite minimal. Although the discussion has focused on gamma-irradiation, these methods are beneficial in the cases of other forms of irradiation of hydrogenated aromatic polymers which contain some residual levels of unsaturated.

EXAMPLES

[0087] The present invention will be described in greater detail by way of specific examples. The following examples are offered for illustrative purposes only, and are not intended to limit the invention in any manner. Those of skill in the art will readily recognize a variety of noncritical parameters which can be changed or modified to yield essentially the same results.

Testing Methodology and Instrumentation

[0088] Brunauer-Emmett-Teller (BET) N2-adsorption measurements were performed at 77 K on a Quantachrome Autosorb-6iSA analyzer to characterize the surface area and pore volume. Particle size analysis of the supports was performed on a Malvern Panalytical Zetasizer Dynamic Light Scattering (DLS) instrument. The amount of catalytic metal in the catalysts of the present invention was determined using inductively coupled plasma atomic emission spectroscopy (ICP- AES) on a PerkinElmer Optima 8300 ICP-OES Spectrometer. The catalytic metal was dissolved by aqua regia, followed by dilution with deionized H2O and filtration to remove the solid support to obtain a clear metal solution. The metal nanoparticles were characterized by transmission electron microscopy using an FEI Tecnai F20 TEM operating at 200 keV. The metal dispersion in the metal nanoparticles was measured by static H2-O2 titration technique. The EE chemisorption experiments were performed on a Micrometrics 3Flex instrument. Approximately 600 mg of the catalyst powder was loaded in a quartz tube and subjected to pretreatment that consisted of EE reduction (50 standard cubic centimeter per minute) at 200 °C for 4 hr, followed by evacuation at 200 °C for 4 hr and cooling down to 35 °C under evacuation for another 30 min. Then, O2 was admitted to the catalyst at 35 °C and 1 atm to contact the catalyst for 60 min. After evacuating the O2 out at 35 °C for 1 hr, the first EE uptake was measured over a pressure range at 35 °C by EE adsorption isotherm. After evacuating the EE out at the same temperature, the second EE uptake was measured at the same condition as the first EE adsorption isotherm. The amount of chemisorbed EE was calculated from difference between the first EE uptake and the second EE uptake. Because the reaction PtO (surface) + 3/2 EE — > PtH (surface) + FEO took place, the stoichiometry of 3 : 1 for the adsorbed H atom and the surface Pt atom was used. The metal dispersion was normalized by the surface metal atoms over the total metal atoms in the catalysts measured from ICP analysis. The conversion of aromatic rings during hydrogenation was determined by comparing the Fourier Transfer Infrared (FT-IR) spectrum of the final polymer composition using a FT-IR spectrometer (NICOLET iS50 FT-IR) with that of unsaturated polystyrene. The unsaturated aromatic rings showed a distinct IR absorptions at about 700 cm' ¹ due to out-of-plane bends for the C-H bond attached to the aromatic rings. The conversion was 100 % for the Pt catalysts of the present invention. The molecular weight of the final composition was measured by gel permeation chromatography (GPC) and showed no scission of the polymer chains after the hydrogenation reaction.

Example 1

(Method of Preparing the Composition of the Present Invention)

[0089] A determined amount of the catalyst of any of the catalyst described in the specification, preferably a Pt/AhCh catalyst) was placed in a stainless reactor (Parr Series 5000 Multiple Reactor System, Parr Instrument Company, 100 mL) with cyclohexane (30 mL, solvent) and polystyrene (PS-155, SABIC® (Saudi Arabia), average molecular weight M _w = 235,000, 2 g). The ratio of polystyrene to catalyst was 10: 1. The reactor was purged first with N2 for three times, and then with H2 three times to remove air and moisture and the charged with high-pressure H2 to the desired reaction pressure, about 500 and 1000 psi (3.4 MPa to 6.9 MPa). After the desired pressure has been reached the reactor content was heated to a set temperature between 140 °C and 200 °C, at a rate of 1 °C /min, and maintain at the final set temperature for a certain time, generally from 1 hr to 12 hr. After the reaction finished, the reactor was cooled to room temperature, the pressure discharged to atmospheric pressure (101 kPa), the contents in the reactor recovered, and the solid catalyst was separated from the polymer solution using centrifugation or filtration.

[0090] The polymer solution (8-10% PVCH wt.% in cyclohexane) was poured into acetone (2:1 ratio of acetone to cyclohexane solution ) to precipitate the polymer. The precipitated polymer was isolated through filtration, and then washed with acetone once or twice and dried under vacuum at 120 °C to 130 °C. [0091] The crude PVCH polymer resin had a YI of 10.92 as measured in accordance with ASTM E313 by molding the crude PVCH polymer into a plaque having a thickness of 3.25 mm, and an iron content of 1.5 ppm as measured by ICP-OES. The degree of hydrogenation was 97.6%.

Example 2 (Carbon Black Treatment)

[0092] The crude PVCH polymer composition (e.g., a resin) of Example 1 (35 g) was added to cyclohexane (500 mL) and agitated at 23 °C at atmospheric pressure until the resin dissolved (about 1 hour). Carbon black (Norit SX Plus, 10 g) was added to the crude PVCH polymer / cyclohexane solution and the solution was agitated at 23 °C at atmospheric pressure for 12 hours. The carbon black was removed by filtration to produce a treated PVCH solution. The treated PVCH solution was poured into acetone (1000 mL) at 23 °C and atmospheric pressure to precipitate the PVCH composition of the present invention. The PVCH composition was dried under vacuum 120 °C to 130 °C. The dried PVCH composition of the present invention had a YI vale of 5.51. In light of the immediate decrease of approximately 50%, it is reasonably expected that further treatments of the carbon black treated PVCH resin would lower the YI value to 3.25 and even lower.

Example 3 (Further hydrogenation)

[0093] The crude PVCH polymer composition (e.g., a resin) of Example 1 was subjected to further hydrogenation. A solution of crude PVCH polymer composition (10 wt.%) / cyclohexane and catalyst of the present invention was placed in a stainless reactor (Parr Series 5000 Multiple Reactor System, Parr Instrument Company, 100 mL). The crude PVCH polymer to catalyst ratio was 6: 1. The reactor was purged first with N2 for three times, and then with H2 three times to remove air and moisture and the charged with high-pressure H2 to the desired reaction pressure, about 1000 psi (3.4 MPa to 6.9 MPa). After the desired pressure has been reached the reactor content was heated to a temperature of 180 °C, at a rate of 1 °C /min, and maintained at the final set temperature for a certain time, generally from 1 hr to 12 hr. After the reaction finished, the reactor was cooled to room temperature, the pressure discharged to atmospheric pressure (101 kPa), the contents in the reactor recovered, and the solid catalysts was separated from the polymer solution using centrifugation or filtration. The resulting PVCH composition of the present invention had a hydrogenation level of 100% and a YI value of 3.24.

Example 4

(Properties of the Polymer Composition of the Present Invention)

[0094] The PVCH polymer composition of the present invention had a tensile modulus of 3000

MPa, a tensile strength of 42 MPA and a tensile elongation of 2% as measured by ASTM D638; an IZOD impact (notched) value of 26 J/M as measured by ASTM D256; a heat deflection temperature of 131 °C at 0.45 MPa as measured by ASTM D648; a light transmission value of 94% and a Haze value of #% as measured by ASTM DI 003; and a glass transition temperature of 146 °C as measured using differential scanning calorimetry (DSC) at 5 °C / min. The flexural properties of the PVCH polymer resin were not measured, but it is believed they would not change from the crude PVCH polymer and would be a flexural modulus of 3170 MPa and a flexural strength of 101 MPA as measured by ASTM D790.

Example 5 (Prophetic Example: Processing under mild condition)

[0095] The crude PVCH polymer composition from example 1 (100 g) and stabilizing additive (0.5 g) will be molded into a bar (133 mm long x 12.8 mm wide x 3.25 mm thick) at a temperature from 90 °C to 105 °C and at 10 bar pressure to yield a polymer composition of the present invention processed under mild conditions. The molded bar will have a YI value of 3 or less. The produced bar will be used for flexural property testing.

Example 6 (Prophetic Example: Re-precipitation)

[0096] A 8 to 10 wt.% crude PVCH resin in cyclohexane will be agitated at 23 °C at atmospheric pressure until the resin is dissolved (about 1 hour). The polymer solution will then be poured into acetone (2: 1 ratio of acetone to cyclohexane solution ) to precipitate the polymer. The precipitated polymer will be isolated by filtration, and then will be washed with acetone once or twice and then dried under vacuum at 120 °C to 130 °C.

Example 7

(Prophetic Example: Method of Reducing YI of a crude PVCH Polymer) [0097] Commercial PVCH resin (PCC resin 35 g) having an initial YI value of 10.92 can be added to cyclohexane (500 mL) and agitated at 23 °C at atmospheric pressure for 1 hour until the resin is dissolved. Carbon black (10 g) can be added to the crude PVCH polymer / cyclohexane solution and the solution will be agitated at 23 °C at atmospheric pressure for 12 to 24 hours. The carbon black will be removed by filtration to produce a treated PVCH solution. The polymer will be isolated by adding an anti-solvent to the treated PVCH solution at 23 °C at atmospheric pressure to produce the PVCH composition of the present invention having a YI value of 3.0 or less.

Example 8 (Synthesis of Pt on low pore volume TiCh Catalyst)

[0098] TiC>2 (commercial TiCh), calcined at static air at 820 °C for 5 h, surface area of 10.4 m ² /g, pore volume of 0.24 cm ³ /g, a median particle diameter (D50) of less than 2 microns, 6 grams) was dispersed in deionized H2O (60 mL). Ammonium hydroxide solution (30 wt.%, 0.78 mL) was added into the mixture, and the slurry stirred for 30 min. Tetraammineplatinum(II) chloride (from 106 mg) dissolved in H2O (2 mL) was added into the slurry and then the mixture was stirred for 1.5 hrs. The resulting catalyst precursor/ support material was separated from the slurry using vacuum filtration. The solid catalyst precursor/ support material was washed (3 times) with deionized water (100 mL), and then dried in a drying oven at 95 °C for 3 hours to produce the catalyst precursor/support material as a dry powder. The catalyst precursor/support dry powder was reduced in a horizontal tube furnace using 10 % H2 balanced N2 with a total flowrate of 500 standard cubic centimeter per min under the following conditions: a temperature rate of 10 °C /min from 20 °C to 400 °C and keep at 400 °C for 1 hr before cooling to room temperature to produce the Pt/TiCh catalysts of the present invention. The final Pt loading was determined to be 0.33 wt.% by ICP analysis. The Pt/TiCh catalysts prepared through the above methods had highly dispersed small crystalline Pt nanoparticles with the size of 1 to 2 nm and a metal atom dispersion of 40 % to 60 %.

Example 9 (Synthesis of Pt on low pore volume SiCh Catalyst)

[0099] SiCh (commercial silica, calcined at static air at 820 °C for 5 h, having a surface area of 17.2 m ² /g, a pore volume of 0.22 cm ³ /g, and a median particle diameter (D50) of less than 5 microns, 6 grams) was dispersed in deionized H2O (60 mL). Ammonium hydroxide solution (30 wt.%, 0.78 mL) was added into the mixture, and the slurry stirred for 30 min. Tetraammineplatinum(II) chloride (106 mg) dissolved in H2O (2 mL) was added into the slurry and then the mixture was stirred for 1.5 hrs. The resulting catalyst precursor/ support material was separated from the slurry using vacuum filtration. The solid catalyst precursor/support material was washed (3 times) with deionized water (100 mL) and then dried in a drying oven at 95 °C for 3 hours to produce the catalyst precursor/support material as a dry powder. The catalyst precursor/support dry powder was reduced in a horizontal tube furnace using 10 % H2 balanced N2 with a total flowrate of 500 standard cubic centimeter per min under the following conditions: a temperature rate of 10 °C /min from 20 °C to 400 °C and keep at 400 °C for 1 hr before cooling to room temperature. The catalyst of the present invention had a Pt weight loading of 0.41 wt.% as determined by ICP analysis. The particle size was 1 to 2 nm and the metal atom dispersion was 40 % to 60 %.

Example 10 (Preparation of Pt on low pore volume AI2O3 catalyst)

[00100] AI2O3 (having a specific surface area of 8.4 m ² /g, a pore volume of 0.19 cm ³ /g, and a median particle diameter of less than 1 micron, 6 grams) was dispersed in deionized H2O (60 mL). Hydrochloric acid (1.6 mL, 0.1 M HC1) was added into the mixture, and the slurry stirred for 30 min. H2PtCle (125 mg) dissolved in H2O (2 mL) was added into the slurry and then mixture was stirred for 1.5 hrs. The resulting catalyst precursor/support material was separated from the slurry using vacuum filtration. The solid catalyst precursor/support material was washed (3 times) with deionized water (100 mL) and then dried in a drying oven at 95 °C for 3 hours to produce the catalyst precursor/support material as a dry powder. The catalyst precursor/support dry powder was reduced in a horizontal tube furnace using 10 % H2 balanced N2 with a total flowrate of 500 standard cubic centimeter per min under the following conditions: a temperature rate of 10 °C /min from 20 °C to 400 °C and keep at 400 °C for 1 hr before cooling to room temperature to produce the Pt/ALCL catalyst of the present invention. The final Pt loading was determined to be 0.17 wt.%, the Pt nanoparticles were 1 to 2 nm in size, and the metal atom dispersion was 40 to 60%.

Example 11

(Preparation of Pt on low pore volume AI2O3 catalysts-Impregnation Method) [00101] AI2O3 (having a specific surface area of 8.8 m ² /g, a pore volume of 0.21 cm ³ /g, and a median particle diameter of less than 100 microns) was used in the impregnation preparation of Pt on low pore volume AI2O3. A EhPtCk stock solution Pt (3.6 wt.%) was prepared by dissolving EbPtCk in de-ionized H2O. Then EhPtCk stock solution (0.7 g, 0.025 g Pt in the solution) was diluted with deionized H2O (4.5 g). The diluted EbPtCk solution was added slowly to the AI2O3 (5.0 g), and the mixture was agitated and mixed to wet the solid and form a Pt catalyst precursor/ AI2O3 composition. The Pt catalyst precursor/ AI2O3 composition was dried in the oven overnight at 90 °C. Then the dried sample was reduced in a horizontal tube furnace using 10 % H2 balanced N2 with a total flow rate of 500 standard cubic centimeter per min under the following conditions: a temperature rate of 5 °C /min from 20 °C to 200 °C and keep at 200 °C for 1 hr before cooling to room temperature to produce the 0.5 wt.% Pt/AhCh catalyst of the present invention.

Example 12

(Preparation of Pt on low pore volume AI2O3 support)

[00102] AI2O3 (having a specific surface area of 8.8 m ² /g, a pore volume of 0.21 cm ³ /g, and a median particle diameter of less than 100 microns) was used in the preparation of a catalyst of the present invention (Pt on low pore volume AI2O3). AI2O3 (6 g) were dispersed in deionized H2O (60 mL). FBPtCL (125 mg) dissolved in H2O (2 mL) was added into the slurry and then mixture was stirred for 2 hrs. The resulting catalyst precursor/support material was separated from the slurry using vacuum filtration. The solid catalyst precursor/support material was washed (3 times) with deionized water (100 mL) and then dried in a drying oven at 95 °C for 3 hours to produce the Pt catalyst precursor/ AI2O3 support material as a dry powder. The Pt catalyst precursor/ AI2O3 support dry powder was reduced in a horizontal tube furnace using 10 % H2 balanced N2 with a total flowrate of 500 standard cubic centimeter per min under the following conditions: a temperature rate of 10 °C /min from 20 °C to 400 °C and keep at 400 °C for 1 hr before cooling to room temperature to produce the Pt/AhCh catalyst of the present invention. The final Pt loading was determined to be 0.16 wt.%.

****

[00103] Although embodiments of the present application and their advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the embodiments as defined by the appended claims. Moreover, the scope of the present application is not intended to be limited to the particular embodiments of the process, machine, manufacture, composition of matter, means, methods and steps described in the specification. As one of ordinary skill in the art will readily appreciate from the above disclosure, processes, machines, manufacture, compositions of matter, means, methods, or steps, presently existing or later to be developed that perform substantially the same function or achieve substantially the same result as the corresponding embodiments described herein can be utilized. Accordingly, the appended claims are intended to include within their scope such processes, machines, manufacture, compositions of matter, means, methods, or steps.