High structure carbon black and plastic compositions containing same

Abstract

Polymer compositions containing high structure filler materials and methods for preparing such compositions while retaining structure.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Application No. 63 / 236,153, filed August 23, 2021, the entire contents of which are incorporated herein by reference.

[0002] The present disclosure relates to carbon black materials, and in particular to high structure carbon black materials, as well as methods of making and using such carbon black materials. [Background technology]

[0003] Carbon black materials can be utilized in a variety of applications to impart desirable properties to polymeric materials. In various embodiments, carbon black materials can impart electrical properties, such as increased conductance or increased resistivity, to materials incorporating them. Conductive carbon black can be used in a variety of applications, including batteries.

[0004] The electrical conductivity of polymers containing carbon black fillers can be related to the structure of the carbon black filler. Although high structure carbon black can be produced, this high structure is usually reduced or degraded when the filler is incorporated into a polymer system. Thus, there is a need for improved high structure filler-containing polymeric materials and methods for their production. These and other needs are met by the compositions and methods of the present disclosure. Summary of the Invention

[0005] In accordance with the object(s) of the present invention embodied and generally described herein, the present disclosure relates in one aspect to a carbon black material, and in particular to a high structure carbon black material.

[0006] In one embodiment, the disclosed polymer composition comprises a carbon black filler and a melt processable polymer, wherein a tape sample prepared by extruding the polymer composition at an extrusion temperature (° C.) and a screw speed (RPM) using a single or twin screw extruder having a screw diameter of about 16 mm and a length to diameter ratio of about 25:1 exhibits a percolation threshold that is at least 5 weight percent less than a reference tape sample extruded from a substantially identical reference composition in the same single or twin screw extruder at the same feed rate (g / min) but at (i) a reference extrusion temperature (° C.) that is at least 5% lower than the extrusion temperature at which the tape sample is extruded, and (ii) a reference screw speed (RPM) that is at least 50% higher than the screw speed at which the tape sample is extruded, wherein the percolation threshold is at least 5 weight percent less than the reference tape sample extruded from the same single or twin screw extruder at the same feed rate (g / min), but at (i) a reference extrusion temperature (° C.) that is at least 5% lower than the extrusion temperature at which the tape sample is extruded, and (ii) a reference screw speed (RPM) that is at least 50% higher than the screw speed at which the tape sample is extruded, 6 The weight percent of carbon black filler in a melt processable polymer that exhibits a surface resistivity of less than ohms / sq.

[0007] In another aspect, a process for preparing a polymer composition is disclosed, the process comprising the steps of obtaining a polymer melt from a melt-processable polymer in a mixing device, mixing a carbon black filler at a temperature (° C.) and a shear rate (s -1 ) into the polymer melt using a mixing device to provide a polymer composition, wherein a solid sample obtained from the polymer composition is mixed in the mixing device at (i) a reference temperature (° C.) that is at least 5% lower than the temperature at which the polymer composition is mixed, and (ii) a reference shear rate (s 2 ) that is at least 50% higher than the shear rate at which the polymer composition is mixed. -1 ) and the percolation threshold is at least 5 weight percent lower than a solid reference sample obtained from a substantially identical reference composition mixed with 10% water, and the percolation threshold is about 10% lower than the solid reference sample obtained from the solid reference sample. 6 The weight percent of carbon black filler in a polymer composition that exhibits a surface resistivity of less than Ω / sq.

[0008] In a further embodiment, a solid sample of the polymer composition comprising a melt-processable polymer and a carbon black filler in an amount ranging from about 5% to about 30% by weight of the polymer composition is obtained by subjecting the solid sample of the polymer composition to a melt-processable polymer having a melt-processable polymer and a carbon black filler in an amount ranging from about 5% to about 30% by weight of the polymer composition. 6 Polymer compositions are disclosed that exhibit surface resistivities of less than Ω / sq.

[0009] Additional aspects of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by the practice of the invention. The advantages of the invention will be realized and attained by means of the elements and combinations particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention as claimed.

[0010] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate several aspects and, together with the description, serve to explain the principles of the invention. [Brief description of the drawings]

[0011] [Figure 1] 1 is a plot of resistivity versus carbon black loading for an exemplary polypropylene formulation including Birla Carbon Black BCD9114B, BCD9110P, and Birla Carbon Corporation's CONDUCTEX 7055 Ultra Carbon Black (referred to in this application as "C7055U"), showing that the polymer formulation prepared under aggressive compounding processing conditions (low temperature, high screw speed, high shear) has a lower percolation concentration of BCD9114. [Diagram 2] 1 is a plot of resistivity versus carbon black loading for an exemplary polypropylene formulation containing Birla Carbon BCD9114B, BCD9110P, and C7055U carbon blacks, showing that a polymer formulation prepared under mild compounding processing conditions (high temperature, low screw speed, low shear) exhibits a 5% reduction in percolation concentration compared to the same formulation prepared under aggressive compounding processing conditions. [Diagram 3]1 shows a plot of aggregate size distribution for two exemplary carbon blacks, Birla Carbon BCD9110 and C7055U. [Figure 4] 1 is a plot of pore volume versus average pressure for two exemplary carbon blacks, Birla Carbon BCD9110 and C7055U, showing that BCD9110 has a higher pore volume than C7055U. [Diagram 5] FIG. 1 is a plot of resistivity versus carbon black loading for two Birla Carbon / polypropylene blends prepared under aggressive processing conditions compared to mild processing conditions, showing an 8 wt% decrease in percolation threshold for the blend prepared according to mild blend processing conditions versus aggressive out-of-business processing conditions. [Figure 6] 1 is a plot of V' / V for BCD9110 dry carbon black formulations in polypropylene prepared according to mild and aggressive processing conditions. [Figure 7] 1 is a plot showing the weight percent BCD9110 carbon black versus aggregate size retention of dry carbon black for formulations prepared in polypropylene under mild and aggressive processing conditions. [Figure 8] A plot of resistivity versus carbon black loading for PP / C7055U blends prepared by mild and aggressive blending processes is shown, showing that mild treatment reduces the percolation concentration by approximately 10 wt% relative to the same blends prepared under aggressive processing conditions. [Figure 9] 1 is a plot of V' / V for C7055U dry carbon black for formulations in polypropylene prepared according to mild and aggressive processing conditions. [Figure 10] 1 is a plot showing the weight percent C7055U carbon black and aggregate size retention of dry carbon black versus formulations prepared in polypropylene under mild and aggressive processing conditions. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] The present invention may be understood more readily by reference to the following detailed description of the invention and the examples included therein.

[0013] Before the present formulations, compositions, articles, systems, devices, and / or methods are disclosed and described, it is to be understood that they are not limited to a particular synthesis method unless otherwise specified, or to a particular reagent unless otherwise specified, as they may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, exemplary methods and materials are described herein.

[0014] All publications mentioned herein are incorporated herein by reference to disclose and describe the methods and / or materials in connection with which the publications are cited.

[0015] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, exemplary methods and materials are described herein.

[0016] As used herein, unless specifically indicated to the contrary, the singular forms "a," "an," and "the" include the plural unless the context clearly dictates otherwise. Thus, for example, reference to a "filler" or a "solvent" includes a mixture of two or more fillers or solvents, respectively.

[0017] As used herein, ranges can be expressed as from "about" one particular value and / or to "about" another particular value. When such a range is expressed, another embodiment includes from the one particular value and / or to the other particular value. Similarly, when values ​​are expressed as approximations, it is understood that by using the antecedent "about," the particular value forms another embodiment. It will be further understood that the endpoints of each range are significant in relation to the other endpoint, and independently of the other endpoint. Also, certain values ​​are disclosed herein, and each value is understood to be disclosed herein as "about" that particular value in addition to the value itself. For example, if a value of "10" is disclosed, then "about 10" is also disclosed. Also, it is understood that each unit between two particular units is disclosed. For example, if 10 and 15 are disclosed, then 11, 12, 13, and 14 are also disclosed.

[0018] When a number is preceded by "about," the number may vary by plus or minus 10%, unless otherwise stated.

[0019] The term "percolation threshold" refers to the minimum concentration of carbon black in a polymer formulation that can exhibit electrical conductivity. In one embodiment, the percolation threshold is set at about 10 6 The weight percent of carbon black filler in the polymer formulation exhibits a surface resistivity of less than Ω / sq. In another embodiment, the percolation threshold is about 10 4 The weight percent of carbon black filler in a polymer formulation that exhibits a surface resistivity less than Ω / sq.

[0020] The term "substantially identical reference composition" refers to a composition in which the components of the composition and the amounts of those components are substantially identical in all respects, by weight percent (plus or minus 10 weight percent, e.g., plus or minus 5 weight percent, plus or minus 2 weight percent, plus or minus 1 weight percent). In some embodiments, "substantially identical reference composition" refers to a composition in which the components of the composition and the amounts of those components are identical in all respects, within the understood margin of measurement error. The reference composition is substantially identical in terms of the type and amount of melt-processable polymer, carbon black, and any other additives, but exhibits different physical properties (e.g., carbon black aggregate size, surface resistivity, among other properties) due to differences in the method of mixing the reference composition relative to the composition of the present invention.

[0021] As used herein, the terms "optional" or "optionally" mean that the subsequently described event or circumstance may or may not occur, and that the description includes instances in which the event or circumstance occurs and instances in which the event or circumstance does not occur.

[0022] Disclosed are the components used to prepare the compositions of the invention, and the compositions themselves used within the methods disclosed herein. These and other materials are disclosed herein, and when combinations, subsets, interactions, groups, etc. of these materials are disclosed, it is understood that each of the various individual and collective combinations and permutations of these compositions are specifically contemplated and described herein, although they cannot be specifically mentioned and explicitly disclosed. For example, when a particular composition is disclosed and discussed, and a number of modifications that can be made to some of the molecules that comprise the composition are discussed, each and every combination and permutation of the composition and possible modifications is specifically contemplated, unless specifically indicated to the contrary. Thus, when classes of molecules A, B, and C, as well as classes D, E, and F, are disclosed, and an example of a combination molecule, AD, is disclosed, each of the combinations AE, AF, BD, BE, BF, CD, CE, and CF, individually and collectively, are considered to be disclosed, even if each is not individually described. Similarly, any subset or combination of these is also disclosed. Thus, for example, the subgroups AE, BF, CE are considered to be disclosed. This concept applies to all aspects of this application, including, but not limited to, steps in the methods of making and using the compositions of the present invention. Thus, when there are various additional steps that can be performed, it is understood that each of these additional steps can be performed in any particular embodiment or combination of embodiments of the method of the present invention.

[0023] Each of the materials disclosed herein is commercially available and / or methods for its preparation are known to those of skill in the art.

[0024] It is understood that the compositions disclosed herein have certain functions. Disclosed herein are certain structural requirements for performing the disclosed functions, and it is understood that there are various structures that can perform the same functions related to the disclosed structures, and that these structures will generally achieve the same results.

[0025] Unless indicated otherwise, component parts are measured in parts by weight, temperature is in ° C. or is at ambient temperature, and pressure is at or near atmospheric.

[0026] As briefly discussed above, the present disclosure provides carbon black materials, and in particular high structure carbon black materials. In various aspects, such carbon black materials can impart desirable electrical properties in certain applications, such as in plastics.

[0027] Morphological properties of carbon black include, for example, particle size / fineness, surface area, aggregate size / structure, aggregate size distribution, and aggregate shape. Particle size is a measure of the diameter of the primary particles of carbon black. Carbon black's roughly spherical particles have an average diameter in the nanometer range. Particle size can be measured directly by electron microscopy or indirectly by surface area measurements. The average particle size can be an important factor in determining the dispersibility, tensile strength, tear resistance, hysteresis, and abrasion resistance of rubber products, while in liquid and plastic systems the average particle size can strongly affect the relative tinting strength, UV stability, and electrical conductivity of composites. For the same structure, smaller particle size provides higher tensile strength, tear resistance, hysteresis, and abrasion resistance, stronger tinting, UV resistance, and improved ease of dispersion.

[0028] Carbon black particles coalesce to form larger clusters or aggregates, which are the primary dispersible units of carbon black. The size and structure of the aggregates are controlled in the reactor. Measurements of aggregate structure can be obtained from electron microscopy or oil absorption. Structure has historically been measured by absorption of N-dibutyl phthalate, or DBP, but has now been replaced by oil absorption, or OAN (ASTM D2414-18, ISO 4656 / 1). Another measure of structure is oil absorption by compression, or COAN (ASTM D3493-18), where the carbon black sample is mechanically compressed before the oil absorption measurement is taken. The difference between the OAN and COAN values ​​can be an indication of the stability of the carbon black structure. Grades with a high number of primary particles and relatively large aggregates can be high structure grades with bulky aggregates with more voids and higher oil absorption. High structure carbon black can increase electrical conductivity.

[0029] The basic methods for producing carbon black are well known. Generally, carbon black is produced by partial oxidation or pyrolysis of a hydrocarbon gas or liquid, where a hydrocarbon feedstock (hereinafter "feedstock hydrocarbon") is injected into a hot gas stream, where the feedstock hydrocarbon is pyrolyzed and converted to smoke before being quenched by a water spray. The hot gas is generated by burning a fuel in a combustion section. The hot gas flows from the combustion section into a reaction section in communication with the combustion section. The feedstock hydrocarbon is introduced into the hot gas as it flows through the reaction section, thereby forming a reaction mixture containing the particles that form the carbon black. The reaction mixture flows from the reactor to a cooling section in communication with the reaction section. At one point in the cooling section, one or more quench sprays, for example of water, are introduced into the flowing reaction mixture, thereby reducing the temperature of the reaction mixture below the temperature required for carbon black formation and terminating the carbon-forming reaction. The black particles are then separated from the hot gas stream. By controlling and manipulating the reactor conditions, a wide variety of carbon blacks can be produced.

[0030] Most carbon black reactors include a cylindrical combustion section axially connected to one end of a reaction section, which is usually cylindrical or frusto-conical. A reaction choke is often axially connected to the other end of the reaction section. The reaction choke has a diameter substantially smaller than that of the reaction section and connects the reaction section to a cooling section, which is usually cylindrical and has a diameter substantially larger than that of the reaction choke.

[0031] The carbon black material of the present invention can be produced using techniques generally known in the carbon black art. Various methods for producing the carbon black of the present invention are described below and in the Examples. Variations of these methods can be determined by one of ordinary skill in the art. In one embodiment, the carbon black of the present invention can be produced in a carbon black reactor as generally described in U.S. Pat. Nos. 4,927,607 and 5,256,388, the disclosures of which are incorporated herein by reference in their entirety. Other carbon black reactors can be used, and one of ordinary skill in the art can determine which reactor is suitable for a particular application. The feedstocks, combustion feeds, and quenching materials are well known in the carbon black art. The selection of these feeds is not critical to the carbon black of the present invention. One of ordinary skill in the art can determine which feeds are suitable for a particular application. The amounts of feedstocks, combustion feeds, and quenching materials can also be determined by one of ordinary skill in the art to be suitable for a particular application.

[0032] Carbon black is well known to exist as a collection of clustered aggregates with a wide range of surface areas and structures or absorptive capacities. The absorptive capacity or structure of the aggregates is manifested by its effect on the viscosity of the polymeric formulation, with higher structure resulting in higher viscosity. From a more fundamental, morphological perspective, the structure is manifested by the degree of shape and / or complexity of the aggregates, with low structure aggregates having more compact spherical or ellipsoidal structures and high structure aggregates having more branched and open structures that can encapsulate significant amounts of polymer. In certain embodiments, the larger the aggregate size and / or the more branching present within the aggregate, the higher the electrical conductivity of composites incorporating such carbon blacks.

[0033] Conventional high structure carbon black can be added to polymer composites to obtain electrical conductivity, but the expected electrical conductivity or percolation density cannot be achieved because the structure of the carbon black is degraded during processing. In one aspect, the present disclosure provides carbon blacks and processing conditions to tailor the electrical conductivity and optimize the percolation density of polymer / carbon black composites.

[0034] Polymer composites incorporating conventional high structure carbon black typically exhibit poor conductive performance. In one aspect, this is believed to be due, in part, to the breakdown of the structure of the high structure carbon black during compounding processing in polymers under high shear fields. In one aspect, the present disclosure provides processing conditions that minimize the level of breakdown of the carbon black structure for optimized conductive performance.

[0035] In one aspect, the methods described herein can provide a conductive composition comprising high structure carbon black.

[0036] In one aspect, the methods described herein can be applied to a variety of conductive carbon black materials. Traditional compounding methods include mixing one or more resins with one or more fillers in an apparatus such as a twin screw extruder. When the filler material includes a high structure filler, such as high structure carbon black, the shear forces generated during compounding and / or extrusion or injection molding can result in the filler losing structure. For example, high compounding shear forces can break down carbon black agglomerates, resulting in reduced filler structure in the resulting polymeric article and reduced conductivity values.

[0037] In one embodiment, the high structure carbon black of the present invention is combined with a polymer, such as polypropylene, under mild and / or low shear processing conditions. In such an embodiment, percolation concentrations can be achieved using about 5% less carbon black by weight than similar compositions and methods using aggressive high shear mixing conditions. Such improved conductivity can be attributed to a higher retention of structure due to the mild and / or low shear processing conditions.

[0038] Thus, in one embodiment, the disclosed polymer composition comprises a carbon black filler and a melt processable polymer, wherein a tape sample prepared by extruding the polymer composition at an extrusion temperature (° C.) and a screw speed (RPM) using a single or twin screw extruder having a screw diameter of about 16 mm and a length to diameter ratio of about 25:1 exhibits a percolation threshold that is at least 5 weight percent less than a reference tape sample extruded from a substantially identical reference composition in the same single or twin screw extruder at the same feed rate (g / min) but at (i) a reference extrusion temperature (° C.) that is at least 5% lower than the extrusion temperature at which the tape sample is extruded, and (ii) a reference screw speed (RPM) that is at least 50% higher than the screw speed at which the tape sample is extruded, 6 Less than Ω / sq, e.g., about 10 4The weight percent of carbon black filler in a melt processable polymer that exhibits a surface resistivity of less than ohms / sq.

[0039] In a further embodiment, the tape sample exhibits a percolation threshold that is 5 to 15 weight percent less, e.g., 5 to 10% or 5 to 8% less, than the reference tape sample. In one embodiment, the reference extrusion temperature is 5% to 15%, e.g., 5 to 10% or 5 to 8% lower than the extrusion temperature at which the tape sample is extruded. In a further embodiment, the reference screw speed is 50% to 200%, e.g., 150% higher than the screw speed at which the tape sample is extruded.

[0040] In one embodiment, the tape samples and reference tape samples may be prepared using a twin screw extruder, such as a PRISM twin screw extruder having a screw diameter of 16 mm and a length to diameter ratio of 25: 1, at a feed rate of 30 g / min. In this embodiment, the loading of carbon black filler may range from 5 to 25% by weight of the polymer composition, for example, 5 to 25% by weight of a polypropylene polymer composition.

[0041] Similarly, in one aspect, the disclosed process for preparing a polymer composition includes obtaining a polymer melt from a melt-processable polymer in a mixing device, and mixing the carbon black filler at a temperature (° C.) and a shear rate (s -1 ) into the polymer melt using a mixing device to provide a polymer composition, wherein a solid sample obtained from the polymer composition is mixed in the mixing device at (i) a reference temperature (° C.) that is at least 5 weight percent lower than the temperature at which the polymer composition is mixed, and (ii) a reference shear rate (s s ) that is at least 50% higher than the shear rate at which the polymer composition is mixed. -1 ) and the percolation threshold is at least 5% lower than that of a solid reference sample obtained from a substantially identical reference composition mixed with 10% water, and the percolation threshold is about 10 ... 6 Less than Ω / sq, e.g., about 10 4 The weight percent of carbon black filler in a polymer composition that exhibits a surface resistivity of less than Ω / sq.

[0042] In one embodiment, a solid sample of the polymer composition prepared by this process exhibits a percolation threshold that is 5 to 15 weight percent less, e.g., 5 to 10% or 5 to 8% less, than a solid reference sample. In one embodiment, the reference temperature is 5% to 15%, e.g., 5 to 10% or 5 to 8% lower than the temperature at which the solid sample is obtained. In a further embodiment, the reference shear rate is 50% to 200%, e.g., 150% higher than the shear rate at which the solid sample is obtained.

[0043] In one aspect of this process, obtaining the polymer melt from the melt-processable polymer and mixing the carbon black filler into the melt-processable polymer can occur simultaneously, e.g., the carbon black filler can be mixed into the polymer as the polymer melt is being prepared. In another aspect, obtaining the polymer melt and mixing the carbon black filler into the polymer melt can occur sequentially, e.g., the polymer melt can be obtained first and then the carbon black filler can be mixed into the polymer melt in one or more addition steps.

[0044] In one embodiment, regardless of how the polymer composition is made, the polymer composition comprises a melt processable polymer and a carbon black filler in an amount ranging from about 5% to about 30% by weight of the polymer composition, and a solid sample of the polymer composition is heated to about 100° C. 6 Less than Ω / sq, e.g., about 10 4 Polymer compositions are disclosed that exhibit a surface resistivity of less than Ω / sq. In one embodiment, the carbon black filler can have the following aggregate size distribution: about 25 weight percent to about 50 weight percent have a particle size less than 400 nm, and about 40 weight percent to about 65 weight percent have a particle size in the range of 400 nm to 700 nm. In another embodiment, the carbon black filler in powder form has an aggregate size distribution of about 45 nm to about 50 weight percent. 2 / g ~ approx. 75m 2 Nitrogen surface area (NSA) in the range of 45 m / g 2 / g ~ approx. 75m 2In a further embodiment, the carbon black filler in bead form has at least one or all of the following properties: a statistical thickness surface area (STSA) in the range of about 45 m / g, an oil absorption in the range of about 175 cc / 100 g to about 275 cc / 100 g, and a compressed oil absorption (COAN) in the range of about 85 cc / 100 g to about 135 cc / 100 g. 2 / g ~ approx. 75m 2 Nitrogen surface area (NSA) in the range of 40 m / g 2 / g ~ approx. 75m 2 The composition has at least one or all of the following properties: a statistical thickness surface area (STSA) in the range of about 1000 cc / 100 g to about 220 cc / 100 g, an oil absorption in the range of about 130 cc / 100 g to about 220 cc / 100 g, and a compressed oil absorption (COAN) in the range of about 75 cc / 100 g to about 135 cc / 100 g. In an embodiment of this composition, the melt-processable polymer can be a thermoplastic or thermosetting polymer. In one embodiment, the melt-processable polymer is a polyolefin, such as polyethylene or polypropylene. In a further embodiment, the melt-processable polymer can be an acetal, an acrylic, a polyamide, a polystyrene, a polyvinyl chloride, an acrylonitrile-butadiene-styrene, a polycarbonate, or a mixture thereof.

[0045] The structural decomposition of carbon black can be analyzed using transmission electron microscopy with automated image analysis (TEM / AIA) after extracting the carbon black from the formulation by pyrolysis according to ASTM procedure D3849. Additionally, the high shear viscosity can be measured at 230°C using a capillary rheometer.

[0046] In one aspect, the present technology can reduce and / or prevent all or part of the structural degradation of high structure carbon black.

[0047] In another aspect, the present technology can enable higher electrical conductivity in polymeric materials at lower carbon black loading levels while maintaining desirable mechanical properties and / or viscosity.

[0048] The filler of the present invention can comprise any filler having a tufted structure. In one embodiment, the filler can comprise a carbon black material. In another embodiment, the filler can comprise a conductive or semi-conductive carbon black. In yet another embodiment, the filler can comprise a high structure carbon black. In another embodiment, the filler can comprise a carbon black having an oil absorption (OAN) of at least about 220, 225, 230, 235, 240, 245, 250, 255, 260 cc / 100g, or more, as measured by ASTM D2414. In other embodiments, the filler can include carbon black having an oil absorption of about 215 to about 240, about 220 to about 240, about 220 to about 230, about 220 to about 250, about 220 to about 280, about 230 to about 270, about 240 to about 260, about 245 to about 265, about 250 to about 270, or about 250 to about 260 cc / 100 g. In still other embodiments, the carbon black can have an oil absorption less than or greater than the specific values ​​or ranges described herein, and the invention is not intended to be limited to any particular oil absorption.

[0049] In another embodiment, the filler can include carbon black having a compression oil absorption (COAN) of about 90 to about 130, about 95 to about 125, about 100 to about 120, about 105 to about 125, about 105 to about 115, about 110 to about 115, about 100 to about 125, about 110 to about 115, or about 110 to about 120 cc / 100 g as measured by ASTM D3493. In yet another embodiment, the carbon black can have a compression oil absorption less than or greater than the particular values ​​or ranges described herein, and the invention is not intended to be limited to any particular compression oil absorption.

[0050] In various embodiments, the carbon black of the present invention has a nitrogen surface area (NSA) as measured by ASTM D6556 of about 50 to about 70, about 55 to about 65, about 57 to about 65, about 55 to about 62, about 60 to about 65, or about 58 to about 64 m. 2 In another embodiment, the carbon black may have a molecular weight of about 65 m / g. 2 / g, approximately 64m 2 / g, approximately 63m 2 / g, approximately 62m 2 / g or less than 61m 2 In yet other embodiments, the carbon black may have a nitrogen surface area value less than or greater than the specific values ​​or ranges set forth herein, and it is not intended that the invention be limited to any particular nitrogen surface area.

[0051] In various embodiments, the carbon black of the present invention has an external surface area, or statistical thickness surface area (STSA), as measured by ASTM D6556, of from about 50 to about 70, from about 55 to about 65, from about 57 to about 65, from about 55 to about 62, from about 60 to about 65, or from about 58 to about 64 m 2 / g. In yet other embodiments, the carbon black can have a statistical thickness surface area less than or greater than the specific values ​​or ranges set forth herein, and it is not intended that the invention be limited to any particular statistical thickness surface area.

[0052] In various embodiments, the carbon black of the present invention has an iodine adsorption, as measured by ASTM D1510, of about 50 to about 80, about 55 to about 70, about 55 to about 65, about 57 to about 65, about 55 to about 62, about 60 to about 65, or about 58 to about 64 m. 2 In yet other embodiments, the carbon black can have an iodine loading less than or greater than the specific values ​​or ranges described herein, and it is not intended that the invention be limited to any particular iodine loading.

[0053] In another embodiment, the carbon black can have a ratio of oil absorption with compression to oil absorption (i.e., COAN / OAN) of at least about 0.45, at least about 0.47, at least about 0.49, at least about 0.51, at least about 0.53, at least about 0.55, at least about 0.57 or more.

[0054] In one embodiment, the carbon black has an average molecular weight of about 55 to about 65, about 55 to about 60, about 58 to about 62, or about 57 to about 61 m. 2 / g NSA, about 55 to about 65, about 55 to about 60, about 58 to about 62, about 55 to about 59, about 57 to about 60, or about 57 to about 61 m 2 / g STSA, about 220 to about 240, about 215 to about 230, about 218 to about 228, about 220 to about 230, or about 220 to about 225 cm 3 / 100g OAN, and about 95 to about 115, about 100 to about 115, about 105 to about 115, about 100 to about 120, about 106 to about 112, or about 104 to about 114 cm 3 / 100g COAN.

[0055] In one embodiment, the carbon black has an average molecular weight of about 55 to about 65, about 55 to about 60, about 58 to about 62, or about 57 to about 61 m. 2 / g NSA, about 55 to about 65, about 55 to about 60, about 58 to about 62, or about 57 to about 61 m 2 / g STSA, and about 240 to about 260, about 245 to about 260, about 250 to about 260, about 248 to about 258, or about 250 to about 255 cm 3 / 100g OAN.

[0056] In other embodiments, the carbon black can have an ash level of less than about 0.5, less than about 0.4, less than about 0.3, less than about 0.2, less than about 0.1, less than about 0.05, less than about 0.04, less than about 0.03, or less than about 0.02 weight percent.

[0057] In one embodiment, the carbon black filler in powder form used in the polymer composition is about 45 ml 2 / g ~ approx. 75m 2 Nitrogen surface area (NSA) in the range of 45 m / g 2 / g ~ approx. 75m 2 / g range, an oil absorption in the range of about 175 cc / 100 g to about 275 cc / 100 g, and a compressed oil absorption (COAN) in the range of about 85 cc / 100 g to about 135 cc / 100 g.

[0058] In a further embodiment, the carbon black filler in bead form used in the polymer composition is about 45 m 2 / g ~ approx. 75m 2 Nitrogen surface area (NSA) in the range of 40 m / g 2 / g ~ approx. 75m 2 / g range, an oil absorption in the range of about 130 cc / 100 g to about 220 cc / 100 g, and a compressed oil absorption (COAN) in the range of about 75 cc / 100 g to about 135 cc / 100 g.

[0059] In one embodiment, the carbon black in the polymer composition can have at least one of the properties listed in Tables A and B below. In an embodiment, the carbon black in the polymer composition can exhibit at least a combination of the NSA and STSA values ​​listed in Tables A and B. In a further embodiment, the carbon black in the polymer composition can exhibit at least a combination of the NSA, STSA, and OAN values ​​listed in Tables A and B. In a further embodiment, the carbon black in the polymer composition can exhibit at least a combination of the NSA, STSA, OAN, and COAN values ​​listed in Tables A and B. In a further embodiment, the carbon black in the polymer composition can exhibit at least a combination of the NSA, STSA, OAN, COAN, and 325 mesh values ​​listed in Tables A and B. In a further embodiment, the carbon black in the polymer composition can exhibit at least a combination of the NSA, STSA, OAN, COAN, 325 mesh, and ash values ​​listed in Tables A and B. In a further embodiment, the carbon black in the polymer composition can exhibit a combination of the NSA, STSA, OAN, COAN, 325 mesh value, ash content, and sulfur content values ​​listed in Tables A and B. [Table 1] [Table 2]

[0060] In one specific embodiment, the carbon black can include Birla Carbon BCD9110 or BCD911x series carbon blacks available from Birla Carbon, Marietta, Georgia, USA. In one specific embodiment, the carbon black can include Birla Carbon BCD9114 carbon black available from Birla Carbon, Marietta, Georgia, USA. In a further embodiment, the carbon black can include Birla Carbon's CONDUCTEX 7055 Ultra Carbon Black (referred to in this application as "C7055U"). In yet other embodiments, the filler can include any other carbon black suitable for use in the present method.

[0061] In another embodiment, the carbon black may have a void volume retention of at least 100% under an average pressure of 1 MPa, 71% under an average pressure of 5 MPa, 59% under an average pressure of 10 MPa, 49% under an average pressure of 20 MPa, 39% under an average pressure of 40 MPa, 31% under an average pressure of 80 MPa, and / or 24% under an average pressure of 160 MPa.

[0062] In another embodiment, the carbon black can have a void volume (V′ / V) of about 4.6 as determined by TEM imaging.

[0063] In another embodiment, the carbon black can be in powder or bead form. In other embodiments, the filler can include a surface-modified carbon black, such as, for example, an oxidized carbon black.

[0064] In one embodiment, the carbon black can have about 23% by weight of agglomerates greater than about 700 nm in size, about 35% by weight of agglomerates between about 400 and about 700 nm in size, and about 42% by weight of agglomerates less than about 400 nm in size.

[0065] In other embodiments, the aggregate size composition can be converted to a polypropylene polymer with moderate shear input from about 6% by weight of aggregates greater than about 700 nm in size, about 48% by weight of aggregates between about 400 nm and about 700 nm in size, and about 46% by weight of aggregates less than about 400 nm in size.

[0066] In one embodiment, the carbon black filler in the polymer composition can have the following aggregate size distribution: about 25 weight percent to about 50 weight percent having a particle size less than 400 nm, and about 40 weight percent to about 65 weight percent having a particle size in the range of 400 nm to 700 nm.

[0067] In another embodiment, upon input of a similar mild shear force to polypropylene, the converted carbon black (i.e., after treatment) can have a void volume (V′ / V) of 2.8 as determined by TEM imaging images.

[0068] Upon further aggressive shearing of the polypropylene, the aggregate size composition may be converted from the original state to about 1% by weight of aggregates greater than about 700 nm in size, about 29% by weight of aggregates between about 400 and about 700 nm in size, and about 70% by weight of aggregates less than about 400 nm in size. Upon aggressive shearing of the polypropylene, the aggregates greater than about 700 nm in size may be converted to aggregates primarily less than about 400 nm in size. Upon aggressive shearing of the polypropylene, the converted carbon black may have a V' / V of about 2.2 as determined by TEM imaging images.

[0069] In one embodiment, mildly sheared carbon black, i.e., carbon black treated under mild conditions as described herein, has a molecular weight of about 9.1×10 at 15 wt. % carbon black loading in polypropylene. 2 Ωcm, and at a loading of 20 wt. % it can have a volume resistivity of about 32 Ωcm.

[0070] In another embodiment, aggressively sheared carbon black has a melting point of about 8.0×10 at 15 wt. % carbon black loading in polypropylene. 12 Ωcm, approximately 1.7x10 at 20% loading by weight 7 In another embodiment, the gently sheared carbon black can have a percolation concentration of about 13% by weight in polypropylene. In yet another embodiment, the aggressively sheared carbon black can have a percolation concentration of about 21% by weight in polypropylene.

[0071] The amount of carbon black utilized in a particular polymer system can vary depending on the polymer and the desired properties of the final product. In various embodiments, the carbon black loading can be about 5%, 7%, 9%, 11%, 13%, 15%, 17%, 19%, 21%, 23%, 25%, 27%, 29%, 30%, 31%, 33%, 35%, 40%, 45%, 50%, 55%, 60% or more by weight; in other embodiments, the carbon black loading can be about 15% to about 60% by weight, about 15% to about 50% by weight, about 15% to about 40% by weight, about 15% to about 30% by weight, about 15% to about 30% by weight, about 18% to about 30% by weight, about 20% to about 27% by weight, about 22% to about 30% by weight, or about 25% to about 35% by weight. In still other embodiments, the specific loading of carbon black or other fillers may vary depending on the particular polymer, carbon black, and desired properties of the final product. In such embodiments, the filler loading may be less than or greater than any particular value described herein. In any instance where carbon black is referenced herein, the application should be deemed to also include reference to such concentrations or loadings with any other suitable fillers or combinations of fillers.

[0072] The polymer can include any polymer or mixture of polymers suitable for use in the present invention. In one embodiment, the polymer or mixture of polymers is melt processable. In one embodiment, the polymer can include a thermoplastic polymer. In another embodiment, the polymer can include a thermoset polymer. In various embodiments, the polymer can include an olefin, such as, for example, polyethylene or polypropylene. In other embodiments, the polymer can include an acetal, an acrylic, a polyamide, a polystyrene, a polyvinyl chloride, an acrylonitrile butadiene styrene, a polycarbonate, or a mixture thereof.

[0073] In various specific embodiments, the polymer can include polypropylene, such as, for example, Ravago Selten's PBM-20NB, which has a melt flow index of 20, or Ravago PBM-80N, which has a melt flow index of 80.

[0074] In other embodiments, the composition can include other ingredients such as, for example, antioxidants, processing aids, oils, waxes, release agents, and / or other materials commonly used in the processing of polymeric materials.

[0075] In various embodiments, the polymer and carbon black can be contacted or mixed using any suitable means. In one embodiment, the carbon black and polymer can be mixed using a twin screw extruder, such as a PRISM twin screw extruder. In another embodiment, the carbon black and polymer can be mixed using a continuous mixer. EXAMPLES

[0076] Various exemplary embodiments of the present invention are detailed below. These embodiments are intended to be illustrative and not to limit the scope of the present invention. In each of the following examples, the following processes, equipment, and conditions were used unless otherwise indicated.

[0077] 1. Example 1 The physical and structural properties of two carbon blacks, namely Birla Carbon BCD9110 and BCD9114, exhibited the properties shown in Table 1. These carbon blacks were evaluated as fillers in thermoplastic polymers. [Table 3]

[0078] FIG. 1 is a plot of resistivity versus carbon black loading for exemplary polypropylene formulations containing Birla Carbon BCD9114B, BCD9110P, and C7055U carbon blacks, showing that the percolation concentration of BCD9114 is lower in the polymer formulations prepared under aggressive compounding processing conditions (low temperature, high screw speed, high shear).

[0079] In contrast, Figure 2, a plot of resistivity versus carbon black loading for an exemplary polypropylene formulation containing Birla Carbon BCD9114B, BCD9110P, and C7055U carbon blacks, shows that the polymer formulation prepared under mild compounding processing conditions (high temperature, low screw speed, low shear) further reduces the percolation concentration of BCD9114 by 5% compared to the same formulation prepared under aggressive compounding processing conditions. These data indicate that the conductivity of the polymer formulation was improved by the mild processing conditions.

[0080] 2. Example 2 Two high structure carbon blacks, Birla Carbon C7055U and BCD9110, were compounded in polypropylene at multiple loading levels using a twin screw extruder under two sets of conditions, one aggressive (low temperature, high screw speed, high shear) and the other mild (high temperature, low screw speed, low shear) to demonstrate their effectiveness.

[0081] The physical and structural properties of the two carbon blacks evaluated are shown in Table 2. These carbon blacks were evaluated as fillers in thermoplastic polymers. As shown, in powder form compared to bead form, BCD9110 had a significantly higher OAN than C7055U, but only a slightly higher COAN. [Table 4]

[0082] The aggregate sizes of the two carbon blacks are shown below in Table 3. The corresponding aggregate size distribution plots are shown in Figure 3. The void volume plots are shown in Figure 4. [Table 5]

[0083] Aggressive and mild compound processing conditions were evaluated using BCD9110 and C7055U samples according to the parameters shown in Table 4. Samples were compound processed using PRISM TSE: D=16mm, L / D=25 [Table 6]

[0084] In this manner, both polypropylene composites showed a significant improvement in conductive performance with a 10 wt% reduction in percolation concentration when treated under milder than more aggressive conditions. The improvement in conductive performance is based on the higher structure retention of carbon black under milder treatment conditions, as demonstrated by TEM imaging images.

[0085] Thus, the disclosed method can optimize the conductive performance of polymer / carbon black composites by modifying processing conditions: the polymer composite can achieve higher conductivity at lower carbon black loadings while maintaining suitable mechanical properties and viscosity.

[0086] As shown in Figure 5 and Table 5, the polypropylene / BCD9110 tape prepared according to mild processing conditions exhibited a reduction in percolation concentration of approximately 8 wt % relative to the same compound prepared according to aggressive compound processing conditions. [Table 7]

[0087] Examination of structure retention and aggregate size retention showed that carbon black compounded under milder process conditions had higher structure retention and greater aggregate size retention than compounds prepared under more aggressive process conditions, which correlated with improved conductivity performance. The results are shown in Table 6 and Figures 6-7. [Table 8]

[0088] Referring to Figure 8 and Table 7, it can be seen that the PP / C7055U blends prepared by mild blending treatment show approximately a 10 wt% decrease in percolation concentration relative to the same blends prepared under aggressive processing conditions. [Table 9]

[0089] Referring to Figures 9-10 and Table 8, it can be seen that when prepared under mild processing conditions, the polypropylene / C7055U blends had higher carbon black structure retention and larger residual aggregate size, which correlated with improved conductive performance compared to blends prepared under aggressive conditions. [Table 10]

[0090] It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope or spirit of the invention. Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.

Claims

1. 1. A polymer composition comprising: a) a carbon black filler; b) a melt-processable polymer; a tape sample prepared by extruding the polymer composition at an extrusion temperature (°C) and a screw speed (RPM) using a single or twin screw extruder having a screw diameter of about 16 mm and a length to diameter ratio of about 25:1 exhibits a percolation threshold that is at least 5 weight percent less than a reference tape sample extruded from a substantially identical reference composition in the same single or twin screw extruder at the same feed rate (g / min) but (i) at a reference extrusion temperature (°C) that is at least 5% lower than the extrusion temperature at which the tape sample was extruded, and (ii) at a reference screw speed (RPM) that is at least 50% higher than the screw speed at which the tape sample was extruded; The percolation threshold is about 10 6 a weight percent of carbon black filler in said melt-processable polymer exhibiting a surface resistivity of less than ohm / sq.

2. 10. The polymer composition of claim 1, wherein the tape sample exhibits a percolation threshold that is 5 to 15 weight percent less than the reference tape sample.

3. The polymer composition of claim 1 or 2, wherein the reference extrusion temperature is 5% to 15% lower than the extrusion temperature at which the tape sample is extruded.

4. 3. The polymer composition of claim 1, wherein the reference screw speed is 50% to 200% higher than the screw speed at which the tape sample is extruded.

5. The carbon black filler in the polymer composition is a) about 25 weight percent to about 50 weight percent having a particle size of less than 400 nm, and 3. The polymer composition of claim 1 or 2, wherein b) the polymer composition has an aggregate size distribution of about 40 weight percent to about 65 weight percent with particle sizes in the range of 400 nm to 700 nm.

6. The percolation threshold is about 10 4 3. The polymer composition of claim 1 or 2, wherein the weight percent of carbon black filler in the melt-processible polymer exhibits a surface resistivity of less than ohm / sq.

7. The carbon black filler in powder form is a) About 45m 2 / g ~ approx. 75m 2 Nitrogen surface area (NSA) in the range of / g, b) About 45m 2 / g ~ approx. 75m 2 Statistical thickness surface area (STSA) in the range of / g, c) an oil absorption in the range of about 175 cc / 100 g to about 275 cc / 100 g; and 3. The polymer composition of claim 1, having at least one of the following properties: d) a compressed oil absorption (COAN) in the range of about 85 cc / 100 g to about 135 cc / 100 g.

8. The carbon black filler in bead form is a) Approximately 45m 2 / g ~ approx. 75m 2 Nitrogen surface area (NSA) in the range of / g, b) About 40m 2 / g ~ approx. 75m 2 Statistical thickness surface area (STSA) in the range of / g, c) an oil absorption in the range of about 130 cc / 100 g to about 220 cc / 100 g; and 3. The polymer composition of claim 1, having at least one of the following properties: d) a compressed oil absorption (COAN) in the range of about 75 cc / 100 g to about 135 cc / 100 g.

9. 3. The polymer composition of claim 1 or 2, wherein the melt-processible polymer is a thermoplastic or thermosetting polymer.

10. 3. The polymer composition of claim 1 or 2, wherein the melt-processable polymer is a polyolefin.

11. 11. The polymer composition of claim 10, wherein the polyolefin is polyethylene or polypropylene.

12. 3. The polymer composition of claim 1 or 2, wherein the melt-processible polymer is an acetal, acrylic, polyamide, polystyrene, polyvinyl chloride, acrylonitrile butadiene styrene, or polycarbonate.

13. 3. The polymer composition of claim 1 or 2, comprising up to 40% of said carbon black filler by weight of said polymer composition.

14. 1. A process for preparing a polymer composition comprising: a) obtaining a polymer melt from a melt-processable polymer in a mixing device; b) The carbon black filler is subjected to a temperature (°C) and a shear rate (s -1 into the polymer melt using the mixing device to provide the polymer composition; A solid sample obtained from the polymer composition is mixed in the mixing device at (i) a reference temperature (°C) that is at least 5% lower than the temperature at which the polymer composition is mixed, and (ii) a reference shear rate (s) that is at least 50% higher than the shear rate at which the polymer composition is mixed. -1 exhibiting a percolation threshold that is at least 5 weight percent lower than a solid reference sample obtained from a substantially identical reference composition mixed with The percolation threshold is about 10 6 the weight percent of carbon black filler in said polymer composition exhibiting a surface resistivity of less than Ω / sq.

15. 15. The process of claim 14, wherein the solid sample exhibits a percolation threshold that is 5 to 15 weight percent less than the solid reference sample.

16. 16. The process of claim 14 or 15, wherein the reference temperature is 5% to 15% lower than the temperature at which the solid sample is obtained.

17. 16. The process of claim 14 or 15, wherein the reference shear rate is 50% to 200% lower than the shear rate at which the solid sample is obtained.

18. The carbon black filler in the polymer composition is a) about 25 weight percent to about 50 weight percent having a particle size of less than 400 nm, and 16. The process of claim 14 or 15, wherein b) the aggregate size distribution is from about 40 weight percent to about 65 weight percent with particle sizes in the range of 400 nm to 700 nm.

19. The percolation threshold is about 10 4 16. The process of claim 14 or 15, wherein the weight percent of carbon black filler in the polymer composition exhibits a surface resistivity of less than ohm / sq.

20. The carbon black filler in powder form is a) Approximately 45m 2 / g ~ approx. 75m 2 Nitrogen surface area (NSA) in the range of / g, b) About 45m 2 / g ~ approx. 75m 2 Statistical thickness surface area (STSA) in the range of / g, c) an oil absorption in the range of about 175 cc / 100 g to about 275 cc / 100 g; and d) a compression oil absorption (COAN) in the range of about 85 cc / 100 g to about 135 cc / 100 g.

21. The carbon black filler in bead form is a) Approximately 45m 2 / g ~ approx. 75m 2 Nitrogen surface area (NSA) in the range of / g, b) About 40m 2 / g ~ approx. 75m 2 Statistical thickness surface area (STSA) in the range of / g, c) an oil absorption in the range of about 130 cc / 100 g to about 220 cc / 100 g; and d) a compression oil absorption (COAN) in the range of about 75 cc / 100 g to about 135 cc / 100 g.

22. 16. The process of claim 14 or 15, wherein the melt-processable polymer is a thermoplastic or thermosetting polymer.

23. 16. The process of claim 14 or 15, wherein the melt-processable polymer is a polyolefin.

24. 24. The process of claim 23, wherein the polyolefin is polyethylene or polypropylene.

25. 16. The process of claim 14 or 15, wherein the melt-processable polymer is an acetal, acrylic, polyamide, polystyrene, polyvinyl chloride, acrylonitrile butadiene styrene, or polycarbonate.

26. 16. The process of claim 14 or 15, wherein the polymer composition comprises up to 40% of the carbon black filler by weight of the polymer composition.

27. 16. The process of claim 14 or 15, wherein steps (a) and (b) are carried out simultaneously or sequentially.

28. 1. A polymer composition comprising: a) a melt-processable polymer; b) a carbon black filler in an amount ranging from about 5% to about 30% by weight of the polymer composition; A solid sample of the polymer composition is prepared by mixing the polymer composition with a solid sample of about 10 6 A polymeric composition exhibiting a surface resistivity of less than ohm / sq.

29. A solid sample of the polymer composition is prepared by mixing the polymer composition with a solid sample of about 10 4 30. The polymer composition of claim 28, exhibiting a surface resistivity of less than ohm / sq.

30. The carbon black filler is a) about 25 weight percent to about 50 weight percent having a particle size of less than 400 nm, and 30. The polymer composition of claim 28 or 29, wherein b) the polymer composition has an aggregate size distribution of from about 40 weight percent to about 65 weight percent with particle sizes in the range of 400 nm to 700 nm.

31. The carbon black filler in powder form is a) Approximately 45m 2 / g ~ approx. 75m 2 Nitrogen surface area (NSA) in the range of / g, b) About 45m 2 / g ~ approx. 75m 2 Statistical thickness surface area (STSA) in the range of / g, c) an oil absorption in the range of about 175 cc / 100 g to about 275 cc / 100 g; and 30. The polymer composition of claim 28 or 29, having at least one of the following properties: d) a compressed oil absorption (COAN) in the range of about 85 cc / 100 g to about 135 cc / 100 g.

32. The carbon black filler in bead form is a) Approximately 45m 2 / g ~ approx. 75m 2 Nitrogen surface area (NSA) in the range of / g, b) About 40m 2 / g ~ approx. 75m 2 Statistical thickness surface area (STSA) in the range of / g, c) an oil absorption in the range of about 130 cc / 100 g to about 220 cc / 100 g; and 30. The polymer composition of claim 28 or 29, having at least one of the following properties: d) a compressed oil absorption (COAN) in the range of about 75 cc / 100 g to about 135 cc / 100 g.

33. 30. The polymer composition of claim 28 or 29, wherein the melt-processable polymer is a thermoplastic or thermoset polymer.

34. 30. The polymer composition of claim 28 or 29, wherein the melt-processable polymer is a polyolefin.

35. 35. The polymer composition of claim 34, wherein the polyolefin is polyethylene or polypropylene.

36. 30. The polymer composition of claims 28 or 29, wherein the melt-processible polymer is an acetal, acrylic, polyamide, polystyrene, polyvinyl chloride, acrylonitrile butadiene styrene, or polycarbonate.

Images