Methods for volatiles reduction in post-consumer resins

Abstract

The present disclosure relates to polymeric resin compositions and articles manufactured therefrom. In at least one embodiment, a method of making a pelletized polymeric resin, includes blending a carbon nanotube component with a polymer component having a first volatiles content to form a polymeric resin, the polymer component comprising a post-consumer resin (PCR). The method includes extruding the polymeric resin to form polymeric resin extrudate. The method includes pelletizing the polymeric resin extrudate to form a pelletized polymeric resin. The polymer component of the pelletized polymeric resin has a second volatiles content that is less than the first volatiles content.

Description

METHODS FOR VOLATILES REDUCTION IN POST-CONSUMER RESINS Field of the Invention

[0001] The present disclosure relates to polymeric resin compositions and articles manufactured therefrom.Background of the Invention

[0002] Polymers, especially synthetic plastics, are ubiquitous in daily life due to their relatively low production costs and good balance of material properties. Synthetic plastics are used in a wide variety of applications, such as packaging, automotive components, medical devices, and consumer goods. To meet the high demand of these applications, tens of billions of pounds of synthetic plastics are produced globally on an annual basis. The overwhelming majority of synthetic plastics are produced from increasingly scarce fossil sources, such as petroleum and natural gas. Additionally, the manufacturing of synthetic plastics from fossil sources produces CO2 as a by-product.

[0003] The ubiquitous use of synthetic plastics has consequently resulted in millions of tons of plastic waste being generated every year. While the majority of plastic waste is landfilled via municipal solid waste programs, a significant portion of plastic waste is found in the environment as litter, which, at the very least, is unsightly. Plastic waste is often washed into river systems and ultimately out to sea.

[0004] Plastics recycling has emerged as one solution to mitigate the issues associated with the wide-spread usage of plastics. Recovering and re-using plastics diverts waste from landfills and reduces the demand for virgin plastics made from fossil-based resources, which consequently reduces greenhouse gas emissions. In developed regions, such as the United States and the European Union, rates of plastics recycling are increasing due to greater awareness by consumers, businesses, and industrial manufacturing operations. The majority of recycled materials, including plastics, are mixed into a single stream which is collected and processed by a material recovery facility (MRF). At the MRF, materials are sorted, washed, and packaged for resale. Plastics can be sorted into individual materials, such as high-density polyethylene (HDPE) or poly(ethylene terephthalate) (PET), or mixed streams of other common plastics, such as polypropylene (PP), low-density’ polyethylene (LDPE), poly(vinyl chloride) (PVC), polystyrene (PS), polycarbonate (PC), and polyamides (PA). The single or mixed streams can then be further sorted, washed, and reprocessed into a pellet that is suitable for re-use in plastics processing, for example blow and injection molding.

[0005] Though post-consumer resins are sorted into predominately uniform streams and are washed with aqueous and / or caustic solutions, the final reprocessed pellet often remains highly contaminated with unwanted waste impurities, such as volatiles, such as spoiled food residue andresidual perfume components. The need for high quality. “virgin-like” recycled resin may be especially important for food and drug contact applications, such as food packaging. However, the post-consumer resins have malodor due to the presence of such volatiles remaining, even at ppm levels. Such malodor can be limited by mixing the post-consumer resins with virgin polymer resins, but typically large amounts of virgin polymer resins need to be used, defeating the purpose of pursuing use of post-consumer resins.

[0006] Mechanical recycling, also known as secondary recycling, is the process of converting recycled plastic w aste into a re-usable form for subsequent manufacturing. A more detailed review' of mechanical recycling and other plastics recovery processes are described in S. M. Al-Salem. P. Lettieri, J. Baeyens, “Recycling and recovery routes of plastic solid waste (PSW): A review,” Waste Management, Volume 29, Issue 10, October 2009, Pages 2625-2643, ISSN 0956- 053X. While advances in mechanical recycling technology have improved the quality of recycled polymers to some degree, there are fundamental limitations of mechanical decontamination approaches, such as the physical entrapment of contaminants within a polymer matrix. Thus, even with the improvements in mechanical recycling technology, the contamination in currently available recycled plastic waste prevents broader usage of recycled resins by the plastics industry'.

[0007] Accordingly, a need still exists for articles made from reclaimed post-consumer resins having reduced or eliminated malodor and that have comparable physical properties as articles made from virgin resins.Summary of the Invention

[0008] The present disclosure relates to polymeric resin compositions and articles manufactured therefrom.

[0009] In at least one embodiment, a method of making a pelletized polymeric resin, includes blending a carbon nanotube component with a polymer component having a first volatiles content to form a polymeric resin, the polymer component comprising a post-consumer resin (PCR). The method includes extruding the polymeric resin to form polymeric resin extrudate. The method includes pelletizing the polymeric resin extrudate to form a pelletized polymeric resin. The polymer component of the pelletized polymeric resin has a second volatiles content that is less than the first volatiles content.

[0010] In some embodiments, a method of making a pelletized polymeric resin includes blending a carbon nanotube component with a polymer component having a first volatiles content of about 50 ppm to about 100 ppm to form a polymeric resin, the polymer component comprising a postconsumer resin (PCR). The method includes extruding the polymeric resin to form polymeric resin extrudate. The method includes pelletizing the polymeric resin extrudate to form a pelletizedpolymeric resin. The polymer component of the pelletized polymeric resin has a second volatiles content of about 0. 1 ppm to about 50 ppm.Detailed Description of the Invention

[0011] The present disclosure relates to polymeric resin compositions and articles manufactured therefrom. Polymeric resin compositions include carbon nanotubes mixed with the resin. It has been discovered that carbon nanotubes can adsorb volatiles disposed in the polymeric resin, substantially reducing malodor of pellets (and articles thereof) formed from the polymeric resin composition. Without being bound by theory, the inner diameter and bent, tubular geometry of carbon nanotubes provides strong adsorption of such volatiles in and / or on the carbon nanotubes. The reduced or eliminated malodor allows a substantial increase in the amount of post-consumer resin that may be utilized in articles thereof, rendering added virgin polymer to the pellets / articles merely optional. In addition, although ppm levels of volatiles in a post-consumer resin can lead to substantial malodor, such ppm levels of volatiles also allow low amounts of carbon nanotubes to be utilized in the post-consumer resin which negates unwanted discoloration that would be provided by an otherwise large amount of carbon nanotubes in the post-consumer resin.

[0012] Volatiles can include a hydrocarbon, an acetaldehyde, acetic acid, acetone, carbon tetrachloride, an aromatic compound, 2-hydroxyethyl methacrylate. D-limonene, benzaldehyde, cinnamaldehyde. a-pinene, |3-pinene, galoxolide. a-terpinol. o-cymene, terpinolene, eucalyptol, linalool, or combinations thereof. Also, the volatiles may include low molecular weight aromatic and olefinic hydrocarbons and the like.

[0013] The amount of volatiles present in a post-consumer resin can be determined by any suitable method, such as gas chromatography -mass spectrometry (GC-MS), differential thermal analysis (DTA), or thermogravimetric analysis (TGA).

[0014] As used herein, the term “post-consumer resin” (PCR) refers to a polymeric material that is produced after the end consumer has used the material and has disposed of the material in a waste stream.

[0015] As used herein, the term “substantially free of odor” means odor comparable in both character and intensity to virgin polymer as detected by a normally functioning human nose.

[0016] As used herein, the term “virgin” or “virgin-like” means essentially contaminant-free, pigment-free, odor-free, homogenous, and similar in properties to virgin polyethylene.

[0017] Malodor analysis can be performed by placing about 3 g of a polymer (e.g., PCR) sample in a 20 rnL glass vial and equilibrating the sample at room temperature for at least 30 min. After equilibration, each vial is opened and the headspace is sniffed by a trained grader to determine odor intensity and descriptor profile. Odor intensity can be graded according to the following scale: 5 = Very Strong; 4 = Strong; 3 = Moderate; 2 = Weak to Moderate; 1 = Weak; 0 = No odor.Carbon Nanotubes

[0018] Carbon nanotubes can include multi-walled carbon-nanotubes such as single-walled carbon nanotubes (SWNTs), double-walled carbon nanotubes (DWNTs), multiwall carbon nanotubes (MWNTs), bucky tubes, fullerene tubes, tubular fullerenes, graphite fibrils, or combinations thereof. Carbon nanotubes can be synthesized using any suitable process or can be obtained from any suitable commercial source. Carbon nanotubes may be functionalized carbon nanotubes using any suitable functionalization method or can be obtained in functionalized form from any suitable commercial source.

[0019] Carbon nanotubes can be of a variety and range of lengths, diameters, number of tube walls, chiralities (helicities), etc., and can be made by any known technique including arc discharge [Ebbesen, Amu. Rev. Mater. Sci. 1994, 24, 235-264], laser oven [Thess et al.. Science 1996, 273, 483-487], flame synthesis [Vander Wai et al., Chem. Phys. Lett. 2001, 349, 178-184], chemical vapor deposition [U.S. Pat. No. 5,374,415], wherein a supported [Hafner et al., Chem. Phys. Lett. 1998, 296, 195-202] or an unsupported [Cheng et al., Chem. Phys. Lett. 1998. 289, 602-610; Nikolaev et al., Chem. Phys. Lett. 1999, 313, 91 -97] metal catalyst may also be used, and combinations thereof. Depending on the embodiment, the CNTs can be subjected to one or more processing steps. In some embodiments, the CNTs have been purified. Exemplary purification techniques include, but are not limited to, those by Chiang et al. [Chiang et al., J. Phys. Chem. 5 2001, 105, 1157-1161; Chiang et al., J. Phys. Chem. 5 2001, 105, 8297-8301], In some embodiments, the CNTs have been cut by a cutting process. See Liu et al., Science 1998, 280, 1253-1256; Gu et al., Nano Lett. 2002, 2(9), 1009-1013; Haddon et al., Materials Research Society) Bulletin, 2004, 29, 252-259. The terms “carbon nanotube” and “nanotube” will be used interchangeably herein.

[0020] Without being bound by theory, the diversity in electronic structure of CNTs arises from the unique quantinization of the electronic wavevector of the 1-D system through the conceptual rolling of a graphene plane into a cylinder forming the nanotube [M. S. Dresselhaus, G. Dresselhaus, P. C. Eklund, Science o f Fullerenes and Carbon nanotubes, Academic Press. San Diego, 1996; R. Saito, G. Dresselhaus, M. S. Dresselhaus, Physical Properties of Carbon Nanotubes, Imperial College Press, London, 1998], The vector in units of hexagonal elements connecting tw o points on this plane can provide the nanotube chirality in terms of two integers: n and m. When |n-m|=3q or zero, where q is an integer, the nanotube is metallic or semimetallic, while the remaining species are semi-conducting with a geometry-dependent bandgap [Reich et al., Physical Review B, 2000, 62, 4273-4276],

[0021] Carbon nanotube chemistry' has been correctly described using a pyramidization angle formalism [S. Niyogi et al., Acc. of Chem. Res., 2002, 35, 1105-1113], Here, chemical reactivityand kinetic selectivity are related to the extent of s character due to the curvature-induced strain of the sp2-hybridized graphene sheet. Because strain energy per carbon is inversely related to nanotube diameter, this model predicts smaller diameter nanotubes to be the most reactive, with the enthalpy of reaction decreasing as the curvature becomes infinite. While this behavior is most commonly the case, the role of the electronic structure of the nanotubes in determining their reactivity may be important — especially when desiring selectivity among a population of similardiameter CNTs (such as is often the case with SWNT product).

[0022] Carbon nanotubes are vermicular carbon deposits having diameters less than 50 nm, such as less than 2 nm, such as about 0.5 nmto about 2 nm. Carbon nanotubes can be either multi walled (i.e., have more than one graphite layer on the nanotube axis having an outer diameter of about 10 nm to about 50 nm) or single walled (i.e., have only a single graphite layer on the nanotube axis and having an outer diameter of about 0.5 nm to about 2 nm). Other types of carbon nanotubes are also known, such as fishbone fibrils (e.g., resembling nested cones), etc. As produced, carbon nanotubes may be in the form of discrete nanotubes, aggregates of nanotubes (i.e., dense, microscopic particulate structure comprising entangled or bundled carbon nanotubes) or a mixture of both. In some embodiments, carbon nanotubes are of a single diameter d, wherein d is within the range of 0.8 to 2.2 nm, at least 80% of said multiplicity' of single walled carbon nanotubes having the diameter d within the range d ±5% of d.

[0023] Carbon nanotubes also differ physically and chemically from other forms of carbon such as standard graphite and carbon black. Standard graphite, because of its structure, can undergo oxidation to almost complete saturation. Moreover, carbon black is amorphous carbon generally in the form of spheroidal particles having a graphene structure, such as carbon layers around a disordered nucleus. On the other hand, carbon nanotubes have one or more layers of ordered grapheme carbon atoms disposed substantially concentrically about the cylindrical axis of the nanotube. These differences, among others, make graphite and carbon black poor predictors of carbon nanotube chemistry'.

[0024] Multi walled and single walled carbon nanotubes differ from each other. For example, multi walled carbon nanotubes have multiple layers of graphite along the nanotube axis while single walled carbon nanotubes only have a single graphitic layer on the nanotube axis.

[0025] The methods of producing multi walled carbon nanotubes also differ from the methods used to produce single walled carbon nanotubes. Specifically, different combinations of catalysts, catalyst supports, raw materials and reaction conditions are required to yield multi walled versus single walled carbon nanotubes. Certain combinations will also yield a mixture of multi walled and single walled carbon nanotubes.

[0026] Processes for forming multi walled carbon nanotubes are well known. E.g., Baker and Harris, Chemistry and Physics of Carbon, Walker and Thrower ed., Vol. 14, 1978, p. 83; Rodriguez, N., J. Mater. Research, Vol. 8, p. 3233 (1993); Oberlin, A. and Endo, M., J. of Crystal Growth, Vol. 32 (1976), pp. 335-349; U.S. Pat. No. 4.663,230 to Tennent et al.; U.S. Pat. No. 5.171,560 to Tennent et al.; lijima., Nature 354, 56, 1991; Weaver, Science 265 1994; de Heer, Walt A., “Nanotubes and the Pursuit of Applications,” MRS Bulletin. April, 2004; etc. All of these references are herein incorporated by reference.

[0027] Processes for making single walled carbon nanotubes are also known. E.g., “Singleshell carbon nanotubes of 1-nm diameter”, S lijima and T Ichihashi Nature, vol. 363, p. 603 (1993); “Cobalt-catalysed growth of carbon nanotubes with single-atomic-layer walls,” D S Bethune, C H Kiang, M S DeVries, G Gorman, R Savoy and R Beyers Nature, vol. 363, p. 605 (1993); U.S. Pat. No. 5,424,054 to Bethune et al.; Guo, T., Nikoleev, P., Thess, A., Colbert, D. T., and Smally, R. E., Chem. Phys. Lett. 243: 1-12 (1995); Thess, A., Lee, R., Nikolaev, P., Dai, H., Petit, P., Robert, J.. Xu, C.. Lee, Y. IL. Kim. S. G., Rinzler, A. G., Colbert, D. T.. Scuseria. G. E., Tonarek, D., Fischer, J. E., and Smalley, R. E., Science, 273: 483-487 (1996); Dai., H., Rinzler, A. G., Nikolaev, P., Thess, A., Colbert, D. T., and Smalley, R. E., Chem. Phys. Lett. 260: 471-475 (1996); U.S. Pat. No. 6,761,870 (also WO 00 / 26138) to Smalley, et. al; “Controlled production of single-wall carbon nanotubes by catalytic decomposition of CO on bimetallic Co — Mo catalysts,” Chemical Physics Letters, 317 (2000) 497-503; Maruyama, et. al. “Low-temperature synthesis of high-purity single walled carbon nanotubes from alcohol,” Chemical Physics Letters, 360, pp. 229-234 (Jul. 10, 2002); U.S. Pat. No. 6,333,016 to Resasco, et. al.; R. E. Morjan et al.. Applied Physics A, 78,253-261 (2004); Maruyama, et al. Chemical Physics Letters 375, 553-9 (2003). All of these references are hereby incorporated by reference.

[0028] In some embodiments, carbon nanotubes are predicted to have very high stiffness and axial strength, as a result of perfect structure and of their very high aspect ratios (L / D) compared to commonly used high strength fiber [Rao A M, Richter E, Bandow S, Chase B, Eklund P C, Williams K A. Fang S, Subbaswamy K R. Menon M. Thess A, Smalley R E. Dresselhaus G, Dresselhaus M S, Science 1997, 275, 187-191], MWNT are typically 3-100 nm in diameter and with aspect ratio typically less than 100. The MWNT consists of 5 concentric graphene layers up to about 50 layers. However, the number of layers is very difficult to control. SWNT on the other hand consists of a single graphene layer with diameter typically in the range of 1.2-3 nm and with very large (104-105) aspect ratio. The values of the Young's modulus for SWNTs and MWNTs were identified experimentally to be in the Tera-Pascal range, thus much exceeding that value for any other reinforcement materials, including the record number of about 800 GPa forfamous carbon whiskers, first made by Roger Bacon, “Growth. Structure and Properties of Graphite Whiskers”, Journal of Applied Physics, 31, 283 (1960).

[0029] The nanotubes combine into bundles with discrete tubules clearly visible on the periphery'. The observed length of these tubes in bundles is more than 1 pm. The HRTEM micrographs revealed that most of the tubules consist of two concentric nearly cylindrical graphene layers, double wall nanotubes (DWNTs). In general, the outer diameter of DWNTs range in between 3.4 nm to 5.5 nm while that of the inner tube varied between 2.7 to 4.7 nm. Along with the bundles some discrete separated DWNTs were also observed. The shape of separate DWNTs is often distorted. The periodic change of the width of tubule longitudinal section from 3.75 nm to 5.0 nm along the tube length is quite common and occurs with an interval of about 30 nm, DWNTs have rounded double layered terminating caps at the end. The shape of the caps is nearly hemispheric, which implies the chiral symmetry' for the tube structure. Notably, the interlayer distance measured in the tubule walls is 0.39-0.41 nm, which is larger than that usually observed for MWNTs (0.34- 0.36 nm). and thus imparts to DWNTs better opportunities for appropriate intercalation.

[0030] Carbon nanotube structures include assemblages, mats, plugs, networks, rigid porous structures, extrudates, etc. Assemblages are carbon nanotube structures which have relatively uniform properties in one, preferably two and most desirably three dimensional axis of the three dimensional assemblage. (E.g., U.S. Pat. No. 5.691,054 hereby incorporated by reference). Two dimensionally uniform assemblages take the form of mats. Three dimensionally uniform assemblages may take the form of the container in which they are formed and are typically7called plugs. Multi walled carbon nanotube mats may have a thickness between 0.02 and 0.50 millimeters and a density of approximately 0.20 g / cc. Generally, assemblages are formed by de-aggregating the carbon nanotube aggregate structure, and then reassembling them to form assemblages. Multi walled carbon nanotube assemblages may have a bulk density7of from 0.001 to 0.50 gm / cc and at least two dimensions greater than about 0.02 mm. Assemblages may also have at least two dimensions greater than 0.2 mm.

[0031] Networks are formed by linking individual functionalized carbon nanotubes together by using a linking molecule between the functionalized groups located on the surface of the carbon nanotubes. (E.g., PCT / US97 / 03553 or WO 97 / 32571, hereby incorporated by reference). In general, a matlike or pluglike network may have a lower density than the corresponding assemblage, but still within the range of 0.001 to 0.50 g / cc.

[0032] Rigid porous structures are formed by either linking the individual functionalized carbon nanotubes in an assemblage together without the use of a linking molecule, or by gluing carbon nanotube aggregate structures together with a gluing agent. (E.g., U.S. Pat. No. 6,099,965, hereby incorporated by reference).

[0033] Rigid porous structures of multi walled carbon nanotubes may have a surface area greater than about 100 m2 / gm, may be substantially free of micropores and may have a crush strength greater than about 2 lb / in2. Rigid porous structures may even have surface area greater than 200 m3 / gm2. Rigid porous structures of multi walled carbon nanotubes may have densities greater than density greater than 0.8 g / cm3. U.S. Pat. No. 6.099,965, which is incorporated by reference above, provides examples of rigid porous structures, for example, Example 5 describes a sample made from '‘as is” nanotube aggregates using phenolic resin / Polyethylene Glycol (PEG) / Glyccerine to hold the aggregates together. The partially dried slurry was pressed and cut into pellets, which can be pyrolized to remove PEG / Gly cerine and convert the phenolic resin to carbon with a surface area of 351 m2 / g. See page 23, lines 40-60.

[0034] Single walled carbon nanotubes typically have smaller diameter than most multi walled carbon nanotubes. Thus, structures created from single walled carbon nanotubes (“single walled carbon nanotube structures) will have significantly greater specific surface area (sqm / gm) and lower density than structures created from multi-walled carbon nanotubes (“multi walled carbon nanotube structures”). Surface area can be a critical performance parameter for many applications that use carbon nanotubes structures, such as those listed in this application.

[0035] Additionally, single w alled carbon nanotube structures can have smaller effective pore size than multi walled carbon nanotube structures. Having a smaller effective pore size may be beneficial in many applications. For example, smaller pores provide a higher specific surface which aids adsorption of volatiles. In addition, smaller pores are subject to smaller rates of diffusion of volatiles from the nanotubes. However, the pores must be large enough for the volatiles to absorb into the carbon nanotubes in the first place. Thus, the advantages of smaller pores should be balanced against other considerations. Parameters, like total porosity, pore size distribution, etc. may be important qualifiers of effective pore size. Thus, while multi walled carbon nanotube assemblages, netw orks, rigid porous structures and extrudates may have specific surface areas between 30 and 600 sqm / gm, the corresponding single walled assemblages, networks, structures and extrudates may have specific surface areas between 1000 and 2500 sqm / gm.

[0036] In some embodiments, a combination of SWNTs and DWNTs is utilized. The mixed structures may have a density of about 0.001 to about 0.50 g / mL, such as about 0.05 to about 0.5 g / mL. The mixed structure may have a surface area of about 300 to about 1800 sqm / g. such as about 500 to about 1000 sqm / g. The ratio of single walled carbon nanotubes to multi w alled carbon nanotubes in the carbon nanotube structure may range from about 1 / 1000 to about 1000 / 1 by w eight, or about 1 / 100 to about 100 / 1, or about 1 / 10 to about 10 / 1.Post-Consumer Resins

[0037] Post-consumer resins of the present disclosure may be sourced from post-consumer, postindustrial, post-commercial, and / or other special waste streams. For example, post-consumer resins can be waste polymers derived from curbside recycle streams where end-consumers place used polymers from packages and products into a designated bin for collection by a waste hauler or recycler. Post-consumer waste polymers can also be derived from in-store "take-back" programs where the consumer brings waste polymers into a store and places the waste polymers in a designated collection bin. An example of post-industrial waste polymers can be waste polymers produced during the manufacture or shipment of a good or product that are collected as unusable material by the manufacturer (i.e., trim scraps, out of specification material, start-up scrap). An example of waste polymers from a special waste stream can be waste polymers derived from the recycling of electronic waste, also know n as "e-waste." Another example of waste polymers from a special waste stream can be w aste polymers derived from the recy cling of automobiles. Another example of waste polymers from a special waste stream can be w aste polymers derived from the recycling of used carpeting and textiles.

[0038] Post-consumer resins of the present disclosure may be a homogenous composition of an individual polymer or a mixture of several different polymer compositions. Non-limiting examples of post-consumer resins include homopolymers and copolymers of polyolefins, such as polyethylene and isotactic polypropylene, polyesters, such as poly(ethylene terephthalate), vinyl polymers, such as poly(vinyl chloride), styrenic polymers, such as polystyrene, polyamides, such as poly(hexamethylene adapamide), polycarbonates, such as poly(bisphenol-A carbonate), polyacrylates, such as poly(methyl methacrylate), polysiloxanes, such as poly(dimethylsiloxane), thermoplastic elastomers, such as styrene-butadiene block copolymers and ethylene-propylene rubber, and other dissolvable polymers.

[0039] Post-consumer resins may also contain various pigments, dyes, process aides, stabilizing additives, fillers, and other performance additives that were added to the polymer during polymerization or conversion of the original polymer to the final form of an article. Non-limiting examples of pigments are organic pigments, such as copper phthalocyanine, inorganic pigments, such as titanium dioxide, and other pigments that may be apparent to those having ordinary skill in the art. A non-limiting example of an organic dye is Basic Yellow751. Non-limiting examples of process aides are antistatic agents, such as glycerol monostearate and slip-promoting agents, such as erucamide. A non-limiting example of a stabilizing additive is octadecyl-3-(3,5-di- tert.butyl-4-hydroxyphenyl)-propionate. Non-limiting examples of fillers are calcium carbonate, talc, and glass fibers.

[0040] As mentioned above, post-consumer resins can include one or more volatiles, such as a hydrocarbon, an acetaldehyde, acetic acid, acetone, carbon tetrachloride, an aromatic compound,2-hydroxyethyl methacrylate, D-limonene, benzaldehyde, cinnamaldehyde, a-pinene, p-pinene. galoxolide, a-terpinol, o-cymene, terpinolene, eucalyptol, linalool, or combinations thereof.

[0041] In some embodiments, resins of the current disclosure include one or more polymeric components, where at least one component includes a polymer having at least one ethylene monomeric unit. In some embodiments, polymeric components of the present disclosure include copolymer compositions, namely polymers derived from two or more structurally distinct monomers. In some embodiments, a resin is a polymeric resin, wherein a polymeric resin includes a blend of two or more polymer components. More specifically, resins of the present disclosure can include a polymeric resin comprising two or more polymeric components. Resins of the present disclosure can be useful as manufacturing materials, as a result of chemical resistance and environmental stress crack growth resistance (ESCR).

[0042] In at least one embodiment, a polymeric resin for use in the production of blow molded products includes a blend of a first polymeric component and a second polymenc component. In some embodiments, the first polymeric component is a high density polyethylene (HDPE) base resin. In some embodiments, the polymeric resin further includes a post-consumer resin (PCR), which can be readily and / or commercially sourced. Such materials and products produced from the polymeric resin exhibit sufficient physical properties, mechanical properties, chemical resistant properties, impact strength, hardness, and environmental stress crack resistance (ESCR) suitable for commercial products and uses.HDPE Base Resin

[0043] In some embodiments, the HDPE base resin has a density (as determined by ASTM1505) of about 0.940 g / cm3to about 0.975 g / cm3, such as about 0.940 g / cm3to about 0.960 g / cm3, such as about 0.940 g / cm3to about 0.955 g / cm3, such as about 0.953 g / cm3.

[0044] In some embodiments, the HDPE base resin has a high load melt index (HLMI) (as determined by ASTM D-1238, 190°C with a 21.6 kg load) of about 2 g / 10 min to about 10 g / 10 min, such as about 4 g / 10 min to about 8 g / 10 min, such as about 5.5 g / 10 min to about 7.5 g / 10 min.

[0045] In some embodiments, the HDPE base resin includes a weight average molecular weight (Mw), as determined by gel permeation chromatography (GPC), of about 180,000 g / mol to about 400,000 g / mol. such as about 215,000 g / mol to about 375,000 g / mol, such as about 275,000 g / mol to about 375,000 g / mol.

[0046] In some embodiments, the HDPE base resin has an ESCR (as determined by ISO 16770; 3.5 MPa, 2% Arkopal N100, 80 °C) of about 10 hrs to about 125 hrs, such as about 15 hrs to about 100 hrs, such as about 25 hrs to about 75 hrs, such as about 35 hrs to about 65 hrs.

[0047] In some embodiments, the HDPE base resin can include any suitable commercially available resin, such as Hostalen ACP 5231 D, Hostalen ACP 5331 A, Lupolen 4261 AG Q 469, Hyperzone HY 4008, Hyperzone HY55430, and combinations thereof. In at least one embodiment, the HDPE base resin is sourced from LyondellBasell Industries N.V.Post-Consumer Resin (PCR)

[0048] The PCR can be sourced from any appropriate plastic waste streams, such as polyethylene PCR sourced from recycled intermediate bulk containers (IBC), drums, and / or pipes. In additional or alternative embodiments, the PCR can further be sourced from suitable resins used in small blow molding applications. Without being bound by theory’, blending the HDPE base resin with the PCR allows an operator to tune the rheological properties of the polymeric resin, so as to produce a resin suitable for use in general purpose large flow molding applications. However, because volatiles content of post-consumer resins of the present disclosure can be adsorbed by carbon nanotubes, added virgin resin (such as an HDPE) can be reduced or eliminated. Examples of such applications can include, but are not limited to, outdoor recreational equipment (e.g., kayaks and playground equipment).

[0049] In some embodiments, the PCR has a density (as determined by ASTM1505) of about 0.910 g / cm3to about 0.970 g / cm3, such as about 0.920 g / cm3to about 0.955 g / cm3. such as about 0.935 g / cm3to about 0.945 g / cm3, such as about 0.941 g / cm3. In at least one embodiment, the PCR has a melt index (as determined by ASTM D-1238, 190°C with a 2.16 kg load) of about 0.3 g / 10 min to about 10 g / 10 min, such as about 0.3 g / 10 min to about 10 g / 10 min, such as about 0.3 g / 10 min to about 5 g / 10 min such as about 0.3 g / 10 min to about 2 g / 10 min.

[0050] In some embodiments, the PCR has a high load melt index (as determined by ASTM D- 1238. 190°C with a 21.6 kg load) of about 10 g / 10 min to about 60 g / 10 min, such as about 10 g / 10 min to about 50 g / 10 min, such as about 10 g / 10 min to about 40 g / 10 min.

[0051] In one or more embodiments, the PCR is selected from an ultra-high molecular weight polyethylene (UHMWPE), ultra-low molecular weight polyethylene (ULMWPE), high molecular weight polyethylene (HMWPE), high density polyethylene (HDPE). medium density polyethylene (MDPE), linear low density polyethylene (LLDPE), low density polyethylene (LDPE), very-low density polyethylene (VLDPE), and combinations thereof. In some embodiments, the PCR is a copolymer of polyethylene of any one or more selected from the group previously described.

[0052] In at least one embodiment, the PCR is HDPE homopolymer and / or a copolymer thereof. In some embodiments, the HDPE PCR homopolymer includes a weight average molecular weight (Mw), as determined by GPC, of about 180,000 g / mol to about 400,000 g / mol, such as about 200,000 g / mol to about 360,000 g / mol, such as about 225,000 g / mol to about 350,000 g / mol.

[0053] In some embodiments, the HDPE PCR homopolymer has a density of about 0.925 g / cm3to about 0.965 g / cm3, such as about 0.935 g / cm3to about 0.955 g / cm3, such as about 0.945 g / cm3to about 0.955 g / cm3. In at least one embodiment, the HDPE PCR homopolymer has a melt index (as determined by ASTM D-1238, 190°C with a 2.16 kg load) of about 1 g / 10 min to about 60 g / 10 min. such as about 10 g / 10 min to about 50 g / 10 min, such as about 20 g / 10 min to about 40 g / 10 min such as about 25 g / 10 min to about 35 g / 10 min.

[0054] In some embodiments, the PCR is a HDPE PCR copolymer comprising any one or more comonomers selected from propylene, 1 -butene, 1 -hexene, 1 -octene, 4-methyl-l -pentene, and any combination thereof. In some embodiments, the HDPE copolymer PCR includes about 90. 1 mol % to about 99.9 mol % of ethylene units, such as about 91 mol % to 99 mol %, such as about 92 mol % to 98 mol %, such as about 93 mol % to 97 mol %, such as about 94 mol % to 96 mol %. In at least one embodiment, the HDPE copolymer or homopolymer PCR is sourced from postconsumer waste products, such as products formed from HDPE copolymer resins typically used for small blow molding applications.

[0055] In some embodiments, the HDPE copolymer PCR includes a backbone architecture of at least one of a random copolymer, a block copolymer, an alternating copolymer, or a gradient copolymer. In one or more embodiments, the HDPE copolymer PCR is a random copolymer. In one or more embodiments, the HDPE copolymer PCR includes a molar ratio of ethylene units to any one or more comonomer units of about 60:40 to about 99: 1, such as about 70:30 to about 90: 10, such as about 75:25 to about 85: 15.

[0056] In some embodiments, the HDPE copolymer PCR includes a weight average molecular weight (Mw), as determined by GPC. of about 200,000 g / mol to about 400,000 g / mol. such as about 225,000 g / mol to about 375,000 g / mol. such as about 250,000 g / mol to about 375.000 g / mol.

[0057] In some embodiments, the HDPE copolymer PCR has an ESCR (as determined by ASTM DI 693; 100% Igepal®, Cond B) of about 10 hrs to about 50 hrs, such as about 20 hrs to about 40 hrs, such as about 25 hrs to about 35 hrs.

[0058] In at least one embodiment, the PCR includes at least one of HDPE homopolymer PCR sourced from one or more intermediate bulk containers and / or HDPE copolymer PCR sourced from resins used in small blow molding applications. In some embodiments, the PCR includes both HDPE PCR and HDPE copolymer PCR at a weight ratio of about 50:50 to about 99: 1, such as 60:40 to about 90: 10, such as 70:30 to about 80:20, such as 75:25 to about 85: 15.

[0059] In some embodiments, the PCR includes one or more polymers selected from the group consisting of low density polyethylene (LDPE), medium density polyethylene (MDPE), polypropylene, polyester, acrylic resin, polyvinyl alcohol, polyvinyl chloride, polyvinyl acetate, polyvinyl ether, ethylene-vinyl acetate copolymers (EVA), ethylenevinyl alcohol copolymers(EVOH). ethylene-acrylic acid copolymers, any one or more nylons, and the like, and mixtures thereof. In at least one embodiment, such one or more polymers includes less than 15 wt% of the PCR, such as about 0.01 wt% to about 15 wt%, such as about 0.01 wt% to about 10 wt%, such as about 0.01 wt% to about 5 wt%, such as about 0.01 wt% to about 2.5 wt%, such as about 0.01 wt% to about 1 wt%.

[0060] In some embodiments, the PCR further includes one or more compatiblizers, such as grafted copolymers of maleic anhydride with HDPE, LLDPE, and / or LDPE. In at least one embodiment, the one or more compatibilizers includes less than 15 wt% of the PCR, such as about 0.01 wt% to about 15 wt%, such as about 0.01 wt% to about 10 wt%, such as about 0.01 wt% to about 5 wt%, such as about 0.01 wt% to about 2.5 wt%, such as about 0.01 wt% to about 1 wt%.

[0061] In some embodiments, the PCR further includes one or more tie layer material. A tie layer is commonly used in multi-layered film applications as an adhesive applied to prevent film delamination. A tie layer material typically includes a polyolefin base resin as the predominant component and one or more grafted polyolefins. In at least one embodiment, the one or more tie layer materials includes less than 15 wt% of the PCR, such as about 0.01 wt% to about 15 wt%, such as about 0.01 wt% to about 10 wt%, such as about 0.01 wt% to about 5 wt%, such as about 0.01 wt% to about 2.5 wt%, such as about 0.01 wt% to about 1 wt%.

[0062] In one or more embodiments, the compositional summation of the one or more additional polymers, one or more compatibilizers, and one or more tie layer materials of the PCR includes less than 15 wt% of the PCR, such as about 0.01 wt% to about 15 wt%, such as about 0.01 wt% to about 10 vvt%, such as about 0.01 wt% to about 5 wt%, such as about 0.01 wt% to about 2.5 wt%, such as about 0.01 wt% to about 1 wt%.Post-Extrusion Polymeric Resin and Components Thereof

[0063] In one or more embodiments, the post-extrusion polymeric resin includes about 50 wt% to about 100 wt% of base resin (such as PCR having carbon nanotubes), such as about 75 wt% to about 95 wt% base resin, alternatively about 20 wt% to about 80 wt% base resin. In at least one embodiment, base resin includes at least 50 wt% of the post-extrusion polymeric resin.

[0064] In one or more embodiments, the post-extrusion polymeric resin includes about 1 wt% to about 50 wt% of PCR, such as about 5 wt% to about 25 wt% PCR, such as about 10 wt% to about 20 wt% PCR.

[0065] In one or more embodiments, the post-extrusion polymeric resin includes a weight ratio of base resin to additional polymer of about 60:40 to about 90: 10, such as about 70:30 to about 90: 10, such as about 75:25 to about 90: 10.

[0066] In some embodiments, the post-extrusion polymeric resin can further include any one or more additives. Suitable additives include, but are not limited to UV stabilizers, flame retardants,fillers, and pigments. Additives are important in establishing the long term stability of the polymeric resin as well as the resulting material’s chemical and impact resistance.

[0067] In one or more embodiments, the post-extrusion polymeric resin further includes one or more UV stabilizers in an amount of about 1500 ppm to about 2500 ppm, such as about 1750 ppm to about 2250 ppm, such as about 2000 ppm. Suitable UV stabilizers include, but are not limited to, hindered amine light stabilizers ("HALS"). Examples of HALS include: Chimassorb 944, Chimassorb 994, Chimassorb 905, Tinuvin 770, Tinuvin 992, Tinuvin 622, Tinuvin 144, and Spinuvex A36 available from Geigy; and Cyasorb UV 3346 and Cyasorb UV 944 commercially available American Cyanamide. Particularly preferred UV stabilizers are Cytec UV 3346 and Chemasorb 944 (poly[N,N-bis(2,2,6,6-tetramethyl-4-piperidinyl)-l,6-hexanediamine-co-2,4- dichloro-6-morpholino-l,3,5-triazine).

[0068] In one or more embodiments, the post-extrusion polymeric resin further includes one or more flame retardants. Flame retardants include, for example, halogen-containing compounds, antimony oxides, or phosphorus compounds. Suitable flame retardants include, but are not limited to aluminum trihydrate, antimony oxide (Sb2Ch), and decabromobiphenyl oxide ("decabrome").

[0069] In one or more embodiments, the post-extrusion polymeric resin includes 0.01 wt% to about 5 wt% of one or more additives, such as about 0.01 wt% to about 2.5 wt%, such as about 0.01 wt% to about 1 wt%. In one or more embodiments, the polymeric resin includes about 1 wt% or less of additives (such as flame retardant).

[0070] In one or more embodiments, the one or more components blended with the base resin, the carbon nanotubes, and any additional polymers via any one or more suitable methods known to one of ordinary skill in the art. Such blending methods can include solution processing, thermal processing, and / or mechanical processing. In some embodiments, melt screw extrusion is implemented to form the polymeric resin extrudate (post-extrusion polymeric resin), which can then be further processed via pelletization to form a pelletized polymeric resin. Melt blending is one suitable method for preparing the post-extrusion polymer blend of the present disclosure, although any suitable polymer blending techniques available to those of ordinary skill in the art may be used. Techniques for melt blending of a polymer with additives of all types are known to those of ordinary skill the art and can typically be used with the present disclosure. In one type of melt blending operation useful with the present disclosure, the individual components of the blend are combined in a mechanical extruder or mixer, and then heated to a temperature sufficient to form a polymer melt.

[0071] The mechanical mixer can be a continuous or batch mixer. Examples of suitable continuous mixers include single screw extruders, intermeshing co-rotating twin screw' extruders such as Wemer & Pfleiderer ZSK™ extruders, counter-rotating twin screw extruders such as thosemanufactured by Leistritz™. and reciprocating single screw kneaders such as Buss ™ co-kneaders. Examples of suitable batch mixers are lateral 2-roll mixers such as Banbury™ or Boling™ mixers. The temperature of the melt, residence time of the melt within the mixer, and the mechanical design of the mixer are several well-known variables that control the amount of shear to be applied to the composition during mixing, and can be readily selected by one of ordinary’ skill in the art based on the disclosure of the disclosure herein.

[0072] The polymeric resins disclosed herein may be pelletized via strand pelleting or commercial underwater pelletization. Pellets of the polymeric resin may then be easily processed into shaped articles by injection molding, profile extrusion, blow molding, and other forming processes to give products which have well balanced properties suitable for commercial applications.

[0073] In at least one embodiment, pellets of the polymeric resin are formed in a continuous process. As such, components of the polymeric resin are fed into a continuous mixer, a single screw or twin screw extruder via volumetric or gravimetric feeders. The extruder is heated to a temperature sufficient to melt the polymers, for example between 165 °C and 190 °C. The components are fed into an extruder and mixed / blended together in a molten state. The extruder speed may be from about 1 to about 100 revolutions per minute (rpm), more typically from about 10 to about 50 rpm. The gas from the extruder may be evacuated by a vacuum pump. The polymeric resin extrudate is typically cooled (e g., in a water bath or underwater pelletizer) and pelletized to form pellets of the polymeric resin having carbon nanotubes.

[0074] In at least one embodiment, pellets of the polymeric resin are formed in a batch process. As such, components of the polymeric resin (such as carbon nanotubes) are added to a mixing device, such as a Banbury mixer, and heated to a temperature sufficient to melt the polymer, such as about 100 °C to about 155 °C. The mixing speed is typically about 35 to about 75 rpm. The output from the mixer was cooled and pelletized to form pellets of the polymeric resin.

[0075] In one or more embodiments, the polymeric resin, or pellets thereof, is useful for making articles by injection molding, blow molding, rotomolding, and compression molding. In at least one embodiment, the polymeric resin can be implemented into an extrusion blow molding process to manufacture jerry cans comprising recycled PCR material.

[0076] In embodiments wherein the polymeric resin includes a PCR base resin and one or more additional polymers, the polymeric resin exhibits intermediate physical and mechanical properties in comparison the input materials. That is to say that such resulting physical and mechanical properties are tailorable via altering the feed of the polymeric components and / or additives.

[0077] In some embodiments, the polymeric resin has a density (as determined by ASTM DI 505) of about of about 0.940 g / cm3to about 0.975 g / cm3, such as about 0.940 g / cm3to about 0.960 g / cnf , such as about 0.940 g / cm3to about 0.955 g / cm3, such as about 0.948 g / cm3.

[0078] In some embodiments, the polymeric resin has a melt index (as determined by ASTM D- 1238, 190°C with a 2.16 kg load) of about 0.05 g / 10 min to about 1 g / 10 min, such as about 0.05 g / 10 min to about 0.5 g / 10 min, such as about 0.05 g / 10 min to about 0.1 g / 10 min.

[0079] In some embodiments, the polymeric resin has a high load melt index (as determined by ASTM D-1238, 190°C with a 21.6 kg load) of about 2 g / 10 min to about 20 g / 10 min. such as about 5 g / 10 min to about 15 g / 10 min, such as about 8.5 g / 10 min to about 12.5 g / 10 min, such as about 10 g / 10 min.

[0080] In some embodiments, the polymeric resin has an ESCR (as determined by ASTM D1693; 100% Igepal®, Cond B) of greater than 1000 hrs.

[0081] It should be noted that an object of the present disclosure is that the polymeric resin may be implemented into extrusion blow molded articles formed from post-consumer waste products, articles such as playground equipment, outdoor recreational equipment (e.g., kayaks), and the like. Furthermore, it is an object of the present disclosure to provide hollow plastic articles whose structure has one or more layers which have PCR content, and also to provide a process for their production. Such products can be produced via blow molding or co-extrusion blow molding processes.

[0082] In at least one embodiment, hollow plastic articles can be produced via a process comprising: (1) molding a blow molded article in a blow molding and / or co-extrusion blow molding machine, whereby the blow molding cavity formed by the two mold contours is shaped in such a way that said cavity essentially matches the outer contour of the plastic hollow article to be fabricated and, in addition, it has a circumferential indentation and / or protuberance, preferably located in the middle relative to the nip-off edge, (2) separation of the indentation and / or protuberance, which yields at least two sheets, (3) optionally, prior to joining the sheets together to form a hollow article, installation of the built-in components on the inside of the sheets, and (4) joining the sheets together to form a hollow article, optionally by means of welding and / or gluing.

[0083] The principle of the process for the production of plastic hollow articles consists first of the conventional fabrication of a blow molded article in a regular blow molding or co-extrusion blow molding machine. The cavity formed by the two mold contours is shaped in such a way that the cavity essentially matches the outer contour of the plastic hollow article or plastic tank to be manufactured. In one or more embodiments, the above-mentioned blow molding cavity or the blowing mold used for the process additionally has a circumferential indentation and / or protuberance, preferably located in the middle relative to the nip-off edge. "Circumferential", as defined herein, means that the indentation and / or protuberance preferably extends around the entire blow molded article or plastic hollow article. Therefore, the modified configuration of the contact areas of the mold, which is new in comparison to the commonly employed blow ing molds, allowsthe creation of a hollow plastic article that has an indentation and / or protuberance (a groove or bead) extending around the container.

[0084] In the second step of the process, the described indentation and / or protuberance is separated, preferably in the perpendicular direction with respect to the above-mentioned indentation and / or protuberance. Two half shells or sheets are obtained by this separation procedure, which is to say, for instance, by cutting, grinding or punching out the indentation and / or protuberance that encircles the hollow plastic article. In some embodiments, the half shells obtained are glued and / or welded together to form a hollow article.

[0085] In at least one embodiment, it is provided that the hollow plastic articles manufactured bymeans of the process according to this disclosure are preferably employed as playground and outdoor recreational equipment (e.g., kayaks), pipes, automotive dunnage, truck bedliners, and the like.EMBODIMENTS LISTING

[0086] The present disclosure provides, among others, the following aspects, each of which can be considered as optionally including any alternate embodiments:Clause 1. A method of making a pelletized polymeric resin, comprising: blending a carbon nanotube component with a polymer component having a first volatiles content to form a polymeric resin, the polymer component comprising a post-consumer resin (PCR); extruding the polymeric resin to form polymeric resin extrudate; and pelletizing the polymeric resin extrudate to form a pelletized polymeric resin, wherein the polymer component of the pelletized polymeric resin has a second volatiles content that is less than the first volatiles content.Clause 2. The method of Clause 1, wherein the first volatiles content is about 0.1 ppm to about 100 ppm.Clause 3. The method of Clauses 1 or 2, wherein the second volatiles content is about 0.01 ppm to about 50 ppm.Clause 4. The method of any of Clauses 1 to 3, wherein the carbon nanotube component is about 0.001 ppm to about 1,000 ppm of the polymeric resin.Clause 5. The method of any of Clauses 1 to 4, wherein a weight ratio of volatiles of the first volatile content to the carbon nanotube is about 1: 100 to about 100: 1.Clause 6. The method of any of Clauses 1 to 5, wherein the second volatiles content is about 20 wt% less than a wt% of the first volatiles content.Clause 7. The method of any of Clauses 1 to 6, wherein the second volatiles content is about50 wt% less than the wt% of the first volatiles content.Clause 8. The method of any of Clauses 1 to 7. wherein the second volatiles content is about 99 wt% less than the wt% of the first volatiles content.Clause 9. The method of any of Clauses 1 to 8, wherein the first volatiles content comprises a volatile selected from the group consisting of a hydrocarbon, an acetaldehyde, acetic acid, acetone, carbon tetrachloride, an aromatic compound. 2-hydroxyethyl methacrylate, D-limonene, benzaldehyde, cinnamaldehyde, a-pinene, P-pinene, galoxolide, a-terpinol, o-cymene, terpinolene, eucalyptol, linalool, and combinations thereof.Clause 10. The method of any of Clauses 1 to 9, wherein: the second volatiles content comprises a volatile selected from the group consisting of a hydrocarbon, an acetaldehyde, acetic acid, acetone, carbon tetrachloride, an aromatic compound, 2-hydroxyethyl methacrylate, D-limonene, benzaldehyde, cinnamaldehyde, a-pinene, P-pinene, galoxolide, a-terpinol, o-cymene, terpinolene, eucalyptol, linalool, and combinations thereof; and the volatile of the first volatiles content is the same as the volatile of the second volatiles content.Clause 11. The method of any of Clauses 1 to 10, wherein the carbon nanotube comprises one or more single-walled carbon nanotubes.Clause 12. The method of any of Clauses 1 to 11, wherein the carbon nanotube comprises one or more double-walled carbon nanotubes.Clause 13. The method of any of Clauses 1 to 12, wherein the PCR comprises one or more polymers selected from the group consisting of ultra-high molecular weight polyethylene (UHMWPE). ultra-low molecular weight polyethylene (ULMWPE), high molecular weight polyethylene (HMWPE), high density polyethylene (EIDPE), medium density polyethylene (MDPE), linear low density polyethylene (LLDPE), low density polyethylene (LDPE), very -low density polyethylene (VLDPE), and combinations thereof.Clause 14. A method of making a pelletized polymeric resin, comprising: blending a carbon nanotube component with a polymer component having a first volatiles content of about 50 ppm to about 100 ppm to form a polymeric resin, the polymer component comprising a post-consumer resin (PCR); extruding the polymeric resin to form polymeric resin extrudate; and pelletizing the polymeric resin extrudate to form a pelletized polymeric resin, wherein the polymer component of the pelletized polymeric resin has a second volatiles content of about 0. 1 ppm to about 50 ppm.Clause 15. The method of Clause 14, wherein the carbon nanotube component is about 0.001 ppm to about 1,000 ppm of the polymeric resin.Clause 16. The method of Clauses 14 or 15, wherein the carbon nanotube component is about 1 ppm to about 100 ppm of the polymeric resin.Clause 17. The method of any of Clauses 14 to 16, wherein a weight ratio of volatiles of the first volatile content to the carbon nanotube is about 1: 100 to about 100: 1.Clause 18. The method of any of Clauses 14 to 17, wherein the carbon nanotube component comprises one or more single-walled carbon nanotubes.Clause 19. The method of any of Clauses 14 to 18, wherein the carbon nanotube component comprises one or more double-walled carbon nanotubes.Clause 20. The method of any of Clauses 14 to 19, wherein: the first volatiles content comprises a volatile selected from the group consisting of a hydrocarbon, an acetaldehyde, acetic acid, acetone, carbon tetrachloride, an aromatic compound, 2-hydroxyethyl methacrylate. D-limonene, benzaldehyde, cinnamaldehyde, a-pinene, P-pinene, galoxolide. a-terpinol. o-cymene, terpinolene, eucalyptol, linalool, and combinations thereof; the second volatiles content comprises a volatile selected from the group consisting of a hydrocarbon, an acetaldehyde, acetic acid, acetone, carbon tetrachloride, an aromatic compound, 2-hydroxyethyl methacrylate, D-limonene, benzaldehyde, cinnamaldehyde, a-pinene. P-pinene, galoxolide, a-terpinol, o-cymene, terpinolene, eucalyptol, linalool, and combinations thereof; and the volatile of the first volatiles content is the same as the volatile of the second volatiles content.

[0087] Overall, polymeric resin compositions of the present disclosure include carbon nanotubes mixed with the resin. It has been discovered that carbon nanotubes can adsorb volatiles disposed in the polymeric resin, substantially reducing malodor of pellets (and articles thereof) formed from the polymeric resin composition. The reduced or eliminated malodor allows a substantial increase in the amount of post-consumer resin that may be utilized in articles thereof, rendering added virgin polymer to the pellets / articles merely optional. In addition, although ppm levels of volatiles in a post-consumer resin can lead to substantial malodor, such ppm levels of volatiles also allow low amounts of carbon nanotubes to be utilized in the post-consumer resin which negates unwanted discoloration that would be provided by an otherw ise large amount of carbon nanotubes in the post-consumer resin.

[0088] The phrases, unless otherwise specified, "consists essentially of' and "consisting essentially of' do not exclude the presence of other steps, elements, or materials, whether or not, specifically mentioned in this specification, so long as such steps, elements, or materials, do not affect the basic and novel characteristics of the present disclosure, additionally, they do not exclude impurities and variances normally associated with the elements and materials used.

[0089] For the sake of brevity, only certain ranges are explicitly disclosed herein. However, ranges from any lower limit may be combined with any upper limit to recite a range not explicitlyrecited, as well as. ranges from any lower limit may be combined with any other lower limit to recite a range not explicitly recited, in the same way, ranges from any upper limit may be combined with any other upper limit to recite a range not explicitly recited. Additionally, within a range includes every point or individual value between its end points even though not explicitly recited. Thus, every point or individual value may serve as its own lower or upper limit combined with any other point or individual value or any other lower or upper limit, to recite a range not explicitly recited.

[0090] All documents described herein are incorporated by reference herein, including any priority' documents and or testing procedures to the extent they are consistent with this text. As is apparent from the foregoing general description and the specific embodiments, while forms of the present disclosure have been illustrated and described, various modifications can be made without departing from the spirit and scope of the present disclosure. Accordingly, it is not intended that the present disclosure be limited thereby. Likewise, the term “comprising” is considered synonymous with the term “including” for purposes of United States law. Likewise whenever a composition, an element or a group of elements is preceded with the transitional phrase “comprising,” it is understood that we also contemplate the same composition or group of elements with transitional phrases “consisting essentially of,” “consisting of.” “selected from the group of consisting of.” or “is” preceding the recitation of the composition, element, or elements and vice versa.

[0091] While the present disclosure has been described with respect to a number of embodiments and examples, those skilled in the art, having benefit of this disclosure, will appreciate that other embodiments can be devised which do not depart from the scope and spirit of the present disclosure.

Claims

CLAIMS1. A method of making a pelletized polymeric resin, comprising: blending a carbon nanotube component with a polymer component having a first volatiles content to form a polymeric resin, the polymer component comprising a post-consumer resin (PCR); extruding the polymeric resin to form polymeric resin extrudate; and pelletizing the polymeric resin extrudate to form a pelletized polymeric resin, wherein the polymer component of the pelletized polymeric resin has a second volatiles content that is less than the first volatiles content.

2. The method of claim 1, wherein the first volatiles content is about 0.1 ppm to about 100 ppm.

3. The method of claim 2, wherein the second volatiles content is about 0.01 ppm to about 50 ppm.

4. The method of claim 1, wherein the carbon nanotube component is about 0.001 ppm to about 1,000 ppm of the polymeric resin.

5. The method of claim 1, wherein a weight ratio of volatiles of the first volatile content to the carbon nanotube is about 1 : 100 to about 100: 1.

6. The method of claim 1, wherein the second volatiles content is about 20 wt% less than a \\1% of the first volatiles content.

7. The method of claim 6, wherein the second volatiles content is about 50 wt% less than the wt% of the first volatiles content.

8. The method of claim 7, wherein the second volatiles content is about 99 wt% less than the wt% of the first volatiles content.

9. The method of claim 1, wherein the first volatiles content comprises a volatile selected from the group consisting of a hydrocarbon, an acetaldehyde, acetic acid, acetone, carbon tetrachloride, an aromatic compound, 2-hydroxyethyl methacrylate, D-limonene, benzaldehyde, cinnamaldehyde, a-pinene, P-pinene, galoxolide, a-terpinol, o-cymene, terpinolene, eucalyptol, linalool, and combinations thereof.

10. The method of claim 9, wherein: the second volatiles content comprises a volatile selected from the group consisting of a hydrocarbon, an acetaldehyde, acetic acid, acetone, carbon tetrachloride, an aromaticcompound, 2-hydroxyethyl methacrylate, D-limonene, benzaldehyde, cinnamaldehyde, a- pinene, -pinene, galoxolide, a-terpinol, o-cymene, terpinolene, eucalyptol, linalool, and combinations thereof; and the volatile of the first volatiles content is the same as the volatile of the second volatiles content.

11. The method of claim 1 , wherein the carbon nanotube comprises one or more single-walled carbon nanotubes.

12. The method of claim 1 , wherein the carbon nanotube comprises one or more double-walled carbon nanotubes.

13. The method of claim 1, wherein the PCR comprises one or more polymers selected from the group consisting of ultra-high molecular weight polyethylene (UHMWPE), ultra-low molecular weight polyethylene (ULMWPE), high molecular weight polyethylene (HMWPE), high density polyethylene (HDPE), medium density polyethylene (MDPE), linear low density polyethylene (LLDPE), low density polyethylene (LDPE), very-low density polyethylene (VLDPE), and combinations thereof.

14. A method of making a pelletized polymeric resin, comprising: blending a carbon nanotube component with a polymer component having a first volatiles content of about 50 ppm to about 100 ppm to form a polymeric resin, the polymer component comprising a post-consumer resin (PCR); extruding the polymeric resin to form polymeric resin extrudate; and pelletizing the polymeric resin extrudate to form a pelletized polymeric resin, wherein the polymer component of the pelletized polymeric resin has a second volatiles content of about 0.1 ppm to about 50 ppm.

15. The method of claim 14, wherein the carbon nanotube component is about 0.001 ppm to about 1 ,000 ppm of the polymeric resin.

16. The method of claim 15, wherein the carbon nanotube component is about 1 ppm to about 100 ppm of the polymeric resin.

17. The method of claim 14, wherein a weight ratio of volatiles of the first volatile content to the carbon nanotube is about 1 : 100 to about 100: 1.

18. The method of claim 14, wherein the carbon nanotube component comprises one or more single-walled carbon nanotubes.

19. The method of claim 14, wherein the carbon nanotube component comprises one or more double-walled carbon nanotubes.

20. The method of claim 14, wherein: the first volatiles content comprises a volatile selected from the group consisting of a hydrocarbon, an acetaldehyde, acetic acid, acetone, carbon tetrachloride, an aromatic compound, 2-hydroxy ethyl methacrylate, D-limonene, benzaldehyde, cinnamaldehyde, a- pinene, P-pinene. galoxolide, a-terpinol, o-cymene. terpinolene, eucalyptol, linalool, and combinations thereof; the second volatiles content comprises a volatile selected from the group consisting of a hydrocarbon, an acetaldehyde, acetic acid, acetone, carbon tetrachloride, an aromatic compound, 2-hydroxy ethyl methacrylate, D-limonene, benzaldehyde, cinnamaldehyde, a- pinene, P-pinene. galoxolide. a-terpinol. o-cymene. terpinolene, eucalyptol, linalool, and combinations thereof; and the volatile of the first volatiles content is the same as the volatile of the second volatiles content.