BR112020021530A2 - ADDITION OF ADDITIVES THAT CONFER BIODEGRADABILITY TO PLASTIC MATERIALS - Google Patents

Abstract

methods for making a plastic material that is not biodegradable by itself are described in this document by mixing the plastic material with a carbohydrate-based polymeric material that is formed from a) one or more starches and a plasticizer (e.g., glycerin), b) an additive known in the art as an oxo material and / or an additive that interacts with microbes that contributes to the biodegradation of the non-biodegradable material. the carbohydrate-based polymeric material is less crystalline than non-biodegradable materials, for example, because it is substantially amorphous and because it has a crystallinity of not more than 20%. when tested under conditions that cause biodegradation, the blend will biodegrade to a greater extent than the content of the carbohydrate-based polymer.

Description

Invention Patent Descriptive Report for "ADDITION OF ADDITIVES THAT CONFER BIODEGRADABILITY TO PLASTIC MATERIALS".

BACKGROUND

[0001] Plastics based on traditional petrochemicals are formulated to be strong, light and durable. For this reason, they are used in large quantities in countless consumer products. However, these plastics are generally non-biodegradable to a significant extent, and as a result, hundreds of millions of tons of plastic are found in landfills or floated in the ocean. In an attempt to reduce the amount of plastic waste, some articles typically produced using petrochemical-based plastics are being produced using biodegradable materials.

[0002] Petrochemical-based plastic materials, such as large amounts of polyethylene and polypropylene, as well as various other plastics (polyethylene terephthalate polyester, polystyrene, ABS, polyvinyl chloride, polycarbonate, nylon and the like) are not, typical and similar readily biodegradable. As is typically the case even for so-called “green” plastics of such materials, which can be sourced from renewable or sustainable sources, rather than petrochemical raw materials.

[0003] Recently, efforts have been made to make such plastic materials gradually degradable by adding degradable UV and / or OXO additives (eg, such as PDQ-M, PDQ-H, BDA, and OxoTerraTM Willow Additive) Ridge Plastics, LifeLine Additive OX1014, or organic additives (for example, such as Enso Restore® by Enso, EcoPure® Bio-Tec Environmental Additive, ECM Biofilms ECM matrix batch granule additive or BioSphere®). degradable OXO additives are known to break the long carbon chains of materials that make materials more susceptible to biodegradation. The degradation of plastic materials in this way is through the action of UV and / or oxygen. usually instituted by microorganisms, bacteria or fungi. The use of such additives is often disapproved by some plastic industry associations (eg SPC, APR, FPA and / or BPI), and governing bodies such as the European Union and some states, specifically California. It is believed that the degree of degradability (particularly any biodegradability) and that the rate of degradation caused is often very slow, and UV and / or OXO additives can simply initiate structural fragmentation or degradation that accelerates physical deterioration of such plastic materials into small pieces (“microplastics”) of the structural base plastic material, rather than the current desired conversion of the plastic into natural materials, such as carbon dioxide (CO2), water (H2O), and / or methane (CH4). Some jurisdictions, such as the European Union and some states, have adopted policies to discourage or even propose a ban on the use of such additives or at least disregarding the biodegradability claims of plastics containing the additives because such claims are misleading.

[0004] Such government agencies believe that OXO additives can simply accelerate the breakdown of the macrostructure of the plastic article by itself due to exposure to UV light (from exposure to the sun) and / or oxygen. Such specialized plastics, in reality, may not biodegrade to any desirable degree within a certain period (for example, 5 years, 3, years or 1 year), but simply lose strength, break and break into small pieces. The result can be a pile of small pieces of polyethylene or other basic plastic material that results from the bottle, film or other article that physically degrades over time due to the presence of UV and / or OXO additives. However, the weight fraction of polyethylene or other plastic base material can remain substantially the same, without any significant biodegradation to the base elements actually occurring. The degradation can be, primarily, physical, since the article becomes brittle, breaks and breaks into small pieces, leaving several small fragments of polyethylene or other base polymer. The application of the term “biodegradable” to such plastic materials can be considered as erroneous, since the complete biodegradation of the polymeric material, by itself, may not really occur (for example, in which substantial fractions of the plastic would be degraded in CO2, CH4 , H2O and the like).

[0005] In addition, manufacturers of plastics considered biodegradable may incorporate chemical degradation additives, such as organic materials, which operate separately or in combination with OXO additives to achieve a certain biodegradation. However, these additives are also considered by some to be of limited value, since any biodegradation can be very slow. In addition, the composition of additives is typically a trade secret, although some conclude that the additives are similar or identical to those among UV and / or OXO additives. Because of doubts as to whether chemical additives actually cause adequate biodegradation to base elements, some plastic industry and regulatory associations similarly disapprove the inclusion of so-called organic additives in plastic compositions, specifically with any claims that they cause biodegradation. really.

[0006] The terms “OXO additive” and “UV additive” can be used, in this document and interchangeably, to refer to chemical agents, which under exposure to oxygen or UV radiation, cause the disintegration of chains of plastic polymer in fragments, with or without complete biodegradation.

[0007] The term “chemical additive” is used in this document to refer to materials, often organic, that can be mixed with plastic products to cause the degradation and / or biodegradation of plastic materials through interaction with microbes in a disposal environment. Additives can operate on the secretions of microorganisms, such as enzymes, or they can provide nutrition that stimulates the cultivation and colonization of microorganisms. Such a function can be described as "cell-mediated" degradation or biodegradation.

[0008] The term "degradation additive" is used in this document to refer to one or both OXO additives and / or chemical additives that are mixed with plastics, such as polyolefins; for example, polyethylene, polypropylene and the like, to stimulate the degradation of polymer chains through oxidation and / or chemical attack and / or microbial dissimilation.

[0009] The term “biodegradation”, as used in this document, refers to the conversion of a total or part polymer into base elements, such as carbon dioxide, methane and / or water.

SUMMARY

[0010] Applicant's copending application No. 15 / 691,588 reveals a method for imparting biodegradability to plastic articles, which are not typically biodegradable otherwise, by adding a fraction of a carbohydrate-based polymeric material (known commercially as NuPlastiQ® (made available by the Applicant) which, surprisingly, it was found that it gives complete biodegradability to such plastic materials when mixed with them and exposed to conditions in which the microbes are in sufficient quantity, such as that found in landfills, in composting conditions and / or in marine environments.

[0011] The present application relates to compositions and methods for achieving optimized biodegradability in blends of a conventional substantially non-biodegradable plastic with a carbohydrate-based polymeric material, such as NuPlastiQ®, made available by the Applicant, through the addition of a degradation additive as previously described to a mixture of carbohydrate-based polymer and non-biodegradable plastic. Although blends of carbohydrate-based polymer and non-biodegradable plastic achieve complete levels of biodegradability and,

even, complete biodegradability, the presence of the degradation additive can significantly optimize the biodegradability (for example, the rate and / or the extent) of such blends.

[0012] Consequently, the present invention achieves the benefit of the combined effects of prior art degradation additives and Applicant's NuPlastiQ material on biodegradable plastics, such as polyethylene and other plastic polymers. Therefore, although it is believed that the presence of a degradation additive (such as an OXO additive) in conventional non-biodegradable plastics, such as polyethylene and polypropylene, can cause the degradation of plastics in the presence of ultraviolet light and / or oxygen, and which apparently results in fragmentation and possibly limited biodegradation (rather than substantially complete biodegradation), the presence of the degradation additive in plastic blends that include the Applicant's starch-based composition, known as NuPlastiQ® in the presence of microorganisms together with ultraviolet light and / or oxygen, causes the biodegradation of plastic more quickly or more completely than occurs with mixtures that do not include the additive. Similar results are achieved when an additive, often an organic additive, such as the one previously identified, is included for its ability to interact with microorganisms that contribute to the actual biodegradation of polymeric plastic materials. Typically, the degradation additive is present in the blend in a concentration of about 0.3% by weight to about 5% by weight of the final blend, depending on the potency of the additive, the final proportions of this can be readily determined by routine testing for effectiveness. The additive (or additives) can be incorporated with NuPlastiQ before mixing with non-biodegradable plastic, mixed with non-biodegradable plastic before mixing with NuPlastiQ or the same can be added to a blend in which non-biodegradable plastic and NuPlastiQ are being merged at the time the plastic product is being manufactured. The degradation additive is introduced through any known conventional blending or extrusion operation in order to mix routine components, such as compatibilizers, antioxidants, etc. in the plastics industry.

[0013] NuPlastiQ / biodegradable mixtures containing the aforementioned additives can achieve a level of biodegradation (ie, breakdown of carbon dioxide and / or methane and / or water) in landfill, marine and / or composting environments or even in environments for disposal with exposure to sunlight in the case of OXO additives, which is faster and, at times, more complete than a plastic without the degradation additive. The extent of biodegradation can be measured in several tests, for example, including ASTM D 5338 (anaerobic conditions, such as in landfills) and ASTM D 6400 (aerobic conditions, such as in composting).

[0014] The compositions and methods of this invention demonstrate the ability to impart optimized biodegradability to various plastic materials that, before the development of NuPlastic®, were believed to not be significantly biodegradable otherwise, examples of which can be included , but without limitations, polyethylene, polypropylene and other polyolefins, such as polystyrene. This phenomenon also applies to other materials, such as polyesters (polyethylene terephthalate), ABS, polyvinyl chloride, nylon, polycarbonate and combinations thereof.

[0015] Mixtures of such plastics with the carbohydrate-based polymeric material, NuPlastiQ, and the degradation additive can be mixed and heated (for example, melted) for use in forming extruded plastic products, injection molded plastic products , blow-molded plastic products, blown, extruded or forged sheet film or film products, thermoformed plastic products and the like using standard plastic industry equipment from mixing and composing polymeric materials with necessary ingredients.

BRIEF DESCRIPTION OF THE DRAWINGS

[0016] In order for the manner in which the other advantages and objectives of the invention that are mentioned above to be obtained, a more particular description of the invention briefly described above will be presented for reference in specific modalities thereof, as illustrated in the drawings attachments. Understanding that these drawings represent only typical modalities of the invention and should not, therefore, be considered as limiting its scope, the invention will be described and explained with additional specificity and details through the use of the attached drawings in which:

[0017] Figure 1 illustrates a flow chart of an exemplary process for forming an article from the compositions of the present invention, including a carbohydrate-based polymeric material (NuPlastiQ) and one or more degradation additives. As shown, the carbohydrate-based polymer and the degradation additive are mixed with the non-biodegradable plastic in 104; however, the additive can be pre-mixed with one of the materials before mixing all three ingredients.

[0018] Figure 2 illustrates the components of an exemplary manufacturing system for producing articles that include the biodegradable materials of this invention.

[0019] Figure 3 shows X-ray diffraction patterns for an exemplary carbohydrate-based polymeric material, NuPlastiQ, commercially available from BioLogiQ compared to that of the blend of native corn starch and native potato starch used to form NuPlastiQ. It is believed that NuPlastiQ's unique structure, which includes its amorphous nature, contributes to its properties of deeply merging with a non-biodegradable polymer, such as polyethylene.

DETAILED DESCRIPTION I. DEFINITIONS

[0020] All publications, patents and all patent applications cited in this document, either above or below, are incorporated into this document in its entirety for reference to the same extent that each publication, patent or individual patent application was specifically and individually indicated to be incorporated by reference.

[0021] The term "understand" which is synonymous with "include", "contain" or "characterized by", is inclusive or open and does not exclude additional elements, not recited or method steps.

[0022] The term "consist essentially of" limits the scope of a claim to specific steps or materials "and those that do not materially affect the basic or innovative feature (or features)" of the claimed invention.

[0023] The term “consist of”, as used in this document, excludes any non-specific element, step or ingredient in the claim.

[0024] The terms "one," "one," "a / o" and similar referents used in the context of the description of innovative resources (specifically, in the context of the following claims) must be interpreted as covering both the singular and the plural, unless otherwise indicated in the present document or, of course, contradicted by the context. Therefore, for example, the reference to a "starch" can include one, two or more starches.

[0025] "Film", as used herein, refers to a continuous, thin article that includes one or more polymeric materials that can be used to separate areas or volumes, to retain items, to act as a barrier and / or as a printable surface.

[0026] "Bag", as used in this document, refers to a container produced from a flexible and relatively thin film that can be used to hold and / or transport goods.

[0027] "Bottle", as used in this document, refers to a container that can be produced from the plastics currently developed, typically with a thickness greater than a film, and that typically include a relatively narrow neck of adjacent to an opening, such bottles can be used to hold a wide variety of products (for example, drinks, personal care products such as shampoo, conditioner, cream, soap, cleansers and the like).

[0028] Unless otherwise stated, all percentages, proportions, parts and quantities used and described in this document are by weight.

[0029] Numbers, percentages, proportions or other values declared in this document can include that value, and also other values that are close to or approximate the declared value, as would be observed by a person skilled in the art. A declared value must therefore be interpreted broadly enough to cover values that are at least close enough to the declared value in order to perform a desired function or achieve a desired result, and / or the values that are between the declared value. Declared values include at least the variation to be expected in a typical manufacturing process, and may include values that are within 25%, 15%, 10%, within 5%, within 1%, etc. of a declared value. Furthermore, the terms "substantially", "similarly", "about" or "approximately", as used herein, represent a quantity or state close to the declared quantity or state that still performs a desired function or that achieves a desired result. For example, the term "substantially" "about" or "approximately" may refer to an amount that is within 25%, within 15%, within 10%, within 5% or within 1% of an quantity or declared value.

[0030] Some tracks are revealed in this document. Additional ranges can be defined between any values disclosed in this document as being an example of a particular parameter. All such tracks are contemplated and are within the scope of the present disclosure. In addition, the recitation of ranges of values in this document is intended to serve as an abbreviated method of individual reference for each separate value that is covered by the range. Unless otherwise indicated in this document, each individual value is incorporated in the specification as if it had been individually recited in this document.

[0031] All numbers that express quantities of ingredients, constituents, conditions and so on used in the specification and in the claims should be understood as being modified in all examples by the term "about". Although the numerical ranges and parameters established later in the broad scope of the invention are approximations, the numerical values established in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors that necessarily result from the standard deviation found in their respective test measurements.

[0032] The phrase “exempt from (a) of” or similar phrases, as used in this document, means that the composition comprises 0% of the declared component, that is, the component was not intentionally added to the composition. However, it will be appreciated that such components that may, incidentally, form under appropriate circumstances, may, incidentally, be present within another included component, for example, as an accidental contaminant or the like.

[0033] The phrase "substantially free of" or similar phrases, as used in this document, means that the composition preferably comprises 0% of the declared component, although it will be possible to observe that very small concentrations may possibly be present, for example, through accidental formation, accidental contamination or even by intentional addition. Such components may be present, if they are in quantities less than 1%, less than 0.5%, less than 0.25%, less than 0.1%, less than 0.05%, less than 0.01% , less than 0.005% or less than 0.001%.

[0034] The term “non-biodegradable”, as used in this document and referring to a material, means that the material (free of additives added to make it biodegradable) does not degrade (particularly, biodegraded), for example, in dioxide carbon or methane to a significant extent over a limited period of time (for example, one year, 3 years or 5 years) when exposed to several typical disposal conditions, such as sunlight, in the ocean, or at a landfill. However, it is understood that, due to sufficient time and exposure to conditions of sunlight, oxygen and degrading microbes, the most polymeric materials (for example, even those that are typically considered “non-biodegradable”) will eventually degrade or will even biodegrade, usually to a limited extent, for an extended period of time (for example, decades or centuries).

[0035] The term "biodegradable", as used in this document and referring to a material, means that the material containing NuPlastiQ in the presence of biodegradation additives, as described in this document, biodegrades basic elements such as carbon dioxide , methane and / or water. II. INTRODUCTION

[0036] The present disclosure relates, among other things, to methods for imparting biodegradability to a plastic material that, by itself, is not biodegradable otherwise, by mixing such plastic material with (a) a polymeric material to carbohydrate based (for example, based on starch), which is specifically selected due to its ability to impart biodegradability to plastic material which is not, in itself, biodegradable, and (b) a degradation additive. The carbohydrate-based polymeric material is known as “NuPlastiQ” and is made available by the Applicant. The method includes the appropriate treatment of the additive, such as exposure to oxygen, UV radiation and the inclusion of the degradation additive under conditions in which the additive is activated in the presence of biodegradable microbes. The degradation additive is one or more of: (i) a material known in the art as an OXO additive (whose function is to facilitate degradation by oxygen and / or UV and / or (ii) a chemical composition known to attract , colonize and / or interact with (such as providing nutrition and / or reaction with secretions, eg enzymes) microorganisms, with the microorganisms stimulating or causing the degradation of the plastics mentioned in an environment conducive to such biodegradation , such as soil, a composting environment and / or a landfill. Such methods are particularly beneficial in that they allow various plastic items to be disposed of in order to be biodegraded in a landfill, compost pile or environment similar disposal, instead of continuing to exist in its polymeric and stable state indefinitely.

[0037] Furthermore, the biodegradation of such articles does not occur readily when the articles are stored in typical storage and use environments (for example, stored in a home, office, warehouse or the like), but in reality, the biodegradation usually begins to occur only when the article is placed in an environment that simulates, or is the environment of, a landfill or compost or other typical disposal environments in which the microorganisms that facilitate degradation are present. For example, such conditions may include (i) a temperature that is somewhat elevated above normal "use" or "storage" ambient temperatures, (ii) exposure to high humidity levels, (iii) exposure to specific classes of microbes indigent to landfills or composting and similar disposal environments or ocean / marine environments. The high temperature and humidity will not cause the biodegradation of such articles unless the necessary microorganisms are present as well. The combination of such conditions causes articles formed from such a mixture of materials to begin to biodegrade.

[0038] Although the mechanisms by which such biodegradation of typically non-biodegradable polymers is made possible by blending with the carbohydrate-based polymeric material, and one or more degradation additives may not be understood, it is believed that blending of the two plastic materials, coupled with possibly specific characteristics of the polymeric material based on carbohydrate (NuPlastiQ) which, deeply, mixes with the non-biodegradable material, causes the breaking of the polymeric chains of the plastic through the microorganisms that attack the bonds of the polymer. The presence of suitable microbes, in a way, breaks the hygroscopic barrier associated with non-biodegradable plastic materials, allowing microbes that would degrade the carbohydrate material not only biodegrade the carbohydrate-based polymeric material, but also biodegrade the non-biodegradable plastic molecules normally adjacent. Carbon bonds are broken, and biodegradation can be confirmed based on tests that capture and measure the escaped carbon dioxide and / or methane. Such results are surprising, unexpected and particularly advantageous. The degradation additives described in this document operate within that environment in order to optimize the function of the microorganisms and / or to make the plastic material in a form in which it can be more adequately attacked by the microorganisms.

[0039] The articles can be produced by mixing the carbohydrate-based polymeric material and one or more degradation additives with the non-biodegradable plastic material otherwise, in any order, by heating the mixture and molding (for example, example, injection molding) the mixture, extruding the mixture, blowing the mixture, blowing the mixture (for example, blowing a film), by thermoforming the mixture or the like. It is also contemplated the mixture of the carbohydrate material and the non-biodegradable material, without the degradation additive, in order to form a mixture of the components without the additive, and, subsequently, to add the degradation additive in quantities described in the present document for the mixing the carbohydrate material and the non-biodegradable plastic at a previous point, possibly shortly before, to manufacture a plastic product, such as a film or an injection molded part. Several other plastic manufacturing processes will be apparent to those skilled in the art of the present disclosure.

[0040] The articles described in this document can be produced in the form of any conceivable structure, including, without limitation, bottles, boxes, other containers, plates, films, bags and the like. Thin films for bags and film wrappers (for example, to wrap around or top of a product) can easily be produced using blown film equipment.

[0041] Examples of suitable carbohydrate-based or starch-based polymeric materials that have been shown to be capable of imparting biodegradability to non-biodegradable plastic materials otherwise for use in forming such articles are available at BioLogiQ, under the trademarks of “NuPlastiQ,” and formerly “ESR” (“Eco Starch Resin”). Specific examples of NuPlastiQ include, but are not limited to, NuPlastiQ GP, NuPlastiQ XP, NuPlastiQ XD, NuPlastiQ BC, NuPlastiQ MB and NuPlastiQ BC. Under the ESR trademark, such materials were previously referred to as GS-270, GS-300 and GS-330. Specific characteristics of such NuPlastiQ materials will be described in more detail in this document. Other carbohydrate-based or starch-based polymeric materials may also be suitable for use as long as they are able, and specifically selected for the purpose, to impart biodegradability to plastic materials that are not otherwise biodegradable. NuPlastiQ is further described in Claimant's dependent requests No. 15 / 481,806 and 15 / 481,823, both filed on April 7, 2017 and which are incorporated into this document in its entirety for reference.

[0042] Examples of suitable degradation additives are materials known in the art, which under conditions of exposure to ultraviolet light and / or oxygen, degrade or fragment to a certain extent polymeric materials, such as polyethylene, polypropylene, other polyolefins,

terephthalate polyethylene, other polyesters, polystyrene, ABS, polyvinyl chloride, nylon and polycarbonate.

Representative additives are OXO additives (for example, such as PDQ-M, PDQ-H, BDA and OxoTerraTM by Willow Ridge Plastics and OX1014 by Lifeline). With such additives, photo-oxidation is generally the triggering step in the oxidation process.

UV radiation leads to the formation of an active radical which, in turn, can lead to the cleavage of C-C bonds.

In general, OXO additives are salts of transition metals, such as cobalt, iron, manganese, magnesium, nickel and / or zinc, although other transition metals can be used.

OXO additives do not include heavy metals, such as lead, mercury or cadmium.

Suitable salts include salts of carboxylic acids and dithiocarbamates, although other salts such as halides (e.g., chlorides), nitrates, sulfates, acetates, chlorates and the like are possible.

Some of such OXO additives are described in “Transition Metal Salts,” published by the Association of Biodegradable Plastic with OXO and incorporated into this document in its entirety for reference, http://www.biodeg.org/Transition%20Metal% 20Salts% 201.pdf., And Noreen L.

Thomas, Andrew R.

McLauchlin, Jane Clarke, and Stuart G.

Patrick, “Oxo- degradable plastics: degradation, environmental impact and recycling”, Institute of Civil Engineering, Waste and Resource Management, volume 165, Expedition WR3, https://dspace.lboro.ac.uk/dspace- jspui / bitstream /2134/13941/4/warm165-133.pdf, incorporated by reference in its entirety into this document.

OXO additives are typically used in an amount ranging from about 0.3% to 5% by weight of the final carbohydrate-based plastic / polymer blend, depending on their potency, and the optimized level can readily , be determined by routine testing.

Representative quantities include no more than 0.3%, no more than 1%, no more than 1.5%, no more than 2%, no more than 2.5%, less than 5% , less than 3%, less than 2% or less than 1% of the final blend of NuPlastiQ or other polymeric material based on carbohydrate and non-biodegradable plastic.

[0043] Other similarly suitable degradation additives of the OXO type that facilitate the degradation of plastics in the presence of ultraviolet light, and, in some cases, visible light, are titanium dioxide, which include TiO2 with poly (methyl methacrylate) grafted to same (PMMA) as described in Ying Luo, Xianming Dong and Chaoqun Zhang, “Accelerating the degradation of polyethylene composite mulches”, Plastics Research online, May 19, 2017, incorporated herein in its entirety for reference; copper phthalocyanine (CuPc) sensitized with TiO2, photocatalyst used in polyethylene as described in Jing Shang, Ming Chai and Yougfa Zhu, “Photocatalytic Degradation of Polystyrene Plastic under Fluorescent Light,” Environ. Sci. Technol. 2003, 37 (19), p. 4,494 to 4,499, incorporated in this document in its entirety as a reference; ceria (annealed at elevated temperatures), zinc oxide annealed at temperatures of about 250 ° C and copper sulfide photocatalysts, as described in Apeksha Gupta, Y.N. Lakshmi, R. Manivannan, S. Noyel Victoria, “Visible Range Photocatalysts for Solid Phase Photocatalytic Degradation of Polyethylene and Polyvinil Chloride, JCChems, vol. 62, nº 1 (2017) (incorporated in this document in its entirety for reference); and, finally, vanadium (III) acetylacetonate (VAc), serpentine and Cloisite 30B (CL) as described in Zehra Oluz and Teoman Tincer, “Additives for ultraviolet-induced oxidative degradation of low-density polyethylene”, Applied Polymer Science, Wiley Online Library, January 18, 2016, incorporated herein in its entirety for reference. These materials are typically used in the quantities previously established.

[0044] OXO additives are typically effective under conditions of exposure to UV light and oxygen.

[0045] Other degradation additives suitable for use in combination with Applicant's NuPlastic® or other carbohydrate-based polymeric material, as described in this document, are the materials conducive to the cultivation and activity of microorganisms known to produce, for example, secreting, substances, such as enzymes, that attack plastics, such as polyethylene, and / or other polymers, such as polyvinyl chloride. Examples are organic chemical additives, such as Enso's Restore®, EcoPure® by Bio-Tec Environmental, Batch Matrix ECM Granules 1M by ECM Biofilms, Biodegradable 201, Biodegradable 302 from BiosphereTM and TDPA ™ available from EPI Environmental Technologies, Inc. Typically, these additives are compositions, often organic, and are known to grow and multiply organisms useful in biodegradable environments. Such materials are known to stimulate microbial action, such as by reacting with enzymes secreted by microorganisms and / or by providing a food source for microorganisms to cause them to colonize and multiply. These materials optimize the biodegradation of polymers, for example, polyolefins, through mechanisms such as hydrolysis, methanogenesis and acetogenesis.

[0046] Some microbes that multiply in the presence of chemical additives, typically from organic materials, secrete enzymes, such as laccase, amylase or lipase that act on the carbon-carbon bonds of polymers, or, otherwise, facilitate the breaking down of plastic molecules, which can be more completely biodegraded when merged with the Applicant's NuPlastiQ. A representative fungus that contributes to the enzymes needed for this phenomenon is Cochliobolus sp. Examples of organic carbohydrate degradation additives that contribute to the production of an enzyme, laccase, from such fungi are sugars, such as maltose, lactose, xylose, glucose and galactose. Nitrogen sources, such as peptone, urea, ammonium nitrate, yeast extract and ammonium sulfate, can also be added to cultures that produce laccase. Laccase is known to facilitate the breakdown of polyvinyl chloride. The function of the materials mentioned above to promote the cultivation of the laccase enzyme by the microorganisms Aspergillus niger and Lysinibacillus eylanilyticus SD B9 (T) in order to degrade polyvinyl chloride can be found in Tirupati Sumathi,

Buddolla Viswanath, Akula Sri Lakshmi and D.V.R. SaiGopal, “Production of Lacase by Cochliobolus sdp. Isolated from Plastic Dumped Soils and Their Ability to Degrade Low Molecular Weight PVC ”, incorporated in this document in its entirety as a reference; and Biochemistry Research International, 2016; 9519527 incorporated into this document in its entirety as a reference. The action of microorganisms, Aspergiillus niger and Lysinibacillus xilaanilyticus grown in the culture medium containing ammonium nitrate, magnesium sulfate, potassium hypophosphate, calcium chloride and potassium chloride, followed by treatment with glucose, malt extract, peptone, asparagine , magnesium sulfate, potassium hypophosphate, and thiamine hydrochloride to degrade polyethylene, with and without UV radiation, is addressed by Atefeh Esmaeili, Ahmad Ali Pourbabaee, Hossein Ali Alikhani, Farzin Shabani Ensieh Esmaeili in “Biodegradation of low-Density Polyylene (LDPE) by Mixed Culture of Lysinibacillus xilaanilyticus and Aspergillus niger in Soil, ”Plos One, published on September 23, 2013, incorporated herein in its entirety for reference.

[0047] A debate on other bacteria and fungi that are known to be active in the biodegradation of polyethylene and polypropylene can be found in Sudhakar, Arkatkar, Doble, Bhaduri and Uppara, Biodegradation of polyethylene and polyproylene, Indian journal of Biotechnology, Vol. 7, January 2008, p. 9 to 22.

[0048] The chemical additives described above can be used in an effective amount depending on their individual activity, typically about 0.3% to 5% by weight of the non-biodegradable plastic material in the blend, or of the blend as a whole, although others quantities can be used depending on their potency in achieving the desired biodegradation result. Chemical additives can be effective in anaerobic conditions, such as in landfills and in oceanic environments.

[0049] The blends of this invention can also be significantly biodegradable in ocean environments in which the degradation additives that are known to grow the microbes necessary for biodegradation in the oceans are included in the blends.

[0050] In addition, it is contemplated, according to this invention, the presence in the mixtures of both types of additives, that is, both the OXO and the chemical additive may be present in the mixtures of non-biodegradable plastic / NuPlastiQ. The hypothesis is raised that the mechanism of biodegradable plastics, according to this invention, first breaks the long polymer chains of the plastic and is followed by the assimilation of the smallest molecules of the constituent by the microbes. The combined action of the NuPlastiQ material with an OXO additive followed by the assimilation of the microbes grown by the microbial nutrient degradation additives, as described in this document, stimulates this mechanism in a wide range of environments, landfills, compost and the ocean. Such a process is sometimes referred to as “cell mediation”.

[0051] Additives can be added using standard additive mixing methods in the plastics industry, such as mixing with the carbohydrate-based polymer before making the final blend, mixing in the non-biodegradable plastic material before to blend or can be mixed in the combined blend of non-biodegradable / polymer based on carbohydrate. The additives can also be incorporated into a matrix batch, such as with the carbohydrate-based polymer before mixing with the plastic-based polymer. The Applicant supplies the batch mixes of NuPlastiQ matrix and conventional plastic materials under the BioBlend trademark, for example, which include, but are not limited to, BioBlend XP, BioBlend XD and BioBlend BC.

[0052] In mixtures of non-biodegradable plastic / NuPlastiQ that contain one or more of the degradation additive (or degradation additives), a complete portion or all of the carbon atoms in the merged product can be converted by the microorganisms into CO2 and or CH4 . The conversion rate depends on several factors, such as the thickness of the part, number of microorganisms, type of microorganisms, proportion of C12 (material from fossil fuel) and C14 (material from renewable sources) in the product, the type of plastics in the mix, the strength of the carbon bonds in the plastic, etc.

[0053] Although the mixtures of NuPlastiQ and polyolefins are biodegradable without further additives, in general, the presence of a degradation additive, as described in this document, can optimize the biodegradation of the merged plastic products by increasing the rate and quantity disintegration or fragmentation of the mixture. OXO additives are believed to work by causing the macrostructure of plastic components to disintegrate in the presence of oxygen or ultraviolet light. It is generally believed that increasing the rate and extent to which carbon bonds are broken down into smaller fragments allows the microorganisms present to more readily dissolve the plastic. When the molecular weight of carbon chains is reduced and the surface area is increased, microorganisms can more easily access and consume materials. Chemical additives are believed to contribute to biodegradation by attracting microorganisms that consume or generate enzymes that break down plastic materials, with the generation of exhaust gases, such as carbon dioxide. Both types of degradation additives optimize the effects of NuPlastiQ on degrading polymer chains.

[0054] Plastic products that merely contain degradation additives without the presence of the carbohydrate-based material, NuPlastiQ, can begin to fragment or disintegrate when they are subjected to environments in which oxygen and / or light and / or useful microbes are present in sufficient concentration to cause the plastic to disintegrate. However, it is generally unlikely that complete biodegradation will occur, and the degradation additive, by itself, may not be able to have the desired effect, that of causing sufficient biodegradation in base elements, such as carbon dioxide and methane. But if the product is made using NuPlastiQ®, then the plastic would still be able to biodegrade in anaerobic conditions or in conditions without light, and the presence of degradation additives is believed to optimize the rate and extent of actual biodegradation. . III. EXAMPLE ARTICLES AND METHODS

[0055] Figure 1 illustrates an exemplary process 100 that can be used to impart biodegradability to a plastic material that, by itself, is not otherwise biodegradable. In 102, process 100 may include the provision of one or more non-biodegradable plastic (for example, polymeric) materials (for example, including, but not limited to, polyethylene, polypropylene, other polyolefins, polystyrene, ABS, polyvinyl chloride, nylon or polycarbonate). In 104, process 100 may include the supply of one or more carbohydrate-based polymeric materials, such as NuPlastiQ, specifically selected for inclusion in the blend for its recognized ability to impart biodegradability to the non-biodegradable plastic material otherwise provided in 102 Carbohydrate-based polymeric materials and otherwise non-biodegradable plastic materials can be supplied in a desired manner, such as in granules, powders, clots, slurry and / or liquids. In specific embodiments, the materials may be in the form of granules. The method additionally includes mixing the plastic material with the carbohydrate-based polymeric material before mixing with the non-biodegradable plastic. In 106, the degradation additive is mixed into the carbohydrate polymer and non-biodegradable plastic, although, as mentioned, the additive can be supplied to a polymeric component before mixing or to the final blend of the carbohydrate / plastic-based polymer blend .

[0056] Such simple blending, surprisingly, provides the biodegradable plastic blended material, and such material, typically, did not previously have such a characteristic. Such blends are also biodegradable to a greater extent than just the amount of carbohydrate-based material, which indicates that normally non-biodegradable plastic is also biodegradable. As a result, the mixture of such materials is completely biodegradable, and articles formed from such a mixture are similarly biodegradable. For illustrative purposes, although polyethylene alone is not biodegradable, the Applicant has found that mixing polyethylene with carbohydrate-based polymeric materials, NuPlastiQ, has characteristics as described in this document and that the degradation additive imparts biodegradability to polyethylene , so that not only the polymeric material based on carbohydrate biodegrades, but so that the polyethylene mixed with them also becomes biodegradable as a result of its merging with the polymeric material based on carbohydrate and with the additive.

[0057] Such blends can be formed in the manufacture of a desired article by any conceivable process. An example of this would be an extrusion process. For example, the non-biodegradable plastic material and the carbohydrate-based polymeric material selected for their ability to impart biodegradability plus the degradation additive can be used to feed an extruder (for example, on one or more feeders). The different materials can be used to feed the extruder in the same chamber, in different chambers, at approximately the same time (for example, through the same feeder), or at different times (for example, through different feeders, one being introduced into the extruder before, together with the thread than the other), etc. It will be apparent that several merge possibilities are possible.

[0058] In some cases, the non-biodegradable plastic material may include a polyolefin. For example, such plastic materials may include, but are not limited to, polyethylene, polypropylene, other polyolefins, polyester, polystyrene, ABS, polyvinyl chloride, nylon, polycarbonates and the like. Such plastic material can come from petrochemical sources, or from so-called “green” or sustainable sources (for example, “green” PE, bioPET and the like).

[0059] Polymeric carbohydrate-based materials can be formed from a plurality of materials (e.g., a mixture) that includes one or more starches. For example, the one or more starches can be produced from one or more plants, such as corn starch, tapioca starch, cassava starch, wheat starch, potato starch, rice starch, sorghum starch and the like . In some embodiments, a mixture of different types of starches can be used, which the Applicant has found to result in a synergistic increase in resistance. A plasticizer can also be present within the mixture of components, from which polymeric carbohydrate materials are formed. Water can also be used in the formation of the carbohydrate-based polymeric material, although only a small and insignificant amount of water is present in the finished carbohydrate-based polymeric material.

[0060] The one or more carbohydrate-based polymeric materials can be formed from mainly starch. For example, at least 65%, at least 70%, at least 75% or at least 80% by weight of the carbohydrate-based polymeric material can be attributable to one or more starches. In one embodiment, 65% to 90% by weight of the finished carbohydrate-based polymer material can be assigned to one or more starches. In addition to the negligible water content, the balance of the finished carbohydrate-based polymer material can be attributed to a plasticizer (eg glycerin). The preceding percentages may represent the percentage of starch relative to the starting materials, from which the carbohydrate-based polymeric material is formed, or that the fraction of the finished carbohydrate-based polymeric material that is derived from the plasticizer, or attributable to the even, (for example, at least 65% of the carbohydrate-based polymeric material can be attributed to (formed from) starch (or starches) as a starting material). Although a certain amount of water can be used in the formation of the carbohydrate-based polymeric material, substantially, the balance of the carbohydrate-based polymeric material can be attributed to glycerin or another plasticizer. Very little residual water (for example, less than 2%, typically not more than about 1%) may be present in the finished carbohydrate-based polymer material.

[0061] For example, materials from which the one or more carbohydrate-based polymeric materials are formed can include at least 12%, at least 15%, at least 18%, at least 20%, at least 22% , not more than 35%, not more than 32%, not more than 30%, not more than 28% or not more than 25% by weight of a plasticizer. Such percentages may represent that the fraction of the finished carbohydrate-based polymer material is derived from, or attributable to, the plasticizer (for example, at least 12% of the carbohydrate-based polymeric material can be attributed to (formed from do) plasticizer as a starting material).

[0062] Exemplary plasticizers include, but are not limited to, glycerin, polyethylene glycol, sorbitol, polyhydric alcohol plasticizers, organic compounds formed with hydrogen bonds that do not have a hydroxyl group, sugar alcohol anhydrides, animal proteins, proteins vegetables, aliphatic acids, phthalate esters, dimethyl and diethylsuccinate and related esters, glycerol triacetate, glycerol mono and diacetates, monoglycerol, di, and tripropionates, butanoates, looms, lactic acid esters, citric acid esters, acid esters adipic, stearic acid esters, oleic acid esters, other acid esters or combinations thereof. Glycerin may be preferred.

[0063] The finished carbohydrate-based polymer material can include no more than 5%, no more than 4%, no more than 3%, no more than 2%, no more than 1.5%, not more than 1.4%, not more than 1.3%, not more than 1.2%, not more than 1.1% or not more than 1% by weight of water. The NuPlastiQ materials available from BioLogiQ are examples of such finished carbohydrate-based polymeric materials, although it will be noted that other available materials (for example, at some future time) may also be suitable for use.

[0064] In some embodiments, mixtures of different starches can be used in the formation of the carbohydrate-based polymeric material. It has been found that the use of such a mixture of different starches (for example, derived from different plants) is surprisingly associated with a synergistic increase in the strength of articles that include such carbohydrate-based polymeric materials. In such a mixture of starches, a starch may be present in the mixture in an amount of at least 1%, at least 2%, at least 3%, at least 4%, at least 5%, at least 10%, at least 15 %, at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, not more than 95%, not more than 90%, not more than 85%, not more than 80%, not more than 75%, not more than 70%, not more than 65%, not more than 60%, not more than 55%, not more than 50% or 10% at 50% by weight relative to the combined weight of the plurality of starches. Some exemplary non-limiting mixtures may include 90% of a first starch and 10% of a second starch or 30% of a first starch, and 70% of a second starch or 50% of a first starch and 50% of a second starch. Mixtures of more than two starches (for example, using 3 or 4 different starches) can also be used.

[0065] Examples of carbohydrate-based polymeric materials (for example, starch-based) suitable for use in film formation and other articles are available at BioLogiQ, located in Idaho Falls, Idaho, under the NuPlastiQ trademark . Specific examples include, but are not limited to, NuPlastiQ GP, NuPlastiQ XP, NuPlastiQ XD and NuPlastiQ BC. Additional details regarding starch and glycerin fractions or other plasticizers used in the formation of NuPlastiQ are described in other Applicant patent applications, which have already been incorporated by reference in this document. NuPlastiQ can be supplied as a granule. The physical characteristics for the two examples of NuPlastiQ materials,

previously referred to as GS-270 and GS-300, are shown in Table 1 below. TABLE 1

PROPERTY METHOD OF GS-270 GS-300

TEST VALUE VALUE

NOMINAL NOMINAL Density ASTM D-792 1.40 g / cm3 1.42 g / cm3

THERMAL PROPERTIES Flow rate of ASTM D-1238 1.98 g / 10 min 1.95 g / 10 min melting 200 ° C / 5 kg Temp. Melting ASTM D-3418 166 to 180 ° C 166 to 180 ° C Range Temp. ASTM D-3418 transition glass 81 to 100 ° C 81 to 100 ° C glass

MECHANICAL PROPERTIES Resistance to ASTM D-638> 30 MPa> 14 MPa stress to yield Resistance to ASTM D-638> 30 MPa> 14 MPa stress to break Young ASTM D-638 module 1.5 GPa 1.5 GPa Elongation at ASTM D-638 <10% <10% breaks Resistance to ASTM D-5628 3.5 kg 4.5 kg impact (Dart)

ADDITIONAL PROPERTIES Water content ASTM D-6980 ≤1.5% or ≤1% ≤1.5% or ≤1%

[0066] The features previously shown for GS-270 and GS-300 are exemplary of other NuPlastiQ products available from BioLogiQ, although the values may vary somewhat. For example, NuPlastiQ products by BioLogiQ can generally have a glass transition temperature ranging from about 70 ° C to about 100 ° C. People skilled in the art will note that the glass transition temperature can be indicative of the degree of crystallinity. The values for the melting temperature range, density, Young's modulus and water content can be identical or similar to those shown previously in Table 1. Some characteristics may similarly vary in a certain way (for example, ± 25% or ± 10% ) from the values shown for GS-270 and GS-300. NuPlastiQ has an amorphous structure (for example, more amorphous than the typical raw starch). For example, the typical crude starch powder has a mainly crystalline structure (for example, greater than 50%), although NuPlastiQ has a mainly amorphous structure (for example, less than 10% crystalline).

[0067] NuPlastiQ materials have a low water content, as described. Since this material absorbs moisture, it has a plastic behavior and is flexible. When removed from a humid environment, the material dries and becomes rigid again (for example, it has less than about 1% water content again). The moisture present in NuPlastiQ (for example, in the form of granules) can be released as steam during processing, such as that shown in Figure 1. As a result, films or other articles produced from a polymeric material starch-based mixed with a non-biodegradable plastic material can have even less water content, since the non-biodegradable plastic material will typically include none or an insignificant amount of water, and the water in NuPlastiQ can typically be released during the manufacture of a desired article.

[0068] The low water content in the carbohydrate-based polymeric material, NuPlastiQ, may be important, since the significant water content may result in incompatibility with the non-biodegradable plastic material, particularly if the article requires the formation of a film thin. For example, as the water vaporizes, this can result in pores within the film or other article, as well as other problems. When blowing a thin film, the used carbohydrate-based polymeric material may preferably include no more than about 1% water.

[0069] Low water content is not achieved in the NuPlastiQ material through esterification, as it is common in some conventional TPS materials that can include relatively low water content. Such esterification can be expensive and complex to perform. Furthermore, NuPlastiQ materials that are exemplary of the carbohydrate-based polymeric materials employed in this document typically also do not actually include any identifiable starch or identifiable glycerin, as such, since the starting materials of the material carbohydrate-based polymeric reacted and / or altered mechanically, physically or chemically. The X-ray diffraction patterns of exemplary carbohydrate-based polymeric materials as described below (for example, and shown in Figure 3) evidence such a chemical or physical change, showing that the finished polymeric material can be substantially free of starch in such a way identifiable and native. That is, the carbohydrate-based polymeric material is not always recognized as a mixture that includes starch and glycerin. It is believed that the low water content achievable in the carbohydrate-based polymeric material is due, at least in part, to the physical or chemical alteration of the starch and plasticizer materials in a thermoplastic polymer, which does not retain water as it would retain a starch native or conventional thermoplastic starches.

[0070] Returning to Figure 1, processing at relatively high temperatures can result in some releases of volatilized glycerin (for example, visible in smoke). If necessary (for example, when the stored granules may have absorbed additional water), drying of the granules can be performed by simply introducing hot dry air, for example, at 60 ° C for 1 to 4 hours, which is sufficient to repel any absorbed water. The granules must be dried to less than about 1% moisture content before processing, particularly if a film is formed. NuPlastiQ granules can simply be stored in a sealed container with or without a desiccant in a dry place, away from heat to minimize water absorption and to prevent unwanted degradation.

[0071] In addition to NuPlastiQ being thermoplastic, NuPlastiQ can also be thixotropic, which means that the material is solid at room temperature,

but it flows like a liquid when heat, pressure and / or frictional movements are applied. Advantageously, NuPlastiQ granules can be used in the same way as petrochemical-based granules (any typical non-biodegradable plastic resin granules) in standard plastic production processes. NuPlastiQ materials and products produced from them can have gas barrier characteristics. Products (eg films) produced using such granules have oxygen gas barrier characteristics (for example, see Examples of the Applicant's previous deposits, already incorporated by reference). NuPlastiQ materials can be non-toxic and edible, produced using raw materials that are all edible. NuPlastiQ and products produced from them can be water resistant, but soluble in water. For example, NuPlastiQ can resist swelling under heated and humid conditions to the point that the granules (eg 3 to 4 mm in size) of the granules may not completely dissolve in boiling water within 5 minutes, but a granule will dissolve in your mouth within about 10 minutes. NuPlastiQ can be stable, as it may not exhibit any significant retrogradation, even if left in relatively high humidity conditions, and the characteristic differs from many other thermoplastic starch materials. Certainly, products produced with NuPlastiQ can also have these characteristics. If NuPlastiQ is stored under humid conditions, the excess water absorbed can simply be evaporated, and since the water content is no more than about 1%, it can be used in the formation of a film or other article .

[0072] NuPlastiQ material typically does not undergo biodegradation under typical storage conditions, even in relatively humid conditions, since the other typical conditions of a landfill, compost or similar disposal environment containing the specific necessary microorganisms do not are present. Certainly,

when such conditions are present, not only is NuPlastiQ biodegraded, but also non-biodegradable plastic materials otherwise mixed with it, surprisingly, biodegraded.

[0073] NuPlastiQ can be competitive in cost, being manufactured at a cost that is competitive with traditional polyethylene plastic resins. NuPlastiQ can be mixed with other polymers, which include, but are not limited to, PE, PP, PET, polyester, polystyrene, acrylonitrile butadiene styrene (ABS), polyvinyl chloride, nylon and others. Although previous non-biodegradable polymers can be made biodegradable by mixing with NuPlastiQ, it will be noted that NuPlastiQ can also be mixed with polymers that are already biodegradable and / or compostable, such as polylactic acid (PLA), poly (butylene adipate-co-co -tereftalate) (PBAT), polybutylene succinate (PBS), polycaprolactone (PCL), polyhydroxyalkanoates (PHA), others called thermoplastic starches, as well as several others. PBS, PCL and PHA are polyesters. EcoFLEXTM plastic, PBAT, is an example of a plastic material with which the carbohydrate-based polymeric material, NuPlastiQ, can be mixed. For example, the present methods are not limited to mixing the carbohydrate-based polymeric material (eg NuPlastiQ) with only a non-biodegradable plastic material, as it will be noted that biodegradable plastics (in addition to NuPlastiQ) can also be incorporated into the blend , if desired.

[0074] As an additional explanation, PLA is compostable, which means that it can degrade under high temperature conditions (ie, composting conditions), but it is not, technically, "biodegradable". Some of the materials listed above, such as PBS, PCL and PHA, can be both biodegradable and compostable. EcoFLEXTM (PBAT) is certified as compostable. Green FTC guidelines state that a plastic cannot make an unqualified claim about being “degradable” unless it will degrade within a “reasonably short period of time” (most recently, defined as being within 5 years) “After usual disposal”.

[0075] In some embodiments, NuPlastiQ could be supplied in a matrix batch formulation that can include the carbohydrate-based polymeric material and one or more of the degradation additives as described above, and an amount of one or more compatibilizers. The matrix batch may also include one or more non-biodegradable plastic materials. Such granules by matrix batch formulation can be mixed with granules of the non-biodegradable plastic material at the time of processing. Any conceivable proportions can be used in the mixture of such different granules, depending on the desired percentage of NuPlastiQ and / or compatibilizer and / or conventional non-biodegradable plastic material in the finished article. Or a batch batch comprising the non-biodegradable plastic and one or more of the degradation additives can be provided.

[0076] NuPlastiQ includes a very low water content. For example, although crude starch (for example, used in the formation of NuPlastiQ) can typically include about 13% water by weight, the finished NuPlastiQ granules available from BioLogiQ include less than about 1% water. NuPlastiQ materials are biodegradable and, as described in this document, are not only the degradable material based on starch, NuPlastiQ, but also, when mixed with other polymers, such as non-biodegradable PE, PP, PET, polyester, polystyrene, ABS, polyvinyl chloride, nylon and other non-biodegradable plastic materials, the mixed material that includes NuPlastiQ and the one or more degradation additives become substantially and completely biodegradable, particularly when the degradation additives, as described in this document , are present. Such results are very surprising and particularly advantageous. Typical thermoplastic starch materials do not exhibit such characteristics when mixed with other plastic materials.

[0077] The NuPlastiQ materials described, as suitable for use in this document and as the carbohydrate-based polymeric material (for example, starch-based) are substantially amorphous. For example, crude starch powder (for example, as used in the production of NuPlastiQ and various other thermoplastic starch materials) has approximately 50% crystalline structure. The NuPlastiQ materials available from BioLogiQ differ from several other commercially available thermoplastic starch (TPS) materials in characteristics of crystallinity versus amorphous. For example, on p. 62 to 63 of “Thermoplastic Starch Composites and Blends” a PhD thesis by Kris Frost (September 2010) states “of particular interest in TPS are the completeness of gelatinization during processing, and any subsequent trend towards retrogradation to form crystals type V amylose ”. Frost continues, “Gelatinization involves the loss of granular and crystalline structures by heating with water and generally including other plasticizers or modifying polymers. Retrogradation is due to the rewinding of helical amylose coils. The starch molecules affected during gelatinization slowly rewind in their native helical dispositions or new unique helical conformations known as the V-type, which cause TPS films to quickly become brittle and lose optical evidence ”. Therefore, conventional TPS tends to reform a crystalline structure after the gelatinization process used to produce TPS from raw starch. In contrast, the NuPlastiQ material available from BioLogiQ does not revert back to a mostly crystalline structure. In addition, it can maintain a relatively high and stable degree of optical evidence, so as to be useful in the formation of relatively optically evident films (for example, particularly sandwiching NuPlastiQ which contains layers between the polyethylene or other layers of polyolefin) .

[0078] In contrast to typical TPS materials, NuPlastiQ materials which are suitable examples of polymeric starch-based materials for use in forming articles described in the present application have an amorphous microstructure and physical characteristics. The difference in molecular structure between conventional TPS and NuPlastiQ materials is evidenced by NuPlastiQ materials, as described in this document, as they are much less crystalline than conventional thermoplastic starch-based materials as shown by ray diffraction X, shown in Figure 3, which compares results of the diffraction pattern for the NuPlastiQ material available by BioLogiQ compared to a blend of native raw corn starch and native raw potato starch from which NuPlastiQ in Figure 3 was formed . The diffraction pattern of NuPlastiQ, as seen in Figure 3, is much less crystalline (for example, less than about 10% crystallinity) than that of native starch blending (about 50% crystallinity). The difference in the diffraction pattern shows that a complete chemical change occurred in the material, due to the processing of native starches in NuPlastiQ. For example, although there is a prominent diffraction peak between 20-25 ° with native starch, none of such a peak is shown in NuPlastiQ. Native starch additionally shows a strong peak at about 45 ° (at an intensity of 0.5 to 0.6), the peak of which is considerably reduced in NuPlastiQ (only at about 0.25 to 0.3). Across the entire spectrum, diffraction intensities are higher for native starches than for NuPlastiQ, with the exception of about 18 ° to about 22 °, as shown. The high diffraction intensity seen in a wide spectrum is indicative of greater crystallinity of native starches compared to NuPlastiQ. Several other differences also exist, as shown.

[0079] For illustrative purposes, the carbohydrate-based polymeric material (for example, starch-based) used in the production of films, according to the present disclosure, may have a crystallinity of less than about 40%, less than about 35%, less than about 30%, less than about 25%, less than about 20%, less than about 15%, less than about 10%, less than about 8%, less than about 6%, less than about 5% or less than about 3%. Any suitable test mechanism to determine crystallinity can be used, for example, including, but not limited to, FTIR analysis, X-ray diffraction methods, symmetric reflection and transmission techniques. Several suitable test methods will be apparent to those skilled in the art.

[0080] In addition to the differences in the microstructure of the finished NuPlastiQ compared to the starting materials, films, bottles, plates, disposable utensils, plates, cups or other articles produced from a blend that includes the polymeric material based on carbohydrate, NuPlastiQ and the degradation additives described in this document are different from articles that are otherwise similar, but formed using conventional TPS and starch powder or only non-biodegradable plastic materials. For example, articles formed by mixing carbohydrate-based polymeric materials, such as NuPlastiQ as described in this document, with a non-biodegradable plastic material and with the degradation additive do not have "sea-island" features that are common when mixing conventional TPS materials with polymeric materials, such as polyethylene. The properties of the different films can be seen by comparing the physical properties of films, as shown in Table 11 of Example 5 of Applicant's patent application No. U.S. 15 / 481,806, already incorporated by reference. In particular, this table compares the physical properties of films made from a mixture of polymeric materials based on carbohydrates, as contemplated in this document, with non-biodegradable polyethylene versus a conventional TPS mixed with PE (Cardia BL-F). In addition to the differences in properties seen in Table 11 of Example 5 of Applicant's U.S. Patent Application 15 / 481,806, film based on conventional TPS materials, such as Cardia BL-F, mixed with PE is not biodegradable and non-compostable. The presence of degradation additives does not have a desirable effect on the microstructure of the finished materials that contain NuPlastiQ and that add to the blend's biodegradability.

[0081] As described in this document, the mixture of polymeric materials based on carbohydrate and the degradation additive with a non-biodegradable plastic material results not only in the carbohydrate-based material being biodegradable, but also in the non-biodegradable plastic material if really biodegradable (even when the non-biodegradable plastic material alone is not significantly biodegradable otherwise). Such a result does not occur when mixed with typical TPS materials. Such differences in biodegradability, of course, illustrate that there are significant structural and / or chemical differences in the resulting films and in other articles, since the entire composite structure (i.e., the film or other structure) is now capable of being biodegraded.

[0082] Without being linked to any specific theory, it is believed that the carbohydrate-based polymeric resin, NuPlastiQ, can reduce the crystallinity of the mixed products, interrupting the crystallinity and / or higoscopic characteristics of polyethylene or other plastic material non-biodegradable in a way that allows water and bacteria to degrade the dispositions and bonds of non-biodegradable molecules otherwise from the blend, together with the carbohydrate-based polymeric resin material. That is, the long chains of polyethylene polymer or other non-biodegradable plastic material are more easily broken by chemical and mechanical forces that exist in environments that are rich in bacteria and microorganisms, when mixed with the carbohydrate-based polymeric materials , as contemplated in this document. Subsequently, microorganisms that naturally exist in a disposal environment (for example, in a landfill) can consume the remaining small molecules, so that they are converted back to natural components (such as CO2, CH4, and H2O). It is believed that this degradation effect is optimized when the plastic component (PE, PP, etc.) is fragmented by the action of the OXO additive, since the fragments are more accessible to microbes in the soil, landfill, etc., than they would be otherwise. When a degradation additive, as described in this document, such as an organic additive that attracts microorganisms is also present, the biodegradation of the plastic material is more allowed by the action of the microorganisms. OXO additives increase the surface area of the non-biodegradable polymer subject to attack by microorganisms.

[0083] For example, truly biodegradable plastics decompose into natural elements or compounds, such as carbon dioxide, methane, water, inorganic compounds or biomass through microbial assimilation (for example, the enzymatic action of microorganisms in plastic molecules) . The biodegradation of plastics can be allowed by first breaking the polymer chains through chemical or mechanical action, but it can only be completely accomplished by decomposing the molecules through microbial assimilation.

[0084] Plastics made from petrochemical raw materials or derived from plant sources start life as monomers (for example, small single molecules that can react chemically with other small molecules). When monomers are joined together, they become polymers ("multiple parts"), and can be known as plastics. Before being joined together, several monomers are readily biodegradable, although after being linked together through polymerization, the molecules become so large and united in such dispositions and bonds that microbial assimilation by microorganisms is not practical within of any reasonable period in many instances. However, NuPlastiQ compositions with the degradation additive of this invention provide increased biodegradability.

[0085] Polymers are formed with both crystalline structures (regularly packaged) and amorphous structures (randomly arranged). Many polymers contain a high degree of crystallinity with some amorphous regions randomly arranged and completely involved with the polymeric structure.

[0086] The NuPlastiQ materials available by BioLogiQ are formed from starch starting materials that are highly crystalline, but in which the finished plastic resin material, NuPlastiQ, has low crystallinity (substantially amorphous). Such starch-based polymer materials are used as a starting material in the production of articles as described in this document. NuPlastiQ is therefore plastic that is made of starch. Because of their natural and starch-based origin and their carefully controlled types of bonds, the plastic molecules (sizes and connections) produced with NuPlastiQ are highly susceptible to biodegradation through enzymatic reactions caused by the introduction of moisture (water) and bacteria or other microorganisms. The presence of the degradation additives that is described in this document optimizes, further optimizes, this biodegradation.

[0087] Polyolefins, such as rigid forms of polyethylene and polypropylene, have a high degree of crystallinity and are made by converting monomeric molecules (whether derived from petroleum or derived from ethanol or other small building block molecules derived from from plant sources) in long polymer chains. The bonds created when connecting the monomers to form long polymer chains are strong and difficult to break. Films and other articles formed from such polymeric materials are not biodegradable. Even if a particular article was formed from a mixture of conventional non-biodegradable plastic material and conventional TPS, it would not normally suddenly acquire the characteristics of biodegradability (other than the starch portion of the mixture that can sometimes biodegrade).

[0088] As described in copending application No. 15 / 691,566, filed on August 30, 2017, the Applicant has developed a process for imparting biodegradability to a non-biodegradable plastic material by otherwise mixing such plastic material with the polymeric materials based on carbohydrate with low crystallinity, for example, NuPlastiQ. The invention of this application further facilitates biodegradation by adding a degradation additive to the blended materials, such as an OXO additive or chemical material, as described in this document. Typically, the non-biodegradable plastic material has greater crystallinity (for example, particularly, in the case of PE or PP).

[0089] In addition to biodegradability, the resulting blend can often have a greater elastic modulus (hardness or strength) than polyethylene or other non-biodegradable plastic material, and can be used to make plastic films or other articles that are more stronger than the same articles produced with pure polyethylene or other non-biodegradable pure plastic material. Such characteristics of increased strength are described in U.S. Patent Applications No. 14 / 853,725 and 15 / 481,806, which are hereby incorporated by reference.

[0090] Returning to Figure 1, in 106, process 100 includes mixing one or more non-biodegradable plastic materials, one or more degradation additives and one or more carbohydrate-based polymeric materials (NuPlastiQ) to produce a mixing of materials. In some cases, the mixing of the one or more non-biodegradable plastic materials and the one or more carbohydrate-based materials and the one or more degradation additives can be performed with the use of one or more mixing devices. In a specific implementation, a mechanical mixing device can be used to mix the one or more non-biodegradable plastic materials, the one or more carbohydrate-based polymeric materials and the additive (or additives). In an implementation, at least a portion of the components of the material mix can be combined in an apparatus, such as an extruder, an injection molding machine or the like. In other implementations, at least a portion of the components of the material mix can be combined before being used to power the device.

[0091] The one or more carbohydrate-based polymeric materials and degradation additives may be present in the material mixture in an amount sufficient to impart biodegradability to the specific non-biodegradable plastic material with which the carbohydrate-based polymeric material is mixed. Such a limit level of the carbohydrate-based polymeric material may depend on the material with which they are being mixed. For illustrative purposes, the carbohydrate-based polymeric material may be included in an amount of at least 0.5%, at least 1%, at least 2%, at least 3%, at least 4%, at least 5%, at least 10%, at least 15%, at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, not more than 99%, not more than than 95%, no more than 90%, no more than 80%, no more than 70%, no more than 60%, no more than 50%, from 2% to 98%, from 20% to 40%, 10% to 40%, 20% to 30%, 50% to 80% or 40% to 60% by weight of the mixture of materials. More than one carbohydrate-based polymeric material and / or more than another plastic material can be included in the mix, if desired.

[0092] The non-biodegradable plastic material can be present in the mixture of materials in an amount of at least 0.5%, at least 1%, at least 2%, at least 3%, at least 4%, at least 5% at least 10%, at least 15%, at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at least 50%, no more than 99%, not more than 95%, not more than 90%, not more than 85%, not more than 80%, not more than 75%, not more than 70%, not more than 65 %, or not more than 60%, from 2% to 98%, from 50% to 90%, from 65% to 75%, from 20% to 50% or from 40% to 60% by weight of the mixture of materials .

[0093] Degradation additives can be added, for example, in an amount of at least 0.1%, 0.3%, at least 0.5%, at least 1%, at least 1.5%, at least at least 2%, at least 4% at least 5%, not more than 10%, from 0.5% to 2%, from 1.5% to 2.5% by weight of the mixture of materials.

[0094] A compatibilizer can be present in the mix of materials. The compatibilizer can be mixed with the non-biodegradable plastic material, the carbohydrate-based polymeric material, mixed with both, or supplied separately. Generally, the compatibilizer can be provided with at least one of the polymeric materials, for example, included in a matrix batch formulation. The compatibilizer may be a modified polyolefin or other modified plastic, such as a polypropylene grafted with maleic anhydride, a polyethylene grafted with maleic anhydride, a polybutane grafted with maleic anhydride or a combination thereof. The compatibilizer can also include an acrylate-based copolymer. For example, the compatibilizer can include an ethylene methylacrylate copolymer, an ethylene butylacrylate copolymer or an ethylene ethylacrylate copolymer. In addition, the compatibilizer may include a poly (vinylacetate) based compatibilizer. In one embodiment, the compatibilizer may be a grafted version of the non-biodegradable plastic material (for example, polyethylene grafted with maleic anhydride in which the non-biodegradable plastic material is polyethylene) or a copolymer (for example, a block copolymer) in which a of the blocks is the same monomer as that of the non-biodegradable plastic material (for example, a styrene copolymer in which the non-biodegradable plastic material is polystyrene or ABS).

[0095] The mixture of materials may include at least 0.5%, at least 1%, at least 2%, at least 3%, at least 4%, at least 5%, not more than 50%, not more than 45%, not more than 40%, not more than 35%, not more than 30%, not more than 25%, not more than 20%, not more than 15%, not more than than 10%, not more than 9%, not more than 8%, not more than 7%, not more than 6%, from 0.5% by weight to 12%, from 2% to 7% or from 4% to 6% by weight of a compatibilizer.

[0096] One or more additional additives, as known to be useful in the plastics industry, can be included in the mix of materials in an amount of at least 0.5%, at least 1%, at least 1.5%, at least minus 2%, at least 2.5%, at least 3%, at least 4%, of not more than 10%, not more than 9%, not more than 8%, not more than 7%, not more than 6%, not more than 5%, 0.2% to 12%, 1% to 10%, 0.5% to 4% or 2% by weight to 6% by weight of mixture.

[0097] Although mainly described in the context of a mixture of thermoplastic materials that can be fused together, to form a desired blend, in some embodiments, it may be possible to mix the carbohydrate-based polymeric material capable of conferring biodegradability and the one or more degradation additives with a plastic material that is not thermoplastic (for example, that is thermoset, for example, as for silicone). For example, resin components that are precursors of such non-biodegradable and non-thermoplastic plastic material can be mixed with the carbohydrate-based polymeric material, where polymerization or other formation of the non-thermoplastic material can occur in the presence of the polymeric material at carbohydrate-based and degradation additive (or degradation additives), which result in a finished article that is a mixture of the carbohydrate-based polymeric material, the degradation additive (or degradation additives) and a thermoset or other plastic material non-thermoplastic, in which the carbohydrate-based polymeric material and the additive (or additives) can impart biodegradability to the plastic non-thermoplastic material by mixing the two.

[0098] Referring to Figure 1, at 108, particularly when the materials are thermoplastic, process 100 may include heating the mixture of materials. In one implementation, the material mix can be heated to a temperature of at least 100 ° C, at least 110 ° C, at least 115 ° C, at least 120 ° C, at least 125 ° C, at least 130 ° C , at least 135 ° C, at least 140 ° C, no more than 250 ° C, no more than 190 ° C, no more than 180 ° C, no more than 175 ° C, no more than 170 ° C, no more than 165 ° C, no more than 160 ° C, no more than 155 ° C, no more than 150 ° C, from 95 ° C to 250 ° C, from 120 ° C to 180 ° C or 125 °

° C to 165 ° C.

[0099] The material mixture that includes the normally non-biodegradable plastic material and the carbohydrate-based polymeric material and the degradation additive (or degradation additives) can be heated in one or more chambers of an extruder. In some cases, one or more chambers of the extruder can be heated to different temperatures. The speed of one or more threads of the extruder can be of any desired rate.

[0100] In 110, an article is produced using the mixture of materials that include NuPlastiQ and the degradation additive. In some cases, the article may include a film. In other cases, the article can be formed from a film. In other embodiments, the article may have a design-based format, such as a mold (for example, injection molded). Any conceivable article formed from plastic can be formed from the mixture, for example, including, but not limited to, films, bags, bottles, caps, lids, plates, boxes, plates, glasses, utensils and the like. When the article is a film, the film can be formed using a matrix by injecting a gas into the heated mixture of the material to form the film (i.e., blowing the film). Films can be sealed and / or otherwise modified to be in the form of a bag or other item.

[0101] When the article is a film, the film can be comprised of a single layer or of multiple layers. The film or any individual layers may have a thickness of at least 0.001 mm, at least 0.002 mm, at least 0.004 mm, at least 0.01 mm, at least 0.02 mm, at least 0.03 mm, at least 0 , 05 mm, at least 0.07 mm, at least 0.10 mm, not more than 2 mm, not more than 1 mm, not more than 0.5 mm, not more than 0.1 mm, from about 0.05 mm to about 0.5 mm, or from 0.02 mm to 0.05 mm. Although there may be some overlap in the thickness values for film and sheet articles, it will be possible to observe that sheet materials of greater thickness than such film values can certainly be supplied, produced by any plastic manufacturing process. wanted.

[0102] Films or other articles may have strength characteristics that are defined through testing, such as a cannula drop impact test (ASTM D-1709), breaking stress resistance test (ASTM D-882 ), stress strain elongation test (ASTM D-882), a secant module test (ASTM D-882) and / or an Elmendorf tear test (ASTM D-1922). Films can have a cannula drop impact test value of at least 150 g, at least 175 g, at least 200 g, at least 225 g, at least 250 g, at least 275 g, at least 300 g, no more than 400 g, no more than 375 g, no more than 350 g, or no more than 325 g, 140 g, 425 g, 200 g, 400 g, 250 g, 350 g, 265 g 330 g. In an implementation, these values can be for any film thickness. In another implementation, these values can be for a 0.0254 mm thick film formed from the mixture of materials.

[0103] The article may have a stress-breaking strength test value of at least 24.13 MPa (3.5 kpsi), at least 25.51 MPa (3.7 kpsi), at least 26.89 MPa (3.9 kpsi), at least 28.27 MPa (4.1 kpsi), at least 29.65 MPa (4.3 kpsi), or at least 29.65 MPa (4.5 kpsi) , no more than 37.92 MPa 5.5 kpsi), no more than 36.54 MPa (5.3 kpsi), no more than 35.16 MPa (5.1 kpsi), no more than 33 , 78 MPa (4.9 kpsi), or not more than 32.41 MPa (4.7 kpsi), from 24.13 MPa to 37.92 MPa (3.5 kpsi to 5.5 kpsi), or 28.27 MPa at 33.78 MPa (4.1 kpsi to 4.9 kpsi).

[0104] The article can have a tensile strength test value at break in the transverse direction of at least 22.06 MPa (3.2 kpsi), at least 23.44 MPa (3.4 kpsi), at least 24 , 82 MPa (3.6 kpsi), at least 26.20 MPa (3.8 kpsi), at least 27.58 MPa (4.0 kpsi), at least 28.96 MPa (4.2 kpsi), no more than 39.30 MPa (5.7 kpsi), not more than 37.92 MPa (5.5 kpsi), not more than 36.54 MPa (5.3 kpsi), not more than 35, 16 MPa (5.1 kpsi), not more than 33.78 MPa (4.9 kpsi), not more than 32.41 MPa (4.7 kpsi),

no more than 29.65 MPa (4.5 kpsi), from 22.06 MPa to 39.30 MPa (3.2 kpsi to 5.7 kpsi) or from 24.82 MPa to 34.47 MPa (3, 6 kpsi to 5.0 kpsi).

[0105] The article can have a stress stretching test value in the machine direction break of at least 550%, at least 560%, at least 570%, at least 580%, at least 590%, at least 600 %, at least 610%, at least 620%, not more than 725%, not more than 710%, not more than 700%, not more than 680%, not more than 665%, not more than than 650%, no more than 635%, from 550% to 750% or from 600% to 660%.

[0106] The article can have a stress elongation at break value in the transverse direction of at least 575%, at least 590%, at least 600%, at least 615%, at least 630% or at least 645% , not more than 770%, not more than 755%, not more than 740%, not more than 725%, not more than 710%, not more than 695%, not more than 680%, from 575% to 775% or from 625% to 700%.

[0107] When applicable, the article may have a Elmendorf tear strength test value in the machine direction of at least 280 g / mil, at least 300 g / mil, at least 320 g / mil, at least 340 g / thousand, or at least 360 g / thousand, not more than 450 g / thousand, not more than 430 g / thousand, not more than 410 g / thousand, not more than 390 g / thousand, or not more than 370 g / mil, from 275 g / mil to 475 g / mil or from 325 g / mil to 410 g / mil.

[0108] When applicable, the article may have an Elmendorf tear strength test value in the transverse direction of at least 475 g / mil, at least 490 g / mil, at least 500 g / mil, at least 525 g / mil thousand, at least 540 g / mil, or at least 550 g / mil, no more than 700 g / mil, no more than 680 g / mil, no more than 650 g / mil, no more than 625 g / thousand, not more than 600 g / thousand, not more than 580 g / thousand, or not more than 570 g / thousand, from 475 g / thousand to 725 g / thousand or from 490 g / thousand to 640 g /thousand.

[0109] When applicable, the article may have a secant modulus of machine test elasticity value of at least 137.89 MPa (20 kpsi), at least 151.68 MPa (22 kpsi), at least 165, 47 MPa (24 kpsi), at least 179.26 MPa (26 kpsi), at least 193.05 MPa (28 kpsi), or at least 206.84 MPa (30 kpsi), not more than 275.79 MPa ( 40 kpsi), not more than 262.00 MPa (38 kpsi), not more than 248.21 MPa (36 kpsi), not more than 234.42 MPa (34 kpsi), or not more than 220, 63 MPa (32 kpsi), from 137.89 MPa to 275.79 MPa (20 kpsi to 40 kpsi) or from 172.37 MPa to 241.31 MPa (25 kpsi at 35 kpsi).

[0110] When applicable, the article may have a secant modulus of elasticity test value in the transverse direction of at least 137.89 MPa, at least 137.89 MPa (20 kpsi), at least 151.68 MPa (22 kpsi ), at least 165.47 MPa (24 kpsi), at least 179.26 MPa (26 kpsi), at least 193.05 MPa (28 kpsi), or at least 206.84 MPa (30 kpsi), no more than than 275.79 MPa (40 kpsi), not more than 262.00 MPa (38 kpsi), not more than 248.21 MPa (36 kpsi), not more than 234.42 MPa (34 kpsi), or no more than 220.63 MPa (32 kpsi), from 137.89 MPa to 275.79 MPa (20 kpsi to 40 kpsi) or 172.37 MPa to 241.31 MPa (25 kpsi to 35 kpsi).

[0111] In some cases, articles that include a polymeric material based on carbohydrates formed from a mixture of two or more starches have values of strength properties that are higher than those of articles that include a polymer based material of carbohydrates formed from a single starch. For example, an article that includes a polymeric carbohydrate material formed from a mixture of two or more starches may have a cannula drop impact test value (in grams or g / mil thickness) that is at least about 10% larger than an article, wherein the carbohydrate-based polymeric material is formed from a single starch, at least about 25% higher, at least about 50% higher, at least about 75% higher, 10% higher than 150% higher or 60% higher than 120% higher than the same article, but which includes a polymeric material based on carbohydrates formed from a single starch. Details of such increased resistance are found in

U.S. Patent Nos. 14 / 853,725 and 15 / 481,806, already incorporated by reference. In the absence of exposure to significant sunlight or degrading microorganisms, the presence of the degradation additive (or degradation additives) is not expected to have a detrimental effect on the physical properties of the mixture.

[0112] When subject to biodegradation testing (for example, whether testing for biomethane potential or any applicable standard ASTM, such as ASTM D-5511, ASTM D-5526, ASTM D-5338 or ASTM D-6691, the articles of this invention, which include NuPlastiQ and degradation additives, significantly biodegrade. Under such testing, and within a certain period of time (for example, 30 days, 60 days, 90 days, 180 days, 365 days (1 year), 2 years, 3 years, 4 years or 5 years, articles may show complete biodegradation of the total polymeric content and / or the non-biodegradable plastic content (in addition to the carbohydrate-based polymeric content). Biomethane potential testing is typically conducted for 30 or 60 days, although sometimes for 90 days. Tests with longer periods of time are more typically performed under any of the aforementioned ASTM standards. Articles made from the compositions of this invention may show biodegradation q ue is higher than the content of the carbohydrate-based polymeric material therein, which indicates that the other plastic material (or other plastic materials) are also biodegradable (or have the potential to biodegrade under a biomethane potential test).

[0113] Particularly, when articles are subjected to testing that simulates biodegradation under landfill or under other degradation conditions (for example, composting conditions or sea conditions) for 180 days, 200 days, 365 days (1 year), 2 years, 3 years or 5 years, biodegradation may be greater than the weight percentage of the carbohydrate-based polymeric materials (NuPlastiQ) within the article. That is, the inclusion of the carbohydrate-based polymeric materials and the degradation additive described (or degradation additives) can result in at least certain biodegradation of the non-biodegradable plastic material (whose materials alone are not significantly biodegradable).

[0114] For example, an article, such as a film that is formed from a mixture of carbohydrate-based polymeric materials, the degradation additive (or degradation additives) and PE, may show biodegradation after such periods of time which are greater than the weight fraction of the carbohydrate-based polymeric materials in the film, which indicates that PE (normally not thought to be biodegradable) is actually biodegraded, with the carbohydrate-based polymeric material. Such results are surprising and particularly advantageous.

[0115] Biomethane potential testing determines the potential for anaerobic biodegradation based on methanogenesis as a percentage of the total methanogenesis potential. Biomethane potential testing can be used to predict the biodegradability of the samples tested according to an ASTM D-5511 standard and biomethane potential testing can be conducted using one or more conditions from the ASTM D-5511 standard . For example, a biomethane potential test can be performed at a temperature of about 52 ° C. In addition, biomethane potential testing may have some conditions that are different from those of ASTM D-5511, for example, to speed up the test to be complete within the typical 30, 60, or sometimes over the 90 days . Biomethane potential testing can employ an inoculum that has 50% to 60% by weight of water and 40% to 50% by weight of organic solids. For example, an inoculum used in testing biomethane potential can have 55% by weight of water and 45% by weight of organic solids. Biomethane potential testing can also be performed at other temperatures, such as from 35 ° C to 55 ° C or from 40 ° C to 50 ° C.

[0116] When subjected to biodegradation testing, an article made from the compositions of this invention that has a quantity of carbohydrate-based polymeric material, degradation additive and non-biodegradable plastic material, as described in this document, may exhibit optimized biodegradation , as a result of the introduction of the additive and the carbohydrate-based polymeric material, NuPlastiQ, in the article. For example, at least 5%, at least 10%, at least 15%, at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90% or even at least 95 % of non-carbohydrate polymeric material (for example, non-biodegradable plastic material) can biodegrade for a period of at least about 1 year, at least about 2 years, at least about 3 years or at least about 5 years when subject to landfill, composting and / or maritime conditions (or conditions that simulate them). Such biodegradation is particularly notable and advantageous. Therefore, not only the biodegraded carbohydrate-based polymeric material, but also the non-biodegradable plastic material.

[0117] With the increased time, the amount of biodegradation can be very high, such that, in at least some implementations, substantially the entire article biodegrades (for example, biodegradation of at least about 85%, at least about 90 % or at least about 95% within 180 days, or 200 days, or 365 days (1 year), within 2 years, within 3 years, within 5 years or other period).

[0118] Figure 2 illustrates the components of an exemplary manufacturing system 200 for producing the articles according to the present disclosure. In some cases, fabrication system 200 can be used in process 100 of Figure 1. In an illustrative example, fabrication system 200 is an extruder, such as a single screw extruder or a double screw extruder.

[0119] In one implementation, one or more non-biodegradable plastic materials, one or more degradation additives and one or more carbohydrate-based polymeric materials are provided through a first feeder 202 and a second feeder 204. A compatibilizer may be included with one or both of the materials (for example, in a batch of the same matrix).

[0120] The one or more carbohydrate-based polymeric materials, the one or more degradation additives and the one or more non-biodegradable plastic materials can be mixed in a first chamber 206 to produce a mixture of materials. In some cases, the mixture of materials may include from 5% by weight to 40% by weight of the one or more carbohydrate-based polymeric materials, from 60% by weight to 94% by weight of one or more non-biodegradable plastic materials, from 0.1 to 5% by weight of the degrading additive and from 1% by weight to 9% by weight of the one or more compatibilizers. The ranges, of course, can be varied outside of the previous ranges, depending on the desired characteristics.

[0121] In the exemplary implementation shown in Figure 2, the mixture of materials can pass through several chambers, such as the first chamber 206, a second chamber 208, a third chamber 210, a fourth chamber 212, a fifth chamber 214 and an optional sixth chamber 216. The material mix can be heated in chambers 206, 208, 210, 212, 214,

216. In some cases, a temperature in one chamber may be different from a temperature in another chamber. In an illustrative example, the first chamber 206 is heated to a temperature of 120 ° C to 140 ° C; the second chamber 208 is heated to a temperature of 130 ° C to 160 ° C; the third chamber 210 is heated to a temperature of 135 ° C to 165 ° C; the fourth chamber 212 is heated to a temperature of 140 ° C to 170 ° C; the fifth chamber 214 is heated to a temperature of 145 ° C to 180 ° C; and the optional sixth chamber 216 is heated to a temperature of 145 ° C to 180 ° C.

[0122] The heated mixture can then be extruded using a 218 die to form an extruded object, such as a film, sheet or the like. Injection molding, thermoforming or other plastic production processes can be used for the manufacture of various articles, such as utensils, plates, glasses, bottles, caps or lids, therefore, or similar. When blowing the film, a gas can be injected into the extruded object to expand it with a pressure of 105 bar to 140 bar. The resulting tube 220 can be made using laminators 222 to create a film 224 with a thickness, typically, from 0.02 mm (about 0.8 mil) to 0.05 mm (about 2 mil). Even the thinnest films can be produced using blends as described in this document, for example, with a thickness as small as 0.1 mil (0.004 mm). Of course, thicknesses greater than 0.0508 mm can also be achieved. In some cases, film 224 may be comprised of a single layer. In other cases, film 224 can be comprised of multiple layers. When multiple layers are present, at least one of the layers can include the carbohydrate-based polymeric material and the degradation additive. In some embodiments, the carbohydrate-based polymeric material and the degradation additive may be present in one or more outer layers. In another embodiment, the carbohydrate-based polymeric material and the additive may be present in an inner layer. When no carbohydrate-based polymeric material is included in the outer layer (or outer layers), biodegradation of the outer layer (or outer layers) may not occur.

[0123] The concepts described in this document will be better described in the following examples. EXAMPLE 1

[0124] Samples with the compositions shown in Table 2 are tested for about 180 days to determine the biodegradability characteristics with the use of biomethane potential for anaerobic biodegradation based on methanogenesis as a percentage of total methanogenesis potential. The biomethane potential test aims to determine whether the tested materials have any significant potential for biodegradation. Such a test can be conducted at a temperature of about 52 ° C using an inoculum with about 55% by weight of water and about 45% by weight of organic solids. The test is performed in accordance with ASTM D-5511 for 180 days. A positive cellulose control and a negative control of 100% polyethylene are used for comparison. The results indicate that the sample formed from a mixture of a carbohydrate-based polymer (NuPlastiQ® GP), low density polyethylene and the degradation additive, Enso Restore ™ or OXO-Terra ™, (shown in% in weight) biodegrades to an extent that is greater than the amount of NuPlastiQ® in the sample, which indicates that some of the non-biodegradable polyethylene is otherwise biodegradable in addition to the biodegradation of the carbohydrate-based polymeric material. The positive sample substantially degrades and the negative control sample shows little or no degradation. TABLE 2

LLDPE NuPlastiQ No. Polietilen modified with Sample Form Additive (%) o (%) maleic anhydride degradation (%) Highlight 1 0 100 none 1% OXO 2 20 74 5% Terra ™ Willow Ridge Film 1% of Enso 3 20 74 5% Restore ™ IV film. CONCLUSION

[0125] To conclude, although the various implementations have been described in specific languages in relation to structural resources and / or methodological acts, it should be understood that the matter defined in the attached representations is not necessarily limited to resources or acts specifics described. In contrast, specific remedies and actions are revealed as exemplary ways to implement the claimed matter.

[0126] To conclude, it should be understood that the modalities of innovative resources revealed in this document are illustrative in relation to the principles of innovative resources.

Other modifications can be employed, which are within the scope of innovative resources.

Therefore, for illustrative purposes, but not for limitation, alternative configurations of innovative features can be used in accordance with the teachings of this document.

Consequently, innovative resources are not limited, precisely, to what is shown and described.

Claims (20)

1. Method for imparting biodegradability to a plastic material that, by itself, is not biodegradable in any other way, and the method is characterized by understanding: providing a plastic material that is not biodegradable in itself; supplying one or more carbohydrate-based polymeric materials formed from a carbohydrate and a plasticizer; provide at least one degradation additive that, in combination with at least one of oxygen, ultraviolet light or microbial action, allows the biodegradation of the plastic material which is not, in itself, biodegradable; merge the polymeric material based on carbohydrate, the plastic material and the degradation additive; where at least 25% of the carbon atoms in the plastic material become carbon atoms of at least one of carbon dioxide or methane within about 180 days in simulated landfill conditions, simulated composting conditions or simulated marine conditions. 2. Method according to claim 1, characterized in that the degradation additive comprises a material that optimizes the biodegradation of the polymeric material through the action of ultraviolet light and / or oxygen. Method according to claim 2, characterized in that the degradation additive comprises a salt of a transition metal. Method according to claim 3, characterized in that the salt is an iron, magnesium, manganese or cobalt salt. Method according to claim 3, characterized in that the degradation additive comprises a cobalt salt. 6. Method according to claim 1, characterized in that the degradation additive comprises a composition that cultivates one or more microorganisms that optimize the biodegradation of the plastic material that is not, by itself, biodegradable. Method according to claim 1, characterized in that the degradation additive comprises at least one of a sugar or a nitrogen-containing material. Method according to claim 6, characterized in that the additive comprises one or more of malt, maltose, lactose, xylose, glucose, galactose, peptone, yeast extract or asparagine extract. Method according to claim 6, characterized in that the additive comprises xylose. Method according to claim 6, characterized in that at least one microorganism secretes the laccase enzyme. Method according to claim 6, characterized in that the microorganism comprises one or more fungi. Method according to claim 6, characterized in that the microorganism comprises one or more bacteria. 13. Method according to claim 2, characterized in that the additive comprises at least one of grafted poly (methyl methacrylate) titanium dioxide, titanium dioxide sensitized with copper phthalocyanine, ceria, zinc oxide, copper sulfide, or vanadium (III) acetylacetonate. 14. Method according to claim 6, characterized in that the additive interacts with the enzymes secreted by the microorganism to cause the hydrolysis of the non-biodegradable polymer. 15. Method for imparting biodegradability to a plastic material that, by itself, is not biodegradable in any other way, the method being characterized by understanding: providing a plastic material that is not biodegradable in itself; supplying one or more carbohydrate-based polymeric materials formed from a carbohydrate and a plasticizer; provide at least one degradation additive that, in combination with at least one of oxygen, ultraviolet light or microbial action, allows the biodegradation of the plastic material which is not, in itself, biodegradable; merge the polymeric material based on carbohydrate, the plastic material and the degradation additive; where at least 25% of the carbon atoms in the plastic material become carbon atoms of at least one of carbon dioxide and methane within about three years in simulated landfill conditions, simulated composting conditions or simulated marine conditions. 16. Biodegradable composition characterized by comprising: a polymer not normally biodegradable; a carbohydrate-based polymeric material formed from a carbohydrate and a plasticizer; and a degradation additive comprising at least one of (i) an OXO additive, (ii) a sugar or other organic material that provides nutrition and / or a cultivated environment for microorganisms that biodegrade the normally non-biodegradable polymer, or ( iii) an inorganic salt that provides nutrition and / or a cultivated environment for microorganisms that biodegrade the normally non-biodegradable polymer. 17. Composition according to claim 16, characterized in that the degradation additive comprises an OXO degradant which is a salt of a transition metal. 18. Composition according to claim 16, characterized in that the salt is a cobalt, nickel, magnesium, manganese, iron or zinc salt. 19. Composition according to claim 16, characterized in that the degradation additive comprises an organic material that provides nutrition for microorganisms present in an environment in which the composition is discarded. 20. Composition according to claim 16, characterized in that the degradation additive interacts as a catalyst with enzymes produced by the microorganisms to stimulate the hydrolysis of the non-biodegradable polymer.