WO2019209834A1 - Ajout d'additifs conférant une biodégradabilité à des matières plastiques - Google Patents

Ajout d'additifs conférant une biodégradabilité à des matières plastiques Download PDF

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Publication number
WO2019209834A1
WO2019209834A1 PCT/US2019/028733 US2019028733W WO2019209834A1 WO 2019209834 A1 WO2019209834 A1 WO 2019209834A1 US 2019028733 W US2019028733 W US 2019028733W WO 2019209834 A1 WO2019209834 A1 WO 2019209834A1
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Prior art keywords
carbohydrate
biodegradable
materials
nuplastiq
degradation
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PCT/US2019/028733
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English (en)
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Bradford LAPRAY
Donald R. Allen
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BiologiQ, Inc.
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Priority to BR112020021530-9A priority Critical patent/BR112020021530A2/pt
Priority to KR1020207033615A priority patent/KR20210024448A/ko
Priority to EP19793589.3A priority patent/EP3784732A4/fr
Priority to JP2020558940A priority patent/JP2021523957A/ja
Priority to CN201980042207.6A priority patent/CN112513168A/zh
Publication of WO2019209834A1 publication Critical patent/WO2019209834A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/012—Additives activating the degradation of the macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/10—Metal compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0033—Additives activating the degradation of the macromolecular compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1545—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/06—Biodegradable

Definitions

  • Plastics materials such as large quantities of polyethylene and polypropylene, as well as numerous other plastics (polyethylene terephalate polyester, polystyrene, ABS, polyvinyl chloride, polycarbonate, nylon, and the like) are typically not readily biodegradable. Such is typically the case even for so called“green” plastics of such materials, which may be sourced from renewable or sustainable sources, rather than petro- chemical feedstocks.
  • UV and/or OXO degradable additives e.g., such as PDQ-M, PDQ-H, BDA, and OxoTerraTM Additive from Willow Ridge Plastics, 0X1014 Additive from LifeLine, or organic additives (e.g., such as Enso Restore® by Enso, EcoPure® Additive by Bio-Tec Environmental, ECM Masterbatch Pellets additive by ECM Biofilms, or BioSphere®).
  • OXO degradable additives are known to break up the long carbon chains of materials which makes the materials more susceptible to biodegradation.
  • the degree of degradability (particularly any biodegradability) and the rate of degradation caused is often thought to be too slow, and the UV and/or OXO additives may simply initiate structural fragmentation or degradation that accelerates physical deterioration of such plastic materials into small pieces (“micro plastic”) of the underlying base plastic material, rather than the desired actual conversion of the plastic into natural materials such as carbon dioxide (C0 2 ), water (H 2 0), and/or methane (CH 4 ).
  • micro plastic small pieces
  • CO 2 0 carbon dioxide
  • H 2 0 water
  • CH 4 methane
  • Some jurisdictions such as the European Union and some states have adopted policies discouraging or even proposing banning the use of such additives or at least barring claims of biodegradability of plastics containing the additives because such claims are deemed misleading.
  • OXO additives may simply accelerate break-up of the macro-structure of the plastic article itself due to exposure to UV light (from sun exposure) and/or oxygen.
  • Such specialty plastics may not actually biodegrade to any appreciable degree within a given time frame (e.g., 5 years, 3, years, or 1 year), but simply lose strength, crack, and break up into small pieces.
  • the result can be a pile of small pieces of polyethylene or other base plastic material that results as the bottle, film, or other article physically degrades over time due to the presence of the UV and/or OXO additives.
  • the weight fraction of polyethylene or other base plastic material may remain substantially the same, with no significant biodegradation to base elements actually occurring.
  • the degradation may be primarily physical, as the article becomes brittle, cracks, and breaks up into small pieces, leaving many small fragments of polyethylene or other base polymer.
  • Application of the term“biodegradable” to such plastic materials may be considered a misnomer, as complete biodegradation of the polymeric material itself may not actually be occurring (e.g., where substantial fractions of the plastic would be degraded into C0 2 , CH 4 , H 2 0, and the like).
  • makers of plastics said to be biodegradable may incorporate chemical degradation additives, such as the organic materials, that operate separately or in combination with the OXO additives to achieve some biodegradation.
  • these additives also are considered by some to be of limited value because any biodegradation may be very slow.
  • the composition of the additives is typically a trade secret, although some conclude the additives are similar or identical to those of the UV and/or OXO additives. Because of doubts that the chemical additives actually cause adequate biodegradation to base elements, some plastic industry associations and regulators similarly frown upon the inclusion of the so-called organic additives in plastic compositions especially with any claims that they cause true biodegradation.
  • UV additive may be used herein interchangeably to refer to chemical agents that under exposure to oxygen or UV radiation cause disintegration of plastic polymer chains into fragments, with or without substantial biodegradation.
  • the term“chemical additive” is used herein to refer to materials, often organic, that may be mixed with plastic products to cause degradation and/or biodegradation of plastic materials by interacting with microbes in a disposal environment.
  • the additives may operate with secretions of the microorganisms, such as enzymes or may provide nutrition that encourages growth and colonization of the microorganisms. Such a function may be described as“cell mediated” degradation or biodegradation.
  • degradation additive is used herein to refer to either or both OXO additives and/or chemical additives that are mixed with plastics, such as polyolefins, e.g. polyethylene, polypropylene and the like to promote degradation of the polymer chains by oxidation and/or chemical attack and/or microbial dissimilation.
  • plastics such as polyolefins, e.g. polyethylene, polypropylene and the like to promote degradation of the polymer chains by oxidation and/or chemical attack and/or microbial dissimilation.
  • biodegradation refers to conversion of a polymer in whole or in part to base elements such as carbon dioxide, methane, and/or water.
  • Applicant’s copending application 15/691,588 discloses a method for lending biodegradability to plastic articles, that are typically not otherwise biodegradable, by addition of a fraction of a carbohydrate-based polymeric material (known commercially as NuPlastiQ ® (available from Applicant) which has surprisingly been found to lend substantial biodegradability to such plastic materials when blended therewith and exposed to conditions where microbes are found in sufficient quantities such as are found in landfills, compost conditions and/or marine environments.
  • a carbohydrate-based polymeric material known commercially as NuPlastiQ ® (available from Applicant) which has surprisingly been found to lend substantial biodegradability to such plastic materials when blended therewith and exposed to conditions where microbes are found in sufficient quantities such as are found in landfills, compost conditions and/or marine environments.
  • the present application is directed to compositions and methods for achieving enhanced biodegradability in blends of a conventional, substantially non-biodegradable plastic with a carbohydrate-based polymeric material such as NuPlastiQ® available from Applicant, by adding a degradation additive as described above to a blend of the carbohydrate based polymer and the non-biodegradable plastic. While the blends of the carbohydrate based polymer and the non-biodegradable plastic achieve substantial levels of biodegradability and even complete biodegradability, the presence of the degradation additive can significantly enhance the biodegradability (e.g., rate and/or extent) of such blends.
  • a carbohydrate-based polymeric material such as NuPlastiQ® available from Applicant
  • the present invention achieves the benefit of the combined effects of the prior art degradation additives and Applicant’s NuPlastiQ material in biodegrading plastics such as polyethylene and other plastic polymers.
  • a degradation additive such as an OXO additive
  • conventional non- biodegradable plastics such as polyethylene and polypropylene
  • the presence of the degradation additive in plastic blends that include Applicant’s starch-based composition known as NuPlastiQ® causes biodegradation of the plastic either faster or more completely than occurs with blends that do not include the additive.
  • the degradation additive is present in the blend at a concentration of from 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 which can be readily determined by routine testing for effectiveness.
  • the additive(s) may be incorporated with the NuPlastiQ prior to blending with the non-biodegradable plastic, blended with the non-biodegradable plastic prior to blending with NuPlastiQ or it may be added to a blend in which the non-biodegradable plastic and NuPlastiQ are being blended at the time that the plastic product is being manufactured.
  • the degradation additive is introduced by any conventional extrusion or blending operation known for blending routine components, such as compatibilizers, antioxidants, etc. in the plastics industry.
  • the NuPlastiQ/biodegradable blends containing the foregoing additives may achieve a level of biodegradation (i.e., breakdown into carbon dioxide and/or methane and/or water) in landfill, marine, and/or compost environments, or even in discarded environments with sunlight exposure in the case of OXO additives, that is faster and sometimes more complete than a plastic without the degradation additive.
  • the extent of biodegradation may be measured in various tests, e.g., including by ASTM D 5338 (anaerobic conditions such as landfills) and ASTM D 6400 (aerobic conditions, such as composting).
  • compositions and methods of this invention demonstrate the ability to lend enhanced biodegradability to several plastic materials that prior to the development of NuPlastic ® were believed not otherwise significantly biodegradable, examples of which may include, but are not limited to 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.
  • Blends of such plastics with the carbohydrate-based polymeric material, NuPlastiQ, and the degradation additive may be mixed and heated (e.g., melted) for use in forming extruded plastic products, injection molded plastic products, blow molded plastic products, blown film plastic products, extruded or cast sheet or films, thermoformed plastic products, and the like using standard equipment of the plastics industry from mixing and compounding the polymeric materials with necessary ingredients.
  • FIG. 1 illustrates a flow diagram of an exemplary process for forming an article from compositions of the present invention including a carbohydrate-based polymeric material (NuPlastiQ) and one or more degradation additives.
  • a carbohydrate-based polymeric material NuPlastiQ
  • the degradation additive are mixed with the non-biodegradable plastic at 104; however, the additive may be premixed with either material prior to preparing the mixture of all three ingredients.
  • FIG. 2 illustrates components of an example manufacturing system to produce articles including biodegradable materials of this invention.
  • FIG. 3 shows X-ray diffraction patterns for an exemplary NuPlastiQ carbohydrate- based polymeric material commercially available from BioLogiQ as compared to that of the blend of native corn starch and native potato starch used to form the NuPlastiQ. It is believed that the unique structure of the NuPlastiQ, including its amorphous nature, contributes to its properties of blending intimately with a non-biodegradable polymer such as polyethylene.
  • Frm refers to a thin continuous article that includes one or more polymeric materials that can be used to separate areas or volumes, to hold items, to act as a barrier, and/or as a printable surface.
  • Bing refers to a container made of a relatively thin, flexible film that can be used for containing and/or transporting goods.
  • Bottle refers to a container that can be made from the presently disclosed plastics, typically of a thickness greater than a film, and which typically includes a relatively narrow neck adjacent an opening. Such bottles may be used to hold a wide variety of products (e.g., beverages, personal care products such as shampoo, conditioner, lotion, soap, cleaners, and the like).
  • products e.g., beverages, personal care products such as shampoo, conditioner, lotion, soap, cleaners, and the like.
  • Numbers, percentages, ratios, or other values stated herein may include that value, and also other values that are about or approximately the stated value, as would be appreciated by one of ordinary skill in the art.
  • a stated value should therefore be interpreted broadly enough to encompass values that are at least close enough to the stated value to perform a desired function or achieve a desired result, and/or values that round to the stated value.
  • the stated 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 stated value.
  • the terms“substantially”, “similarly”,“about” or“approximately” as used herein represent an amount or state close to the stated amount or state that still performs a desired function or achieves a desired result.
  • the term“substantially”“about” or“approximately” may refer to an amount that is within 25% of, within 15% of, within 10% of, within 5% of, or within 1% of, a stated amount or value.
  • phrase‘free of or similar phrases as used herein means that the composition comprises 0% of the stated component, that is, the component has not been intentionally added to the composition. However, it will be appreciated that such components may incidentally form under appropriate circumstances, may be incidentally present within another included component, e.g., as an incidental contaminant, or the like.
  • composition preferably comprises 0% of the stated component, although it will be appreciated that very small concentrations may possibly be present, e.g., through incidental formation, incidental contamination, or even by intentional addition. Such components may be present, if at all, in amounts of 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%.
  • non-biodegradable as used herein with regard to a material means that the material (free of additives added to render it biodegradable) does not degrade (particularly biodegrade), e.g., to carbon dioxide or methane to a significant extent in a limited time period (e.g. one year, 3 years, or 5 years) when exposed to various typical disposal conditions, such as sunlight, in the ocean, or in a landfill.
  • biodegradable as used herein with regard to a material means that the material which contains NuPlastiQ in the presence of biodegradation additives as described herein does biodegrade to base elements such as carbon dioxide, methane and/’ or water.
  • the present disclosure is directed to, among other things, methods for lending biodegradability to a plastic material that itself is not otherwise biodegradable by blending such plastic material with (a) a carbohydrate-based (e.g., starch-based) polymeric material, that is specifically selected for its ability to lend biodegradability to the plastic material that is not itself biodegradable, and (b) a degradation additive.
  • a carbohydrate-based polymeric material is known as“NuPlastiQ” and is available from Applicant.
  • the method includes treatment appropriate to the additive, such as exposure to oxygen, radiation by UV, and inclusion of the degradation additive under conditions that the additive is activated in the presence of biodegrading microbes.
  • the degradation additive is one or more of: (i) a material known in the art as an OXO additive (which functions to facilitate degradation by oxygen and/or UV, and/or (ii) a chemical composition known to attract, colonize, and/or interact with (such as by providing nutrition and/or reacting with secretions e.g., enzymes) of microorganisms, which microorganisms promote or cause degradation of the plastics mentioned in an environment conducive to such biodegradation, such as the soil, a compost environment and/or landfill.
  • OXO additive which functions to facilitate degradation by oxygen and/or UV
  • a chemical composition known to attract, colonize, and/or interact with such as by providing nutrition and/or reacting with secretions e.g., enzymes
  • Such methods are particularly beneficial in that they allow numerous plastic items that are thrown out to be biodegraded in a landfill, compost pile or similar disposal environment, rather than continuing to exist in their polymeric, stable state, indefinitely.
  • biodegradation of such articles does not readily occur where the articles are stored in typical storage and use environments (e.g., stored in a home, office, warehouse, or the like), but biodegradation generally only begins to occur where the article is placed in an environment that simulates or is that of a landfill or compost or other typical disposal environment where microorganisms facilitating degradation are present.
  • such conditions may include (i) a temperature that is somewhat elevated above normal ambient“use” or“storage” temperatures, (ii) exposure to elevated moisture levels, (iii) exposure to particular classes of microbes indigent to landfills or compost and similar disposal environments, or marine/ocean environments. Elevated temperature and moisture will not cause biodegradation of such articles unless the necessary microorganisms are also present.
  • the combination of such conditions causes the articles formed from such a blend of materials to begin to biodegrade.
  • the presence of suitable microbes somehow breaks the hygroscopic barrier associated with the non-biodegradable plastic materials, allowing the microbes that would biodegrade the carbohydrate material to not only biodegrade the carbohydrate-based polymeric material, but also to biodegrade the adjacent normally non-biodegradable plastic molecules as well.
  • the carbon bonds are broken and the biodegradation can be confirmed based on tests that capture and measure the carbon dioxide and/or methane that is off-gassed.
  • the degradation additives described heroin operate within this environment to enhance the function of the microorganisms and/or render the plastic material in a form that it may more suitably be attacked by the microorganisms.
  • Articles can be produced by mixing the carbohydrate-based polymeric material and one or more degradation additives with the otherwise non-biodegradable plastic material, in any order, heating the mixture, and molding (e.g., injection molding) the mixture, extruding the mixture, blow molding the mixture, blow-forming the mixture (e.g., forming a blown film), thermoforming the mixture, or the like.
  • molding e.g., injection molding
  • a plastic product such as a film or injection molded part.
  • the articles described herein can be produced in the form of any conceivable structure, including, but not limited to bottles, boxes, other containers, sheets, films, bags, and the like. Thin films for bags and film wraps (e.g., for wrapping around or over a product) can easily be made using blown film equipment.
  • suitable carbohydrate-based or starch-based polymeric materials that have been shown to lend biodegradability to otherwise non-biodegradable plastic materials for use in forming such articles are available from BioLogiQ, under the tradenames “NuPlastiQ,” and formerly“ESR” (“Eco Starch Resin”).
  • NuPlastiQ include, but are not limited to NuPlastiQ GP, NuPlastiQ XP, NuPlastiQ XD, NuPlastiQ BC, NuPlastiQ MB and NuPlastiQ BC. ETnder the tradename ESR, such materials have previously been referred to as GS-270, GS-300, and GS-330. Specific characteristics of such NuPlastiQ materials will be described in further detail herein. Other carbohydrate- based or starch-based polymeric materials may also be suitable for use so long as they are capable of, and specifically selected for the purpose of lending biodegradability to plastic materials that are otherwise not biodegradable. NuPlastiQ is further described in applicant’s copending applications 15/481,806 and 15/481,823 both filed on April 7, 2017 and which are incorporated by reference in their entirety herein.
  • suitable degradation additives are materials known in the art to, under conditions of exposure to ultraviolet light and/or oxygen, degrade or fragment to some extent polymeric materials such as polyethylene, polypropylene, other polyolefins, polyethylene terephalate, other polyesters, polystyrene, ABS, polyvinyl chloride, nylon and polycarbonate.
  • Representative additives are OXO additives (e.g., such as PDQ-M, PDQ-H, BDA, and OxoTerraTM from Willow Ridge Plastics, and 0X1014 from Lifeline). With such additives, photooxidation is generally the triggering step in the oxidation process. ETV radiation leads to active radical formation which in turn may lead to cleavage of C-C bonds.
  • OXO additives are salts of transition metals such as cobalt, iron, manganese, magnesium, nickel and/or zinc, although other transition metals may be used.
  • OXO additives do not include heavy metals such as lead, mercury or cadmium.
  • Suitable salts include the salts of carboxylic acids and dithiocarbamates, although other salts such as halides (e.g., chlorides), nitrates, sulfates, acetates, chlorates and the like are possible.
  • OXO additives are described in“Transition Metal Salts,” published by the OXO- biodegradable Plastic Association and incorporated herein in its entirety by reference, http://www.biodeg.org/Transition%20Metal%20Salts%20l.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, Issue WR3, https://dspace.lboro.ac.uk/dspace- jspui/bitstream/2l34/l394l/4/warml65-l33.pdf, incorporated herein by reference in its entirety.
  • the OXO additives are typically used in an amount ranging from about 0.3% to 5% by weight of the final carbohydrate-based polymer/plastic blend, depending on their potency, and the optimum level can readily be determined by routine testing. Representative amounts include not more than 0.3%, not more than 1%, not more than 1.5%, not more than 2%, not more than 2.5%, less than 5%, less than 3%, less than 2%, or less than 1% of the final blend of the NuPlastiQ or other carbohydrate-based polymeric material and non-biodegradable plastic.
  • Suitable other similar OXO type degradation additives that facilitate degradation of plastics in the presence of ultra-violet light, and in some cases, visible light, are titanium dioxide, including Ti0 2 having grafted thereto poly(methyl methacrylate) (PMMA) as described in Ying Luo, Xianming Dong, and Chaoqun Zhang, “Accelerating the degradation of polyethylene composite mulches,” Plastics Research online, 19 May 2017, incorporated herein in its entirety by reference; copper phthalocyanine (CuPc) sensitized Ti0 2 photocatalyst used in polyethylene as described in Jing Shang, Ming Chai and Yougfa Zhu,“Photocatalytic Degradation of Polystyrene Plastic under Fluorescent Light,” Environ.
  • Ti0 2 having grafted thereto poly(methyl methacrylate) (PMMA) as described in Ying Luo, Xianming Dong, and Chaoqun Zhang, “Accelerating the degradation of polyethylene composite mulch
  • the OXO additives are typically effective under conditions of oxygen and UV light exposure.
  • suitable degradation additives to be used in combination with applicant’s NuPlastic® or another carbohydrate-based polymeric material as described herein are materials conducive to growth and activity of microorganisms known to produce, e.g., secrete, substances such as enzymes that attack plastics such as polyethylene and/or other polymers such as polyvinyl chloride.
  • suitable degradation additives such as Restore ® from Enso, EcoPure ® by Bio-Tec Environmental, ECM Masterbatch Pellets 1M by ECM Biofilms, Biodegradable 201, Biodegradable 302 from Biosphere,TM and TDPATM available from EPI Environmental Technologies, Inc.
  • these additives are compositions, often organic, and known to nurture and multiply useful organisms in biodegradability environments.
  • Such materials are known to promote microbial action such as by reaction with enzymes secreted by the microorganisms and/or to provide a food source for microorganisms causing them to colonize and multiply.
  • These materials enhance biodegradation of polymers, e.g., polyolefins, through mechanisms such as hydrolysis, methanogenesis and acetogenesis.
  • Some microbes which multiply in the presences of the chemical additives typically organic materials, secrete enzymes such as laccase, amylase, or lipase that act on the carbon-carbon bonds of polymers, or otherwise facilitate breakdown of plastic molecules that can be more completely biodegraded when blended with applicant’s NuPlastiQ.
  • a representative fungi that contributes needed enzymes to this phenomenon is Cochliobolus sp.
  • organic carbohydrate degradation additives that contribute to 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 may also be added to cultures producing laccase.
  • Laccase is known to facilitate the breakdown of polyvinyl chloride.
  • the function of the aforementioned materials in encouraging the growth of the enzyme laccase from the microorganisms Aspergillus niger and Lysinibacillus eylanilyticus SD B9 (T) to degrade polyvinyl chloride can be found in Tirupati Sumathi, Buddolla Viswanath, Akula Sri Lakshmi and D.V.R. SaiGopal, “Production of Laccase by Cochliobolus sdp.
  • the chemical additives described above may 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 other amounts may be used depending on their potency in achieving the desired biodegradation result.
  • the chemical additives may be effective in anaerobic conditions such as landfills and ocean environments.
  • the blends of this invention may also be significantly biodegradable in ocean environments where degradation additives known to nurture necessary microbes for biodegradation in the oceans are included in the blends.
  • Also contemplated according to this invention is the presence in the blends of both types of additives, that is both the OXO and the chemical additive may be present in the NuPlastiQ/non-biodegradable plastic blends.
  • the mechanism of biodegrading plastics according to this invention is first breaking down the long polymer chains of the plastic followed by assimilation of the smaller constituent molecules by microbes.
  • the combined action of the NuPlastiQ material with an OXO additive followed by assimilation by microbes nurtured by microbe nutrient degradation additives as described herein encourages this mechanism in a wide range of environments, landfills, compost and ocean. Such a process is sometimes referred to as“cell mediation.”
  • the additives may be added by standard methods of mixing additives in the plastics industry, such as by mixing with the carbohydrate-based polymer prior to making the final blend, mixing into the non-biodegradable plastic material prior to blending or may be mixed into the combined blend of the carbohydrate based polymer/non-biodegradable plastic.
  • the additives also may be incorporated into a master batch, such as with the carbohydrate-based polymer prior to blending with the plastic based polymer.
  • Applicant provides masterbatch blends of NuPlastiQ and conventional plastic materials under the tradename BioBlend, e.g., including, but not limited to, BioBlend XP, BioBlend XD, and BioBlend BC.
  • a substantial portion or all of the carbon atoms in the blended product can be converted by microorganisms into C0 2 and or CH 4.
  • the rate of conversion depends on several factors such as thickness of the part, number of microorganisms, type of microorganisms, ratio of C 12 (fossil fuel sourced material) and C 14 (renewably sourced material) in the product, type of plastics in the blend, the strength of the carbon bonds in the plastic, etc.
  • blends of NuPlastiQ and polyolefins are biodegradable without further additives
  • a degradation additive as described herein may enhance the biodegradation of the blended plastic products by increasing the rate and amount of disintegration or fragmentation of the blend.
  • OXO additives are thought to work by causing the disintegration of the macro-structure of the plastic components in the presence of oxygen or ultraviolet light. Increasing the rate and extent to which the carbon bonds are broken down into smaller fragments is thought generally to enable microorganisms present to more readily dissimilate the plastic. When the molecular weight of the carbon chains is reduced and surface area increased, microorganisms may more easily access and consume the materials.
  • the chemical additives are thought to contribute to biodegradation by attracting microorganisms that consume or generate enzymes that break down the plastic materials, with generation of off-gases such as carbon dioxide. Both types of degradation additives enhance the effects of NuPlastiQ in degrading polymer chains.
  • Plastic products that contain merely the degradation additives without the presence of the carbohydrate based material, NuPlastiQ may begin to fragment or disintegrate when they are subjected to an environments where oxygen and/or light and/or helpful microbes are present in sufficient concentration to cause disintegration of the plastic.
  • true substantial biodegradation is often unlikely to occur and the degradation additive of itself might not be able to have the desired effect of causing enough biodegradation into base elements such as carbon dioxide and methane.
  • the product is made using NuPlastiQ ® , then the plastic would still be able to biodegrade in anaerobic conditions or conditions without light, and the presence of the degradation additives are believed to enhance the rate and extent of true biodegradation.
  • FIG. 1 illustrates an exemplary process 100 that may be used to lend biodegradability to a plastic material that itself is not otherwise biodegradable.
  • the process 100 can include providing one or more non-biodegradable plastic (e.g., polymeric) materials (e.g., including, but not limited to polyethylene, polypropylene, other polyolefins, polystyrene, ABS, polyvinyl chloride, nylon, or polycarbonate).
  • the process 100 can include providing one or more carbohydrate-based polymeric materials, such as NuPlastiQ, specifically selected for inclusion in the blend for its recognized ability to lend biodegradability to the otherwise non-biodegradable plastic material provided at 102.
  • the carbohydrate-based polymeric materials and the otherwise non-biodegradable plastic materials can be provided in a desired form, such as pellets, powders, curdles, slurry, and/or liquids. In specific embodiments, the materials can be in the form of pellets.
  • the method further includes blending the plastic material with the carbohydrate-based polymeric material prior to blending with the non-biodegradable plastic
  • the degradation additive is mixed into the carbohydrate polymer and non-biodegradable plastic, although as mentioned, the additive may be provided to either polymeric component prior to blending or to the final blend of the carbohydrate-based polymer/plastic blend.
  • Such blends are also biodegradable to an extent greater than the amount of just the carbohydrate-based material indicating that the normally non-biodegradable plastic is also biodegrading.
  • the blend of such materials is fully biodegradable, and articles formed from such a blend are similarly biodegradable.
  • polyethylene itself is not biodegradable
  • Applicant has discovered that blending polyethylene with the NuPlastiQ carbohydrate-based polymeric materials having characteristics as described herein and the degradation additive, lends biodegradability to the polyethylene, so that not only does the carbohydrate-based polymeric material biodegrade, but the polyethylene blended therewith also becomes biodegradable as a result of its blending with the carbohydrate-based polymeric material and the additive.
  • Such blends may be formed in manufacture into a desired article through any conceivable process.
  • An example of such would be an extrusion process.
  • the non-biodegradable plastic material and the carbohydrate-based polymeric material selected for its ability to lend biodegradability plus degradation additive can be fed into an extruder (e.g., into one or more hoppers thereof).
  • the different materials can be fed into the extruder into the same chamber, into different chambers, at approximately the same time (e.g., through the same hopper), or at different times (e.g., through different hoppers, one being introduced into the extruder earlier on along the screw than the other), etc. It will be apparent that many blending possibilities are possible.
  • the non-biodegradable plastic material can include a polyolefin.
  • plastic materials may include, but are not limited to polyethylene, polypropylene, other polyolefins, polyester, polystyrene, ABS, polyvinyl chloride, nylon, polycarbonates, and the like.
  • plastic material may be sourced from petrochemical sources, or from so-called“green” or sustainable sources (e.g.,“green” PE, bioPET, and the like).
  • the carbohydrate-based polymeric materials can be formed from a plurality of materials (e.g., a mixture) including one or more starches.
  • 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.
  • a mixture of different types of starches may be used, which Applicant has found to result in a synergistic increase in strength.
  • a plasticizer may also be present within the mixture of components from which the carbohydrate-based polymeric materials are formed. Water may also be used in forming the carbohydrate-based polymeric material, although only a small to negligible amount of water is present in the finished carbohydrate- based polymeric material.
  • the one or more carbohydrate-based polymeric materials can be formed from mostly starch. For example, at least 65%, at least 70%, at least 75%, or at least 80% by weight of the carbohydrate-based polymeric material may be attributable to the one or more starches. In an embodiment, from 65% to 90% by weight of the finished carbohydrate-based polymeric material may be attributed to the one or more starches. Other than negligible water content, the balance of the finished carbohydrate-based polymeric material may be attributed to a plasticizer (e.g., glycerin).
  • a plasticizer e.g., glycerin
  • the percentages above may represent starch percentage relative to the starting materials from which the carbohydrate-based polymeric material is formed, or that fraction of the finished carbohydrate-based polymeric material that is derived from or attributable to the plasticizer (e.g., at least 65% of the carbohydrate based polymeric material may be attributed to (formed from) the starch(es) as a starting material).
  • some water may be used in forming the carbohydrate-based polymeric material, substantially the balance of the carbohydrate-based polymeric material may be attributed to glycerin, or another plasticizer. Very little residual water (e.g., less than 2%, typically no more than about 1%) may be present in the finished carbohydrate-based polymeric material.
  • the 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%, no greater than 35%, no greater than 32%, no greater than 30%, no greater than 28%, or no greater than 25% by weight of a plasticizer.
  • Such percentages may represent that fraction of the finished carbohydrate-based polymeric material that is derived from or attributable to the plasticizer (e.g., at least 12% of the carbohydrate based polymeric material may be attributed to (formed from) the plasticizer as a starting material).
  • Exemplary plasticizers include, but are not limited to glycerin, polyethylene glycol, sorbitol, polyhydric alcohol plasticizers, hydrogen bond forming organic compounds which do not have a hydroxyl group, anhydrides of sugar alcohols, animal proteins, vegetable proteins, aliphatic acids, phthalate esters, dimethyl and diethylsuccinate and related esters, glycerol triacetate, glycerol mono and diacetates, glycerol mono, di, and tripropionates, butanoates, tearates, lactic acid esters, citric acid esters, adipic acid esters, stearic acid esters, oleic acid esters, other acid esters, or combinations thereof. Glycerin may be preferred.
  • the finished carbohydrate-based polymeric material may include no greater than 5%, no greater than 4%, no greater than 3%, no greater than 2%, no greater than 1.5%, no greater than 1.4%, no greater than 1.3%, no greater than 1.2%, no greater than 1.1%, or no greater than 1% by weight water.
  • the NuPlastiQ materials available from BioLogiQ are examples of such finished carbohydrate-based polymeric materials, although it will be appreciated that other materials available elsewhere (e.g., at some future time) may also be suitable for use.
  • mixtures of different starches may be used in forming the carbohydrate-based polymeric material.
  • Use of such a mixture of different starches e.g., coming from different plants) has been found to surprisingly be associated with a synergistic increase in strength in articles including such carbohydrate-based polymeric materials.
  • a starch in such a mixture of starches, can 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%, no greater than 95%, no greater than 90%, no greater than 85%, no greater than 80%, no greater than 75%, no greater than 70%, no greater than 65%, no greater than 60%, no greater than 55%, no greater than 50%, or from 10% to 50% by weight relative to the combined weight of the plurality of starches.
  • Some non-limiting exemplary 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 (e.g., using 3 or 4 different starches) can also be used.
  • Examples of suitable carbohydrate-based (e.g., starch-based) polymeric materials for use in forming films and other articles are available from BioLogiQ, located in Idaho Falls, Idaho, under the tradename NuPlastiQ. Specific examples include, but are not limited to NuPlastiQ GP, NuPlastiQ XP, NuPlastiQ XD, and NuPlastiQ BC. Additional details relative to fractions of starch and glycerin or other plasticizers used in forming NuPlastiQ are described in Applicant’s other patent applications, already incorporated herein by reference. NuPlastiQ may be provided in pellet form. Physical characteristics for two examples of NuPlastiQ materials, previously referred to as GS-270 and GS-300, are shown in Table 1 below.
  • NuPlastiQ products from BioLogiQ may generally have a glass transition temperature ranging from about 70°C to about l00°C. Those of skill in the art will appreciate that glass transition temperature can be indicative of degree of crystallinity. Values for melting temperature range, density, Young’s Modulus, and water content may be identical or similar to those shown above in Table 1. Some characteristics may similarly vary somewhat (e.g., ⁇ 25%, or ⁇ 10%) from values shown for GS-270 and GS-300.
  • NuPlastiQ has an amorphous structure (e.g., more amorphous than typical raw starch).
  • typical raw starch powder has a mostly crystalline structure (e.g., greater than 50%), while NuPlastiQ has a mostly amorphous structure (e.g., less than 10% crystalline).
  • the NuPlastiQ materials have a low water content, as described. As this material absorbs moisture, it exhibits plastic behavior and becomes flexible. When removed from a humid environment, the material dries out and becomes stiff again (e.g., again exhibiting less than about 1% water content).
  • the moisture present in NuPlastiQ (e.g., in pellet form) may be released in the form of steam during processing such as that shown in FIG. 1.
  • films or other articles produced from a starch-based polymeric material blended with a non-biodegradable plastic material may exhibit even lower water content, as the non- biodegradable plastic material typically will include no or negligible water, and the water in the NuPlastiQ may typically be released during manufacture of a desired article.
  • Low water content in the carbohydrate-based NuPlastiQ polymeric material can be important, as significant water content can result in incompatibility with the non- biodegradable plastic material, particularly if the article requires formation of a thin film. For example, as the water vaporizes, this can result in voids within the film or other article, as well as other problems.
  • the carbohydrate-based polymeric material used may preferably include no more than about 1% water.
  • the finished polymeric material may be substantially devoid of starch in such identifiable, native form.
  • the carbohydrate-based polymeric material is not always recognized as a mixture including starch and glycerin.
  • the low water content achievable in the carbohydrate-based polymeric material is believed to be due at least in part to the physical or chemical alteration of the starch and plasticizer materials into a thermoplastic polymer, which does not retain water as would native starch, or conventional thermoplastic starches.
  • processing at relatively high temperatures may result in some release of volatized glycerin (e.g., visible as smoke).
  • drying of pellets can be performed by simply introducing warm dry air, e.g., at 60°C for 1-4 hours, which is sufficient to drive off any absorbed water.
  • Pellets should be dried to less than about 1% moisture content prior to processing, particularly if forming a film.
  • NuPlastiQ pellets may simply be stored in a sealed container with or without a desiccant in a dry location, away from heat to minimize water absorption, and to prevent undesired degradation.
  • NuPlastiQ may also be thixotropic, meaning that the material is solid at ambient temperature, but flows as a liquid when heat, pressure and/or frictional movement are applied.
  • pellets of NuPlastiQ can be used the same as petrochemical based pellets (any typical non- biodegradable plastic resin pellets) in standard plastic production processes.
  • NuPlastiQ materials and products made therefrom may exhibit gas barrier characteristics. Products (e.g., films) made using such pellets exhibit oxygen gas barrier characteristics (e.g., see Examples of Applicant’s previous filings, already incorporated by reference).
  • NuPlastiQ materials may be non-toxic and edible, made using raw materials that are all edible.
  • NuPlastiQ and products made therefrom may be water resistant, but water soluble.
  • NuPlastiQ may resist swelling under moist heated conditions to the point that pellets (e.g. with a size of 3-4 mm) thereof may not completely dissolve in boiling water within 5 minutes, but a pellet will dissolve in the mouth within about 10 minutes.
  • NuPlastiQ may be stable, in that it may not exhibit any significant retro gradation, even if left in relatively high humidity conditions, which characteristic differs from many other thermoplastic starch materials. Of course, products made with NuPlastiQ may also exhibit such characteristics. If NuPlastiQ is stored in humid conditions, the excess absorbed water can simply be evaporated away, and once the water content is no more than about 1%, it can be used in forming a film or other article.
  • the NuPlastiQ material also does not typically undergo biodegradation under typical storage conditions, even in relatively humid conditions, as the other conditions typical of a landfill, compost or similar disposal environment containing the particular needed microorganisms are not present. Of course, where such conditions are present, not only does the NuPlastiQ biodegrade, but otherwise non-biodegradable plastic materials blended therewith surprisingly also biodegrade.
  • NuPlastiQ can be cost competitive, being manufactured at a cost that is competitive with traditional polyethylene plastic resins.
  • NuPlastiQ can be mixed with other polymers, including, but not limited to PE, PP, PET, polyester, polystyrene, acrylonitrile butadiene styrene (ABS), polyvinyl chloride, nylon, and others.
  • NuPlastiQ can also be blended with polymers that already are biodegradable and/or compostable, such as polylactic acid (PLA), poly(butylene adipate-co-terephthalate) (PBAT), polybutylene succinate (PBS), polycaprolactone (PCL), polyhydroxyalkanoates (PHA), other so-called thermoplastic starches, as well as various others.
  • PBS, PCL, and PHA are polyesters.
  • EcoFLEXTM plastic, PBAT is an example of a plastic material with which the NuPlastiQ carbohydrate-based polymeric material may be blended.
  • the present methods are not limited to blending the carbohydrate-based polymeric material (e.g., NuPlastiQ) with only a non-biodegradable plastic material, as it will be appreciated that biodegradable plastics (other than NuPlastiQ) can also be incorporated into the blend, if desired.
  • carbohydrate-based polymeric material e.g., NuPlastiQ
  • biodegradable plastics other than NuPlastiQ
  • PLA is compostable, meaning that it can degrade under elevated temperature conditions (i.e., composting conditions), but is technically not “biodegradable”.
  • Some of the above listed materials, such as PBS, PCL, and PHA may be both biodegradable and compostable.
  • EcoFLEXTM PBAT
  • FTC Green guidelines stipulate that a plastic cannot make an unqualified claim that it is “degradable” unless it will degrade within a“reasonably short period of time” (most recently defined as within 5 years)“after customary disposal”.
  • the NuPlastiQ could be provided in a masterbatch formulation that may 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 masterbatch may also include one or more non-biodegradable plastic materials.
  • Such masterbatch formulation pellets could be mixed with pellets of the non- biodegradable plastic material at the time of processing. Any conceivable ratios may be used in mixing such different pellets, depending on the desired percentage of NuPlastiQ and/or compatibilizer and/or conventional non-biodegradable plastic material in the finished article.
  • a masterbatch comprising the non-biodegradable plastic and one or more of the degradation additives may be provided.
  • NuPlastiQ includes very low water content.
  • raw starch e.g., used in forming NuPlastiQ
  • the finished NuPlastiQ pellets available from BioLogiQ include less than about 1% water.
  • NuPlastiQ materials are biodegradable, and as described herein, not only is the starch-based NuPlastiQ material biodegradable, but when blended with other polymers, such as non-biodegradable PE, PP, PET, polyester, polystyrene, ABS, polyvinyl chloride, nylon, and other non- biodegradable plastic materials, the blended material which includes NuPlastiQ and the one or more degradation additives becomes substantially entirely biodegradable, particularly when the degradation additives as described herein are present. Such results are quite surprising, and particularly advantageous. Typical thermoplastic starch materials do not exhibit such characteristics when blended with other plastic materials.
  • the NuPlastiQ materials described as suitable for use herein as the carbohydrate- based (e.g., starch-based) polymeric material are substantially amorphous.
  • raw starch powder e.g., such as is used in making NuPlastiQ and various other thermoplastic starch materials
  • TPS thermoplastic starch
  • the NuPlastiQ materials that are suitable examples of starch-based polymeric materials for use in forming articles described in the present application have an amorphous microstructure, and physical characteristics.
  • the difference in the molecular structure between conventional TPS and NuPlastiQ materials is evidenced by the NuPlastiQ materials as described herein being much less crystalline than conventional thermoplastic starch-based materials as shown by X-ray diffraction, shown in FIG. 3, comparing diffraction pattern results for NuPlastiQ material available from BioLogiQ as compared to a blend of native raw corn starch and native raw potato starch from which the NuPlastiQ in FIG. 3 was formed.
  • the diffraction pattern of the NuPlastiQ as seen in FIG. 3 is much less crystalline (e.g., crystallinity of less than about 10%) than that of the native starch blend (crystallinity of about 50%).
  • the difference in diffraction pattern evidences that a substantial chemical change has occurred in the material, due to processing from the native starches into NuPlastiQ. For example, while there is a prominent diffraction peak between 20-25° with the native starch, no such peak is exhibited in the NuPlastiQ.
  • the native starch further shows a strong peak at about 45° (at an intensity of 0.5 to 0.6), which peak is greatly reduced in the NuPlastiQ (only of about 0.25 to 0.3).
  • the diffraction intensities are higher for the native starches than for the NuPlastiQ, with the exception of from about 18° to about 22°, as shown.
  • the elevated diffraction intensity seen across a wide spectrum is indicative of greater crystallinity of the native starches as compared to the NuPlastiQ. Numerous other differences also exist, as shown.
  • the carbohydrate-based (e.g., starch-based) polymeric material used in making 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 for determining crystallinity may be used, e.g., including but not limited to FTIR analysis, X-ray diffraction methods, and symmetrical reflection and transmission techniques. Various suitable test methods will be apparent to those of skill in the art.
  • blending of the carbohydrate-based polymeric materials and degradation additive with a non-biodegradable plastic material results in not just the carbohydrate-based material being biodegradable, but the non-biodegradable plastic material actually becomes biodegradable (even where the non-biodegradable plastic material alone is not significantly otherwise biodegradable). Such results do not occur when blending with typical TPS materials.
  • Such differences in biodegradability clearly illustrate that there are significant structural and/or chemical differences in the resulting films and other articles, as the entire composite structure (i.e., the film or other structure) is now capable of being biodegraded.
  • the carbohydrate- based polymeric resin may reduce the crystallinity of the blended products, interrupting the crystallinity and/or hygoscopic barrier characteristics of the polyethylene or other non-biodegradable plastic material in a way that allows water and bacteria to degrade the arrangements and linkages of otherwise non-biodegradable plastic molecules of the blend along with the carbohydrate-based polymeric resin material.
  • the long polymer chains of polyethylene 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 blended with carbohydrate-based polymeric materials as contemplated herein.
  • the microorganisms that exist naturally in a disposal environment can consume the remaining smaller molecules so that they are converted back into natural components (such as C0 2 , CEE, and FhO). It is believed that this degradation effect is enhanced when the plastic component (PE, PP, etc) is fragmented by action of the OXO additive, as the fragments are more accessible to microbes in the soil, landfill, etc., than they would otherwise be.
  • a degradation additive as described herein such as an organic additive that attracts microorganisms is also present
  • the biodegradation of the plastic material is further enabled by action of the microorganisms.
  • the 0X0 additives increase the surface area of the non-biodegradable polymer subject to attack by microorganisms.
  • biodegradable plastics decompose into natural elements or compounds such as carbon dioxide, methane, water, inorganic compounds, or biomass via microbial assimilation (e.g., the enzymatic action of microorganisms on the plastic molecules).
  • Biodegradation of plastics can be enabled by first breaking down the polymer chains via either chemical or mechanical action but may only be fully accomplished through decomposition of the molecules by microbial assimilation.
  • Plastics made from petrochemical feedstocks or derived from plant sources begin life as monomers (e.g., single small molecules that can react chemically with other small molecules). When monomers are joined together, they become polymers ("many parts"), and may be known as plastics. Before being joined together, many monomers are readily biodegradable, although after being linked together through polymerization, the molecules become so large and joined in such arrangements and linkages that microbial assimilation by microorganisms is not practical within any reasonable time frame in most instances. However the NuPlastiQ compositions with the degradation additive of this invention impart increased biodegradability.
  • Polymers are formed with both crystalline (regularly packed) structures and amorphous (randomly arranged) structures. Many polymers contain a high degree of crystallinity with some amorphous regions randomly arranged and entangled throughout the polymeric structure.
  • NuPlastiQ materials available from BioLogiQ are formed from starting starch materials which are highly crystalline, but in which the finished NuPlastiQ plastic resin material exhibits low crystallinity (substantially amorphous). Such starch-based polymer materials are used as a starting material in the production of articles as described herein. NuPlastiQ is, therefore, plastic that is made from starch. Because of its natural, starch-based origin and carefully controlled linkage types, the molecules (size and links) of plastic made with NuPlastiQ are highly susceptible to biodegradation by enzymatic reactions caused from the introduction of humidity (water) and bacteria or other microorganisms. The presence of the degradation additives describes herein enhances further enhances this biodegradation.
  • Polyolefins such as rigid forms of polyethylene and polypropylene have a high degree of crystallinity and are made by converting monomer molecules (whether petroleum derived or derived from ethanol or other small building block molecules derived from plant sources) into long chain polymers. 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 given article were formed from a blend of conventional non-biodegradable plastic material and conventional TPS, it would not normally suddenly acquire biodegradability characteristics (other than the starch portion of the blend which may sometimes biodegrade).
  • Applicant has developed a process for lending biodegradability to an otherwise non- biodegradable plastic material by blending such plastic material with the carbohydrate- based polymeric materials having low crystallinity e.g. NuPlastiQ.
  • the invention of this application facilitates further biodegradation by adding a degradation additive to the materials blended, such as an OXO additive or chemical material as described herein.
  • a degradation additive such as an OXO additive or chemical material as described herein.
  • the non-biodegradable plastic material has higher crystallinity (e.g., particularly in the case of PE or PP).
  • the resulting blend may often have a higher elastic modulus (stiffness, or strength) than polyethylene or other non-biodegradable plastic material, and can be used to make plastic films or other articles that are stronger than the same articles made with pure polyethylene or other pure non-biodegradable plastic material.
  • a higher elastic modulus stiffness, or strength
  • Such increased strength characteristics are described in ET.S. Patent Application Nos. 14/853,725 and 15/481,806, already incorporated herein by reference.
  • the process 100 includes mixing the one or more non- biodegradable plastic materials, the one or more degradation additives and the one or more carbohydrate-based polymeric materials (NuPlastiQ) to produce a mixture of materials.
  • 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 using one or more mixing devices.
  • 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(s).
  • At least a portion of the components of the mixture of the materials 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 mixture of the materials can be combined before being fed into the apparatus.
  • the one or more carbohydrate-based polymeric materials and degradation additives can be present in the mixture of materials in an amount sufficient to lend biodegradability to the particular non-biodegradable plastic material that the carbohydrate-based polymeric material is blended with.
  • Such threshold level of the carbohydrate-based polymeric material may depend on the material they are being blended with.
  • 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%, no greater than 99%, no greater than 95%, no greater than 90%, no greater than 80%, no greater than 70%, no greater than 60%, no greater than 50%, from 2% to 98%, from 20% to 40%, from 10% to 40%, from 20% to 30%, from 50% to 80%, or from 40% to 60% by weight of the mixture of materials. More than one carbohydrate-based polymeric material, and/or more than one other plastic material may be included in the blend, if desired.
  • 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 greater than 99%, no greater than 95%, no greater than 90%, no greater than 85%, no greater than 80%, no greater than 75%, no greater than 70%, no greater than 65%, or no greater 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.
  • the degradation additives may 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 2%, at least 4% at least 5%, no greater than 10 %, , from 0.5% to 2%, from 1.5% to 2.5% by weight of the mixture of materials.
  • a compatibilizer may be present in the mixture of materials.
  • the compatibilizer can be mixed with the non-biodegradable plastic material, the carbohydrate-based polymeric material, mixed with both, or provided separately. Often the compatibilizer may be provided with at least one of the polymeric materials, e.g., included in a masterbatch formulation.
  • the compatibilizer can be a modified polyolefin or other modified plastic, such as a maleic anhydride grafted polypropylene, a maleic anhydride grafted polyethylene, a maleic anhydride grafted polybutene, or a combination thereof.
  • the compatibilizer can also include an acrylate based co-polymer.
  • the compatibilizer can include an ethylene methyl acrylate co-polymer, an ethylene butyl-acrylate co-polymer, or an ethylene ethyl acrylate co-polymer.
  • the compatibilizer can include a poly(vinylacetate) based compatibilizer.
  • the compatibilizer may be a grafted version of the non- biodegradable plastic material (e.g., maleic anhydride grafted polyethylene where the non- biodegradable plastic material is polyethylene) or a copolymer (e.g., a block copolymer) where one of the blocks is of the same monomer as the non-biodegradable plastic material (e.g., a styrene copolymer where the non-biodegradable plastic material is polystyrene or ABS).
  • the non- biodegradable plastic material e.g., maleic anhydride grafted polyethylene where the non- biodegradable plastic material is polyethylene
  • a copolymer e.g., a block copolymer where one of the blocks is of the same monomer as the non-biodegradable plastic material (e.g., a styrene copolymer where the non-biodegradable plastic material is polystyrene or ABS).
  • the mixture of materials may include at least 0.5%, at least 1%, at least 2%, at least
  • One or more additional additives as known to be useful in the plastics’ industry can be included in the mixture of materials in an amount of at least 0.5%, at least 1%, at least 1.5%, at least 2%, at least 2.5%, at least 3%, at least 4%, of no greater than 10%, no greater than 9%, no greater than 8%, no greater than 7%, no greater than 6%, no greater than 5%, from 0.2% to 12%, from 1% to 10%, from 0.5% to 4%., or from 2% by weight to 6% by weight of the mixture.
  • thermoplastic materials that can be melted together, to form a desired blend
  • the resin components that are precursors of such non-thermoplastic non-biodegradable plastic material may be blended with the carbohydrate-based polymeric material, where polymerization or other formation of the non-thermoplastic material may occur in the presence of the carbohydrate-based polymeric material and the degradation additive(s), resulting in a finished article that is a blend of the carbohydrate-based polymeric material, the degradation additive(s), and a thermoset or other non-thermoplastic plastic material, where the carbohydrate-based polymeric material and additive(s) may lend biodegradability to the non-thermoplastic plastic material upon blending of the two together.
  • the process 100 may include heating the mixture of materials.
  • the mixture of materials can be heated to a temperature of at least l00°C, at least 1 l0°C, at least H5°C, at least l20°C, at least 125 °C, at least l30°C, at least l35°C, at least l40°C, no greater than 250°C, no greater than l90°C, no greater than l80°C, no greater than l75°C, no greater than l70°C, no greater than l65°C, no greater than l60°C, no greater than l55°C, no greater than l50°C, from 95°C to 250°C, from l20°C to l80°C, or from l25°C to l65°C.
  • the mixture of materials including the ordinarily non-biodegradable plastic material and the carbohydrate-based polymeric material and degradation additive(s) can be heated in one or more chambers of an extruder. In some cases, one or more chambers of the extruder can be heated at different temperatures. The speed of one or more screws of the extruder can be any desired rate.
  • an article is produced using the mixture of materials including NuPlastiQ and the degradation additive.
  • the article can include a film.
  • the article can be formed from a film.
  • the article can have a shape based on a design, such as a mold (e.g., injection molded). Any conceivable article formed of plastic may be formed from the mixture, e.g., including but not limited to films, bags, bottles, caps, lids, sheets, boxes, plates, cups, utensils, and the like.
  • the film can be formed using a die by injecting a gas into the heated mixture of 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 article.
  • the film can be comprised of a single layer or multiple layers.
  • the film or any individual layers can 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, no greater than 2 mm, no greater than 1 mm, no greater than 0.5 mm, no greater than 0.1 mm, from about 0.05 mm to about 0.5 mm, or from 0.02 mm to 0.05 mm. While there may be some overlap in thickness values for film and sheet articles, it will be appreciated that sheet materials of greater thickness than such film values may of course be provided, produced by any desired plastic manufacturing process.
  • Films or other articles can have strength characteristics that are characterized through testing, such as a dart drop impact test (ASTM D-1709), tensile strength at break test (ASTM D-882), tensile elongation at break test (ASTM D-882), a secant modulus test (ASTM D-882), and/or an Elmendorf Tear test (ASTM D-1922).
  • ASTM D-1709 dart drop impact test
  • ASTM D-882 tensile strength at break test
  • ASTM D-882 tensile elongation at break test
  • ASTM D-882 secant modulus test
  • Elmendorf Tear test ASTM D-1922
  • Films can have a dart 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 greater than 400 g, no greater than 375 g, no greater than 350 g, or no greater than 325 g, from 140 g to 425 g, from 200 g to 400 g, from 250 g to 350 g, from 265 g to 330 g.
  • such values may be for whatever the thickness of the film is.
  • such values may be for a 1 mil thickness film formed from the mixture of materials.
  • the article can have a tensile strength at break test value in the machine direction of at least 3.5 kpsi, at least 3.7 kpsi, at least 3.9 kpsi, at least 4.1 kpsi, at least 4.3 kpsi, or at least 4.5 kpsi, no greater than 5.5 kpsi, no greater than 5.3 kpsi, no greater than 5.1 kpsi, no greater than 4.9 kpsi, or no greater than 4.7 kpsi, from 3.5 kpsi to 5.5 kpsi, or from 4.1 kpsi to 4.9 kpsi.
  • the article can have a tensile strength at break test value in the transverse direction of at least 3.2 kpsi, at least 3.4 kpsi, at least 3.6 kpsi, at least 3.8 kpsi, at least 4.0 kpsi, at least 4.2 kpsi, no greater than 5.7 kpsi, no greater than 5.5 kpsi, no greater than 5.3 kpsi, no greater than 5.1 kpsi, no greater than 4.9 kpsi, no greater than 4.7 kpsi, no greater than 4.5 kpsi, from 3.2 kpsi to 5.7 kpsi, or from 3.6 kpsi to 5.0 kpsi.
  • the article can have a tensile elongation at break test value in the machine direction 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%, no greater than 725%, no greater than 710%, no greater than 700%, no greater than 680%, no greater than 665%, no greater than 650%, no greater than 635%, from 550% to 750%, or from 600% to 660%.
  • the article can have a tensile elongation at break test 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%, no greater than 770%, no greater than 755%, no greater than 740%, no greater than 725%, no greater than 710%, no greater than 695%, no greater than 680%, from 575% to 775%, or from 625% to 700%.
  • the article can have an Elmendorf tear force 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/mil, or at least 360 g/mil, no greater than 450 g/mil, no greater than 430 g/mil, no greater than 410 g/mil, no greater than 390 g/mil, or no greater than 370 g/mil, from 275 g/mil to 475 g/mil, or from 325 g/mil to 410 g/mil.
  • the article can have an Elmendorf tear force 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, at least 540 g/mil, or at least 550 g/mil, no greater than 700 g/mil, no greater than 680 g/mil, no greater than 650 g/mil, no greater than 625 g/mil, no greater than 600 g/mil, no greater than 580 g/mil, or no greater than 570 g/mil, from 475 g/mil to 725 g/mil, or from 490 g/mil to 640 g/mil.
  • the article can have a secant modulus of elasticity test value in the machine direction of at least 20 kpsi, at least 22 kpsi, at least 24 kpsi, at least 26 kpsi, at least 28 kpsi, or at least 30 kpsi, no greater than 40 kpsi, no greater than 38 kpsi, no greater than 36 kpsi, no greater than 34 kpsi, or no greater than 32 kpsi, from 20 kpsi to 40 kpsi, or from 25 kpsi to 35 kpsi.
  • the article can have a secant modulus of elasticity test value in the transverse direction of at least 20 kpsi, at least 22 kpsi, at least 24 kpsi, at least 26 kpsi, at least 28 kpsi, or at least 30 kpsi, no greater than 40 kpsi, no greater than 38 kpsi, no greater than 36 kpsi, no greater than 34 kpsi, or no greater than 32 kpsi, from 20 kpsi to 40 kpsi, or from 25 kpsi to 35 kpsi.
  • articles including a carbohydrate-based polymeric material formed from a mixture of two or more starches have values of strength properties that are greater than articles including a carbohydrate-based polymeric material formed from a single starch.
  • an article including a carbohydrate-based polymeric material formed from a mixture of two or more starches can have a dart drop impact test value (in grams or g/mil of thickness) that is at least about 10% greater than an article where the carbohydrate- based polymeric material is formed from a single starch, at least about 25% greater, at least about 50% greater, at least about 75% greater, from 10% greater to 150% greater or from 60% greater to 120% greater than the same article but including a carbohydrate-based polymeric material formed from a single starch.
  • the articles of this invention When subjected to biodegradation testing (e.g., whether biomethane potential testing, or any applicable ASTM standard, such as ASTM D-5511, ASTM D-5526, ASTM D-5338, or ASTM D-6691, the articles of this invention, including NuPlastiQ and the degradation additives significantly biodegrade. Under such testing, and within a given time period (e.g., 30 days, 60 days, 90 days, 180 days, 365 days (1 year), 2 years, 3 years, 4 years, or 5 years, the articles may show substantial biodegradation of the total polymeric content, and/or the non-biodegradable plastic content (apart from the carbohydrate-based polymeric content).
  • biodegradation testing e.g., whether biomethane potential testing, or any applicable ASTM standard, such as ASTM D-5511, ASTM D-5526, ASTM D-5338, or ASTM D-6691
  • the articles of this invention including NuPlastiQ and the degradation additive
  • Biomethane potential testing is typically conducted over 30 or 60 days, although sometimes for as long as 90 days. The longer time period tests are more typically performed under any of the above mentioned ASTM standards. Articles made from the compositions of this invention may show biodegradation that is greater than the carbohydrate-based polymeric material content thereof, indicating that the other plastic material(s) are also biodegrading (or exhibit the potential to biodegrade under a biomethane potential test).
  • the biodegradation can be greater than the weight percent of carbohydrate-based polymeric materials (NuPlastiQ) within the article.
  • carbohydrate-based polymeric materials and degradation additive(s) can result in at least some biodegradation of the non-biodegradable plastic material (which materials alone are not significantly biodegradable).
  • an article such as a film that is formed from a blend of the carbohydrate-based polymeric materials
  • the degradation additive(s) and PE may exhibit biodegradation after such periods of time that is greater than the weight fraction of the carbohydrate-based polymeric materials in the film, indicating that the PE (normally not thought to be biodegradable) is actually being biodegraded, with the carbohydrate-based polymeric material.
  • Biomethane potential testing determines the potential for anaerobic biodegradation based methanogenesis as a percent of total methanogenesis potential. Biomethane potential testing can be used to predict biodegradability of the tested samples according to the ASTM D-5511 standard and the biomethane potential testing can be conducted using one or more conditions from the ASTM D-5511 standard. For example, the biomethane potential testing can take place at a temperature of about 52°C. Additionally, the biomethane potential testing can have some conditions that are different from those of ASTM D-5511, e.g., to accelerate the test so to be completed within the typical 30, 60, or sometimes as long as 90 days.
  • Biomethane potential testing can employ an inoculum having from 50% to 60% by weight water and from 40% to 50% by weight organic solids.
  • an inoculum used in biomethane potential testing can have 55% by weight water and 45% by weight organic solids.
  • Biomethane potential testing can also take place at other temperatures, such as from 35°C to 55°C or from 40°C to 50°C.
  • an article made from the compositions of this invention having an amount of carbohydrate-based polymeric material, degradation additive and non-biodegradable plastic material as described herein can exhibit enhanced biodegradation, as a result of the introduction of the additive and carbohydrate-based polymeric material NuPlastiQ into the article.
  • the non-carbohydrate-based polymeric material may biodegrade over 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 subjected to landfill, composting, and/or marine conditions (or conditions simulating such). Such biodegradation is particularly remarkable and advantageous. Thus not only does the carbohydrate-based polymeric material biodegrade, but the non- biodegradable plastic material does as well.
  • the amount of biodegradation can be very high, such that in at least some implementations, substantially the entire article biodegrades (e.g., 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).
  • substantially the entire article biodegrades (e.g., 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).
  • FIG. 2 illustrates components of an example manufacturing system 200 to produce articles according to the present disclosure.
  • the manufacturing system 200 can be used in the process 100 of FIG. 1.
  • the manufacturing system 200 is an extruder, such as a single screw extruder or a twin screw extruder.
  • one or more non-biodegradable plastic materials, one of more degradation additives and one or more carbohydrate-based polymeric materials are provided via a first hopper 202 and a second hopper 204.
  • a compatibilizer may be included with either or both materials (e.g., in a masterbatch thereof).
  • the one or more carbohydrate-based polymeric materials, 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.
  • the mixture of materials can 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 the one or more non- biodegradable plastic materials, from 0.1 to 5% by weight of degrading additive and from 1% by weight to 9% by weight of the one or more compatibilizers.
  • the ranges of course may be varied outside the above ranges, depending on desired characteristics.
  • the mixture of materials can pass through a number of 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 mixture of materials can be heated in the chambers 206, 208, 210, 212, 214, 216.
  • a temperature of one of the chambers can be different from a temperature of another one of the chambers.
  • the first chamber 206 is heated to a temperature from l20°C to l40°C; the second chamber 208 is heated to a temperature from l30°C to l60°C; the third chamber 210 is heated to a temperature from l35°C to l65°C; the fourth chamber 212 is heated to a temperature from l40°C to l70°C; the fifth chamber 214 is heated to a temperature from l45°C to l80°C; and the optional sixth chamber 216 is heated to a temperature from l45°C to l80°C.
  • the heated mixture can then be extruded using a die 218 to form an extruded object, such as a film, sheet, or the like.
  • an extruded object such as a film, sheet, or the like.
  • Injection molding, thermoforming, or other plastic production processes may be used to manufacture various articles such as utensils, plates, cups bottles, caps or lids therefore, or the like.
  • a gas can be injected into the extruded object to expand it with a pressure from 105 bar to 140 bar.
  • the resulting tube 220 can be drawn up through rollers 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).
  • the film 224 can be comprised of a single layer. In other cases, the film 224 can be comprised of multiple layers. Where multiple layers are present, at least one of the layers may include the carbohydrate-based polymeric material and the degradation additive. In some embodiments, the carbohydrate-based polymeric material and degradation additive may be present in one or more outer layers. In another embodiment, the carbohydrate-based polymeric material and additive may be present in an inner layer. Where no carbohydrate- based polymeric material is included in the outer layer(s), biodegradation of the outer layer(s) may not occur.
  • Samples with compositions shown in Table 2 are tested for about 180 days to determine biodegradability characteristics using biomethane potential for anaerobic biodegradation based on methanogenesis as a percent of total methanogenesis potential.
  • the biomethane potential test is intended to determine whether the materials tested exhibit any significant potential for biodegradation. Such may be conducted at a temperature of about 52°C using an inoculum having about 55% by weight water and about 45% by weight organic solids. The test is carried out in accordance with ASTM D-5511 for 180 days. A positive control of cellulose and a negative control of 100% polyethylene is used for comparison.
  • the positive sample substantially degrades and the negative control sample shows little or no degradation.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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Abstract

L'invention concerne des procédés permettant de rendre biodégradable un matériau plastique qui n'est pas lui-même biodégradable, par mélange du matériau plastique avec un matériau polymère à base de glucide formé à partir a) d'un ou de plusieurs amidons et d'un plastifiant (par exemple, de la glycérine), b) d'un additif connu dans l'état de la technique sous la forme d'un matériau OXO et/ou d'un additif interagissant avec des microbes qui contribuent à la biodégradation du matériau non biodégradable. Le matériau polymère à base de glucide est moins cristallin que les matériaux non biodégradables, par exemple, car il est sensiblement amorphe, et présente une cristallinité inférieure ou égale à 20 %. Lorsqu'il est testé dans des conditions provoquant une biodégradation, le mélange se dégrade biologiquement dans une mesure supérieure à la teneur en polymère à base de glucide.
PCT/US2019/028733 2018-04-23 2019-04-23 Ajout d'additifs conférant une biodégradabilité à des matières plastiques WO2019209834A1 (fr)

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BR112020021530-9A BR112020021530A2 (pt) 2018-04-23 2019-04-23 Adição de aditivos que conferem biodegradabilidade aos materiais plásticos
KR1020207033615A KR20210024448A (ko) 2018-04-23 2019-04-23 플라스틱 물질로의 생분해성 부여 첨가제의 추가
EP19793589.3A EP3784732A4 (fr) 2018-04-23 2019-04-23 Ajout d'additifs conférant une biodégradabilité à des matières plastiques
JP2020558940A JP2021523957A (ja) 2018-04-23 2019-04-23 プラスチック材料に生分解性を付与する添加剤の添加
CN201980042207.6A CN112513168A (zh) 2018-04-23 2019-04-23 将生物降解性助剂添加到塑料材料中

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US62/661,387 2018-04-23

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JP2024060282A (ja) * 2022-10-19 2024-05-02 国立大学法人高知大学 フィラー、環境適合性プラスチック、環境適合性プラスチック繊維、およびｐｇａイオンコンプレックスの使用

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CN115052925B (zh) * 2020-02-28 2024-05-10 伊利诺斯工具制品有限公司 可生物降解的多重包装件载体
JP2023016665A (ja) * 2021-07-21 2023-02-02 南亞塑膠工業股▲分▼有限公司 生分解性組成物、生分解性ラップフィルム及びその製造方法
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CN116855403B (zh) * 2023-06-08 2024-05-28 上海交通大学 降解聚氯乙烯的芽孢杆菌pvc-6b及其生产的菌剂与应用

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EP3784732A4 (fr) 2022-01-19
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CN112513168A (zh) 2021-03-16
BR112020021530A2 (pt) 2021-01-19

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