HK1199276B - Chemical additives to make polymeric materials biodegradable - Google Patents

Abstract

The present invention is a new additive material that is physically blended with polymeric material to create at least a partially biodegradable product.

Description

Chemical additives for making polymeric materials biodegradable

The application is a divisional application of an application named as chemical additive for making polymer materials biodegradable, wherein the PCT international application date is 2007/US 2007/083245, the PCT international application number is 200780044197.7, and the PCT international application number is 31/10, 2007.

Cross Reference to Related Applications

This application relates to U.S. provisional application serial No. 60/855,430 entitled "Chemical Additives to Make biodegradable Polymeric materials" filed by John a. lake, equal to 31/10/2006, and the specification of which is incorporated herein by reference.

Background

Field of the invention (technical field):

the present invention relates to a novel additive material that is physically blended with a polymeric material to impart biodegradability to an article formed from the polymeric material.

Plastics are produced industrially in large quantities and are at the same time widely used in everyday life and industrial fields as their use increases greatly. It is desirable to produce plastics that withstand the forces of nature. Many plastics do not degrade in the natural environment, and therefore in recent years, environmental pollution and destruction due to discarded plastics have occurred. Therefore, in recent years, it has been desired to develop plastics that can be biodegraded in the natural environment.

Us patent 7,037,983 issued to Huang et al on 5/2/2006 teaches a method of preparing functional biodegradable polymers and a method of modifying biodegradable polymers using direct chemical reaction of biodegradable polymers in vinyl monomers. Huang chemically incorporates the additive material into the chemical chain of the polymer.

U.S. patent application publication 2004/0076778 teaches a biodegradable bag that is taught to include a laminated film obtained by the following process: laminating a sealing layer comprising a biodegradable polymer, a barrier layer having oxygen barrier properties and water vapor barrier properties, and a substrate layer comprising a support barrier layer comprising a biodegradable polymer, said laminated film being heat-sealed so that the sealing layer is inside. Seed microorganisms (seed microbes) for degrading the polymers in the layer are not taught.

U.S. patent application publication 2004/0068059 teaches that a mixture made of three components, an aliphatic diol, an aliphatic dicarboxylic acid and an aliphatic hydroxycarboxylic acid or its anhydrous cyclic compound (lactone), is subjected to polycondensation to synthesize a low molecular weight polyester copolymer having a weight average molecular weight of 5,000 or more, preferably 10,000 or more, and a bifunctional coupling agent is added to the polyester copolymer in a molten state. Further, a high molecular weight aliphatic polyester copolymer containing polylactic acid and a high molecular weight aliphatic polyester. These copolymers can be degraded by microorganisms present in soil or water.

U.S. patent application publication 2003/0157214 teaches a composition of graft copolymers of polyhydroxy compounds. The composition provides an efficient method for manufacturing environmentally friendly chewing gum.

Furanone (furanone) derived compositions are known in the art to have a variety of applications. For example, U.S. patent 6,296,889 describes the use of certain furanone compounds in conjunction with 1-nonen-3-one to enhance the aroma of dairy and coffee. Specific furanones (e.g., 3, - (3, 4-difluorophenyl) -4- (4- (methylsulfonyl) phenyl) -2- (5H) -furanone, 3-phenyl-4- (4- (methylsulfonyl) phenyl) -2- (5H) -furanone, and 5, 5-dimethyl-4- (4- (methylsulfonyl) phenyl) -3- (3-fluorophenyl) -5H-furan-2-one) have been shown to be cyclooxygenase-2 (COX-2) inhibitors for the treatment of certain inflammatory disorders (U.S. patent 5,474,995, U.S. patent 6,239,173). The versatility of the use of furanone derivatives is further illustrated by the discovery of certain halogenated furanones isolated from the australian red seaweed Delisea nulcha as marine antifouling agents capable of preventing the growth of various seaweeds, invertebrates and bacteria on marine structures (U.S. patent No. 6,060,046).

U.S. patent 5,599,960 issued to Boden et al on 4.2.1997 teaches a mixture of 3, 5-dimethyl-pentenyl-dihydro-2 (3H) -furanone isomers with organoleptic properties. The mixture has a sweet, lactonic, tonka-bean jasmine fragrance accompanied by a strong green (green), citrus, sweet, lactonic top note and lemon peel and lemon base note and is a pleasant smell. Such fragrances are highly desirable in several types of perfume compositions, perfume products, colognes, deodorant compositions and odor masking agent compositions.

Summary of The Invention

One embodiment of the present invention provides a biodegradable additive for a polymeric material, the biodegradable additive comprising: a chemoattractant compound; glutaric acid or derivatives thereof; carboxylic acid compounds having a chain length of 5 to 18 carbon atoms; a polymer; and a swelling agent. Furthermore, the additive may additionally comprise one or more of the following: microorganisms that can digest the polymeric material, compatibilizing additives, positive chemotactic agents for attracting microorganisms, metals for inducing rust, colorants, and/or inks, and/or metal particles for increasing or decreasing light reflection, increasing strength, slowing or preventing the destruction of the layer or altering the time of destruction, or carrier resins.

In a preferred embodiment, the polymer is selected from polydivinylbenzene, ethylene vinyl acetate copolymer, polyethylene, polypropylene, polystyrene, polyterephthalate, polyester, polyvinyl chloride, polymethyl methacrylate, polycarbonate, polyamide, and any copolymer of said polymers.

In a preferred embodiment, the carrier resin is selected from polydivinylbenzene, ethylene vinyl acetate copolymer, maleic anhydride, acrylic acid with polyolefin.

In a more preferred embodiment, the microorganisms and furanones are disposed in a capsule to facilitate controlled release of the material.

The furanone may be, for example, 2(3H) -furanone having methane, dihydro-4, 5-dimethyl, 3, 4, 5-trimethyl-5H-furan-2-one compound, but is not limited thereto.

In accordance with another embodiment, a method for forming a layered polymer plastic is disclosed, the method comprising: providing at least one layer of a polymer; and layering a product around the polymer to form a new biodegradable product. In a preferred embodiment, one layer comprises a microorganism suitable for degrading a polymer. In a preferred embodiment, the microorganisms are coated on the at least one layer using a vapor deposition process. In a more preferred embodiment, the laminae are biaxially oriented. In another preferred embodiment, the layering is shaped like a honeycomb hexagonal shape. In an alternative embodiment, the inner layer is rigid with respect to mechanical stress. In yet another alternative embodiment, at least one layer comprises a perfume. In a preferred embodiment, at least one layer is one or more of the following: odor attractants for microorganisms, initiators for modified polymers, having perforations.

In response to the need for better and more efficient ways to make polymeric materials biodegradable, the present invention teaches how to make additive materials and how to efficiently use these materials to make polymeric materials biodegradable.

It is therefore an object of the present invention to make a variety of polymeric materials biodegradable, regardless of their chemical composition.

It is a further object of the present invention to prepare a biosafety and biodegradable polymeric material without having to chemically modify the polymer molecules.

It is another object of the present invention to provide an additive material that can be made biodegradable for most polymeric compositions by merely mixing the additive material with the polymeric material at any time prior to the polymeric material being formed into an article for sale.

One aspect of the present invention provides controlled release techniques for controlled release of fragrance into a gaseous environment during polymer degradation.

These and other objects of the present invention will become apparent to those skilled in the art upon review of this specification and the claims appended hereto.

Brief Description of Drawings

Figure 1 illustrates one embodiment of making a polymer biodegradable with layering of additives.

Figure 2 illustrates size exclusion chromatography of a polymer composite in the presence and absence of an additive.

Detailed Description

As used herein, "1 (a)" means one or more.

As used herein, a "chemoattractant" is an inorganic or organic substance that has a chemotactic inducer effect in motile cells.

As used herein, a "polymer" is a synthetic and/or natural macromolecule composed of smaller units called monomers that are linked together.

Polymer and method of making same

Polymers are synthetic and natural macromolecules consisting of smaller units called monomers linked together. Thermoplastics are a class of polymers that can be melted or deformed, melted to a liquid when heated, and solidified to a brittle, very glass-like state when cooled sufficiently. Most thermoplastics are high molecular weight polymers whose chains are linked by: weak van der waals forces (e.g., polyethylene); strong dipole-dipole interactions and hydrogen bonding (e.g., polyamides); or a stack of aromatic rings (e.g., polystyrene). Thermoplastic polymers are distinguished from thermoset polymers in that, unlike thermoset polymers, they can be remelted and remolded. Many thermoplastic materials are addition polymers; such as vinyl chain-growth polymers such as polyethylene and polypropylene.

The major types of thermoplastics include linear low density polyethylene, high density polyethylene, polyvinyl chloride, low density polyethylene, polypropylene, polystyrene, and other resins. The main classes of thermosetting polymer resins include polyesters, one of which is polyethylene terephthalate and polyurethane.

Certain polymers are taught in the literature as not biodegradable or only very slowly biodegradable. A preferred embodiment of the present invention enables a broader range of polymers to be biodegraded to such a range, significantly reducing their environmental impact without adversely affecting their desirable physical properties.

These polymers include polystyrene, polyurethane, polyethylene, polypropylene, or polycarbonate plastic. Polymers made from groups such as aldehyde, methyl, propyl, ethyl, benzyl, or hydroxyl, and petroleum-based polymers are also taught as being non-biodegradable. One embodiment of the present invention is to increase the biodegradability of a non-biodegradable polymer by adding a biodegradable polymer additive to the polymer composition.

Biodegradable polymers

Biodegradation is generally understood to consist of enzymatic hydrolysis, non-enzymatic hydrolysis or both. The enzyme may be an endo-enzyme that cleaves an internal strand bond within the strand, or an exo-enzyme that cleaves a terminal monomer unit sequentially.

Biodegradation is a functional decline of a material, for example a decrease in the known, determinable strength, substance, transparency or good dielectric properties of a material when exposed to a living environment, which itself can be very complex, and the decrease in said properties can be attributed to physical or chemical actions as a primary step in the fine processing chain.

A biodegradable polymer is a high molecular weight polymer that degrades to lower molecular weight compounds due to the action of microorganisms and/or macroorganisms or enzymes. Natural polymers are defined as those biosynthesized by different routes in the biosphere. Of these, proteins, polysaccharides, nucleic acids, lipids, natural rubber and lignin are biodegradable polymers, but the rate of such biodegradation can vary from hours to years, depending on the nature of the functional groups and the degree of complexity. Biopolymers are organized in different ways in different proportions. This hierarchical architecture of natural polymers allows the formation of polymers that are truly environmentally adaptable using relatively few starting molecules (i.e., monomers) that vary in order and configuration on molecular, nanometer, micro, and macro scales.

In another aspect, the repeat units of the synthetic polymer are hydrolyzable, oxidizable, thermally degradable, or otherwise degradable. Natural polymers also use these degradation modes, e.g. oxidation or hydrolysis, so there is no difference between natural and synthetic polymers in this sense. Catalysts that promote degradation (catabolism) in nature are enzymes, which are divided into six different classes depending on the reactions catalyzed. These include oxidoreductases for catalyzing redox reactions, transferases for catalyzing transfer reactions of functional groups, hydrolases for catalyzing hydrolysis, lyases for catalyzing reactions that add double bonds, isomerases for catalyzing isomerization reactions and ligases for catalyzing the formation of new bonds using ATP.

The oxidizable polymers typically biodegrade slower than the hydrolyzable polymers. Even polyethylene, which is rather inert towards direct biodegradation, shows biodegradation after initial photooxidation. Oxidized polymers are more brittle and hydrophilic than non-oxidized polymers, which also generally results in materials with increased biodegradability. According to one embodiment of the present invention, means are provided for accelerating the oxidation of a polymer (e.g., a polyolefin).

For example, by combining nickel dithiocarbamate (photo antioxidant) and iron dithiocarbamate (photo pro-oxidant), a wide range of embrittlement times can be obtained.

One embodiment of the present invention provides increased susceptibility to biodegradation of the polymer by way of an additive comprising a biopolymer. In this way, a polymer blend is obtained which is more sensitive to biodegradation.

Granular starch mixed with polyethylene is combined with an unsaturated polymer, a thermal stabilizer and a transition metal to produce a material with increased susceptibility to photo-oxidation, pyrolysis and biodegradation. This particular material also has an induction time before degradation may begin. However, the use of starch alone in, for example, polyethylene requires a considerable amount in order to actually cause an increase in the rate of biodegradation.

According to one embodiment, fillers are added to the composition to be added to the polymer to increase biodegradability.

Microbial or enzymatic attack of pure aromatic polyesters is increased by exposure to certain microorganisms such as trichosporium (trichosporium), arthrobacter (athroberia) and Asperyillus negs.

The degradation of aliphatic polyesters can be seen as a two-step process: the first step is depolymerization, or surface etching. The second step is enzymatic hydrolysis, which produces a water-insoluble intermediate that can be assimilated by the microbial cells.

Polyurethane degradation can occur by fungal degradation, bacterial degradation, and degradation by polyurethane enzymes.

Microorganisms

Various microorganisms, including bacteria and fungi, help degrade polymeric materials. Preliminary examination of cellulose, Plastic and Rubber Materials in Waste separation Isolation test plants, and Possible Effects of Magnesium Oxide Safety Factor Calculations, for U.S. EPA irradiation and Indoor Air Office preparations (Preliminary Review of the differentiation of cellular, Plastic, and Rubber Materials in the Water insulation Pilot Plant, and Point Effects of Magnesium Oxide Safety Factor calculation, Preliminary for U.S. EPA Office of Radiation and index Air) (2006, 9, 11). Actinomycetes are a class of bacteria that are predominantly found in soil and can grow in low nutrient environments. They can survive, although mostly aerobic, under both aerobic and anaerobic conditions. The most important role of actinomycetes is to break down organic nutrients such as cellulose, and they are one of the few bacteria that can consume lignocellulose.

Fungi (molds) generally require oxygen and a pH range of 4.5 to 5 to proliferate. The fungus grows at a temperature of up to 45 c, although the most suitable growth rate typically occurs at a temperature between 30 c and 37 c. Since most fungi require oxygen, they may only be suitable for cellulose, plastic or rubber (CPR) degradation before termination and for a relatively short time (composting environment). There is some evidence that anaerobic fungi can degrade lignocellulosic materials.

Biodegradation can affect the polymer in a number of ways. Microbiological processes that can affect polymers include mechanical damage caused by cell growth, direct enzymatic action leading to disruption of the polymer structure, and secondary biochemical actions caused by excretion of substances other than enzymes, which can directly affect the polymer or alter environmental conditions, such as pH or redox conditions. Although microorganisms such as bacteria are often very specific to the substrate used for growth, many can be adapted to other substrates over time. Microorganisms produce enzymes that catalyze reactions by binding to specific substrates or combinations of substrates. The conformation of these enzymes determines their catalytic reactivity towards polymers. Changes in pH, temperature and other chemical additives may induce conformational changes in these enzymes.

Microbial and plastic degradation

For enzymatic degradation of synthetic plastic polymers, polymers containing hydrolysable groups in the polymer backbone will be particularly prone to microbial attack, as many microorganisms are capable of producing hydrolytic enzymes (enzymes that catalyze hydrolysis). In general, aliphatic polyesters, polyurethanes, polyethers, and polyimides are more susceptible to degradation by commonly occurring microorganisms. Generally, higher molecular weight polymers and branched polymers are more resistant to microbial degradation. Polyethylene and polyvinyl chloride are considered to be relatively resistant to microbial degradation. However, some strains have been identified that can degrade polyethylene, including rhodococcus and brevibacillus borstelensis (b.borstelensis).

In any assessment of microbial degradation of plastic materials, the ability of the microbes to adapt to new nutrient sources is very significant. Evidence of bacterial adaptation to plastic degradation has been shown in some cases. For example, it was found that the bacterium began to proliferate after 56 days of contacting Pseudomonas aeruginosa with polyamide-6 polymer. Inoculation of the previously untreated polyamide with these bacteria resulted in immediate growth on the new substrate. A single species of bacteria can perform several different steps of chemical destruction or biodegradation. Most toxic compounds are degraded or biodegraded by groups of so-called consortia (consortia). Each of the groups functions at a particular stage of the degradation process and one or more of them are required together to complete the degradation or biodegradation or detoxification process. Contaminated containers containing such things as pesticides, metals, radioactive elements, mixed waste, etc. can be used to contain microorganisms that will detoxify and break down the contaminants and biodegrade the container.

Other microorganisms which may contribute to biodegradation are psychrophiles, mesophiles, thermophiles, actinomycetes, saprophytes, Pythium humicolata, acremonium, Alternaria, agarichum, arthrinium, ascospores, Aspergillus spp., Aspergillus caesiellus, Aspergillus candidus, Aspergillus carneus, Aspergillus clavatus, Aspergillus deflectus, Aspergillus flavus, Aspergillus fumigatus, Aspergillus glaucus, Aspergillus nidulans, Aspergillus ochraceus, Aspergillus oryzae, Aspergillus parasiticus, Aspergillus penicilloides, Aspergillus restrictus, Aspergillus sydowi, Aspergillus terreus, Aspergillus ustus, Aspergillus versicolor, Aspergillus/Penicillium analogs, aureobasidium, Basidiomycetes, Tetrabosporium, Bipolar mould, Bacillus sp., Brevibacillus borsteum, Gray sp., Candida sp., Chaetomium sp., Cladosporium fulvum, Cladosporium herbarum, Cladosporium macrocarum, Cladosporium sphaerosporium, conidia, conidobolus, Cryptococcus neoformans, Cryptostroma corticale, Cunninghamella, curvularia, dreschellera, epicoccum, epidermophyton, fungi, Fusarium solanaceous, Geomyces sp., Mucorymus, helicomyces, bipolaris, Histoplasma histolytica, humilla, hyphalema mycelia, membranaceella, microsporium, moulds, Cladosporium sp., Mucor sp., mycelium, myxomyces, nigrospora, Sporotrichum sp., periconia, ascomycetes, peronospora, myceliospora, Sporotrichum sp., Pithium sp., Pithizomyces, Rhizomucor sp., Rhizomucococcus, rhodococcus, rhodobacter, Rhodotorula, rust, saccharomyces, scopulariopsis, sepedonium, serpula lacrymans, Ustilago, spegazzinia, sporoschisma, sporothrix, Sporotricum, Stachytrium, Stereomyces, synphylium, Syncephalum, Thermonospora fusca DSM cedzxf, Torula, trichocladium, Trichoderma sp., Trichophytium sp., Trithecium, trichotiracerium, ulohium, verticillium sp., Wallemia sp., and yeast.

One or more furanone compounds can be incorporated to act as chemical attractants for bacteria (chemoattractants) and or as odorants for degradation of polymers. Some furanones, particularly certain halogenated furanones, are quorum sensing inhibitors (quorum sensing inhibitors). Quorum sensing inhibitors are generally low molecular weight molecules that result in a significant reduction in quorum sensing microorganisms. In other words, halogenated furanones kill certain microorganisms. Halogenated furanones prevent bacterial colonization in bacteria such as Vibrio fischeri (v. fischeri), Vibrio harveyi (Vibrio harveyi), Serratia fici (Serratia ficaria), and others. However, natural furanones have no effect on pseudomonas aeruginosa, but synthetic furanones can have an effect on pseudomonas aeruginosa.

Some furanones, including those listed below, are actually chemoattractant reagents for bacteria. Suitable furanones may include, but are not limited to: 3, 5 dimethylyenyl dihydro 2(3H) furanone isomer mixture, emoxyfuran and N-acyl homoserine lactone.

The bacteria listed above that have been shown to be attracted to furanone compounds include, but are not limited to, chromobacterium violaceum (c.

Other chemoattractant reagents include sugars that cannot be metabolized by bacteria. Examples of such chemical attractants may include, but are not limited to: galactose, galactonate, glucose, succinate, malate, aspartate, serine, fumarate, ribose, pyruvate, oxalacetate and other L-and D-saccharide structures, but is not limited thereto. Bacteria that are attracted to these sugars include, but are not limited to, escherichia coli and salmonella. In a preferred embodiment, the sugar is a non-esterified starch.

One embodiment of the present invention is used with any carrier resin, such as ethylene-vinyl acetate copolymer, having an additive component of (organoleptic) organoleptics, namely cultured colloids and natural or artificial fibers. When combined with any of the plastic resins in a minor amount, the present invention renders the final products biodegradable while maintaining their desirable properties.

An important attribute of the present invention is that it is used without having to significantly modify existing methods of making plastic products. The resulting polymer and the resulting plastic product exhibit the same desirable mechanical properties and have a shelf life effectively similar to that of the additive-free product, yet, when discarded, are capable of being metabolized to inert biomass at least in part by anaerobic and aerobic microbial communities that are commonly found almost anywhere on earth.

This biodegradation process can occur aerobically or anaerobically. It may occur in the presence or absence of light. Traditional polymers can now biodegrade in landfill and compost environments within a reasonable time, defined by EPA as an average of 30-50 years.

One embodiment of the present invention is clearly distinguished from other "degradable plastics" that are currently emerging in the market because it does not attempt to replace the existing formulations of commonly used resins, but instead enhances them by making them biodegradable. One embodiment of the present invention is superior to those existing in the market for several reasons. For example, photo-degradable products cannot be degraded in landfills due to lack of sunlight (they are typically covered by another layer of garbage before degradation can occur). At the same time, these photo-degradable products present difficult conditions of storage before use, due to their reactivity to light. Similarly, plastic products made with large amounts of corn starch and cottonseed filler do not destroy the molecular structure of the plastic component of the product, are only partially destroyed in commercial composting facilities, are very expensive to manufacture, and often do not achieve the desired physical properties.

One embodiment of the invention contemplates a method in which the microorganisms are first attracted by a chemotactic agent (chemo-taxis) and then allowed to metabolize the molecular structure of the plastic film by the microorganisms in the environment. The membrane may degrade into an inert, environmentally benign form of the humic substance. An example of attracting microorganisms by a chemotactic agent is the use of a positive chemotactic agent such as flavored polyethylene terephthalate pellets, starch D-sugars that are not metabolized by the microorganism, or furanones that attract the microorganism, or any combination thereof.

In a preferred embodiment, several proprietary bioactive compounds are incorporated into masterbatch pellets that are readily added to plastic resins and colorants. The biodegradation process begins with one or more proprietary swelling agents that, when combined with heat and moisture, swell the molecular structure of the plastic.

After the swelling agent or agents create space within the molecular structure of the plastic, the combination of bioactive compounds found after significant laboratory testing attracts microbial communities, which break chemical bonds and metabolize the plastic through natural microbial processes.

One embodiment of the present invention provides an improved formulation of additive materials that can be added to a variety of polymeric materials and colorants and mixed into a material that renders them biodegradable without having to chemically modify the polymer molecules. This is important to preserve the formability of the polymeric materials so they can be used for their essential purpose of forming articles which can then be sold in commercial quantities for consumer use. Once the product is used, it can be discarded and sent to a landfill where once the product is buried in an oxygen-deficient environment, the product will biodegrade in a reasonably short time, thereby specifically eliminating the serious environmental problems associated with plastic disposal.

According to one embodiment of the invention, the additive comprises a furanone compound, glutaric acid, hexadecanoic acid compound, polycaprolactone polymer, a carrier resin which serves to help place the additive material in a uniform form within the polymeric material to ensure proper biodegradation. Additives may also include organic chemicals for organoleptic properties such as swelling agents, i.e., natural fibers, cultured colloids, cyclodextrins, polylactic acid, and the like.

The additive material renders biodegradable a variety of polymeric materials, which are generally non-biodegradable. Examples of such polymeric materials include linear and branched addition polymers, copolymers, and condensation polymers. It includes aliphatic and aromatic based polymeric materials. More particularly, the additives are effective in making polyethylene, polypropylene, polyvinyl acetate, polylactic acid, polycaprolactone, polyglycolic acid, polylactic-co-glycolic acid, polyvinyl chloride, polystyrene, polyterephthalate and polyesters, polyamides biodegradable so they can be simply added to landfills and initiate biodegradation in the presence or absence of oxygen.

According to one embodiment of the invention, the additive comprises a mixture of furanone compounds, glutaric acid, hexadecanoic acid compounds, polycaprolactone polymers, organoleptic swelling agents (natural fibers, cultured colloids, cyclodextrins, polylactic acid, etc.) and a carrier resin which serves to help place the additive material in a uniform form in the polymeric material to be made biodegradable to ensure proper biodegradation. Preferably, the furanone compound is in the range of 0 to 20 wt% or more. In a more preferred embodiment, the furanone compound is 20 to 40 wt%, more preferably 40 to 60 wt%, even more preferably 60 to 80 wt%, or preferably 80 to 100 wt% of the total additive. Glutaric acid is in the range of 0-20 wt% or more of the total additives. In a more preferred embodiment, the glutaric acid is 20 to 40 wt%, more preferably 40 to 60 wt%, even more preferably 60 to 80 wt%, or preferably 80 to 100 wt%, 20 to 40%, 40 to 60%, 60 to 80%, or 80 to 100 wt% of the total additive. The palmitic acid compound is in the range of 0 to 20 weight percent of the total additive or greater. In a more preferred embodiment, the palmitic acid is 20 to 40 wt.%, more preferably 40 to 60 wt.%, even more preferably 60 to 80 wt.%, or preferably 80 to 100 wt.%, 20 to 40%, 40 to 60%, 60 to 80% or 80 to 100 wt.% of the total additive. The polycaprolactone polymer is in the range of 0-20% by weight or more of the total additives. In a more preferred embodiment, the polycaprolactone is 20-40 wt.%, more preferably 40-60 wt.%, even more preferably 60-80 wt.%, or preferably 80-100 wt.%, 20-40%, 40-60%, 60-80% or 80-100 wt.% of the total additive. Natural or artificial organoleptic swelling agents (e.g., natural fibers, cultured colloids, cyclodextrins, or polylactic acid) are in the range of 0 to 20 weight percent or more of the total additives. In a more preferred embodiment, the organoleptic swelling agent is 20-40% by weight, more preferably 40-60% by weight, even more preferably 60-80% by weight, or preferably 80-100% by weight, 20-40%, 40-60%, 60-80% or 80-100% by weight of the total additive. Scanning electron microscopy (SEC) photographs of scientific analysis have provided evidence of biodegradation occurring over a three month period using mixtures of the above compounds. See the examples discussed further below with respect to SEC photographs.

The glutaric acid compound may be, for example, propylglutaric acid, but is not limited thereto.

The polycaprolactone polymer may be selected from, but is not limited to: polycaprolactone, poly (lactic acid), poly (glycolic acid), poly (lactic-co-glycolic acid).

The swelling agent may be selected from, but is not limited to, the group: natural fibers, cultured colloids, organoleptic compounds, cyclodextrins.

The carrier resin may be selected from, but is not limited to: ethylene vinyl acetate, polyvinyl acetate, maleic anhydride, and acrylic with polyolefins.

Once the additive is formulated, it must be brought into a form that will uniformly distribute the additive in the polymeric material that is desired to be made biodegradable. This may be accomplished by granulating, pulverizing, preparing an emulsion, suspension, or other medium of similar uniform consistency.

In a preferred embodiment, the additive is blended with the polymeric material just prior to feeding the polymeric material into a molding machine for forming the desired article or final polymeric product.

Any carrier resin (e.g., polyvinyl acetate, ethyl vinyl acetate, etc.) may be used with one embodiment of the present invention, wherein the polyolefin or any plastic material compatible with these carrier resins may be chemically bonded and allow for dispersion of the additives.

Current additives that do not contain a carrier resin can be used in varying proportions and blended with any plastic product, biodegradable additive or product such as polylactic acid, oxygen degradable additive, or non-plastic product (non-polyolefin or plastic material).

Furthermore, the additive of the present invention will work in conjunction with the renewable resource (green) plastic product example dupont Sorano. The invention will also work with any form of moulding process that is created for the production of the finished product, i.e. injection, thermoforming, blowing, extrusion, gravure (roto), spraying or dipping into other layers on top of a layer (laminating layer inter-layer).

In another preferred embodiment, the invention is a film having one or more layers, wherein each layer comprises a different product or combination of products, to allow the manufacture of new biodegradable products with improved properties. These properties would include: all the advantages of polylactic acid products (meeting the ASTM D-6400-99 standard for biodegradability within 90 days) and the advantages of polyethylene plastic layers, which make their shelf life indefinite and provide protection against strength, light, oxygen, moisture, heat and mechanical stress. The microorganisms may be applied to the layer using vapor deposition, with other materials in other layers and optionally more than one microorganism. For example, each microorganism may be selected for its ability to produce one or more beneficial byproducts, such as methane, ozone, or oxygen.

Further, any of the layers may have micro-perforations or perforations of different sizes and shapes that will allow for different amounts of moisture, water, liquids, gases, etc. to be made into a less permeable biodegradable polymer layer by using biodegradable additive technology. Once a gaseous, liquid or moisture substance passes through the outer layer (which has a different size, size and shape, as well as physical and chemical properties), the inner layer will begin to biodegrade at a predetermined rate. For example, a bottle with a thin layer of polyethylene plastic with a biodegradable additive on the outside can maintain a complete shelf life because the inner layer contacting the liquid isolates the liquid from the polylactic acid (starch based) biodegradable material on the outside of the bottle. Also, the inner material provides rigidity against mechanical stress. Once the bottles are placed in a landfill, moisture and microbes will attack the exterior of the bottles and degrade them quickly. Eventually, the inner layer of the membrane will come into contact with the microorganisms and biodegrade at a different time rate.

Another embodiment is a multilayer biaxially oriented film (made from polypropylene, polyethylene, polystyrene, etc.) having one or more layers of a starch-based material, or a green recyclable polyethylene terephthalate material, or a combination of one or more materials combined with a conventional plastic material with a new biodegradable additive, such as a plastic with an additive according to one embodiment of the invention, covering one or more layers of a composite polymeric material.

With the present invention, any variation of the layering method may be employed, and/or some other design like honeycomb hexagonal shape or any other may be used.

In a further preferred embodiment, the metal is part of an additive composition for causing rusting with or without a layering process. Metals enhance the strength of a given article while allowing them to rust completely and degrade it. All types of metal particles can be included in the mixture to make new variants of different properties. Since the rust particles are airborne, the new material will begin to rust and degrade once it comes into contact with moisture.

The colorant, ink and metal particles are preferably added to the additive or in any combination with the additive to any layer. Colorants, inks, and metal products increase or decrease light (UV) reflection, increase strength, slow or prevent destruction of the layer, or alter the destruction time, i.e., degrade or biodegrade at a particular time.

In another preferred embodiment, the marker incorporated for quality control (it is important to know that the design load weight% of the additive of the invention is present) is part of the additive. Materials such as: CS131, C-14, phosphorescent materials, minerals that emit light in the dark, alpha emitting particles with short half-lives, the concentration of which can be easily measured with currently used instruments, and easily used to ensure the quality and efficacy of the additives.

The present invention is biodegradable high impact polystyrene, polypropylene, polyethylene terephthalate, high density polyethylene, low density polyethylene and others. The biodegradability of these materials was tested using scanning electron microscopy when mixed into plastics at 1% -5% additive loading weight.

The following is an example of a layer composition of a preferred embodiment. Multilayer films, such as ultra-multilayer polyethylene terephthalate (trade mark Tetoron MLF), are a very thin film technology that laminates 200 to 300 more layers of two polymer films on the following non-limiting examples:

layer 1(UV or light blocking layer), layer 2 (biodegradable microbial layer suspended in plastic), layer 3 (perfume or fragrance layer), layer 4 (microbial odor attractor layer), layer 5 (green product layer such as Dupont Sarano TM), layer 6 (initiator layer of modified polymer, i.e. light, heat, high energy, free radicals), layer 7 (memory polymer layer that returns the molecule to its original shape when a preset temperature or condition is reached), layer 8 (one or more perforated or microperforated layer with additives that allow moisture/water or some specific inducer in gas or liquid form to pass through the perforations and into the inner layer, allowing the stimulation of microbes (bacteria, mold fungi, yeast, enzymes, etc.) and the start of the biodegradation process).

Referring now to fig. 1, one embodiment of forming a biodegradable polymer is illustrated. The layers may be rearranged into most any combination, and additional layers may be added or removed as desired. One or more microbial layers (layer 2 in the example) include: carbon dioxide-phagocytizing microorganisms (thermophiles) and pseudomonas putida, which are naturally produced in soil and can survive on styrene. The microorganisms may be suspended and resuspended upon interaction with water or other fluids. The microorganism may be an oil-phagocytizing microorganism, such as Alcanivorax borkumens.

An example of a suitable microorganism to be incorporated in the additive according to the invention is a so-called chemoheterotrophic prokaryote. These bacteria act as decomposers to destroy cadavers, dead plants and waste nitrogen-fixing prokaryotes. Many prokaryotes live in symbiotic relationships with other organisms, such as mutualistic symbiosis and paradoxical symbiosis. In order for a particular form of microorganism (mold, fungus, bacteria, etc.) to play a role in the decomposition/biodegradation of plastics, suitable nutrients in the plastic are important to the microorganism on which it feeds (in the case of nitrogen-fixing bacteria, it will be a nitrogen, sulfur-fixing bacterial sulfur, etc.). Microorganisms can also remain dormant when suspended in a thin matrix of some plastic or other compound. When they come into contact with an initiator, such as water, the microorganisms are activated in use and begin to break down or biodegrade plastics containing specific nutrients, such as nitrogen, which must be present in order to grow. Once the nutrients are lost, the microorganisms die and return to the soil.

In a preferred embodiment, the microorganisms and the furanone material are dispersed in a capsule to facilitate controlled release of the additive. The capsule appears to contain the microorganisms and furanones and to separate them from the polymer so that in the molten state it is not mixed directly into the polymer.

In another preferred embodiment, the additive comprises one or more antioxidants for controlling the rate of biodegradation. The antioxidant can be enzymatically coupled to the biodegradable monomer such that the resulting biodegradable polymer retains antioxidant functionality. The antioxidant-coupled biodegradable polymer can be manufactured to yield an antioxidant-coupled polymer that degrades at a rate consistent with the rate at which the antioxidant is effectively administered. Antioxidants are selected based on the particular application, and the biodegradable monomers can be synthetic or natural.

In yet another preferred embodiment, one or more supercritical fluids are used to disperse the additives in the polymeric composition. Supercritical fluids are used to diffuse additives into the base polymer resin or even the finished polymer product. This supercritical internal diffusion process can be applied repeatedly without destroying or damaging the polymer system. This establishes the overall reversibility of the process. The process for treating a polymer resin with a supercritical fluid comprises: (1) supercritical diffusion of one or more additives into a polymer resin; (2) simultaneously compounding in supercritical fluid; and (3) further processing, in addition to known methods, to obtain an impregnated or inter-dispersed polymer resin to obtain the desired end product or products.

In a further preferred embodiment, the microorganism is genetically engineered (genetically engineered) and tailored for a specific biodegradable polymeric material. Genetically engineered microorganisms with proteases are particularly effective for biodegradable plastics (e.g., polycaprolactone). These genetically engineered microorganisms are designed to excrete beneficial gases and energy binary products. These microorganisms use enzyme-based methods of monomer, oligomer, and polymer synthesis and polymer modification.

Example 1: example compositions of preferred embodiments for addition to high density polyethylene are shown below. In order to make the high density polyethylene biodegradable, the additive components were mixed together in the following proportions:

a furanone compound in a range of equal to or greater than about 0-20%, or about 20-40%, or about 40-60%, or about 60-80%, or about 80-100% by weight of the total additive load; glutaric acid in a range of equal to or greater than about 0-20%, or about 20-40%, or about 40-60%, or about 60-80%, or about 80-100% by weight of the total additives; a palmitic acid compound in a range of equal to or greater than about 0-20%, or about 20-40%, or about 40-60%, or about 60-80%, or about 80-100% by weight of the total additive; a polycaprolactone polymer in a range of equal to or greater than about 0-20%, or about 20-40%, or about 40-60%, or about 60-80%, or about 80-100% by weight of the total additives; polycaprolactone, poly (lactic acid), poly (glycolic acid), and poly (lactic-co-glycolic acid), in the range of equal to or greater than about 0-20%, or about 20-40%, or about 40-60%, or about 60-80%, or about 80-100% by weight of the total additives; and natural or artificial organoleptic swelling agents (natural fibers, cultured colloids, cyclodextrins, polylactic acid, and the like) in the range of equal to or greater than about 0-20%, or about 20-40%, or about 40-60%, or about 60-80% or about 80-100% by weight of the total additives.

Test results from several independent test laboratories have determined the biodegradability of plastic test films, foams and other forms using biodegradable formulations. This test concludes that the films, foams, and other forms are biodegradable under short-term or long-term anaerobic and aerobic conditions.

Example 2:

samples of polyvinyl chloride foam with additives (sample a) and samples of polyvinyl chloride foam without additives (sample B) were examined under a Scanning Electron Microscope (SEM). Samples of polyvinyl chloride foam with additives (sample C) and samples of polyvinyl chloride foam without additives (sample D) were also sonicated in detergent for 5 minutes to remove attached biofilm and microbial colonies. A sub-sample of about 1cm square was cut out of the larger sample in preparation for imaging.

Sample analysis was performed on a JEOL 5800LV SEM. The SEM was equipped with an Oxford Instruments energy dispersive X-ray spectrometer (EDX) and an Oxford X-ray analyzer and imaging system. The acceleration voltage was 15kV and the electron beam current was about 0.01 nA.

It was observed that the surface of sample a showed a large amount of biofilm attached. The biofilm occupies depressions (depressions) in the surface. In other areas, biofilms and colonies are located in large continuous recesses. Also observed are cracks in the polyvinyl chloride, which are exposed by the shrinkage of the biofilm during drying.

It was observed that after removal of the microbial community, the sample C surface showed a shallow recess under the microbial community. The contours of these recesses are irregular, reflecting the irregular contours of the microbial community.

It was observed that the surface of sample B showed a large amount of biofilm attached. It was observed that the surface of sample D showed no biofilm or colonies. Only a few wells were observed that could be identified as being associated with microbial communities. The recesses visible on the surface of sample D were much less prevalent than on sample C.

Based on the above examples, it is evident that the microbial community is embedded into the treated sample surface, mostly occurring in shallow recesses. The microorganisms are strongly associated with the treated surface and more colonies are present than in the untreated sample. The valleys under the colonies indicate that they degrade the material faster than untreated polyvinyl chloride due to the presence of additives in the treated samples. No additives were present in the reference sample and there the microbial degradation was much slower.

Example 3:

samples of polyethylene terephthalate with additives (sample a) and polyethylene terephthalate without additives (sample B) were examined under SEM. Both samples were washed with a mild detergent in an ultrasonic cleaner.

This sample was analyzed in the same manner as in example 2 using the same instrument.

It was observed that the sample a surface showed foam only below the surface, broken foam on the surface, nearly parallel streaks and scratches, and other mechanical damage. Sample a showed clear evidence of biodegradation.

It was observed that the surface of sample B showed a very smooth surface, with most of the defects being caused by machining.

Sample a showed a clear difference from sample B. For example, sample a showed a lot of foam that could be generated from microbial gas in plastic, as well as unpaired band defects of unknown origin, with a detached skin. Sample B showed a small effect. Sample a was severely degraded while sample B was only slightly degraded.

Example 4:

samples of expanded polystyrene foam with additives (sample a) and without additives (sample B) were examined under SEM.

This sample was analyzed in the same manner as in example 2 using the same instrument.

It was observed that the surface of sample a showed several types of surface damage, such as large coarse pores and rough edges and cracks around the pores.

It was observed that the surface of sample B showed smooth pores that are likely to be relevant to the foam preparation process.

There was surface degradation in sample a and it is believed that the jagged pores in sample a had a different origin than the smooth pores on sample B. Sample a showed a clear difference from sample B. Thus, the change in sample a is a result from the additive.

Example 5:

samples of high impact polystyrene nursery plant label with additive (sample a) and high impact polystyrene nursery plant label without additive (sample B) were examined under SEM.

This sample was analyzed in the same manner as in example 2 using the same instrument.

Sample a was observed to have many irregular pits and smaller crater-like holes in the surface. Surface layer cracking and peeling produce large pits. Smaller crater-like holes can be seen in the shallow pits. The small holes had no apparent connection to the tension cracks visible around the large pits.

It was observed that the sample B surface showed an inherent surface roughness, but showed little in terms of degradation. A small number of surface defects were observed, but they are likely due to mechanical damage rather than degradation.

Sample a and sample B showed a clear difference. Sample a showed a large number of pits and cracks that did not appear in sample B. The surface of sample a was strongly altered. Since the major changes occurred only on sample a, they are likely the result of the additives used to treat sample a.

Example 6:

samples of the foam package with the additive (sample a) and without the additive (sample B) were examined under SEM. In addition, the polyvinyl chloride foam sample with the additive (sample C) and the polyvinyl chloride foam sample without the additive (sample D) were sonicated in a detergent for 5 minutes to remove attached biofilm and microbial colonies.

This sample was analyzed in the same manner as in example 2 using the same instrument.

It was observed that the sample a surface showed a diverse and vigorous microbial community attached to the foam packaging. Curved pits also exist in the foam package as the plastic decomposes by adhering bacteria.

Sample C was observed to show a large number of small round pits on the surface. These pits may be due to direct dissolution by bacteria attached to the surface.

It was observed that the surface of sample B was smooth even with a large number of attached microorganisms. This population appeared to be different from the population observed on sample a.

Sample D was observed to be smooth and fairly featureless in surface, but exhibited a pattern of roughly parallel ridges. There were some pits, but they were much smaller than the bacteria, indicating that the pits were probably not caused by bacteria.

Samples a and C show clear differences from samples B and D. Pits and surface defects were widely distributed on samples a and C, but rarely on samples B and D. The full size pits and other surface features are very extensive throughout samples a and C, and typically less in samples B and D. Since they are of the same size as the bacteria, the pits on samples a and C are likely to be associated with microbial destruction of the plastic.

Example 7:

samples of shoes, shoe soles and shoe logo brands (sample a) made of polyethylene polymer material with 1 weight load (weight load)% of additive, samples of shoe soles and shoe logo brands (sample B) with 5 weight load% of additive and samples of shoes, shoe soles and shoe logo brands without additive (sample C) were placed in an anaerobic digester environment similar to a landfill. The sample is placed in a container located below a large diameter waste drain pipe that flows at a relatively constant rate and temperature. The sample was completely covered in waste liquid. The samples were covered in waste for 253 days.

At the end of 4 months, 6 months and 8 months, samples A, B and C were collected and washed with warm water and soap in an ultrasonic cleaner and used for testing of plastics biodegradability.

Attenuated total reflectance analysis

Attenuated Total Reflectance (ATR) analysis was performed on all samples from example 7. ATR spectra of these samples were recorded on a Perkin-Elmer 16PC spectrometer. All samples were measured at 4000 to 800cm^-1Is scanned. The spectra show slight changes in samples A and B relative to sample C. In a comparison of ATR spectra from 4 month labeling to 8 month labeling, sample a showed a significant increase in biodegradability. The biodegradability of sample a increased from 2.7% to 15.8%.

The 4 month marked ATR spectrum from sample B showed a degradation rate of 7.65%.

Differential Scanning Calorimetry (DSC) study

The mechanical and thermal properties of the sample in example 7 are significantly dependent on the crystal structure, crystallinity, molecular weight and branching. The melting temperature range and glass transition point vary strongly with the type of polymer.

For the samples, the interest is mainly focused on the glass transition temperature (Tg), melting range and heat of fusion (crystallinity) of the material, and decomposition.

The DSC results show that for sample B, the exothermic (crystallization) peak shifts to a different temperature relative to sample C. This transfer is due in part to biodegradation.

Based on the above analytical data, samples a and B were undergoing biodegradation.

Referring now to fig. 2, Size Exclusion Chromatography (SEC) analysis of polyethylene samples with or without additives was performed using 98% Tetrahydrofuran (THF) and 2% triethylamine as mobile phases. The samples submitted were: 1) shoe (reference-no Bio-Batch (Bio-Batch) additive), 2) shoe sole (reference), 3) shoe Mogo brand (reference), 4) shoe (treated-containing 5 wt.% Bio-Batch), 5) shoe sole (treated-containing 1 wt.% Bio-Batch), 6) shoe sole (treated-containing 5 wt.% Bio-Batch), 7) shoe Mogo brand (treated-containing 1 wt.% Bio-Batch), 8) shoe Mogo brand (treated-containing 5 wt.% Bio-Batch).

The sample was dissolved in the mobile phase and filtered prior to analysis. Based on the chromatograms given above, the peak in the reference sample at a retention time of 4.5 minutes disappeared in 5% of the biological batch samples and decreased in 1% of the biological batch samples. The disappearance of this high molecular weight peak is an indication of material degradation. Also another indication is the increase in the peak area of the low molecular weight fraction at retention time 9.4 minutes. Taken together, it shows that the samples tested above have undergone about 4% degradation.

Nevertheless, the last treated sample tested at 8 months was clearly distinguished from the reference sample when touched. They are more ductile and flexible than the reference samples. This is due to the deterioration of the chemical composition in the treated sample relative to the reference sample.

Based on FTIR/ATR, DSC and SEC analysis, it is clear that the sample shows evidence of about 4% biodegradation.

Example 8

Further ATR analysis was performed on the polystyrene treated with the additive (sample a) and the untreated polystyrene (sample B). The ATR spectrum of sample B1 shows peaks at 2913.33, 2850.43, 2360 and 2333.33, 1236.66 and 1016.66. The treated samples showed peaks at 2915.21, 2847.22, 2362.31, 2336.88, 1736.55, 1460.41, 1238.22, and 1017.78. Since the main absorption of the treated polystyrene is about 2935-2860cm^-1And at 1460 and 724cm^-1There is also absorption and thus the compound is a long linear aliphatic chain. The peak at 1736 may be an amide or carboxylate (carboxylate or ketone, which is indicative of the presence of a carbonyl group (C ═ O)). The treated samples showed evidence of microbial degradation.

Example 8

To demonstrate biodegradability in samples A treated with additives and samples B not treated with additives, 1cm samples of polypropylene were examined by SEM. SEM analysis was performed as described in example 1.

Sample a shows that a large number of pits are created by the microbial community and biofilm. The size of the pores and pits range from about 1-2 μm to over about 10-50 μm. The wells contain visible microorganisms. Furthermore the surface shows flaking and) ridges, which are partly due to microbial action in the surface.

A smooth surface is shown in reference sample B, which is free of pits and holes observed in sample a. Untreated sample B did not show an outer skin formed on the treated sample.

While the invention has been described in detail with particular reference to these preferred embodiments, other embodiments can achieve the same results. Variations or modifications of the present invention will be obvious to those skilled in the art and it is intended to cover in the appended claims all such variations and equivalents. The entire disclosures of all references, applications, patents, and publications cited above are hereby incorporated by reference.

Claims (16)

1. A mixture for use as a biodegradable additive for enhancing biodegradation of a polymeric material when added thereto, the mixture comprising:

a furanone;

carboxylic acid compounds having a chain length of 5 to 18 carbon atoms; and

a polymer, wherein the polymer is selected from the group consisting of: polydivinylbenzene, ethylene vinyl acetate copolymers, polyethylene, polypropylene, polystyrene, polyester, polyvinyl chloride, polycarbonate, polyamide, and any copolymer of the polymers.

2. A mixture for use as a biodegradable additive for enhancing biodegradation of a polymeric material when added thereto, the mixture comprising:

a furanone;

glutaric acid; and

a polymer, wherein the polymer is selected from the group consisting of: polydivinylbenzene, ethylene vinyl acetate copolymers, polyethylene, polypropylene, polystyrene, polyester, polyvinyl chloride, polycarbonate, polyamide, and any copolymer of the polymers.

3. A mixture for use as a biodegradable additive for enhancing biodegradation of a polymeric material when added thereto, the mixture comprising:

a furanone; and

a polymer, wherein the polymer is selected from the group consisting of: polydivinylbenzene, ethylene vinyl acetate copolymers, polyethylene, polypropylene, polystyrene, polyester, polyvinyl chloride, polycarbonate, polyamide, and any copolymer of the polymers.

4. The mixture of any of claims 1-3, wherein the polyester is aliphatic.

5. The mixture of any of claims 1-3, wherein the polyester is aromatic.

6. A method of forming a biodegradable layered polymer plastic or composite, the method comprising:

providing one or more layers of a polymer, said polymer not being biodegradable, said polymer being selected from the group consisting of: polydivinylbenzene, ethylene vinyl acetate copolymers, polyethylene, polypropylene, polystyrene, polyester, polyvinyl chloride, polycarbonate, polyamide, and any copolymer of said polymers; and

layering the polymer around the polymer layer with a composition comprising a chemical attractant sugar or furanone compound to attract microorganisms, glutaric acid, and a carboxylic acid compound having a chain length of 5 to 18 carbon atoms other than glutaric acid to form the biodegradable layered polymer plastic or composite wherein the polymer is at least partially biodegradable.

7. The method of claim 6, wherein at least one layer comprises a microorganism suitable for degrading the polymer.

8. The method of claim 7, wherein the microorganisms are applied to at least one layer by vapor deposition.

9. The method of claim 6, wherein at least one layer has perforations.

10. The method of claim 6, wherein at least one layer is biaxially oriented.

11. The method of claim 6, wherein at least one layer is shaped like a honeycomb hexagonal shape.

12. The method of claim 6, wherein at least one layer is rigid to mechanical stress.

13. The method of claim 6, wherein at least one layer comprises a perfume.

14. The method of claim 6, wherein at least one layer comprises an initiator that modifies the polymer.

15. The method of claim 6, wherein at least one layer of the composite material comprises a paper composition.

16. The method of claim 15, wherein at least one layer of the composite material comprises a metallic composition.