WO2015066588A1 - Thermoplastic polymer compositions having co-continuous plate-like morphology - Google Patents

Thermoplastic polymer compositions having co-continuous plate-like morphology

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Publication number
WO2015066588A1
WO2015066588A1 PCT/US2014/063637 US2014063637W WO2015066588A1 WO 2015066588 A1 WO2015066588 A1 WO 2015066588A1 US 2014063637 W US2014063637 W US 2014063637W WO 2015066588 A1 WO2015066588 A1 WO 2015066588A1
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WO
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Application
Patent type
Prior art keywords
polymer
composition
layer
acid
thermoplastic
Prior art date
Application number
PCT/US2014/063637
Other languages
French (fr)
Inventor
Norman Scott Broyles
April Renae HOLLINGER
Gary Wayne Gilbertson
Hugh Joseph O'donnell
Original Assignee
The Procter & Gamble Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date

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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/02Starch; Degradation products thereof, e.g. dextrin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE, IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C47/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C47/0009Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the articles
    • B29C47/0011Particle-shaped
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE, IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C47/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C47/0009Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the articles
    • B29C47/0021Flat flexible articles, e.g. sheets, foils or films
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE, IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C47/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C47/0009Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the articles
    • B29C47/0026Hollow flexible articles, e.g. blown foils or films
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE, IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C47/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C47/08Component parts, details or accessories; Auxiliary operations
    • B29C47/78Heating or cooling the material to be extruded or the stream of extruded material or of a preformed part
    • B29C47/88Heating or cooling the stream of extruded material
    • B29C47/8815Heating or cooling the stream of extruded material cooling
    • B29C47/884Heating or cooling the stream of extruded material cooling of flat articles, e.g. using specially adapted supporting means
    • B29C47/8845Heating or cooling the stream of extruded material cooling of flat articles, e.g. using specially adapted supporting means cooling drums
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/06Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/18Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/22Layered products comprising a layer of synthetic resin characterised by the use of special additives using plasticisers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/32Layered products comprising a layer of synthetic resin comprising polyolefins
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE, IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C47/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C47/08Component parts, details or accessories; Auxiliary operations
    • B29C47/12Extrusion nozzles or dies
    • B29C47/14Extrusion nozzles or dies with broad opening, e.g. for sheets
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00Layers arrangement
    • B32B2250/055 or more layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00Resin or rubber layer containing a blend of at least two different polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/40Properties of the layers or laminate having particular optical properties
    • B32B2307/402Coloured
    • B32B2307/4026Coloured within the layer by addition of a colorant, e.g. pigments, dyes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/70Other properties
    • B32B2307/716Degradable
    • B32B2307/7163Biodegradable

Abstract

A multi-layered masterbatch composition in the form of a pellet is provided. The masterbatch composition has at least 8 contiguous layers arranged in a plate-like morphology, wherein the at least 8 contiguous layers include at least one thermoplastic polymer A layer comprising a thermoplastic starch and at least one thermoplastic polymer B layer comprising a polyolefin, wherein the thermoplastic starch and the polyolefin are immiscible.

Description

THERMOPLASTIC POLYMER COMPOSITIONS

HAVING CO-CONTINUOUS PLATE-LIKE MORPHOLOGY

FIELD OF THE INVENTION

The present invention generally relates to multi-layered thermoplastic polymer compositions.

BACKGROUND OF THE INVENTION

Many methods for forming layered plastic compositions are known in the art, some examples being described in 3,557,265; 3,759,647; 3,773,882; 3,884,606; 6,582,807; and WO/2011/019408. Many common thermoplastic polymers, including those that are renewable, are not suitable for solo use in stand-alone applications. For example, thermoplastic starch ("TPS") has low melt strength and low extensibility, making it typically, commercially unsuitable for processing into stand alone thin films. TPS also suffers from mechanical performance deficiencies. One example of a thermoplastic starch composition is described in 6,605,657. Furthermore, TPS is a very hydrophilic, moisture-sensitive material, making it inherently unsuitable for most purposes. Due in part to its relatively low cost, thermoplastic starch ("TPS") is a very popular renewable thermoplastic polymer, despite its processing and property issues. Because of its many limitations, however, TPS is typically used only as a minor component in polymer blends with higher performing and more easily processed materials.

Certain thermoplastic polymers, such as polyolefins ("PO"), are commonly used to produce thin films for consumer product packaging because of their excellent processability. As a result, common film- manufacturing equipment is optimally designed for making polyolefin-based films. Replacing or modifying this manufacturing equipment to run other types of polymers would require high development costs and excessive capital expenditures, making this option impractical for most manufacturers. Rather than synthesize a totally new polymeric material having the desired attributes, it can be less expensive and less time-consuming to formulate polymer blends that combine the desirable properties of each polymer present. However, most thermoplastic polymers are incompatible with one another and thus do not easily form stable blends. Instead, they form immiscible, phase- separated blends due in part to high interfacial tension at their interfaces. Immiscible blend performance depends not only upon the properties of the individual components but also upon the blend morphology and the interfacial properties between the blend phases. In order to make a uniformly processable blend exhibiting the desired performance characteristics, the blend's morphology and interfacial properties are typically controlled through compatibilization of the polymers.

Compatibilization is commonly achieved through addition of a polymeric compatibilizing agent ("compatibilizer"), such as a block or graft copolymer, having compatibility or miscibility with both immiscible polymers. The choice of compatibilizer depends not only upon miscibility of the particular compatibilizer with the blend's different polymers, but also upon its effect on chemical reactivity, processing, and rheology. The compatibilizer must maintain each component's desired properties in the blend, while minimizing the undesired properties. In addition to the complications of identifying a suitable compatibilizer, compatibilizing agents can be very expensive. The increased cost of the final product, especially when it is a disposable film, article, or package, commonly makes the use of compatibilizers a cost disadvantage.

Accordingly, it would be desirable to provide a method for making stable blends of immiscible polymers that contain a minimum of added compatibilizer. It would also be desirable to provide such polymer compositions that are suitable for manufacturing thin packaging films.

SUMMARY OF THE INVENTION

A multi-layered masterbatch composition in the form of a pellet is provided. The

masterbatch composition has at least 8 contiguous layers arranged in a plate-like morphology, wherein the at least 8 contiguous layers include at least one thermoplastic polymer A

layercomprising a thermoplastic starch and at least one thermoplastic polymer B layer comprising a polyolefin, wherein the thermoplastic starch and the polyolefin are immiscible.

Additional features and advantages of the present invention will be revealed in the following detailed description. Both the foregoing summary and the following detailed description and examples are merely representative of the invention, and are intended to provide an overview for understanding the invention as claimed. BRIEF DESCRIPTION OF THE DRAWINGS

For a more complete understanding of the disclosure, reference should be made to the following detailed description and accompanying drawing wherein:

FIG. 1 depicts the typical change in binary immiscible polymer blend morphology as the amount of Polymer B is increased relative to the amount of Polymer A.

FIG. 2 depicts a binary immiscible polymer blend having discrete phase morphology, where Polymer A is the continuous (e.g., major) phase and Polymer B is the discrete (e.g., minor or discontinuous) phase.

FIG. 3 depicts a binary immiscible polymer blend having a tube-like morphology. FIG. 4 depicts a binary immiscible polymer blend having plate-like morphology, where

Polymer A and Polymer B are in the form of alternating repeating planar layers.

FIG. 5 is a cross-sectional view of a nanolayered film representative of the present invention, comprising 20% of an immiscible thermoplastic polymer A (polypropylene, "PP")) and 80% of an immiscible thermoplastic polymer B (polyethylene, "PE"), observed with SEM (10 micron x 10 micron view). The film has a co-continuous morphology with a planar, plate-like configuration.

FIG. 6 is a cross-sectional view of a conventional pellet, comprising 67% TPS / 33%

LLDPE, observed with SEM (10 micron x 10 micron view). The pellet has a tube-like morphology.

FIG. 7 is a cross-sectional view of a film not of the present invention, comprising 25% TPS / 75% LLDPE, made by re-extruding the TPS/LLDPE pellet of FIG. 6 with a LLDPE matrix (e.g., dilution) polymer, observed with SEM (10 micron x 10 micron view). The morphology is discrete phase heterophasic with LLDPE being the continuous phase and TPS being the discrete phase. The TPS domains are distinct and largely spherical, while the polyethylene phase is continuous.

FIG. 8 depicts a typical co-extrusion apparatus for the manufacture of multilayer polymer sheets. FIG. 9a depicts a co-extrusion apparatus for the manufacture of nano layered pellets

("NLP"s).

FIG. 9b depicts the nano layered pellet of the present invention being mixed with matrix polymer for feeding into a conventional extrusion process. FIG. 10 is a cross-sectional view of a nano layered pellet comprising 80% of an immiscible polymer A (PE) and 20% of an immiscible polymer B (PP), observed with SEM (10 micron x 10 micron view). The morphology is plate like and co-continuous.

FIG. 11 is a cross-sectional view of a nano layered film comprising 20% of an immiscible polymer A (PP) and 80% of an immiscible polymer B (PE), made by re-extruding (via single-screw extruder) the pellet of FIG. 10 with a matrix (e.g., dilution) polymer B, observed with SEM (10 micron x 10 micron view). This sample shows a plate-like structure, wherein at least some of the plates are considered co-continuous.

FIG. 12 is a cross-sectional view of the same nano layered film as in FIG. 11, observed with SEM (10 micron x 10 micron view) at a different sampling point on the film.

While the specification concludes with claims particularly pointing out and distinctly claiming the subject matter that is regarded as the present invention, it is believed that the invention will be more fully understood from the following description taken in conjunction with the accompanying drawings. Some of the figures may have been simplified by the omission of selected elements for the purpose of more clearly showing other elements. Such omissions of elements in some figures are not necessarily indicative of the absence of particular elements in any of the exemplary aspects, except as may be explicitly delineated in the corresponding written description. The drawings are not necessarily to scale.

DETAILED DESCRIPTION OF THE INVENTION I. DEFINITIONS

As used herein, the following terms shall have the meaning specified thereafter:

"Article" refers to the composition in its hardened state, at or near 25°C ("room

temperature"). The articles can be in the form of a consumer product or portion thereof (e.g., a bottle, an automotive part, a component of an absorbent hygiene product), or can be used for subsequent re-melt and/or manufacture into other articles (e.g., pellets, fibers, films, recycled articles).

"Bio-based content" refers to the amount of carbon from a renewable resource present in a material as a percent of the mass of the total organic carbon in the material, as determined by ASTM D6866-10, method B. Note that any carbon from inorganic sources such as calcium carbonate is not included in determining the bio-based content of the material.

"Bio-based polyolefin" refers to a polyolefin made from a renewable material obtained from one or more intermediate compounds (e.g., sugars, alcohols, organic acids). In turn, these intermediate compounds can be converted to olefin precursors.

"Biodegradable" refers generally to a material that can degrade from the action of naturally occurring microorganisms, such as bacteria, fungi, yeasts, and algae; environmental heat, moisture, or other environmental factors. If desired, the extent of biodegradability may be determined according to ASTM Test Method 5338.92. "Co-continuous phase domains" refers to two or more continuous phase domains that are substantially co-extensive in a lengthwise direction within a specified distance, such as within a 10 micron x 10 micron lengthwise, cross-sectional photomicrograph (SEM) or, on a larger scale, across 80%, 90% or about 100% of the length of a composition or article. In some instances, the co- continuous phase domains may be adjacent each other and in some instances the co-continuous phase domains may further be contiguous. In some instances, just some or all of the phase domains within the SEM (or such other distance), composition or article may be co-continuous (e.g., greater than 10%, 25%, 50%, 75% or about 100%). In some instances, the co-continuous phase domains may be in the form of plate-like morphology characterized by multiple continuous phase domains oriented relative to one another in a plate-type configuration wherein the thickness direction, z, is much smaller than the other dimensions, x and y.

A "compatibilized" polymer blend refers to an otherwise immiscible blend where the interfacial tension between phase boundaries has been reduced (e.g., through the addition of a compatibilizing polymer) such that the phases can form a substantially homogenous mixture upon cooling, and the blend generally exhibits macroscopically uniform physical properties throughout its entire volume. Compatibilized polymer blends typically follow "Rule of Mixture" type of laws with equivilance or positive deviations.

"Compatibilizer" refers to a material added to a polymer blend to reduce the interfacial tension between phase boundaries. "Contiguous" means in direct contact with. Where a layer is "contiguous," it is in direct contact with at least one adjacent layer, although the direct contact need not extend across the entire layer.

"Continuous phase domain" refers to a phase domain in a composition or article (e.g., a molded a film, a fiber, etc.) through which a continuous path may be drawn without crossing another phase domain boundary within a specified distance, such as within a 10 micron x 10 micron lengthwise, cross-sectional photomicrograph or, on a larger scale, across 80%, 90% or about 100% of the length of a composition or article. In some instances, a continuous phase domain may be provided in the shape of a plate-like layer. For example, not by limitation, the plate-like layers shown in the multi-layered composition of FIG. 4 are some examples of continuous phase domains. In contrast, some discontinuous phase domains are shown in FIG. 2.

"Copolymer" refers to a polymer derived from two or more polymerizable monomers. When used in generic terms the term "copolymer" is also inclusive of more than two distinct monomers, for example, ter-polymers. The term "copolymer" is also inclusive of random copolymers, block copolymers, and graft copolymers. As used herein, the terms "copolymer and "polymer" are inclusive of homo-polymers and copolymers that can exhibit both homogeneous and heterogeneous morphologies.

"Copolypropylene ("coPP")" refers to a copolymerization of propylene and another monomer such as ethylene or an alpha-olefin exemplified by a propylene-ethylene block, or random copolymer.

"Discontinuous" or "discrete" or "dispersed" phase domain refers to a phase domain in a composition or article that is surrounded by another phase domain. The discontinuity of a phase domain may be best viewed thru a lengthwise, cross-section of the composition or article. In some instances, a discontinuous phase domain may be provided in the shape of a plate-like layer that terminates (in the x dimension) within another phase domain having the shape of a plate-like layer. In some instances, a discontinuous phase domain may be easily viewed within a 10 micron by 10 micron SEM of the composition or article. Some non-limiting examples of discontinuous phase domains are shown in FIG. 12. "Final" means that a polymer, polymeric composition, product, or the like, is substantially of the same compositional makeup and/or substantially the same physical form in which it is intended to be used, sold, or otherwise supplied.

"Film" refers to a sheet-like material wherein the length and width of the material far exceed the thickness of the material. As used herein, the terms "film" and "sheet" are used interchangeably.

"Immiscible" means that a mixture forms multiple phases upon cooling (i.e., immiscible in the solid state). Even if miscible in the molten state with shear or extension, many polymer combinations become immiscible upon cooling, resulting in multiple phases at solid temperatures. By definition, immiscible polymers are incompatible with one another. "Incompatible" means that when immiscible thermoplastic polymers are melt-mixed with shear or extension at temperatures above their softening and/or melting points, the composition does not form a substantially homogenous mixture upon cooling and does not generally exhibit macroscopic ally uniform physical properties through the blend's entire volume. There is little to no interpenetration at the phase boundaries, due to high interfacial tension. "Miscible" means that when thermoplastic polymers are melt-mixed with shear or extension at temperatures above their softening and/or melting points, the mixture forms a single phase upon cooling. By definition, miscible polymers are compatible with one another.

As used herein, "matrix polymer" or "matrix polymer composition" means a polymer used to dilute a masterbatch. As used herein, "masterbatch" or "masterbatch composition" means a polymer composition that is used or intended for use as a feed stock in a later molding, casting, compacting or other shape/forming operation. In some instances, the masterbatch composition may be reheated and/or melted as part of the later shape/forming operation. Articles can be formed either from the masterbatch composition or from a melt-mixture of the masterbatch composition with one or more matrix polymers.

"Morphology" of a polymer blend describes the structures and shapes observed, such as by microscopy, of the different phase domains present within the composition.

"Minimum melt processing temperature" of a polymer or polymer composition means the lowest temperature or temperature range at which that polymer or composition can be maintained to enable it to be effectively melt processed while minimizing or avoiding thermal degradation of the polymer or composition. The minimum melt processing temperature will of course vary depending upon the materials being processed, and this can be readily determined by a person skilled in the art.

"Pellet" and "Pellets" refers broadly to any kind of feedstock used as a raw material for a later molding, compacting, casting or other shape/forming operation (e.g., injection molding, blow molding, transfer molding, compression molding, thermoform molding, rotational molding, etc.). Pellets may be provided in wide variety of shapes, including but not limited to shapes substantially in the form of disks or cylinders or spheres. Pellets may be provided in any size suitable for use as a feedstock, sometimes as a feedstock for a screw type extruder. For example, in some instances, pellets may be provided substantially in the shape of a cylinder or disk or sphere having a diameter from about 1 mm, 2 mm or 3 mm to about 10 mm, 6 mm or 4 mm. In some instances, pellets may have a mass from about lmg to about 1,000 mg.

A "phase domain" or "phase" is a region of a material that is uniform in chemical composition and physical state.

A "plate-like morphology" is characterized by an arrangement or stacking of layers, wherein at least some of the layers have a plate-like shape. The plate-like shape of multiple layers may yield a striated appearance when viewed in a cross-section thru the thickness of the layers (see, e.g., FIG. 10). "Plate-like" refers to a layer that is thin in the "z" thickness dimension, relative to the other dimensions, x and y. X may be extremely large relative to y and vice versa. Some non-limiting examples of plate-like layers (viewed in cross-section thru the thickness of the layer) are shown in FIGS. 4, 5, 10, 11 and 12. In some instances, the top and bottom surfaces of a plate-like layer may be generally or substantially parallel to each other and/or substantially flat or planar. In some instances, the plate-like layer may have a length (in the longest dimension, x or y) to thickness (z dimension) ratio of greater than 4:1, or greater than 5:1, or greater than 10:1, or greater than 100:1, or greater than 1000:1.

"Renewable" refers to a material that can be produced or is derivable from a natural source which is periodically (e.g., annually or perennially) replenished through the actions of plants of terrestrial, aquatic or oceanic ecosystems (e.g., agricultural crops, edible and non-edible grasses, forest products, seaweed, or algae), or microorganisms (e.g., bacteria, fungi, or yeast). "Renewable resource" refers to a natural resource that can be replenished within a 100 year time frame. The resource may be replenished naturally, or via agricultural techniques. Non-limiting examples of renewable resources include plants (e.g., sugar cane, beets, corn, potatoes, citrus fruit, woody plants, lignocellulosics, hemicellulosics, cellulosic waste), animals, fish, bacteria, fungi, and forestry products. They may be naturally occurring, hybrids, or genetically engineered organisms. Natural resources such as crude oil, coal, and peat which take longer than 100 years to form are not considered to be renewable resources.

"Stable" refers to polymeric compositions that do not exhibit gross symptoms of polymer phase segregation (e.g., phase segregation that would render the composition unsuitable for the desired use).

As used herein, the terms "substantially no", "substantially free of, and/or "substantially free from" mean that the indicated material is at the very minimum not deliberately added to the composition to form part of it, or, most desirably, is not present at analytically detectable levels. It is meant to include compositions whereby the indicated material is present only as an impurity in one of the other materials deliberately included. In some instances, "substantially no" or "substantially free of means the indicated material has a concentration less than 1%, 0.5%, 0.25%, 0.1% or 0.01% by weight of the composition.

As used herein, articles such as "a" and "an" are understood to mean one or more of what is claimed or described. As used herein, the terms "include", "contain", and "has", as well as their various verb tenses, are meant to be non-limiting.

All percentages and ratios are calculated by weight of the total composition, unless otherwise indicated.

Unless otherwise noted, all component or composition levels are in reference to the active portion of that component or composition, and are exclusive of impurities, for example, residual solvents or by-products, which may be present in commercially available sources of such

components or compositions.

Although various polymers and/or polymer layers are referred to throughout the specification in terms of certain letter designations (e.g., polymer A, compatibilizer layer C, additional polymer P), it should be understood that these designations are made only for the purpose of facilitating understanding of the present invention in the context for which they are defined, and thus have no inherent meaning outside that context. The letter designations and abbreviations set forth in the Examples apply only to the examples, and are only for the purpose of facilitating understanding of the examples. II. IMMISCIBLE POLYMER COMPOSITIONS 1. Traditional Immiscible Polymer Blends

The performance of immiscible polymer blends is largely determined by the morphology of the mixture. Factors such as viscosity ratio, interfacial tension, mechanical energy input, deformation input, mixing shear, and thermal history influence the morphology of immiscible polymer blends. Additionally, the relative concentration of each polymer present in the blend influences the type of morphology developed. FIG. 1 depicts the general effect of polymer concentration on immiscible binary polymer blend morphology.

Immiscible binary systems where one polymer is present at a much greater concentration than the other generally have a heterophasic morphology, with a discrete minor phase dispersed as droplets throughout a continuous major phase. A diagram exemplifying discrete phase heterophasic morphology is shown in FIG. 2. The geometry of the discrete phase can vary from spherical, to ellipsoidal, to rod-like depending on the factors mentioned previously. Increasing the amount of the minor component will gradually lead to the formation of a more continuous dispersed phase until a fully continuous structure forms inside the continuous matrix phase. The geometry of these phases can vary from tube-like to plate-like. Tube-like morphology is depicted by FIG. 3, while plate-like morphology is depicted by FIG. 4.

Co-continuous morphologies are often formed near the point of phase inversion, and depend not only upon component concentration but also upon the components' rheological properties and various other aforementioned factors, such as shear during mixing. In practice, the plate-like continuous morphology is rarely observed due to the enthropic penalty associated with such a high degree of order. However, when it can be achieved, optimal mechanical properties can result. It has been found that each component' s properties contribute more fully to the properties of the blend when incompatible blends have a continuous plate-like morphology. Accordingly, among immiscible polymer blends, those having continuous plate-like morphologies are often the most desired. FIG. 6 and FIG. 7 are SEM photographs showing the morphologies of two TPS/PE blends that are not of the present invention. The TPS/PE composition in the form of a pellet (e.g., masterbatch) shown in FIG. 6 is representative of a typical blended, tube-like morphology. The masterbatch pellet of FIG. 6 was melt-mixed with a PE matrix polymer and re-extruded to form the article (i.e., film) of FIG. 7. The material shown in FIG. 7 is heterophasic, with a PE continuous phase and discrete phase TPS domains that are distinct and largely spherical.

2. Multi-layered thermoplastic polymer masterbatch composition

Traditional multi-layered film compositions may be made by multilayer extrusion, wherein two or more polymers can be arrayed in an alternating layered structure. Multilayer polymer films are typically produced by co-extrusion devices such as that generally set forth in FIG. 8.

FIG. 8 exemplifies a multi-component (e.g., A, B, C, D) coextrusion system for producing a film consisting of four extruders (e.g., 1, 2, 3, 4), each connected by a melt pump to a coextrusion feedblock. The feedblock for this four component system mechanically combines the individual A, B, C, and D streams into four parallel layers (ABCD) (i.e., 4-layered film). From the feedblock, this multi-layered stream may be subsequently passed through a series of layer multiplying devices

("multipliers") in order to further increase the final number of layers via mechanical manipulation. Repeating this process can be used to produce hundreds or even thousands of layers in a film or sheet. Thus, in one aspect the multi-layered composition (e.g., film) comprises repeating film structures, with each structure comprising a layer of each component polymer (e.g.,

ABCD ABCD ABCD ABCD). The multilayered stream is finally passed into an extrusion die and is extruded to form a multi-layered film in which each layer is generally parallel to the major surface of adjacent layers.

This traditional layering system works well for cast film extrusion where the equipment can be modified (though expensive) to produce such layered films. However, this method has somewhat limited application due to the capital cost involved in adding the layering system and multiple extruders. Accordingly, the benefits of multi-layering have been limited to manufacturers that can afford to purchase this expensive layering equipment.

In some instances, the present invention provides an improved multi-layering manufacturing process for producing masterbatch compositions comprising alternating layers of a thermoplastic starch containing layer and a polyolefin containing layer, which may then be later used in a forming or shaping operation to form a film, fiber, molded article, etc. Typically, the masterbatch composition may be provided in the form of pellets, to facilitate storage, transport, and ease of use. FIG. 9a and FIG. 9b illustrate one example of this improved multi-layering manufacturing process whereby the multi-layer composition leaving the multiplier block assembly passes through a pelletizer, shaping the multi-layer composition into the form of pellets (FIG. 9a).

Pellets produced by this method can be used in any polymer processing operation to form articles (e.g., packaging films) without the need to invest in expensive capital equipment, such as twin-screw extruders. The pellets can be re-melted and reformed into the final desired product, such as through use of an injection molder, thermoformer, or extrusion blow molder. In some instances, the pellets may be melt-mixed in an extruder with a matrix (i.e., dilution) polymer to form the final polymer composition for use in a non-woven process, a cast or blown film process, an injection molding process, a blow molding process, or the like (FIG. 9b). Acquiring pre-made pellets enables manufacturers having only simpler manufacturing apparatuses, such as single-screw extruders, to take advantage of multi-layered technology. Preferably, each layer of the masterbatch composition is contiguous to one or more other layers. It is anticipated that the multi-layer compositions can have multiple alternating layers (e.g., two, three, four, or more) that repeat as a unit throughout the multilayer composition. At least one layer each of immiscible thermoplastic polymer "A" and immiscible thermoplastic polymer "B" are arranged in a repeating "AB" configuration. For instance, {AB}x where x = an integer from 1 to 25,000, represents a multi-layer composition having from 1 to 25,000 repeating units of adjacent layers A and B (e.g., where x = 3, three layers of A and three layers of B are ordered relative to one another in the pattern "ABABAB").

Each layer A and B comprises or consists essentially of immiscible thermoplastic polymer A and thermoplastic polymer B, respectively. In some instances, a layer may comprise from about 70%, 80% or 90% to about 95% or 100% by weight of the layer of the immiscible thermoplastic polymer (e.g., thermoplastic starch or polyolefin). In some instances, the masterbatch composition may comprise a weight ratio of polyolefin: thermoplastic starch from about 0 to about 9:1 or about 1:4 to about 2:3. In some instances, the masterbatch composition may comprise from about 10% to 100% or about 50% to 80% by weight of the masterbatch composition of the thermoplastic starch and from about 0% to 50% or about 20% to 40% by weight of the masterbatch composition of the polyolefin. In some instances, the masterbatch composition may also include compatibilizer C. In some instances, the ratio of thermoplastic starch:compatibilizer is about 1:1 or about 40:1. In some instances, the masterbatch composition may comprise about 60% thermoplastic starch, about 30% compatibilizer and about 10% of a polyolefin by weight of the masterbatch composition. Each immiscible thermoplastic polymer A and B comprises one or more thermoplastic polymer compounds, and the layer comprising the thermoplastic polymer may optionally comprise one or more additives as known in the art (e.g., filler, colorant, UV- stabilizer, fragrance). In one aspect, each immiscible thermoplastic polymer can comprise from 0% to 20% additive, or from 0% to 10%, or from 0% to 5%, or from 5% to 20%, or from 5% to 10%, or from 2% to 10%, by total weight of that immiscible thermoplastic polymer. Each immiscible thermoplastic polymer A and B may be substantially free of compatibilizer.

Optionally, compatibilizer, in the form of a layer (e.g., tie layer), can be used to improve interfacial interaction between the incompatible polymer layers. Typically, the compatibilizer layer consists essentially of compatibilizer material. The compatibilizer material can include any suitable material or material combinations. Traditionally, when a compatibilizer is used to stabilize an incompatible polymer blend, high levels of compatibilizer are needed. This is because the immiscible polymers, and consequently their interfaces, are distributed throughout the entire blend. Accordingly, compatibilizer would also be distributed throughout the entire blend in order to reach the interfaces located throughout due to diffusion time limitations. Other methods have included lamination or multi-layer extrusion, where compatibilizer is included as an additive in one or more of the incompatible polymer composition layers. This method also requires a high level of compatibilizer, since an adequate amount of compatibilizer must be available at, or migrate to, the interface of the incompatible contiguous layers in order to be effective. Such migration is limited by thermodynamic and kinetic phenomena. The present invention makes use of compatibilizer in a more efficient, effective manner by allowing compatibilizer to be situated only in regions where it is needed, namely at the interface between immiscible layers. In this way, compatibilizer can be situated at essentially 100% of the interfacial surfaces between immiscible polymer layers, but does not need to be located in areas where compatibilizer is not needed (e.g., dispersed throughout the entire volume of the

composition). In some instances, it may be possible to eliminate the compatibilizer completely such that the masterbatch composition is substantially or completely free of a compatibilizer, particularly when the thermoplastic polymer A layer comprises a thermoplastic starch and the thermoplastic B layer comprises a polyolefin.

When present, the compatibilizer is in the form of one or more compatibilizer layers, which consist essentially of a compatibilizer "C". The compatibilizer can comprise one or more thermoplastic compatibilizer compounds (e.g., the polymeric compatibilizer can be one or a mixture of more than one thermoplastic compatibilizer compound), and can optionally comprise one or more additives as known in the art (e.g., filler, colorant, UV- stabilizer, fragrance). In one aspect, the compatibilizer C can comprise from 0% to 20% additive, or from 0% to 10%, or from 0% to 5%, or from 5% to 20%, or from 5% to 10%, or from 2% to 10%, by total weight of compatibilizer C. When compatibilizer is included in the masterbatch, all masterbatch layers except for compatibilizer layer C are substantially free of compatibilizer. When a compatibilizer layer is provided, it may be disposed between the thermoplastic polymer A layer and the thermoplastic polymer B layer. In some embodiments, the layers may be arranged as a repeating unit of [ACBC]X, wherein A is thermoplastic polymer A layer, B is the thermoplastic polymer B layer and C is the compatibilizer layer and x is an integer indicating the number of repeating units. In other embodiments, the layers may be arranged as a repeating unit of [BCAC]X.

The multi-layered thermoplastic polymer masterbatch of the present invention may comprise from 0.4% to 40%, or from 0.4% to 10%, or from 0.4% to 3%, or from 0.25% to 2.5%, or from 0.625% to 3%, or from 0.625% to 2.5% compatibilizer, by weight of the total masterbatch composition.

It is contemplated that the multi-layer masterbatch composition can include layers of other thermoplastic polymeric materials as desired. The masterbatch of the present invention can optionally comprise at least one additional thermoplastic polymer "P", in the form of at least one additional thermoplastic polymer layer P. Additional thermoplastic polymer P can comprise one or more thermoplastic polymer compounds and can optionally comprise one or more additives as known in the art (e.g., filler, colorant, UV-stabilizer, fragrance).

In one aspect, additional thermoplastic polymer P can comprise from 0% to 20% additive, or from 0% to 10%, or from 0% to 5%, or from 5% to 20%, or from 5% to 10%, or from 2% to 10%, by total weight of additional polymer P. Polymer layer P is substantially free of compatibilizer. The composition of each layer may be the same or different, depending upon the desired final composition. The polymer comprising a particular layer of the composition may be one or a mixture of one or more individual polymers. For example, the layers may differ in one or more of the following characteristics: type of polymer, additives within the polymer, flexural modulus, processing temperature, Tg (glass transition temperature) and tensile strength.

Although not required, one or more layers may contain additives if desired. Such additives include, but are not limited to, colorants, pigments, carbon black, glass fibers, fillers, impact modifiers, antioxidants, stabilizers, flame retardants, reheat aids, acetaldehyde reducing compounds, oxygen scavenging compounds, reinforcing agents, combinations thereof, and the like. The multilayer masterbatch of the present invention comprises at least eight contiguous layers of two or more polymers. The multilayer composite may have as many as 50,000 layers or more. For example, in one aspect the composition can comprise from 8 layers to 50,000 layers, or from 128 layers to 50,000 layers, or from 700 layers to 40,000 layers, or from 200 layers to 10,000 layers, or from 200 layers to 1000 layers of two or more polymers, where each polymer layer is contiguous with at least one other polymer layer. In some instances where an AB layer repeating unit is utilized, the multi-layered masterbatch composition may comprise from about 4, 50, 64 or 350 to about 25,000, 20,000, 5,000 or 500 each of the thermoplastic polymer A layer and the

thermoplastic polymer B layer.

In one aspect of the invention, substantially all of the layers in the masterbatch, for example at least 70%, or from 90% to 100%, or from 95 to 100%, or from 90 to 100% of the polymer layers are contiguous with at least two other polymer layers, except for the end layers, which are contiguous with only one other layer.

It will be appreciated that the respective polymer layers can have substantially the same or different thicknesses. The thickness of each of the layers of the composition need not be the same, depending upon desired properties. By altering the relative flow rates or the number of layers, while keeping the film or sheet thickness constant, the individual layer thickness can be controlled.

The masterbatch of the present composition can be in any suitable form. For example, it can be in the form of an extruded article (or portions thereof) such as pellets, film, rope, ribbons, or other desired shape. In one aspect, the masterbatch composition is in the form of a multi-layered pellet. These multi-layered pellets can be re-melted, either alone or melt-mixed with a matrix polymer (i.e., diluent polymer), to form polymeric articles.

The multilayer masterbatch can have an overall thickness ranging from 0.03 mm to 25 mm (e.g., in the form of a pellet), or from 0.03 mm to 1.5 mm, or from 0.5 to 1.5 mm, or < 25 mm. In one aspect where the masterbatch is in the form of a pellet, the pellet's dimensions are 3.175 mm x 3.175 mm.

One example of a multi-layered pellet produced from a masterbatch composition of the present invention is represented in FIG. 10. The pellet has -4000 layers and comprises 80% of an immiscible Polymer A and 20% of an immiscible polymer B, the layers being shown in FIG. 10 being in the form of a co-continuous plate-like morphology.

3. Multi-layer Compositions Comprising a Matrix Polymer

The masterbatch composition can be used as is, or it can be further combined (e.g., diluted) with a matrix polymer to make the final polymeric composition. The multilayer masterbatch composition can be present in the final polymeric composition at a level of from 10% to 100% based on the total weight of the finished composition. In one aspect, the final composition can comprise from 20% to 70%, or from 30% to 60%, or from 30% to 50%, or can consist essentially of, the multi-layered masterbatch composition.

In one aspect, the present invention provides a method for making a polymer composition having a co-continuous plate-like morphology. The method comprises: (a) providing a masterbatch according to the present invention;

(b) providing a matrix polymer;

(c) melt mixing said masterbatch with said matrix polymer to form said composition having a co-continuous plate-like morphology; and

(d) optionally shaping said composition into the form of an article.

The matrix polymer composition comprises the balance of ingredients which, in combination with the masterbatch composition, form the final polymer composition (e.g., article) having a co- continuous, plate-like morphology. The matrix polymer composition can comprise one or more separate compositions, which can be combined with the masterbatch either separately or together to form the final polymer composition. In particular aspects, the matrix polymer composition comprises a thermoplastic polymer plus any other desired ingredients. Any suitable thermoplastic polymer, including polymer mixtures, can be used as the matrix polymer. Typically, a matrix polymer comprises a polymer that is also present in the masterbatch or is miscible with another polymer of the masterbatch composition.

Melt mixing may be performed using techniques and equipment well known in the art.

Commonly, melt mixing is achieved using continuous extrusion equipment, such as single screw extruders. Melt mixing is conducted for sufficient time and at a suitable temperature to blend the masterbatch with the other ingredients. Those skilled in the art will appreciate that melt mixing is generally performed within a suitable temperature range and that this range will vary depending upon the nature of the polymer(s) being processed.

The final composition can desirably provide articles (e.g., extruded, molded) having a multilayer, co-continuous plate-like morphology. When in the form of a film, the final thickness of each individual layer can be from 1 nm to 10,000 nm, or from 10 nm to 10,000 nm, or from 10 nm to 1000 nm, or from 10 nm to 100 nm, or from 15nm to 50 nm, or from 15 nm to 30 nm. The thickness of the entire sheet can be from 1 μιη to 1000 μιη, or from 1 μιη to 100 μιη, or from 10 μιη to 75 μιη, or from 12 μιη to 50 μιη, or any increments therein.

The masterbatch pellets of FIG. 10 (polymer A/polymer B) were melt-mixed and re-extruded (via single screw extruder) with a polymer B matrix polymer according to the method of the present invention. Surprisingly, it was found that even with the re-melting and shear flow experienced in reprocessing, the multi-layered co-continuous plate-like morphology is largely maintained in the final polymeric composition (e.g., an article such as a packaging film) as shown by the SEM photograph of FIG. 11, at least when viewed in at least some 10 micron x 10 micron, lengthwise, cross-sectional SEMs. A single-screw extruder can be used for this process, since lower levels of energy (e.g., stress and shear) are required to obtain the desired morphology when the masterbatch of the present invention is used in place of a traditional masterbatch polymer blend. The ability to use a single-screw rather than a twin-screw extruder can provide cost-savings through decreased energy usage, as well as by eliminating the need to purchase a more expensive twin-screw extruder.

It should be noted that, as mentioned above, the final polymeric composition of the present invention largely maintains the plate-like morphology of the masterbatch composition, but may not not entirely maintain it when viewed in some 10 micron x 10 micron SEMS (see, e.g., FIG. 12). Instead, the final polymeric composition may comprise a plurality of smaller multi-layer plate segments. These segments are small sections of the multi-layered continuous plate-like masterbatch composition. While not wishing to be limited by theory, it is believed that when the plurality of pellets (or other segment forms) are added to the extruder (e.g., shoveled into the extruder) for re-melting, their orientation relative to one another and to the direction of shear will essentially be random. As the pellets are melt- mixed (for example, with a matrix polymer), one would reasonably expect that their characteristic multi-layer plate-like morphology would be lost to the forces of shear and heat, especially considering that the pellets are randomly oriented and thus the direction of shear relative to the direction of the pellets' plates would also vary randomly. The expected loss of plate-like morphology would be magnified even further by the effects of dilution with a matrix polymer. Thus, one would not expect the morphology of the final polymer composition to resemble the plate-like morphology, and in some instances co-continuous plates when viewed in a 10 micron x 10 micron, lengthwise cross-sectional SEM, that is so highly desired.

Surprisingly, however, it has been discovered that the final polymer composition of the present invention does retain a somewhat plate-like , contiguous morphology, despite the effects of melt- mixing and combination with a matrix polymer. FIG. 11 shows a film made according to the present invention that comprises 20% of an immiscible polymer A / 80% of an immiscible polymer B, made by re-extruding (via single-screw extruder) the Polymer A-Polymer B pellet of FIG. 10 with a polymer B matrix (e.g., dilution) polymer. This sample shows a plate-like morphology of finite length (i.e., plates are not infinitely long), yet relative to their thickness they are still very "platelike". Thus, the plate-like layered structure is largely maintained, and some of the plates may even be co-continuous. FIG. 12 shows the same film as in FIG. 11 but at a different sampling point on the film. This sample shows a plate-like structure of finite length (i.e., plates are not infinitely long), yet relative to their thickness they are still very "plate-like" and some of the plate morphologies are also continuous within the 10 micron x 10 micron SEM with some of the plates also being co-continuous, although perhaps not continguous. Creating a polymer composition by combining the masterbatch composition of the present invention with other ingredients can provide a final polymer composition that exhibits improved compatibility between its constituent components, relative to compositions having the same formulation but created via conventional means (e.g., melt mixing all ingredients simultaneously). Without wishing to be limited by theory, it is believed that the inclusion of the masterbatch composition having a cocontinuous plate-like morphology gives rise to the improved compatibility between the constituent components of the masterbatch composition and other ingredients comprising the composition. Nano layering the masterbatch composition creates much more interfacial area between phases than is possible with traditional compatibilization and mixing. This increase in interfacial area results in improved compatibility beyond that previously observed with blends of incompatible materials. The improved compatibility between components in polymer compositions of the present invention is at least in part believed to be responsible for the compositions' excellent physical and mechanical properties. The planar configuration enables alteration of the stress transfer mechanism, which leads to alterations in ultimate mechanical properties, etc. In contrast, the tubular structures can fracture more easily under stress or melt processing, rendering the morphology heterophasic in most applications.

Another advantage of preparing a polymer composition in accordance with the present invention is that melt mixing may be performed at a minimum melt processing temperature. This is in contrast with methods where the separate ingredients are simultaneously melt-mixed in a single melt process to prepare the final polymer composition. Using this latter type of methodology, it is typically necessary to employ temperatures above the minimum melt processing temperature to achieve sufficient melting and/or to form a compatibilizer in situ. A notable disadvantage of performing the melt mixing process at a temperature above the minimum processing temperature is that lower-melting polymers can thermally degrade. This can have the effect of reducing the physical and mechanical properties of the resulting polymer composition. Given that there is no need to form compatibilizer in situ during melt mixing of the matrix polymer and the masterbatch composition in accordance with the present invention, high melt mixing temperatures can advantageously be avoided.

This method could potentially replace twin-screw extrusion as the process method of choice for material mixing. Twin screw extruders are effective mixers, but do not typically produce plate- like, or even co-continuous plate-like, morphology. III. THERMOPLASTIC POLYMERS

Thermoplastic polymers, as used herein, are polymers that melt and then, upon cooling, crystallize or harden, but can be re-melted upon further heating. Suitable thermoplastic polymers for use herein typically have a melting temperature from 60°C to 300°C, from 80°C to 250°C, or from 100°C to 215°C. The molecular weight of the thermoplastic polymer is sufficiently high to enable entanglement between polymer molecules and yet low enough to be melt extrudable. Suitable thermoplastic polymers can have weight average molecular weights of 1000 kDa or less, 5 kDa to 800 kDa, 10 kDa to 700 kDa, or 20 kDa to 400 kDa. The weight average molecular weight is determined by the specific ASTM method for each polymer, but is generally measured using either gel permeation chromatography (GPC) or from solution viscosity measurements.

The thermoplastic polymers can be derived from renewable resources or from fossil-based materials. The thermoplastic polymers derived from renewable resources are bio-based, such as bio- produced ethylene and propylene monomers used in the production of polypropylene and

polyethylene. Renewable material properties are essentially identical to fossil-based product equivalents, except for the presence of carbon-14 in the bio-based thermoplastic polymer. To determine the level of renewable materials present in an unknown composition (e.g., in a product made by a third party), ASTM D6866 test method B can be used to measure the biobased content by measuring the amount of carbon-14 in the product. Materials that come from biomass (i.e.

renewable sources) have a well-characterized amount of carbon-14 present, whereas those from fossil sources do not contain carbon-14. Thus, the carbon-14 present in the product is correlated to its bio-based content.

Renewable and fossil based thermoplastic polymers can also be used in combination.

Recycled thermoplastic polymers can also be used, alone or in combination with renewable and/or fossil derived thermoplastic polymers. The recycled thermoplastic polymers can be pre-conditioned to remove any unwanted contaminants prior to compounding or they can be used during the compounding and extrusion process, as well as simply left in the admixture. These contaminants can include trace amounts of other polymers, pulp, pigments, inorganic compounds, organic compounds and other additives typically found in processed polymeric compositions. The contaminants should not negatively impact the final performance properties of the admixture. Biodegradable thermoplastic polymers also are contemplated for use herein. Biodegradable materials are susceptible to being assimilated by microorganisms, such as molds, fungi, and bacteria when the biodegradable material is buried in the ground or otherwise contacts the microorganisms (including contact under environmental conditions conducive to the growth of the microorganisms). Suitable biodegradable polymers also include those biodegradable materials that are

environmentally-degradable using aerobic or anaerobic digestion procedures, or by virtue of being exposed to environmental elements such as sunlight, rain, moisture, wind, temperature, and the like. The biodegradable thermoplastic polymers can be used individually or as a combination of biodegradable or non-biodegradable polymers. Biodegradable polymers include polyesters containing aliphatic components.

Suitable thermoplastic polymers generally include thermoplastic starch, polyolefins, polyesters, polyamides, copolymers thereof, and combinations thereof. For example, the thermoplastic polymer can be selected from the group consisting of TPS, polypropylene, polyethylene, polypropylene co-polymer, polyethylene co-polymer, polyethylene terephthalate, polybutylene terephthalate, polylactic acid ("PLA"), polyhydroxyalkanoates ("PHA"), polyamide-6, polyamide-6,6, and combinations thereof. Various thermoplastic polymers that can be useful in the present invention are discussed in more detail below.

A. Thermoplastic Starch ("TPS")

As used herein, "thermoplastic starch" or "TPS" means a native starch or a starch derivative that has been rendered destructured and thermoplastic by treatment with one or more plasticizers, with at least one starch plasticizer still remaining. Thermoplastic starch compositions are well known and disclosed in several patents, for example: U.S. Patent Nos. 5,280,055; 5,314,934;

5,362,777; 5,844,023; 6,214,907; 6,242,102; 6,096,809; 6,218,321; 6,235,815; 6,235,816; and 6,231,970.

Since natural starch generally has a granular structure, it needs to be destructurized before it can be melt processed like a thermoplastic material. For gelatinization, e.g., the process of destructuring the starch, the starch can be destructurized in the presence of a solvent which acts as a plasticizer. The solvent and starch mixture is heated, typically under pressurized conditions and shear to accelerate the gelatinization process. Chemical or enzymatic agents may also be used to destructurize, oxidize, or derivatize the starch. Commonly, starch is destructured by dissolving the starch in water. Fully destructured starch results when the particle size of any remaining undestructured starch does not impact the extrusion process. Any remaining undestructured starch particle sizes are less than 30μιη (by number average), commonly less 15μιη, more commonly less than 5μιη, or less than 2μιη. The residual particle size can be determined by pressing the final formulation into a thin film (50μιη or less) and placing the film into a light microscope under cross polarized light. Under cross polarized light, the signature maltese cross, indicative of undestructured starch, can be observed. If the average size of the particle is above the target range, the destructured starch has not been prepared properly. An alternative process for measuring the amount and size of undestructured starch is by means of a melt filtration test in which a composition containing the starch is passed through a series of screens that can capture residual undestructured starch. Suitable naturally occurring starches can include, but are not limited to, corn starch, potato starch, sweet potato starch, wheat starch, sago palm starch, tapioca starch, rice starch, soybean starch, arrow root starch, bracken starch, lotus starch, cassaya starch, waxy maize starch, high amylose corn starch, and commercial amylose powder. Blends of starch may also be used. Though many starches are useful herein, the present invention is most commonly practiced with natural starches derived from agricultural sources, which offer the advantages of being abundant in supply, easily replenishable and inexpensive in price. Naturally occurring starches, particularly corn starch, wheat starch, and waxy maize starch, can be the starch polymers of choice due to their economy and availability.

Modified starch may also be used. Modified starch is defined as non-substituted or substituted starch that has had its native molecular weight characteristics changed (i.e., the molecular weight is changed but no other changes are necessarily made to the starch). If modified starch is desired, chemical modifications of starch typically include acid or alkali hydrolysis and oxidative chain scission to reduce molecular weight and molecular weight distribution. Natural, unmodified starch generally has a very high average molecular weight and a broad molecular weight distribution (e.g. natural corn starch has an average molecular weight of up to 60,000,000 grams/mole (g/mol)). The average molecular weight of starch can be reduced to the desirable range for the present invention by acid reduction, oxidative reduction, enzymatic reduction, hydrolysis (acid or alkaline catalyzed), physical/mechanical degradation (e.g., via the thermomechanical energy input of the processing equipment), or combinations thereof. The thermomechanical method and the oxidative method offer an additional advantage when carried out in situ. The exact chemical nature of the starch and molecular weight reduction method is not critical as long as the average molecular weight is in an acceptable range.

A plasticizer can be used to destructurize the starch and enable the starch to flow (i.e., create a thermoplastic starch). The same plasticizer may be used to increase melt processability or two separate plasticizers may be used. The plasticizers may also improve the flexibility of the final products, which is believed to be due to the lowering of the glass transition temperature of the composition by the plasticizer. The plasticizers should be substantially compatible with the polymeric components of the disclosed compositions so that the plasticizers may effectively modify the properties of the composition. As used herein, the term "substantially compatible" means when heated to a temperature above the softening and/or the melting temperature of the composition, the plasticizer is capable of forming a substantially homogeneous mixture with starch.

Nonlimiting examples of useful hydroxyl plasticizers include sugars such as glucose, sucrose, fructose, raffinose, maltodextrose, galactose, xylose, maltose, lactose, mannose erythrose, glycerol, and pentaerythritol; sugar alcohols such as erythritol, xylitol, malitol, mannitol and sorbitol; polyols such as ethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, hexane triol, and the like, and polymers thereof; and mixtures thereof. Also useful herein as hydroxyl plasticizers are poloxomers and poloxamines. Also suitable for use herein are hydrogen bond forming organic compounds which do not have hydroxyl groups, including urea and urea derivatives; anhydrides of sugar alcohols such as sorbitan; animal proteins such as gelatin; vegetable proteins such as sunflower protein, soybean proteins, cotton seed proteins; and mixtures thereof. Other suitable plasticizers are phthalate esters, dimethyl and diethylsuccinate and related esters, glycerol triacetate, glycerol mono and diacetates, glycerol mono, di, and tripropionates, and butanoates, which are biodegradable. Aliphatic acids such as ethylene acrylic acid, ethylene maleic acid, butadiene acrylic acid, butadiene maleic acid, propylene acrylic acid, propylene maleic acid, and other hydrocarbon based acids. All of the plasticizers may be use alone or in mixtures thereof.

Common plasticizers include glycerin, mannitol, and sorbitol, with sorbitol being the most common. The amount of plasticizer is dependent upon the molecular weight, amount of starch, and the affinity of the plasticizer for the starch. Generally, the amount of plasticizer increases with increasing molecular weight of starch. B. Polyolefins ("PO") Common polyolefins include polyethylene ("PE"), polypropylene ("PP"), polymethylpentene ("PMP"), polybutene-1 ("PB-1"), low density polyethylene ("LDPE"), high density polyethylene ("HDPE"), linear low density polyethylene ("LLDPE"), polypropylene ("PP"), and copolymers thereof. The polyolefin component can be a single polymer species or a blend of two or more polyolefins.

Polyolefins typically used herein include polyethylene or copolymers thereof, including low density, high density, linear low density, or ultra low density polyethylenes such that the

polyethylene density ranges from 0.85 grams per cubic centimeter to 0.97 grams per cubic centimeter, or from 0.92 to 0.95 grams per cubic centimeter. The density of the polyethylene is determined by the amount and type of branching and depends on the polymerization technology and co-monomer type. Polypropylene and/or polypropylene copolymers, including atactic

polypropylene, isotactic polypropylene, syndiotactic polypropylene, or combinations thereof can also be used. Polypropylene copolymers, especially ethylene, can be used to lower the melting temperature and improve properties. These polypropylene polymers can be produced using metallocene and Ziegler-Natta catalyst systems. These polypropylene and polyethylene

compositions can be combined together to custom engineer end-use properties.

If the polymer is polypropylene, the polyolefin can have a melt flow index (MFI) of greater than 0.5 g/10 min, as measured by ASTM D-1238, used for measuring polypropylene. Other contemplated melt flow indices include greater than 5 g/10 min, greater than 10 g/10 min, or 5 g/10 min to 50 g/10 min.

Non-limiting examples of suitable commercially available polypropylene or polypropylene copolymers include Basell Profax PH-835™ (a 35 melt flow rate Ziegler-Natta isotactic

polypropylene from Lyondell-Basell), Basell Metocene MF-650W™ (a 500 melt flow rate metallocene isotactic polypropylene from Lyondell-Basell), Polybond 3200™ (a 250 melt flow rate maleic anhydride polypropylene copolymer from Crompton), Exxon Achieve 3854™ (a 25 melt flow rate metallocene isotactic polypropylene from Exxon-Mobil Chemical), and Mosten NB425™ (a 25 melt flow rate Ziegler-Natta isotactic polypropylene from Unipetrol). Other suitable polymers may include; Danimer 27510™ (a polyhydroxyalkanoate polypropylene from Danimer Scientific LLC), Dow Aspun 6811 A™ (a 27 melt index polyethylene polypropylene copolymer from Dow Chemical), and Eastman 9921™ (a polyester terephthalic homopolymer with a nominally 0.81 intrinsic viscosity from Eastman Chemical). C. Polyamides

Other suitable polymers include polyamides or copolymers thereof, such as Nylon 6, Nylon 11, Nylon 12, Nylon 46, Nylon 66; polyesters or copolymers thereof, such as maleic anhydride polypropylene copolymer, polyethylene terephthalate; olefin carboxylic acid copolymers such as ethylene/acrylic acid copolymer, ethylene/maleic acid copolymer, ethylene/methacrylic acid copolymer, ethylene/vinyl acetate copolymers or combinations thereof; polyacrylates,

polymethacrylates, and their copolymers such as poly(methyl methacrylates), polystyrene/methyl methacrylate copolymers, and combinations thereof.

D. Polyesters

Polyesters, especially renewable and/or biodegradable polyesters, may be employed in the present invention. Such polyesters can include aliphatic polyesters, such as polycaprolactone, polyesteramides, polylactic acid (PLA) and its copolymers, polyglycolic acid, polyalkylene carbonates (e.g., polyethylene carbonate), poly-3-hydroxybutyrate (PHB), poly- 3 -hydroxy valerate (PHV), poly-3-hydroxybutyrate-co-4-hydroybutyrate, poly-3-hydroxybutyrate-co-3-hydroxyvalerate copolymers (PHBV), poly-3-hydroxybutyrate-co-3-hydroxyhexanoate, poly-3-hydroxybutyrate-co- 3-hydroxyoctanoate, poly-3-hydroxybutyrate-co-3-hydroxydecanoate, poly-3-hydroxybutyrate-co-3- hydroxyoctadecanoate, and succinate-based aliphatic polymers (e.g., polybutylene succinate, polybutylene succinate adipate, polyethylene succinate); aliphatic-aromatic copolyesters (e.g., polybutylene adipate terephthalate, polyethylene adipate terephthalate, polyethylene adipate isophthalate, polybutylene adipate isophthalate); aromatic polyesters (e.g., polyethylene

terephthalate, polybutylene terephthalate, poly(ethylene 2,5-furandicarboxylate)); and combinations thereof.

1. PLA

A particularly suitable rigid polyester is polylactic acid, which may generally be derived from monomer units of any isomer of lactic acid, the monomeric precursor of PLA. Lactic acid can be obtained either by carbohydrate fermentation or by common chemical synthesis. Also known as "milk acid", lactic acid is the simplest hydroxyl acid with an asymmetric carbon atom and two optically active configurations, namely the L and D isomers, which can be produced in bacterial systems, whereas mammalian organisms only produce the L isomer, which is easily assimilated during metabolism. Lactic acid is mainly prepared by the bacterial fermentation of carbohydrates. These fermentation processes can be classified according to the type of bacteria used. Most fermentation processes use species of Lactobacilli which give high yields of lactic acid. Some organisms predominantly produce the L isomer, such as Lactobacilli amylophilius, L. bavaricus, L. cosei, and L. maltaromicus, whereas L. delbrueckii, L. jensenii or L. acidophilus produce the D isomer or a mixture of L and D. In general, the sources of basic sugars are glucose and maltose from corn or potato, sucrose from cane or beet sugar, etc. After separating the lactate solution from the cells (biomass) and other remaining solid materials, the product is then evaporated, crystallized, and acidified to obtain the crude lactic acid. Before undergoing polymerization, it can be purified by separation techniques such as untra-filtration, nano-filtration, electro-dialysis, and ion-exchange processes.

Synthesis of PLA is a multi-step process which can follow at least three main routes. In one production route, lactic acid is condensation polymerized to yield a low molecular weight, brittle polymer which, for the most part, is unusable, unless external coupling agents are employed to increase its chains length. The second route is the azeotropic dehydrative condensation of lactic acid. This can yield high molecular weight PLA without the use of chain extenders or special adjuvents. The third and main process involves the intermediate step of forming lactides from the lactic acid, which are then subjected to ring-opening polymerization (ROP) to obtain high molecular weight PLA.

The polylactic acid may be a homopolymer or a copolymer, such as one that contains monomer units derived from L-lactic acid and monomer units derived from D-lactic acid. Multiple polylactic acids, each having a different ratio between the monomer unit derived from L-lactic acid and the monomer unit derived from D-lactic acid, may be included at any desired percentage.

The physical properties of polylactide are related to the enantiomeric purity of lactic acid stereo-copolymers. The physical properties of polylactide are related to the enantiomeric purity of the lactic acid stereo-copolymers. Homo-PLA is a linear macromolecule with a molecular architecture that is determined by its stereochemical composition. PLA can be produced that is totally amorphous or up to 40% crystalline. PLA resins containing more than 93 % of L-lactic acid are semi-crystalline, but PLA having 50-93 % L-lactic acid is completely amorphous. Thus, the L/D ratio induces or restrains polymer crystallinity.

Both meso- and D-lactides induce twists in the very regular PLLA architecture.

Macromolecular imperfections are responsible for the decrease in both the rate and the extent of PLLA crystallization. In practice, most PLAs are made up of L and D,L-lactide copolymers, since the reaction media often contain some meso-lactide impurities. Depending on the preparation conditions, PLLA crystallizes into different forms. The alpha-form exhibits a well-defined diffraction pattern, has a melting temperature of 185°C, and is more stable than its beta-counterpart, which melts at 175°C. The latter can be formed at a high draw ratio and high drawing temperature. The c-form is found by epitaxial crystallization. It has been observed that a blend with equivalent PLLA and PDLA contents gives stereocomplexation (racemic crystallite) of both polymers. This stereo-complex gives mechanical properties higher than those of pure PLLA or PDLA and a high Tm equal to 230°C.

The literature reports different density data for PLA, as crystalline parts can have a density of

1.29 compared to 1.25 for the amorphous material. PLA is a slowly crystallizing polymer similar to PET. As with PET, PLA can be oriented by processing. Chain orientation increases the mechanical strength of PLLA plastics. If orientation is performed at low temperature, the resulting PLLA has enhanced modulus without a significant increase in crystallinity. To determine crystallinity levels by DSC, the value, most often referred in the literature concerning the PLA melt enthalpy at 100 % crystallinity, is 93 J/g. Crystallization of the thermally crystallizable but amorphous PLA can be initiated by annealing at temperatures between 75 C and Tm. The annealing of crystallizable PLA copolymers often produces two melting peaks. Different hypothesis have been presented. Some authors found double melting points in PLLA polymers and attributed them to the slow rates of crystallization and recrystallization. The typical Tg of PLA ranges from 50 to 80°C while the Tm ranges from 130 to 180°C. For instance, enantiomerically pure PLA is a semi-crystalline polymer with a Tg of 55°C and a Tm of 180 °C. For semi-crystalline PLA, the Tm is a function of the different processing parameters and the initial PLA structure. Tm increases with the molecular weight (Mw) until a maximum value. Besides, the crystallinity decreases with increasing Mw. Tg is also determined by the proportion of the different types of lactide. Tm depends on the presence of meso-lactide in the structure which produces a Tm reduction.

PLA can be plasticized using oligomeric lactic acid (o-LA), citrate ester, or low molecular weight polyethylene glycol (PEG). The effect of plasticization increases the chain mobility and then favors the PLA organization and crystallization. After plasticization, a crystallinity ranging between 20 and 30 % is obtained. PLA presents a medium water and oxygen permeability level comparable to polystyrene. These different properties associated with its tunability and its availability favor its actual use in different packaging applications (trays, cups, bottles, films). An example of a suitable polylactic acid polymer that may be used in the present invention is commercially available from Biomer, Inc. of Krailling, Germany, under the name BIOMER

(Registered Trademark) L9000. Other suitable polylactic acid polymers are commercially available from Natureworks LLC of Minnetonka, Minn. (NATUREWORKS (Registered trademark) ) or Mitsui Chemical (LACEA (Registered Trademark) ). Still other suitable polylactic acids may be described in U.S. Pat. Nos. 4,797,468; 5,470,944; 5,770,682; 5,821,327; 5,880,254; and 6,326,458, which are incorporated herein in their entirety by reference thereto for all purposes.

The polylactic acid typically has a number average molecular weight ("Mn") ranging from about 40,000 to about 160,000 grams per mole, in some embodiments from about 50,000 to about 140,000 grams per mole, and in some embodiments, from about 80,000 to about 120,000 grams per mole. Likewise, the polymer also typically has a weight average molecular weight ("Mw") ranging from about 80,000 to about 200,000 grams per mole, in some embodiments from about 100,000 to about 180,000 grams per mole, and in some embodiments, from about 110,000 to about 160,000 grams per mole.

The ratio of the weight average molecular weight to the number average molecular weight

("Mw/Mn"), i.e., the "polydispersity index", is also relatively low. For example, the polydispersity index typically ranges from about 1.0 to about 3.0, in some embodiments from about 1.1 to about 2.0, and in some embodiments, from about 1.2 to about 1.8. The weight and number average molecular weights may be determined by methods known to those skilled in the art.

The polylactic acid may also have an apparent viscosity of from about 50 to about 600 Pascal seconds (Pa.s), in some embodiments from about 100 to about 500 Pa.s, and in some embodiments, from about 200 to about 400 Pa.s, as determined at a temperature of 190 deg. C. and a shear rate of 1000 see. The melt flow rate of the polylactic acid (on a dry basis) may also range from about 0.1 to about 40 grams per 10 minutes, in some embodiments from about 0.5 to about 20 grams per 10 minutes, and in some embodiments, from about 5 to about 15 grams per 10 minutes, determined at a load of 2160 grams and at 190 deg. C.

Aliphatic biopolymers such as PLA are biodegradable. The main abiotic degradation phenomena involve thermal and hydrolytic degradation. During the composting state, PLA degrades in a multistep process involving different mechanisms. Primarily, after exposure to moisture by abiotic mechanisms, PLA degrades by hydrolysis.

2. Polvhydroxyalkanoates ("PHAs") PHAs are a family of intracellular biopolymers synthesized by many bacteria as intracellular carbon and energy storage granules. PHAs are mainly produced from renewable resources by fermentation. A wide variety of prokaryotic organisms accumulate PHA from 30 to 80% of their cellular dry weight. Depending on the carbon substrates and the metabolism of the microorganism, different monomers, and thus (co)polymers, can be obtained. PHAs are biodegradable and thus suitable for many packaging uses (e.g., disposable packaging). PHAs can be degraded by abiotic degradation (i.e., simple hydrolysis of the ester bond without requiring the presence of enzymes to catalyze this hydrolysis) or bidegradation (i.e., biotic degradation).

PHAs are generally classified into short-chain-length PHA (sCL-PHA) and medium-chain- length PHA (mCL-PHA) by the different number of carbons in their repeating units. For instance, sCL-PHAs contain 4 or 5 carbons in their repeating units, while mCL-PHAs contain 6 or more carbons in the repeating units. The term mCL was coined because the number of carbons in the monomers roughly corresponds to those of medium-chain-length carboxylic acids.

The main biopolymer of the PHA family is the polyhydroxybutyrate homopolymer (PHB), but also different poly(hydroxybutyrate-cohydroxyalkanoates) copolyesters exist such as

poly(hydroxybutyrate-co-hydroxy valerate) (PHBV), poly(hydroxybutyrate-co-hydroxyhexanoate) (PHBHx), poly(hydroxybutyrate-co-hydroxyoctanoate) (PHBO), and poly(hydroxybutyrateco- hydroxyoctadecanoate) (PHBOd).

Copolymers of PHAs vary in the type and proportion of monomers, and are typically random in sequence. PHB is a highly crystalline polyester (above 50 %) with a high melting point, Tm=173- 180 °C, compared to the other biodegradable polyesters. The Tg is around 5 °C. The homopolymer shows a narrow window for the processing conditions. To ease the transformation, PHB can be plasticized with citrate ester. In contrast, PHBV copolymer processing is easier. Material properties can be tailored by varying the HV content. An increase of the HV content induces an increase in impact strength and decreases in Tm and Tg, crystallinity, water permeability, and tensile strength. Further, PHBV properties can be modified when plasticization occurs, e.g., with citrate ester (triacetin).

PHAs, like the PLAs, are sensitive to processing conditions. Under extrusion, rapid decreases in viscosity and molecular weight are observed due to macromolecular chain cleavage by increasing the shear level, the temperature, and/or the residence time. Regarding the biodegradable behavior, the kinetic of enzymatic degradation is variable according to the crystallinity, the structure, and thus the processing history. Bacterial copolyesters biodegrade faster than homopolymers and synthetic copolyesters.

PHA can replace synthetic non-degradable polymers for a wide range of applications:

packaging, agriculture, leisure, fast- food, and hygiene as well as medicine and biomedical, since PHA is biocompatible.

3. Petroleum-Based Polyesters

A large number of biodegradable polyesters are based on petroleum resources, obtained chemically from synthetic monomers. These include polycaprolactone, aliphatic copolyesters, and aromatic copolyesters, all of which are soft at room temperature.

Poly(e-caprolactone) (PCL) is usually obtained by ROP of e-caprolactone in the presence of metal alkoxides (e.g., aluminium isopropoxide, tin octanoate). PCL is widely used as a PVC solid plasticizer or for polyurethane applications, as polyols. It also finds applications based on its biodegradable character in domains such as biomedicine (e.g. drugs controlled release) and the environment (e.g. soft compostable packaging). PCL shows a very low Tg (-61 °C) and a low Tm (65 °C), which could be a handicap in some applications. Therefore, PCL is generally blended or modified (e.g., copolymerization, crosslinking). PCL can be hydrolyzed and biodegraded by fungi. PCL can easily be enzymatically degraded.

A large number of aliphatic copolyesters based on petroleum resources are biodegradable copolymers. They are obtained by the combination of diols such as 1,2-ethanediol, 1,3-propanediol or 1,4-butadenediol, and of dicarboxylic acids like adipic, sebacic or succinic acid. Polybutylene succinate (PBS) can be obtained by polycondensation of 1,4-butanediol and succinic acid.

Polybutylene succinate/adipate (PBS A) is obtained by addition of adipic acid to 1,4-butanediol and succinic acid polycondensation. Other polycondensation reactions have been used to produce other condensates, such as polycondensation of 1,2-ethanediol, 1,4-butadenediol with succinic and adipic acids to produce aliphatic copolyester. The properties of these copolyesters depend on the structure i.e., the combination of diols and diacids used. The biodegradability of these products depends also on the structure. The addition of adipic acid, which decreases the crystallinity, tends to increase the compost biodegradation rate.

Aromatic copolyesters are often based on terephthalic acid. For instance, the chemical structure of poly(butylene adipate-co-terephthalate) (PBAT).

E. Other Thermoplastic Polymers Other nonlimiting examples of suitable polymers include polycarbonates, polyvinyl acetates, poly(oxymethylene), styrene copolymers, polyetherimides, polysulfones, polyvinyl alcohol, ethylene acrylic acid, polyolefin carboxylic acid copolymers, and combinations thereof. Any other suitable thermoplastic polymers, or combinations thereof, may be used herein. F. Compatibilizer

To improve the compatibility and reduce the surface tension between incompatible polymer layers, any suitable compatibilizer can be incorporated into the compatibilizer (e.g., tie layer) of the present invention. For example, in one aspect where the incompatible polymer layers are polar TPS and non-polar polyolefin layers, suitable compatibilizers can be polymers or copolymers having functional groups that present specific interactions with starch molecules and/or are capable of undergoing chemical reactions with starch functional groups to result in a chemical bond. Many of these compatibilizers have low interfacial tension and/or a partial or full miscibility with the polyolefin. Examples of functional groups that present specific interactions and/or are capable of reacting with starch are: Hydroxyl, carboxyl or carboxylate, tertiary amino and/or quaternary ammonium, sulfoxyl and/or sulfoxylate groups, and vinyl pyrrolidone copolymers.

In one aspect, a compatibilizer having hydroxyl groups is a polymer containing vinyl alcohol units. For example, such compatibilizer can be a poly (vinyl ester) wherein the ester groups are partially hydrolyzed or a copolymer containing vinyl alcohol units as well as other units such as are obtained by copolymerization of vinyl esters, commonly vinyl acetate, with monomers such as ethylene (EVOH), propylene, vinyl chloride, vinyl ethers, acrylonitrile, acrylamide, omega- octadecene, vinyl-butyl ether, vinyl-octadecyl ether, vinyl pyrrolidone and other known monomers, with subsequent hydrolysis of at least some of the vinyl-ester groups. Typical copolymers include, for example, poly (vinyl alcohol-co-vinyl-acetate); ethylene/vinyl alcohol/vinyl acetate copolymers; ethylene/vinyl chloride/vinyl alcohol/vinyl acetate graft copolymers; vinyl alcohol/vinyl

acetate/vinyl chloride copolymers; vinyl alcohol/vinyl acetate/vinyl chloride/diacryl amide copolymers; vinyl alcohol/vinyl butyral copolymers; vinyl alcohol/vinyl acetate/ vinyl pyrrolidone copolymers; vinyl alcohol/styrene copolymers.

In one aspect, a compatibilizer containing carboxylic acid and/or carboxylate groups is a synthetic polymer, such as a copolymer containing carboxylate groups as well as other units such as are obtained by copolymerization of acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, e.g., in their acid or carboxylate form, with monomers such as ethylene, vinyl chloride, vinyl esters such as vinyl acetate, vinyl ethers, acrylic acid esters, acrylonitrile, methacrylic acid esters, maleic acid esters, acrylamide, omega-octadecene, vinyl-butyl ether, vinyl pyrrolidone and other known monomers. If a carboxyl group-containing monomer is used, then at least a part of the carboxyl groups are typically neutralized with a cation. Copolymers containing carboxylate groups include those which can be described as being derived from acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, methylacrylate, methylmethacrylate, acrylamide, acrylonitrile and/or methylvinylether. Other polymers are those that can be described as being derived from acrylic acid, methacrylic acid, maleic acid, methacrylate, ethyl acrylate and/or methylvinylether. Such copolymers may be also copolymerized with ethylene, propylene, or styrene.

Such copolymers include, e.g., poly (acrylic acid-co-vinyl acetate); ethylene/acrylic acid/vinyl acetate copolymers; ethylene/vinyl chloride/acrylic acid/vinyl acetate graft copolymers; acrylic acid/vinyl acetate/vinyl chloride copolymers; acrylic acid/vinyl methylether copolymers; vinyl acetate/acrylic acid/acrylic acid methylester copolymer; vinyl acetate/crotonic acid

copolymers; vinyl acetate/maleic acid copolymers; methacrylic acid/vinyl acetate/vinyl pyrrolidone copolymers; acrylic acid/acrylonitrile copolymer; ethylene/propylene/acrylic acid copolymer; and styrene/acrylic acid copolymer, wherein a part or all of the acid groups are present in their carboxylate form. Copolymers that contain carboxylic groups are typically copolymers of acids with ethylene, e.g. the ethylene-acrylic-acid copolymer in the form of its salt or an ethylene-methacrylic acid copolymer in the form of its salt.

Compatibilizers which contain tertiary amino groups and/or salts thereof and/or quaternary ammonium groups are typically a synthetic polymer, as obtained by the polymerization of monomers containing tertiary amino groups and/or salts thereof and/or quaternary amino groups such as poly (2- vinyl pyridine); poly (4- vinyl pyridine); polyvinyl carbazole, I- vinyl imidazole and/or salts thereof and/or their quaternized derivatives as well as with other polymers as are obtained by copolymerization of such amines with other monomers such as acrylonitrile, butyl methacrylate, styrene and other known monomers. The expression amine salts includes the salts formed with an inorganic or organic acid, e.g. salts with inorganic or organic acids such as HC1, H2SO4, and acetic acid. The expressions "quaternized derivative" and "quaternary ammonium groups" mean

quaternized derivatives of tertiary amines, e.g. quaternized with an alkyl halide such as methyl chloride. Examples include those derived from 2-vinyl-pyridine, 4- vinyl pyridine and vinyl carbazole.

Compatibilizers having sulfonic acid and/or sulfonate functional groups are typically styrene sulfonic acid polymers, styrene sulfonic acid copolymers, and salts thereof. In some aspects, they are block copolymers of sulfonated styrene with unsaturated monomers such as ethylene, propylene, butylene, isobutylene, butadiene, isoprene, and/or styrene. Salts thereof include the corresponding sulfonates and their salts with metal ions or ammonium ions, for instance alkali metal ions, magnesium, zinc, NH4+, sodium, or potassium. In one aspect, the sodium salt is used.

Compatibilizers containing vinyl pyrrolidone are typically copolymers of vinyl pyrrolidone with one or more monomers selected from the group of vinyl esters, vinyl alcohol, allyl alcohol, ethylene, propylene, butylene, isoprene, butadiene, styrene, vinyl ethers, dimethylaminoethyl, methacrylate, and combinations thereof. Typical copolymers of vinyl pyrrolidone with a monomer can be selected from the group consisting of vinyl esters, vinyl alcohol, styrene, dimethylaminoethyl methacrylate, and combinations thereof. Also included are the poly (N- vinyl pyrrolidone-vinyl ester) copolymers and the poly (N- vinyl pyrrolidone-vinyl acetate) copolymers.

These and various other types of compatibilizer materials are discussed below in more detail. These materials may be used alone or in combination with other compatibilizer materials to form the compatibilizer composition / layer of the present invention. One skilled in the art will realize that many of these materials are suitable for use alone or in combination with other compatibilizer materials, while others are not suitable for use alone (e.g., because they are liquid at room

temperature) but are suitable if used in combination with other thermoplastic compatibilizer materials because of their particular chemical and/or physical properties (e.g., low melting point).

1. Polar Homopolymers and Copolymers

The compatibilizers of this class may include homopolymers inherently compatible with both immiscible thermoplastic polymers. For example, where the immiscible polymers are TPS and PO, such may include aliphatic polyesters synthesized from ring-opening polymerizations of lactones or lactides such as polycaprolactone. These materials are unique because they are polar but can have favorable interactions with polyolefins. Polycaprolactone is one example. The material is polar but is known in the art to be melt processable and compatible with polyolefins. Other compatibilizers in this class include aliphatic polyamides synthesized from ring-opening polymerizations such a polycaprolactam and polylaurylactam.

The compatibilizers may also include block copolymers of inherently polar monomers such as amides and ethers. These include amide-ether block copolymers such as polycaprolactam block ether (Pebax MH1657) and polylaurylactam block ether (Pebax MV1074).

Other example compatibilizers of the present class include aliphatic polyesters obtained from reactions of hydroxyacids having two or more carbon atoms (such as lactones or lactides) and diols such as butanediol. Examples include polybutylene succinate.

In some aspects, the efficacy of the compatibilizers in this class can be further improved with addition of typical polyethylene type compatibilizers (5:1 ratio of concentration of compatibilizers of the present class to the typical polyethylene polar copolymer type). For example, the efficacy of the amide-ether block copolymer compatibilizers can be greatly enhanced by combination with polyethylene-acrylic ester- maleic anhydride terpolymer in a 5:1 or less ratio.

2. Non-polymeric materials with both polar and non-polar functionality Non-polymeric materials having both polar and non-polar functionality can be used in combination with thermoplastic polymer materials to form the compatibilizer layer. The appropriate amount of non-polymeric material that can be included in the compatibilizer composition will vary based upon the particular application and the thermoplastic polymer material it is combined with to form the tie layer. The skilled artisan will be able to determine the proper amount of non-polymeric material that can be included, if desired, for the particular end-use application.

These compatibilizers can include non-polymeric surfactants containing both polar and non- polar functionalities such as fatty acid soaps. Examples include: lipids, epoxidized lipids, castor oil, hydrogenated castor oil, and ethoxylated castor oil. For instance, the oil, wax, or combination thereof can comprise a mineral oil or wax, such as a linear alkane, a branched alkane, or

combinations thereof. The oil, wax, or combination thereof can be selected from the group consisting of soy bean oil, epoxidized soy bean oil, maleated soy bean oil, corn oil, cottonseed oil, canola oil, beef tallow, castor oil, coconut, coconut seed oil, corn germ oil, fish oil, linseed oil, olive oil, oiticica oil, palm kernel oil, palm oil, palm seed oil, peanut oil, rapeseed oil, safflower, sperm oil, sunflower seed oil, tall oil, tung oil, whale oil, tristearin, triolein, tripalmitin, 1,2-dipalmitoolein, 1,3-dipalmitoolein, l-palmito-3-stearo-2-olein, l-palmito-2-stearo-3-olein, 2-palmito-l-stearo-3- olein, trilinolein, 1,2-dipalmitolinolein, 1-palmito-dilinolein, 1-stearo-dilinolein, 1,2-diacetopalmitin, 1,2-distearo-olein, 1,3-distearo-olein, trimyristin, trilaurin, capric acid, caproic acid, caprylic acid, lauric acid, lauroleic acid, linoleic acid, linolenic acid, myristic acid, myristoleic acid, oleic acid, palmitic acid, palmitoleic acid, stearic acid, and combinations thereof. a. Soaps

The term "soap" as used herein refers to fatty acid metal salts that have a softening, phase transition or melting point exhibited by a reduction in crystallinity or an endothermic process upon heating as measured in a differential scanning calorimeter (DSC) from 20°C to 300°C. For example, the fatty acid salt can be a metal salt having a melting point above 70°C, or above 100°C, or above 140°C. The soap can have a melting point that is lower than the melting temperature of the polyolefin in the composition.

The soap can be present in the compatibilizer layer at a weight percent of 5 wt% to 60 wt%, based upon the total weight of the composition. Other contemplated wt% ranges of soap include 8 wt% to 40 wt%, 10 wt% to 30 wt%, 10 wt% to 20 wt%, or from 12 wt% to 18 wt%, based upon the total weight of the compatibilizer layer.

The soap can be dispersed within the polyolefin such that the soap has a droplet size of less than 10 μιη, less than 5 μιη, less than 1 μιη, or less than 500 nm within the polyolefin. As used herein, the soap and the polymer form an "intimate admixture" when the soap has a droplet size less than 10 μιη within the polyolefin. The soap can comprise metal salts of fatty acid, such as magnesium stearate, calcium stearate, zinc stearate or combinations thereof. In some aspects, other soaps may include those derived from metal salts of the following metals found in group 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 ,15, 16 of the periodic table of the elements using the IUPAC naming system implemented in 1988; sodium, potassium, rubidium, cesium, silver, cobalt, nickel, copper, manganese, iron, chromium, lithium, lead, thallium, mercury, thorium, and beryllium are examples of some of these metals but are not limited to them. The fatty acid can be selected from a group consisting of carbon- 12 to carbon-22 aliphatic chain carboxylic acids, alternatively from carbon-14 to carbon-18. Non- limiting examples of specific fatty acids contemplated include capric acid, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, and mixtures thereof. Exemplary soaps include magnesium stearate, calcium stearate, zinc stearate or combinations thereof. In one aspect, the amount of other metal salt soaps is less than 50% of the amount of the primary soap, by weight of the primary soap present, or less than 25%, or less than 10%, or less than 5%.

The soap can contain fatty acids derived from various sources. The fatty acid can have a variety of chain lengths. The carbon chain lengths are mostly between C12 and C18, but may contain small fractions (e.g., less than 50 wt%) of other chain lengths. These fatty acids have common names of lauric, myristic, palmitic, stearic, oleic, linoleic, linolenic acids, and includes mixtures thereof. These fatty acids can be saturated, unsaturated, have varying degrees of saturation (e.g., partially saturated), or any variations or combinations thereof. For example, the fatty acids can comprise saturated fatty acids, such as stearic acid. These fatty acids can also be functionalized fatty acids, such as those epoxidized and/or hydroxylated. An example of a functionalized fatty acid is epoxidized oleic acid. An exemplary functionalized fatty acid also includes 12-hydroxystearic acid.

As used herein, the terms "wax" and "oil" describe the sources of the fatty acids used to produce the soap. Non-limiting examples of fatty acids used to produce soap can include beef tallow, castor wax, coconut wax, coconut seed wax, corn germ wax, cottonseed wax, fish wax, linseed wax, olive wax, oiticica wax, palm kernel wax, palm wax, palm seed wax, peanut wax, rapeseed wax, safflower wax, soybean wax, sperm wax, sunflower seed wax, tall wax, tung wax, whale wax, and combinations thereof. Non-limiting examples of specific triglycerides include triglycerides such as, for example, tristearin, tripalmitin, 1,2-dipalmitoolein, 1,3-dipalmitoolein, 1- palmito-3-stearo-2-olein, l-palmito-2- stearo-3-olein, 2-palmito-l-stearo-3-olein, 1,2- dipalmitolinolein, 1,2-distearo-olein, 1,3-distearo-olein, trimyristin, trilaurin and combinations thereof. Non- limiting examples of specific fatty acids contemplated include capric acid, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, and mixtures thereof. Other specific waxes contemplated include hydrogenated soy bean oil, partially hydrogenated soy bean oil, partially hydrogenated palm kernel oil, and combinations thereof. Inedible waxes from Jatropha and rapeseed oil can also be used. The wax can be selected from the group consisting of a hydrogenated plant oil, a partially hydrogenated plant oil, an epoxidized plant oil, a maleated plant oil, and combinations thereof.

Specific examples of such plant oils include soy bean oil, corn oil, canola oil, and palm kernel oil. The soap can alternatively comprise fossil-based materials. Specific examples of fossil- based (e.g., mineral) materials include paraffin (including petrolatum), Montan wax, as well as polyolefin waxes produced from cracking processes, such as polyethylene derived waxes.

Fossil-based (e.g., mineral) waxes and/or oils can be combined with bio-derived renewable materials in any desired proportion. For example, the soap can have greater than 10%, or greater than 50%, or from 30-100%, or from 1-100% bio-based content, (i.e., renewable biobased materials), based upon the total weight of soap present.

Soaps can be water dispersible or water insoluble. Water dispersible herein means disassociating to form a micellar structure when placed in water or other polar solvent. Water soluble soaps include sodium and potassium stearate and other metal ions from group 1 metals of the periodic table of the elements. Water insoluble soaps include metal ions from group 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 ,15, 16 of the periodic table of the elements using the IUPAC naming system implemented in 1988; examples include magnesium stearate, calcium stearate, and zinc stearate. If 50 weight percent or more of the soap is removed in the water test, then the soap is water soluble. b. Oils & Waxes

An oil or wax, as used in the compatibilizer composition, is a lipid, mineral oil (or wax), or combination thereof. An oil is used to refer to a compound that is liquid at room temperature (e.g., has a melting point of 25 °C or less) while a wax is used to refer to a compound that is a solid at room temperature (e.g., has a melting point of greater than 25°C). The wax can also have a melting point lower than the melting temperature of the highest volumetric polymer component in the composition. The term wax hereafter can refer to the component either in the solid crystalline state or in the molten state, depending on the temperature. The wax can be solid at a temperature at which the thermoplastic polymer and/or thermoplastic starch are solid. For example, polypropylene is a semicrystalline solid at 90°C, which can be above melting temperature of the wax. A wax, as used in the disclosed composition, is a lipid, mineral wax, or combination thereof, wherein the lipid, mineral wax, or combination thereof has a melting point of greater than 25°C. In one aspect, the melting point is above 35°C, or above 45°C, or above 50°C. The wax can have a melting point that is lower than the melting temperature of the thermoplastic polymer in the composition. The terms "wax" and "oil" are differentiated by crystallinity of the component at or near 25°C. In all cases, the "wax" will have a maximum melting temperature less than the thermoplastic polymer, commonly less than 100°C and most commonly less than 80°C. The wax can be a lipid. The lipid can be a monoglyceride, diglyceride, triglyceride, fatty acid, fatty alcohol, esterified fatty acid, epoxidized lipid, maleated lipid, hydrogenated lipid, alkyd resin derived from a lipid, sucrose polyester, or combinations thereof. The mineral wax can be a linear alkane, a branched alkane, or combinations thereof. The waxes can be partially or fully hydrogenated materials, or combinations and mixtures thereof, that were formally liquids at room temperature in their unmodified forms. When the temperature is above the melting temperature of the wax, it is a liquid oil. When in the molten state, the wax can be referred to as an "oil". The terms "wax" and "oil" only have meaning when measured at 25°C. The wax will be a solid at 25°C, while an oil is not a solid at 25°C. Otherwise they are used interchangeably above 25°C.

The lipid can be a monoglyceride, diglyceride, triglyceride, fatty acid, fatty alcohol, esterified fatty acid, epoxidized lipid, maleated lipid, hydrogenated lipid, alkyd resin derived from a lipid, sucrose polyester, or combinations thereof. The mineral oil or wax can be a linear alkane, a branched alkane, or combinations thereof. The waxes can be partially or fully hydrogenated materials, or combinations and mixtures thereof.

Non-limiting examples of oils or waxes contemplated in the compositions disclosed herein include beef tallow, castor oil, coconut oil, coconut seed oil, corn germ oil, cottonseed oil, fish oil, linseed oil, olive oil, oiticica oil, palm kernel oil, palm oil, palm seed oil, peanut oil, rapeseed oil, safflower oil, soybean oil, sperm oil, sunflower seed oil, tall oil, tung oil, whale oil, and

combinations thereof. Non-limiting examples of specific triglycerides include triglycerides such as, for example, tristearin, triolein, tripalmitin, 1,2-dipalmitoolein, 1,3-dipalmitoolein, l-palmito-3- stearo-2-olein, l-palmito-2- stearo-3-olein, 2-palmito-l-stearo-3-olein, trilinolein, 1,2- dipalmitolinolein, 1-palmito-dilinolein, 1-stearo- dilinolein, 1,2-diacetopalmitin, 1,2-distearo-olein, 1,3-distearo-olein, trimyristin, trilaurin and combinations thereof. Non- limiting examples of specific fatty acids contemplated include capric acid, caproic acid, caprylic acid, lauric acid, lauroleic acid, linoleic acid, linolenic acid, myristic acid, myristoleic acid, oleic acid, palmitic acid, palmitoleic acid, stearic acid, and mixtures thereof. Because the wax may contain a distribution of melting temperatures to generate a peak melting temperature, the wax melting temperature is defined as having a peak melting temperature 25°C or above as defined as when > 50 weight percent of the wax component melts at or above 25°C. This measurement can be made using a differential scanning calorimeter (DSC), where the heat of fusion is equated to the weight percent fraction of the wax. The oil/wax number average molecular weight, as determined by gel permeation chromatography (GPC), should be less than 2kDa, commonly less than 1.5kDa, still more common less than 1.2kDa.

Because the oil/wax may contain a distribution of melting temperatures to generate a peak melting temperature, the oil melting temperature is defined as having a peak melting temperature 25°C or below as defined when > 50 weight percent of the oil component melts at or below 25°C. This measurement can be made using a differential scanning calorimeter (DSC), where the heat of fusion is equated to the weight percent fraction of the oil.

The oil or wax can be from a renewable material (e.g., derived from a renewable resource). Non-limiting examples of renewable resources include plants (e.g., sugar cane, beets, corn, potatoes, citrus fruit, woody plants, lignocellulosics, hemicellulosics, cellulosic waste), animals, fish, bacteria, fungi, and forestry products. These resources can be naturally occurring, hybrids, or genetically engineered organisms. Natural resources such as crude oil, coal, natural gas, and peat, which take longer than 100 years to form, are not considered renewable resources. Mineral oil, petroleum, and petroleum jelly are viewed as a by-product waste stream of coal, and while not renewable, it can be considered a by-product oil.

Specific examples of mineral wax include paraffin (including petrolatum), Montan wax, as well as polyolefin waxes produced from cracking processes, for example polyethylene derived waxes. Mineral waxes and plant derived waxes can be combined together. Plant based waxes can be differentiated by their carbon- 14 content. c. Grease

A grease is an admixture of a soap and an oil and/or wax. The soap and oil/wax exist in a ratio dispersed within the thermoplastic polymer. The ratio of oil/wax to soap can typically be approximately 1:1, 2:1, 5:1, 10:1, 50:1 or 100:1. The grease intimate admixture is represented by an increased zero shear rate viscosity of the grease vs. the oil/wax in the grease alone. The grease intimate admixture can be prepared before combining with a thermoplastic polymer or

simultaneously with preparing the admixture with a thermoplastic polymer, in order to form a compatibilizer composition for use as a tie layer.

The grease can have a droplet size of less than 10 μιη within the solid thermoplastic polymer. Alternatively, the droplet size can be less than 5 μιη, less than 1 μιη, or less than 500 nm. The composition can comprise, based upon the total weight of the composition, from 5 wt% to 60 wt% grease, from 8 wt% to 40 wt% grease, or from 10 wt% to 30 wt% grease. Each droplet may contain a range of soap and/or oil/waxes such that a uniform distribution of each component exists within each droplet or each droplet may contain 100% soap and no oil/wax, or a droplet may contain 100% oil/wax and no soap. In one aspect, the droplets can contain both the soap and oil/waxes. For example, more that 10% of the droplets can contain soap and oil/wax, or greater than 25%, or from 10% to 50%, or from 25% to 80%.

One exemplary way to achieve a suitable dispersion of the grease within the thermoplastic polymer such that they are in intimate admixture is mixing, in a molten state, the thermoplastic polymer and the grease or grease components at a sufficient shear rate. The thermoplastic polymer is melted (e.g., exposed to temperatures greater than the thermoplastic polymer's solidification temperature) to provide the molten thermoplastic polymer and mixed with the grease or grease components. The thermoplastic polymer can be melted prior to addition of the grease or grease components or can be melted in the presence of the grease components (unless specified otherwise, grease and grease components are used interchangeably). It should be understood that when the thermoplastic polymer is melted, the temperature is sufficient that the grease can also be in a liquid crystalline, softened or in the molten state. The term grease as used herein can refer to the component either in the solid (optionally crystalline) state, liquid crystalline, softened or in the molten state, depending on the temperature. It is not required that the grease be solidified at a temperature at which the polymer is solidified. For example, polypropylene is a semi-crystalline solid at 90°C, which is above the melting point of some grease or grease mixtures.

The polymer-grease composition can further comprise an additive, desirably an additive that is grease soluble or grease dispersible. For example, the additive can be a perfume, dye, pigment, nanoparticle, antistatic agent, filler, or combinations thereof. Other additives can include nucleating agents.

Further, the thermoplastic polymer, the grease, and/or the polymer- grease composition can be sourced from renewable materials (e.g., bio-based). For example, the polymer-grease composition can have greater than 10%, or greater than 50%, or from 30-100%, or from 1-100% bio-based content. 3. Low Molecular Weight materials with both polar and non-polar functionality The compatibilizer layer can comprise non-polymer/low molecular weight oligomers or waxes including oxidized waxes such as oxidized, low molecular weight polyethylene, having a weight average molecular weight of less than 10,000 Daltons, or less than 5,000 Daltons, and in a particular aspect from 60 to 10,000 Daltons. Examples include oxidized polyethylene wax under the trade name KGT 4, available from Jingjiang Concord Plastics Technology Co., Ltd. (Jiangsu, China); AC 316, AC330, and AC395 available from Honeywell Performance Additives,

Morristown, New Jersey, USA; and Epolene™ Series from Westlake Plastics, Houston, Texas, USA.

4. Bulk Phase/In- situ Compatibilizers Bulk phase/in-situ compatibilizers can be formed in-situ by modifying the bulk phase to be inherently more polar such as through oxidation. For example, in the case of PO, this type of compatibilization is characterized by the polar functionality being present on the predominance of polyolefin chains representing the bulk phase, which is unlike traditional compatibilizers with polar functionality where only a minority of the chains in the bulk polyolefin phase actually contain polar functionality.

In some aspects where PO is modified to function as a compatibilizer, the amount of compatibilizer (i.e., modified PO) can range from 1% to 100%, or from 1% to 95%, or from 55% to 95%, by weight, of the compatibilizer layer.

The modification can be accomplished in a number of ways including peroxide modification, plasma modification, corona modification, and grafting such as anhydride functionality. The modification can also be accomplished by not preventing oxidation through reduced or eliminated usage of anti-oxidants in the various melt processing steps. The bulk polyolefin phase can be oxidized or modified off-line with known methods in the art as referenced in US Patent Nos.

5,401,811; 3,322,711 issued May 1967 to Bush et al.; 4,459,388 issued July 1984 to Hettche et al.; 4,889,847 issued December 1989 to Schuster et al.; and 5,064,908 issued November 1991 to

Schuster et al.

Further, post-reactor grafting of maleic anhydride to bulk polyolefin can result in an aspect where the grafting per polymer chain is low but overall polar functionality remains sufficient. As disclosed by "Functionalized Polyolefins: Compatibiliser & Coupling Agents for Alloys, Blends & Composites (Devendra Jain), maleic anhydride is reactively grafted after the primary polyolefin is produced.

Additionally, low concentrations of dicumyl peroxide can modify the molecular structure of LLDPE through reactive extrusion, such as disclosed in "Study of low concentrations of dicumyl peroxide on the molecular structure modification of LLDPE by reactive extrusion" (Valeria D.

Ramos et al., Polymer Testing, Volume 23, Issue 8, December 2004, Pages 949-955).

Ionizing radiation (e.g., electron beams, gamma rays) can be used to modify polyolefin properties and lead to improved compatibilization. For example, depending upon dosage, electron beams can be used to add functionality to polyolefins by producing cross-links or by creating oxidized regions on the chains. During irradiation, free radicals can be produced by breakage of covalent bonds in the polymer, creating an oxidized polymer surface. Electron beam irradiation can create compatibility by creating strong intermolecular networks. In some aspects, free radical formation leads to PO cross-linking. Controlled electron beam modifications can also create a compatible interphase around the modified PO. For instance, electron beam irradiation can be used to generate (-OH) and (C=) surface groups, transforming the once hydrophobic surface into a hydrophilic one.

G. Additives

The compositions disclosed herein can further include any suitable additive(s) as desired. Non-limiting examples of classes of additives contemplated in the compositions disclosed herein include perfumes, dyes, pigments, nanoparticles, antistatic agents, fillers, and combinations thereof. The compositions disclosed herein can contain a single additive or a mixture of additives. For example, both a perfume and a colorant (e.g., pigment and/or dye) can be present in the composition. The additive(s), when present, is/are typically present in a weight percent of 0.05 wt% to 20 wt%, or 0.1 wt% to 10 wt %, based upon the total weight of the composition. As used herein the term "perfume" is used to indicate any odoriferous material that is subsequently released from the composition as disclosed herein. A wide variety of chemicals are known for perfume uses, including materials such as aldehydes, ketones, alcohols, and esters. More commonly, naturally occurring plant and animal oils and exudates including complex mixtures of various chemical components are known for use as perfumes. The perfumes herein can be relatively simple in their compositions or can include highly sophisticated complex mixtures of natural and/or synthetic chemical components, all chosen to provide the desired scent. Typical perfumes can include, for example, woody/earthy bases containing exotic materials, such as sandalwood, civet and patchouli oil. The perfumes can be of a light floral fragrance (e.g. rose extract, violet extract, and lilac). The perfumes can also be formulated to provide desirable fruity scents, (e.g. lime, lemon, and orange). The perfumes delivered in the compositions and articles of the present invention can be selected for an aromatherapy effect, such as providing a relaxing or invigorating mood. As such, any suitable material that exudes a pleasant or otherwise desirable odor can be used as a perfume active in the compositions and articles of the present invention.

A pigment or dye can be inorganic, organic, or a combination thereof. Specific examples of pigments and dyes contemplated include pigment Yellow (C.I. 14), pigment Red (C.I. 48:3), pigment Blue (C.I. 15:4), pigment Black (C.I. 7), and combinations thereof. Specific contemplated dyes include water soluble ink colorants like direct dyes, acid dyes, base dyes, and various solvent soluble dyes. Examples include, but are not limited to, FD&C Blue 1 (C.I. 42090:2), D&C Red 6(C.I. 15850), D&C Red 7(C.I. 15850:1), D&C Red 9(C.I. 15585:1), D&C Red 21(C.I. 45380:2), D&C Red 22(C.I. 45380:3), D&C Red 27(C.I. 45410:1), D&C Red 28(C.I. 45410:2), D&C Red 30(C.I. 73360), D&C Red 33(C.I. 17200), D&C Red 34(C.I. 15880:1), and FD&C Yellow 5(C.I. 19140:1), FD&C Yellow 6(C.I. 15985:1), FD&C Yellow 10(C.I. 47005:1), D&C Orange 5(C.I. 45370:2), and combinations thereof.

Contemplated fillers include, but are not limited to, inorganic fillers such as, for example, the oxides of magnesium, aluminum, silicon, and titanium. These materials can be added as inexpensive fillers or processing aides. Other inorganic materials that can function as fillers include hydrous magnesium silicate, titanium dioxide, calcium carbonate, clay, chalk, boron nitride, limestone, diatomaceous earth, mica glass quartz, and ceramics. Additionally, inorganic salts, including alkali metal salts, alkaline earth metal salts, phosphate salts, can be used. Additionally, alkyd resins can also be added to the composition. Alkyd resins can comprise a polyol, a polyacid or anhydride, and/or a fatty acid.

Additional contemplated additives include nucleating and clarifying agents. Specific examples, suitable for polypropylene, for example, are benzoic acid and derivatives (e.g., sodium benzoate and lithium benzoate), as well as kaolin, talc and zinc glycerolate. Dibenzlidene sorbitol (DBS) is an example of a clarifying agent that can be used. Other nucleating agents that can be used are organocarboxylic acid salts, sodium phosphate and metal salts (e.g., aluminum dibenzoate). In one aspect, the nucleating or clarifying agents can be added in the range from 20 parts per million (20 ppm) to 20,000 ppm, or from 200 ppm to 2000 ppm, or from 1000 ppm to 1500 ppm.

Contemplated surfactants include anionic surfactants, amphoteric surfactants, or a combination of anionic and amphoteric surfactants, and combinations thereof, such as surfactants disclosed, for example, in U.S. Patent Nos. 3,929,678 and 4,259,217, and in EP 414 549,

WO93/08876, and WO93/08874.

Contemplated nanoparticles include metals, metal oxides, allotropes of carbon, clays, organically modified clays, sulfates, nitrides, hydroxides, oxy/hydroxides, particulate water- insoluble polymers, silicates, phosphates and carbonates. Examples include silicon dioxide, carbon black, graphite, grapheme, fullerenes, expanded graphite, carbon nanotubes, talc, calcium carbonate, betonite, montmorillonite, kaolin, zinc glycerolate, silica, aluminosilicates, boron nitride, aluminum nitride, barium sulfate, calcium sulfate, antimony oxide, feldspar, mica, nickel, copper, iron, cobalt, steel, gold, silver, platinum, aluminum, wollastonite, aluminum oxide, zirconium oxide, titanium dioxide, cerium oxide, zinc oxide, magnesium oxide, tin oxide, iron oxides (Fe203, Fe304) and mixtures thereof. Nanoparticles can increase strength, thermal stability, and/or abrasion resistance of the compositions disclosed herein, and can give the compositions electric properties.

Contemplated anti- static agents include fabric softeners that are known to provide antistatic benefits. These can include those fabric softeners having a fatty acyl group that has an iodine value of greater than 20, such as N,N-di(tallowoyl-oxy-ethyl)-N,N-dimethyl ammonium methylsulfate.

In particular aspects, the filler can comprise renewable fillers. These can include, but are not limited to, lipids (e.g., hydrogenated soybean oil, hydrogenated castor oil), cellulosics (e.g., cotton, wood, hemp, paperboard), lignin, bamboo, straw, grass, kenaf, cellulosic fiber, chitin, chitosan, flax, keratin, algae fillers, natural rubber, non-thermoplastic starch (e.g., granular starch), nanocrystalline starch), nanocrystalline cellulose, collagen, whey, gluten, and combinations thereof.

III. ARTICLES OF MANUFACTURE

The masterbatch compositions can be used to make articles in a variety of forms, including fibers, films, and molded articles. As used herein, "article" refers to the composition in its hardened state at or near 25°C. The articles can be used in their present form (e.g., a bottle, an automotive part, a component of an absorbent hygiene product), or can be used for subsequent re-melt and/or manufacture into other articles (e.g., pellets, fibers).

For example, the article can be a packaging material, such as a film, or assembly made from the composition. The film can be fabricated to be part of a packaging assembly. The packaging assembly can be used to wrap consumer products, such as absorbent articles including diapers, adult incontinence products, pantiliners, feminine hygiene pads, tampons, or tissues. In other iterations, the invention relates to a consumer product having a portion made using a flexible polymeric film, such as described herein. The polymeric film can be incorporated as part of consumer products, e.g., baffle films for adult and feminine care pads and liners, or outer cover of diapers or training pants. Additional non-limiting examples of article forms of the present invention are set forth in more detail below.

Fibers

A masterbatch composition having a plate-like morphology may be used to make fibers. The term "fiber" is defined as a solidified polymer shape with a length to thickness ratio of greater than 50. Fibers can be spun from a melt of the composition as disclosed herein. For example, melt spinning can be used to create fibers from a multi-layered co-continuous plate-like masterbatch composition.

Continuous filaments or fibers can be produced through spunbond methods. Essentially continuous or essentially discontinuous filaments or fibers can be produced through melt fibrillation methods such as meltblowing or melt film fibrillation processes. Alternatively, non-continuous

(staple fibers) fibers can be produced. For example, drawn fibers may be crimped and/or cut to form non-continuous fibers (staple fibers) used in a carding, airlaid, or fluidlaid process. Various methods of fiber manufacturing can also be combined to produce a combination technique.

Exemplary fibers forming a base substrate include continuous filaments forming spunlaid fabrics. Spunlaid fabrics are defined as unbonded fabrics having basically no cohesive tensile properties formed from essentially continuous filaments. Continuous filaments are defined as fibers with high length to diameter ratios, with a ratio of more than 10,000:1. Continuous filaments that compose the spunlaid fabric are not staple fibers, short cut fibers, or other intentionally-made short length fibers. The continuous filaments, defined as essentially continuous, are on average more than 100 mm long, or more than 200 mm long. The continuous filaments are also not crimped, intentionally or unintentionally. Essentially discontinuous fibers and filaments are defined as having a length less than 100 mm long, or less than 50 mm long.

The fibers can be converted to nonwovens by different bonding methods. Continuous fibers can be formed into a web using industry standard spunbond type technologies while staple fibers can be formed into a web using industry standard carding, airlaid, or wetlaid technologies. Typical bonding methods include: calender (pressure and heat), thru-air heat, mechanical entanglement, hydrodynamic entanglement, needle punching, and chemical bonding and/or resin bonding.

Thermally bondable fibers are required for the pressurized heat and thru-air heat bonding methods.

The fibers of the present invention may also be bonded or combined with other synthetic or natural fibers to make nonwoven articles. The synthetic or natural fibers may be blended together in the forming process or used in discrete layers. Suitable synthetic fibers include fibers made from polypropylene, polyethylene, polyester, polyacrylates, and copolymers thereof and mixtures thereof. Natural fibers include cellulosic fibers and derivatives thereof. Suitable cellulosic fibers include those derived from any tree or vegetation, including hardwood fibers, softwood fibers, hemp, and cotton. Also included are fibers made from processed natural cellulosic resources such as rayon.

The fibers of the present invention may be used to make nonwovens, among other suitable articles. Nonwoven articles are defined as articles that contain greater than 15% of a plurality of fibers that are continuous or non-continuous and physically and/or chemically attached to one another. The nonwoven may be combined with additional nonwovens or films to produce a layered product used either by itself or as a component in a complex combination of other materials, such as a baby diaper or feminine care pad.

The nonwoven products may find use in filters for air, oil and water; vacuum cleaner filters; furnace filters; face masks; coffee filters, tea or coffee bags; thermal insulation materials and sound insulation materials; nonwovens for one-time use sanitary products such as diapers, feminine pads, tampons, and incontinence articles; biodegradable textile fabrics for improved moisture absorption and softness of wear such as micro fiber or breathable fabrics; an electrostatically charged, structured web for collecting and removing dust; reinforcements and webs for hard grades of paper, such as wrapping paper, writing paper, newsprint, corrugated paper board, and webs for tissue grades of paper such as toilet paper, paper towel, napkins and facial tissue; medical uses such as surgical drapes, wound dressing, bandages, dermal patches and self-dis solving sutures; and dental uses such as dental floss and toothbrush bristles. The fibrous web may also include odor absorbents, termite repellants, insecticides, rodenticides, and the like, for specific uses.

The resultant fibers or fiber webs may also be incorporated into other materials such as saw dust, wood pulp, plastics, and concrete, to form composite materials, which can be used as building materials such as walls, support beams, pressed boards, dry walls and backings, and ceiling tiles; other medical uses such as casts, splints, and tongue depressors; and in fireplace logs for decorative and/or burning purpose. Further articles of the present invention include disposable nonwovens for hygiene and medical applications. Hygiene applications include such items as wipes, diapers, feminine pads, and tampons. Films

A masterbatch composition having a plate like morphology may be used to form a film. The film can be processed using conventional procedures for producing films on conventional coextruded film-making equipment. In general, polymers can be melt processed into films using either cast or blown film extrusion methods both of which are described in Plastics Extrusion Technology-2nd Ed. , by Allan A. Griff (Van Nostrand Reinhold-1976) .

Cast film is extruded through a linear slot die. Generally, the flat web is cooled on a large moving polished metal roll (chill roll). It quickly cools, and peels off the first roll, passes over one or more auxiliary rolls, then through a set of rubber-coated pull or "haul-off" rolls, and finally to a winder. In blown film extrusion, the melt is extruded upward through a thin annular die opening. This process is also referred to as tubular film extrusion. Air is introduced through the center of the die to inflate the tube and causes it to expand. A moving bubble is thus formed which is held at constant size by simultaneous control of internal air pressure, extrusion rate, and haul-off speed. The tube of film is cooled by air blown through one or more chill rings surrounding the tube. The tube is next collapsed by drawing it into a flattened frame through a pair of pull rolls and into a winder.

A coextrusion process requires more than one extruder and either a coextrusion feedblock or a multi-manifold die system or combination of the two to achieve a multilayer film structure. U.S. Patent Nos. 4,152,387 and 4,197,069, incorporated herein by reference, disclose the feedblock and multi-manifold die principle of coextrusion. Multiple extruders are connected to the feedblock which can employ moveable flow dividers to proportionally change the geometry of each individual flow channel in direct relation to the volume of polymer passing through the flow channels. The flow channels are designed such that, at their point of confluence, the materials flow together at the same velocities and pressure, minimizing interfacial stress and flow instabilities. Once the materials are joined in the feedblock, they flow into a single manifold die as a composite structure. Other examples of feedblock and die systems are disclosed in Extrusion Dies for Plastics and Rubber, W. Michaeli, Hanser, New York, 2nd Ed., 1992, hereby incorporated herein by reference. It may be important in such processes that the melt viscosities, normal stress differences, and melt

temperatures of the material do not differ too greatly. Otherwise, layer encapsulation or flow instabilities may result in the die leading to poor control of layer thickness distribution and defects from non-planar interfaces (e.g. fish eye) in the multilayer film.

An alternative to feedblock coextrusion is a multi-manifold or vane die as disclosed in U.S. Patent Nos. 4,152,387, 4,197,069, and 4,533,308, incorporated herein by reference. Whereas in the feedblock system melt streams are brought together outside and prior to entering the die body, in a multi-manifold or vane die each melt stream has its own manifold in the die where the polymers spread independently in their respective manifolds. The melt streams are married near the die exit with each melt stream at full die width. Moveable vanes provide adjustability of the exit of each flow channel in direct proportion to the volume of material flowing through it, allowing the melts to flow together at the same velocity, pressure, and desired width.

Since the melt flow properties and melt temperatures of polymers vary widely, use of a vane die has several advantages. The die lends itself toward thermal isolation characteristics wherein polymers of greatly differing melt temperatures, for example up to 175° F (80° C), can be processed together.

Each manifold in a vane die can be designed and tailored to a specific polymer. Thus the flow of each polymer is influenced only by the design of its manifold, and not forces imposed by other polymers. This allows materials with greatly differing melt viscosities to be coextruded into multilayer films. In addition, the vane die also provides the ability to tailor the width of individual manifolds, such that an internal layer can be completely surrounded by the outer layer leaving no exposed edges. The feedblock systems and vane dies can be used to achieve more complex multilayer structures. The films as disclosed herein can be formed into fluid pervious webs suitable for use as a topsheet in an absorbent article. As is described below, the fluid pervious web is desirably formed by macroscopically expanding a film as disclosed herein. The fluid pervious web contains a plurality of macroapertures, microapertures or both. Macroapertures and/or microapertures give the fluid pervious web a consumer-desired fiber-like or cloth-like appearance than webs apertured by methods such as embossing or perforation (e.g. using a roll with a multiplicity of pins) as are known to the art. One of skill in the art will recognize that such methods of providing apertures to a film are also useful for providing apertures to the films as disclosed herein. Although the fluid pervious web is described herein as a topsheet for use in an absorbent article, one having ordinary skill in the art will appreciate these webs have other uses, such as bandages, agricultural coverings, and similar uses where it is desirable to manage fluid flow through a surface. The macro and microapertures can be formed by applying a high pressure fluid jet comprised of water or the like against one surface of the film, desirably while applying a vacuum adjacent the opposite surface of the film. In general, the film is supported on one surface of a forming structure having opposed surfaces. The forming structure is provided with a multiplicity of apertures therethrough which place the opposed surfaces in fluid communication with one another. While the forming structure may be stationary or moving, an exemplary execution uses the forming structure as part of a continuous process where the film has a direction of travel and the forming structure carries the film in the direction of travel while supporting the film. The fluid jet and, desirably, the vacuum cooperate to provide a fluid pressure differential across the thickness of the film causing the film to be urged into conformity with the forming structure and to rupture in areas that coincide with the apertures in the forming structure.

The film passes over two forming structures in sequence. The first forming structure being provided with a multiplicity of fine scale apertures which, on exposure to the aforementioned fluid pressure differential, cause formation of microapertures in the web of film. The second forming structure exhibits a macroscopic, three-dimensional cross section defined by a multiplicity of macroscopic cross section apertures. On exposure to a second fluid pressure differential the film substantially conforms to the second forming structure while substantially maintaining the integrity of the fine scale apertures.

Such methods of aperturing are known as "hydroformation" and are described in greater detail in U.S. Patent Nos. 4,609,518; 4,629,643; 4,637,819; 4,681,793; 4,695,422; 4,778,644;

4,839,216; and 4,846,821. The apertured web can also be formed by methods such as vacuum formation and using mechanical methods such as punching. Vacuum formation is disclosed in U.S. Patent No. 4,463,045. Examples of mechanical methods are disclosed in U.S. Patent Nos. 4,798,604; 4,780,352; and 3,566,726. Molded Articles

Masterbatch compositions disclosed herein can be formed into molded or extruded articles. A molded article is an object that is formed when injected, compressed, or blown by means of a gas into shape defined by a female mold. Molded or extruded articles may be solid objects such as, for example, toys, or hollow objects such as, for example, bottles, containers, tampon applicators, applicators for insertion of medications into bodily orifices, medical equipment for single use, surgical equipment, or the like. Molded articles and processes for preparing them are generally described, e.g., in U.S. Patent No. 6,730,057 and U.S. Patent Publication No. 2009/0269527.

The masterbatch composition herein is suitable for producing container articles, such as for personal care products, household cleaning products, and laundry detergent products, and packaging for such articles. Personal care products include cosmetics, hair care, skin care, and oral care products, i.e., shampoo, soap, tooth paste. Accordingly, further disclosed herein is product packaging, such as containers or bottles comprising the composition described herein. A container can refer to one or more elements of a container, e.g., body, cap, nozzle, handle, or a container in its entirety, e.g., body and cap. The molded articles can be prepared using a variety of techniques, such as injection molding, blow molding, compression molding, or extrusion of pipes, tubes, profiles, cables, and the like.

Injection molding is a multi-step process by which the composition is heated until it is molten, then forced into a closed mold where it is shaped, and finally solidified by cooling. Three common types of machines that are used in injection molding are ram, screw plasticator with injection, and reciprocating screw devices (see Encyclopedia of Polymer Science and Engineering, Vol. 8, pp. 102-138, John Wiley and Sons, New York, 1987 ("EPSE-3").

Blow molding is used for producing bottles and other hollow objects (see EPSE-3). In this process, a tube of molten composition known as a parison is extruded into a closed, hollow mold. The parison is then expanded by a gas, thrusting the composition against the walls of a mold.

Subsequent cooling hardens the plastic. The mold is then opened and the article removed. Compression molding involves charging a quantity of a composition as disclosed herein in the lower half of an open die. The top and bottom halves of the die are brought together under pressure, and then molten composition conforms to the shape of the die. The mold is then cooled to harden the plastic. Extrusion is used to form extruded articles, such as pipes, tubes, rods, cables, or profile shapes. Compositions are fed into a heating chamber and moved through the chamber by a continuously revolving screw. Single screw or twin screw extruders are commonly used for plastic extrusion. The composition is plasticated and conveyed through a pipe die head. A haul-off draws the pipe through the calibration and cooling section with a calibration die, a vacuum tank calibration unit and a cooling unit. Rigid pipes are cut to length while flexible pipes are wound. Profile extrusion may be carried out in a one step process. Extrusion procedures are further described in Hensen, F., Plastic Extrusion Technology, p 43-100.

Tampon applicators are molded or extruded in a desired shape or configuration using a variety of molding or extrusion techniques to provide an applicator comprising an outer tubular member and an inner tubular member or plunger. The outer tubular member and plunger can be made by different molding or extrusion techniques. The outer member can be molded or extruded from a composition as disclosed herein and the plunger from another material.

Generally, the process of making tampon applicators involves an injection molding apparatus. The injection molding process is typically carried out under controlled temperature, time, and speed and involves melt processing the composition such that the melted composition is injected into a mold, cooled, and molded into a desired plastic object. In one aspect, the composition can be charged directly from the melt-mixing extruder into an injection molding apparatus and then melt molded into the desired tampon applicator.

One example of a procedure of making tampon applicators involves extruding the

composition at a temperature above the melting temperature of the composition to form a rod, chopping the rod into pellets, and injection molding the pellets into the desired tampon applicator form.

The compounders that are commonly used to melt blend thermoplastic compositions are generally single-screw extruders, twin-screw extruders, and kneader extruders. Examples of commercially available extruders suitable for use herein include the Black-Clawson single-screw extruders, the Werner and Pfleiderer co-rotating twin-screw extruders, the HAAKE.RTM. Polylab System counter-rotating twin screw extruders, and the Buss kneader extruders. General discussions of polymer compounding and extrusion molding are disclosed in the Encyclopedia of Polymer Science and Engineering, Vol. 6, pp. 571-631, 1986, and Vol. 11, pp. 262-285, 1988; John Wiley and Sons, New York.

The tampon applicators can be packaged in any suitable wrapper provided that the wrapper is soil proof and disposable. Wrappers made from biodegradable materials that create minimal or no environmental concerns for their disposal are contemplated. It is also contemplated that the tampon applicators can be packaged in wrappers made from paper, nonwoven, cellulose, thermoplastic, or any other suitable material, or combinations of these materials.

Regardless of the method by which the molded article is made, the process can involve an annealing cycle. The annealing cycle time is the holding time plus cooling time of the process of making the molded article. With process conditions substantially optimized for a particular mold, an annealing cycle time is a function of the composition. Process conditions substantially optimized are the temperature settings of the zones, nozzle, and mold of the molding apparatus, the shot size, the injection pressure, and the hold pressure. Annealing cycle times provided herein are at least ten seconds less than an annealing cycle time to form a molded or extruded article from a composition as disclosed herein. A dogbone tensile bar having dimensions of 1/2 inch length (L) (12.7 mm)x 1/8 inch width (W) (3.175 mm) x 1/16 inch height (H) (1.5875 mm) made using an Engel Tiebarless ES 60 TL injection molding machine as provided herein provides a standard article as representative of a molded or extruded article for measuring annealing cycle times herein.

The holding time is the length of time that a part is held under a holding pressure after initial material injection. The result is that air bubbles and/or sink marks, desirably both, are not visually observable on the exterior surface, desirably both exterior and interior surfaces (if applicable), with the naked eye (of a person with 20—20 vision and no vision defects) from a distance of 20 cm from the surface of the molded or extruded article. This is to ensure the accuracy and cosmetic quality of the part. Shrinkage is taken into account by the mold design. However, shrinkage of 1.5% to 5%, from 1.0% to 2.5%, or 1.2% to 2.0% can occur. A shorter holding time is determined by reducing the holding time until parts do not pass the visual test described supra, do not conform to the shape and texture of the mold, are not completely filled, or exhibit excessive shrinkage. The length of time prior to the time at which such events occur is then recorded as a shorter holding time. The cooling time is the time for the part to become solidified in the mold and to be ejected readily from the mold. The mold includes at least two parts, so that the molded article is readily removed. For removal, the mold is opened at the parting line of the two parts. The finished molded part can be removed manually from the opened mold, or it can be pushed out automatically without human intervention by an ejector system as the mold is being opened. Depending on the part geometry, such ejectors may consist of pins or rings, embedded in the mold, that can be pushed forward when the mold is open. For example, the mold can contain standard dial-type or mechanical rod-type ejector pins to mechanically assist in the ejection of the molded parts. Suitable size rod-type ejector pins are 1/8" (3.175 mm), and the like. A shorter cooling time is determined by reducing the cooling time until parts become hung up on the mold and cannot readily pop out. The length of time prior to the time at which the part becomes hung up is then recorded as a shorter cooling time.

IV. ANALYTICAL METHODS

1. Validation of Polymers Derived from Renewable Resources A suitable validation technique is through 14C analysis. A small amount of the carbon dioxide in the atmosphere is radioactive. This 14C carbon dioxide is created when nitrogen is struck by an ultra-violet light produced neutron, causing the nitrogen to lose a proton and form carbon of molecular weight 14 which is immediately oxidized to carbon dioxide. This radioactive isotope represents a small but measurable fraction of atmospheric carbon. Atmospheric carbon dioxide is cycled by green plants to make organic molecules during photosynthesis. The cycle is completed when the green plants or other forms of life metabolize the organic molecules, thereby producing carbon dioxide which is released back to the atmosphere. Virtually all forms of life on Earth depend on this green plant production of organic molecules to grow and reproduce. Therefore, the 14C that exists in the atmosphere becomes part of all life forms and their biological products. In contrast, fossil fuel-based carbon does not have the signature radiocarbon ratio of atmospheric carbon dioxide.

Assessment of the renewably based carbon in a material can be performed through standard test methods. Using radiocarbon and isotope ratio mass spectrometry analysis, the bio-based content of materials can be determined. ASTM International, formally known as the American Society for Testing and Materials, has established a standard method for assessing the bio-based content of materials. The ASTM method is designated ASTM D6866-10. The application of ASTM D6866-10 to derive a "bio-based content" is built on the same concepts as radiocarbon dating, but without use of the age equations. The analysis is performed by deriving a ratio of the amount of organic radiocarbon (14C) in an unknown sample to that of a modern reference standard. The ratio is reported as a percentage with the units "pMC" (percent modern carbon).

The modern reference standard used in radiocarbon dating is a NIST (National Institute of Standards and Technology) standard with a known radiocarbon content equivalent approximately to the year AD 1950. AD 1950 was chosen since it represented a time prior to thermo-nuclear weapons testing which introduced large amounts of excess radiocarbon into the atmosphere with each explosion (termed "bomb carbon"). The AD 1950 reference represents 100 pMC.

"Bomb carbon" in the atmosphere reached almost twice normal levels in 1963 at the peak of testing and prior to the treaty halting the testing. Its distribution within the atmosphere has been approximated since its appearance, showing values that are greater than 100 pMC for plants and animals living since AD 1950. It has gradually decreased over time with today's value being near 107.5 pMC. This means that a fresh biomass material such as corn could give a radiocarbon signature near 107.5 pMC.

Combining fossil carbon with present day carbon into a material will result in a dilution of the present day pMC content. By presuming 107.5 pMC represents present day biomass materials and 0 pMC represents petroleum derivatives, the measured pMC value for that material will reflect the proportions of the two component types. A material derived 100% from present day soybeans would give a radiocarbon signature near 107.5 pMC. If that material was diluted with 50% petroleum derivatives, for example, it would give a radiocarbon signature near 54 pMC (assuming the petroleum derivatives have the same percentage of carbon as the soybeans).

A biomass content result is derived by assigning 100% equal to 107.5 pMC and 0% equal to 0 pMC. In this regard, a sample measuring 99 pMC will give an equivalent bio-based content value of 92%.

Assessment of the materials described herein is performed in accordance with ASTM D6866. The mean values encompass an absolute range of 6% (plus and minus 3% on either side of the bio- based content value) to account for variations in end-component radiocarbon signatures. It is presumed that all materials are present day or fossil in origin and that the desired result is the amount of bio-based component "present" in the material, not the amount of bio-based material "used" in the manufacturing process.

In one aspect, the polymer composition has a bio-based content from 5% to 100%, or from 5% to 95%, or from 20% to 100%, or from 20% to 90%, or from 60% to 100%, or from 60% to 90%, or from 70% to 100%, or from 70% to 90%, or from 80% to 100%, or from 80% to 95% bio- based content, as measured using ASTM D6866-10, method B.

In order to apply the methodology of ASTM D6866-10 to determine the bio-based content of a composition, a representative sample of the composition must be obtained for testing. In one aspect, a representative portion of the composition can be ground into particulates less than about 20 mesh using known grinding methods (e.g., Wiley® mill), and a representative sample of suitable mass taken from the randomly mixed particles.

2. SEM

Scanning Electron Microscopy ("SEM") is the primary method used for characterizing the morphology of materials produced by the described invention. Samples are freeze fractured with liquid N2 in the cross -direction ("CD") by thickness plane (i.e., the plane with the machine direction normal to the plane). For samples containing flexible/low modulus materials, the samples can also be prepared by dipping in liquid N2 and then slicing with a razor blade. The samples are sputter coated with ~ 4 angstroms of gold using a Denton Vacuum sputter coating device. The samples are then attached to an SEM stage using double sided conductive tape. A Hitachi S-3500N SEM is used for the analysis. Samples are examined at lOkV using a continuous scanning mode under full vacuum conditions. Micrographs are captured and measured using software provided with the Hitachi S-3500N.

3. Sample Extraction

Visually discerning a hybrid polymer's phase architecture can often be made easier by dissolving a phase, thereby creating void area in place of the phase, prior to viewing the sample. For example, before viewing via SEM, the TPS/PE hybrids of FIG. 6 was extracted with acid to dissolve the TPS phase, as follows.

A 1 mm length (machine-direction) x 7.5 mm width (cross -direction) specimen is subjected to hydrolytic degradation in an approximately 20% to 25% aqueous solution of HC1 at 60 degrees Celsius for 96 to 150 hours. Extracted samples are vigorously washed with distilled water and dried at 60 degrees Celsius in a vacuum oven for 48 hours. The regions formerly occupied by TPS are seen as voids, but the PE architecture is left intact. This enables visual differentiation between the two phase domains that make up the material's morphological architecture.

It should be noted that with a tube-like morphology (e.g., FIG 6), the TPS domains can be completely extracted due to the connectivity of both phases to the external surface. However, with a heterophasic (e.g., FIG. 7) or a plate-like morphology, the TPS domains cannot be completely extracted, since all of the TPS in these phase architectures is not connected to the external surface.

For hybrids other than TPS/PO, one skilled in the art, having extensive knowledge in polymer chemistry, will be able to determine the appropriate materials/methods to use for different polymeric blends.

4. Layer Thickness

Layer thickness can be measured using the methodology set forth in ISO 4593:1993, Plastics - Film and sheeting - Determination of thickness by mechanical scanning.

EXAMPLES

The following prophetic examples are given solely for the purpose of illustration and are not to be construed as limitations of the present invention. Ingredients are identified by chemical name, or otherwise defined below.

Prophetic Example 1 : Production of Plate-like Blends of -20% TPS and Polyolefin

A TPS Material may be commercially procured (e.g., from Cardia Bioplastics), although in such instances the TPS material may contain some additives (such as polyolefins). One material that may be suitable is available from Cardia Bioplastics, Inc. under the tradename BLF-02.

Alternatively, the TPS Material may be separately be made. One method for making a TPS Material comprises the following steps. 50 kg of Ethylex 2005, 11 kg of glycerol, 5 kg of sorbitol, 0.5 kg of stearic acid, and 0.3 kg of calcium stearate are blended in a high speed Henschel mixer for 15 minutes resulting in mixture A. Mixture A is added via a loss-in- weight feeder at 18 kg/hr into the fed throat of a vented ZSK 30 twin screw extruder having a temperature profile of

80/125/130/150/170/170/170/150°C, screw speed of 300 rpm, vacuum of -10 psi, and output of 18 kg/hr. The extruder is outfitted with a three-hole strand die, air cooling system, and a pelletizer. Pellets are collected (TPS #1). .

Production of Film: Three Collin single stage extruders are connected to a CAB AC five- layer feedblock from EDI. All three extruders are 30 mm 30:1 L/D with Maddock mixing elements, 4 barrel heat zones, and 3 downstream heat zones for piping and adapters. Extruder A delivers 100% Dow Primacor 3340 to layer A. Primacor serves as a tie layer between the incompatible TPS and polyolefin. Extruder A operates at 5 RPM and a temperature profile of

60/160/170/170/170/170/170°C. Extruder B delivers 100% of TPS #1 discussed above. Extruder B operates at 25 RPM and a temperature profile of 60/130/170/170/170/170/170°C. Extruder C delivers 80% Dowlex 2045G and 20% ExxonMobil LD- 129.24. Extruder C operates at 70 RPM and a temperature profile of 80/160/190/190/190/190/190°C. The 5-layer EDI feedblock connects to a Layer Multiplication Technology (LMT) system from EDI, which contains four 4X multiplication zones. As such, the 5-layer CAB AC structure leaving the 5-layer feedblock enters the first multiplication section of the LMT and converts into a 20-layer structure of

CABACCABACCABACCABAC. The 20-layer structure enters the second 4X multiplier and produces an 80 layer structure of CABAC{CABAC}i4CABAC. The 80 layer structure enters the 3rd multiplication section and produces a 320 layer structure of CABAC{CABAC}62CABAC. Finally, the 320 layer structure enters the 4th multiplication section and produces a 1280 layer structure of CABAC{CABAC}254CABAC. The overall content of ABC is approximately 5 vol% : 25 vol% : 70 vol%. The film may have outer skins comprising polyolefin, which are included in calculating the 70 volume percent PE in the composition. The 1280 layer structure leaving the LMT is fed to the core layer of a 3-layer SES feedblock system from EDI. A fourth extruder, Extruder S, adds skins to the multiplied layer (now called "E"). The material in Extruder S is 80% Dowlex 2045 and 20% ExxonMobil LD 129.24. A Collin 30 mm 30:1 extruder with 4-heat zones and 3-downstream zones supplies the skin material S. The extruder operates at 25 RPM and utilizes the following

temperature profile: 60/170/200/200/200/200/200°C. The material exiting the 3-layer feedblock connects to a 300 mm wide single manifold flex-lip die from EDI. The die lip is set to 0.75 mm with a 12 cm melt curtain. The melt exiting the die is drawn to the final target film thickness of 50 micron and is quenched between a rotating nip with a chrome finish operating at 15 m/min using a Collin cast film system. The film is wound on a constant tension rewinder.

Prophetic Example 2: Production of Plate-like Blends of -20% PLA and Polyolefin Production of Film: Three Collin single stage extruders are connected to a CAB AC five- layer feedblock from EDI. All three extruders are 30 mm 30:1 L/D with Maddock mixing elements, 4 barrel heat zones, and 3 downstream heat zones for piping and adapters. Extruder A delivers 100% Arkema Lotader 8840 to layer A. Extruder A operates at 5 RPM and a temperature profile of 60/160/170/170/170/170/170°C. Extruder B delivers 100% NatureWorks 4043D. Extruder B operates at 25 RPM and a temperature profile of 60/130/190/190/190/190/190°C. Extruder C delivers 80% Dowlex 2045G and 20% ExxonMobil LD- 129.24. Extruder C operates at 70 RPM and a temperature profile of 80/160/200/200/200/200/200°C. The 5-layer EDI feedblock connects to a Layer Multiplication Technology (LMT) system from EDI, which contains four 4X multiplication zones. As such, the 5-layer CAB AC structure leaving the 5-layer feedblock enters the first multiplication section of the LMT and converts into a 20-layer structure of

CABACCABACCABACCABAC. The 20-layer structure enters the second 4X multiplier and produces an 80 layer structure of CABAC{CABAC}i4CABAC. The 80 layers structure enters the 3rd multiplication section and produces a 320 layer structure of CABAC{CABAC}62CABAC.

Finally, the 320 layer structure enters the 4th multiplication section and produces a 1280 layer structure of CABAC{CABAC}254CABAC. The overall content of A:B:C is approximately 5 vol%:25 vol%: 70 vol% (vol% = % by volume). The 1280 layer structure leaving the LMT feeds to the core layer of a 3-layer SES feedblock system from EDI. A fourth extruder, Extruder S, adds skins to the multiplied system. The material is 80% Dowlex 2045 and 20% ExxonMobil LD 129.24. A Collin 30 mm 30:1 extruder with 4-heat zones (7 total with adapters and pipe) supplies the skin material. The extruder operates at 25 RPM and utilizes the following temperature profile:

60/150/200/200/200/200/200°C. The material exiting the 3-layer feedblock connects to a 300 mm wide single manifold flex-lip die from EDI. The die lip is set to 0.75 mm with a 12 cm melt curtain. The melt exiting the die is drawn to the final target film thickness of 50 micron and quenched between a rotating nip with a chrome finish operating at 15 m/min using a Collin cast film system. The film is wound on a constant tension rewinder.

Prophetic Example 3: Production of Plate-like Blends of -20% TPS and Polyolefin from

Nanolayered Pellets

Production of TPS Material ("TPS #2"): 50 kg of Ethylex 2005, 11 kg of glycerol, 5 kg of sorbitol, 0.5 kg of stearic acid, and 0.3 kg of calcium stearate are blended in a high speed Henschel mixer for 15 minutes resulting in mixture A. Mixture A is added via a loss-in-weight feeder at 18 kg/hr into the feed throat of a vented ZSK 30 twin screw extruder having a temperature profile of 80/125/130/150/170/170/170/150°C, screw speed of 300 rpm, vacuum of -10 psi, and output of 18 kg/hr. The extruder is outfitted with a three-hole strand die, air cooling system, and a pelletizer. Pellets are collected (referred to as TPS #2 in the examples herein).

Production of NLP ("NLP #1"): Three Collin single stage extruders connect to a CAB AC five-layer feedblock from EDI. All three extruders are 30 mm 30:1 L/D with Maddock mixing elements, 4 barrel heat zones, and 3 downstream heat zones for piping and adapters. Extruder A delivers 100% Dow Primacor 3340 to layer A. Primacor serves as a tie layer between the incompatible TPS and polyolefin. Extruder A operates at 5 RPM and a temperature profile of 60/160/170/170/170/170/170°C. Extruder B delivers 100% of TPS #1 discussed above. Extruder B operates at 70 RPM and a temperature profile of 60/130/170/170/170/170/170 °C. Extruder C delivers 80% Dowlex 2045G and 20% ExxonMobil LD-129.24. Extruder C operates at 25 RPM and a temperature profile of 80/160/190/190/190/190/190°C. The 5-layer EDI feedblock connects to a Layer Multiplication Technology (LMT) system from EDI, which contains six 4X multiplication zones. As such, the 5-layer CAB AC structure leaving the 5-layer feedblock enters the first multiplication section of the LMT and converts to a 20-layer structure of

CABACCABACCABACCABAC. The 20-layer structure enters the second 4X multiplier and produces an 80 layer structure of CABAC{CABAC}i4CABAC. The 80 layers structure enters the 3rd multiplication section and produces a 320 layer structure of CABAC{CABAC}62CABAC. The 320 layer structure enters the 4th multiplication section and produces a 1280 layer structure of

CABAC{CABAC}254CABAC. The 1280 layer structure enters a 5th multiplication unit producing 5120 layers. Finally, the 5120 layer material enters a 6th multiplication producing 20,480 layers. The overall content of A:B:C is approximately 5 vol%:70 vol%: 25 vol%. The 20,480 multiplied layer structure leaving the LMT feeds to a rectangular strand die for pelletization. The nanolayered pellets contain 20,480 layers of polyolefin/compatibilizer/TPS/compatibilizer/polyolefin.

Production of Film: 20 kg of the NLP #1 pellets produced in the above is dry blended with 29 kg of Dowlex 2045G and 5 kg of ExxonMobil LD-129.24 material. The dry blend is added to the feed hopper of a 30 mm 30:1 L/D Collin 4 zoned single stage single screw extruder with a Maddock mixing element. The extruder is operated at 80 rpm and with a temperature profile of 80, 160, 180, and 180. The extruder is connected to the core layer of a three-layer feedblock (ACA) from EDI, which connects to a 300 mm single manifold flex-lip die from EDI and cast film system from Collin. The skin layers A are fed by a single 30 mm single screw extruder operating at 20 rpm with an 80 wt% Dowlex 2045G and 20 wt% ExxonMobil LD- 129.24 blend and a temperature profile of 80/160/190/190°C. The die lip is set to 0.75 mm with a 12 cm melt curtain. The melt exiting the die is drawn to the final target film thickness of 50 micron and quenched between a rotating nip with a chrome finish operating at 15 m/min using a Collin cast film system. The film is wound on a constant tension rewinder.

Prophetic Example 4: Production of Plate-like Blends of -20% PLA and Polyolefin from

Nanolayered Pellets

Production of NLP ("NLP #2"): Three Collin single stage extruders connect to a CAB AC five-layer feedblock from EDI. All three extruders are 30 mm 30:1 L/D with Maddock mixing elements, 4 barrel heat zones, and 3 downstream heat zones for piping and adapters. Extruder A delivers 100% Arkema Lotader 8840 to layer A. Lotader serves as a tie layer between the incompatible PLA and polyolefin. Extruder A operates at 5 RPM and a temperature profile of 60/160/170/170/170/170/170°C. Extruder B delivers 100% of NatureWorks 4043D. Extruder B operates at 70 RPM and a temperature profile of 60/130/170/170/170/170/170 °C. Extruder

Cdelivers 80% Dowlex 2045G and 20% ExxonMobil LD- 129.24. Extruder C operates at 25 RPM and a temperature profile of 80/160/190/190/190/190/190°C. The 5-layer EDI feedblock connects to a Layer Multiplication Technology (LMT) system from EDI, which contains six 4X multiplication zones. As such, the 5-layer CAB AC structure leaving the 5-layer feedblock enters the first multiplication section of the LMT and converts into a 20-layer structure of

CABACCABACCABACCABAC. The 20-layer structure enters the second 4X multiplier and produces an 80 layer structure of CABAC{CABAC}i4CABAC. The 80 layers structure enters the 3rd multiplication section and produces a 320 layer structure of CABAC{CABAC}62CABAC. The 320 layer structure enters the 4th multiplication section and produces a 1280 layer structure of CABAC{CABAC}254CABAC. The 1280 layer structure enters a 5th multiplication unit producing 5120 layers. Finally, the 5120 layer material enters a 6th multiplication producing 20,480 layers. The overall content of A:B:C is approximately 5 vol%:70 vol%: 25 vol%. The 20,480 multiplied layer structure leaving the LMT feeds to a rectangular strand die for pelletization. Nanolayered pellets contain 20,480 layers of polyolefin/compatibilizer/PLA/compatibilizer/polyolefin.

Production of Film: 20 kg of the NLP #2 pellets are dry blended with 29 kg of Dowlex

2045G and 5 kg of ExxonMobil LD- 129.24 material. The dry blend is added to the feed hopper of a 30 mm 30:1 L/D Collin 4 zoned single stage single screw extruder with a Maddock mixing element. The extruder operates at 80 rpm and with a temperature profile of 80, 160, 180, and 180°C. The extruder connects to the core layer of a three-layer feedblock (ACA) from EDI, which also connects to a 300 mm single manifold flex-lip die from EDI and cast film system from Collin. The skin layers A are fed by a single 30 mm single screw extruder operating at 20 rpm with an 80 wt% Dowlex 2045G and 20 wt% ExxonMobil LD-129.24 blend and a temperature profile of

80/160/190/190°C. The die lip is set to 0.75 mm with a 12 cm melt curtain. The melt exiting the die is drawn to the final target film thickness of 50 micron and quenched between a rotating nip with a chrome finish operating at 15 m/min using a Collin cast film system. The film is wound on a constant tension rewinder.

The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm."

It should be understood that every maximum numerical limitation given throughout this specification includes every lower numerical limitation, as if such lower numerical limitations were expressly written herein. Every minimum numerical limitation given throughout this specification will include every higher numerical limitation, as if such higher numerical limitations were expressly written herein. Every numerical range given throughout this specification will include every narrower numerical range that falls within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.

All documents cited in the Detailed Description are, in relevant part, incorporated herein by reference; the citation of any document is not to be construed as an admission that it is prior art with respect to the present invention. To the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall govern.

While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

Claims

CLAIMS What is claimed is:
1. A multi-layered masterbatch composition in the form of a pellet, comprising:
at least 8 contiguous layers arranged in a plate-like morphology, wherein the at least 8 contiguous layers comprise at least one thermoplastic polymer A layer comprising a thermoplastic starch.
2. The multi-layered masterbatch composition according to claim 1, further comprising at least one thermoplastic polymer B layer comprising a polyolefin, wherein the thermoplastic starch and the polyolefin are immiscible.
3. The masterbatch composition according to claim 2, further comprising at least one
compatiblizer C layer disposed between the at least one thermoplastic polymer A layer and the at least one thermoplastic polymer B layer, wherein the at least one compatibilizer layer comprises a compatibilizer and wherein the masterbatch composition comprises from 0.2% to 40% of the compatibilizer by weight of the masterbatch composition.
4. The masterbatch composition according to claim 3, wherein the compatibilizer comprises an ethylene acrylic acid copolymer or an ethylene methacrylic acid copolymer.
5. The masterbatch composition according to any one claims 2 to 4, wherein the polyolefin is selected from the group consisting of polyethylene, polypropylene, and combinations thereof.
6. The masterbatch composition according to any one of claim 2 to 5, wherein the masterbatch composition has an overall thickness of from 0.03 mm to 6.35.
7. The masterbatch composition according to any one of claims 2 to 6, wherein the
thermoplastic polymer A layer and the thermoplastic polymer B layer are planar and co- continuous.
8. The masterbatch composition according to any one of claims 2 to 7, wherein each
thermoplastic polymer A layer comprises from 70% to 100% by weight of the thermoplastic starch and each thermoplastic polymer B layer comprises from 70% to 100% by weight of the polyolefin.
9. The masterbatch composition according to any one of claims 2 to 8, wherein the masterbatch composition comprises from 10% to 90% of the thermoplastic starch by weight of the masterbatch composition and from 5% to 85% of the polyolefin by weight of the masterbatch composition.
10. An extruded or cast film formed from the pellets comprising the masterbatch composition according to any one of claim 2 to 9.
11. The extruded or cast film according to claim 10, wherein the extruded or cast film comprises a plurality of co-continuous plate-like morphologies in at least one 10 micron x 10 micron, lengthwise, cross-sectional SEM taken from the extruded or cast film.
12. A molded article formed from pellets comprising the masterbatch composition according to any one of claims 2 to 9.
13. The molded article according to claim 12, wherein the molded article comprises a plurality of co-continuous plate-like morphologies in at least one 10 micron x 10 micron, lengthwise, cross-sectional SEM taken from the molded article.
14. A fiber formed from pellets comprising the masterbatch composition according to any one of claims 2 to 9.
15. The fiber according to claim 14, wherein the fiber comprises a plurality of co-continuous plate-like morphologies in at least one 10 micron x 10 micron, lengthwise, cross-sectional SEM taken from the fiber.
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