Composite biodegradable polymer-based materials, articles thereof and methods for making same - Patents.com

Abstract

A composite biodegradable polymer-based material is disclosed that includes a biodegradable polymer matrix, at least 5 wt. % of a biodegradable plasticizer, and at least 2 wt. % of a biodegradable filler configured to stabilize the biodegradable plasticizer in the polymer matrix.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application is an international patent application claiming the benefit of priority to U.S. Patent Application No. 17 / 520,675, filed November 11, 2021, and U.S. Provisional Patent Application No. 63 / 156,454, filed March 4, 2021, and No. 63 / 208,073, filed June 8, 2021, the contents of which are incorporated herein by reference in their entireties.

[0002] The present invention relates generally to biodegradable polymer-based materials. More specifically, the present invention relates to composite biodegradable polymer-based materials, articles thereof and methods of making same. [Background technology]

[0003] The fashion industry is responsible for around 8% of the total greenhouse gas emissions in the world. Furthermore, due to the frequent changes in "fashion", most of the products in this industry are constantly being replaced with a very low recycling rate. This makes the fashion industry one of the biggest polluters in the world. While natural fibers such as cotton and silk can decompose into harmless substances over time, all synthetic fibers / materials are predicted to last for hundreds of years.

[0004] The development of biodegradable polymeric materials is one of the most promising ways to reduce pollution from synthetic polymers. Biodegradable polymers are polymers that are designed to break down through bacterial degradation processes to produce natural by-products such as gases (CO2, N2), water, biomass and inorganic salts.

[0005] Known biodegradable polymers include both natural polymers such as polysaccharides (e.g., starch) and synthetic polymers such as polyesters, as well as combinations of both synthetic and natural polymers. A promising synthetic polymer is polybutylene adipate terephthalate (PBAT). However, both polyester-based biodegradable polymers and PBAT-based biodegradable polymers are not suitable for use in the fashion industry due to their mechanical properties. The polyester-based biodegradable polymers are too weak and / or very hygroscopic, and PBAT is too hard and rigid for fashion articles.

[0006] Thus, there is a need for biodegradable polymers that are both strong and flexible enough for use in fashion articles, and that are waterproof, at least until the intentional biodegradation process begins (eg, in a composter). Summary of the Invention

[0007] Some aspects of the invention may be directed to a composite biodegradable polymer-based material comprising a biodegradable polymer matrix, at least 5% by weight of a biodegradable plasticizer, and at least 2% by weight of a biodegradable filler. In some embodiments, the biodegradable plasticizer is in a liquid state at a temperature between 10 and 50° C., and the biodegradable filler is present in the composite in an amount sufficient to retain the biodegradable plasticizer in the polymer matrix. In some embodiments, the composite is substantially free of water.

[0008] In some embodiments, the biodegradable polymer matrix comprises at least one of polybutylene adipate terephthalate (PBAT), polyhydroxyalkanoate (PHA) and copolymers thereof, polybutylene succinate PBS and copolymers thereof, polylactic acid PLA and copolymers thereof, polyglycolic acid (PGA), poly(lactic-co-glycolic acid) (PLGA) polyvinyl alcohol, and thermoplastic polyurethane TPU and copolymers thereof. In some embodiments, the composite biodegradable polymer-based material may further comprise at least 30% by weight of the biodegradable polymer matrix.

[0009] In some embodiments, the biodegradable polymer matrix may comprise 1-28% by weight of polyvinyl acetate or any copolymer thereof based on the total weight of the composite.

[0010] In some embodiments, the biodegradable plasticizer is selected from acetyl tributyl citrate (ATBC), acetyl triethyl citrate (ATEC), isosorbide diester oil, isopentyl epoxy soyate, bis(2-(2-butoxyethoxy)ethyl) adipate, citric acid oil, and glycerol. In some embodiments, the composite biodegradable polymer-based material may further comprise at least 8% by weight of a biodegradable plasticizer. In some embodiments, the composite biodegradable polymer-based material may further comprise at least 15% by weight of a biodegradable plasticizer.

[0011] In some embodiments, the biodegradable filler is selected from food waste, spices, starch-based products, cellulose, and seaweed.

[0012] In some embodiments, the composite biodegradable polymer-based material is characterized by a porosity of at least 50% by volume, hi some embodiments, the porosity has a pore size between 1 micron and 3 mm.

[0013] Some aspects of the present invention may be directed to articles of manufacture made by injection molding of the composite biodegradable polymer-based material according to any of the embodiments of the present invention.

[0014] Some further aspects of the present invention may be directed to products produced by 3D printing of the composite biodegradable polymer-based material according to any of the embodiments of the present invention.

[0015] Some further aspects of the present invention may be directed to products made by extrusion of the composite biodegradable polymer-based material according to any of the embodiments of the present invention.

[0016] Some aspects of the invention may be directed to a method of making a composite biodegradable polymer-based product, comprising mixing together a biodegradable polymer matrix, at least 5% by weight of a biodegradable plasticizer, and at least 2% by weight of a biodegradable filler configured to stabilize the biodegradable plasticizer in the polymer matrix, and molding the mixture using at least one of extrusion, injection molding, and 3D printing to form the composite biodegradable polymer-based product. In some embodiments, the biodegradable plasticizer is in a liquid state at a temperature between 10 and 50° C., and the biodegradable filler is present in the composite in an amount sufficient to retain the biodegradable plasticizer in the polymer matrix.

[0017] In some embodiments, the mixing occurs in an extruder. In some embodiments, the extruded mixture is injected into a mold to form the article. In some embodiments, the mixture is extruded to form a filament. In some embodiments, the filament is fed to a 3D printer to print a 3D object. In some embodiments, the extruded mixture is extruded into a die to form a film.

[0018] The invention, however, both as to its organization and method of operation, together with its objects, features and advantages, may best be understood by reference to the following detailed description when read in conjunction with the accompanying drawings. [Brief description of the drawings]

[0019] [Figure 1] 1 is a flow chart of a method of making an article from a composite biodegradable polymer-based material according to some embodiments. [Diagram 2] 1 shows images of samples made from composite biodegradable polymer-based materials according to some embodiments. [Diagram 3] 1 shows images of a flipflop made from composite biodegradable polymer-based materials according to some embodiments of the present invention.

[0020] It will be appreciated that for simplicity and clarity of illustration, elements shown in the figures have not necessarily been drawn to scale. For example, dimensions of some of the elements may be exaggerated relative to other elements for clarity. Further, where considered appropriate, reference numerals may be repeated among the figures to indicate corresponding or analogous elements. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0021] Those skilled in the art will appreciate that the present invention can be embodied in other specific forms without departing from its spirit or essential characteristics. The above-described embodiments are therefore to be considered in all respects as illustrative and not limiting of the invention described herein. The scope of the present invention is therefore indicated by the appended claims rather than by the above description, and all changes that come within the meaning and range of equivalence of the claims are therefore intended to be embraced therein.

[0022] In the following detailed description, numerous specific details are set forth to provide a thorough understanding of the present invention. However, it will be understood by those skilled in the art that the present invention can be practiced without these specific details. In other instances, well-known methods, procedures, and components have not been described in detail so as not to obscure the present invention. Some features or elements described with respect to one embodiment may be combined with features or elements described with respect to other embodiments. For clarity, discussion of the same or similar features or elements may be omitted.

[0023] Some aspects of the present invention may be directed to composite biodegradable polymer-based materials and articles or products made from such materials. Further aspects may be directed to methods of making such articles or products. The composite biodegradable polymer-based materials according to some embodiments of the present invention may include a polymer matrix, such as a PBAT matrix, and a relatively large amount (e.g., more than 5 wt%) of a plasticizer (e.g., an oil-based plasticizer). The plasticizer may be used to soften the PBAT to the extent required for fashion products such as footwear, bags and belts. The main challenge in adding a relatively large amount of plasticizer to the PBAT is that the plasticizer tends to leak out of the PBAT matrix, thus reducing the softening effect and forming an undesirable oily layer on the made article.

[0024] In some embodiments, additives may be added to the mixture to stabilize and maintain the plasticizer in the PBAT matrix.The inventors have surprisingly found that natural materials can be used to stabilize the plasticizer in the PBAT matrix when added in specific amounts.These materials are also found to provide additional properties such as color, texture and aroma to the final product (e.g., cinnamon-scented flip-flops, coffee-scented wallets, etc.).

[0025] As used herein, "product" may include any article that can be made from a polymer, such as a finished product (e.g., fashion articles, toys, packaging, kitchenware, and disposable dishes), a semi-finished product (e.g., yarn), and a raw material provided for further processing (e.g., filaments for 3D printing). The product can be made using any known manufacturing method, such as extrusion, injection molding, and three-dimensional (3D) printing.

[0026] As used herein, a fashion article may be footwear, wallets, belts, bags, smartphone covers, bracelets, and the like.

[0027] As used herein, a "biodegradable material" may be any material configured to substantially degrade (e.g., degrade about 50%, about 70%, about 80%, about 90%, about 95%, 99% or more by weight of the material (including any range therebetween)) by enzymatic (e.g., microbial) degradation processes. In some embodiments, biodegradable materials degrade to produce natural by-products. In some embodiments, the term "biodegradable" as used herein also encompasses the term "bioerodible," which describes a composition / article that degrades under environmental conditions into smaller fractions and thus substantially loses its structure and / or mechanical properties. In some embodiments, the term "bioerosion" refers to erosion of a composition / article that is initiated by microorganisms and results in at least partial degradation of the composition / article.

[0028] Biodegradable materials may be from synthetic and / or natural sources. In some embodiments, bacterial decomposition of biodegradable materials may of course be a source of hydrocarbon gases.

[0029] In some embodiments, the composite biodegradable polymer-based material may be substantially free of water since no water is added during any of the processing steps and none of the ingredients are provided in aqueous solution. In some embodiments, the composite biodegradable polymer-based material may only contain residual amounts of water that are naturally contained in the biodegradable filler. In some embodiments, the amount of water in the biodegradable filler (e.g., natural fiber) is 15% or less by weight, typically 6% or less by weight. In some embodiments, the total amount of biodegradable filler in the composite is at most 10% by weight, so the total amount of moisture / water in the composite may not exceed 1.5%, 1.3%, 1.2%, 1%, 0.8%, 0.7%, 0.6% or less by weight. In some embodiments, the less water, the better.

[0030] In some embodiments, any addition of water to the composite is superfluous. In some cases, adding water is not even recommended. Any additional amount of water may impair the appearance, functionality and feel, as in any product list including fashion articles, toys, packaging, kitchenware and disposable dishes, you would not want to have wet flip-flops or wet disposable plates.

[0031] In some embodiments, the claimed composites may be foams containing at least 30% by volume porosity, at least 50% by volume porosity, or even at least 70% by volume porosity.

[0032] The composite biodegradable polymer-based material according to some embodiments of the present invention may include a biodegradable polymer matrix and at least 5 wt.% of a biodegradable plasticizer. The composite biodegradable polymer-based material may further include at least 2 wt.% of a biodegradable filler configured to stabilize the biodegradable plasticizer in the polymer matrix. In some embodiments, the biodegradable plasticizer is in a liquid state at a temperature between 10 and 50° C., and the biodegradable filler is present in the composite in an amount sufficient to retain the biodegradable plasticizer in the polymer matrix.

[0033] In another aspect, provided herein is a material comprising a biodegradable polymer in the form of a polymer matrix, at least 2% by weight of a biodegradable filler, and at least 5% by weight of a biodegradable plasticizer, wherein the biodegradable filler and / or biodegradable plasticizer are dispersed in the polymer matrix. In some embodiments, the biodegradable filler and / or biodegradable plasticizer are uniformly dispersed in the polymer matrix. In some embodiments, the material is a composite. In some embodiments, the material of the invention is biodegradable. In some embodiments, the material of the invention consists essentially of the biodegradable polymer, the biodegradable filler, and the biodegradable plasticizer. In some embodiments, the material of the invention is solid at temperatures ranging from -50 to 60°C, -50 to 40°C, and 40 to 60°C, including all ranges therebetween.

[0034] In some embodiments, the terms "material" and "biodegradable polymer-based material" are used interchangeably herein.

[0035] In some embodiments, the biodegradable plasticizer is located within an inner portion of the polymer matrix. In some embodiments, the outer portion of the polymer matrix is ​​substantially free of biodegradable plasticizers and / or biodegradable fillers. In some embodiments, the biodegradable plasticizer modifies the mechanical properties of the composite of the present invention. In some embodiments, the material of the present invention comprises a sufficient amount of biodegradable plasticizer to impart elasticity thereto. In some embodiments, the material of the present invention is an elastic material. In some embodiments, the material of the present invention is an elastic or viscoelastic material. In some embodiments, the weight / weight (w / w) concentration of the biodegradable plasticizer is sufficient to impart elastic or viscoelastic properties to the material of the present invention.

[0036] In some embodiments, the w / w concentration of biodegradable filler in the composite of the present invention is sufficient to substantially retain the biodegradable plasticizer in the polymer matrix. In some embodiments, the w / w concentration of biodegradable filler in the composite of the present invention is sufficient to retain at least 85%, at least 90%, at least 95%, at least 97%, at least 99%, at least 99.5%, at least 99.9% (including all ranges therebetween) of the initial weight content of the biodegradable plasticizer. In some embodiments, the w / w concentration of biodegradable filler in the composite of the present invention is sufficient to retain the biodegradable plasticizer in the polymer matrix.

[0037] In some embodiments, the w / w concentration of the biodegradable filler in the composites of the present invention is sufficient to substantially prevent leakage of the biodegradable plasticizer from the interior portion of the polymer matrix.

[0038] In some embodiments, the composite has a strength of up to 200 Kg / m 2 at least 90%, at least 95%, at least 97%, at least 99%, at least 99.5%, at least 99.9% by weight of the biodegradable plasticizer is substantially retained in the polymer matrix when exposed to a pressure of

[0039] In some embodiments, the composite is a porous material. In some embodiments, the polymer matrix is ​​characterized by a porosity of 10-99 volume %, 10-20 volume %, 20-50 volume %, 50-70 volume %, 70-80 volume %, 80-90 volume %, 90-99 volume % (including all ranges therebetween). In a non-limiting example, the porosity is 70-85 volume %. In some embodiments, the pore size is 1 micron-1 mm, 1 micron-2 mm, and 0.5 micron-3 mm, and all values ​​therebetween.

[0040] In some embodiments, the composites include a single biodegradable polymer type or multiple chemically distinct biodegradable polymers (e.g., polymer blends). In some embodiments, the biodegradable polymers of the present invention are thermoplastic polymers. In some embodiments, the biodegradable polymers of the present invention are polyesters such as PCL, PLA, PGA, PLGA, PBAT, polyhydroxyalkanoates (PHAs) and their copolymers (e.g., PHB, PHBV, PHH x and the like), polyols (e.g. polyvinyl alcohol), polyalkoxylates (e.g. PEG, PPG, and the like), polybutylene succinates PBS and copolymers thereof, polylactic acids PLA and copolymers thereof, polyvinyl acetate and copolymers thereof, starch based polymers, polydioxanones, polyhydroxybutyric acids, polyhydroxyvaleric acids, polyphosphoesters, polyamides (e.g. nylon, polyamino acids) (including any copolymers thereof), thermoplastic polyurethanes TPU and copolymers thereof and any copolymers and any combinations thereof.

[0041] In some embodiments, soft modified polymers such as polyvinyl acetate and its copolymers may be added to the biodegradable polymer matrix to produce softer biodegradable composites. Such biodegradable polymer systems may further be used to bind and retain biodegradable plasticizers. In some embodiments, the soft biodegradable polymer composition may soften the biodegradable material to the extent required, for example, by the fashion industry.

[0042] As known in the art, polyvinyl acetate is not considered a "biodegradable polymer". However, the inventors have surprisingly found that the addition of up to 35% by weight of polyvinyl acetate to a polymer matrix can result in a biodegradable polymer composition when the other polymer is a biodegradable polymer. Such compositions can be completely degraded by biological processes. In some embodiments, the biodegradable polymer matrix may comprise 20-35% by weight of polyvinyl acetate, e.g., 22%, 26%, 28%, 30% by weight of the total weight of the biodegradable material. In some embodiments, the remainder of the biodegradable polymer matrix may comprise other biodegradable polymers, such as PBAT and PHA.

[0043] In some embodiments, the biodegradable polymer matrix may comprise 1-35, 1-32, 1-30, and 1-28 wt% of the total weight of the composite, such as 1, 2, 5, 8, 10, 12, 15, 18, 20, 22, 24, 26, 27 wt% of the total weight of the composite of polyvinyl acetate or any copolymer thereof.

[0044] In some embodiments, the addition of 20-35 wt% polyvinyl acetate may cause the biodegradable material to soften to the extent required, for example, as required by the fashion industry. For example, a biodegradable material according to some embodiments of the present invention comprising 28 wt% polyvinyl acetate may have a Shore A hardness of 70-80. Omission of polyvinyl acetate may result in an increase in hardness to at least Shore 80A and up to Shore 50D.

[0045] In some embodiments, the w / w concentration of the biodegradable polymer in the composite is at least 15%, at least 15%, 20%, 25%, 30%, 35%, 40%, 45%, 55%, 60%, 65%, 75% and more (including all ranges therebetween). In some embodiments, the w / w concentration of the biodegradable polymer in the composite is 15-80%, 15-90%, 15-50%, 50-75%, 50-80%, 50-60%, 60-75%, 60-80%, 80-95%, 80-90% (including all ranges therebetween).

[0046] In some embodiments, the biodegradable polymers of the present invention are solid at temperatures ranging from -50 to 60°C, -50 to 40°C, or 40 to 60°C (including all ranges therebetween).

[0047] Some embodiments of the invention may be directed to composites that may include one or more additional polymers (e.g., bioerodible and / or non-degradable polymers). For example, the polymer matrix may be polyesters and their copolymers, polyamides and their copolymers, styrenic polymers and their copolymers, and the like.

[0048] In some embodiments, the biodegradable plasticizer is incompatible (e.g., immiscible) with the biodegradable polymer of the present invention. In some embodiments, the biodegradable plasticizer of the present invention is liquid at temperatures ranging from -80°C to 80°C, -10°C to 60°C, 0°C to 60°C, 0°C to 50°C, 10°C to 50°C (including all ranges therebetween).

[0049] In some embodiments, the biodegradable plasticizer is a small molecule. In some embodiments, the biodegradable plasticizer is an organic small molecule having a MW of less than 1,000 Daltons (Da). In some embodiments, the biodegradable plasticizer has a MW of 100-1,000 Da, 100-300 Da, 100-200 Da, 200-500 Da, 200-1000 Da, 200-300 Da, 100-500 Da, 100-800 Da, 300-500 Da, 100-1,000 Da, 500-800 Da, 500-1,000 Da, 800-1,000 Da (including every range therebetween). Each possibility represents a separate embodiment of the present invention.

[0050] In some embodiments, the biodegradable plasticizer is or includes a single chemical species or multiple chemically distinct chemical species. In some embodiments, the biodegradable plasticizer is or includes an alkyl citrate (e.g., acetyl tributyl citrate (ATBC), triethyl citrate), an isosorbide diester oil, an epoxidized oil (e.g., isopentyl epoxy soyate), an alkoxylated carboxylic acid (e.g., bis(2-(2-butoxyethoxy)ethyl) adipate), a citrate oil, an oil, a fatty acid or fatty acid ester, a mono- or diglyceride, including any ester thereof and a polyol (e.g., glycerol, oligosaccharides), or any combination thereof.

[0051] In some embodiments, the biodegradable plasticizer is or includes any one of acetyl tributyl citrate (ATBC), isopentyl epoxy soyate, bis(2-(2-butoxyethoxy)ethyl) adipate, citrate oil, glycerol, or any combination thereof. Additional biodegradable plasticizers are well known in the art. In some embodiments, more than 5 wt%, for example 10 wt%, 15 wt%, 20 wt% and more are added to the composite to further soften the polymer matrix. In some embodiments, all added plasticizer can remain in the polymer matrix throughout the life of the product. In some embodiments, the w / w concentration of biodegradable plasticizer in the composite of the present invention is 5-20%, 5-10%, 10-15%, 15-20%, 5-10%, 5-15%, 5-7%, 5-13%, 13-20% (including all ranges therebetween).

[0052] In some embodiments, the composite may further comprise at least 2 wt%, e.g., 3 wt%, 5 wt% and more of a biodegradable filler to stabilize a relatively large amount of plasticizer in the polymer matrix, hi some embodiments, the w / w concentration of the biodegradable filler in the composite of the present invention is 1-10%, 2-10%, 2-7%, 2-5%, 5-10% (including all ranges therebetween).

[0053] In some embodiments, the biodegradable filler may be naturally derived. For example, the biodegradable filler may be selected from food waste, spices, starch-based products (e.g., grains), cellulose (e.g., wood chunks), waste particulate materials (e.g., compost and / or wood waste such as wood chips, sawdust, etc.), vegetable materials (e.g., wheat flour, buckwheat flour, semolina flour, corn flour, corn starch, corn meal, rice flour, tapioca flour, potato flour, soy flour, ground flax meal, flax flour, hemp flour), and seaweed, etc. In addition to stabilizing the plasticizer, the filler can also impart color (e.g., pigments), scent, and texture to the composite. Some examples of samples made with various fillers are shown in FIG. 2. In some embodiments, additional biodegradable materials, such as natural pigments, may be added.

[0054] In some embodiments, the composite biodegradable polymer-based material may be used to make articles such as final products, semi-finished products or feedstock for the creation of other products, as discussed below with respect to the flow chart of Figure 1. In some embodiments, the semi-finished product may be an extruded flat strand used to make a belt, and the feedstock may include strip / strand filament that is fed and extruded into a 3D printer to print the product.

[0055] Reference is made to FIG. 1, which is a flow chart of a method for making a composite biodegradable polymer-based product according to some embodiments of the present invention. In step 110, all the components of the composite biodegradable polymer-based material may be mixed to form a mixture. The mixture may include a biodegradable polymer matrix (e.g., PBAT), at least 5% by weight of a biodegradable plasticizer, and at least 2% by weight of a biodegradable filler, as disclosed above. In a non-limiting example, all the components may be inserted into a twin-screw extruder, heated above the melting or softening point of the relevant matrix, and mixed together to form a mixture. In some embodiments, other mixing equipment and techniques may be used to mix the mixture.

[0056] In some embodiments, the method is carried out without any added water, hi some embodiments, none of the components provided are provided in an aqueous solution.

[0057] In some embodiments, the mixture may be molded in step 120 to form the composite biodegradable polymer-based product. For example, the mixture may be directly extruded to form elongated (e.g., spooled) strips or strands that are used as a final product or raw material for further products. Alternatively, the mixture may be injection molded into a final shape (e.g., footwear). In a non-limiting example, an injection molding machine may be used to form final products such as flip-flops and smartphone covers. Additionally or alternatively, the extruded filaments (e.g., strands) made from the biodegradable polymer composite may be loaded into a 3D printer to be remelted and printed using any known method. In some embodiments, the composite biodegradable polymer system may be extruded into a die to form a film (e.g., a sheet).

[0058] In some embodiments, the method may include foaming the mixture by introducing a controlled amount of porosity into the biodegradable polymer composite. For example, a gas such as CO2 may be added into the melt mixture during the formation of the part (e.g., during actual extrusion of the melt or actual injection). In yet another example, any type of foaming agent such as sodium bicarbonate may be added to the mixture to form a foam by the release of CO2 by pyrolysis. In some embodiments, the amount of porosity may depend on the amount of agent added, such as, for example, 30% to 85% by volume, 50% to 85% by volume, and 60% to 80% by volume. In some embodiments, the pore size is 1 micron to 1 mm, 1 micron to 2 mm, and 1 micron to 3 mm, and all values ​​in between.

[0059] Experimental Results Reference is now made to FIG. 2, which shows images of eight samples made from composite biodegradable polymer-based materials according to some embodiments of the present invention. The samples were placed in an aluminum mold and pressed using a 12 ton laboratory press. All samples were made with a PBAT matrix along with various biodegradable plasticizers and different fillers (e.g., ground powders). Some of the fillers included natural pigments such as 484C and 7771C. Table 1 summarizes the various compositions.

[0060] [Table 1]

[0061] Each sample has a different color (not evident in the black and white image) and a different aroma. For example, samples B and C have a light brownish color from coffee flakes and a coffee aroma. In yet another example, sample E has an eggplant purple color and sample F has a dark red color. Sample G has a honey-like color and a cinnamon aroma.

[0062] Further experimental compositions showing different biodegradable polymer matrices with different plasticizers and different fillers are shown in Table 2.

[0063] [Table 2]

[0064] Further experimental compositions showing different biodegradable polymer matrices with different plasticizers and different fillers are shown in Table 3.

[0065] [Table 3]

[0066] Reference is now made to Figure 3, which is an image of a flip-flop made from a composite biodegradable polymer-based material according to some embodiments of the present invention. The composite of the flip-flop in Figure 3 included a PBAT matrix, 15 wt% ATBC plasticizer, and 3 wt% seaweed powder. The result was a greenish, flexible flip-flop without an oily surface. Immediately after mixing the mixture in the extruder, the flip-flop was injection molded into its final shape.

[0067] In some embodiments, all tested samples were completely degraded in compost according to acceptable practices. For example, the two types of flip-flops discussed with respect to FIG. 3 were inserted into plastic netting and buried in a compost pile to a depth of 50-100 cm. After 98 days (e.g., about 3 months), the flip-flops were completely biologically degraded.

[0068] The mechanical properties of various samples were measured according to known standards. Shore hardness was measured according to ASTM D2240 to measure the hardness of polymers, elastomers and rubbers. The tested Shore hardness of samples according to embodiments of the present invention was 65-95 Shore A hardness and 15-50 Shore D hardness. The results show sufficient hardness for all fashion articles such as flip-flops, wallets, belts, etc.

[0069] As shown in the figure, the composite biodegradable polymer-based material can be a promising environmentally friendly material for the fashion industry as well as other industries such as toy manufacturers, packaging manufacturers, kitchenware manufacturers and disposable plate manufacturers.

[0070] Unless expressly stated, the method embodiments described herein are not limited to a particular order or sequence. Moreover, all process steps described herein are for illustrative purposes only, and other different process steps may be used. Furthermore, some of the described method embodiments or elements thereof may occur or be performed at the same time.

[0071] While certain features of the invention have been illustrated and described herein, many modifications, substitutions, changes and equivalents will occur to those skilled in the art, and it is therefore to be understood that the appended claims are intended to cover all such modifications and changes as fall within the true spirit of the invention.

[0072] Various embodiments have been shown, each of which may of course include features from the other embodiments shown, and embodiments not specifically described may include various features described herein.

Claims

1. At least 30% by weight of a biodegradable polymer matrix comprising 5-35% by weight of polyvinyl acetate or a copolymer thereof based on the total weight of the matrix; 5 to 26 weight percent of a biodegradable plasticizer; 2 to 20% by weight of a biodegradable filler; A composite biodegradable polymer-based material comprising: A composite biodegradable polymer-based material, characterized in that the biodegradable plasticizer is in a liquid state at a temperature between 10 and 50°C, and the biodegradable filler is present in the composite in an amount sufficient to retain the biodegradable plasticizer in a polymer matrix, and the biodegradable polymer-based material has a porosity of at least 10% by volume.

2. 10. The composite biodegradable polymer-based material of claim 1, characterized in that it is substantially free of water.

3. 2. The composite biodegradable polymer-based material of claim 1, wherein the biodegradable polymer matrix comprises at least one of polybutylene adipate terephthalate (PBAT), polyhydroxyalkanoate (PHA) and its copolymers, polybutylene succinate PBS and its copolymers, polylactic acid such as PLA and its copolymers, polyglycolic acid (PGA), PLGA, caprolactone, polyvinyl alcohol, and thermoplastic polyurethane TPU and its copolymers.

4. 2. The composite biodegradable polymer-based material of claim 1, wherein the biodegradable plasticizer is selected from the group consisting of alkyl citrates (e.g., acetyl tributyl citrate (ATBC)), epoxidized oils, isosorbide diester oils, alkoxylated carboxylic acids (e.g., bis(2-(2-butoxyethoxy)ethyl) adipate), citrate oils, and polyols.

5. 2. The composite biodegradable polymer-based material of claim 1, wherein the biodegradable filler is selected from food waste, vegetable materials, waste materials, spices, starch-based products, cellulose and seaweed.

6. 10. The composite biodegradable polymer-based material of claim 1 comprising at least 30% by weight of a biodegradable polymer matrix.

7. 10. The composite biodegradable polymer-based material of claim 1 comprising at least 8% by weight of a biodegradable plasticizer.

8. 10. The composite biodegradable polymer-based material of claim 1 comprising at least 15% by weight of a biodegradable plasticizer.

9. 10. The composite biodegradable polymer-based material of claim 1 characterized by a porosity of at least 50% by volume.

10. 10. The composite biodegradable polymer-based material of claim 9, wherein the porosity has a pore size between 1 micron and 3 mm.

11. A composition comprising: at least 15% by weight of a biodegradable polymer matrix; 5 to 26 weight percent of a biodegradable plasticizer; 2 to 20% by weight of a biodegradable filler; An article made from a composite biodegradable polymer-based material comprising: The biodegradable plasticizer is in a liquid state at a temperature between 10 and 50°C, and a biodegradable filler is present in the composite in an amount sufficient to retain the biodegradable plasticizer in the polymer matrix, the product having a porosity of at least 10% by volume.

12. 12. The article of manufacture of claim 11 made by one of injection molding, 3D printing and extrusion.

13. 12. The product of claim 11, characterized in that it is substantially free of water, having a maximum of 10% by weight of water.

14. 1. A method for making a composite biodegradable polymer-based product, comprising: at least 15% by weight of a biodegradable polymer matrix; 5 to 26 weight percent of a biodegradable plasticizer; 2 to 20% by weight of a biodegradable filler; wherein the biodegradable plasticizer is in a liquid state at a temperature between 10 and 50° C. and the biodegradable filler is present in the composite in an amount sufficient to retain the biodegradable plasticizer in a polymer matrix; foaming the mixture by introducing a controlled amount of porosity into the biodegradable polymer composite; forming the mixture using at least one of extrusion, injection molding, and 3D printing to form a composite biodegradable polymer-based product; A method comprising:

15. 15. The method of claim 14, carried out without any addition of water.

16. 15. The method of claim 14, wherein the mixing occurs in an extruder.

17. The method of claim 14, wherein the mixture is injected into a mold to form the article.

18. The method of claim 14, wherein the mixture is extruded to form filaments.

19. 20. The method of claim 18, further comprising feeding the filament to a 3D printer for printing a 3D object.

20. The method of claim 14, wherein the mixture is extruded through a die to form a film.

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