TW202302345A - Curative - Google Patents

Abstract

A curative for epoxidized plant-based oils and epoxidized natural rubber is created from the reaction between a naturally occurring polyfunctional acid and an epoxidized plant-based oil is disclosed. The curative may be used to produce at least one of six different materials, wherein each type of material may be configured as a thermosetting elastomer that is crosslinked with ß-hydroxyester linkages. The materials may be configured as a leather-like material, a foam material, a molded elastomer, a coating, an adhesive, and/or a rigid or semi-rigid material. Illustrative articles made from any combination of the six materials may be recycled using a mechano-chemical process to de-crosslink the thermosetting elastomer.

Description

Hardener

The present invention relates to a method for producing natural products, which can be produced by using the curing agent disclosed in the present invention. This natural product has physical properties similar to those of synthetically coated fabrics, leather and foam.

Depending on the complexity of the final design, footwear construction employs various manufacturing methods. The simplest designs may use only one or two different types of materials, as seen in flip-flops, slippers, loafers and Crocs™. In these types of footwear, one material may be used for the entire footbed, while the same or a different material may be used for the top strap. At the other extreme, some high-performance running shoe or hiking boot may use 10-20 different types of materials to achieve its special properties.

It would be desirable to be able to manufacture footwear that is fully recyclable without requiring deconstruction of the shoe. This can be relatively easy to achieve in simple designs that can be molded from a specific thermoplastic (whether foamed, solid, or both). In more complex footwear that includes an upper of one type of material, a midsole foam of another type of material, and an outsole rubber of another, the recycling of such shoes requires deconstruction. US11026477 discloses a shoe composed of bio-based and/or recycled material and seeks to minimize the amount of different material types; however such a shoe ultimately still requires deconstruction at the end of its life cycle in order to be fully recycled.

Cross References to Related Applications This non-provisional utility patent application claims Provisional Patent Application Nos. 63/145,939, filed February 4, 2021; 63/274,443, filed November 1, 2021; and 63/297,569, all of these earlier applications are hereby incorporated by reference in their entirety

Statement Regarding Federally Sponsored Research or Development This application did not use US federal funds to research or create the inventions described and disclosed herein.

Before referring to the methods and devices of the present invention disclosed and described below, it should be noted that these methods and devices are not limited to specific methods, specific components or specific implementations. In addition, it should also be understood that the terms used herein are only used to describe specific embodiments/aspects, and are not limiting.

In this specification and the appended claims, unless the context clearly states otherwise, the singular "a/a/kind" and "the" also include references to plural things. Numerical ranges herein can be expressed as starting from "about" one particular value, and/or ending "about" another particular value. When such a range of values is presented herein, another embodiment includes starting from the aforementioned specific value, and/or ending with the aforementioned another specific value. Likewise, when a value is expressed as an approximation (beginning with the word "about"), the aforementioned specific value constitutes another embodiment. It is also to be understood that either endpoint of each range is meaningful, either relative to or irrespective of the other endpoint.

"Optional" or "optionally" means that the following event or circumstance may or may not exist, and that such description includes instances where said event or circumstance exists and instances where said event or circumstance does not exist.

The term "aspects" when referring to methods, devices and/or components thereof does not imply that the constraints, functions or components . It is part of the content, and does not limit the scope of its methods, devices and/or components, unless otherwise stated in the appended claims.

In the description of this specification and the scope of the patent application, the word "comprising" means "including but not limited to", that is, it does not exclude other components, integers or steps (for example). "Exemplary" means "an example of" and does not imply a preferred or ideal implementation. The word "such as" is not limiting and is used for illustration only.

The components that can be used to implement the method and apparatus of the present invention will be disclosed below. These and other building blocks will be disclosed herein with the understanding that when combinations, sub-collections, interactions or groups of the above-mentioned building blocks are disclosed herein, or even if the text does not expressly disclose various individual or collective combinations of the above-mentioned items or Arrangement, all methods and devices of the present invention include any one of them. The above description is applicable to all aspects of the present application, including but not limited to the steps of the method of the present invention. It should therefore be understood that if there are additional steps that can be performed, each of the additional steps can be performed in any particular embodiment or combination of embodiments of the method of the present invention.

The method and device of the present invention can be more easily understood through the reference of the following preferred aspects and the detailed description including examples and the preceding and following descriptions of the accompanying drawings. When referring to general features of configuration (or design) and/or terms such as corresponding components, aspects, characteristics, functions, methods and/or materials of construction, etc., the corresponding terms may be used interchangeably.

It should be understood that the application of the teachings of the present invention is not limited to the details of construction and the arrangement of components presented in the following description or shown in the drawings. The invention is capable of other embodiments and of being practiced or carried out in various ways. In addition, it should be understood that words and terms used herein to refer to the orientation of a device or an element (such as "front", "rear", "upward", "downward", "top", "bottom", etc.) It is used to simplify the relevant description, and it does not express or imply that the device or element it refers to must have a certain orientation. In addition, terms such as "first", "second" and "third" are used for description in this article and the appended patent claims, and are not used to express or imply relative importance or meaning.

[1. Curing agent (prepolymer)] The present invention discloses a curing agent, which consists of epoxidized triglycerides (which can be vegetable oils, such as vegetable oils and/or nut oils and/or microbial oils, such as oils produced by algae or yeast), naturally occurring polyfunctional Carboxylic acid, and at least partially grafted hydroxyl-containing solvent. Examples of such epoxidized triglycerides comprising vegetable oils are epoxidized soybean oil (ESO), epoxidized linseed oil (ELO), epoxidized corn oil, epoxidized cottonseed oil, epoxidized canola oil, epoxidized Canola oil, epoxidized grapeseed oil, epoxidized poppyseed oil, epoxidized tung oil, epoxidized sunflower oil, epoxidized safflower oil, epoxidized wheat germ oil, epoxidized walnut oil and other epoxidized vegetable oils (EVO) . In general, any polyunsaturated triglyceride with an iodine value of 100 or higher can be epoxidized and used without limitation in the curing agents disclosed in this specification, unless otherwise stated in the claims below. The triglycerides are generally considered biodegradable. Naturally occurring polyfunctional carboxylic acids include citric, tartaric, succinic, malic, maleic, and fumaric acids. Although the specific illustrated embodiments may represent an oil and/or acid, such embodiments are not limiting in any way unless otherwise stated in the claims below.

The curing agent disclosed in the present invention is carried out in a solvent capable of simultaneously dissolving epoxidized vegetable oil and naturally occurring polyfunctional carboxylic acid, the reaction product between the epoxidized vegetable oil and the naturally occurring polyfunctional carboxylic acid. Wherein, the aforementioned solvent includes at least a part of hydroxyl-containing solvent (such as alcohol), which reacts with at least a part of the carboxylic acid functional groups contained in the polyfunctional carboxylic acid. The curing agent is an oligomeric structure of epoxidized vegetable oil terminated by a carboxylic acid, which is called a prepolymer curing agent. Curing agents are viscous liquids that are soluble in unmodified epoxidized vegetable oils and other epoxidized polymers of vegetable origin (such as epoxidized natural rubber).

In general, the terms "curing agent", "prepolymer", and "prepolymer curing agent" are used to indicate the same and/or similar chemical structures as disclosed in this first part. However, curing agents, prepolymers, and prepolymer curing agents perform different functions in different applications to produce different end products. For example: when the curing agent is used with monomeric resins containing epoxy groups (such as EVO), its function is to increase the molecular weight necessary for the resulting polymer backbone, so it can be used as a prepolymer in these applications. Yet another example: when a curing agent is used in an application with pre-existing high molecular weight epoxy-containing polymers (as disclosed herein below), the curing agent is primarily used to attach those pre-existing high molecular weight polymers, so In these applications it may simply be referred to as a curing agent. Finally, when the curing agent is used in applications with a large amount of epoxy-containing monomer and a portion of the existing high molecular weight epoxy-containing polymer, it has the function of increasing the molecular weight and linking the existing high molecular weight polymer , so the aforementioned curing agent can be referred to as a prepolymer curing agent.

The generation of curing agents known in the prior art eliminates the risk of porosity caused by solvent evaporation during curing. Also, the oligomeric curing agent may contain substantially all of the polyfunctional carboxylic acid, so no additional curing agent is required during the curing process. For example: citric acid is immiscible with epoxidized soybean oil (ESO), but it can be made to react with each other in a suitable solvent. The amount of citric acid can be selected to produce a curing agent such that substantially all of the epoxy groups of the ESO in the curing agent react with the carboxylic acid groups of the citric acid. Using a sufficient excess of citric acid, the degree of prepolymerization can be limited so that no gel fractions are formed. That is, the target class of curing agents are low molecular weight (oligomeric) citric acid terminated ester products formed by the reaction of carboxylic acid groups on citric acid with epoxy groups on ESO. The solvent used in the reaction medium contains at least a part of hydroxyl-containing solvent (such as an alcohol), which is grafted with at least a part of polyfunctional carboxylic acid during the curing agent production process. Although specific exemplary embodiments may represent a certain type of alcohol (such as IPA, ethanol, etc.), unless otherwise stated in the claims below, such embodiments are not intended to be limiting in any form.

Exemplary oligomeric curing agents can be made at a weight ratio of ESO to citric acid in the range of 1.5:1 to 0.5:1, which corresponds to a molar ratio of epoxy groups to carboxylic acid groups in the range of about 0.43 : 1 (weight ratio 1.5 : 1) to 0.14 : 1 (weight ratio 0.5 : 1). In an exemplary embodiment, the weight ratio of ESO to citric acid is 1:1, so that the molar ratio of epoxy groups to carboxylic acid groups is 0.29:1. When too much ESO is added in the process of making the curing agent, the solution may gel, and it will be difficult to further add ESO to make the target resin. Attention should be paid to the stoichiometric equivalents of epoxy groups on ESO (molecular weight about 1000 g/mol, functionality 4.5 epoxy groups per molecule) and the stoichiometric amount of carboxylic acid groups on citric acid Equivalents (molecular weight 192 g/mol, functionality 3 carboxylic acid groups per molecule), the weight ratio is about 100 parts of ESO to 30 parts of citric acid. When the weight ratio of ESO:citric acid is higher than 1.5:1, a curing agent with too high molecular weight (ie, viscous) may be formed, which limits its ability to incorporate unmodified epoxidized vegetable oil or epoxidized natural rubber. When the weight ratio of ESO:citric acid is below 0.5:1, too much citric acid is present, and ungrafted citric acid may precipitate out of solution after solvent evaporation.

In addition to controlling the ratio of ESO to citric acid, it has been found through experiments that selective control of the amount of alcohol used as a solvent can also be used to adjust the physical properties of the elastomer produced with the curing agent. The alcoholic solvent itself is incorporated into the elastomer via formation of ester linkages with polyfunctional carboxylic acids. A mixture of two or more solvents can be used to adjust the amount of hydroxyl-containing solvent grafted onto the citric acid-terminated oligomeric curing agent. Figure 1 shows a schematic diagram of the chemical reactions involved in making an exemplary embodiment of a curing agent of the present disclosure.

For example: without restriction or limitation, isopropanol (IPA), ethanol or other suitable non-limiting alcohols, unless otherwise stated in the scope of the following claims, the aforementioned alcohols can be used to dissolve citric acid in The composition of the solvent system of ESO. IPA, alcohols, or other suitable alcohols can form ester linkages by condensation with citric acid. Since citric acid has three carboxylic acids, this grafting will reduce the average functionality of the citric acid molecules reacted with ESO. This will favor the production of oligomeric structures that are more linear and less highly branched. Acetone can be used as a component of the solvent system that makes citric acid and ESO miscible, but unlike IPA or ethanol, acetone itself cannot be grafted onto citric acid-terminated oligomerization curing agents. Indeed, it is known that the reactivity of the prepolymer in the production of oligomerization curing agents is determined in part by the ratio of alcohol to acetone used to miscible citric acid and ESO. That is, in a mixture of similar amounts of citric acid and ESO, under similar reaction conditions, a solution with a relatively high ratio of alcohol to acetone produces a curing agent that is more effective than a solution with a relatively low ratio of alcohol to acetone. The resulting curing agent has a longer, less highly branched chain structure.

In general, a curing agent can be adapted to produce a castable resin with additional unmodified epoxidized vegetable oil. The improved process disclosed herein by applicants provides a substantially void-free elastomeric product.

[2. Coating material] A. Overview The curing agents disclosed above can be used as prepolymers and can be mixed with additional epoxidized vegetable oils as resins, which can be applied to most backing materials/backing layers to produce a material with excellent tear strength, elasticity, Dimensional stability, manufacturing integrity of faux leather material. In the present invention, the terms "substrate material" and "substrate layer" can be used interchangeably according to specific circumstances. However, in certain articles disclosed herein, the backing material may consist of a resin-impregnated backing layer. According to an exemplary embodiment of a coating material using a prepolymer, an exemplary fabric backing material/backing layer may be a woven cotton fleece (as shown in Figures 2A and 2B and described in further detail below). If the resin is formulated to be relatively low tack, the exposed flannel may remain on the resin coated fabric core. This will provide a warm texture to the surface of the article. Other textile backing materials/backing layers may include various woven substrates (e.g. plain weave, twill, satin weave, denim), knitted substrates and non-woven substrates without limitation, provided that within the scope of the appended claims If otherwise stated, follow its instructions.

In other embodiments, the resin can be applied in a fixed layer thickness to a non-adhesive surface (eg, silicone or polytetrafluoroethylene (PTFE)) or textured paper. When the film is applied in an even layer, a layer of backing material can be placed over the liquid resin. The liquid resin wicks into the fabric layer (i.e. the backing material) and forms a permanent bond with the fabric during the curing process. The article will then be placed in an oven to complete the resin curing. The curing temperature is ideally at 60°C to 100°C for 4 hours to 24 hours, more desirably 70°C to 90°C. Longer cure times are also possible. As an alternative, the liquid resin can be applied in a fixed layer thickness on a non-adhesive surface (e.g. silicone or PTFE) or textured paper, after which the fabric can be covered over the liquid resin, then another non-adhesive surface can be covered over the resin and on the fabric. The assembly can be placed in a heated compression molding machine to complete curing. The curing temperature in the compression mold can optionally be higher than in the oven because the molding pressure minimizes the generation of air bubbles (voids) in the final article. The curing temperature in the compression mold may be 80°C to 170°C, more desirably 100°C to 150°C, and the time is desirably 5 to 60 minutes, more desirably 15 to 45 minutes.

The resin may be optically transparent and have a yellowish tinge. The unpigmented resin can be used to make oilcloth-like materials, and the fabric can be waterproof and windproof at the same time, and the fabric pattern can be seen in the resin. The coated fabric produced in this embodiment can be cured in an oven (without a die) or in a heated press. These coated fabrics can be used in clothing, especially for outerwear or waterproof accessories: including but not limited to ladies' purses, handbags, backpacks, duffle bags, luggage, briefcases, hats, etc.

New embossed articles are produced by means of the resin-bonded nonwoven mats according to the invention, which consist of virgin or recycled textile fibers. In particular, nonwoven webs of about 7 mm to 20 mm thickness can be impregnated with the resin of the invention. After impregnation, the nonwoven web can be pressurized in a heated hydraulic press at a nominal pressure of 10 psi to 250 psi, more desirably 25 psi to 100 psi. The nonwoven web with resin may be pressed between silicone release liners, one of which may have an embossed pattern. The embossed pattern may comprise relief features having a depth of 1mm to 6mm, more desirably 2mm to 4mm. When the resin prepared according to the present invention is further dyed by structural pigments such as mica pigments of various shades, many of which have pearlescent properties, and the resin is compression molded to a nonwoven web with an embossed pattern, it creates Articles of aesthetically pleasing patterns. The structural colors are preferably aligned at the embossed features, creating a sharp contrast and visual depth corresponding to the embossed pattern. Alternatively, the present invention may impart color to articles manufactured by the present invention by adding mineral pigments from other source rocks and treatments to the cast resin, as described herein without limitation, unless otherwise stated in the appended patent application If otherwise stated in the scope, it shall be followed.

An embodiment of the present invention also discloses that the resin coated fabric can be made by roll-to-roll processing. In the roll-to-roll processing of textured coated fabrics, including leather-like materials, the textured paper is often used as a carrier film to allow the resin and fabric to move through the oven for a specified amount of time. The resin of the present invention may require a longer curing time than the PVC or polyurethane resin used in the prior art, so the production line speed may be slower accordingly or a longer curing oven may be made to produce a longer curing time. Vacuum degassing the resin before casting allows higher temperatures to be used for curing (due to less residual solvent, humidity and residual air), which can speed up curing time and increase line speed.

As an alternative, specific catalysts are known in the art to accelerate the addition of carboxylic acids to epoxy groups. Basic catalysts can be added to the resin; some exemplary catalysts include pyridine, isoquinoline, quinoline, N,N-dimethylcyclohexylamine, tributylamine, N-ethyl phenoline, dimethylaniline, tetra Butyl ammonium hydroxide and other similar molecules. Other quaternary ammonium or phosphonium molecules are known catalysts for the addition of carboxylic acids to epoxy groups. Various imidazoles are likewise known catalysts for this reaction. Zinc salts of organic acids are known to improve cure rates and impart beneficial properties to cured films, including improving their moisture resistance. (See "Catalysis of the Epoxy-Carboxyl Reaction" by Werner J. Blank, Z. A. He and Marie Picci at the International Waterborne, High-Solids and Powder Coatings Symposium[ Catalysis of Epoxy Carbonyl Reaction], February 21-23, 2001, .) Accordingly, any suitable catalyst may be used without limitation unless otherwise stated in the appended claims.

B. Implementation Although the following exemplary embodiments and methods have specific reaction values (such as: temperature, pressure, and reagent ratios, etc.), the embodiments and methods are for exemplary purposes only and do not limit the scope of the present invention, unless in the attached application If otherwise stated in the patent scope, it shall be followed.

First Exemplary Embodiment and Method The prepolymer was used to manufacture the coating material of the first embodiment (ie the curing agent disclosed above), and 18 parts of citric acid were dissolved in 54 parts of warm IPA. In this solution, only 12 parts of ESO were added. The IPA was evaporated (above about 85°C) with continued heating and stirring. It was found that this made it possible to make viscous liquids that could be heated above 120°C without gelling (even if heated for a long time). The viscous liquid prepolymer can be cooled to below 80°C. Add 88 parts of ESO to this viscous liquid. The final liquid resin will polymerize into a solid elastomer product at about 150°C in 1-5 minutes. The coating material (which can be used as a substitute for natural animal skin leather) as a reaction product can be formed by using epoxidized triglycerides and the aforementioned prepolymers, without limitation in scope of the present invention, unless hereinafter If there are other explanations in the appended patent scope, the explanations shall be followed.

Second Exemplary Embodiment and Method In this exemplary embodiment, 30 parts citric acid are dissolved in 60 parts warm IPA. To this solution, 20 parts of ESO were slowly added with stirring. The IPA evaporates with continued heating and stirring (above 85°C, ideally above 100°C). This viscous liquid prepolymer can be cooled to below 80°C (ideally below 70°C) and is added with 80 parts of ESO and various structural pigments and 0.5 parts of zinc stearate (as an internal mold release agent) . The product resin was poured onto the cellulose fabric and allowed to cure at about 120°C for 10-30 minutes. After initial curing, the material was placed in an oven at 80°C for overnight post-curing (approximately 16 hours). The surface of the material will be ground flat (and polished if necessary). The product material will have imitation leather properties.

Third Exemplary Embodiment and Method Prepolymers were made by dissolving 50 parts citric acid in 100 parts warm IPA and speeding up with mixing. After the citric acid had dissolved, 50 parts of ESO was added to the stirred solution. The mixture was placed on a heating plate, and the IPA was evaporated under continuous heating and stirring. These solutions were made multiple times at various heating plate temperatures and airflow conditions. Even after prolonged heating and stirring, product amounts greater than the mass of ESO and citric acid alone were repeatedly obtained. Depending on the evaporation rate of IPA (judged at least by air flow, mixing rate, and heating plate temperature), 2.5 to 20 parts of IPA were grafted onto the citric acid terminated oligomeric prepolymer. Also, a mixed solvent of acetone and IPA can be used as the reaction medium, wherein the ratio between acetone and IPA determines the amount of residual carboxylic acid functional groups on the prepolymer and the amount of branches in the prepolymer. Higher IPA content can produce more linear structures. As shown in Figure 1, IPA is grafted on citric acid through ester chains, which caps some carboxylic acid functional groups and reduces the effective functionality of citric acid. A lower amount of IPA can produce a more highly branched structure by remaining more carboxylic acid functional groups.

Fourth Exemplary Embodiment and Method Prepolymers were made by dissolving 50 parts citric acid in 100 parts warm IPA and speeding up with mixing. After the citric acid is dissolved, add 50 parts of ESO and 15 parts of dewaxed golden shellac into the stirred solution. The mixture was placed on a heating plate, and the IPA was evaporated under continuous heating and stirring. Shellac can increase the viscosity of the prepolymer product.

Fifth Exemplary Embodiment and Method Prepolymers were made by dissolving 45 parts citric acid in 90 parts warm IPA and speeding up with mixing. After the citric acid had dissolved, 45 parts of ESO was added to the stirred solution. The mixture was placed on a heating plate, and the IPA was evaporated under continuous heating and stirring.

Sixth Exemplary Embodiment and Method Prepolymers were made by dissolving 45 parts of citric acid in 30 parts of warm IPA and 60 parts of acetone and speeding up with mixing. After the citric acid had dissolved, 45 parts of ESO was added to the stirred solution. The mixture was placed on a heating plate, and the acetone and IPA were evaporated under continuous heating and stirring. These solutions were made multiple times at various heating plate temperatures and airflow conditions. Even after prolonged heating and stirring, the amount of product greater than the mass of ESO and citric acid alone was repeatedly obtained, but the amount of grafted IPA was less than that in the prepolymer prepared according to the fifth exemplary embodiment (even though In both cases the ratio of ESO to citric acid was 1:1). Also, the prepolymer produced according to the fifth embodiment is less viscous than the prepolymer produced according to the sixth embodiment.

Generally speaking, it is believed that when there is more IPA content in the production of prepolymer, it can make more IPA grafted on the carboxylic acid site of citric acid, thereby reducing the average functionality of citric acid and making less high Branched oligomeric prepolymers. In no case was it found that capping the citric acid with IPA would inhibit the eventual cure of the resin under reaction conditions.

Seventh Exemplary Embodiment and Method The prepolymer produced by the fourth exemplary embodiment was mixed with additional ESO to bring the total calculated amount of ESO to 100 parts. The mix cures to a clear, elastomeric resin. According to the tensile test of ASTM D412, the tensile strength was 1.0 MPa, and the elongation at break was 116%.

Eighth Exemplary Embodiment and Method The prepolymer was produced by dissolving 45 parts of citric acid in 20 parts of IPA and 80 parts of acetone under heating and stirring. After the citric acid is dissolved add 35 parts of ESO and 10 parts of shellac into the stirred solution. The prepolymer produced after evaporation of the solvent was cooled. The prepolymer was mixed with an additional 65 parts of ESO to bring the total amount of ESO to 100 parts. The mixed resin is cast on a silicone mat to form a transparent sheet. The mechanical properties of the material are obtained by tensile testing according to ASTM D412. The tensile strength is 1.0 MPa and the elongation is 104%, which results in a calculated modulus of 0.96 MPa.

Ninth Exemplary Embodiment and Method Prepolymer was produced by dissolving 45 parts of citric acid in 5 parts of IPA and 80 parts of acetone under heating and stirring. After the citric acid has dissolved, add 35 parts ESO and 10 parts shellac to the stirred solution. The prepolymer produced after evaporation of the solvent was cooled. The prepolymer was mixed with an additional 65 parts of ESO to bring the total amount of ESO to 100 parts. The mixed resin is cast on a silicone mat to form a transparent sheet. The mechanical properties of the material are obtained by tensile testing according to ASTM D412. The tensile strength is 1.8 MPa and the elongation is 62%, resulting in a calculated modulus of 2.9 MPa. It can be seen from the eighth and ninth exemplary embodiments that a lower amount of IPA during the manufacture of the prepolymer produces a prepolymer that is more highly crosslinked with a higher modulus and lower elongation resin. These reaction products are more like plastic than rubber in their properties.

Tenth Exemplary Embodiment and Method Prepolymer was produced by dissolving 25 parts of citric acid in 10 parts of IPA and 80 parts of acetone under heating and stirring. After the citric acid has dissolved, add 20 parts ESO and 5 parts shellac to the stirred solution. The prepolymer produced after evaporation of the solvent was cooled. The prepolymer was mixed with an additional 80 parts of ESO to bring the total amount of ESO to 100 parts. The mixed resin is cast on a silicone mat to form a transparent sheet. The mechanical properties of the material are obtained by tensile testing according to ASTM D412. The tensile strength is 11.3 MPa and the elongation is 33%, resulting in a calculated modulus of 34 MPa. It can be known from the tenth exemplary embodiment that, under proper design of the prepolymer and the final resin mixture, plastic materials with high strength and high modulus properties can be produced by the method disclosed in the present invention.

Eleventh Exemplary Embodiment and Method The prepolymer of the sixth exemplary embodiment was mixed with additional ESO to bring the total amount of ESO to 100 parts. The mixed resin is cast on a silicone mat to form a transparent sheet. The mechanical properties of the material are obtained by tensile testing according to ASTM D412. The tensile strength is 0.4 MPa and the elongation is 145%, which results in a calculated modulus of 0.28 MPa.

It can be known from the foregoing eleventh exemplary embodiment that, under proper design of the prepolymer and the final resin mixture, the method disclosed in the present invention can be used to manufacture high-elongation elastomeric materials. Thus, with proper prepolymer design, the inventive method can be used to make materials ranging from hard, plastic materials to highly elongated elastomeric materials. In general, grafting higher amounts of IPA at the time of prepolymer formation reduces the stiffness of the product material. Higher amounts of dissolved shellac result in a stronger material with somewhat higher stiffness. Modulus can be lowered by using citric acid dosages above or below stoichiometric equilibrium (relative to the final mix formulation). Amounts of citric acid close to stoichiometric equilibrium (about 30 parts by weight to 100 parts ESO by weight) generally produce the stiffest materials; unless offset by high amounts of IPA grafted on carboxylic acid groups during prepolymer formation.

An advantageous attribute of animal leather is its elasticity over a wide range of temperatures. Leather substitutes of synthetic polymers of PVC or polyurethane may become particularly hard at temperatures below -10°C or below -20°C (according to CFFA-6a - Cold Crack Resistance - Roller [Cold Crack Resistance - Roller] method test). Materials prepared by certain embodiments of the present disclosure may have poor cold cracking resistance properties. In the following examples, formulations with improved cold crack resistance properties are provided. The anti-cold cracking properties can be improved by adding elastic plasticizers. Some natural vegetable oils may exhibit good low-temperature fluidity, especially polyunsaturated oils are preferred. The oil can be any non-epoxidized triglyceride (such as disclosed in Section 1 above), which has a relatively high iodine value (such as greater than 100), which is not limiting in scope of the present invention unless a patent application is attached If otherwise stated in the scope, it shall be followed. Alternatively, monounsaturated oils may be added as plasticizers; an exemplary oil may be castor oil, which is heat stable and not prone to rancidity. Also, the fatty acids and fatty acid salts of these oils can be used as plasticizers. Accordingly, the scope of the present disclosure is not limited by the presence of plasticizers or their specific chemical characteristics unless otherwise stated in the appended claims.

Another approach is to use a polymeric additive which can give better low temperature flexibility. A preferred polymeric additive is epoxidized natural rubber (ENR). The ENRs available in the market have different levels of epoxidation. For example, the epoxidation degree of 25% of the double bond produces a grade of ENR-25, and the degree of epoxidation of a double bond of 50% produces a grade of ENR-50. A higher degree of epoxidation increases the glass transition temperature T _g . The lower the T _g is, the better it is, which is conducive to enhancing the cold crack resistance of the final resin, so ENR-25 is a better grade as a polymeric plasticizer. Even a lower degree of epoxidation may be beneficial to further reduce the cold crack resistance temperature of the final resin. However, the disclosed scope of the present invention is not limited thereto, unless otherwise stated in the appended claims.

Twelfth Exemplary Embodiment and Method Mix ENR-25 and ESO in a two-roll rubber mixing mill. Slowly add ESO, found that up to 50 parts of ESO can be added to 100 parts of ENR-25, until the viscosity is reduced to the point where it can no longer be mixed with the mill. The sticky material is then transferred to a container and further mixed in a Flacktek® Speedmixer. When a total of 300 parts of ESO is finally added to 100 parts of ENR-25, a fluid mixture is obtained. The phases of the resulting mixture did not separate.

The materials of the twelfth exemplary embodiment can be mixed in a single step by various known methods, which is not limited in scope unless otherwise stated in the appended claims. In particular, so-called Sigma Blade mixers can be used to produce a homogeneous mixture of ENR and ESO in one step. Likewise, a kneader, such as a Büss kneader, is known to those skilled in the art to produce such mixtures using a continuous mixing type arrangement. The foregoing homogeneous mixture can be blended with the prepolymers described in the preceding examples and formed into a malleable resin as a faux leather material with improved cold crack resistance. Also, the material prepared with the ENR-modified ESO disclosed in the twelfth exemplary embodiment exhibits improved tear strength, elongation, and abrasion resistance compared to a resin without ENR.

C. Additional processing The articles produced by the present invention can be finished by any method of the prior art. The method includes, but is not limited to, embossing, branding, sanding, grinding, polishing, calendering, painting, waxing, dyeing, coloring, etc., unless otherwise stated in the appended claims. Exemplary results can be obtained by impregnating the resins of the present invention onto woven or nonwoven mats and curing these articles. After the article has cured, portions of the surface can be abraded to remove imperfections and expose portions of the substrate. This surface exhibits many properties similar to animal skin leather, as shown in Figures 3-7. In special applications, the surface can be treated with a natural oil or wax protectant.

D. Applications/Exemplary Products The coated fabrics, ENR-based materials and/or oilcloth-like materials produced by the present invention can be used in applications where animal hide leather and/or synthetic resin coated fabrics are used today. Such applications may include, but are not limited to, belts, purses, backpacks, shoes, table tops, seats, etc. unless otherwise stated in the appended claims. Many of these articles are consumables, are not biodegradable and are not recyclable if made from alternative synthetic materials. If these articles were instead prepared according to the present invention, they would be biodegradable and would present no handling issues, as the biodegradability of similar polymers made from ESO and natural acids has been studied and known. Refer to the literature of Shogren et al., Journal of Polymers and the Environment [ Polymer and Environmental Journal ], Vol. 12, No. 3, July 2004. Also, unlike animal skin leather, which requires extensive processing to make it durable and stable (some of which use toxic chemicals), the materials provided by the present invention may require less processing and use environmentally friendly chemicals. Also, the size of animal skin leather is limited, and may contain defects that reduce the production efficiency of large pieces. The materials disclosed in this invention do not have the same limitations on size.

When the liquid resin precursor described in the above exemplary embodiments and methods is applied to the cotton linter fabric and placed on a heated surface (a heating plate), the cross-section of the resulting material is as depicted in Figures 2A and 2B. When the surface temperature of the heating plate is about 130°C–150°C, the resin reacts in about 1–5 minutes. Resin tack can be controlled by controlling the time the resin polymerizes before being poured on the surface. By controlling the viscosity, the degree of penetration to the surface can be controlled and various effects can be achieved in the product. For example, a low-viscosity resin can penetrate the fabric 102 and produce a suede or brushed texture as shown in FIG. 2A , and produce a natural imitation leather material 100 with a suede texture. A higher viscosity resin can only partially penetrate the fabric 102 and produce a shiny, polished surface as shown in FIG. 2B, and produce a natural leather-like material 100' with a shiny finish. In this way, various variations can be produced to mimic natural animal skin leather products. 2A and 2B, the natural leather-like material 100 with a suede texture 100 has more fabric extension hairs 103 extending from the fabric 102 to the polymer 104 than the natural leather-like material 100' with a glossy texture. In the natural leather-like material 100' with a glossy texture, most of the fabric extensions 103 terminate in polymer 104.

As an alternative, articles with resin-free suede-like (i.e. relatively soft) surfaces can be made by embedding flannel onto an immiscible glue (eg, silicone vacuum paste) applied to a heated plate. The resin can be poured over the flannel surface, but will not penetrate the incompatible gel. After curing, the immutable colloid can be removed from the article and impart a suede feel. Those with ordinary knowledge know that the natural leather-like material disclosed in the present invention is produced as a reaction product between epoxidized vegetable oil and a naturally occurring multifunctional acid impregnated on a cotton flannelette substrate, and without limitation, the formed The product of the aforementioned reaction in the article is thus only partially impregnated onto the substrate, while one side of the article is substantially unimpregnated flannel. Although cotton fleece is used in these examples, any suitable flannel and/or fabric may be used, including but not limited to linen, hemp, ramie, and other cellulosic fibers, without limitation , unless otherwise stated in the appended claims. In addition, nonwoven substrates can be used as well-recycled substrates (upcycling). Brushed knits can be used to impart extra stretch to the final product. Random mats such as Pellon, also known as batting, can be advantageously used as a base for certain articles. In another exemplary embodiment, the backing layer and/or backing material of a textile may be composed of protein-based fibers including, but not limited to, wool, silk, alpaca, musk ox, llama, camel Horsehair, cashmere wool and angora wool, unless otherwise stated in the appended claims.

Other exemplary products made in accordance with the present invention are shown in Figures 3 through 8B. Figure 3 depicts a sheet of material that can be used as a natural imitation leather material, while Figures 4 to 6 show various natural imitation leather materials that can be used to make a wallet. Figures 4A, 4B and 4C show a plurality of holes on the material, wherein the holes can be formed by conventional drill bits, without limitation, unless otherwise stated in the appended claims. Comparing Figures 4A, 4B, and 4C shows that the method of making this material can be configured to impart a wide variety of textures thereon, including but not limited to smooth, grainy, soft, etc. (e.g., similar to various animal skin leathers), except in There are other explanations in the appended scope of patent application.

The blocks of material shown in Figures 5 and 6 can be cut with a laser. Unlike animal hide leather, laser cutting does not carbonize or degrade the edges of the aforementioned natural faux leather material along the cut line. Fig. 6 shows a finished wallet made of the natural imitation leather material made by the present invention. The separate parts shown in Figure 5 can be combined by conventional means (e.g. sewing) to form a simple credit card holder or card holder (as shown in Figure 6), which has the appearance one would expect from a similar product made of animal hide and leather , hardness and strength. The natural imitation leather material can be processed into a finished product by sewing and/or other methods by traditional methods, which is not limited in scope unless otherwise stated in the appended claims. As shown in FIG. 7 and detailed above, fabrics may be impregnated with resin in accordance with the present invention to provide various properties to the article.

Also, the resin produced by the present invention can be dyed according to the color of natural animal skin leather. In particular the use of structural and/or mineral pigments which do not contain any harmful substances. An example of an exemplary structured pigment is Jaquard PearlEx® pigment. Mixing relatively low doses of structural pigments can produce natural leather-like materials with excellent visual aesthetics. Another illustrative example of suitable pigments is available from Kreidezeit Naturfarben GmbH (GmbH). Again, a slight sanding of the surface of the resulting product yields a material that closely resembles tanned and dyed animal hide leather.

While certain examples disclosed herein can be configured to use only one layer of fabric, other exemplary samples use multiple layers of fabric and result in a thicker faux leather product. Since the reaction between the epoxy group and the carboxyl group does not generate any condensation by-products, there is no inherent limit to the possible cross-sectional thickness. Typically, resin-coated fabrics and nonwovens are used in applications such as office furniture, including: seating, writing surfaces, room dividers; on apparel, including: outerwear, shoes, and belts; and on accessories, including handbags, wallets, luggage, hats and wallets; and in residential decor, including wallpaper, floor coverings, furniture surfaces and curtain trim. Materials made in accordance with the present invention may be used in any of those applications or other applications arising herein or hereafter, depending on the suitability of the material, without limitation in scope unless otherwise stated in the appended claims. In addition, the current application of animal leather has the possibility of using the material produced by the present invention.

Also, the current application of petrochemical-based elastic films; especially the application of PVC and polyurethane coated fabrics, has the possibility of using the materials made by the present invention. Furthermore, the resin of the present invention basically does not emit any vapor when it is cured at the time and temperature described in the present invention. Therefore, the resin prepared by the present invention can also provide thicker applications than conventional films. For example: This resin can be used to cast 3D objects in a suitable mold. A top view of such a 3D object configured as a sphere produced by the present invention is shown in FIG. 8A , and its side view is shown in FIG. 8B . The spheres may be resin-based and produced from epoxidized soybean oil and citric acid-based formulations plus structural pigments. Simple tests have shown it to have very low resilience and are expected to have excellent shock-absorbing properties.

3D cast resin items in the prior art usually consist of styrene-extended polyesters (phosphophthalic or isophthalic systems). These articles can currently be composed of two-part epoxy resins or two-part polyurethane resins. Such articles may currently be composed of silicone casting resins. One example of an application currently offered by two-part epoxies is the thick film coating of tables and decorative inlays, where the epoxies can be selectively pigmented to produce pleasing aesthetic designs. The aforementioned applications can be successfully replicated with casting resins produced by the present invention. Also, chessmen can be successfully molded with the resin produced by the present invention without generating harmful gas or being trapped by air. Therefore, the various materials produced by the present invention have wide application, and the specific use of the final product produced by any method of the present invention is not limited to any particular application, unless otherwise stated in the appended claims.

E. Resin coatings, products and methods In various exemplary embodiments disclosed herein, natural products may have physical properties similar to synthetic coated fabrics, animal-based leather products, and foam products. As disclosed, the physical properties of natural products can be further enhanced to increase flexibility.

prior art Coatings exist on many consumer products where such coatings are applied to provide surface protection and/or coloration. Additionally, in some consumer products, coatings may primarily be used to improve the tactile feel (i.e., tactile feel) of a surface. In one class of materials, animal-based leather and leather-like materials, surface coatings can be provided to provide surface protection, coloration, and improved feel. For animal-based leather, such coatings can be substantially absorbed into the substrate and complement the natural feel of the leather. Such coatings may be based on oils, waxes and/or polymers (both natural and synthetic). Coatings may or may not be required when producing petrochemical-based leather alternatives (such as those based on PVC or PU), but when used, they are often petrochemical-based as well. When developing non-petrochemical and non-animal-based leather alternatives (i.e. materials based entirely on plant-derived ingredients), it may also be desirable to provide a coating that provides an additional surface to the non-petrochemical and non-animal-based leather alternative Protection, coloring and/or improved haptics.

overview In general, exemplary embodiments of coatings can be produced entirely from plant-derived ingredients. Such coatings may be particularly applicable to imitation leather materials produced from epoxidized natural rubber based formulations, but are not limited thereto unless otherwise stated in the appended claims. As further disclosed in US Patent #10,400,061, coatings produced according to the present invention may be configured as essentially the reaction product between epoxidized vegetable oils and multifunctional naturally occurring acids such as citric acid. The coating has been found to greatly improve the feel of the product so coated.

Exemplary Embodiments and Detailed Description Animal-based leather materials exhibit tactile qualities that are particularly smooth to the touch, even for textured articles. The relationship between the dynamic coefficient of friction and the static (or "separation") coefficient of friction has been found to be the key to quantifying this property. In general, rubber materials tend to have a high grip, which may be reflected in the actual values of the coefficients of friction (both static and dynamic), which are usually significantly higher than the dynamic coefficients of friction.

Certain leather-like materials, which are alternatives to animal-based leather, have been found to exhibit characteristic rubber-like coefficient of friction values; especially when such materials are formulated from epoxidized natural rubber (ENR). Formulations based on ENR with a 25% epoxidation level tended to have higher friction than formulations based on ENR with a 50% epoxidation level. This is consistent with polymer theory that relates the glass transition temperature ( _Tg ) to the coefficient of friction. That is, a higher _Tg results in a lower coefficient of friction, while a lower _Tg results in a higher coefficient of friction. According to records, in general, for every percentage change in the degree of epoxidation, the _Tg will increase by 1 degree Celsius. The coefficient of friction effect of _Tg changes is due to the rate at which polymer chains can rearrange to engage contacting surfaces. Unfortunately, many consumer products require materials with a low _Tg to prevent the article from becoming hard or brittle at reduced ambient temperatures (as might be encountered in winter). Thus, the _Tg (based on ENR with lower epoxidation levels) of materials formulated for low temperature flexibility tends to make the material system more abrasive, which adversely affects the tactile feel of the article.

Therefore, it is desirable to have an article configuration with a base material with a low _Tg and a coating with a relatively high _Tg , while the coating should remain flexible enough to avoid cracking at low temperatures. Furthermore, testing the coefficient of friction in a way that captures data consistent with what the human hand perceives is challenging. In general, tests between animal-based leather and stainless steel plates and between animal-based leather and silicone plates give data that are not of the order of magnitude of the coefficient of friction (COF) that can be detected by the human hand. In contrast, animal-based leather tested against PTFE-coated fiberglass baking sheets showed similar static and dynamic coefficients of friction, while also giving relatively low absolute values reflecting the feel of the human hand. Using the same test method and applying it to materials produced according to the various methods disclosed in US Patent #10,400,061, the data shown in Table 1 were obtained.

[Table 1] Test results for animal-based leather and two imitation leather materials. test material back surface Dynamic COF Static COF Resin-coated vegetable-based leather PTFE coated fiberglass 0.15 0.59 Uncoated plant-based leather based on ENR PTFE coated fiberglass 0.44 0.46 Red Leather - Smooth Front PTFE coated fiberglass 0.17 0.17

From Table 1, we see that the static and dynamic COF of animal-based leather is low, while the COF of ENR-based uncoated plant-based leather material is relatively high. In the first row we see coating this material with a resin that is the reaction product between epoxidized soybean oil (ESO) and citric acid (various exemplary embodiments of which can be produced by the method disclosed in US 10,400,061) Data that lowered the dynamic COF to values closer to animal-based leather. This results in significantly improved tactile qualities compared to uncoated ENR-based imitation leather materials.

Specifically, the coatings in Table 1 for resin-coated vegetable-based leather can be formulated by preparing a curing agent as disclosed in US 10,400,061 and then mixing the curing agent with additional ESO to prepare a temperature-curable resin . In the first stage of hardener manufacture, citric acid is dissolved in isopropanol, ethanol, or a combination of acetone and alcoholic solvents. In the second stage of hardener manufacture, ESO or a similar epoxy-containing vegetable-based triglyceride oil is added to the dissolved citric acid solution and allowed to react, while simultaneously removing the miscible solvent. An exemplary curing agent formulation may use 50 parts citric acid to 50 parts ESO to 400 parts miscible solvent. After the hardener has formed and the miscible solvent has evaporated, approximately 100 parts hardener is mixed with another 100 parts ESO to make the coating resin. This coating resin can be further diluted with solvents to make it easier to spray or spread. Example dilutions for ease of spreading may require mixing the resin with an equal mass of isopropanol, ethanol, or acetone. Subsequently, the diluent solvent is allowed to evaporate, and the resin-coated substrate can be placed in an oven or heated press to complete the curing reaction between the curing agent and the epoxidized vegetable-based triglyceride oil. In an exemplary embodiment, the coating resin may require curing at 150°C for 10 minutes. The texture of the coating resin may be determined by textured release paper or textured silicone sheet to give the desired look and feel, without limitation in scope, unless otherwise stated in the appended claims illustrate.

Another exemplary embodiment of a coating formulated according to the methods disclosed herein consists of a resin coating formulation that can be produced based on a ratio of 100 parts curing agent to 100 parts ESO, which can be further modified for ease of application . Specifically, this mixture can be diluted with acetone, isopropanol or ethanol in a ratio of 1:1 (mixed resin:solvent) to 1:20 (mixed resin:solvent). In general, any chemically suitable solvent having a boiling point of about 55 degrees Celsius to about 85 degrees Celsius may be used with the various exemplary embodiments of the coating, without limitation in scope unless otherwise stated in the appended claims. Thinner thinners will allow for easy spraying of thin coats, while thicker thinners may be better for roller application. In another exemplary embodiment, it has been found that the inclusion of a thickening polymer can help improve the feel of the cured film and prevent extrusion of the resin during the molding step. Such thickening polymers may include, but are not limited to (unless otherwise stated in the appended claims) shellac, cellulose acetate, cellulose acetate phthalate, hydroxypropyl cellulose, and other naturally occurring or natural Derivatized polymers (not limiting in scope unless otherwise stated in the appended claims) which are soluble in acetone, isopropanol, ethanol or other suitable solvents (not limiting in scope except in As otherwise stated in the scope of the appended patent application). In general, any thickener that has a desired effect on the coating during use for its intended application may be used to produce the coatings disclosed herein. Otherwise stated in the patent scope.

Resin coatings may contain release additives such as waxes to improve feel and aid release from textured paper. In an exemplary embodiment, olive wax has been found to be particularly advantageous for such purposes. In other exemplary embodiments as disclosed herein, ultraviolet (UV) light stabilizing additives such as micro- _TiO2 or nano- _TiO2 may be added to improve the photostability of the coating and protect the underlying material without departing from the invention spirit and are not limiting in scope unless otherwise stated in the appended claims.

It has been found that curing the coating resin by molding the coating resin between the ENR-based rubber substrate disclosed in US 10,400,061 and textured silicone or textured paper produces a material particularly suitable for requiring low dynamic COF, low gloss. The appearance and tactile qualities of consumer products with a light, “dry” feel.

It is generally understood that the _Tg of a material is related to the COF and that resin coatings as disclosed herein have a _Tg higher than that of epoxidized natural rubber, even at epoxidized levels of 50%. Furthermore, resin coatings may have a relatively high crosslink density and thus may exhibit poor conformability to the human hand. These properties may contribute to the preferred "hand" of the material.

Industrial Applicability Various exemplary embodiments of resin coatings as disclosed herein may be particularly useful for coating leather that can be used in wallets, handbags, wallets, shoes, belts, and similar consumer products typically made of leather or PU/PVC faux leather. ENR based rubber base, not limiting in scope unless otherwise stated in the appended claims. Exemplary embodiments of the coatings disclosed herein may be particularly advantageous when used to coat ENR-based rubbers due to the inherent material compatibility between the coating and the substrate. For example, and without limitation in scope, unless otherwise stated in the appended claims, thin coatings (e.g., less than 200 microns) as applied using textured silicone or textured paper have been found to be sufficiently flexible to withstand -15°C bending without delamination or cracking; while such coating materials are susceptible to cracking when subjected to bending at low temperatures as bulk material (thickness > 500 microns).

Oven curing such coatings untextured may result in a glossy surface with a less desirable tactile feel than a press cured and textured coating. In some exemplary embodiments, press curing of the coating may occur simultaneously with curing of the substrate ENR-based rubber material. In other exemplary embodiments, the substrate may be cured in a first step, the coating applied in a second step, and the coating cured on textured silicone or textured paper in a third step.

In other exemplary embodiments, the resin coating may be applied directly to the fabric to provide water resistance. In such exemplary embodiments, higher dilution levels of the coating solution (eg, about 3%-6% solids) can result in fabrics that are water resistant while maintaining a soft hand to the fabric. Higher solids yield more barrier resistance while the substrate hardens.

Materials manufactured and/or coated in accordance with any of the teachings of the present invention may be used as flooring, exercise mats, padding, shoe insoles, shoe outsoles, or sound absorbing panels, without limitation except as claimed in the appended claims otherwise stated in .

Materials fabricated and/or coated according to any of the teachings of the present invention can be molded into complex three-dimensional and multi-layered articles. A 3D article can be composed of multiple formulations at different locations within the article at the same time to have functionality everywhere.

Resilient memory foam using vegetable oil can be used in applications where polyurethane is currently used. These applications can be used in shoes, seating, flooring, exercise mats, bedding, and sound-absorbing panels without limitation in scope unless otherwise stated in the appended claims. Many of these items are consumable and, if made of synthetic materials, are non-biodegradable and non-recyclable. If such articles are prepared from the materials of the present invention, they will be biodegradable and present no disposal problems.

Although the methods described and disclosed herein may be configured for use with coatings composed of natural materials, the scope of the present disclosure, any individual process step and/or its parameters, and/or any device used in combination is not limited by the scope of the present disclosure. This limitation, rather, covers all beneficial and/or advantageous uses thereof, without any limitation, except as otherwise stated in the appended claims.

[3. Epoxy rubber] A. Overview The coated fabrics disclosed in Section 2 above use a liquid phase adhesive resin which can flow into the fabric or nonwoven substrate. The resulting cured material has mechanical properties reflecting a highly branched structure with limited polymer elasticity (moderate strength and moderate elongation) between crosslinks. One way to increase mechanical properties is to start reactions with polymeric materials that have a more linear structure and can be cured with lower crosslink densities. The incorporation of shellac resin (a high molecular weight natural resin) in the coated fabric formulation increases strength and elongation and makes the material more plasticized. The material formulation disclosed in Section 3 - epoxy rubber can exhibit excellent mechanical properties (very high strength and higher elongation), and its material elasticity does not decrease at room temperature (eg about 15°C-30°C) .

The present invention discloses an epoxidized natural rubber (ENR)-based natural material that does not contain animal-based substances and is substantially free of petrochemical-containing materials. In a specific embodiment, the natural material can be used as a leather-like material (which can replace animal skin leather and/or petrochemical-based leather-like products (such as PVC, polyurethane, etc.)), which is not limiting in scope, except in There are other explanations in the appended scope of patent application. In addition, the ENR-based natural materials disclosed herein can be formulated to be substantially free of allergens that may cause allergies in a particular individual. The materials disclosed in this invention are more cost-effective and scalable than other materials proposed for petrochemical-free vegan leather. With specific treatments, the aforementioned natural materials can also be made waterproof, heat-resistant and elastic at low temperatures. This beneficial attribute is applicable to any ENR-based natural material produced in accordance with the present invention, and also to those that have been additionally processed for specific applications, as disclosed and discussed herein.

In at least one embodiment, the elastomeric material formed is composed of at least one first polymer material and a curing agent, the first polymer material is further composed of epoxidized natural rubber, and the curing agent is as described in section 1. One of the described reaction product compositions between polyfunctional carboxylic acid and epoxidized vegetable oil. Compared with the curing agent, the volume ratio of the first polymer material of the formed elastomeric material may be larger. The formed elastomer material, wherein the degree of epoxidation of the epoxidized natural rubber can also be between 3% and 50%, which is not limited in scope, unless otherwise stated in the scope of the appended patent application. Another embodiment of the elastomeric material can be composed of a first polymer material and a curing system, the aforementioned first polymer material is composed of epoxidized natural rubber, and the aforementioned curing system is a non-sulfur-based and non-peroxide-based curing system , wherein the curing system contains more than 90% reactants of biological origin.

In another embodiment, the reaction product of epoxidized natural rubber and a curing agent can form an article, wherein the curing agent is the reaction product of a naturally occurring polyfunctional carboxylic acid and an epoxidized vegetable oil. In another embodiment, an article consisting of epoxidized natural rubber and fillers including cork flour and precipitated silica can be formed and molded into a leather-like textured sheet. In another embodiment, an article is formed wherein the reaction product further comprises fillers of cork powder and silica. In another embodiment, an article is formed or constructed wherein the reaction products of two or more layers have substantially different mechanical properties where the difference in mechanical properties results from a difference in the composition of the filler.

B. Exemplary Methods and Products Epoxidized natural rubber (ENR) is a commercially available product under the trade name Epoxyprene® (Sanyo Corp.). Two grades of 25% epoxy and 50% epoxy are available, namely ENR-25 and ENR-50. However, in certain embodiments, it is believed that ENRs having a degree of epoxidation between 3% and 50% can be used without limitation in scope unless otherwise stated in the appended claims. One with ordinary knowledge will know that ENR can also be prepared from protein denaturation or removal of latex starting products. During the epoxidation of natural rubber, allergen activity is significantly reduced – Epoxyprene literature reveals that latex allergen activity is only 2-4% of that of untreated natural rubber latex products. A major improvement for those who may be allergic to latex. ENR is used in the materials disclosed in this invention to impart elongation, strength and low temperature elasticity to the disclosed and patent-pending products.

ENR has traditionally been cured using chemistries commonly found in the rubber compound literature, such as sulfur-cured systems, peroxide-cured systems, and amine-cured systems. The present invention discloses a specially prepared curing agent with carboxylic acid functionality, which can be used as the curing agent fully disclosed in the foregoing section 1 of the present invention. There are many naturally occurring polyfunctional carboxylic acid-containing molecules including, but not limited to, citric acid, tartaric acid, succinic acid, malic acid, maleic acid, and fumaric acid. None of these molecules are miscible in ENR and thus have limited effectiveness and utility. Hardeners made from, for example, citric acid and epoxidized vegetable oils are soluble in ENR. In particular, epoxidized soybean oil (ESO) and citric acid curing agents are known to prepare excess citric acid to prevent gelation of ESO. Citric acid itself is immiscible in ESO, but it has been advantageously found that solvents such as isopropanol, ethanol and acetone (by way of example and not limitation of scope unless otherwise stated in the appended claims) can be used to prepare citric acid and Homogeneous solution of ESO. Figure 1 shows that in this solution, excess citric acid reacts with ESO and produces a carboxylic acid terminated oligomer material (still liquid). The miscible solvent contains at least a portion of the hydroxyl-containing (ie alcohol) solvent which at least partially reacts with some of the carboxylic acid functional groups on the citric acid. Most of the solvent is removed at elevated temperature and/or under vacuum, leaving behind a curing agent that is miscible with ENR. By so structuring the curing agent, the resulting material is substantially free of petrochemical derived components.

First Exemplary Embodiment and Manufacturing Process of Curing Agent for Preparation of ENR-Based Materials The curing agent was prepared by dissolving 50 parts citric acid in a warm mixture of 50 parts isopropanol and 30 parts acetone. After the citric acid has dissolved, add 15 parts shellac flakes (golden dewaxed) to the mixture along with 50 parts ESO. The mixture was heated and stirred continuously until all volatile solvents evaporated. Notably, the total residues were greater than citric acid, ESO, and shellac, indicating that some isopropanol (IPA) was grafted (via an ester bond) onto the citric acid-terminated hardener. Changing the ratio of IPA to acetone can change the degree of grafting of IPA onto the curing agent.

Second Exemplary Embodiment and Preparation Process of ENR-Based Materials 25% epoxidized epoxidized natural rubber (ENR-25) was mixed with 100 parts of rubber and 30 parts of the curing agent prepared in the first example. Also, 70 parts of crushed cork powder (MF1 from Amorim) was added as filler. The mixture was prepared on a two-roll rubber mill with normal mixing operations. The mixture was compressed into tablets and molded at 110°C for 30 minutes. It is properly cured and has elongation and strain recovery similar to sulfur and peroxide cure systems.

Third Exemplary Embodiment and Preparation Process of ENR-Based Materials 25% epoxidized epoxidized natural rubber (ENR-25) was mixed with 100 parts of rubber and 45 parts of the curing agent prepared in the first example. Also, 70 parts of crushed cork powder (MF1 from Amorim) was added as filler. The mixture was prepared on a two-roll rubber mill with normal mixing operations. The mixture was compressed into tablets and molded at 110°C for 30 minutes. It can be fully cured, but has some of the properties of an over-crosslinked system; including lower tear strength and very high resilience.

Fourth Exemplary Embodiment and Preparation Process of ENR-Based Materials 25% epoxidized epoxidized natural rubber (ENR-25) was mixed with 100 parts rubber and 15 parts curing agent prepared in the first example. Also, 70 parts of crushed cork powder (MF1 from Amorim) was added as filler. The mixture was prepared on a two-roll rubber mill with normal mixing operations. The mixture was compressed into tablets and molded at 110°C for 30 minutes. It is cured, but has a relatively low state of cure; it has properties such as low resilience and low strain recovery.

Fifth Exemplary Embodiment and Manufacturing Process of ENR-Based Materials 25% epoxidized epoxidized natural rubber (ENR-25) was mixed with 100 parts of rubber and 30 parts of the curing agent prepared in the first example. Also, 70 parts of crushed cork powder (MF1 from Amorim) was added as filler. Also, add 20 parts recycled fiber (taken from recycled textiles). The mixture was prepared on a two-roll rubber mill with normal mixing operations. The mixture was compressed into tablets and molded at 110°C for 30 minutes. It is fully cured and additionally has a relatively high tensile modulus due to the fiber content.

Sixth Exemplary Embodiment and Manufacturing Process of ENR-Based Materials 25% epoxidized epoxidized natural rubber (ENR-25) was mixed with 100 parts of rubber and 30 parts of the curing agent prepared in the first example. Also, 60 parts of crushed cork powder (MF1 from Amorim) was added as filler. Also, 80 parts recycled fiber (taken from recycled textiles) was added. The mixture was prepared on a two-roll rubber mill with normal mixing operations. The mixture was compressed into tablets and molded at 110°C for 30 minutes. It is fully cured and additionally has a very high tensile modulus due to the fiber content.

Seventh Exemplary Embodiment and Manufacturing Process of ENR-Based Materials 25% epoxidized epoxidized natural rubber (ENR-25) was mixed with 100 parts of rubber and 60 parts of the curing agent prepared in the first example. Also, 35 parts of ESO was added as a reactive plasticizer. Also, 350 parts of crushed cork powder (MF1 from Amorim) was added as filler. Also, add 30 parts recycled fiber (taken from recycled textiles). The mixture was prepared on a two-roll rubber mill with normal mixing operations. The mixture was compressed into tablets and molded at 110°C for 30 minutes. It is fully cured, rigid and additionally has a relatively high tensile modulus due to the fiber content.

Eighth Exemplary Embodiment and Manufacturing Process of Curing Agent for ENR-Based Material The curing agent was prepared by dissolving 50 parts citric acid in a warm mixture of 110 parts isopropanol. After the citric acid has dissolved, add 50 parts ESO to the mixture along with 10 parts beeswax. The mixture was heated and stirred continuously until all volatile solvents evaporated. The total residue was greater than citric acid, ESO, and beeswax, indicating that some isopropanol (IPA) was grafted (via an ester bond) onto the citric acid-terminated hardener. The reduced liquid mixture was added to fine precipitated silica (Ultrasil 7000 from Evonik) to prepare a 50 wt% dry liquid concentrate (DLC) for easy addition in subsequent processing.

Ninth Exemplary Embodiment and Manufacturing Process of ENR-Based Materials 25% epoxidized epoxidized natural rubber (ENR-25) was mixed with 100 parts of rubber with 50 parts of cured DLC prepared in the eighth embodiment and an additional 30 parts of fine precipitated silica. Mixing the cured DLC prepared in the eighth exemplary embodiment can eliminate some of the stickiness in the process that is encountered when mixing without DLC as a pre-dispersed curing agent. The resulting mixture was press cured at approximately 50 psi at 110°C for 30 minutes to produce translucent slabs.

The material of this embodiment has properties similar to animal skin leather; including slow recovery after folding, shock damping properties and high tear strength. The total (55 parts) silica loading and this particular curing agent are believed to contribute to the "loss" properties of the material. Without being limited by theory, it is possible that the total silica loading approaches the percolation threshold and produces particle-particle interactions that lead to depletion properties, which are not limiting in scope unless otherwise stated in the appended claims . Formulation of polymers at _Tg near room temperature (eg, about 15°C - 30°C) is a more likely mechanism for lossy material, which is also a means for poorer cold crack resistance.

Tenth Exemplary Embodiment and Preparation Process of ENR-Based Materials 25% epoxidized epoxidized natural rubber (ENR-25) is mixed with 100 parts of rubber and 30 parts of hemp fiber called "cottonized". The mixture is mixed using a two-roll rubber mill and tightly clamped Disperse the fibers evenly. To this masterbatch were added 50 parts of the cured DLC prepared in the eighth embodiment, and 30 parts of fine precipitated silica. The resulting mixture was press cured at approximately 50 psi at 110°C for 30 minutes to produce translucent slabs. The material of the tenth exemplary embodiment has similar properties to the material of the ninth exemplary embodiment, except that the former has a lower elongation at break and a higher tensile modulus due to the fiber content.

Eleventh Exemplary Embodiment and Preparation Process of ENR-Based Materials The desired black color was achieved by mixing ENR-25 with coconut charcoal to obtain a black batch of ENR-based material. In addition to the black colorant, other ingredients are added to produce a workable batch of rubber. Other ingredients may include clay, precipitated silica, additional epoxidized soybean oil, castor oil, essential oil odorants, tocopherol (vitamin E, which acts as a natural antioxidant), and curing agents. The material was then cured in a stretch plate mold at 150°C for 25 minutes to complete the cure.

Twelfth Exemplary Embodiment and Preparation Process of ENR-Based Materials A brown batch of ENR based material was obtained by mixing EN-25 with cork powder to achieve the desired brown color and texture. In addition to cork flour, other ingredients are added to produce a workable batch of rubber. Other ingredients may include clay, precipitated silica, additional epoxidized soybean oil, essential oil odorants, tocopherol (vitamin E, which acts as a natural antioxidant), and prepolymer curing agent. The material was then cured in a stretch plate mold at 150°C for 25 minutes to complete the cure.

The tensile stress-strain curves of the materials prepared in the eleventh and twelfth embodiments are shown in FIG. 9 . It can be seen that in this particular example, the cork powder filled brown batch (twelfth embodiment) has a higher modulus than the black batch (eleventh embodiment). In these two exemplary embodiments, the brown batch (twelfth embodiment) has a Shaw hardness of 86 and the black batch (eleventh embodiment) has a Shaw hardness of 79.

The optimal amount of additional material can vary depending on the specific application of the ENR-based material, and Table 2 shows various ranges for this.

[Table 2] Acceptable and ideal ranges of other points. Element Ideal range (percentage of total product weight) Acceptable range (total product weight percent) ENR-25 40-60 20-90 Hardener 2-10 1-50 cork 3-10 0-70 Toner 0-15 0-50 Precipitated silica 15-35 0-50 EVO 0-10 0-30 non-reactive vegetable oil 0-10 0-30 odorant 0.5-3 0-10 Vitamin E/Antioxidant 0.2-2 0-4 Mineral fillers (eg: clay) 0-15 0-50

Other Ingredient Variations: Amounts of clay, precipitated silica, additional epoxidized soybean oil, castor oil, and/or curing agents can be used to vary the modulus of the batch/formulation within the range typical of traditional rubber formulations. For those skilled in rubber compounding, it is known that rubber formulations can be selectively compounded ranging from about 50 Shore hardness to about 90 Shore hardness. The exemplary formulations indicate that these blends fall within the expected range of properties for epoxidized natural rubber. Furthermore, it is known that traditionally compounded natural rubber can achieve strength values of 10-25 MPa. The eleventh exemplary embodiment exhibits physical properties consistent with conventional compounded natural rubber.

Materials made according to the invention can be further reinforced with continuous fibers to make stronger products. Reinforcement methods may include, but are not limited to, the use of woven textiles, non-woven fabrics, unidirectional strands, and ply unidirectional layers, unless otherwise stated in the appended claims. The method of reinforcement is ideally from natural fibers and yarns. Exemplary yarns include, but are not limited to, cotton, jute, hemp, ramie, agar, coconut fiber, kapok fiber, silk or wool, and combinations thereof, unless otherwise stated in the appended claims. Regenerated cellulose fibers such as viscose rayon, Modal® (a special viscose from Lenzing), lyotropic fibers (also known as Tencel® from Lenzing), or cuproamine rayon may be used without They are used with limitations to suit a particular application unless otherwise indicated in the appended claims. As an alternative, reinforcement methods may require the strength of synthetic fiber yarns based on para-aramid fibers, meta-aramid fibers, polybenzimidazole, polybenzoxazole and similar high strength fiber. In other exemplary embodiments, a reinforcing layer and/or material may be composed of protein-based fibers including, but not limited to, wool, silk, alpaca, musk ox, lean camel, vicuna, cashmere, and Angora, unless otherwise stated in the appended claims. Exemplary natural yarns may advantageously be treated by natural fiber fusion processing to improve their strength, reduce their cross-sectional diameter, and improve the bonding properties of the fibers to the elastomer. These yarns can be plied into threads, providing interpenetration characteristics between the reinforcement and the elastomer, and increasing the strength of the reinforcement. In certain applications, the reinforcement is preferably a unidirectional reinforcement using plied layers as compared to braided and knitted reinforcements. Braided and knitted reinforcements can provide product stiffness but create stress concentration properties around the yarn and fiber and negatively affect its tear strength. Conversely, unidirectional reinforcements at various ply angles can avoid this stress concentration feature. In a similar manner, a non-woven mat can be used as a reinforcement material because it does not contain directional stress-concentrating features, but is capable of long reinforcing fiber lengths at high fiber volume fractions. In a similar manner, overall blended fiber content improves stiffness but at certain volume and weight fractions reduces tear strength. When the total fiber content exceeds 50 phr (in traditional rubber compounding parlance), an improvement in tear strength is observed, especially when the fiber length is uniformly dispersed and well maintained during processing.

Molding and curing of the materials of the present invention require only moderate pressure to produce void-free articles. While conventional rubber curing systems generate gas and thus require molding pressures typically greater than 500 psi and often close to 2000 psi, the compounds disclosed herein require only 20 psi-100 psi molding pressures, or more specifically 40 psi-80 psi to produce Cured, non-porous product. The actual pressure required may depend on the desired material flow and details in the final product. This low molding pressure allows the use of relatively less expensive lower tonnage presses. Low pressure also allows the use of less expensive tools; the embossed textured papers of the present invention can produce suitable patterns on the elastic materials of the present invention, and these textured papers can be reused many times without loss of pattern detail. Even with open tools, the material has sufficient edge strength, which allows for faster tool cleaning and significantly reduces tool costs.

The low molding pressure also allows this elastomeric material to be molded directly to the surface of the elastic and porous core substrate. For example, the material can be overmolded over non-woven insulating mats for resilient flooring products or automotive interior products with soft-touch and sound-absorbing properties. Similarly, the product can be overmolded onto cork or similar low compressive strength substrates without damaging the substrate.

As previously stated, certain catalysts known to accelerate the addition of carboxylic acids to epoxy groups may be used in the formulations of the present invention without limitation unless otherwise stated in the appended claims.

Animal skin leather has special characteristics different from general composite elastomers in terms of elongation, elasticity, loss modulus and hardness. In particular, animal skin leather can fold itself without cracking, and is largely unaffected by temperature. That is, it has no brittle material phase at low temperatures. Animal leather also has shock-damping properties that are less common than typical composite elastomer compounds. Animal hide leather recovers slowly after being creased or folded, but generally fully recovers with minimal plastic deformation. The composite materials disclosed in the exemplary embodiments and methods of the present invention can mimic the aforementioned properties.

C. Additional processing The articles produced by the present invention can be finished by any method of the prior art. The method includes, but is not limited to, embossing, branding, sanding, grinding, polishing, calendering, painting, waxing, dyeing, coloring, etc., unless otherwise stated in the appended claims. The article can be constructed to exhibit many of the properties similar to animal hide leather. In special applications, the surface can be treated with a natural oil or wax protectant.

D. Application/Additional Exemplary Products According to the materials disclosed in the present invention, molded articles can be used as petrochemical-related imitation leather products and/or plant-related substitutes for animal skin leather products. In an exemplary embodiment, the article may be molded substantially as a sheet with various textures depending on the desired application. The sheet may be used without limitation in durable goods such as: upholstery, seats, belts, shoes, handbags, purses, backpacks, belts, equestrian supplies, wallets, phone cases and other similar articles, Unless otherwise stated in the appended claims. Alternatively, the material can be molded directly into the shape of the final product, for example: shoe soles, toes, heel cups, shoe uppers, purses, saddles and saddle parts, helmet covers, chair armrests and similar applications.

The materials disclosed in the present invention can be overmolded on elastic materials and thus be used as flooring, sports mats or sound absorbing panels. Similarly, these materials can be overmolded on garments, such as knee patches or elbow patches for improved wear resistance in areas of the garment. Likewise, motorcycle apparel (eg leather pants) and equestrian equipment can be overmolded with materials according to the invention, providing improved localized abrasion resistance and protection.

The materials of the present invention can be molded into complex 3D articles and multi-layered articles. That is, certain formulations of the invention may provide improved tear strength, while other formulations of the invention may provide improved abrasion resistance. These formulations can be layered and co-molded to provide an article with improved overall properties when compared to an article made from only one formulation. 3D articles may be molded without limitation to have additional product features, joints, and other functionality, unless otherwise stated in the appended claims. A 3D article can be composed of multiple formulations at different places within the article at the same time to have functionality everywhere.

A functional example of molding is shown in Figures 10A and 10B, which provide a perspective view of a portion of a belt made of ENR-based material. In particular, as shown in Figure 10A, the narrowing features (right side of Figure 10A) can be molded into a sheet that is cut into strips. The reduced thickness (possibly due to the absence of backing material/backing layer (e.g. non-woven padding) in the area of reduced thickness) enables the creation of a folded buckle retaining area substantially similar in thickness to the portion of the belt that is not folded upon itself , as shown in Figure 10B, the area of reduced thickness engages the buckle. Again, the regions folded back on themselves may ideally be combined with an additional resin or ENR based material molded between the folded regions with a cure cycle similar to that used during the initial molding of the sheet.

Figure 11 shows a series of retention grooves and ridges that can be molded into the belt ends to provide friction based retention features. That is, portions of belts made of woven nylon or other fabric are fastened and held on to the wearer by friction between the ribs woven into the belt and the metal rods used in the clasp. Such features may be advantageous because they avoid the stress concentrations that develop around the retaining holes in conventional belt buckles. When making the ENR-based material of the present invention, the retaining grooves and ridges and/or other features used to hold a portion of the belt in place can be easily molded by forming matching features in the manufacturing mold (which can be silicone or metal) to Belt sheet.

The ENR based material configured for use as a belt can be produced as a sheet and molded in the pattern shown at 12 . As shown in Figure 12, the sheet can be composed of various layers, where each outer sheet can be composed of an ENR-based material (e.g., "Sheet Rubber Preform" in Figure 12) with one or more fibers formed in between Backing material/underlay layer composition. In the exemplary embodiment shown in Figure 12, the backing material may consist of a woven reinforcement or a non-woven pad. However, any suitable backing material/backing layer may be used without limitation in scope, unless otherwise stated in the appended claims. At least one backing material may be a coated fabric (as shown in Figure 12, the layer labeled "Non-Woven Mat"), which may be constructed as described in Section 2 above. Textured paper can be positioned adjacent to one or both layers of ENR-based material to provide the desired aesthetics to the outer layers of the sheet and the resulting product. Finally, a silicone release sheet can be placed adjacent to one or two layers of textured paper for use.

The relatively low pressure required to produce properly cured samples using ENR-based materials allows the use of low-cost paper and silicone tools. In polyurethane and vinyl leather alternatives use so called textured paper to get the desired texture. These textured papers are also effective for creating patterns in the ENR-based materials of the present invention. Figure 12 depicts an advantageous molding configuration in which silicone release sheets can be molded under temperature and pressure as the topmost and bottommost layers of the sandwich. If texture is desired on the "outside" of the belt, the textured paper can be adjoined to the silicone sheet. It may be advantageous to use a release aid treatment to facilitate easy release and reuse of the textured paper. Both silicone and vegetable oil can promote the easy release and reuse of textured paper, but any release agent can be used without limitation, unless otherwise stated in the appended claims.

A sheet of uncured rubber preform can be loaded into the interlayer next to the textured paper. A non-woven mat and/or woven reinforcement may be placed between the rubber preform sheets. In an exemplary embodiment, the non-woven mat may comprise recycled textiles, hemp fibers, coconut coir fibers, or other environmentally friendly (biodegradable) fibers and/or combinations thereof, without limitation in scope, unless otherwise stated in the accompanying patent application Scope otherwise stated. In an exemplary embodiment, the woven reinforcement layer may comprise jute burlap or a similar open structure woven product that is high strength and biodegradable. In another exemplary embodiment, so-called cotton monk cloth can be used as the woven reinforcement layer, without limitation in scope, unless otherwise stated in the appended claims. In some configurations, open structure braided products have relatively good tear strength compared to tight braids. In another exemplary embodiment, a reinforcement layer (woven or nonwoven) may be constructed of protein-based fibers including, but not limited to, wool, silk, alpaca, musk ox, lean camel, vicuna, Cashmere wool and angora wool, unless otherwise stated in the appended claims.

ENR-based materials configured for leather replacement can be used in applications where animal skin leather is currently used. Such applications may include, but are not limited to, belts, purses, backpacks, shoes, table tops, seats, etc. unless otherwise stated in the appended claims. Most of these products are consumables. If they are made of petrochemical imitation leather products, they are not biodegradable and cannot be recycled. If such articles are prepared from the materials of the present invention, they will be biodegradable and present no disposal problems. Also, unlike animal skin leather, which requires extensive processing to make it durable and stable (some of which use toxic chemicals), the materials provided by the present invention may require less processing and use environmentally friendly chemicals. Also, the size of animal skin leather is limited, and may contain defects that reduce the production efficiency of large pieces. The material disclosed in at least one embodiment of the present invention is not limited in size, and the reaction between epoxy groups and carboxyl groups does not produce any condensation by-products, so there is no inherent limitation on the possible cross-sectional thickness. limit.

In another application of materials produced according to the present invention, leather replacement materials (which may be configured as ENR-based materials) may be used in footwear, particularly upper portions of footwear. Typically, it is contemplated that the leather replacement material can be bonded to the fabric backing. In one exemplary embodiment, the fabric backing may be composed of rayon (e.g., Tencel, Lyocell, etc.), while in another exemplary embodiment, the fabric backing may be of canvas, hemp, or other suitable Material composition. It is contemplated that the optimum fabric backing may vary depending on the particular application, and thus in no way limits the scope of the invention unless otherwise stated in the appended claims. It is further contemplated that for at least some applications, leather replacement materials and fabric backings may have the following properties: ● Tensile strength (ASTM D 5035-2011) 600 N/5cm, ● Elongation (ASTM D 5035-2011) 80% +/-20 ● Color fastness to rubbing (rubbing) (ISO 20433 : 2012), dry≥4 and wet≥4 ● Adhesion strength between layers of coating material/leather substitute material (can be configured as ENR-based material) and textile backing material, 2.5 N/mm • Bally flex at room temperature (eg, about 15°C-30°C). ASTM D 6782-13 (23±1), 100,000 cycles, pass ● Abrasion - Taber (ASTM D 3884-09, H-22, 1000 g, > 1000 cycles), Pass ● Color fastness to washing (ISO-105-C06 : 2010), ≥4 However, these characteristics are not meant to be limiting in any way and are for illustrative purposes only, unless otherwise stated in the appended claims.

In general, it has been observed through testing that when silica is added as a type of filler to a leather substitute material (which can be configured as an ENR-based material), the results can be compared to those found in leather substitute material layers without silica filler. Shown is a higher cohesive strength within the leather substitute material layer. It has also been observed that silica fillers can help improve fatigue life/Bally deflection, especially when rice hulls are also used as fillers. In addition, because silica does not hide certain properties of other materials (for example, silica provides a degree of translucency as a filler material in some applications), when used with rice husk, the speckle, texture and/or or other characteristics (or other filler materials in other exemplary embodiments) may be more pronounced than when using filler materials other than silica. It is expected that rice hull ash may replace silica as a filler in certain applications to achieve the desired properties of the resulting material.

It was further found that using Tencel as a backing fabric resulted in composites (ie leather substitutes adhered to a fabric backing) exhibiting higher tensile elongation compared to using cotton as a backing fabric. However, the specific configuration of the backing fabric and/or leather substitute material, the method of bonding different layers, dimensions, etc. may also affect its characteristics, which are not limiting in scope, unless otherwise stated in the appended claims.

[4. Mechanochemically Modified Thermosetting Materials] A. Prior Art Prior art It is known that imitation leather materials are based on synthetic polymers such as polyurethane (PU) and polyvinyl chloride (PVC). These materials have been made to have tactile interfaces that resemble animal leather in many ways. Animal leather is based on a collagen structure, which is generally filled with waxes and oils to provide a surface that is both soft and smooth – commonly known as "creamy". PVC, for example, can be kept below Tg by combining the polymer itself, which can have a glass transition temperature _Tg above room temperature (e.g., above about 23°C), with a plasticizer, which can remove the stiffness of the overall material. Elasticity at room temperature (eg below about 23°C) achieves a similar tactile interface. In another example, PU can achieve a similar tactile interface by combining so-called hard block domains ( _Tg above room temperature) and soft block domains ( _Tg below room temperature) and synthesized as a polymer backbone. In these examples, phases or ingredients with a _Tg above room temperature (collagen, PVC polymer, and PU hard blocks), and phases or ingredients with a _Tg below room temperature (tanning agents and oils of animal leather , PVC plasticizer and PU soft block domain). The combination of a phase or component with a _Tg above room temperature and a phase or component with a _Tg below room temperature can produce a favorable tactile interface incorporating softness of the overall object without frictional surfaces.

Materials based on natural rubber or other similar polymers such as epoxidized natural rubber tend to have a single polymer phase with a T _g below room temperature; therefore compounds based on natural rubber (NR) or epoxidized rubber (ENR) should be used when developing leather Alternative materials tend to have undesirable friction surfaces. It would be desirable to combine the beneficial low temperature elasticity and softness offered by NR or ENR with a smooth or creamy surface-to-touch interface to create leather replacement materials.

B. Overview Disclosed herein are combinations of plant-based all-natural polymers that can be combined with ENR to produce a polymer blend that has _{a Tg} close to room temperature (e.g., about 15°C-30°C) in relation to providing a tactile interface ) while maintaining the excellent low-temperature elasticity of ENR.

In another embodiment, a combination of plant-based all-natural polymers is disclosed that can combine ENR with another optional plasticizer that further suppresses the glass transition temperature to provide excellent low-temperature elasticity (down to -10 °C or lower).

Disclosed herein is an exemplary method for selectively reversing covalent chemical crosslinks (where reversing is also possible) by mechanochemical treatment at low temperature (e.g., below 70°C) and high shear in thermoset materials. called "de-crosslinking"), which can be performed by repeatedly passing the thermoset material through the narrow gap (<1 mm) of a two-roll rubber mill (rubbing ratio about 1.25 : 1) or by mixing through an internal mixer. This method finds that the crosslinks can be mainly isolated to partially reverse the cure. Such mechanochemically modified thermosets can be used as ENR mixture components to produce leather-like replacement materials with improved tactile interfaces.

As used herein, the term "thermosetting material" is meant to include, without limitation, all thermosetting materials, unless otherwise stated in the appended claims, including resin (liquid) precursors, colloidal precursors, Those thermoset materials made from semi-solid precursors, thermoplastic precursors, and/or combinations thereof.

Various methods exist to determine the power per unit volume of the thermoset material required to selectively break the crosslinks of the thermoset materials disclosed herein, and the scope of the present disclosure is limited to the aforementioned specific methods, unless patented below Scope otherwise stated. An exemplary method for determining the power per volume of the aforementioned thermoset material may be mixed on a two-roll mill with a roll gap of 0.5 mm. Power consumption can be 5 000W (5 kW). When the thermoset filled the nip width of 30 cm, since the experiments showed little mechanochemical de-crosslinking at this 1.5 mm or greater roll gap, it can be assumed that the main energy input to the thermoset occurs below the 1.5 mm roll gap. For a mill configuration with a roll radius of 75 mm (6 inch roll), this corresponds to an arc of approximately 13° (+/- 6.5° from the closest point). From this it can be estimated that the volume of material in the roll gap across the entire width of the mill is approximately 7.5 ml. Therefore, a reasonable instantaneous power input calculation to achieve mechanochemical decrosslinking is 5000 W/0.0075 L (liter) = 6.67 x 10 ⁵ W/l.

However, in some instances, the power consumption of a two-roll mill can be as low as 2000 W (2 kW). The mill geometry, roll pitch and mill width remained unchanged. In these examples, the instantaneous power input to achieve mechanochemical decrosslinking is 2000 W/0.0075 L (liter) = 2.67 x 10 ⁵ W/l.

By experimenting with selective decrosslinking of thermosets through mechanochemical processes, the lowest shear change was observed, mechanochemical decrosslinking can occur at a minimum roll gap of 0.8 mm, with an estimated power consumption of 2000 W ( 2kW). In this example, the estimated volume of the thermoset material at high shear near the nip can be as high as 10 ml. In this example, the instantaneous power input to achieve mechanochemical decrosslinking is 2000 W/0.01 L (liter) = 2x10 ⁵ W/l.

In the foregoing exemplary embodiments, mechanochemical decrosslinking can be characterized by very high instantaneous power per volume shear mixing, followed by staged cooling such that the temperature of the thermoset being mixed does not exceed about 70°C ( Above this temperature the thermoset begins to recure, i.e. recrosslink). In a two-roll mill, the high-shear mixing zone is estimated to occur at an arc length of approximately 13°, so it is extrapolated that the estimated low-cut or no-cut cooling time occurs during the remaining circumference of the mill (also i.e. move the remaining about 347°). Correspondingly, the high shear time that a thermoset material may experience is approximately 13/360, or 3.6% of the total mixing time. As such, the maximum material temperature is limited despite the instantaneous high power input (per unit volume).

Disclosed herein is the reaction product of an epoxidized plant-derived triglyceride, an example being epoxidized soybean oil (ESO), and a naturally occurring multifunctional carboxylic acid, an example being citric acid, wherein the thermosetting reaction product comprises ß -Hydroxy esters serve as linkages between polyfunctional carboxylic acids naturally present in epoxidized plant-derived triglycerides. The inventors have discovered that the aforementioned ß-hydroxy ester linkages can be selectively or reversibly broken by mechanical shear. That is, the thermoset matrix is derived from small and highly branched precursor molecules, which can be converted into millbases by high shear mixing. The mechanical conversion thermoset was found to be able to be recured into a thermoset by reapplying heat without adding additional curing functionality (i.e., without adding the original epoxidized plant-derived triglyceride or carboxylate). acid functional groups).

Disclosed herein are epoxidized natural rubbers which are crosslinked by carboxylic acids containing curing agents. The cross-linking between the epoxy group and the carboxylic acid curing agent forms a ß-hydroxyester. This ß-hydroxyl ester is known to be capable of thermally induced transesterification. These reactions have been used to make so-called "self-healing" and recyclable thermosets. Prior art has assumed that the transesterification reaction proceeds under zero-sum rearrangement, where the total number of bonds is generally stable. The literature of Leibler et al. states that "the basic concept is to achieve reversible exchange reactions by transesterification, thereby rearranging the network topology. , while keeping the total number of linkages and the average functionality of the crosslinks constant".

The present inventors have unexpectedly discovered that when a high molecular weight polymer based on a carbon-carbon backbone is paired with ß-hydroxyl ester crosslinks, the aforementioned crosslink bonds can be selectively and reversibly broken only by mechanical shear. That is, high molecular weight elastomers such as epoxidized natural rubber that have been crosslinked (vulcanized) by ß-hydroxyl esters can be mechanically treated by extremely high shear such that the high molecular weight linear rubbers are largely preserved and the crosslinked Linkages can then be selectively broken to regenerate their original functionality. The resulting product can be remolded without the addition of other curing agents. Regrind rubber—showing that not only the curing agent is selectively destroyed, but also the carboxylic acid functionality and epoxide functionality are broken during the process of breaking the crosslink bonds. regeneration. The guideline for this cure functionality has not been disclosed yet.

The reaction product of epoxidized plant-derived triglycerides and naturally occurring polyfunctional carboxylic acids is disclosed herein as a mixture of virgin epoxidized natural rubber and a mechanically converted thermoset material (which can be formulated as a thermoset resin). The reaction product can ideally be produced by the method disclosed in Section 2 - Coating Materials, and the scope is not particularly limited unless otherwise stated in the following claims. The mechanical conversion thermosetting material can be used as a curing agent for original epoxidized natural rubber. It has been found that the mixing of the mechanically converting thermoset and the formulation can occur simultaneously.

C. Detailed description Thermoset materials (and in particular thermoset resins) and thermoset elastomers are known in the art. In most instances, the intermolecular covalent bonds have strength characteristics comparable to those of the precursor intermolecular covalent bonds. In such materials, mechanical shearing results in conversion of the thermosetting material into granules or powders, which can be used as fillers for new materials, but does not allow the thermosetting material to be reduced to a high molecular weight gum, which has substantially the same properties as the original precursor material or similar characteristics. Partially ionically cross-linked materials can flow under high shear or high temperature when charge coordination is formed along the polymer backbone, but this reversible thermal curing situation is not common in covalent bonds between thermoset materials.

Crosslinking of epoxy groups and carboxylic acid curing agents to form ß-hydroxyl esters is understood in the prior art. The ß-hydroxyl esters are known to thermally induce transesterification reactions. These reactions have been used to make so-called "self-healing" and recyclable thermosets. Prior art has assumed that the transesterification reaction proceeds under zero-sum rearrangement, where the total number of bonds is generally stable. The literature of Leibler et al. states that "the basic concept is to achieve reversible exchange reactions by transesterification, thereby rearranging the network topology. , while keeping the total number of linkages and the average functionality of the crosslinks constant".

ß-Hydroxy ester crosslinks have been unexpectedly found to be selectively and reversibly broken (ie decrosslinked) by mechanical shear alone. That is, a thermoset with ß-hydroxyl ester linkages, such as the thermoset resin shown in Figure 13 (where the small arrow on the right side of the figure indicates the reaction site of the compound), can be mechanically processed by very high shear, so that when Thermosets are converted when crosslinks are selectively broken to regenerate their original functionality. As a result, the product-converted thermoset can be recured without adding additional curing agent, showing that not only the curing agent is selectively destroyed, but also the carboxylic acid functionality and epoxy functionality can be regenerated after the crosslinking is destroyed, As shown in Figure 15. The guideline for this cure functionality has not been disclosed yet.

i. Recycled thermosetting material based on epoxidized natural rubber The present inventors found that by cross-linking carbon-carbon backbone-based high molecular weight polymers (such as epoxidized natural rubber) with ß-hydroxyl esters, the aforementioned cross-links can be selectively and reversibly broken only by mechanical shear. That is, high molecular weight elastomers such as epoxidized natural rubber that have been crosslinked (vulcanized) by ß-hydroxyl esters can be mechanically treated by extremely high shear such that the high molecular weight linear rubbers are largely preserved and the crosslinked Linkages can then be selectively broken to regenerate their original functionality. The resulting product, reground rubber, can be remolded without the addition of other curing agents, which has been decrosslinked (also known as devulcanization)—displaying the selective destruction of not only the curing agent, but also the carboxylic acid functionality. and epoxidized functionality is regenerated during the breakage of the crosslink bonds. The guideline for this cure functionality has not been disclosed yet.

It is known to those of ordinary skill that the rubber compound of epoxidized natural rubber (ENR-25) disclosed in Section 1 above and the carboxylic acid functional curing agent can be mixed with additional fillers and additives. In an exemplary embodiment, the compound comprises powdered cork and precipitated silica. In Figure 16, the moving die rheometer (MDR) measured at 150°C for 30 minutes to obtain a series of rheometer signs. Initial indications indicated a characteristic cure profile with a brief induction time followed by a 30 minute cure modulus. The rheometer samples were then reground on a laboratory scale (6 inch diameter by 12 inch wide) two-roll rubber mill. The sample showed an unstable condition after passing through the mill several times, and it gradually became fluid under continuous stirring, similar to uncured rubber. This particular sample exhibited a higher initial modulus in the second rheometer curve (second indication in Figure 16), but then cured at a similar rate to about the same final hardness. Samples of this particular material were then reground and cured. This step was repeated 11 times - the 6th and 11th cure indications are shown in Figure 16. It can be observed that the general shape of the preceding cure curves is similar to all cure experiments; the modulus decreases with increasing number of cycles, but each time the sample can be recured without more curing agent. The 12th cure curve ("12th indication, adding curing agent" in Figure 16) reflects that adding a small amount of curing agent can increase the modulus of the sample.

The series of cure curves in Figure 16 show that the compounds can be decrosslinked by the application of mechanical shear only, without additional heating (ie, the rolls of the two-roll mill were not heated in these experiments). In addition, the rheometer indicated that the curing agent could recrosslink the epoxidized natural rubber after mechanical decrosslinking. The transesterification of the present invention differs from the prior art in that it is not necessary to maintain the total number of crosslinks to regenerate a solid material with mechanical integrity. The curing agent can regenerate itself after being sheared by mechanical force.

In another set of experiments, the same recipe used in Figure 16 was applied to a series of rising temperatures in the rheometer. Data for temperatures of 150°C, 175°C, 200°C and 225°C are shown in FIG. 17 . It can be seen that the state of cure increases as the temperature increases up to 200°C. There is little evidence for a transition at 200°C. Initial cure followed by a rapid transition was observed at 225°C, which was nearly complete by the 30 minute test. Evidence shows that the crosslink bonds are substantially weaker than epoxidized natural rubber itself, which begins thermal oxidation at about 250°C. Therefore, it can be speculated that mechanical pressure is sufficient to break a weak subset of covalent bonds – in this case ß-hydroxyester crosslinks.

ii. Recycled thermosets based on epoxidized vegetable oils and naturally occurring polyfunctional acids It was unexpectedly discovered that the present invention finds the reaction product of two small molecules, such as epoxidized soybean oil (ESO) and citric acid, where the thermoset material (configured as a thermoset resin for this illustrative embodiment) Covalently bonded to ß-hydroxyl esters, which can be converted into grindable gums only by mechanical shear. That is, highly branched elastomers can be converted to more linear and extended materials by reversible disruption of a subset of ß-hydroxyester covalent linkages as shown in FIG. 15 . The aforesaid grindable pastes may further advantageously be used in two or more ways. In a preferred exemplary embodiment, the grindable gum can then be combined with any number of fillers, plasticizers or functional additives and recured without the need for additional epoxidized vegetable derived triglycerides ( such as ESO) or naturally occurring polyfunctional carboxylic acids such as citric acid. In another preferred embodiment, the abradable adhesive can be formed into sheets without the addition of additional fillers, plasticizers, or combinations of functional additives, and recure into a transparent film (either by itself or by contact). backing fiber or other backing material). In another preferred exemplary embodiment, the grindable gum can then be combined with virgin epoxidized natural rubber, wherein the epoxidized natural rubber is crosslinked by mechanical shearing of the thermosetting resin to regenerate the carboxylic acid functional groups.

By way of example and not limitation, most processes and parameters are described in detail below unless otherwise stated in the scope of the following claims. The values of the following parameters are for illustrative purposes only and are not limiting unless otherwise stated in the claims below. Other parameter values, methods, equipment, etc. can be used without limitation, unless otherwise specified in the scope of the following patent application.

[instance 1] Charge 100 parts of citric acid, 100 parts of ESO, and 400 parts of isopropanol (IPA) into a reaction vessel with vacuum capability. The mixture was heated slowly for 8 hours under moderate vacuum (>50 Torr) with constant stirring. IPA was condensed and removed from solution during the reaction. At the end of the reaction period, when essentially all unbound and unreacted IPA was removed, the temperature of the reaction vessel was raised rapidly and the reaction was stopped when the reaction products reached 110°C.

[Example 2] 109 parts of the reaction product of Example 1 were mixed with 100 parts of ESO to produce a curable resin. The resin can be cured overnight at 80°C or within two hours at 125°C to produce elastomeric solids.

[Example 3] The cured elastomeric solids of Example 2 were repeatedly passed through a tight nip zone on a rubber mill. The coefficient of friction ratio is 1.25:1 and the aforementioned nip area is set to be less than 0.5 mm. After a few passes, the powder material begins to convert, producing a grindable gum within 3 to 7 minutes of mixing. The abrasive compound can be sheeted and recured into a clear film or it can be combined with fillers, plasticizers, and/or functional additives to produce a compound that can be cured under heat (e.g. at 150° C for 5 minutes) to make a thermoset elastomer. Grindable gums can be combined with epoxidized natural rubber (ENR) and ENR-based compounds and act as curing agents for ENR.

[Example 4] 109 parts of the reaction product of Example 1 were mixed with 100 parts ESO along with 7 parts propylene glycol and 3.5 parts olive derived emulsifying wax to form a curable resin. The resin can be cured overnight at 80°C or within two hours at 125°C to produce elastomeric solids.

[Example 5] The cured elastomeric solid of Example 4 was repeatedly passed through the tight nip zone on the rubber mill. The coefficient of friction ratio is 1.25:1 and the aforementioned nip area is set to be less than 1 mm. After a few passes, the powder material begins to convert, producing a grindable gum within 3 to 7 minutes of mixing. The abrasive compound can be sheeted and recured into a clear film or it can be combined with fillers, plasticizers, and/or functional additives to produce a compound that can be cured under heat (e.g. at 150° C for 5 minutes) to make a thermoset elastomer. The material of Example 5 was masticated more easily than the material of Example 3. Grindable gums can be combined with epoxidized natural rubber (ENR) and ENR-based compounds and act as curing agents for ENR.

iii. Thermoset mixtures based on virgin ENR and recycled thermosets based on epoxidized vegetable oils and naturally occurring polyfunctional acids By combining mechanochemically regenerated thermosets (which were found to regenerate the original chemical functionalities of epoxy groups and carboxylic acid groups) with pristine ENR, the regenerated functional groups can be cured without the need for additional curing agents (ie, crosslinking) the epoxy groups in the ENR. Illustrate in the following examples.

[Example 6] 40 parts of ENR-50 was mixed with 63 parts of cured resin of Example 4 in the preceding paragraph. The present inventors have discovered that mixing ENR-50 with the cured resin of Example 4 has sufficient shear to cause the cured resin to be mechanochemically broken (decrosslinked) and become a source of carboxylic acid functionality and cure ENR-50. The mixture of elastic rubber materials can be further mixed with fillers, plasticizers and functional additives to produce a compound which can then be cured into an elastic solid. In an exemplary embodiment, fillers may include cork powder, ground rice hulls, activated carbon, activated charcoal, kaolin, metakaolin, precipitated silica, talc, mica, corn starch, mineral pigments, and/or combinations thereof, which do not Restrictive unless otherwise stated in the scope of the following patent application; the aforementioned plasticizers may also include reactive plasticizers such as epoxidized soybean oil, semi-reactive plasticizers such as glycerin, propylene glycol and castor oil, non-reactive plasticizers Agents such as naturally occurring triglyceride vegetable oils and/or various combinations, which are not limiting unless otherwise stated in the following patent claims; the aforementioned functional additives may include antioxidants (such as tocopheryl acetate (vitamin E )), UV absorbers (such as submicron TiO ₂ ), antiozonants, curing retardants (such as alkaline sodium salt and soda lime glass powder), curing accelerators (such as specific zinc chelates), and/ or combinations thereof, which are not limiting unless otherwise stated in the claims below. It was found that materials made using this processing step and using this ingredient can have good elasticity and a creamy touch down to -10°C.

[Example 7] 80 parts of ENR-50 are mixed with 21 parts of the curable resin of example 4 in the preceding paragraph. The present inventors have discovered that mixing ENR-50 with the cured resin of Example 4 has sufficient shear to cause the cured resin to be mechanochemically broken (decrosslinked) and become a source of carboxylic acid functionality and cure ENR-50. The mixture of elastic rubber materials can be further mixed with fillers, plasticizers and functional additives to produce a compound which can then be cured into an elastic solid.

The molding materials according to Example 6 and Example 7 have properties that make them useful as leather substitute materials. The blending of a relatively low T _g material such as ENR-50 with a relatively high T _g material such as a conversion resin can produce bulk materials with excellent tactile feel and low temperature elasticity down to -10°C. Furthermore, the glass transition temperature of bulk materials can be lowered by adding plasticizers such as propylene glycol without negatively affecting the tactile properties of the materials. Conversely, it has been found that plasticizers such as propylene glycol (which can be produced by a catalytic process of hydrogenolysis to convert vegetable sources of glycerol and hydrogen to propylene glycol) can simultaneously act as plasticizers and contribute to surface friction by reducing surface friction. Creates a "creamy" feel.

In these examples, it has been found that combining high molecular weight ENR and conversion resins produces an ideal balance of handling strength, low temperature elasticity, and room temperature elasticity. Without being bound by theory, there may be domains rich in resin based starting thermoset and domains rich in ENR in the final compound. Mixing of the aforementioned regions may limit the local extensibility of the compound, thereby reducing the frictional feel. To demonstrate this theory, the reground resin depicted in Figure 15 was stirred into ethanol overnight; the solution resulted in some small pieces of coagulated material at the bottom of the vessel that could not be dissolved. This means that during the regrinding operation, a portion of the thermoset is mechanochemically modified by shear, and once the shear falls below a certain threshold, the remaining thermoset lacks sufficient shear to break the ß-hydroxyester crosslinks. Therefore, the decrosslinking effect is not uniformly distributed throughout the material; that is, partially crosslinked areas remain during regrinding. As a result, the compound of combined ENR and regrind resin will have a portion of the aforementioned cross-linked resin that is still present during mixing and acts as an area that imparts a locally higher _Tg , thereby reducing the rubbing feel.

In another exemplary embodiment, it may be desirable to configure a material such that it exhibits a relatively high _Tg , and an exemplary method for increasing the _Tg of an ENR-50 rubber compound is disclosed hereafter, but Other suitable methods for increasing the _Tg of ENR-50 rubber compounds according to the present invention may be used, which are not limiting in scope unless otherwise stated in the appended claims. Typically, ENR-50 has a _Tg of -24°C as prepared. It has been unexpectedly found that standard compounds based on ENR-50 with mineral fillers such as clay and talc together with curing agents prepared according to the methods disclosed elsewhere in this application; i.e., naturally occurring polyfunctional carboxylic acids ( For example, the reaction product of citric acid) together with epoxidized triglycerides (eg, ESO) can be further fabricated to have plastic-like properties such that the resulting material can be configured as a rigid or semi-rigid material. In an exemplary embodiment, these attributes were found to emerge when phytic acid was incorporated into the formulation at loadings as low as 2 phr and then heat treated. This compound was mixed and molded and its initial properties were found to be a tensile strength of 11.9 MPa and an elongation of 120%. After heat treatment at 100°C for 168 hours, the compound was found to be a rigid plastic with a strength of 14.8 MPa and an elongation of 16.7%. It was found that reheating the compound (from room temperature (e.g., about 15°C-30°C) to 60°C) reduces stiffness and increases elongation; thus, heat treatment not only causes embrittlement (the characteristics), it also causes a sharp shift in _Tg from -24°C to >20°C. This rigid or semi-rigid (eg plastic) material can be further filled with fiber reinforcements to further improve the tensile strength of the material.

5. Application Recycling of thermosets is a particularly challenging issue for the polymer materials industry. Some proposed solutions to this challenge include solvent-induced depolymerization, grinding of waste and recombination with new binders, and thermal depolymerization. These methods are not easy to integrate into the existing production process. In contrast, the mechanically directed decrosslinking of thermoset materials according to the present invention uses the same equipment and methods that were originally used to mix the materials. Thus, low percentages of recycled material can be used to mold articles all the way up to 100% recycled material. These materials can be used in articles that are substantially the same as articles made from the original material.

It has advantageously been found in the manufacture of imitation leather materials that at least partly recycled and regenerated materials contained in sheet-like products, which have a natural texture, are particularly pleasing - with surface undulations in the range of 1-10 mm, which on the mould. No textures are required in the . This surface relief is similar to the bison or buffalo leather products shown, which are ideal for a variety of applications.

Incorporate scrap (e.g., product trim, defective articles, end-of-life articles, etc.) into articles without significant loss of mechanical properties or the addition of additional virgin material in a way not previously possible with thermoset materials closed-loop manufacturing. More importantly, the material is still biodegradable and derived from plant-based raw materials without containing petrochemical-derived precursors.

From a handling standpoint, the use of pre-cured thermoset materials as curing agents for ENR is particularly advantageous. The present inventors have found that the curing agents disclosed in Section 1 and applied in Section 3 can cause stickiness to some compounds, especially when mixing. The use of pre-cured thermoset resins disclosed herein can significantly reduce the tackiness of the batch during processing and simultaneously reduce the tack/friction of the molded article.

[5. Foam Materials] A. Prior Art Most resilient foam products on the market are based on synthetic polymers, especially polyurethane. A key attribute that differentiates so-called memory foam from other foam products is the glass transition temperature ( _Tg ) of the polymer. Rigid foams are usually composed of polymers with a _Tg well above room temperature, an illustrative example of this product is polystyrene foam (commonly used in hard insulating panels and insulated drinking cups). Flexible and resilient foams are usually composed of polymers with a _Tg well below room temperature, an illustrative example of this product is an ethylene-propylene rubber (EPR/EPDM) based car door weatherseal. Natural products can also be found in the hard and flexible/elastic categories. Balsa is a generally porous, foam-like material that is substantially rigid at room temperature (eg, about 15°C-30°C). Natural rubber latex can be foamed by the Talalay or Dunlop process and produce flexible and elastic foam products consisting essentially of naturally occurring polymers. To date, no ubiquitous naturally occurring foam has a _Tg close to room temperature (eg, about 15°C-30°C) and can produce lossy foam, a key attribute of memory foam materials.

Natural materials for making flexible foam products today often use natural rubber latex. In order for a latex product to be stable against temperature excursions, the polymer must be vulcanized (ie cross-linked). Vulcanization of natural rubber can be carried out by several known methods; sulfur vulcanization is most commonly used, but peroxide or phenolic cure systems can also be used. While sulfur and zinc oxide curing systems may vulcanize natural rubber latex, other chemicals are often added to increase cure rates, limit recovery, and provide other functional benefits (e.g., antioxidants, antiozonates, and/or UV stabilizers ). These additional chemicals may produce chemosensitivity in certain individuals. Additionally, natural rubber latex itself may cause an allergic reaction in certain individuals due to the natural proteins present in latex.

Similar natural rubber latex formulations can also be used as the glue for fiber mats to produce resilient foam-like products. Notably, coconut fibers can be bonded together by natural rubber latex to form a non-woven mat to create an essentially all-natural mat or mattress material. Despite various claims of "all natural" in the prior art, curing systems and additives to natural rubber may contain synthetic chemicals that may create chemical sensitivities in certain individuals; moreover, natural rubber latex itself may be susceptible to degradation due to residual proteins. Causes allergic reactions in certain individuals.

Additionally, footwear midsoles are often made from EVA foam used in performance footwear. EVA foam has low density, high energy resilience, good compression set, and is easy to shape and process. EVA is a petrochemical polymer that is neither biobased nor biodegradable. Accordingly, what is desired is a foam that has the energy return (resilience) and compression set properties that satisfy EVA while being 100% biobased.

B. General A foam product using epoxidized vegetable oil is disclosed, wherein the prepolymer curing agent is also composed of a naturally occurring and naturally derived product of biological origin. The disclosed foam products are produced without the use of additional blowing agents. Foam products can be created with or without the need to inject air into the pre-cured liquid resin. The disclosed foam products can have a _Tg close to room temperature (eg, about 15°C-30°C), thus resulting in a lossy product. Also, foam products can be formulated to have a _Tg below room temperature (eg, less than about 23°C) and result in a flexible, elastic product. The properties of memory foam can be achieved by the polymers prepared according to the present invention. These polymers are the reaction products of the prepolymer curing agents described herein and epoxidized vegetable oils. The reaction mixture may also contain other natural polymers and modified natural polymers as detailed below.

In a particular embodiment, the foam product may contain a fraction of epoxidized natural rubber. Notably, the process of producing epoxidized natural rubber also reduces free proteins that may produce allergic reactions in certain individuals. Epoxidized natural rubber has a greater than 95% reduction in allergic reactions compared to untreated natural rubber.

The present invention discloses a castable resin comprising EVO (and/or an optionally epoxidized triglyceride as previously described) in combination with a prepolymer curing agent (as disclosed in Section 1 above), and in an example In a preferred embodiment, ENR that has been dissolved in EVO.

The prepolymer curing agents disclosed in Section 1 can be manufactured to eliminate the risk of porosity when cured in a certain temperature range, but to generate gas during curing when carried out in a second higher temperature range. In addition, the oligomeric prepolymer curing agent can contain substantially all of the multifunctional carboxylic acid, thereby eliminating the need for additional solvents during the curing process. For example: citric acid is immiscible in ESO, but they can react with each other in a suitable solvent. The amount of citric acid can be selected so as to produce a prepolymer curing agent that reacts substantially all of the epoxy groups of the ESO in the prepolymer curing agent with the carboxylic acid groups of the citric acid. Using a sufficient excess of citric acid, the degree of prepolymerization can be limited so that no gel fractions are formed. That is, the target prepolymer curing agent is a low molecular weight (oligomeric) citric acid terminated ester-product formed by the reaction between the carboxylic acid groups on citric acid and the epoxy groups on ESO.

Exemplary oligomeric prepolymer curing agents can be produced with a weight ratio of ESO to citric acid in the range of 1.5:1 to 0.5:1. If too much ESO is added during prepolymer curing agent formation, the solution will gel and it will be difficult to incorporate further ESO to produce the target resin. It should be noted that, calculated by weight, the stoichiometric equivalent weight ratio of epoxy groups on ESO and carboxylic acid groups on citric acid is 100 parts of ESO and about 30 parts of citric acid. When the ratio of ESO:citric acid is higher than 1.5 : 1, a prepolymer curing agent with too high molecular weight (ie viscosity) may be formed, which will limit its use as casting resin. If the ratio of ESO:citric acid is below 0.5:1, too much excess citric acid is found and ungrafted citric acid may precipitate out of solution after evaporation of the solvent.

In addition to controlling the ratio of ESO to citric acid, according to the present disclosure, the physical properties of the resulting elastomeric foam can be adjusted by selectively controlling the amount of alcohol used as a solvent. Alcohol solvents can themselves bind to elastomers by forming ester linkages with polyfunctional carboxylic acids which are reversible and therefore gaseous when the material is cured at temperatures higher than required to produce a non-porous product. A mixture of two or more solvents can be used to adjust the amount of alcohol-containing solvent grafted onto the citric acid terminated oligomeric prepolymer curing agent.

For example: without limitation in scope, isopropanol (IPA) or ethanol may be used as a component of the solvent system for making citric acid and ESO miscible unless otherwise stated in the appended claims. IPA or ethanol can form ester bonds through condensation reaction with citric acid. Since citric acid has three carboxylic acids, this grafting will reduce the average functionality of the citric acid molecules reacted with ESO. This will favor the production of oligomeric structures that are more linear and less highly branched. Acetone can be used as an ingredient in solvent systems that make citric acid miscible with ESO, but unlike IPA or ethanol, acetone by itself cannot graft onto citric acid-terminated oligomeric prepolymer curing agents. Indeed, during the preparation of the oligomeric prepolymer curing agent, it was found that the reactivity of the prepolymer curing agent was determined in part by the ratio of IPA or ethanol to acetone used to dissolve the ESO into citric acid. That is, in reaction mixtures with similar amounts of citric acid and ESO, and under similar reaction conditions, prepolymer curing agents produced from solutions with relatively high ratios of IPA or ethanol to acetone were more effective than those produced using relatively A low ratio of IPA or ethanol to acetone produces a prepolymer curing agent, resulting in a less viscous product. Furthermore, the amount of IPA or ethanol grafted onto the prepolymer curing agent determines the extent to which such IPA or ethanol is released when the formulated resin is foamed at a temperature higher than that required to produce a non-porous resin product.

C. Exemplary Methods and Products An exemplary mixture for making resilient memory foam is made from a combination of inputs comprising a prepolymer curing agent, a liquid mixture of epoxidized natural rubber and epoxidized vegetable oil, and may contain unmodified epoxidized vegetable oil.

In a first exemplary embodiment of the foam, an elastic memory foam was prepared using a prepolymer curing agent and by dissolving 50 parts citric acid in 125 parts warm IPA and mixing accelerated (see Figure 1). After the citric acid had dissolved, 50 parts of ESO was added to the stirred solution. The solutions are ideally mixed and reacted at a temperature of 60°C-140°C, optionally under gentle vacuum (50-300 Torr). One exemplary batch was mixed in a jacketed reactor vessel at a jacketed temperature of 120°C (solution temperature about 70°C-85°C) and the IPA evaporated while the citric acid was grafted onto the ESO. At the end of the reaction sequence, approximately 12 parts of IPA were grafted onto 100 parts of combined ESO and citric acid. Therefore, temperatures above the boiling point of IPA and evacuation can no longer produce IPA concentrate in the concentration system. Calculations show that approximately 31% of the initial carboxylic acid sites on citric acid react with the epoxy groups on ESO (assuming all epoxides are converted to ester linkages during the reaction) and approximately 27% of the carboxylic acid sites Reaction with IPA forms side chain esters, approximately 42% remains unreacted and available for crosslinking with the resin in subsequent processing steps. However, these calculations are for illustrative purposes and do not limit the scope of the invention unless otherwise stated in the appended claims.

In a second exemplary embodiment of the foam material, elastic memory foam is produced by a rubber-containing resin precursor. Epoxidized natural rubber can be included in an amount of less than 25 weight percent (25 wt %) in the resin matrix formulation and still produce a pourable liquid. The preparation of rubber-containing precursors can be performed in two stages without the use of solvents for rubber dissolution. In the first stage, 100 parts of epoxidized natural rubber (ENR-25) was mixed with 50 parts of ESO using rubber mixing techniques (two-roll mill or internal mixer). A very soft glue will be obtained which cannot be further mixed efficiently on rubber processing equipment, but by applying heat (eg: 80°C), a Flacktek Speedmixer or other low horsepower equipment (eg: a sigma-blade mixer ) mixes additional ESO into the rubber and produces a flowable liquid containing 25% ENR-25 and 75% ESO.

The third exemplary embodiment of the foam material can also produce a resilient memory foam-like product. In this embodiment, the foamed resin is prepared by mixing and curing. For this exemplary embodiment, 40 parts of the prepolymer curing agent of the first exemplary embodiment of the foam was added to 80 parts of the rubber-containing resin of the second exemplary embodiment. The resulting composition was then mixed with a Flacktek Speedmixer until a homogeneous solution was obtained (about 10 minutes of mixing). The resin is cured by the following two methods:

1. The resin is cured like a muffin on a hot baking sheet (PTFE coated) at 200°C (nominal temperature). The forming material has the same memory foam properties as similar homogeneous articles; in particular lossy behaviour. A description of the resulting material is shown in Figure 13.

2. The resin is evacuated after mixing and placed on the same hot baking tray at 200°C. In this example, pores were observed with the heating element (measured at 210°C), but not at the pan without the heating element (measured at 180°C). A depiction of the resulting material is shown in FIG. 14 .

From the two methods, it follows that there are two possibilities for creating pores. One source could be small air bubbles incorporated during mixing. Additional experiments showed that the presence of ENR-25 in the resin was an important factor in stabilizing this bound air and preventing coalescence of air bubbles during the curing stage. A second source of porosity is outgassing, which may result from removal of grafted IPA at temperatures of 200°C or higher.

As previously stated, certain catalysts known to accelerate the addition of carboxylic acids to epoxy groups may be used in the formulations of the present invention without limitation unless otherwise stated in the appended claims.

Referring now to FIGS. 20 and 20A , there are shown foams suitable for certain footwear applications in which the foam is substantially or completely free of petrochemical inputs and does not require petrochemical blowing agents. Such a foam board is generally shown in Figure 20 and a detailed view of the outer surface and its cross-section is shown in Figure 20A. The foam is based on epoxidized natural rubber and cured using a curing agent prepared according to the previous description. Furthermore, the foam can be made into plates with a thickness between approximately 2.5 mm and 25 mm, where heat transfer can be accomplished by heating plates applied to the two planar surfaces.

Referring now to FIG. 21 , which provides a depiction of an exemplary embodiment of a method of making such a foam, the top heated plate (floating platen 210 ) may be sized and/or configured to apply 0.5 psi and A vertical pressure of 2.0 psi prevents it from developing non-planar properties and prevents any large air pockets (potentially introduced by mixing and/or tableting) from growing into large defects. Expanding foam 200 may be positioned between floating platen 210 and lift platen 220 . However, other methods of making foams with desired properties in accordance with the present invention are not limited in scope unless otherwise stated in the appended claims.

[Table 3] Exemplary ranges of ingredients. Element Parts/percent rubber Ingredient category ENR-25 100 polymer cork powder 0-40 filler starch 0-100 filler Precipitated silica 0-10 filler Epoxidized soybean oil 0-10 plasticizer castor oil 0-10 plasticizer vegetable based wax 0-1 Release agent Curing agent (as defined above) 5-20 Hardener

As shown in Table 3, foams produced according to the present invention may include a range of different components, and the specific components and their relative proportions in the foam in no way limit the scope of the invention unless otherwise stated in the appended claims. In an exemplary embodiment, epoxidized natural rubber 25 (ENR-25) may be mixed with fillers such as cork flour, corn starch, silica, plasticizing oil, and curing agent prepared according to the present invention as described in detail above. This mixture can be sheeted to a thickness of approximately one-half the final target thickness on a two-roll mill or calender. Calendered sheets can be placed between two heated steel plates for curing (vulcanization) and foaming. In an exemplary embodiment, a multi-layer press, such as that shown in FIG. 16, may be used wherein the weight of a single platen is applied at 0.5 psi to 2.0 psi on the calendered sheet.

As the mixture expands, heat from the top (floating) platen 210 and bottom (fixed) or lifting platen 220 transfers heat into the compound to simultaneously cure the rubber. Cure time may be directly affected by sheet thickness and can range from 5 minutes to 2 hours (where thicker sheets may require longer cure times). The curing temperature is preferably between 120°C and 180°C, or even more preferably between 130°C and 170°C, and even more preferably between 140°C and 160°C, without limitation unless otherwise stated Otherwise stated in the scope of patent application. After curing, foam boards made according to the present invention can exhibit the performance attributes shown in Table 3. However, foams produced in accordance with the present invention may be configured to exhibit other properties and/or other ranges of values and/or properties shown in Table 4, which are not limiting in scope except in the appended claims otherwise stated.

[Table 4] Exemplary properties of the foam produced according to the present invention. density resilience dynamic compression deformation energy efficiency 0.35-0.55 g/ ^cm3 >20% >10% >60%

Foams made according to the invention can be used for midsoles, insoles and foam padding for shoe tongues of various thicknesses. Particularly useful is the use of foams according to the invention in shoe midsoles. Foams produced in accordance with the present invention may be adapted for use in other products, without limitation, unless otherwise stated in the appended claims.

D. Application/Additional Exemplary Products The materials of the present invention can be used as flooring, sports mats, padding, shoe insoles, shoe outsoles or sound-absorbing panels without limitation in scope unless otherwise stated in the appended claims.

The materials of the present invention can be molded into complex 3D articles and multi-layered articles. A 3D article can be composed of multiple formulations at different locations within the article at the same time to have functionality everywhere.

Resilient memory foam using vegetable oil can be used in applications where polyurethane is currently used. These applications can be used in shoes, seating, flooring, exercise mats, bedding, and sound-absorbing panels without limitation in scope unless otherwise stated in the appended claims. Many of these articles are consumables and, if made of synthetic materials, are not biodegradable and are not recyclable. If such articles are prepared from the materials of the present invention, they will be biodegradable and present no disposal problems.

[6. Other products] overview It is an object of various embodiments of the present invention to provide methods for the manufacture of various articles (including but not limited to footwear, unless otherwise stated in the appended claims), wherein the articles may be composed of various types of materials, which Materials all use one or more polymers of the same class for all functional parts within them. That is, the continuous polymer phases of all types of materials are mutually compatible.

In addition, it is another object of exemplary embodiments of the present invention to provide materials of the type that all use one or more polymers of the same class, wherein the polymers are bio-based (i.e., wholly or largely derived from agricultural source) with nominal or no detectable synthetic and/or petroleum-based composition. Unless otherwise stated in the appended claims, such materials include, but are not limited to: foam materials for midsole and/or insole components, solid molded materials for outsole components, Sheet-good materials, adhesive materials that can be used to bond components together, coating materials that can be used to provide a better tactile feel and possibly coat one or more textile materials, textile materials (e.g. for use as knit upper or backing of sheet material), and/or rigid or semi-rigid material (which may be used for various components such as buckles, buckles, eyelets, zippers, loops, eyelets, clips and/or similar components, It is not limiting in scope unless otherwise stated in the appended claims).

Another object of exemplary embodiments of the present invention is to provide a machining technique that allows the material to be reformed into new articles comprising a homogeneous blend of various types of input materials for the entire article thing. Another object of exemplary embodiments of the present invention is to provide a machining technique that utilizes mechanochemical reactions to enable blended type input materials to be remolded (using thermoset molding chemistry) into new articles. Other objects of the exemplary embodiments of the present invention may be utilized, inherent and/or expressed herein without limitation in scope unless otherwise stated in the appended claims.

Materials that may be suitable for inclusion in such exemplary embodiments of articles of footwear include, but are not limited to (unless otherwise stated in the appended claims): according to US 10,400,061; US 10,882,950; US 10,882,951 and other Those materials produced by the techniques disclosed in the related pending applications. Such materials can utilize mechanochemically reversible thermosetting curing agents. Materials using this technology (one or more epoxidized polymers and ß-hydroxyesters as cure sites) are able to be uniformly incorporated regardless of the starting form, be it sheets, molded parts, foams, coated layer material, rigid or semi-rigid material or adhesive interlayer, which is not limiting in scope unless otherwise stated in the appended claims.

In general, at least six types of materials can be fabricated in accordance with the present invention that can be used in various articles of manufacture as disclosed herein or for a particular material or combination of materials, which is not limiting in scope unless otherwise stated in the appended claims There are instructions. These different material types can share at least one common chemical composition (chemistry), each of which can include β-hydroxy ester linkages, and wherein in various exemplary embodiments, each type of material can be composed only of naturally occurring hybrid formulation (and without the use of any animal skin leather), yet exhibit desirable performance characteristics for a wide range of applications. That is, these materials can be completely free of petrochemicals, synthetic chemicals, and/or animal skin leathers, while at the same time performing similarly or better than prior art materials. The commonality of the chemical composition in the various materials disclosed herein can lead to various advantages including, but not limited to, virtually any combination and/or configuration of the various materials during mechanochemical processes such as those disclosed herein for recycling materials miscibility, which is not intended to be limiting unless otherwise stated in the appended claims. The materials may be combined with each other during processing in any order, number, layer, thickness, configuration, etc. suitable for the materials and their particular application, which is not limiting in scope unless otherwise stated in the appended claims.

The first material may be configured as an imitation leather material as described in detail above, wherein the imitation leather material may be used as a substitute for the applications currently served by synthetic leather and/or animal skin leather, which is not limiting in scope unless otherwise stated Otherwise stated in the scope of patent application. Such a material may consist of a thermoset elastomer cross-linked with beta-hydroxyester bonds, wherein said first material is defined as a leather-like material having a glass transition temperature generally below room temperature (eg, below about 23°C) , wherein the first material may be configured to be substantially planar and have a thickness in the range of about 0.3 mm to 2.5 mm, without limitation in scope unless otherwise stated in the appended claims.

The second material can be composed of the same thermoset elastomer cross-linked with β-hydroxyester linkages, where the second material can be defined as having a glass transition temperature typically not above room temperature or slightly above room temperature (e.g., about 23°C or about 20 to about 30°C) and have a density of less than 0.7 g/cc, although not limiting in scope unless otherwise stated in the appended claims.

The third material can be composed of the same thermoset elastomer crosslinked with β-hydroxyester linkages, where the third material can be defined as having a glass transition temperature typically not above room temperature or slightly above room temperature (e.g., about 23°C or about 20 to about 30°C), wherein the third material can be cast and/or molded into a three-dimensional shape, but it is not limiting in scope unless otherwise stated in the appended claims .

The fourth material may consist of the same thermoset elastomer crosslinked with β-hydroxyester bonds, wherein the fourth material may be defined as a coating material having a glass transition temperature generally below room temperature (eg, below about 23°C), Wherein the fourth material can be configured to have a thickness of 10 to 100 micrometers, which is not limited in scope, unless otherwise specified in the appended claims.

The fifth material may consist of the same thermoset elastomer crosslinked with β-hydroxyester bonds, wherein the fifth material may be defined as an adhesive material having a glass transition temperature generally below room temperature (eg, below about 23°C), And the thickness of the fifth material is 1 mm or less, which is not limiting unless otherwise specified in the appended claims. Furthermore, it is contemplated that an adhesive material may generally be positioned between two substrates, either of which may be one of the other materials disclosed herein, without limitation in scope unless otherwise stated in the appended claims.

The sixth material may consist of the same thermoset elastomer crosslinked with β-hydroxyester bonds, where a sixth material is defined as a rigid or semi-rigid material with a glass transition temperature generally above room temperature (eg, above about 23°C), And wherein the sixth material is substantially amorphous in structure, but it is not limiting in scope unless otherwise stated in the appended claims.

These six materials can be combined with each other in almost any combination to create an article with a desired set of properties and/or functional attributes. That is, the first material can be bonded to the second material, third material, fourth material, fifth material and/or sixth material; the second material can be bonded to the third material, fourth material, fifth material and and/or the sixth material; the third material may be bonded to the fourth material, the fifth material, and/or the sixth material; the fourth material may be bonded to the fifth material and/or the sixth material; and the fifth material may be in any suitable form Combinations, sequences and/or layers (which are not limiting in scope, unless otherwise stated in the appended claims) of combinations, sequences and/or layers are incorporated into the sixth material. Furthermore, an article may include more than one layer of a particular type of material separated by layers for other types of material in any suitable configuration (eg, a layer of a second material sandwiched between two layers of a first material) , which are not limiting in scope unless otherwise stated in the appended claims. The common chemical composition between the six materials, and in particular the β-hydroxyester linkages, allows any and all combinations of the six materials to be miscible in certain types of recycling processes as detailed below, including but not limited to mechanochemical Treatment (which selectively and/or reversibly breaks the β-hydroxy ester linkages or "decrosslinks" the material), unless otherwise stated in the appended claims.

Detailed description Exemplary embodiments of articles of footwear produced in accordance with the present invention may include one or more types of materials utilizing a molded and cured polymer matrix in which beta-hydroxy esters are the crosslinks between the epoxidized polymer inputs . Exemplary embodiments of articles of footwear according to the present invention may also include textile components, which are not limiting in scope unless otherwise stated in the appended claims. In an exemplary embodiment, the textile components are preferably made from bio-based inputs such as: cotton, regenerated cellulose, various animal fibers (wool, silk, alpaca, etc.), protein Fibers (soy protein, casein) and man-made bio-based fibers (eg, polyhydroxyalkanoates, polylactic acid), which are not limiting in scope unless otherwise stated in the appended claims. For some applications it may be preferable to use epoxidized natural rubber (ENR) based foams as a continuous polymer matrix cured (vulcanized) by ß-hydroxyesters. In one exemplary application, a preferred curing agent can be prepared according to US 10,400,061, which is incorporated herein by reference in its entirety.

Mechanochemical recycling of articles of footwear as manufactured in accordance with exemplary embodiments of the present invention may involve at least two steps: (1) preshredding of the article of footwear; (2) high shear mixing of the shredded material ( Such as can be done by a two-roll mill commonly used in rubber compounding or an internal mixer commonly used in rubber compounding); (3) forming the homogeneously mixed elastomeric material into preforms of appropriate size (whether by calendering or extrusion or other suitable process); and/or (4) molding the desired article by heat and pressure to produce a shaped thermoset material.

I. Foam Foams are used in footwear components as midsoles, insoles, tongue padding, and/or around the collar area of a shoe. Foams of various thicknesses and densities are possible within the framework of the invention disclosed herein. In one exemplary embodiment, the foam may be produced by mixing batches of ENR-based material containing a substantial (>10 wt %) content of cork flour. It has been found that certain types of cork flour can be incorporated into ENR-based formulations and entrain trapped air that may expand when cured at low pressure, resulting in foams with densities less than 0.75 g/cc. Even more preferably, certain formulations can withstand low pressure curing and achieve densities of less than 0.6 g/cc. Even more preferably, certain formulations have been found to achieve densities of less than 0.5 g/cc even though they do not contain chemical blowing agents.

In a specific exemplary embodiment, a formulation containing 100 parts of ENR is combined with a total of 35 parts of various cork flours along with 15 parts of natural plasticizers, 10 parts of precipitated silica, and curing agents (as further described in US 10,400,061) to Formulations that were tableted out and cured with low pressure (0.5-4 psi), it has been found that curing without pressure may result in a sheet that is not smooth and may have large trapped air pockets. Low pressure curing creates an optimal balance of sufficient pressure to reduce the tendency of large trapped air pockets to expand while still allowing air to expand to produce pores on the scale of 0.1-3 mm. The curing temperature may be 120°C - 180°C, or even more preferably 130°C - 170°C, and in some cases 140°C - 160°C. Simultaneously with the curing process is the expansion of the entrained air to form voids. That is, a sheet (or article) can be placed in an oven at one (higher) density, and the sheet (or article) expands as heat is applied to achieve a target thickness and a second (lower) density. Just after expansion, and even during expansion, a curing reaction may initiate and may serve to properly chemically fix the new dimensions. In an exemplary embodiment, a sheet placed in an oven or between hot plates at a thickness of 5 mm may expand to a sheet of 9-11 mm thickness after expansion and curing. Surprisingly, it has been found that vertical pressure applied to the preform can be sufficient to restrict lateral growth while allowing vertical growth. That is, the thickness of the sheet can grow while the transverse dimension remains relatively unchanged.

If oven curing is used, it is preferable to place a preheated metal plate on top of the foam sheet to apply the target pressure range (0.5-4 psi). In one exemplary embodiment, a preheated metal mold can be placed on top of the preform by making a preform sized approximately half as thick as the final target thickness (including any convolution or thickness variation required) And expanding the preform to the final target shape to create a custom molded shape. In one exemplary embodiment, the custom molded shape may be a shoe midsole. In this case, a midsole preform can be formed by pressing a rubber compound into a shape substantially similar to the profile of the final midsole—but about half the final target thickness. The midsole preform can then be placed between two heated metal molds (one side can be a simple plate) to simultaneously foam and cure the material. The heat from the metal mold (again, one side can be a simple plate) will cause the entrained air to expand and increase the thickness of the rubber, reducing the density, and the rubber will cure.

For articles that do not require complex contours, sheet-like preforms can be produced by calendering or extruding a rubber compound to a thickness less than the final target thickness. That is, a calendered sheet of 5 mm can be foamed to a final thickness of 9-11 mm. In some cases, the thickness of the final foam will require a preform thickness beyond the range manageable with calendering. In such cases, sheet extrusion can be used to produce sheet preforms that are substantially free of large entrapped air pockets.

II. Outsole Outsoles used in many articles of footwear are three-dimensional molded components that include features that provide traction, provide wear-resistant materials, and interface with other components of the shoe. Rubber outsoles are well known in the art; they are usually made from thermoset (i.e. vulcanized) elastomers, but can also be made from thermoplastic elastomers (TPE) - of which there are many suitable subtypes including but not limited to: Ethylene Acetate Vinyl ester copolymer (EVA), styrene butadiene styrene (SBS), styrene ethylene butadiene styrene (SEBS), other styrenic block copolymers (usually TPS), polyether block amide Amine (TPA), Copolyester (TPC), Thermoplastic Polyurethane (TPU), Thermoplastic Polyolefin (TPO). Additionally, outsoles can be made from thermoplastic vulcanizate (TPV); which is a compound containing cross-linked rubber in a thermoplastic matrix. Highest performance outsole made from thermoset elastomer. Of the most common thermoset elastomers available for outsoles, the most widely used are natural rubber (NR), styrene-butadiene rubber (SBR), butadiene rubber (BR) and ethylene propylene diene rubber (EPDM). Polychloroprene (CR) or nitrile rubber (NBR) can be used in oil resistant sole formulations.

According to an exemplary embodiment of the present invention, a preferred thermoset elastomeric outsole formulation may be based on epoxidized natural rubber (ENR). ENR is commercially available in two grades: ENR-25 and ENR-50, which are differentiated according to their degree of epoxidation; 25% of the double bonds in ENR-25 are converted to epoxides, while 50% of the double bonds in ENR-50 are Double bonds are converted to epoxides. According to an exemplary embodiment, ENR-25 may be used for the outsole base rubber. ENR can be crosslinked (vulcanized) by means known in the art for unsaturated elastomers; including but not limited to sulfur vulcanization, peroxide vulcanization, alkylphenol vulcanization (so-called "resin cure"), and radiation vulcanization. In addition, since ENR contains epoxy functional groups, there are other curing mechanisms that can be used that are particularly suitable for reaction with epoxy functional groups. Polyfunctional amines, polyfunctional acids, and polyphenolic compounds can all be used to crosslink epoxidized polymers such as ENR. Among the simple multifunctional molecules that can be used to crosslink ENR, the biobased Priamine™ molecule (all multifunctional amines) from Croda is one approach. Another group of polyfunctional molecules that can be used to crosslink ENR are polyfunctional carboxylic acids. For certain exemplary embodiments, preferred naturally occurring or naturally derived polyfunctional carboxylic acids include, but are not limited to, unless otherwise stated in the appended claims: citric acid, tartaric acid, succinic acid, malic acid, malic acid, Toric acid, oxalic acid, azelaic acid, dodecanedioic acid, malonic acid, sebacic acid, glutaric acid, glucaric acid, fumaric acid, saffron acid, muconic acid, citraconic acid, mesaconic acid , itaconic acid, pentyndioic acid, glutamic acid, aspartic acid, acetone dicarboxylic acid, aconitic acid, agaric acid, and phytic acid. Another class of potential curing agents are those that are reaction products between multifunctional naturally occurring carboxylic acids and epoxidized vegetable oils; such reaction products are further disclosed in US 10,400,061.

When manufacturing outsoles according to the invention with certain classes of curing agents, those compounds are able to be recovered according to mechanochemical processing and are miscible with other products using the closely related curing system and polymer type, whether they be foam or sheet shape. For example, an outsole made with ENR cured with a polyfunctional carboxylic acid could be mechanochemically recycled simultaneously (and miscibly) with a foam or sheet (used as a shoe upper) made with ENR also cured with a polyfunctional carboxylic acid. This is true whether the ENR of one element (or sub-element) is ENR-25 and another element (or sub-element) of the shoe uses ENR-50 as the base rubber. Furthermore, ENR-based components (or subcomponents) can be mechanochemically treated simultaneously (and miscibly) with materials that are reaction products between multifunctional carboxylic acids and epoxidized vegetable oils. Various types of such mechanochemical treatments are disclosed in US 10,882,951.

Outsole thermoset elastomer compounds formulated according to the present invention can use only bio-based and mineral-based fillers. Non-marking soles can be formulated without carbon black as a filler; instead, they can use precipitated silica as the primary reinforcement. As an alternative, rice hull ash can be used as an alternative silica source, which confers similar primary enhancement benefits. In some exemplary embodiments, mineral fillers that may be used include talc, mica, wollastonite, clay, sepiolite, muskovite, and other silicates and aluminates. In some exemplary embodiments where translucency is not required, agricultural by-products may be used as fillers. Common agricultural by-products include, but are not limited to, materials such as cork meal, ground rice husk, ground coir fiber, cellulose powder, various ground nut powders, and ground grasses such as Miscanthus powder. In general, high performance outsole compounds may contain one or more primary reinforcing fillers and may contain various expanding fillers that improve processing without significantly affecting strength and abrasion resistance attributes.

III. Manufacture of Adhesives Many types of footwear are constructed using adhesives. Adhesives can complement stitching as an anchoring aid, they can be the primary attachment medium between the midsole and upper (and/or other footwear/article components), they can be the and/or other footwear/article components), and they can be used to secure sole rims or other elements to the exterior of the shoe surface. Many adhesives used in footwear construction are elastomeric and are used as contact adhesives (with high initial tack). Many are solvent-based to facilitate dispensing and spreading of the adhesive. Many are thermoset plastics that cure with heat. Most adhesives in use today are petrochemical based.

According to the present invention, the entire class of adhesives based on exemplary embodiments of bio-based resins can be used in various articles/footwear. In an exemplary embodiment, the adhesive may be a 2-component (2K) thermoset system comprising a curing agent prepared as disclosed in US 10,400,061 and an epoxidized vegetable base oil. In an exemplary embodiment, the binder is solvent-free and substantially non-petrochemical. In an exemplary embodiment, the epoxide and carboxylic acid reaction is catalyzed to allow the thermosetting reaction to occur in less than 30 minutes at about 100°C-150°C, resulting in a fully vulcanized adhesive. In an exemplary embodiment, the adhesive may be catalyzed prior to use such that a temperature of less than 100° C. and a time of less than 30 minutes are sufficient to cure the adhesive.

In another exemplary embodiment of a suitable adhesive prepared in accordance with the present invention, the adhesive may be a 1-part (1K) thermoset system comprising a material where Partially reacted to completion at the first reaction temperature), and then cooled to a temperature for storage below room temperature (e.g., below about 23°C), and preferably at refrigerated temperatures (e.g., below about 5°C), and even more preferably at deeper freezing temperatures (eg, below about -15°C). The 1K thermoset system can react with naturally occurring multifunctional carboxylic acids and epoxidized vegetable-based triglycerides at a first reaction temperature. At this first reaction temperature, naturally occurring polyfunctional carboxylic acids (e.g., citric acid) can be mixed with epoxidized vegetable-based triglycerides (e.g., epoxidized soybean oil, ESO) using miscible solvents (e.g., acetone, isopropanol, or ethanol) miscibility. At the first reaction temperature, it has been found that a stable intermediate product can be produced which results in a stoichiometrically balanced but not fully polymerized prepolymer. After the first reaction has sufficiently proceeded - in an exemplary embodiment this may take 16-32 hours, or more preferably this may take 20-28 hours - the temperature may be lowered to a second temperature at which The temperature allows vacuum extraction of residual miscible solvents. The second temperature may be between about 15°C and 40°C, or more preferably between 20°C and 30°C. At this second (lower) temperature, the rate of reaction can be slowed down significantly so that the solvent can be removed without causing excessive prepolymer growth (and thus viscosity increase). After removal of the solvent (in exemplary embodiments this may be done by vacuum), the reaction product may be stored at sub-ambient temperature (as already described). This 1K thermosetting adhesive system can be applied to various articles, article parts and/or footwear parts, and then cured (vulcanized) at about 100°C - 150°C in less than 30 minutes to secure the adhesive joint . In an exemplary embodiment, the adhesive may be catalyzed prior to use such that a temperature of less than 100° C. and a time of less than 30 minutes are sufficient to cure the adhesive.

IV. Coated Textiles Often, for certain applications, it may be desirable to configure one or more portions of an article as a coated textile. In particular, but without limitation in scope, all or a portion of the upper may consist of a coated fabric unless otherwise stated in the appended claims.

In an exemplary method of making such a coated textile, a resin prepared according to the present invention may be diluted in a solvent. Unless otherwise stated in the appended claims, the resulting solution may be applied to fabrics and/or textiles by any suitable method using any suitable equipment. It is contemplated that for some applications the solution may be sprayed, rolled or padded onto fabrics and/or textiles.

After the solution is applied to the fabric and/or textile, the solvent can be allowed to evaporate and the resin can be cured. Solvent evaporation can be accomplished at ambient pressure and/or temperature or at reduced pressure and/or elevated temperature, which is not limiting in scope unless otherwise stated in the appended claims. Resin curing may be achieved at ambient pressure and/or temperature or at elevated temperature and/or pressure, which is not limiting in scope unless otherwise stated in the appended claims.

In an exemplary embodiment of a method of making a coated fabric and/or textile (which is not limiting in scope unless otherwise stated in the appended claims), the coated fabric and/or textile can be produced in the absence of a solvent Or manufactured with minimal use of solvents. In such a method, aqueous emulsions may be prepared with resins formulated as hereinbefore described above, wherein the aqueous emulsions may then be applied to fabrics and/or textiles. In this approach, aqueous emulsions can be prepared using solvent-free or poor-solvent resins that can be mixed with suitable surfactants under relatively high shear conditions. Utilizing proper dilution of the resin in the aqueous emulsion and proper application of the aqueous emulsion to the fabric and/or textile (e.g. sufficiently small emulsion droplets, flow rate and flow characteristics of the aqueous emulsion, etc.) may result in coating the fabric and/or Desirable properties of the textile (eg, sufficient coverage, penetration of the fabric and/or textile, etc.).

The treated fabric and/or textile may be allowed to dry at ambient pressure and/or temperature or at reduced pressure and/or elevated temperature after application of the aqueous emulsion to the fabric and/or textile, without limitation in scope, Unless otherwise stated in the appended claims. Resin curing may be achieved at ambient pressure and/or temperature or at elevated temperature and/or pressure, which is not limiting in scope unless otherwise stated in the appended claims.

The resulting coated textiles and/or fabrics can exhibit various desirable properties including, but not limited to, increased water repellency properties, increased durability, increased strength, and/or combinations thereof, unless otherwise stated in the appended claims There are instructions.

V. Incorporation into footwear/article (examples of various forms) Footwear is often produced from a combination of material types; most often from different material families. In some cases, various material types (foam, fabric, strapping, etc.) can be made from the same (or closely related) material family. For example, a shoe may have a polyester fabric upper, be closed with polyester laces, it may have a polyester copolymer foam, and it may even have a polyester copolymer thermoplastic elastomer outsole. In this case, the entire shoe (made of the relevant thermoplastic) can hypothetically be recycled by melting all components and molding a new product (shoe component or replacement) from the blended material. In this case, when trying to keep all materials in the same family, the performance applicability of the available options for various parts may be somewhat limited. Furthermore, there may be certain components (such as those listed above, without limitation in scope, unless otherwise stated in the appended claims) that function better with thermoset polymers instead of thermoplastic polymers. Furthermore, the thermoplastic polymers most commonly used in footwear components are neither biobased nor biodegradable.

Exemplary embodiments of the present invention provide combinations of various material types from a common family of thermoset polymers. Furthermore, exemplary embodiments of the thermoset polymers of the present invention may be mechanochemically recyclable using a high shear low temperature mixing process as disclosed in US 10,882,951. It has been found that incorporation into fabrics (for example, cotton uppers or cellulose backing fabrics for imitation leather materials) does not inhibit mechanochemical recyclability, as these fabrics are dispersed into the resulting blended product and act as fibers of the compound reinforcements. Accordingly, exemplary embodiments of articles of footwear contemplated by the present invention may include instances of two or more material types (e.g., a foam and an outsole, or a foam/outsole unit and an ENR-based material upper (with fabric backing or no fabric backing), or foam and outsole with fabric upper, etc.), where these materials can be co-molded, or alternatively bonded with an adhesive from the same family of thermosetting polymers. The mechanochemically recyclable nature of ENR-based material curing agents or resin-based adhesives (as discussed in this paper) could allow the entire footwear to be subjected to the same mechanochemical recycling process without the need to separate the component components.

In one exemplary embodiment of an article configured in accordance with the present invention, the article may be configured as a slide sandal having the material combination described above. In this embodiment, a three-component composition may include an outsole, a foam, and a strip of ENR-based material. The outsole can be molded in a compression mold as is commonly practiced in the art. The outsole may consist of an ENR based compound cured using a curing agent formulated according to US 10,400,061. Tapes made of ENR-based compounds also cured with a curing agent formulated according to US 10,400,061 may be provided. The belt may optionally be fabric backed by co-molding the fabric backing with the ENR based compound cured with a curing agent formulated according to US 10,400,061. In one exemplary embodiment, the strap may be bonded between the outsole and the foam footbed. In one embodiment, after the outsole is molded, it can be coated on the back with an adhesive as disclosed herein. In one embodiment, an uncured foam preform can be placed over a pre-molded and adhesive-coated outsole with a heated weight placed on top of it to provide sufficient pressure (approximately 0.5-4 psi) to cause vulcanization between the outsole and the foam, and still allow the foam preform to both "lift" (i.e. actually increase in thickness and thus become a less dense foam) and cure (i.e. vulcanize).

In an exemplary embodiment, the preferred curing and foaming temperature may be 110°C-170°C, or even more preferably 120°C-160°C, for 10-90 minutes, or even more Preferably it is 15-60 minutes. In this approach, the shape of the top heating weight determines the final shape and contour of the footbed while controlling foam growth. A sandal manufactured according to this embodiment can be composed of three variants (four if the adhesive is included) of the same material family, resulting in an article that can be mechanochemically recycled at the end of its life. Alternatively, according to this exemplary embodiment, the sandal is composed of non-petrochemically derived materials and can therefore be returned to the ground to biodegrade.

Reference is now made to FIGS. 23A-23D , which provide schematic illustrations of four steps in an exemplary method for making one type of article that may be configured as a sandal. Generally, in a first step as shown in FIG. 23A, a pair of outsoles may be produced using compression molding techniques, wherein the compression molding process may be performed at a specific temperature or temperatures, pressure or pressures, and/or their completed within the scope. Sole preform 401a may be positioned in mold 400 at a particular temperature and pressure for a particular amount of time to form sole (or outsole) 401b. In a second step, as shown in Figure 23B, adhesive material 403 may be applied to a surface of one or more outsoles 401b to secure strap 402 to outsole 401b. A third step is shown in FIG. 23C, where an uncured foam-in-place layer (foam footbed pre-form 404a) can be applied on the upward facing surface of the outsole 401b such that the foam-in-place layer can cover one or more of the straps 402. ends. Finally, in a fourth step as shown in Figure 23D, a metal plate (which may be preheated) 405 may be positioned over the foam footbed preform 404a to facilitate the foaming process and/or to create cross-linking of the material to produce The foamed/foamed footbed 404b, and the article can be placed in an oven to cure.

In an exemplary embodiment of an article configured as a clog-like shoe (colloquially referred to as the trademark Crocs®), the outsole/sole 401b may be pre-molded in a first step using an ENR-50 based compound and Cured with curing agent formulated according to US 10,400,061. The outsole/sole 401b may optionally be coated with an adhesive material 403 as disclosed herein on the back of the outsole/sole 401b. The adhesive material 403 coated outsole/sole 401b may be placed in a rubber injection molding tool manufactured to form the entire body of the clog-like shoe. In this exemplary embodiment, the foaming compound may be injected into a heated mold and the combination of heat from tooling and shear-generated heat (during injection) may cause vulcanization and foaming of the compound. The foam and adhesive-coated outsole are simultaneously cured to the foam body. It may be preferable to avoid the use of any petrochemical blowing agents to create thermoset foams, instead relying on the moisture in the compounded ingredients which become steam during the molding and curing process. Lignocellulosic fillers and starches are two exemplary types of fillers that can carry controlled levels of moisture that may generate vapors during the molding and curing processes that create the foam. This technique (steam-expandable starch) is known in the food industry (e.g. making "corn muffins") but has not been used as a formulation method for thermoset elastomers to create foam.

Reference is now made to FIGS. 23A-23D , which provide schematic illustrations of four steps in another exemplary method of making a type of article that may be configured as an injection molded clog or a Croc® style shoe. Generally, in a first step as shown in FIG. 24A, a pair of outsoles or soles 401b may be produced from one or more sole preforms 401a using a mold 400 using compression molding techniques, which may be performed at specific One or more temperatures, one or more pressures and/or their ranges. In a second step, as shown in Figure 24B, an adhesive material 403 may be applied to a surface of one or more outsoles/soles 401b. A third step is shown in FIG. 24C , where one or more outsoles/soles 401b with adhesive material 403 applied thereon may be positioned within an injection molding tool or foamed compound mold 406 . Finally, in a fourth step as shown in Figure 24D, the foaming compound can be injected into the foaming compound mold 406 through the injection port 406a using the injection barrel 407, so that one or more outsole/ The sole 401b is injection molded with its adjacent adhesive material 403 .

In yet another exemplary embodiment of an article according to the present invention that may be configured as footwear, a shoe may be manufactured using multiple material types from the same family. Such exemplary embodiments may be configured with uppers, outsoles, and midsoles utilizing leather-like materials. In this exemplary embodiment, a pre-molded outsole may be manufactured using an ENR-50 based compound and cured using a curing agent formulated according to US 10,400,061. The outsole/sole 401b may optionally be coated with an adhesive material 403 as disclosed herein on the back of the outsole. A mold 406 may be provided which contains the outsole/sole 401b and also has a heated last 408 around which a prefabricated and/or preformed upper 409 (which may be configured not to fully but only partially wrap) The last. The last 408 may form one half of the mold cavity (inside the shoe) and the outsole/sole 401b (and the side of the tool holding it) may form the other half of the mold cavity. A prefabricated/preformed upper 409 may be compressed between the last 408 and the outsole half of the mold cavity, creating a cavity into which the foaming compound may be injected. Foaming compound can be injected through the outsole half of the mold or directly through the last side of the tool to fill the space between the pre-molded outsole/sole 401b and last 408; while wrapping and gluing to the package On upper 409 (at least in part) around last 408 . During this manufacturing process, the foamed compound may be used as a midsole (and/or insole) and may subsequently initiate bonding to and between the outsole/sole 401b and upper 409 .

Reference is now made to FIGS. 25A-25F , which provide schematic illustrations of six steps in another exemplary method of making a type of article that may be configured as a shoe with various sole and upper portions. Generally, in a first step as shown in FIG. 25A, a pair of outsoles/soles 401b may be produced using compression molding techniques, wherein the compression molding process may be performed at a specific temperature or temperatures, pressure or pressures, and / or complete within their bounds. In a second step, as shown in Figure 25B, an adhesive material 403 may be applied to one surface of the outsole(s)/sole(s) 401b. Additionally, foam injection holes 401c may be made in a portion of each outsole/sole 401b if not done in step one. A third step is shown in Fig. 25C, where a portion of the pre-formed upper 409 portion of the shoe may be wrapped around a portion of the one or more outsoles/one or more soles 401b.

In a fourth step as shown in FIG. 25D , the upper 409 portion of the shoe and the outsole/sole 401b may be inverted for positioning in a mold 406 , which may be configured as a foam compound mold 406 . In a fifth step shown in FIG. 25E , outsole/sole 401b and upper 409 may be positioned relative to mold 406 . Finally, Figure 25F shows a sixth step where the midsole compound (which may be configured as a foam compound and/or foam material as disclosed in detail herein, without limitation in scope unless otherwise stated in the attached application otherwise specified in the scope of patents) is injected into the injection hole 401c formed in the outsole/sole 401b. However, the foregoing examples of exemplary manufacturing methods for articles configured as shoes in no way limit the scope of the invention unless otherwise indicated in the appended claims.

These three exemplary embodiments of articles and methods of making them are neither exhaustive nor exclusive, but are intended to serve as examples of the types of construction that can be used to combine multiple material types, all of which belong to the same broad material family, and the invention is not limited to articles configured as footwear, unless otherwise indicated in the appended claims. Common cure systems (relying on the reaction between carboxylic acids and epoxides to facilitate crosslinking with ß-hydroxyl ester linkages) allow the blending and bonding of various form factors of materials - whether it is an elastomeric outsole compound, or Adhesive layer, imitation leather sheet, rigid or semi-rigid and/or plastic-like material and/or foam. Unless otherwise stated in the appended claims, textiles may be incorporated into such shoe constructions without limitation.

VI. Recycling methods Exemplary embodiments of articles configured as articles of footwear manufactured in accordance with the present invention may comprise polymers that are thermoset plastics manufactured with similar curing (vulcanizing) chemistries. The particular curing chemistry detailed in US 10,400,061 is unique in its ability to produce elastomers that can be mechanochemically recycled according to US 10,882,951. This recycling method can utilize very high specific power input while limiting the heating of the material.

Recycling of articles (which may be configured as footwear) using the materials disclosed herein may be mechanochemically recycled without requiring any pretreatment other than removal of metallic hard bodies that may have been added to the article (so as not to damage processing equipment) , to produce a metal-free mixture. In an exemplary embodiment, mechanochemical recovery can be performed in two stages. In the first stage, the articles to be recycled (eg, footwear) can be fed into a rubber mixer. A rubber mixer can be used to break down a product (eg, footwear) and make a homogeneous mixture—in fact, the mixer may not be able to provide the specific amount of energy required to make the mixture a grindable compound (due to gaps in the rubber mixer limitations and the heat buildup therein), but it is capable of producing rubber fluff, an exemplary embodiment of which is depicted in FIG. 22 .

In the second stage, this fluff can be fed into a two-roll rubber mill with a nip set at 0.2 mm-2.0 mm, or more preferably at 0.4 mm-1.6 mm. The friction ratio of the grinder must be set at 1.1 - 1.5 or even better 1.2 - 1.4 to generate the energy input requirements for producing a grindable paste. However, other values for these gaps may be used in other embodiments, which are not limiting unless otherwise stated in the appended claims. Two-roll rubber mills allow for a combination of sufficient cooling (to prevent scorch, ie resolidification) and the specific energy required. After making the mixture a grindable rubber compound, it can be molded again into a new article; a part of footwear or another article suited to the properties of the material (now a mixture of various inputs, which may include as recycled articles (eg footwear) part of the milled textile).

In another exemplary embodiment, recycling can be performed in a single stage, where articles (eg, footwear) can be delivered directly to a two-roll mill and the entire shredding, blending, and production of the grindable compounding ingredients are performed in one implemented in steps.

VII. Sample Artifacts In this invention, footwear is of particular interest, but there are similar articles that are elastomeric solids/molded parts, elastomeric foams, rigid or semi-rigid like plastics that can also be manufactured and/or recycled according to the methods disclosed herein Combination of materials, adhesives, coatings and/or flexible sheets (for example, imitation leather materials and/or textiles). For example, a handbag with elastomeric corners, sheet sides, and foam bottom can be similarly manufactured and/or recycled according to the methods disclosed herein. Thus, the present invention is applicable to virtually any kind of bag including, but not limited to, purses, clutches, satchels, messenger bags, pouches, backpacks, shoulder bags, and/or similar bags/sacks, without limitation in scope. , unless otherwise stated in the appended claims. Computer backpacks or bags may also be manufactured using a combination of elastomeric solid corners and handles, flap sides, and foam cushioning to protect electronics; such articles may be manufactured and/or recycled according to the methods disclosed herein, any other suitable Articles of manufacture may be so, without limitation in scope, unless otherwise stated in the appended claims.

Various combinations of the six materials having a common chemical composition beta-hydroxyester linkages can be used to manufacture additional articles, where such articles include, but are not limited to, furniture and parts thereof (e.g., coverings, cushions, structural members, etc.), luggage and its components (e.g., exterior coverings, cushions, bumpers, handles, buckles, buckles, zippers, etc.), electronics enclosures and/or accessories (e.g., cell phone, tablet and/or mobile computer enclosures and/or cover) and/or similar articles, which are not limiting in scope unless otherwise stated in the appended claims.

And, by analogy, such articles are combinations of materials from the same material family, using the same curing system, but manifested in different material forms—any such article—can be recycled by mechanochemical methods. Mixtures of those input materials can likewise be made into millable rubber compounds and thus molded into new articles, which are not limiting in scope unless otherwise stated in the appended claims.

Although the methods described and disclosed herein may be configured to use curing agents composed of natural materials, the scope of the present disclosure, any individual process step and/or its parameters, and/or any device used in combination is not limited by the scope of the present disclosure. This limitation, rather, covers all beneficial and/or advantageous uses thereof, without any limitation, except as otherwise stated in the appended claims.

The materials of construction of the device and/or its components used in a particular process may vary depending on the application of the process, but it can be considered that polymers, synthetic materials, metals, metal alloys, natural materials and/or combinations of the above Combinations may be particularly suitable for certain applications. Therefore, without departing from the spirit and scope of the present invention, the aforementioned elements can be constructed with any materials known by those skilled in the art or developed in the future that are suitable for the specific application of the present invention, but if within the scope of the appended patent application If otherwise stated, follow its instructions.

Having described the preferred aspects of various processes, devices, and products made therefrom, those skilled in the art will be able to know other features of the present invention, as well as various modifications and modifications of the embodiments and/or aspects described herein. Variations, all such modifications and changes can be made without departing from the spirit and scope of the present invention. Therefore, the methods and implementations shown and described herein are for exemplary purposes only, and the scope of the present invention covers all processes, devices and/or structures that can provide various advantages and/or features of the present invention, but if If otherwise stated in the appended scope of patent application, it shall be followed.

Although the aforementioned chemical process, process steps, components, equipment used, products produced and impregnated substrates in accordance with the content of the present invention are described through preferred aspects and specific examples, the scope of the content of the present invention is not limited to the above specific Embodiments and/or aspects, because the various aspects of the implementations and/or aspects are for illustration and not for limitation. Therefore, the processes and implementations shown and described herein are by no means limiting the scope of the present invention, but if otherwise specified in the appended claims, they shall be interpreted accordingly.

Although certain drawings are drawn to exact scale, all dimensions provided herein are for illustrative purposes only and in no way limit the scope of the invention unless otherwise stated in the appended claims . Please note that the welding process, apparatus and/or equipment used in accordance with the content of the present invention, and/or the impregnated and reactive substrates made therefrom are not limited to the specific embodiments shown and described herein, and are in accordance with the disclosure of the content of the present invention The range of features is defined by the appended claims. Those skilled in the art can modify the described embodiments and make changes without departing from the spirit and scope of the present disclosure.

All features, components, functions, advantages, aspects, configurations, process steps, process parameters, etc. of a chemical process, process steps, substrates and/or impregnated and reacted substrates may be used alone or in conjunction with each other, It depends on whether the characteristics, components, functions, advantages, aspects, configurations, process steps, process parameters, etc. are compatible. Accordingly, there are an infinite number of variations in the context of the invention. The various modifications and/or mutual substitutions of the features, components, functions, aspects, configurations, process steps, process parameters, etc. are in no way limiting the scope of the present invention, but if they are within the scope of the attached patent application If otherwise stated, follow its instructions.

Of course, the present disclosure covers all alternative combinations of one or more of the individual features mentioned, including those which can be learned from the text and/or the drawings and/or which are inherent in the disclosure. All the different combinations mentioned above constitute the content of the present invention and/or various alternatives of its components. The embodiments provided herein are intended to illustrate the best known implementations of the devices, methods and/or components disclosed herein for those skilled in the art to utilize. The scope of the patent application should be interpreted as including all alternative implementations allowed by the prior art.

Unless clearly stated in the scope of the patent application, all the above-mentioned processes and methods should never be interpreted as having to perform the steps in a specific order. Therefore, when the method item in the scope of patent application does not indicate the sequence of steps, or when the scope of patent application and the description do not specify and limit the specific sequence of steps, the sequence should not be inferred in any aspect. This principle applies to any unexpressed interpretation basis that may appear in this article, including but not limited to: logical matters related to the arrangement of steps or operating procedures, obvious meanings derived from grammatical organization or punctuation marks, The type and number of implementation methods.

[References] [Non-Patent Document 1] "Self-healable polymer networks based on the cross-linking of epoxidized soybean oil by an aqueous citric acid solution Internet of Things]”, Facundo I. Altuna, Valeria Pettarin, Roberto JJ Williams, Green Chem. [Green Chemistry], 2013, 15, 3360. [Non-Patent Document 2] "Silica-Like Malleable Materials from Permanent Organic Networks [from permanent organic network of silica-like malleable materials]", D. Montarnal, M. Capelot, F. Tournilhac and L. Leibler, Science [Science], 2011, 334 , 965–968.

100: Natural imitation leather material (suede texture) 100': Natural imitation leather material (glossy texture) 102: Fabric 103: fabric extension wool 104: polymer 200: Expanding foam 210: floating platen 220: lifting platen 400: Mold 401a: Sole prefabricated parts 401b: sole 401c: Foam Injection Hole 402: with 403: Adhesive material 404a: Foam Footbed Preform 404b: Foam/foam footbed 405: metal plate 406: Foaming composition mold 406a: injection port 407: Syringe 408: shoe last 409: prefabricated upper

The drawings are incorporated in and constitute a part of this specification, in order to provide drawings for the embodiments, and explain the principles of the method and system of the present invention together with the following. [ FIG. 1 ] is a chemical reaction formula and a schematic diagram of at least one exemplary embodiment of a curing agent of the present invention. [Fig. 2A] depicts an epoxidized natural rubber-based material produced using a relatively low-viscosity resin that can penetrate a flannel substrate and produce a suede or brushed finish. [Fig. 2B] depicts an epoxidized natural rubber-based material produced using a relatively high-viscosity resin that penetrates only part of the flannel substrate and produces a glossy finish. [Fig. 3] is an image of a natural leather substitute produced according to the content of the present invention. [FIG. 4A, 4B and 4C] is a part of an epoxidized natural rubber-based material, which is produced according to the present invention and can be used to make wallets, wherein each version of the epoxidized natural rubber-based material is made of different textures. [Fig. 5] is a diagram of a plurality of epoxidized natural rubber-based materials, which are produced according to the present invention and can be used to make wallets. [Fig. 6] is a diagram of a plurality of pieces of epoxidized natural rubber-based material, produced according to the present invention, assembled into a simple credit card holder or card having the appearance, hardness, and strength that a person of ordinary skill would expect natural animal skin leather to have. set. [ Fig. 7 ] is a resin-impregnated fabric usable in accordance with the present invention. [Fig. 8A] is a top view of the ball made by the present invention. [Fig. 8B] is a side view of the ball made by the present invention. [Fig. 9] is a graphical representation of 2 stress-strain curves for 2 different epoxidized natural rubber (ENR) matrix materials. [FIG. 10A] is a drawing of ENR-based materials configured to engage the inherent properties of a belt buckle. [ FIG. 10B ] Is a drawing of the ENR-based material of FIG. 10A after engaging a belt buckle. [ FIG. 11 ] is a drawing of an ENR-based material, which is formed with grooves and ridges. [ FIG. 12 ] is a drawing of an exemplary embodiment of a molding system that can be used for a specific ENR-based material. [Fig. 13] is a chemical representative diagram of a cured thermosetting material. [Fig. 14] is a chemical representative diagram of mechanochemical reversibility. [Fig. 15] is a series of diagrams of the mechanochemical treatment process of a thermosetting material. [Figure 16] is a series of rheometer data of a material undergoing repeated mechanochemical treatment. [Figure 17] is a series of rheometer data after increasing the curing temperature. [ Fig. 18 ] Shows a foamed product produced in one embodiment of the present invention, which is a muffin-shaped disc. [ Fig. 19 ] shows the porosity gradient in relation to the change in curing temperature. [ Fig. 20 ] Shows a foam board manufactured according to various aspects of the present invention. [ FIG. 20A ] A detailed view of a part of the foam board shown in FIG. 20 . [ Fig. 21 ] An exemplary method of manufacturing the foam board shown in Fig. 20 and Fig. 20A is shown. [ Fig. 22 ] shows the material manufactured with the compound according to the present invention, which has been ground for recycling. [ FIGS. 23A-23D ] provide schematic diagrams of four steps of an exemplary method of manufacturing one type of article. [ FIGS. 24A-23D ] provide schematic diagrams of four steps of another exemplary method of making one type of article. [ FIGS. 25A-25F ] provide schematic diagrams of four steps of another exemplary method of making one type of article.

none

Claims (104)

An article of manufacture comprising: a. A first material comprising a thermosetting elastomer cross-linked with β-hydroxyester bonds, wherein said first material is defined as a leather-like material having a glass transition temperature generally below room temperature, wherein said the first material is generally planar and has a thickness of about 0.3 mm to 2.5 mm; b. A second material comprising said thermoset elastomer crosslinked with beta-hydroxy ester linkages, wherein said second material is defined as having a glass transition temperature of not greater than about 25°C and a density of less than 0.7 g/ cc of foam; and, c. A third material comprising said thermoset elastomer crosslinked with beta-hydroxy ester linkages, wherein said third material is defined as a molded elastomeric material having a glass transition temperature of not greater than about 25°C , wherein said third material is three-dimensionally shaped, wherein said first material is bonded to said second material or said third material, and wherein said second material is bonded to said first material or said first material Three materials. The article of claim 1, further comprising: a fourth material comprising the thermoset elastomer crosslinked with β-hydroxy ester bonds, wherein the fourth material is defined as having a glass transition temperature Coating materials, typically below room temperature, wherein the fourth material has a thickness of 10 to 100 microns, wherein the fourth material is bonded to the first material, the second material, or the third material . The article of claim 2, further comprising: a fifth material comprising the thermoset elastomer crosslinked with β-hydroxy ester bonds, wherein the fifth material is defined as having a glass transition temperature An adhesive material, typically below room temperature, wherein the fifth material has a thickness of 1 mm or less, and wherein the fifth material is positioned between the first material and the second material, the second material and the third material, the third material and the fourth material, the first material and the fourth material, or the second material and the fourth material and bonded thereto superior. The article of claim 3, further comprising: a sixth material comprising the thermosetting elastomer crosslinked with β-hydroxy ester bonds, wherein the sixth material is defined as having a glass transition temperature A rigid or semi-rigid material, generally above room temperature, wherein said sixth material is substantially amorphous in structure, wherein said sixth material is bonded to said first material, said second material, said on the third material, the fourth material or the fifth material. An article of manufacture comprising: a. A first material comprising a thermosetting elastomer cross-linked with β-hydroxyester bonds, wherein said first material is defined as a leather-like material having a glass transition temperature generally below room temperature, wherein said the first material is generally planar and has a thickness of about 0.3 mm to 2.5 mm; b. A second material comprising said thermoset elastomer crosslinked with beta-hydroxy ester linkages, wherein said second material is defined as having a glass transition temperature of not greater than about 25°C and a density of less than 0.7 g/ cc of foam; and, c. a fourth material comprising said thermoset elastomer crosslinked with beta-hydroxyester linkages, wherein said fourth material is defined as a coating material having a glass transition temperature generally below room temperature, wherein The thickness of the fourth material is 10 to 100 microns, wherein the first material is bonded to the second material or the fourth material, and wherein the second material is bonded to the first material or the second material. The article of claim 5, further comprising: a third material comprising the thermosetting elastomer crosslinked with β-hydroxy ester bonds, wherein the third material is defined as having a glass transition temperature A molded elastomeric material of not greater than about 25°C, wherein said third material is three-dimensionally shaped, wherein said third material is bonded to said first material, said second material, or said fourth material. The article of claim 6, further comprising: a fifth material comprising the thermosetting elastomer crosslinked with β-hydroxy ester bonds, wherein the fifth material is defined as having a glass transition temperature An adhesive material, typically below room temperature, wherein the fifth material has a thickness of 1 mm or less, and wherein the fifth material is positioned between the first material and the second material, the second material and the third material, the third material and the fourth material, the first material and the third material, the first material and the fourth material, or the second material between and bonded to the fourth material. The article of claim 7, further comprising: a sixth material comprising the thermoset elastomer crosslinked with β-hydroxy ester bonds, wherein the sixth material is defined as having a glass transition temperature A rigid or semi-rigid material, generally above room temperature, wherein said sixth material is substantially amorphous in structure, wherein said sixth material is bonded to said first material, said second material, said on the third material, the fourth material or the fifth material. An article of manufacture comprising: a. a first material comprising a thermosetting elastomer cross-linked with a β-hydroxy ester bond, wherein the first material is defined as a leather-like material with a glass transition temperature generally below room temperature, wherein the the first material is generally planar and has a thickness of about 0.3 mm to 2.5 mm; b. A second material comprising said thermoset elastomer crosslinked with beta-hydroxy ester linkages, wherein said second material is defined as having a glass transition temperature of not greater than about 25°C and a density of less than 0.7 g/ cc of foam; and, c. a fifth material comprising said thermoset elastomer crosslinked with beta-hydroxy ester linkages, wherein said fifth material is defined as an adhesive material having a glass transition temperature generally below room temperature, wherein The thickness of the fifth material is 1 mm or less, and wherein the fifth material is positioned between and bonded to the first material and the second material. The article of claim 9, further comprising: a third material comprising said thermoset elastomer crosslinked with β-hydroxy ester bonds, wherein said third material is defined as having a glass transition temperature A molded elastomeric material of not greater than about 25°C, wherein said third material is three-dimensionally shaped, wherein said third material is bonded to said first material, said second material, or said fifth material. The article of claim 10, further comprising: a fourth material comprising the thermoset elastomer crosslinked with β-hydroxy ester bonds, wherein the fourth material is defined as having a glass transition temperature A coating material, typically below room temperature, wherein said fourth material has a thickness of 10 to 100 microns, wherein said fourth material is bonded to said first material, said second material, said third material, or said fifth material. The article of claim 1, further comprising: a sixth material comprising the thermoset elastomer crosslinked with β-hydroxy ester bonds, wherein the sixth material is defined as having a glass transition temperature A rigid or semi-rigid material, generally above room temperature, wherein said sixth material is substantially amorphous in structure, wherein said sixth material is bonded to said first material, said second material, said on the third material, the fourth material or the fifth material. An article of manufacture comprising: a. a first material comprising a thermosetting elastomer cross-linked with a β-hydroxy ester bond, wherein the first material is defined as a leather-like material with a glass transition temperature generally below room temperature, wherein the the first material is generally planar and has a thickness of about 0.3 mm to 2.5 mm; b. a second material comprising said thermoset elastomer crosslinked with β-hydroxyester bonds, wherein said second material is defined as having a glass transition temperature of not greater than about 25°C and a density of less than 0.7 g/ cc of foam; and, c. a sixth material comprising said thermoset elastomer crosslinked with beta-hydroxyester linkages, wherein said sixth material is defined as a rigid or semi-rigid material having a glass transition temperature generally above room temperature , wherein the sixth material is substantially amorphous in structure, wherein the first material is bonded to the second material or to the sixth material, and wherein the second material is bonded to the first material or the second material. The article of claim 13, further comprising: a third material comprising said thermoset elastomer crosslinked with β-hydroxy ester linkages, wherein said third material is defined as having a glass transition temperature A molded elastomeric material of not greater than about 25°C, wherein said third material is three-dimensionally shaped, wherein said third material is bonded to said first material, said second material, or said sixth material. The article of claim 14, further comprising: a fourth material comprising said thermoset elastomer crosslinked with β-hydroxy ester bonds, wherein said fourth material is defined as having a glass transition temperature A coating material, typically below room temperature, wherein said fourth material has a thickness of 10 to 100 microns, wherein said fourth material is bonded to said first material, said second material, said third material, or the sixth material. The article of claim 15, further comprising: a fifth material comprising said thermoset elastomer crosslinked with β-hydroxy ester bonds, wherein said fifth material is defined as having a glass transition temperature An adhesive material, typically below room temperature, wherein the fifth material has a thickness of 1 mm or less, and wherein the fifth material is positioned between the first material and the second material, the second material and the third material, the third material and the fourth material, the first material and the third material, the first material and the fourth material, the second material and the The fourth material, the first material and the sixth material, the second material and the sixth material, the third material and the sixth material, or the fourth material and the between and bonded to the sixth material. An article of manufacture comprising: a. A first material comprising a thermosetting elastomer cross-linked with β-hydroxyester bonds, wherein said first material is defined as a leather-like material having a glass transition temperature generally below room temperature, wherein said the first material is generally planar and has a thickness of about 0.3 mm to 2.5 mm; b. a third material comprising said thermoset elastomer crosslinked with beta-hydroxyester linkages, wherein said third material is defined as a molded elastomeric material having a glass transition temperature of not greater than about 25°C , wherein the third material is three-dimensionally shaped; and, c. a fourth material comprising said thermoset elastomer crosslinked with beta-hydroxyester linkages, wherein said fourth material is defined as a coating material having a glass transition temperature generally below room temperature, wherein The thickness of the fourth material is 10 to 100 microns, wherein the first material is bonded to the third material or the fourth material, and wherein the third material is bonded to the first material or the Fourth material. The article of claim 17, further comprising: a second material comprising said thermoset elastomer crosslinked with β-hydroxy ester bonds, wherein said second material is defined as having a glass transition temperature A foam material not greater than about 25°C and having a density of less than 0.7 g/cc, wherein the second material is bonded to the first material, the third material, or the fourth material. The article of claim 18, further comprising: a fifth material comprising said thermoset elastomer crosslinked with β-hydroxy ester linkages, wherein said fifth material is defined as having a glass transition temperature An adhesive material, typically below room temperature, wherein the fifth material has a thickness of 1 mm or less, and wherein the fifth material is positioned between the first material and the second material, the second material and the third material, the first material and the fourth material, the second material and the fourth material, the first material and the third material, or the third material between and bonded to the fourth material. The material according to claim 19, wherein, the sixth material, said sixth material comprises said thermosetting elastomer cross-linked with β-hydroxy ester bonds, wherein said sixth material is defined as having a glass transition temperature generally high A rigid or semi-rigid material at room temperature, wherein the sixth material is substantially amorphous in structure, wherein the sixth material is bonded to the first material, the second material, the third material, said fourth material or said fifth material. An article of manufacture comprising: a. A first material comprising a thermosetting elastomer cross-linked with β-hydroxyester bonds, wherein said first material is defined as a leather-like material having a glass transition temperature generally below room temperature, wherein said the first material is generally planar and has a thickness of about 0.3 mm to 2.5 mm; b. A third material comprising said thermoset elastomer crosslinked with beta-hydroxyester linkages, wherein said third material is defined as a molded elastomeric material having a glass transition temperature of not greater than about 20°C , wherein the third material is three-dimensionally shaped; and, c. a fifth material comprising said thermoset elastomer crosslinked with beta-hydroxy ester linkages, wherein said fifth material is defined as an adhesive material having a glass transition temperature generally below room temperature, wherein The thickness of the fifth material is 1 mm or less, and wherein the fifth material is positioned between and bonded to the first material and the third material. The article of claim 21, further comprising: a second material comprising said thermoset elastomer crosslinked with β-hydroxy ester linkages, wherein said second material is defined as having a glass transition temperature A foam material not greater than about 25°C and having a density of less than 0.7 g/cc, wherein the second material is bonded to the first material, the third material, or the fifth material. The article of claim 22, further comprising: a fourth material comprising said thermoset elastomer crosslinked with β-hydroxy ester bonds, wherein said fourth material is defined as having a glass transition temperature A coating material, typically below room temperature, wherein said fourth material has a thickness of 10 to 100 microns, wherein said fourth material is bonded to said first material, said second material, said third material, or said fifth material. The article of claim 23, further comprising: a sixth material comprising said thermoset elastomer crosslinked with β-hydroxy ester linkages, wherein said sixth material is defined as having a glass transition temperature A rigid or semi-rigid material, generally above room temperature, wherein said sixth material is substantially amorphous in structure, wherein said sixth material is bonded to said first material, said second material, said on the third material, the fourth material or the fifth material. An article of manufacture comprising: a. A first material comprising a thermosetting elastomer cross-linked with β-hydroxyester bonds, wherein said first material is defined as a leather-like material having a glass transition temperature generally below room temperature, wherein said the first material is generally planar and has a thickness of about 0.3 mm to 2.5 mm; b. a third material comprising said thermoset elastomer crosslinked with beta-hydroxyester linkages, wherein said third material is defined as a molded elastomeric material having a glass transition temperature of not greater than about 25°C , wherein the third material is three-dimensionally shaped; and, c. A sixth material comprising said thermoset elastomer cross-linked with beta-hydroxy ester linkages, wherein said sixth material is defined as a rigid or semi-rigid material having a glass transition temperature generally above room temperature , wherein the sixth material is substantially amorphous in structure, wherein the first material is bonded to the third material or to the sixth material, and wherein the third material is bonded to the first material or the sixth material. The article of claim 25, further comprising: a second material comprising said thermoset elastomer crosslinked with beta-hydroxy ester bonds, wherein said second material is defined as having a glass transition temperature A foam material not greater than about 25°C and having a density of less than 0.7 g/cc, wherein the second material is bonded to the first material, the third material, or the sixth material. The article of claim 26, further comprising: a fourth material comprising said thermoset elastomer crosslinked with β-hydroxy ester bonds, wherein said fourth material is defined as having a glass transition temperature A coating material, typically below room temperature, wherein said fourth material has a thickness of 10 to 100 microns, wherein said fourth material is bonded to said first material, said second material, said third material, or the sixth material. The article of claim 17, further comprising: a fifth material comprising said thermoset elastomer crosslinked with β-hydroxy ester linkages, wherein said fifth material is defined as having a glass transition temperature An adhesive material, typically below room temperature, wherein said fifth material has a thickness of 1 mm or less, and wherein said fifth material is positioned between said first material and said second material, said first material and the third material, the first material and the fourth material, the first material and the sixth material, the second material and the third material, the second material and the The third material, the second material and the fourth material, the second material and the sixth material, the third material and the fourth material, the third material and the A sixth material, or between and bonded to the fourth material and the sixth material. An article of manufacture comprising: a. A first material comprising a thermosetting elastomer cross-linked with β-hydroxyester bonds, wherein said first material is defined as a leather-like material having a glass transition temperature generally below room temperature, wherein said the first material is generally planar and has a thickness of about 0.3 mm to 2.5 mm; b. a fourth material comprising said thermoset elastomer crosslinked with beta-hydroxyester linkages, wherein said fourth material is defined as a coating material having a glass transition temperature generally below room temperature, wherein The fourth material has a thickness of 10 to 100 microns; c. a fifth material comprising said thermoset elastomer crosslinked with beta-hydroxy ester linkages, wherein said fifth material is defined as an adhesive material having a glass transition temperature generally below room temperature, wherein The thickness of the fifth material is 1 mm or less, and wherein the fifth material is positioned between and bonded to the first material and the fourth material. The article of claim 29, further comprising: a second material comprising said thermoset elastomer crosslinked with β-hydroxy ester linkages, wherein said second material is defined as having a glass transition temperature A foam material not greater than about 25°C and having a density of less than 0.7 g/cc, wherein the second material is bonded to the first material, the fourth material, or the fifth material. The article of claim 30, further comprising: a third material comprising said thermoset elastomer crosslinked with beta-hydroxy ester linkages, wherein said third material is defined as having a glass transition temperature A molded elastomeric material of not greater than about 25°C, wherein said third material is three-dimensionally shaped, wherein said third material is bonded to said first material, said second material, said fourth material, or the fifth material. The article of claim 31, further comprising: a sixth material comprising said thermoset elastomer crosslinked with beta-hydroxy ester linkages, wherein said sixth material is defined as having a glass transition temperature A rigid or semi-rigid material, generally above room temperature, wherein said sixth material is substantially amorphous in structure, wherein said sixth material is bonded to said first material, said second material, said on the third material, the fourth material or the fifth material. An article of manufacture comprising: a. A first material comprising a thermosetting elastomer cross-linked with β-hydroxyester bonds, wherein said first material is defined as a leather-like material having a glass transition temperature generally below room temperature, wherein said the first material is generally planar and has a thickness of about 0.3 mm to 2.5 mm; b. a fourth material comprising said thermoset elastomer crosslinked with beta-hydroxyester linkages, wherein said fourth material is defined as a coating material having a glass transition temperature generally below room temperature, wherein The fourth material has a thickness of 10 to 100 microns; c. A sixth material comprising said thermoset elastomer cross-linked with beta-hydroxy ester linkages, wherein said sixth material is defined as a rigid or semi-rigid material having a glass transition temperature generally above room temperature , wherein the sixth material is substantially amorphous in structure, wherein the first material is bonded to the fourth material or to the sixth material, and wherein the fourth material is bonded to the first material or the sixth material. The article of claim 33, further comprising: a second material comprising said thermoset elastomer crosslinked with beta-hydroxy ester linkages, wherein said second material is defined as having a glass transition temperature A foam material not greater than about 25°C and having a density of less than 0.7 g/cc, wherein the second material is bonded to the first material, the fourth material, or the sixth material. The article of claim 34, further comprising: a third material comprising said thermoset elastomer crosslinked with beta-hydroxy ester linkages, wherein said third material is defined as having a glass transition temperature A molded elastomeric material of not greater than about 25°C, wherein said third material is three-dimensionally shaped, wherein said third material is bonded to said first material, said second material, said fourth material, or The sixth material. The article of claim 35, further comprising: a fifth material comprising said thermoset elastomer crosslinked with beta-hydroxy ester linkages, wherein said fifth material is defined as having a glass transition temperature An adhesive material, typically below room temperature, wherein said fifth material has a thickness of 1 mm or less, and wherein said fifth material is positioned between said first material and said second material, said first material and the third material, the first material and the fourth material, the first material and the sixth material, the second material and the third material, the second material and the The fourth material, the second material and the sixth material, the third material and the fourth material, the third material and the sixth material, or the fourth material and the between and bonded to the sixth material. An article of manufacture comprising: a. A first material comprising a thermosetting elastomer cross-linked with β-hydroxyester bonds, wherein said first material is defined as a leather-like material having a glass transition temperature generally below room temperature, wherein said the first material is generally planar and has a thickness of about 0.3 mm to 2.5 mm; b. a fifth material comprising said thermoset elastomer crosslinked with beta-hydroxy ester linkages, wherein said fifth material is defined as an adhesive material having a glass transition temperature generally below room temperature, wherein the fifth material has a thickness of 1 mm or less; c. A sixth material comprising said thermoset elastomer cross-linked with beta-hydroxy ester linkages, wherein said sixth material is defined as a rigid or semi-rigid material having a glass transition temperature generally above room temperature , wherein the sixth material is substantially amorphous in structure, wherein the first material is bonded to the fifth material or to the sixth material, and wherein the fifth material is bonded to the first material or the sixth material. The article of claim 37, further comprising: a second material comprising said thermoset elastomer crosslinked with beta-hydroxy ester bonds, wherein said second material is defined as having a glass transition temperature A foam material not greater than about 25°C and having a density of less than 0.7 g/cc, wherein the second material is bonded to the first material, the fifth material, or the sixth material. The article of claim 38, further comprising: a third material comprising said thermoset elastomer crosslinked with beta-hydroxy ester linkages, wherein said third material is defined as having a glass transition temperature A molded elastomeric material of not greater than about 25°C, wherein said third material is three-dimensionally shaped, wherein said third material is bonded to said first material, said second material, said fifth material, or The sixth material. The article of claim 39, further comprising: a fourth material comprising said thermoset elastomer crosslinked with beta-hydroxy ester linkages, wherein said fourth material is defined as having a glass transition temperature A coating material, typically below room temperature, wherein said fourth material has a thickness of 10 to 100 microns, wherein said fourth material is bonded to said first material, said second material, said third material, The fifth material, or the sixth material. The article of claim 1, wherein the thermoset elastomer is essentially the reaction product between a naturally occurring multifunctional carboxylic acid and an epoxidized triglyceride. The article of claim 1, wherein the cross-linking of the thermosetting elastomer with β-hydroxy ester bonds is performed using a reaction product between a naturally occurring multifunctional carboxylic acid and an epoxidized triglyceride. The article of claim 1, wherein said article is further defined as being an article of footwear, and wherein said first material is further defined as being an upper of said article of footwear. The article of claim 43, wherein said second material is further defined as being a midsole of said article of footwear, and wherein said third material is further defined as being an outsole of said article of footwear. The article of claim 4, wherein the sixth material is further defined as being a rigid or semi-rigid component of an article of footwear. The article of claim 1, wherein the article is further defined as a package. The product according to claim 1, wherein the thermosetting elastomer cross-linked with β-hydroxy ester bonds is further defined as capable of de-cross-linking the β-hydroxy ester bonds through a mechanochemical process. An article of manufacture comprising: a. A second material comprising said thermoset elastomer crosslinked with beta-hydroxyester linkages, wherein said second material is defined as having a glass transition temperature of not greater than about 25°C and a density of less than 0.7 g/ cc of foam; b. a third material comprising said thermoset elastomer crosslinked with beta-hydroxyester linkages, wherein said third material is defined as a molded elastomeric material having a glass transition temperature of not greater than about 25°C , wherein the third material is three-dimensionally shaped; and, c. a fourth material comprising said thermoset elastomer crosslinked with beta-hydroxyester linkages, wherein said fourth material is defined as a coating material having a glass transition temperature generally below room temperature, wherein The thickness of the fourth material is 10 to 100 microns, wherein the second material is bonded to the third material or the fourth material, and wherein the third material is bonded to the second material or the Fourth material. The article of claim 48, further comprising: a fifth material comprising said thermoset elastomer crosslinked with beta-hydroxy ester linkages, wherein said fifth material is defined as having a glass transition temperature An adhesive material, typically below room temperature, wherein said fifth material has a thickness of 1 mm or less, and wherein said fifth material is positioned between said second material and said third material, said second material and the fourth material, or between and bonded to the third material and the fourth material. The article of claim 49, further comprising: a sixth material comprising said thermoset elastomer crosslinked with beta-hydroxy ester linkages, wherein said sixth material is defined as having a glass transition temperature A rigid or semi-rigid material, generally above room temperature, wherein said sixth material is substantially amorphous in structure, wherein said sixth material is bonded to said first material, said second material, said on the third material, the fourth material or the fifth material. An article of manufacture comprising: a. A second material comprising said thermoset elastomer crosslinked with beta-hydroxyester linkages, wherein said second material is defined as having a glass transition temperature of not greater than about 25°C and a density of less than 0.7 g/ cc of foam; b. a third material comprising said thermoset elastomer crosslinked with beta-hydroxyester linkages, wherein said third material is defined as a molded elastomeric material having a glass transition temperature of not greater than about 25°C , wherein the third material is three-dimensionally shaped; and, c. a fifth material comprising said thermoset elastomer crosslinked with beta-hydroxy ester linkages, wherein said fifth material is defined as an adhesive material having a glass transition temperature generally below room temperature, wherein The thickness of the fifth material is 1 mm or less, and wherein the fifth material is positioned between and bonded to the second material and the third material. The article of claim 51, further comprising: a fourth material comprising said thermoset elastomer crosslinked with β-hydroxy ester linkages, wherein said fourth material is defined as having a glass transition temperature Coating materials, typically below room temperature, wherein the fourth material has a thickness of 10 to 100 microns, wherein the fourth material is bonded to the second material, the third material, or the fifth material . The article of claim 52, further comprising: a sixth material comprising said thermoset elastomer crosslinked with beta-hydroxy ester linkages, wherein said sixth material is defined as having a glass transition temperature A rigid or semi-rigid material, generally above room temperature, wherein said sixth material is substantially amorphous in structure, wherein said sixth material is bonded to said first material, said second material, said on the third material, the fourth material or the fifth material. An article of manufacture comprising: a. A second material comprising said thermoset elastomer crosslinked with beta-hydroxyester linkages, wherein said second material is defined as having a glass transition temperature of not greater than about 25°C and a density of less than 0.7 g/ cc of foam; b. a third material comprising said thermoset elastomer crosslinked with beta-hydroxyester linkages, wherein said third material is defined as a molded elastomeric material having a glass transition temperature of not greater than about 25°C , wherein the third material is three-dimensionally shaped; and, c. A sixth material comprising said thermoset elastomer cross-linked with beta-hydroxy ester linkages, wherein said sixth material is defined as a rigid or semi-rigid material having a glass transition temperature generally above room temperature , wherein the sixth material is substantially amorphous in structure, wherein the second material is bonded to the third material or to the sixth material, and wherein the third material is bonded to the second material or the sixth material. The article of claim 54, further comprising: a fourth material comprising said thermoset elastomer crosslinked with beta-hydroxy ester linkages, wherein said fourth material is defined as having a glass transition temperature Coating materials, typically below room temperature, wherein the fourth material has a thickness of 10 to 100 microns, wherein the fourth material is bonded to the second material, the third material, or the sixth material . The article of claim 55, further comprising: a fifth material comprising said thermoset elastomer crosslinked with beta-hydroxy ester linkages, wherein said fifth material is defined as having a glass transition temperature An adhesive material, typically below room temperature, wherein the fifth material has a thickness of 1 mm or less, and wherein the fifth material is positioned between the second material and the third material, the second material and the fourth material, the second material and the sixth material, the third material and the fourth material, the third material and the sixth material, or the fourth material between and bonded to the sixth material. An article of manufacture comprising: a. A second material comprising said thermoset elastomer crosslinked with beta-hydroxyester linkages, wherein said second material is defined as having a glass transition temperature of not greater than about 25°C and a density of less than 0.7 g/ cc of foam; b. a fourth material comprising said thermoset elastomer crosslinked with beta-hydroxyester linkages, wherein said fourth material is defined as a coating material having a glass transition temperature generally below room temperature, wherein The fourth material has a thickness of 10 to 100 microns; and, c. a fifth material comprising said thermoset elastomer crosslinked with beta-hydroxy ester linkages, wherein said fifth material is defined as an adhesive material having a glass transition temperature generally below room temperature, wherein The thickness of the fifth material is 1 mm or less, and wherein the fifth material is positioned between and bonded to the second material and the fourth material. The article of claim 57, further comprising: a third material comprising said thermoset elastomer crosslinked with beta-hydroxy ester linkages, wherein said third material is defined as having a glass transition temperature A molded elastomeric material of not greater than about 25°C, wherein said third material is three-dimensionally shaped, wherein said third material is bonded to said second material, said fourth material, or said fifth material. The article of claim 58, further comprising: a sixth material comprising said thermoset elastomer crosslinked with beta-hydroxy ester linkages, wherein said sixth material is defined as having a glass transition temperature A rigid or semi-rigid material, generally above room temperature, wherein said sixth material is substantially amorphous in structure, wherein said sixth material is bonded to said first material, said second material, said on the third material, the fourth material or the fifth material. An article of manufacture comprising: a. A second material comprising said thermoset elastomer crosslinked with beta-hydroxyester linkages, wherein said second material is defined as having a glass transition temperature of not greater than about 25°C and a density of less than 0.7 g/ cc of foam; b. a fourth material comprising said thermoset elastomer crosslinked with beta-hydroxyester linkages, wherein said fourth material is defined as a coating material having a glass transition temperature generally below room temperature, wherein The fourth material has a thickness of 10 to 100 microns; and, c. A sixth material comprising said thermoset elastomer cross-linked with beta-hydroxy ester linkages, wherein said sixth material is defined as a rigid or semi-rigid material having a glass transition temperature generally above room temperature , wherein the sixth material is substantially amorphous in structure, wherein the second material is bonded to the fourth material or to the sixth material, and wherein the fourth material is bonded to the second material or the sixth material. The article of claim 60, further comprising: a third material comprising said thermoset elastomer crosslinked with beta-hydroxy ester linkages, wherein said third material is defined as having a glass transition temperature A molded elastomeric material of not greater than about 25°C, wherein said third material is three-dimensionally shaped, wherein said third material is bonded to said second material, said fourth material, or said sixth material. The article of claim 61, further comprising: a fifth material comprising said thermoset elastomer crosslinked with beta-hydroxy ester linkages, wherein said fifth material is defined as having a glass transition temperature An adhesive material, typically below room temperature, wherein the fifth material has a thickness of 1 mm or less, and wherein the fifth material is positioned between the second material and the third material, the second material and the fourth material, the second material and the sixth material, the third material and the fourth material, the third material and the sixth material, or the fourth material between and bonded to the sixth material. An article of manufacture comprising: a. A second material comprising said thermoset elastomer crosslinked with beta-hydroxyester linkages, wherein said second material is defined as having a glass transition temperature of not greater than about 25°C and a density of less than 0.7 g/ cc of foam; b. a fifth material comprising said thermoset elastomer crosslinked with beta-hydroxy ester linkages, wherein said fifth material is defined as an adhesive material having a glass transition temperature generally below room temperature, wherein the fifth material has a thickness of 1 mm or less; and, c. A sixth material comprising said thermoset elastomer cross-linked with beta-hydroxy ester linkages, wherein said sixth material is defined as a rigid or semi-rigid material having a glass transition temperature generally above room temperature , wherein the sixth material is substantially amorphous in structure, wherein the second material is bonded to the fifth material or to the sixth material, and wherein the fifth material is bonded to the second material or the sixth material. The article of claim 63, further comprising: a third material comprising said thermoset elastomer crosslinked with beta-hydroxy ester linkages, wherein said third material is defined as having a glass transition temperature A molded elastomeric material of not greater than about 25°C, wherein said third material is three-dimensionally shaped, wherein said third material is bonded to said second material, said fifth material, or said sixth material. The article of claim 64, further comprising: a fourth material comprising said thermoset elastomer crosslinked with beta-hydroxy ester linkages, wherein said fourth material is defined as having a glass transition temperature Coating materials, typically below room temperature, wherein said fourth material has a thickness of 10 to 100 microns, wherein said fourth material is bonded to said second material, said third material, said fifth material, or the sixth material. 48. The article of claim 48, wherein the thermoset elastomer is essentially the reaction product between a naturally occurring multifunctional carboxylic acid and an epoxidized triglyceride. 48. The article of claim 48, wherein the crosslinking of the thermosetting elastomer with beta-hydroxy ester linkages is performed using a reaction product between a naturally occurring multifunctional carboxylic acid and an epoxidized triglyceride. The article of claim 48, wherein said article is further defined as being an article of footwear, and wherein said first material is further defined as being an upper of said article of footwear. The article of claim 68, wherein said second material is further defined as being a midsole of said article of footwear, and wherein said third material is further defined as being an outsole of said article of footwear. The article of claim 53, wherein said sixth material is further defined as being a rigid or semi-rigid component of an article of footwear. The article of claim 1, wherein the article is further defined as a package. The product according to claim 1, wherein the thermosetting elastomer cross-linked with β-hydroxy ester bonds is further defined as capable of de-cross-linking the β-hydroxy ester bonds through a mechanochemical process. An article of manufacture comprising: a. A third material comprising said thermoset elastomer crosslinked with beta-hydroxy ester linkages, wherein said third material is defined as a molded elastomeric material having a glass transition temperature of not greater than about 25°C , wherein the third material is in a three-dimensional shape; b. a fourth material comprising said thermoset elastomer crosslinked with beta-hydroxyester linkages, wherein said fourth material is defined as a coating material having a glass transition temperature generally below room temperature, wherein The fourth material has a thickness of 10 to 100 microns; and, c. a fifth material comprising said thermoset elastomer crosslinked with beta-hydroxy ester linkages, wherein said fifth material is defined as an adhesive material having a glass transition temperature generally below room temperature, wherein The thickness of the fifth material is 1 mm or less, and wherein the fifth material is positioned between and bonded to the third material and the fourth material. The article of claim 73, further comprising: a sixth material comprising said thermoset elastomer crosslinked with beta-hydroxy ester linkages, wherein said sixth material is defined as having a glass transition temperature A rigid or semi-rigid material, generally above room temperature, wherein said sixth material is substantially amorphous in structure, wherein said sixth material is bonded to said third material, said fourth material, or said On the fifth material. An article of manufacture comprising: a. A third material comprising said thermoset elastomer crosslinked with beta-hydroxy ester linkages, wherein said third material is defined as a molded elastomeric material having a glass transition temperature of not greater than about 25°C , wherein the third material is in a three-dimensional shape; b. a fourth material comprising said thermoset elastomer crosslinked with beta-hydroxyester linkages, wherein said fourth material is defined as a coating material having a glass transition temperature generally below room temperature, wherein The fourth material has a thickness of 10 to 100 microns; and, c. A sixth material comprising said thermoset elastomer cross-linked with beta-hydroxy ester linkages, wherein said sixth material is defined as a rigid or semi-rigid material having a glass transition temperature generally above room temperature , wherein the sixth material is substantially amorphous in structure, wherein the third material is bonded to the fourth material or to the sixth material, and wherein the fourth material is bonded to the third material or the sixth material. The article of claim 75, further comprising: a fifth material comprising said thermoset elastomer crosslinked with beta-hydroxy ester linkages, wherein said fifth material is defined as having a glass transition temperature An adhesive material, typically below room temperature, wherein said fifth material has a thickness of 1 mm or less, and wherein said fifth material is positioned between said third material and said fourth material, said third material and the sixth material, or the fourth material and the sixth material are bonded thereto. An article of manufacture comprising: a. A third material comprising said thermoset elastomer crosslinked with beta-hydroxy ester linkages, wherein said third material is defined as a molded elastomeric material having a glass transition temperature of not greater than about 25°C , wherein the third material is in a three-dimensional shape; b. a fifth material comprising said thermoset elastomer crosslinked with beta-hydroxy ester linkages, wherein said fifth material is defined as an adhesive material having a glass transition temperature generally below room temperature, wherein the fifth material has a thickness of 1 mm or less; and, c. A sixth material comprising said thermoset elastomer cross-linked with beta-hydroxy ester linkages, wherein said sixth material is defined as a rigid or semi-rigid material having a glass transition temperature generally above room temperature , wherein the sixth material is substantially amorphous in structure, wherein the third material is bonded to the fifth material or to the sixth material, and wherein the fifth material is bonded to the third material or the sixth material. An article of manufacture comprising: a. a fourth material comprising said thermoset elastomer cross-linked with beta-hydroxyester linkages, wherein said fourth material is defined as a coating material having a glass transition temperature generally below room temperature, wherein The fourth material has a thickness of 10 to 100 microns; b. a fifth material comprising said thermoset elastomer crosslinked with beta-hydroxy ester linkages, wherein said fifth material is defined as an adhesive material having a glass transition temperature generally below room temperature, wherein the fifth material has a thickness of 1 mm or less; and, c. A sixth material comprising said thermoset elastomer cross-linked with beta-hydroxy ester linkages, wherein said sixth material is defined as a rigid or semi-rigid material having a glass transition temperature generally above room temperature , wherein the sixth material is substantially amorphous in structure, wherein the fourth material is bonded to the fifth material or to the sixth material, and wherein the fifth material is bonded to the fourth material or the sixth material. An article of manufacture comprising: a. a first material comprising a thermoset elastomer crosslinked with beta-hydroxy ester linkages; b. a second material comprising said thermoset elastomer crosslinked with beta-hydroxy ester linkages, and, c. A third material comprising a thermoset elastomer crosslinked with β-hydroxy ester bonds, wherein the first material is bonded to the second material or to the third material, wherein the second a material bonded to the first material or the third material, and wherein the first material, the second material, and the third material are selected from the group consisting of: i. a leather-like material having a glass transition temperature generally below room temperature, wherein said first material is generally planar and has a thickness of about 0.3 mm to 2.5 mm; ii. Foam materials with a glass transition temperature not greater than about 25°C and a density less than 0.7 g/cc; iii. A molded elastomeric material having a glass transition temperature of not greater than about 25°C, wherein the molded elastomeric material is three-dimensional in shape; iv. Coating materials having a glass transition temperature generally below room temperature, wherein said coating material has a thickness of 10 to 100 microns; v. Adhesive materials having a glass transition temperature generally below room temperature, wherein the adhesive material has a thickness of 1 mm or less; and, vi. A rigid or semi-rigid material having a glass transition temperature generally above room temperature, wherein said rigid or semi-rigid material is substantially amorphous in structure. 79. The article of claim 79, wherein the thermoset elastomer is essentially the reaction product between a naturally occurring multifunctional carboxylic acid and an epoxidized triglyceride. 79. The article of claim 79, wherein the crosslinking of the thermoset elastomer with beta-hydroxy ester linkages is performed using a reaction product between a naturally occurring multifunctional carboxylic acid and an epoxidized triglyceride. The article of claim 79, wherein said article is further defined as being an article of footwear, and wherein said first material is further defined as being an upper of said article of footwear. The article of footwear recited in claim 82, wherein said second material is further defined as being a midsole of said article of footwear, and wherein said third material is further defined as being an outsole of said article of footwear . The article of claim 83, further comprising: a fourth material, wherein the fourth material is defined as the rigid or semi-rigid material, and wherein the fourth material is a component of the article of footwear. The article of claim 79, wherein said article is further defined as being a bag. The article of claim 79, wherein the thermosetting elastomer crosslinked with β-hydroxy ester bonds is further defined as capable of decrosslinking the β-hydroxy ester bonds through a mechanochemical process. A method for recovering products, said method comprising the steps of: a. removing metallic hard parts from said article such that said article is substantially free of any metallic material to produce a metal-free mixture; b. Mechanochemical treatment of said metal-free mixture with a rubber internal mixer; c. causing the rubber mixer to break down the metal-free mixture into a generally homogeneous mixture; d. mechanochemically treating said generally homogeneous mixture in a relatively low temperature and relatively high shear process; and, e. Subjecting the generally homogeneous mixture to the relatively low temperature and relatively high shear process until the generally homogeneous mixture is processed into a grindable gum. The method of claim 87, wherein said relatively low temperature and relatively high shear process is further defined as being performed via a two-roll rubber mill. The method of claim 87, wherein said article is further defined as constructed from a first material, a second material, and a third material, wherein said first material, second material, and third material define is a thermosetting elastomer cross-linked with β-hydroxy ester bonds, wherein the first material is defined as a leather-like material whose glass transition temperature is generally lower than room temperature. The method of claim 89, wherein said second material is further defined as a foam material having a glass transition temperature of not greater than about 25°C and a density of less than 0.7 g/cc, and wherein said first material is bonded to said second material. The method of claim 90, wherein said third material is further defined as a molded elastomeric material having a glass transition temperature of not greater than about 25°C, wherein said third material is three-dimensionally shaped, wherein said first Three materials are bonded to either the first material or the second material. A method for recovering products, said method comprising the steps of: a. mechanochemically treating said article with a rubber mixer, wherein said article only comprises materials that can be processed by said rubber mixer; b. causing the rubber mixer to break down the product into a generally homogeneous mixture; c. mechanochemically treating said generally homogeneous mixture in a relatively low temperature and relatively high shear process; and, d. Subjecting the generally homogeneous mixture to the relatively low temperature and relatively high shear process until the generally homogeneous mixture is processed into a grindable gum. The method of claim 92, wherein said article is further defined as constructed from a first material, a second material, and a third material, wherein said first material, second material, and third material define is a thermosetting elastomer cross-linked with β-hydroxy ester bonds, wherein the first material is defined as a leather-like material whose glass transition temperature is generally lower than room temperature. The method of claim 93, wherein said second material is further defined as a foam material having a glass transition temperature of not greater than about 25°C and a density of less than 0.7 g/cc, and wherein said first material is bonded to said second material. The method of claim 94, wherein said third material is further defined as a molded elastomeric material having a glass transition temperature of not greater than about 25°C, wherein said third material is three-dimensionally shaped, wherein said first A third material is bonded to either the first material or the second material. The method of claim 92, wherein said relatively low temperature and relatively high shear process is further defined as being performed via a two-roll rubber mill. A method for manufacturing an article, said method consisting of the steps of: a. selecting a first material, a second material, and a third material, wherein said first material, said second material, and said third material are selected from the group consisting of: i. A leather-like material having a glass transition temperature generally below room temperature, wherein said first material is generally planar and has a thickness of about 0.3 mm to 2.5 mm; and wherein said leather-like material is bonded with beta-hydroxy esters Cross-linked thermoset elastomers; ii. Foams having a glass transition temperature of not greater than about 25°C and a density of less than 0.7 g/cc, and wherein the foam is a thermoset elastomer crosslinked with beta-hydroxy ester linkages; iii. A molded elastomeric material having a glass transition temperature of not greater than about 25°C, wherein said molded elastomeric material is a three-dimensional shape, and wherein said molded elastomeric system is a thermoset elastomer crosslinked with beta-hydroxy ester linkages ; iv. Coating materials having a glass transition temperature generally below room temperature, wherein the coating material has a thickness of 10 to 100 microns, and wherein the coating material is a thermosetting elastomer crosslinked with beta-hydroxy ester bonds; v. Binder materials having a glass transition temperature generally below room temperature, wherein the binder material has a thickness of 1 mm or less, and wherein the binder material is a thermoset elastomer crosslinked with beta-hydroxy ester bonds; as well as, vi. Rigid or semi-rigid materials having a glass transition temperature generally above room temperature, wherein said rigid or semi-rigid material is substantially amorphous in structure, and wherein said rigid or semi-rigid material is made of beta-hydroxyester Bonded cross-linked thermosetting elastomers; b. bonding said first material to said second material; c. bonding the third material to the first material or the second material. 97. The method of claim 97, wherein the thermoset elastomer is essentially the reaction product between a naturally occurring multifunctional carboxylic acid and an epoxidized triglyceride. 97. The method of claim 97, wherein the crosslinking of the thermosetting elastomer with beta-hydroxy ester linkages is performed using a reaction product between a naturally occurring multifunctional carboxylic acid and an epoxidized triglyceride. 97. The method of claim 97, wherein said article is further defined as being an article of footwear, and wherein said first material is further defined as being a leather-like material forming an upper of said article of footwear. The method recited in claim 100, wherein said second material is further defined as a foam material forming a midsole of said article of footwear, and wherein said third material is further defined as a foam material forming said article of footwear outer Bottom of molded elastomer. The method as described in Claim 101, further comprising the following steps: a. selecting a fourth material, wherein said fourth material is defined as said rigid or semi-rigid material, and wherein said fourth material is a component of said article of footwear; and b. bonding the fourth material to the first material, the second material, or the third material. The method of claim 97, wherein said article is further defined as a package. The method according to claim 97, wherein the thermosetting elastomer cross-linked with β-hydroxy ester bonds is further defined as capable of de-cross-linking the β-hydroxy ester bonds through a mechanochemical process.

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